Asian Workshop on Polymer Processing
1 - 4 December 2015. University Town (U-Town)
of NUS

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Asian Workshop on Polymer Processing
1 - 4 December 2015. University Town (U-Town) of NUS
1st December 2015
Time
1:30 PM

Programme
Transport for AWPP EXCO meeting Centre @ University Town from Park Avenue Rochester Hotel, transport will then proceedto Kent Vale then to University Town.
Asian Workshop on Polymer Processing (AWPP) EXCO Meeting

2:00~5:00 PM

Venue: Conference Room 2, Stephen Riady Centre, 2 College Avenue West, University Town, National University of Singapore,
Singapore 138607

4:30 PM

Please note that the AWPP EXCO Meeting is strictly for invited guests only.
Transport for AWPP Welcome Reception @ University Town from Park Avenue Rochester Hotel, transport will then proceedto Kent Vale then to University Town.
AWPP 2015 – Welcome Reception

5:00~7:00 PM

Venue: University Town, National University of Singapore, 8 College Avenue West, Education Resource Centre (ERC), Level 2,
Ngee Ann Kongsi Auditorium, Singapore 138608

7:15 PM

Transport will leave University Town for Kent Vale and then to Park Avenue Rochester Hotel.

Asian Workshop on Polymer Processing
1 - 4 December 2015. University Town (U-Town) of NUS
2nd December 2015
Time

Programme

8:00~8:30 AM
8:00 AM

Conference Registration
Transport to Conference Venue @ University Town, NUS from Park Avenue Rochester Hotel. Transport will then proceed to Kent Vale.
Delegates at Kent Vale should be ready for pick up at 08:15 at the main drop-off point at Kent Vale. The drop-off point is across the roundabout in Kent Vale in frontof the main entrance.
Conference Venue: University Town, National University of Singapore, 8 College Avenue West, Education Resource Centre (ERC), Level 2, Ngee Ann Kongsi
Auditorium, Singapore 138608

8:30~8:45 AM
8:45~9:25 AM

Opening Address by Prof He Chaobin (Chairman, AWPP)
Plenary Lecture
Polymeric Membranes for Clean Water and Clean Energy
Neal Tai-Shung Chung (NUS, Singapore)
Session Chair: He Chaobin

9:25~10:05 AM

Plenary Lecture
Processing Thermoplastic High Performance Composites
Florian Doetzer (Composite Cluster Singapore Pte Ltd., Singapore)
Session Chair: He Chaobin

10:05~10:30 AM

10:30~11:00 AM

11:00~11:15 AM

Session-1: Materials from biomass
Session Chair: Li Xu
Keynote Presentation
Biodegradable Polymer Composites of Poly(lactic acid) Blends and Natural
FibersS. Pivsa-Art (RMUTT, Thailand)
Keynote Presentation
Recent Dvelopment of Direct Fiber Feeding Injection Molding
H. Hamada (Kyoto Institute of Technology, Japan)

11:15~11:30 AM

Tea breakSession-2: Extrusion based processes
Session Chair: Pramoda Kumari Pallathadka
Keynote Presentation
Polyethylene-Thermally Reduced Graphene Nanocomposites: Comparison ofMasterbatch and Direct Melt Mixing Approaches on Mechanical, Thermal,
Rheological and Morphological Properties
V. Mittal (The Petroleum Institute, Abu Dhabi, UAE)
Invited Talk
Effect of Cross-sectional Configuration on Die Swell Behavior ad Spin-line Stability
in Bicomponent Melt Spinning Process
W. Takarada (Tokyo Institute of Technology, Japan)
Invited Talk
Polymer Melt Differential 3D Printing and Advanced Manufacturing
W. Yang (Beijing University of Chemical Technology, China)

11:30~ 11:45 AM

Invited Talk
Nanocomposites based on Biomass Charcoal with Multifunction
A. Qin (Guilin University of Technology, China)

11:45~12:00 PM

Invited Talk
Effect of Cellulose Nanofiber on Scratch Resistance of Poly(vinyl alcohol)
Composites
S. Konagaya (Nagoya University, Japan)
Oral Presentation
Studies of Mechanical Properties of High Density Polyethylene/Vietnamosasa
Pusilla Fiber Composite for Decoration Applications
S. Suadaow (RMUTT, Thailand)

12:00~12:15 PM

12:15~12:30 PM

12:30~1:30 PM

Oral Presentation
Fiber-breakage Evaluation of Melts passing through Check-ring based on Newlydeveloped Heating Cylinder with Multi-ports for In-process Sampling
M. Sai (University of Tokyo, Japan)
Oral Presentation
Study on feedstock of metal injection molding
N. Kayamori (Doshisha University, Japan)
Oral Presentation
Effect of Titanium Dioxide On the Interface of Poly(lactic acid) between Sheath-core
FibersN. Roungpaisan (RMUTT, Thailand)

Oral Presentation
Fiber Structure Development in High-speed Melt Spinning of Sheath-core
Bicomponent Fibers consisting of Aliphatic Copolyesters of Different Copolymer
Composition
Q. Qing (Tokyo Institute of Technology, Japan)
Lunch Break1:30~2:00 PM

2:00~2:30 PM

2:30~2:45 PM

2:45~3:00 PM

3:00~3:15 PM

3:15~3:30 PM

3:30~4:00 PM

4:00~4:15 PM

Session-3: Polymers for energy and sustainability
Session-4: Modeling and Simulation
Session Chair: Jiang Zhenyu
Session Chair: Warintorn Thitsartarn
Keynote Presentation
Keynote Presentation
In Silico Processing of Polymers
Electrospinning of Porous Polymer Nanofibers and their Applications as
A.Soldera (University of Sherbrooke, Quebec, Canada)
Functional Materials
X. Lu (NTU, Singapore)
Keynote Presentation
Keynote Presentation
Measurement of Gas-pressure Distributions inside Mold Cavity during Gas-venting
Nanostructured Additive-enhanced High Performance Superhydrophobic
Process by Small-diameter Melt Pressure Sensor
Coating Materials
H. Yokoi (University of Tokyo, Japan)
J. Xu (A*STAR IMRE, Singapore)
Invited Talk
Invited Talk
Molecular Simulation of the Effect of Chain Tacticity on Demixing ofGreen Chemistry: Preparation of Environmentally-benign Graft Copolymers via
Polyethylene/Propropylene Blends
Emulsion System
V. Vao-soongnern (Suranaree University of Technology, Thailand)
K. Ishimoto (RMUTT, Thailand)
Invited Talk
Invited Talk
Melt-mixing by Pitched-tip Kneading Disks in a Twin-screw extruder
Modification of chemically stable polymeric materials 63. Improvement in the
T. Kajiwara (Kyushu University, Japan)
adhesion property of polymeric materials, FRP and CFRPs for car-use
H. Kanazawa (Fukushima University, Japan)
Oral Presentation
Invited Talk
Polymer Processing Simulation Challenges in Describing Highly Elastic Flows
Study on Fabricating Carbon Nano Fiber by Cotton Candy Method
K. Tomioka (Nitto Denko Corporation, Japan)
R. Takematsu (Kyoto Institute of Technology, Japan)
Oral Presentation
Invited Talk
Evaluation of Distributive Mixing in an Internal Mixer by Partially Filled Flow
Development of Poly(lactic acid)/Gelatin/Shellac Blend for Green Composite
AnalysisFilm from
K. Higashi (Kobe Steel, Ltd., Japan)
K. Nilgumhang (RMUTT, Thailand)
Tea BreakSession-5: Polymer characterization:
Session-6: Polymer nanotechnology:
Session Chair: Pramoda Kumari Pallathadka
Session Chair: Prof. Ashok Misra
Keynote Presentation
Invited Talk
Effect of Surface Pre-treatment of Substrate on Wettability of Metal Nano-ink
Dynamic Mechanical Properties of Sisal Fiber Cellulose
T. Saito (Tokyo Institute of Technology, Japan)
Microcrystal/unsaturated Polyester in-situ Composites
C. Wei (Guilin University of Technology, China)

4:15~4:30 PM

Invited Talk
Multi-element Analysis of Polymer Using Wavelength Dispersive XRF
H.R. Low (Bruker, Singapore)

4:30~4:45 PM

Invited Talk
The Flameretardancy Study of PVA using for Cardboard Bed
Y. Mizutani (Kyoto Institute of technology, Japan)

4:45~5:00 PM

Oral Presentation
Invited Talk
Preparation of The Carbon Nano Fiber Using Cotton Candy Method
Size, Shapes and Superstructures of Polymeric Materials with a SAXS/WAXS
A. Tada (Ohgi Technological Creation Co., Ltd., Japan)
Instrument
S. Rodrigues (Xenocs, France)
Oral Presentation
Oral Presentation
Development of PEEK-Nano-SIC Composites for High Performance Coating andAnalysis on Crystallization Behavior of Equi-biaxially Stretched Amorphous
Adhesive Appplications
Poly(ethylene Terephthalate) Films
A. K. Kadiyala (Indian Institute of Technology Delhi, India)
S. Shibata (Tokyo Institute of Technology, Japan)
Transport will leave University Town for Kent Vale and then to Park Avenue Rochester Hotel.

5:00~5:15 PM

5:30 PM

Invited Talk
2D Array Nanohole Processing on Ultrathin Polymer Films with Gold Nanoparticles
K. Yamada (Kyoto Institute of Technology, Japan)

Asian Workshop on Polymer Processing
1 - 4 December 2015. University Town (U-Town) of NUS
3rd December 2015
Programme

Time
8:00 AM

Transport to Conference Venue @ University Town, NUS from Park Avenue Rochester Hotel. Transport will then proceed to Kent Vale.
Delegates at Kent Vale should be ready for pick up at 08:15 at the main drop-off point at Kent Vale. The drop-off point is across the roundabout in Kent Vale in frontof the main entrance.

Conference Venue: University Town, National University of Singapore, 8 College Avenue West, Education Resource Centre (ERC), Level 2, Ngee Ann Kongsi
Auditorium, Singapore 138608
Plenary Lecture
Foamability of Multi-Phase Polymeric Materials
A. K. Ghosh (IIT Delhi, India)
Session Chair: Leong Yew Wei
Plenary Lecture
Material Development for Automotive Application
T. Kitayama (Sumitormo Chemical Co. Ltd., Japan)
Session Chair: Leong Yew Wei

8:45~9:25 AM

9:25~10:05 AM

10:05~10:30 AM
Session-7: Nanocomposite
Session Chair: Takushi Saito
10:30~11:00 AM

11:00~11:30 AM

11:30~ 12:00 PM

12:00~12:15 PM

12:15~12:30 PM

12:30~12:45 PM

12:45~1:45 PM

1:45~2:15 PM

2:15~2:45 PM

2:45~3:00 PM

3:00~3:15 PM

3:15~3:30 PM

3:30~3:45 PM

3:45~5:30 PM

Tea breakSession-8: Biodegradable materials
Session Chair: Sommai Pivsa-Art

Keynote Presentation
Keynote Presentation
Functional Polynorbornenes: Ultra-hgh Tg Thermosetting Fibers and Composites Redox-responsive poly(amido amine)s from trifunctional amines forbioapplications
J.C. Claverie (UQAM, Canada)
Y. Liu (A*STAR IMRE, Singapore)
Keynote Presentation
Keynote Presentation
Enhancing Dispersion of Nanoparticles in Molten Polymers
Towards high-performance polypropylene/expanded graphite/carbon
nanotubes ternary composites with significantly enhanced thermal and electrical N. Phonthammachai (SCG Chemicals Co., Ltd., Thailand)
conductivity via constructing double percolated filler network
Q. Fu (Sichuan University, China)
Keynote Presentation
Keynote Presentation
Processing Conditions and Properties of Nonwoven Kenaf Reinforced Acrylic
Synergistic Dispersion of Carbon Nanomaterials in Polymer Nanocomposites
Based Polyester Composites
T. Liu (Fudan University, China)
Z. A. M. Ishak (Universiti Sains Malaysia, Malaysia)
Invited Talk
Invited Talk
Dynamic Mechanical Analysis and Heat Seal Property of Biodegradable Polymer Controlled Urea and Ammonium Sulfate Released from Polylactic acid for Slow
Released Fertilizer Application
Blends and Composite Films
S. Niamlang (RMUTT, Thailand)
S. Thumsorn (RMUTT, Thailand)
Invited Talk
Invited Talk
Influence of Reactive Agents on Flow Property and Mechanical Properties ofGraphene Nanoplatelet/Poly(butylene adipate-co-terephathalate) Hybrids:
Biodegradable Polyesters
Physical Properties
S. Suttiruengwong (Silpakorn University, Thailand)
R. Gupta (RMIT University, Australia)
Invited Talk
Oral Presentation
Biodegradable and Renewable Poly(lactide)-lignin Composites: Synthesis,
Development of starch based bio-film and life cycle assessment
Interface and Toughening Mechanism
X. Zhang (A*STAR SIMTech, Singapore)
Y.Sun (NUS, Singapore)
Lunch BreakSession-10: Polymer blendsSession-9: Molding based processes
Session Chair: Mohit Sharma
Session Chair: Toshitaka Kanai
Keynote Presentation
Semi-interpenetrating Network of Polyoxymethylene with Oligo-benzoxazine via
Reactive Blending
S. Chirachanchai (Chulalongkorn University, Thailand)
Keynote Presentation
The Relationship Between Morphology and Impact Toughness of Poly(L-lacticacid)/Poly(ethylene oxide) Blends
C. Chan (The Hong Kong University of Science and Technology, China)
Invited Talk
Invited Talk
Physical Degradation Theory and Physical Regeneration Method for Recycling of Adhesion Behavior of "Warm-off" Type Acrylic PSAS
H. Murakami (Nagasaki University, Japan)
Waste Plastics
S. Yao (Fukuoka University, Japan)
Oral Presentation
Invited Talk
Preparation of Poly(lactic acid) Nanofiber by Nanofiber by Cotton Candy Method
Melt Transcription Molding Process with Higher Precision and Productivity for
R. Wongpajan (Kyoto institute of Technology, Japan)
Thin Thermoplatic Products with Micro- and Nano-structured Surface
K. Furuki (The Japan Steel Works, Ltd., Japan)
Keynote Presentation
Fabrication of Micro-needle Array using Biocompatible Polymers by Precision
Molding
H. Ito (Yamagata University, Japan)
Keynote Presentation
Skin Structure and Scratch Behavior of Injection Molded Polypropylene
M. Kotaki (Kaneka Americas Holding, Inc. USA)

Oral Presentation
Oral Presentation
Control of Glass Transition Temperature In Immiscible Rubber BlendHigh Expansion Open-cell Polylactide (PLA) Foam from Blends with Fibrillar
N. Kuhakongkiat (Japan Advanced Institute of Science and Technology, Japan)
Polytetrafluoroethylene (PTFE)
S. Ishihara (Kyoto University, Japan)
Oral Presentation
Oral Presentation
PP/LLDPE Hybrid in Axial Powder Flow Apparatus
Measurement of Demolding Resistance In Incline Direction to Texturing Cavity
E. Junsri (RMUTT, Thailand)
Surface using 3-Component Force Transducer
K. Daiki (University of Tokyo, Japan)
Poster Session and Tea Break
Venue: University Town, National University of Singapore, 8 College Avenue West, Education Resource Centre (ERC), Level 2, Ngee Ann Kongsi Auditorium,
Singapore 138608
Results of Top 3 posters will be announced at 17:15.

5:45 PM
6:00~8:30 PM

Transportation from University Town to Conference Banquet Venue
Conference Banquet
Venue: Kent Ridge Guild House, Level 2, Cluny & Dalvey Rooms, 9 Kent Ridge, Drive, Singapore 119241

8:45 PM

Transport will leave Kent Ridge Guild House for Kent Vale and then to Park Avenue Rochester Hotel.

Asian Workshop on Polymer Processing
1 - 4 December 2015. University Town (U-Town) of NUS
4th December 2015
Time
8:45 AM

Programme
Transport to Conference Venue @ University Town, NUS from Park Avenue Rochester Hotel. Transport will then proceed to Kent Vale.
Delegates at Kent Vale should be ready for pick up at 09:00 at the main drop-off point at Kent Vale. The drop-off point is across the roundabout in Kent Vale in frontof the main entrance.

9:30~10:00 AM

10:00~ 10:15 AM

10:15~10:30 AM

10:30~10:45 AM

10:45~11:00 AM

11:00~12:00 PM
12:00:00 PM
1:00~3:00 PM

Session-13: Functional Polymers
Session Chair: Anup Gosh
Keynote Presentation
Effect of Pre-annealing on 3-D Orientation Development Behavior During
Simultaneous and Sequential Biaxial Stretching of Poly(ethylene naphthalate)
Films
T. Kikutani (Tokyo Institute of Technology, Japan)
Invited Talk
Solid Electrolyte Function of Side-chain Crystalline Block Co-polymer
S. Yao (Fukuoka University, Japan)

Session-14: High Performance Polymers
Session Chair: Warintorn Thitsartarn
Keynote Presentation
Spinnability and Theoretical Analysis of the Spunbond Process for Polypropylene
T. Kanai (KT Polymer, Japan)

Invited Talk
Durability and Properties of Jute Fiber Treatment in Green Filled Rubber
W.Ariyawiriyanan (RMUTT, Thailand)
Oral Presentation
The Flameretardancy Study of Corrugated Cardboard using for Cardboard Bed
Y. Mochizuki (Kyoto Institute of Technology, Japan)

Invited Talk
Evaluation of grass fiber reinforced engineering plastics for water heater
H. Nishimura (Kyoto Institute of Technology, Japan)
Oral Presentation
Analysis of Dispersive Behavior and Mixing State of Filler Mixed into SBR and BR
S. Kaneko (Doshisha University, Japan)

Invited Talk
Percolation model for reinforcement efficiency of carbon nanotubes inthermoplastic composites
Z. Jiang (South China University of Technology, China)

Oral Presentation
Poly(lactic acid)/Polypropylene Blends for Cosmetic Case Products
J. Kordsa-Art (RMUTT, Thailand)

Oral Presentation
Measurement of Three-Dimensional Temperature Distributions Inside Cavity Filling
Melts using Integrated Thermocouple Sensor
S. Ishida (The University of Tokyo, Japan)
Lunch BreakTransport will leave University Town for Kent Vale and then to Park Avenue Rochester Hotel. (For Delegates not attending Fusion World Tour)
Fusion World Tour

Venue: 1 Fusionopolis Way, #13-10, Connexis North, Singapore 138632
Information for Group 1 (13:00 – 14:00)
Transportation will be provided at 12:15 from University Town to Fusionopolis.
After the tour, transportation will be provided from Fusionopolis to Park Avenue Rochester Hotel, then to Kent Vale.

Information for Group 2 (14:00 – 15:00)
Transportation will be provided at 13:15 from University Town to Fusionopolis.
After the tour, transportation will be provided from Fusionopolis to Park Avenue Rochester Hotel, then to Kent Vale.

Asian Workshop on Polymer Processing
1 - 4 December 2015. University Town (U-Town) of NUS
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Poster Information
Swarna, "Influence of Suspending Medium on Rheological Behavior of Shear Thickening Fluids ", Indian Institute of Technology Delhi,
India
T. Konno, "Structure and Engineering Properties of PMMA Nano-alloy obtained by High Speed Shearing Process ", Yamagata University,
Japan
Y. Yamada, "Evaluation of Higher-order Structure and Thermal Properties of High Thermal Conductivity PC Composites obtained by
Structural Phase Separation Method ", Yamagata University, Japan
H. Suenaga, "Evaluation of Structure-physical Properties of Reactive Molded Polyamide 6 and its FRTP ", Yamagata University, Japan
T. Sako, "Surface Localization of Poly(methyl methacrylate) in a Blend with Polycarbonate ", Japan Advanced Institute of Science andTechnology, JapanR. Watanabe, "Self-healing behavior of Styrene-butadiene-styrene Triblock Copolymer ", Japan Advanced Institute of Science andTechnology, JapanK. Yoshida, "Interphase Transfer of Plasticizer between Immiscible Rubbers ", Japan Advanced Institute of Science and Technology, Japan
S. Sato, "Anomalous Molecular Orientation of Extruded Sheet for Polypropylen/polybutene-1 Blends ", Japan Advanced Institute of
Science and Technology, Japan
S. Iwasaki, "Development of Evaluation Method Capable of Judging the Appropriate Product Lifetime of the Rubber Material Used In
Residential-use Cogeneration Systems ", Osaks Gas Co. Ltd., Japan
R. Hasuo, "Synthesis and Characterization of a Side-chain Crystalline Silicone PSA ", Nagasaki University, Japan
S. Tabuchi, "Warm-off" Type Acrylic PSA containing a Side-chain Crystalline Graft Copolymer ", Nagasaki University, Japan
M.S. Huang, "Effect of Clamping Force Set Value on Injection Molding Qualities ", National Kaohsiung First University of Science andTechnology, Taiwan
H. Kanazawa, "Modification of Chemically Stable Polymeric Materials 64. Improvement In the Hydrophilic and Adhesion Properties ofPolymeric Materials and FRPs ", Fukushima University, Japan
M. Sugimoto, "Improved Elongational Viscosity of Polycarbonate Melts ", Yamagata University, Japan
S.K. Hong, "Numerical Simulation of Injection/compression Molding for Multiscale Structure ", Korea Institute of Industrial Technology(KITECH), Republic of Korea
N. Oda, "Long Time Structure Constitution of Amorphous Polymer ", Fukuoka University Graduate School, Japan
K. Hirakawa, "Creation of Polar Solvent Type TR Fluid and its Function ", Fukuoka University Graduate School, Japan
Y. Hasebe, "TR Fluid Function for Differences in the Chemical Structure of the Side Chain Crystallizable Block Copolymer ", Fukuoka
University Graduate School, Japan
S. Jamornsuriya, "Atomistic Simulation of Gas Diffusion in Glassy Poly(Vinyl Pyrrolidone) Matrix ", Suranaree University of Technology,
ThailandC. Y. Chang, "A Highly Efficient REEL to REEL Hot Embossing Process for Fabrication of Polymer Microlens Array ", National Kaohsiung
University of Applied Sciences, Taiwan
H.W. Bai, "Towards High-performance Poly(L-lactide) Melt Spun Fibers by Tailoring Crystallization with the Aid of Nucleating Agent ",Sichuan University, China
G. Wang, "Novel Biomedical Materials Based on Carbon Dots ", A*STAR IMRE, Singapore
W. Ren, "Synthesis and Antimicrobial Activities of Quaternized PEI-g-chitosan Polycations ", A*STAR IMRE, Singapore
Z. M. Png, "Valorization of Palm Resource for Grease Lubricant ", A*STAR IMRE, Singapore
J. He, "Controlled Growth of MOF-based Hybrid Nanomaterials ", A*STAR IMRE, Singapore
C. C. Yap, "Hydrothermal Synthesis of Carbon Spheres from Glucose ", A*STAR IMRE, Singapore
X. Zhang, "Effect of Modified Starch and Nanoclay on Biodegradability and Mechanical Propertied of Polylactic Acid Ternary Blends ",A*STAR IMRE, Singapore
H. Yan, "Structural Engineering of Polyurethane for Multiple Functional Coatings ", A*STAR IMRE, Singapore

POLYMERIC MEMBRANES FOR CLEAN WATER AND CLEAN ENERGY
Oral presentation(Neal) Tai-Shung Chung1,2
1

Department of Chemical and Biomolecular Engineering,
National University of Singapore, Singapore 117585, Singapore
2
Water Desalination & Reuse Center, King Abdullah University of Science and Technology,
23955-6900 Saudi Arabia
Corresponding author email address: chencts@nus.edu.sg
Abstract - Clean water, clean energy, global warming and affordable healthcare are four major concerns globally
resulting from clean water shortages, high fluctuations of oil prices, climate changes and high costs of healthcare. Clean
water and public health are also highly related, while energy is essential for sustainable prosperity.
Among many potential solutions, advances in membrane technology are one of the most direct, effective and feasible
approaches to solve these sophisticated issues. Membrane technology is a fully integrated science and engineering
which consists of materials science and engineering, chemistry and chemical engineering, separation and purification
phenomena, environmental science and sustainability, statistical mechanics-based molecular simulation, process andproduct design.
In this presentation, we will introduce our efforts on materials design and polymeric membrane development for cleanwater production and osmotic power generation, then highlight our recent development on functional membranes forbiofuel separation, natural purification and separation.
The osmotic power generation via the mixing of water streams with different salinities across a semi-permeable
pressure retarded osmosis (PRO) membrane is one of our foci. If the osmotic power generator is integrated with thereverse osmois (RO) plant using its retentate as the draw solution, not only are we able to mitigate the disposal issues ofRO retentate, but also lower the overall energy consumption for RO plants. As a result, seawater desalination will bemuch cost-effective and this integration will entirely revolutionize the future desalination industry and energy
production.
Keywords: membrane technology, clean water, clean energy, osmotic energy, biofuel, gas separation

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

PROCESSING THERMOPLASTIC HIGH PERFORMANCE COMPOSITES
Keynote presentation
Florian Doetzer 1
1 Composite Cluster Singapore, Singapore

Corresponding author email address: doetzer@compositecluster.com
Abstract
High performance composites, originally developed in Aerospace & Defense applications, have traditionally used
thermoset matrix materials. However, with the needs for automation, short production cycles and low processing cost,
the interest in thermoplastic matrix systems has risen sharply.
While companies like ourselves are developing new processing and manufacturing methods for thermoplastic
composites, there is a also a growing need for modification of raw materials (Matrix-polymers and Reinforcement
fibers) according to specific product needs. The successful application of new processing and design solutions
requires a close collaboration between materials experts and design & manufacturing engineers.
Important points will be highlighted during the presentation and range from material compliance in challenging
environmental conditions to compatibility of new material combinations. Additionally, inherent advantages ofthermoplastic composites, such as fast processing times or adhesive-free bonding, will be put into perspective withthe development of new processing and design solutions.
Keywords: Composites, CFRP, Thermoplastic, AFP

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Foamability of Multi-Phase Polymeric Materials
Prof. Anup K.GhoshCentre of Polymer Science and Engineering
Indian Institute of Technology Delhi, New Delhi
Blending with other polymers and/ or fillers is a well-established and widely used methodof enhancing and modifying the properties of a polymer. Immiscible polymer blends by
and large out-number miscible ones. Thus, there is a huge spectrum of multi-phase
polymeric materials comprising of immiscible blends and filled polymers. Foaming ofpolymeric materials results in significant weight reduction and also leads to newproperties. Thus, the foaming of multi-phase polymeric materials is of immense academic
and commercial interest. It has been well established that the morphology of multi-phasematerials determines not only their own properties, but also the morphology and otherproperties of their foams. In case of polymer blends, a smaller size of the dispersed
domains results in superior properties of the blends and better foam morphology. In caseof filled polymers, the quality of dispersion (exfoliation/ intercalation in case ofnanocomposites) again governs the extent of property enhancement and also the qualityof foams. The morphology of multiphase polymeric materials is by and large governed bytheir rheological properties. The rheological properties of any polymeric system can betuned by proper selection of process parameters. In fact, rheology can be used as a tool topredict and control morphology, which in turn controls foamability. The key to successful
foaming of a multi-phase polymeric materials thus lies in gaining a complete
understanding of the rheological properties of the polymer (s) involved and in proper
selection of process parameters, so as to achieve the desired morphology of both themulti-phase system as well as its foam.

MATERIAL DEVELOPMENT FOR AUTOMOTIVE APPLICATION(Oral Presentation)
Takeo Kitayama
Corporate Planning and Coordination Office, Sumitomo Chemical Co., Ltd.
27-1, Shinkawa 2-chome, Chuo-ku, Tokyo 104-8260, Japan
Email: kitayamat1@sc.sumitomo-chem.co.jp
Abstract

To meet the demand for growing Asian market, Sumitomo Chemical has expanded the petrochemicalcomplex to Singapore as the very first one in other parts of Asia than Japan in 1984. Futhermore thelarge-scaled petrochemical complex has been constructed at Saudi Arabia in 2009. Now new
techology for polymer modification realized the characteristic improvement of thermoplastic
materials such as S-SBR and PP compounds which can contribute to the automotive industry.
Keywords: S-SBR, PP compounds, Singapore, Saudi Arabia

1. Introduction
In recent years, with increasing environment
concern for energy saving, various thermoplastic
materials have been used in such fields as
automobiles, electronics and medicals. However
the thermoplastics for general use cannot satisfy
all requirements in the market. The appearanceof the thermoplastics with higher performance
have been expected. Many studies were carriedout on polymer and composite development inorder to comply with the demands for
performance enhancement.
In the automotive application, engineering
plastics and metals have been extensively
replaced by polypropylene (PP) based materials
in automotive parts such as bumper facias,
instruments panels and door trims in order toachieve weight reductions and cost savings.
The growth of PP compounds for automotive
applications has thus far been supported by the
improved performance of PP resins – which
serve as the base of PP compounds – andadvancements in compound technology. With
respect to the former, catalysts and thepolymerization process have been continually,energetically improved in order to control the
primary and higher-order structures of polymers.
Regarding the latter, improvements in theperformance and dispersibility of elastomers, aswell as the control of particle size, dispersion
and interface of inorganic fillers, have been
attempted up to the present time.
The other plastic materials, which cancontribute automotive industries, are considered
to be rubbers which can apply for tires.

The market for solution styrene-butadiene
rubber (S-SBR) which is mainly used for thetreads ofthe energy-saving tires forautomobiles has continued to expand rapidly
while the fuel efficiency requirements forautomobiles have been tightened worldwide. Itis estimated that the annual S-SBR demand for2011 will be between 400 and 350 thousands
tons.
Energy-saving performance is achieved
through a variety of improvements andinnovations from the fundamental structure of
the tire to various types of materials, but among
these the role played by the tread, which is thepart coming into contact with the surface of theground, is particularly important. This means
providing polymer materials that give energysaving performance and road surface grip, whichis related to safety, in the trade-off between
these two properties, and this is an area where
the most is expected of the manufacturers ofpolymers for tires.
Sumitomo chemical has diversified andaccumulated a variety of technologies to create
new value in the 100-year history. In 1958,
petrochemical production in Japan was started
for the first time and later on, after experience of“oil-crisis”, it was expanded in Singapore to
pursue competitive feedstock and growing Asianmarket in 1984. This project was the very first
petrochemical complex in Asian region except
Japan.
Afterwards, in 2009, a world-scale integrated
oil refining and petrochemical complex was
built up in Saudi Arabia. The technologicalinnovations such as polymer and composite

development are believed to be the basis of the
global expansion.
In this report, recent accomplishments ofplastic and rubber developments through Asianmarket situation and our production expansion
are presented.
2. Market trend of plastic materials
Plastic materials have been extensively used
for diverse range of applications due tooutstanding mechanical properties, excellent
moldability and low cost production. One of theindustries that used large quantity of plastic
materials is the automobile and the number of
automotive production is projected to increase in
future in Asia, and China in particular (Fig.1).

Figure1. Projected global automobile production
PP, which is one of the general plastic
materials, accounts for more than half of allplastic materials used in automobiles and theweight of PP in one middle class automobile hasreached more than 65kg in our calculation. PP
compounds are used variety of parts in
automobile and several grades of PP compounds,
with their diverse performance characteristics,
have been developed by compounding withvarious other materials in order to satisfy theperformance requirements. Besides the PP
compounds growth, PP production is expected
to see significant growth by about 3% in theworld and the higher growth ratio in Asia.
Considered in terms of environment concern,transportation sector makes up to 20% of carbon
dioxide emissions in Japan and approximately
90% of that is from automobiles.
With this background, the Ministry of Land,
Infrastructure,
Transport
andTourism
established the FY 2015 fuel economy standards
based on the Act on the Rational Use of Enegy.
According to these standards, in FY 2015,

improvements on an average of 23.5% overactual performance in FY 2004 are required forthe fuel economy of passenger cars.
3. Business footprint
3-1. Singapore projectIn 1984, we have located petrochemicalcomplex in Singapore because of various
advantages the country offers, including its
geographical proximity to the vigorously
growing Asian market, and availability of astable supply source for the raw materials. The
cracker’s current capacity of Singapore complex
is about one million tons per year with two lines.
The downstream productions are also run, which
are PP, polyethylene (PE) and polymethyl
methacrylate (PMMA). Besides, there are otherproducts (EO, EG, PO, SM) operated by ourpartners. Each of those downstream products ishighly valued by customers with its quality andstable supply and the business performances aregoing well.
A new solution styrene-butadiene rubber (SSBR) manufacturing plant constructed in
Singapore.
In 2014, the S-SBR is manufactured by our
proprietary production process technology andadvanced polymer modification technology thatis a key to achieving higher productperformance and has won high praise from
customers in the tire manufacturing industries
both in Japan and overseas for being a highly
fuel-efficient tire material with outstanding
abrasion resistance.
3-2. Rabigh projectIn 2005, we established PetroRabigh, a joint
venture with Saudi Aramco, to develop large
scaled complex in Rabigh, Saudi Arabia. The
operation began in 2009, and Phase 2 expansion
will get completed next year (2016). Main
product slate in Phase 1 project contains PE, PP
and propylene oxide (PO). PP compounding
production was carried out in “Rabigh Plus TechPark” located next to PetroRabigh.
In phase 2, the expansion includes building a
new aromatics complex at the project site, using
additional ethane and naphtha as feedstock. The
project’s main products will be ethylene
propylenerubber(EPR),
thermoplastic
polyolefin (TPO), PMMA, low density
polyethylene/ethylene vinyl acetate (LDPE /EVA), para-xylene/benzene,
phenol/acetone.

cumeneand

4. New solution SBR
To maintain strength in tires, the raw rubber
starting material must first of all be vulcanized,
and it must be compounded with a filler(reinforcing filler) to improve strength. The
designs for compounding in passenger car tire
treads have been greatly transfigured in the last
20 years or so. Silica is used frequently insteadof the carbon black that has been known for along time as a filler. From the standpoint of fuelefficiency performance and wet grip
performance, using silica as a filler, in otherwords, silica compounding, is an indispensable
technology for high-performance fuel efficienttires that started in Europe and has spread to therest of the world.
Since the surface of silica is coated withhydrophilic silanol groups, its affinity forhydrocarbon polymers is typically lower thancarbon black, and there are difficulties in that
good dispersion is difficult and without
modification the reinforcing properties areinferior.
By introducing polar functional groups andincreasing the polarization of the polymer itself,
we can expect to have a good direct effect on theaffinity for the hydrophilic silica. With silica
compounding, we cannot expect physicalbinding as is seen between carbon and rubbercomponents; therefore, the introduction of polarfunctional groups to the polymer chain is evenmore important.
4-1. Alkoxysilyl group modified SBR
If one alkoxy group of the tri-alkoxysilane
compound reacts with the living polymer SBR,
SBR(1) with two alkoxy groups and functionalgroup F introduced to the chain terminal is
obtained (Fig.2). If two alkoxy groups of the trialkoxysilane compound react with the living
polymer SBR, two SBR chains are bonded, anda coupled polymer (2) with one remaining
alkoxy group and functional group F introduced
at the bonding site is produced. In addition, if
three alkoxy groups of the tri-alkoxysilane
compound react identically with the living
polymer SBR, only functional group F isintroduced, and a three branch star polymer (3)having no alkoxy groups is produced. It
becomes important to increase the proportion of

production of SBR (1) with many alkoxysilylgroups introduced to express fuel efficiency
performance in silica compounding systems.

Figure2. Resulting SBR structures (1)-(3)4-2. Next generation multifunctional SBR
We have not only introduced multiple
functional groups at the chain terminals but also
along the chain at multiple sites.
We synthesized polymers with the same typeof functional group introduced in different
numbers and sites. Specifically, we synthesized
ones with the functional groups introduced on
both ends of the polymer chain and ones withthe functional groups introduced in the middle
and at the end of the chain of the polymer forpolymers where to functional groups wereintroduced, and for polymers where threefunctional groups were introduced, we
synthesized ones where the functional groups
were introduced at substantially even intervals
along the chain. The structures and performance
evaluation results for the polymers obtained aresummarized in Table 1. A value measured usinga Lubke resilience tester at 60℃ according to
JIS K-6255 was used for the resilience, which is
one index of fuel efficiency performance. The
larger the value for resilience is the more
superior fuel efficiency performance is indicated.

