POSTERPRESENTATIONSAsian Workshop on Polymer Processing, 6-9 November 2016

PP001

INTEGRATED ENGINEERING OF HIGH-PERFORMANCECARTILAGE/BONE PROSTHESIS FOR JOINT REPLACEMENTChen Chen1,2, Yi Hou1,2, Benxiang He3, Li Zhang1,21

Analytical & Testing Center, Sichuan University, Chengdu, China, 2Research Center for Nanobiomaterials, Sichuan University, Chengdu, China, 3Sport Hospital Attached to Chengdu Sport University,
Chengdu, China
Introduction: Cartilage injury is a common disease in clinic. It is well known that articular cartilage lacks
self-repair ability due to its non-vascular distribution, and some reports have shown that the damaged
cartilage for adults was hard to self-repair if its diameter was larger than 3 mm. The design and industrial
manufacturing of an artificial joint prosthesis that needs to just cut off the damaged part and can be inserted
into the subchondral bone are of important significance to the bio-fixation, bringing a bright future for thejoint replacement caused by cartilage damage. Combining the excellent mechanical properties andbiocompatibility of ethylene-vinyl acetate copolymer (EVA) and hydroxyapatite/polyamide66 (HA/PA66),
an integrated approached to cartilage/bone prosthesis was proposed and designed by a two-step injection
molding method, in which the upper layer was made of EVA acting as the cartilage and the underlying
layer was HA/PA66 composite as the artificial bone. The proposed methodology opens new possibilities tohigh-performance joint replacement materials.
Methods: A two-step injection molding was adopted to prepare the integrated cartilage/bone prosthesis.
Specifically, the two-cavity mold was customized according to the actual size of an adult New Zealandwhite rabbit shoulder joint without and with the part of articular cartilage. Firstly, HA/PA66 was injected
into the cavity without cartilage layer and cooled for 15 min, then taken out and drilled some holes on thelinking surface, and then put into another cavity as the underlying bone. Secondly, EVA was injected into
the cavity with the HA/PA66 part under 100 °C and 40 MPa and cooled for 20 min, then taken out to obtainan integrated cartilage/bone prosthesis.
Results: A two-step injection molding strategy is developed to structure an integrated cartilage/bone
artificial joint, in which the outer layer composed of ethylene-vinyl acetate copolymer serve as the flexible
and wear-resistant upper cartilage layer, and strong and biocompatible hydroxyapatite/polyamide66
composites as the underlying bone layer. The artificial joint has demonstrated good mechanical properties,
excellent biocompatibility and impressive bioactivity, meeting the requirements to accelerate boneregeneration and early-stage bio-fixation. The artificial joint materials we have devised are of tremendous
promise in the fields of joint replacement.
Discussion: The integrated EVA-HA/PA66 joint prosthesis prepared in the study showed excellent
mechanical and bio-tribological properties, and the mechanical bonding between upper and underlying
layer was improved greatly by the adoption of hole-structure. Furthermore, the underlying bone could wellintegrate with the surrounding bone after being implanted for 12 weeks. The integrated cartilage/ bone joint
prosthesis shows a great potential for applications in joint replacement.
Keywords: Joint prosthesis, Integrated engineering, EV6, PA66, Joint replacement

Asian Workshop on Polymer Processing, 6-9 November 2016

PP002METAL-POLYMER DIRECT JOINING: EFFECT OF INJECTEDPOLYMER TEMPERATURE NEAR JOINT AREA
Shotaro Kadoya, Fuminobu Kimura, Yusuke Kajihara
The University of Tokyo, Tokyo, Japan
Metal-polymer direct joining has been receiving attentions because of its advantages such as light weightand high productivity. However, direct joining has not been applied to industries so much because thereliability is not sufficient. We need to elucidate the joining mechanism and to optimize the joining
conditions for proper applications. We focus on one of the direct joining methods called Injection Molded
Direct Joining (IMDJ). IMDJ consists of two elemental techniques, metal surface roughening and insert
injection molding. In IMDJ process, melted polymer flows into metal surface structures, and then metaland polymer are joined directly and hardly. In our previous study, it is suggested that the polymer
temperature (PT) considerably affects the replication ratio, which has relation to the joint strength.
Therefore, in this work, we measured the polymer state during molding process and evaluated the joint
strength in order to reveal the PT dependence on the joint strength.
We first roughened aluminum alloy (A5052) surface with a chemical etching method (NMT process,Taiseiplas). The surface structure sizes were around 20 nm. Secondly we produced metal/polymer (PBT)
lap joints. In this molding process, we changed some conditions; polymer flow path, injection speed, andcylinder temperature, in order to control the PT in the cavity. In terms of the flow path, we changed theflow direction by using two different gate position. The flow path affects the PT in the timing when thecavity is filled, that is, we can change the time difference between the timing when polymer passes the joint
area (tpass) and when the cavity is filled (tfill). Finally we carried out the tensile test with the original tester.
The tensile test results show several suggestions about the relation between the PT and the joint strength.
First, the result about the flow path shows that the joint becomes stronger when the time difference between
tpass and tfill is short. When the time difference is short, the PT at tfill is high enough, which means polymer
liquidity is high; therefore, the replication ratio becomes high. Secondly, the injection speed has negative
effect to the joint strength although the positive correlation between the speed and the replication is wellknown in general transfer molding like emboss processing. This result suggests that other factors than PT
affect the replication in our study, where the metal surface structure sizes are much smaller than generaltransfer molding. Finally, the cylinder temperature does not affect the strength. We discuss this result fromthe viewpoint of the injection speed. Since injected polymer gets cold as soon as flowing into the cavity,
the PT on the joint area at tfill should be low when the injection speed is low (tpass and tfill are not close).
When the injection speed is high (tpass and tfill are close), pack pressure is applied to still hot polymer, andthen the cylinder temperature (equal to the PT at tpass) should affect the strength more effectively. We will
examine the cylinder temperature dependence with high injection speed for future work.
Keywords: Direct joining, insert molding, joint shear strength, polymer temperature.

Asian Workshop on Polymer Processing, 6-9 November 2016

PP003

A STUDY ON OPTICAL AND MECHANICAL PROPERTIES BY
REPROCESSING FOR INJECTION-MOLDED OPTICAL GRADEPOLYCARBONATE
Junhan Lee1,2, Jongsun Kim2, kyunghwan Yoon1, Jeongjin Kang2
1

Department of Mechanical Engineering, Dankook University, Yongin-si, Gyeonggi-do, Republic of Korea,
Molds and Dies Technology Group, Korea Institute of Industrial Technology, Bucheon-si, Gyeonggi-do,
Republic of Korea
2

The reprocessing of optical grade polycarbonate(PC) was studied to estimate the feasibility of recycled
optical products. Injection molding and shredding processes were selected as reprocessing methods. Virginresin was injection-molded to samples and those were shredded and molded under the same conditions
again. Then, the effects of reprocessing on optical and mechanical properties of PC after up to two
reprocessing cycles were evaluated and discussed.
As optical properties total and direct transmittance were measured using spectrometer for visible range for
3.5 inch light guide plate(LGP). Because LGP is one of the important components of back light unit(BLU)
in liquid crystal display(LCD) acting as a light source, the present study focused on LGP’s opticalproperties. Mechanical properties, i.e., tensile strength, flexural strength, and impact strength andrheological property of viscosity were measured, too.
The results showed that the mechanical and rheological properties were changed slightly as reprocessing.
However, optical properties were changed with significant tendency as reprocessing. As the number ofreprocessing increased, the total transmittance was decreased at low wavelength range and its color shift
was changed systematically to yellow as shown in Figure 1. On the other hand, direct transmittance did not
decline significantly(Fig.2), but higher color shift to yellow direction was found than total transmittancedata(Fig.3).

Fig. 1 Total transmittanceFig. 2 Direct transmittanceFig. 3 Yellow index

Keywords: Polycarbonate, Injection molding, Reprocess, Optical properties, Mechanical properties
Acknowledgement: This research is supported by the project [No. JE160002 (PJE1602B)] from Korea
Institute of Industrial Technology, KITECH.

Asian Workshop on Polymer Processing, 6-9 November 2016

PP004PRECISE MEASUREMENT OF SHEAR STRESS DISTRIBUTION
ON CAVITY SURFACE OF INJECTION MOLD DURING FILLINGPROCESSSATOSHI MORI
University of Tokyo, 4-6-1 Komaba, Meguro-ku,Tokyo, Japan
Introduction: There has been no method for precisely measuring shear stress distribution on the cavity
surface. The authors successfully developed a mold with a structure capable of step-change adjustment
for conducting high precision measurement experiments on shear stress (Fig.1).
Measuring Method: A 3-component force transducer was directly connected to the bottom of block A,
and shear force F acting on A was measured. To enable the height between A and B to be adjusted freely,
block B was installed after assembling A and S. This allows step-change to be set below 5μm. Front
speed v was measured using two pressure sensors installed before and after block A. Shear stress
distribution was calculated by the equation in Fig.1 using v and F. Experiments were conducted using PP
and PS, and at different injection rates, with and without step-changes.
Results and discussion: Shear stress distribution without step-change (Fig.2) consists generally of thesefour patterns: ①stepped start, ②constant transition, ③slight rise, and ④slight decrease. At ①, stress atstart is greater the higher is the injection rate. At ②, stress transitions constantly the higher is the injection
rate, and stress is more conspicuous with PP than PS. Fig.3 shows the generation models of shear stress
distributions. The shear stress of a certain area ②corresponding to the shear viscosity of the molten statein which no solidified area has formed, ③increases with the growth of the solidified area, then④decreases due to the effects of shear heating and shear-thinning around the wall. If there is step-change,
flow speed suddenly increases due to peeling flow at the step-change side (Fig.4). This indicates theeffect of asymmetric fountain flow along the cavity thickness.
Keyword: Injection Molding, Shear Stress Distribution, Filling Process

Fig.3 Generation model of shear stress distribution
near flow front area

Fig.1 Calculation method of shear stress distribution
based on shear force curve measured

Fig.2 Shear stress distributions measured under different
injection rates (without step-change)

Fig.4 Shear stress distributions near flow front areawith and without step-change

Asian Workshop on Polymer Processing, 6-9 November 2016

PP005A STUDY ON THE FABRICATION OF 8 INCH LIGHT GUIDEPLATE BY ROLL STAMPING PROCESSHyunjun Na1,2, Seokkwan Hong2, Jongsun Kim2, Jeongho Hwang3, Kyunghwan Yoon1, Jeongjin Kang2
1

Department of Mechanical Engineering, Dankook University, Yongin, Republic of Korea, 2Molds and Dies
Technology Group, Korea Institute of Industrial Technology(KITECH), Bucheon, Republic of Korea,
3
Micro and Nano Technology Group, Korea Institute of Industrial Technology(KITECH), Ansan, Republicof Korea
LCD (Liquid Crystal Display) is one of the most widely used display types in these days. LCD has BLU(Back Light Unit) because of its non self luminous properties, which serves as a light source to TFT (ThinFilm Transistor) LCD panel. BLU is composed of LED, LGP (Light Guide Plate), diffuser sheet and prism
sheets. Among those LGP has an important role to convert point light to plane light source. It is gradually
becoming thinner and larger in these days. Presently, there are three methods for fabricating LGP, i.e.,
injection molding, extrusion and roll to roll. In the present study, roll stamping process was tried for
fabricating micro patterns directly on transparent plastic sheet. The transcription ratio on the sample andluminance level of finally assembled BLU were measured and compared with commercially available
injection-molded LGP.
For roll stamping process PC sheet, width of 110.65 mm, length of 180 mm and thickness of 0.6 mm, wasused. Micro patterned stamper was fabricated by laser ablation method. Roll surface temperature of 80℃
and linear velocity of roll surface of 3.5 m/min were found as the best conditions for repeatability of final
product through preliminary experiments. By applying uniform stamping force of 400 kgf, 800 kgf, 1,000
kgf, 1,600 kgf and 3,200 kgf to the sample surface the transcription ratio and luminance level were
measured under the same roll surface temperature and linear velocity.
As a result, luminance level of light admitting area was increased as transcription ratio increases and thatof light facing area was decreased. Also, luminance uniformity was increased as transcription ratio
increased. However, when the transcription ratio was increased in a certain level, luminance uniformity
reached the maximum of 80% as shown in Figure 1. Interestingly, luminance level made by roll stamping
was even higher than commercially available injection-molded LGP for the cases when rather highstamping forces were applied to the roll as shown in Figure 2.

Fig. 1 Luminance uniformity and transcription ratio vs stamping force

Fig. 2 Luminance level (stamping force 1,000 kgf)
Keywords : Roll stamping, micro pattern, transcription ratio, luminance uniformity, LGP
Acknowledgement: This research is supported by the project (No. IZ160009) from Bucheon-si andsupported by the project (No. JG-15-0009) from Ministry of Strategy and Finance, MOSF and Korea
Institute of Industrial Technology, KITECH.
Asian Workshop on Polymer Processing, 6-9 November 2016

PP006

DOUBLE POROUS GEL-SLIPS FILMS WITH LONG-TERM ANTICORROSION PROPERTY
Sachiko Nishioka, Mizuki Tenjimbayashi, Seimei Shiratori
Keio University, Yokohama, Kanagawa, Japan
Introduction: Innovative anti-fouling coating of slippery liquid-infused porous surface (SLIPS),
immobilizing omniphobic lubricant on micro porous structure, was reported for multi-functional antifouling surface in 2011 by T. S. Wang et al. Although the development of SLIPS for wide range ofapplication, the crucial challenges of preventing a loss of lubricant (in charge of anti-fouling) from
evaporation or other liquid contact remain. Herein, we designed lubricant stability improved SLIPS, that
gradually feed lubricant on surface from lubricant pool sandwiched by double porous films inspired GELSLIPS. As a result, a double porous GEL-SLIPS performed hydrophobicity over a longer duration than thatof conventional SLIPS.
Methods: Double porous GEL-SLIPS films is composed of 3 layers of porous polymer film/ lubricant /porous polymer film. Porous polymer film was fabricated by non-solvent induced phase separation
technique of Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). A Fe plate were coated withporous polymer film, Perfluoropolyether (PFPE) lubricant, and porous polymer film, in this order.
Lubricant retaining property was visually observed by corrosion of samples. Samples were immersed into
pure water to observe corrosion area.
Results: Figure shows the elapsed time images of Fe plate corrosion
for 6 weeks. We prepared 3 type samples of bare, SLIPS coated, andDouble porous GEL-SLIPS coated Fe plate. Bare Fe plate was rottedwithin a day whereas, corrosion time was prolonged to 5 days on SLIPScoated Fe plate. Double porous GEL-SLIPS coated Fe plate kept anticorrosion at least for 6 weeks.
Discussion: Corrosion on metal plate occurs when a surface comes into
contact with corrosion medium such as water. PFPE lubricant have agood barrier to corrosion medium because of its hydrophobicity. Thatmeans double porous GEL-SLIPS prevent a corrosion longer than
SLIPS. Comparing the double porous GEL-SLIPS with SLIPS, top of
the porous polymer controlled feeding of lubricant to prevent a loss of
lubricant.
Keywords: Slippery Liquid Infused Porous Surface, long-term
stability, anti-corrosion

Figure.
Time-elapsed
images of corrosion test
on coated Fe plates
conducted for 6 weeks.

