S. Polymer Materials and Engineering · S. Polymer Materials and Engineering Organizers: Guangxian...

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S. Polymer Materials and Engineering

Organizers: Guangxian Li, Chul B Park, Guangye Liu, Shugao Zhao

S-01

Precisely Functionalized Molecular Nanoparticles Are Unique Elements for Macromolecular Science: From

“Nanoatoms” to Giant Molecules

Stephen Z. D. Cheng

Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron

In this talk, we present a unique approach to the design and synthesis of “giant molecules” based on “nano-atoms”

for engineering structures across different length scales and controlling their macroscopic properties. Herein,

“nano-atoms” refer to shape-persistent molecular nanoparticles (MNPs) with precisely-defined chemical

structures and surface functionalities that can serve as elemental building blocks for the precision synthesis of

“giant molecules” by methods such as a sequential click approach and other efficient organic transformations.

Typical “nano-atoms” include those based on fullerenes, polyhedral oligomeric silsesquioxanes, polyoxometalates,

and folded globular proteins. The resulting “giant molecules” are precisely-defined macromolecules. They include,

but are not limited to, giant surfactants, giant shape amphiphiles, and giant polyhedra. Giant surfactants are

composed of “nano-atoms” tethered with flexible polymer tails of various compositions and architectures at

specific sites that have drastic chemical differences such as amphiphilicity. Giant shape amphiphiles are built up

by covalently-bonded molecular segments with distinct shapes where the self-assembly is driven by the shape of

the molecular segment as well as the chemical interaction. Giant polyhedra are either made of a large MNP or by

deliberately placing “nano-atoms” at the vertices of a polyhedron. Giant molecules capture the essential structural

features of their small-molecule counterparts in many ways but possess much larger sizes; therefore, they are

recognized in some cases as size-amplified versions of those counterparts and often, they bridge the gap between

small-molecules and traditional macromolecules. Highly diverse, sometime completely unexpected,

thermodynamically stable and metastable hierarchal structures are commonly observed in the bulk, thin-film, and

solution states of these giant molecules. Controlled structural variations by precision synthesis further reveal a

remarkable sensitivity of their self-assembled structures to the primary chemical structures. Unconventional

nanostructures can be obtained in confined environments or through directed self-assembly. All the results

demonstrate that MNPs are unique elements for macromolecular science, providing a versatile platform for

engineering nanostructures that are not only scientifically intriguing, but also technologically relevant.

S-02

Shape memory polymers for medical applications using solid phase orientation and micromoulding

P D Coates, P Caton-Rose, B Whiteside, K Nair, D Vgenopoulos, B Thomson, G P Thompson.

University of Bradford

It is increasingly recognised that the properties of polymers depend on their chemical nature and the structure

which is imparted during processing. Solid phase orientation processing of polymers at temperatures above Tg

but below their melting point, provides the major route to imparting a wide range of polymer molecular

orientation. It unlocks the potential of molecular orientation for the achievement of a range of enhanced physical

properties, including enhanced stiffness, yield strength and creep resistance, anisotropy of thermal conductivity,

barrier properties, and drug elution rates. Fibre or tape drawing, solid phase extrusion and die drawing are the

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major routes for the manufacture of oriented products, with a range of draw ratios (strains) from low (around 2) up

to very high (>20) levels, depending on the polymer selected.

Solid phase orientation is also an attractive route to making ‘shape memory’ products which have potential for

applications such as cementless soft tissue fixations which can adapt to surrounding bone topology. We have

extensive research into a range of polymers; the focus here is on bioresorbable polymers (PLAs and modified

PLAs). We describe the die drawing process (Figure 1) to make oriented PLA samples. Choice of draw ratio

fixes the recovery behaviour, so providing a route to ‘tailored’ property products, for example devices which

change shape in-situ on exposure to temperature or, potentially, body fluid, but matching the stiffness of bone.

Prototype devices have been manufactured from resorbable (modified PLAs) or inert polymers, with inorganic

particles and suitable plasticisers, all having known clinical history. The devices may be programmed to

mechanically function (e.g. expand to form a fixation in bone, Fig 2) and then degrade to expose known inorganic

salts/scaffolds which can be used to promote osteogenesis. In the case of medical implants such as tissue

fixations, the shape recovery typically needs to take place at an appropriate temperature to avoid tissue damage

(less than ~50C), or - more challenging (but part of our research) - be driven by exposure to body fluids, and to

occur in an acceptable timescale to the operating clinicians (e.g. less than 15s), and to retain fixation strength over

required timescales (months for bioresorbables, permanent for non-resorbables).

Die drawing produces essentially 2-d profiles. Consequently a net-shape process for 3-d product manufacture

has been explored, namely precision micromoulding, to explore products containing a shape memory element,

caused by frozen-in orientation in the moulded product (Figure 3). The recovery achieved in micromoulded

specimens is encouraging, with recovery of up to almost 50% for moulded PDLGA. This is low compared to

values achievable in solid phase die drawing where almost 100% recovery is obtainable – and in the latter case,

the initial strains which drive recover can be carefully controlled throughout the specimen, whereas in

micromoulding these are locallised and not currently well controlled. Even so, precision moulding could

potentially provide devices with end fixations which do not recover and a section which does recover (e.g. to draw

together a fracture surface on fixation shape recovery).

Our research in this area includes collaborations with leading Chinese research groups in Sichuan University

(SKLPME), Changchun (CIACCAS) and Beijing (ICCAS), for detailed scientific evaluations of structure

developments associated with polymer processing and orientation.

S-03

Research Advance in Heat Resistant Polymer Materials

Xigao Jian

Dalian University of Technology

S-04

Polymer-Based Aerogels toward High Fire Resistance

Yu-Tao Wang, Ke Shang, Yu-Zhong Wang

College of Chemistry, National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), State Key

Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610064, China

Polymer/inorganic particle aerogels were fabricated through a simple, environmentally-friendly freeze drying

process, in which water was used as a solvent. Poly(vinyl alcohol) (PVA) and renewable ammonium alginates

were chosen as the polymer matrixes in the research. With the incorporating of inorganic particles, the hybrid

aerogels exhibit high thermal stabilities and fire resistance. All the results combine to suggest promising prospects

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for use of these aerogel composites in the area of fire safety.

PVA-based aerogels with nanoscale silica, halloysite, montmorillonite (MMT), and laponite were prepared.

Layered microstructures were observed for the samples except with PVA/laponite, which exhibited irregular

network morphologies. With the incorporation of inorganic nanofillers, thermal stabilities increased and the heat

release, smoke release, and carbon monoxide production of the aerogel samples which were measured by cone

calorimetry (CC) were all significantly decreased. These values are much lower than those for commercial

expanded polystyrene foam.

In order to improve further the flame retardancy of PVA/ MMT aerogels, we used ammonium polyphosphates

(APP) modified with piperazine (PA-APP). In combustion testing, all of PVA/MMT/PA-APP aerogels achieved

V-0 ratings and got a higher limiting oxygen index (LOI) values than the PVA/MMT aerogel. Moreover, the

aerogel with 1% PA-APP5(the content of piperazine is 5% in PA-APP) significantly decreased the total heat

release (THR) value to 5.71 MJ/m2 in CC test. Compared with PVA/MMT/APP aerogel, the compressive modulus

of PVA/MMT/PA-APP aerogel was increased by 93.4% due to the increase of interfacial adhesion between

polymer matrix and PA-APP fillers. All the tests results indicated that the incorporation of PA-APP not only

enhanced the fire resistance of aerogels, but also maintained their compress properties.

We used the above similar method to prepare alginates-based aerogels. A simple and economic post-crosslinking

method provided the greatest enhancement of mechanical properties of alginate-based aerogels. Both of the

high-solid-content and corss-linked alginate aerogel show a three dimension network microstructure in the

scanning electron microscopy (SEM) test. With the addition of nano particles (nano-scale magnesium hydroxide,

nano-scale aluminum hydroxide, layered double hydroxide, sodium montmorillonite and Kaolin), the

polymer/inorganic particle aerogels exhibit high thermal stabilities and achieve inherent non-flammability with

LOI higher than 60%. CC tests show the low flammability of alginate aerogel itself and inorganic particles further

suppress its flammability. A kind of novel non-flammable material could be expected.

This work was financially supported by the National Natural Science Foundation of China (Grant 51320105011)

and Program for Changjiang Scholars and Innovative Research Team in University (IRT. 1026)

S-05

Solubility of Physical Blowing Agents in Semi-Crystalline Polymers: Consideration of Rigid Amorphous

Fraction

Jung Hyub Lee, Hassan Mahmood, Chul B. Park

Mechanical and Industrial Engineering department at University of Toronto

Objective: It is well-known that physical blowing agents (PBAs) such as CO2 and N2 cannot penetrate into highly

ordered molecular structures of crystals. However, the effect of crystallinity on gas solubility is not limited to

crystalline regions but extends into the amorphous part of polymers. Molecular chains under the influence of

adjacent crystals form an interfacial layer commonly referred to as Rigid Amorphous Fraction (RAF). The present

study investigates the effect of RAF on the solubility of PBAs in semi-crystalline polymers using PLA and CO2 as

a case study.

Methods: PLA samples of various RAF contents were generated through cold crystallization and variation in the

stereochemistry of the polymers. The phase compositions were characterized through differential scanning

calorimetry and incorporated into the analysis of CO2 solubility determined via the gravimetric method using a

magnetic suspension balance. The measurements were performed under the CO2 pressure of 45 bar at 70?C which

was above the Tg of PLA. A mathematical approach based on the three phase model of semi-crystalline polymers

was applied to differentiate the overall solubility into the contributions of RAF and MAF (mobile amorphous

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fraction).

Results: The samples containing similar degrees of crystallinity (approximately 30%) exhibited different amounts

of RAF ranging from 25 to 45%. Accordingly, the CO2 solubility measurements yielded different results. With the

increase in the RAF content, the CO2 solubility decreased linearly. The differentiation of the overall solubility

showed that the CO2 solubility in RAF was 4%, whereas in MAF it was 7%.