Table 1. Evaluation results of multi-functional
polymers.

While there was always a functional group
introduced on one end of the polymer in both ofthe polymers where two groups were introduced,
the polymers with three groups introduced all
introduced the functional groups along the chain.
In the case of the functional groups used thistime, the resilience value gave better results inall cases than for the polymers with one
modified terminal. The more the number offunctional groups is increased, the higher the
resilience is, and in comparing two types ofpolymers with two functional groups introduced,
the polymers with functional groups introduced
at both terminals gave better results than thepolymers with functional groups in the middle
and chain terminal. It is predicted that theseresults will vary greatly according to the type offunctional group introduced, and it is possiblethat performance not possible up to now will be
expressed through molecular design that makes
use of the characteristics of functional groups.

BIODEGRADABLE POLYMER COMPOSITES OF POLY(LACTIC ACID)BLENDS AND NATURAL FIBERS
Oral presentation
S. Pivsa-Art1*, W. Pivsa-Art1,2, H. Yamane2 and H. Ohara2
1

Department of Chemical and Materials Engineering, Faculty of Engineering, Rajamangala University of Technology
Thanyaburi, Thailand
2
Department of Biobased Materials Science, Kyoto Institute of Technology,Kyoto, Japan
Corresponding author email address: sommai.p@en.rmutt.ac.th

Abstract - Polymer composites are essential materials due to their advantages on light weight, high mechanicalproperties and good processability. Polymers for the composites are petroleum-based plastics and are durable todegradation which resulted in environmental problems from their wastes. Therefore, biodegradable polymers andnatural fibers are attractive materials for environmental friendly composites. Poly(lactic acid) is a biodegradable
polymer having potential to replace the conventional plastic. The PLA/biodegradable polymer blends and natural fibers
were fabricated and their properties were evaluated for processing applications. Poly(3-hydroxybutyrate-co-valerate)(PHBV) poly(butylenesuccinate-co-adipate) (PBSA) were selected to blend with PLA. PLA/PHBV blends reinforced
with bamboo fibers (BF) were prepared using a twin screw extruder. The content of BF in composites was 5, 10 and 20
phr. Their mechanical properties were slightly decreased due to phase separation of the polymers and the reinforced
fibers. For another composites fabrication method, the PLA/PBSA blend reinforced with jute fiber using Micro-braiding
technique was developed. It was found that polymer blends of PLA/PBSA of 90:10 and 85:15 by weight could be
fabricated to fibers suitable to prepare braided yarns. The unidirectional oriented braid yarns with core jute fibers werecompressed at 180 oC to give the biocomposites. The ratio of polymers and fibers was 73:27 by weight. The melting
temperatures of PLA in the fibers from polymer blends and in the compressed samples were found to be similar in therange of 149-153oC. The results indicated that the different fabrication process has no effect to the thermal property ofthe blends. The tensile strength of PLA/PBSA/Jute composites increased up to 65% compared with the polymer blends.
The braided yarn of PLA/PBSA ratio 85:15 by weight reinforced with jute as a core was prepared to analyze thebiodegradability. The braided yarn shows slightly decreasing of their mechanical property but their biodegradability is
excellent. The ratio of PLA/PBSA was 85/15. Compression molding of the braided yarn gave composites but theirmechanical properties were decreased. Biodegradability measurement of the braided yarns of PLA/PBSA/Jute shows
potential for agricultural application of the composites.
Keywords: Polymer composites, Biodegradable polymers, Poly(lactic acid), Natural fibers.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

RECENT DEVELOPMENT OFDIRECT FIBER FEEDING INJECTION MOLDING
Oral presentation
Hiroyuki HAMADA 1
1
Department of Advanced Fibro-Science, Kyoto Institute of Technology, Japan
Corresponding author email address: hhamada@kit.ac.jp
Abstract -GF/Recycled-PET
1. Introduction
In this study aims to produce the fiber reinforced thermoplastics in order to receive the superior properties. This
technique called the direct fiber feeding injection molding is known as DFFIM, which can reduces compounding
processes that leads to the fiber breakage during also. The glass fiber reinforce RPET composite (GF/RPET) werestudied the effect of processing windows and effect of glass fiber loading co ntent on mechanical properties.
2. Experimental
The high quality commercial recycled PET pellets (RPET), which were recycled from pet plastic bottle, were
supplied by Negoro Sangyo Co., Ltd. with IV of 0.65 dl/g and molecular weight of 12,600 g/mol. The EX-1844 gradeof glass fiber roving with the number of bundle is 2000 and 4000 from Nippon Electric Glass Co., Ltd., Japan with thesizing agent for PET were used as reinforcing fiber. The dumbbell specimens were made by 30 tons injection machine(TOYO MACHINERY & METAL CO.,LTD TI-30F6, Japan). The matrix feeding screw speed (MFS) were varied
from 20, 40 and 60 rpm and screw speed of injection unit was fixed at 180 rpm. The injection temperature was set at200-270o C with 60o C cooling temperature and 20 second cooling time.
3. Effect of fiber content on mechanical properties
Fig. 2 (a) and (b) show tensile properties and flexural properties of GF/RPET composite, respectively. They indicatethat the decreasing of MFS, which led to be higher fiber loading content in GF/RPET composites, has an effect withimproving of the mechanical properties. All of tensile modulus, tensile strength, flexural modulus and flexural strength
values directly significantly increase with increasing fiber loading content of GF/RPET composite.

Fig.1 Concept of DFFIM(Direct Fiber Feeding Injection Molding)Fig. 2 (a) Tensile properties and (b) Flexural properties
Keywords: DFFIM, Injection Molding, Glass Fiber, Composite materials

Proceedings of the Asian W orkshop on Polymer Processing Annual Conference ~ AW PP 2015 ~ December 01-04, 2015, Singapore

POLYETHYLENE-THERMALLY REDUCED GRAPHENE
NANOCOMPOSITES: COMPARISON OF MASTERBATCH AND DIRECT
MELT MIXING APPROACHES ON MECHANICAL, THERMAL,RHEOLOGICAL AND MORPHOLOGICAL PROPERTIES
Oral presentation
V. Mittal1 *, and A.U. Chaudhry 2
1

Department of Chemical Engineering, The Petroleum Institute, Abu Dhabi, UAE
2
Deaprtment of Materials Engineering, Colorado School of Mines, USA
Corresponding author email address: vmittal@pi.ac.ae

Abstract - Two routes of nanocomposite generation viz. masterbatch method and direct melt mixing were co mpared in
the current study in relation with the properties of the polyethylene -thermally reduced graphene nanocomposites
compatibilized with functional poly mers. Filler d ispersion was observed to improve in the masterbatch method d ue topreferential interactions of compatib ilizer with the filler, before melt mixing with the matrix poly mer. Th is alsotranslated into improved mechanical p roperties as more than 2 times increment in tensile modulus was observed in thecomposite HDPE/ G/ 5 EAA/MB (41%, masterbatch method) as compared to HDPE/ G/5 EAA/MM (20%, melt mixing
method). In addition, different compatibilizers also influenced the properties to different extent owing to their physicalinteractions with the filler, however, co mposites generated with masterbatch were always superior in extent of property
enhancements. Increasing the compatibilizer content to 10% also caused varying degree of matrix plasticizat ion. The
storage modulus as well as the comp lex viscosity of the HDPE/ G/5 EAA/M B co mposite was the highest as compared to
HDPE/ G/ 5 EMAZ/MB and HDPE/ G/5 EVA -MA/MB co mposites. HDPE/ G/ 5 EAA/MB and HDPE/ G/5 EMAZ/MB
composites did not show any decrease in degree of crystallinity as compared to pure polymer, whereas thecorresponding composites generated with melt mixing exh ibited slight decrease in the crystallin ity. The co mposites
were observed to have enhanced thermal stability as co mpared to HDPE. 5% EAA based composites exhib ited evenhigher thermal stability than HDPE/ G co mposites due to imp roved filler d ispersion. Composites generated withmasterbatch approach had also higher degree of phase mixing than the corresponding melt mixed co mposites. In
addition, optimization of chemical binding of the filler with the comaptibilizer during t he masterbatch approach would
also be discussed for polyethylene-chlorinated polyethylene nanocomposites with graphene.

(a)

(b)

Figure 1. Comaprison of morphology of nanocomposites genertd by (a) direc t melt mixing and (b) masterbatch
approach.

(EAA: ethylene acrylic acid copolymer, EVA-MA: ethylene vinyl acetate-graft-maleic anhydride, EMAZ: ethylene
methacrylic acid copolymer with zinc ion, MB: masterbatch approach, MM: melt mixing approach)

Keywords: thermally reduced graphene, nanocomposites, morphology, modulus, co mpatibilizer, thermal stability.

Proceedings of the Asian W orkshop on Polymer Processing Annual Conference ~ AW PP 2015 ~ December 01-04, 2015, Singapore

EFFECT OF SURFACE PRE-TREATMENT OF SUBSTARATEON WETTABILITY OF METAL NANO-INK
Oral presentation
1

T. Saito1*, Y. Yokoyama1, T. Kawaguchi1 and I. Satoh1
Department of Mechanical and Control Engineering, Tokyo Institute of Technology, Japan
Corresponding author email address: tsaito@mep.titech.ac.jp

Abstract - Metal nano-particle has great potential to change optical, thermal, and electric properties. One attractive
application in recent years is the printable electronic circuits as metal nano-ink. To ensure the reliability of the printed
circuits, improvement of the adhesion strength between metal nano-ink and substrate is important. In this study, thin
Au coat was introduced to the substrate surface, and their effects on the spreading of silver nano-ink was experimentallyinvestigated. In the experiment, the contact angle variation of the silver nano-ink was measured on glass plate andpolyimide film which surface treatment condition was individually changed. The stain size of a single droplet was alsomeasured so as to discuss the control of the circuit width. The results showed that the contact angle of the ink wascomplexly changed with the Au coat thickness. Therefore, precise design of surface treatment is important to correctly
control the spreading process for metal nano-ink.
Keywords: Nano-ink, Surface treatment, Surface wetting
1. Introduction
Metal nano-ink has great possibility to the fabrication technique of printable electronics such as electric circuits anddevices, and inkjet printing or screen printing is often used for this purpose. However, the authors believe that metal
nano-ink still has more possibility for broader application. As the fundamental knowledge, the wetting control of nanoink and the improvement of adhesion strength to the substrate are important. In this study, thin Au coat was sputtered tothe substrate surface so as to control the wetting condition of silver nano-ink, and its effect on the adhesion strength of
the ink was experimentally investigated.
2. Experimental Procedure
Nano-silver ink (A-1, Mitsubishi Materials Electronic Chemicals Co., Ltd.) was used in this study. Cover glass plate(S7213, Matsunami Glass Ind., Ltd.) and polyimide film of 12.5 m thickness (Kapton 50H, DuPont-Today Co., Ltd.)
were used as the substrates. The substrate surface was coated with Au thin layer as the pre-treatment by using physicalvapor deposition (SC-701AT, Sanyu Electron Co., Ltd.). Coated thickness was controlled by the sputtering time and it
was evaluated as 33, 100, 200, 300, and 400 Å.
To investigate the influence of pre-treatment for substrate, contact angle was measured by the contact angle meter(DMs-400, Kyowa Interface Science Co., Ltd.) For each measurement, 1 L of nano-silver ink was precisely measured
and moved to the substrate surface with the specially designed needle. Instantaneous contact angle was measured at 1
second after the needle release. After 24 hours dry at the room temperature, adhesion strength change with and without
pre-treatment was evaluated by the texture analyzer (TA_XT 2i, Stable Micro Systems Ltd.), and the stain diameter ofthe ink was measured. Measurement conditions for the adhesion test was as follows; Probe diameter 5 mm, 2 seconds
pushing at 49.05 N, Pull up rate of the probe 2mm/s.
3. Results and Discussion
As shown in Fig. 1 (a), the contact angle on the metal surface
was larger than that of glass and polymer surface. However, theadhesion strength was improved in case of the metal surface(Fig. 1 (b)). From these results, it was indicated that the
wettability of the nano-ink consisting of dispersed nano-particles
and solvent was unrelated to the adhesion strength. Effect on theadhesion strength by Au coat for the substrates was investigated,
and its impact was not large enough. To improve the reliabilityof the micro-scale wiring, the small spreading size and strong
adhesion of the nano-ink are desirable. Therefore, the obtained
data points through the measurement were plotted as theadhesion strength vs stain size of the nano-ink. The result showedthat good adhesion strength of 11.6 MPa was obtained on the glass
substrate with Au coat of 200 Å, and its stain size was 3.0 mm.

(a)

(b)

Fig. 1 Variation of the contact angle andadhesion strength

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

ELECTROSPINNING OF POROUS POLYMER NANOFIBERS AND THEIRAPPLICATIONS AS FUCTIONAL MATERIALS
Oral presentation (keynote speech)
Xuehong Lu*, Junhua Kong, Yuliang Dong, Huiqing Wu
School of Materials Science and Engineering, Nanyang Technological University, Singapore
Abstract Electrospinning has been well established as an effective route for producing polymer nanofibers. In
comparison with various methods used to generate polymer nanofibers, electrospinning is one of the easiest techniques
to obtain long nanofibers with uniform diameter. Furthermore, it allows facile manipulation of nanofiber morphology,
such as creating surface pores or interpenetreating pores in the nanofibers. Such porous polymer nanofibers haveattracted increased attention in recent years owing to their potential for a wide variety of applications. In this keynote
talk, our recent work on electrospun porous polymer nanofibers will be introduced, with the focuses on morphology
control, nanofiber collection method, fabrication of porous polymer nanocomposite nanofibers and applications ofelectrospun porous polymer and nanocomposite nanofibers as functional materials for various applicatons.
Firstly, the potential of surface-modified electrospun porous polymer nanofibers for enhacing moisture wickingof textiles (Fig. 1) and improving functions of water treatment membranes will be discussed. Then, a liquid collection
method for modifying electrospun porous polymer nanofibers will be introduced. This method allowed us to use porous
polystryrene nanofibers as templates to create prous carbon nanofibers with novel morphologies for energy storage
applications (Fig. 2). Finally our recent work on electrospun porous nanocomposite nanofibers will also be introduced.
The effects of incoporation of different types of inorganic nanoparticles on the prorous morphology of the nanofibers aswell as the underlying mechanism will be illustrated.
(ai)

(aii
)

Fig. 1 (ai) FESEM images of electrospun porous polystyrene (PS) nanofibers coated with polydopamine (PDA) and(aii) the cross-sectional view of a coated PS porous nanofiber. (b) Change of water contact angle of the coated solid andporous PS nanofibrous mats with time.

Fig. 2 (Left) (a) Collection of electrospun PS porous nanofibers using ethanol. (b1-b3) Morphology of the as-prepared
PS nanofibers. (Right) (a) A scheme showing that the surface pores could be used as templates to create PDA
nanocups. (b1-b3) FESEM images of the fibers after removing PS. (c-e) Morphology of the carbonized PDA nanocups.
Keywords: electrospinning, nanofibers, functional materials

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

NANOSTRUCTURED ADDITIVE-ENHANCED HIGH PERFORMANCE
SUPERHYDROPHOBIC COATING MATERIALS
Oral presentation
Y. Hong and J. W. Xu*
Institute of Materials Research and Engineering, Agency for Science, Technology and Research (A*STAR), Singapore
Corresponding author email address: jw-xu@imre.a-star.edu.sg
Abstract - Superhydrophobic coatings are able to deliver many functions such as water-repellent, anti-sticking,contamination prevention, reducing fluid drag and self-cleaning. Therefore they have been paid much attention becauseof its wide potential applications in many areas, including energy conversion, waterproof textiles, smart structural
coating materials, and microfluidics. Numerous artificial superhydrophobic surfaces have been developed by using a
low surface energy material in combination with a particular surface roughness. Morphologies of superhydrophobic
surface can be facilely controlled by various nanostructures, such as nanoparticles, nanowires, nanotubes. On the other
hand, fluorine-containing materials and even perfluoropolymers were widely used for superhydrophobic coating due tolow friction coefficient and reduced adhesion to surfaces. This talk will summarize recent advance of superhydrophobic
materials in my group and a variety of potential industry applications will be addressed.

Figure 1. The wetting behavior of water droplets on various commercial textiles

Keywords: Superhydrophobic coating; Polyhedral oligomeric silsesquioxane; Nanostructured additives.
References:(1) Tuteja, A.; Choi, W.; Ma, M.; Mabry, J. M.; Mazzella, S. A.; Rutledge, G. C.; McKinley, G. H.; Cohen, R. E. Science
2007, 318, 1618-1622.
(2) Ganesh, V. A.; Nair, A.S.; Raut, H.K.; Tan, T.T.Y.; He, C.; Ramakrishna, S.; Xu, J. J. Mater. Chem., 2012, 22,
18479-18485.
(3) Xu, J.; Li, X.; Cho, C. M.; Toh, C. L.; Shen, L.; Mya, K. Y.; Lu, X.; He, C. J. Mater. Chem., 2009, 19, 4740–4745.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

IN SILICO PROCESSING OF POLYMERS
Oral presentation
A. Soldera*
Department of Chemistry, Quebec Center for Functional Materials, Universitéde Sherbrooke, Canada
Email address: Armand.Soldera@USherbrooke.ca
Abstract –This presentation is an overview of the simulation tools available to assist engineers and experimentalists in the design
and the processing of materials. There is definitively a gap between the traditional engineering approach and theatomistic simulation methodology. While one works with complex systems constituted of polymers whose very
structure is known only from industries commercializing them, the other studies ideal systems. The polymers are
therein mainly pure homopolymers with low number of defects. The question that will be thus addressed in thispresentation is: Is simulation able to tackle problems encountered by polymer engineers during the synthesis, processing
and scale-up of various compounds? One method allowing to answer this question is to reveal the domain where the
TOP-DOWN and BOTTOM-UP approaches actually intersect.
In fact, the link between the micro- and the macro-structures is far from being straightforward. To describe realsystems, a series of models with a specific set of rules and restrictions following chemical, physical andthermodynamical guiding principles is required. These models must be chosen accurately to efficiently describe thesystem of interest. More specifically, each scale needs a certain level of approximation to address the specific problem.
To ascertain accuracy of the representation, validation with experiments is a crucial step. To illustrate this intimate link
between experiments and simulation in addressing engineering problems, several examples stemming fromcollaborations between our lab and engineers from various industries are discussed.
The first part is dedicated to the preparation of the simulated system. Reaching the mechanical equilibrium, as it isexperimentally the case, is shown to be the crucial step. To extract efficient conclusions from simulations, a validation
step is nevertheless mandatory. As it is shown in the figure below, a linear relationship is demonstrated between
simulated and experimental glass transition temperatures for a series of vinylic polymers. Further and more complex
simulations can then be fostered. In particular, predicting the effect of pressure on the melting temperature could be ofgreat interest in the processing of novel polymeric compounds. Finally, examples related to an increase in performanceof polyelectrolyte membranes for fuel cells are investigated, with an emphasis on the possible increase in proton
conductivity through the effect of polydispersity and the shearing of membranes.

Keywords: molecular dynamics, glass transition, melting temperature, PEMFC
Figure: Simulated and experimental glass transition temperatures for a series of vinylic polymers.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

MEASUREMENT OF GAS-PRESSURE DISTRIBUTIONSINSIDE MOLD CAVITY DURING GAS-VENTING PROCESSBY SMALL-DIAMETER MELT PRESSURE SENSOR
Oral presentation
H. Yokoi1* and T. Shimizu1
1
Institute of Industrial Science, The University of Tokyo, Japan
Corresponding author email address: hiyokoi@iis.u-tokyo.ac.jp

Abstract - Based on the newly-developed measuring mold in which the measurement point can be shifted by moving
the cavity block with the thin sensor installed, gas-pressure distributions were successfully measured to evaluate thegas-venting performance for different gas-vent configurations. The results are summarized in the following. (1) Gasvent effects decreased exponentially according to the decrease in the cross-sectional area of the gas-vent flow channels.
(2) Under the same cross-sectional area of the gas-vent flow channel, the shallower the gas-vent channel, the less thegas-vent effects become. (3) Moreover, even in the same total cross-sectional area, multi-grooves vent units have poorer
gas-vent effects than single-groove ones.
Keywords: Gas-vent, Gas pressure distributions, Injection molding

1. Introduction
In the designing of the gas-venting system for
injection molds, it is very important to efficiently
discharge air or gas out of the mold cavity in a shorttime during the melt filling process. However, little
technical data is available on how much the setup
positions and the detailed profiles of gas-ventsystems influence the gas-venting performance
because there are no practical evaluation methods.
Under such circumstances, we have developed amethod of measuring gas-pressure distribution
inside a mold cavity during the melt filling stage
using a thin-diameter pressure sensor which can be
moved along the cavity width direction1). By
applying this measuring mold, we attempted tomeasure the pressure distributions just before thegas-vent zone under different configurations of gasvent system in order to evaluate each gas-venting
performance.
2. Fundamental Structure of Measuring Mold of
Gas-pressure Distributions and Experimental
Methods
In this experiment, we measured the gas pressure
distributions inside a tiny region in front of the gasvent zone parallel to the cavity end wall. Since thediameter of conventional gas-pressure sensors is
usually too large to measure the pressure at any
minute spot, a piezoelectric sensor with a thinpressure head for measuring melt pressures was
utilized instead of the conventional one. For the
purpose of measuring the whole area from the cavity
center to cavity sides, the sensor-installed block-

Movableblock

Cavity(Stationaryside)

Sensorhousing

Movable
area

Screw

Screw

Fig.1 Mold structure for measuring gas pressure
distributions (Movable side)

insert can be driven along the cavity width inside astationary-side mold base (Fig.1). The rectangularcavity size is 75mm in length, 30mm in width, and
2mm in thickness, the parting-face structure ofwhich is shown in Figs. 2 and 3. At the end of thecavity, a gas-vent block is fixed as shown in Fig.4.
Based on this mold structure, we can easily evaluate
gas-venting performance by measuring the pressure
distribution for each block by changing the gas-vent
block with different configurations of gas-ventsystems. Table 1 shows the dimensions of each gasventing system from V0 to V10. In the experiments,
all the gas/air was released not through the parting

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Table 1 Dimension of gas-vent zone forthe evaluation experiment

O-ringGas-vent zone
(Concave 0.02)
Vent groove

Shapew [mm]

h [mm]

V0
V1
V2
V3
V4
V5
V6
V7
V8
V9
V10

0
5
10
15
5
5
2.5
5
5
0.5
0.5

―
1
1
1
1
2
1
1
3
1
1

t [mm]

A*1 [mm2]

0
0
0.015
0.15
0.015
0.30
0.015
0.45
0.03
0.30
0.015
0.15
0.015
0.075
0.0075
0.075
0.015
0.15
0.015
0.15
0.00750.075*1 ; A=w×t×20

Cavity-end
block

Vent holeFig.2 Dimension of cavity block for stationary side
(Unit: mm)

Sensorhousing
for a setofpressure
sensors
sensorfaces but through venting holes due to the complete
sealing mechanism of the parting faces in between
movable and stationary molds, as well as in between
all the block-inserts.
As for the thin-diameter melt pressure sensor, the6006B (Priamus System Technologies AG) of
1.8mm in diameter was used. Along the line (y =1mm) away from the cavity end (y = 0mm), gaspressures are measured by shifting the sensor’s
location every 2mm from the cavity side (x = 1mm)to the center (x = 15mm) . The resin used is ABS220(Asahi Kasei Chemicals Corp.), and the molding
conditions are as follows; Resin temperature =220°C, Mold temperature = 40°C, Injection rate (IR)= 16.8 cm3/s, 50.6 cm3/s.

3. Results and Discussions

Cavity-end
block
Measuringpoint

Movable area

Fig.3 Cavity-end block and pressure measuring
points (Unit: mm)w(1) V0-V8

w
h

h

t

(2) V9,V10

Fig.4 Dimension of cavity-end block

Figure 5 exemplifies the gas pressure curves
measured with V0 and V1 in IR = 50.6cm3/s and x =1mm, where the injection start time is 0s. In the caseof V0 (No gas-vent condition), the gas pressure
rapidly increased as the melt approached to the endof cavity, then hesitated for a moment just before themelt reached the sensor head, and suddenly rose as if
it draw a vertical line, which corresponds to themelt’s compression stage. The reason why the risingtendency of gas pressure curves once hesitated may
be because the melt front velocity instantaneously
decreased due to the high gas pressure generated
through the gas compression process by the flowing
melts. Compared to V0, the gas pressure in V1
dropped significantly, and there were no hesitation
tendency and vertical rising behaviors of thepressure curve, which were observed in V0 justbefore the melt reached the sensor head. Because ofProceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Pressure(MPa)

12

8

V1

4
0

V0
0

0.1

0.2

0.3

0.4

Time(s)Peak of gas pressure (MPa)Fig.5 Change curves of gas pressure measured bycavity pressure sensor (IR = 50.6cm3/s,
x = 1mm)

Cavity center

15
10
5

IR16.8
IR50.6

0
0

2

4

6

8 10 12 14 16x (mm)(1) Shape V0

Peak of gas pressure (MPa)the gas-venting effect from the cavity end in V1, thegas was not compressed rapidly, resulting in thephenomenon of less rise in pressure.
In order to more precisely analyze the correlation
between the gas-vent configurations and the pressure
distributions along the cavity width direction, we
compared the widthwise pressure profiles drawn
with peak values extracted at each position forvarious gas-vent configurations. The examples of themeasurement result are described in Fig.6. The gaspressure gradually drops toward the cavity side,from the cavity center up to around x = 5-7mm, thenit starts to rise, even though there is no obvious
correlation with the setup location of gas-vent zone.
Such a behavior of the gas pressure change curve isthought to be caused by a specific cavity filling
pattern called “ear flow”, where the flow front
advances more near both cavity sides to form a dent
filling pattern. As a result, the flow front advanced
more at two locations away from both cavity sides
by 5 to 7mm, to contact the cavity end wall at the
two locations at the very beginning. The gaspressure dropped due to the easy release process ofthe compressed gas toward both sides of the abovementioned contact zone. Subsequently the extruded
gas was compressed resulting in the rise of the gaspressure around the cavity side (x = 0mm) andcenter (x = 15mm) areas.
For the purpose of quantitatively evaluating theventing effect for each gas-vent configuration, we
attempted to relatively compare the average data ofall the gas-pressure peak values within a measuring
range right before the end wall of the cavity end.
Here, it can be assumed that the higher the gaspressure, the higher is the gas-compression ratio, i.e.,
the lower the gas-venting effect becomes. The
relationship between the average gas-pressure andtotal cross-sectional area “S” of the gas-vent flow
channel at low injection rates (IR = 16.8cm3/s) isdemonstrated in Fig.7. When the land width “h” ofthe gas-vent channel is 1mm, the smaller area “S”
was found to damage the gas-venting effectexponentially. Moreover, the multi-grooves gas-ventproved to have rather low venting performancecompared to the single-groove gas-vent, which
consisted of the same gas-vent depth “t” and area
“S” as those in the above multi-grooves vent. In thesame area “S” but at a different depth “t”, theventing effect of the multi-grooves unit drasticallydiffers from that of the single-groove unit as the area
“S” decreases, especially in gas-vent channel
narrower than 0.2mm2. In addition, the shallower thedepth “t” of the gas-vent channel, the lower was thegas-venting effect.

Gas-vent zone

Cavity center

1.5
1IR16.8
IR50.6

0.5
0
0

2

4

6

8 10 12 14 16x (mm)(2) Shape V1
Fig.6 Distribution of the peak values of gas pressure
along the cavity width direction just before thecavity-end

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, SingaporeAverage of peak gas pressure (MPa)10t=0.00075

h=1

1

h=2
h=3

t=0.0150.1

h=1 V10t=0.015t=0.03

0.01
0

0.1

0.2

0.3

0.4

0.5

Cross-sectional area of gas-vent channel (mm2)Fig.7 Relationship between the average of gas peak pressure and the cross-sectional area of gas-vent channel

4. Conclusions
We succeeded in measuring not only the timesequential pressure change curves at minute spots
but also the widthwise distributions of gas-pressure
peak values along the end zone of the cavity as a
final melt filling area by using a thin-diameterpressure sensor, which is usually applied formeasuring melt pressures. Based on the measuringmold in which the measurement point can be shiftedby moving the cavity block with the thin sensor
installed, gas-pressure distributions were measured
to evaluate the gas-venting performance for different
gas-vent configurations.

The results are summarized in the following.
(1) Gas-vent effects decreased exponentiallyaccording to the decrease in the cross-sectional
area of the gas-vent flow channels.
(2) Under the same cross-sectional area of the gasvent flow channel, the shallower the gas-ventchannel, the less the gas-vent effects become.
(3) Moreover, even in the same total crosssectional area, multi-grooves vent units havepoorer gas-vent effects than single-groove ones.
Reference
1) H.Yokoi, H.Yokoyama: JSPP Tech. Papers,
pp.51-52 (2013) in JapaneseProceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Fig.5 Relationship between the average of gas peak

FUNCTIONAL POLYNORBORNENES: UTLRA-HIGH Tg
THERMOSETTING FIBERS AND COMPOSITES
Oral presentation
B.Commarieu1, J. Potier1, M. Compaore1, B. Goodall2, X. Li3, and J.C. Claverie1*
1

Quebec Center fur Functional Materials, NanoQAM, Dept of Chemistry, UQAM, Montreal, Canada
2
Valicor Renewables, Dexter, MI, USA
3.Institute of Materials Research and Engineering (IMRE), Agency for Science,
Technology and Research (A*STAR), 3 Research Link, Singapore 117602
Corresponding author email address: claverie.jerome@uqam.ca
Abstract - Insertion polynorbornene (PNBE) is a thermoplastic polymer with very high Tg (> 300 oC) which exhibits
excellent optical and electrical properties. Although it is extremely simple to produce it from cheap and widely
available feedstocks, currently, no suitable processing technique exists for this polymer. In this work, we have preparedfunctional polynorbornenes which exhibit the same desirable properties as PNBE (very high Tg, excellent optical andelectrical properties) and we propose three novel techniques to process it.
In the first technique, low to medium molecular weight PNBEs bearing epoxy pendant groups were prepared. These
polymers could be cross-linked with hardeners, in the same way as a conventional epoxy thermosetting resin. The
resulting epoxy coatings have very high Tg (as high as 350 oC). and excellent mechanical properties ( 4 GPa modulus,
CTE of 50 10-6 m/m/ oC at 250 oC).
In the second technique, the functional PNBE is electrospinned to yield high-Tg microfibers with excellent thermal
resistance. These fibers can be thermally cross-linked, rendering the fibers insoluble in any solvent.
Last, nanocomposites can readily be prepared upon mixing the functional PNBE with a suitable filler, such as carbon
nanotubes (CNT). In this case, conducting composites exhibiting record high conductivity (as high as 10,000 S/m) canbe prepared.
Overall, highly conducting microfibers with excellent chemical, thermal and mechanical resistance can be preparedfrom these PNBEs.

Keywords: Polynorbornene, Nanocomposites, Microfibers, Thermosets

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

TOWARDS HIGH-PERFORMANCE POLYPROPYLENE/EXPANDEDGRAPHITE/CARBON NANOTUBES TERNARY COMPOSITES WITHSIGNIFICANTLY ENHANCED THERMAL AND ELECTRICALCONDUCTIVITY VIA CONSTRUCTING DOUBLE PERCOLATED FILLER
NETWORK
Oral presentation
K. Wu1, Y. Xue1, W.X. Yang1, S.G. Chai2, F. Chen1 and Q. Fu1*
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan
University, Chengdu 610065, China
2
Guangdong Shengyi Technology Limited Corporation, Dongguan, 523039, China
Corresponding author email address: qiangfu@scu.edu.cn
Abstract - Carbon based fillers, such as carbon nanotubes (CNTs) and expanded graphite (EG), are often used to
improve the thermal and electrical conductivity of polymer matrix. Unfortunately, although a typical percolation
phenomenon of electrical conductivity is usually observed as the filler content reaches to the threshold, thermal
conductivity usually presents a trend of a linear increase with filler content. In this work, we will report the importanceof the formation of double percolated filler network in polypropylene (PP) matrix with dense CNTs network locatedwithin loosened EG network in tailoring electrical and thermal properties of polymer composites. Besides achieving amuch high electromagnetic interference shielding effectiveness of 58.5 dB, a sharp increase of both thermal andelectrical conductivity is observed for the first time. Morphological observation via TEM, SEM and rheology confirm
the formation of tiny-sized CNTs network within EG network as the CNTs content is above 2 wt %. And effective
medium theory model reveals that formation of double percolated filler network, in which three types of connections
exist between EG and EG, EG and CNTs as well as CNTs and CNTs, could effectively reduce the interface thermal
resistance of CNTs. Our work provides a new strategy for the preparation of polymer composites with excellent thermaland electrical conductivity via constructing double percolated filler network.
1

Keywords: double percolated filler network, thermal conductivity, electrical conductivity

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

SYNERGISTIC DISPERSION OF CARBON NANOMATERIALS IN
POLYMER NANOCOMPOSITES
Oral presentation
T.X. Liu*
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science,
Fudan University, China
Corresponding author email address: txliu@fudan.edu.cn
Abstract - Homogeneous dispersion or full exfoliation of nanoparticles in polymer matrices is one of the mostimportant factors to achieve high-performance and multifunctional polymer nanocomposites. In the past years, ourresearch group is making efforts to realize homogeneous and stable dispersion and high orientation of carbon
nanomaterials (e.g., graphene, carbon nanotubes) in aqueous and organic media as well as polymer matrices by using
physical “hybridization” approach via effective combination (via hydrogen bonding, π-π stacking, electrostaticinteraction, etc) among different kinds of nanoscale building blocks (e.g., carbon nanomaterials, clay) (Figure 1). The
hybrid nanofillers thus prepared are prone to be homogeneously and stably dispersed in different media or polymer
matrices, which are beneficial for fabricating high-performance polymer nanocomposites. In this presentation, somerecent work progress on achieving co-exfoliation or synergistic dispersion and stabilization of carbon nanomaterials inaqueous and organic media and polymer matrices are discussed.
Keywords: Carbon nanomaterials; Hybridization; Synergistic dispersion; Polymer nanocomposites.

