PLENARYAND
KEYNOTECONTRIBUTIONS
AND
PANEL
DISCUSSION
Asian Workshop on Polymer Processing, 6-9 November 2016

PL001DESIGN AND FABRICATE POLYMERIC MEMBRANES FOR WATER
REUSE, SEAWATER DESALINATION AND OSMOTIC POWER
GENERATION(Neal) Tai-Shung Chung
National University of Singapore, Singapore, Singapore
Clean water, clean energy, global warming and affordable healthcare are four major concerns globally resulting
from clean water shortages, high fluctuations of oil prices, climate changes and high costs of healthcare. Clean
water and public health are also highly related, while clean energy is essential for sustainable prosperity.
Among many potential solutions, advances in membrane technology are one of the most direct, effective andfeasible approaches to solve these sophisticated issues. Membrane technology is a fully integrated science andengineering which consists of materials science and engineering, chemistry and chemical engineering, separationand purification phenomena, environmental science and sustainability, statistical mechanics-based molecularsimulation, process and product design.
In this presentation, we will introduce our efforts on membrane development for water reuse, seawater
desalination and osmotic power generation.

Asian Workshop on Polymer Processing, 6-9 November 2016

PL002CHANGINGLANDSCAPE
IN
CHALLENGES AND OPPORTUNITIESPOLYMERRESEARCH:

Sadhan Jana
University of Akron, Akron, Ohio, USA
Polymer research landscape has changed significantly in last 15 years. The polymer conversion industries havereached a level of maturity with an almost irreversible impact on fundamental research on polymer processing.
No longer do we see full scale reports in current literature on the dynamics of screw extrusion, flow behavior in
injection molding, rheological issues of stretch blow molding, or structure formation in film blowing, although
no one believes that all fundamental problems in polymer processing have been unequivocally solved. The
availability of funding largely dictates the scope of contemporary polymer research. Consequently, a large
majority of active researchers are currently pursuing the unknowns in biomaterials processing or materials
development in the areas of thin films, nanocomposites, multifunctional materials that change color, emit light,
harvest solar energy, change shape on application of stimuli, etc. The fundamental principles of mass,
momentum, and energy balances still apply to these new problems, but the length scales of interest are a now a
few orders of magnitude smaller than what we are used to. In this talk, several examples will be presented torelate the length and time scales to polymeric materials performance in applications involving hysteresis inrubber compounds, drug delivery, air clarification, and coalescing filtration. In the first example, polymer
building block synthesis from monomers and their organization in the mesoporous macroscale structures will be
discussed in relation to airborne nanoparticle filtration as well as drug release. In the second example, nanoscalesurface engineering of carbon black particles will be discussed with the objective of obtaining low rolling
resistance rubber compounds. The third example discusses the use of polymer nanofibers with interpenetrating
network morphology in removing water droplets from ultralow sulfur diesel fuel where a balance of surface
energy and surface area is a key parameter.
Keywords: polymer processing, nanomaterials, functional materials, mesoporous

Asian Workshop on Polymer Processing, 6-9 November 2016

PL003

BIOPOLYMERS AND REACTIVE PROCESSING
Jinghua Yin, Qiang Shi
ChangChun Institute of Applied Chemistry, Changchun, China
Introduction: The purpose of the abstract is to describe the preparation of biopolymers with reactive processing
and establish the basic principle for the development of urgently-needed biomaterials with reactive processing.
Methods: Surface modification and reactive extrusion were used to fabricate biopolymers based on thethermoplastic elastomer and polyolefin, the biocompatibility, antibacterial activity and function of the
biopolymers were investigated.
Results: We proposed kinetics equations for reactive processing and demonstrated that the grafting reaction
and molecular structure of final products were dependent on the “cave effect” of macromolecular initiator,
monomer concentration and temperature; Furthermore, we designed novel catalysis and grafting-assistantsystem to enhance the grafting degree of products to 5 times that of products with conventional system, andpaved new way to modify commodity polymers chemically and biologically by the combination of reactive
processing and surface engineering.
Based on the fundamental research, we set up the new technology for preparation, industrial assembly andintegration of functionalized polyolefin film. The film possessed the antifogging period for more than 14
months. In addition, we established the new technology for reaction assembly, controlling couple reactions
between the different functional groups, as well as grafting and in-situ compositing during reactive extrusion.
With these new technologies, anti-irradiated and biocompatible biopolymers with high strength and elasticity
were developed, which showed the potential to completely replace the polyvinyl chloride (PVC) and eliminate
the harm of plasticizers in PVC biomedical supplies.
Discussion: The current knowledge of reactive processing and development of biopolymers were summarized.
In addition, how the surface structure affected the biocompatibility and functionality of biomaterials weredetailed discussed. The urgently-needed biomaterials in industry and the perspective of biomaterials prepared byreactive processing were proposed.
Keywords: Biopolymers, Reactive processing, Biocompatibility

Asian Workshop on Polymer Processing, 6-9 November 2016

PL004INNOVATION – A METHOD MAKES IT EASY!
Roger La Salle
Matrix Thinking, Melbourne, Australia
The word innovation has been so misused in recent time that not only has it’s very meaning been lost, so too themeans to undertake innovation in a simply systematic and structured way that always yields an outcome.
The session presents the “how to” of innovation.
Keywords: Innovation, invention, opportunity, matrix thinking, creativity

Asian Workshop on Polymer Processing, 6-9 November 2016

PL005

THE FUTURE OF MAKING THINGS
Matthew McKnight
Autodesk, Sydney, Australia
Everywhere we look today, we see fundamental changes in how things are designed and made. Across the world
and the world’s industries things have evolved as new technologies are transforming the way people create
products, buildings, infrastructure, stories, and more.
And we know that technology has always disrupted how things are made. And we know that technology willcontinue to allow customers to break new ground in the way things are designed and made. And this creates newopportunities and challenges for the future going forward and in the ways that we are going to create a betterworld.
This presentation will give you Autodesk’s perspective on three important characteristics of the future of how
things are going to be made. First, what sorts of disruptions are shaping the way consumers and producers makebuildings, infrastructure, stories, and products? What are the implications of those disruptions for the way we’regoing to work? And what techniques can we employ to manage those disruptions as we enter upon this new eraof making things.

Asian Workshop on Polymer Processing, 6-9 November 2016

PL006

ADAPTATION OF RECYCLING TECHNOLOGIES AND BUSINESSMODELS FOR PLASTICS IN A CIRCULAR ECONOMY
Edward Kosior1,2
1

Nextek Limited, London, UK, 2Brunel University London, London, UK

Introduction: Over the last 10 years there have been rapid advances in recycling technologies for plastics
packaging and the accelerating adoption of these materials in closed loops by brand owners and supermarkets,
however there are substantial technical and business challenges facing the recycling and polymer processing
industries now and in the near future related to the collection of plastics in developed and developing countries.
Methods: The evolution of closed loop recycling technologies for plastics has been based on high speed
automatic sorting to achieve high purities and robust decontamination technologies that can restore the materials
to food grade quality. This has been achieved with PET, HDPE and PP by utilizing the concept of a “challengetest” that defines the degree of decontamination that a recycling process can achieve. The emergence of new
regulations for food contact recycled plastics in Europe has created a need to be able to distinguish between
packaging that has been used for food grade or non-food grade applications in the last cycle. The recycling offilms and black plastics is still challenging both economically and technically.
Results: New recycling technologies based on using fluorescent labels have emerged that can sort plastics into
categories based on the prior application as well as specifying food grade status. This is specifically required in
PET and HDPE food grade recycling where the purity limits have been set at 95% and 99 % respectively by
EFSA in Europe. Recent sorting results have shown that high speed automatic sorting can achieve purity levelsof at least 99% and yields in the region of 90%.
Discussion: The emergence of recycled polymers of high purity and with consistent physical properties has
allowed these materials to be used in place of virgin plastics at levels in the range of 25% to 50%. This has
allowed brand owners and product retailers to close the loop on packaging in both food grade and non-foodgrade applications. While these achievements have been reached for some applications and have created a
growing demand for post consumer packaging, there is still a leakage of plastics waste from this cycle that ends
up in waterways and oceans creating negative impacts for coastal regions, sea-life and bird-life and ultimately
human life. The strategies for limiting and reversing this leakage need to be enacted at international and local
levels.
Keywords: Plastics, Recycling, Food-grade, Oceans, Closed-Loop

Asian Workshop on Polymer Processing, 6-9 November 2016

KN001ISSUES IN THE EXTRUSION OF LARGE DIAMETER SMOOTH AND
CORRUGATED PLASTIC PIPE
John Vlachopoulos
McMaster University, Hamilton, Canada
Large diameter PE (Melt Index 0.1-0.3) , PP (Melt Flow Rate about 0.3) and Rigid PVC (K-value 66-68) pipes
are used for sewage and storm-water management. Diameters frequently exceed 1000 mm. Double wall pipes
with a smooth inner wall and corrugated external wall exhibit enhanced stiffness and certain advantages overconcrete and steel installations. Pipes sections are frequently joined by belled couplings at one end, fitting thenext. Such pipes are expected to withstand heavy loads as cars, trucks and other vehicles may travel over thesoil below which they are buried. They are expected to pass certain compression tests and they are designed tolast for at least 50 years without serious reduction of the water carrying capacity and load bearing
characteristics.
Single screw extruders are used for PE and PP and counter-rotating twin screw extruders for PVC. The molten
polymer must be free of unmelts and of excellent quality as it arrives at the die entry and must have a good melt
strength as it exits. Static mixers are usually beneficial for temperature homogenization and gear pumps can also
be beneficial for precise output control to the die. Dies are usually of the “spiderleg” variety. Behind the
spiderlegs, weldlines form which may have detrimental effects on the mechanical properties. Careful control oftemperatures is required in the die to prevent problems associated with heat transfer imbalance. To reduce thecost, Calcium Carbonate filler is frequently added. As a result, the melt viscosity increases and consequently thetemperature rise due to viscous dissipation. The end product has increased stiffness and reduced ductility. In
PVC extrusions several external and internal lubricants must be added to facilitate the flow and increase thedegree of gelation (fusion). Partially melted PVC exhibits some sort of microcrystalline 3D structure and uponrecrystallization may not produce a pipe of the required mechanical properties.
Problems associated with weldlines can be minimized by increasing temperature and pressure (longer die).
Special spiderleg designs are sometimes used to enhance molecular inter-diffusion across the interfaces forming
a weldline. Temperatures must be kept relatively low to avoid polymer degradation and to have good melt
strength, which is particularly important for profiled (corrugated) pipes. However, for PVC if the temperature is
low the polymer may not be fully fused. There is a narrow operating temperature window for PVC. Calcium
Carbonate filler must be used with moderation due to potential negative impact on mechanical properties. For
high output of good quality pipe, fillers and other additives must be well dispersed and distributed in thepolymer mass and the extruder must be operated under carefully monitored and controlled conditions.
Keywords: Die design, Weldlines, Fillers, Mechanical Properties

Asian Workshop on Polymer Processing, 6-9 November 2016

KN002ASSEMBLING BLOCK COPOLYMERSSAFETY AND SPILL RECOVERYFOR

ENHANCEDOIL

Tao Zhang1, Zhiguang Xu1, Yuanpeng Wu1,2, Qipeng Guo1
1

Deakin University, Geelong, Victoria, Australia, 2Southwest Petroleum University, Chengdu, China