Asian Workshop on Polymer Processing, 6-9 November 2016

PP007SLIPPERY SMOOTH SURFACE WITH HOT
REPELLENCY FABRICATED ON EPOXY SUBSTRATEWATER

Ryo Togasawa1, Mizuki Tenjimbayashi1, Takeshi Matsubayashi1, Takeo Moriya1, Koji Fujimoto2, Seimei
Shiratori1
1

Keio University, Yokohama, Japan, 2SNT.co, Tokyo, Japan

Introduction: In recent years, surfaces repellent to hot liquids have attracted much attention and they will
have a lot of applications, such as repellent coating of hot fluidic food. Only a few reports have achieved
hot liquids repellency which require fluorine materials and specific rough structure. Depending on fluorinecompounds with low surface tension and complicated structure hampers development of biocompatible
coating and usage in practical field. Here, we fabricated smooth slippery surface which holds biocompatible
lubricant layer by OH-π interaction. This surface showed not only hot water repellency but also durability
against boiling in hot water.
Methods: First, we fabricated a base layer by spin-coating
phenyltriethoxysilane via sol-gel method on a hydrophilic
substrate (glass or commercial aluminum can). After drying,oleic acid was casted on the base layer as a lubricant. Hot
water repellency was analysed by measuring contact angles
and sliding angles of water droplets with various
temperatures. In addition, we conducted the boiling test, inwhich the film was immersed in hot water at 90C for 30
minutes.
Results: The result of sliding angle of water droplets withvarious temperature (Fig. (a)) demonstrates that this slippery
surface repelled hot water droplet of 80C at very low sliding
angle (1). As shown in Fig. (b), this coating maintained its
low sliding angle after the boiling and even the retort test
(boiling test with closed vessels leading to high pressure).
Discussion: The smooth base layer made it possible tofabricate hot water repellent coating without any fluorinematerials. The fact that the sliding property was maintained
after both boiling tests shows that OH-π interaction
between the base layer and oleic acid functions under hot
water. This film will be applicable to coatings for foodcontainers and drink cans.

Fig. (a) Variations of contact angles
and sliding angles of water droplet
with various temperatures. (b) Sliding
angles both before tests and after theboiling test or the retort test.

Keywords: Slippery surface, hot water repellency,
biocompatibility, low sliding angle

Asian Workshop on Polymer Processing, 6-9 November 2016

PP008

PREPARATION AND CHARACTERISATION OF PLA BASEDNANOCOMPOSITES WITH STARCH NANOCRYSTALS AS
REINFORCEMENTS
Pooja Takkalkar, Nhol Kao, Gregory Griffin
RMIT, Melbourne, Victoria, Australia
The demand for the generation of environmentally friendly material is increasing due to the problems posedby extensive use of petroleum based products. One of the “green” materials emerging in the market
nowadays is biodegradable nanocomposites. Among the biopolymer matrices being used for the making of
bio plastics, starch and PLA are extensively used materials, due to numerous advantages such as low cost,abundant availability, biodegradability, biocompatibility, nontoxicity and renewability.
Starch is a polysaccharide which accommodates energy in plants. It is the second most abundant biomass
material in nature. The applications of bio plastics at present are limited due to various reasons such as
higher cost compared to conventional petroleum based plastics, lack of sophisticated methods developed
for large scale production and other major limitations on the functionality.
Nanocomposites prepared from polysaccharide nanocrystals of starch and biodegradable polymer like PLA
can be examined to have superior properties. This study will involve the preparation of starch nanocrystals(SNC) from waxy maize starch and incorporation of the SNC, with concentration in the range of 1-5 wt%,
in PLA matrix using melt processing as well as a solvent casting and evaporation technique withdichloromethane (DCM) as the solvent to form a homogeneous dispersion. The prime focus of this research
will be to investigate the mechanical, barrier, thermal, morphological and rheological responses of the PLASNC nanocomposite.
Keywords: Starch nanocrystals, Nanocomposites, PLA

Asian Workshop on Polymer Processing, 6-9 November 2016

PP009EFFECTS OF PROCESSING CONDITIONS ON TiO2 NANOFILLER
LOCI, MORPHOLOGY, MECHANICAL PROPERTIES AND
DEGRADABILITY OF TIO2-PLA/LDPE NANOCOMPOSITE FILMS
Tatiya Trongsatitkul
The School of Polymer Engineering, Institute of Engineering, Suranaree University of Technology, Nakhon
Ratchasrima, Thailand
TiO2 photocatalyst played an important role in enhancing degradation of plastic film. It could also act assolid compatibilizer for immiscible blends such as in PLA/LDPE system. This work aimed to investigate
effects of processing parameters i.e. mixing temperature, time, and order on TiO 2 nanofiller loci,morphology, mechanical properties, and degradability of (10:90) PLA/LDPE nanocomposite films. TiO2
nanoparticle showed a preferential localization at the interface when introduced into the internal mixer after
LDPE and PLA had been thoroughly mixed at 150 C. The optimum mixing time for TiO2 nanofiller
incorporation was about 3-6 minutes to obtain a well-dispersed and uniform composite. Compressed filmof this TiO2-PLA/LDPE nanocomposite possessed significant improvements in morphology andmechanical properties including elastic modulus, yield strength, and elongation at break. However, thedegradability of the film was lower than that of the film with TiO 2 photocatalyst located within LDPE
matrix. This was found to be due to TiO2 nanofiller induced photodegradation in LDPE but, at the sametime, inhibited microbial growth in PLA which was necessary for biodegradation.
Keywords: polymer blend film, PLA, LDPE, photodegradation, biodegradability, solid compatibilizer,
TiO2 nanoparticle

Asian Workshop on Polymer Processing, 6-9 November 2016

PP010COMPRESSIONMOLDINGPROCESSPOLYBENZIMIDAZOLE MATERIALSMODIFIED

moonki Jeong, Sangyong Nam
Gyeong sang nam do, JinJu, Republic of Korea
Introduction: Polybenzimidazole is well known for having a superior heat resistance and has goodmechanical properties as good as heat resistance. PBI parts which is produced by using a compression
molding process are promising materials in extreme environments. In this study, we synthesized PBI using
a popular method and various equipment are utilized to confirm whether synthesis is succeeded. Aftercleaning and drying, hot press was used for compression molding process with a lot of comparisons.
Modified carbon nano tubes, graphene and graphene oxide introduced imidazole group are compared andpresented which filler has a better dispersion and a higher flexural strength and modulus. The dispersion
was carried out using an ultrasonic processor and flexural test was performed 3-point bending test method.
Methods: Basic synthetic method is used. (3,3-diaminobenzidine, isophthalic acid and polyphosphoricacid) In case of pure PBI sintered body, after some preprocessing, compression molding process was
conducted to use fine PBI powder. Operation temperature is 560℃ and working pressure is 73MPa (12ton).
Results: Specially fixed size ( 126mm x 12.6mm x 4mm ) was prepared to measure a flexural strengthand modulus. A lot of variables such as temperature, pressure, size of powders, ratio of materbatch also
were considered during a compression molding process. Furthermore, Fillers like CNT, Graphene also usedin order to find out its correlation.
Discussion In case of temperature, the best result was 430℃ ( nearby the Tg ) and 73MPa ( 12ton ) was
the best pressure. If the high pressure was applied, over-sintering was occurred. The other hand, when the
low pressure is applied, material have a lot of pores. Modified CNT-PBI has a higher flexural modulus thanpure PBI but flexural strength show the tendency to decrease. In case of Im-GO, both properties wereincreased slightly.
Keywords: Compression molding, Polybenzimidazole, Flexural modulus, Im-GO, Modified MWCNT

Asian Workshop on Polymer Processing, 6-9 November 2016

PP011

MANIPULATEDORIENTATIONCONTROLPOLYPROPYLENE CONTAINING RUBBER DISPERSION

OF

Yoshiaki Funahashi1, Takayuki Maeda2, Masayuki Yamaguchi1
1

Japan Advanced Institute of Sciecne and Technology, Nomi, Ishikawa, Japan, 2New Japan Chemical,
Kyoto, Japan
Introduction: The nucleating agent, N, N’–dicyclohexyl–2, 6-naphthalenedicarboxamide, was found to bedissolved into a molten polypropylene (PP). It appears as needle-shape crystals during cooling process andshows a nucleating ability for PP. PP molecules show epitaxial crystallization on the surface of the needle
crystals of the nucleating agent. Because of this phenomenon, PP molecules orient perpendicular to theflow direction at extrusion. In this research, the orientation of PP molecules as well as the deformation ofrubber particles were investigated.
Methods: Polypropylene (PP), ethylene-butene-1 rubber (EBR), and N,N’–dicyclohexyl–2,6naphthalenedicarboxamide (NA) were employed in this study. PP with NA and EBR (PP/EBR = 70/30
wt%, NA = 1000ppm for PP) were fed into an extruder with a ribbon-shaped die at 200˚C and cooled at
100˚C by a chill roll. PP/EBR without NA was prepared in the same method.
Results and Discussion: The cut surface was observed by scanning electron microscope (SEM) after theetching treatment by xylene. Fig. 1 shows SEM photographs of the (PP+NA)/EBR blend. The rubber
particles are deformed to the machine direction. Furthermore, X-ray diffraction patterns demonstrate that
PP chains orient perpendicular to the flow direction, which is attributed to the epitaxial crystallization of
PP chains on the surface of the needle-shape nucleating agents. As a result, the deformation direction ofrubber particles is perpendicular to the molecular orientation of PP matrix.

Fig. 1 SEM photograph of (PP+NA)/EBR
Keywords : molecular orientation, polypropylene, ethylene-butene rubber

Asian Workshop on Polymer Processing, 6-9 November 2016

PP012POLYHIPES FROM IONOMER STABILIZED HIGH INTERNALPHASE EMULSIONS FOR OIL SPILL RECOVERYTao Zhang, Qipeng Guo
Deakin University, Geelong, Victoria, Australia
PolyHIPEs are promising as an absorbent for oil spill recovery due to their interconnected macro-porous
structures. Recently, we have investigated high internal phase emulsions (HIPEs) and their application for
efficient reclamation of spilled oils [1-6]. Herein, we present a continuous method to produce polyHIPEs
for oil spill reclamation. The polyHIPEs were prepared from light induced polymerization of sulfonatedpolystyrene stabilized high internal phase emulsions (SPS-HIPEs). The SPS-HIPEs contains seawater as
the dispersed aqueous phase and commercial monomers such as tetraethyl orthosilicate and butyl acrylate
as the continuous phase. Sulfonated polystyrene was obtained from used polystyrene foams, realizing agreen transformation of waste polystyrene. PolyHIPEs from SPS-HIPEs (SPS-polyHIPEs) obtained a highgel fraction of 93 % under UV irradiation for only 5 minutes, showing possibility to produce the polyHIPE
monoliths continuously. SPS-polyHIPEs can be much greener in comparison to polyHIPEs from particlesor surfactant-stabilized HIPEs, and no purification is required before use. SPS-polyHIPEs exhibit
interconnected macro-pores, and the sizes of pores as well as pore throats are controlled simply with thevolume fraction of the internal phase. These monoliths are hydrophobic with water contact angle over 140o.
SPS-polyHIPEs show excellent performances for oil spill reclamation, including high absorption rate ofreaching saturated absorption in 3 to 5 minutes, high absorption capacity to a series of oils and organic
solvents, a high recovery rate at about 85% and a high reusability for 20 times. A continuous process is
illustrated using SPS-polyHIPEs as an absorbent for oil spill reclamation.
Keywords: PolyHIPEs, sulfonated polystyrene, high internal phase emulsion, spill recovery
References:
1 T. Zhang and Q. Guo, Chem. Commun. 2013, 49, 5076.
2 T. Zhang and Q. Guo, Chem. Commun. 2013, 49, 11803.
3 T. Zhang, Y. Wu, Z. Xu and Q. Guo, Chem. Commun. 2014, 50, 13821.
4 Y. Wu, T. Zhang, Z. Xu and Q. Guo, J. Mater. Chem. A 2015, 3, 1906.
5 T. Zhang, Z. Xu, Z. Cai and Q. Guo, Phys. Chem. Chem. Phys. 2015, 17, 16033.
6 T. Zhang and Q. Guo, Chem. Commun. 2016, 52, 4561.