Figure 1. Proposed mechanism for the assisted-dispersion of reduced graphene oxide (r-GO) with nanoclay (sodium
montmorillonite) as an effective dispersant.
Acknowledgements: The financial support from the National Natural Science Foundation of China (51125011,
51433001) is appreciated.
References
1. C. Zhang, L. L. Ren, X. Y. Wang, T. X. Liu, J. Phys. Chem. C 2010, 114, 11435-11440.
2. C. Zhang, W. W. Tjiu, W. Fan, Z. Yang, S. Huang, T. X. Liu, J. Mater. Chem. 2011, 21, 18011.
3. C. Zhang, S. Huang, W. W. Tjiu, W. Fan, T. X. Liu, J. Mater. Chem. 2012, 22, 2427.
4. Z. Yang, M. K. Liu, C. Zhang, W. W. Tjiu, T. X. Liu, H. Peng, Angew. Chem. Int. Ed. 2013, 52, 3996.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Redox-responsive poly(amido amine)s from trifunctional amines forbioapplications
Oral presentation
Ye LiuInstitute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3ResearchLink, Singapore 117602. Email: ye-liu@imre.a-star.edu.sg
Abstract - Through exploring the large difference in thiol concentration between intra- and extracellular space, thiolresponsive disulfide containing polymers, which will be stable in intracellular spaces but be degraded in extracellularspaces, are promising for many bioapplications such as targeted drugs/genes delivery and bioimaging[1, 2]. On the basisof our previous fundamental understanding of the reactivity sequence of three types of amines in trifunctional amino
compounds in Michael addition polymerization[3-5], we develop thiol-responsive linear and hyperbranched poly(amino
ester)s via Michael addition polymerization of trifunctional amines and disulfide-containing bisacrylamides. Theselinear and hyperbranced thiol-responsive poly(amido amine)s from trifunctional amines are explored for drugsdelivery,[6, 7] gene delivery,[8] bioimaging,[9] and MRI[10].
References:
1. Bauhuber, S., Hozsa, C., Breunig, M., & Gopferich, A. Advanced Materials, 2009, 21, 3286-3306.
2. Meng, F.H., Hennink, W. E., Zhong, Z.. Biomaterials, 2009, 30, 2180-2198.
3. Liu, Y. Wu, D. C., Ma, Y. X. Tang G. P., Wang S., He, C. B., Chung, T. S., Goh, S. T. Chemical Communications,
2003, 2630-2631.
4. Wu, D. C., Liu, Y., He, C. B., Chung, T. S., Goh, S. T. Macromolecules, 2004, 37, 6763-6770.
5. Wu, D. C. Liu Y., Chen, L., He, C. B., Chung, T. S., Goh, S. T.. Macromolecules 2005, 38, 5519-5525.
6. Wu, D. C., Loh, X. J., Wu, Y. L., Lay, C. L., Liu, Y. Journal of the American Chemical Society, 2010, 132, 1514015143.
7. Cheng W. R., Wang G., Pan X. Y., Zhang Y., Tang B. Z., Liu Y. Macromolecular Bioscience, 2014, 14, on-line.
8. Ping Y., Wu, D. C. Kumar N. J., Cheng W. R., Lay C. L., Liu Y., Biomacromolecules, 2013, 14, 2083-2094.
9. Cheng W. R., Kumar N. J., Zhang Y., Liu Y. Macromolecular Bioscience, 2014, 14, 347.
10. Cheng W. R., Rajendran R., Gu L. Q., Ren W., Zhang Y., Chuang K. H., Liu Y. J. Mater. Chem. B., accepte

Keywords: Michael addition polymerization; trifunctional amines; redox-responsive; drug delivery; gene delivery.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Enhancing Dispersion of Nanoparticles in Molten Polymers

Nopphawan Phonthammachai
Composite Research, R&D Center, SCG Chemicals Co., Ltd.
Nanoparticle dispersion in polymer matrix is one of the key challenges
controlling the properties of composite structure, especially in molten polymer
systems. Many efforts have been paid to improve the dispersion through particle
modifications using surfactant, organic molecules and liquid media. The aggregationof particles was minimized but still cannot reach fully exfoliated or mono-dispersed
level, while the organic residue left inside composite structure causing the poor
properties and scale-up development is also a concern. Therefore, the combination
between chemical treatment and processing technique was proposed. The in situ
grafting of targeted surface modified molecules those were not affecting the thermal
stability and overall properties, but improving the particle dispersion in molten
polymeric system, was applied. Together with unique processing technique, thedispersion of nanoparticles was dramatically enhanced.

PROCESSING CONDITIONS AND PROPERTIES OF NONWOVEN
KENAF REINFORCED ACRYLIC BASED POLYESTER COMPOSITES
Oral presentation
M.S. Salim1, M.F. Ahmad Rasyid2 and Z.A Mohd. Ishak*1

School of Materials and Mineral Resources Engineering,
Universiti Sains Malaysia, Engineering Campus, 14300, Nibong Tebal, Pulau Pinang
2

Cluster for Polymer Composites
Science and Engineering Research Centre, Universiti Sains Malaysia,
Engineering Campus, 14300 Nibong Tebal, Pulau Pinang
Corresponding author email address: zarifin@usm.my

The awareness of green and more sustainable products and technologies has gained muchinterest in the recent years. Realizing the importance of using eco-friendly material, a new
cross-linkable acrylic-copolymer resin has been introduced as an alternative for the
production of greener composites due to the non-corrosive, no volatile-organic compounds(VOCs) and no emission of carcinogenic gases during cross-linking. Within this current
work, the dependence of the mechanical properties of nonwoven kenaf fibre (KF) reinforced
acrylic based polyester composites on the processing variables (temperature, time andpressure) of the compression moulding has been studied. Prior to moulding, nonwoven KF
with areal density of 1300 g/m2 was impregnated by acrylic based resin using impregnation
line. Through optimization of the processing conditions, a light weight composite ofconsisting of 45wt% fiber weight fraction with flexural strength and modulus of 49.50 MPa
and 4.32 GPa respectively, has been produced. The curing behaviour of acrylic resin wasinvestigated by differential scanning calorimetry (DSC). As expected, the time required forcuring was found to decrease with the increases of temperature. Figure 1 shows the effect ofpressing time and pressure on the flexural strength and modulus of the composite fabricatedat 200oC .
20 Bar

30 Bar

55
50
45
40
35
30
25
20

10 Bar20 Bar

30 Bar

270

360

5

180

270
Pressing time (s)360

Flexural Modulus (GPa)Flexural Strength (MPa)

10 Bar

4
3
2
1
0
180

Pressing time (s)Figure 1: Flexural properties of composites at different processing conditions
It is known that the mechanical behaviour of fibre-reinforced composites is dependent on acomplex interplay of the properties of the constituent phases of resin, fibre, and the interfacial
region (wettability). Surface treatment was applied to natural fibre in order increase thewettability towards resin aiming at enhancing the mechanical properties of the developed
Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

composites. A prominent treatment of mercerization by NaOH was conducted to the KF toinvestigate the surface modification and the changes in surface energy. The AFM
topographies of treated KF are shown in Fig 2 (a-b) and Table 1 exhibits the outcomes offibre characterization and effect of fibre treatment on the flexural properties of composites.

Figure 2: Surface topography of KF a) untreated, b) alkali treated
The increasing value of area peak density of alkali treated KF indicates the increasing amountof peaks per unit area on KF surface due to the removal of lignin and hemicellulose. Thisoccurrence provides better interfacial adhesion between fibre and matrix by enhancing thespecific contact area, promoting friction between them; thus higher mechanical properties of
the resulting composites can be expected. The improvement in interfacial adhesion may
quantitatively shown by surface energy evaluation. Higher value of surface energy for alkali
treated KF suggest that better wettability towards acrylic resin could be achieved. This
explains for the superior properties of the alkali treated composite as compared to theuntreated counterpart.
Table 1: Effect of alkali treatment on the properties of KF and its composites

KF
treatment

Density(g/cm3)Area
peakdensity(µm-1)

Untreated
Alkali

1.25
1.39

10.60
37.10

Composites
Surface
Energy(mN/m)
58.66
97.05

FlexuralStrength
(MPa)

49.5
59.9

Flexural
Modulus
(GPa)
4.32
5.01

The optimal flexural properties was obtained using pressing temperature, pressing
time and pressing pressure of 200oC, 360s and 10 Bar, respectively. It was observed thatalkali treatment.plays a significant role in intensifying the wettability of KF and an effective
method to further enhance the properties of the composites. The developed of nonwoven KF
reinforced acrylic based polyester composite has the potential to be integrated for automotive
applications due to their high specific stiffness and strength values.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

FABRICATION OF MICRO-NEEDLE ARRAYUSING BIOCOMPATIBLE POLYMERS BY PRECISION MOLDINGKN presentation
Hiroshi Ito
Graduate School of Science and Engineering, Yamagata University,
4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan
Corresponding author email address: ihiroshi@yz.yamagata-u.ac.jp
Abstract –We have studied the surface structure formation by precision processing technology. The micro-needle array wasproduced from a biocompatible material that was a relatively minimal effect on the human skin by needle remaining.
Microneedle array features were fabricated by micro-injection molding and casting using biocompatible polymers suchas polycarbonate (PC), polypropylene (PP), polylacticacid (PLA) and polyvinyl alcohol (PVA). PC and PP based
microneedle array features with high aspect ratio for needle height was fabricated by several injection molding
techniques. Injection compression molding and injection molding with super critical carbon dioxide fluid with orwithout vacuum process inside the cavity of mold were performed. Effects of process parameters on processability andsurface replication of the molded parts were evaluated. The height replication ratio for micro-needle was improved byusing injection compression molding. Moreover, the effect of vacuum process inside cavity of mold under filling
process was small. However the height replication ratio for micro-needle showed the highest values using the injection
molding with super critical carbon dioxide fluid with vacuum inside the cavity of mold process. In addition, the thermal
nanoimprint with surface modification of polyvinyl alcohol was coated with hyaluronic acid solution biocompatible
material was applied. The replication ratio of fabricated micro-needle array was also measured by 3D laser microscope.
The molded article surface morphology was observed by scanning electron microscope. The presence of hyaluronic
acid on the surface of the micro needle array was measured by the fourier transform infrared spectrophotometer. The
micro-needle array surface indentation was measured by using a nano indenter. This study was found that, thehyaluronic acid can be able to coat on micro needle array surface with the thickness of the hyaluronic acid lower than
10 μm. The micro-needle array with the maximum in the replication rate of 94% of the micro-needle array can be
fabricated and its elastic modulus was about 0.63 GPa.

Keywords: Precise molding, Micro-needle array, Biocompatible polymers, casting, thermal imprint

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

SKIN STRUCTURE AND SCRATCH BEHAVIOR OF
INJECTION MOLDED POLYPROPYLENE
Masaya Kotaki

Kaneka US Material Research Center, Kaneka Americas Holding, Inc.,
800 Raymond Stotzer Pkwy, College Station, TX 77843, USA*email: masaya.kotaki@kaneka.com

Abstract

Surface appearance is an important characteristic of products in many different applications. Damages
created on the surface significantly reduce the quality of the products in many cases. Therefore theunderstanding of the surface fracture mechanisms and the means to improve the resistance to the surface
damages are required to improve the quality of products. The objective of this study was to understandthe relationship between structure near the surface and surface fracture behavior under scratch loading ofpolypropylene (PP).
A progressive load scratch test according to ISO 19252 was performed in this study to investigate surface
fracture behavior of injection molded PP. Effects of injection speed, molecular weight of PP and slipping
agent on scratch behavior are investigated. Highly oriented skin structure was obtained at ultra-highinjection speed of 1000 mm/s. Skin structure was also significantly influenced by molecular weight andslipping agent in terms of molecular orientation, crystalline orientation and types of crystalline structure.
The skin structure was characterized by Raman spectroscopy and wide-angle X-ray diffraction (WAXD).
The results showed that the degree of molecular/crystalline orientations and -phase content in the skinlayer significantly improved scratch properties of PP (Fig.1).

(a)

(b)

Fig. 1 Polarized optical micrographs of transverse subsurface of scratch damages; (a) low molecularweight and (b) high molecular weight injection molded PP.

SEMI-INTERPENETRATING NETWORK OF POLYOXYMETHYLENEWITH OLIGO-BENZOXAZINE VIA REACTIVE BLENDING
N. Mantaranon1, V. Jiratrakan3, and S. Chirachanchai1,2,*
1
The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, Thailand
2
Center for Petroleum, Petrochemical, and Advanced Materials, Chulalongkorn University, Bangkok, Thailand
3
Thai Polyacetal Co.,LTD, Padaeng Industrial Estate,1Padaeng Rd., Map-Ta-Phut, Rayong 21150, Thailand*
Corresponding author email address: csuwabun@chula.ac.th
Abstract – Polyoxymethylene (POM) is an engineering thermoplastic using in daily life products such as gears,
springs, chains, screws, nuts, fan wheels, pump parts, valve bodies, etc. However, POM is sensitive to acid hydrolysis
and oxidation including thermal degradation. In term of chemical structure, the degradation of POM results informaldehyde, which not only leads to the instability but also the generation of toxic vapor. To overcome this limitation,in the past, various approaches such as copolymerization with trioxyethylene1, blending with other thermoplastics2 orformaldehyde absorbing agents3 were reported. The fact that benzoxazine is a phenolic resin obtained from phenol,
amine, and formaldehyde via Mannich reaction and polybenzoxazine can be obtained by further curing via ring opening
polymerization, this leads us to an idea to stabilize POM by allowing benzoxazine formed in POM. Here, by simply
adding bis-phenol A and methylamine and carrying out the reactive melt-blending with POM, the benzoxazines andoligobenzoxazines is successfully generated in POM matrices as confirmed by FTIR and 1H NMR. The process also
leads to oligobenzoxazine as identified by GPC to conclude the semi-interpenetrating network of POM andbenzoxazines. The polymer obtained exhibits attractive properties such as non-formaldehyde generation, flame
retardance, and dimensional stability. The presention will include other related properties of the semi-interpenetrating
polymer obtained, especially in the forms of sheets and nanofibers.
Keywords: Polyoxymethylene, Reactive blending, Benzoxazine, Semi-interpenetrating network.

1.
2.
3.

Masamoto, J.; Iwaisako, T.; Chohno, M.; Kawamura, M.; Ohtake, J.; Matsuzaki, K. Journal of Applied Polymer Science
1993, 50 (8), 1299-1305.
Pielichowski, K.; Leszczyńska, A. Journal of Thermal Analysis and Calorimetry 2004, 78 (2), 631-637.
Hu, Y.; Ye, L.; Zhao, X. Polymer 2006, 47 (8), 2649-2659.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

The Relationship Between Morphology and Impact Toughness ofPoly(L-lactic acid)/Poly(ethylene oxide) Blends
Oral presentation
Jin-Ze Lia, Jerold M. Schultzb, and Chi-Ming Chan*a,caDepartment of Chemical and Biomolecular Engineering
The Hong Kong University of Science and Technology
Clear Water Bay
Hong Kong.
b

Department of Chemical Engineering,
University of Delaware, Newark, Delaware 19716.
USA
c

Division of Environment
The Hong Kong University of Science and Technology
Clear Water Bay
Hong Kong.
Corresponding author email address:kecmchan@ust.hk

Abstract - The morphology of unannealed and annealed poly(L-lactic acid)/poly(ethylene oxide) (PLLA/ PEO) (80/20)
and (50/50) blends were studied using polarized optical microscopy (POM), scanning electron microscopy (SEM) andtime-of-flight secondary ion mass spectrometry (ToF-SIMS). Samples were annealed at temperatures between 90 and
125 oC. The size of PLLA spherulites increased dramatically with annealing temperature. SEM analyses of the wateretched PLLA/PEO blend samples and ToF-SIMS analyses of the blend thin films indicated that the PEO content andthickness of the interspherulitic boundary region was higher in the (50/50) blend than in the (80/20) blend. The impact
strength of the PLLA/PEO (80/20) blend was higher than that of the neat polymer for all preparation conditions, and forboth the impact strength decreased with increasing crystallization temperature (and therefore also with increasing
spherulite size). The impact strength of the (50/50) blend was always higher than those of the neat polymer and the(80/20) blend, and increased remarkably with crystallization temperature. The size of the PEO-rich domains within thespherulites was significantly larger in the (50/50) blend than in the (80/20) blend. The size of the intraspherulite PEOrich domians, the size of the spherulites, and the width and PEO content of the boundary layer all acted to determine theimpact toughness of the PLLA/PEO blends. It is suggested that the (50/50) blend exhibits this behavior because it could
undergo plastic deformation within and between PLLA spherulites and sustain a higher level of stress in theinterspherulitic regions.

Keywords: blends, poly(lactic acid); poly(ethylene oxide); spherulite size; interspherulitic boundary width, impact
toughness.
Acknowledgement
The work described in this paper was fully supported by the Research Grants Council of the Hong Kong Special
Administrative Region, China (grant nos. 600210 and 600513).

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

EFFECT OF PRE-ANNEALING ON 3-D ORIENTATION DEVELOPMENTBEHAVIOR DURING SIMULTANEOUS AND SEQUENTIAL BIAXIAL
STRETCHING OF POLY(ETHYLENE NAPHTHALATE) FILMS
Oral presentation
T. Abe, W. Takarada and T. Kikutani *Department of Organic and Polymeric Materials, Graduate School of Science and Engineering
Tokyo Institute of Technology, Japan
Corresponding author email address: kikutani.t.aa@m.titech.ac.jp
Abstract - Effect of pre-annealing on orientation development behavior of poly(ethylene naphthalate) (PEN) films wasinvestigated through in-situ measurement of stress and three dimensional optical retardation during the batch-typesimultaneous and sequential biaxial stretching process. Amorphous and non-oriented PEN films were pre-annealed
under the conditions of different temperatures and periods before the stretching. Degree of pre-annealing was evaluatedtrough the analysis of crystallinity applying the Differential Scanning Calorimetry (DSC) measurement.
It is well known that naphthalene ring tends to orient parallel to theα(010) α(100)α(100)
film surface along with the orientatio of molecular chain in the film (a) α(010)
plane in both uni-axial and bi-axial stretchings of PEN films. Theα(-110)refractive index anisotropy of the resultant films is significantlyMDMD
affected by the planar orientation of naphthallene ring sinceβ(020)
ND
TD
polarizability in the direction parallel to the planar naphthalene ring ismuch higher than that in the perpendicular direction. Typical wideThrough View
Edge View
angle X-ray diffraction patterns of PEN films after simultaneous equibiaxial stretching to the draw ratio of 3 x 3 and after squenatial biaxial
α(010) α(100)α(010)
stretching to the MD (Machine direction) x TD (Transverse direction) (b)α(100)
draw ratios of 3 x 3.33 are shown in Fig. 1. Difference in the intensity
distribution of -form (010) reflection in the through view clearyα(-110)indicates the different orientation mode between simultaneous andsequential stretchings. In addition, apparance of -form (-110)
Through View
Edge View
reflection in ND (noraml direction) in the edge and end views indicatesthe planar orientation of naphthalene ring.
α(010) α(100)Effect of the degree of pre-annealing on 3-D refractive indices forα(-110)the simultaneous and sequential biaxial strething is shown in Fig. 2. Incase of simultaneous biaxial strething, refractive index in the MD
increased whereas that in ND decreased with the increase of thecrystallinity of original film, which corresponds to the degree of preEnd View
anneling. On the other hand, in case of the films of sequenatial biaxial
Fig.1 WAXD patterns of (a) simultanestretching, refractive indices in MD and TD decreased whereas that inously and (b) sequentially stretched PEN
ND increased with the increase of crystallinity. It should be noted thatfilms.
the difference between MD (or TD) and ND refractive indicescorresponds to the out-of-planebirefringence.
These
results
indicated that the effect of prenTD
annealing is opposite for the twodifferent stretching modes, i.e. innMDcase of the simultaneous biaxial
nMD
stretching, orientaion of molecular
chaing and/or naphthalene ringalong the film plane was enhanced,
nND
nND
whereas in case of the sequential
biaxial stretching, such orientation(b)(a)
was suppressed by the preannealing.
Keywords: poly(ethylene
naphthalate), biaxial stretching,planar orientation, birefringenceFig.2 Variations of the 3-D refractive indices of (a) simultaneously and (b)sequentially stretched PEN films with the degree of pre-annealing.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

SPINNABILITY AND THEORETICAL ANALYSIS OF THE SPUNBONDPROCESS FOR POLYPROPYLENE
Oral presentation
Toshitaka Kanai1*
1

KT Polymer: 5-7-14 Kuranamidai, Sodegaura, Chiba, Japan - toshitaka.kanai@ktpolymer.com

ABSTRACT:The spinnability of the spunbond process for polypropylene (PP) was investigated and narrow molecular weight
distribution PP had good spinnability. Furthermore, adding low modulus polypropylene (LMPP) to PP could control the
crystallization speed and gave good spinnability. A small amount of LMPP was found to stabilize the high speed
spinning of PP and very fine fibers were obtained. The theoretical analysis of the spunbond process was set up andapplied to PP and its blends. The effect of blending LMPP to high tacticity PP on the spinnability of the spunbond
process was investigated. From the calculated results, it was speculated that the improvement of spinnability originatedfrom the suppression of crystallization speed, strain rate in the spinning process and high molecular weight.
Keywords: spunbond, polypropylene, spinnability, crystallization speed

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

NANOCOMPOSITES BASED ON BIOMASS CHARCOAL WITH MULTIFUNCTION
Oral presentation
1

Aimiao Qin *, Ning Tian1, Lei Liao2，Jianwu Sun1 and Chun Wei1
College of Materials Science and Engineering, Guilin University of Technology, China
2
College of Environmental Science and Engineering, Guilin University of Technology, China
Corresponding author email address: 2005032@glut.edu.cn
1

Abstract Nanocomposites with multifunction based on bamboo charcoal (BC) and sisal fiber charcoal (SFC) including nano-metaloxide/BC and nano-metal oxide/SFC were successfully prepared via precipitation-impregnation and hydrothermal method, respectively.
Structures and morphologies of the nanocomposites were characterized by XRD, SEM, EDS, and etc. The nanocomposites exhibited
well properties of adsorption, photocatalysis degradation and energy storage. The effects of experiment conditions on the nanocomposite
properties were studied. For removal of organic dyes, the results showed that smaller particle size of biomass charcoal in the composites
and at slow pH value of the dye solution had a better ability of absorption and photocatalytic degradation. For example, when the particle
size of BC was smaller than or equal to 75μm, the removal rate of rhodamine B (RhB), methylene blue and acid fuchsin was close to
90% under UV irradiation for 15min, the highest removal rate of nano-ZnO/BC composite for RhB and acid fuchsin was at the pH = 2
and pH = 5.4, respectively. Using as anode materials for lithium-ion batteries, nanostructured metal oxide/SFC composites exited ahigher specific capacity and cycle stability, and also showed a synergistic effect on the electrochemical performance. Furthermore, thesynthesis conditions such as temperature, heating rate and reaction time had much effect on the performance of nanocomposites based on
BC and SFC.
Keywords: Nanocomposite; biomass charcoal; bamboo charcoal; sisal fiber charcoal; multifunction

90

(b)

(a)

90

70
60
50

250-550m
120-250m
75-120m
≤75m

40
30
0

15

30

45

60
75
Time / min

90

105

120

Removal rate / %Removal rate / %8080

250-550m
120-250m
75-120m
≤75m

70

60

0

15

30

45

60
75
Time / min

90

105

120

Figure 1 Removal rate of organic dyes by nano-ZnO/BC composites with different particle size of BC:(a) RhB, (b) acid fuchsin.

(a)

(b)

Potential / V vs Li/Li

+

3.0
2.5
2.0

Circle 1
Circle 2
Circle 10
Circle 20
Circle 30

1.5
1.0
0.5
0.0
0

200

400

600
-1

Capacity / mAh.g

Figure 2 SEM image(a) and discharge/charge curves (b) of iron metal/SFC nanocomposite

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

800

EFEECT OF CELLULOSE NANOFIBER ON SCRATCH RESISTANCE OF
POLY(VINYL ALCOHOL) COMPOSITES
Oral presentation
S. Konagaya1*, T. Ooshio2, H. Furuhashi1, T.Yamada2 and K. Noma3
1

2

Graduate School of Engineering, Nagoya University, Japan
Graduate School of Natural Science & Technology, Kanazawa University, Japan
3
Division of Research and Development, Fujidenolo Co. Ltd., Japan
Corresponding author email address: konagaya@apchem.nagoya-u.ac.jp

Abstract – Recently scratch resistance of the plastic or glass surface has been required to be improved for theirapplication to the touch panels and smart phones. Addition of hard nano-particles such as silica (SiO2), alumina (Al2O3)
and carbon nanotube (CNT) to the polymer composites have been studied and actually used for the improvement ofscratch resistance [1,2]. The mixtures of such nano-particles with polymer binders and cross-linking agents are usuallycoated on the glass or plastic substrates in order to improve the scratch resistance.
Cellulose nanofiber (CeNF) is a promising material for the improvement of mechanical properties (tensile strength,
modulus) of polymer composites now, since it has high crystallinity and high modulus. The tensile strength of PVA was
increased twofold by the addition of 10 wt% CeNF. However there is no study on the effect of CeNF on the scratch
resistance of the polymer composites. Then the authors have been studying the effect of CeNF on the scratch resistanceof poly(vinyl alcohol) (PVA) composites.
PVA/CeNF composites were prepared from the mixture of CeNF/H2O dispersion, aqueous PVA solution and a crosslinking agent (CL). The product mixture was coated on the glass substrate and dried at 110 °C for 1 hour. At that time
the thickness of the dried PVA composites was adjusted to be around 10μm to get a reproducible data. The scratch
resistance (pencil hardness) of the PVA composites was evaluated according to the pencil hardness test (JIS K5600-54). The larger the n number of pencil hardness (nH) is, the higher the scratch resistance is.
The pencil hardness of PVA/CeNF composites was increased from 2H to 5H with the increase of CeNF addition to
40 wt%. However the PVA/CeNF composites with 50 wt% CeNF showed lower pencil hardness (4H). It was found outthat 30-40 wt% CeNF addition contributed to the enhancement of pencil hardness, but the excess addition of CeNF
decreased the pencil hardness. In order to get a higher pencil hardness, CL was applied to the PVA/CeNF composites
according to the above procedure. PVA/CeNF/CL (CL/PVA(g/g)= 0.2) exhibited a higher pencil hardness (6H) than
PVA/CeNF composites, at the CeNF concentration of 30-40 wt%. It was made clear that CeNF addition was effective
for the enhancement of pencil hardness (scratch resistance) of PVA composites.
In this paper the effect of CeNF on the pencil hardness (scratch resistance) of PVA composites will be spoken indetail.
References[1] A.Wakahara, J. Jpn. Soc. Colour Mater., 87 [9],311-316(2014)[2] A. Nagasaka, Cabon (Tanso) 2013[No.259], 255-260(2013)
Keywords: Cellulose nanofiber, Poly(vinyl alcohol), Composite, Pencil hardness, Scratch resistance

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

EFFECT OF CROSS-SECTIONAL CONFIGURATIONON DIE SWELL BEHAVIOR AND SPIN-LINE STABILITY
IN BICOMPONENT MELT SPINNING PROCESS
Oral presentation
Y. Chen, W. Takarada* and T. Kikutani
Department of Organic and Polimeric Materials, Tokyo Institute of Technology, Japan
Corresponding author email address: takarada.w.aa@m.titech.ac.jp
Abstract – Various kind of bicomponent fibers have been developed to change mechanical properties or add newfunctionalities to fiber materials. In bicomponent fibers, two or more materials are extruded through single spinnerethole and spun into single filament. Typical cross-sectional configuration of bicomponent fibers are Side-by-side, SeathCore (S/C), Islands-in-the-Sea (S/I) and Blend. Cross-sectional configuration has an effect not only on the fiber
characteristics but also on the spinning behavior or spin-line stability in melt spinning process. In this study,
bicomponent melt spinning of polystyrene (PS) and polypropylene (PP) with the composition of 1:1 was performed
using a spinning die for the preparation of S/I fibers with 1519 islands in the fiber cross-section and spinning behavior
and die swell was investigated in several spinning temperatures.
It was found that the die swell was much larger for the S/I spin-line in comparison with that for the S/C spin-line. With
the increase of the extrusion temperature, the die swell tended to be decreased. On the other hand, the die swell of blend
spinning increased with the extrusion temperature. The peak position of swelling shifted to downstream in the order of
Blend > S/I > S/C. These results suggested that the die swell in the S/C and S/I spinning is governed by the viscoelastic
effect whereas that in the blend spinning is caused mainly by the interfacial tension between the two components. Spinline stability decreased with increasing spinning temperature in Blend spinning whereas spin-line was stable in all
spinning temperature in S/I or S/C spinning. This results show that the peak position of swelling has greater impact on
spin-line stability than swelling ratio.
Keywords: melt spinning; die swell; interfacial tension.
250℃
290℃
270℃
230℃

250℃
290℃
250℃
290℃
270℃
230℃
270℃
230℃

Blen
Figure 1. Photographs of free-fall S/I, S/C and blend spin-lines of PP/PS dnear the spinneret at different extrusion
S/I

S/C

temperatures. For the spinning of blend fibers, S/C type spinneret was used.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

POLYMER MELT DIFFERENTIAL 3D PRINTING AND
ADVANCED MANUFACTURING
B.H.Chi1,2, Y. An1,2, Z.W. Jiao1, and W.M. Yang1,2*
1
College of Mechanical and Electrical Engineering, Beijing University of Chemical Technology, Beijing, China
2State Key Laboratory of Organic-Inorganic Composite, Beijing University of Chemical Technology, Beijing, China
Corresponding author email address: yangwm@mail.buct.edu.cn
Abstract: 3D printing has become one of the most important research fields in the advanced manufacturing technology.
In this paper, polymer melt differential 3D printing technology is proposed, this technology can solve problems in the
traditional 3D printing, such as materials have special requirements and buckling instability of the filamentous
materials. A new polymer melt differential 3D printing device is presented in this paper, this device mainly composedof a melting and plasticizing unit, solenoid valve control unit, three-dimensional motion platform, temperature control
unit, pulse pressure controller and other parts. The schematic diagram and photo of the polymer melt differential 3D
printing device is shown in Figure 1. The experimental research of printing cartilage tissue engineering scaffold withpolyurethane elastomer was made, and the effect of process conditions on the accuracy of printing products was studied.
Meanwhile, the advanced manufacturing of the polymer, which is related to 3D printing, is introduced in this paper.

Fig.1 the schematic diagram and photo of polymer melt differential 3D printing experimental system
Keywords: 3D printing; polymer; melt differentiation; advanced manufacturing

GREEN CHEMISTRY: PREPARATION OF ENVIRONMENTALLYBENIGN GRAFT COPOLYMERS VIA EMULSION SYSTEM
Oral presentation
Kiyoaki Ishimoto1*, Warunee Ariyawiriyanan1, Amorn Chaiyasat2, and Sommai Pivsa-Art1
1

Department of Materials and Metallurgical Engineering, Faculty of Engineering,
Rajamangala University of Technology Thanyaburi, Thailand
2
Department of Chemistry, Faculty of Science and Technology,
Rajamangala University of Technology Thanyaburi, Thailand
Corresponding author email address: ishimoto_k@en.rmutt.ac.th

AbstractPolymeric material has been a key factor so far, making our daily life comfortable and convenient. On the other
hand, our society is nowadays faced with environmental problems caused by these products, such as rapid climatechanges due to increasing carbon dioxide levels, the shortage of fossil resource, and the disposal of plastic waste.
In order to take measures to mitigate and resolve these serious issues, it is specific and effective to employ
renewable resources as starting materials in materials fields from the viewpoint of green plastic. Much effort has, infact, been paid to replace the conventional oil-based polymer with biobased polymer (BBP) derived from biomass forbuilding a sustainable society. Poly(lactic acid) (PLA) is the representative of BBP and has been already used in a wide
variety of fields. In the former study, the synthesis and characterization of graft copolymers was performed using PLAcontaining macromonomers via miniemulsion system. First, macromonomers having a methacryloyl group withdifferent PLA chain length were prepared via ring-opening polymerization of lactide, a six-membered cyclic dimer oflactic acid, in the presence of 2-hydroxyethyl methacrylate as initiator and tin octoate (Sn(Oct)2) as catalyst. Radical
copolymerization of the macromonomers was then carried out with other vinyl monomers via macromonomer
technique, or grafting through method to produce graft copolymers with PLA as side chain. The copolymerization inwater as solvent provided a stable emulsion system. Additonally, this investigation revealed correlative relationshipbetween the length of PLA and the properties of their products.
The present research was especially focusd on biodegradable function graft copolymers have, and designed to
examine the properties of their products as well as their behaviors of the monomers used in emulsion system. In thiscase, it doesn’t matter whether a starting material for the synthesis is based on oil resource or renewable biomass.
Macromonomers having polymerizable group with various chain length was firstly prepared via ring-opening
polymerization of cyclic compounds using an initiator catalyzed by Sn(Oct)2. Secondly, graft copolymers weresynthesized by using the resultant macromonomers and other vinyl monomers in water to characterize their products.
These studies would be reported throughout this workshop.
Keywords: Green Chemistry, Macromonomer Technique, Emulsion System

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Modification of chemically stable polymeric materials 63. Improvement in theadhesion property of polymeric materials, FRP and CFRPs for car-use
Oral presentation
H. Kanazawa and A. Inada
Department of Industrial Systems, Faculty of Symbiotic Systems Science,
Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan: kana@sss.fukushima-u.ac.jp
Abstract Hydrophobic polymeric materials such as polypropylene, polyethylene, PET were modified by a new
combination method of physical and chemical processes. The modified materials gave a durable hydrophic property.
and the improvement in adhesion, property. Poly(methyl pentene), silicone resin and engineering plastics of which
modification is difficult by corona or plasma discharge treatments were modified well. Especially, polymer composites
such as GFRP and CFRP for cars and aircrafts were improved, and thre adhesion property of CFRP was increasedmuch more than usual plasma discharge or a peel ply method. Modified polymeric materials were coated with waterbased paints. The modified materials gave a high durability as compared with a plasma treatment and the othermethods.
Keywords: surface modification, adhesive property, PP, GFRP, CFRP, water-based paint coating, printingin

1. Introduction
Polyolefins such as polypropylene (PP),polyethylene (PE), ultrahigh molecular weight PE(UHMWPE) and poly(methyl pentene) (PMP), etc.
are chemically stable and their durable
modification is not easy. We tried to combine
two or three methods, and found that the
combination of some modification techniques was
effective for the modification of these stable
polymeric materials. The obtained hydrophilic
property was not lost for several years. TheGFRP and CFRP boards were modified and theadhesion property was compared with usual
plasma treatments and a peel ply method.

2. Experimental

the presence of catalysts.
2.4 Adhesion strength and analysis
A bonding strength of a polymeric material
bonded to other materials was measured by atensile tester, Shimadzu AGS-H5KN.
IR and XPS spectra of materials were observed.