Conclusion: The results illustrate the significance of RAF when determining gas solubility in semi-crystalline

polymers. The third phase, RAF, which is often neglected in polymer processing should be taken into

consideration as it has a visible effect on the properties of polymer/gas mixtures. Gas solubility in RAF of a

semi-crystalline polymer is significantly lower than that in MAF

S-06

Biomimetic Preparation of Silica Nanoplates and Nanocomposites

Zhibo Li

Qingdao University of Science and Technology

S-07

Nanocelluloses for Water Purification

Benjamin S. Hsiao

Stony Brook University

The fabrication of nanocellulose fibrous scaffolds can be accomplished by chemical and mechanical processes of

natural polymeric celluloses from varying resources, where some sources can provide “effortless extractability” w

ith very low energy consumption. Nanofibrous scaffolds have very unique properties including interconnected por

es, a very large surface-to-volume ratio and a high capacity for surface modifications, making them ideal candidat

es for fabrication of high throughput separation membranes (e.g. microfiltration and ultrafiltration) and/or highly e

fficient sorptive media. Directed water channels in the barrier layer of reverse osmosis and nanofiltration membra

nes can also be formed through the formation of interface between the nanofibers and barrier layer polymer matrix

, while the gap thickness can be regulated by physical interactions or chemical bonding. In the present context, ad

vances in fundamental studies on cellulose microfibrils, the building block from the cell wall of any plant, and thei

r interactions with metal ions by means of synchrotron x-ray and neutron techniques have provided us with new in

sight into the design and fabrication of highly permeable nanofibrous membranes, having a hierarchically tiered st

ructure, that can enable higher flux, higher retention and lower energy consumption water purification. Nanocellu

loses may serve as a revolutionary platform technology for the design and fabrication of low cost, sustainable and

highly efficient filtration and sorptive media.

S-08

Recycling Waste Polymer Materials by Solid-State Shear Milling Technology

Qi Wang, Shibing Bai, Fasen Sun, Shuangqiao Yang

State Key Laboratory of Polymer Materials Engineering (Sichuan University), Polymer Research Institute of Sich

uan University, Chengdu 610065, China

Recycling of the continuously increased waste polymer materials (WPM) is a big and challenging issue worldwid

e due to the difficulties in sorting and separating of the multi-component WPM and the reprocessability of the cros

s-linked WPM. This paper reports a novel solid-state shear milling (S3M) technology to efficiently recycle WPM.

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We have developed a solid-state shear milling equipment, which has a unique structure, and acts as three-dimensio

nal scissors, therefore has multi-functions such as strong shearing, pulverization, dispersion, and cutting of the cro

ss-linked bonds, offering a way to solve the problems in recycling WPM. Firstly, the complicated waste polymer b

lends and composites could be ultra-finely pulverized to micro/nanoscale particles at room temperature. The doma

in size and performance of the materials were controlled by the particle size and distribution rather than the compa

tibility and the melt viscosity of the compounds, solving the problems of sorting and separation of the WPM. Seco

ndly, the cross-linked WPM could be partially decrosslinked by S3M and thermally reprocessed. A series of the W

PM that can’t be recycled by the conventional methods, such as waste cross-linked polyethylene (XLPE) cables,

waste printed circuit boards (WPCB) as well as waste artificial turf, etc., have been successfully recycled by S3M

technology. Taking the recycling of waste cross-linked polyethylene (XLPE) cables as an example, the waste XPE

cables with more than 10 kinds of components were pulverized to fine powders, the cross-linking structure was p

artially destroyed, the gel fraction decreased from 67% to 24%, endowing the recycled material good thermal proc

essability. The tensile strength and the elongation at break of the recycled XLPE samples reached 24MPa and 700

% respectively, comparable to those of the pristine HDPE material. The recycled XPE was successfully used to m

anufacture geomembranes, etc. This work was supported by national high technology research and development p

rogram (2012AA063003) of China.

S-09

Multifunctional Structural Elements by Micro Injection Moulding Technology

Gerhard Ziegmann

Technik University Claustha

Injection Moulding is well known since many years as a very efficient technology for producing complex

structural parts with different polymer systems. Within the last decades the functionality of polymer systems was

improved dramatically by embedding functional particles or fibres in the polymer in order to improve strength and

stiffness or impact resistance as well as to implement particles to provide electrical or magnetic conductivity

within the structure. By using micro- or nanostructured particles the microinjection technology could be used to

produce very small structures with combined functionalities. In this presentation some structural elements,

produced by microinjection moulding technology are discussed in detail.

S-10

Breakthrough Water Purification Technologies based on Nanofibrous Membranes, in the Advanced Fibers

and Nanocomposites session

Meifang Zhu

Donghua University

S-11

Multi-Shape Memory Effect of Hemiphasmid Side-Chain Liquid Crystalline Polynorbornene

RuiYing Zhao, ErQiang Chen

Beijing National Laboratory for Molecular Sciences, Department of Polymer Science and Engineering and Key

Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry, Center for Soft

Matter Science and Engineering, Peking University, Beijing 100871, China.

Recently, we are interesting in side-chain liquid crystalline (LC) polymers bearing the side-chain of hemiphasmid

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moiety which contains a rod-like mesogen linked with a half-disk end group. Using ring-opening metathesis

polymerization (ROMP) method, we synthesized hemiphasmid side-chain LC polynorbornene (LCPNb) with the

number-average molecular weight (MW) of ~3.0×105 g mol-1. Same as the other hemiphasmid side-Chain LC

polymers we reported, which possessed the main-chains of polystyrene, polymethacrylate and polyacetylene,

LCPNb could also self-organize into a hexagonal columnar LC phase when the size of flexible tails on the

half-disk was properly chosen. The dimension of columnar lattice could approach to 10 nm. The columnar phase

formation can be understood from the nano-segregation among the main-chain, the rod-like mesogen and the

flexible tails. More importantly, the supramolecular column in the columnar phase shall contain several chains

(e.g., ~5 chains) laterally associated together rather than a single chain. This packing model of “multi-chain

column” of columnar phase provides a new type of physical crosslinking. Taking advantage of such physical

crosslinks, which were robust, LCPNb exhibited excellent shape memory effect. It rendered both the shape fixity

(Rf) and shape recovery (Rr) admirably high (approaching 100%), even when a strain of 700% was applied. With

a broad LC-to-isotropic transition, LCPNb could present the multi-shape memory effect, exampled by its triple-

and quadruple-shape memory with high Rf and Rr at each step. To the best of our knowledge, LCPNb is the first

example of shape memory polymer based on columnar LC phase.

S-12

Rubber behavior in contact with engine lubricants

Laina Guo

Materials Department Manager Hutchinson S.A - Research Center

Elastomers are widely used in automotive under hood applications and are subject to high stresses such as prolong

ed contact with engine lubricants and temperature.

The aim of this study is to analyze the degradation modes of different elastomers such as ACM, AEM and FPM in

function of the type of lubricant and aging duration at high temperature.

Degradation modes have been highlighted for the various families of elastomers tested in this study and improvem

ents have been made to optimize the resistance of these elastomers in lubricants.

S-13

Hierarchically Cross-linked Hydrogel with Tough, highly Stretchable and Self-healing Propertie-s

Xuming Xie

Tsinghua University

S-14

Microcellular Foams of Cellulose Nanofiber/Polymer Nanocomposite and their Mechanical/Sound

Properties

Masahiro Ohshima

Kyoto University

S-15

Colloidal Systems by Self-assembly of Amphiphilic Block Copolymers for Sustained Drug Delivery

Suming Li

1. Institut Européen des Membranes, Université de Montpellier, 34095 Montpellier, France

2. Institute of High Performance Polymers, Qingdao University of Science and Technology, 53 Zhengzhou Road,

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Qingdao 266042, China

Biocompatible membranes have been attracting much attention for uses in medical implants such as drug delivery

devices, artificial organs and diagnostic systems. On the other hand, colloidal systems such as hydrogels,

nanoparticles, micelles, nanotubes and polymersomes prepared by self-assembly of amphiphilic copolymers have

been widely investigated for applications in the field of sustained drug delivery. Compared to conventional drug

delivery routes, colloidal systems present numerous advantages such as constant blood drug concentration,

reduced drug dosage, decreased drug administration frequency, reduced side effects, etc.

Among the various amphiphilic copolymers, polylactide/poly(ethylene glycol) (PLA/PEG) block copolymers

appear the most promising due to their outstanding biocompatibility and bioresorbability. Various PLA/PEG block

copolymers with AB, ABA or BAB-type structures are synthesized by ring-opening polymerization and click

chemistry. Self-assembled aggregates in aqueous solution are prepared from the copolymers by direct dissolution,

nanoprecipitation or dialysis. Various architectures, such as spherical micelles, anisotropic micelles, worm-like

micelles, nanotubes and polymersomes are observed from transmission electron microscopy (TEM), cryo-TEM

and atomic force microscopy (AFM) measurements. The parameters influencing the structure of aggregates are

considered, such as copolymer chain structure, molar mass, PEG fraction, copolymer concentration and

stereocomplexation between L- and D-PLA blocks. Paclitaxel, a highly hydrophobic anticancer drug, is

encapsulated in the core of worm-like micelles. The results show that prolonged drug release can be achieved, and

that the drug release rate mainly depends on the degradation of micelles. Therefore, this work gives new insights

on the self-assembly behavior of PLA-PEG block copolymers in aqueous solution which present great interest for

biomedical and pharmaceutical applications.