Asian Workshop on Polymer Processing, 6-9 November 2016

PP013

MODULUS ENHANCEMENTADDITION OF METAL SALTOF

POLYCARBONATE

BY

Takumi Sako, Azusa Miyagawa, Masayuki Yamaguchi
Japan Advanced Institute of Science and Technology, Nomi, Ishikawa, Japan
Introduction: Polycarbonate (PC) is widely employed in industrial fields because of its excellent
transparency and mechanical toughness. However, Young’s modulus is low as compared with other plastic
glasses. Therefore, the modulus enhancement is required to widen applications.
In this study, we propose a new method to enhance the Young’s modulus of PC without losing its
transparency and mechanical toughness by the addition of a specific metal salt.
Methods: The blend films of PC with 5 wt% of lithium perchlorate (LiClO4) were prepared by the solution
casting method using tetrahydrofrane (THF). Pure PC films were also prepared by the same method tocompare properties.
The temperature dependence of oscillatory tensile moduli, such as storage modulus E’ and loss modulus
E”, were measured by a dynamic mechanical analyzer. Tensile properties were examined by a uniaxial
tensile machine at room temperature.
Results: Table 1 shows E’ at room temperature and glass transition temperature (Tg) measured by the
dynamic mechanical measurement. As shown in this table, E’ at room temperature increases by the additionof LiClO4. However, the glass transition temperature (Tg) is not affected.
Tensile properties of the films are summarized in Table 2. The strain at break, indicating the mechanicaltoughness, is not affected by the addition of LiClO4. Furthermore, higher yield stress and Young’s modulus
are detected for PC/LiClO4 (5%). Moreover, it is mentioned that the transparency is not affected by the
LiClO4 addition.
Table 2 Tensile properties
Table 1 E’ at 25 oC and Tg

Yield stress Strain at break
[MPa]
[-]

Modulus[GPa]

E' [GPa]T g [oC]

Pure PC

49.3

0.626

1.82

Pure PC

1.94

152

PC/LiClO4 5%

58.3

0.616

1.97

PC/LiClO4 5%

2.19

153

Discussion: The effect of the addition of LiClO4 on the mechanical properties of PC is discussed in thisresearch. It is found that the addition of LiClO4 enhances the Young’s modulus of PC without losing themechanical toughness, heat resistance, and transparency.
Keywords: Polycarbonate, Modulus enhancement, Antiplasticization

Asian Workshop on Polymer Processing, 6-9 November 2016

PP014INTERPHASE TRANSFER OF LIQUID IN
POLYMER BLENDS AND ITS APPLICATIONIMMISCIBLE

Mitsunari Sugiyama, Masayuki Yamaguchi, Guesnier Mathieu
Japan Advanced Institute of Science and Technology, Nomi-City, Ishikawa, Japan
Introduction: Because of the light scattering at interface between phases, immiscible polymer blends areopaque in general. When the refractive index difference between phases is minimal, however, even an
immiscible blend with phase separation is transparent. Therefore, the light transmittance of an immiscible
polymer blend can be controlled by adjusting the difference in the refractive index.
In this study, the difference in the refractive index is controlled by the transfer phenomenon of a lowmolecular-weight compound with high refractive index in an immiscibe polymer blend.
Methods: Commercially available poly(ethylene-co-vinyl acetate) (EVA) and poly(vinyl butyral) (PVB)
were employed. The refractive indices of EVA or PVB are 1.486 and 1.488, respectively. Tricresyl
phosphate (TCP), as a low-molecular-weight liquid, was added to the blend. The refractive index of TCP
is 1.554. The blend was compressed into a flat sheet using a compression-molding machine. Temperaturedependence of light transmittance of these sheets was measured by a UV-Vis spectrophotometer.
Results: Temperature dependences of light transmittance of EVA/PVB/TCP (50/50/10) are shown in the
figure. The light transmittance of the blend decreases with the ambient temperature. As a result, the blend
is fairly transparent at low temperature, while it becomes opaque at high temperature.

Transmittance (%)

80

60

5oC
o

15 C

40

o

25 C
20

40oC
o

0
200

400

600
800
Wavelength (nm)

60 C
1000

Light transmittance of EVA/PVB/TCP
Discussion: The temperature dependence of the light transmittance, i.e., light scattering, is originated frominterphase transfer of TCP. Becauce TCP has high refractive index, its transfer phenomenon affects therefractive index of each phase in the blend strongly.
Keywords: immiscible polymer blend, plasticizer, light transmittance, the refractive index

Asian Workshop on Polymer Processing, 6-9 November 2016

PP015THE
INFLUENCEOF
MICRO-NANO
LAMINATEDTECHNOLOGY ON DIELECTRIC PROPERTERTIES OF
CNTs+HIPS/HIPS MULTILAYERED COMPOSITESYing AN, LKuntian DAI, Zhiwei JIAO, Yang ZHANG, Weimin YANG
Beijing University of Chemical Technology, Beijing, China
In order to study the influence of multilayered composites containing alternating layers on the dielectric
properties of polymer composites, in this paper, various alternated microlayers of high impact polystyrene
with carbon nanotube (CNTs+HIPS)/high impact polystyrene (HIPS) multilayered composites wereprepared by using self-made micro-nano lamination extrusion device, and the contents of CNTs in the
CNTs+HIPS layer was 6%. The experimental results show that the thickness of alternating micro-layers is
uniform, the electrical resistivity of CNTs+HIPS/HIPS multilayered composites present significantly
anisotropy between extrusion direction and thickness direction. The multilayered composites reflect highly
conductive properties in the extrusion direction and insulating properties in the thickness direction, due tothe HIPS layers blocking the conductive network formation in the thickness direction of composites system.
The dielectric constant increases obviously with the increase in the number of layers, for example, thedielectric constant of the 128 layers is increased by 4.9 times than that of the 2 layers when the frequency
is 100Hz. This because of that the interfaces between CNTs+HIPS layers and HIPS layers are increased,
which is useful to accelerate the effect of interfacial polarization so that more electrical charges willaccumulate at interfaces, and the effect of interfacial polarization is improved. The alternating layers
structure of CNTs+HIPS/HIPS multilayered composites can not only increase the dielectric constant, butalso keep the low dielectric loss at low frequency (<10 4Hz) . The results show that the micro-nanolamination extrusion technique provides a simple and easy method for preparing multilayered polymer
composites with high dielectric constant and low dielectric loss. Figure 1 shows that the schematic diagramof micro-nano lamination extrusion device.

A、B: extruder C: confluence segment D: laminated elements E: dieFig. 1 The schematic diagram of micro-nano lamination extrusion device
Keywords: Micro-nano lamination extrusion, Alternating layers, Dielectric properties, high impact
polystyrene composites, carbon nanotube

Asian Workshop on Polymer Processing, 6-9 November 2016

PP016

GRAPHENE BASED POLYURETHANE NANOCOMPOSITES: A
NOVEL MATERIAL FOR EMI SHIELDING COATINGS
Taruna Bansala, Mangala Joshi, Samrat Mukhopadhyay
Indian Institute of Technology, Delhi, Delhi, India
The Increasing uses of several electronic systems produce a lot of electromagnetic radiation pollution incurrent state. Thus there is a rapid rise in interest of scientific community to research for suitable absorbing
materials for EMI shielding. Graphene has been explored to improvise better microwave absorption in awide range of frequency. Graphene, a flat monolayer of carbon atoms tightly packed into a 2D honeycomb
lattice, has acquired tremendous consideration owing to its unique properties such as superior electricalconductivity, thermal stability and extraordinary mechanical properties.
In our research group, chemically reduced graphene oxide (CRG) sheets, thermally reduced graphene sheets(TRG) and PVP-stabilized silver nanoparticle decorated graphene nanohybrid (Ag-PVP-CRG) weresynthesized and studied for microwave absorption so that they can be used as potential RAM materials forstealth and electromagnetic interference (EMI) shielding coatings. CRG and Ag-PVP-CRG were preparedthrough chemical route and TRG through thermal exfoliation and annealing process. The microwave
shielding and dielectric properties of the graphene sheets in the form of pellets were studied in the Ku band
region (12.4–18 GHz). It was observed that the presence of Ag nanoparticle, residual functional groups andconductivity significantly changes the contribution of graphene sheets towards the microwave absorbing
performance and dielectric losses. Absorption loss is found to be the dominant mechanism for EMI
shielding. EMI shielding effectiveness (SE) values for CRG, TRG and Ag-PVP-CRG at 2mm thickness inthe Ku-band region were found to be 80 dB, 45 dB and 58 dB respectively and electrical conductivity value
obtained for CRG, TRG and Ag-PVP-CRG are 124.9 Scm-1, 62.7 Scm-1 and 0.25 Scm-1 respectively.
Further, the graphene sheets based polyurethane coating and nanocomposites were prepared and studied
for shielding performance. The SE was found to be affected by the dispersion of graphene sheets inside thepolyurethane matrix, as agglomeration of sheets restrict the electrical network formation of graphene sheets
inside the TPU matrix. The electrical conduction and dielectric losses are important parameters to attaineffective EMI attenuation. Thus, the present work showed great potential of graphene sheets and its
polyurethane based nanocomposites as an effective candidate as a microwave absorbing material alongwith superior dielectric behaviour.
Keywords: Graphene, EMI Shielding, Microwave frequency, Silver nanoparticles.

Asian Workshop on Polymer Processing, 6-9 November 2016

PP017

SELECTIVE LOCALIZATION BEHAVIOUR OF
NANOFILLERS IN IMMISCIBLE POLYMER PAIRSCARBONBOWEN FAN
Japan Advanced Institute of Science and Technology, Nomi, Japan
Introduction:
Due to their excellent properties, carbon nanofillers are good candidates to improve mechanical propertiesof polymeric materials. In this study, the transfer behaviour of carbon nanofillers, i.e, multi-walled carbon
nanotube (MWCNT) and graphene nanoplatelet (GnP), between immiscible polymer pairs during meltmixing or laminating is investigated.
Methods:
For melt-mixing, a composite of polycarbonate (PC) and GnP (80/20) was mixed with polyethylene (PE)at 300 oC for 20 min using an internal-batch mixer. The blend ratio of PC/GnP to PE was 50/50 (w/w), i.e,
PC/GnP/PE = 40/10/50. In the case of laminating, a pure PC sheet was annealed with a PE composite sheet,i.e, PE/MWCNT (97/3) or PE/GnP (97/3), at 300 oC for 20 min. Then, the laminated sheets were quenchedand separated. In addition, the laminating test was also performed for the laminated sheets comprising ofpure PE and PC composite.
Results:
It is found that GnPs move from PC to PE phase during melt mixing, even if GnP is first dispersed into PC.
On the contrary, the transfer of GnPs from PC to PE cannot be detected during annealing treatment.
Furthermore, it is found that both MWCNTs and GnPs move from PE to PC during annealing. The amountof MWCNTs on the surface of the separated PC sheet is larger than that of GnPs.
Discussion:
The transfer phenomenon of GnPs from PC to PE during melt-mixing process is attributed to the adsorptionof PE molecules on the GnP surface at high-temperature-mixing with the aid of oxygen. In the laminatedsheet system, the transfer behaviour is attributed to the difference in the interfacial tension between filler
and polymer with an aid of Brownian motion. In addition, the results indicate that MWCNTs can transfer
faster than GnPs, demonstrating that the size and shape of nanofillers play a important role on the transfer.
Graphene nanoplatelets, Carbon nanotube, Interphase transfer, Brownian motion

Asian Workshop on Polymer Processing, 6-9 November 2016

PP018FABRICATIONOFELECTRICALLYCONDUCTIVE
GRAPHENE/POLYSTYRENECOMPOSITESVIAACOMBINATION OF LATEX AND LAYER-BY-LAYER ASSEMBLYAPPROACHESWei Fan, Chao Zhang, Tianxi Liu
Donghua University, Shanghai, China
Introduction: Due to its excellent physical properties, graphene acting as reinforcing fillers has attracted
intense interests. To achieve a controlled distribution, the formation of a conductive network composed ofgraphene sheets within polymer matrix is of critical importance. In this work, polystyrene (PS)microspheres wrapped by graphene oxide (GO) sheets were prepared via layer-by-layer assembly of
oppositely charged GO sheets onto PS microspheres. The deposited GO was then reduced and thecomposite films with a graphene conductive network were prepared by hot-pressing. The morphology ofgraphene conductive network was studied and the thermal and electrical properties of the composite films
were measured. The as-prepared composites showed an improved thermal stability as well as electricalconductivity with a percolation threshold as low as 0.2 vol%. The combination of latex technology andlayer-by-layer self-assembly method thus demonstrated an efficient and facile approach to fabricate
electrically conductive graphene/polymer composites.
Methods: The PS microspheres were prepared by a dispersion polymerization method. Graphite oxide wassynthesized by Hummers method and exfoliated to give a brown dispersion of GO under ultrasonication.
The resulting GO suspension is negatively charged over a wide pH condition. Positively charged GO wassynthesized by formation of an amide bond between PEI and GO in the presence of EDC and NHS. The
obtained GO-g-PEI was dispersed in water to form a stable and positively charged solution. The GO
wrapped PS microspheres were prepared by alternating deposition of GO and GO-g-PEI on the PS
microsphere template via LBL assembly, and then reduced by hydrazine at 90 °C for 4 h. Finally,
conductive (RGO)n/PS composite films were obtained by a hot-pressing processs.
Results: The RGO/PS composites exhibit a conductivity percolation threshold when the number of bilayer
is between 0.5 and 1. The electrical conductivity increases dramatically from 7*10 -7 to 0.02 S/m as thenumber of bilayer increases to two (i.e., n = 2) with slight increase to 0.05 S/m when n = 3. In addition, thethermal stability of (RGO)n/PS composites is significantly enhanced, as compared with neat PS. The
temperature at 5% weight loss is 402 °C for the (RGO) 3/PS composites, which is almost 25°C higher than
the neat PS. The morphology of the hot-pressed composite films was observed by TEM. The distributionof RGO sheets is rather uniform and only very few agglomerations can be observed. When the bilayer
number n = 1, some ribbon-like features (i.e., RGO sheets) are clearly seen in the PS matrix. These RGO
sheets are non-continuously distributed in the matrix. With the increase of the bilayer number, the noncontinuous ribbon-like features become longer and tend to intertwine together. As the bilayer number
increases to 3, oval-shaped PS microspheres can still be discerned with a clear outline or “shell” of thewrapped graphene deposited on them. This graphene network will form conductive pathways in theinsulating PS matrix, leading to an improved electrical conductivity.
Discussion: The conductive graphene networks or pathways thus formed in the polymer matrix can greatly
improve the electrically conductive properties of the composites. More significantly, the use of organic
solvents are avoided throughout the whole experiments, including the preparation of the graphene wrapped
PS microspheres and construction of the graphene/PS composite films. Through the combination of latex
technology and LBL assembly, a facile, efficient and environmentally friendly method has been developed
to fabricate electrically conductive graphene/PS composites with improved dispersion uniformity andcontrollable filler contents. This strategy can be anticipated to provide a platform for the preparation ofgraphene-based polymer composites with high performance and multifunctionality for potential
applications in various areas.
Keywords: Graphene, Nanocomposites, Electrical properties