Accidental spills during oil storage and transportation can cause irrecoverable damage to environments andhuman health. Recently we have investigated the enhancement of oil safety and spill recovery by use of
assembling block copolymers (BCPs) to stabilize high internal phase emulsion (HIPE) gels [1-7]. Oil safety canbe enhanced via a novel and safe approach to transform oils into assembled BCP stabilized HIPE hydrogels. The
BCP, namely (4-vinyl pyridine)-block-poly(ethylene glycol)-block-poly(4-vinyl pyridine) (4VPm-EGn-4VPm)
can assemble and significantly stabilize HIPE hydrogels. The assembled BCP is effective to trap a variety ofoils, including xylene, toluene, canola oil, blended vegetable oil, gasoline, diesel and engine oil. The volume
fraction of the dispersed oil in hydrogels can be up to 89%. Oils trapped in these hydrogels are releasable bytuning pH values of the aqueous phase, and after naturalization the aqueous phase with BCPs is reusable tostabilize HIPE hydrogels. Oil spill recovery can be achieved with assembled sulfonated polystyrene-blockpoly(ethylene-ran-butylene)-block-polystyrene (SSEBS) [4-5]. SSEBS reacted with polystyrene-block-poly(2vinyl pyridine), polyproplenimine dendrimers, -NH2 modified Fe3O4 particles or benzoxazine molecule to form
polymer organogels with nanostructures. These polymer organogels were used to stabilize HIPE organogels [24], and porous polymers (HIPE xerogels) were obtained after removal of water and solvents from the HIPE
organogels. These porous polymers have a low density, and the sizes of pores vary from several to tens of
micrometres. These xerogels can absorb a variety of oils and organic solvents, showing high absorption rate andabsorption capacity. The absorbed oils or organic solvents can be easily recovered by simple squeezing out, andthese xerogels can be used over 20 times. The xerogels can be collected with help of a magnet by incorporationof Fe3O4 particles. Therefore, assembled block copolymers are also an excellent candidate for enhanced spillrecovery.
Keywords: Block copolymer, high internal phase emulsion, oil safety, spill recovery.
References:
1. T. Zhang, Z. Xu, Y. Wu and Q. Guo, Ind. Eng. Chem. Res. 2016, 55, 4499.
2. T. Zhang and Q. Guo, Chem. Commun. 2013, 49, 5076.
3. T. Zhang and Q. Guo, Chem. Commun. 2013, 49, 11803.
4. T. Zhang, Y. Wu, Z. Xu and Q. Guo, Chem. Commun. 2014, 50, 13821.
5. Y. Wu, T. Zhang, Z. Xu and Q. Guo, J. Mater. Chem. A 2015, 3, 1906.
6. T. Zhang, Z. Xu, Z. Cai and Q. Guo, Phys. Chem. Chem. Phys. 2015, 17, 16033.
7. T. Zhang and Q. Guo, Chem. Commun. 2016, 52, 4561.

Asian Workshop on Polymer Processing, 6-9 November 2016

KN003REMOVAL PROTEINS FROM NATURAL RUBBER LATEX ANDAPPLICATION
Trung Nghia Phan1, Thu Ha Nguyen1, Thuong Nghiem Thi1, Seiichi Kawahara2
1

Hanoi University of Science and Technology, Hanoi, Viet Nam, 2Nagaoka University of Technology, Nagaoka,
Viet Nam
Introduction: Removal of proteins from natural rubber is one of the key-technologies to cure a serious issue ofthe latex allergy. i.e. hypersensitive allergy (Type I) which is mediated by immunoglobulin E (IgE). Various
techniques to remove proteins from natural rubber have been developed in the last three decades. Amongtechniques, the deproteinization with urea and surfactant and non-polar organic solvent are of great interest to
prepare low-protein and non-protein natural rubber latex. In the present study, an attempt to prepare
deproteinized natural rubber (DPNR) with urea, surfactant and acetone was carried out. The protein content of
the product obtained was determined through Kjeldahn method. The stability of resulting latex was evaluatedthrough mechanical stability test (MST).
Methods: High ammoniated natural rubber (HANR with nitrogen content of 0.297%) latex was purchased fromGolden Hope Plantation. Deproteinization of HANR was made by incubating latex with 0.1%w/w urea, 1%w/w
sodium dodecyl sulfate (SDS) and acetone for 1h followed by centrifugation at 12.103 rpm. The deproteinized
natural rubber latex was dried in reduced pressure at 50 oC for a week (DPNR).
The resulting samples were subject to Kjeldahn test and MST.
Results:
Table 1: nitrogen content of resulting DPNR
Number of centrifugation

1

2

3

4

Sample

DPNR1

DPNR2

DPNR3

DPNR4

Nitrogen content (%)

0.01

0.007

0.005

0.005

Table 2: MST result for resulting sample
Sample

HANR

DPNR1

DPNR2

DPNR3

Time for coagulation (s)

360

720

700

650

Discussion: nitrogen content of natural rubber decreased significantly after incubation with urea and acetone.
The MST result shows that natural rubber latex is stable after the removal of proteins. The results confirm theefficiency of urea and acetone onto the removal process.
Keywords: deproteinized natural rubber, natural rubber latex, stability

Asian Workshop on Polymer Processing, 6-9 November 2016

KN004

ALIGNMENT OF NANO-CARBON MATERIALS BY EXTERNALFIELDS
Chun Wang1,2, Shuying Wu2, Raj Ladani2, Jin Zhang3, Adrian Mouritz2, Anthony Kinloch4
1

University of New South Wales, Sydney, Australia, 2RMIT University, Melbourne, Australia, 3Deakin
University, Geelong, Australia, 4Imperial College London, London, UK
Introduction: Polymers generally have low mechanical and electrical properties compared to structural fibres
such as glass fibres and carbon fibres, resulting in poor structural and functional performance in the throughthickness direction of composite laminates. Recent research on nano-reinforcement, such as carbon nanotubes(CNTs), carbon nanofibres (CNFs), and graphene nanosheets (GNS), have indicated promising reinforcement
efficiency as well as the ability to enhance electric and thermal properties of the polymers. However, nanoreinforcements are commonly dispersed in polymers by ultrasonication or shear force leading to random
distribution and orientation. External fields such as electric and magnetic fields have been shown to offer aconvenient approach to preferentially align nano-carbon materials. The aim of this presentation is to report
recent progress in aligning and chaining nano-carbon fillers to selectively enhance the mechanical andfunctional properties of thermoset polymers and fibre composites.
Methods: Nano-carbon materials (carbon nanofibers and graphene nanoplatelets) are first dispersed in liquid
epoxy resin before adding curing agent. Alternating electric field is then applied to align the nano-carbon
material during the curing process of the epoxy. Mechanical, thermal and electrical properties of the resultant
nano-composite material are then measured in directions parallel and perpendicular to the alignment direction.
Results: The electrical conductivity of the nanocomposites with aligned CNFs and GNPs are increased byabout ten and seven orders of magnitude, respectively. The percolation threshold of the nanocomposites
containing aligned nano-reinforcements is about 50% lower that of their randomly-orientated counterparts. The
values of the fracture energy of the nanocomposites containing 0.5 wt% of randomly-oriented CNFs or GNPs
increased by up to about 200%, compared to the unmodified epoxy. An additional improvement in fractureenergy of up to about 40% has been achieved by aligning the nano-reinforcement transverse to the crack growth
direction.
Discussion: The efficacy of the alignment of the nano-reinforcement on the improvement in the electricalconductivity and the fracture energies of the nanocomposites has been found to diminish at higher
concentrations of the nanoreinforcement. Further research is needed to align nano-carbon materials of highconcentration.
Keywords: Include 2 to 5 keywords at the bottom of your abstract, separated by commas

Asian Workshop on Polymer Processing, 6-9 November 2016

KN005

FLAMMABILITY OF POLYMER COMPOSITES WITH NATURALFIBRES
Debes Bhattacharyya, Nam Kyeun Kim
University of Auckland, Auckland, New ZealandIntroduction: Extensive studies have been carried out on the thermal decomposition and fire resistance ofpolymeric materials to reduce their high flammability. Although addition of flame retardant (FR) has proven tobe effective in fire retardancy, some of them containing halogens, have negative effects on the environment andhuman health [1]. Thus, it is desirable to develop an environment friendly fire retardant system for polymericcomposites. Natural fibres are increasingly being considered as a group of alternative reinforcement materials incomposites due to their certain inherent advantages, namely biodegradability and CO 2 neutrality, over thesynthetic materials. Wool as a natural protein fibre is naturally a less flammable material because of a relatively
high content of cysteine (10 wt%), which is a sulphur containing amino acid, and nitrogen (15-16 wt%) in thefibre [2]. It is also observed that wool fibres produce char in an intumescent manner upon combustion . On theother hand, lignocellulose fibres, such as flax and kenaf, although, which might act as combustion sources incomposites, the amount of lignin content can contribute to beneficial char formation and provide a thermal
barrier [3]. Therefore, the fire growth can be controlled by selecting suitable combination of materials in thecomposites. The char-forming tendency of the natural fibres can be increased with the addition of phosphorus
based FR [4]. In particular, as a halogen-free intumescent FR, ammonium polyphosphate (APP) contains
phosphorus and nitrogen, which can contribute to an improved fire retardancy for polyolefin under combustion[5]. In this research, two different types of natural fibres, namely wool and kenaf, have been selected toinvestigate the effects of fibres with FRs on the flammability of thermoplastic polymer composites. In addition,
the burning behaviour of thermoset polymer composite with natural fibre has also been explored. Standard
flammability test methods (e.g. cone calorimeter and UL-94) have been employed to evaluate the fire
performance of materials and the char structure has been studied by scanning electron microscope (SEM). A
preliminary study has been carried out on fire dynamics simulation and some results will be presented.
Methods: The constituent materials in this research are commercially available polymers, such as thermoplastic
PP and thermoset epoxy resin, natural fibres (e.g. wool, kenaf and flax) and other additives, such as APP andmaleic anhydride PP. The short natural fibre (average fibre length of 2.9 mm)-PP composites were fabricated bymelt blending and compression/injection moulding processes. Furthermore, the resin transfer moulding (RTM)
was used to create flax based thermoset polymer composites. The flax fabric and an infusion grade epoxy resin
were selected as reinforcement and matrix, respectively.
Thermal characterisations of the raw materials and composites were conducted by thermogravimetric analysis(TGA). Flammability of the neat polymer and composites was examined using the vertical burn test (UL-94)
and the cone calorimeter test. In particular, the cone calorimeter provided a large range of quantitative data offire-reaction properties, such as heat release rates and smoke production, for a detailed analysis of composites
flammability. Microstructures of fire residues were also examined under the SEM. In addition, mechanicalproperties of the composites were evaluated by tensile, flexural and charpy impact tests. Fire simulation was
based on a specially developed Fire Dynamics Simulator package.
Results: TGA results, Error! Reference source not found.(a), demonstrate that the neat PP does not create any
residues, but the addition of wool and APP increases the amount of residues (19.1 %) at 700 °C due to the
combined effect of the fibre and FR on char formation. Moreover, the cone calorimeter results indicate that thechar forming ability of wool and FR in the composite remarkably reduce the peak heat release rate (PHRR)(81.2 %) compared to that of the neat polymer. Error! Reference source not found.(b) shows char surface
formedduring the cone calorimeter test. Furthermore, the composite containing wool and FR can also achieve a direct
self-extinguishment (V-0 rating). Lignocellulose fibres, such as flax and kenaf, do not produce char as dense as
the wool char; however, the presence of lignin in fibres and reaction with FR under combustion lead to effective
char formation, thus reducing the composites flammability.

