ORAL
CONTRIBUTIONSAsian Workshop on Polymer Processing, 6-9 November 2016

OC001

MORPHOLOGY AND PROPERTIES OF SILICONE RUBBER WITH
SUPERCRITICALCARBONDIOXEANDALTERNATING
MULTILAYERED CO-EXTRUTION
Zhang Fengshun1, Liu Tao1,2, Guo Shaoyun2
1

Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, China, 2The State Key
Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University,, Chengdu,
China
Introduction: The properties of silicone rubber foams are depended on the cell structure, such as cellmorphology, cell distribution and cell density. Moreover, the cell structure of foams is often determined by thefoaming conditions and processing methods. Nevertheless, the most cells in silicone rubber foams are uneven anddisordered in the two-dimensional or three-dimensional, meanwhile, it is difficult to obtain microcellular silicone
rubber foam with the conventional techniques.
Methods: In this work, processing conditions on the cell morphology of microcellular silicone rubber foams areinvestigated supercritical CO2. foaming technology in order to decrease the cell diameter and improve the cellstructure. And the silicone rubber foaming sheet is designed as alternating multilayered structure of foaming layerswith chemical bubbling method and film layers through the multilayer co-extrusion system.
Results: The silicone rubber foams with the cell diameter of 10 μm and cell density exceeding 108 cells/cm3 wereachieved by using supercritical CO2. The density of foam could be changed by adjusting the pre-crosslink degreeand saturation pressure. The foamed silicone rubber and unfoamed silicone rubber were designed as foaming
layers and film layers, respectively. The cell structure changed from spheres to rods and saucer shape, withincreasing layer number. The compressive response of the foaming silicone rubber showed anisotropic
characteristics, and the compressive performance of parallel to layer interface direction was better than that ofperpendicular direction.
Discussion: The preparation of silicone rubber foams with microcellular and multilayered structure provide anovel and convenient method for the functional elastomer foams.
Keywords: silicone rubber, foams, multilayered structure, supercritical CO2.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC002RHEOLOGICAL CONTROL AND 3D-PRINTING
RUBBER-BASED CELLULAR ARCHITECTURESOF

SILICON

Chengzhen Geng, Fengmei Yu, Ai Lu, Xiuli Zhao
Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, China
Introduction: Creating lightweight materials with desired mechanical properties has long been an engineering
pursuit, and the rise of three-dimensional (3D) printing techniques has made the fabrication of lightweight, porous
materials with tailored architectures not only possible but also feasible. A variety of cellular materials based onplastics, metals and ceramics with engineered mechanical responses (such as mechanically metamaterials) was
created, but 3D printing of cellular rubbers is still a challenge. Here, a 3D direct ink writing technique was adopted
to print a viscoelastic silicon rubber/nano silica system into orderly arranged sub-millimeter struts. Uniquecompressive stress-strain behaviours have been demonstrated in these specially designed cellular architectures.
Methods: The materials were purchased from Chongqing Polycomp International Corporation (China). They
were compounded at a given ratio using a Thinky planetary mixer for 15 min at 2000 rpm and centrifugated for
15 min at 2000 rpm for de-aeration. 3D printing was realized using a fluid dispenser (808GX, MUSASHI, Japan),which was programmed using a dispensing robot (shotmaster 350PC-GX, MUSASHI, Japan) with control
software. Rheological measurements were performed on an ARES-G2 stress-controlled rheometric system with aparallel-plate geometry. Mechanical properties were measured using a DMA RSA-G2 machine according to ISO
527-4.
Results: By controlling the size, content and interface of nano silica, the rheological behaviour of siliconrubber/nano silica composite could be tailored, and a viscoelastic system with a solid-like rheological behaviour(G’ >G”) at low oscillation stress and a liquid-like rheological behaviour (G” >G’) at high oscillation stress could
be obtained. At a stress higher than the crossover of G’ and G” in the dispensing nozzle, the liquid-like composite
could flow and be printed onto the substrate as a strut. On the substrate, the stress in the nozzle is released, andthe composite shows a solid-like behaviour without a change of its morphology, so the printed strut could be“solidified” on the substrate. In this way, the system is printable and 3D-printed silicon architectures could be
prepared. Typical structures and properties of the architectures are shown in Figure 1. Obviously, the architectures
could be greatly varied. By manipulating the architectures of the printed 3D patterns, materials with unique stressstrain behaviour, such as mechanically self-adapting materials with a reversible compressive strain softening
behaviour, and quasi-constant modulus materials with a linear compressive stress-strain behaviour, could beobtained.

Fig. 1 Typical structures and compressive properties of the printed cellular architectures.
Discussion: By tailoring the rheological behaviour of the liquid silicon rubber/nano silica system via filler network
control, cellular rubbers with specially designed architectures could be 3D-printed, and several kinds of materials
with unique mechanical responses were achieved. This work not only paves a feasible way to control the porous
structure of elastomers, but also suggests the ability to tailor mechanical properties of cellular materials via micropatterned design, which may find potential applications in emerging fields or replacement of traditional foams.
Keywords: 3D Printing, Elastomer, Cellular Solids, Stress-Strain Behaviour

Asian Workshop on Polymer Processing, 6-9 November 2016

OC003MECHANICAL PROPERTIES AND MORPHOLOGIES OF RECYCLEPC / RECYCLE-PET BRENDS FABRICATED BY HIGH-SHEARROTATIONAL PROCESSING
Akira Ishigami1, Shotaro Nishitsuji1, Tomokatsu Wagatsuma2, Hiroshi Ito1
1

Yamagata University, Yamagata, Japan, 2Aita shokai inc., Yamagata, Japan

Introduction: Currently, the recycling of plastic materials such as general-purpose resin and engineering plastics
has been carried out extensively. However, mechanical properties of plastic materials were gradually decreases
by repeating adds heat history on reuse. Therefore, it is often inexpensively provided to low grade products. On
the other hand, polymer blends and blends with various polymer materials have been studied to assess theirperformance, which transcends that of single polymers. Nevertheless, depending on the selected materials andtheir combinations, they can be immiscible. Sometimes, their physical properties become worse. In this study
aims to development of novel polymer blends used recycle PC and Recycle PET fabricated by high-shear
rotational processing.
Methods: Recycle-Polycarbonate (R-PC) was used (S3000; Aita shokai inc.) with recycle-poly (ethylene
terephthalate) (R-PET) (R-100; Aita shokai inc.) was used. The R-PC and R-PET blending ratio were 9:1, 8:2 and
7:3 (wt). We used a high-shear rotational processing machine (NHS2-28; Niigata Machine Tecno Co., Ltd.) for
melt mixing of the R-PC/R-PET blends. We conducted melt mixing at 280 °C. Screw rotation speeds were 0, 500,
1000, and 1500 rpm. The 0 rpm is low shear product by a single screw. Mixing times were 10 s and 30 s. After
high-shear processing, dumbbell specimens were molded using hot press machine. Thermal properties were
measured using a M-DSC (Q100; TA Instruments). Morphology was observed using a TEM (JEM2100F; JEOL
Ltd). Tensile tests were measured Strograph (VGS-E01; Toyo Seiki Seisaku-Sho Ltd.).
Results:
The results of M-DSC measurement were shown
respectively in Fig .1. TEM images of R-PC/R-PET = 7:3 were
portrayed in Fig .2. The stress-strain curves in tensile tests are depicted
in Fig .3.

Fig .1 M-DSC measurement results.

Fig .2 TEM image of R-PC/R-PET = 7:3(a) 0 rpm, (b) 1000 rpm/10 s.

Discussion: M-DSC measurement results confirmed that T c of R-PET
in R-PC/R-PET was shifted to the high temperature side and T m wasshifted to the low temperature side. The shift amount increases with
Fig .3 Tensile test results.
increased screw rotation speed. These results suggest that the R-PET
domains were dispersed similarly to islands in the R-PC matrix. They
were finely distributed by high shear processing. TEM images of RPC/R-PET = 7:3 shows the R-PET domain diameter in R-PC/R-PET was about 1um in the mixed condition of 0rpm. The R-PET domain under the mixing condition of 1000 rpm/10 s was not observed. As a result, it was foundthat the R-PC and R-PET were compatibilized. The stress-strain curves in tensile tests are depicted in Fig .3. The
R-PC/R-PET = 9:1 and 8:2 fabricated under mixed condition of 1000 rpm/10 s were lower breaking strain thanthat of neat R-PC. The R-PC/R-PET = 7:3 fabricated under mixed condition of 1000 rpm/10 s was higher breaking
strain than that of neat R-PC.
Keywords: Polymer blends, compatibilizing, High-shear rotational processing
Asian Workshop on Polymer Processing, 6-9 November 2016

OC004

CONTROL OF PHASE SEPARATION STRUCTURE IN POLYMERBLENDS FABRICATED BY HIGH-SHEAR PROCESS
Yuki Kodama, Akira Ishigami, Hiroshi Ito
Research Center for GREEN Materials and Advanced Processing (GMAP), Graduate School of Organic
Materials Science, Yamagata University, Yonezawa, Yamagata/Tohoku, Japan
Introduction In general, polymer blends are well known for using as functional materials in the various industrial
fields. However, demand for high performance of polymeric materials was dramatically increased which related
the research and innovation growth. The polymer alloy is the latest of the state of the art technology that greatly
extend the performance capabilities of polymer blends. In the fabrication method, the control of phase separationof the structures is necessary to realize.
The purpose of this research was focused on the control of polymer blend internal structures and also thedevelopment of the saving materials weight and low cost materials used. The polyamide6 (PA6) having a highmechanical property was blended with polypropylene (PP) having light weight and inexpensive using the novel
high speed rotational or high-shear process. The effect of viscosity ratios on internal structures and mechanicalproperty of the novel polymer alloy were investigated. The internal structure was controlled by rotational speed
and melt mixing time.
Methods
1.Materials The material used in this experiment are three PA6
grades are T852 (MFR:5 g/10 min) , T802 (MFR:26 g/10 min) andT840 (MFR:80 g/10min) (TOYOBO CO., Ltd) and three PP grades
are J105 (MFR:9 g/10 min), J108 (MFR:45 g/10 min) and S119
(MFR:60 g/10 min) (Prime Polymer CO., Ltd) and threecompatibilizing agents PP-g-MAH Yumex1010 (Sanyo Chemical
Industries, Ltd), Admer QE800 and Admer AT2606 (Mitsubishi
Chemical Co., Ltd). PA6/PP ratio 70/30 (w/w %) were used, thePP-g-MAH were added 5.0 w/w % of the blended resins.
2.Experiment High shear processing machine (NHSS2-28, Niigata
Machine Techno Co., Ltd.) were used for polymers blending
process. The design of the internal feedback screw is shown in
Fig.1.

Fig.1 Schematic diagram for screw used in
the high shear rotational mixer.
(a)

(b)

PP Domain
20µm

20µm

High-speed rotation (Max: 3,000 rpm) is a novel of molding
process using the extensional flow at the time of the feedback flowin the hole passage of internal mixing and screw for blending
technique. In this study, the blending temperature of 230 ºC,
rotation speed of 500 and 3,000 rpm, mixing time of 10 and 30 s.

(c)

The blended samples were molded using micro-injection molding
machine (AU3E-s, Nissei Plastic Industrial Co., Ltd.) and that were
followed by fabricating small dumbbell specimen (JIS7162 1BB).

Fig.2 The SEM images of (a) T840/J108(MFR=80:45), (b) T840/S119 (MFR=
80:60) and (c) T840/S119/Yumex 1010

Condition:500rpm/10s
2µm

3.Characterization The tensile test (Strograph VGS-E01, Toyo
Seiki Seisaku-sho, Ltd.) was carried out by tensile speed of 5
mm/min. The specimen internal structures were observed by using
SEM (TM1000, Hitachi High-Technologies Corp.).
Results and Discussion The results of the SEM images and tensile
test result of blending materials which obtained by high shearprocess were shown Fig.2 and Fig.3. By the results, it can be
confirmed PP domain size was decreased from about 20-40 µm to
10-20 µm by decreasing the PA6/PP MFR ratio 80:45 to 80:60 (SeeFig3. Tensile property of PA6, PP and
Fig. 2 (a, b)). Moreover, adding the PP-g-MAH obtained PP nanoPA6/PP bending materials.
domain less than 2 μm, it was indicated that PP-g-MAH promote
the fine dispersion as Figure 2 (c). The nano-dispersion of PP in
PA6 improve the elongation and toughness due to the uniform of phase structure lead the deformation difficulty.
Keyword: Polymer alloy, High-shear processing, Morphology
Asian Workshop on Polymer Processing, 6-9 November 2016

OC005EPOXY-ANHYDRID BASED THERMOSETS REINFORCED BY
INORGANIC NANOPARTCLES: EFFECTS ON SHELF-LIFETIME,THERMAL AND THERMO-MECHANICAL PROPERTIES
Andrea Johanna Wanner1, Andreas Moser2, Karin Wewerka3, Gerald Pinter2, Wolfgang Kern4,1
1

Polymer Competence Center Leoben, Leoben, Austria, 2Institute of materials science and testing of polymers,
Leoben, Austria, 3Institute for Electron Microscopy and Nanoanalysis (FELMI), Graz, Austria, 4Institute ofchemistry of polymeric materials, Leoben, Austria
The increasing use of nanoparticles as performance-enhancing fillers in resins for industrial applications has
stimulated research for the stable dispersion of nanoparticles in thermosets. The modification of the interface
between the particles and surrounding resin matrix is a key strategy to ensure compatibility of the particles withthe polymer matrix and to avoid aggregation of nanoparticles. However, surface modification of the nanoparticles
can have significant effects on the shelf lifetime of the resin as well as on the thermo-mechanical properties of the
final composite.
In this work, inorganic nanoparticles, in particular silica and aluminium oxide nanoparticles with different
functionalization of their surface were embedded in an epoxy/anhydride system and the impact on the stability
and the shelf life time of the non-cured resin was determined. Furthermore, investigations on the effect ofnanoparticles on thermo-mechanical as well as thermal properties and the curing kinetics of the thermoset were
performed.
Characterization of the non-cured system was done by rheological investigations and infrared spectroscopy. To
characterize the thermo-mechanical properties as well as the curing behavior different analytical methods, suchas differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and infrared spectroscopy were
employed. Moreover, electron microscopy images show the distribution of the modified nanofillers within thepolymer matrix.
The different properties of the nanocomposites compared to those of the neat resin can be correlated with thepresence of nanoparticles and interactions of the polymer with the dispersed particles. Noteworthy, the stability
and shelf lifetime of the nanodispersions are dominated by the interface. Differences in mechanical and thermal
properties become more pronounced with the addition of nanoparticles to the polymer matrix; this is due to thealtered curing behavior of the epoxy/anhydride resin upon addition of nanoparticles.
This research work was performed within the K-project “PolyComp” at the Polymer Competence Center LeobenGmbH (PCCL, Austria). Funding is provided by the Austrian Government and the State Government of Styria.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC006

MODIFIED SISAL FIBERS CARBON AS CATHODE MATERIALS FOR
LITHIUM-ION BATTERY
Aimiao Qin1,2, Rui Du1, Jianwu Sun1
1

Guilin University of Technology, Guilin/Guangxi, China, 2Guangxi Experiment Center of Information Science,
Guilin/Guangxi, China
Introduction: With the increasing of environment concerns and the development of electronic devices, there isa growing demands for the lithium ion batteries with high power and energy density. However, the graphitic
carbon which is widely used for the anode materials only have a theoretical specific capacity of 372 mAhg-1,
which can not meet the demands of high specific capacity lithium ion batteries. So it is necessary to develop green
and high specific capacity anode materials for lithium ion batteries.
Methods: A kind of microporous sisal fiber carbon (SFC) was prepared by carbonization of sisal fiber under
nitrogen protection at high temperature and then modified by hydrothermal method under different conditions.
The structure and morphology of the product were characterized by XRD, SEM and Raman spectra. The
electrochemical properties of the product were characterized by CV and constant current charge-discharge and soon. The hydrothermal modified conditions such as temperature, acid/alkaline agents and etc. on theelectrochemical properties of SFC were discussed.
Results: (1) Modified SFC with hydrothermal temperature at 140℃ had a significantly higher capacity than thatof other temperature, (2) SFC displayed higher capacity when hydrothermal modified in acid solution than indeionized water and alkaline system, (3) SFC modified in hydrothermal system exhibited a significant change inmicrostructure.
Discussion: Hydrothermal treatment is an effective method for SFC and other biomass carbons to improve theirelectrochemical performance.
Keywords: sisal fiber carbon; hydrothermal treatment; anode material; electrochemical performance

Asian Workshop on Polymer Processing, 6-9 November 2016

OC007ENGINEERING PLASTIC COMPOSITES REINFORCED BY NOVELHEATPROOF CELLULOSE NANO-FIBER
Takeshi SEMBA1, Kunio TAGUMA1, Masataka TAWARA1, Satoshi NISHIOKA1, Akihiro ITO1, Kazuo
KITAGWA1, Hiromasa KATAOKA2, Hiroyuki YANO3, Fumiaki NAKATSUBO3
1

Kyoto Municipal Institute of Industrial Technology and Culture, Kyoto city/Kyoto, Japan, 2Seiko PMC
Corporation, Tokyo city/Tokyo, Japan, 3Kyoto University, Uji city/Kyoto, Japan
Introduction: Cellulose nanofibers (CNFs) have many useful properties, including high strength and low thermal
expansion, and are also environmentally friendly, readily renewable, safe, and biodegradable. But theconventional CNF could not stand the heat while polymer processing such as melt compounding and injection
molding, especially in engineering plastic matrixes. Recently, novel chemical modified pulp endowed high heat
resistance, compatibility with thermoplastics and fibrillation ability while compounding was developed. In thisstudy the CNF reinforced engineering plastics which is impossible to materialize by conventional technology wasevaluated.
Methods: Thermogravimetric analysis (TGA) for chemical modified pulps, bending test for composites consistedof engineering plastics and the chemical modified pulps, and observation for cellulose fiber in engineering plastic
matrixes were done.
Results and discussion: The reduction temperature of 1wt% of the pulp from TGA was improved more than 50℃,
and the improvements was different according to degree of chemical treatment. Fig.1 shows bending modulus andstrength of the CNF/polyamide6 composites as a function of degree of hydroxyl group substitution (DS) incellulose. The maximum bending modulus of composites was 5400MPa which is 2.6times of neat PA6, and the
maximum bending strength was 160MPa which is more than 68MPa from neat PA6. Interestingly, the impact
strength of composites was same as neat PA6, although the composites exhibited high bending properties. Fig.2
shows SEM photograph of the CNF extracted from PA6 matrix by solvent extraction. The structured CNF in thebest composites was quite fine, long, and also network structure was observed. The size was from tens to hundredsof nano-meter. The nano and high aspect ratio fibers was formed while polymer processing owing to inhibit
cellulosic hydrogen bond by chemical treatment. And the CNF must contribute the high bending properties withkeeping impact strength.
Keywords: Cellulose, Nanofiber, Pulp, Chemical treatment.