Asian Workshop on Polymer Processing, 6-9 November 2016

PP019BIODEGRADABILITY STUDIESCELLULOSE NANOCOMPOSITESOF

NANOCRYSTALLINE

MAHALAXMI RAMAMURTHI GANAPATHI, DALE CLARKE, NHOL KAO
ROYAL MELBOURNE INSTITUTE OF TECHNOLOGY, MELBOURNE, VICTORIA, Australia
Introduction:
Most petrochemical polymers being used widely cause environmental pollution as they are not easily
degradable and remain in landfills for many years. Renewable, bio-compatible, bio-polymers such as
polylactic acid (PLA), nanocrystalline cellulose (NCC), are expected to degrade easily in a waste stream
into carbon dioxide (CO2), water vapour (H2O) and in some cases (aerobic degradation) methane (CH 4)
gas. This work aims to establish a simple screening tool method to determine the exact rate of degradationof these polymers especially the nanocomposite systems
Methods:
The approach used here is abiotic and involves the use of hydrolysis and photo-degradation.
In hydrolysis method, among the 2 pathways i.e. acidic and alkaline; the latter was preferred since literature
showed it being at least 100 times faster. The hydrolytic medium was 1M NaOH where the polymer samples
PLA, PLA-NCC (1% to 5% w/w) and HDPE were immersed (23C/50-60% relative humidity) away fromlight. The control solution was plain deionised water. The weight loss in comparison to initial was recorded
over time. Simultaneously accelerated weathering testing was done using QUV and SUN methods,
observing for visual changes.
Results:
It was evident from changes in physical appearance between H2O and NaOH samples, that whilst the
samples of PLA and PLA/NCC underwent significant degradation due to hydrolysis, the HDPE control
samples were relatively unchanged. The surface of PLA and PLA/NCC samples exposed to NaOH for theduration of the test were etched, appearing textured and dull rather than smooth and shiny when comparedto their appearance before exposure. This work explains the disintegration of samples in solution. The
degradation was found to follow general integrated second order reaction rate equation. This is used to
explain the possible mechanism of degradation under such conditions simultaneously comparing with some
reported results.
Discussion and conclusion:
From the literature found, there are 2 broad approaches to study degradation of such bio-polymers and theircomposites with NCC, viz. biotic (microbial process) and abiotic (non-microbial). In the biotic process,composting is the most commonly used method wherein the polymer sample is buried in the inoculatedsoil. In another method the polymer is submerged in activated sludge sourced from municipal sewage
treatment facilities. In the abiotic process, degradation is non-microbial and uses acid/base hydrolysis,
photolysis / weathering methods. The main action is cleavage of key linkages in the polymer chain into
smaller fragments. However the biotic process is usually time-consuming and involves use of bio-hazard
substances. The abiotic process is relatively simple saving time. The method developed here is a simple,
easy laboratory screening tool. Among others, the main types of monitoring are weight loss in solid testing,concentration changes when using liquids, yellowness index in case of photolysis / weathering studies andtensile properties.
The rate of hydrolysis of PLA/NCC and PLA samples in an alkaline solution with pH=14 was determined
experimentally. It was found that the addition of 1 wt% NCC to PLA resulted in a rate of hydrolysis
approximately double the rate of neat PLA. This is concurrent with expectations mirrored in literature.
Thus it appears that abiotic methods of simulating degradation on biopolymers like PLA, PCL, etc are a
viable avenue to investigate further as against the biotic method. Additional research into the rate ofdegradation of PLA/NCC in acid could be performed, to compare hydrolysis rates.
Keywords: Polylactic acid (PLA), nanocrystalline cellulose (NCC), hydrolysis, biodegradation.
Asian Workshop on Polymer Processing, 6-9 November 2016

PP020EFFECT OF GRAPHENE NANOPLATELET EMBEDDING ON
PHYSICAL PROPERTIES OF POLY LACTIDE AND POLY
(BUTYLENE ADIPATE-CO-TEREPHTHALATE)
Sima Kashi, Rahul Gupta, Nhol Kao, Sati Bhattacharya
RMIT University, Melbourne, Victoria, Australia
Biodegradable poly lactide (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) were used in
preparation of two series of bio-nanocomposites with 0-15 wt% graphene nanoplatelets (GNPs). Effect of
GNP embedding on various properties of PLA/GNP and PBAT/GNP nanocomposites was determined via
different techniques and the two systems were systematically compared. It was observed that addition of
GNPs enhances thermal stability of both polymers effectively. In particular, degradation of PLA wassignificantly reduced due to the presence of GNPs. Differential scanning calorimetry measurements
revealed that crystallinity of PBAT decreased slightly with increasing GNP loading while crystallinity of
PLA increased markedly. The glass and melting temperatures of the matrices did not vary considerablywith GNP incorporation. Electrical permittivity of both PLA and PBAT increased with increasing GNP
loading. However, while dielectric constants of both systems had comparable values for the same
concentration of GNPs, PLA nanocomposites exhibited higher values of dielectric loss than PBAT
nanocomposites for filler loadings of 9-15 wt%.

Asian Workshop on Polymer Processing, 6-9 November 2016

PP021

FACILEFABRICATIONOFVERSATILE
PMMA/CNFNaYF4:Yb/Er COMPOSITE MICROSPHERES BY PICKERINGEMULSION SYSTEM
Hongxia Liu, Yang Xu, Changbin Zhou
Colledge of Materials Science and Engineering, Guilin University of Technology, Guilin, China
Herein, we report a straightforward method to fabricate multifunctional model drug methyl red-loaded
polymethyl methacrylate (PMMA)/cellulose nanofiber (CNF)-NaYF4:Yb/Er CRs by Pickering emulsion
system. The CRs obtained with relatively uniform size distribution exhibited both strong upconversion anddownconversion luminescence and fine drug release performance. Considering the facile operation process
and versatile properties of the CRs, this work offers an easy and universal method to prepare various
multifunctional CRs for meeting the requirements of diverse applications.
Introduction: Composite microspheres (CRs) have drawn increasing attention because of their attractive
and combined optical, catalytic, electronic and magnetic properties. Rare-earth upconversion nanoparticles(UCNPs), which can convert a near-infrared excitation into a visible emission, are attractive luminescentnanomaterials due to their low auto-fluorescence and toxicity, absence of photo-damage, and high light
penetration depth. On the other hand, cellulose nanofibers (CNFs) possess high specific stiffness andstrength, low density, excellenty biodegradability and biocompatibility, which make them promising for
applications in drug delivery and tissue engineering. Despite significant progress on CRs in recent years,
however, the CRs based on the combination of UCNPs and CNFs have rarely been reported.
In this work, we present a simple and effective method to direct preparation of multifunctional model drug
methyl red (MR)-loaded PMMA/CNF-NaYF4:Yb/Er CRs by Pickering emulsion system. NaYF4:Yb/Ernanoparticle was chosen as a representative UCNP, because it has been demonstrated as one of the mostefficient UCNPs.
Methods: For synthesis of MR-loaded PMMA/CNF-NaYF4:Yb/Er CRs, typically, 1.5 mL of the aqueous
dispersion of 0.1% (w/w) CNFs and 0.05% (w/w) UCNPs was used as water phase. Subsequently, 0.5 mLof the dichloromethane solution of 2% (w/w) PMMA and MR (2 mg/mL) as oil phase was added into thewater phase. After hand-shaking emulsification, the stable O/W Pickering emulsion co-stabilized by CNFs
and UCNPs was obtained. After evaporation of dichloromethane from the emulsion by shaken at 40 oC for
48 h, MR-loaded PMMA/CNF-NaYF4:Yb/Er CRs were obtained. For comparison, Pickering emulsion only
stabilized by CNFs was prepared according to the above method.
Results: We have demonstrated an easy and viable strategy to preparation of versatile MR-loaded
PMMA/CNF-NaYF4:Yb/Er CRs through Pickering emulsion system by using water-dispersible UCNPs
and CNFs as stabilizers. The obtained CRs simultaneously exhibited strong upconversion anddownconversion luminescence and excellent drug release property (see Fig.1). There is no doubt that thisapproach can be extended to prepare other functional CRs. This study thus provides opportunity to fabricate
multifunctional CRs for various applications.
Discussion: The upconversion luminescence spectra of the MR-loaded PMMA/CNF-NaYF4:Yb/Er and
PMMA/CNF CR were measured under excitation of 980 nm. As depicted in Fig. 4a, the MR-loaded
PMMA/CNF-NaYF4:Yb/Er CRs presented four obvious emission peaks at 407, 524, 542 and 656 nm,
which are assigned to the 4H9/2-4I15/2, 2H11/2-4I15/2, 4S3/2-4I15/2 and 4F9/2-4I15/2 transitions for Er3+, respectively.
In contrast, no emission peak can be detected for the MR-loaded PMMA/CNF CRs. Moreover, thePMMA/CNF-NaYF4:Yb/Er CRs can also exhibit strong downconversion luminescence with the emission
peak at 584 nm because of the introduction of MR (Fig. 4b). Based on the dual modal luminescence
property, the PMMA/CNF-NaYF4:Yb/Er CRs with potential tracking capability hold great promise foradvanced biomedical applications.
Fig. 4. (a) Upconversion luminescence spectra of the MR-loaded
PMMA/CNF-NaYF4:Yb/Er (1) and PMMA/CNF (2) CRs (λex =980 nm). Inset: Photographs of water dispersion of MR-loaded
PMMA/CNF-NaYF4:Yb/Er CRs under daylight and excitation of
980 nm laser. (b) Emission spectrum of the MR-loaded
PMMA/CNF-NaYF4:Yb/Er CRs (λex = 490 nm).
Keywords: Composite materials; Functional microsphere; Cellulose nanofiber; Luminescence;
Upconversion nanoparticle

Asian Workshop on Polymer Processing, 6-9 November 2016

PP022HYBRID COMPOSITE USING CARBON NANO TUBE AND
NATURAL FIBER
Omid Nabinejad, Sujan Debnath, M. E. Rahman and Ian J. Davies
Curtin University, Sarawak Campus, Malaysia
Natural fibre composites (NFCs) are widely used in theconstruction, automotive, aerospace and packaging
industries due to their several environmental andstructural advantages. Compared to synthetic-fiberreinforced composites they are environmentallyfriendly, inexpensive to synthesis and possess highspecific strength. However, the hove some drawbacks
which limit their application. Hybrid composites using
natural fibre and nanoparticles have been an area ofintensive research over the last few years due to theircapacity to improve the properties of the natural fibre
composite by nanoparticles. In the present work, ahybrid composite was prepared with natural fibre from Low abrasion resistance with rough surface inplant resources and nanoparticles either MWCNT or worn area for neat polymer
Glassflake reinforced in unsaturated polyester. The
major issue is the preferential reaction of curing
elements in thermoset resins with the natural fibre cells
instead of participating in the polymerization reaction,
where it was found to delay the curing reaction ofthermoset resins (polyester, vinylester and epoxy) bydecreasing the peak exothermic temperature andincreasing the time to peak. Depends on the resin type,selecting a suitable surface treatment for the natural
fibre was observed to mitigate this effect and improve
the rate of curing reaction. It was also reduced thedegradation temperature of the natural fibre composite. Higher abrasion resistance with smooth
Besides, natural filler loading deteriorated the water surface in worn area for hybrid Composite
absorption of the polymer composite. While it was
improved the wear resistance, the more filler, the less mass loss rate resulted. However, utilizing MWCNT
as nanoparticles improved the resistance of hybrid polymer composite in both water absorption wear test.

Reduction in the rate of curing reaction of thermoset
resins due to the reaction of catalyst with natural
fiber instead of polymer

Natural fiber reduced the degradation temperature ofnatural fiber composite

Keywords: natural fiber composite, carbon nano tube, water absorption, abrasion test, curing rate ofpolyester

Asian Workshop on Polymer Processing, 6-9 November 2016

PP023

CRYSTALLIZATION BEHAVIOR AND MORPHOLOGY OFOCTAVINYL-POLYHEDRAL OLIGOMERIC SILSESQUIOXANESREINFORCED
POLY(ETHYLENE
SUBERATE)
NANOCOMPOSITES
Kangjing Zhang, Zhaobin Qiu
State Key Laboratory of Chemical Resource Engineering, MOE Key Laboratory of Carbon Fiber andFunctional Polymers, Beijing University of Chemical Technology, Beijing, China
Introduction: Polyhedral oligomeric silsesquioxanes (POSS) possess a structure of cube-octamericframeworks consisting of an inorganic cube-like core and eight organic corner groups, which may not only
increase the thermal stability and mechanical properties but also act as nucleating agent for the
crystallization of semicrystalline polymers. To our knowledge, poly(ethylene suberate) (PESub) andoctavinyl-polyhedral oligomeric silsesquioxanes (ovi-POSS) nanocomposites have not been reported sofar. In this work, the PESub/ovi-POSS nanocomposites at low ovi-POSS loadings were prepared via asolution mixing method; moreover, the effects of ovi-POSS on the crystallization behavior and morphologyof PESub in the nanocomposites were studied in detail.
Methods: The PESub/ovi-POSS nanocomposites with 0.5, 1 and 2 wt % of ovi-POSS were prepared via asolution casting method and investigated with several techniques.
Results: The dispersion and morphology of ovi-POSS in the PESub matrix were first investigated with
SEM on the fractured surfaces of the nanocomposites. A fine dispersion of Ovi-POSS was observed in the
PESub matrix; moreover, the cubic crystals of ovi-POSS were also found in the polymer matrix. The
nonisothermal melt crystallization behavior of PESub/ovi-POSS nanocomposites was studied with DSC ata cooling rate of 5 oC/min. The overall isothermal melt crystallization kinetics of PESub/ovi-POSS
nanocomposites was investigated with DSC in a wide crystallization temperature range and analyzed by
the Avrami equation. The crystalline morphology and crystal structure of PESub/ovi-POSS
nanocomposites were studied with POM and WAXD.
Discussion: The nonisothermal melt crystallization behavior of PESub was enhanced in the
nanocomposites, as the nonisothermal melt crystallization peak temperatures were higher in the
nanocomposites than in neat PESub. The overall isothermal melt crystallization rates were faster in the
nanocomposites than in neat PESub, although the crystallization mechanism remained unchanged. Both thenonisothermal and isothermal melt crystallization behaviors of PESub in the nanocomposites wereapparently affected by the ovi-POSS loading. At a ovi-POSS loading of 0.5 wt%, the nanocomposite
exhibited the highest nonisothermal melt crystallization peak temperature and fastest isothermal
crystallization rate. With further increasing the ovi-POSS loading, the crystallization rates of thenanocomposites slightly decreased but were still faster than that of neat PESub. The crystalline morphology
study revealed that ovi-POSS obviously increased the nucleation density of PESub spherulites in the
nanocomposites, indicating the nucleating agent effect. The crystal structure of PESub was not modified in
the nanocomposites.
Keywords: Crystallization, Morphology, POSS, Nanocomposites
Part of this research was financially supported by the National Natural Science Foundation, China(51373020, 51573016 and 51521062).