Asian Workshop on Polymer Processing, 6-9 November 2016

KN006OVERCOME THE CONFLICT BETWEEN STRENGTHTOUGHNESS IN POLYMERS AND COMPOSITESAND

Chaobin He1,2
1

National University of Singapore, Singapore, Singapore, 2Institute of Materials Research & Engineering,Singapore, Singapore
Abstract: Strength and toughness are two most important prerequisites for polymer applications. Unfortunately,
these two properties are often in conflict [1-2]. In this presentation, an effective and yet practical approach isdeveloped to simultaneously strengthen and toughen poly (L-lactide) (PLLA) using a simple rigid filler-g-rubber“reinforcing element”. This element consists of a rigid graphene oxide (GO) sheet covalently linked with poly
(caprolactone-co-lactide) (PCLLA) rubbery layer and a PDLA outer layer, which can be easily synthesized andincorporated into PLLA matrix to yield composites with well-tailored GO/PLLA interfaces. It is demonstrated
that by adding the “reinforcing element”, i.e., GO-graft-rubber-graft-poly (D-lactide), PLLA exhibits muchhigher tensile strength and toughness, which could be attributed to the rigid GO and rubbery PCLLA working intandem during deformation, and the strong interaction between PDLA and PLA matrix due to formation ofstereocomplex. [3-11] It is further demonstrated that our reinforcing strategy is much better than those tradition
methods, i.e. using either rigid filler or rubber particles separately, or the combination of the two. This approach
could be considered as a general design principle for reinforcing composite materials where both strength andtoughness are the key concerns. Furthermore, theses designed concept has also been successfully demonstrated
in various other polymer systems. [12-13]
Keywords: Strength. Toughness. Composites. Polymers.
References[1] Wang K, Chen L, Wu JS, Toh ML, He CB*, Yee AF*, “Epoxy Nanocomposites with Highly Exfoliated Clay:
Mechanical Properties and Fracture Mechanisms” Macromolecules 2005, 38, 788-800[2] He CB, Liu TX, Tjiu W, Sue HJ, Yee, AF* “Microdeformation and Fracture Mechanisms in Polyamide-6/ Organoclay
Nanocomposites” Macromolecules 2008, 41, 193-202[3] Lin TT, Liu XY and He CB* “A DFT study on poly(lactic acid) polymorphs” Polymer, 51, 2779-2785, 2010
[4] Lin TT, Liu XY and He CB* “Ab Initio Elasticity of Poly(lactic acid) Crystals” J. Phys Chem B, 114, 3133-3139, 2010
[5] Lin TT, Liu XY, He CB* “Calculation of Infrared/Raman Spectra and Dielectric Properties of Various Crystalline
Poly(lactic acid)s by Density Functional Perturbation Theory (DFPT) Method” J. Phys. Chem. B, 116, 1524-1535, 2012[6] Sun Y and He CB* “Synthesis and Stereocomplex Crystallization of Poly(lactide)-Graphene Oxide Nanocomposites”
ACS Macro Lett, 1, 709-713, 2012[7] Sun Y and He CB* “Synthesis, stereocomplex crystallization, morphology and mechanical property of poly(lactide)carbon nanotube nanocomposites” RSC Adv, 3, 2219-2226, 2013[8] Ye SM, Lin TT, Tjiu WW, Wong PK, He CB* “Rubber toughening of poly(lactic acid): Effect of stereocomplex
formation at the rubber-matrix interface” J. Appl. Polym. Sci., 128, 2542-2547, 2013[9] Sun Y and He CB* “Biodegradable “Core-Shell” Rubber Nanoparticles and Their Toughening of Poly (lactides)”,Macromolecules, 46, 9625-9633, 2013[10] Yang Sun, Liping Yang, Xuehong Lu, Chaobin He* “Biodegradable and renewable poly (lactide)–lignin composites:
synthesis, interface and toughening mechanism” Journal of Materials Chemistry A 3, 3699-3709, 2015[11] Li ZB, Tan B., Lin TT, He CB* “Recent advances in stereocomplexation of enantiomeric PLA-based copolymers andapplications” Progress in Polymer Science, 2016, on-line[12] Songlin Liu, Xiaoshan Fan, Chaobin He* “Improving the Fracture Toughness of Epoxy with Nanosilica-Rubber CoreShell Nanoparticles” Composite Science and Technology, 2016, 125, 132-140[13] Warintorn Thitsartarn, Xiaoshan Fan, Yang Sun, Jayven Chee Chuan Yeo, Du Yuan, Chaobin He* “Simultaneousenhancement of strength and toughness of epoxy using POSS-Rubber core–shell nanoparticles” Composite Science andTechnology, 118, 63-71, 2015

Asian Workshop on Polymer Processing, 6-9 November 2016

KN007

PROCESSING OF WOOD BIOPOLYMER COMPOSITES
Bronwyn Laycock1, Steven Pratt1, Luigi Vandi1, Clement Chan1, Des Richardson2, Alan Werker3
1

University of Queensland, St Lucia, Australia, 2Norske Skog, Tasmania, Australia, 3AnoxKaldnes AB, Lund,
SwedenThe use of wood plastic composites (WPCs) has been rapidly growing in the past decades. Recently,
polyhydroxyalkanoates (PHAs) have received substantial attention as biodegradable and biorenewable polymers
with properties very similar to petroleum-derived plastics such as polypropylene. They are particularly attractive
for composite applications because of the low melt viscosity for better compounding and the ultimate
biodegradability at end of life, regardless of disposal environment. This project represents the first attempt toengineer a high performance wood-biopolymer composite from pulp and paper waste. This aim is to develop an
optimised composite formulation through a study on the effect of the inclusion of processing conditions as wellas processing additives on pine wood flour or fibre composites with PHA. To explore the commercial viabilityof the composites, the materials were produced both at laboratory scale and at pilot plant scale using
industrially-relevant levels of wood filler loading (50 wt%) through extrusion.

Asian Workshop on Polymer Processing, 6-9 November 2016

KN008PROCESSING-INDUCEDMICROMECHANICAL
NANOCOMPOSITES

CLAY
ORIENTATIONPROPERTIES
OF

AND
NYLON

Tianxi Liu1, Lu Shen2
1

Donghua University, Shanghai, China, 2Institute of Materials Research and Engineering, Singapore, Singapore

Introduction: In this study, the nanoindentation technique is used to study the anisotropy characteristics ofmechanical properties of the injection-molded nylon 6 (PA6)/clay nanocomposites. The elastic and plastic
properties as well as creep behavior of neat PA6 and its nanocomposites have been comparatively evaluated as afunction of clay loading. An attempt has been made to correlate the observed mechanical properties with themorphological changes due to the addition of nanoclay and the injection process.
Methods: The morphologies of the PA6/clay nanocomposites were studied by using a Philips CM300-FEG
transmission electron microscope (TEM) under an accelerating voltage of 200 kV. Thin sections (with thicknessof about 80 nm) for TEM observations were cut from the cross-section of the injection-molded bars undercryogenic conditions by using a Leica ultramicrotome with a diamond knife. The indentation tests were
performed using an UMIS-2000H Nanoindentation system (Australian Scientific Instruments) with a Berkovich
indenter (three-faced pyramid diamond).
Results: The indentation results indicate that clay addition enhances the polymer’s hardness and modulus withincreasing the clay concentration. With addition of only 2.5 wt% of clay, the modulus of the polymer has
improved by about 74%, from 1.06 to 1.84 GPa, as compared with its neat counterpart; while with addition of
10 wt% of clay, the modulus is enhanced by approximately 128%. The TEM image clearly shows clay
orientation (along the injection flow direction) induced by melt-processing. At higher magnification under TEM,
the well exfoliated clay nanoplatelets were clearly observed. TEM image taken from the near-surface region
shows the clay distribution pattern in the nanocomposite, illustrating an uneven distribution of clay in theinjection-molded sample, as also confirmed by optical microscopy. That is, the content of clay increases fromthe sample surface to the inner region of the molded specimen. It is, therefore, expected that the inhomogeneous
clay distribution in the injection-molded samples could lead to the different distribution of mechanicalproperties in the material. Nanoindentation is further used to detect the localized deformation behavior, and alsoenables one to explore the mechanical anisotropy and the hardness/modulus distribution profiles resulted fromthe melt processing. The orientation of polymer chains and the distribution of clay platelets significantly affectthe localized mechanical behavior of the nanocomposites. The hardness and modulus along the injection-molded
flow direction are higher than those measured in the direction perpendicular to the melt flow. The
nanoindentation results also prove that the core portion of the injection-molded specimens of PA6 and its
nanocomposites generally possesses higher hardness and modulus than the outer part of the specimens, which is
caused by the processing-induced uneven distribution of both crystallinity and nanoclay within the molded
products.
Discussion: The nanoindentation behavior and morphology of the injection-molded specimens of PA6/clay
nanocomposites prepared by melt-compounding have been studied. The elastic and plastic properties as well as
creep behavior of PA6 and its nanocomposites are comparatively evaluated as the function of clay loading byusing nanoindentation technique. The anisotropic characteristics in mechanical properties are studied byindenting the injection-molded specimens in two different directions (i.e. parallel and perpendicular to theinjection direction). The uneven distribution of both the clay nanofiller and the crystallinity of the polymericmatrix induced by melt-processing lead to the variation of the mechanical property of the nanocomposites incertain directions and locations within the molded specimens. The microstructural and morphological changes
of PA6 upon incorporating with clay nanofiller are evidenced by transmission electron microscopy and smallangle X-ray scattering, which are closely correlated with the anisotropy of the mechanical properties observed
by nanoindentation.
Keywords: Nylon, clay, orientation, nanocomposites, nanoindentation

Asian Workshop on Polymer Processing, 6-9 November 2016

KN009JUST-IN-TIME BONE-SPECIFIC
MANUFACTURE

ADDITIVE

BONE

IMPLANT

Milan Brandt1, Darpan Shidid1, Martin Leary1, Peter Choong2
1

Centre for Additive Manufacturing, RMIT University, Melbourne, Australia, 2St Vincents Hospital, Melbourne,
Australia
Additive Manufacturing (AM) allows for the generation of highly efficient lattice structures that are not feasible
with traditional manufacturing processes. A particularly useful application of AM lattice structures is the
fabrication of customized bone implants.
AM lattice structures can be fabricated such that strength and biocompatibility requirements are satisfied.
Systematic design of the lattice elements can also ensure that the implant stiffness is statisticallyindistinguishable from the surrounding bone, thereby eliminating stress shielding effects.
This work reports on research at RMIT on a novel application of AM technologies such that a custom bone
implant is designed and fabricated during a surgical procedure for just-in-time implantation. This innovation isespecially relevant for osteosarcoma surgery.

Asian Workshop on Polymer Processing, 6-9 November 2016

KN010ORIENTATION INDUCED -IPP
RELATED PHASE TRANSITIONCRYSTALLIZATIONAND

Shouke Yan
Beijing University of Chemical Technology, Beijing, China
We have checked the orientation-induced crystallization of iPP by recrystallizing its highly oriented fibres after
incomplete melting. Considering that the morphological features of the thin fibres are difficult to be monitored,
self-induced crystallization of iPP melts by its homogeneity fibres with varying melting extent was studied. The
single iPP fibre/matrix composites were produced by a procedure in which the iPP matrix thin film was firstheated to 200 °C for 10 min to erase possible effects of thermal history of the sample on the subsequent
crystallization and then moved to a preheated hot plate, where the iPP matrix was kept in the molten or
supercooled molten state at the moment of fibre introduction. As the iPP molten or supercooled molten thinlayer reached equilibrium at the desired temperature, homogeneous iPP fibres tightly fixed on a metal frame
were introduced into the iPP matrix at different temperatures. After introduction of the fibres, the single iPP
fibre/matrix composites were moved quickly to another hot plate set at desired temperature for isothermal
crystallization.
Through systematic studies, it was found that the kinetic requirement is a sufficient condition only to ensure thegrowth of the β-iPP crystals, while the fast growing α-iPP crystals will otherwise embed the generated β-nuclei.
The local order and environment of the macromolecular chains just before nucleation taking place are importantfor β-nucleation of iPP. It is suggested that the formation of the β-iPP nuclei is restricted in a certain chainorientation window of the iPP melts. Considering that isochiral chains are involved in the β-iPP crystals,
microdomains with isochiral chains may be produced through chains rotation. These isochiral chain aggregatestransform into β-iPP nuclei during cooling process and initiate the growth of β-iPP crystals.
REFERENCES
1.

H. Li, S. Jiang, J. Wang, D. Wang, S. Yan, Macromolecules, 2003, 36, 2802.

2.

H. Li, X. Zhang, X. Kuang, J. Wang, D. Wang, L. Li, S. Yan, Macromolecules, 2004, 37, 2847.

3.

H. Li, X. Zhang, Y. Duan, D. Wang, S. Yan, Polymer, 2004, 45, 8059.

4.

X. Sun, H. Li, X. Zhang, J. Wang, D. Wang, S. Yan, Macromolecules, 2006, 39, 1087.

5.

X. Sun, H. Li, J. Wang, S. Yan, Macromolecules, 2006, 39, 8720.

6.

X. Sun, H. Li, I. Lieberwirth, S. Yan, Macromolecules, 2007, 40, 8244.

7.

H. Li, X. Sun, S. Yan, J. M. Schultz, Macromolecules, 2008, 41, 5062.

8.