S-16

Preparation of Poly(ethylene terephthalate) Foams Using Supercritical CO2 as blowing agent

Ling Zhao, Tao Liu

State Key Laboratory of Chemical Engineering, East China University of Science and Technology,

Shanghai200237, P. R. China

Nowadays, poly(ethylene terephthalate)（PET）foams have been widely used in applications such as packaging,

thermal insulation, optical reflection, and structure materials in wind energy, marine and transportation. Some

processes using supercritical CO2 as blowing agent have been explored to tailor the structure of PET foams or

improve the manufacture process of PET foams for high efficiency. The sandwich structural microcellular PET

with expansion ratio of 1.2~10 were fabricated successfully based on the coupling effect of CO2 diffusion and

induced crystallization, which could be expected to meet both the excellent surface performance and light-weight

requirements. Crystalline PET foams with higher expansion ratio were prepared using periodical CO2-renewing

saturation strategy, which could limit the induced crystallization and thus increase the diffusivity as well as

concentration of CO2 in PET matrix. The melt foaming temperature window of different modified PETs and

PET/clay nanocomposites was determined by their viscoelastic properties and non-isothermal crystallization

properties under high pressure CO2, and the expansion ratio of their foams between 10-50 times were controllably

produced.

Keywords: Poly(ethylene terephthalate); Foam; Supercritical CO2; Crystallization; Viscoelastic property

S-17

The Synthesis and Characterization of Co-Polypropylene Elastomer

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HUANG Qigu1, WANG Jing1, HE Lei1, NAN Feng1, LI Hongming1,2, WANG Fan1,

QIAN Jinhua3, YI Jianjun2, WANG Kefeng2, YANG Wantai1

1. State Key Laboratory of Chemical Resource and Engineering, Key Laboratory of carbon fiber and functional

polymer, Ministry of Education, College of Materials Science and Engineering, Beijing University of Chemical

Technology, Beijing 100029, China

2. Polyolefin Laboratory, Petrochemical Research Institute, Petro China, Beijing 102206, China

3. Science and Technology Management Department，China National Petroleum Corporation

Objective: Thermoplastic elastomers (TPEs) have been given much attention in these decades because TPEs

combine the advantages of rubber and thermoplastic materials. There are two phases, a crystalline hard phase and

a elastomeric soft phase, in TPEs, mainly responsible for thermoplastic, elastomeric properties, respectively. This

paper report that the methodology for the synthesis of copolymers of propylene catalyzed by the novel

non-metallocene catalysts. [N, Si, P] multi-chelated non-metallocene complexes are used as the precursors,

cocatalyst presented, for the coordination polymerization to form a new kind of thermoplastic elastomer with

well-defined structure and component. The research focuses on the relationship among the non-metallocene

complex structure, the catalytic property and the structure and property of the tri-copolymer of

propylene/ethylene/higher α-olefins, the main parameters of the copolymerization and thecopolymerization

mechanism.

Methods: The new terpolymers were determined by FT-IR, 13C NMR, DSC, Wide angle X-ray diffractograms

(WAXD). Furthermore, the stress-strain behavior was measured with ASTMD1708 microtensile specimens cut

from the films. Dynamic mechanical thermal analysis (DMTA) was carried out with a Polymer Laboratories

dynamic mechanical thermal analyzer.

Results: The catalytic activity was as high as 1.09×107 gP (molM)−1 h−1 for terpolymerization of ethylene and

propylene with higher α-olefins catalyzed by titanium complex. The mole fraction of ethylene, propylene, and

1-octene can be concluded by 13C NMR. With the random segments increasing, the intensity of all reflection

peaks derived from α-form of iPP decreased. A decrease in stereo-regularity of polypropylene resulted in the

decrease of the intensity of all reflection peaks. The decrease in stereo-regularity of polypropylene was related to

the decrease of the crystallinity, which caused by the increase of higher α-olefins or ethylene incorporation. When

higher α-olefins incorporation increased, the melting point temperature of the copolymers decreased. As higher

α-olefins incorporation was more than 7 mol%, the melting enthalpy became weak. The stress and strain at break

were as high as 14.21 MPa and 621.36%, respectively, for PEPO, which indicated that the isotactic propylene

terpolymers can be used as elastomer, so did other co-(ter-)polymers.

Conclusion: These isotactic propylene co-(ter-)polymers consist of different length of crystallizable isotactic

polypropylene (iPP) sequences and rubbery amorphous blocks alternating with higher α-olefins or ethylene

incorporation. The distribution and mole fraction of polymers were analyzed by 13C NMR. The results of FT-IR

showed that there were different length of iPP segments in polymers, which resulted in the various melting point

as exhibited by DSC. There was no crystallizable polyethylene present in WAXD patterns and DSC after SAA,

from which, we can conclude that ethylene only participate in forming the random segments. The elastomeric

block copolymers showed good mechanical properties and good transparency.

Keywords: Elastomers of co-polypropylene; Catalysts; Synthesis; Characterization

S-18

Milli/microfluidic assisted fabrication of milli-scale PDVB foam shell by photopolymerization

Lin Zhang

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China Academy of Engineering Physics

Milli-scale monodisperse, low-density, porous polymeric foam shells have been important in many elds, as for

instance, heterogeneous catalysis, ion exchanges, controlled drug-release, inertial fusion energy (IFE) and so forth.

In previous works, various foam shells have been researched for laser-induced inertial confinement fusion (ICF)

targets, including resorcinol–formaldehyde aerogel (RF), trimethylpropane trimethacrylate (TMPTMA), and

poly(divinyl benzene) (PDVB). PDVB is supposed to the most suitable one because it could prevent the reduction

of an energy yield caused by oxygen. Currently, these foam shells for cryogenic laser targets are typically formed

from concentric water in oil in water (W/O/W) droplets.Millimeter-size poly (divinylbenzene) hollow shells were

prepared by photo-polymerization with microfluide technique. Monodisperse double emulsions were fabricated by

a co-axial microfluidic chip in one-step and their size was easily varied by changing the flow conditions. The

rapid and convenient photopolymerization at room temperature is used to avoid some questions which caused by

heat-polymerization, such as, poor stability of the emulsion droplet, density-mismatch and agglomerate. After the

processing ofphotopolymerization and supercritical drying, highly monodisperse and spherical PDVB foam shells

with controllable sizes and geometry were prepared to satisfy the inertial fusion energy (IFE) experiments, in large

diameter( 0.8-6.1mm), low density(50-300mg/cm3), with high concentration(CV < 1.0%). Different morphologies

of the inwall and outwall of PDVB shells were obtained. Furthermore, a reasonable growth mechanism of PDVB

shells was proposed.

S-19

Self-Assembly and Properties of Colloidal Spheres

Limin Wu, Min Chen, Lifeng Hu, Wen Fan

Department of Materials Science and State Key Laboratory of Molecular Engineering of Polymers, Fudan Univers

ity, Shanghai 200433, China

Colloidal spheres have drawn tremendous interests in the past decades because they and their assemblies have the

enhanced even novel properties and can find potential applications in catalysts, gas sensors, optical devices, electr

onics, opto-electronic devices, surface-enhanced Raman scattering devices, solar cells, high-performance display

units, capacitors, and transistors.

Many physical and chemical methods have been developed to fabricate these colloidal spheres and their ordered s

uperstructures. Recently, we have developed several novel methods, including “Pickering emulsification polymeri

zation”, “Nano-solid- -fluid assembly”, “Oil-water interfacial self-assembly”, etc., to fabricate these spheres and t

heir assembles. For example, oil-water interfacial self-assembly has come to be considered an ideal strategy for th

e assembly of various low-dimensional nanostructures into nanofilms. The low-dimensional nanostructures are we

ll dispersed in water, and then an oil phase is added to form an oil-water interface. After the addition of an appropr

iate amount of inducer, the decreased interfacial energy causes the nanostructures self-assembled into closely pack

ed monolayer nanofilms at the interface.

Very recently, we have developed this self-assembly procedure to fabricate monolayer or multilayer nanofilm-base

d devices, using organic/inorganic core-shell composite spheres, inorganic particles, polymer particles as the build

ing blocks.3,4 In this talk, I will give some examples to demonstrate the recent works in my group.

S-20

Special Liquid Crystal Materials and the Preparation Technology of Light Transmittance Adjustable Films

Huai Yang, Lanying Zhang

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Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing, 100871

With the rapid development of economy, the global non-renewable energy exhaustion and air pollution have

become serious problems. As a result, development of materials with efficient energy saving effect and related

technologies have practical significance. Due to the rich hierarchy structures (molecular structure, phase structure,

phase interface, orientation and arrangement etc.) and soft material characteristics, liquid crystal materials exhibit

rapid response characteristics under external stimulations such as light, electricity, and heat, and has been widely

used in areas of display, light transmittance controllable films and other functional materials.

In this work, we present our recent work on the development of brightness enhancement films for LCD, thermally

controllable light transmittance adjustable films, and electrically controllable light transmittance adjustable films

as well as the related preparation technology of the key materials.

S-21

Better Understanding of Natural Rubber Consistency

Benoit Le ROSSIGNOL

R&D Department – Materials Development Director Centre de Recherche

The objective of the Canaopt project (French collaborative project) is to study the factors which impact on the con

sistency of natural rubber. A study of the influence of clones, countries and production parameters on physical and

chemical properties of the raw material like molecular weight, polydispersity, gel content, non-rubber content has

been conducted, by integrating the functional properties of the compounds for anti-vibration applications.

3 grades of natural rubber have been studied: TSR3CV, TSR10 and TRS10CV, produced in Asia and Africa. For th

e TSR3CV it has been highlighted a clonal effect while for the TSR10CV the clonal effect is secondary but on the

other hand processing factors as storage conditions of coagulum , drying conditions and chemical treatment (NHS

) are most important.

The objective of the project is to share these data with producers in order to get a better control of the quality and t

o reduce variability of natural rubber.