Asian Workshop on Polymer Processing, 6-9 November 2016

PP024

BIO-ACTIVE CLAY BASED HDPE NANOCOMPOSITES: A
POTENTIAL FUNCTIONAL PLASTIC
Anasuya Roy, Mangala Joshi, B S Butola
Indian Institute of Technology Delhi, New Delhi, Delhi, India
The ever-increasing concern for improvement of well-being and hygiene in our daily life owing to improved
living standards throughout the world impacted the overall global research attention. In such times,
investigation on antimicrobial materials has emerged as one of the primary research fields. Polyethylene
represents an important class of commodity plastics having wide range of applications in our daily life andcurrent living status demands high quality functional products of HDPE. Target applications are everyday
commodity plastic items such as kitchen dustbins, crates that are used for transportation and storage of fooditems, baby toys, pipes, buckets and mugs, inner linings of washing machines etc.
Human history has seen clay being used in various applications because of its advantageous high ion
absorption capacity along with its non-toxic nature and easy availability. Two types of antimicrobial clays,
a copper based and a silver based has been synthesized by ion exchange reaction with sodium
montmorillonite (Na-MMT) clay. The modification is confirmed by characterization techniques like XRD
which revealed a disordered intercalated morphology and EDX which quantified the amount of copper andsilver loading on these clays. Antibacterial assay and minimum inhibitory concentration (MIC) of
synthesized two types of antibacterial clays is studied and compared. Both types of modified clays showed
excellent bioactivity and low values of MIC.
Further, the synthesized clays were incorporated into HDPE to prepare antimicrobial HDPE nanocomposite
films via melt mixing route in a twin screw extruder with varying clay concentrations. The nanocomposites
were characterized using tools such as SEM and XRD which suggested uniform dispersion of clays in
HDPE matrix. Tensile testing of the nanocomposites revealed the reinforcing effect of clays on the host
HDPE matrix. The nanocomposites exhibited exceptional antibacterial activities of approximately 99.8%
and a comparative analysis has been performed between the two types of HDPE nanocomposites to evaluate
their effect against harmful bacteria. These bioactive materials can be potential candidates for replacingsome commodity applications of HDPE plastics.
Keywords: HDPE, MMT, Nanoclay, Nanocomposites, Antibacterial

Asian Workshop on Polymer Processing, 6-9 November 2016

PP025RHEOLOGICAL BEHAVIOR OF HDPE/NATURAL NEEDLE LIKE
CLAY NANOCOMPOSITES UNDER SHEAR AND EXTENSIONAL
FLOW
Vishwa Pratap Singh1, G. S. Kapur2, Veena Choudhary1
1Centre for Polymer Science and Engineering, Indian Institute of Technology New Delhi, India 110016,
New Delhi, India, 2ndian Oil Corporation Ltd. Research & Development Centre, Faridabad, Haryana,India
In the present study, high density polyethylene (HDPE)-based composites containing different amounts ofsepiolite [1-10 wt %] and different types of compatibilizers, PE-g-MAH [Optim and Fusabond] wereprepared by melt compounding in a corotating twin screw extruder. These composites were preparedthrough masterbatch route containing 20% sepiolite with HDPE. The effect of sepiolite loading andcompatibilizer type on the rheological behavior of HDPE-sepiolite nanocomposites was investigated witha strain-controlled rheometer. The melt-extensional properties such as extensional viscosity melt strengthand drawability were investigate by using Rheotens set up and extensional viscosity was examined by using
two different methods i.e. Rheotens set up and capillary Rheometer. High shear viscosity and melt fracture
analysis were also carried out using Capillary rheometer.
It was found that the storage modulus, loss modulus and complex viscosity in oscillatory rheometry werehighest for nanocomposite prepared using 10% w/w sepiolite. Incorporation of varying amounts of sepioliteenhanced the melt strength and extensional viscosity with slight reduction in drawability at high filler
loading. These properties were further increased significantly with the addition of compatibilisers to the
HD/Sepiolite composites. Extensional viscosity calculated from Wagner’s master curve using Rheotens
data as well as calculated by modified Cogswell method using convergent flow analysis from capillary data
exhibited good agreement. High shear viscosity increased upon increasing filler content with slight decreasein onset of melt fracture at 10% w/w sepiolite loading. On the other hand, incorporation of compatibilisers
did not affect the shear viscosity with slight increase in the onset of melt fracture.
Keywords: HDPE, Sepiolite, PE-g-MAH, Extensional properties, Melt fracture

Asian Workshop on Polymer Processing, 6-9 November 2016

PP026EVALUATION OF DAMAGE TOLERANCE ON FILAMENTWOUND CFRP LAMINATES SUBJECTED TO LOW-VELOCITYIMPACT
Kodai Suzuki, Satoshi Kobayashi
Tokyo Metropolitan University, Tokyo, Japan
Introduction: Composite pressure vessels are nowadays used as fuel tanks of fuel cell vehicles andhydrogen filling stations. Although they have advantages such as high specific strength and stiffness, it isdifficult to predict impact damage behaviour and associated residual properties. Therefore high cost cyclicpressurization test on an impacted vessel have been conducted. In this study, alternative test method for
cyclic pressurization after impact is proposed. Filament wound composite laminates simulated as shoulder
part of composite pressure vessels were subjected to low-velocity impact. Damage propagation was
examined by destructive and non-destructive inspection. Residual tensile strength was measured with atensile test and compared to virgin specimens.
Methods: Carbon-epoxy composite laminates were fabricated with
wet filament winding as illustrated in Fig. 1 and separated frommandrel after cure. Stacking sequence of laminates was [±18]5. Lowvelocity impact test was carried out with a drop-weight impact test
apparatus. The impactor had a mass of 5 kg and a 16 mm
hemispherical nose. The impact energies were 5 and 8 J that induce
barely visible impact damage. Damage propagation was examinedby microscopic observation to cross-section and X-ray photographs.
Tensile test was carried out with universal testing machine for the
specimens with and without impact.
Results: From cross-section and X-ray photographs, the specimen
impacted by 5 J impact energy had a few matrix cracks and longer
splitting with wide crack opening on the back face while specimenby 8 J had many matrix cracks and shorter splitting with narrow
opening. The damage through-the-thickness showed pine-treepattern both 5 and 8 J. Results of tensile tests showed that no clear
difference in tensile strength among each condition, as shown in Fig.
2.

Motor
MandrelFeed Eye
Tension Stabilizer
BobbinFigure 1 Schematic of filament
winding process.

Figure 2 Influence of impact on
tensile strength.

Discussion: Although there were differences in damage formation between impacted at 5 and 8 J, bothtensile strengths were similar to the result without impact. It seems that all impact damages were matrix
damage such as crack and splitting which do not affect tensile strength considerably. Keywords:
Composites, Filament winding, Low-velocity impact

Asian Workshop on Polymer Processing, 6-9 November 2016

PP027

IMPROVEMENTOF
PHOTODEGRADATIONPOLYPROPYLENE NANOCOMPOSITESIN

Etsuko Takubo, Yusuke Hiejima, Koh-hei Nitta
Kanazawa University, Kanazawa, Japan
Introduction: As well as known, the photodegradation of isotactic polypropylene (iPP) materials is aserious problem for extending their applicability. In this work, we investigated the additional effects ofcarbon nanodots (CDs), showing obvious UV absorption, on the photodegradation of iPP by examining thechange in tensile properties on irradiation.
Experimental Methods: The CDs particles with ca. 10 nm in diameter were prepared from the aqueous
solution of citric acid and ethylendiamine. iPP(Mw=38104, Mw/Mn=4.9), free from photo-stabilizers,
was used as base polymer. The iPP based
nanocomposites were kneaded by mixing rollers with afixed amount (60 to 600 ppm) of CDs in which a
polycarbonate (PC) resin was used as compatibilizer.
The iPP nanocomposites were then pressed at 180˚Cand under 200 kg·cm-2, and quenched into a 100˚Cwater bath to prepare the sample sheets with 100 m
thickness.
Irradiation tests were carried out using ATLAS,SUNTEST cps plus. The sheets were irradiated withxenon lamp (550W/m2) at 63˚C for 24 h. The tensile
properties of the sample sheets were investigated at
25˚C and under the elongation speed of 20 mm/min.
Results and Discussion: Fig.1 compares the stress-strain curves of photoirradiated iPP and photoirradiated
iPP/CDs nanocomposites (600 ppm) with that of virgin iPP. It was found that the virgin iPP is embrittled
by photodegradation after 24 h irradiation, whereas the addition of nano CDs particles drastically improves
photodegradation, and their elongation and strength are comparable with those of the virgin iPP. This isbecause CDs act as inhibitor of photodegradation due to their high ability of UV absorption. Furthermore,
we examined the effects of the CDs contents on photostability of iPP. The photo-stability became graduallypoor with the CDs contents less than 240 ppm.
Keywords:

nanocomposite, polypropylene, carbon nanodots, photostability

Asian Workshop on Polymer Processing, 6-9 November 2016

PP028

EFFECTS OF MOISTURE ON THE PROPERTIES OF UNCUREDAND CURED EPOXY-ANHYDRIDE BASED THERMOSETS
Andrea Johanna Wanner1, Melanie Brasch2, Andreas Moser3, Michael Feuchter3, Wolfgang Kern4,1
1

Polymer Competence Center Leoben, Leoben, Austria, 2Isovolta AG, Werndorf, Austria, 3Institute ofmaterials science and testing of polymers, Leoben, Austria, 4Institute of chemistry of polymeric materials,
Leoben, Austria
Epoxy resin is a widely used material when preparing polymeric matrix composites, providing excellent
mechanical strength, good adhesive properties and convenient processing routes. In many industrial
applications the epoxy resin is cured with anhydrides (e.g. hexahydrophthalic anhydride) after the additionof metal-organic or amine accelerators. However, the resin and the anhydride hardener are sensitive tomoisture absorbance, what affects the shelf lifetime of the uncured system. Furthermore, the mechanicalproperties of the final thermoset change when the resin / anhydride composition is stored under humid
conditions before curing.
In this work, the influence of humidity on the shelf lifetime of the uncured epoxy / anhydride system wasinvestigated. Moreover, the effect of moisture absorption on the final properties of the thermoset wasinvestigated. Characterization of the effects of moisture absorption was done by rheological investigations,
NMR spectroscopy and infrared spectroscopy. To characterize the curing behavior as well as the thermomechanical properties of the cured system various analytical methods, such as differential scanningcalorimetry (DSC), dynamic mechanical analysis (DMA) and infrared spectroscopy were employed.
The high sensitivity of the anhydride hardener to moisture results in the formation of a dicarboxylic acid,
which is - in contrast to the liquid anhydride - a solid material. Thus, an increase of viscosity during storage
under humid environment can be monitored. Upon hydrolysis of the anhydride the acidic product can also
catalyze the curing reaction, what leads to a decreasing shelf lifetime. Differences in mechanical andthermal properties of the resulting thermoset become more pronounced with longer storage of the uncured
system under humid conditions; this is due to altered curing behavior of the dicarboxylic acid with the resin
compared with the anhydride / epoxy reaction when cured with a metal-organic or amine accelerator.
This research work was performed within the K-project “PolyComp” at the Polymer Competence Center
Leoben GmbH (PCCL, Austria). Funding is provided by the Austrian Government and the State
Government of Styria.

Asian Workshop on Polymer Processing, 6-9 November 2016

PP029EFFECT OF TOUGHNESS-ENHANCING ADDITIVIES ON THE
HIGH TG THERMOSET RESIN FOR CARBON FIBER
REINFORCED COMPOSITESJin Woo Yi, Eun Song Lee, Dong Gi Seong, Sang Woo Kim, Moon Kwang Um
Korea Institute of Materials Science (KIMS), Changwon, Gyeongnam, Republic of Korea
Carbon fiber-reinforced polymer composites with the superior mechanical properties and low density havebeen considered as one of the promising lightweight materials for structural parts. Recently, automotive
industry requires a mass production system of the composite parts, in which cost reduction and fast speedof manufacturing process are needed. Liquid molding-based process is one of approaches for high speed
process of composite products and some companies have already produced the composite parts including
a matrix resin with a low glass transition temperature (Tg). The parts can show a problem of dimensional
stability especially when they are painted and dried at a high temperature oven. Therefore, there is a demandfor developing a new thermoset resin which has a high Tg as well as fast cure characteristic. In this work,
we develop a new thermoset resin exhibiting a high Tg/fast-curing property. The resin system consists ofgeneral epoxy resins, multifunction epoxy resins and amine hardeners. However, since the resin has poor
toughness due to the brittle characteristics, a toughness-enhancing additive is necessary. The mechanicalproperties such as tensile, compressive, and shear properties for the composites as well as resin itself aremeasured. The Tg of resin and corresponding composites was measured by DSC and TMA. Experimental
results showed that the resin system could be cured at ~ 120℃ and simultaneously have a high Tg of morethan 160℃. In particular, effect of toughness-enhancing additives on the toughness of the developed resin
is discussed. The resin system is applied to the fabrication process, HP-RTM and the feasibility as a matrix
resin in the structural composite materials for automotive is evaluated. From this work, we can provide a
new resin system which is suitable for automotive composite parts.
Keywords: Thermoset resin, Glass transition temperature, Toughness, Composites

Asian Workshop on Polymer Processing, 6-9 November 2016

PP030

CHARACTERIZATION OF RHEOLOGICAL PROPERTIES OF
PCS (POLYCARBOSILANE) IN THE VICINITY OF CAPILLARYNOZZLE OF MELT SPINNING PROCESS
Joo-Hyung LEE, Wan-Gyu HAHMKITECH (Korea Institute of Industrial Technology), Ansan, Gyeonggi-do, Republic of Korea
Silicon carbide (SiC) fibers have attracted the attention of many researchers as a high-performance
reinforcement material due to their excellent thermos-mechanical properties such as high tensile strength,
high wear resistance, low thermal expansion, etc. at high temperature of over 1000°C Melt spinning process
is one of the most useful commercial spinning processes to produce thermoplastic fibers. It has beenreported that SiC fibers can be produced from thermoplastic polycarbosilane (PCS) precursors by using themelt spinning process, followed by the curing and pyrolysis, and the precise control of structure andformation of PCS as-spun fiber in melt spinning process has emerged as one of important elements to obtainhigh-performance and high value SiC fibers. However, the studies on the fiber formation and rheologicalbehavior of PCS in melt spinning process is relatively still rarer. In this study, the characteristic rheologicalbehaviors of PCS in the vicinity of capillary nozzle under industrial melt spinning conditions wasinvestigated. PCS was melted by using single-screw extruder under an atmosphere of N2 gas, and extruded
through spinning nozzle by metering gear pump. Hole diameter of capillary nozzle in the spinning nozzle
was 0.3mm with L/D 5.0. Entrance pressure (ΔP) of molten PCS in the vicinity of capillary nozzle wasmeasured with a pressure sensor positioned between the gear pump and the nozzle by changing throughput
rate (shear rate) and nozzle temperature. Shear rate at wall and nozzle temperature were controlled in theindustrial spinning conditions of 2000 ~ 3500 sec -1 and 280 ~ 295°C, respectively. Apparent dynamic
viscosity (poise) of molten PCS in the capillary nozzle were calculated by using Hagen-Poiseuille Eq..
Poise of molten PCS showed drastic decrease from 1,303 to 324 g/(cm∙sec) as nozzle temperature increased
from 280 to 295°C at the shear rate of 3500 sec-1. It is also interesting to note that the PCS showed a shear
thickening behavior as shear rate increased from 2000 to 3500 sec -1 at the nozzle temperature of 280°C andthe behavior showed a tendency to decrease as nozzle temperature increased. These characteristicrheological behaviors are rare behaviors cannot be generally observed in the commercial thermoplastic
polymer such as PET, Nylon, PP, etc., and it is speculated that these results seemed to be cause by theunique and complex non-linear molecular structures with various branches of PCS polymer.
SiC fibers, polycarbosilane, rheology, melt spinning