Q. Liu, X. Sun, H. Li, S. Yan, Polymer, 2013, 54, 4404.

9.

H. Li, S. Yan, Macromolecules, 2011, 44, 417.

10. X. Sun, H. Li, X. Zhang, D. Wang, J. M. Schultz, S. Yan, Macromolecules, 2010, 43, 561.

Keywords: Polypropylene, Single polymer composite, Orientation-induced -crystallization

Asian Workshop on Polymer Processing, 6-9 November 2016

KN011ADVANCED MANUFACTURING TECHNOLOGY OF POLYMERREALIZED BY MULTIPLE DIVIDING AND COMBINING OFPOLYMER MELTWEIMIN YANG
BEIJING UNIVERSITY OF CHEMICAL TECHNOLOGY, BEIJING, CHINA
Since the emergence of synthetic phenolic resin in 1907, the synthesis, processing and application of polymer
materials have boomed. Polymer materials are becoming increasingly significant in modern manufacturingindustry due to their numerous advantages. However, the manufacturing mode in polymer processing is stillunchanged: small products are produced by small devices, dies or molds, and large products are produced byhuge devices. In order to solve the bottleneck problems in the manufacturing of micro products with highprecision and large-sized component with complex construction, a concept of multiple dividing and combiningof polymer melt (or can be called “differential and integral method (DI method in brief)” in maths) for advanced
manufacturing technology of polymer was proposed. Based on this concept, nanofiber, micro parts, and micronano laminated membrane, and giant tyres, and etc were created by applying custom designed mold for melt
multiple dividing and combining, and other assisting methods like high voltage or planetary gear pump. For
example, micro-nano laminated membrane was created by using parallel units of lamination mold for melt
multiple dividing and combining, and the thickness of each layer can be well controlled to reach tens ofnanometers. In another implementation, split hot runners were used to generate micro flow melts to supply tothe needleless melt electrospinning nozzles, which enabled the mass production of nanofiber from polymer melt.
In addition, this idea was also introduced into 3D manufacturing of polymer melt, in which the polymer pellets
were directly melt and then divided into controlled micro drops to form complex parts. A series o f new methodsof polymer processing and molding, new equipments, and new technologies of product application have been
invented based on this concept. Some industrial application results have proved the concept a valuable guide to
break through the restriction of traditional manufacturing of polymer melt.
Keywords: polymer melt; multiple dividing, combining, mold

FIGURE 1. Equipments, principle, and product of melt DI injection molding, DI nano-composites extrusion
molding and melt differential electrospinning.

Asian Workshop on Polymer Processing, 6-9 November 2016

KN012FABRICATION OF HIGH-PERFORMANCE STEREOCOMPLEXEDPOLYLACTIDEPRODUCTS
WITH
GOOD
OPTICAL
TRANSPARENCY VIA LOW-TEMPERATURE SINTERINGDONGYU BAI, HONGWEI BAI, QIANG FU
SICHUAN UNIVERSITY, CHENGDU, CHINA
Stereocomplexation between enantiomeric poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) provides aneffective way to greatly enhance mechanical strength, heat resistance and hydrolysis resistance of eco-friendly
polylactide (PLA). Unfortunately, although the fabrication of semicrystalline polymers including PLA generally
involves melt processing at temperatures typically higher than their melting temperatures, it is still a hugechallenge to obtain high-performance stereocomplexed polylactide (sc-PLA) products from melt-processed
PLLA/PDLA blends due to the poor melt memory effect of stereocomplex (sc) crystallites to restore exclusive
sc crystallization after complete melting at an elevated temperature of ca. 240-260 °C, which generally leads toonly the formation of a product with mixed homochiral (hc) and sc crystallites, and the substantial thermal
degradation of PLA chains induced by this processing. Herein, we report a facile and robust route to addressthese obstacles by low-temperature sintering of sc-PLA powder at temperatures as low as 180-210 °C for the
first time. The results confirm that enantiomeric PLA chain segments can interdiffuse across interfaces ofadjacent powder particles and subsequently co-crystallize into new sc crystallites capable of tightly welding theinterfaces during the sintering process, thus sc-PLA products with 100% sc crystallites, excellent heat resistanceand good transparency have been successfully fabricated. We believe this work could open a new avenue for thedesign and fabrication of high-performance, optically transparent sc-PLA-based products.
Keywords: polylactide, stereocomplex, sintering

Asian Workshop on Polymer Processing, 6-9 November 2016

KN013NEW STATIC EXTENSIONAL MIXING ELEMENTS FOR TWINSCREW EXTRUSION: COMPUTATIONAL AND EXPERIMENTAL
VALIDATION
Joao Maia1, Sidney Carson1, Jose Covas2
1

Case Western Reserve University, Cleveland, OH, USA, 2University of Minho, Guimaraes, Portugal

We have recently developed a new type of mixing element for twin-screw extrusion, dubbed the Extensional
Mixing Element (EME), for the purposes of imparting extension-dominated mixing on polymer melts during
processing. Even though extensional flows are much more efficient in dispersion processes during polymer
compounding or blending, most mixing action in standard processing equipment is shear-dominated. The EME
was built as a static mixer for the inside of the barrel of a twin-screw extruder, the unit riding along bearings andstaying stationary while the rest of the extruder screw spins, forcing material through hyperbolic converging anddiverging channels at a specific extension rate.
Here we demonstrate the improved dispersive mixing capabilities of the EME when compared to a standard
shear kneading block (KB) in the blending of immiscible polymers (polypropylene/polystyrene blends at 80/20
wt.% ratio and of viscosity ratios up to 10) and the compounding of polymer/carbon nanocomposites withcarbon fillers of different morphologies (spherical, high aspect ratio, 2D sheets). The results clearly indicate that
the EME configurations show much improved dispersion by comparison with the KB one and, therefore, can bea game-changer in the field of polymer blending and compounding.
Keywords: extensional mixing, twin-screw extrusion, blending, compounding

Asian Workshop on Polymer Processing, 6-9 November 2016

KN014

BIAXIAL STRETCHABILITY AND FILM THICKNESS UNIFORMITYOF POLYPROPYLENE
Toshitaka Kanai
KT Polymer, Sodegaura, Chiba, Japan
In recent years, polymer film is essential in our lives. Among them, polypropylene has good physical properties,
for example, tensile strength, elastic modulus and transparency. Recently, it was found that the stretchability ofpolypropylene (PP) is improved by blending a small amount of low modulus polypropylene (LMPP). The
LMPP is a low tacticity polypropylene. There are a few researches that reported the relationship between
dynamics in a stretching process and physical properties. The purpose of this research is to investigate the effectof blending LMPP, which has different characteristic of resin such as tacticity and a molecular weight, on PP
and to study the mechanism of the structure formation in a biaxial stretching process.
LMPP blends reduced the yield values during the stretching process and increased the stress build up ratio. As aresult, they improved film thickness uniformity of biaxially stretched film and reduced film break during the
production line.
F300SP:A, S901:B, X901L:C, S400:D
Table1 Characteristic of resins

AB,AC,AD mean 5wt%LMPP blends

Furthermore, as the stretchable temperature window
was widened to low temperature side, the thickness
uniformity was improved in the wide stretchable

Fig.1 Stress-total stretching ratio curves temperature.

The blending LMPP to PP reduces the crystallizaton speed,
the spherulite size and increases the thickness of amorphous
phase in the lamella without changing the thickness of
crystal phase, namely melting temperature.
As a result, the blending of LMPP on PP could improve
the film thickness uniformity and expand the stretchable
temperature width, especially the lower temperature
window. The superstructure formation data during stretchingprocess will be also presented in the presentation.
Fig.2 Thickness uniformity & stretchable temp.
Key words: stretchable temperature, thickness uniformity, low modulus polypropylene

Asian Workshop on Polymer Processing, 6-9 November 2016

KN015

GF/PP INJECTION MOLDING BY DFFIM
Akio Kataoka2, Akihiko Imajo1, Hiroyuki Hamada1
1

Kyoto Institute of Technology, Kyoto-shi, Kyoto, Japan, 2Nihon Yuki Co., Ltd., Sagamihara-shi, Kanagawa,Japan
Introduction: Composites has become widely using in recently years especially glass fiber composites. DFFIM
is recent developed injection molding system for short fiber reinforced composites. In this system vent typeinjection machine with controllable unit is used and continues fiber can be inserted vent hole. The continues
fiber cut to short fiber in the screw, and finally short fiber in the screw, and finally short fiber composites can becreated. There are several merits of DFFIM・Fiber contents controlled・Different fibers inserted
・Surface treatment to continues fiber archived
Therefore our own composites can be fabricated. This paper, mainly discussed the influence of filament numberof fiber bundles on the glass fiber reinforced polypropylene (GF/PP) composites. Furthermore, we discussed
influence of sizing agent adhesion rate on the fiber dispersible in molding by using DFFIM process.
Methods: The injection molding machine (TI-30F6 type clamping force 30t) was made by Toyo Machinery &Metal Co., Ltd., while the vented plasticizing unit and the determination of the resin supply device (Hugrey
Feeder HF-Ⅰtype) both were manufactured by Nippon Oil Machine Manufacture Co., Ltd. The glass fiber
bundles were EX-1659 series supplied by Nippon Electric Glass Co., Ltd., Japan and which has already sized by
Polypropylene (PP). There are two different kinds of glass fiber bundles: each bundle contains 2 000 glass fibers
and 4 000 glass fibers respectively and the diameter of glass fiber is 17 micrometer. The PP obtainedcommercially from Sumitomo Chemical Co., Ltd., Japan, were chosen as resin and its trade name is PP (X101S
Homo-polymer). The melt mass flow rate of PP is 30.
Results: It is found out that the filament number of fiber bundles fed has changed, the mechanical properties of
GF/PP composites could be different even if they have the same fiber mass contents. It also found that theagglomeration of fibers occurred in composites could be improved through changing fiber bundles number.
Keywords: GFPP, Injection molding, Mechanical property, DFFIM

Asian Workshop on Polymer Processing, 6-9 November 2016

KN016

THE MOLD IN THE FOCUS
Clemens Holzer, Thomas Lucyshyn
Montanuniversitaet Leoben, Leoben, Austria
Introduction: While injection molding machines have been developed to an advanced technological level, inmany cases the mold, where the final part is shaped, is only a passive black box. This situation is the motivation
to put the mold into the focus of research for improved part quality and process efficiency covering thefollowing topics: simulation, sensors, actuators, multi-component injection molding, microstructured injection
molded parts and quality control concepts. In this contribution, selected results from the fields of sensors,
actuators and microstructured parts will be presented.
Methods: In a concept study a proof of principle of a wireless in-mold sensor for the detection of the melt front
was performed. A movable pin is pushed against a resonant body by the passing melt front resulting in a distinct
sound which is transported to the mold surface via structure-borne sound and detected by a microphone. The
results are compared with the signal of a conventional temperature sensor.
In the field of actuators a new concept to actively influence the forming of weld lines (especially important for
short fiber reinforced materials) is presented. A movable insert redirects the melt front in the region of a weld
line and thus influences the shape of the weld line as well as the local fiber orientation. The insert is finally
pushed out of the cavity by the increasing melt pressure and is removed to its starting position after demolding
by a spring.
For the production of microstructured injection molded parts the filling stage as well as the demolding stage are
crucial for optimal part quality and stable process conditions. An instrumented measuring mold was developed
to measure the demolding energy as quantitative method to evaluate the influence of polymer, process, structure
geometry and mold surface on the demolding process.
Results: The acoustic sensor was able to detect the arriving melt front, even for two cavities using one
microphone, but two resonant bodies with different eigenfrequencies to distinguish them.
The actuators used to influence the weld line geometries resulted in impressively improved mechanicalproperties. The strength at break under flexural load was increased by up to almost 70%.
The results of the developed demolding measurement mold showed for example the capability of mold coatings
to improve the demolding or also the different demolding behaviour of different polymers combined with theirprocessing conditions.
Discussion: The contribution shows the importance and potential of the mold in improving or even enabling
challenging products. Information from the inside of the mold and, moreover, active intervention of the shaping
process in the mold can help extending the possibilities of an advanced injection molding process.
Keywords: Injection molding, sensors, actuators, demolding, microstructures