3. Results
3.1 Improvement in the adhesive property of
CFRP (epoxy resin)
CFRP (epoxy resin) boards for car and aircraft
use are adhered to each other using epoxy resin
adhesives. But, the CFRP boards modified by thepresente KANA method gave the adhesion
strength higher than unmodified ones. Table 1
gives the results of the tensile strength test of
unmodified-unmodified CFRP boards, plasmatreated–plasma-treated CFRP boards, peel ply
treated–peel ply treated CFRP boards, and KANA
modified-Kana modified CFRP boards. The
highest shear strengh was obtained in the adhesionof KANA-modified boards. The adhesion
property of plasma treated or peel-ply treated
CFRP boards is known to be lost with time. But,
KANA treated CFRP boards can be adhered to

2.1 Materials
Polymeric materials were used after washingwith methanol. Commercial chemical reagentsand hydrophilic reagents were used after a simple
purification.
2.2 Adhesives
Poly(vinylpyrrolidone), starch, wood-use bonds,
PVAC-water mixture, cyanoacrylate (CA), CAprimer set, tape type epoxy resin adhesives, etc.
were used.
2.3 Treatment
Polymericmaterials Table 1 Adhesion shear strength test of CFRP (epoxy resin) boards adhered using epoxy
were
activatedby adhesive and failure styles
chemical oxidations or
specimen
Shear strength (MPa) Ratio(mod./unm.) Failure style
UV,
energyunmodified-unmd.
25.4
1.00
interfaceirradiations.
The
35.2
1.40
cohesion
activated
polymeric plasma-plasmapeel
ply-peel
ply
35.0
1.38
cohesionmaterials were treatedwith chemical reagents KANA–KANA
51.3
2.02
cohesion+material

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

each other even a month after the treatment.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

MONLECULAR SIMULATION OF THE EFFECT OF CHAIN TACTICITY ON
DEMIXING OF POLYETHYLENE/ POLYPROPYLENE BLENDS
Oral presentation
Visit Vao-soongnern*
Laboratory of Computational and Applied Polymer Science (LCAPS), School of Chemistry, Institute of Science,
Suranaree University of Technology, Nakhon Ratchasima, Thailand. E-mail: visit@sut.ac.th
Abstract - The molecular origin of the demixing behavior for 50:50 (wt/wt) polyethylene/polypropylene (PE/PP) withdifferent tacticity of PP at the melts (473 K) was investigated by Monte Carlo simulation of coarse-grained polymer
model. Isotactic (iPP), atactic (aPP) and syndiotactic (sPP) polypropylenes were used for blending with PE. Coarsegraining polymer chains were represented by 50 beads, corresponding to C100H202 and C150H302 for PE and PP,
respectively. The simulation was performed on a high coordination lattice incorporating intramolecular interactions
from the Rotational Isomeric State (RIS) model and intermolecular interactions Lennard-Jones (LJ) potential functionof ethane and propane units. Chain dimensions, the characteristic ratio (Cn) and self-diffusion coefficient (D) of PE in
the blends are sensitive to the stereochemistry of PP chains. Compared with neat PE melts, PE dimension was relatively
unchanged in PE/iPP and PE/aPP blends but slightly decreased in PE/sPP blends. PP dimension was increased in
PE/iPP and PE/aPP but decreased in PE/sPP mixture in comparison with neat PP melts. In addition, diffusion of PE andPP chains in PE/PP mixture was decreased and increased, respectively. Interchain pair correlation functions were used
to detect the immiscibility of the mixtures. The tendency of demixing of PE/aPP and PE/iPP blends were weaker thanthat of PE/sPP blend.
Keywords: Polyethylene, polypropylene, blends, tacticity, molecular simulation
Ref. 1. Vao-Soongnern V., Polymer Science - Series A, 56, 928 (2014)
2. Takhulee A. , Vao-Soongnern V., Polymer Science - Series A, 56, 936 (2014)

Figure 1 A cross section view of representative
snapshots for PE/sPP blends (PE and PP beads aredenoted by red and gray color, respectively)

Figure 2 A cross section view of representative
snapshots for PE/iPP blends (PE and PP beads aredenoted by red and gray color, respectively)
1.8
1.6

1.0

Pair correlation function

Pair correlation function

1.2

0.8
0.6
0.4
Pure PE
PE/aPP
PE/sPP
PE/iPP

0.2

2

3

4

5

6

7

1.2
1.0
0.8
0.6
gPE-PE in PE/sPP

0.4

gsPP-sPP in PE/sPP

0.2

0.0
1

1.4

8

Shell index

Figure 3 Pair correlation functions, gPE-PE (i), formonomers of PE chains in the pure PE melt and
PE/aPP, PE/iPP and PE/sPP blends.

gPE-sPP in PE/sPP

0.0
1

2

3

4

5

6

7

8

Shell index

Figure 4 Pair correlation functions, gPE-PE (i), gsPP-sPP (i)and gPE-sPP (i) for 50:50 by weight of PE/sPP blend.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

MELT-MIXING BY PITCHED-TIP KNEADING DISKS IN A TWIN-SCREWEXTRUDER
Oral presentation
T. Kajiwara1*, Y. Nakayama1, H. Takemitsu1, S. Esaki1, T. Takeuchi2, K. Kimura2 and H. Tomiyama2
1
Department of Chemical Engineering, Kyushu University, Japan
2
Reseach & Development H.Q., The Japan Steel Works Ltd., Japan
Corresponding author email address: kajiwara@chem-eng.kyushu-u.ac.jp
Abstract –Twin screw extruders are widely used as a continuous mixing equipment of polymeric materials such as
polymer blends and polymer composites. Our research group has been studied on the development of computer
simulation technique to predict the materials behavior in a twin-screw extruder and the evaluation method of mixing
performance based on the simulation results. The simulation has applied to evaluate the mixing by pitched-tip kneading
discs whose tips are pitched to the screw axis. We have studied the performance of mixing elements with different
combinations of stagger and tip directions for pitched-tip kneading discs. In this study, we carry out the twin-screw
extrusion expariment for a blend of ABS (acrylonitrile-butadiene-styrene copolymer) and AS (acrylonitrile-styrene
copolymer). We performed the morphology observation via scanning electron microscope and evaluated the diameter
distribution of despersed rubber particles. We also measured the rheological properties. We compared these results withthe mixing performance obtained by the previous simulation, and discussed the melt mixing mechanism by pitched-tip
kneading discs and reliability of the numerical simulation.
Keywords: Twin Screw Extruder, Polymer Blend, Numerical Simulation, Rheological Property, Morphology

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

POLYMER PROCESSING SIMULATIONCHALLENGES IN DESCRIBING HIGHLY ELASTIC FLOWS
Oral presentation
Koki Tomioka*
Department of Advanced Process Development, Nitto Denko Corporation, Japan
Corresponding author email address: kouki_tomioka@gg.nitto.co.jp
Abstract –Film casting is a widely used production process in industry. In this process, a molten polymer is extruded into a flat
shape through a die, and then stretched in air by using a roll. A uniform film thickness is generally desired. However,
the thickness of the film often becomes non-uniform due to phenomena such as draw resonance and die swell. Thesephenomena are strongly influenced by the viscoelasticity of the molten polymer, and it is desirable to develop
mathematical models that can describe this influence.
A major challenge in developing such models is the description of strongly elastic flows. This is also known as theHigh Weissenberg-Number Problem (HWNP) since the Weissenberg number (product of fluid relaxation time andcharacteristic shear rate) characterizes the level of elasticity in the flow. The challenge arises because constitutive
equations for polymeric liquids are highly nonlinear and very steep stress gradients can develop as a result.
Numerical methods developed before ~2000 only work for values of the Weissenberg less than ~10. Yet in film
forming processes the Weissenberg number may be ~100. In the past decade, new methods to overcome theselimitations have been developed. These methods are based on preserving the positive definiteness of the polymer
conformation tensor, which characterizes the polymer deformation. The presentation will discuss various methods for
dealing with the HWNP and their implementation in the computational fluid dynamics package OpenFOAM.
Keywords: Viscoelastic, Extrusion Process, High Weissenberg-Number Problem, Log Conformation Representation

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Evaluation of Distributive Mixing in an Internal Mixer
by Partially Filled Flow Analysis
Oral presentation
K. Higashi1, S. Yamada1, K. Fukutani1, and Y. Yamane2
1

2

Mechanical Engineering Research Laboratory, Kobe Steel, Ltd., Japan
Industrial Machinery Engineering Department, Machinery Business, Kobe Steel, Ltd., Japan
Corresponding author email address: higashi.kosuke@kobelco.com

Abstract – Internal mixers are widely used in rubber compounding for tires. It is not sufficiently
examined the distributive mixing in the mixer and a relation between a flow in the chamber and thecompounding qualities. Therefore, it is important to establish flow analysis technique for developing
better performance mixers and rotors. In this study, three-dimensional numerical study has been carriedout to investigate the mixing flow in the batch mixers. It is assumed that mixer was partially or fully
filled with isothermal rubber in the simulation. Banbury type two-wing rotors were selected as a mixing
rotor. Fill factor was changed from 60 to 100 %. Phase difference between two rotors was changed from0 to 90 deg. Particle tracking method was applied, and flow rate in a cross-section of chamber was alsostudied for the evaluation of distributive mixing. From the results, it was suggested that the flow througha certain cross section in a chamber does not necessarily enhance the distributive mixing, and that fill
factor has significant effect on the distributive mixing. In addition, it was considered that phasedifference between two rotors has a correlation with both the flow rate and the distributive mixing.
Keywords: Batch Mixer, Mixing

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

DYNAMIC MECHANICAL PROPERTIES OF SISAL FIBER CELLULOSE
MICROCRYSTAL / UNSATURATED POLYESTER IN-SITU COMPOSITES
Oral presentation
2

C. Wei *, D.M. Zeng , J. Lv , C.B. Yu1,Hongxia liu1, Hongyan Li1, Aimiao Qin1
1

1

1

College of Materials Science and Engineering, GuilinUniversity of Technology, Guilin
2

Super-Dragon Engineering Plastics Co., Ltd., Guangzhou

Corresponding author email address: 1986024@glut.edu.cn
Abstract: Sisal is a natural material and a potential additive to reinforce composites. In this paper, sisal fiber cellulose
microcrystal (SFCM) was obtained from sisal fiber and sisal fiber cellulose microcrystal / unsaturated polyester (SFCM/ UPR) in-situ resins were prepared via in-situ polymerization. Moreover, SFCM / UPR composites were produced withmethods of rolling and molding. In our previous work, the mechanical properties and tribological properties of SFCM /UPR composites were significantly increased. Based on the previous studies, our further research focuses on the
dynamic mechanical properties of SFCM / UPR composites. It is demonstrated that SFCM could significantly improvethe dynamic mechanical properties of composites, the effect is closely related with the amount of SFCM, its dispersion
in UPR matrix and interfacial interaction. When the content of SFCM was 3 wt%, at 50 °C, the storage modulus of
SFCM / UPR composite was 33.22 % higher than that of pure UPR. In addition, the glass transition temperature (T g)
was shifted to a higher temperature by 7.5 °C and loss modulus was decreased by 16.24 %. The equilibrium value ofrelaxation modulus at 120 min was 30.52 % higher than that of pure UPR composite. Besides, the equilibrium value ofcreep strain at 120 min was decreased by 41.61 % compared with pure UPR composite.
Keywords: dynamic mechanical properties; sisal fiber cellulose microcrystal; unsaturated polyester; in-situ
polymerization; composites

8000
6000
4000
2000
0
50

100

150

200

0%
1%
3%
5%

500
400
300

0.14

(b)

200

0.10

100

0.08
0.06
0.04
0.02
0.00

0

250

(c)

0%
1%
3%
5%

0.12

Tan Delta

10000

(a)

Loss Modulus (MPa)

0%
1%
3%
5%

50

100

T (°C)

150

200

50

250

100

150

200

250

T (°C)

T (°C)

Figure 1. (a) The storage modulus、(b) loss modulus and (c) Tan δ of pure UPR and SFCM / UPR composites atdifferent temperatures
1350
1300
1250
1200
1150
1100
1050
1000
950
900
850
800
750

0.26

0% (a)
1%
3%
5%

0.24
0.22

Strain (%)

Relaxation Modulus (MPa)Storage Modulus (MPa)

12000

(b)

0%
1%
3%
5%

0.20
0.18
0.16
0.14
0.12

20

40

60

80

Time (min)

100

120

20

40

60

80

100

120

Time (min)Figure 2. (a) Stress relaxation properties and (b) creep properties of pure UPR and SFCM / UPR composites

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

MULTI-ELEMENT ANALYSIS OF POLYMER USING WAVELENGTHDISPERSIVE XRF
Oral presentation
H.R. Low
Bruker Singapore Pte Ltd
Corresponding author email address: hou_ran.low@bruker.com
Abstract - XRF analysis can be an integral part for the quality control procedures in polymer production facility toensure the best polymer quality. With quick and hassle-free sample preparation, a wavelength dispersive XRF canprovide critical information about catalyst residues, additive concentrations and even hazardous elements (RoHS) in
polymers. Bruker provides unrivaled solution packages that are efficient and reliable for a wide range of polymer
chemistry.

Keywords: WDXRF, EDXRF, RoHS, polymer processing.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

THE FLAMERETARDANCY STUDY OF PVAUSING FOR CARDBOARD BED
Oral presentation
1

Yoshihiro. Mizutani , Yusaku. Mochizuki1, Masayuki. Okoshi1 and Hiroyuki. Hamada1
1
Department of Advanced Fibro Science, Kyoto Institute of technology, Japan
Corresponding author email address: mizutani@jpacks.co.jp
Abstract - Corrugated cardboards have a truss structure, so these have advantageous in terms of specific strength,
workability, price and recycling efficiency. For these properties, corrugated cardboards are used as packing materials.
The cardboard came to be often used at the shelters at the time of the disaster by East Japan earthquake disaster.
refugees is forced to lie on the floors of the gymnasium directly in Japanese shelters, but the serious second healthy
damage and disaster related death. It is thought that the cardboard are effective means to prevent them. In this research
we tried to study about the flameretardancy (FR) of a corrugated cardboards using for Polyvinyl Alcohol (PVA).The
reason why it is necessary to add the function of FR- corrugated cardboards by fire disaster in Japanese shelters. The
coating PVA on the cardboard is possible to be recyclable, because PVA has water solubility. Also the reason using
PVA is to protect from the toxicity of flameretardant, which is used to the cardboards. We studied the FR-PVA for
different with decomposition point of FR agent. We measured combustion behavior of the PVA with 4 kinds offlameretardant. In the result, we could get the combustion behavior of PVA with each flameretardant.

Fig.1 Peak Heat Release Rate
The combustion behavior of cardboard bed was measured by using large combusting furnace. A part of the
combusting behavior of cardboard bed was clarified from the experiment and it became important data for our further
study.
Keywords: Cardboard, Combustion, Flameretardancy, PVA..

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Size, shapes and superstructures of polymeric materials with a SAXS/WAXS instrument
Author :Sergio Rodrigues *, Pierre Panine, Manuel Fernandez- Martinez, Sandra Desvergne, Frederic
Bossan, Ronan Mahé , Peter Høghøj , Xenocs, Sassenage, France*corresponding author: sergio.rodrigues@xenocs.com
Nanostructured materials hold major expectations but understanding their properties requires theinvestigation a large number of compositions or process combinations necessitating characterization
requirements over broad length scales. Moreover new materials based on a bottom up approach, i.e.
self-assembly of complex materials as such as block copolymer are of significant interest for a wide
range of applications but still require control and understanding of their morphology, both for
fundamental studies or for routine quality verification.
Small Angle X-ray Scattering (SAXS) is a powerful measuring method for investigating nanostructured
materials providing information in the range from 1 nm to beyond 150 nm such as nanoscalemorphology, mesoscale phase identification, surface to volume ratio of internal structures as few
examples. The method requires little sample preparation, is non-destructive and in contrast to
microscopy probes a large volume of the sample enabling a statistically meaningful result. However,the same technique can be applied to surface only in the so-called “grazing incidence geometry”.
When combined with Wide Angle X-ray Scattering (WAXS) one can also get information on crystalline
structure.
Major developments in components and subassemblies achieved the past years offer capabilities forfast routine measurements, screening process parameters or samples. Moreover, most of the timesuch experiment can be conducted with sample maintained in normal atmospheric conditions,
without further preparation, enabling a simplified access to the nanostructure information.
This presentation will summarize major developments on SAXS/WAXS instrumentation emphasizing
impact for polymeric materials characterization. High throughput characterization of microinjected
semicrystalline polymers will be shown emphasizing the nanostructure and processing relationships.
Capability to measure simultaneously nanoscale structure and crystalline features during in-situ
studies such as temperature controlled measurements will also be highlighted. More-over, highbrightness, ultra-low divergence beam coupled to increased sample to detector distance now
enables to extend the probe length to few hundred of nanometers in the UltraSAXS regime, suchcapability will be discussed with in-situ stretching application example. Finally we will be showing
GISAXS measurements on block copolymers as an example of characterization of self-assembled
structures.

2D ARRAY NANOHOLE PROCESSING ON ULTRATHIN POLYMERFILMS WITH GOLD NANOPARTICLES
Oral presentation
K. Yamada1*, C. Narita1 and Y. Tsuboi2
1

Department of Advanced Fibro-Science, Kyoto Institute of Technology, Japan
2
School of Science, Osaka City University, Osaka, Japan
Corresponding author email address: kazushi@kit.ac.jp

Abstract - We present a novel laser processing technique that enables us to form nanoholes (d < 30 nm) on a polymer
film. The important feature of the present technique is the utilization of a hybrid target, which contains an organic
polymer and metal nanoparticles. The Au nanoparticles were fixed to a glass substrate (avoiding aggregation of thenanoparticles) by a technique involving a self-assembled monolayer of 3-aminopropyltrimethoxysilane or ultrathinblock-co-polymer film. The film was coated with a thin poly film, and then irradiated with a nanosecond 532 nm pulsed
laser light. After laser irradiation for a target, nanoholes with diameters of ca.30 nm were formed, which were allayed
two-dimensionally in the observation area. The light excited the resonant plasmon absorption band of the Au
nanoparticles. Subsequently, the particles underwent explosive vaporization via a superheated state, resulting in theformation of nanoholes within the film.
We have demonstrated a novel technique for sub-wavelength laser processing, in which nanoholes of several
tens-of-nanometers in diameter were formed by utilizing a polymer/metal hybrid film and resonant plasmon absorption.
In this presentation, the relevant aspects of the nanohole formation process and the mechanism underlying the process
are presented.
Keywords: Laser Ablation, Nano-processing, Gold nanoparticles, Plasmon resonance.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

DYNAMIC MECHANICAL ANALYSIS AND HEAT SEAL PROPERTY OF
BIODEGRADABLE POLYMER BLENDS AND COMPOSITE FILMS
Oral presentation
S. Thumsorn1,2*, S. Pivsa-Art2, K. Yamada2, K. Miyata3 and H. Hamada2
1

Department of Textile Engineering, Rajamangala University of Technology Thanyaburi, Thailand
2
Department of Advanced Fibro-science, Kyoto Institute of Technology, Japan
Department of Polymer Science and Engineering, Yamagata University, Japan
Corresponding author email address: supaphorn.t@rmutt.ac.th

Abstract - Biodegradable polymers of poly(lactic acid) (PLA) and poly(butylene succinate) (PBS) were compoundedwith PBS and thermoplastic starch (TPS) in twin screw extruder. PBS contents were from 0-20 wt%. TPS wascompounded at the contents of 0-5 wt%. Talc filler was added at the content of 3 phr during compounding the blends.
PLA/PBS, PLA/PBS/TPS blends and the composite with talc were fabricated into films using cast film process. The
samples were defined to A1, A2 and A3 for PLA/PBS film at 90/10, with TPS 5 wt% and with talc 3 phr, respectively.
The other film sampls were namely B1, B2 and B3 for PLA/PBS film at 80/20, with TPS 5 wt% and with talc 3 phr,
respectively. The films were heat sealed at temperature of 85 C to 100 C with varied heat sealed time of 0.5 s and 1.0
s at constant pressure of 0.2 MPa. The effects of blend ratios, TPS contents and talc filler on dynamic mechanicalproperties, crystallization and peel properties of these biodegradable blends and composite films were investigated. The
additional of talc significantly enhanced dynamic mechanical properties and crystallinity of the composite films. The
blends and composite films were peeled at the setting heat sealed temperature, except the PLA/PBS blend films.
However, the incorporation of TPS decreased peel strenght of the polymer blends films while the adding of talc
increased peel strength of the PLA/PBS composite films at PBS content 10 wt% when increasing heat seal temperature..
Keywords: biodegradable polymer, crystallization, composite film, heat seal.
3.5

A1
B2

2.5
2.0

1.5

1.4

A2
B3

(b)

A1
B2

1.2

B1
A3

A2
B3

0.3

1.0
0.2

Tan 

3.0

B1
A3
Storage Modulus GPa)

Storage modulus (GPa)

(a)

0.1

0.8
0.6

0.0

90

1.0

100

110

120

0.4

Temperature (C)

0.5

0.2

0.0

0.0

40

50

60
70
Temperature (C)

80

90

40

60

80
100
Temperature (C)

120

Figure 1. Dynamic mechanical properties (a) storage modulus (b) Tan  of PLA/PBS films with TPS and talc.

0.5 s

1.0 s

25.0
20.0
15.0

10.0
5.0
0.0

30.0

(b) 95 C

0.5 s

25.0

1.0 s

20.0
15.0

10.0
5.0

A2

A3

B1

B2

B3

(c) 100 C

25.0

0.5 s

1.0 s

B2

B3

20.0

15.0
10.0
5.0

0.0

0.0

A1

Peel strength (N/15 mm)

30.0(a) 85 C

Peel strength (N/15 mm)

Peel strength (N/15 mm)

30.0

A1

A2

A3

B1

B2

B3

A1

A2

A3

B1

Figure 2. Peel strength of PLA/PBS films with TPS and talc at various heat seal temperatures.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

GRAPHENE NANOPLATELET/ POLY (BUTYLENE ADIPATE-COTEREPHTHALATE) HYBRIDS: PHYSICAL PROPERTIES
Oral presentation
Sima Kashi, Rahul K. Gupta* and Sati N. Bhattacharya
School of Civil, Environmental and Chemical Engineering, RMIT University, Melbourne, Victoria, Australia
Corresponding author email address: rahul.gupta@rmit.edu.au
Abstract – Biodegradable Poly (butylene adipate-co-terephthalate) (PBAT) / graphene nanoplatelet (GNP) hybrids
were prepared via melt blending by using a Haake internal mixer at six different concentrations of GNPs (0-15 wt%).
The effect of the GNP-reinforcements on the mechanical and thermal properties of the hybrids was determined.
Measurements demonstrated that addition of GNPs to PBAT significantly improved its Young’s modulus. The hybridwith 15 wt% of GNPs exhibited a Young’s modulus 5 times higher than that of neat PBAT. However, the thermal
stability of pristine PBAT was not much affected by GNP incorporation. Viscoelastic behaviours of the hybrids werecharacterized by dynamic oscillatory rheological tests using a rotational rheometer. Both storage (G') and loss (G'')
moduli of pure PBAT were enhanced by addition of GNPs over the entire frequency range. At high frequencies (>10
rad/s), G' and G'' of PBAT gradually increased with increasing the GNP content of the matrix. The hybrid with 15 wt%
GNPs exhibited storage and loss moduli of 3.8 and 3.4 times higher than those of pure PBAT at a frequency of 100
rad/s, respectively. On the other hand, at frequencies below 0.1 rad/s, storage moduli of hybrids with 12 and 15 wt% of
GNPs were markedly higher than those of other hybrids and showed a pseudo- plateau trend which is attributed to theformation of 3D network of GNPs. Steady shear measurements were also carried out for PBAT/GNP hybrids. Apparent
viscosity of the matrix monotonically increased with the GNP loading and reached 168kPa.s at 15 wt% of GNPs, which
was about 10 times higher than pure PBAT’s viscosity. Shear thinning flow behaviour was observed for all the samples.
As the GNP loading was increased above 6 wt% a stronger shear thinning trend was observed.

Keywords: biodegradable polymer, Graphene nanoplatelet, hybrid

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

DEVELOPMENT OF STARCH BASED BIO-FILM AND LIFE CYCLEASSESSMENT
Oral presentation
Zhang Xiwen1*, Zhang Xikui2, Yek Wei Ming1, Tan Yee Shee1, Munirah Abdul Manan1, Li Xu2
1

Singapore Institue of Manufacturing Technology, Singapore
Institute of Material Research and Engineering, Singapore
Corresponding author email address: zhangxw@SIMTech.a-star.edu.sg
2

A Abstract
PLA and starch are two promising candidates for biodegradable polymer blends. However, hydrophobic PLA
and hydrophilic starch are thermodynamically immiscible. This study has developed a thermoplastic starch(TPS)/biopolymer/nanoclay ternary composites film through co-extrusion with nanoclay as both
reinforcements and compatibilizer. The biodegradable film (bio-film) has been manufactured throughconventional film forming technology for subsequent characterization, mechanical properties andbiodegradation investigation. Interphase compatibility, morphology, structure and mechanical properties
relationship has been investigated and correlated. After incorporation of nanoclay, the inferface between
PLA and TPS has improved (Figure 1). Tensile strength of nanoclay reinforced PLA/TPS film with up-to
50wt% of TPS can meet the strength requirments of commercial plastic bags (Figure 2). Furthermore,biodegradation rate of the can be controlled by changing TPS and nanoclay content.

Li

Figure 1. SEM for PLA/TPS films with and without nanoclay.

Figure 2. Tensile strength of PLA/TPS biofilms.

Carbon footprint, material cost and energy consumption have been calculated and compared. As a result,bio-film developed in this study achieves lower carbon footprint as compared with the commercial ones
(Figure 3), i.e. 3.03 kg CO2e/kg of reduction in average (Compared to commercial LDPE and PP film). The
material cost of the bio-film was also reduced around 26% compared to pure PLA film.

Figure 3 Comparison of Carbon Footprint of Bio-Film with Petrochemical Films

Keywords: PLA, Thermoplastic starch, Biodegradable film, Life cycle assessment

Controlled Urea and Ammonium Sulfate Released from Polylactic acid forSlow Released Fertilizer Application
Sumonman Niamlang, Sommai Pivsa-Art, Apisit Banpean, Navapon Rungruji, Kajana Tarapun
Department of Material and Metallurgical Engineering, Faculty of Engineering
Rajamangala University of Technology Thanyaburi, Klong 6, Thanyaburi, Pathumthani 12110
Abstract— This research work aims to fabricate slow release fertilizer form biodegradable plastics. Urea andAmmonium sulfate were selected as model fertilizer for rice. Poly( lactic acid), PLA was selected as the model
biodegradable plastic. PLA was synthesized by 2-Steps Direct PolycondensatFion and confirm the successfully
by NMR. Urea/PLA and ammonium sulfate/PLA was prepared in laboratory scale as slow released fertilizer. To
investigate to effect of acidity of released condition, the released characteristics of fertilizer from PLA werestudied in buffer solution at pH of 4, 5.5 and 8 for 1400 hr. All released conditions show similar behavior, theamount of released fertilizer increases at first stage and becomes saturated after 200 hr. The amount of released
fertilizer increases with increasing acidity of buffer solution. At released condition pH 4, hydrolysis reaction of
PLA occurred thus fertilizer can easily move out from PLA. Thus these fertilizer can control the amount andrate of released fertilizer by controlling pH condition. The green released fertilizer can be mixed with rapid
fertilizer for controlling long term released. Moreover, PLA will not pollute the environmental area because
PLA can degrade to natural molecule after 3 months.
Keywords : Polylactic acid, Slow Released Fertilizer, Urea, Ammonium Sulfate.

INFLUENCE OF REACTIVE AGENTS ON FLOW PROPERTY ANDMECHANICAL PROPERTIES OF BIODEGRADABLE POLYESTERS
Oral presentation
S. Suttiruengwong1*, P. Rattanaudom1, S. Mongkolkitikul1, T. Wongwirat1, S. Pivsa-Art2 and M. Seadan3
1

Department of Materials Science and Engineering, Faculty of Engineering and Industrial Technology, Silpakorn
University, Nakhon Pathom, 73000, Thailand
2
Department of Chemical and Materials Engineering, Faculty of Engineering,Rajamangala
University of Technology Thanyaburi, Klong 6, Thanyaburi, Pathumthani, 12110, Thailand
1
Department of Physics, Faculty of Science, Silpakorn University, Nakhon Pathom, 73000, Thailand
Corresponding author email address:suttiruengwong_s@su.ac.th

Abstract - This research aimed to study the influence of two reactive agent systems, peroxides and chain extenders on
the flow and mechanical properties of Poly(lactic acid) (PLA), Poly(butylene adipate-co-terepthalate) (PBAT) andPoly(butylene succinate) (PBS). Two different types of peroxide, Perkadox®14S (Di (tert-butylperoxyisoproply)
benzene) and Luperox®101L (2,5-bis (tert-butylperoxy) -2,5-dimethylhexane) were selected and compared. For the
chain extender system, Bioadimide®100/Bioadimide®500 and Joncryl®ADR436 were used. The experiments werecarried out in an internal mixer. The torques of all melt-blended samples were recorded. The tensile specimens werethen prepared by compression molding and tested according to ASTM D638. For the peroxides system, the results
indicated that upon increasing the amount of peroxides (0-0.1 phr), melt flow index values (MFI) decreased regardlessthe types of the peroxide used. This could be due to the possible crosslinking reaction, leading to the higher melt
viscosity. The gel content analysis showed that, in the case of PBS, the gel fractions of around 37% and 30% wereobtained with 0.1 phr of Luperox® and Perkadox® respectively. However, no gel contents were found in the case of
PLA and PBAT samples. According to the tensile results, the addition of Luperox® in PBS exhibited the better
elongation at break compared to Perkadox®, which was 8 folds higher than that of neat PBS. The addition of peroxides
in both PLA and PBAT did not change mechanical properties significantly. For the chain extender system, the effect of
mixing temperature between 170ºC and 190ºC on the properties of three bioplastics was also investigated. Jorcryl® was
kept constant at 0.5 phr and the concentrations of the fixed ratio of Bioadimide®100/Bioadimide®500 (2:1) were varied
from 0-2.0 phr. Upon increasing the BioAdimide contents, MFI values of PBS tended to decrease while in the case of
PLA and PBAT, these values increased slightly. MFI values did not change significantly when changing the mixing
temperatures for all three polymers. The thermal degradation due to high processing temperature could be compensatedby the reaction of anti-hydrolysis and chain extended reactions. For mechanical properties, it was found that at the
mixing temperature of 190 ºC, the modulus and tensile strength of PLA increased by 8.6% and 21.04% respectively
compared to that of neat PLA. The elongation at break of PBS at the both mixing temperatures was significantly
increase approximately by 20 times compared to that of neat PBS.
Keywords: Reactive agents, Biodegradable plastics, Polyesters, Rheological Property

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

PHYSICAL DEGRADATION THEORY AND PHYSICAL REGENERATIONMETHOD FOR RECYCLING OF WASTE PLASTICS
Oral presentation
Nozomi Takenaka, Waka Hayashida, Aya Tominaga, Ryoko Nakano, Hiroshi Sekiguchi, Shigeru Yao*
Dept. of Chemical Engineering, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka, Japan. 814-0180
Corresponding author email address: shyao@fukuoka-u.ac.jp
Abstract - For recycling plastics, the ideal approach would be to use material recycling, which is reusing without
incurring chemical changes, and to employ thermal recycling only for materials that are difficult to reuse, or whenmaterial recycling is impractical. However the ratio of material recycling is still remained about 30% for in these 13
years. The reasons are, 1: the physical properties of products made from recycled plastics are inferior to those madefrom virgin plastics, 2: people believed that the origin of the low physical properties of recycled plastics is thought to bea chemical degradation which arise from the heat, ultraviolet light or oxidation in the process of using, 3: the chemicaldegradation is thought to be irreversible because it associate with molecular chain session, 4: researchers at university
or research institute also think as it is and did not pay attention for plastic recycling.
In this time, we investigated molecular properties of model recycled plastics and mechanical properties of various
molding conditions. At that time, we found that the reason of low physical properties is not chemical degradation but
physical degradation and physical regeneration is possible. Recently, we found that the theory can extend to the real
recycled packaging plastics and we can increase tensile properties of these plastics by choosing molding conditions.
Keywords: Containers and packaging recycle resin, Physical Degradation, Physical regeneration

Figure 1 Schematic diagram of physical degradation process of plastics

Figue 2 Shapes of test peace after elongation measurements

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

MELT TRANSCRIPTION MOLDING PROCESS WITH HIGHERPRECISION AND PRODUCTIVITY FOR THIN THERMOPLASTICPRODUCTS WITH MICRO- AND NANO-STRUCTURED SURFACE
Oral presentation
K. Furuki1*, A. Naito1, S.Ochi1, M.Hara1, H.Ito1 and K.Yakemoto1
1
The Japan Steel Works, Ltd., Hiroshima Research Laboratory,
Corresponding author email address: kenichi_furuki@jsw.co.jp
Abstract - Thermoplastic devices with fine surface topography are unlimitedly applicable, such as cell culture, sensorsof bio-molecules like DNA, hydrophilic/ hydrophobic surfaces, and/or optical devices. To produce micro- and nanostructures in high grade, we developed a melt transcription molding (MTM) process. It consists of plasticizing, coating
molten polymer on a mold stamp, compressing and releasing from the mold. The fine patterns on the stamp aretranscribed to a molded product. We have shown that MTM is effective to mold thin products (≧50μm) with the finepatterns from nanometers to micrometers scale with high aspect ratio (ASP) up to 20 (Fig.1, 2). However, the issue wasthe cycle time is still long, compared to that of an injection molding process. In this study, we developed shortened
cycle time while keeping high transcription performance using the following methods:(1) A new die with modified design was developed to obtain smoother surface of coated polymer under lower stamp
temperature. By using it, the roughness was greatly improved even under the stamp temperature 30℃ lower than theprevious die (Table 1). The heating and cooling time was shortened due to lowered stamp temperature.
(2) A new coating process control was developed for better thickness uniformity. The coating velocity was controlled tomake the transient flow of molten polymer change at the start of coating (Fig.3). In case of the coated area of
W80×L100×Thickness 0.1mm, the thickness distributions were controlled less than 10μm (Fig.4).
(3) When the compression starts early at lower stamp temperature, then the thermal expansion of polymer increases thecavity pressure and enhances the transcription. In case of the polystyrene (PS) products, 14 chips on the product withthe patterns of ASP 5 were uniformly transcribed (Transcription ratio> 98%) in the cycle time 75s.
(4) High speed coating (~100 mm/s) was adopted to reduce the enthalpy loss of molten polymer due to less heatradiation. This enabled to mold 2mm thickness products of polycarbonate (PC) (Tg=146 ℃) at the stamp temperature
145℃.
When PC product was transcribed at 145℃, it could be released at the same temperature. As a result, heat and cool ofthe stamp was eliminated, and the shortest cycle time 37.7s Table 1 Comparison of the roughness(Ra) of polymer
was attained in case of PC products with the thickness
coated by using previous die and new one.
2mm (Table 2).
Stamp temperature
Key word：Thermoplastics, Transcription, Nanometer,
Surface

Surface roughness ofcoated polymer Ra

Previous die
New die

160℃
1.60μm
0.62μm130℃
7.01μm
0.61μm･Ra is the arithmetic average of the absolute values･Material used : PC, Molten polymer temperature : 275℃

Fig.1 SEM image of microgrids made of PS.

Fig. 2 SEM image of nano holes
made of PMMA.

MAX=0.102mm
MIN=0.099 mm
AVERAGE=0.101mm
RANGE=0.003mm

Fig.4 The thickness distribution of a PMMA product.
Table 2 Cycle time to mold PC products with 2mm thickness.

Fig.3 Schematic illustration of the coating operation of MTM.
Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

ADHESION BEHAVIOR OF "WARM-OFF" TYPE ACRYLIC PSAS
Oral presentation
S. Yamaguchi1,2, S. Kawahara1, R. Shibahara3, S. Tabuchi3 and H. Murakami4*
1

2

Nitta Corporation, Nara, Japan
Department of Science and Technology, Graduate School of Engineering, Nagasaki University, Nagasaki, Japan3
Department of Advanced Engineering, Grasuate School of Engineering, Nagasaki University, Nagasaki, Japan
4
Division of Materials Science, Grasuate School of Engineering, Nagasaki University, Nagasaki, Japan
Corresponding author email address: hiroto@nagasaki-u.ac.jp

Abstract - Pressure-sensitive adhesives (PSAs) whose adhesion can be controlled by external stimuli are useful for
temporary attachment in industrial processes. Especially, the adhesion controls with a change in temperature andexposure to light are of interest. A side-chain crystalline acrylic PSA possesses a "cool-off" function, because thecrystalline unit undergoes a reversible order-disorder transition with a change in temperature. Below the transition

temperature, the PSA behaves as a hard plastic. Above the transition temperature, the crystalline unit changes toan amorphous state and become soft and flexible, leading to an appearance of tackiness. In contrast, an acrylic
PSA containing a low-molecular weight acrylic copolymer with the long alkyl side-chain crystalline unit as a"warm-off" component (WOC) shows a "warm-off (WO)" function in which the PSA loses its adhesion above thetransition temperature. However, no detail mechanism of the WO function is understood. In this presentation, we
describe i) adherend dependence of the WO tapes, ii) in-situ optical microscope observation of the interface
between the PSA tape and adherend, and iii) design of WOC. From these results we propose a possible
mechanism of WO function.
Keywords: Acrylic PSA, Side-chain Crystalline Copolymer, Warm-off Function

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

SOLID ELECTROLYTE FUNCTION OF SIDE-CHAIN CRYSTALLINEBLOCK CO-POLYMER
Oral presentation
Yusuke Sano, Ryoko Nakano, Hiroshi Sekiguchi, Shigeru Yao*
Dept. of Chemical Engineering, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka, Japan. 814-0180
Corresponding author email address: shyao@fukuoka-u.ac.jp

Abstract - Side-Chain Crystalline Block Co-Polymer (SCCBC), which is composed of a side-chain crystalline
monomer unit and a functional monomer unit (which can confer solvent-compatibility, polarity, etc.), can beadsorbed to a polyethylene crystal through crystalline supramolecular interaction. By using this interaction, we canmodify not only the surface but also the inner pores of a porous polyethylene membrane to give various properties. In
this study, we used a monomer with ethylene oxide repeating units as a functional unit, and evaluated its potential asa solid electrolyte for use in a Li ion secondary bat-tery. The properties of the solid electrolyte were excellent
compared to those of a non-modified porous membrane at low temperature. In addition, the solid electrolyte did notshow temperature-dependence, and the Li+ ion conductivity remained nearly constant throughout the temperature
range of 30°C to 60 ºC. However, at high temperature (above 70 ºC), the conduc-tivity began to decrease. This
characteristic may make it useful for sensing temperature and for self-controlling thermal runaway.
Keywords: Solid electrolyte, Filling Membrane, Side-Chain Crystalline Block Co-Polymer, Crystalline
Supramolecular Interaction

Figure 1. Typical chemical structure ofside-chain crystalline block copolymer.