Asian Workshop on Polymer Processing, 6-9 November 2016

PP031

SALT-TOLERANTHYDROGEL-COATED
MESH
WITH
SUPERHYDROPHILIC/UNDERWATER
SUPEROLEOPHOBIC
PROPERTY FOR EFFECTIVE OILWATER SEPARATION
Takeshi Matsubayashi, Mizuki Tenjimbayashi, Kengo Manabe,
Masatsugu Komine, Seimei Shiratori
Keio University, Yokohama, Kanagawa, Japan
Introduction: Extraction of oil from seawater is a worldwide urgent
issue due to frequent oil spill accidents and increasing oily waste water,which have bad influence on human health and marine environment.
Recently, based on wettability. However, oilwater separationin complicated and harsh environment such as high salt
Figure 1. Photo images of (a)concentration of seawater is challenging. In nature, surface ofwater in air and (b) oil
seaweed S. Japonica is inherently superoleophobic in highly
underwater
depositedonsaline conditions. Here, taking advantage of alginate gel as aalginate-coated mesh.
bioinspired material of seaweed, we fabricated hydrogel-coatedmesh with calcium alginate. Alginate-coated mesh exhibits
effective separation of oil/water mixture without oil pollution.
Methods: Polyester mesh was cleaned and hydrophilized by KOH
treatment. Hydrophilic mesh was firstly dipped intopolyethyleneimine (PEI) solution. After dried by air flow, themesh was immersed into sodium alginate solution andsubsequently gelled in CaCl2.
Results: Water contact angle in air (Fig. 1a; <5°) and
Figure 2. Separating theunderwater oil contact angle (Fig. 1b; 160°) indicate that
mixture of oil and water (dyedalginate-coated mesh possesses superhydrophilicity andwith brilliant blue).
underwater superoleophobicity. Moreover, oilwater separation
was carried out by putting alginate-coated mesh between two
glass pipes. 200 mL of oil-water mixture is poured into the mesh and the separation is achieved solely bygravity with separation efficiency >99%, where water penetrates through the mesh while oil is rejected.
Discussion: Superhydrophilic/underwater superoleophobic property of alginate-coated mesh indicate thatthe mesh has higher affinity to water than that to oil. Retained water on alginate gel blocks the permeationof oil to realize efficient oilwater separation without polluted by oil contamination.
Keywords: oilwater separation, underwater superoleophobicity, hydrogel, calcium alginate

Asian Workshop on Polymer Processing, 6-9 November 2016

PP032ONE STEP FORMATION OF JANUS TEXTILES AND GRADIENTFUNCTIONAL FILMS VIA SPRAY DISTANCE CONTROL OF
NANOPARTICLES/POLYMER COMPOSITE
Kaichi Sasaki, Mizuki Tenjimbayashi, Kengo Manabe, Seimei Shiratori
Keio university, Yokohama, Kanagawa, Japan
Introduction: Bioinspired by lotus leaves, many researchers have attempted to impart superhydrophobic
properties both for scientific interest and commercial applications. Despite considerable efforts, only
limited success has been achieved in terms of mechanical durability. To overcome these problems, ourgroup previously reported mechanically durable superhydrophobic surfaces by spraying
nanoparticles/polymer composite. Recently, we discovered spraying distance between sprayer and substrate(SD) can strongly affect on nanoparticles/polymer ratio, surface roughness, and penetrance of spraying
solution into fibril substrates. Here, we newly developed 2 types of advanced superhydrophobic materialusing SD controlled one step spraying; 1. an asymmetric superhydrophobic/superhydrophilic Janus textile
is designed by controlling the wettability and penetrance of spraying solution. 2. Gradient density
superhydrophobic coating is designed by continuously SD changing spray method (Gradient spray method).
These advanced coatings and a coating method can contribute to scientific and industrial fields.
Methods: A cocktail of hydrophobic SiO2 nanoparticles and ethyl-alpha-cyanoacrylate (EAC) in acetone
is sprayed for composite coating. EAC was used to enhance the mechanical durability. We changed a SD
ranging from 10 to 60 cm and measured water contact angle (WCA), surface morphology, and thepenetrance into textiles.

Figure a) Photo image of superhydrophobic/
superhydrophilic Janus membrane. b) Elemental
distributionofgradient
densitysuperhydrophobic coating in depth-probe.
Results: Water contact angle value and surface
roughness of coatings are increased as the increase of a SD; i.g. the coating of SD=10 cm performedhydrophilicity (WCA=75.0°) and smooth structure (Rrms=1.097 μm) whereas the coating of SD = 30 cm
performed superhydrophobicity (WCA=154.5°) and roughened structure (Rrms=20.256 μm). Moreover, thepenetrance of the solution become small as the increase of a SD, that textile became both sidesuperhydrophobic in case of SD=10 cm while textile showed Janus property in SD=30 cm (Figure a).
Furthermore, we designed gradient density structure by changing SD from 10 cm to 50 cm continuously.
The depth directional elementary revealed the gradient density (Figure b).
Discussion: The changes along with SD are induced by the evaporation ratio of solvent and following
instant polymerization of EAC (i.e. SD: high = solvent evaporated and EAC polymerized mixture deposits
on substrate).
Keywords: superhydrophobicity, spray, mechanical durability, Janus, gradient

Asian Workshop on Polymer Processing, 6-9 November 2016

PP033

A BIOLOGICALLY INSPIRED ATTACHABLE, SELF-STANDING
NANOFIBRE SHEET FOR VERSATILE USE IN OIL–WATERSEPARATION
Mizuki Tenjimbayashi, Kaichi Sasaki, Jyunichiro Abe, Seimei Shiratori
Keio University, Yokohama, Japan
Introduction: Oil pollution in water is a worldwide problem, causing long-term eﬀects on the health ofliving organisms and the environment. Recent approaches to oil–water separation are based on the selective
wetting of oils, chemicals and water onto 2D or 3D
porous materials. Although the development of selectivewetting materials enabled highly effective separation,
there are still challenges of practical use in terms of cost,scale and material dimension limiting the strategy. Here,
Uloborus walckenaerius spider webs provided theinspiration for attachable, self-standing nanoﬁbre sheets(NF-S). The developed product adds selective wettability
against oil–water mixtures to both 2D and 3D materials
by attaching or covering them, leading to successful
separation through a facile, scalable and low-cost
process.
Methods: The NF-S was fabricated by anelectrospinningofpoly(vinylidene
fluoride-cohexafluoropropylene) (PVDF-HFP) and ethyl-alphacyanoacrylate (Et-CA) mixture to adjust strength and elastic properties. The threshold of wetting/de-wetting
were analysed by measuring contact angle of EtOH/water mixture varying surface tension γ with ratio. In
addition, wetting/de-wetting behaviours on the NF-S were observed by time-lapsed imaging of
air/water/oil/NF-S interfaces.
Results: Contact angles measurement with different surface tension liquid (Fig. (a)) reveals that there is a
threshold of wetting/dewetting between 36.1–38.6 mN m−1. Thus water (γ=72.8mN m-1) does not penetrate
the NF-S whereas gasoline, Decane, n-Dodecane, Hexadecane, Toluene (γ=21.6-32.0mN m-1) penetrate thesurface.
Discussion: The results revealed wetting/de-wetting threshold to study separation conditions of single
liquid/NF-S interfaces. We further considered a case of oil/water coexisting on NF-S. When oil was caston NF-S, we found a part of oil being infused on NF-S to form oil layer whereas most oil penetrates NF-S
(Fig. (b), left). Thus, oil infused NF-S blocked water penetration because liquids were immiscible (Fig. (b),right) to realize successful separation from mixture.
Keywords: oil-water separation,
nanofibre, slippery surface

electrospinning,

Fig. shows (a) Contact angles ofliquids with different surface tensionsand (b) photo images of oil on NF-S
(left) and water on oil-infused NF-S
(right).

Asian Workshop on Polymer Processing, 6-9 November 2016

PP034

COPPER
PLATED
ELECTRODEVIADEPOSITION

NANOFIBERSAS
AUTOCATALYTIC

TRANSPARENT
ELECTROLESS

Ryohei Yoshikawa1, Takeshi Matsubayashi1, Issei Takenaka1, Kengo Manabe1, Andrea Testa2, Luca
Magagnin2, Seimei Shiratori1
1

Keio University, Yokohama, Japan, 2Politecnico de Milano, Milano, Italy

Introduction: Transparent Conductive Electrode (TCE) is widely used in optical and electrical devices liketouch panel and solar cells. Recently, not only Indium-doped Tin Oxide (ITO), but also ITO alternative
such as metal nanowires are attracted because ITO has problem in depletion. TCE is also promising material
as a heater for de-icing and de-fogging in automobile windows. Using metal nanowires (NWs) for heater
is sometimes undesirable because high conductive metal such as Ag or Cu is highly sensitive to oxygenand humidity. In this study, we fabricated Cu nanowire including a little amount of Ni and P by electrolessdeposition and investigated heater properties. This electrode can be applied to automobile windows as a deicing and de-fogging heater.
Methods: Procedure of fabricating Cu plated nanofibers
is shown in scheme 1. Poly vinyl butyral (PVB) and
SnCl2 was dissolved in ethanol and electrospun onto PET
substrate. After that, substrate with nanofibers was
activated in PdCl2 aqueous solution. As a copper plating
bath, CuSO4·5H2O was dissolved in ion exchanged water(IEW) with NiSO4·6H2O. Activated nanofibers were
immersed in plating bath.

Scheme 1. Fabrication method ofcopper plated PVB nanofibers

Results: Figure 1 shows scanning electron microscopic
images and energy dispersive x-ray spectroscopic imagesof Cu plated nanofibers. The average diameter ofnanofiber before plating was 143 nm. After plating, theaverage diameter increased to 1.78 m. Additionally, wedemonstrated de-icing test to evaluate heater property.
Discussion: By controlling electrospinning and platingtime, transmittance and sheet resistance were tuned. From
fig. 1, Cu is plated along with PVB nanofibers with Ni
and P. The weight ratio was 84.7%, 10.4%, 4.9%,
respectively. Cu plated nanofibers including Ni and P can
improve anti-corrosive property.

Figure 1. Scanning Microscopic
Images and Energy Dispersive X-ray
Spectroscopic Images of nanofibers.

Keywords: nanofiber, electrospinning, electroless deposition, heater, de-icing

Asian Workshop on Polymer Processing, 6-9 November 2016

PP035OPTIMIZATIONOFACID
HYDROLYSISFOR
NANOCRYSTALLINE CELLULOSE PRODUCTION FROM RICEHUSK PULP USING RESPONSE SURFACE METHOD
Md. Sakinul Islam, Nhol Kao, Rahul Gupta, Sati Bhattacharya
RMIT University, Melbourne, VIC 3001, Australia
Introduction: Nanocrystalline Cellulose (NCC) is one of the most abundant renewable bio-nano-materials,
produced in massive quantities from lignocellulosic biomass. For the production of NCC, the classic andmost widely used method is acid hydrolysis of a purified cellulose starting material. Different inorganic
acids, most commonly sulfuric and hydrochloric acid, have been used for this purpose under various processparameters. The choice of process conditions and parameters inevitably affect NCC yield. The mostefficient way to optimize a production process and maximize yield is the Design of Experiments (DOE)
method. DOE is a systematic approach for determining the relationship between different processparameters (x1, x2, x3 etc.) and process outputs (y1, y2, y3 etc.). In this study, three factors was used toanalyse the production of NCC from rice husk pulp by sulfuric acid hydrolysis to elucidate the relationships
between the acid concentration (X3), hydrolysis temperature (X2), hydrolysis time (X1) and NCC yield.
Methodology: The Box-Behnken experimental design of acid hydrolysis for NCC production fromdelignified rice husk pulp was performed by response surface method (RSM). Fifteen experimental runs
(Table 1) were performed at different time, temperature and acid concentrations in order to optimize theprocess.
Table 1: Box-Behnken design of aid hydrolysis by RSM
Experiment

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

Time (X1)

155

10

300

155

155

155

300

10

155

300

10

10

155

300

155

Temp. (X2)

100

100

70

70

70

100

70

40

40

100

70

70

40

40

70

Conc. (X3)

70

60

70

60

60

50

50

60

70

60

70

50

50

60

60

The production of NCC was considered as a main response from this experimental investigation as denotedby Y in the Equation 1. The experimental data were analyzed by the response surface regression procedureusing the following second order polynomial equation:n
Y = β0 + ∑ni=0 βi Xi + ∑ni=1 βii Xi2 + ∑n−1
i=1 ∑j=i+1 βij X i Xj + ϵ …………………………….... [1]Results and Discussion: Response surface plots and contour plots are based on the model equations
obtained in the regression analysis. The response surface plots of NCC production indicate that the response
passes through a maximum and then decreases. Figures 1(a, b) and 1(c, d,) represent the contour andresponse surface plots of the NCC production. The optimized conditions for maximum NCC production
are time (200 minutes), temperature (50 °C) and concentration (60 %).
Contour Plot of NCC vs Con, Time
1.0

0.5

Con

Surface Plot of NCC vs Time, Con
NCC< 10
10 – 20
20 – 30
30 – 40
40 – 50> 50

Hold Values
Temp 0Hold Values
Temp 0

0.0

60
40
NC C

-0.5

20

1

0

0

T ime

-1

-1.0
-1.0

(a) NCC vs X1, X2

0

-0.5

0.0
Time

0.5

C on

1.0

(b) NCC vs X1, X3(c) NCC vs X1, X2

1-1(d) NCC vs X1, X3Figure 1: Contour (a, b), and surface (c, d) plotting of NCC at various parameters
The model Eq. 2 was obtained for all responses, where X1, X2 and X3 are the parameters such as time,
temperature (temp.) and concentration (conc.), respectively. The factors with positive coefficients have apositive effect on the NCC production and vice versa. From these responses it can be seen that NCC
production first increased, reach a maximum and then decreased as the process parameters increased. R2
value is the percentage of response variable variation that is explained by its relationship with one or morepredictor variables. The R2values for this study was 0.72. For the model to be valid, R2 should be greaterthan 0.8. The value achieved for R2 in this study is an indication of moderately fitting of experimental databy the response surface method.
YNCC = 52+11.375 (X1)-4.625 (X2)-1.5 (X3)-25.25 (X12)-5.25 (X22)-10.5 (X32)-6.5 (X1.X2)-1.75 (X1.X3)1.25 (X2.X3) …………………………………………………………. [2]Keywords: Modeling, Optimization, Acid Hydrolysis, Cellulose Pulp, Response Surface Method