Fig.1 Bending modulus and strength
as a function of DS.

Fig.2 SEM observation results of
CNF extracted from composites.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC008INTERFACIAL PROPERTIES OF LDPE/UHMWPE SINGLEPOLYMERCOMPOSITESPRODUCEDBY
EXTRUSIONCALENDERGING PROCESSJian Wang, Ziran Du
Beijing Institute of Technology, Beijing, China
Introduction: Single-polymer composites (SPCs), composed of the matrix and reinforcement with samechemical compositions, get the advantages of light weight, high specific strength, easy recyclability. The methodsof preparing SPCs have been reported such as the hot compaction, film stacking, powder impregnation, injection
molding, etc. However, the traditional processing methods were not easy to achieve continuous production ofindustry yet restricted the development of SPCs. In this research, a process of extrusion–calendering was used torealize continuous production of single-polymer composites (SPCs). Low density polyethylene (LDPE) was usedas the matrix, and ultra-high molecular weight polyethylene (UHMWPE) fabric was used as the reinforcement.
The effect of die temperature on the interlayer bonding strengths was mainly invesigated.
Methods: The UHMWPE fabric coated by LDPE melt in a specially designed die, and then they were moved out
and passed through the calender, the LDPE/UHMWPE SPCs could be finally prepared. The theoretic temperature
range of 145-160 °C was chosen. The interfacial properties of the SPCs were evaluated through T-peel
tests. Scanning electron microscopy was also used to determine the fiber-matrix interfacial adhesion and theeffects of different die temperatures.
Results and Discussion: Fig. 1 reveals that the interfacial strength increased with temperature raised. The 160°C achieving an average value of 22.4 N/10mm, but the consecutive T-peel test could not be performed thoroughly
in virtue of the sample breaking off in the middle. In Fig. 2, with the temperature raised, there is a surface
roughness increasing of the fabric where the fiber bundles shrink and become tight. Fig. 2a shows many fibrils
are attached to the fabric surface but fiber bundle maintains the original structure. From Fig. 2b, it is not easy toobservably distinguish the single filament since they almost were melted to form a whole, and there is a continuous
sheet layer of matrix in the gap of fiber bundles, which directly leads to the further improvement of the interlayer
bonding strength. As the surface has been badly damaged (in Fig. 2c) so that the vestiges left after stripping nearlythroughout the entirely surface of fabric, such a strong bonding seriously impeded the T-peel testing.

aFig. 1 Peel load as a function of die temperaturesbcFig. 2 Peel fracture surfaces of specimens manufactured at (a, b)
150 °C, (c)160 °C.

Keywords: low density polyethylene (LDPE); ultra-high molecular weight polyethylene (UHMWPE); singlepolymer composites (SPCs); extrusion; calendaring

Asian Workshop on Polymer Processing, 6-9 November 2016

OC009AN IMPROVEMENT OF GAS TRANSMISSION RATE OF PLA BY
STEREOCOMPLEXATION OF PLLA/PDLA-PEG-PDLA
Suthawan Buchatip, Atitsa Petchsuk
National Metal and Materials Technology Center, Pathum Thani, Thailand
In this research, we improved the gas transmission rate of PLA by adding modified microporous or hydrophilicmaterials such as polyethylene glycol block copolymer. PDLA-PEG-PDLA triblock copolymer was prepared via
ring-opening polymerization in bulk process using tin octoate as a catalyst. Poly(ethylene glycol) with number
average molecular weight of 2000 and 6000 g/mol were used as macro-initiator. Two compositions of lactyl unit
(L): oxyethylene (EO) including 2:1 and 5:1 were prepared. Stereocomplexes of PDLA-PEG-PDLA and PLLA
were prepared by using twin screw extruder at 180C and fabricated into tubing with thickness of 30 µm in orderto improve gas permeability and mechanical properties.
Gas transmission rate results showed that an addition of triblock copolymer with various PDLA/PEG ratios could
significantly enhance the O2 and CO2 permeability of polymer film. This was probably due to hydrophilicity of
the PEG facilitated the permeability of those gases. Tensile strength and modulus of PLLA/PDLA-PEG6000(2:1)PDLA stereocomplexe were 21% and 4% higher than PLLA with porous material, respectively. Elongation atbreak of all stereocomplex was slightly higher than that of PLLA and PLLA with porous material. These
stereocomplex films can potentially be used as fruit bag for mangos’ quality enhancement during growth.
Keywords: triblock copolymer, gas permeability, stereocomplex

Asian Workshop on Polymer Processing, 6-9 November 2016

OC010AN ADVANCED PREPARATION AND CHARACTERIZATION OF THE
PET NANOCOMPOSITES WITH VARIOUS ORGANOMODIFIED LDH
AS CATALYSTS
Naveen Bunekar1,3, Tsung Yen Tsai1,2
1Department of Chemistry Chung Yuan Christian University, Chung Li, Taoyuan, Taiwan, 2Master program in
Nanotechnology Chung Yuan Christian University, Chung Li, Taoyuan, Taiwan, 3Center for Nanotechnology
Chung Yuan Christian University, Chung Li, Taoyuan, Taiwan
Various polyethylene terephthalate (PET)/ sulfanilic acid salt-modified layered double hydroxide (LDH-SAS)
nanocomposites were prepared via in situ interlayer polymerization of bis-hydroxy ethylene terephthalate(BHET). Hydrothermally synthesized modified LDH applied for nanocomposite synthesis. The preparedorganomodified LDHs were characterized by different methods, including X-ray diffraction, differential scanningcalorimetry, thermogravimetric analysis, and particle size analysis. After that in situ synthesized PET/LDH-SAS
nanocompsites were characterized by diverse methods, including X-ray diffraction, transmission electronic
microscope, thermogravimetric analysis, intrinsic viscosity measurements. The results of the study revealed that
the PET/LDH-SAS nanocomposites possess a better state of nanolayer dispersion, thus making it easier for theoligomer to enter the gallery of LDH-SAS layers. Thus, the polymer chains can be included between the LDHs
layers during the polymerization of the polymer matrix. The gas barrier, mechanical properties, as well as better
thermal properties as compared with the pristine PET. Moreover, the PET/LDH-SAS nanocomposites showed
higher crystallization temperature, degree of crystallinity, and maximum degradation temperature than that of thepristine PET.
Keywords: Polyethylene terephthalate, Layered double hydroxide, Polycondensation, Hydrothermal,
Nanocompsites.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC011PRECURSOR DEVELOPMENT FOR HIGH PERFORMANCE AND
LOW COST CARBON FIBRESJackie Cai
CSIRO, Geelong, Victoria, Australia
Introduction:
Carbon fibre (CF) is currently undergoing a global renaissance, due to a new range of applications for CF,
particularly for the automotive, aerospace and wind energy sectors, and due to the high growth rate in capacity
anticipated over the next ten years. The key technical issues that need to be addressed at present are improving
the fibre quality and performance, and reducing production cost. It is widely recognised that CF precursor
composition and quality determine the ultimate performance of carbon fibres, and also have a significant impact
on processing properties and production cost. Polyacrylonitrile (PAN) based precusor is by far the predominantprecursor material used globally for commercial production of CF. Our research has therefore focused on thedevelopment of new generation of PAN based precursors to address the outstanding quality, performance and costissues. This presentation reports on the most recent precursor development at CSIRO, which involves a welldefined PAN precursor with a high molecular weight and low polydispersity index for improved CF performanceand quality, and a new PAN copolymer that enables low cost processing of quality CF.
Methods: Well-defined PAN precursor polymers with a high molecular weight and low polydispersity index
were prepared in a pilot scale by RAFT polymerisation. They were then processed into the precursor fibres bysolution spinning in organic and inorganic solvent systems respectively. A new PAN copolymer containing abifunctional comonomer component was also developed for low cost CF processing. These precursor polymers
and fibres were characterized. Comparative studies were also carried out for assessing the properties andperformance of the new precursors against their conventional controls.
Results:Comprehensive characterisation results on the new precursor polymers and fibres will be presented, andcompared with those of the conventional control polymers and fibres.
Discussion: New and advanced carbon fibre precursors were developed and evaluated. The results of this study
demonstrated significant advantages of the new precursors over the conventional controls in terms of theirprocessing properties, fibre quality and/or cost benefits.
Keywords: carbon fibre, precursor, polyacrylonitrile, RAFT, comonomer

Asian Workshop on Polymer Processing, 6-9 November 2016

OC012TERPENE BASED CHEMICALS: (1) BIO-AROMATICS TO PRODUCEKNOWN MONOMERS -UTILISING PYROLYSIS AND (2)FUNCTIONALMONOMERSFORIMPROVEDPOLYMERPERFORMANCE
Mike O'Shea1, Benjiman Leita1, Adam Meyer1, Nicholas Ebdon1, Asitha Balachandra1, Heng Taing1, James
Mardel1, Birgit Unterweger2, Geoff Dumsday1
1

CSIRO, Vic, Australia, 2Monash University, Vic, Australia

Introduction: Valuable chemicals and polymers modifiers have been produced utilising the cyclic terpenes
feedstock's provided by nature. These terpenes (pinene and cineole) have been sourced from woody biomass(pine and eucalypt) sources. We have been able to utilise efficient pyrolysis and downstream chemical conversion
to produce a range of aromatic chemicals including 100% Bio-PET. We have also utilised chemical andbiocatalysis (fermentation) to produce functional monomers that have been used as modifying monomers for
known polymers or to produce novel polymers. Applications for the functional terpene include coatings, resins,
plasticisers and engineering polymers with improved mechanical, thermal properties etc
Methods: To produce the Bio-Aromatics we have used gas pyrolysis aided by the use of metal doped gamma
alumina catalysts. This predominately produced p-cymene. The p-cymene has been oxidised to produce
terephthalic acid which has in turn be used to produce Bio-PET. For the functional terpenes we converted alphapinene to produce 2,6 dihydroxy cineole (DHC). This monomer has been utilised in a range of different polymers:
Polyesters (PET), Polyurethanes, polycarbonate, high temperature acrylics and to produce plasticisers for PVC
Results and Discussion: Bio-Aromatics: p-cymene intermediate “aromatic platform chemical” was produced
from a range of terpene feedstocks (including mixed feeds). Conversion of cineole to p-cymene has been achieved
at 95%+ conversion and 100% selectivity. From the p-cymene we have been able to produce good quality 100%
Bio-PET ( utilising MEG produced from sugar).
Functional Terpene Monomers: DHC modified PET with improved thermal properties ( Tg> 150C whenreplacing MEG with DHC) has been produced. This could have applications in stiffness and hot fill properties
for PET based container applications. Fatty acid esters of DHC as plasticisers for PVC have shown to perform
as well as DEHP/ DOP ( Di-Octyl phthalate:which is under considerable regulatory pressure) DHC and relatedmonomers have been attached to methacrylic acid. The resultant polymers we shown to be tough, clear andscratch resistant with improved thermal properties ( Tg ! 160C and Tm ~ 295C)
Keywords: Renewable Feedstock’s, Sustainability, Biomass, Terpene, Cineole, PET, Polyester, PVC,
Polycarbonate, Polyurethane

Asian Workshop on Polymer Processing, 6-9 November 2016

OC013

POLY (MELAMINE-FORMALDEHYDE) MICROCAPSULESSELF HEALING POLYMER COMPOSITESFORSHILPI SHARMA, VEENA CHOUDHARY, LEENA NEBHANIINDIAN INSTITUTE OF TECHNOLOGY (IIT), DELHI, India
In the development of self healing composite through microencapsulation approach, control of capsules shell wall
thickness is a key issue because it influences the self healing performance due to following reasons - themicrocapsules walls must be resistant to diffuse out of healing agent, capsules with thin walls may leads to lossof core material during storage and causes difficulties in handling during processing of the composites. In thisarticle, we investigated systematically the effect of melamine to formaldehyde ratio taken in the initial feed on theencapsulation efficiency, core content, shell wall morphology, the mean particle size distribution and thermal
stability of the microcapsules. Epoxy loaded poly (melamine-formaldehyde) (PMF) microcapsules were preparedby in-situ polymerization using emulsion technique. Structural (FTIR and 1H-NMR), morphological (OM andSEM), particle size distribution and thermal (TGA & DSC) characterization was done to investigate the effect ofmelamine to formaldehyde ratio on the microcapsules. Free flowing; white coloured, odourless microcapsuleswith density 1.202 g/cm3 were obtained by in situ polymerization. Encapsulation efficiency decreased as theformaldehyde content increased. FTIR and 1H-NMR spectra showed the presence of epoxy as a core material.
OM & SEM micrographs showed that the capsules are almost spherical with a perfect periphery, but have atendency to agglomerate. OM & SEM showed that the capsules synthesized with a lower formaldehyde amountpossess the rough, porous and uneven morphology Both OM and SEM analysis revealed that with increasing
formaldehyde content the thickness of shell wall increases. Particle size distributions of microcapsules were foundin the range of 0.1 to 1000 μm. The mean particle size distribution of microcapsules decreases (from 83-66 µm)
as the formaldehyde ratio increases. Thermal analysis showed that the capsules were thermally stable up to 300°
C. Thermal stability increased as the ratio of melamine to formaldehyde increases.

Optimized microcapsules
Keywords: microcapsule, epoxy resins, poly (melamine-formaldehyde) (PMF)

Asian Workshop on Polymer Processing, 6-9 November 2016

OC014NOVEL
THERMOPLASTIC
CELLULOSEDERIVATIVES:STRUCTURAL DESIGN, SYNTHESIS, AND PROPERTIES
Zhangyan Chen1,2, Jinming Zhang1, Jun Zhang1,21Institute of Chemistry, Chinese Academy of Sciences (ICCAS), Beijing, China, 2University of Chinese Academyof Sciences, Beijing, China
Melting processing of cellulose is of special interest, however, it still remains a great challenge, because cellulose
has extensive hydrogen-bonded and partially crystallized structure that makes it not melt-processible. Graft
copolymerization is a practical way to alter the physical and chemical properties of cellulose. We developed aneffective method for grafting L-lactide (LLA) from unmodified cellulose by ring-opening polymerization underhomogeneous conditions. By using 4-dimethylaminopyridine (DMAP) as an organic catalyst, cellulose-graftpoly(L-lactide) (cellulose-g-PLLA) copolymers with a molar substitution of PLLA (MSPLLA) in a range of 0.9912.28 were successfully synthesized in an ionic liquid, 1-allyl-3-methylimidazolium chloride (AmimCl). The
amount and length of grafted PLLA chains in cellulose-g-PLLA copolymers could be well controlled by adjusting
the molar ratios of LLA monomer to cellulose. When content of grafted PLA in copolymers is above 60wt%, thecellulose-g-PLLA copolymers exhibited thermoplastic behaviour, indicating the intermolecular andintramolecular hydrogen bonds in cellulose molecules had been effectively destroyed. By using a conventional
thermal processing method, fibers and disks of cellulose-g-PLLA copolymers were successfully prepared. Using
AmimCl as the reaction media, we also synthesized cellulose acetate-graft-PLLA (CA-g-PLLA) and cellulose
propionate-graft-PLLA (CP-g-PLLA) copolymers by first acylation of cellulose with corresponding acylation
reagents, and followed by ring-opening polymerization of LLA monomer initiated from residual hydroxyl groups
in cellulose esters. These two copolymers with proper substituted acyl group content and amount and length ofgrafted PLLA chains also exhibited thermoplastic behaviour.
Using ionic liquids as the reaction media, we also synthesized a series of novel cellulose esters. The effect of
substituents on thermal properties of cellulose derivatives was studied. Compared to cellulose and cellulose
acetate, cellulose esters with bulky substituents showed clear glass transition temperatures (T g) and flowing
temperature (Tf). Introducing both soft segment and bulky substitutes might further decrease T g and Tf of cellulose
esters. Therefore, homogeneous cellulose esterification in ionic liquids is an alternative practical way to synthesize
thermoplastic cellulose derivatives.
Keywords: Cellulose, Ionic liquids, Cellulose graft copolymers, Cellulose esters, Thermoplastic

Asian Workshop on Polymer Processing, 6-9 November 2016

OC015MECHANICAL PROPERTIES OF PEANUT HUSK COMPOSITE
MATERIAL USING INJECTION MOLDING
Kento Iwasawa1, Yoshihisa Sumita2, Susumu Takahashi1, Masahiro Hosoya3, Kiyoshi Shinoda3, Sivanantham
Aravindan4, Janakarajan Ramkumar5
1

Nihon Unuversity, Narashino, Chiba, Japan, 2Hinode Resin Industry Co., Ltd, Kawagoe-shi, Saitama, Japan,
Chiba Industrial Technology Research Institute, Chiba-shi, Chiba, Japan, 4IIT Delhi, Hauz Khas, New Delhi,
India, 5IIT Kanpur, Kanpur, Uttar Pradesh, India
3

Introduction: It is important to use biomaterials for reducing environmental impact. Peanuts are one of the mostpopular nuts in the world. The peanut husks are removed to get peanuts. The most husks are discarded as anindustrial waste. In this paper, the composite materials using peanuts husks and polypropylene (PP) weredeveloped. Higher mass content of peanut husks in the material can reduce the mass of PP. It means that the costof products can be reduced by increasing the content of peanut husks. The mechanical properties of the material
were investigated.
Methods: The pellets of peanut husk powder and PP were produced by using a kneading machine and an
extruder. The size of the powder is between 0.25~0.5mm and less them 0.25mm. Hydrogenated styrenic
thermoplastic elastomer was used as additive to increase adhesive property. The mass content of peanut husk wasvaried from 0% to 30%. The pellets were applied to from specimen using injection molding. The tensile andbending tests were performed to evaluate mechanical properties. The test speed was 5mm/min performed in room
temperature.
Results: Tensile strength, elongation and Young’s modulus are investigated from the results of tensile tests.
Fig.1 show the results of tensile test. Bending strength and bending modulus are examined from the results ofbending test. Tensile strength is increased with decreasing the content of peanut husks. Elongation is increased
with decreasing the contents of peanut husks. Elongation is increased by additives. Bending strength is increased
with decreasing the content of peanut husks. Bending modulus is increased with increasing the content of peanuthusks.
Discussion: Because of high rigidity of peanut husks comparing to PP, Young’s modulus of the composite
material is higher than that of PP. More investigation is required to find the reason of decreasing tensile strengthand elongation with increasing the content of husks.