Figure 2. Schematic of the crystalline supramolecularinteraction mechanism of the adsorption of SCCBC on apolyethylene surface. The side-chain crystalline units areadsorbed onto the PE crystalline surface and construct a
pseudo crystal.

Figure 3. Temperature-dependence of Li+ ion
conductivity of a mod-PE2 membrane used as asolid electrolyte.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

DURABILITY AND PROPERTIES OF JUTE FIBER TREATMENT IN
GREEN FILLED RUBBER
Oral presentation/Poster presentation (Please select one)
W.Ariyawiriyanan1*, P. Pantamanatsopa1 and H.Hamada2
1
Department of Materials and Metallurgical Engineering,Rajamangala University of Technology Thanyaburi,
Thailand2
Department of Advanced Fibro-Science, Kyoto Institute of Technology, Japan*Corresponding author email address: warunee@rmutt.ac.th

Abstract – Optimal conditions for jute fiber surface treatment, durability and properties green filled rubbers havebeen investigated. In this study, dilute NaOH solution and HANR latex were used as surface cleaning agent andcoupling agent, respectively. Surface treatments of jute fiber were carried out in the presence of NaOH solution, HANR,
and NaOH solution together with HANR. For jute fiber samples treated with HANR and NaOH solution together with
HANR, thickness of latex coated layer was controlled by variation of dipping times and %DRC of HANR. It was foundthat the thickness of latex layer coated on jute fibers using HANR with 10-50 %DRC were not affected by the dipping
times while this is not the case for HANR with 60 %DRC. The jute fibers treated using HANR with higher %DRC
provided higher durability than those treated using NaOH solution and NaOH solution/HANR. The mechanicalproperties of untreated and treated jute fibers were examined. Only higher elongation was obtained from treated jutefibers with an increase of %DRC., The tenacity of all treated jute fibers was lower than that of the untreated jute fibers.
Therefore, in this study, the treated jute fibers used as reinforced agent for natural rubber were prepared using
NaOH/HANR with 10 % DRC. SEM micrographs revealed that spaces between jute fibers treated using NaOH/HANR
and natural rubber was much closer than that of untreated jute fibers. This was due to miscibility between HANR coatedlayer and natural rubber leading to an increasing of interfacial adhesion between jute fiber and natural rubber. As
expected, the tensile strength obtained from composite rubbers reinforced using treated jute fibers were higher than thatof composite rubbers reinforced using untreated jute fibers.
Keywords: jute fiber, natural rubber, durability, surface treatment
FIGURES CAN BE USED BUT THE LENGTH OF THE ABSTRACT SHALL BE KEPT WITHIN ONE A4 PAGE

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

PERCOLATION MODEL FOR REINFORCEMENT EFFICIENCY OF
CARBON NANOTUBES IN THERMOPLASTIC COMPOSITES
Oral presentation
Zhenyu Jiang1*, Hui Zhang2, Jingfeng Han1, Zejia Liu1, Yiping Liu1, Liqun Tang1
1
School of Civil Engineering and Transportation, South China University of Technology, Guangzhou 510640, China
2
National Center for Nanoscience and Technology, Beijing 100190, China
Corresponding author email address: zhenyujiang@scut.edu.cn
Abstract - Considerable experimental work on carbon nanotube-reinforced composites has shown that thereinforcement efficiency of carbon nanotubes (CNTs) starts to be lower than the theoretical expectation when CNT
loading is above a critical value. This critical value is considered to be coincide with the electrical percolation thresholdof CNTs within hosting polymers, which is related to the onset of formation of percolating CNT network. Based on thisconcept, a percolation model is proposed to describe the sharp decrease in the reinforcement efficiency of multiwalled
CNTs dispersed in thermoplastics around the percolation threshold, which is estimated via a numerical simulation of
randomly curved CNTs generated according to the statistics on geometrical features of CNTs in transmission electron
microscope images. The percolation model, integrated into the well-known Halpin-Tsai equations, is verified using theexperimental data of a wide variety of thermoplastics reinforced with multiwalled CNTs obtained by different researchgroups. The developed mechanical model achieves a good agreement with the measured moduli of nanocomposites, anddemonstrates an excellent prediction capability over a wide range of CNT loading up to 13 vol%, as shown in Figure 1.

Figure 1. Measured moduli of MWCNT-reinforced thermoplastics (including (a) PEEK, (b) PP, (c) HDPE,
and (d) PLA) and the results predicted using the proposed model.
Keywords: Carbon nanotubes; Thermoplastics; Modelling; Percolation threshold; Mechanical properties

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

EVALUATION OF GRASS FIBER REINFORCED ENGINEERING
PLASTICS FOR WATER HEATER
Oral presentation
Kazuhisa Igawa1, Atsushi Takeda2, Kazushi Yamada2, and Hiroyuki Nishimura2
1
Residential Energy System Development Department, Osaka Gas Co., Ltd., Osaka, Japan2
Department of Advanced Fibro-Science, Kyoto Institute of Technology, Kyoto, Japan
Corresponding author email address: hnishimu@kit.ac.jp

Abstract
Although grass fiber reinforced engineering plastics are widely used for parts of the water heater in Japan, it is not
sufficient for evaluation of long-term performance of them under hot water environment. In this study, the long-term
performance of glass fiber reinforced polyphenylene sulfide (PPS), modified polyphenyleneether (mPPE), andpolypropylene (PP) were investigated for thermal resistance due to hot water immersion and hot air exposure. The
acoustic emission analysis was conducted to investigate the cause of an initial change in mechanical properties by thethree point bending test. The tensile test and the Izod impact test were also conducted.
Figure 1 (a) and (b) show the tensile strengths of the glass fiber reinforced PPS after hot air exposure and hot water
emersion at 80, 100, 120 °C. Although the tensile strength of the glass fiber reinforced PPS was almost constant withthe elapsed time after hot air exposure, the tensile strength of the glass fiber reinforced PPS gradually decreased withthe elapsed time. The reduction of the tensile strength was attributed to the interfacial debonding between a glass fiberand a matrix resin after hot water immersion.

(a)(b)
Figure 1 Tensile strengths of glass fiber reinforced PPS (a) in hot air and (b) in hot water at 80, 100, 120 °C.

Keywords: GFRP, water heater, PPS, hot water immersion, hot air exposure, interfacial strength

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Studies of Mechanical Properties of High Density
Polyethylene/Vietnamosasa Pusilla Fiber Composite for
Decoration Applications
Oral Presentation

Supranee Suadaow1, Sumonman Naimlang1*
1Department of Material and Metallurgical Engineering, Faculty ofEngineering, Rajamangala University of Technology Thanyaburi,
Klong 6, Thanyaburi, Pathumthani 12110
E-mail: sumonman.n@en.rmutt.ac.th*
Abstract
A vietnamosasa pusilla, VP is a weed which has high growth rate
and toughness. The development of high density polyethylene (HDPE)/VP
composite for decoration applications was studied in this research work. VPfiber was prepared by immersing dried VP leaf in 5%w/w of NaOH for 24
hr. Immersed VP leaf was then immersed in 5%w/w of HCl for 10 hr. The
extracted VP fiber was dried in oven at 60 C for 24 hr. Extracted VP fiber
was grinded and sieved. VP fiber was mixed with HDPE by two roll mill.
The HDPE/VP composite was fabricated by compression molding at 250
MPa and 190 C. To investigate the effect of amount of VP on mechanicaland physical properties of composite, HDPE/VP composites at various
amount of VP (0, 1, 5, 10 and 20 %w/w) were prepared. The brown like
HDPE/VP composite was produced for decoration application. The tensile
strength increase with increasing amount of VP fiber because VP fiber act
as filler in composite system.

Keywords: High density polyethylene; Vietnamosasa pusilla fiber;
Decoration application

FIBER STRUCTURE DEVELOPMENT IN HIGH-SPEED MELT SPINNING
OF SHEATH-CORE BICOMPONENT FIBERSCONSISTING OF ALIPHATIC COPOLYESTERS
OF DIFFERENT COPOLYMER COMPOSITION
Oral presentation
Qing Qin, Wataru Takarada and Takeshi Kikutani*
Department of Organic and Polymeric Materials, Graduate School of Science and Engineering,Tokyo Institute of technology, Japan
Corresponding author email address: kikutani.t.aa@m.titech.ac.jp
Abstract - Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) is one of the PHB based co-polymers known as amelt-processable aliphatic co-polyester. Difficulty arises in the processing of PHBH because its glass transition
temperature is below the room temperature while its crystallization rate is extremely low. Especially for the PHBH withhigh 3-hydroxyhexanoate (3HH) composition the fibers did not crystallize in the spin-line and stuck together on the
take-up bobbin as shown in Fig.1 (a) even though stress-induced crystallization was expected to occur at high take-up
velocities. Therefore, in this research, sheath-core bicomponent spinning was carried using PHBH with low 3HH
composition of 5.4 mol% as the sheath component and that with high 3HH composition of 10.4 mol% as the corecomponent. There was no sticking among fibers on the take-up bobbin and well separated fibers were collected at hightake-up velocities as shown in Fig.1 (b). Structure of individual components as well as mechanical properties of thebicomponent fibers were investigated. WAXD patterns of the as-spun bicomponent PHBH fibers prepared at extrusion
temperature of 180 oC are shown in Fig.2. The as-spun fibers prepared at 0.5 km/min showed α-form crystals of noorientation. The crystalline orientation increased gradually with an increase in the take-up velocity and the appearanceof equatorial reflection corresponding to highly oriented β-form crystals was confirmed at the take-up velocity of 5
km/min. Birefringence measurement of the sheath and core components using an interference microscope revelaed thatthe molecular orientation of the sheath component of low 3HH content was high while that of the core component ofhigh 3HH content was extremely low even at high take-up velocities especially when extrusion temperature was high.
This result corresponds to the overlapping of the crystalline reflections of highly oriented and low orientedα-form
crystals. In any case, the processability of PHBH with high 3HH composition was improved through the bicomponent
spinning with low 3HH composition PHBH and the fibers with fairly high mechanical properties were obtained.
Keywords: high-speed melt spinning, bicomponent fiber, crystalline orientation

Fig. 1 Photographs of as-spun PHBH fibers prepared at
180oC: (a) single component PHBH fiber ofhigh 3HH composition, (b) bicomponent PHBH
fibersFig. 2 WAXD patterns of as-spun bicomponent PHBH
fibers consisting of PHBHs of low and high 3HHcomposition as the sheath and core components,
respectively. The fibers were prepared at the total
throughput rate of 10 g/min and extrusion
temperature of 180 oC.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

FIBER-BREAKAGE EVALUATION OF MELTS PASSING THROUGHCHECK-RING BASED ON NEWLY-DEVELOPED HEATING CYLINDER
WITH MULTI-PORTS FOR IN-PROCESS SAMPLING
Oral presentation
1

S.Ma1*, K.Shibata2, H.Yokoi3

Institute of Industrial Science, The University of Tokyo, Japan – masai@iis.u-tokyo.ac.jp
2
TOYO MACHINERY & METAL CO., LTD., Japan – k-shibata@toyo-mm.co.jp
3
Institute of Industrial Science, The University of Tokyo, Japan – hiyokoi@iis.u-tokyo.ac.jp
4-6-1, Komaba, Meguro-ku, Tokyo, 153-8505, Japan
Abstract - In the injection molding of long fiber reinforced resins, the greatest challenge in realizing high strength
molded products is minimizing the breakage of fibers during the plastication process inside the heating cylinder andduring flow inside the mold. The breakage of fibers during the plastication process and while they are flowing past thecheck-ring (CHR) is a common problem faced at the manufacturing site. But to date, no systematic research has been
carried out. In the past, static visualization experiments applied to the analysis of such breakage based on the screwcooling and pulling-out method, which requires complicated work. For this reason, the authors developed a heating
cylinder with multi-ports on the wall for extracting the melted resin from the cylinder inside to perform in-processsampling of the resin. In this study, the new device was used to sample melted resin before and after CHR andinvestigate the effects of the shapes of the CHR on glass fiber breakage. From the experiment result, it is clearly
demonstrated that the breakage of fiber can be minimized to the extent when there is enough space (large d, large λ,small θ, no claw) for melted resin to gently flow and pass the CHR. In addition, it was confirmed that the length of
CHR does not affect glass fiber breakage significantly.
Keywords: Glass fiber reinforced resin / Inprocess multi-port sampling / Fiber-breakage evaluation/ Check-ring

1．Introduction

In recent years, long fiber reinforced resins are
drawing widespread attention in various industries as ametal substitute with good impact-resistance and highrigidity, and which is lightweight. However, thetendency for fibers to break easily is a problem, andminimizing this breakage is becoming an increasingly
important task in the plastication process. During theplastication process, the glass fiber reinforced pellet is
dropped into the hopper, and melted while beingtransported to the nozzle by the screw. It must passthrough the check-ring(CHR), before the injection
from the nozzle. The influence of the CHR on the fiber
length is a common problem faced at most molding
sites, but to date, systematic studies have not been
performed to investigate the degree of this influence by
the CHR. The screw pulling-out method is one possiblemeans of investigating this. Frozen samples of melted
resin can be collected before and after the CHR, andthen the fiber length distribution can be measured by
the ashing method. However, because there is a need torepeat the same experimental procesures to cool down
the cylinder and pull out the screw for sampling frozen
resins per each experimental condition, such as
different screw rotational speeds, CHR configurations,etc., which are extraordinarily time-consuming andcomplicated works. For this reason, the authors
developed a heating cylinder with multi-ports on thewall for drawing the melted resin inside the cylinder toperform in-process sampling of the resin. The extruder
with sampling cylinder1) developed in previous studies
were referred to build the sampling device. In thisstudy, the melted resin before and after the CHR was
sampled using this device to investigate the effectsof the CHR shape on the glass fiber breakage. The
summary is reported below.
2. Experimental Device and Molding Conditions
2)

The developed multi-port sampling cylinder wasthen mounted on an injection molding machine Si-80V(mold clamping force of 80tonf, screw diameter of
36mm, TOYO MACHINERY & METAL CO., LTD.).
The laser microscope used was the LEXT OLS4000(Olympus Corp.). The resins used were long glass
fiber reinforced PP containing 50wt% glass fiber (L5050P; Prime Polymer Co., Ltd). The glass fiber
diameter used was 13μm and the fiber length (setvalue) was 8mm. The cylinder temperature was set at230/230/230/220/210℃ from the nozzle side. Fig. 1
shows the newly-developed heating cylinder mountedwith a sampling device and Fig. 2 shows thefundamental structure. The valve pin built into theinner wall surface of the cylinder is open to convey
the melted resin to the outside through theconnecting pipe. Fig. 3 shows the relationships
between the screw with compression ratio of 1.8(FF1) and cylinder axial coordinate. Fig. 4 shows theProceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Fig.4 Schematic of check-ring configuration
Fig.1 Appearance of in-process muli-port
sampling cylinder

Table 1 Check-ring profiles

00 : Changed parameterFig.2 Fundamental structure of in-situ sampling
equipment from heating cylinder

Fig.3 Relationships between screw andcylinder axial coordinate

schematic diagram of the CHR including
characteristics such as (1) CHR length L, (2) contact
face angle θ, (3) CHR stroke λ, (4) radial clearance
between CHR and screw head d and (5) number ofclaws n. In our experiments, the nine CHR shapes
shown in Table 1 were used while varying thesecharacteristics. The experiments were conducted bymoving the screw backward by 68mm in order to set
the CHR between C2 and C3 and compare the fiber
length before and after the CHR. After melting
conditions stabilized, samples were taken at therotation speed of 150rpm, and the glass fibers wereextracted by ashing the resin. Fiber length wasmeasured by a microscope to evaluate the fiber
length distribution.

Fig.5 Comparison of glass fiber length distribution
between samples of C2, Type0 and Type1

3. Experiment Results and Discussion
In preliminary experiments2), among the fullflight screws with different compression ratios, FF1
showed the best effect for minimizing the breakageof fiber particularly at high rotation speeds. For thisreason, FF1 was adopted in the following
experiments to provide plasticized resin with thelongest fiber length until just before reaching theCHR. The results of the experiments also confirmedthat the fiber length distribution of the sample taken
immediately after the CHR at C3 is nearly the sameas that taken from the nozzle. We particularly
focused our evaluation on fibers shorter than 2.7mm(fiber length exceeding 2.7mm is 3% or less at the
maximum.).

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

(a) CHR length L(d) Radial clearance between CHR and screw head d(b) Contact face angle θ(e) Number of claws n(c) CHR stroke λFig.6 Deviation of the fiber length distribution of samples at C3 from those at C2 (before check-ring)

1) CHR length L:
Fig.5 shows the effects of CHR length on thefiber length distribution before and after the CHR.
The vertical axis is the logarithmic scale. Since theC2 data is common to all the conditions and theeffects on fiber breakage can be evaluated from thedeviations of C3 from the distribution of C2, theinfluence of all the conditions was evaluated by thedeviation from C2 as follows. Fig. 6 summarizes theresults. Comparing the fiber length distribution
before and after the CHR in Fig.6 (a), the presenceof fibers shorter than 0.6mm increases dramaticallyand suddenly decreases when the fiber length islonger than 0.6mm, continuing to decrease until theProceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

fiber length is 1.8mm long. When CHR is 35mm
long, it does not affect fibers longer than 1.2mm, but
fibers shorter than 0.9mm shows the tendency tobreak.
2) Contact face angle θ:
Fig. 6 (b) shows the effects of the contact faceangle θ on the fiber length distribution. Like Fig.6(a),it changes drastically from increase to decrease
when the fiber length is around 0.6mm in length
regardless of θ. It seems that when θ increases, thefiber existence ratio increases when fiber length isshorter or around 0.6mm. The deviation to C2(before the CHR) approaches zero when the fiber
length is 0.9mm and θ is 45 °, when the fiber
length is 1.8mm and θ is 60 °, or when the fiber
length is 2.4mm or longer and θ is 90 °. The fibers
were found to not break easily in the above range.
The experimental results showed that when the
inflow angle θ changes suddenly, which is the inlet
to the inside of CHR, the mutual restraint and fiber
curvature between long fibers tend to increase. The
localized shear rate in the corner also increases.
These results suggest that the breakage of fiber may
be promoted when they pass CHR at a higher angle.
3) CHR stroke λ:Fig. 6(c) shows the effect of λ on the fiber length
distribution. Although there is not too muchdifference of the fiber length distribution between
λ=1.8 and λ=2.3mm, it was confirmed that fibers
longer than 0.9mm hardly break when λ=2.8mm. It
was also found that long fibers are also less likely to
break if there is sufficient clearance for the melted
resin to pass through CHR.
4) Radial clearance between CHR and screw head d:
Fig.6 (d) shows the effect of d on the fiber length
distribution. Compared to the slight increase whend=2.5mm, when d=1.5mm, the area in which thefiber length is shorter than 0.6mm increases
conspicuously, indicating that the fiber breaks easily.
However, when the fiber is longer than 0.6mm and dequals to 1.5mm, breakage is promoted, causing
significant decrease in each fiber length range. On
the other hand, when d=2.5mm, the minus range
decreases and fibers longer than 1.5mm seems tobreak less easily. These results indicate that the
space between the CHR and screw head is the flow
path of the melted resin, which may serve as animportant controlling factor for maintaining the fiber
length uniform.
5) Number of claws n:
Fig.6 (e) shows the effect of the number of CHR
claws on the fiber length distribution. When there
are claws, the fiber length distribution shows that

Table 2 Weight-average (Lw) of fiber lengths and the ratioof fibers with length longer than 2.7mm (Sampled
at C2&C3)

the deviation does not converge to zero for any fiber
length of more than 0.6mm, which means that fiber
breakage is promoted. Particularly when the fiber
length ranges from 0.6 to 1.5mm, the fiber breakage
ratio increases. When CHR has claws that co-rotatewith the screw head, the melted resin flows into thegap of the CHR stroke. The shearing action always
works on the inlet in the orthogonal direction. It is
assumed that long fiber breaks easily because of thenarrow gap at the CHR outlet side caused by thefitting clearance between the claws and screw head.
6) Comparison of influential factors:
The weight average fiber length Lw is calculatedby the formula (1). Table 2 compares Lw and theratio of fibers longer than 2.7mm. α indicates thebroken state, especially for long fibers. Both Lw andα are correlated roughly. From the comparison
between Lw of C2 and α based on the different
shapes of CHR, the fiber length is most affected
when d=2.5mm and λ=2.8mm， and subsequently
affected by λ=2.3mm and θ=45°. Conversely, it was
confirmed that fiber breakage occurs when θ=90 °,d=1.5mm and CHR with claws. The comparison of
α shows that glass fibers break intensively whenθ=90 ° and d=1.5mm.
∑ 𝑛 𝐿2

𝐿𝑤 = ∑ 𝑖 𝐿
𝑛𝑖(1)

4. Conclusion
In this study, the authors successfully evaluatedfiber breakage using different shapes of CHR which
melted resin passes, using the sampling device. The

results clearly demonstrated that fiber breakage can be
minimized when there is enough space (large d, large
λ, small θ, no claw) for melted resin to gently flow
and pass the CHR. The length of the CHR does nothave considerable influence.

Reference
1) T.Nishio；et al : KOBUNSHI RONBUNSHU,
47(4), p.331 (1990)
2) S.Ma; H.Yokoi : AWPP 2013, India, CD (2013).

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

STUDY ON FEEDSTOCK OF METAL INJECTION MOLDING
Oral presentation
N.Kayamori1*, and T. Tanaka1
1*

Applied Materials Engineering Laboratory, Department of Science and Engineering, Doshisha University,1-3,
Tatara Miyakodani, Kyotanabe,Kyoto,610-0321,Japan
duo0533@mail4.doshisha.ac.jp
Abstract –Recently, Metal Injection Molding (MIM) has been focused as a method of metal parts manufacturing,
because hard material such as titanium and so on, and products with complicated shape can be manufactured by MIM.
There are four processes in MIM. They are consisted of compounding, injection molding, defatting and sintering. In thecompounding process, kneader is generally used. However, kneader is poor productivity for batch type. Hence, twin
screw extrude which is good in productivity for continuous processing was focused in this study. However, thedispersion state of the feedstock compounded with twin screw extruder is worse than the one made by conventionalkneading machine. So, the improvement of the dispersibility of feedstock manufactured by twin screw extruder isnecessary in our experiment. Therefore, as the purpose in this study, relationship of mixing condision and dispersibilityof feedstock was investigated because dispersibility of metal powder depend on the mixing condition in twin screw
extruder. Mixing condion refers to rotation speed, mixing temperature, and feed rate.
As the material of MIM, water atomized 316L stainless powder was used. The binder system consists ofpolypropylene, paraffine wax, camauba wax and stearic acid.
The X-rays CT scanning that the aggregation of metal poweder could be observed three-dimensionally was used as anevaluation method of the dispersion state of feesstock. The example about image of X-ray CT scan is showed in fig.1.
The metal powder area is indicated white color, and the resin area is indicated the black color. In the image of the X-ray
CT scanning, area-equivalent circle diameter of metal powder was calculated from a white area. This area-equivalentcircle diameter is used for evaluation index of dispersibility of feedstock. Additionary, segregation of metal powder isappeared in the image (Fig.1). The index of segregation level is used CV index about density of feedstock. This CV
index also used for evaluation index of dispersibility of feedstock. If CV index becomes low , the dispersibility offeedstock is improved.
As a result, first, the relationship rotation speed and area-equivalent circle diameter and CV index was showed in
Fig.2. The increase rotation speed decrease area-equivalent circle diameter and CV index. That is showed improvementof dispersibility of metal feedstock. Second, the relationship temperature and area-equivalent circle diameter and CV
index was showed in Fig.3. The reduction of mixing temperature decrease area-equivalent circle diameter and CV
index. That is showed improvement of dispersibility of feedstock. Third, the relationship feed rate and area-equivalentcircle diameter and CV index was showed in Fig.4. The reduction of feed rate decrease area-equivalent circle diameterand CV index. That is showed improvement of dispersibility of feedstock.
Metal powder

resin

100μm

0.02
Area-equivalent circle diameter
CV index

0.01
0100rpm standard 300rpm

0.05
0.04
0.03
Area-equivalent circle diameter

0.02

0.01

CV index

0
180℃

standard

220℃

Fig.2
Fig.3
Keywords: Metal Injection Molding, dispersibility, twin screw extruder, compounding

23
22
21
20
19
18
17
16
15
14

0.06
0.05
0.04
0.03
Area-equivalent circle diameter

0.02

CV index

0.01
0

1kg/h

standard

Fig.4

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

3kg/h

CV index

0.03

23
22
21
20
19
18
17
16
15
14

Average of Area-equivalent circle
diameter(μm)

0.04

Average of Area-equivalentcircle diameter(μm)

0.05

CV index

23
22
21
20
19
18
17
16
15
14

CV index

Average of Area-equivalentcircle diameter(μm)

Fig.1

EFFECT OF TITANIUM DIOXIDE ON THE INTERFACE OF
POLY(LACTIC ACID) BETWEEN SHEATH-CORE FIBERS
Oral presentation
N. Roungpaisan1*, N. Srisawat1, N. Suwannamek2, C. Prahsarn2
1

Department of Textile Engineering, Faculty of Engineering, Rajamangala University of Technology Thanyaburi,
Pathumthani 12110, Thailand
2
National Metal and Materials Technology Center, 114 Paholyothin Rd., Klong Luang, Pathumthani 12120, Thailand*
E-mail: nanjaporn_r@rmutt.ac.th
Abstract – The sheath/core(S/C) cross sectional is the one of bicomponent fibers. One of polymer is a center fully
surronded by second component(sheath). The shape was designed for improving surface specials funtion while thestrength can provide at core region. Sheath/core bicomponent fiber were prepared by Hill Lab Scale Bicomponent
Extruder Fed Spinning Machine, using different amout of TiO2 (1, 1.5, and 2%w/w) at the sheath region was diluted by
TiO2-PLA masterbacth and neat PLA at core region which spun together into one fiber. With various ratio(S/C) 0/100,
10/90, 30/70, 50/50 and 70/30, respectively. Cross-sectional features and fracture of the fiber, as well as morphologies
at sheath and core interfaces, of the TiO2-PLA/PLA fibers were investigated, using optical microscope and scanningelectron microscope. The strong of the color(K/S) of the TiO2-PLA/PLA fibers was measured, using spectrometer todetermine the coloring effect of titanium dioxide content by CIELAB system. Crystalinity and mechanical propertes
were studied x-ray diffraction and tensile testing. In order to adjust the strong of color value, we can lower sheath/core
ratio
from
70/30
to
50/50
which
containTiO2
inthesheathpart
1.5-2%.
However, for mechanical property, the optimum TiO2 loading is 1-1.5% and the S/C ratio is 10/90-30/70.
These conditions presented the better tensile property than neat PLA.
Keywords: Sheath-core bicomponent, polylactic acid, interface of phase

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Study on Fabricating Carbon Nano Fiber by Cotton Candy Method
Oral presentation
Ryo Takematsu1, Akihiro Tada2, Masayuki Okoshi1, Hiroyuki Inoya1 and Hiroyuki Hamada1
1

Department of Advanced Fibro-Science, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto, 606-8585,
Japan
2
OHGI TECHNOLOGICAL CREATION CO., LTD. 4-13, 3-chome, Nakano, Otsu City, Shiga Prefecture 520-2114
Corresponding author email address: takematsu4@yahoo.co.jp
Abstract
Recently, it has been possible to make a preparation of nano fibers in the technology field1. Nano fibers have several
excellent properties such as mechanical properties and adhesive properties. Therefore, nano fibers are expected to apply
in various field including energy sector, electronics sector, medical sector and so on.
Several methods for fabricating nano fibers were reported by researchers, and among which electrospinning method is
one of the most famous methods2. The electrospinning method can fabricate the nano fibers by dissolved resin in thesolution with a high voltage. In the result, it is possible to make the nano fibers to stretch the dissolved resin byelectrostatic repulsion. But the electrospinning method results in large cost because of keeping the high voltage during
the produce. Besides, the electrospinning method does not have enough stretching process. Therefore, the nano fibers
fabricated by electrospinning method are low crystallinity and weak mechanical properties.
In this research, We introduce the novel method that called Cotton Candy Method (CCM). Polyacrylonitrile (PAN)that was precursor of carbon fiber was solved in N-methylpyrrolidone (NMP). This solution was blown and stretched byair. After that stretched nano fiber was caught in water. NMP is good solvent for PAN, but water is poor solvent for
PAN. This simple process can fabricate PAN nano fibers. Since the CCM does not need a high voltage, this novel
method is expected to produce in large volume in a low cost way. In addition, the carbon nano fiber was fabricated bycarbonizing PAN nano fiber. Fig. 1(a) shows SEM observation of PAN nano fiber, Fig.1 (b) shows that of carbon nanofiber by CCM. From results of SEM observation, average diameter of nano fiber by CCM was determined about 300 nm.
CCM has a great potential for nano fiber industry.

(a)

(b)

Fig.1 (a) PAN nano fiber, (b) Carbon nano fiber

Reference(1). S. Petrik, Industrial Production Technology for Nanofibers, NANOFIBERS – PRODUCTION, PROPERTIES AND
FUNCTIONAL APPLICATIONS, Pages3-17, 2011(2). J.M Deitzel, J Kleinmeyer, D Harris and N.C Beck Tan, The effect of processing variables on the morphology ofelectrospun nanofibers and textiles, Polymer, Volume 42, Issue 1, January 2001, Pages 261–272
Keywords: nano fiber, carbon fiber, Polyacrylonitrile

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Development of Poly(lactic acid)/Gelatin/Shellac Blend forGreen Composite Film from
Kewalee Nilgumhang1, Anin Memon2, Sumonman Naimlang1*
1

Department of Material and Metallurgical Engineering, Faculty of Engineering, Rajamangala University ofTechnology Thanyaburi, Klong 6, Thanyaburi, Pathumthani 12110
2
Department of Industrial Engineering, Faculty of Engineering, Rajamangala University of Technology
Thanyaburi, Klong 6, Thanyaburi, Pathumthani 12110

Abstract— Polylactic acid (PLA) is one of the most interesting biodegradable polymers and commercially
produced thermoplastic that is derived from renewable resources. However, the limitation of PLA is the stiffness
and brittleness. In this research, PLA/Gelatin/Shellac blends films were fabricated to improve the flexibility of
blend film. To study the effect of gelatin and shellac, the PLA/Gelatin/Shellac blend films were fabricated atvarious blending ratio (%w/w of PLA: Gelatin: Shellac is 90:10:0, 80:10:10, 70:10:20, 60:10:30, 90:0:10 and
70:20:10 for PLA:GEL:SH 90:10:0, PLA:GEL:SH 80:10:10, PLA:GEL:SH 70:10:20, PLA:GEL:SH
60:10:30and PLA:GEL:SH 70:20:10, respectively.) The yellow-orange PLA/Gelatin/Shellac blends films weresuccessfully prepared. The tensile strength of blend films increase with increasing amount of shellac and gelatin.
These blend films will be new class of green film without non-toxic substance which can degrade in composed
environment.
Keywords— Shellac, Biodegradable plastic, Poly(Lactic acid), Gelatin, Solvent Casting.

ANALYSIS ON CRYSTALLIZATION BEHAVIOR
OF EQUI-BIAXIALLY STRETCHEDAMORPHOUS POLY(ETHYLENE TEREPHTHALATE) FILMS
Oral presentation
S. Shibata, W. Takarada1 and T. Kikutani1*
Department of Organic and Polymeric Materials, Graduate School of Science and Engineering,Tokyo Institute of Technology, Japan
Corresponding author email address: kikutani.t.aa@m.titech.ac.jp
Abstract – To investigate the effect of biaxial stretching on crystallization rate, amorphous poly(ethylene terephthalate)(PET) films with various degrees of molecular orientation were prepared through the simultaneous equi-biaxial stretchingof amorphous and isotropic PET films to various draw ratios at 90 °C. Crystallization and melting behaviors of the films
were analyzed using the fast scanning chip calorimetry (FSC) and the conventional differential scanning calorimetry(DSC). In the FSC measurement, significant data fluctuation caused by the thermal shrinkage of the oriented films wasobserved at around the glass transition temperature Tg as shown in Fig. 1 (a). We found however that it is possible toshrink the film without crystallization through heating the oriented films up to 120 oC and immediately cooling down toa temperature below Tg at high heating and cooling rates. Eventually, data fluctuation in the FSC measurement was
satisfactorily suppressed as shown in Fig. 2(b). Based on this technique, measurement of the cold crystallization
behaviors was conducted at various heating rates applying the time-temperature profiles including the pre-thermal
treatment as shown in Fig.2. The models for crystallization kinetics proposed by Ozawa1) and Nakamura2) were combined
to calculate the non-isothermal crystallization rate of un-stretched and stretched PET films. The results analyzed fromthe DSC and FSC measurements are shown in Fig. 3. Even after applying the thermal shrinkage, the highly stretchedfilms showed crystallization rate more than 1000 times higher than that for the un-stretched film.
Keywords: poly(ethylene terephthalate), crystallization rate, molecular orientation
(b)

(a)

50 K/s200 K/s

Exothermic up

Exothermic up

100 K/s
100 K/s

200 K/s
500 K/s

500 K/s

1000 K/s

Temperature/ oC

Temperature/ oC

Temperature

Crystallization rate/ s-1

Fig. 1 (a) FSC thermograms without pre-thermal treatment and (b) those after pre-thermal
treatment for PET films stretched to the draw ratio of 2.5×2.5.

Time

Fig. 2 Time-temperature profile for analysis of cold
crystallization behavior of stretched PET films.

102

3.0 x 3.0

2.5 x 2.5

101
100
10-1

un-stretched

10-2
10-3
10-4
120

130

140

150

160

170

Temperature /oC
Fig. 3 Non-isothermal crystallization rate for PET
films of various MD×TD draw ratios analysedfrom the results of DSC and FSC measurements.

Reference
1) T. Ozawa, Polymer, 12, 150 (1971)
2) K. Nakamura, K. Katayama, T. Amano, J. Appl. Polym. Sci., 17, 1031 (1973)

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Preparation of The Carbon Nano Fiber Using Cotton Candy Method
Oral presentation
Akihiro Tada1, Ryo Takematsu2, Hiroyuki Inoya2, Masayuki Okosi2 Hiroyuki Hamada2
OHGI TECHNOLOGICAL CREATION CO., LTD. 4-13, 3-chome, Nakano, Otsu City, Shiga
520-2114, Japan
21
Department of Advanced Fibro-Science, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto, 606-8585,
Japan
1

Corresponding author email address: tada.akihiro@ohki-techno.com
Abstract
Carbon based nanomaterials (fullerene and carbon nanotube, etc.) have been actively studied since the 1980s. These
have the potential of attractive applications such as specific shape and physical properties. Therefore a variety of
research and development have been expanded. However, carbon-based nanomaterials produced by the vapor
deposition. it is necessary to reduce the cost under the production line.
In this study we focused on carbon nano fiber in the carbon-based nanomaterials. Carbon Nano Fibers (CNF) are
expected to various applications. However, the CNF have a high cost. Therefore We are trying to make a preparation of
precursor of the CNF using Cotton Candy Method (CCM). CCM is a method of forming a fiber with only air injection.
Therefore it is possible to make a cost saving by CCM, because it does not require heating and the electric field.
In this study, We have been planing to make a preparation of the CNF by using the CCM.
The fiber diameter is about 270nm of the CNF by using CCM. The process of carbonization is two steps. The one
stage is process of producing a flameproofed fiber. Under the process conditions istemperature 250 ℃ , rate of
temperature rise 5 ℃ / min, holding time 1 h, oxygen concentration of 20% atmosphere. The other stage is process of
producing a carbon nanofiber. Under the process conditions is temperature 1000 ℃, rate of temperature rise 7 ℃ / min,holding time 10 min, Nitrogen atmosphere.
The nanofiber after the carbonization process (carbon nanofiber) is shown in Figure1. Fig.1 shows the SEM image ofcarbon nanofiber. The Result of the SEM image diameter of about 270 nm of carbon nanofiber and keep fiber form after
carbonization process.
Fig.2 shows the raman spectrum of the CNF. The spectrum consists of two broad peak around 1590 and 1370 cm-1: theG band and D-band respectively. The G-band is due to E2g symmetry corresponding to the bond stretching vibration of
the in-plane pairs of sp2 site, and the D-band is due to A1g symmetry corresponding to the breathing vibration of 6-foldaromatic rings. The intensity ratio, I(D)/I(G) and G band position have been reported to depended on the sp 2 content incarbon nanofiber. The I(D)/I(G) and G-band position of our carbon nanofiber were about 3.5 and 1575 cm-1, suggestingthat the main bonding configuration of carbon atoms is sp 2. Comparing this result with the general carbon fibers is
considered to have the same carbon structure from that nearly the same peak was obtained.
In the Future, we are planning to study on the carbonization treatment method and the carbon nanofiber
characterization.