S-22

Advanced polymer nanocomposites: unrevealing the role of the spatial distribution of graphene and its

derivatives

T. Zhai1, L.Wang1, GG.Buonocore1, M.Lavorgna1, H.Xia2, L.Ambrosio3

1. Institute of Polymers, Composites and Biomaterials, National Research Council, P.le Fermi, 1-80055 Portici

(NA), Italy

2. State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University,

Chengdu 610065, China

3. Department of Chemical Science and Materials Technology, National Research Council (DSCT-CNR), P.le

A.Moro, 1 - 00185, Roma, Italy

It is well known that the ultimate properties of multifunctional polymer-based composites mainly depend both on

the quality of graphene and its derivatives (i.e the presence of defects and/or the aspect ratio) and the spatial

distribution of graphene nanofiller: homogeneous dispersion, 2D-layer seemly to a continuous graphene layer or

alternatively 3D-graphene network. This talk will review some of activities carried out within the Joint Lab on

Graphene-based Nanocomposites established between the National Research Council of Italy and the State Key

11

Laboratory of Polymer Materials Engineering of Sichuan University. These activities are mainly addressed to

investigate the effect of tailoring the graphene spatial distribution for the design of advanced polymer-graphene

composites. In details the following materials will be presented:

A) Layer-by-layer (LBL) assembly technique has been adopted for fabricating alternating multilayered coatings of

reduced graphene oxide (rGO) and high amorphous vinyl alcohol (HAVOH) deposited on PET substrate. The

coating with 30 layers of HAVOH/rGO (~200nm) leads to a decrease of oxygen permeability of about one order

of magnitude compared to the bare PET substrate.

B) An innovative approach, based on latex mixing and co-coagulation process, has been developed by SKPLME

to prepare rubber/rGO nanocomposites with a 3D-graphene segregated network. In details both natural

rubber-based composites and bromobutyl rubber-based composites were prepared and their functional and

mechanical properties were compared with those related to composites characterized by an homogeneous

dispersion of 2D fillers. Chemical characterization highlighted that during rubber vulcanization by using sulfur

(S8) the graphene platelets significantly affected the crosslinking of rubbers and produced an effective rubber-2D

filler interfaces. The segregated morphology enabled a significant enhancement of the barrier properties, which

was ascribed to the increment of the equivalent aspect ratio of the graphene derivatives filler as consequence of

the assembly and confinement of nanoparticles between the rubber latex microspheres.

C) The solution-casting approach has been adopted for the preparation of chitosan/GO composite films as well as

HAVOH/GO composites films for packaging applications. The materials are characterized by a homogeneous

orientation of graphene and its derivatives platelets. The simultaneous presence of boron crosslinkers and GO in

the case of chitosan based composites and mercapto-based siloxane and GO and nanocellulose in the case of

HAVOH based composites lead to a significant increment of tensile strength and elongation at break, a reduction

of the water permeability and an increment of the hydro-thermal stability.

D) Finally formulated water blown polyurethane foam (PUF) with open cell structure were used for the tailoring

of the 3D network of reduced graphene oxide useful for the preparation of piezoresistive materials. A considerable

portion of biosuccinium polyol, as renewable polyol was used in the formulation. A dramatic change in resistance

was observed when the conductive foam was compressed. Alternatively conductive CNTs/rGO/chitosan aerogels

were prepared by unidirectionally freeze-drying process. The rigid network formed by CNTs and rGO, not only

provided a high efficient conductive network inside the aerogel walls, but also mechanical enhanced the aerogel

skeleton.

Keywords: Graphene, Morphology, Layer-by-layer deposition, Self-assembly, Segregation

S-23

Degradation of polymer materials – from the very beginning

Rui Yang, Jiaohong Zhao, Xuan Liu, Ying Liu, Jian Yu

Department of Chemical Engineering, Tsinghua University, Beijing, 100084, P. R. China

Objective: Degradation of polymer materials under service conditions are generally slow, with gradual changes of

physical and chemical structures. Therefore, stability evaluation of polymer materials are time-consuming and exp

ensive. To detect very early degradation evidence is crucial for fast evaluation of stability.

Methods: A novel in-situ stability evaluation strategy by Fourier transform infrared spectroscopy (FTIR) was deve

loped to monitor trace CO2 and other volatiles as the degradation products of polymer materials, for example, pol

ypropylene (PP)/CaCO3composite and PP/SiO2 composite. The catalytic degradation reaction from the interface

was demonstrated by interface enlargement experiments that were characterized by scanning electron microscopy

(SEM) and pyrolysis gas chromatography-mass spectrometry (Py-GC/MS).

12

Results: PP composites were exposed to UV light and humidity at elevated temperatures. At the optimal condition,

CO2 is the characteristic degradation products and CO2 formation rate reflected the stability of PP composites. P

P composites with various inorganic fillers, different filler particle sizes and surface treatments were evaluated. Th

e results were compared to that from conventional exposure weathering, and they showed excellent correspondenc

e. It is worth noting that the conventional procedure generally last for months, or even years, but this method can

detect very early aging so it only needs several hours to judge the stability.

In order to further investigate the reason why various PP composites behaved differently, interface enlargement ex

periments were carefully designed and carried out. The results demonstrated that catalytic degradation reaction of

PP happened at the interface, and small molecular weight degradation products diffused into the matrix and induce

d further degradation.

Conclusion: By the novel in-situ stability evaluation method, various PP composites were distinguished in several

hours, much shorter than conventional exposure weathering. The interface between PP and inorganic particles was

proved to be the starting place for catalytic degradation of PP.

S-24

Making the Edges of 2D Polymers Visible

Yingjie Zhao1, Zhibo Li2, A. Dieter Schlüter2

1. Qingdao University of Science and Technology, Qingdao

2. Swiss Federal Institute of Technology, ETH Zürich

This work proves the existence of defined edge groups of a 2D polymer and that they can be chemically addressed.

Hexagonally prismatic 2D polymer single crystals with anthracene-based edge groups exposed are reacted with

the isotopically enriched dienophiles maleic anhydride and a C18-alkyl chain-modified maleimide. In both cases

the corresponding Diels-Alder adducts are confirmed by solid state NMR spectroscopy. The same applies to a

maleimide derivative which carries a BODIPY dye which was chosen for its fluorescence to be out of the range of

the self-fluorescene of the 2D polymer crystals stemming from contained template molecules. If excited at = 633

nm, the (100) faces fluoresce and thus the rims of the crystals when lying on a hexagonal face. Lamda mode laser

scanning microscopy confirms this fluorescence to originate from the BODIPY dye. Micromechanical exfoliation

of the dye-modified crystals results in thinner sheet packages which still exhibit BODIPY fluorescence right at the

rim of these packages. This work establishes the chemical nature of the edge groups of a particular 2D polymer

and is also the first implementation of an edge group modification very much as one is used to end group

modifications of linear polymers.

13

Figure 1. (a) Synthetic scheme for surface functionalization of the 2D polymer crystal through Diels–Alder

reaction; (b) CLSM image of modified crystal by excitation at 488, 633 nm and transmission image.

Keywords: 2D polymers; single crystal; edge modification; fluorescence labeling; solid state NMR.

S-25

Fibre Orientation, Dispersion and Length Reduction in Long Glass Fibre Reinforced Injection Moudling

Phil Caton-Rose1, Phil Coates1, Pete Hine2

1. University of Bradford

2. University of Leeds

In this paper we investigate the fibre orientation, length distribution and dispersion developed within a centre gate

d disc geometry both experimentally and, in the cases of fibre orientation and length, through numerical analysis

within Autodesk Simulation Moldflow Insights.

Primary goals of this investigation are:

to compare the differences and similarities between short and long fibre orientation developed within the disc regi

on of the sample

to evaluate, in the long fibre reinforced case, the fibre length distribution at various locations within the moulding,

including the sprue and nozzle sections

to evaluate, in the long fibre reinforced case, the fibre dispersion at various locations within the moulding, includi

ng the sprue and nozzle sections

to assess the mechanical performance predictions within AutoDesk Simulation Moldflow compared to experiment

al deformation

Fibre length distributions and fibre orientations within Autodesk Simulations Moldflow Insight have also been con

ducted, with parameters for orientation models provided by previous work.

Initially, two different nozzle geometries have been tested, as fibre breakage and dispersion of longer fibres has be

en shown to be highly dependent on the early stages of the injection moulding process [2, 3].

Fibre lengths within the component, sprue and nozzle sections has been measured using an in-house developed sy

stem based on a high resolution flatbed scanner. Micro-CT has been used to visualise the fibre dispersion within th

e component, sprue and nozzles. Here the effect of decreased exit diameter in the nozzle section is clearly demons

trated, with aligned fibres appearing in the 6 mm case and a complex flow shown in the 3 mm.

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S-26

Heparin-like/mimicking Polymer Functionalized Blood Purification Membranes

Changsheng Zhao, Weifeng Zhao, Shudong Sun

College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan

University, Chengdu 610065, China

The general conception of heparin-like/mimicking polymers is usually defined as the heparan sulfates or synthetic

sulfated/carboxylated polymers with comparable biologically mimicking the functionalities of heparin, especially

the anticoagulant activity. Herein, we synthesized several heparin-like polymers for the modification of blood

purification membranes. In the studies, polyethersulfone (PES) was chosen as a representive membrane matrix

material due to its excellent physiochemical performance and widely usage in hemodialysis. The

heparin-mimicking membranes showed decreased protein adsorption, greatly suppressed platelet adhesion, and

prolonged clotting times compared to pristine PES membrane, which confirmed the enhanced blood compatibility

of the modified membranes. The cell culture and 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide

(MTT) assays revealed that the membranes had a favorable trend in terms of endothelial cell proliferation and cell

morphology. Moreover, the membranes showed good antifouling property. The heparin-mimicking polymers had

great potential in the modification of membranes used for future portable hemodialyzer.