Asian Workshop on Polymer Processing, 6-9 November 2016

KN017

EXTENSIONAL FLOW MIXING OF IMMISCIBLE POLYMERS WITH
NANOPARTICLE STABILIZATION
Matthew Thompson, Sushant Agarwal, Rakesh Gupta
West Virginia University, Morgantown, WV, USA
Polymer blending allows one to combine the attractive attributes of two or more polymers while compensating
for the unfavourable ones. Most polymer mixtures are thermodynamically incompatible, and blending gives rise
to a two-phase microstructure. This morphology generally determines the mechanical and rheological propertiesof the blend which then determine its applications. Morphology development typically involves deformation of
the dispersed phase followed by drop breakup. However, drop coalescence competes with this process, andultimately there is a balance between these two competing processes. An extensional flow field is known topromote drop breakup and is especially important for viscosity ratios exceeding 3.8, while coalescence isattenuated by compatibilizers that modify the interface between the polymer phases. Nanoparticles with tuned
surface chemistry may also be used as compatibilizers. A combination of extensional flow and nanoparticle
stabilization should, therefore, result in a fine, stable morphology.
Blend systems examined include polycarbonate (PC)/styrene acrylonitrile (SAN) and polystyrene (PS)/linear
low-density polyethylene (LLDPE). However, results are presented primarily on blends of high-density
polyethylene (HDPE) dispersed in polystyrene (PS). Here, the viscosity ratio exceeds 3.8 over a very wide range
of deformation rates. Coarse blends having a range of dispersed phase concentrations were formulated using
shear flow in an internal mixer or in a twin-screw extruder. These were subjected to extensional flow inconverging dies of different geometries and where more than one stretching episode was possible; thetemperature, total strain and strain rates were varied in a systematic manner. Experiments were repeated in thepresence of fumed nanosilica of different sizes and surface treatments that altered the extent of hydrophobicityof the nanoparticles. The mixing sequence was varied including preloading the nanosilica in thethermodynamically non-preferred polymer phase.
Scanning electron microscopy was used to determine the size and size distribution of the dispersed phase. The
material was sectioned in the flow direction as well as perpendicular to it. In some cases, PS was dissolved withtoluene leaving behind HDPE spheres. It was found that extensional flow reduced the volume-average diameter,
especially with increasing strains and strain rates. Finding suitable conditions for the nanoparticles to selectively
localize at the HDPE/PS interface was challenging, but relatively small amounts of nanoparticles dispersed in
the PS matrix decreased the volume-average diameter of HDPE drops. When the silica was pre-loaded into the
HDPE, very coarse initial blends were produced which then exhibited dramatic decreases in phase size withextensional flow. These and other results are properly organized and presented.
Keywords: Extensional flow blending, nanoparticle stabilization, HDPE/PS, fumed nanosilica.

Asian Workshop on Polymer Processing, 6-9 November 2016

KN018CARBON NANOTUBES AND GRAPHENE BASEDNANOCOMPOSITES: RECENT DEVELOPMENTSPOLYMER

Arup R. Bhattacharyya
Department of Metallurgical Engineering & Materials Science Indian Institute of Technology Bombay, Powai,
Mumbai, India
Carbon nanotubes (CNTs) and graphene based polymer nanocomposites have gained enormous research interestin the academic as well as industrial community due to the outstanding traits associated with CNTs andgraphene. However, the ‘agglomerate’ morphology of CNTs (or graphene) in the respective polymer matrix
poses a challenge to translate the outstanding properties associated with CNTs/graphene.
In this context, multiwalled carbon nanotubes (MWCNTs) have been ‘dispersed’ with the aid of an organic
modifier; Na-salt/Li salt of 6-amino hexanoic acid (Na-AHA, Li-AHA). Na-AHA modified MWNTs have beenshown to exhibit a lower electrical percolation threshold in various polymer matrices, which include polyamide
6 (PA6), polypropylene (PP) and various binary and ternary blends of PP, PA6 and acrylonitrile butadienestyrene copolymer (ABS) blend [1-10]. Moreover, the role of organic modifier in developing hybrid compositesof MWCNTs and expanded graphite (EG) will also be discussed. The talk will focus on the ‘processingmorphology-property’ relationship studies in the respective composites, which may serve as the basis for thedevelopment of MWNTs/graphene based polymer composites for industrial applications.
[1]. P. V. Kodgire, A. R. Bhattacharyya, S. Bose, N. Gupta, A. R. Kulkarni, A. Misra, Chem. Phys. Lett., 2006,
432, 480-485.
[2]. S. Bose, A. R. Bhattacharyya, P. V. Kodgire, A. R. Kulkarni, A. Misra, J. Nanosci. Nanotech., 2008, 8,
1867-1879.
[3] S. Bose, A. R. Bhattacharyya, R. A. Khare, A. R. Kulkarni, P. Pötschke, Macromol. Symp., 2008, 263, 1120.
[4]. S. Bose, A. R. Bhattacharyya, R. A. Khare, A. R. Kulakarni, T. U. Patro, P. Sivaraman, Nanotechnology,
2008, 19, 335704.
[5]. S. Bose, A. R. Bhattacharyya, A. R. Kulkarni, P. Pötschke, Comp. Sci. Tech., 2009, 69, 365-372.
[6]. B. Panda, A. R. Bhattacharyya, A. R. Kulkarni, Polym. Engg. Sci., 2011, 51, 1550-1563.
[7]. R. A. Khare, A. R. Bhattacharyya, A. S. Panwar, S. Bose, A. R. Kulkarni, Polym. Engg. Sci., 2011, 51,
1891-1905.
[8]. P. B. Tambe, A. R. Bhattacharyya, S. S. Kamath, A. R. Kulkarni, T.V. Sreekumar, A. Srivastav, K. U.
Bhasker Rao, Y. Liu, S. Kumar, Polym. Engg. Sci., 2012, 52, 1183–1194.
[9]. A. V. Poyekar, A. R. Bhattacharyya, R. A. Khare, A. S. Panwar, G. P. Simon, S. Dhar and J.K. Mishra,
Polym. Engg. Sci., 2015, 52, 443-456.
[10]. A. V. Poyekar, A. R. Bhattacharyya, A. S. Panwar, G. P. Simon, Polym. Engg. Sci., 2015, 52, 429-442.

Asian Workshop on Polymer Processing, 6-9 November 2016

KN019SMART MAGNETORHEOLOGICAL SUSPENSIONS: FABRICATION,
CHARACTERIZATION AND APPLICATION
Hyoung Jin Choi
Inha University, Incheon, Republic of Korea
Introduction: Magnetorheological (MR) suspensions are the type of smart and intelligent magneto-responsive
materials that possess outstanding phase transition characteristics from a liquid-like to a solid-like state under anapplied external magnetic field. Therefore, MR suspensions have been applied for a wide range of industrial
applications in the areas such as vibration dampers, microfluidics and shock absorbers. Soft-magnetic carbonyliron (CI) particles are known to be superior candidate of MR suspensions due to their high saturation
magnetization and appropriate particle size, however, they have severe sedimentation problem due to the large
density mismatch between the magnetic particles and medium oil. Magnetite (Fe 3O4) and its composites havealso attracted much attention due to the relative low density compared with CI particles. Therefore, our efforts
on improving the stability of MR suspensions and MR characteristics of the magnetic particles along with theirrheological analysis will be delivered.
Methods: Various polymerization techniques such as dispersion polymerization and Pickering emulsion
polymerization in addition to solvent casting were applied for preparing the composites with magnetic core andpolymer shell for suitable magneto-response as well as dispersion stability.
Results: Coating the surface of CI particles produced favourable core-shell structure along with apparently
decreased density for synthesized composite particles with PMMA, PS, PVB, and PANI (Fig. 1). MR
performance of the polymer/magnetic nanocomposites were investigated via steady shear and oscillation mode
tests using a rotational rheometer under applied magnetic fields. Yield stress and flow curve were analyzed
based on the model equations which are analogous to electrorheological fluids, while their dispersion stability
were investigated using a Tubiscan.

Fig. 1: SEM of magnetic hybrid particles: a) CI/PMMA, b) CI/cross-linked PMMA and c) CI/PS
Discussion: The magnetic hybrid nanocomposites with a polymer is a novel process to decrease the particle
density for better dispersion stability. Therefore, the operation of MR suspensions and their re-dispersion could
be more controllable, thus bringing a positive influence on their MR properties. In addition, the Pickering
emulsion polymerization using iron oxides is considered to be an interesting method for fabricating smart
magneto-responsive hybrid materials.
Keywords: Magnetorheological, Suspension, Core-shell, Magnetic particle

Asian Workshop on Polymer Processing, 6-9 November 2016

KN020

INFLUENCE OF BLENDING, NUCLEATION AND ANNEALING ON
MORPHOLOGY AND PROPERTIES OF INJECTION MOULDEDPOLY (L-LACTIDE)
HANS-JOACHIM RADUSCH1,2, ANDRÉ WUTZLER2, WERNER ANTON1
1

UNIVERSITY HALLE-WITTENBERG, HALLE, GERMANY, 2POLYMER SERVICE GMBH, MERSEBURG,GERMANY
Introduction: Polylactide (PLA) is one of the nature based polymers, which is already commercialized forseveral applications, but it is still strongly under research and development concerning both the polymer basis
and the processing technology to overcome some material immanent disadvantages and to ensure optimal
structure-property relationships. Because PLA shows a very slow crystallization behavior under high coolingrates - like usual in injection molding - it tends to solidify in the amorphous state that is resulting e.g. ininsufficient heat resistance. The disadvantageous brittleness as well as the rather slow crystallization behavior ofpolylactide (PLA) leading to insufficient mechanical properties and limited application performance can be
influenced by different procedures like blending with other polymers, addition of nucleation agents as well as
annealing during or after processing.
Methods: Blends of PLA and ethylene-co-vinyl acetate (EVA) were melt mixed using a twin screw extruder
ZE25/36D (Berstorff). The blends were injection molded by an injection molding device ES 200/50 HL(Engel). The annealing of the injection molded specimens was realized in a compression molding tool underpressure at specific temperatures. The investigation of melting and crystallization behaviour was performed
using a DSC 820 (Mettler Toledo). The phase morphology was characterized by optical microscopy, scanningelectron microscopy as well as atomic force microscopy. Mechanical testing was performed using a tensile
tester Z005 (Zwick) and impact strength tester HIT 5.5P (Zwick). Heat deflection temperature (HDT) was
measured by means of a HDT tester (Coesfeld).
Results and Discussion: Injection molding of PLA with increased crystallinity is only possible by using
suitable nucleation agents, but also annealing - especially off-mold annealing - is an advantageous way to
improve the crystallinity of PLA parts and their heat resistance and modulus at passable injection molding cycle
time. It could be shown that blending of PLA with EVA is a promising way, which leads to PLA blends withheterogeneous phase morphology that results in an improved impact strength. The investigation revealed that
only low amounts of EVA (approx. 7.5%) are sufficient to increase the impact toughness of PLA markedly. For
the generation of an optimal stiffness-toughness balance the impact modified PLA has been annealed forincreasing the crystallinity and Young´s modulus. Annealed PLA-EVA blends did not show a drop-down of the
HDT values with increasing EVA content until 7.5 %.
Keywords: PLA, EVA, blends, injection molding, stiffness-toughness balance

Asian Workshop on Polymer Processing, 6-9 November 2016

KN021

SUPER TOUGHNED BIODEGRADABLE POLYLACTIDE BLENDSWITH NON-LINER COPOLYMER INTERFACIAL ARCHITECTURE
OBTAINED VIA FACILE IN-SITU REACTIVE COMPATIBILIZATIONSUPRAKAS SINHA RAY1,2, VINCENT OJIJO1
1