Asian Workshop on Polymer Processing, 6-9 November 2016

PP036NUMERICAL SIMULATION OF SLOT-COATING FLOWS OF
CONCENTRATED DISPERSION SYSTEMS OF DISC-LIKE
PARTICLES USING STOCHASTIC COMPUTATION FOR
PARTICLE MOTION
Takehiro Yamamoto1, Tomohiro Shimizu2
1

Osaka Electro-Communication University, Neyagawa, Osaka, Japan, 2Osaka University, Suita, Osaka,Japan
Slot coating flows of concentrated dispersion systems of disc-like particles were numerically simulated. In
this simulation, stochastic simulations of the orientation motion of disc-like particles were coupled with themacroscopic computation of coating flows. In addition, the effect of evaporation of solvent from the film
interface was considered.
In the stochastic simulation of the particle motion, disc-like particles were approximately described byoblate spheroidal particles, and the interaction among the particles was expressed using a Maier-Saupe typemean field potential function. Furthermore Brownian configuration field method was applied to computethe particle orientation field. The macroscopic calculation of coating film flows was performed using thefinite element method. The SUPG/PSPG method was employed to numerically stabilize the flow
computation.
In the present study, slot-coating flows of concentrated suspension of disc-like particles were numericallyanalyzed. The present simulation captured that the particles highly oriented to make the direction of its
rotation axis nearly perpendicular to the flow near the free surface of a film just downstream of a die exit.
The orientation relaxed as the particle flowed downstream. However, the increase in the particle
concentration due to solvent evaporation from the film surface derived the phase transition from isotropic
states to nematic states and hence the particle orientation was fixed and the degree of the orientation
increased again and kept relatively high values.
The orientation distribution of particles can be evaluated from the simulation results. The change in theorientation distribution along the flow provided detail information of processes such as the particle
orientation near the die exit, the orientation relaxation, and re-orientation due to the solvent evaporation.
Such information is a characteristic result of the stochastic simulation considering individual behavior ofparticles and is useful for the analysis of theprocessing of functional coating films. The
coupling of the stochastic simulation for
microstructures of dispersion system and themacro flow computation is therefore aneffective methodology of the numericalsimulation of polymer processing consideringflow-induced structures in materials.
Keywords: Disc-like particles, Dispersion
systems,
Coating
flows,
Orientation
distribution, Stochastic simulation

Asian Workshop on Polymer Processing, 6-9 November 2016

PP037ENHANCEMENT OF MECHANICAL PROPERTIES FOR
POLY(METHYL METHACRYLATE) BY ADDITION OF LOWMASS COMPOUND
Ayumi Kiyama1, Yoshiharu Fukui2, Shogo Nobukwawa3, Masayuki Yamaguchi1
1School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi,
Ishikawa, Japan, 2Mitsuboshi Belting Ltd., 1-21, Hamazoedori, Nagata-Ku, Kobe, Hyogo, Japan,
3
Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showaku, Nagoya, Aichi, Japan
Introduction: PMMA is widely employed owing to its high transparency and high modulus. However,further enhancement of the rigidity is required for various applications to avoid the hard-coating process.
In this study, a small amount of a low-mass compound (LMC) is added into poly(methyl methacrylate)(PMMA) and several measurements are performed to study the effect of LMC. The antiplasticizing
behaviour of PMMA is observed, and the storage modulus E’ at room temperature is increased.
Methods: A commercially available PMMA and poly(ethylene terephthalate) oligomer (C2Ph) were meltmixed in an internal batch mixer at 200 °C. After mixing, flat sheet samples were obtained by using acompression-molding machine. The temperature dependence of the oscillatory tensile moduli in the solidstate, such as storage modulus E’ and loss modulus E’’, was measured from -100 to 180 °C using a dynamic
mechanical analyzer.
11

Discussion: A conventional plasticizer is known todecrease the modulus due to the increase in the free volume
fraction of a polymer. In contrast, C2Ph enhances themodulus in the glassy region, which is known as antiplasticizing behaviour. Furthermore, it is obvious that the
C2Ph addition barely affects therelaxation mode, i.e.,
localized motion, which is different from the antiplasticized polycarbonate.

10 Hz

log [E' (Pa)], log [E'' (Pa)]Results: Fig.1 shows the temperature dependence ofdynamic tensile modulus at 10 Hz for PMMA and
PMMA/C2Ph (90/10). The glass-transition temperature (Tg),
defined as the peak temperature in the E” curve, is shifted to
low temperature by adding C2Ph, which is known as aplasticizing behaviour. Moreover, it should be noted that thestorage modulus E’ at room temperature for the blend isfound to be higher than that for the pure PMMA.

10

E'

9
8
E''
7
6
-100

-50

0

50
100
o
Temp. ( C)

150

200

Fig. 1 Temperature dependence of(circles) tensile storage modulus E’ and(diamonds) loss modulus E’’ for(closed symbols) PMMA and (opensymbols) PC/C2Ph at 10Hz.

Keywords: poly(methyl methacrylate), antiplasticization

Asian Workshop on Polymer Processing, 6-9 November 2016

PP038EVOLUTION OF FIBRE MORPHOLOGY AND RHEOLOGY IN A
POLYMER COMPOSITE
Deverpiran Vishak Perumal1, Sati Bhattacharya1, Rahul Gupta1, Franco Costa2
1

RMIT University, Melbourne, Victoria, Australia, 2Autodesk Australia Pty Ltd, Melbourne, Victoria,
Australia
The purpose of this work is to understand the effects of changing fibre orientation on the rheologicalbehaviour of molten glass fibre/polymer composites. Pellets containing 30% by weight of short glass fibres
in a polyamide-6 matrix were compression moulded at 250°C to prepare 25mm diameter discs forrheological testing. A rotational rheometer with a parallel plate configuration was used with the gap set
between 1mm and 2mm to ensure that gap effects are negligible. Samples were subjected to steady shear
rates ranging from 0.01s-1 to 10s-1 in the clockwise direction and the transient rheological response provided
quantitative evidence of the viscosity overshoot and the steady state viscosity. Once the viscosity reacheda steady state, the sample was cooled to room temperature using a fan blower and carefully removed fromthe rheometer for morphological analysis. Fibre orientation and volume fraction data were captured using
an X-ray Computed Tomography (X-CT) machine with a voxel resolution of 2μm and power rating of 2W.
Post processing of the X-CT images was carried out using VGStudio Software to measure the extent offibre orientation at steady state conditions. With an increasing shear rate, it was observed that the magnitudeof the viscosity overshoot and steady state viscosity decreased while the extent of fibre orientation at steadystate increased in the shearing direction. Samples containing different fibre orientation states were thensubjected to dynamic oscillatory shearing between 0.01rads-1 to 100rads-1 using a strain amplitude that lay
within the Linear Viscoelastic Region (LVR) of the sample. Following validation of the Cox-Merz rule,
shear viscosity for a particular shear rate and state of fibre orientation was obtained from the oscillatory
testing results. Using this data, an attempt will be made to develop a constitutive model to predict thetransient rheological behaviour incorporating shear rate, shear stress, fibre orientation and time.
Keywords: Fibre orientation, Transient viscosity, Computed tomography, Polymer composites

Asian Workshop on Polymer Processing, 6-9 November 2016

PP039CARBON/IRON OXIDE COMPOSITE NANOFIBER AS SELFSTANDING ANODE FOR LITHIUM ION BATTERY
Koki Kawase, Jyunichiro Abe, Yuta Kobayashi, Seimei Shiratori
Keio University, Yokohama, Japan
Introduction: Lithium ion batteries (LIBs) are the most popular energy storage in the various fields. LIBs
demand more energy density for improving performance. Most studies were related to two types ofapproach. First one is the use of the active materials having higher theoretical capacity like iron oxide andsilicon than graphite (372 mAh/g). The problem is that those materials are difficult to be used because ofvolume changes while charge and discharge. Second approach is the reduction of the non-active materials
like conductive agent, binder, separator, electrolyte. However the electrode should have good conductivity
itself. Here, based on both approaches, we fabricated pressed iron oxide/carbon composite nanofibers(ICNF) as self-standing anode for LIBs. We investigated for theeffects of pressure and temperature in carbonization which is
Figure 1. Scanning Electron
important to conductivity.
Microscope images of pressed
ICNF (left) and ICNF (right).
Methods: Bicomponent nanofibers were fabricated via
electrospinning of polyacrylonitrile (PAN) and Iron(III) Nitrate
Nonahydrate dissolved in N,N-dimethylformamide. The nanofibers
were first pressed and then heated in two steps to obtain pressed
ICNF. The morphology and crystallinity and electrochemical
performance were analysed.
Results: While press treatment increased junctions of fibers which
improved conductivity, the surface morphology of the pressed ICNF
was rough which can be caused by high density of iron oxide nearby surface. The highest discharge capacity of ICNF and pressed
ICNF was 609.3 mAh/g and 572.7 mAh/g, respectively. The
discharge capacity of ICNF maintained 60.5% at 2500 mAh/g
compared to the highest one at 100 mAh/g. Press treatment increased
the density of fibers which improved capacity per volume from 138.2
mAh/cm3 to 325.8 mAh/cm3.

Figure 2. Discharge capacity ofpressed and without pressed
ICNF at various currents.

Discussion: It was found that press treatment changed crystallinity
and surface morphology. This probably decreased rate performanceof pressed ICNF nevertheless press treatment improved conductivity.
Keywords: electrospinning, carbon nanofiber, Li ion battery

Asian Workshop on Polymer Processing, 6-9 November 2016

PP040

IMPROVEMENT OF THE PERFORMANCE OF SELF-STANDING
ANODE FOR LITHIUM ION BATTERY BY OPTIMIZINGELECTRODEPOSITION OF IRON OXIDE ON CARBON
NANOFIBER
Yuta Kobayashi, Junichiro Abe, Kouki Kawase, Seimei SHiratori
Keio university, Yokohama, Kanagawa, Japan
Introduction: The improvement on specificcapacity of lithium ion battery (LIB) is required.
Iron oxide is a promising material for its hightheoretical capacity and abundance. However, ironoxide is difficult to be used because of volume
changes while charge/discharge and poor Figure 1. Sheet
Figure 2. Coulombic
conductivity. In order to overcome these problems,
resistance of CNF.
efficiency of CNF
composition of iron oxide and carbon nanofiber
treated at 1000ºC.
(CNF) has been studied. CNF fabricated by heating electrospun
polymer nanofiber has good conductivity and canaccommodate expansion of iron oxide. In this study,
electrodeposition was used because it is simple way andpolymer nanofiber can be carbonized at high temperature
1 µm
5 µm
without catalysis effect of iron oxide which enables to improve
conductivity. The CNF deposited by iron oxide can be self(a)(b)
standing electrode which does not require non-active
Figure 3. (a) Scanning electroncomponents. Here, we investigated the effects of temperature
microscopy, (b) transmission
parameters during the fabrication process of CNF on theelectron microscope image ofconductivity and fiber structure. Effects of pH in solvent andiron oxide on CNF.
applying voltage were also studied to control morphology of deposited iron oxide.
Methods: Polyacrylonitril dissolved in N,N-dimethylformamide was electrospun. The electrospun
nanofiber then stabilized and carbonized at 1000°C. Iron oxide was electrodeposited in FeSO4 (pH=4.1).
And then, CNF was annealed to get CNF deposited by iron oxide. Morphology and electrochemicalmeasurement of the fiber was performed.
Results: Sheet resistance of CNF decreased from 3.7×10 6 Ω/sq. (700°C) to 4.1×102 Ω/sq. (1000°C) (Fig.
1). Coulombic efficiency of CNF treated at 1000ºC was 100.8% after 100 cycles (Fig. 2). From these results,
it was found that treatment at higher temperature can improve the performance of the battery. Depositediron oxide with needle-like morphology was on the CNF (Fig. 3(a) (b)).
Discussion: It was found that conductivity of CNF increased with treatment at high temperature, which can
improve rate capability without any conductive agents. From Fig. 3(b), while surface area increased bynanorods structure, the thickness of iron oxide was not uniform.
Keywords: lithium ion battery, iron oxide, electrodeposition, carbon nanofiber

Asian Workshop on Polymer Processing, 6-9 November 2016

PP041

NEAR-INFRARED REFLECTIVE FILM FOR HEAT SHIELDINGWINDOWS VIA LAYER BY LAYER METHOD
Chiaki Nakamura, Takeshi Matsubayashi, Kengo Manabe, Kyu-Hong Kyung, Seimei Shiratori
Keio University, Yokohama, Japan
Introduction: Energy saving is one of the most important worldwide issues in our environment.
Especially, heat shielding for windows is highly demanded because a main source of energy consumption
in buildings is cooling devices which is used for maintaining
comfortable room temperature. In order to reduce the energy used
for cooling inside buildings, it is effective to shut off near-infrared(IR) light passing through windows from outside sunlight. In thiswork, we fabricate layer by layer deposited thin polymer films withdesigned film thickness and refractive index to selectively reflect
near IR light for the application of heat shielding window.
Methods: Aqueous solution of cationic Titanium(IV)-bis(ammonium lactate)dihydroxide (TALH) and anionic Poly(diallyl
dimethyl ammonium chloride) (PDDA) was alternatively adsorbed
onto cleaned glass substrates by electrostatic force as a highrefractive index layer (H-layer). Colloidal dispersion of SiO2
and PDDA solution was likewise deposited on the substrates
Figure 1. Film thickness and refractive
to form low refractive index layer (L-layer).
index with different number of bilayer(a: High refractive index layer, b: Low
Results: In order to reflect IR light with wavelength () of
refractive index layer). (c) Measured
900 nm, film thickness (d) should be designed as d=/4n
and calculated transmittance of thewhere n is refractive index of H- and L-layer. Therefore,
film.
desirable parameters are as below: n=1.7 and d=132 nm for
H-layer, and n=1.3 and d=173 nm for L-layer. We measurefilm thickness and refractive index of H- and L-layer with different number of bilayer to decide optimal
number of bilayer (Fig. 1a,b). When we piled up H- and L-layer 5 times alternatively, the film showednearly 50% reflection at the wavelength of 1200 nm (Fig. 1c).
Discussion: Reflection peak at around 1200 nm in transmission spectra was observed, which was larger
than that of theoretical value (900 nm). We considered that this was due to the change of film growth in thelatter part of film deposition.
Keywords: near infrared reflection, layer by layer, optical thin film, heat shielding