S-27

New Understanding on the Formation of Phase Structure of Thermoplastic Vulcanizate (TPV) During

Dynamic Vulcanization

Ming Tian1,2, Hanguang Wu1, Nanying Ning1,2, Hongchi Tian2,Youping Wu1,2, Liqun Zhan1,2

1. Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University

of Chemical Technology, Beijing 100029, China

2. Key Laboratory of carbon fiber and functional polymers, Ministry of Education, Beijing University of

Chemical Technology, Beijing 100029, China

In our study, the minimum size of the rubber phase in the EPDM/PP blend at the early stage of dynamic

vulcanization was firstly calculated to be in the range of 25 nm and 46 nm by using the critical breakup law of the

viscoelastic droplets in matrix. Meanwhile, the real size of rubber phase in Thermoplastic Vulcanizate (TPV) at

both the early stage and the final stage of dynamic vulcanization were observed by using Peak Force Tapping

Atomic Force Microscopy (PF-AFM). The results indicated that EPDM phase indeed broke up into nano-scale

particles at the early stage of dynamic vulcanization, consistent well with the calculated result. More interesting, it

was firstly revealed that the micro-meter sized rubber particles commonly observed in TPV were actually the

agglomeration of nano-scale rubber particles with a diameter of 40-60 nm. We further revealed a new mechanism

for the morphological evolution and microstructure formation of TPV during dynamic vulcanization. Our results

indicated that the occurrence of phase inversion of the dynamically vulcanized blend was dominated by the

formation and agglomeration of rubber nanoparticles rather than the increased viscoisty ratio of EPDM and PP as

previously reported. This study provides guidance to control the microstructure of TPV to prepare high

performance TPV products for a wide range of industrial applications.

S-28

Graphene nanosheets: promising application in improving the thermo-oxidative stability of isotactic

polypropylene

15

Miuqiu Kong

Sichuan University

S-29

Cavitation and Plastic Deformation upon Stretching of Poly(ε-caprolactone)

Zhiyong Jiang, Yongfeng Men

State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese

Academy of Sciences, 5625 Renmin Street, 130022 Changchun, China

The evolution of crystalline lamellae and cavities during the tensile deformation of isothermally crystallized

poly(ε-caprolactone) (PCL) was investigated as a function of deformation ratio using in situ small-, ultrasmall-,

and wide-angle X-ray scattering techniques. The cavities were modelled as cylinder-shaped objects which are

oriented along the stretching direction and randomly distributed in the samples,1 and their dimensions were

evaluated by direct model fitting of scattering patterns. At small deformations, crystalline block slips within the

lamellae were activated resulting in the initiation of cavities with a radius of several to tens of nanometers. The

orientation of these cavities at the onset of cavity formation was related to the network modulus of the amorphous

phase. Upon further stretching the cavities reoriented gradually towards the stretching direction and were found to

cluster in the interfibrillar regions at moderate strains where the stress-induced fragmentation and recrystallization

process just set in. Accordingly, the long spacing of the newly developed lamellae along the stretching direction

remained essentially constant after the lamellar-to-fibrillar transition, regardless of the degree of cavitation which

occurred in the samples. The cooperative deformational behavior mediated via slippage of fibrils (stacks of

lamellae with their normal parallel to the stretching direction) was evidenced when being deformed to large strains.

The extent of this slippage depended on the crystallization temperature, which could be traced back to the

significantly different coupling forces imposed by chains connecting adjacent fibrils.2 The interaction between

fibrils decreased with increasing crystallization temperature due to cavities acting as an effective diluent of the

interfibrillar entanglements thus increasingly facilitating further sliding of the fibrils leading finally to more

shrinkage of the stretched interlamellar amorphous layers during stretching. However, a fraction of the polymer

chains with their orientation perpendicular to the stretching direction were still preserved even at large

macroscopic deformations, which corroborated the occurrence of cavities in those lamellar stacks whose normals

are perpendicular to the stretching direction.

Acknowledgment: This work is financially supported by the National Natural Science Foundation of China

(21134006 and 51525305).

S-30

The effect of filler orientation on the crystal structure and dielectric property of P(VDF-HFP) composite

film

Huijian Ye, Tiemei Lu, Chunfeng Xu, Zhu Meng, Mingqiang Zhong, Lixin Xu

Zhejiang University of Technology

High energy storage capacitors have been widely used in pulse power supplies, military defense, electromagnetic

weapons, particle accelerators and biomedical fields. It is the main focus to improve the dielectric properties, and t

hus enhance the energy density and breakdown strength of dielectric material. Poly(vinylidene fluoride) (PVDF) a

nd its copolymers are important candidates for high energy pulse capacitor. In this work, P(VDF-HFP) was selecte

d as matrix to explore the influence of annealing and stretching process on crystal structure and dielectric properti

16

es. Graphene/P(VDF-HFP) composite films were prepared by solution casting to investigate the effect of graphene

on the crystal structure and dielectric properties. The orientation of graphene in the composite films was studied a

fter stretching process, and the relationship between graphene orientation and dielectric properties of composite fil

ms was also developed. The details are as following:

The influence of annealing temperature and heat-retained time on the crystal structure and dielectric property of P(

VDF-HFP) obtained by solution casting is investigated. The effect of stretching conditions, such as stretching rati

os, temperatures and rates of extension, on the relative fraction of β-phase and dielectric properties of P(VDF-HFP

) films was investigated. The fraction of β-phase in PVDF film increases greatly and reaches the peak of 99.7% aft

er uniaxial stretching. Accordingly the dielectric constant of the stretched film increases by 100% and achieves up

to 28.8, as well as the dielectric loss being as low as 0.007.

The free-defected graphene with a concentration up to 0.97 mg/mL and less thickness (<5 layers) was obtained by

liquid exfoliation. The crystal phase and the crystallinity of the graphene/P(VDF-HFP) composite films were inve

stigated by Fourier transform infrared spectroscopy (FTIR) and wide angle X-ray diffraction (WAXRD), respectiv

ely. The transformation of α to β-phase in P(VDF-HFP) was induced by the addition of graphene. The content of β

-phase in 0.5 vol% composite film is up to 87.5% with the dielectric constant of 25.1(100 Hz) and decreased surfa

ce resistivity. The effect of stretching process on orientation structure and dielectric properties of graphene/P(VDF

-HFP) was investigated. The kinetic equation of the relationship between the orientation angle and stretching ratio

of the graphene was derived based on the Jeffery equation in uniaxial stretching flow field. The orientation angle o

f the graphene in the composite films with different stretching ratios was characterized by scanning electron micro

scopy (SEM). The experimental orientation angles of graphene were close to the theoretical values. The dielectric

properties of graphene/P(VDF-HFP) was affected significantly by deformation. When the stretching ratio was 2, t

he dielectric constant of the sample was 34.1 (100 Hz). With the increase of stretching ratio, the dielectric constant

of composite films decreased and the dielectric loss remained steady.

S-31

Manipulation Strategies for Cellular Structure of Microcellular Polymer Foams.

Hanxiong Huang

South China University of Technology

S-32

Thin Polymer Films for Optoelectronics – Impact of Molecular Weight and Casting Solvents on Aggregatio

n Behavior

Christoph Bubeck

Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany

Thin films of conjugated polymers are attracting much interest because of their application in optoelectronics, for

example as organic light emitting diodes, photovoltaic cells, field effect transistors, optical slab waveguides, etc. T

heir physical properties depend significantly on the film morphology which, however, is difficult to control. This

work concentrates on an improved understanding of the impact of molecular structure and film preparation conditi

ons on the morphology of thin films. It is observed that the relative amount of amorphous regions versus crystallin

e or aggregated regions of the film can be influenced (i) by molecular weight and type of side chain substitution, a

nd (ii) by the choice of solvent and film casting temperature. Optimization of the influences (i) and (ii) enables als

o to control the orientation of polymer chains with respect to the layer plane.

The experimental studies concentrate primarily on the model polymer poly[2-methoxy-5-(28-ethylhexyloxy)-1,4-

17

phenylenevinylene] (MEH-PPV). Additionally, other model polymers such as poly(3-alkylthiophene)s (P3ATs) ha

ve been studied also. Thin films were prepared by means of spin coating. The chain packing properties and the cha

in orientation with respect to the layer plane were characterized by means of UV-Vis and polarized infrared reflect

ion-absorption spectroscopy, respectively. Prism coupling of optical slab waveguides was used to determine the an

isotropy of the refractive index and the waveguide propagation loss which depend sensitively on the film morphol

ogy.

The following trends are observable in several polymers similarly: Higher molecular weight favors the aggregatio

n of the rigid-rod type polymers and their preferred orientation parallel to the layer plane. Higher boiling temperat

ures of the solvents, as well as lower casting temperatures result in an increasing amount of aggregated polymer c

hains. It turns out that the film morphology can be controlled by means of suitable design of molecular structure a

nd film preparation conditions. The design rules described above enable the fabrication of thin films with either a l

ow, or a large amount of aggregated regions, depending on the type of application. It is also possible to control the

orientation of the polymer backbones by suitable choice of parameters.

S-33

Controlling the Nanostructure Morphology of Block Copolymers in Bulk and Thin Films

E. Bhoje Gowd, S. Nagarajan, Deepthi Krishnan

Materials Science and Technology

CSIR-National Institute for Interdisciplinary Science and Technology (CSIR-NIIST)

Block copolymers consisting of chemically dissimilar blocks usually self-assemble on nanometer length scale.

These materials have received widespread attention due to their potential applications in nanofabrication. In the

first part of the talk, the orientation changes of perpendicular cylindrical microdomains in

polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) thin films upon annealing in different solvent vapors were

investigated. The selectivity of the solvent to constituting blocks together with the geometry of drying determines

the orientation of the cylindrical microdomains with respect to the substrate plane. Preferential swelling of the PS

matrix in the vapour of the selective solvent (1,4-dioxane) induces a morphological transition from cylindrical to

ellipsoidal as a transient structure to spherical microdomains; subsequent solvent evaporation resulted in

shrinkage of the matrix in the vertical direction, merging the ellipsoidal domains into the perpendicularly aligned

cylinders. On the other hand, the swelling of the P4VP perpendicular cylinders (C^) in chloroform, a non-selective

solvent vapour leads to the reorientation to in-plane cylinders through a disordered state.