70
60
50
40
30
20
10
0

Tensile strength
Young's modulus

2.1
1.8
1.5
1.2
0.9
0.6
0.3
0

Young's modulus[GPa]Tensile strength [MPa]

Keywords: Peanut husk, Injection molding, Composite material, Biomass

Test pieces
Fig.1 The results of tensile test

Asian Workshop on Polymer Processing, 6-9 November 2016

OC016TRNSPARENT CONDUCTIVE MATERIALS PREPARED BY POLY(3,4ETHYLENEDIOXYTHIOPHENE) DOPED WITH POLY(STYRENESULFONIC ACID) (PEDOT:PSS) AND BISPHENOL COMPOUNDS AS A
SECONDARY DOPANT
Shigeji Konagaya1, Yoshiichi Tawara2, Hiroko Furuhashi3, Mariko Terada3, Mai Inoue3, Tsukasa Torimoto3
1

Nagoya Industrial Science Research Institute, Nagoya, Aichi, Japan, 2Asahi Yukizai co. ltd., Nagoya, Aichi,
Japan, 3Nagoya University, Nagoya, Aichi, Japan
Introduction: Indium tin oxide (ITO) has been used as a transparent conductive material since it has highconductivity and high transparency. Nevertheless ITO involves some problems such as poor mechanicalflexibility, indium scarcity and high production cost. So a novel conductive transparent material is now required
as a replacement for ITO. Many researchers have studied new transparent conductive materials such as conductive
polymers, metal nanowires, and nano-carbons such as carbon nanotube and graphene. Among them conductive
polymer PEDOT:PSS has been attracting considerable attention, since it has a high conductivity and transparency
when it is coated as a thin film. However it has not conductivity enough to be replaced for ITO. Recently lots ofsecondary dopants such as ethylene glycol, DMF and DMSO have been proposed and applied to PEDOT:PSS
films for the conductivity enhancement. The authors have been studying the effect of bisphenol compounds onthe conductivity enhancement of PEDOT:PSS and the development of transparent conductive materials withhigher conductivity and transparency than ITO.
Methods: PEDOT:PSS and a bisphenol compound such as 4,4’-dihydroxydiphenylsulfone (BPSO), 4,4’dihdroxydiphenylsulfide (BPS), 4,4’-dihydroxydiphenylether (BPO), 2,4’-dihydroxydiphenylsulfone (24-BPSO)
were dissolved in the iso-propanol/water mixture (75/25(w/w)). The product solution was coated on the glass plateand dried on the hot plate (100℃, 0.5 hr). The surface resistivity (Rs) of the thin films was evaluated with thefour-point probe device and the volume resistivity (ρ) was calculated from Rs value and the film thickness.
Results: It was found that there was a large difference in the conductivity enhancement effect among the speciesof bisphenol compounds. The addition of BPSO or 24-BPSO contributed to the conductivity enhancement of
PEDOT:PSS, while BPO and BPS showed no conductivity enhancement effect on PEDOT:PSS, but increase ofits ρ value. The authors succeeded in the development of transparent conductive materials with superior
performance (Rs: 152 Ω/□, Transmittance(550nm): 88%) to ITO from the composites of PEDOT:PSS, BPSO,
other additives and polymer binders.
Discussion: Bisphenol compounds such as BPSO and 24BPSO contribute to the conductivity enhancement of
PEDOT:PSS, which is possibly attributable to their good solubility and higher acidity. Conductive films withsuperior conductivity and transparency to ITO films has been developed from the composites of PEDOT:PSS,
BPSO and polymer binders.
Keywords: PEDOT:PSS, ITO, bisphenol, conductivity, transparency

Asian Workshop on Polymer Processing, 6-9 November 2016

OC017

HIGH-PERFORMANCECOBALT-BASEDHETEROGENEOUS
ELECTROCATALYSTS SYNTHETIZED BY ELECTROSPINNING
Yuee Miao, Tianxi Liu
Donghua University, Shanghai, China
Introduction: The increasing demand for clean and sustainable energy has inspired extensive exploration ofadvanced energy conversion and storage systems with high efficiency, low cost and environmental benignity,
such as supercapacitors, lithium-ion batteries, fuel cells, and metal-air batteries. Nevertheless, the sluggish kineticsof oxygen reduction reaction (ORR) on the cathode side definitely limits the successful commercialization of highefficiency fuel cells and metal-air batteries. Pt-based materials have been considered as the most active noble
metal ORR electrocatalysts, but largely constrained in practical applications due to their scarcity, poor durability
and severe crossover effects. Therefore, non-precious metal-based and even metal-free electrocatalysts are newly
emerging as promising candidates for high-performance fuel cell and metal-air battery applications.
Methods: The self-standing membrane of nitrogen-doped carbon nanofibers (NCNF) has been prepared by the
combination of electrospinning, in-situ polymerization and high-temperature carbonization processes. Then,nanocubic-Co3O4 coated NCNF composite membranes were prepared by a one-step hydrothermal reaction at 150ºC for 3 h. For comparison, Co3O4 powder without the NCNF fiber membrane template was hydrothermally
prepared under the same condition.
Results: Under an initial aniline concentration of 0.02 M, nitrogen-doped CNFs (denoted as NCNF-0.02) are
obtained, which exhibit an increased fiber diameter of about 215 nm with uniformly distributed needle-like
nanoparticles on the fiber surface. After hydrothermal reaction, nanocubic-Co3O4 particles with a mean size of
20-30 nm are uniformly distributed on the surface of NCNF-0.02 at a proper concentration of Co(OAc)2•4H2O,
forming NCNF-0.02@Co3O4-0.2 composite fibers with an obvious coaxial structure. Electrochemical test
indicates that pure Co3O4 powder exhibits rather poor current response toward ORR with the Epeak potential at0.37 V. In contrast, CNF fiber membrane with intertwined conductive network structure exhibits higher current
response with an obvious Epeak potential at -0.35 V. Moreover, introducing nitrogen doping in NCNF-0.02 fiber
membrane results in more positive Epeak potential (0.24 V) with largely increased current density. When Co 3O4
is incorporated under a low initial molar weight (0.05 mmol) of Co(OAc) 2, nanocubic-Co3O4 particles with a mean
size of 100 nm are sparsely scattered on NCNF-0.02 fiber membrane, resulting in slight positive shift of the Epeak
potential (0.21 V). With the molar weight further increased to 0.2 mmol, Co 3O4 nanoparticles with smaller sizeof about 20-30 nm are uniformly distributed on NCNF-0.02 fiber surface, thus leading to more positive Epeak
potential (0.18 V) with higher current density, which outperforms most of the previously reported Co/carbon
based catalysts.
Discussion: The novel self-standing membrane of nitrogen-doped carbon nanofibers (NCNF) has been developed,
acting as a three-dimensionally networked and conductive template for immobilization of electrochemically active
Co3O4 particles. Thus, nanocubic-Co3O4 coated NCNF (NCNF@Co3O4) composite fiber membrane withhierarchical structures is obtained, which subtly combines the synergistic effects between the electroactive
nanocubic-Co3O4, efficient surface nitrogen doping and highly conductive NCNF network. Therefore, the
NCNF@Co3O4 composite exhibits excellent catalytic activity toward oxygen reduction reactions with positive
Epeak potential, high current density and superior durability over the commercial Pt/C catalyst, being a promising
noble metal-free catalyst for practical fuel cell applications.
Keywords: Electrospinning, Nanocomposites, Electrocatalysts

Asian Workshop on Polymer Processing, 6-9 November 2016

OC018OVER-MOLDED CONTINUOUS WOVEN JUTE/POLYLACTIDE ECOCOMPOSITES
Abdulmounem Elcheck wis, Guralp Ozkoc
Kocaeli University Department of Chemical Engineering, Kocaeli, Turkey
Introduction: In recent years, the use of natural products, such as natural fibres and polymers, has gained attention
in industrial applications due to their low environmental impact. The growth of natural material applications has
contributed to the reduction of CO2 emission. The best match to obtain ecologically friendly composite materials
is the combination of natural fibres with a biodegradable matrix. Poly(lactic acid), a biodegradable, renewable,
linear aliphatic polyester, is widely used to produce biodegradable composite materials. A new thermoplastic
composite technology so called “organic hybrid composites” holds promise to obtain lightweight structuralcomposite components for automotive parts. In this process, a thermoplastic carbon or glass continuous fibre
composite reinforcing sheet is over-moulded using matrix polymer in an injection moulding process. By inspiringfrom that new technology, it is aimed in this study is to process novel continuous jute fibre reinforced overmoulded polylactide composites.
Methods: Continuous jute fibre/PLA composite layers were prepared via film stacking method in a hot press.
The fibre orientation was varied as 0, 45 and 90. The properties of these continuous fibre reinforced layers
were determined via mechanical tests and scanning electron microscopy (SEM). The best combination wasdetermined to use as reinforcing layer for over-moulded composite (OMC) manufacturing. The OMCs wereprepared using an Xplore laboratory injection-moulding device. The mechanical, thermo-mechanical andmorphological properties were investigated.
Results: Mechanical tests showed that the best properties for reinforcing jute/PLA layers was obtained when 45
orientation was used, therefore this construction was used to produce OMCs. The mechanical tests showed thatflexural modulus and strength of OMCs was improved in comparison to neat PLA nearly without altering thedensity. The DMA results showed that the thermo-mechanical resistance of PLA was enhanced. SEM pictures
showed that the jute/PLA interphase needs to be improved to further increase the properties.
Discussion: It was successfully demonstrated that all-ecological continuous natural fibre reinforced overmoulded PLA composites were processed. The one of the biggest advantage of this novel technique is the increaseof mechanical properties of PLA without altering the density.
Keywords: polylactide, jute fiber, composites, over-molding, mechanical properties, thermomechanicalproperties

Asian Workshop on Polymer Processing, 6-9 November 2016

OC019DESIGN AND FABRICATIONS OF FUNCTIONAL NANOFIBERS AND
NANOFIBROUS
MEMBRANESFORENVIRONMENTANDHEALTHCARE: CHALLENGES AND OPPORTUNITIESAutchara Pangon, Nakarin Subjalearndee, Bunnakorn Suntamit, Nipon Phanomkate,Varol Intasantapresented by Wannee Chinsirikul
Nano Functional Textile Laboratory, National Nanotechnology Center, National Science and Technology
Development Agency, Thailand
Introduction: This presentation aims to address research capabilities of Nano Functional Textile laboratory at
National Nanotechnology Center (NANOTEC), Thailand by highlighting on-going research on nanofiber
fabrication and potential applications. Based on nanomaterials and polymer processing technology, three defined
research schemes spanning across the value chain of textile industries are nanofunctional finishing processes,
microfiber fabrications and nanofibrous membranes.
Methods: Syntheses, modification, characterizations and processing of multifunctional nanofibers andnanofibrous membranes of PVA based polymers were investigated. First example involves water-based
multicomponent solutions containing polymer, UV resistant, antibacterial and water repellent agents. Preparedpolymer was electrospun into nanofiber by Nanospider machine. Filtration property of the developed nanofibrous
membranes against airborne Tuberculosis (TB) bacteria were studied. Second example is fabrication of chitosan
nanofibers through electrospinning. Multicarboxylic acids, as environmentally friendly crosslinkers, were selected
and used in chitosan electrospinning for fine-tuning physicochemical properties of the nanofibers.
Results: For the nanofibrous PVA based membranes, unique interplay among the functional components anddeveloped structure of the multifunctional nanofibers led to mechanical-robust, flexible and water-resistantmaterials with flow-through capacity and size-selectivity towards TB bacteria. In the case of crosslinked waterbased chitosan nanofibers, it was found that nanofibers could be effectively developed from solution
electrospinning of chitosan/chitin whisker composite in non-toxic solvent system. The study on osteoblast cellbiocompatibility revealed a potential use of these nanofibrous chitosans for tissue engineering scaffolds.
Discussion: Key findings of our developed PVA and chitosan nanofibers and/or nanofibrous membranes basedon material-process-structure-property relationships will be discussed. Efforts in linking these functional
nanomaterials into applications, such as nanofiltration for counteracting the airborne Tuberculosis bacteria andmaterial for tissue engineering scaffolds, will also be covered.
Keywords: nanofibers, nanofibrous membranes, multifunction.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC020

PREPARATION AND PROPERTIES OF ULTRA HIGH MOLECULARWEIGHT POLYETHYLENE FIBER VIA DRY SPINNING
Xinwei WANG1,2, Yongfei SUN1,2, Han ZHENG1,2, Yumei ZHANG1,2, Xiangyang WU1,2
1

Shanghai Research Institute of Chemical Industry, Shanghai, China, 2State Key Laboratory of Polyolefins andCatalysis, Shanghai, China
Introduction: Ultra High Molecular Weight Polyethylene (UHMWPE) fiber is well known as one of highperformance fibers together with carbon fiber and Kevlar. Currently, two routes are applied in UHMWPE fibers
production. Decalin is used as solvent in dry route, while mineral oil is used in wet route. Comparing to wet route,
dry route has advantages of short process, fast spinning, good product quality, directly recycled solvent andenvironment friendly. Wet route is widely researched in labs, on the other hand, research of dry route is relatively
scarcity.
Methods: In this paper, high-performance UHMWPE fibers with 4 million molecular weight were prepared byadvanced dry route pilot line, which was designed independently by Shanghai Research Institute of Chemical
Industry (SRICI). The mechanical properties, thermal properties and microstructure of UHMWPE fibers withdifferent draw ratio were characterized by electronic testing machine, SEM and DSC.
Results: Fig.2 showed that crystallinity degree of UHMWPE fibers increased from 49.57 percent to 72.17 percent
with increasing drawing ratio. Comparing to as-spun fiber, well-drawn fiber’s breaking strength increased from
2.35 cN/dtex to 31.53 cN/dtex, as well as 15.68 cN/dtex to 1054.78 cN/dtex improvement in breaking modulus(As shown in Fig.3).