Council for Scientific and Industrial Research, Pretoria, Gauteng, South Africa, 2University of Johannesburg,
Johannesburg, Gauteng, South Africa
Both industry and academia have shown great interest in biopolymers in recent years, including polylactide(PLA). PLA, which is the main representative of the biodegradable and bio-resourced polymers, is a linear
aliphatic thermoplastic polyester that is generally produced through ring-opening polymerization of the lactide
monomer that is obtained from the fermentation of renewable resources, such as corn. Although it is expected bea sustainable alternative to traditional petroleum-based plastics, its low flexibility, low impact strength, poor
thermal stability during melt processing, low melt strength and slow crystallization rates could limit its
widespread application.
In this work, these problems are addressed through a facile melt blending of PLA with a soft and biodegradable
polymer, poly[(butylene succinate)-co-adipate] (PBSA). In-situ compatibilization of these immiscible blends
was achieved via melt mixing the blends with a multifunctional reactive oligomer that led to the formation of
non-linear copolymer architecture at the interface. Joncryl was used to not only compatibilize PLA/PBSA
blends but also to improve the thermal stability, melt strength and crystallizability of the PLA. It was
hypothesized that at the interphase of the two polymers, there are in situ generated copolymers, which are nonlinear due to the multi-functionality of the Joncryl.
Scanning electron microscopy showed a drastic reduction of the dispersed phase size upon compatibilization,even at very low quantities of the chain extender. Rheological probing of the structures revealed gel-likebehavior in oscillatory experiments and enhanced viscosities for the compatibilized blends, and long-chain
branched topology for the components. The impact strength of PLA improved from 4.6 to 38.4 kJ/m 2 for the
blend with 40wt% PBSA and 0.6wt% chain extender. Likewise, the elongation-at-break increased from 6% for
PLA to 179% for the blend containing 40wt% PBSA and 0.6wt% chain extender. Importantly, these super-toughblends lost little of their tensile strength while simultaneously exhibiting improved thermal stability and better
crystallizability. The toughening is attributed to improved interfacial adhesion and the resultant morphology,
while the formation of LCBs enhanced the melt strength, strain hardening and crystal nucleation of thecomponents. The thermal stability is ascribed to the chain extension and hence improved the molecular weight.
In summary, significant improvement in toughness along with the concurrent enhancement of crystallizability,
melt strength, strain hardening and thermal stability will expand PLA’s applications.
Keywords: Multi-functional chain extender; Polylactide/Poly[(butylene succinate)-co-adipate] blends; Reactive
compatibilization, Super-toughAsian Workshop on Polymer Processing, 6-9 November 2016

KN022

PHOTODEFORMABLE LIQUID
BIOINSPIRED APPLICATIONSCRYSTAL

POLYMERSAND

Yanlei Yu, Jiu-an Lv, Yuyun Liu, Jia Wei
Department of Materials Science & State Key Laboratory of Molecular Engineering of Polymers, Fudan
University, Shanghai, China
To mimick the structure and function of biological systems, the search for smart materials that respond to external stimuli
with shape or size change has attracted increasing attention. Azobenzene-containing liquid crystal elastomers (LCEs) possesslarge and reversible shape changes characteristics through the orientation change of liquid crystals (LC) induced by light andallow the temporal, localized, remote and isothermal triggering actuation. Hence, scientists take nature as a best source ofinspiration and make it possible to develop diverse light-driven LCE actuators such as walking devices inspired by worms,
oscillatory cantilevers inspired by hummingbirds and microrobots that behave like human hands and arms. Recently, stimuliresponsive microactuators were fabricated from LCEs using replica molding technique and inkjet printing technology, whichhave promoted the development of the field of surface-responsive surfaces where small geometric variations often lead todramatic changes in surface properties, such as roughness and wettability. However, existing photodeformable CLCPs showpoor processibility owing to chemical crosslinking, which thus are incompatible to common solution and melt processing.
Here, we report a new linear liquid crystal polymer (LLCP) with the unique combination of excellent processibility,
macroscopic self-organization, mechanical robustness, and reversible photodeformation. The number-average molecularweight of the LLCP reached 3.6  105 g mol-1, which is at least one order magnitude larger than generally usedazobenzene LC polymers. Tensile tests show that the LLCP fiber owns moderate elastic modulus (96 ± 19MPa), high toughness (319 ± 41 MJ m-3), high strength (~ 20 MPa) and large elongation at break (2089 ± 275%). Thanks to the rational structure design and the excellent mechanical properties of the LLCP, we were able,
for the first time, to fabricate structurally defined and tubular microactuators (TMAs) via a solution processing
method. The microactuators exhibit the good capabilities to propel a wide diversity of liquids over a long distance withdesirable velocity by photo-induced asymmetric deformation, which is a conceptually novel principle to precisely
manipulate liquids. We further used the LLCP to construct a large nano-structured superhydrophobic surface by electrospun.
In initial state, the water droplet rolled down the inclined superhydrophobic mat. Interestingly, the moving water droplets
was pinned on any directed area upon UV light irradiation due to the increase of the adhesive force of the irradiated points
on the mat. After visible light irradiation, the irradiated area returned to a low adhesion state and thus the droplets could rolldown again. We anticipate that the above work will prompt the applications of photodeformable LCPs in fields ranging fromcontrollable micro-scale liquid transfer and micro-reaction systems, to micromechanical systems (MEMS), lab-on-a-chip andbeyond.

Keywords: Liquid crystal polymer, Azobenzene, Photoresponsive, Deformation, Microactuator

Asian Workshop on Polymer Processing, 6-9 November 2016

KN023ADVANCED PROCESSING TECHNOLOGIES FOR POLY(VINYL
ALCOHOL) BASED FUNCTIONAL MICRO/ NANOCOMPOSITESQi Wang, Li Li, Ning Chen
State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University,
Chengdu, Sichuan, China
Introduction: Poly (vinyl alcohol)(PVA), a multi-hydroxyl polymer with high polarity, has excellent
comprehensive properties, especially the good compatibility with most organic and inorganic materials, so is
expected to be used as a novel plastic and to prepare environmentally friendly, high performances and functional
PVA based micro/nanocomposites without introducing any coupling agents and interfacial modifiers. The key isto establish advanced processing technology to realize its thermal processing and get high performances. In thispaper, the novel highly filled PVA based biomedical micro/nanocomposites with high performances wereprepared by combing the molecular complexation and the solid state shear milling (S3M) technologies
developed in our research group, and their micro-injection molding processing was studied.
Methods: The melting behaviour of samples was analyzed by using a TA Q20 thermal analyzer (USA) at aheating rate of 10oC/min from room temperature to 250 oC. The thermogravimetric analysis (TGA) was
performed on a TA-Q50 (USA) from 30 to 600oC at a scanning rate of 10oC/min under nitrogen atmosphere.
The morphology of sample was observed on an Inspect (FEI, Japan) SEM Instrument. Mechanical properties ofsamples were measured using Instron 4302 tensile tester (USA).
Results: Through molecular complexation formed among amido contained compounds, water and PVA, wide
thermal processing window (wider than 80oC) of PVA was obtained, and environmentally-friendly PVA based
biomedical micro/nanocomposites, e.g., PVA/hydroxyapatite (HA), PVA/gelatine/HA and PVA/β-tricalcium
phosphate(β-TCP), etc., were prepared in a quite large scale via thermal processing by taking advantages of thepretty good compatibility of PVA and organic and inorganic fillers. By adopting solid-state mechanochemical
technology to modify the interfaces of fillers, the dispersion and interfacial compatibility of fillers in PVA were
further improved, and high performances of PVA based composites were achieved by adjusting the multi-levelstructure of PVA products during processing. The micro-injection molding of PVA based composites, especiallyhighly filled PVA based composites, was firstly realized on a MicroPower 5 micro-injection molding machine.
Discussion: Water state was the governing condition for the stable thermal processing of PVA and PVA based
composites. The hydrogen bonding formed among PVA, water and amido contained compounds made water
exist in PVA matrix as bound water, thus avoiding the intensive evaporation of water and realizing the stable
thermal processing of PVA. The interactions of the hydrophilic groups (–OH, PO42+) and the metal ion (Ca2+) on
the surfaces of the bio-micro/nano particles with water further manipulated the states of water in the composites
and made more bound water formed. Therefore, more water could be remained in system and played a role ofplasticizing, endowing PVA micro/nanocomposites with wide thermal processing window, wider than 80 oC.
Solid state shear milling (S3M) based on our self-designed mechanochemical reactor, which acts as the threedimensional scissors, offering strong shear force in both radial and tangential directions and squeezing force innormal direction, has excellent pulverizing, mixing, and activating effect on the materials in-between. Taking
the advantages of the S3M, the excellent dispersion of bio-micro/nanoparticles, even at high content (40wt%), in
PVA matrix was achieved, thus improving the compatibility and processability of PVA based composites. The
obtained PVA based composites had high tensile strength and improved water resistance.
PVA based biomedical micro/nanocomposites were typical pseudoplastic fluid, and had low shear viscosity athigher shear rate, satisfying the requirement of micro-injection molding for the high melt flowability. The
micro-injection molding of PVA based composites was successfully realized on a MicroPower 5 micro-injection
molding machine, the micro-injection molding process was analysed and the effects of the inorganic filler
content, the injection speed, pressure and temperature on the structure and properties of the polymer micro-parts
were systematically investigated. Under the high shear force and high temperature gradient of micro-injection
molding, the micro-injection samples had higher crystallinity and higher mechanical properties as comparedwith the samples obtained by conventional injection molding. The micro-samples had excellent replication
property, good cell compatibility and blood compatibility, and would have potential applications in drugdelivery, drug release, articular cartilage, subchondral bone, etc.
Keywords: poly(vinyl alcohol), functional micro/nanocomposites, advanced processing technologies

Asian Workshop on Polymer Processing, 6-9 November 2016

KN024

FORMATIONAND
SELF-ORGANIZATIONOFSURFACE
NANODROPLETS TOWARDS POLYMERIC MICROPATTERNS
Xuehua Zhang
RMIT University, Melbourne, Australia
Micropatterns of polymer provide a simple route towards modifying the surface properties and have found use
in a diverse array of fields, including microelectronics, optics and biomedicines. It is possible to modify asurface at the nano, micro and the macro scales to produce unique physical characteristics and chemicalfunctionality from microscopic monomer droplets before the polymerization. Polymerizable nanodroplets canbe produced on a solid–liquid interface in a simple step of solvent exchange in which a good solvent of oil isdisplaced by a poor solvent. In our work, we experimentally and theoretically investigate the formation ofmonomer nanodroplets by the solvent exchange process under well-controlled flow conditions. We findsignificant effects from the flow rate and the flow geometry on the droplet size. We develop a theoreticalframework to account for these effects. The talk will further discuss a basic principle for the symmetricalarrangement of surface nanodroplets during their growth under simple flow conditions. In our model system,
nanodroplets nucleate at the rim of spherical cap microstructures on a substrate. We find that, while growing,
the nanodroplets self-organise into highly symmetric arrangements, with respect to position, size, and mutual
distance. We show and explain how the nanodroplets acquire the symmetrical spatial arrangement during theircompetitive growth and why and how the competition enhances the overall growth rate of the nucleated
nanodroplets. This mechanism behind the nanodroplet self-organisation promises a simple approach for thelocation control of droplets with a volume down to attoliters. Those monomer droplets can be polymerized,
producing desired polymeric microstructures on surfaces.
References
1. Xuehua Zhang, Ziyang Lu, Huanshu Tan, Lei Bao, Yinghe He, Chao Sun and Detlef Lohse. Formation of
surface nanodroplets under controlled flow conditions.
PNAS, 9253-9257 (2015).
2. Shuhua Peng, Detlef Lohse, Xuehua Zhang, Growth of surface nanodroplets in competition, ACS Nano 9(12), 11916–11923 (2015).
3. Lei Bao, Amgad Rezk, Leslie Yeo, Xuehua Zhang, Highly-ordered femtoliter surface nanodroplets. Small
11(37), 4850-4855 (2015).