Fig.1. SEM image of carbon nanofiber.

Fig.2 Raman spectra of carbon nanofiber

Keywords: nano fiber, carbon fiber, cotton candy method,

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

DEVELOPMENT OF PEEK- NANO- SIC COMPOSITES FOR HIGHPERFORMANCE COATING AND ADHESIVE APPLICATIONS
Oral presentation/Poster presentation
Ajay Kumar Kadiyala and Jayashree Bijwe
Industrial Tribology Machine Dynamics & Maintenance Engineering Centre (ITMMEC), Indian Institute of Technology
Delhi, Hauz Khas, New Delhi, 110016 India.
Abstract –Polyetheretherketone (PEEK) as a high performance polymer having excellent mechanical properties and their fairly
good retention at high temperature, good chemical resistance and high long-term working temperatures. It is considered
to be one of the most prospective polymers for biomedical applications, the automotive industry, electronics, spacecraft
design etc. The efforts for performance enhancement are continuously being done by the researchers and nanocomposites are most favoured area now a days. However, developing nano- composites based on PEEK with uniform
distribution of nano-particles (NPs) is most challenging since it cannot be processed using solution method where probesonication technique can be employed.
In the present work a novel emulsion based dispersion of PEEK and SiC nano filler is reported first time. The emulsion
was then dried in oven to remove the solvents. The coating was carried out on a stainless steel substrate by using
electrostatic powder spray technique. The composites were characterized using FTIR-ATR, XRD, SEM, DSC, TGA,
Contact angle and Raman spectroscopic measurements. The scratch hardness and scratch adhesion of the composites
showed significant improvement with addition of 1% SiC, while 15 % micro SiC proved to be best performer. The
adhesion strength results also showed almost two times improvement with addition of SiC particles and the adhesivestrength was retained to a significant level up to 300 ºC. The fracture analysis of adhesives joints showed very goodinteraction between filler and matrix interface, which lead to improvement in adhesive strength properties.
Keywords: nanocomposite, PEEK emulsion based composites, high temperature adhesives.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

BIODEGRADABLE AND RENEWABLE POLY (LACTIDE)-LIGNINCOMPOSITES: SYNTHESIS, INTERFACE AND TOUGHENINGMECHANISM
Oral presentation
Yang Sun,a Liping Yang,b Xuehong Luc and Chaobin Hea,d, *aDepartment of Materials Science & Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore
117576. Email: msehc@nus.edu.sgbInstitute of Chemical and Engineering Science, Agency for Science, Technology and Research (A*STAR), 1 Pesek
Road, Jurong Island, Singapore 627833
cSchool of Materials Science and Engineering, Nanyang Technological University, Block N4.1, Nanyang Avenue,
Singapore 639798
dInstitute of Materials Research and Engineering, Agency for Science, Technology and Research (A*STAR), 3 ResearchLink, Singapore 117602. Email: cb-he@imre.a-star.edu.sg
Corresponding author email address: msehc@nus.edu.sg; cb-he@imre.a-star.edu.sg
Abstract - Poly (lactide) (PLA)-lignin composites were fabricated by blending lignin-g-rubber-g-poly (D-lactide)
copolymer particles and commercial poly (L-lactide) (PLLA) in chloroform. To synthesize the copolymer, poly (caprolactone-co-lactide) (PCLLA) rubbery layer was formed via lignin-initiated ring opening copolymerization of caprolactone/L-lactide mixture, followed by the formation of poly (D-lactide) (PDLA) outer segments via
polymerization of D-lactide. The PDLA segments may contribute to strong interfacial interactions between ligninrubber-PDLA and PLLA matrix by stereocomplexation which was observed using differential scanning calorimetry(DSC), Fourier transform infrared spectroscopy (FT-IR) and wide angle X-ray scattering (WAXS). The quasi-random
structure of PCLLA and the formation of outer PDLA segments were characterized by nuclear magnetic resonance(NMR). A Tg of ~-36 C for PCLLA was detected by DSC, which confirms the rubbery characteristic of the synthesized
copolymer. The resulting renewable and biodegradable composites exhibited a six-fold increase of elongation at break
and a simultaneous improvement of tensile strength and Young’s modulus albeit to a lesser extent. Light scattering,
WAXS, small angle X-ray scattering (SAXS) and scanning electron microscope (SEM) studies suggested that goodlignin dispersion, rubber-initiated crazing and strong filler-matrix interactions due to stereocomplexation are theeffective mechanisms behind the excellent mechanical performances.
Keywords: Poly (lactide), lignin, nanocomposite, toughening, interface

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

HIGH EXPANSION OPEN-CELL POLYLACTIDE (PLA) FOAM FROMBLENDS WITH FIBRILLAR POLYTETRAFLUOROETHYLENE (PTFE)
Oral presentation
S. Ishihara, and M. Ohshima
Department of Chemical Engineering, Kyoto University, Kyoto, Japan 615-8510
Corresponding author email address: ishihara.shota.85r@st.kyoto-u.ac.jp
Abstract – Polymer blends of Polylactide (PLA) and fibrillar polytetrafluoroethyrene (PTFE) were foamed by foam
injection molding with core-back operation. PTFE has a fibrillar morphology in the PLA and increases shear andelongational viscosities, which suppresed bubble growth and increased bubble nucleation rate. By controlling the coreback distance, the open-microcellular foam with 80 % open cell content (OCC) of fibrillar structure was produced.
Keywords: Core-back Foam Injection Molding, Open Cell Foam, Polylactide, Polytetrafluoroethylene

1. INTRODUCTION
There have been many investigations of PLA
foam aiming to lower the material cost by weight
reduction and replace the traditional petroleumbased plastics by the biodegradable polymer.
However, PLA was considered as a difficult
polymer to be foamed because of its slower
crystallization rate and lower melt tension [1].
In this study, blending the fibrillar PTFE,
viscoelastic properties were modified andmicrocellular foams with higher expansion andopen cell content were prepared in core-backfoam injection molding process. The effect ofPTFE on cell structure was investigatedsuppressed and bubble nucleation was enhanced.
As a result, cell structure became uniform and fine.
Fig. 2 shows cellular structure of crosssectional area parallel to the core-back directionof threefold expansion PLA/PTFE (97/3) foam.
By increasing expansion ratio (core-backdistance), fibrillar structures were obtained and
OCC was increased to 80%(a) PTFE 0 wt. %(b) PTFE 3.0 wt. %20μm

2. EXPERIMENTAL
PLA (TP-4000, Unitika), whose melt flow rate
is 3 g/10 min and D-isomer concentration was
1.5 %, was used as received. Acrylic modified
PTFE (Metablen A3000, Mitsubishi Rayon) was
added to PLA. N2 gas (99.7 %, Izumi Sangyo)
was used as blowing agent. PLA/PTFE blend
foams were prepared by varying the PTFE content
as well as expansion ratio in core-back foam
injection molding process. The cell structure wasobserved by SEM (Mighty-8, Technex).
3. RESULTS AND DISCUSSION
Fig. 1 shows cellular structure of crosssectional area perpendicular to the core-backdirection of twofold expansion PLA/PTFE foams.
The cell size of PLA/PTFE foams was reduced byaddition of PTFE.
It is known that PTFE has fibrillar morphology
in PP or PLA. Due to this morphology,
entanglement of polymer chain was enhanced andshear viscosity and elongational viscosity wereincreased. Then, the bubble growth was

20μm

Fig. 1 SEM images of cross-sectional area of
twofold expansion PLA/PTFE foams prepared at
foaming temperature, 95°C, and different PTFE
contents, (a) 0 and (b) 3.0 wt.%(a) Expansion ratio = 2(b) Expansion ratio = 5

20μm

20μm

Fig. 2 SEM images of PLA/PTFE foams at thesame foaming temperature (110°C) and weightfraction of PTFE (3.0 wt. %), but different
expansion ratios (a) 2 and (b) 5
4. CONCLUSIONHigh expansion open cell PLA foams wereobtained by blending fibrillar PTFE.
REFERENCE
1. L. T. Lim et al., Prog. Polym. Sci., Vol. 33 pp.
820-852 (2008).

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

MEASUREMENT OF DEMOLDING RESISTANCE IN
INCLINE DIRECTION TO TEXTURING CAVITY SURFACEUSING 3-COMPONENT FORCE TRANSDUCER
Oral presentation
D. KATAYAMA1, S.OWADA2, and H. YOKOI3
Institute of Industrial Science, The University of Tokyo - d-ktym@iis.u-tokyo.ac.jp
2
Institute of Industrial Science, The University of Tokyo - showada7@iis.u-tokyo.ac.jp
3Institute of Industrial Science, The University of Tokyo - hiyokoi@iis.u-tokyo.ac.jp
4-6-1, Komaba, Meguro-ku, Tokyo, 153-8505, JAPAN1

Abstract - Transcription defects occurring on the textured surface of plastic molded products are due to the complicatedcombination of various factors. One of the main factors is the lateral force working on the textured patterns as a resultof the shrinkage of resin or demolding at the incline surface. In this study, we proposed a method which measuresdemolding resistance generated during demolding in the incline direction. The measurement mold we used mounts acavity block drive mechanism and 3-component force transducer, which allow measurement of the demolding
resistance including the lateral force during demolding at inclined angle (inclined demolding) to the textured surface.
We conducted demolding resistance measurement experiments using PS, a cavity with textured surface, and thedemolding incline angle set to 45 degrees. The results showed that the demolding resistance in the melt flow direction
increases proportionately to the mold gap, and then starts to decrease gradually after a certain threshold. We were able
to specifically clarify the changes in the demolding resistance where the peak increases with increasing holding
pressure. In addition, the magnified observation of the surface of the molded product confirmed that the anisotropy of
the reflected light and the deformation of textured shapes remain after demolding, suggesting that in inclined
demolding, these two defects should be caused by forcibly sliding along the inclined demolding direction in between
the bumps of molded products and textured cavity surfaces.
Keywords: Injection molding, Demolding resistance, Textured surface, Inclined demolding
Introduction
During the texturing process in injection molding,many different patterns with concave and convex
shapes such as stain-embossed finish and grain leather
patterns are formed on the product surface.
Transcription defects of these textured surfaces often
occur, whereas many of the factors have not been
analyzed in detail. The authors therefore conductedvisualization analysis of the demolding process on
stain-embossed finish to investigate the correlation
with the transcription rate distribution of molded
products. In a previous study, it was revealed that
anisotropy occurs due to the deformation of the
textured shapes during the demolding process as aresult of the shrinkage of the molded product1).
Generally, the textured surfaces of molded products are
positioned at the inclined surface to the mold opening
direction. For this reason, like the results reported
above, most of the demolding process is carried out by
inclined demolding to the textured cavity surface. Thisis thought to cause defects such as non-uniform
transcription of textured patterns on the molded
products observed after demolding. With the aim toanalyze the correlation between demolding defects anddemolding resistance, in this study, we have developed
a new mold for measuring inclined demolding
resistance, based on the measurement mold used formeasuring the demolding resistance in the moldopening direction in a previous report2). We also
conducted molding experiments to analyze thecorrelation between the inclined demolding process
and surface characteristics of the molded product. The
following discusses the results.
Experimental Device
Fig.1 shows the experiment device developed inthis study. The movable side of the mold is mountedwith an elevating mechanism which can move thecavity block upward. As a result, during the demoldingof the molded sample, demolding movements are
generated in the parallel direction to the textured
surface by the rise of the elevating mechanism whenthe mold opens in the perpendicular direction to theparting face as shown in Fig.2. The combination ofthese two movements realizes inclined demolding. At
the stationary mold side, a transducer (washer type3-component force transducer 9067, Kistler Japan Co.,
Ltd.) is mounted in the preloaded state between the
movable block B (textured cavity surface) and baseblock C. This enables measurement of the force
generated on the textured surfaces as in the melt flow
direction (X-component), and the force working in the
thickness direction (Z-component). The cavity has arectangular shape with textured surface (Fig.3), and therunner has a submarine gate. This structure allows
inclined demolding of only the molded productseparated from the runner part during demolding. Table
1 shows the molding conditions for measuring
demolding resistance when the demolding angle is set
at 45 degrees in the direction perpendicular to theProceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Servo motor
aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa
aStationaryside
Movable side
X

X

Ball screw
Movable block B

Cavity YYZ

Texturedsurface areaA

Fan gate
3-component
force transducer
Base block C
Submarine gateA

Texturedsurface[Movable side] [Stationary side]
Movable cavity block P. L.
A-A cross section

Z(Unit; mm)Movable block B

Fig.3 Cavity shape with textured surface.
Table 1 Molding conditions.

3-component
force transducer

Injection molding machine

NEX110 (NISSEI PLASTIC INDUSTRIAL CO., LTD.)Resin

GPPS 679 (PS Japan Corporation)
220 – 230 – 230 – 220 – 210 – 60

Cylinder temp. [℃]
Injection rate[

Base block C]

20

Mold temp. [℃]60

Holding pres. [MPa]30, 50

Textured surface

TH115 (TANAZAWA HAKKOSHA CO.,LTD.)

Demolding incline angle [deg]45[Movable side] [Stationary side]
Movable cavity block P. L.
Fig.1 Fundamental structures of measurement mold of
demolding force.

Rotate[Movable side] [Stationary side]
Lifting-up movement
driven by ball screw

Resultant movement

Mold-open
movement

Gap sensor(Z direction)
CavityFan gate

Gap sensor(X direction) Generation of
inclined demolding process
Fig.2 Schematic process of inclined demolding between
molded product and cavity surface on stationary side.
cavity surface. The molding machine used was the
NEX100 (NISSEI PLASTIC INDUSTRIAL CO.,LTD.). Stain-embossed finish of Ra 10µm was used as
the textured surface.

Result and Discussion
Figs.4 to 8 show the measurement curves of the 3component forces obtained from molding experiments.
Figs.4 to 6 demonstrate the graphs of the 3-component
forces at the holding pressure of 30MPa. Fig.4 shows
the 3-component force measurement curves of allprocesses from P1 to P4 taking the x-axis as the timeaxis. P1 to P4 indicate the injection process, pressure
holding process, cooling process, and demolding
process. After the pressure holding process finished,
the screw moves back so that the metering process canstart. Fig.5 enlarges only the demolding process
together with the mold gap (Z-gap). Fig.6 shows the
3-component force of the same demolding data taking
the x-axis as the mold gap. The rising amount of thecavity block (X-gap) is also demonstrated. Figs.7 and 8
correspond to Figs.5 and 6 but with holding pressure
set to 50MPa.
As the mold open mechanism of the molding
machine used in this experiment is operated by a toggle
mechanism, it is clear that the X- and Z-components in
Fig.5 are exhibiting complicated behaviors. After thehigh pressure mold-clamping operation is canceled at
t1, the mold starts to open from t2, and demolding
completes at t6. Mold opening operations pause at t3,
and resume at t4. For this reason, the mold gap (Z-gap)
does not increase monotonously. In contrast, when themold gap is expressed using the x-axis, theProceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

X-component increases proportionately with the Z-gap
and X-gap from t2 to t5 as shown in Fig.6. The
X-component becomes maximum at t5, and starts todecrease until demolding completes at t6. For thisreason, the surface of the molded product and textured
cavity surface continue to contact until t5 (Z-gap =56µm), after which partial demolding starts from t5. It
is thought that the gradual decrease in the demolding
resistance reflects the progress of partial demolding to
the whole cavity surface.
When the holding pressure is increased to 50MPa,
the slope of the X-component becomes 3.5 times thatof 30MPa as shown in Fig.8. The peak value also
increases by 3.2 times. It means that the increase in the
restraint force between the molded product andtextured surface of the mold has been specificallymeasured.
In a precedent study, the demolding resistance of
the L&S micropattern was successfully measured,
where a large demolding resistance was obtained in theperpendicular direction to the cavity surface2). In
contrast, such large resistances are not found in the
Z-component measurement of textured surfaces in thisexperiment (demolding resistance is taken to be
negative value). This means that with this textured
pattern made up of the tapered face and curved face,
aaaaa

t3
t1

t2

the demolding resistance in the perpendicular directionof the textured surface should be very small comparedto the demolding resistance in the diagonal direction.

P4
P1

P2

Z
Demolding
process; DX

Y

Fig.4 Change curves with time of 3 component
forces measured in all the processes from filling
start to end of demolding (Holding pressure:
30MPa).

t1
t2
t3

t5
t4

P3

t6

t6

t4

X-gap

t5

XYZ

Y Z
Z-gap

Fig.5 Detailed curves with time around thedemolding process corresponding to D in Fig.4(Holding pres.: 30MPa).

t1'

t3' t4' t5'

Fig.6 Change curves of indicated property withmold gap (Z-gap) during the demolding process(Holding pres.: 30MPa).

t1'

t2'
t6'

X

t6'

t2'

t3'
t4' t5'

Z
X

X

Z-gap
Y

Fig.7 Detailed curves with time around thedemolding process (Holding pres.: 50MPa).

X-gap

YZ

Fig.8 Change curves of indicated property withmold gap (Z-gap) during the demolding process(Holding pres.: 50MPa).

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

p-p cross
q-q crossaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa
qsectionq p section 0
0

S

p

q

(a) Area P. Height [µm]r(b) Area Q Height [µm]r-r crosssection0r

S; Scratchedpattern

0.1mm

R

Q

P

10mm

(c) Area R Height [µm]Fig.9 Overall appearance of the molded
sample (Holding pres.: 50MPa).
Fig.9 shows a photo of the external view of the
product molded at the holding pressure of 50MPa.
When the photo was shot, the light was shone from the
top right of the figure. For this reason, the area aroundthe fan gate P and back of the ejector pin Q are whitish,
confirming that the anisotropy of the reflected light has
occurred. Next, the P and Q areas and general surface
R were magnified, observed, and compared under alaser microscope. Fig.10 shows the results. In the P and
Q areas, damaged areas S can be seen elongating in theup and down directions on the textured pattern. These
areas show a consistent incline angle between 14 to 18
degrees. The same damage was found on the textured
surface formed using the holding pressure of 30MPa,
but it was minor. Taking into account that the peakvalue of the X-component of the demolding resistanceat the holding pressure of 50MPa is 3.2 times that of
30MPa, it was concluded that these anisotropies of thereflected light differ in degree according to thedifferent fixed states depending on the molding
conditions and positions. In the inclined demolding
process, anisotropy is thought to have been generated
by the scratches from rubbing by the textured patternon the resin transcribed surface being moved
diagonally upwards by the textured pattern on themold.
Conclusion
Experiments on the measurement of inclined
demolding force were conducted using a newly

Fig.10 Observation of the molded surfaces andcross-sectional profiles by a laser-microscope.
developed measurement mold mounted with a
3-component force transducer. It was found that
demolding resistance including the resistance along thecavity side can be measured. In molding experiments
using PS and demolding incline angle of 45 degrees,
the X-component, a force working in the melt flow
direction, was found to increase proportionately withthe mold gap amount and with the rising amount of thecavity block, confirming that the increase in theholding pressure causes the X-component peak value
to increase sharply. In addition, it is assumed that the
X-component decreases with the mold gap amount,
resulting in the progress of partial demolding.
Furthermore, magnified observation of the surface ofthe molded product revealed that the demolding
progresses with the transcribed shape of the textured
pattern interfering with the mold textured surface. This
causes part of the textured surface to deform, resulting
in the anisotropy of the reflected light.
Reference
1) N. Masuda, H. Yokoi, Analysis on the Generation
Process of Irregular Brightness Change Pattern
Appeared on Textured Molding Surfaces, AWPP
2014 Proceeding, #1225, 2014.
2) T. Ueda, H. Yokoi, Measurement of Demolding
Resistance in Direction Vertical to TranscribedSurface without Bending Deformation of Molded
Product, AWPP 2014 Proceeding , #1227, 2014.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

PREPARATION OF POLY(LACTIC ACID) NANOFIBER BY
COTTON CANDY METHOD
Oral presentation
R. Wongpajan1, S. Thumsorn1,2, H. Inoya1, M. Okoshi1 and H. Hamada1
1

2

Department Advanced Fibro-Science, Kyoto institute of Technology, Japan
Department of Textile Engineering, Rajamangala University of Technology Thanyaburi, Thailand
Corresponding author email address: cussu_think@hotmail.com

Abstract - Poly(lactic acid) (PLA) is well known for biodegradable polymer, which is synthesized from renewable
resources such as tropical and corn starch. According to environmental consideration, biodegradable of PLA is
promising for applied in various kinds of industrial applications. This research is focus on preparation of PLA
nanofibers by cotton candy method. The barrel temperatures were varied from 230, 240, 250, 260 and 270 C. PLA wasfed and subsequently spun through the spinneret, which has controlled the air pressure of 0.2, 0.3, 0.4 and 0.5 MPa andhot air at the spinneret. The screw speed was set at 10 rpm. The effect of barrel temperature on morphology, thermal
properties and crystallization behavior of PLA nanofiber was investigated. Morphology of nanofiber is determined byscanning electron microscope (SEM). Thermal properties and crystallinity are examined using differential scanningcalorimetry (DSC). Figure 1 shows morphology of PLA nanofiber at 260 C and 270 C that were obtained withmagnification of 10,000. The diameters of PLA nanofiber are 1.0991 and 1.6376 m for 260 C and 270C,
respectively. It was found that the fiber diameter at 260 C was smaller than that of 270 C. However, PLA nanofiber
size was not uniformity. The DSC results show clearly glass transition and cold crystallization temperature in thenanofiber at 270 C, which indicated that this nanofiber was slow crystallization during process. On the other hand, it
can be seen higher intensity of melting temperature in the nanofiber at 260 C. It was considering that the nanofiber atlower processing temperatures would be smaller diameter and would be presented higher crystallinity than that ofhigher temperature. The effect of air pressure on morphology and thermal properties of PLA nanofibers are elucidated.
Keywords: poly(lactic acid), nanofiber, extrusion, high pressure, hot air

Figure 1 Longitudinal SEM photographs of the PLA nanofiber.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

CONTROL OF GLASS TRANSITION TEMPERATURE IN IMMISCIBLE
RUBBER BLEND
Oral presentation
N. Kuhakongkiat, K. Yoshida, S. Nobukawa and M. Yamaguchi*
School of Materials Science, Japan Advanced Institute of Science and Technology, Japan
1-1 Asahidai, Nomi, Ishikawa, JAPAN 923-1291
Corresponding author email address: m_yama@jaist.ac.jp
Abstract – Interphase transfer phenomenon was used to control the glass transition temperature, Tg, of immiscible
rubber pair as a function of ambient temperature. In this study, the laminated sheets composed of ethylene-propylene
rubber (EPR) and poly(isobutylene) (PIB), in which di-(2-ethylhexyl) adipate (DOA) is added, are separated after
annealing at various temperatures.
Figure 1 shows the temperature dependence of tensile loss modulus E´´at 10 Hz for pure rubbers and the rubberswith 10 phr of DOA. It is found that Tg of each rubber, defined as the peak temperature of the E´´curve, shifts tolower temperature by the addition of DOA, demonstrating that DOA acts as a plasticizer for both rubbers.
Furthermore, a single peak of E´´for both blends suggests that DOA is miscible with each rubber.
Figure 2 shows E´´for separated sheets after annealing at -20 oC and 40 oC for 5 days. It is demonstrated that Tgof EPR shifts to low temperature after annealing at -20 oC and high temperature at 40 oC. Correspondingly, Tg of PIB
also changes by the annealing procedures.
These experimental results suggest that DOA shows interphase transfer even in a blend of EPR and PIB, havingphase-separated structure. When EPR is a matrix, the blend is flexible in winter season due to a large amount of theplasticizer in the matrix, and vice versa in summer season.
Keywords: Immiscible rubber, Liquid transfer, Plasticizer

9

9

10 Hz

10 Hz
PIB

log [E'' (Pa)] + log [E'' (Pa)] + 

PIB



8
EPR


8

EPR




7
-75

-70

-65
-60
o
Temperature ( C)

-55

-50

Figure 1
Temperature dependence of the tensile
loss modulus E´´for the samples of (open symbols)
pure rubber and (closed symbols) rubber containing 10
phr of the DOA; (top) PIB and (bottom) EPR

7
-75

-70

-65
-60
o
Temperature ( C)

-55

-50

Figure 2
Temperature dependence of tensile
loss modulus E” for the samples after annealing at(closed symbols) -20 oC and (open symbols) 40 oC;(top) PIB and (bottom) EPR

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

PP/LLDPE HYBRID IN AXIAL POWDER FLOW APPARATUS
Oral presentation
E. Junsri1*, N. O-Charoen1 and H. Hamada

2

1

Department of Materials and Metallurgical Engineering, Faculty of Engineering, Rajamangala University ofTechnology Thanyaburi, Pathum thani 12110
2
Department of Advanced Fibro Science, Kyoto Institute of Technology, Sakyo-ku, Kyoto, Japan 606-8585
Corresponding author email address: ektinai.js@gmail.com

Abstract - In this study, the axial powder flow apparatus was used in molding the hybrid polymers
between polypropylene copolymer and linear low-density polyethylene (LLDPE). Materials were prepared in powder
form by pulverizer and mixed by dry blend method at ratio 50 : 50 (wt%). The variations of temperature inside the moldand state changes of PP/LLDPE hybrid were investigated. Differential scanning calorimeter (DSC) and Optical
microscope (OM) use to determine thermal properties and phase separation in the hybrid respectively. Mechanicalproperties of the hybrid was monitored by compressive strength method. The results showed that the mechanicalproperties of the hybrid decreased when compared with PP and LLDPE pure. The result from melt flow index (MFI) of
the hybrid shown that LLDPE improves the flow properties in PP. However, the PP/LLDPE hybrid was successfully inprocessability using the axial powder flow apparatus at ratio 50 : 50 (wt%) with the internal air temperature 170 ˚c androtational speed 7 rpm.
Keywords: Polypropylene, Linear low-density polyethylene, Rotational molding, Two-layer structures.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

THE FLAMERETARDANCY STUDY OF CORRUGATED CARDBOARD
USING FOR CARDBOARD BED
Oral presentation
Yusaku. Mochizuki1, Yoshihiro. Mizutani1, Masayuki. Okoshi1, Hiroyuki. Hamada1
1
Department of Advanced Fibro Science, Kyoto Institute of Technology, Japan
Corresponding author email address: mczk0520@gmail.com
Abstract - Recently Corrugated Cardboard is available for not only packing materials but we use the cardboard for
furniture and cots at refuges. The reason why the cardboard has the characteristics of lightness, high strength, cheapness
and recycle ability. In particular, there is the strong needs to add flameretardancy to cardboard bed for prevention of
second disaster. Our purpose in this study is to add the flameretardancy to the cardboards with keeping the recycle
ability. The cardboard of combusting behavior was measured by using a calorimeter. We used Ammonium Sulfate, TriOctyl Phosphate (TOP) and Tri-Butyl Phosphate (TBP) as flameretardant. Also we used 3 kinds of commercial
flameretardant to compare with Ammonium Sulfate, TOP and TBP. As the result, Ammonium Sulfate showed great
flameretardancy to cardboards. By adding Ammonium Sulfate to cardboard, It is possiple to decrease exponentially theHeat Release Rate (HRR).
[Fig.1] [Fig.2]

Fig.1 HRR of Ammonium Sulfate

FIG.2 PEAK-HRR OF EACH FLAMERETARDANT
We are planning to use the cardboard bed. Therefore we are trying to add the flameretardancy for cardboard. The
combustion behavior of cardboard bed was measured by using large combusting furnace. A part of the combusting
behavior of cardboard bed was clarified from the experiment and it became important data for our further study..
Keywords: Cardboard, Combustion, Flameretardancy, PVA.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

POLY(LACTIC ACID)/POLYPROPYLENE BLENDSFOR COSMETIC CASE PRODUCTS
Oral presentation
J. Kordsa-Art1, R. Wongpajan2, H. Hamada2 and S. Pivsa-Art1*
1

Department of Materials and Metallurgical Engineering, Faculty of Engineering,
Rajamangala University of Technology Thanyaburi, Pathumthani, Thailand
2
Department of Advanced Fibro Science, Kyoto Institute of Technology, Kyoto, Japan
Corresponding author email address: sommai.p@en.rmutt.ac.th
Abstract - Cosmetic cases are conventionally produced from polypropylene (PP) or Acrylonitrile-butadiene-styrene(ABS) copolymers. However, these polymers are non-degradable and their wastes cause problems to environment.
Addition of environmental friendly material to the petroleum-based polymer will reduce the amount of non-degradedparts. Poly(lactic acid) (PLA) is a biodegradable polymer having high potential for industrial applications from its
mechanical property. Blending of PLA and PP increased the biodegradable part of the polymer blends. But due to phaseseparation of PLA and PP, we studied the effects of a compatibilizer for the blends. The polymer blends were preparedwith PLA:PP ratios of 100:0, 80:20, 60:40, 50:50, 40:60, 20:80 and 0:100 with addition of 1, 3 and 5 wt% ofpolypropylene-graft-maleic anhydride (PP-g-MAH) as a compatibilizer. The product samples were prepared with
injection molding process and subjected to thermal, mechanical properties chemical properties morphology analysis andpercent of compatibility of PP-g-MAH. The thermal analysis confirmed that addition of PP-g-MAH has no effect on
crystalline melting temperature of the polymer components but the impact strength was increased. The highest impact
strength was found with PLA:PP ratio 40:60 with 3 wt% of PP-g-MAH. The results are in agreement with morphology
study of polymer blends confirmed the adhesion of PLA and PP by assistance of PP-g-MAH. The addition of moreamount of PP-g-MAH resulted in high polarity of a compatibilizer and decreased the compatibility with PLA. The
tensile strength of polymer blends increased with increasing amounts of PLA. The research results confirmed theapplication of polymer blend system with injection molding process.
Keywords: Poly(lactic acid), Polypropylene, Polypropylene-graft-maleic anhydride, Cosmetic case

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Analysis of Dispersive Behavior and Mixing State of Filler Mixed into
SBR and BR
Oral presentation
Shonosuke Kaneko1*, Asahiro Nagatani2 and Tatsuya Tanaka1
1

Department of Mecanical Engineering, Doshisha University, Japan
2
Hyogo Prefectural Institute of Technology , Japan
Corresponding author email address: duo0527@mail4.doshisha.ac.jp
Abstract - Rubber products which are consisted of other polymers or fillers such as carbon black (CB) are made byinternal mixer. This process is called mixing process. And it is known that this process affects the later product quality
greatly. Mixing and dispersion process cannot be seen directly because internal mixer is a sealed type mixer.
Generally, the mixing state is examined based on relationship a torque (or electricity power) and mixing time curve(i.e. mixing chart). Method to decide mixing time is an important problem in rubber mixing technique.
In addition, it was known to be decided by a unit work as for the Mooney viscosity in the mixer, even if the volumeof mixer is defferent by past document[1]. It was revealed that this relationship is established in the case of the different
number of revolutions. Then, it is assumed that the internal mixer has the role as the viscometer. The viscosity depends
on shear speed and temperature in the case of shearthinny materials. Therefore temperature was remarked as a
judgment of mixing time. In other words, the state of the mixing or dispersion state can be estimated from relations of
the shear stress and the temperature. In this study, relationship with parameter which is provided from internal mixer
and filler dispersion in rubber or the viscosity was investigated.
As experiment, SBR, BR, CB, silica was used for materials. These are used for raw materials of the tire. After testingwith a smaller internal mixer, a larger internal mixer was used for discussing the difference of volume. The dispersion
state of compound mixed by larger mixer dose not equal to the one of smaller mixer because of the difference of power
capacity and heat transfer. Laboplastmil (toyoseikiseisakusyo) has 0.1L capacity and MIXTRON (Kobe Steel) has
1.63L capacity were used for mixing. All materials were introduced into the mixer at the same time. The torque,mixing time, consumption electricity and temperature of the materials were measured during mixing. The evaluation of
the filler dispersion was performed by TEM, viscoelastic examination. The viscosity was measured Mooneyviscometer and capillary rheometer.
As a result, relationship instantaneous electric power and total electric power was showed in Fig1. And therelationship the parameter which divided instantaneous electric power by the number of revolutions and total electric
power curve was piled up even if the number of revolutions was changed (Fig2). When the number of revolutions waschanged, the average shear stress calculated from the shear rate in the tip clearance and the fill factor was the samelevel.And It was revealed that the relationship the reciprocal of temperature and the logarithm of the shear stress were
proportion in the end part of mixing.
[1] O’CONNOR,G.E., Putman, J.B. : Rubber Chem. Thecnol.,57, 799 (1978)

Keywords: mixer, dispersion, rubber, shear stress, viscosity

Fig1. Instantaneous power －Total power curves

Fig2. Converted curves in consideration of the number of
revolutions

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

MEASUREMENT OF THREE-DIMENSIONAL TEMPERATURE
DISTRIBUTIONS INSIDE CAVITY FILLING MELTS
USING INTEGRATED THERMOCOUPLE SENSOR
Oral presentation
S. Ishida, N. Masuda, H. Yokoi*
Institute of industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo, 153-8505, Japan*
Corresponding author email address: hiyokoi@iis.u-tokyo.ac.jp
Abstract Integrated thermocouple sensors capable of high precision measurement of temperature distribution insidemelts filling into the cavity have such drawbacks as complicated measurement work, difficulty to change the sensor
position, and poor sensor durability. In this study, the authors developed a measurement mold capable of moving thethese sensors to anywhere in the cavity, and maintaining the sensors at both the stationary and movable sides of themold. Experiments were then conducted to clarify that the mold is capable of three-dimensional measurement of
temperature distribution by moving the sensors gradually from the center of the cavity to the side of the cavity. In
molding experiments using a rectangular caivty with a thickness of 3mm and PP, it was found that cooling effects
along the cavity wall are promoted at low injection rate, and that the closer the sensor moves to the cavity side, thetemperature drops more sharply. On the other hand, at high injection rate, shear heating effect becomes more
conspicuous as the sensor moves toward the side, resulting in the sudden increase in the temperature. Such dramatic
temperature changes were confirmed to be limited to the area near the side of the cavity wall to the area where the wall
thickness is 2 to 3 times more (about 7 to 10 mm).
Keywords: Injection molding, Gap-width temperature profile, Flowing melt, Integrated Thermocouple Sensor
1.

Introduction

In injection molding, the clarification of the
distribution of resin temperature in the mold is an
important research task for understanding various
molding phenomena. Some of the authors developed amethod of measuring temperature distribution insidemelts filling into the cavity by patterning pure metals
made of copper and nickel on a thin board, andforming a row of thermocouples at high integration rate,installing the sensors perpendicularly to the moldcavity face and parallel to the flow direction of the melt,
and have been conducting studies on the measurementof temperature distribution along the thickness of thecavity under various conditions1)-4). As the sensors aresupported only at one end, assymetrical force works on
the sensor face near the cavity side, causing the sensors
to turn over and become damaged. For this reason,
there is a need to support the sensors on both ends fromthe stationary and movable sides in non assymetricalflow fields. In preceding studies, some of the authors
conducted experiments in which the complicated job ofremoving the support block of the movable mold forevery shot was carried out. To change the position of
the sensors, the cavity has to be rebuilt each time.
T hus, in this s tud y, the author s d evelop ed ameasurement mold which allows the sensors to be
moved to any position inside the cavity, and thesensors to be supported at both the stationary andmovable sides of the mold. Measurement experiments
were then conducted on continuouous molding using
this mold to clarify temperature distribution inside thecavity three-dimensionally, and the results confirmed

the usefulness of the method. The study and results arereported below.
2.