Fig.1 Flowchart of UHMWPE fiber production by Dry Spinning (SRICI) Fig.2 DSC graph of different fibers
draw ratio
Fig.3 Mechanical properties of different fibers draw ratio
Discussion: In the process, the disorder macromolecular chains was straightened, and amorphous regions turned
into crystalline regions gradually, which resulted in well-ordered and compact micro-structure. Highly crystallized
fiber showed better mechanical performance because uniform chains required more energy to break.
Keywords: Ultra High Molecular Weight Polyethylene fiber, dry spinning process, draw ratio, crystallization,mechanical performance

Asian Workshop on Polymer Processing, 6-9 November 2016

OC021Visualization Analysis of Asymmetric Fountain Flow Phenomena by
Dynamic Observation of Melt Front Behaviors
JINGRU GUO, HIDETOSHI YOKOI
the University of Tokyo, Tokyo, Japan
Introduction: In the injection molding of fiber reinforced resins, inappropriate fiber behavior and fiber orientation
characteristics during the mold filling process are known to cause deterioration of the surface properties of molded
products and reduction of the mechanical strength of the molded products. In this study, we observed the melt
front behaviors of long glass fiber reinforced resin in the flow front area, and clarified the relationship between
the fiber content and mechanism of asymmetric fountain flow (FF) phenomenon.
Methods: We mounted a high-speed camera to a driving unit to observe the gate side from the open end of themold cavity and videoed the FF at 500 frames per second while moving the camera according to the flow rate of
the resin. Based on the obtained images, we measured the moving speed and movement trajectory of the FF tracer
for each content (Refer to Fig.1).
Results: We found that the FF in the case of resins with the fiber content ratio of 0wt% is always symmetrical.
However, as the fiber content increased, FF gradually transitioned from symmetrical to asymmetrical, and became
asymmetrical for the first time when the fiber content ratio was 3wt% or above. There were no significant changes
in the mode of the FF above 30wt% (Refer to Fig.2).
Discussion: We believe that the mechanism by which the melt front behavior changes according to the fiber
content is due to the inconsistencies of the fiber length and fiber distribution. Fibers longer than the cavity plate
thickness extend so that they cross both the cavities at the stationary side and movable side of the mold diagonally.
Then, at the next moment, they are retrained at one side of both cavity walls (e.g. A) and are pulled back. Whenthe amount of fiber increases, it causes the fibers to entangle, resulting in the swinging phenomenon of the entire
front part of the flow front and the continuous generation of asymmetrical FF (Refer to Fig.3)
Keywords: Injection molding, Long-fiber reinforced PP, Asymmetric fountain flow, Visualization, Flow front

Asian Workshop on Polymer Processing, 6-9 November 2016

OC022

DIRECT JOINING OF INJECTION MOLDED POLYMER ON
ABRASIVE BLASTED METAL: INVESTIGATION OF MOLDING
CONDITIONS
Fuminobu Kimura1, Yuta Tamura1, Eiji Yamaguchi2, Yusuke Kajihara1
1

The Universty of Tokyo, Tokyo, Japan, 2SINTOKOGIO, Toyokawa, Japan

Introduction: Injection molded plastic can be directly joined with a metal of which surface is roughened (finestructured) in advance. This process is injection molded direct joining (IMDJ). We focused on abrasive blasting
to roughen the surface of the metal. The IMDJ using the abrasive blasting (blasting-IMDJ) is a promisingproduction technology since it can be easily introduced for industrial lines. It is, however, difficult to apply theblasting-IMDJ to the real industry in current state. The blasting-IMDJ has not been well investigated and thus
does not hold an enough reliability for the applications. To improve the reliability, this study reports investigationsof relationships between molding conditions and joining strength.
Methods: To investigate effects of molding conditions, we produced single lap-joint samples (A5052 aluminumalloy/polybutylene terephthalate) under varied molding conditions. Note that blasting conditions were fixed (Blast
media: alumina grain, #150 (100 μm). Size of resultant surface fine-structures: tens μm). In this study, we focusedon three parameters of the molding conditions; polymer temperature, injection speed, and cavity pressure. Eachcondition was controlled separately to avoid interference of the conditions. Since the cavity pressure cannot be
controlled directly by the molding machine and can be affected by the polymer temperature, the injection speed,
and injection volume, we adjust the injection volume to let the pressure be desired values. The joining samples
were evaluated by a tensile-shear test to measure the strength of the joining.
Results: The values of the conditions except cavity pressure had positive correlations with the joining strength inlimited ranges. In the investigated range of the polymer temperature, peak strength was obtained at 270°C. If thetemperature was higher than this value, the strength decreased. For the injection speed, the strength was saturated
over the speed of 100 mm/s. Although these two conditions affected the strength, the cavity pressure had no
relation with the strength.
Discussion: The condition-strength relations are similar to relations of a (micro-)replication by injection molding.
It means that joining strength could relate with a ratio of replication to the surface fine-structure. The higher
temperature and the higher injection speed kept the higher polymer fluidity during molding and thus provided thehigher replication ratio. Thermal degradation of the polymer under too high temperature made decrease of thestrength. The strength saturation under the high injection speed was obtained by the saturation of the replication(full replication). Regarding the effect of cavity pressure, even the lowest pressure condition could provide full
replication; then, the strength was not affected in used pressure range (20-60 MPa for holding pressure, 60-120
MPa for packing pressure). To make clear above discussions, we will observe interfaces of the joining samples
and confirm effects of the condition variations on the replication ratios in future work.
Keywords: Metal/plastic direct joining, Injection molding, Roughened surface, Abrasive blasting

Asian Workshop on Polymer Processing, 6-9 November 2016

OC023

UNDERSTANDING HYDROSTATICPOLYETHYLENE PRESSURE PIPESPRESSURE

TESTINGOF

TOM KOURLASQENOS PTY LTD, VICTORIA, Australia
Introduction:
The pressure pipe market is the fastest growing polyethylene market segment both in Australia and globally.
Polyethylene pipe has gained market share dominance in applications such as the transportation of drinking water,
management of waste fluids as well as the transportation of mining slurries and natural gas.
The design of base polymer resin structure used in polyethylene pipes is fundamental in meeting the demanding
engineering requirements of the pipe system which must securely transport the contained fluids under pressure
throughout a 100 year service life. Consequently the pipe market is highly regulated and pipes must adhere tocomprehensive product and installation standards.
Methods:
In order to qualify polyethylene for use in pressure pipes, the polyethylene compound must undertake acomprehensive hydrostatic pressure testing in accordance with International Standard ISO9080 – ‘Plastics piping
and ducting systems- Determination of long term hydrostatic strength of thermoplastics materials in pipe form byextrapolation’.
Results:
This testing consists of pressure testing of a number of polyethylene pipe specimens at varying pressures andtemperatures. The results obtained are used to generate pressure curves for use in design of pipe lines.
Discussion:
This presentation aims to provide an understanding of the effect of testing parameters on the hydrostatic
performance of polyethylene pipes. The effects of hoop stress, temperature and pipe dimensions on theperformance of pipes in hydrostatic pressure tests will be discussed.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC024A STUDY ON INFLUENCE OF RESIN TEMPERATURE ON FILLINGBALANCE OF MULTI-CAVITY MOLD
Norimichi Masuda, Hidetoshi Yokoi
Institute of Industrial Science, The University of Tokyo, Meguro-ku, Tokyo, Japan
Introduction: Filling imbalance, a problem encountered with multi-runners, has been clarified to be closely
related to asymmetrical temperature distribution in the secondary runner. In this study, we investigated the effects
of a main runner installed with a partition at the center for reducing asymmetrical temperature distribution along
the width of the secondary runner by measuring the temperature distribution along the widths of both thesecondary runner and main runner.
Methods: Using a system which moves the measurement points through a round rotary block structure installedwith an infrared thermometer, the sensor position was moved for each shot to measure the temperature distribution
along the width of the runner. In the experiments conducted, the temperature distribution along the widths of themain runner and secondary runner of a two-cavity mold with T-shaped runner was measured under high injection
rates in a main runner installed with a partition in the center and a main runner without partition for comparisons(Refer to Fig.1).
Result: The main runner without the partition showed increase in the temperature near the runner wall than thatat the center of the runner. In the secondary runner, the temperature was high at the outer circumference, resulting
in asymmetrical temperature distribution. In the main runner installed with a partition at the center, the temperature
at the center increased significantly. The increase in the temperature at the inner circumference of the secondary
runner means that the asymmetrical temperature distribution has decreased considerably (Refer to Fig.2).
Discussion: In the main runner installed with a partition in the center, the temperature of the melt at the center
increased due to the shear heating at the partition wall, and this melt flows into the inner side of the secondary
runner. These results clarify that the partition installed in the center of the main runner reduces asymmetricaltemperature distribution along the width of the secondary runner.
Keywords: Injection molding, Multi-cavity, Filling balance, Temperature distribution

Asian Workshop on Polymer Processing, 6-9 November 2016

OC025MOLD AND MOLDED HISTORY DEPENDENCE OF MECHANICALPROPERTIES OF RECYCLED AMORPHOUS PLASTICS
Shigeru Yao, Makoto Oda, Ryoko Nakano, Hiroshi Sekiguchi
Fukuoka University, Fukuoka, Japan
Introduction: Previously, we had investigated systematic evaluation of molecular properties, physical properties
and inner structures of recycled semi-crystalline plastics. From the investigation, we had found that main reasonof the poor physical properties of semi-crystalline recycled plastics is physical degradation and can regenerate themechanical properties by selecting the best physical molding condition.
In this time, we investigated the effect of the difference of the mold and molding conditions on the melt
viscoelasticity and the tensile properties.
Samples: For the amorphous polymer samples, we used virgin TOPAS (TOPAS ADVANCED POLYMERSGmb, 5013-L10), recycled TOPAS (From Leiz Advanced Technology Corp.), virgin Polystyrene (TOYO Styrene
GP(G200C)) and recycled polystyrene (From Shinei kasei Co. Ltd.)
Methods: We measured viscoelastic properties of these samples and evaluated the change of molecular weight.
The longest relaxation time also evaluated from the results. For the tensile properties, wwe made thin films bycompression molding with changing molding temperature and time and compared the results.
Results: From the results, in the case of amorphous polymer, the molecular weight after molding much depends
on the type of mold. And also, even after keeping the long enough in molten state than the longest relaxation time,molding history remains. We found that, the physical properties were better than the virgin plastics. Addition, by
keeping even more prolonged molten state, it was also found that it would have a ductile characteristics. From the
SAXS experiments, we had the suggesting results that the transition comes from the construction of higher
structure in the inner structure of amorphous plastics.
Discussion: By this study, we know that the molding history remains much after the longest relaxation time evenfoe the amorphous plastics.
Keywords: Amorphous Plastic, Recycle, Tensile Property, Relaxation Time, Molding history

Fig. The tensile test results of thin films of Polystyrene.
Press temperature : 210℃ Press time : 2min

Asian Workshop on Polymer Processing, 6-9 November 2016

OC026

TRANSPARENT OIL/WATERPOLYESTER MESHSEPARATIONFILTER

USING

Seimei Shiratori, Naoyuki Yokoi, Kengo Manabe, Mizuki Tenjimbayashi
Keio University, Yokohama, Japan
Introduction: For the practical applications of transparent superhydrophobic surfaces, it is critical that they
possess long-term durability of the selfassembled nanostructures against mechanical wear, shear, and liquid flow.
In this study, we investigate the possibility of a highly transparent and superhydrophobic thin film with enhanced
mechanical abrasion resistance by combining a see-through hydrophobic mesh with a hydrophobic SiO2
nanoparticle hierarchical structure.
Methods: Superhydrophobic surfaces are fabricated using three steps. (1) Chemical and morphological changes
are generated in the polyester mesh by alkaline treatment of NaOH. (2) Second, alkaline treatment causes
hydrophobic molecules of perfluorodecyltrichlorosilane to react with the hydroxyl groups on the fiber surfaces
forming covalent bonds by using the chemical vapordeposition method. (3) Hydrophobicity is enhanced bytreating the mesh with SiO2 nanoparticles modified withperfluorooctyltriethoxysilane using a spray method.
Results: The results were shown in Fig.1 and Fig.2.The transmittance of the fabricated superhydrophobic mesh
is approximately 80% in the spectral range of 400−1000 nm. The water contact angle and the water sliding angle
remain greater than 150° and lower than 25°, respectively, and the transmittance remains approximately 79% after
100 cycles of abrasion under approximately10 kPa of pressure. The mesh surface exhibits a good resistance toacidic and basic solutions over a wide range of pH values (pH2−14), and the surface can also be used as an
oil/water separation material because of its mesh structure.

Fig.1 Transparent Superhydrophobic Mesh

Fig.2 Oil/ Water Separation (a) n-octane (b) water

Discussion: The combination of the see-through mesh and the SiO2 nanoparticle hierarchical structure is aneffective and simple method for improving the abrasion resistance and transparency of these superhydrophobic
films. This simple but novel and effective method may be useful for the improvement of highly transparent
superhydrophobic surfaces for various applications.
Keywords: superhydrophobic, transparency, polyester, durability, oil/water separation

Asian Workshop on Polymer Processing, 6-9 November 2016

OC027

IONIC LIQUID-ASSISTED ENERGY-SAVING PREPARATION OF
STARCH-BASED ELECTRO-CONDUCTIVE MATERIALS
Fengwei Xie1, Binjia Zhang2,6, Ling Chen6, Rowan W. Truss1, Peter J. Halley1, Robin D. Rogers3,4, Tony
McNally5
1

The University of Queensland, Brisbane, Queensland, Australia, 2Huazhong Agricultural University, Wuhan,
Hubei, China, 3The University of Alabama, Tuscaloosa, AL, USA, 4McGill University, Montreal, QC, Canada,
5
University of Warwick, Coventry, UK, 6South China University of Technology, Guangzhou, Guangdong, China
Introduction: Polymer processing should be developed to be “greener” by minimising the energy consumption.
While significant progress has been made to develop various polymeric materials for new and enhanced properties
using traditional polymer processing techniques, limited research has been reported on optimising the processing
itself to achieve the same or even better polymer melt state. This work concerns the melt processing of a natural
biopolymer, starch, which has poor processability. Due to its biodegradability and readiness for modification,
starch-derived materials have attracted much interest in the recent decades for various applications. Nonetheless,the processing of starch is mostly carried out using solution methods. Here, we report a novel and simple way toassist the melt processing of starch, which is also instrumental to the processing of other semi-crystalline naturalpolymers.
Methods: The starch was firstly pre-mixed with aqueous ionic liquid (IL) for ca. 1 h. Then using a simple onestep compression moulding process at a moderate temperature (about 50 °C) for the pre-mix, the starch-based
electro-conductive films were obtained. The temperature used here was much lower than the widely-reported
temperatures for starch processing.
Results: With IL-water treatment, flexible starch-based electro-conductive films were successfully developed atlargely reduced temperature. Therefore, a novel energy-saving processing for starch was established. The films
displayed electro-conductivity as high as approx. 10-2 S/cm.
Discussion: For these starch films, the ratio of starch/IL/water, the processing temperature and the relative
humidity (RH) could prominently alter the multi-scale structure and thus affect the electro-conductivity.
Specifically, the increased temperature and the reduced starch content were preferable for the melting of starch,i.e., the disruption of the granule ghosts, lamellae and crystallites and the formation of denser fractals. These
structural changes enhanced the links between starch molecular chains but hindered the movement of electroconductive ions, leading to an enhanced mechanical properties but a weakened conductivity. With increased RH,
more water molecules were trapped into the film especially into its melted starch areas. The water molecules
reduced the links between the ghosts and the melted starch, the rearrangement of starch and the compactness offractal gels, which decreased the mechanical properties but enhanced the electro-conductivity. Again, the watermolecules reacted with [OAc]− to release [OH]−, and exchanged protons with H-2 of the imidazolium cations; so
the conductivity was enhanced. Hence, this work deomostrate that using a cost-effective process starch-based
electro-conductive materials can be easily prepared, which have the potential for high-value applications such as
biosensors.
Keywords: electro-conductive materials; ionic liquid; energy-saving; compression moulding; biopolymers

Asian Workshop on Polymer Processing, 6-9 November 2016

OC028IMPROVING CELL MORPHOLOGIES AND MECHANICALPROPERTIES OF INJECTION MOLDED POLYAMIDE 6 FOAMS BY
USING HYDROPHOBIC MODIFIED CELLULOSE NANOFIBER
Akihiro Ito1, Takeshi Semba1, Kunio Taguma1, Masataka Tawara1, Satoshi Nishioka1, Kazuo Kitagawa1,
Masahiro Ohshima2, Hiroyuki Yano2
1

Kyoto Municipal Institute of Industrial Technology and Culture, Kyoto, Japan, 2Kyoto University, Kyoto, Japan

Introduction: Foamed resins have many excellent properties such as lightweight, heat and electric insulation,
sound and shock absorption, and so on, while their mechanical strength and heat resistance are weaker than unfoamed (solid) resins. In order to improve mechanical properties, it is effective to reinforce foam matrix andreduce bubble size. Cellulose nanofiber (CNF) is expected to be a bland new polymer reinforcement, because of
its abundant resources and excellent physical properties. In this study, hydrophobic modified CNF/polyamide 6(PA6) composites were prepared, and foaming behaviours of them and physical properties of the obtained foams
were investigated.
Methods: Foamed test pieces were produced by the physical foaming process with using an injection molding
machine, and N2 as blowing agent. Cross section observation of the foams by SEM were done. Flexural tests ofthe test pieces were also done.
Results and Discussion: Cell morphologies of the foams are shown in Fig. 1. Cell size of modified CNF5% foams
was much smaller than that of PA6 and mineral5% foams. This is because that modified CNF, which has anaffinity for PA6 increased the viscosity of PA6 and inhibited coalescences of bubbles. Specific flexural modulus
of solid and foamed test pieces were summarized in Fig. 2. Modified CNF increased flexural modulus of PA6higher than mineral. Moreover, decreasing relative density by foaming raised specific flexural modulus ofmodified CNF/PA6 at the relative density more than 0.7. This is because the bubble of the foams with the relative
density less than 0.7 collapsed and the flexural modulus of the foams decreased. It was found that the modified
CNF was more effective filler than mineral to decrease the bubble size and increase the mechanical properties offoams.

Skin layer

Near skin layer

PA6 2.5倍発泡

CenterAc-CNF5%（低粘度MB）
PA6 2.5倍発泡
PA6bubble size

Near skin layer

CenterAc-CNF5%（低粘度MB）
PA6
ミネラル5%
2.5倍発泡mineral5%

Near skin layer

CenterAc-CNF5%（低粘度MB）
ミネラル5%
modified
CNF5%

almost the same

比曲げ弾性率[GPa] [GPa]flexural modulus
Specific

Keywords: cellulose nanofiber, polyamide 6, foaming, lightweight material
5◆ Modified CNF10%

4
3

foam

solid

● Modified CNF5%▲ Modified CNF3%■ Modified CNF1%〇 Mineral5%
× PA6

2
1
0

0
ミネラル5%

0.2

0.4 0.6 0.8 1
Relative
density比重[-] [-]

1.2

1.4

drastically reduced

Fig. 1 Cell morphologies of foams

Fig.2 Relationship between Specific flexural modulus
and relative density of solid and foamed test pieces

Asian Workshop on Polymer Processing, 6-9 November 2016

OC029PROCESS FOR SOLVINGPOLYETHYLENE FILMSHEATSEALING

PROBLEMSIN

Steve Mirams
Qenos Pty Ltd, Melbourne, Victoria, Australia
Heat sealing is a common type of process in the manufacture of packaging from flexible films. The integrity ofthe process is critical for ensuring the protection of the package contents, while a fast trouble-free process iscritical for the commercial viability of the packaging plant. Polyethylenes are widely used in flexible films for
packaging due to the excellent sealing characteristics of these polymers.
The presentation will give an overview of the more common problems that may occur during these sealing
processes. A procedure for finding the root causes and their solutions will be described. An understanding of thesealing process at the molecular level is a key part of solving problems. Knowledge of the heat sealing propertiesof the polymers in the film is also important, and this can be gained through examining heat sealing curves.
Further valuable information can be gained by collecting information about the occurrence of the problem, using
tools such as problem analysis questioning and fishbone diagrams. In this work, these tools have been tailored to
be able to be readily used for solving problems in heat sealing. Validation tests for the causes are then conducted.
A number of case studies where this procedure has been used will be described. The problem analysis tools led
to different types of validation testing in each case. Examples of the validation testing included Differential
Scanning Calorimetry, Hot Tack testing on a laboratory tester, and trials on the industrial sealing equipment. Afterusing the problem solving tools followed by the validation testing, the root causes were quickly identified andsolutions were implemented. These examples demonstrate the effectiveness of this problem solving process.
Keywords: Sealing, films, polyethylene

Asian Workshop on Polymer Processing, 6-9 November 2016

OC030MASTERBATCH INNOVATION - TOWARDS 2020
Neil Whelan
Axieo Masterbatch, Victoria, Australia

I would like to discuss the topic of Innovation and how that relates to our Customers Expectations within the MB
Industry today and indeed for the remainder of this decade. Whilst I am going to put some emphasis on my homemarket, I am also going to talk about this overall region and its global context.
In so doing, I would like to discuss
1.
2.
3.