The introduction of crystallizable blocks in block copolymers control the solid state structure and generate

fascinating morphologies due to the complex interplay between microphase separation and crystallization. In the

second part of the talk, the structural evolution of poly(ʟ-lactide) (PLLA) during heating of the amorphous ABA

triblock copolymers will be discussed. For that purpose, two triblock ABA copolymers

poly(ʟ-lactide-b-dimethylsiloxane-b-ʟ-lactide) (PLLA-b-PDMS-b-PLLA) and poly(ʟ-lactide-b-ethylene

glycol-b-ʟ-lactide) (PLLA-b-PEG-b-PLLA) containing poly(ʟ-lactide) were synthesized. Upon heating of the

glassy PLLA-b-PDMS-b-PLLA triblock copolymer, the amorphous PLLA transiently transformed to the

mesophase just above the Tg of PLLA block (~ 45 °C) before crystallizing into the regular a form. The Tg of the

PLLA in the PLLA-b-PDMS-b-PLLA triblock copolymer is located at 45 °C, which is almost matching to that of

the PLLA homopolymer demonstrating the immiscible nature of PLLA and PDMS. On the other hand, heating of

the glassy PLLA-b-PEG-b-PLLA triblock copolymer, the mesophase of PLLA was found to appear at a lower

temperature due to the reduction in the Tg of PLLA block in the miscible triblock copolymer system. These results

suggested that the formation of the mesophase was clearly faster in miscible triblock copolymers due to the

18

enhanced molecular mobility of the amorphous PLLA.

S-34

Study on the self-assembly mechanism of cellulose nanocrystal under flow-field and construction of its

functional hybrid materials

Ping Liu, Fuchun Nan, Jianming Zhang

Key Laboratory of Rubber-Plastics, Ministry of Education, Qingdao University of Science & Technology,

Qingdao 266042, China

Among the many potential applications of cellulose nanocrystals(CNC), it is notable for the striking ability to

self-organize into chiral nematic (cholesteric) liquid crystal phase in concentrated solution．In-depth study of CNC

self-assembly mechanism and regulation methods will provide a theoretical basis for the development of

composites with the self-assembled structure of CNC. In a recent work[1-2], we have found that vacuum-assisted

self-assembly (VASA) technique is very effective to fabricate highly oriented, large area and smooth films. This

finding overcomes the pitfalls of the EISA method and show great promise for potential future applications.

Herein, we will report our recent progress on investigate the self-assembly mechanism of cellulose nanocrystal

under flow-field. Meanwhile, a series of functional hybrid materials based on this technique will be introduced.

S-35

Solution blow spun high performance co-polyimide nanofibers

Jing Li, Junrong Yu1, Jing Zhub, Zuming Hu1, Yan Wang2

1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, 201620,

Shanghai (P. R. China)

2. College of Material Science and Engineering, Donghua University, 201620, Shanghai (P. R. China)

Solution blow spinning is an innovative nanofiber fabricating method with high productivity. In the paper,

co-polyimide nanofiber membrane were efficiently fabricated by solution blow spinning followed by imidization

from precursor polyamic acid(PAA) nanofiber. The morphologies and structures of the obtained PAA and PI

nanofiber were examined. The characteristics of the polyimide nanofiber such as pore size, porosity, thermal

stability and mechanical strength were also investigated. The results show that the PI nanofibrous membrane

possess properties of high porosity, small pore size, excellent thermal performance and mechanical properties,

which indicate the solution blow spinning PI nanofibers will have great potential applications in various fields.

Keywords: nanofibers;solution blow spinning;co-polyimide

S-36

In-situ SAXS study on the initiation of cavitation during deformation of annealed precursor iPP film

Bijin Xiong, Yongfeng Men


Academy of Sciences, Renmin Street 5625, 130022 Changchun, P.R. China

The polypropylene film with well oriented lamellar structure has been largely studied due to its important

application in fabrication of mircoporous membranes. Annealing of casted precursor film has been proved to be an

efficient way to enhance the void fraction during the stretch. However, the mechanism of the cavitation formation

upon stretch of precursor films still remains uncertain.

This work mainly focus on the initiation of cavitation during uniaxial stretching of the annealed precursor iPP

19

films. Ultra-small angle X-ray scattering was used to probe the cavitation upon stretching. The experiments were

performed with a series of annealed precursor films with wide distribution of microstructures (crystallinity is from

0.44 to 0.6, crystalline thickness is from 5 to 12 nm) which were prepared by annealing at different temperatures.

The films were stretched in machine (MD), transverse (TD) and dialogue (DD) directions, in order to investigate

the orientation dependence of the cavitation.

Stretch in MD, three major results were observed: (1) the onset strain of cavitation decreases with increasing

crystalline thickness and annealing temperature; (2) The critical stress for the onset of cavitation is roughly a

constant of 47 MPa, independently to the microstructure; (3) the initial average length of cavitation is close to

long period, which means the formation of cavitation accompanied with fragmentation of lamellae. A model on

cavitation formation has been proposed according to this observation (Figure 1).

In annealed precursor films, cavitation behavior shows strong orientation dependence as well. Stretch in MD,

stress whitening appears homogeneously in the whole films and last until break at very large strain, whereas when

stretch in TD craze-like cavities appear accompanied with fast break of the sample just beyond yield.

Figure 1. Length of cavitation and the corresponded formation mechanisms.

S-37

Supercritical Carbon Dioxide Foaming Behavior in Polystyrene System with Carbonaceous Additives

Pengjian Gong, Shuo Zhai, Minh-Phuong Tran, Chul B. Park, Xia Liao, Guangxian Li

Sichuan University

Carbonaceous materials are frequently added to polymers to enhance their performance or introduce an extra

functionality. The large interface between carbonaceous additives and polymer matrix are supposed to reduce the

interfacial tension and increase the bubble nucleation. However, for commercial foaming-grade polystyrene (PS),

adding carbonaceous material decreases cell density and increases cell size, especially at a low foaming pressure

of 6.9MPa. Carbonaceous materials increase PS viscosity, hinders PS molecular chain movement and hence

constrain bubble nucleation. With increasing CO2 pressure, the CO2 plasticization degree increases and therefore

viscosity has less effect on bubble nucleation.

S-38

Manipulation of nanocarbon materials by using pyrene-functionalized polymers

Yehai Yan, Jian Cui, Shuai Zhao

Qingdao University of Science and Technology

H

20

Owing to unique and excellent combination of mechanical, electrical, thermal, and optical properties, nanocarbons

such as CNTs and graphene are extensively regarded as a class of revolutionary material that hold high potential f

or a great variety of applications ranging from composites to electronic devices. Despite the great promise, this cla

ss of material still confronts many challenges prior to its successful transfer into real applications. Of which, unifo

rm dispersion of nanocarbons into diverse media is a top priority, since it permits one toexplore and understand th

e physical properties and chemistries of nanocarbons at the molecular level as well as to integrate them into variou

s application entities through the widely adaptable solvent- assisted techniques. Noncovalent functionalization of

nanocarbons proves an effective solution to reach such objective. Under this rubric, the low molecular weight orga

nic compounds, natural and synthetic polymers, and even inorganic nanoparticles have been employed as dispersa

nts/stabilizers for dispersion of nanocarbons. Among them, the pyrenyl compounds, particularly pyrene-functional

ized polymers, have drawn specific attention on account of their strong π-stacking interaction with nanocarbons. I

n this report, we will present our attempts on the manipulation of pristine SWNTs and graphene by using pyrene-f

unctionalized polymers and passingly discuss their promising applications in polymer composite, biomedical, and

so on.

S-39

Information Integration Framework for Polymer Processing

Furong Gao

The Hong Kong University of Science and Technology

S-40

Controllable preparation and recognition mechanism of surface protein imprinted magnetic polymer micro

spheres

Qiuyu Zhang

Northwestern Polytechnical University

S-41

Light Responsive Shape Memory and Self Healing Polymer

Hongji Zhang

Jiangnan University

S-42

A New Method for Producing Gradient Density Sol-gel Materials

Xiao Pang


Density gradient porous materials have played a important role in areas of aerospace, biomaterials and high-energ

y absorption experiments. In order to accurately control the process of forming gradient, a new method was propo

sed to produce density gradient porous materials. Using the fabrication of gradient density trimethylolpropane tri

methacrylate (TMPTMA) foams as an example, this method was introduced in detail. By using dibutyl phthalate a

s the solvent and benzoin methyl ether as the photoinitiator, gradient density TMPTMA foams were fabricated afte

r the ultraviolet (UV) curing and CO2 supercritical drying. The microstructure and density distribution of foams w

ere characterized by scanning electron microscopy (SEM), UV-visible absorption spectrum and X-ray phase contr

ast. The results obtained indicated that this approach was an effective method for the preparation of gradient densit

21

y foams and this method might be suitable for producing gradient density materials derived from a sol-gel process.

S-43

The fiber dimensions of Lyocell fiber and ramie fiber in poly(L-lactic acid)-based composites after compoun

ding and injection moulding process

Minmin Yu, Zhao Ge, Huihui Zhang, Huili Shao

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science a

Engineering, Donghua University, Shanghai, 201620,P.R.China.

Aim: The aim of this work was to investigate the dimensions of two kinds of reinforcing fiber (Lyocell fiber and r

amie fiber) in poly(L-lactic acid)-based composites after compounding and injection moulding process.

Method: The fiber dimensions were characterized by high-resolution Fiber Quality Analyzer(FQA), which can pro

vide the data of number-average fiber length(Ln), weight-average fiber length(Lw), average fiber width(FW) and t

heir distributions. Moreover, the fines originated from the fiber wall by bending and peeling were provided by the

FQA as well (number-average content, Fn, and weight-average, Fw, respectively). All FQA measurements collecte

d the data of more than 10000 fibers, minimizing the personal error in a great extent.