Asian Workshop on Polymer Processing, 6-9 November 2016

KN025

3D PRINTED BIODEGRADABLE CAGE FOR THE TREATMENT OF
SEGMENTAL BONE DEFECT
Ying-Chao Chou2, Tzu-Min Chang1, Shih-Jung Liu1,2
1

Chang Gung University, Tao-Yuan, Taiwan, 2Chang Gung Memorial Hospital, Tao-Yuan, Taiwan

This study developed a new biodegradable polymeric cage to convert corticocancellous bone chips into a
structured strut graft for treating segmental bone defects. A biodegradable truncated-pyramid cage was designed
and manufactured to serve as the bone graft. Commercially available PLA filaments with a diameter of 3.0 mm
were used as the material for the bone cage 3D printing. The cage was fabricated using a fused-depositionmodeling (FDM) type 3D printer with a printing resolution of 200 mm [1-4]. A total of 24 adult New Zealandwhite rabbits underwent a left femoral segmental bone defect creation. The experimental results show thathigher leg length ratios and 3-point bending strengths demonstrated improved final bony ingrowths within thebone defects for rabbits implanted with the 3D printed cages. Through this bone graft converting technique,orthopedic surgeons can treat segmental bone defects by using bone chips but with imitate characters ofstructured cortical bone graft.
The present experimental results indicate that using 3D printing PLA can be remodeled into a cage of any
geometric shape to fill the bone. With this 3D printed cage, the orthopedic surgeons will be able to convert small
corticocancellous bone chips into a structured bone graft to avail both the osteoconductive and mechanicalproperties. Through this bone graft converting technique, the surgeons can merge different sources of bone graft
to serve as an adequate strut bone graft for the treatment of large bone defects without experiencing donor sitemorbidity and graft resource limitations.
Keywords: biodegradable bone cage; 3D printing; polylactide (PLA); structured strut bone graft.
Reference
1.

Serra T, Ortiz-Hernandez M, Engel E, Planell JA and Navarro M. Relevance of PEG in PLA-based blends
for tissue engineering 3D-printed scaffolds. Mater Sci Eng C Mater Biol Appl 2014,38,55–62.

2.

Mohanty S, Larsen LB, Trifol J, Szabo P, Burri HV, Canali C, Dufva M, Emnéus J and Wolff A.
Fabrication of scalable and structured tissue engineering scaffolds using water dissolvable sacrificial 3D
printed moulds. Mater Sci Eng C Mater Biol Appl 2015, 55,569–578.

3.

Castro NJ, Patel R and Zhang LG. Design of a novel 3D printed bioactive nanocomposite scaffold for
improved osteochondral regeneration. Cell Mol Bioeng 2015, 8, 416–432.

4.

Wang J, Yang M, Zhu Y, Wang L, Tomsia AP and Mao C. Phage nanofibers induce vascularized
osteogenesis in 3D printed bone scaffolds. Adv Mater 2014, 26, 4961–4966.

Asian Workshop on Polymer Processing, 6-9 November 2016

KN026POLY IONIC LIQUID BASED FLEXIBLE ELECTROLYTE
PLATFORM FOR CLEAN ENERGY: OPPORTUNITIES AND
CHALLENGES
Namita Roy Choudhury1,2, Mona Taghavikish2, Surya Subianto2, Naba Dutta1,2
1

University of Adelaide, Adelaide, Australia, 2University of South Australia, Adelaide, Australia

This presentation will cover the challenges, opportunities and our most recent research endeavour in thedevelopment of advanced flexible material for clean energy conversion systems; and our recent findinds insteering the development of functional nanomaterials using click chemistry [1-9]. A profound drawback of thecurrent electrochemical energy storage systems are their inability to operate at temperature higher than 100oC
for extended period due to electrolyte degradation and separator instability. This arises because conventionalaqueous or low boiling organic electrolyte used in those systems cannot sustain high temperature. We employeda novel approach in the design of flexible membrane material and use ionic liquids (ILs) in various
morphologies. ILs are liquid-phase organic salts (i.e., ionic compounds) with negligible vapour pressure, highthermal stability, and intrinsic solubility. The properties of non-volatility, low toxicity, and especially wide
electrochemical potential window (as high as 5 V), make ILs very suitable for applications in electrochemicalenergy storage and safe electrolytes. Moreover, room temperature ionic liquid (RTIL) derivatives can be madewith polymerisable moiety (PIL) that can be processed to films or for making polymer-based flexible
electrolyte. Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes, the repeating unit of which has ionicliquid (IL) character. The incorporation of IL moieties into the polymer chain combines some of the uniquecharacters of ILs with the common features of polymers. Our research shows that the relationship between ionic
conductivity and network structure depends on both the concentration of ionic group and network flexibility.
The synergistic effect produces immediately a variety of new (multi)functional materials with promising results
for a variety of electrochemical applications.
Keywords: Poly ionic liquid, ionic conductivity, flexible electrolyte, clean energy
References
1. M. Mistry, N. Roy Choudhury; N. K. Dutta,; R. Knott Langmuir 2010, 26:1907.
2. M. Mistry, N. Roy Choudhury, N. K. Dutta, R. Knott J. Memb. Sci. 2010, 351:168.
3. S. Subianto, M. Mistry, N. Roy Choudhury, N. Dutta, R. Knott, ACS : Appl. Mat.&Int. 2009, 1:1173.
4. M. Mistry, S. Subianto, N. R. Choudhury, N. K. Dutta Langmuir 2009, 25:9240.
5. M. K. Mistry, N. Roy Choudhury, N. K. Dutta, R. Knott, Z. Shi, S. Holdcroft, Chem. Mater. 2008, 20:6857.
6. S. Mayavan, N. Roy Choudhury and N.K. Dutta, Advanced Materials, 2008, 20:1819.
7. S. Subianto, N. Roy Choudhury and N.K. Dutta J. Polym. Sci.: Polym Chem. 2008, 46:5431.
8. M. Taghavikish, S. Subianto, N. K Dutta, N.Roy Choudhury, ACS Appl Mater & Interf. 2015. 7(31):17298306.
9. M. Taghavikish, S. Subianto, N. K Dutta, L. De Campo, J. Mata, C. Rehm, N. Roy Choudhury, ACS Omega(in press), July 2016

Asian Workshop on Polymer Processing, 6-9 November 2016

KN027

CONTROLLED
FOAMINGOFPOLYPROPYLENE/GAMMAIRRADIATED CROSSLINKED ELASTOMER BLENDS
Srishti Singh, Anindya Dutta, Anup Ghosh
Indian Institute of Technology Delhi, New Delhi, India
Currently a high demand in automotive industries motivated to make a comparative study between thepolypropylene/elastomer (radiated and non-radiated) blends along with the effect of compositional variation andprocessing parameter dependence on foamability of polypropylene. The importance of crosslinking, which isachieved by exposing the elastomer under gamma radiation and therby influencing final foam morphology infoams has been described. The introduction of crosslinked elastomer into the polypropylene matrix improved
the foamability of polypropylene. In this study, a film grade polypropylene (MFI=3 g/10min) is used as the basematrix and Vamac Ultra IP as the elastomer. The rheological, mechanical (tensile) and morphological propertiesof blends are studied by means of parallel plate rheometer; UTM (universal testing machine) and SEM(scanning electron microscopy) respectively. Foaming is done in a high pressure autoclave at three different
temperatures using supercritical CO2 as a blowing agent. SEM analysis and density measurements were done forthe foamed samples.
The density of foamed blends decreased with increasing elastomer content. With the increase in elastomer
content, domain size of crosslinked elastomer increased in blends and thus led to the bigger cells during
foaming process, in spite of having its high gas entrapment capacity for its interconnected chains. Despite
having reduced cell growth in PP/uncrosslinked blend (having low gas entrapment capacity); a foam
microstructure could be attained with high cell density due to the smaller domains of elastomer in to the PP
matrix. Cell size of foams increased with increasing foaming temperature. Foams obtained at 155 °C showed
good balance of microcellular structure along with higher cell density. Tensile properties of foams showed apromising improvement and can be correlated with the foam morphology.
Keywords: polypropylene, gamma irradiation, batch foaming, supercritical CO2

Asian Workshop on Polymer Processing, 6-9 November 2016

KN028EVALUATION OF LONG-TERM PERFORMANCE OF PLASTIC
PIPES FOR HOT WATER APPLICATIONHIROYUKI NISHIMURA, TAKEHIRO FUJII, HIDEO HIRABAYASHI, KAZUHISA IGAWA, KAZUSHIYAMADA
KYOTO INSTITUTE OF TECHNOLOGY, KYOTO, JAPAN
Abstract The polymer electrolyte fuel cells (PEFC) residential cogeneration system has been commercializedin Japan. The number of commercialized PEFC cogeneration systems have reached 150, 000 in total in 2015.
The expected number of PEFC is 1,400,000 in 2020. The waste heat can be used for hot water supply andcentral heating. Hot water distribution pipes connecting a gas cogeneration system with the water heater andterminal appliances are very important. As the advanced residential cogeneration system is expensive, the longer
lifetime of the heating and hot water supply system is required for consumers, the reliable plastic pipes havebeen developed. Polyethylene of raised temperature resistance (PERT) as non-crosslinked polyethylene has beenused as pipe materials for hot water supply and space heating in Japan as well as conventional cross-linked
polyethylene (PEX). In this study, three grades of PERT resin were selected and pipes were extruded with thesimilar design of antioxidants. The measurement of oxidation induction time and air permeability was conducted
after hot water circulation test.
Keywords: polyethylene pipe, hot water circulation test, oxidation induction time, degradation, actual operating
condition
Hot water circulation test Figure 1 shows an illustration of the device used in hot water circulation test. The
straight and bent pipes specified by ISO 10508 used were 10 mm in the inner diameter, 13 mm in outer
diameter, and 2,000 mm in length, and the fittings at both ends of the pipe were made of plastics. Hot water at
110 °C, supplied by the water heater, was constantly circulated. The internal pressure was 250 kPa which is the
maximum operating pressure for heating. The circulation rate of the hot water was 2 L/min. The evaluation iscontinued while checking the deterioration condition by taking out the samples at regular intervals. Also,
keeping the constant heating circuit, the circulation water was replaced at 10 L/week in order to sustain theconcentration of the dissolved oxygen in the pipe.
Lifetime comparison The lifetime of the pipes at 110 °C at 250 kPa in the hydrostatic stress rupture test wascompared with that in the hot water circulation test. As a result, the failure time was 14,705 hours in thehydrostatic stress rupture test, whereas the failure time was 13,452 hours in the hot water circulation test which
was approximately 9 % shorter. Figure 2 also shows the OIT changes by DSC with testing time as a parameterof the circulated hot water and hydrostatic hot water. It is considered that antioxidants contained in a resin were
eluted into the circulated hot water and the antioxidants were relatively consumed more quickly.

Figure 1 Hot water circulation test.

Figure 2 OIT changes with testing time as a parameter ofcirculated and hydrostatic hot waters.