Customer Trends
Innovation Methods
Measures of Innovation & relevance to this region

Masterbatch as you would all know, is an industry sector exposed to and servicing virtually all sectors of theplastics industry, hence we all have a quite wide involvement and influence within the industry.
Ever increasingly, the reverse also applies – i.e. all sectors of the plastics industry in turn, affect the MB industry– particularly in a strongly competitive environment.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC031BIREFRINGENCE CONTROL OF POLYMERIC FILMSANISOTROPIC STRUCTURE AND ITS OPTICAL APPLICATION

BY

Hikaru Shimada1, Shogo Nobukawa2, Masayuki Yamaguchi1
1

Japan Advanced Institute of Science and Technology, Nomi, Ishikawa, Japan, 2Nagoya Institute of Technology,
Nagoya, Aichi, Japan
Introduction: A technical trend for an optical retardation film is to adjust the retardation in a broad range ofvisible light. In case of a quarter-wave plate, the retardation has to be a quarter of wavelength. It means that thebirefringence of a quarter-wave plate has to increase with wavelength. Although this extraordinary wavelength
dispersion is necessary for advanced displays, the orientation birefringence of general polymers decreases withwavelength. In this study, we focus on the form birefringence originated from structural anisotropy in a film tocontrol the wavelength dispersion.
Methods: The films were prepared by a solution-cast method. Cellulose triacetate (CTA) and Diisodecyl adipate(DIDA) were dissolved into a mixture solvent of dichloromethane and methanol with 9/1 weight ratio. The
solution containing 4 wt% of CTA was evaporated at room temperature to obtain a film. The films were uniaxially
stretched by a tensile machine with a temperature controller. The hot-stretching was performed after holding at
the drawing temperature for specific periods. The hot-stretched films were immediately quenched by cold air
blowing at a draw ratio of 1.5 to avoid relaxation of molecular orientation. The films were immersed into methanol
to remove the plasticizer. Then, they were dried in vacuo at room temperature.
Results: A hot-stretched CTA film containing DIDA shows negative orientation birefringence with ordinary
wavelength dispersion, as similar to that of a pure CTA film; the absolute value of the birefringence decreases
with wavelength. However, after extracting DIDA from the stretched film by immersion into an organic solvent,the birefringence of the film dramatically changes from negative to positive with extraordinary wavelength
dispersion; the magnitude of the birefringence increases with the wavelength. The SEM observation reveals thatthe film contains numerous ellipsoidal pores elongated to the stretching direction. Moreover, light transmittanceof the porous film increases by decreasing heating time and increasing strain rate at hot-stretching process.
Discussion: The results indicate that the ellipsoidal pores provide the form birefringence as a positive value.
Therefore, the combination of form birefringence and orientation birefringence provides extraordinary wavelength
dispersion. Moreover, the formation of dispersed phase, and thus the form birefringence as well as lighttransmittance can be controlled by conditions at hot-stretching process.
Keywords: birefringence, anisotropic structure, optical film

Asian Workshop on Polymer Processing, 6-9 November 2016

OC032

PREPARATION OF MULTI-FUNCTIONAL GREENHOUSE COVER
FILM WITH UV FILTRATION, NIR REFLECTION AND GOOD LIGHT
DIFFUSION
Duangruthai Srinun, Atitsa Petchsuk, Doungporn Sirikittikul
National Metal and Materials Technology Center, Pathum Thani, Thailand
In tropical areas, cultivation is limited by an excess heat occurring due to high radiation levels. About 40% of thesolarradiation
reachingtheearth
surfaceisthenear-infrared
radiation(NIR; 700 – 2000 nm) which is the main source of heat load. Planting in the greenhouse is becoming popularsince it is possible to manipulate light as well as other environmental factors to improve plant productivity andquality.
The incorporation of NIR reflective particles (pure metal, metal oxide, etc.) into polymer film is an effective way
to reduce temperature inside the greenhouse. However, the ideal greenhouse film should not only reflect NIR but
also minimize the UV transmission (250 – 400 nm) in order to protect plant cells. Moreover, the film must permit
the photo-synthetically active radiation (PAR; 400 – 700 nm) in accordance with photosynthetic requirement ofplants.
In this present work, 90% of linear low density polyethylene (LLDPE)/10% of Ethylene vinyl acetate (EVA)
based polymer and 0.5 – 1.0 wt% modified TiO2 and 0.25 - 0.5 wt% aluminium (Al) flake were compounded bytwin-screw extruder. The compounding was then blown into film with 30 µm thickness by using blown film
extruder. Mechanical properties of the resulting film were characterized using tensile testing machine. Light
diffusion was performed by Haze meter and optical properties were measured by UV/Vis/NIR spectrophotometer.
Results showed that 90 µm thickness of 3 layers laminated film exhibiting 14 – 20% NIR reflecting, 56 – 100%
UV blocking, 49 – 75% PAR transmission and 40 – 60% of Haze diffusion could be achieved. However, adding
those additives adversely affected the mechanical properties of the polymer film.
Keywords: greenhouse film, multi-functional film, NIR reflective, optical properties, mechanicalproperties

Asian Workshop on Polymer Processing, 6-9 November 2016

OC033

STRESS-OPTICAL BEHAVIOR OF AMORPHOUS FILMS DURING
TWO-STEP UNI-AXIAL STRETCHING AND SEQUENTIAL BI-AXIAL
STRETCHING PROCESSES
Yuki Takada, Kensuke Nemoto, Wataru Takarada, Takeshi Kikutani
Tokyo Institute of Technology, Tokyo, Japan
Introduction: In the processing of amorphous polymers, structure can be fixed only by cooling the polymer
below its glass transition temperature. Therefore, understanding of structure development and relaxation behavior
was important. In this research, multi-step processing of amorphous polymers was investigated through thesimultaneous measurements of stress and birefringence.
Methods: The films of amorphous polycycroolefine (PCO) was used for this research. The two-step stretching
was conducted at 133 oC. During the stretching and relaxation processes, stress and birefringence were measured
simultaneously.

Birefringence x1000 True stress /MPa

Birefringence x1000 True stress /MPa

Results: The behaviors of stress and birefringence during two-step uni-axial stretching and sequential bi-axial
stretching was shown in Fig. 1.

Time /s(a) Two-step uni-axial stretching

MDStress

Time /s(b) Sequential bi-axial stretchingFig.1 The behaviors of stress andand (b) sequential bi-axial stretching process.

birefringenceduring(a)two-step

uni-axial

stretching

Discussion: In both process, step increase and decrease of stress at the start and end of stretching whereas smoothchange at birefringence. Such stress behavior is considered as the appearance of the effect glassy state. Asymptotic
values of stress and birefringence indicate an existence of the structure which have long-relaxation time. Thisasymptotic values were mainly decided by stretching temperature and total stretching ratio but rarely affected bystretching rate and intermittent holding time.
Keywords: Structure development, Relaxation, Birefringence, Film, Stretching

Asian Workshop on Polymer Processing, 6-9 November 2016

OC034CO2 LASER PERFORATION OF POLYPROPYLENE
PREPARED BY SIMULTANEOUS BIAXIAL STRETCHING

FILMS

Charinee Winotapun1, Chao Sripethdee2, Noppadon Kerddonfag2, Wannee Chinsirikul2, Wataru Takarada1,
Takeshi Kikutani1
1

Tokyo Institute of Technology, Tokyo, Japan, 2National Metal and Materials Technology Center, Pathumthani,
ThailandBiaxially oriented polypropylene (BOPP) films are widely used in all areas of packaging. Films with high oxygen
transmission rate (OTR > 10,000 cc/m2/day) are required for extending shelf life of fresh products such as fruits
and vegetables. Laser perforation is one of the techniques for increasing the gas transmission rate through theformation of tiny holes in the film. The shape and the size of microholes on the films depend on laser perforation
process parameters (focal length and pulse duration) and materials (degree of molecular orientation and film
thickness). Therefore, in this research, BOPP films were produced by simultaneous biaxial stretching of original
PP films to various draw ratios. These films were perforated by CO2 laser under a constant pulse repetition rateof 1 Hz and various pulse energy from 1.8 to 18 mJ, which corresponds to the pulse duration from 30 to 300
microseconds. The diameters of perforated holes increased with increasing pulse energy. For example, for thefilm sample with the equi-biaxial stretching ratio of λMD x λTD 4 x 4, the hole diameters were 103.8, 147.1, 250.4
and 288.3 m for the pulse energies of 4.8, 6.0, 12.0 and 18.0 mJ, respectively. These micro holes showed circularshape because of the isotropic orientation of molecular chains with respect to the axis normal to the film surface.
The volume loss analysed from the cross-sectional shape of microhole also increased with the increase of pulse
energy and reached 400 % for the pulse energy of 18.0 mJ. The size of perforated micro hole was affected not
only by the laser pulse energy but also by the focal length of used lenses. When the focal length was increased
from 38.1 to 63.5 mm, the average size of microhole increased even though the fluence of laser (energy per unit
area) was kept constant. This is mainly due to the increase of focal spot diameter and accordingly the use of higher
pulse energy. It is interesting to note that the starting of the opening of hole is mainly controlled by the fluence oflaser. Furthermore, for clarifying the effect of film thickness, films with the same stretching ratio and different
thickness were also investigated. It was found that the size of microhole decreases with the increase of film
thickness. As a whole, these results clearly demonstrated that the CO2 laser processing is a promising techniquefor producing the perforated films.
Keyword: laser perforation, biaxially oriented polypropylene, food packaging

Asian Workshop on Polymer Processing, 6-9 November 2016

OC035ULTRA HIGH MOLECULE WEIGHT POLYETHYLENE FILTRATION
MATERIALS
Xinwei WANG1,2, Yumei ZHANG1,2, Xun XU1,2, Yongfei SUN1,2
1

Shanghai Research Institute of Chemical Industry, Shanghai, China, 2State Key Laboratory of Polyolefins andCatalysis, Shanghai, China
Introduction: Benefit from its linear long chain structure and high molecule weight, UHMWPE shows highmechanical strength, highly resistance to abrasion and chemicals, low absorption toward water, self-lubricating
and nontoxic, which lead to applications including gas and liquid filtration, medical diagnostic test kits, lowdielectric constant wrap for microwave cables, batteries and other applications where porosity, toughness andaccuracy of gauge are important.
Methods: Herein, we discussed UHMWPE filtration materials by crafting methods: sintering, thermally induced
phase separation (TIPS), melt extrusion-stretching, sol-gel methods, etc.
Results: The porosity, as well as the water flux, decrease with increasing initial UHMWPE concentration. On theother hand, rejection rate towards BSA increase with higher initial UHMWPE concentration (As shown in Fig.1,
Fig.2). We find the breaking strength increase with the increasing UHMWPE concentration as well as higher
stretching ratio (As shown in Fig.3).

1

2

3

Fig.1 Porosity Changes with concentration of UHMWPE
Fig.2 Water flux and BSA rejection rate changes with concentration of UHMWPE
Fig.3 Breaking strength changes with stretching ratio
Discussion: The main reason is when concentration become higher, the membranes’ bone structure grow coarser
and thicker. Moreover, when membranes are stretched, the degree of order become larger. Macromolecule getcloser to each other and force between them grow stronger, which lead to increasing of membranes strength.
Keywords: UHMWPE, TIPS method, sintering method, porous film, permeability, hydrophilic modification,
hollow fiber membrane.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC036

YALLOURN POWER STATION FLOODING CASE STUDY INTO THE
VERSATILITY OF PE100 PIPESPHILIP ADETUNJI
QENOS PTY LTD, VICTORIA, Australia
The urgent diversion of a river through a rapidly constructed pipeline was required to avert a power supply crisisto the state of Victoria. In early June 2012, the Morwell River surged and a levee collapsed allowing the river toflow directly into the open cut coal mine which supplies the Yallourn power station. The flooding caused
US$400m of damage to infrastructure and put the electricity supply to over 1 million homes and businesses at
risk.
With limited coal reserves available to keep the power station operational, a rapid response was required to divert
the river, dewater the coal mine and reinstate the supply of coal to the power station. Polyethylene PE100 pipe
was the only solution that met the project criteria of fast availability, large pipe diameters, adaptable installation
techniques, high integrity joints, abrasion resistance and flexibility. A total of 4km of 1600mm diameter PE100
pipe had to be rapidly manufactured and transported to the installation site. Large diameter pipe welding
equipment was air freighted from the USA and made operational with a commissioning process that employed
destructive weld testing techniques.
The around-the-clock pipeline installation involved welding ten lengths of pipe into 120m strings which were thendragged to the installation site for final joining. In just over 2 months, the tie-ins were completed and the pipeline
commissioned so that the entire Morwell River was flowing through the pipeline and the repair of the mine
infrastructure could begin. Two years later, the pipeline is still in service ensuring effective operation of the mineand securing the supply of power to Victoria.
Polyethylene, PE100, pipe, Yallourn

Asian Workshop on Polymer Processing, 6-9 November 2016

OC037WET SPINNING OF PAN-BASED POLYMERS MADE BY RAFTTECHNOLOGY
Jasjeet Kaur, Keith Millington, Jackie Cai, Colin Brackley
CSIRO, Geelong, Australia
Introduction: Wet spinning is a standard method for making high strength polyacrylonitrile (PAN) based fibres
as carbon fibre precursors. The PAN based polymers synthesised by using RAFT technology (RAFT PAN) are
expected to result in improved carbon fibre precursors, as they have a substantially lower polydispersity index(PDI) than those made by conventional free radical polymerisation. A low PDI PAN polymer means a highconsistency in its polymer structure, and it is free from very high molecular weight fractions, which may cause
difficulties in polymer dissolution, filtration and spinning. This also indicates that the RAFT PAN may havedifferent rheological properties, and require different spinning conditions to maximise the potential of thisadvanced polymer. To date, very limited information is available on wet spinning of RAFT mediated PAN
polymers. In this study, we investigate the special characteristics of the RAFT PAN polymers and their effects on
spinning performance and resultant precursor fibre properties.
Methods: We studied the rheological properties and wet spinning performance of both conventional and RAFT
PAN polymers using dimethyl sulphoxide as a spinning solvent. The precursor fibres were obtained under various
wet spinning conditions, and their morphology, crystallinity and mechanical properties were characterised. .
Results: The results of this study show that RAFT PAN polymers exhibit unique rheological properties. RAFT
PAN solutions have much lower viscosity values than the conventional polymer solutions at same conditions.
They also show more liquid character and gel slower than their conventional controls. These special rheologicalproperties enable a higher polymer content in a spinning solution, which still remains spinnable. Due to thedifferent rheological behaviour, RAFT PAN polymers require to be spun at different spinning conditions. By thetime of this abstract submission, we have produced the RAFT PAN precursor fibres under various wet spinning
conditions. Further optimisation of the spinning parameters is ongoing.
Discussion: The unique rheology of RAFT PAN polymer offers a wider working window for wet spinning
operation and allows a higher solid content in the spinning solution. This is probably attributed to the absence ofvery high molecular weight polymer fractions. The improved spinning performance of the RAFT PAN polymers
are expected to result in improved quality and performance of carbon fibre precursors.
Keywords: wet spinning, polyacrylonitrile, RAFT, rheology, carbon fibre

Asian Workshop on Polymer Processing, 6-9 November 2016

OC038LAMELLAR THICKENING AND THE RESULTANT ABNORMALMELTING BEHAVIOR OF ISOTACTIC POLYPROPYLENE FILMS
Zhenzhen Zhou, Huihui Li, Shouke Yan
Beijing University of Chemical and Technology, Beijing, China
In this work, an abnormal melting behavior of isotactic polypropylene (iPP) was observed by polarized optical
microscopy (POM), i.e., the melting of α-iPP spherulites isothermally crystallized at 135 °C could occur prior tothat of α-iPP spherulites crystallized at 125 °C when heated by 2 °C/min, but the case was opposite if the heating
rate was 10, 20 or 50 °C/min. The changes of lamellar organization during heating process (2 °C/min ) were
investigated by scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD) and in-situ
synchrotron small-angle X-ray scattering (SAXS). The occurrence of lamellar thickening could be revealed by insitu synchrotron SAXS, and it can be found that the initial lamellar thickness of α-iPP spherulites grown at 135°C is over that of spherulites grown at 125 °C, whereas the latter will exceed the former when heated over 160 °C
by means of lamellar thickening. SEM micrographs of iPP sample can also demonstrate the occurrence of lamellar
thickening. Moreover, the change of mixed α-iPP spherulites to negative ones could be observed by POM during
melting process, which could indicate that the amount of tangential lamellae in α-iPP decreased remarkably. Thus,
the abnormal melting behavior should be attributed to the lamellar thickening, which can be described as thefollowing, i.e., the tangential lamellae in the spherulite will melt and recrystallize on the radial lamellae during
heating process, yielding much thicker radial lamellae with higher perfection. Moreover, the amount of tangential
lamellae in spherulites crystallized at 125 °C is more than that in spherulites crystallized at 135 °C, and averagelamellae thickness of spherulites grown at 125 °C can exceed that of spherulites grown at 135 °C via lamellar
thickening process. Consequently, the spherulites crystallized at 135 °C will melt before that of spherulites
crystallized at 125 °C. A schematic diagram showing the lamellar thickening process is present in the following.
Keywords: isotactic polypropylene, lamellar thickening, tangential lamellae, radial lamellae