Experimental System and Method

2.1 Integrated thermocouple sensor
Fig.1 shows the basic structure of the BT resin
substrate integrated thermocouple sensor used in thisstudy. For the base material, BT resin reinforced withfiberglass cloth was used to provide increased
durability compared to the polyimide base. On bothsides of a 100μm thick base, both Cu and Ni were
patterned, and a coupling section was made using athrough-hole. Sixteen measuring points were set,
0.25mm apart.

Fig. 1 Basic structure of BT resin-based sensor(Unit: mm) 4)

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

2.2 Basic Structure of Measurement Mold
Fig. 2 shows the basic structure of the measurement
mold developed in this study. The integrated
thermocouple sensors were sandwiched between thetwo blocks A and B of the stationary side mold, andconnected to the special compensating lead wire. The
measurement block has a structure which enables thesensors to be moved to any positions along the cavity
width using the adjustment bolts installed on both sidesof the mold base, and the sensors positions to be
managed using the contact displacement sensor (AT-V,
made by KEYENCE). The movable side of themeasurement mold installed with two cavity blocks C
and D with left-right symmetrical screw holes. These
cavity blocks C and D can be opened/closed byrotating the shaft extended to outside the mold. This
open/close mechanism is linked to the mold closing
action by the cams and positioning pins installed on
both sides of the stationary side cavity blocks. The
sensor positions are always corresponding to the
open/close central positions of blocks C and D. For thisreason, after the mold is tightened, blocks C and D
move symmetrically and support the sensors on bothsides.

2.3 Measurement Method
Fig.3 shows the shape of the cavity used and themeasurement positions of the sensors. The cavity size
is 120x50mm and 3mm thick. A well cavity isprovided at the end of the cavity. An indirect innerpressure sensor (Type 9221 made by Kistler) is
installed under the ejector pin inside the runner tomeasure the pressure. Fig.4 shows how the sensor
supported on both ends is installed. Taking the positionof the stationary side cavity face to be 0 mm in respect
to the 3 mm thickness of the cavity, 11 measurement
positions No.2 (0.25mm) to No.12 (2.75mm) were seton the coupling. Taking the center of the cavity to be
x=0, the sensors were moved along the cavity width tomeasure at positions x=0, 5, 10, 15, 18, 20, 21, 21.5, 22
mm in this order. The injection molding machine used
was NEX110 (screw diameter of ∅36mm, NISSEIPLASTIC INDUSTRIAL CO., LTD.). The resins used
was PP (J106, Prime Polymer Co.,Ltd.) and themolding conditions are shown in Table 1. The injection
rates were set at 10, 55, and 100cm3/s.

Fig. 3 Cavity shape (Unit: mm)

Fig. 4 Sensor installation method (Unit: mm)Table1 Molding conditions

Fig. 2 Schematic structure of mold

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

3.

Experiment Results and Discussion

Fig. 5 shows the bird’s eye view of the results oftemperature distribution along the thickness of thecavity just before injection molding ends at the various
injection molding rates. It was confirmed thattemperature distribution along the thickness of thecavity can be continuously measured while moving thesensor from the center of the cavity to the side of thecavity.
At the injection rate of 10cm3/s, the temperature
dropped from x=20mm to x=22mm. Under low
injection rates, cooling is promoted due to the long
filling time. The temperature near the wall drops along
the thickness of the cavity, and cooling effects are thehighest near the side of the wall along the width of thecavity because this area is enclosed by walls in three
directions. For this reason, cooling is promoted,
resulting in a sharp drop in the temperature. On theother hand, at high speed conditions above theinjection rate of 55cm3/s, temperature starts to increasearound x=18mm, and the change is larger towards theside of the wall. At high injection rates, shear heating
effects become conspicuous near the wall. On the other
hand, the shortening of the filling time is thought toenhance the cooling effects.
Fig.6 shows the temperature distribution along the
thickness of the cavity at each injection rate, x=0, 20,22mm to compare the temperature distribution profiles.
When x=0mm (center of the cavity), the temperature
distribution is a radial shape at the injection rate of 10
cm3/s. Its shape starts to change to a trapezoid when theinjection rate increases to 55 and then 100cm3/s.
At x=20mm to 22mm, the temperature decreases in
the radial shape at 10 cm3/s. On the other hand, at highinjection rates of 55 and 100 cm3/s and when x=20mm,
the temperature distribution changes to a horn shapewhere the temperature near the wall along the thicknessof the cavity starts to increase from the center of thecavity. At x=22mm, the temperature rises throughout
the whole area and is especially conspicuous at thecenter. The temperature distribution profile graduallychanges to a trapezoid shape again. This may be
because temperature increased throughout the wholearea as a result of the shear heating effects from three
directions, namely two walls along the thickness of thecavity, and the side wall of the cavity. In particular, thetemperature peaked selectively at the horn area. The
rise in temperature is thought to correspond to thepreceding flow of the edge known as ear flow. The
area with conspicuous temperature change at the sideof the cavity was found to be about 7 to 10 mm (x=1815mm) away from the cavity side, and correspond to
the edge which is 2 to 3 times thicker.
In particular, temperature distribution along the
thickness was asymmetrical near the side. This may be
because the closer the sensor is to the wall, the more
the sensor tends to deform during measurement,
causing measurement error. The sensor strength istherefore an issue that must be resolved.

(a) Injection rate 10cm3/s(b) Injection rate 55cm3/s(c) Injection rate 100cm3/s

Fig. 5 Temperature distributions inside cavity fillingmelts (S: Stationary side, M: Movable side, C:
Center of cavity thickness)

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

4.

Conclusion(a) x=0mm(1) The results of measurement experiments
confirmed that the developed mold is able tocontinuously measure temperature distribution
along the thickness of the mold by moving themeasurement position from the center of the cavity
to the side of cavity.
(2) Cooling effects were promoted at low injection
rates, and the temperature decreased sharply thenearer the measurement positions were to thecavity side along the width. It was also confirmedthat at high injection rates above 55cm3/s,
temperature increasing effects by the shear heating
along the width of the cavity increased.

(b) x=20mm(3) The areas where the temperature change along thecavity thickness was large were confirmed to be
the areas where the melt flowed from the cavity
side to the side of the cavity measuring 7 to 10 mm(2 or 3 times greater than the thickness).
(c) x=22mm
References
1) Yokoi, Murata, and Tsukakoshi: Seikei-Kakou, 8,
107 (1996)
2) Murata, Abe, and Yokoi: Seikei-Kakou, 14, 257(2002)
3) Murata, Abe, and Yokoi: Seikei-Kakou, 15, 706(2003)
4) Yokoi, Murata, Takahashi, Anbe, and Nakamura:
JSPP’09 Tech. Papers, 157(2009)
Fig. 6 Temperature profile along cavity thickness forseveral cavity width positions at end of filling
process

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

A HIGHLY EFFICIENT REEL TO REEL HOT EMBOSSING PROCESS FORFABRICATION OF POLYMER MICROLENS ARRAY
Poster presentation
C.Y. Chang* and J.H. Chu
Department of Mold and Die Engineering, National Kaohsiung University of Applied Sciences, Taiwan
Corresponding author email address: cychang@kuas.edu.tw
Abstract - Reel-to-reel (R2R) hot embossing is a promising process for fabrication of micro structures on polymers
with high accuracy and high through-put. This paper reports a novel and high effective method for fabrication ofpolymer microlens array devices based on reel to reel film transfer and gas assisted hot embossing process. Therefore, anovel reel to reel hot embossing system with gas pressure capacity has been designed, constructed and tested. As shownin Fig. 1, the system are composed of a reel to reel mechanism with tension roller, a closed chamber, a nitrogen tankwith a pressure regulator and valves, a heating/cooling plate with vacuum pump. In this study, a large area thin steel
mold with micro-circular holes array pattern is fabricated by photo-lithography and wet chemical etching process. The
roll of plastic film/ thin steel mold stack is placed in a closed chamber and hot plate is heated to processing temperature
which is above the Tg of the plastic material. During the heating process, vacuum pressure is applied to the film toprevent the film from creasing. When the processing temperature is reached, the nitrogen gas is introduced into thechamber to exert gas pressure over the film, forcing the film in close contact with the thin steel mold. Under proper
processing conditions, the softened polymer will just partially fill the micro-circular holes on the surface of thin steel
mold and due to surface tension form a convex lens surface. After the cooling process, the nitrogen gas is vented, thechamber is opened. The microlens array pattern on the surface of plastic film is removed from the thin steel mold. Afterthe reel to reel hot embossing process. The roll of large area polymer microlens array device can be fabricated, as
shown in Fig. 2. Finally, the effects of processing conditions on the shape and quality of fabricated polymer microlens
array were investigated. The geometrical and optical properties of the fabricated polymer microlens arrays were
measured and proved satisfactory. This technique shows great potential for fabrication of polymer microlens array withhigh productivity and low cost.
Keywords: Reel to reel hot embossing, polymer microlens array

FIGURE 1

FIGURE 2

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Modification of chemically stable polymeric materials 64. Improvement in thehydrophilic and adhesion properties of polymeric materials and FRPs
Poster presentation
H. Kanazawa and A. Inada
Department of Industrial Systems, Faculty of Symbiotic Systems Science,
Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan: kana@sss.fukushima-u.ac.jp
Abstract Hydrophobic polymeric materials such as polypropylene, polyethylene, PET were modified by a new
combination method of physical and chemical processes. The modified materials gave a durable hydrophic property.
and the improvement in adhesion, property, water-based paint coating or ink-jet printing. Poly(methyl pentene),silicone resin and engineering plastics of which modification is difficult by corona or plasma discharge treatments weremodified well. Polymer composites such as GFRP and CFRP for cars and aircrafts were improved., and the adhesion
property was increased. The modified materials gave a high durability as compared with a plasma treatment and theother methods.
Keywords: surface modification, adhesive property, polypropylene, GFRP, CFRP, ink-jet printing

1. Introduction
Many techniques were carried out to modify thesurface property of polyolefins. However, their
durable improvement is not obtained. For instance,
when PE or PP materials are treated by a plasma
or a corona discharge treatments, these materials
become water wettable. But the modified property
is lost with time. We found that the combinationof some modification techniques was effective forthe modification of chemically stable polymericmaterials. The obtained hydrophilic property was
not lost for several years. In addition, a waterbased paint coating on the modified materials, anda solvent-bonding are examined.

3. Results
3.1 Modification of silicone resin andpoly(methyl pentene) (PMT) resin.
Silicone rubber has a high water-repellency andits modification is very difficult. We investigated
the technique. A part of silicone rubber sheet
modified by the present method (KANA method)
gave a durable water wettability (Fig. 1).
Polymethylpentene (PMP) is one of the mostdifficult materials to be modified. PMP-madevessels were modified by the present method; theinner wall of the modified one is wettable withwater (Fig.2).

2. Experimental
2.1 Materials Polymeric materials were used
after washing with methanol. Commercial
chemical reagents and hydrophilic reagents wereused after a simple purification.
2.2 Adhesives Poly(vinylpyrrolidone), starch,wood-usebonds,
PVAC-water
mixture,cyanoacrylate (CA), CA-primer set, tape typeepoxy resin adhesives, etc. were used.
2.3 Treatment Polymeric materials wereactivated by chemical oxidations or UV, energy
irradiations. The activated polymeric materials
were treated with chemical reagents in thepresence of catalysts.
2.4 Adhesion strength and analysis A bonding
strength of a polymeric material bonded to othermaterials was measured by a tensile tester,
Shimadzu AGS-H5KN.
IR and XPS spectra of materials were observed.
2.5 Ink-jet printing Epson and Canon printerswere used with water-based ink.

Fig. 1 Modified silicone rubber
sheet wetted with water.

Fig.2 Water-wettability of
unmodified (left) and modified(right) PMP resin vessels.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

CONTROLLED GROWTH OF MOF-BASED HYBRID NANOMATERIALS
Poster presentation
Jiating He, Ray Chin Chong Yap, Siew Yee Wong, Yu Zhang, and Xu Li*
Institute of Materials Research and Engineering, A*STAR. 2 Fusionopolis Way. Innovis, #08-03, Singapore 138634
Corresponding author email address: x-li@imre.a-star.edu.sg
Abstract - Microporous metal-organic frameworks (MOFs) consisting of metal ions assembled together withorganic ligands have become a popular topic due to their large internal surface area, tunable chemical property
and variable cavities, leading to diverse applications in gas storage, 1-4 chemical separation5,6 and drugdelivery.7,8 In order to enhance their performance for different applications, MOFs have been incorporated withother functional nanomaterials to form hybrid nano-structures.9,10 Incorporation of functional nanoparticles into
MOFs is an effective methodology to confer novel physical properties which will bring about newopportunities for future applications. For example, hybrid nanoparticles composed of metal nanoparticles and
MOF can be incorporated in polymer substrate to adsorb and scavenge unflavoured gases or dyes.
Typically, precursors of MOFs are deposited onto pre-synthesized seed nanoparticles uniformly in solution and
MOFs will grow from the modified seed nanoparticles. For such binary hybrid motifs, three kinds of structures
can be obtained in general: concentric core-shell, eccentric core-shell and Janus nano-hybrids Concentric coreshell nano-hybrids are the most common configurations, as a result of simple over-coating of MOFs on seednanoparticles to form a uniform shell or granular domains in colloidal systems. 11,12 Compared to concentriccore-shell configurations, eccentric core-shell and Janus structures which are absent of centro-symmetry
demonstrate higher diversity and complexity. Especially with Janus structures, the exposed surfaces of bothcomponents are expected to exhibit their original surface activities as well as integrated surface activities.
Here, we report a facile strategy that can control the growth of zeolitic im idazolate framework (ZIF-8)
materials on the surface of metal nanoparticles at room temperature. The selective growth is driven by surfacefunctionalization of metal nanoparticles via competitive ligand adsorption. Both hydrophilic and hydrophobic
ligands are employed to adsorb and assemble on surface of metal nanoparticles, resulting in anisotropic surface
domains on nanoparticles with different affinities to ZIF-8 precursors. Ligand ratio is proved to be a key factor
to manipulate the coverage of ZIF-8 on the metal nanoparticles, leading to formation of MOF-based nanohybrids with tunable structures, such as concentric core-shell, eccentric core-shell and Janus nano-hybrids. The
capability to direct ZIF-8 growth by controlling the ligand assembly on the metal nanoparticle surfaces opens
up new opportunities in the synthesis of MOF-based complex nanostructures. The resulting nano-hybrids to beincorporated in polymer films to be applied in fixed-bed catalysis.

Keywords: hybrid nanoparticles, metal-organic framework
1.
2.
3.
4.

Murray, L. J.; Dinca, M.; Long, J. R. Chem. Soc. Rev. 2009, 38, 1294.
Dinca, M.; Dailly, A.; Liu, Y.; Brown, C. M.; Neumann, D. A.; Long, J. R. J. Am. Chem. Soc. 2006, 128, 16876.
Dinca, M.; Long, J. R. Angew. Chem. Int. Ed. 2008, 47, 6766.
Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.; Kim, J.; O'Keeffe, M.; Yaghi, O. M. Science 2003, 300,
1127.
5. Li, J.-R.; Kuppler, R. J.; Zhou, H.-C. Chem. Soc. Rev. 2009, 38, 1477.
6. DeCoste, J. B.; Peterson, G. W. Chem. Rev. 2014, 114, 5695.
7. Ferey, G. Chem. Soc. Rev. 2008, 37, 191.
8. Yaghi, O. M.; O'Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Nature 2003, 423, 705.
9. Lu, G.; Li, S.; Guo, Z.; Farha, O. K.; Hauser, B. G.; Qi, X.; Wang, Y.; Wang, X.; Han, S.; Liu, X.; DuChene, J. S.;
Zhang, H.; Zhang, Q.; Chen, X.; Ma, J.; Loo, S. C. J.; Wei, W. D.; Yang, Y.; Hupp, J. T.; Huo, F. Nat. Chem.
2012, 4, 310.
10. Zhang, W.; Wu, Z.-Y.; Jiang, H.-L.; Yu, S.-H. J. Am. Chem. Soc. 2014, 136, 14385.
11. Huang, X.; Zheng, B.; Liu, Z.; Tan, C.; Liu, J.; Chen, B.; Li, H.; Chen, J.; Zhang, X.; Fan, Z.; Zhang, W.; Guo, Z.;
Huo, F.; Yang, Y.; Xie, L.-H.; Huang, W.; Zhang, H. ACS Nano 2014, 8, 8695.
12. Zhong, H.-x.; Wang, J.; Zhang, Y.-w.; Xu, W.-l.; Xing, W.; Xu, D.; Zhang, Y.-f.; Zhang, X.-b. Angew. Chem. Int.
Ed. 2014, 53, 14235.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

EVALUATION OF STRUCTURE-PHYSICAL PROPERTIES OF REACTIVE
MOLDED POLYAMIDE 6 AND ITS FRTP
Poster presentation
Hiroto Suenaga1, Kentaro Taki2, Hiroshi Ito1＊, and Takashi Inoue1
1 Graduate School of Science and Engineering, Yamagata University, Japan
2 Graduate School of Natural Science and Technology, Kanazawa University, Japan
Corresponding author email address: ihiroshi@yz.yamagata-u.ac.jp
Abstract -Recently, fiber reinforced thermoplastics (FRTP) has attracted attention in the automotive and aviation fields.
However, the thermoplastic resin is used as the matrix of FRTP is very difficult to the fiber bundles impregnate at ahigh melting temperature and high viscosity. Therefore, it has to be noted that in-situ polymerization using monomerwith a low melting temperature and low viscosity is the one of the attractive alternative method. Here, we study the insitu polymerization of ε-caprolactam as a monomer in order to fabricate polyamide 6 (PA6) and its composites by using
reactive molding. The thermal property and the higher order-structure of polymerized PA6 and its composites wereanalyzed by differential scanning calorimeter (DSC). The engineering mechanical properties, mechanical behavior were
evaluated by bending test. The PA6 crystal was melted begins at the temperature of 200 oC was observed. We obtained
the flexural modulus and flexural strength of 1-3.5 GPa and 50-90 MPa respectively. It found that increasing
crystallinity of PA6 has resulted in enhance the flexural modulus and flexural strength in a linear relation. In the case of
FRTP using PA6, the flexural modulus and flexural strength of Carbon FRTP showed 10-15 GPa and 200-250 MPa,
respectively.
Keywords:

in

situ

polymerization,polyamide

6,

mechanicalproperty,

fiber

reinforced

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

compositeTOWARDS HIGH-PERFORMANCE POLY(L-LACTIDE) MELT SPUNFIBERS BY TAILORING CRYSTALLIZATION WITH THE AID OF
NUCLEATING AGENT
Poster presentation
H.W. Bai, H.X. Zhang, and Q. Fu*
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan
University, Chengdu 610065, P. R. China
Corresponding author email address: qiangfu@scu.edu.cn
Abstract - As a biodegradable polymer completely derived from renewable resources, poly(L-lactide) (PLLA) shows atremendous potential to replace some of the traditional petroleum-based and nonbiodegradable polymers in various
applications such as textile fibers. However, the current use of PLLA fiber in large-scale commercial applications still
faces some barriers mainly associated with its poor heat resistance because the low crystallization rate makes it hard to
crystallize during melt spinning. In this work, we propose a facile strategy to address this obstacle via simutaneously
tailoring crytal morphology and lamellae orientation with the aid of the nucleating agent (tetramethylene-dicarboxylic
dibenzoyl-hydrazide, TMC-306) that can be dissolved in PLA melt and re-crystallizing into fibrils capable of serveing
as nucleation templates to induce the crystallization of PLLA amellae perpendicular to their long axis upon cooling.
Taking advantage of elongation flow experienced in melt spinning, TMC-306 fibrils tend to align in PLLA melt along
the flow direction and then induce the formation of highly orientated PLLA lamellae in melt spun fibers. In this way, asignificanlty improved heat resistance and tensile strength are easily achieved.
Keywords: poly(L-lactide), fiber, nucleating agent, crystallization, high performance

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Creation of Polar Solvent Type TR Fluid and its Function
Poster presentation
1

K.Hirakawa1 Y.Kanazawa1 H.Sekiguchi2 R.Nakano2 S.Yao1,2*
Chemical Engineering, Fukuoka University Graduate school, Japan
2
Chemical Engineering, Fukuoka University, Japan
Corresponding author email address: shyao@fukuoka-u.ac.jp

Abstract
In this time, we made a new Side Chain Crystalline Bloch Co-polymer (SCCBC) with using Di(ethylene glycol) ethyl
ether acrylate (DEEA) as a functional monomer units. By using this monomer, we could disperse polyethylene particle
to polar solvent and this dispersion system showed polar solvent type Thermal Rheological (TR) Fluid properties. We
also investigated the artery embolization function of this TR fluid and found this fluid has an ability to become a goodan arterial embolization material.
Keywords: Thermal Rheological Fluid / Living Polymerizations / Side Chain Crystalline Block Co-polymer
Introduction
Recently, we polymerized a block copolymer that wasconstructed of two monomers: a monomer with a longalkane side-chain (more than 10 carbon atoms) andanother monomer with solvent affinity. This block
copolymer has a melting point and shows side-chain
crystallization. Thus, this block copolymer cancrystallize due to its long alkane side-chain (SideChain Crystalline Block Copolymer: SCCBC).
Polymers having long alkyl side chains have been wellknown to exhibit various specific properties. In thistime, we found that this SCCBC is adsorbed on PE
crystal through supramolecular interaction. In addition,
through the use of this supramolecular interaction, the
SCCBC can act as a dispersant for a concentrated PE
particle dispersion, which then shows unique thermalrheological properties. In this time, we made a new
SCCBC with using a functional monomer units. By
using this monomer, we could disperse PE particle topolar solvent and this dispersion system showed polar
solvent type TR Fluid properties. One kind of the polar
solvent type TR Fluid have an ability to be an arterial
embolization material.

added at a concentration of 2mass% of the particle
weight. The viscosity and viscoelastic properties were
measured by a Rheosol-G2000 at 25 ºC, 35 ºC, 45 ºC,
55 ºC.
Results and Discussion
Fig.1 shows the temperature dependence of shear
viscosity. From this figure, viscosity increasesignificantly with increasing the temperature. Thiseffects is reversible and can be called as Thermal
Rheology (TR). Also, Transition temperature of around
40 ºC. This result is thought to be desirable for theapplication of hepatic artery embolization because theTR effect may be expressed in the vicinity of the bodytemperature. Fig.2 shows the images before and justafter the injection of this TR fluid into rabbit renalartery. From the figures, it is obviously shown that thisTR fluid was able to embolization of renal artery. Also,
the embolization kept one week. From theseinvestigations, we had found that this TR fluid can beused as a good arterial embolization material.
10000

25℃
35℃
45℃
55℃

Experimental
For the side-chain crystalline monomer, we used
stearyl acrylate (STA), and for the solvent-affinity
monomer, we used Di(ethylene glycol) ethyl ether
acrylate (DEEA). The block copolymer waspolymerized by sequential monomer addition. The
weight average molecular weight (Mw) of the SCCBC
was about 12,000. The Mw of the STA sequence wasabout 5,000 and that of DEEA was about 7,000. For a
PE particle, we used Ceridust®3620 (Clariant
International Ltd), which has a number average
diameter of 7.4μm. Ethanol and Iomeron was used as
the dispersion solvent. Iomeron is a non-ionic iodinatedcontrast agent. The concentration of particle was
35mass% and the concentration of solvent was
Iomeron:40mass%, Ethanol:25mass%. SCCBC was

η (Pa・s)

1000
100
10

Beforeembolization

1
0.1
0.01

0.1
1
10
S.RATE (sec-1)

Fig.1 Temperature and shear
rate dependence of viscosity.

Afterembolization

100

Fig.2 The application results forTranscatheter Arterial Embolization.

Acknowledgment
This research is supported by the [Practical Research
for Innovative Cancer Control (15ck 0106038h002)]
from Japan Agency for Medical Research anddevelopment, AMED.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

INTERPHASE TRANSFER OF PLASTICIZER BETWEEN IMMISSIBLE RUBBERS
Poster presentation
Kento Yoshida, Nawaphorn Kuhakongkiat, Shogo Nobukawa
and Masayuki Yamaguchi*
School of Materials Science, Japan Advanced Institute of Science and Technology, Japan
Corresponding author email address: m_yama@jaist.ac.jp
Abstract
The transfer phenomenon of a plasticizer between immiscible rubbers was studied at various annealing
temperatures. Natural rubber (NR) and poly(isobutylene) (PIB) were used as an immiscible pair with a liquid paraffinthat acts as a plasticizer.
The laminated rubber sheets containing 10 phr of liquid paraffin obtained by the solution casting were piled
together and annealed at various temperatures for 5 days. After the annealing procedure, the sheets were separated andcharacterized by the dynamic mechanical measurements.
Figure 1 shows the glass transition temperature Tg, i.e., the peak temperature of loss modulus E”, of pure rubbers
and rubbers with 10 phr of the plasticizer. It is found that Tg’s of both NR and PIB were shifted to low temperature by
the plasticizer addition.
Figure 2 shows Tg’s of the separated rubber sheets after annealing at various temperatures. Tg of NR shifts to lowtemperature while that of PIB shifts to high temperature after annealing at 40℃. This is attributed to the interphasetransfer of the plasticizer from PIB to NR during annealing. After annealing at -20℃, in contrast, Tg of NR shifts to hightemperature while that of PIB shifts to low temperature. This is also owing to the interphase transfer of the plasticizer
from NR to PIB during annealing.
Keywords: Polymer blend, Interphase transfer, Plasticizer, Glass transition temperature
NR samples

PIB samples

Figure 1：Tg’s of pure rubbers and rubbers with 10 phr of the plasticizer

NR samples

PIB samples

Figure 2：Tg’s of the separated rubber sheets after annealing at various temperatures

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

IMPROVED ELONGATIONAL VOSCOSITY OF POLYCARBONATE
MELTS
Poster presentation
M. Sugimoto*, T. Isogai, S.K. Sukumaran
Graduate School of Science and Engineering, Yamagata University, Japan
Corresponding author email address: sugimoto@yz.yamagata-u.ac.jp
Abstract – We studied an improvement of elongational viscosity of polycarbonate melts. Polycarbonate as aengineering thermoplastic polymer has favorable mechanical properties such as high elastic modulus and pronounced
toughness and some grades have good transparency depending on the production methods. Generally, polycarbonate isone of the linear polymers and shows low melt strength and very weak strain hardening under elongational flow. Thus
polycarbonate is known to be difficult to apply in some polymer processings. Recently, there has been an increasing
demand for an improvement of the elongational flow behavior of polycarbonate. In this study we studied melt rheology
of some polycarbonates produced by interfacial polycondensation of bisphenol A with phosgene and melt
polymerization of bisphenol-A and diphenyl carbonate. Polycarbonate by interfacial polymerization showed typicalrheological properties: the terminal flow behavior in a low frequency region under dynamic shear flow and smoothincrease of elongational viscosity according to the Trouton rule independent of the strain rates under elongational flow.
Polycarbonate interfacial-polymerized with a functional monomer indicated extended relaxation time: gradual transitionof G’ and G” from rubbery plateau region to the terminal flow region. This behavior is similar to that of polycarbonate
by interfacial polymerization. Furthermore, we modified polycarbonate by melt polymerization by using a chain
extender in a post-reactor stage. The modification enhanced the storage modulus G’ as increasing the content of thereactive agent, though the loss modulus did show a small change in low frequency. The modified polycarbonate did notexhibit time-temperature superposition, while neat polycarbonate showed thermorheological simplicity. Furthermore,
we should note that the modified polycarbonate showed a noticeable increase of the stress under elongational flow,which is never expected for standard polycarbonate. We can say that the modified polycarbonate has high potential toapply the new applications which was known to be difficult to process.
Keywords: Polycarbonate, Elongational viscosity, Viscoelasticity, Relaxation time

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

EFFECT OF CLAMPING FORCE SET VALUE ON INJECTION MOLDINGQUALITIESPoster presentation
M.S. Huang1* and C.Y. Lin1
1
Department of Mechanical and Automation Engineering, National Kaohsiung First University of Science andTechnology, Taiwan
Corresponding author email address: mshuang@nkfust.edu.tw
Abstract - Level of clamping force setting in an injection molding machine is important to the quality of plastic parts aswell as the life duration of processed machines, in which a low clamping force may introduce defects of flashes while ahigh value may engage short shot caused by a poor venting effect. Traditionally, clamping force that is unnecessarily set
at the highest value of machine specification may cause extra energy consumption and a heavy loading of tie bars thatfurtherly risks a short life time of employed machines. This work investigates the effect of clamping force set value on
injection molding quality and further proposes an innovative approach to calculate proper clamping force set value thatfacilitates the yield rate of injection-molded parts as well as energy saving.
Keywords: Clamping force, injection molding machines, tie bar elongation, toggle-type clamping mechanism.

Fig. 1. Structure of a five-point double-toggle clamping mechanism.

Fig. 2. Maximal clamping force increment versus part weight corresponding to various clamping force set value.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Long time structure constitution of amorphous polymer
Poster presentation
1

N.Oda1 A.Tominaga1 H.Sekiguchi2 R.Nakano2 S.Yao1,2*
Chemical Engineering, Fukuoka University Graduate school, Japan
2
Chemical Engineering, Fukuoka University, Japan
Corresponding author email address: shyao@fukuoka-u.ac.jp

Abstract
Recently we had investigated mechanical properties of virgin and recycled amorphous polymers of by-products fromspool site and runner site of injection molding. And we had founded that the mechanical properties depend on not only
the difference of virgin or recycle, but also the molding condition. This results suggest that even amorphous polymer,
the recycled polymer remain its history of molding.
In this time, we investigated long time structure constitution of these samples. And we found that the mechanicalproperties of amorphous polymers depend on the molding conditions and are changing with time gradually.
Keywords: Amorphous polymer, Internal structure, Molding condition, Fracture property, Inner structure
Introduction
It is well known that the crystalline polymer causes theflow induced crystallization and construct specificcrystal structure. Recently, we have investigated about
the recycling of crystalline polymer. In theseinvestigation, we pointed the degradation of themechanical properties of recycle plastics were causedby the memory of flow deformation.
On the other hand, the flow deformation memory
dependence of amorphous polymer has not been wellstudied. In this time, we used the mechanical propertiesof amorphous virgin and recycled plastics of byproducts from spool site and runner site of injection
molding and investigated the mechanical properties ofthis films molded from them. From the investigation,
we had founded that the mechanical properties ofrecycled polymer depended on not only the differenceof virgin or recycle, but also the molding condition.
This results suggest that even amorphous polymer, therecycled polymer remain its history of molding. And
also we have found that mechanical properties of thesesamples can be changed greatly by changing theholding process.
Experimental
In this experiments, we used polystyrene virgin pellets(Fig.1 (a)), crushed waste polystyrene (Fig.1 (b)), andre-pelletized pellets (Fig.1 (c)). Test samples for tensile
tests were press-molded at press temperature 230 ℃,
210℃ and pressure was 40MPa. The thickness of thefilms were about 50μm. Test peace were punched out
in JIS K71132 (1/3) specimen from these thin films.
We also analyzed the internal structure by small-angle
X-ray scattering measurements.
Melt viscoelasticity were measured by rheometer.
Results and Discussion
Figure 2 shows a small-angle X-ray scattering
measurements of thin films molded from virgin pellets.

The results of 2min-press time sample, there is no
scattering at the wide angle. However, increasing thepressing time, the two peaks in wide angle region begin
to appear in the 6 min-press time sample. When press
time increased to 10-minutes, the scattering in the
wide-angle region appeared clearly. This results
suggests that with increasing press time, over the
longest relaxation time of the sample, the constructionof inner structure are processing. The results also effecton the mechanical properties.

Fig.2 Small angle X-ray scattering profiles of virgin polystyrene samples.

Acknowledgment
This research was supported by the Environment
Research and Technology. Development Fund
(3K143013)of the Ministry of the Environment, Japan.
This time, in Shinei Chemical Co., Ltd. and Toyo
Styrene Co., Ltd. who have provided polystyrene, I
would like to thank deeply and wrote here.

(a)

(b)

(c)

Fig.1 (a)Virgin pellets (b)Crushed sample (c) recycle sample

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

VALORIZATION OF PALM RESOURCE FOR GREASE LUBRICANT
Poster presentation
Z.M. Png1, Q. Ye1, H. Yan1, H. Zhou1, J.W. Xu1,2*
Institute of Materials Research and Engineering, Agency for Science, Technology and Research (A*Star), 2
Fusionopolis Way, #08-03, Innovis, Singapore 138634
2
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Correspondence to: Jianwei Xu (Email: jw-xu@imre.a-star.edu.sg)
1

Abstract:
Biomass based valorisation and conversion technology development had become a hot issue in the recent decade 1 as thelarge availability of biomass (~1014 kg annually) would provide an important replacement strategy for the industrial
reliance on fossil based feedstock.
Out of all types of biomass, palm oil in particular is an important business in Southeast Asia. Global annual productionof palm oil is about 60 million tonnes, with Malaysia and Indonesia contributing to 87% of the global output. Palm oilcomprises fatty acids, such as saturated palmitic acid. One major application of palm oil is to prepare biodiesel 2. As ofyet, palm oil’s potential in being a feedstock for specialty chemicals is still relatively unexplored. Palmitic acid is fully
saturated and its corresponding esters should possess high stability towards oxidation.
A method to prepare thickeners for grease lubricants from palm oil derived fatty acids is demonstrated (figure 1). Upon
addition of about 1.5% the thickener to a base oil, the viscosity was found to increase until it becomes a greasy texture.
This thickener is able to function at up to 50 oC with good thermo-reversibility(figure 2) . The prepared grease could be
used for a wide variety of applications including food grade lubricant grease, railroad grease and sewing machinegrease.

Figure 1: Reaction route between palmitic acid and selected polyols to generate ester based thickeners

Figure 2: Thermo-reversibility test of the formed grease lubricants.
1 Tuck, C. O.; Pérez, E.; Horváth, I. T.; Sheldon, R. A.; Poliakoff, M., Valorization of Biomass: Deriving More Valuefrom Waste. Science 2012, 337 (6095), 695-699.
2. Mekhilef, S.; Siga, S.; Saidur, R., A review on palm oil biodiesel as a source of renewable fuel. Renewable andSustainable Energy Reviews 2011, 15 (4), 1937-1949

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Keywords: Grease, lubricant, thickener, oil additive, palm oil

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

SYNTHESIS AND ANTIMICROBIAL ACTIVITIES OF QUATERNIZEDPEI-G-CHITOSAN POLYCATIONSPoster presentation
Wei Ren, and Ye Liu*
Institute of Materials Research & Engineering, A*Star, Singapore
Corresponding author email address: ye-liu@imre.a-star.edu.sg
Abstrct
In order to reduce the threat of antimicrobial-resistant microorganisms as well as to reduce the consumption of limited
fossil fuel resources, it is necessary to develop efficient antimicrobial agents based on natural polymers. In this study,
the biomass-based antimicrobial polymers, quaternized polyethylenimine-graft-chitosan (Q-PEI-g-chitosan) weresynthesized via a two-step reaction (Scheme 1). Firstly, PEI-g-chitosan were synthesized via cationic polymerization of
aziridine with low molecular weight chitosan. Then the PEI-g-chitosan were further quaternized with different
quaternary reagents (methyl iodide, n-butyl bromide, 1-Bromohexane and benzyl bromide) to afford the Q-PEI-gchitosan, and the reaction procedure can be simplified into a one-pot manner. The structure and molecular weight of the
PEI-g-chitosan and the Q-PEI-g-chitosan was characterized by 1H NMR, 13C NMR and GPC. The results show that theamines on the chitosan were successfully grafted with PEI chains, and the length of the PEI chains can be controlled byvarying the molar ratio between aziridine and the amines of the chitosan. Minimum inhibitory concentration (MIC)
antimicrobial activity studies of the obtained Q-PEI-g-chitosan were carried out against Escherichia coli (Gramnegative) and Staphylococcus aureus (Gram-positive). The MIC results reflect that Q-PEI-g-chitosan exhibit good
antimicrobial activities. The Q-PEI-g-chitosan can be used as promising biomass-based antimicrobial agents to reduce
dependence on synthetic antimicrobial polymers based on the limited fossil fuel resource, to reduce the possibilities of
antimicrobial resistance and to reduce usage of small molecular chemical biocides which may cause pollution to theenvironment.