Asian Workshop on Polymer Processing, 6-9 November 2016

KN029APPLICATIONOFHEATTRANSFER
THERMOPLASTIC POLYMER PROCESSINCONTROLIN

Takushi Saito, Tatsuya Kawaguchi, Isao SatohTokyo Institute of Technology, Meguro-ku, Tokyo, Japan
It is generally known that the physical properties of polymer material have strong dependency on temperature.
Therefore, heat transfer monitoring and its control during the processing is very important (especially forthermoplastic materials), and they are the crucial issues for the stable performance of the final products. From
the thermal engineering viewpoint, thermal history of the products can be actively controlled by the knowledge
and techniques of the heat transfer engineering. Radiation heating which is essentially different from theconductive or convective heating was applied on probation to improve the polymer processing. In the
manuscript, fundamental concept of the radiative heat transfer control for the polymer processing wasintroduced, and then its effect in several trials was described.
Keywords: Thermoplastic Polymers, Heat Transfer Control, Radiation Heating

Asian Workshop on Polymer Processing, 6-9 November 2016

KN030

CHARACTERIZATION OF HIGH-STRENGTH FIBERS
Takeshi Kikutani
Tokyo Institute of Technology, Tokyo, Japan
Recent topics regarding the characterization of high-strength fibers will be discussed in this paper. The first
topics is on the weathering resistance of high-strength fibers. It is known that strength of some types of highperformance fibers decreases quickly with exposure to sunlight. In some cases, results of acceleration test
obtained using weathering test instruments may not match with the behavior occurring under “real situation”. In
this research, weathering test of various high performance fibers was performed at the Showa station on East
Ongul Island in Queen Maud Land, Antarctica, 69o00’S 39o35’E. Our main interest was on the effect of UVB
wavelength of ultraviolet light (280 – 315 nm). In terms of the integrated intensity of sunlight, intensity insummer time is the highest, and those in spring and autumn times are similar, however, because of the formationof so-called “ozone hole” only in autumn time, intensity of UVB is higher in Autumn. We can report only
preliminary results this time. Nevertheless, there are indications that some types of high-strength fibers are more
susceptible to UVB exposure.
The second topics is on the characterization of high-strength poly(ethylene terephthalate) (PET) fibers utilizing
laser Raman spectroscopy. In the course of researches for developing high-strength PET fibers, we have foundthat the PET fibers of high mechanical performances can be obtained if drawing and annealing processes areapplied to the undrawn fibers which is prepared applying the low Deborah number condition in the melt
spinning process. Through the modelling of the melt spinning process combining the numerical simulations forspin-line dynamics and course molecular dynamics, we proposed a concept that homogeneous state of molecularentanglement, which can be represented by the narrower distribution of molecular weight between adjacententanglement points, is the key for the development of high-strength and high-toughness PET fibers. To verify
this concept, laser Raman spectroscopy measurements were performed applying tensile load to PET fibers ofvarious mechanical properties. Detailed data analysis for the peak at around 1616 cm-1, which corresponds to thestretching mode of C-C bond in aromatic ring, revealed that the high mechanical performance PET fibers exhibit
the characteristics of 1) narrow peak width and 2) small change of peak width under application of tensile load.
These results matches with the concept of homogeneous state of molecular entanglement.
Keywords: high mechanical performance fibers, light resistance, poly(ethylene terephthalate) fibers, laser
Raman spectroscopy, molecular entanglement

Asian Workshop on Polymer Processing, 6-9 November 2016

KN031

THERMOCHROMIC COMPOSITE FIBRES CONTAINING LIQUID
CRYSTALS FORMED VIA MELT EXTRUSION
Mike O'Shea2, Louise Van der Werff1, Ilias Kyratzis2, Robin Cranston2, Andrea Robinson1, Gary Peeters2
1

Monash University, VIC, Australia, 2CSIRO, VIC, Australia

A three-layered composite fibre has been generated via a modified wire-coating melt co-extrusion process. The
continuous fibre consists of a thermochromic liquid crystalline (TLC) layer encapsulated between a transparent
polypropylene outer sheath and a black polyether ether ketone inner core. The fibres exhibit clear
thermochromic behaviour consistent with the behaviour of unincorporated TLCs, and have been formed into atextile.
Introduction: A wide range of fibres and textiles with colour changing functionalities have been developedand explored to date for both sensory and stimuli responsive applications. Various thermochromic systems,
which change colour in response to a temperature change, have been harnessed to date for the formation ofthermochromic fibrous products. This paper presents a novel method for the incorporation of thermochromicliquid crystalline materials (TLCs) into composite fibres for thermal mapping applications. TLCs have been
exploited for accurate thermal mapping applications in medical, industrial and engineering fields
Methods: Seventy micrometer diameter round continuous monofilament PEEK fibre was sourced from Zyex.
Two different TLC mixtures were incorporated into the composite fibres. The first was a fully sterol-based
ternary mixture containing 20 wt% cholesteryl oleyl carbonate (COC), 40 wt% cholesteryl nonanoate (CN), and20 wt% cholesteryl 2, 4-dichlorobenzoate (CD). Two methods were used to construct the fibres, a melt coextrusion process (AB fibre profile) and a modified wire-coating co-extrusion process (ABC fibre profile). A
twin screw 16-mm Prism Eurolab XL extruder coupled with a Barrell hot melt pump. A Teledyne Isco Series-D
single pump system with thermostated liquid transfer line maintained at 60 °C was also used to deliver the TLC(feed B). These two components were harnessed to feed molten polypropylene (feed A) into a co-extrusion die
at controlled rates to overcoat the PEEK fibre ( Feed C)
Results and Discussion: The presence of the black inner PEEK core was found to be the key for the clear
retention of colour within the fibres against both white and black backgrounds. The temperature-sensitive fibres
and textiles can be applied to a variety of thermal mapping applications, such as in the medical and engineering
fields, due to the tunable nature of TLCs.
Keywords: Biomedical Polymers, Thermochromic, Liquid Crystal, Co-extrusion, Bandage, Textile,

Asian Workshop on Polymer Processing, 6-9 November 2016

KN032OXIDE BASED FLEXIBLE AND STRETCHABLE SENSORS FOR
WEARABLE ELECTRONICS
Philipp Gutruf1,2, Sharath Sriram1,2, Madhu Bhaskaran1,21Functional Materials and Microsystems Research Group, RMIT University, Melbourne, Australia, 2Micro
Nano Research Facility, RMIT University, Melbourne, Australia
Introduction: Electronic devices are pervasive, with smartphones and wearable devices becoming the norm.
The industry trend is towards lighter, energy efficient, and durable devices. Stretchable electronics, especiallythose that are wearable, is where the solution lies. Stretchable (and flexible) electronic devices are used innumerous applications ranging from electronics, energy, and healthcare. Integration of multifunctional oxidethin layers in stretchable devices would create enhanced functionality and performance. This integration has
been limited by the brittle nature of oxides and high temperature processing requirements. In this work, wedemonstrate the integration of a multifunctional metal oxide (zinc oxide, ZnO) on a prevalent, biocompatible,
stretchable substrate, polydimethylsiloxane (PDMS). We exploit the microtectonic surface structure of the ZnO
thin films that is uniquely obtained on stretchable substrates, to demonstrate high performance sensing devices.
Results and Discussion: A transfer technique presented in our previous work [1] was implemented to fabricate
the ZnO/PDMS devices. The process relies on the poor adhesion of platinum to silicon which allows hightemperature oxide thin films to be deposited and defined with standard micro fabrication techniques andsubsequently peeled-off using PDMS. The microtectonic phenomena govern the stretchability of the thin oxide
films. This phenomena occurs when thin, brittle oxide films are incorporated into elastomeric films, the brittle
oxide layer forms micrometer-sized plates which overlap and slide over each other.
Oxygen-deficient ZnO films with a microtectonic surface morphology were defined with electrode pairs andoperated as conductometric sensors. The oxygen-deficient nature of the ZnO allows for higher adsorption of thetest gases (hydrogen and nitrogen dioxide) which directly translates to superior sensitivity. The electricalresistance characteristics of the strained and unstrained microtectonic ZnO/PDMS sensor were acquired in situ
under sequential exposure to zero air, hydrogen, and nitrogen dioxide. It is seen that the microtectonic sensor
shows a higher sensitivity (>20%) and a significantly faster response than the rigid analogue [2]. This is
attributed to an enhanced surface area due to the microtectonic morphology which enables larger number of gas
molecules to interact with the ZnO surface and also the gas permeable nature of PDMS which further maximizes
the exposed area by allowing the diffusion of gas molecules.
The photosensitive nature of ZnO can be utilised for detecting UV radiation. Upon exposure to UV light, theresistance of the device decreases. The oxygen-deficient nature of the ZnO films used in this study attracts
ambient oxygen, resulting in its adsorption on to the oxide surface. The microtectonic morphology of the ZnO
provides a larger surface area for the oxygen adsorption, and hence, a greater proportion of unpaired carriers.
This effect results in enhanced OFF/ON ratios seen in our devices.
Conclusion: The demonstrated gas and UV sensors are transparent, lightweight, stretchable, and highly
sensitive. They are relevant for portable hazardous gas detection, due to their low energy consumption,robustness, and curvilinear adaptability. The transfer process is very versatile and the ability to utilize theprocess to combine any functional oxide material with a stretchable platform allows for a wide range ofpotentially harmful gases to be sensed. This research is a precursor to practical devices that range from wearable
sensors, UV detectors, biocompatible sensors, and high sensitivity environment monitoring.
References[1] P. Gutruf et al, NPG Asia Materials, vol. 5, art. no. e62, 2013.
[2] P. Gutruf, et al, Small, vol. 11, pp. 4532–4539, 2015.
Keywords: gas sensors, UV sensors, wearable electronics

Asian Workshop on Polymer Processing, 6-9 November 2016

KN033ADVANCES IN DEVELOPMENT AND CHARACTERISATION OF
ANHYDROUS PROTON-CONDUCTING POLYMER ELECTROLYTEMEMBRANES
Haijin Zhu, Maria Forsyth
Deakin University, Waurn Ponds, Australia
Introduction: Proton transport has been recognized as an essential process in many biological systems, as wellas electrochemical devices including fuel cells and redox flow batteries. Recent advances in characterisation
techniques, in particular the combination of quantum chemical calculations and solid-state NMR methods, bringabout a more fundamental understanding of the proton transport mechanisms, and therefore allow for a morerational design of new proton-conducting materials.
Methods: Various protic ionic liquids (PIL) and/or organic ionic plastic crystals (OIPC) has been explored as
the potential candidates for proton-conducting membranes. To further enhance the mechanical property andelectrochemical properties, the anion part of an ammonium based PIL was tethered onto a polymer chain byforming a comb-like polymer. A combination of PFG-NMR and solid-state NMR method was used to study the
relationship between the structure and proton transport properties.
Results: A new PIL guanidinium triflate and its composites with triflic acid has been investigated. The protontransport mechanism was elucidated by comparing the diffusion coefficients obtained from NMR and
conductivity measurement. A few orders of magnitude enhancement of conductivity is observed upon additionof HTf to the organic solid, and this appears to follow percolation behaviour with a threshold of approximately
2% HTf. Following that, I’ll show the structure and properties of a novel all-solid polyelectrolyte membrane,[HN122] [PSTFSI]. The PFG-NMR results show a typical restricted diffusion behaviour for the mobile protons
in this polymer membrane. Through a combination investigation of solid-state NMR and PFG-NMR, we wereable to show that the superior proton conductivity is closely related to the self-assembled nano-channel
structures in the material.
Discussion: 1) Protic ionic liquids are promising candidates for the next generation anhydrous protonconducting materials. 2) Careful design of the polymer chemistry as well as the resulting nano-scale structure
are both crucial to the development of a high-performance anhydrous proton conductor.
Keywords: polymer electrolyte, proton-conducting membrane, NMR

Asian Workshop on Polymer Processing, 6-9 November 2016

PANEL DISCISSIONCURRENT & FUTURE TRENDS IN PLASTICSDavid Francis, Marketing and Technology Manager, Qenos, David.Francis@qenos.com will represent start ofthe value chain - polymer and trends from Australian perspective
David Kenworthy, Managing Director, ZEZT and member of Vinidex
david.kenworthy@zezt.com.au will represent views of importance to polymer converter

Executive

Team,

Mitchell Killeen, Director JV and BD Lyondell Basell, Mitchell.Killeen@lyondellbasell.com for representation
on polymer trends from overseas
Prof John Vlachopoulos, McMaster University, Canada, vlachopj@mcmaster.ca on University/Industry
Questions:
1. The Australian Government is promoting an innovation agenda. How does your organisation define
innovation ? Is it different to R&D?
2. Academics are often measured by publications and patents. Research does not always set out to address anidentified problem in the market. Companies, on the other hand, are measured by profit, underpinned by new
products. What is the best way to balance market driven research and blue sky research?
3. The plastics industry often receives negative press around sustainability. What does sustainability mean toyour organisation? How do we ensure that the sustainability message for our industry is accurately reflected tothe broader public?
4. What are the required skills and competencies required for polymer engineers and scientists to drive asustainable polymer industry into the future? How do we ensure that polymer professional will have the rightskill set, today and in the future?
5. Several industries have experienced disruptive change that has required rapid evolution of business models,and of products or services. A recent example of this is the introduction of Uber as a competitive force to thetaxi industry. What are the potential disruptive changes/threats to the polymer processing industry, consideringfactors such as the speed of design and change, new materials, process control, and supply chain planning.
Supplementary Question (subject to time)
6. What are the profitability drivers for our industry?

Asian Workshop on Polymer Processing, 6-9 November 2016