A schematic diagram of iPP melting process with low heating rate.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC039COMPARATIVE INVESTIGATIONS ON DIFFERENT SHEAR
THICKENING SUSPENSIONS FOR IMPACT ENERGY DISSIPATION
Swarna -, Neetu Kumari, Sudip Pattanayek, Anup Ghosh
Indian Institute of Technology Delhi, New Delhi, India
The transition from viscous liquid to solid state as a function of shear rate in dense suspensions has been of interest,
over a decade. Although suspensions comprising of nano or micro sized particles in a Newtonian liquid medium
are ubiquitous, those suspensions showing shear thickening have to fulfil certain criteria to be a shear thickening
fluids (STF). Several physical and chemical properties of both suspended particles and the liquid medium
independently stimulates the uniqueness of the liquid-solid transition. However, even with the development ofscaling relations and predictive models for rheological parameters, the contribution of forces of interactions
present in suspensions responsible for their flow behaviour is still ambiguous. In the current study we consider 3systems as comparative studies correlating with their rheological properties. We present the occurrence of shear
thinning with a high yield stress at large particle concentrations in cornstarch–water, fumed silica-PEG and silicaPEG suspensions. We compare the forces of interactions responsible for all the systems. For 50 wt% of cornstarchin water we observed a continuous shear thickening with a critical shear rate of 21.5 s-1. The viscosity rises from0.026 to 0.239 Pa.s post critical shear rate. However, with the addition of PEG to water (1:1 ratio) at samecornstarch concentration, a shear thinning behaviour is observed with high yield stress. Similarly, 19 wt% of
fumed silica in PEG 400 and 62 wt% of surface functionalized silica in PEG 400 also showed a shear thinningbehaviour with high yield stress. The dynamics rheology of all the suspensions under study however showed highelastic modulus in the frequency range of 0.1 to 100 s -1. The amplitude strain under which linear viscoelastic
behaviour observed is less than 0.1% for all the suspensions. Further, we also present impact behaviour and energy
dissipation analysis for shear thickening suspensions using Abaqus. The direction of energy displacement after
the impact is visually perceived by this simulation technique. By combining the experimental and simulation
results, we provide a route where one can choose the suspensions for suitable applications.
Keywords: Shear thickening suspensions, shear thinning, yield stress, energy dissipation

Asian Workshop on Polymer Processing, 6-9 November 2016

OC040DEGRADABLE POLYMERIC NERVE GUIDES PRODUCED BY FIBRE
EXTRUSION, KNITTING AND ELECTROSPINNING
Mike O'Shea3, Ilias Kyratzis3, Yen Truong3, Robert Kapsa2, Anita Quigley1, Kristian Bulluss2, Kerry Gilmore1
1

University of Wollongong, NSW, Australia, 2St Vincent's Hospital, Melbourne, VIC, Australia, 3CSIRO, VIC,
Australia
Introduction: Injury to nerve tissue in the Peripheral Nervous System (PNS) results in long-term impairment oflimb function, pain, often with associated psychological effects. Minor injuries can be left to regenerate. The
challenge has resulted in the development of nerve guides or conduits produced from various polymers to improve
nerve repair. This study describes the design and fabrication of a nerve regeneration conduit using polylactic acid
(PLA) and (PLA):poly(lactic-co-glycolic) acid (PLGA) and Polyurethanes produced by direct Reactive Extrusionfrom HDI ( hexamethylene di-isocyanate) and PLA and polycaprolactone polyols and short diol chain extenders.
The nerve conduits produced consisted of : an electrospun fibre and knitted outer sheath, shaped profile guidance
fibres surrounded by a neurotrophin-enriched alginate hydrogel.
Methods: Polymers and Nerve Conduit Design: The polymers were first evaluated for cell compatibility using
petri dish evaluation methods. Assembly and Sterilisation: The extruded fibers and knitted/electrospun conduit
sheath were fabricated separately to facilitate sterilization for implantation. Implantation Studies: The nerve
guides were implanted into the 12mm gap in the hamstringsciatic nerve. Analysis of Regeneration: The rats weremonitored for 4 weeks, euthanased and the conduit inspected for cell regrowth.
Results and Discussion: Our results support that the conduit restored some sensation in the axotomized limbs
through support of effective repair of the transected sciatic nerve. However, more detailed functional analyses (egnerve conduction) are still required to fully quantify the extent of functional repair promoted by the conduitdesigned in this study.
Keywords: Biomedical Polymers, Degradable, Nerve Guide, Reactive Extrusion, Fibre, Knitting,Electrospinning, Implant

Asian Workshop on Polymer Processing, 6-9 November 2016

OC041

PREDICTING THE SHAPE AND BOND STRENGTH OF INJECTION
OVERMOLDED STAMP FORMED COMPOSITESFranco Costa1, Mark Bouwman2, Thijs Donderwinkel2, Sebastiaan Wijskamp2, Zhihao Zuo1
1

Autodesk, Inc., Kilsyth, Victoria, Australia, 21ThermoPlastic composites Research Center - TPRC, Enschede,
The Netherlands
Introduction: CAE tools are developed to assist the design validation of hybrid thermoplastic composite partscontaining stamp formed continuous fiber composite sheets which are overmolded by an injection molding
process to add functional design elements and reinforcements.
Methods: A method is developed for coupling the output (residual stresses, anisotropic properties and thickness
changes) of an existing stamp forming simulation software tool (Aniform) into the combined finite element
warpage simulation of the injection overmolding process (Autodesk Moldflow). The stamp formed composite isrepresented in the warpage simulation as a part insert, with local (elemental) anisotropic mechanical properties
computed from the orientation of fibers resulting after the stamp forming process. In a similar way, the fiber
stresses induced by the forming process are mapped into the warpage simulation as element level initial strains in
the part insert (formed composite) as well as the thermo-mechanical strains which will occur in the insert due tocooling to room temperature. These combined initial strains, along with the in-mold residual stresses and coolingstrains of the molding compound are the drivers of warpage in the combined part. A model of the interface bondstrength between the stamp formed composite and the injection molding compound is also developed based on
the temperature history at the bonding interface. Outcomes from the warp simulation and bond strength model
will be compared to experimental results.
Results: A warp deflection result for a combined part having a formed composite inner frame and surrounding
injection overmolded compounds is shown. The properties of the formed composite are anisotropic. A bondstrength factor ranging from zero (no bonding) to one (full bond strength) is computed from the temperature
history at a rectangular overmolding interface for a PA6 polymer. The perimeter of the interface shows lower
bonding effectiveness due to the weaker heating of the insert in regions close to the (cooler) mold surface.

Discussion: Final part shape (warp) prediction is achieved for a combined stamp formed composite and injection
overmolding process. A model for interface bond strength is available for use in a subsequent structural
performance analysis.
Keywords: Injection overmolding, continuous fiber composites, warpage, bond strength

Asian Workshop on Polymer Processing, 6-9 November 2016

OC042

NEW RESINS FOR 3D PRINTING OF RAPID PROTOTYPES
Timothy Hughes, Johan Basuki, Sean Murphy, Malsha Wickramaratna, Asitha Balachandra, Pete CassCSIRO Manufacturing, Clayton, Victoria, Australia
Introduction: Due to its speed and ability to make complex objects with minimal waste, 3D printing is predicted
to revolutionise manufacturing. For this to occur, a wider range of polymer resins with a broader range ofproperties are needed. Here we report on our efforts to develop new 3D printable resins suitable of Digital Light
Projection (DLP) 3D printers.
Methods: Formulation stability was measured by simple visual inspection over time. Cure time of the resin wasinvestigated using photorheometer (ARES). A photocure 3D printer, Titan 1 (Kudo 3D) was used for all 3D
printing. A gradient cure of a tube was used to determine optimum layer exposure time. Small and large parts
were then printed to assess design reproduction. Metrology and physical properties of the 3D printed parts were
investigated.
Results & Discussion: Translation of simple photocure chemistry to a DLP printer is not as straight forwards as
expected. There are many factors which need to be considering when developing resins for DLP printers, namely:
formulation stability, cure time for each layer, plastic deformation, successful initiation of crosslinking reactions,and inhibition of unwanted curing. Here we discuss these requirements and the interplay between them. Softelastic materials are particularly difficult to 3D print due to their low modulus and ease of plastic deformation
during the printing process. We have successfully printed soft elastic pasts (Fig. 1) using an in-house developed
siloxane based resin as well as hard parts with high thermal stability using another in-house developed resin.

Figure 1: (A) Siloxane based 3D printed part deformed. (B) Siloxane based 3D printed part returns to natural
shape post deformation, demonstrating its elasticity.
Keywords: 3D printing, rapid prototyping, photocure, siloxane, photorheology

Asian Workshop on Polymer Processing, 6-9 November 2016

OC043

NANOPOROUS OF PILLARS-LIKE STRUCTURE OBTAINED BY
POLYMER BLENDS – PRECISE MOLDING SYSTEM
Paritat Muanchan1, Akira Ishigami2, Akihiko Nemoto1,2, Takashi Kyotani3, Hiroshi Ito1,2
1

Research Center for GREEN Materials and Advanced Processing (GMAP), Graduate School of Science andEngineering, Yamagata University, Yonezawa, Yamagata/Tohoku, Japan, 2Graduate School of Organic
Materials Science, Yamagata University, Yonezawa, Yamagata/Tohoku, Japan, 3Institute of Multidisciplinary
Research for Advanced Materials, Tohoku University, Sendai, Miyagi/Tohoku, Japan
Introduction: Recently, the fabrication of nanopillar arrays structure with the nanoporous surface (NPPs) has
aroused great attention because of their applications such as sensing materials, drug releasing control, filtrationmaterials, catalyst scaffolds etc. As compared to other fabrication methods, thermal nanoimprint combined anodic
aluminum oxide (AAO) template has been proved to be outstanding performance technique for precisely, shorttime, and high efficiency. In order to produce the nanoporous structure, polymer blend with nano-domain segment
having a great potential for the precursor materials that induced the porous by the selective removal of the nanodomain segment. However, it is still a challenge to fully understand the formation and the transformation of theobtained porous structure.
In this study, AAO-thermal nanoimprint was selected to produce NPPs of the polystyrene (PS) using PS/polyvinyl
alcohol (PVA) blending materials. The PS/PVA blended having PVA micro/nano-domain size of the multiphasestructure in PS matrix was prepared by the high shearing process. The porous structure was obtained using waterselective removal of the imprinted structures. Here, we mainly focused on clarifying the effect of PVA micro/nano-domain on the formation and the transformation of the obtained porous structure. Moreover, we havereported the hydrophobicity and friction property of the obtained structures.
Methods
1. Materials: Commercial grade polymers were used: PS1 (Tg = 87 °C, MFR = 18.0 g/ 10 min at 200 °C GPPS
679; PS Japan Corp.) and PS2 (Tg = 100 °C, MFR = 11.9 g/ 10 min at 220 °C, G210; Toyo Styrene). The PVA (Tg= 26 oC, MFR = 4.0 g/10 min at 190 oC, CP-1210; Kuraray Co., Ltd.) was also used in polymer blend system.
2. Experiment: The high shear machine (NHSS2-28, Niigata Machine Techno Co., Ltd.) were used for blending
process of PS/PVA (90:10 and 70:30 w/w %) materials by 500 rpm at 180 oC. The neat PS and PS/PVA films
with the thickness of 500 µm were fabricated by hot/cold press method. The polymer films were imprinted with
AAO-thermal nanoimprint machine (Izumi Tech) at 120-220 oC, 5.0 MPa for 30 min. The process diagram isshown in figure 1.
3. Characterization: The obtained structures of selected blended materials and nanopillars were observed byfield emission scanning electron microscopy (FE-SEM). The chemical property of blending precursors wasanalysed by attenuated total reflectance (ATR), and the thermal property of obtained polymer films wascharacterized by modulated differential scanning calorimetry (M-DSC).
Results and Discussion: The transformation of the nanopillars structure were presented in Figure 2. The
nanoporous could obtained on the PS nanopillars surface after the water selective removal by using PS/PVA 90:10
w/w% precursor because of the blended precusor having the smaller PVA nano-domain size (30-1,000 nm)
compared with 70:30 w/w% (300-1,000 nm) that able to flow in AAO. In the case of 70:30 w/w% was found thefibers breakup behaviour that nanofibers transformed to nanoparticles. Increase of the imprinting temperature
could be induced the surface transformation of the pillars structures.
Keywords: Nanopillars, Nanoporous, Nanoimprint, Polymer Blends.

Imprint
MachineFig. 1 AAO-thermal nanoimprint system

Fig. 2 Transformation of nanopillars structure.
Asian Workshop on Polymer Processing, 6-9 November 2016

OC044

PHYSICALREGERATIONOFRECYCLEDRESINANDAPPLICATION TO THE REAL CONTAINERS AND PACKAGINGRESIN
Aya Tominaga1, Hiroshi Sekiguchi1, Ryoko Nakano1, Shigeru Yao1, Eiichi Takatori2
1

Fukuoka University, Fukuoka, Fukuoka, Japan, 2TOSOH Analysis and Research Center Co.,Ltd., Yokkaichi, Mie,Japan
Introduction: The poor physical properties of material-recycled plastics are believed to be due to the chemicaldegradation that results from the heat, ultraviolet light or oxidation in the recycling process. Such chemicaldegradation is thought to be irreversible because it is associated with the breaking of molecular chains. However,
our recent research indicated that the molecular properties of material-recycled plastics are restored to the samelevels as those seen in virgin plastics.
In this time, we will report the processes to improve mechanical properties of pre-consumer recycled
polypropylene (Pre-RPP) and real wasted containers and package plastics.
Methods: Table 1 shows the compressed conditions of pre-consumer recycled polypropylene pellet and real
wasted containers and package plastics pellet (polypropylene : polyethylene = 5 : 5).
Table 1 Hot press and cooling conditions producing films.

Hot press conditions

210ºC, 230ºC, 250ºC, 2min, 6min, 10min

Cooling conditions

Slow Cool (SC), Quench

Experiment contents

Tensile test, SEM observation

Results: Fig.1 shows results of Pre-RPP samples after tensile test. Mechanical properties of Pre-RPP improved
dramatically by changing hot pressing and cooling conditions. Fig.2 shows samples of real wasted containers andpackage plastics after tensile test. For the real recycled resin, the mechanical properties also improved by changing
the compression condition.

Fig.1 This picture of samples after tensile test.
(a) Pre-RPP 210 ºC 2min Slow-Cool, (b) PreRPP 210 ºC 10min Slow-Cool, (c) Pre-RPP 210ºC 2min Quench, (d) Pre-RPP 250 ºC 10min
QuenchFig.2 This picture of samples after tensile test.
(a) 180 ºC 2min Slow-Cool, (b) 180ºC 2min
QuenchDiscussion: This result suggests that the main factor of the degradation of recycle plastics is physical degradation
and we can regenerate the physical properties by selectin the molding condition. The results suggest that we canestablish a new recycling process for the wasted plastics.
Keywords: pre-consumer recycled polypropylene / real wasted containers and package plastics / hot pressing andcooling conditions / mechanical properties / physical degradation

Asian Workshop on Polymer Processing, 6-9 November 2016

OC045

EFFECTS OF MICROSTRUCTURE ON THE MECHANICALPROPERTIES OF HIGH DENSITY POLYETHYLENE FOR THE
INJECTION MOLDING APPLICATION
Myung Han Lee, Soonho Sun, Hyunsup Lee, Sunghyun Park, Bog Ki Hong, Changkwon Chung, Yiyoung Choi,
Ki-Soo Lee
LG Chemical, Daejeon, Republic of Korea
The high density polyethylene (HDPE) is one of the most commonly used thermoplastic polymers due to its low
cost, good mechanical properties and versatility. The properties of polyethylene are strongly influenced by its
molecular weight, molecular weight distribution, and branching. We developed the HDPE resins with highprocessability and performance by controlling the microstructure for the injection molding applications such as
cartridge, pail, and bottle cap. In this presentation, we show the relationship between the microstructure andprocessability/performance of HDPE. The presence of long-chain branches in the high molecular part leads tosignificant shear thinning in viscosity, which reduces the injection molding cycle time. Such high processability,
as compared to the conventional products, also allows for a further increase in the polymer molecular weight,
improving the mechanical properties such as impact strength and environmental stress-cracking resistance (ESCR).
However, when injection molded pails filled with water are vertically and horizontally dropped from a height 2.0m, they crack at the side. It is found that this is due to the flow-induced alignment of polymers during the injection
molding process. The proportion of high molecular weight tail is thus reduced to decrease the relaxation time ofpolymer, eventually allowing for resolving the crack issue of pails.
Keywords: polyethylene, injection molding, microstructure, mechanical properties

Asian Workshop on Polymer Processing, 6-9 November 2016

OC046NETWORK STRUCTURES AND PHYSICALCROSSLINKED METALLOCENE EPDM

PROPERTIESOF

Kazuki Mita1, Kiminori Uchida1, Mitsunao Arino2, Yoshiharu Kikuchi2, Kotaro Ichino2
1

Mitsui Chemicals, Inc., Sodegaura, Chiba, Japan, 2Mitsui Chemicals, Inc., Ichihara, Chiba, Japan

Introduction: Ethylene-propylene-diene terpolymer (EPDM) is a synthetic rubber which is used for various
industries, such as automotive, electrical, and construction industries. The olefin polymerization catalysts arenecessary for the polymerization of EPDM. In 1953, the Ziegler-Natta catalyst was found. Industrialization of our
EPDM by using the Ziegler-Natta catalyst began in 1969. And then, a new catalyst, metallocene catalyst was
discovered in 1980. Industrialization of our EPDM by using the metallocene catalyst began in 2008. The
metallocene catalyst has excellent performance in controlling branch structures of polymer chains. We can get
branched EPDM by a metallocene catalyst and linear EPDM by another metallocene catalyst. In this study, we
prepared linear EPDM and branched EPDM, and network structures of the EPDMs crosslinked by peroxide
initiated reactions were investigated by small-angle neutron scattering (SANS) and small-angle X-ray scattering(SAXS).
Methods: Table 1 is a list of the EPDMs used in this study. Sheets of the EPDMs vulcanized by peroxide wereobtained by compression molding. The sheets were immersed in deuterated xylene and swollen sufficiently. The
network structures of the EPDMs in the sheets were investigated by SANS and SAXS. The SANS experiments
were performed at the BL20 Materials and Life Science Experimental Facility of J-PARC under a user program(Proposal No. 2014AM0009). The SAXS experiments were performed at the BL03XU SPring-8 with the approvalof the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2013B7266, 2015A7216).
Results: Figure 1 shows the SANS profile. Branched-V-EP showed larger upturn scattering in the smaller-angle
regions (q = 0.02 ~ 0.05 Å-1) than other two linear EPDMs.
Discussion: The SANS result indicates that the network structures of the linear EPDMs are more homogeneousthan those of the branched EPDM. We will show excellent practical properties of Linear-V-EP having
homogeneous network structures at the venue of AWPP 2016.
Keywords: EPDM, metallocene, neutron scattering, X-ray scattering
Table 1. Characteristics of EPDMs used inthis work.