Asian Workshop on Polymer Processing, 6-9 November 2016

PP042NOVEL EXTENSION OF CONTINUOUS MULTI-LAYERING COEXTRUSION TECHNOLOGIES TO TUBULAR STRUCTURES
Joao Maia, Tyler Schneider
Case Western Reserve University, Cleveland, OH, USA
Layer-multiplying co-extrusion of incompatible polymers was developed in the 1970s by Dow and has
recently evolved to the fabrication of multi-layered nanostructures with thousands of layer, with individual
layer thickness down to a few tens of nanometers. This yields much improved barrier, thermal andmechanical properties and has opened up a whole new range of applications, from GRIN lenses, to ultrahigh barrier packaging, to optical storage, among others. However, when the differences between theviscosity and/or elasticity of the coextruded materials are relatively high, flow instabilities arise during theprocessing that lead to non-uniform layers and non-useful multilayered films. We have recently developed
a new multi-layering die that largely overcomes this issue and is able to layer melts with up to 10:1 viscosity
ratios and 100:1 elasticity ratios and still maintain layer integrity.
In this presentation, we expand this work for the first time away from planar structures, i.e., sheets andfilms, to the multi-layering of rheologically matched and mismatched tubular structures, which opens acompletely new world of applications yet again, from ultra-high barrier blow-molded parts, to medical
devices.
Keywords: Multi-layering co-extrusion, rheology mismatch, high-barrier tubes and pipes

Asian Workshop on Polymer Processing, 6-9 November 2016

PP043POLYETHYLENE MODIFICATION EFFECT OF THE SIDECHAIN CRYSTALLINE BLOCK COPOLYMER WITH HAVING
THE DI (ETHYLENE GLYCOL) ETHYL ETHER ACRYLATE IN
THE FUNCTIONAL SITE.
Yuga Miho1, Hiroshi Sekiguchi2, Ryoko Nakano2, Shigeru Yao1,2
1

Grad. Fukuoka Univ., Fukuoka/Fukuoka, Japan, 2Dep. Fukuoka Univ., Fukuoka/Fukuoka, Japan

Introduction: The Side Chain Crystalline Block Copolymer (SCCBC) is composed with a side chain
crystalline monomer unit and a functional monomer unit. It can be adsorbed to a polyethylene (PE)crystalline surface through crystalline supramolecular interaction.
In this time, we polymerized new functional SCCBC and measured its function.

%T

Methods: The block copolymer was polymerized by living radical polymerization method. Behenyl
acrylate (BHA) was selected as the side chain crystalline monomer and the Di (ethylene glycol) ethyl ether
acrylate (DEEA) was selected as the functional monomer. 140
In thefirst step polymerization, behenyl acrylate (2.03g) was 120
dilutedwith butyl acetate (4.01g), and then added block builder 100
MA®
80(0.162g) as an initiator. The temperature was set to 105°C 60
and
DEEA
polymerization was carried under a nitrogen atmosphere. 40
After 6
BHA
hours, the DEEA solution (12.0g was diluted with 12.0g 20
butyl
SCCBC
0
acetate) was added. After 72 hours, we stopped the
5000
4000
3000
2000
1000
0
polymerization and obtained yellow powder (9.31g). Thecm
polymer was analyzed by FT-IR and elemental
Fig.1 IR spectrums of SCCBC1 (black),
analysis.
DEEA (red) and behenyl acrylate (blue).
-1

The PE film was modified by dipping method with 0.5wt% SCCBC/ butyl acetate solutions. The dipping
time was 60 second. We also modified PE film by coating the SCCBC solution. Evaluation for modifying
functionality of SCCBC was measured by contact angle.
Results: Fig.1 shows the FT-IR spectrums of polymerized SCCBC and each component monomers.
Comparing of these spectrums, the SCCBC spectrum have both specific peaks of each component
monomers. The results of elemental analysis shows thatthe molecular weight of each unit was about 3,800g/mol(BHA): 93,000g/mol (DEEA). Fig2 shows the results ofcontact angle measurement. The contact angle of original
Dipping
Coating
Original
film was 83.3º. The contact angle of dip modified film was
69.7º and coat modified film was 60.8º.
Fig.2 Contact Angle
Discussion: From the results, we polymerized new functional SCCBC by living radical polymerization.
And by using this SCCBC, we can modify the surface properties of PE from hydrophobic to hydrophilic.
Keywords: Side Chain Crystalline Block Copolymer (SCCBC), living radical polymerization, contract
angle, polyethylene (PE), surface modification.

Asian Workshop on Polymer Processing, 6-9 November 2016

PP044

THE EVALUATION OF POSSIBILITY; APPLICATION OF SIDECHAIN CRYSTALLINE BLOCK CO-POLYMER (SCCBC) FOR
PRETREATMENT PROCESS OF NON-ELECTROLYTIC PLATING
Ryoko Nakano, Tomohito Uchino, Hiroshi Sekiguchi, Shigeru Yao
Dept. of Chemicalengineering, Fukuoka Univ., Fukuoka, Japan
Introduction: The non-electololytic plating is widely used as an affective primer technique for nonconductive material. Especially in etch process, acrylonitrile butadiene stylene (ABS) dipped in cronic-acidsulphic solution is generally method. However, it is well known that the harmful wastewater, including
chronic acid has generated. In this study, we investigate the possibility of substitute the side chain
crystalline block co-polymer (SCCBC), which has the alkane-block and tertiary amine- block, for etch
process.
Methods: The degreasing polyethylene (PE) sheet was dipped into modifying solution (SCCBC butyl
acetate solution) at room temperature, pulling and dried, to adsorb Pd-Sn colloid. D was precipitated t HCl.
The Pd catalysed PE sheets was coated by non-electlolyic Ni plating.
Results: The results of observation, the color of Pd catalysed PE film were changed white to brown. Itshows that, the alkane-block had been adsorbed at the PE surface and the tertiary amino-block have covered
PE, thus, Pd-Sn colloid had adsorbed at PE surface. On the other, after non-electrolytic plating, metal layer
had been formed on PE surface, although, many crack have been occurred and detached from PE. This
results from the coating film stress by metal layer.
a)

b)

c)

d)

e)

Figure.1 The image of appearances for un-treated (a), Pd-catalyzed (b), afuter non-electrolytic plating (c),80° C annal (d), and 120° C anneal (e).
Discussion: After metal layer detached from PE, the surface turned white. It seems that, the SCCBC coatedon PE surface, couldn’t withstand the coating film stress by Ni layer. Accordingly, the SCCBC coated PE
was annealed (80° Cor 120°C × 1h). The 80° C annealed sample had not have a change, but the 120° C
annealed sample had the point that held a metal layer.
Keywords: PE, block co-polymer, non-electlolyic plating, coating film stress

Asian Workshop on Polymer Processing, 6-9 November 2016

PP045INFLUENCE OF SELF-ORGANIZATION PROCESS TO THE
POLYIMIDE MEMBRANE PROPERTIES
Naoki Nishikawa1, Hiroshi Sekiguchi2, Ryoko Nakano2, Shigeru Yao1,2
1

Grad, Fukuoka Univ., Fukuoka, Fukuoka, Japan, 2Dep, Fukuoka Univ., Fukuoka, Fukuoka, Japan

Introduction: Polyimide (PI) is known as the typical super engineering plastic with having high glasstransition temperature and elastic modulus. These high physical properties come from the strong
aggregation force between PI molecules. From the fact, the physical and structural properties of PI film
much depend on the self-organization process in the casting process of poly amic acid (PAA) solution. In
this time, we investigated the holding time dependence in the casting process to membrane structure withusing different viscous PAA solution.
Methods: In this time, we used BPDA (acid) and ODA (amine). The molar ratio is 1:1. BPDA and ODA
dried at 80ºC, 24 hours. At first, we dissolved ODA with NMP and stirred for more than 20 minutes at 40ºC. After that, we added NMP solution of BPDA little by little to completely dissolve to BPDA. Under thenitrogen atmosphere, we stirred for about 3 days with mechanical stirrer at 40 ºC. By this process, wepolymerized PAA solution. For the creation of PI membrane, at first, we casted PAA solution about 30μm
thickness by using an applicator on the glass plate. After settling various holding times (0, 10, 60min) as
the self-organization process, we peel off the PAA gel film from the glass plate. And then the gel film wasfixed with a tenter and heated at 300 ºC 30 minutes to produce the PI film. The propertied of PI films wereanalyzed by X-ray diffraction and Scanning Electron Microscope.
Results: The Figure shows the X-ray diffraction patternsof PI films. The settled direction of the film is parallel tothe draw direction of PAA solution. From this figure, at 0
minute holding time, the X-ray diffraction pattern from 10
to 20 degree is almost flat and there is not specific peak inthe scattering profile. On the other hand, with increasing
the holding time to 10 minutes, some peaks begin to appear
around 15 to 20 degree. With increasing the holding time
to 60 minutes, there begin to appear a clear shoulder
around 25 degrees. These results indicate that with increasing the holding time at the stage of PAA solution
casting, the PAA molecules begin to coagulate each other, and create some self-organized structure. The
structure does not destroy in the process of imidization. In addition, almost the same results are obtained in
the perpendicular direction to the draw direction.
Discussion: High viscosity PAA solution will make better structured film than low viscosity solution.
Keywords: Polyimide, Self-organization.

Asian Workshop on Polymer Processing, 6-9 November 2016

PP046LARGE
SCALE
FLOW-MEDIATED
FORMATIONAND
POTENTIAL APPLICATIONS OF SURFACE NANODROPLETS
Haitao Yu, Shuhua Peng, Lei Lei, Tamar Greaves, Jiwei Zhang, Xuehua Zhang
RMIT University, Melbourne, Australia
Microscopic droplets located on a solid substrate in contact with an immiscible liquid promise a broad range
of applications in miniaturised analytical techniques, fabrication of antireflective coatings, high-resolution
near-field imaging techniques and many others. A simple method of producing oil nanodroplets withdesirable morphology is a bottom-up approach called solvent exchange, where nanodroplets nucleate andgrow, as a good solvent of oil is displaced by a poor solvent. In this work, we have achieved the productionof surface nanodroplets over a large surface area on planar or curved surfaces, guided by the principles ofthe solvent exchange. The droplet size is uniform over the entire surface of a planar or curved substrate or
tuneable by varying the local flow rate. The production rate is extremely high at 10^6 nanodroplets per
second. This advance in the nanodroplet production provides a general platform for droplet-based
applications. Here we demonstrate that the application of surface nanodroplets in microextraction ofhydrophobic solute (dye) from its highly diluted aqueous solution and in-situ detection of the dye in a
simple process, and in fabrication of highly ordered array of microlens arrays and polymer-capped
microstructures by simply processes.

Keywords: Nanodroplets, solid-liquid interface, solvent exchange, large scale

Asian Workshop on Polymer Processing, 6-9 November 2016

PP047

EFFECT OF MOLECULAR ORIENTATION ON MECHANICALPROPERTIES OF PERFECTLY BIOABSORBABLE BONE
FIXATION DEVICEMASATO SAKAGUCHI1,2, SATOSHI KOBAYASHI2, SHINJI OGIHARA1
1

TOKYO UNIVERSITY OF SCIENCE, TIBA, JAPAN, 2TOKYO METROPOLITAN UNIVERSITY, TOKYO,
JAPANIntroduction: A composite material that is compounded with bioabsorbable polymer and bioactive
ceramics have been self-reinforced by drawing to improve mechanical properties. Therefore, effect ofmolecular orientation on mechanical properties of the composite material should be investigated. The
purpose in this study is to investigate effect of orientation in matrix on mechanical properties of thecomposite material.
Methods: Effect of molecular orientation on mechanical properties of poly(lactic acid) (PLA) which isbioabsorbable polymer was investigated before that of composite material. PLA screws as specimens areprepared through a series of routes including casting, extrusion drawing and forging. Shear strength,
torsional strength, orientation function and crystallinity of PLA screws were measured.
Results: As a results, shear strength of PLA screw increased with extrusion ratio, while torsional strength
decreased. The investigations of higher order structure were shown that orientation function increased withextrusion ratio and crystallinity did not change.
Discussion: Shear strength and orientation function increased with extrusion ratio. Therefore, drawing iseffective method to improve shear strength of screw, where fibrous structure which was formed during
extruding resisted shear stress in cross-section perpendicular to screw axis. On the other hand, decreasing
torsional strength might be because that the fibrous structure could not hold shear stress in screw axis
direction. It was guessed that this fibrous structure was obtained in matrix of drawn composite material.
Therefore, shear strength in drawn composite material might increase.
Keywords: Poly(lactic acid), molecular orientation, mechanical properties

Asian Workshop on Polymer Processing, 6-9 November 2016

PP048PELLERIZE
CONDITION
DEPENDENCE
OF
WASTE
CONTAINER AND PACKAGE PLASTICS － COMPARISON OF APRESENCE OF MOLTEN RESIN RESERVOIR
Nozomi Takenaka1, Tetsuyoshi Michiue3, Aya Tominaga1, Hiroshi Sekiguchi2, Ryoko Nakano2, Shigeru
Yao1,2, Shunsuke Sugao3, Eiichi Takatori4
1

Grad.Fukuoka Univ., Fukuoka, Japan, 2Dep. Fukuoka Univ., Fukuoka, Japan, 3ECO FEEL CO., Ltd.,
Table.1 Pelletize conditions

Hiroshima, Japan, 4TOSHO A&R Center CO.,Mie, Japan

Fig. 1 Tensile fracture elongation without
reservoir and with reservoir

Ltd.,

Introduction: The environmental impact of a growing volume of wastes, effective recycling of various
products and materials has become an important challenge. The poor physical properties of the materialrecycled plastics had been believed as due to the chemical degradation. Such chemical degradation isirreversible because it is associated with the fracture of molecular chains. However, we have recently foundthat the main reason of this poor physical properties arise from physical degradation. In this time, weinvestigated pelletize condition dependence of recycle containers and package plastics and comparison ofa presence of molten resin reservoir.
Methods: Recycled waste containers and packaging plastic pellet was offered from ECO FEEL Co. LTD.
The pellet was not sorted and that was a mixture of polypropylene and polyethylene. We re-pelletized thepellet by using twin screw extruder. Tensile test pieces were molded by injection molding.
Results: Table 1 shows pelletize conditions. Fig. 1 shows tensile fracture elongation results of injection
molded tensile test pieces. From this result, tensile fracture elongation results with molten resin reservoir
are higher than without reservoir.
Discussion: From the results, the physical properties of injection molded sample are much depend on thepelletize condition and pelletizer form. Especially, the molten resin reservoir is important.
Keywords: Waste container and package plastics, Pelletize condition, Material recycle

Asian Workshop on Polymer Processing, 6-9 November 2016