Results: The results showed that the length of Lyocell fiber and ramie fiber were both reduced drastically after co

mpounding process. They were further reduced by injection moulding step. Moreover, the length of Lyocell fiber

was slightly greater than it of ramie fiber. The FW of Lyocell fiber was smaller and its distribution was narrow, res

ulting in a larger aspect ratio of Lyocell fiber compared with it of ramie fiber. This result implied that Lyocell fiber

was a good kind of reinforcing fiber. In addition to larger particles identified as short fiber segments, the manufac

turing process has also produced a large amount of fines, both by the high shear stresses induced by the flow in th

e processing machine. For fiber-reinforced composites, the specific surface area of reinforcing fiber is an importan

t parameter for improving interface adhesion between the fibers and the matrix. A number content of fines could p

roduce a large specific surface area which provided good adhesion, the stress is transferred effectively between the

load-carrying fiber and the matrix, which increases the mechanical properties. However, although a smaller conte

nt of fines in the Lyocell fiber reinforced poly(L-lactic acid) composites was produced, the composites had a great

er tensile strength, flexural strength and impact strength of poly(L-lactic acid) composites compared with ramie fi

ber-reinforced composites. In contrast, a larger content of fines in ramie fiber-reinforced poly(L-lactic acid) comp

osites only led to improvement of tensile modulus and flexural modulus, respectively. In this work the fines in the

analysis of the relationship between the fiber dimensions and mechanical properties of composites was further inv

estigated.

Conclusions: Lyocell fiber was a good reinforcing fiber due to its narrow distribution of fiber dimensions and larg

e respect ratio, compared with ramie fiber in the poly(L-lactic acid) composites. Moreover, it produced less fines a

fter compounding and injection moulding process, resulting in the improvement of tensile strength, flexural streng

th and impact strength.

S-44

Efficient Production of High-quality Graphene with a Hyperbranched Polyethylene and Its Modification

Effect on UHMWPE

Lixin Xu, Haiping Wang, Huijian Ye

College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014

It is of significant importance to obtain high-quality graphene in large scale through relatively simple process for

22

successful applications of graphene in polymer modification fields. We herein report a facile method for the

efficient production of high-quality graphene with a hyperbranched polyethylene (HBPE) in low-boiling-point

organic solvents and its modification effects on ultra-high molecular weight polyethylene (UHMWPE). A series of

stable graphene dispersions were obtained via liquid-phase exfoliation of graphite with HBPE in chloroform/THF

under assistance of ultrasonication. The graphene concentrations in the resulting dispersions were measured via

UV-Vis spectroscopy and their structures were characterized with high-resolution transmittance electron

microscopy(HRTEM), atomic force microscopy(AFM), X-ray diffraction(XRD), X-ray photoelectron

spectroscopy(XPS) and Raman spectroscopy. The effects from solvent type, feed concentration and molecular

weight, chain topology and composition of the HBPE were systematically examined. Further, a series of

graphene/UHMWPE nanocomposites were prepared by mixing UHMWPE powders and the resulting graphene

dispersions, followed with drying and hot-pressing process. The dispersion status of graphene in the composites

and their modification effects on UHMWPE matrix were then systematically investigated. It is found that graphite

can be effectively exfoliated in chloroform or THF via ultrasonication with the assistance of HBPE to render

stable, high-concentration graphene dispersions. Solvent type, feed concentration, sonication process and HBPE

structure parameters (i.e., molecular weight, chain topology and compositions) all have a significant influence on

the exfoliation of graphite, thus giving effectively adjustable graphene concentrations. The resulting graphene is

confirmed to be free of structural defects and has an average thickness of 3-5 layers. Some HBPE can be

irreversibly adsorbed on the surface of graphene via noncovalent CH-π interactions between them, which results

in the successful exfoliation of graphite. It is also found that the resulting graphene can be selectively dispersed on

the interfaces between UHMWPE powders to form an unique segregated network structure, leading to significant

improvement both in the electrical conductivity and abrasive resistance of UHMWPE matrix. (This work was

financially supported by the National Natural Science Foundation of China (21074117, 21474091) and the Natural

Science Foundation of Zhejiang Province (LY14B040002, LQ16E030009))

S-45

Copolymerization modification of PPTA with 2,5-furan dicarboxylic acid towards high-performance

material with enhanced solubility

Kaiju Luo1, Yan Wang2, Junrong Yu1, Jing Zhu2, Zuming Hu1

1.State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, 201620,

Shanghai (P. R. China)

2.College of Material Science and Engineering, Donghua University, 201620, Shanghai (P. R. China)

This paper described the preparation and characterizations of soluble PPTA-CO-PPF (see scheme 1) copolymer by

direct polycondensation. The chemical structure of polyamide was investigated by 1H NMR and FT-IR spectrum.

The good solubility of copolymer in organic solvents (such as NMP, DMSO,DMAC, DMF) was certified at room

temperature. Their thermal stability and mechanical properties were also observed by TGA analyzer and tensile

testing.

Keywords: PPTA; copolymer; solubility; mechanical and thermal properties

S-46

Water Sensitive Shape Memory Behavior of Bio-based Fibers

Hu Jinlian1, Zhu Yong1, Lv Jing1, Tan Lin1, Xiao Xueliang 1,2

1. Institute of Textiles and Clothing, the Hong Kong Polytechnic University, Hung Hom, Hong Kong;

2. School of Textiles and Clothing, Jiangnan University, Wuxi, 214122, P.R. China

23

Natural bio-based fibers consist of a large amount of hydrogen bonds between intra and inter macromolecules that

offer a basis for water sensitive shape memory (WSSM) behaviors. This work reports our advance in

understanding the bio-based fibers related to WSSM phenomena, such as α-keratin hairs, β-sheeted filaments,

chitosan and collagen fibers. Experimental investigations like qualitative and quantitative study of such fibers

were carried out in detail for WSSM behaviors. All investigated bio-based natural fibers show remarkable WSSM

features that manifest good stability of high shape fixation ratios and reasonable recovery rates after a number of

cycles of deformation programming under water stimulation. The effects of hydration on fiber lateral size,

recovery kinetics, dynamic mechanical behaviors and structural components (crystal, disulfide and hydrogen

bonds) were all systematically studied. WSSM mechanisms were explored based on the variations of structural

components in molecular assemblies of such bio-based fibers. Hybrid structural network models with

single-switch and twin-net-points were thereafter proposed to interpret the WSSM mechanism of bio-based fibers.

These single-switch-twin-netpoint models one side can guide post finishing process of textile materials in

industrial to avoid waste of energy resources, such as temporary shape fixation of formal suits without hanging

operation for them; on the other hand, bio-inspiration of such fibers from structural components and WSSM

mechanism can improve our horizon of bio-based fiber in function knowledge. This original study for WSSM

behavior of bio-based fibers is surely expected to provide inspiration for exploring other natural materials to

reveal their smart functions and making more remarkable synthetic smart materials.

S-47

TBD

Mingqiu Zhang

Sun Yat-sen University

S-48

Multifunctional hydrogels ¾ from high mechanical performances, shape memory to manipulation of stem

cell differentiation

Wenguang Liu

Tianjin University

S-49

Progress in Biodegradable Shape Memory Polymers and Their Biomedical Applications

Hongmei Chen, Lin Wang, Tao Gong, Shaobing Zhou

Key Laboratory of Advanced Technologies of Materials, Ministry of Education, School of Materials Science and

Engineering, Southwest Jiaotong University, Chengdu, 610031, PR China.

Shape memory polymers (SMPs), a family of intelligent polymers, can be fixed into a temporary shape with a

predefined method and subsequently recover their initial shape under certain external stimuli (thermal, electric,

magnetic, solvent, photo) (1, 2). SMPs have been gained an increasing attention because of their unique properties

and potential applications in biomedical field. In these years, we mainly focused on investigating the shape

memory functions of the biodegradable polymers based on poly(ε-caprolactone) (PCL) and polylactide (PLA). By

changing external stimuli, we achieved thermal-induced SMPs, electric-induced SMPs, magnetic-induced SMPs

and solvent-induced SMPs (3-6). These biodegradable SMPs exhibit potential applications in biomedical field due

to the fact that the polymer matrix possesses excellent biocompatibility and biodegradability; moreover, the device

from the polymer can be used for minimally invasive surgery. Here, we introduce their biomedical applications in

24

drug delivery, tissue engineering, artificial vascular grafts, smart polymer stent for the esophageal stenosis therapy

(7-10).

S-50

Shape memory polymer network with thermally distinct elasticity and plasticity

Qian Zhao

State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang

University, Hangzhou 310027, China.

Stimuli-responsive materials with sophisticated yet controllable shape changing behaviors are highly desirable for

real world device applications. Amongst various shape changing materials, the elastic nature of shape memory

polymers allows fixation of temporary shapes that can recover on demand whereas polymers with exchangeable

bonds can undergo permanent shape change via plasticity. Here, we integrate the elasticity and plasticity into a

single polymer network. Rational molecular design allows these two opposite behaviors to be realized at different

temperature ranges without any overlap. By exploring the cumulative nature of the plasticity, we demonstrate easy

manipulation of highly complex shapes that is otherwise extremely challenging. The dynamic shape changing

behavior paves a new way for fabricating geometrically complex multifunctional devices.

S-51

Designing Tunable Multiple-Shape Memory Polymer with Thermoplastic Elastomer Blends

Jiachun Feng

Fudan University

S-52

Magnetic field actuated multiple shape memory composite nanofibers

Fenghua Zhang1, Yanju Liu2, Jinsong Leng1

1. Centre for Composite Materials and Structures, Harbin Institute of Technology (HIT), No. 2 YiKuang Street,

PO Box 3011, Harbin 150080, People`s Republic of China

2. Department of Astronautical Science and Mechanics, Harbin Institute of Technology (HIT), No. 92 West dazhi

Street, PO Box 301, Harbin 150001, People`s Republic of China

As stimuli-response polymers, shape memory polymers (SMPs) and their composites that can change shape when

exposed to various stimuli enable great development of applications. There are different stimulus methods

including heat, electrical and magnetic fields, pressure, solvents, light, etc. Among them, magnetic field triggered

shape recovery behavior attracts great attention in many fields. Magnetic field as an actuation method exhibits

some advantages, including effective and fast heating, non-contact control and uniform heating distribution.

Furthermore, complex and controllable shape changing is needed in special applications. Even SMPs have been

developed well, it is a challenge to fabricate polymer fibers with multiple shape memory effect and remote

control.