Name

Diene
type

Structure ofpolymer chains

Linear-V-EP

VNB

linearBranched-V-EP VNB

branchLinear-E-EP

linearENB

Figure 1. SANS profiles forsamples shown in Table 1.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC047SYNTHESISANDPOLYURETHANEROLYROTAXANESCHARACTERIZATIONOFNOVELELASTOMERSCROSSLINKED
BY

HIROTO MURAKAMI, YOSHIMI TANAKA, NAOYA TABATANAGASAKI UNIVERSITY, NAGASAKI, JAPANIntroduction: Crosslinking structures of polyurethanes (PUs) play critical roles for the appearance of their elastic
properties. Polyrotaxane (PRX) is a macromolecule in which plural ring molecules are interlocked by a linear
axle polymer with bulky terminal cap groups. One of unique properties of PRX is free sliding of the ringmolecules along the linear chain. Therefore, introduction of PRX into the PU structure results in addition of thesliding effect. In this presentation, we describe the synthesis and characterization of PUs crosslinked by PRXs
where the length and filling ratio of the ring molecule are different.
Methods: PRXs, which consist of α-cyclodextrins (CyDs) and poly(oxyethylene)glycols with different chain
lengths (PEG1500, PEG4000, and PEG6000), were synthesized. The filling ratios of CyD are 75 % for PRX1500,
63 and 43 % for PRX4000s, 50 and 37 % for PRX6000s, respectively. The hydroxy groups in CyD were partiallymethylated to enhance their solubility. The PUs were synthesized by a prepolymer method. The prepolymer was
prepared with 4,4'-diphenylmethanediisocyanate (MDI) and poly(oxytetramethylene)glycol 2000 (PTMG2000)
with a ratio of [NCO]MDI/[OH]PTMG = 3.0. Subsequently, the prepolymer and the PRXs were reacted with a ratioof [NCO]total/[OH]total = 1.5. The name of PUs are abbreviated as PUa(b) in which a and b indicate the lengths
and filling ratios of PRXs, respectively.
Results & Discussion: All of the PUs left their gel components in DMSO, indicating the existence of thecrosslinks between the PRXs ATR-FT-IR spectral results revealed that the formation ratio of hydrogen bond
between the PU chains increased with increase in the filling ratio. DSC and dynamic viscoelastic measurements
and tensile tests for the PUs revealed that (i) reorganized-crystallization of the PTMG chains of PU1500(75) easily
occurred; (ii) the thermal and physical behaviours of PU6000(37) and PU4000(43) were almost the same because
CyDs as the crosslink points disperse; (iii) PU6000(50) and PU4000(63) with the moderate filling ratios shows
slow reorganized-crystallization of the PTMG chains. PU4000(63) also showed better tensile performance thanthe other PUs. In conclusion, we have demonstrated the synthesis and characterization of five PUs crosslinked
by PRXs with different chain lengths and different filling ratios of CyD. Characteristics of the PUs depend inlarge part on the filling ratio of CyD in the RRX.
Keywords: Polyurethane elastomer, Polyrotaxane, Crosslink

Asian Workshop on Polymer Processing, 6-9 November 2016

OC048SURFACE CONSTRUCTION ON THERMOPLASTIC ELASTOMERSWITH MICRO/NANO-FABRICATION TOWARDS BIOMEDICALAPPLICATION
Qiang Shi
ChangChun Institute of Applied Chemistry, Changchun, China
Introduction: The purpose of the abstract is to describe the preparation of blood-compatible biopolymers basedon thermoplastic elastomers with micro/nano-fabrication and establish the basic mechanism for the selective
reaction between blood and constructed surface of thermoplastic elastomers.
Methods: Mciro/nano-patterning technique and reactive electrospinning were used to construct the surface on thethermoplastic elastomers to investigate the selective reaction between blood and the surface and develop bloodcompatible biomaterials. The surface structure, blood-compatibility, selective reactions between the blood andbiopolymer surfaces and function of the biomaterials were investigated.
Results: The surface on the thermoplastic elastomers was constructed with mciro/nano-patterning technique andreactive electrospinning. The micro/nano-patterned surface and hierarchical architecture on blood-contacting
surface were developed to reduce thrombus and hemolysis of red blood cells (Figure 1). The surface was also wellmanipulated to control the selective reactions between biopolymers and blood. The selective and specific reaction
between patterned surface and blood plasma in the fresh blood (without adhesion of blood cells on the patterned
surfaces) was realized to investigate the adsorption behaviour of blood plasma on the surface. Then, the selective
reaction between the surface and blood cells was obtained to capture blood cells from the blood in the harmlessmanner. Finally, the smart selection reaction between blood and surface that could capture and release the blood
components on the surface was achieved to establish the reaction mechanism of blood and surface/interface. Basedon the fundamental research, we set up the new technology for preparation of blood-compatible biomaterials andsome biomaterials had been applied in industry.

Figure 1. Constructing blood-compatible surface on thermoplastic elastomer with micro/nano-fabrication
Discussion: The current knowledge of blood-contacting biopolymers and devices were summarized. In addition,
how the surface structure affected the selective reactions between blood and biopolymers, blood-compatibility ofbiomaterials were detailed discussed. The perspective of biomaterials prepared by micro/nano-fabrication was
proposed.
Keywords: Micro/nano-fabrication, selective reaction, blood-compatibility

Asian Workshop on Polymer Processing, 6-9 November 2016

OC049PHASE SEPARATION IN THERMOPLASTIC PROTEIN/POLYESTERBLENDS
Matthew Smith, Johan Verbeek
University of Waikato, Hamilton, New ZealandNovatein thermoplastic protein is produced from bloodmeal and is used for applications in the meat processing
industry. Currently, it has insufficient impact resistance and energy to break for other applications. Blending
Novatein with other polymers is a suitable strategy to overcome this. By tailoring phase morphology it could bepossible to improve impact resistance and energy to break. Novatein was blended with poly(butylene adipate-coterephthalate) (PBAT) in varying compositions between 2 - 30 wt. % PBAT. Poly(2-ethyl-2-oxazoline) (PEOX)
dissolved in water was blended with Novatein prior to melt blending with PBAT using a twin screw extruder.
Poly[(phenyl isocyanate)-co-formaldehyde] (pMDI) was used as a secondary compatibilizer added to theNovatein-PBAT blend before injection moulding. Uncompatibilized blends were also produced as a control.
Uncompatibilized Novatein-PBAT blends show an asymmetric phase inversion whereby a co-continuous
morphology is seen at low PBAT content. The coalescence of PBAT at low wt. % can be attributed hindrance ofminor phase break up due to interfacial tension and a high viscosity ratio. In comparison, the addition ofcompatibilizer caused a reduction in PBAT phase domain size, and shifted the onset of co-continuity of the minor
phase to a higher wt. %. This was attributed to the presence of the dual compatibilizer delaying the onset of minor
phase coalescence. Novatein presents a unique challenge during blending with other polymers due to theabnormally high viscosity ratio which leads to the asymmetric phase morphology seen here and in other Novateinpolyester systems.
Keywords: PBAT, Novatein, Co-continuous, Phase Morphology

Asian Workshop on Polymer Processing, 6-9 November 2016

OC050SMALL- AND WIDE-ANGLE X-RAY SCATTERING STUDIES ON
METALLOCENE EPDM AND EBDM
Kiminori Uchida, Kazuki Mita, Yuji Noguchi, Yuji Ishii, Tatsuya Sakai, Kotaro Ichino
Mitsui Chemicals,inc., Chiba, Japan
Introduction: Ethylene-propylene-diene terpolymer (EPDM), is a synthetic rubbers which is used forautomotive, electrical, and construction industries. Industrialization of our EPDM by using the metallocene
catalyst instead of the Ziegler-Natta catalyst began in 2008. The metallocene catalyst has excellent performancein copolymerization. For example, we can use a new monomer, butene instead of propylene, and get ethylenebutene-diene terpolymer (EBDM).
The new monomer butene influences crystal structures and amorphous structures, which results in excellent
softness at very low temperature. In this study, these structures were studied by using synchrotron radiated smalland wide-angle X-ray scattering method and rheology.
Methods: We prepared EBDM and EPDM having various ethylene contents by using the metallocene catalyst.
The glass transition temperatures (Tgs) of each polymer were measured by using differential scanning calorimetry(DSC). Sheets of each polymer were obtained by compression molding, and hardness (Shore-A) of each sheet
was measured according to JIS. Small- and wide-angle X-ray scattering (SAXS and WAXS, respectively)
measurements under uniaxial stretching were simultaneously carried out using the beamline BL03XU at SPring8, Hyogo, Japan. The SAXS and WAXS measurements were conducted with the approval of SPring-8 (Grant Nos.
2011B7270, 2012A7219 and 2012B7269).
Results: When the Tgs were compared at the same ethylene contents, the Tgs of EBDM were about 10 °C lower
than those same contents of EPDM. Fig. 1 shows WAXS patterns obtained at n = 0, 256, 523 %. Here, n is strainof uniaxial stretching imposed on specimen. In both EPDM and EBDM, scattering intensities along the direction
perpendicular to the draw direction increased with increasing strain.
Discussion: Low Tg indicates that EBDM has excellent softness even in very low temperature. WAXS result
indicates that strain-induced ordering occurred. Degree of the increasing of intensities was smaller in EBDM thanin EPDM, indicating that EBDM is softer than EPDM under deformation.
Keywords: Ethylene-propylene-diene terpolymer (EPDM), metallocene, X-ray scattering

Fig. 1 2-dimensional WAXS patterns of EBDM(a) and EPDM (b) obtained at n = 0, 256 and523 %. Arrows indicate the draw direction.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC051A CASE STUDY IN CABLE EXTRUSION - UNDERSTANDING
RHEOLOGY WITHOUT RHEOMETERS?
Ivan Ivanov
Nexans Olex, Lilydale, VIC, Australia
Introduction: In wire and cable industry, polymer insulation and sheath are applied over conductors by extrusion.
Specially designed “cross-heads” are used to continuously coat the wires or laid-up cores that move in aperpendicular direction, relative to the extruders. Rheology of polymer compounds utilised in this process needs
to be understood, in order to optimise production speed and product quality. While developing a highly filled
compound for a break-through fire resistant application, the material’s interesting rheological behaviour wasstudied. This allowed composition optimisation for improved processing.
Methods: A typical industrial R&D project was initiated after observation of batch to batch variation and poor
processability of certain batches. Two significantly variant batches were analysed and their flow curves obtainedby a capillary rheometer. The material’s extrusion behaviour was studied by using a Brabender Plasticorder / lab
extruder, equipped with a cross-head. Modified compositions were compounded using a Buss kneader. Torqueand pressure readings were taken and correlated to filler content.
Results: The batch with poor processing behaviour was found to be less viscous than the ‘good’ batch, as aconsequence of a lower level of filler. Relatively quick QC methods were identified to assess these two propertiesof the studied compounds, namely %ash (solid residue after calcinations at 900°C) and melt flow index (MFI).
Good correlation was found between MFI, extruder torque and die pressure. This was especially the case in aseries where a single component was varied. More complex situation occurred when trying to correlate data fromthe whole study, where more than two components were varied. .
Discussion: Based on this study, two goals were achieved: - a simple procedure was acquired for compound
quality control and – a new compound was developed, with improved processing behaviour and ultimate
properties. Apparent paradox that compounds with lower melt viscosity showed poor processing behaviour was
explained by the need to achieve sufficient die pressure to exude low molecular weight components to the surface(external lubrication).
Keywords: rheology, extrusion, cable, insulation

Asian Workshop on Polymer Processing, 6-9 November 2016

OC052A TALE OF TWO MOTORS
Ashish Kumar1, Jörg Läuger2
1

MEP Instruments, Melbourne, Australia, 2Anton Paar Germany GmbH, Ostfildern, Germany

A new rheometer platform based on two electronically commutated (EC) synchronous motors was introduced
recently, representing a large step in rheometer innovation. By integrating two independently controlled air
bearing motors on one rheometer, a range of testing possibilities become available (Fig.1). Combined motortransducer (CMT), separate motor transducer (SMT) and counter rotation are just some of the measurement modes
to elucidate material behaviour across a large strain and stress range. The modular design allows the lower motor
to be exchanged for another accessory much like a standard rheometer.
In the counter-rotation mode the motors are set to rotate in opposite directions. The pre-set speed is split between
the two motors, whereas the torque and normal force are measured at the upper motor unit. This mode is aninvaluable tool for microscopy applications – the creation of a stagnation plane allows the real-time observationof structural elements under shear fields (Fig.2). Further typical applications of the counter rotation mode areextensional rheology and the investigation of flow instabilities under different shearing conditions.
In the SMT mode the upper motor is operated solely as a torque transducer, while the lower motor functions
exclusively as a drive unit. In this configuration it is possible to measure low elasticity contributions in samples
with low viscosity, as well as extending the shear rate or strain range in measurements of polymeric samples.
The aim of this paper is to describe new technologies involved and to present measurement results and examples
relevant for polymer rheology and dynamic mechanical thermal analysis (DMTA).
Keywords: Rheology; Stress controlled; Strain controlled; Counter rotation; Superposition

Asian Workshop on Polymer Processing, 6-9 November 2016

OC053

THE POLYMORPHIC CRYSTALLIZATION BEHAVIOUR OF
POLYMER IN THE NANOPOROUS ANODIC ALUMINA OXIDETEMPLATE
Xiaoli Sun, Xiying Dai, Shouke Yan
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing,
China
Introduction: Recently, crystallization of polymer in the cylindrical templates has been widely investigated.
Inorganic templates such as anodic aluminum oxide (AAO) membranes have been mostly employed. The studies
can be divided into several categories. The first one is to study the nucleation mechanism of polymers in thenanopores. The second one is to study the orientation of the polymer crystals in the pores. The influence of
nanopores on the crystal phase is rarely explored. Considering many polymers have polymorphic crystals whichplays an important role on the final properties of materials, it is worthwhile to study the phase transition andpolymorphic behaviour in the confined one dimensional spaces.
Methods: The polymorphic polymer was infiltrated into the AAO templates with different pore diameter andpolymer nanotubes with different diameters were prepared. The crystallization and phase transition behaviour ofthe obtained polymer nanotubes caped in the nanopores have been explored by using X-ray and DSC.
Results: As for the poly(butylene adipate), it has  phase which form at high crystallization temperature and 
phase which form at lower crystallization temperature. In the nonisothermal crystallization process, only 
crystals form in the bulk sample. However, predominant -PBA crystals form in the AAO templates with theorientation of b-axis parallel to the long axis of pore in narrow pores. During the melt recrystallization process,the critical temperature, below which pure -crystals form, is 20 C for bulk PBA. It drops down significantlywith the decrease of pore diameter. Phase transition behaviour of  phase in the heating process depends on poresize. In narrow pores, it melts directly. Only in large pores, it has the chance to transit to  phase.
The poly(vinylidene fluoride) exhibits different crystallization behaviour in the AAO. In the nonisothermal
crystallization process, only  crystals form both in bulk and AAO. The AAO template affects the nucleation
types and melting temperature. The melting temperature of PVDF crystals in the AAO is much higher than thatof bulk which can be attributed to the presence of an interfacial layer of PVDF on the template inner surface. Theinteraction between PVDF and AAO template produces the interfacial layer. In the melt recrystallization process,for the bulk,  crystals show up when the crystallization temperature is above 158 C.  crystals are completely
depressed in AAO when in the pore with the diameter is smaller than 200 nm.
Discussion: The phase transition and polymorphic behaviour of polymer in the confined one dimensional spaces
can be well controlled by the AAO pore size, interfacial interaction and thermal treatment methods. Smaller size
decreases the melting temperature and interfacial interaction improves the melting temperature.
Keywords: polymorphic behaviour; melt; AAO template; pore size; confinement