Scheme 1. Synthetic route for quaternized PEI-g-chitosan
Keywords: Chitosan, antimicrobial agents, antimicrobial activity, polyethyleneimine, biomass-based

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

SELF-HEALING BEHAVIOR OF STYRENE-BUTADIENE-STYRENE
TRIBLOCK COPOLYMER
Poster presentation
Ritsuko Watanabe1 , Shogo Nobukawa1 and Masayuki Yamaguchi1
1School of Materials Science, Japan Advanced Institute of Science and Technology, Japan
Email address: m_yama@jaist.ac.jp

Abstract - Self-healing materials are known to repair their damage automatically and thus show prolonged life time.
Therefore, they have been focused to be used in the wide range of applications. Since most self-healing polymericmaterials that have been developed up to now have network structure, i.e, thermosetting resin, the demand forthermoplastic resins is increasing intensively. In this study, the self-healing behavior of styrene-butadiene-styrene
triblock copolymer (SBS), known as a thermoplastic elastomer (TPE), was investigated. TPE behaves like a crosslinked rubber at room temperature and can be processed as a thermoplastic at high temperature. It consists of hard
segments which play a role as cross-linking points to prevent flow and soft segments showing rubber elasticity. In
general, both ends of soft segments are trapped in the dispersed domains of the hard segment. However, one end ofsome soft segments can move freely without constraints of the domain. They act as dangling chains, which show the
self-healing behavior beyond the glass transition temperature.1)
In this study, a commercially available SBS having 24 wt % of styrene was employed as a polymer. Two types of
specimens were prepared by compression-molding at different temperatures; (1) 200 ℃ at heating and 5 ℃ at coolingand (2) 160 ℃ at heating and 25 ℃ at cooling.
The temperature dependence of loss tangent tan δ is shown in Figure 1. The grass transition temperature ofpolybutadiene(PB) segment is found to be located at -90 ℃, while that of polystyrene(PS) segment is at around 90 ℃.
The figure indicates that PS phase is formed clearly at high cooling temperature. In contrast, rapid cooling, i.e, lowcooling temperature, prohibits the well-developed phase-separation.
The effect of annealing time on self-healing behaviors is investigated. After cutting into two pieces of the sample
specimen, they were attached together at 25 ℃ for 10 min. or 72 hours. Then, the samples were stretched by a tensile
machine. The result is shown in Figure 2. It is found that the stress and strain at break increases with increasing theannealing time with contact. Futhermore, the sample obtained by quench shows better healing behavior.
Reference: 1) M. Yamaguchi, R. Maeda, R. Kobayashi, T. Wada, S. Ono, S. Nobukawa, Polym. Intern., 61, 9 (2012)
Keywords: Self-healing, thermoplastic elastomer, styrene-butadiene-styrene triblock copolymer

2.0

0
10 Hz

Stress (MPa)log [tan 

1.5
tan 

-1

72 hour
10 min1.0

72 hour

0.5

10 min160 - 25 oC

160 - 25 oC-2-150 -100

200 - 5 oC

-50
0
50
o
Temperature ( C)100

Figure 1. Temperature dependence ofloss tangent tanδ of SBS.

150

0200 - 5 oC

0

0.2

0.4

0.6 0.8
Strain

1.0

1.2

1.4

Figure 2. Stress-strain curves of SBS.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

SYNTHESIS AND CHARACTERIZATION OF A SIDE-CHAIN
CRYSTALLINE SILICONE PSA
Poster presentation
R. Hasuo1, S. Yamaguchi2,3, S. Kawahara2 and H. Murakami4*
1Department of Advanced Engineering, Graduate School of Engineering, Nagasaki University, Nagasaki, Japan
2
Nitta Corporation, Nara, Japan3
Department of Science and Technology, Graduate School of Engineering, Nagasaki University, Nagasaki, Japan
4
Division of Materials Science, Graduate School of Engineering, Nagasaki University, Nagasaki, Japan
Corresponding author email address: hiroto@nagasaki-u.ac.jp
Abstract - A side-chain crystalline acrylic pressure-sensitive adhesive (PSA) is one that its adhesion can be controlled
by reversible order-disorder transition of the side-chain crystalline unit with a change in temperature. The adhesion ofacrylic PSAs, however, decreases with a rise in temperature. In contrast, a silicone PSA possesses the highest heat
resistance property among commercially available PSAs. In this study, therefore, we aimed development of a sidechain crystalline silicone PSA whose adhesion can be controlled with the change in temperature. Siloxane polymers
with and without octadecyl group as the long alkyl side-chain were prepared; introduction of the octadecyl group to thesiloxane polymer was carried out by hydorosilylation reaction. The DSC thermogram of the side-chain crystalline
siloxane polymer showed an endothermic peak at 35 °C attributable to melting of the crystalline unit in a heatingprocess and an exothermic peak at 27 °C for recrystallization of the melted side-chain unit in a cooling process. To
obtain the thermosensitive silicone PSA the side-chain crystalline siloxane and a MQ resin were mixed and thencrosslinked by the hydrosilylation reaction with α,ω-divinyl siloxane. The TGA results of the silicon PSA tape andacrylic PSA tape revealed that the silicon PSA tape possesses higher heat resistance compared to that of the acrylic
PSA. Adhesion switching behavior of the silicon PSAs was evaluated by 180° peel test. The silicon PAS without the
crystalline unit kept its adhesion in the range from 20 to 80 °C whereas the silicone PSA with the crystalline unit lost its
adhesion below 30 °C. Dynamic viscoelastic measurements also revealed that the silicon PSA with the crystalline unit
become hard below the transition temperature. These results suggest that the thermosensitive silicone PSA has beensuccessfully prepared.
Keywords: Silicone PSA, Siloxane, Side-chain Crystalline polymer

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

"WARM-OFF" TYPE ACRYLIC PSA CONTAINING A SIDE-CHAIN
CRYSTALLINE GRAFT COPOLYMER
Poster presentation
S. Tabuchi1, S. Yamaguchi2,3, S. Kawahara2 and H. Murakami4*,
1

Department of advanced Engineering, Graduate School of Engineering, Nagasaki University, Nagasaki, Japan
2
Nitta Corporation, Nara, Japan3
Department of Science and Technology, Graduate School of Engineering, Nagasaki University, Nagasaki, Japan
4
Division of Materials Science, Graduate School of Engineering, Nagasaki University, Nagasaki, Japan
Corresponding author email address: hiroto@nagasaki-u.ac.jp
Abstract – An acrylic pressure sensitive adhesive (PSA) bearing a long alkyl side group as its crystalline unit cancontrol its adhesion, because the crystalline unit undergoes reversible order-disorder transition with a change intemperature. Among the PSAs, an acrylic PSA in which a side-chain crystalline polymer with a low molecular weight
is dispersed as particles shows its adhesion below the transition temperature and loses it above the transition
temperature. This behavior is known as a "warm-off" (WO) function; the low molecular weight side chain crystalline
polymer is called a "warm-off" component (WOC). Adhesion-switching behavior of a WO-PSA containing a random
copolymer as a WOC, however, occurs in a broad temperature range due to the presence of the crystalline units withdifferent sizes. To solve this problem we used a copolymer grafted with a side-chain crystalline macromonomer
consisting of only monomers with long alkyl side chain groups as a WOC (graft-WOC). In the DSC thermograms therandom-WOC gave an endothermic peak with a shoulder. The existence of the shoulder is the evidence for thepresence of the different crystalline states. In contrast, a sharp endothermic peak for the graft-WOC was observed
without any shoulders, suggesting that the side chain crystalline unit is unity. The large half-width of the peak is due tothe use of the two long alkyl acrylates. From the peel test results, the peel strength of the PSA containing the randomWOC decreased to less than 1 N/inch with an increase in temperature. However, the difference of the peel strengths
before and after the melting point was very small. In contrast, the PSA containing the graft-WOC kept its adhesion
until the melting point. In addition, rising in temperature until above the melting point caused drastic decrease of thepeel strength to less than 1 N/inch. This result indicates that the WO function is improved by the use of the graft-WOC.
Keywords: Side-chain Crystalline Polymer/ Pressure Sensitive Adhesive / Graft Copolymer

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

Development of evaluation method capable of judging the appropriate productlifetime of the rubber material used in residential-use cogeneration systems
Poster presentation (Please select one)
Shintaro Iwasaki1, Yuji Higuti1
1

Energy Technology Laboratories, OSAKS GAS CO. LTD., Osaka, Japansh-iwasaki@osakagas.co.jp

Abstract Gas equipment is composed of various materials, including polymeric material and metal. It is well-known thatpolymeric material is more prone to degradation than other materials. For this reason, evaluation of the reliability of
individual cases of polymeric material used in gas equipment is important for the safety of equipment utilization.
In Japan, recent years have seen the spread of residential-use cogeneration systems (residential CGS). Residential CGS
contain systems for circulation of hot water because of exhaust heat recovery. As compared to conventional water
heaters, they are operated for a longer duration and used at higher temperature. Coupled with this harsh environment,
there have lately been reports of the occurrence of trouble in the form of degradation of rubber parts owing to residual
chlorine added to tap water. In fact, for residential CGS as well, the change of specification of solenoid valve
diaphragm, from EPDM (ethylene-propylene-diene materials) to FKM (fluoro-rubber), has been made. Therefore,
selection of the type of material for rubber parts used in residential CGS must continue to take account of the effect ofdegradation caused by residual chlorine.
The objective of this research is developing the evaluation method of the long-term durability of rubber material against
residual chlorine in the field, based on laboratory reproduction of degradation caused by the combination of residual
chlorine and temperature. And this paper provides the evaluation results with a focus on the solenoid valve diaphragmas exemplifying a type of rubber part used in residential CGS. The chlorine-water immersion test as the accelerated
aging test was carried out to conduct a comparative evaluation on the durability of EPDM andFKM against the residual
chlorine and determine whether it is possible to use each rubber for 10 years in the field.

Keywords: EPDM, fluoro-rubber, residual- chlorine, accelerated aging test

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

ANOMALOUS MOLECULAR ORIENTATION OF EXTRUDED SHEETFOR POLYPROPYLENE/POLYBUTENE-1 BLENDS
Poster presentation
Sato Shunma1, Shogo Nobukawa1, Takayuki Maeda2 and Masayuki Yamaguchi1*
School of Materials Science, Japan Advanced Institute of Science and Technology, Japan2
New Japan Chemical Co., Ltd., Japan
Email address: m_yama@jaist.ac.jp
1

Abstract
Various processing operations are applicable for isotactic polypropylene (PP), including extrusion. In general,
chain-axis of PP orients to the molecular, i.e., flow direction in extruded films and sheets. In contrast, recent researches
revealed that extruded sheets in which PP molecules orient perpendicular to the flow direction are prepared by using
epitaxial crystallization on the surface of needle crystals of N,N’-dicyclohexyl-2,6-naphthalenedicarboxamide.1.2)
Although this phenomenon is interesting from the scientific point of view, it has poor impact on the industrial
application expect for the manipulated molphology control.3.4) In this study, an extruded sheet in which polymer chainsorient both parallel and perpendicular to the flow direction is prepared by using a miscible blend composed of PP andisotactic poly(butene-1) PB.
Commercially available PP and PB were melt-blended with N,N’-dicyclohexyl-2,6-naphthalenedicarboxamide(New Japan Chemical, NJ StarTR NU-100) as the nucleating agent. The blend ratio of PP/PB was 50/50. The content of
the nucleating agent was 500ppm. The sample was fed into a twin-screw extruder with a ribbon-shaped die. The
temperature of the die and barrel was controlled at 200℃ and the chill-roll was at 100℃. Besides the blend, pure PB
was also extruded at the same condition.
Fig. 1 shows the 2D-XRD pattern of the PB sheet. The figure demonstrates that PB shows I-form crystals whichorient to the flow direction. Fig. 2 shows the edge-view pattern of the extruded blend. As seen in the figure, the (110)plane of trigonal β-form crystals of PP shows strong six spots. The result demonstrates that PP chains orient
perpendicular to the flow directions in the film plane (transversal orientation). Therefore, the sheet has strong
orientation in both MD and TD.
Reference: 1) Uchiyama et al., J. Polym. Sci. Polym. Phys. 47, 424 (2009)
2) Yamaguchi et al., Polymer 50, 1497 (2009)3) Phulkerd et al., J. Polym. Sci. Polym. Phys. 51, 897 (2013)4) Phulkerd et al., Polym. J. 46, 226 (2014)
Keywords: polypropylene, polybutene-1, nucleating agent, molecular orientation, extrusion

Fig. 1 2D-XRD pattern of the
extruded PB sheet.

Fig. 2 2D-XRD pattern atedge-view of the extruded PP/PB
blend sheet.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

NUMERICAL SIMULATION OF INJECTION/COMPRESSION MOLDINGFOR MULTISCALE STRUCTURE
Poster presentation
S.K. Hong1, J.J. Kang1 and K.H. Yoon2*
1

Molds and Dies Technology Group, Korea Institute of Industrial Technology (KITECH), Republic of Korea
2
Department of Mechanical Engineering, Dankook University, Republic of Korea*Corresponding author email address: khyoon@dankook.ac.kr

Abstract – Studies of the micro- or nano-patterned functional surfaces have been actively conducted in various fields.
Because these surface functionalities are highly useful, there are ongoing attempts to develop imitations of thesesurfaces for use in the industry and technology. However, the mass production of such surfaces is difficult because
efficient methods for manufacturing the micro-scale or nano-scale patterns are unavailable at present.
Injection/compression molding (ICM) is advantageous for achieving thickness uniformity and dimensional accuracy.
On the other hand, only a few papers have studied the effects on micro-pattern molding. In the present paper the
relationships between the micro-pattern molding properties and ICM (Fig. 1) conditions using numerical analysis were
investigated. The molding subject (Fig. 2) has the sheet shape with the width, length, and nominal thickness of 160 mm,
90 mm, and 1.12 mm, respectively. The micro-pattern is cylindrically shaped with a diameter and height of 30 µm and14 µm, respectively and a 100-µm gap between the patterns. PMMA TF8 (MFR of 10.0 g/10 min at 230°C, 37.3 N) of
Mitsubishi Rayon was used for the polymer resin. An injection molding machine used in this study consists of an in-linescrew-type injection unit and a toggle-type clamping unit. Simulation was performed for the behavior of the micropattern filled during ICM using a DDM (dual-domain method)-based technique. As a first step the filling simulation ofa macro-scale model was performed, the simulation for the assumed part without the micro-scale patterns, using thecommercial Moldflow software. Next, the filling simulation of a micro-scale model, which is the filling simulation for
one pattern, was performed. The COMSOL Multiphysics software was used for this micro-scale filling simulation. The
following results were obtained in the present study: (i) Solidification of the polymer proceeded faster farther awayfrom the gate. This is the main cause for the lower transcription ratios of micro-pattern far from the gate. (ii) The
temperature history of the polymer is almost the same in CIM (Conventional Injection Molding) and ICM. (iii) The
polymer temperature reached the no flow temperature within the packing stage in CIM and within the compression
stage in ICM. That is, the micro-pattern filling flow stopped even for non-zero cavity pressure. (iv) The improvement inmicro-pattern filling in ICM is only due to the difference in cavity pressures history. Finally, the experimental results
and simulation results for filling behavior of micro-pattern over time were compared as shown in Fig. 3.
Keywords: Injection/Compression Molding, Micro-feature, Finite Element Method, Multiscale structure(a)Fig. 1 Schematic drawing of injection/compression
molding.

Fig. 2 Photograph of injection molded macroscale partand microscale structures.

(b)
Fig. 3 Comparison of molded micro-feature height
between numerical and experimental results at various
distances from gate: (a) CIM and (b) ICM.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

ATOMISTIC SIMULATION OF GAS DIFFUSION IN GLASSY POLY(VINYLPYRROLIDONE) MATRIXPoster presentation
Supanont Jamornsuriya, Visit Vao-soongnern*
Laboratory of Computational and Applied Polymer Science (LCAPS), School of Chemistry, Institute of Science,
Suranaree University of Technology, Nakhon Ratchasima, Thailand. E-mail: visit@sut.ac.th
Abstract - Poly(vinyl pyrrolidone), PVP, is one of biocompatible polymers widely used in pharmaceutical application
especially in tablet coating. The performance of the final coat is strongly affected by the polymer properties and theformulation parameters. Thin film of water soluble polymer like PVP is often applied to improve the stability ofmoisture sensitive products. Understanding the role of specific interaction between penetrant molecules and PVP matrix
at atomistic level is important to elucidate the underlying diffusion mechanism in polymer matrix. In this work, weinvestigate the diffusion characteristics of H2O and O2 gasses in glassy PVP matrix at 298 K by molecular dynamic
simulation. First, rotational isomeric state (RIS) model for a PVP chain was used for generation of a fully atomistic
model for the amorphous material at its bulk density of 1.2 g cm3. The initial structure was relaxed by a combination ofmolecular mechanics and molecular dynamics. The predict Hildebrand solubility parameter is 10.12 + 0.14 cal1/2cm−3/2
and in reasonable agreement with the experimental value (10.8 cal1/2cm−3/2). X-Ray scattering pattern of PVP modelshows two distinct peaks below Q ≈ 2 Å−1. One peak appears around 1.2 Å−1 in the region where usually amorphous“simple” polymers. At lower Q around 0.7 Å−1, a pre-peak is present in consistent with experimental report (J. Chem.
Phys. 134, 054904 (2011)). Then, 10 H2O or 10 O2 were added to these polymer models. After structural equlibration, a
1 ns NVT-MD simulation was carried out to generate the trajectories for analysis. The diffusion of H2O and 10 O2
molecules in the PVP matrix was studied at room temperature (298 K) below the glass transition temperature. The
predicted diffusion coefficients for the two penetrants are remarkably different, as water forms hydrogen bonds with
PVP but oxygen gas does not. The hydrogen bonding of water and the carbonyl groups in PVP is evident in the radial
distribution function (peak at 1.85 Å). Although O2 has larger molecular mass, its diffusion rate is higher. Hence, thehydrogen bond does remarkably influent the slower diffusion of H2O in the PVP matrix. The calculated diffusion
coefficience of H2O (0.22 x 10-6 cm2/s) is about 7 times lower than that of O2 (1.54 x 10-6 cm2/s) in PVP matrix
Keywords: Poly(vinyl pyrrolidone), gas diffusion, molecular dynamics
Acknowledgement: The financial support from Advanced Organic Materials Research group and the Development andPromotion of Science and Technology Talents Project (DPST) is highly appreciated.

Figure 1 Averaged mean square displacement of the
H2O and O2 molecules as a function of time interval in
PVP at 298 and 473 K.

Figure 2 Radial distribution function of (1) thehydrogen (Hw) and oxygen (Ow) atom of water and(2) the oxygen (O2) atom of oxygen gas with theoxygen carbonyl (O=) group in PVP matrix at 298 K.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

INFLUENCE OF SUSPENDING MEDIUM ON RHEOLOGICALBEHAVIOR OF SHEAR THICKENING FLUIDS
Poster Presentation
Swarna1, S. K. Pattanayek2 and A.K.Ghosh1*
1

Center of Polymer Science and Engineering, Indian Institute of Technology Delhi, New Delhi, India
2
Department of Chemical Engineering, Indian Institute of Technology Delhi, New Delhi, India
Corresponding Email: anupkghosh@gmail.com

Shear thickening a type of non-Newtonian phenomenon, manifesting a rise in viscosity with the increase in shear
rate or shear stress after a particular value known as critical shear rate or stress, is observed in a wide range ofsuspensions and is referred as shear thickening fluids (STF). Several properties of both suspended particles andsuspending liquid independently stimulates the uniqueness of liquid-solid transition. In this work, we present theeffect of suspending medium’s characteristics on the viscosity rise owing to solid-like behavior of particle
suspensions. Cornstarch-water based and silica-PEG based systems were evaluated by amending their respective
suspending matrix by addition of polyols. Polyols viz.., glycerine, ethylene glycol and polyethylene glycol (PEG)
were mixed with the matrix in 1:1 ratio which was further utilized in the preparation of different concentrations of
STF by incorporating various quantities of suspending particles (cornstarch and silica). The rheologicalcharacterization of pure STFs was correlated with polyols based STFs and a unique behavior was observed for eachof the additives attributing to OH interactions. Water/Ethylene glycol as suspending medium transits the so called
discontinuous shear thickening activated by jamming of particles to continuous shear thickening at all theconcentrations unlike glycerine and PEG. By addition of glycerine, a strong shear thickening with much lessparticle concentration was observed whereas PEG contributed to shear thinning with increase in particle
concentration. FTIR spectra indicate the increased intermolecular hydrogen bonding associations with polyols
accrediting to exclusive rheological performance of the STFs. In addition, the behavior of non-colloidal andcolloidal Brownian particle suspensions in the suspending medium with respect to the flow properties of STFs was
also explored. Present work provides an understanding and conceptualization of suspending medium’s traits to thatof rheological behavior of different material based STFs.
Keywords: Shear thickening fluids, suspending liquids, polyols, viscosity

SURFACE LOCALIZATION OF POLY(METHYL METHACRYLATE)IN A BLEND WITH POLYCARBONATE
Poster presentation
Takumi Sako, Shogo Nobukawa and Masayuki Yamaguchi*
School of Materials Science, Japan Advanced Institute of Science and Technology, Japan
Corresponding author email address: m_yama@jaist.ac.jp
Abstract
Polycarbonate (PC) is widely employed in industrial applications because of its excellent transparency andmechanical toughness. However, its ability to resist scratches is poor. Therefore, the improvement of an anti-scratch
property is required to widen applications. In this research, we propose a new method to produce a transparent sheet inwhich PMMA is localized at the surface using PC containing a small amount of PMMA to provide the anti-scratch
property.
A commercially available PC (Mn=28,000, Mw=46,000) and PMMA with low molecular weight (Mn=8,900,
Mw=15,000) were used in this study. The samples were melt-mixed and compressed into a film shape. The
concentration of PMMA was 20 wt%. The blend was compressed into flat sheets with a thicknesse of 3 mm by acompression-molding machine. Furthermore, the samples were annealed in the temperature gradient using acompression-molding machine in which temperatures of the top and bottom plates were controlled separately. The
composition of both surfaces was evaluated by attenuated total reflectance Fourier-transform infrared spectroscopy(ATR-FTIR) and size exclusion chromatography.
Figure 1 shows ATR-FTIR spectra for both surfaces of PC/PMMA annealed in the temperature gradient, in which the
top and bottom plates were controlled at 250 °C and 200 °C, respectively. The peaks at 1770 cm-1 and 1730 cm-1 areascribed to PC and PMMA, respectively. The surface at the high temperature side has a stronger peak at 1730 cm-1 anda weaker one at 1770 cm-1, whereas the peak intensities are opposite at the low temperature side. The results
demonstrate that the PMMA concentration is high at the high temperature side and vice versa. Figure 2 shows the size
exclusion chromatographs of samples collected from the surface of the annealed PC/PMMA sheet. The data for pure PC
and PMMA are also shown. This result demonstrates that low molecular weight fraction, i.e., low molecular weight
PMMA is localized at the high temperature side, which is consistent with the ATR-FTIR results.
Since this technique can be applicable to polymer processing, it becomes an important technique for the productionof an ideal plastic glass.
Keywords: Polycarbonate, Poly(methyl methacrylate), Segregation, Annealing
0.6

200 C

Intensity (a. u.)

Absorbance

o

0.4

o

250 C

0.2
PC
0
1800

200 oC
250 oC
Pure PC
Pure PMMA

PMMA
1750

1700
-1

Wavenumber (cm )Figure 1 ATR-FTIR spectra for both surfaces of
PC/PMMA (80/20) annealed under the temperature
gradient for 60 min; temperatures of the top andbottom plates are 250 °C and 200 °C, respectively.

3

4

5

6

log [MW]Figure 2 Size exclusion chromatograph charts as apolystyrene standard for pure PC, pure PMMA andboth surfaces of PC/PMMA annealed under thetemperature gradient for 60 min.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

STRUCTURE AND ENGINEERING PROPERTIES OF PMMA
NANO-ALLOY OBTAINED BY HIGH SPEED SHEARING PROCESS
Poster presentation
Takuya Konno, Yuki Kodama, Akira Ishigami and Hiroshi Ito*
Department of Polymer Science and Engineering, Yamagata University, Japan
Corresponding author email address: ihiroshi@yz.yamagata-u.ac.jp
Abstract - Recently, the reduction of the vehicle weight has been promoted in order to improve fuel efficiency in theautomotive industry. Polymethyl methacrylate (PMMA) has excellent transparency, weather resistance, and rigidity is
expected to substitute material for automotive glass. However, PMMA has a weakness in toughness and impact
resistance. Therefore, we attend to improve the toughness and impact resistance by blending polycarbonate (PC) and
PMMA utilized by a high speed shearing process. The high-speed shearing process has been attracting attention with ahigh resolution is a capable technique to blend the incompatible polymers. PMMA/PC blend is formed to sheet anddumbbell sample by compression molding and injection molding machine respectively. The evaluation of mechanicalproperties are performed to a tensile test, impact test, the surface hardness measurement. The fracture surface
morphology is observed by scanning electron microscope (SEM). In this study, we expect to the toughness and impact
resistance of PMMA are developed by blending method using the high-speed shearing process, the mechanical behavior
is clarified by the effect of the various process parameters. Furthermore, the alternative of automotive materials is
enlarged.
Keywords: PMMA/PC blend, Nano-alloy, High-speed shearing, Mechanical properties, Impact properties

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

NOVEL BIOMEDICAL MATERIALS BASED ON CARBON DOTS
Oral presentation/Poster presentation
G. Wang* and Y. Liu
Institute of Materials Research and Engineering, A*STAR, Singapore
Corresponding author email address: wangg@imre.a-star.edu.sg
Abstract – Carbon dots as novel fluorescent materials have attracted much attention in past decade. Carbon dots in freestate are studied intensively including various ways of preparation and applications based on their tailored properties.
However, the reports on carbon dots clusters are very limited. In this presentation, we introduce the synthesis of two
carbon dots clusters using inorganic silica scaffold and polymer scaffold, respectively. The bioimaging applications
using these materials will also be demonstrated.
Keywords: Biomedical, Carbon Dots, Clusters.

TR fluid function for differences in the chemical structure of
the side chain crystallizable block copolymer
Poster presentation
1

Y.Hasebe1 Y.Kanazawa1 H.Sekiguchi2 R.Nakano2 S.Yao1,2*
Chemical Engineering, Fukuoka University Graduate school, Japan
2
Chemical Engineering, Fukuoka University, Japan
Corresponding author email address: shyao@fukuoka-u.ac.jp

Abstract
Recently, we polymerized a block copolymer that was constructed of side-chain crystalline monomer and a solventcompatible monomer, which we referred to as a side-chain crystalline block copolymer (SCCBC). This SCCBC has a
specific melting point. We found that this SCCBC was adsorbed onto polyethylene (PE) crystal by via supramolecularinteraction. In addition, through this supramolecular interaction, the SCCBC acts as a dispersant for a concentrated PE
particle dispersion, and this dispersion can be considered a Thermal Rheological Fluid.
In this time, we investigated the TR fluid functions of the cases of two different side-chain monomers, one was behenyl
acrylate and other was stearyl acrylate.
Keywords: bolck polymer / micelle / polyethylene / crystalline supramolecular interaction /thermal rheological fluid
Introduction
Recently, we polymerized a block copolymer that wasconstructed of two monomers: a monomer with a longalkane side-chain (more than 10 carbon atoms) andanother monomer with solvent affinity. This blockshows side-chain crystallization. Thus, this block
copolymer can crystallize due to its long alkane sidechain (Side-Chain Crystalline Block Copolymer :SCCBC). We found that the side chain block of the
SCCBC is adsorbed on PE crystal. At this time, PE
crystal and the side chain block of SCCBC areconsidered to form a quasi-crystalline structure.
According to this, the solvent affinity block unit covers
the particle and changes the particle surface easy to wet
solvent. This is because of the SCCBC can act as adispersant for a concentrated PE particle dispersion.
Additionally, we had found that increasing thetemperature of the concentrated PE particle dispersion
system, the viscosity increased to the non-addition
dispersion system. We found this phenomenon was
reversible, when cooling the dispersion the viscosity
decrease to very low value. We call this Fluid as a
“Thermal Rheological (TR) Fluid”.
In this time, we investigated the difference
dependence of the length of side chain.
Experimental
This time, the side chain crystalline sites we used werestearyl acrylate (STA) and behenyl acrylate (BHA).
Synthesis of SCCBC
were living radical
polymerization as previously reported. The PE fineparticle was Ceridust®3620. Diethyl phthalate (DEP)
was used as solvent. The concentration of particle was
40wt%. SCCBC was added 1wt% to PE particle
concentration.
Temperature and shear rate dependence of viscosities
were measured by using a rheometer (Rheosol-G2000).

Results and Discussion
Fig.1 shows the temperature and shear rate dependenceof the shear viscosity. From this figure, the shear ratedependence at low temperature were much depends on
the length of the side-chain. And the transition
temperature also depends on the length of the sidechain. On the other hand, at high temperature, the shear
rate dependence were almost same to the original
dispersion.

(a)

(b)

Fig.1 Temperature and shear rate dependence ofviscosity of 1wt% SCCBC PE particle dispersion. (a)behenyl acrylate (BHA), (b) stearyl acrylate (STA).

Acknowledgment
This research is supported by the 【Practical Research
for Innovative Cancer Control (15ck 0106038h002)】
from Japan Agency for Medical Research anddevelopment, AMED.

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

STRUCTURAL ENGINEERING OF POLYURETHANE FOR MULTIPLE
FUNCTIONAL COATINGS
Poster presentation
Hong Yan,1 Hui Zhou,1 Xiaobai Wang,1 Jianwei Xu1,2*1Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2
Fusionopolis Way, Innovis, Singapore 138634
2
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543. E-mail: jwxu@imre.a-star.edu.sg
Abstract - Versatile polyurethane with predominant properties, e.g. chemical, temperature and abrasion resistant,bondable to various substrates, and highly flexible, have shown great promise in wide applications. For instance, it is
widely used to insulate surfaces such as wood, metal and paint to protect them from rot, corrosion or fading.
Nevertheless, the ability to deliver additional functions on the target surface and comply with the requirements ofmultiple functions usually involves another coating layer or materials. As a result, applications of polymeric materials
and hybrid composites for surface coating still suffer from simplex function and insufficient performance. Nonetheless,the lack of abilities in the preparation of a multi-functional coating material on a substrate and improvement of surface
properties with simple processing constitutes an obstacle to achieving multi-functional coating. With these problems,
utilization of such multi-functional coating materials is inevitably seen as a viable alternative to improve the surface
properties with minimal processing, light weight and low cost. Therefore, the development of truly durable multiple
functional coating based on sole polyurethane is therefore highly desirable for advanced applications.
Herein, we present a method for producing multipurpose polyurethane that contains functional molecular entities in thepolymeric backbone that are addressable or controllable. The tunable functions and applicability of polyurethane byselection of monomeric components from different combinations of macrodiols, diisocynates and chain extender are a
viable method for organization of molecular components into polymeric framework. As a result of grafting functionalmoieties, the prepared polyurethanes were deserved additional functions compared with conventional polyurethanefilms, such as anti-UV, anti-fogging, and superhydrophilicity as well as fluorescence capability for multi-functionalsurface coating.
Keywords: Polyurethane, Multiple Functions, Anti-UV, Anti-Fogging, Superhydrophilicity

Scheme. A schematic illustration for the synthesis of P1~ P5. (P1: R1, R2, R3, R5a; P2: R1, R2, R3, R4a, R5a; P3: R1,
R2, R3, R4b, R5a; P4: R1, R2, R3, R5b; P5: R1, R2, R3, R4a, R5b.)

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

HYDROTHERMAL SYNTHESIS OF CARBON SPHERES FROM GLUCOSE
Poster presentation
R.C.C. Yap, J.T. He, S.Y. Wong and X. Li*
Institute of Materials Research and Engineering (IMRE),2 Fusionopolis Way, Innovis, #08-03, Singapore 138634*Corresponding author email address: x-li@imre.a-star.edu.sg
Abstract:
The uses of sustainable materials as precursors to produce nano-materials are very important to the economy,
environment and health issues. Glucose, a form of carbohydrates and simplest form of sugar is widely found in nature.
Carbon sphere from hydrothermal carbonization have display many superior and promising properties which can beused in many important applications. For example, carbon spheres can encapsulate metal nanoparticles which can beused in drug delivery or water filtration technologies. They can also be decorated with different nano-materials to
exhibits different properties to be use in sensing applications. Mesoporous carbon spheres with high BET surface area
can also be used for super capacitors gas absorption.
The starting materials are glucose mixed with water to form glucose solution. Using a stainless-steel autoclave,carbon spheres can be synthesized from glucose solution. Carbon spheres with average diameter of 150 nm have beensynthesized at 800 ˚C for 3 hours. By using different biomass precursors, the physical size and surface properties ofcarbon sphere can be tuned. A symmetrically study on the different conditions such as concentration, time andtemperature were varied. The particle morphology was compared using SEM and TEM, and the chemical composition
was studied using FTIR and EDX. Large scale production of carbon spheres using hydrothermal reactor was also
demonstrated. The carbon spheres can then be mixed with polymer solution for application in polymer coating
technologies for UV shielding. The UV shielding can be measured using UV-VIS.
Keywords: carbon spheres, glucose, hydrothermal, polymer

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

EVALUATION OF HIGHER-ORDER STRUCTURE AND THERMALPROPERTIES OF HIGH THERMAL CONDUCTIVITY PC COMPOSITESOBTAINED BY STRUCTURAL PHASE SEPARATION METHOD
Poster presentation
Yumi Yamada1, Hiroshi Ito1*, Yuu Takahashi2,Fumio Keitoku2, Hironari Sano2,
and Yuji Fujita2
1
Graduate School of Science and Engineering, Yamagata University, Japan2
Mitubishi Chemical Co., Japan
Corresponding author email address :ihiroshi@yz.yamagata-u.ac.jp
Abstract - This study demonstrates the effects of ceramic filler with high thermal conductivity on the thermal
conductivity of PC/PP blends by structural phase separation method. PC/PP polymer blends in the difference ofviscosities were used as polymer matrix. The PC/PP blends were well known in the phase separation behavior of theblending structure. In this investigation, Boron Nitride (BN) as a high thermal conductive filler with high proper
dispersion into the lower viscosity phase of PC was used. BN disperse in PC/PP blends with the phase separation
structure was observed. PC-based composites with BN-rich phase were successfully fabricated by structural phaseseparation structure method. The results show that thermal conductivity was improved by the creation of high filler
content in the phase.
Keywords: polymer composites, thermal conductivity, polymer blend, phase separation structure

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore

EFFECT OF MODIFIED STARCH AND NANOCLAY ON
BIODEGRADABILITY AND MECHANICAL PROPERTIED OF
POLYLACTIC ACID TERNARY BLENDS
Poster presentation
1

X.K. Zhang, S.X. Wang, S.Y. Wong and X. Li*
Institute of Materials Research and Engineering, A*STAR, Singapore
Corresponding author email address: x-li@imre.a-star.edu.sg

Abstract: Starch-based biopolymer composites reinforced by nanoclay are reported in this paper. The starch was
modified by glycerol and Poly (butylene succinate), which showed good interfacial adhesion to polylactic acid (PLA).
Nanoclay was successfully incorporated into Starch/PLA blends via a twin screw extruder to produce Starch/PLA/Claynanocomposites. It was found that the nanoclay loading affected the mechanical properties and morphology ofstarch/PLA composites. The incorporation of nanoclay particles accelerated the crystallization process of the PLA
matrix; meanwhile, the nanoclay improved the compatibility between starch and PLA. The starch-based composites
incorporating nanoclay presented considerable improvements to the thermal and mechanical properties of PLA, andaccelerated the degradation of PLA and PLA/thermoplastic starch (TPS). This study also suggested that there ispotential for such materials to be used for film applications.

Keywords: Starch, Nanoclay, Polylactic acid, Biodegradability

Proceedings of the Asian Workshop on Polymer Processing Annual Conference ~ AWPP 2015 ~ December 01-04, 2015, Singapore