Asian Workshop on Polymer Processing, 6-9 November 2016

OC055

DIRECT PREPARATION OF NANOFIBER YARN BY NEEDLELESSMELT ELECTROSPINNING WITH ASSISTED SUCTION WIND AND
ROTATING COLLECTORHAOYI LI, XIAOLU MA, JING TAN, HONGBO CHEN, WANLIN HE, WEIMIN YANG
BEIJING UNIVERSITY OF CHEMICAL TECHNOLOGY, BEIJING, CHINA
Melt electrospinning is drawing more and more attention in recent years since it doesn't introduce any toxic
solvent, is suitable for insoluble thermoplastic materials, and avoids any obvious whipping. Oriented nanofiberand even twisting yarn by melt electrospun fiber are urgently wanted for potential applications in high end textile,
high sensitive sensors, and other anisotropic areas. In this work we proposed a needleless melt electrospinningwith assisting suction wind and rotating collector for nanofiber yarn continuous and direct preparation. Welloriented nanofiber strands were prepared by applying suction wind as the multiple jets ejected from the self-madenozzle. Then continuous nanofiber yarn was successfully prepared after the strands were collated by collecting
roller and a rotating disk (the base of the collecting roller). It was found the twisting degree of the yarn can be
precisely controlled by the adjusting the ratio of speed of collecting roller to speed of rotating disk(SCTSR). Xray diffraction(XRD) results showed that the crystallinities increased with the increase of the yarn degree.
melt electrospinning, needleless, nanofiber, yarn,

Fig 1 Schematic diagram of experimental set-up

Fig 2 SEM images of several kinds of roller speed collection and rotation disk speed (×500)

Asian Workshop on Polymer Processing, 6-9 November 2016

OC056

3D NANO CAGE STRUCTURE OF ELECTROSPUN NANOFIBER FOR
HIGH PERFORMANCE AIR FILTER WITH EXTREMELY LOWPRESSURE LOSS
Seimei Shiratori
Keio University, Yokohama, Japan
Introduction: Three dimensional (3D) “Cage Structure” with 20nm diameter of Nylon Nanofiber and Chitosan
Nanofiber with 20nm diameter were successfully fabricated. Slip flow phenomena are of great concern in aerosol
filtration because of their ability to develop low pressure drops and high collection efficiency air filters by using
nanofibers expecting that we can maintain clean ambience with low energy. In this study, we have found that theslip flow is extremely enhanced when using polymer nanofiber of “3D Cage Structure” with less than 40nm in
the average diameter.
Methods: Nylon-6 nanofiber was fabricated by electrospinning method using formic acid and water.
Uniform nanofibers with average diameters of 20 nm were successfully and reproducibly fabricated byelectrospinning of nylon-6 for aiming at high performance air filter. Aerosol collection efficiency(P) of the tested
filters was calculated using laser particle counter. Polyalphaolefin nanoparticles were used as a tested aerosol.
Pressure drop(⊿p) was measured at 5.3cm/m of face velocity. PF value is based on equation(1). Here, P:
penetration percentage and ⊿p: Pressure drop.
PFvalue  ln P
 100
p

(1)

Fig.1 SEM image of 3D Nano Cage

Fig.2

Comparison of Air Cleaning Performance of Air Filter

Results: SEM image of 3D nylon nano cage structure was shown in Fig.1. As shown in the figure,
Nylon nanofiber with 20nm diameter was uniformly fabricated. Comparison of air cleaning performance of
conventional HEPA filter and Nylon Nano Cage filter was shown in Fig.2.
Discussion: By the measurement of filtering characteristics as an air cleaning filter, PF value, which shows thefilter performance of air filter, newly fabricated nanofiber showed 132 and this vale was almost twice of theconventional HEPA (High-efficiency particulate air) filter which is 65, To the best of our knowledge it is thehighest value of the filter media. We consider that this is caused by the slip-flow phenomenon caused by the 3D
Nano Cage Structure of ultra-fine nanofiber.
Keywords: nano fiber, filter, slip flow, nylon, electrospinning

Asian Workshop on Polymer Processing, 6-9 November 2016

OC057

CELLULOSE NANOFIBER-ASSISTED DISPERSION OF CELLULOSE
NANOCRYSTALS@POLYANILINE
IN
WATER
AND
ITS
CONDUCTIVE FILMS
Shiqi Wang, Chun Wei, Jian Lv
Guilin University of Technology, Guilin, Guangxi, China
Recently, polyaniline (PANI) has received a high amount of attention from the nanoscience and nanotechnology
fields. This is because PANI exhibits superior chemical sensing capabilities, unique photothermal effect, andthermoelectric effect, stem cell differentiation promoting effect, catalytic activity, and high electrochemical
performance. However, PANI nanomaterials tend to aggregate and precipitate in water. Additionally, theapplication of PANI nanomaterials has been restricted by its poor ability to be processed and relatively poor
mechanical properties. Therefore, finding a facile, efficient, and controlled method to disperse PANI
nanomaterials is highly desirable undertaking. Currently, there are a number of studies that have focused on thedispersion of PANI nanomaterials. Methods for dispersing PANI nanomaterials have included controlling thereaction, controlling the PH of dispersion, doping it with phosphate ester, adding ionic liquid based polymer
electrolytes, and adding poly(sodium 4-styrenesulfonate) .
The goal of this paper is to investigate the possible use of cellulose nanofibers (CNFs) as dispersants to disperseand stabilize cellulose nanocrystals@polyaniline (CNCs@PANI), which will result in the preparation of highstrength and conductive films. It is potential applied to conductive ink, sensors, flexible supercapacitor,
biomedicine, etc.
In this work, a facile and efficient method for dispersion of cellulose nanocrystals@polyaniline (CNCs@PANI)
nanocomposites in an aqueous solution is reported by using cellulose nanofibers (CNFs) as a dispersant. To begin,
the CNCs@PANI was prepared for the experiment by using CNCs as a template and controlling the reactions to
obtain fiber-like nanocomposites. The nanocomposite was then dispersed in water with the CNFs by means ofmechanical shearing. Centrifugal and storage stability of the nanocomposite were measured, as well as the zeta
potential. The results showed that the CNFs had special dispersion assisting effects for dedoped CNCs@PANI.
The CNCs@PANI dispersion showed good centrifugal and storage stability, and a zeta potential of -30.7 ±0.2
mV was recorded with the addition of 10 wt% CNFs. This CNCs@PANI dispersion was casted to obtain aconductive film, which had tensile strength and electrical conductivity of 26.7 MPa and 104.7 S/m, respectively.
Keywords: cellulose nanocrystals, cellulose nanofibrils, polyaniline, mechanical property, conductivity

Asian Workshop on Polymer Processing, 6-9 November 2016

OC058MECHANICAL PROPERTIES AND MICROSTRUCTURE
POLYMER FILMS WITH LASER WELDING METHOD

OF

Kazushi Yamada1, Chieko Narita1, Kimitoshi Satoh2, Yasuo Kurosaki2
1

Kyoto Institute of Technology, Kyoto, Kyoto, Japan, 2The University of Electro-communications, Chofu, Tokyo,
Japan
In this investigation, we demonstrate various polymer film sealing by using Laser Advanced Welding of Plastics(LAWP) method and try to evaluate the mechanical properties and internal structure of sealed parts. PE, PP, andPTFE films with 50 μm thickness were used as sealing films, and CO 2 laser was applied for laser welding ofpolymer films. As a result, it became to seal for PP film during 4.5-7.5 W of CO2 laser irradiation power and for
PE film during 2-4 W of that. Therefore, we suggest that some kinds of polymer films can be sealed by controllingthe irradiation laser power. The relationship between mechanical properties and microstructure in sealed parts ofpolymer films will be discussed on the basis of the results of peel test, optical microscope, AFM observation, andmicro-Raman spectroscopy.
Introduction: In recent years, laser welding has become established as a new joining technique in plastics
technology, because it selectively exploits certain advantages over conventional methods. Particular mention canbe made of the contact-free energy introduction to the laser welding methods that have been developed and thehigh flexibility that they frequently offer. It is expected that a number of these processes will not only replace
conventional plastic joining processes in the future, but will also serve to open new fields of application and designthat are made possible only through laser welding. Laser advanced welding of plastics (LAWP) method is one of
the laser welding methods, and it is very excellent sealing method for medical plastic bags and various polymer
films. LAWP method is with transparent heat sink in order to cool the excessively heated polymer films by highpower laser irradiation. In addition, this method does not need to dope a dye or to set an absorption layer.
Accordingly, the surface feature of sealed parts is clear and smooth as compared with general heat sealing
methods.
Methods: PE, PP, and PTFE films with 50 μm thickness were used as sealing films. The CO2 laser (Firestar V30,
Synrad Co., Ltd., USA) was used, and the irradiation scans speed was 1 mm/s. The irradiation power was variedin the range of 4 to 15 W.
Results: It became to seal for PP film during 4.5-7.5 W of CO2 laser irradiation power and for PE film during 24 W of that. PTFE film was also sealed as same as the power of PP films, although the peel strength was very
weak as compared with PE and PP films. Therefore, we suggest that some kinds of polymer films can be sealedby controlling the irradiation laser power.
Discussion: Crystallization in sealed part of each film is promoted by irradiation energy of laser. Accordingly,
the relationship between mechanical properties and microstructure in sealed parts of polymer films will be
discussed on the basis of the results of peel test, optical microscope, AFM observation, and micro-Raman
spectroscopy.
Keywords: Laser welding, CO2 laser, polymer film, sealing

Asian Workshop on Polymer Processing, 6-9 November 2016

OC059

PLATEAU TO POWER STATION TO PADDOCK THE MIDLANDSIRRIGATION SCHEMEDavid Kenworthy
Zezt Pty Ltd, Wynyard, Tasmania, Australia
Delivering water from the Highlands of Tasmania to transform drought prone grazing land in southern Tasmania
is a complex engineering project on its own merits with economic benefits to small communities and family farms.
Then delivering power for up to 5000 homes as the water travels down from the plateau, enhances the project
above similar irrigation schemes.
The scheme started with the desire to deliver water 365 days per year to more populous areas in southern
Tasmania, from an area with over 1000 mm of rainfall. From the source at Arthurs Lake, water is piped in 1.2
diameter high pressure gravity pipeline (60 bar) to a mini hydroelectric station (5.5MW) at the foot of the plateau
at 12 bar. From the station, water is delivered via low pressure pipelines and natural waterways to farms to enhance
agricultural land from lower value grazing to higher value cash crops and dairy.
David Kenworthy, managing director of Zezt Pty Ltd, recounts this engineering feat of the longest pipe line in
Tasmania (124 km) transferring 38,500 ML of water from the Tasmanian Highlands at 900m AHD, irrigating
55,000 ha through HDPE pipe, DICL pipe, 5300 welds, 4800 tonne of polyethylene, 1 power station, pumpstations and dams. The innovation used on the project has seen the scheme and its engineers recognized nationwide
as an outstanding engineering feat, including individuals working on the project.
Keywords: Polyethylene, Tasmania, Engineering, Irrigation

Asian Workshop on Polymer Processing, 6-9 November 2016

OC060FABRICATION OF ORGANIC FIELD EFFECT TRANSISTOR BASEDULTRAVIOLET SENSOR USING AZOBENZENE-CONTAINING
FILMS AS GATE DIELECTRICS
Kang Eun Lee, Dong Gi Seong, Youngseok Oh, Moon-Kwang Um
Korea Institute of Materials Science, Changwon, Republic of Korea
Introduction: Many research group have investigated tailoring OFET devices by incorporating functionalities
into OFET devices for the advanced application such as gas sensor, optical switching, memory, and light-emitting
devices. In this study, We functionalized gate dielectric in OFET device to have UV light sensitive property byusing azobenzene derivative.
Methods: In 2011, Faupel group has reported that the capacitance of the azobenzene and PMMA blend film canbe reversibly and largely changed upon irradiation with UV light. So, we presented a OFET device withazobenzene containing film as a photoactive gate dielectric layer for the UV photosensor application.
Results: We fabricated the azobenzene-containing film based OFET by simple method. The device showedreversible photo-response upon alternating irradiation with UV light and visible light as shown in Fig. 1.

Fig. 1. Transfer characteristics of phototransistor under Dark and UV light.
Discussion: In this work, we successfully synthesized azobenzene derivative and prepared azobenzene–
containing blend film. We fabricated OFET UV sensor by simple spin-coating method with the blend film as gate
dielectric layer. The OFET device showed UV light sensitive property which can be used for UV sensor
application.
Keywords: azobenzene, UV sensor, OFET

Asian Workshop on Polymer Processing, 6-9 November 2016

OC061

DEFORMATION BEHAVIOUR OF NOTCHED THERMO-PLASTIC
ELASTOMER SPECIMEN -ANALYSIS OF YIELD STRESS - STRAIN
RELATION Yumiko Isogai1,4, Kenji Furuichi1, Takuya Sumiyama1, Chisato Nonomura1, Takaya Kobayashi2, Masanobu
Murata3, Masanori Wada4, Atsushi Yokoyama4
1

TOYOBO CO., LTD. RESEARCH CENTER, Ootsu,Shiga, Japan, 2Mechanical Design and Analysis Corporation,
Chofu, Tokyo, Japan, 3Nagoya Municipal Industrial Research Institute, Nagoya, Aichi, Japan, 4Kyoto Institute ofTechnology, Kyoto,Kyoto, Japan
Introduction: An analysis of large deformation behaviours of porymeric materials is one of the important issues
in design of molded products. However, it is difficult to explain large deformation behaviour of polymericmaterials by conventional measurements,because of an onset of necking, and heat generation due to plastic
deformation. Thus, we observed simultaneously true stress-true strain relations and heat generation in the tensile
tests by using DIC (Digital Image Correlation) and thermal tracer for thermo-plastic polyester elastomer (TPEE)
1) 2). In the large deformation region, the stress-strain relation of TPEE is influenced by both strain rate and heatgeneration. On the other hand, in the small deformation region near a yield point, heat generation can be ignored,
so that we can separate the influence of strain rate from that of heat generation. In this study, we report relatioships
between yield stress and strain rate of TPEE, and their dependencies on ambient temperature.
Materials and Methods: Thermo-plastic polyester elastomers (PELPRENETMmade by TOYOBO) with surface
hardness D57 (ASTM D2240) were used for tensile tests (including high speed condtions). The specimens with
R-shaped notch were used to control a necking position. Strain analysis using DIC was conducted by Visual
Imaging Correlation-2D (VIC-2D) image analysis system. Digital gray scale images for DIC were obtained via
CCD camera (GRAS-20S4M : Grasshopper). Thermotracer (TH9260 : NEC Avio infrared rays technology) wasused for the temperature measurements. With using above setups, we observed the true stress-true strain relations
with various tensile speeds. From these data under various ambient temperatures, we obtained the relationships
between yield stress and tensile speed, and their temperature dependencies.
Results: Figure 1 shows true stress- true strain relations of TPEE. Stress has tendency to increase with increasing
tensile speed. Figure 2 shows the relationships between tensile speed and yield stress in different ambient
temperatures. For each ambient temperature, the yield stress tends to increase when tensile speed is raised. In
addition, a point of inflection was observed in each ambient temperature. This positions move to faster side oftensile speed with increase of ambient temperatures , as shown by an arrow in Figure 2.
Discussion: The inflection points in the relationship of yield stress and tensile speed appear at the high-speed
tensile conditions. These inflection points correspond to induction of yield mode having a faster relaxation time.
Relaxation time of this fast yield mode depends on the ambient temperature. Thus, time-temperature superposition
principle can be applied to analyse it. To explain these phenomena effected by both heat generation and strain
rate, we have planned to numerical analysis in the future.
1) T. Kanatani et al., Preprints of Seikei-Kakou Annual Meeting ’14, p.203 (2014).
2) Y. Isogai et al., Preprints of Seikei-Kakou Annual Meeting ’14, p.205 (2014).
Keywords: Thermo-plastic elastomer, Thermal imaging, DIC, yield stress -strain rate

Figure1 True stress- true strain relations
with various tensile speeds of TPEE.

Figure 2 Relationships between yield stress andtensile speed in various ambient temperatures.

Asian Workshop on Polymer Processing, 6-9 November 2016

OC062ADVANCED COOLING SIMULATION TECHNOLOGIES FOR THE
INJECTION MOLDING PROCESS
Clinton Kietzmann, Lu Chen, Shishir Ray
Autodesk Australia, Kilsyth, Victoria, Australia
Introduction: Cooling circuit design in plastic injection molding has become the focus for improving part quality
and reducing cycle times. In order to achieve both high quality parts and low cycle times; technologies such as,
rapid heat cycling, conformal cooling, induction heating and thermocouple controlled cooling are commonly used.
Methods: This paper gives an extensive introduction to a 3D finite element method based solver which has beendeveloped to simulate these molding technologies. Rapid heating and cooling cycling heats the mold surface prior
to mold filling using steam, hot water or heater cartridges and cools the mold during the cooling phase with chilledwater resulting in a very good surface finish without compromising the cycle time. In order to achieve the same
effect but in a more efficient way induction heating uses an alternating electromagnetic field to heat the moldduring filling. With conformal cooling, the cooling channels follow the precise geometry of the part in the mold.
This aids in creating a uniform temperature distribution across the surface of the part by targeting hot spots.
Thermocouple controlled cooling has a temperature sensor in the mold that controls the flow of the coolant in thecooling channels. This results in shorter cycle times and lower costs.
Results: Case studies of some of these technologies are presented in this paper and discussed.
Discussion: Advance cooling technologies can now be simulated with confidence by plastic injection molding
engineers. The results presented in the paper comparing the results of the 3D finite element simulation models toactual experimental data show that an excellent correlation is achieved.
Keywords: Injection molding, Autodesk Moldflow, advanced cooling technologies

Asian Workshop on Polymer Processing, 6-9 November 2016