Herein, to meet the requirement of applications, we designed and fabricated composite nanofibers combining

Nafion with magnetic Fe3O4 particles by electrospinning. The composite fibrous membranes with a broad

transition temperature could be triggered in magnetic fields within 30 s. Moreover, the resulting composite

nanofibers can remember more than three shapes. During the shape recovery process, we can control the recovery

order by changing the power and the surface temperature of composite fibrous membranes is near body

25

temperature. The multiple functions in one material will provide more potential in smart textiles, biomedical

engineering, aerospace and so on in the future.

S-53

Self-Healable Conductive Shape Memory Polymer Composites

Hongsheng Luo, Xingdong Zhou, Huaquan Wang, Guobin Yi, Wenjin Ji, Xihong Zu, Jun Peng

Faculty of Chemical Engineering and Light Industry,Guangdong University of Technology, Guangzhou, PR China,

510006.

Self-healable polymers, as one type of very important biomimetic materials, have been extensively studied over

the past decades. Unlike the traditional mechanisms based on the micro-capsules or reversible covalent bonds, the

shape memory-assisted self-healing could be facially achieved by blending a healing agent with the shape

memory polymer matrix. Herein, we explored a conductive self-healable polymer composite via transfer process.

The composites featured superior flexibility, electrical conductivity and self-healing as exposed upon mechanical

damages. The micro-scale cracks could be healed under the heating stimulation, making not only the mechanics

but also the conduction of the composites repaired. Figure 1a schematically illustrates the transfer process of the

fabrication. Briefly Speaking, multi-wall carbon nanotubes (CNTs) after acid treatment were firstly dip-coated

onto a release substrate. The resultant conductive networks were then transferred into a shape memory polymer

matrix containing the healing agent of polycaprolactone (PCL). Finally the composites were peeled off after

solidified in the vacuum. Figure 1b shows the Scanning Electron Microscope (SEM) images of the cracks in the

different healing durations. Obvious evolution of surface morphologies could be observed, indicating that the

heat-induced closure of the interface driven by the shape recovery as well as the re-building of the conductive

networks. The composites were connected into a circuit applied with the voltages of 3V. The LED were turned off

as the sample was cracked, However, the LED gradually enlightened as the sample was triggered to self-heal

under the heating (shown in Figure 1c and 1d). The findings may greatly benefit the application of the smart

polymers in the field of flexible electronics.

S-54

The Relationship Between the Structure and Property of Multi-phase/Multi-component Materials with

Shape Memory Property

DONG Xia, HUANG Miaoming, LIU Xinran, WANG Dujin

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Engineering Plastics, Institute of

Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Nowadays shape-memory polymers (SMPs) have attracted much attention because they are able to remember and

recover their permanent shape after deformation under stimulus such as heat, light, electric field and magnetic

field. As a result, researches on the relationship between the structure and shape memory (SM) property of

materials is of great importance. These studies in this work could be divided into the following categories: the

addition of nano-particles, tailoring gel content, phase structure and molecular structure. The research results are

shown as follows. Firstly, it has been proved that nano-SiO2 has some interaction with the segments of PU,

affecting the orientation behaviors of polyurethane in both drawing and recovery process. In the drawing process,

the hard segments at the domain interface and soft segments of PU-3% have a perpendicular direction at the small

strain, and then possess a parallel orientation at larger deformation, whereas those of PU-0% orient positively

from the beginning to the end. Secondly, gel content is the key issue that conducts the Two-way shape memory

26

(TWSM) behavior and higher gel content would result in the robuster TWSM effect for cross-linked PCL (cPCLx)

samples. It is apparent that the samples would exhibit different elongation and recovery capabilities in the TWSM

process due to the difference of gel content. But the sample with the lowest gel content (cPCL3) almost doesn’t

display TWSM behavior. Thirdly, the phase structure of blends also affects the SM property. For example,

different phase structure can be obtained by changing the composition of blends. Finally, the change of molecular

chains can also tailor the SM property of materials, such as multiphase copolymer.

Keywords: nano-particles; gel content; phase structure; molecular structure

S-55

Shape memory vitrimers

Yan Ji

Department of Chemistry, Tsinghua University, Beijing, China

Vitrimers are a new class of polymers. They are covalently cross-linked like thermosets, but they are

reprocessable at certain conditions. During the processing, new bonds form only when the old ones break. The

crosslinking density remains the same all the time. In this talk, I am going to present our recent work on vitrimers

with shape memory effects. Taking advantage of such new processability, we developed a new strategy to achieve

multi-shape memory effect and created a multi-stimuli responsive and multi-functional polymer network2.

Introducing liquid crystallinity into vitrimers, we found a practical way to solve the processing bottleneck of

liquid crystalline elastomers3. Moreover, based on the photo-thermal effect of carbon nanotubes and other kind of

photo-thermal agents, we endowed vitrimers photo-induced shape memory and light controlled processing4-6.

S-56

Thermosetting epoxy resin /thermoplastic poly(ε-caprolactone) system with combined shape memory and

self-healing properties

Yongtao Yao, Jinsong Leng

National Key Laboratory of Science and Technology on Advanced Composites in Special Environments, Harbin

Institute of Technology, Harbin 150080, P. R. China

A novel and facile strategy was proposed to construct a thermosetting/thermoplastic system with both shape

memory and self-healing properties based on commercial epoxy resin and poly(ε-caprolactone)-PCL.

Thermoplastic material is capable of re-structuring and changing stiffness/modulus when temperature is above

melting temperature. PCL nanofiber was used as plasticisers in epoxy resin based blends, and served as ‘hard

segment’ to fix a temporary shape of the composites during shape memory cycles. In this study, the electrospun

PCL membrane with a porous network structure enabled a homogenous PCL fibrous distribution and optimised

interaction between fiber and epoxy resin. The self-healing capability is achieved by phase transition during

curing of composites. The mechanism of shape memory effect of thermosetting (rubber)/thermoplastic composite

is attributed to structural design of thermoplastic network inside the thermosetting resin/rubber matrix.

S-57

Bio-inspired design of functional hydrogels: from 2D surfaces to 3D networks

Mingjie Liu

School of Chemistry and Environment, Beihang University, Beijing, 100190

Water is essential for life on earth and considered a symbol of purity. 71% of the surface of our planet is covered

27

by water, and our own body is composed of 65% of this simple but vital molecule. Considering increasing

environmental issues, the idea of replacing plastics with water-based materials, so-called hydrogels, seems quite

reasonable. Inspired by the self-cleaning fish scales and articular cartilage, we fabricated a series of functional

hydrogels through the design of 2D surfaces and 3D networks. For example, we developed underwater

superoleophobic hydrogels and extended this concept to design antibiofouling coatings. Furthermore, we

developed a highly anisotropic hydrogel having a large compression resistivity and, in its orthogonal direction, an

ultralow internal friction, so that this material, just like articular cartilage, efficiently insulates horizontal

vibrations even under a heavy weight. We anticipate that these bio-inspired design strategies will open up new

possibilities for developing soft materials with unusual functions.

S-58

Ultrastretchable and Self-Healing Hydrogels Based on Double Dynamic Crosslinking of Acylhydrazone

Bonds and Triblock Copolymer Micelles

Lanyin Zhou, Peng Wang, Guohua Deng

School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640,

China

Dynamic covalent hydrogels with unprecedented stretchability, toughness, and self-healing property have been

prepared by condensation of a three-armed PEO polymer triacylhydrazines (A3) and a PEO-PPO-PEO triblock

copolymer dialdehydes (Pluronic F127 dialdehydes) (B2) in pH 6 buffer solution. A single polymer network

chemically but reversibly cross-linked by acylhydrazone bonds formed in the hydrogel. Uniaxial tensile tests

showed an ultra-high fracture elongation up to 11700% and a fracture toughness up to 14.1 MJ m−3. Cyclic

loading−unloading tests showed remarkable hysteresis and residual strain after cyclic loadings could be recovered

under ambient conditions in 24 h. These dynamic hydrogels are demonstrated to fully self-heal in 24 h at room

temperature by simple contacting. Control experiments showed that dynamic cross-linking of acylhydrazone

bonds and reversible molecular association/dissociation of PF 127 micelles help dissipate energy upon

deformation, providing excellent stretchability and toughness. Intrinsic covalently cross-linked but reversible

nature of the single polymer network makes the hydrogel self-recovery after large deformation while keeps its

self-healing. Coordination of dynamic covalent bonds with physical (noncovalent) interactions in a single polymer

network is a unique method to prepare tough hydrogels with promising properties.

S-59

Processing tough physical hydrogels

Ziliang Wu, Qiang Zheng

Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Enginee

ring, Zhejiang University, Hangzhou 310027, China

In recent years, scientists have developed various tough hydrogels such as double-network (DN) gels, nanocompo

site (NC) gels, and dual-crosslink gels, which have promising applications as structural biomaterials, soft actuator

s, etc.[1-3] However, these gels with permanent network structure usually have poor processibility. To address this

issue, dynamic and adaptable bonds are incorporated as the crosslinks to develop tough gels, in which an effectiv

e energy dissipation mechanism is required. Tough physical hydrogels with hydrogen bond, ionic bond, and hydro

phobic interaction have been successfully prepared, which show dynamic mechanical properties, self-healing, or s

hape memory abilities.[4-6] However, the processibility of tough gels have not yet drawn the attentions, despite of

28

the significance in fabrication of structural elements with gels. Here we demonstrate the processing of tough gels

by compression moulding, extruding, and three-dimensional printing, as done to general polymers. The processing

relies on the distinct strength of noncovalent bonds at different conditions during and after the process.[7,8] The r

aw materials of either viscoelastic liquid or weak gel can be process in complex structure, which change to tough

gels with imposed shapes after the formation or recovery of noncovalent bonds with a high strength. This should p

romote the applications of tough gels as structural biomaterials, soft actuators, etc.

Keywords: tough hydrogels; processibility; dynamic bonds; 3D printing

S-60

RAFT Polymers for Bio-applications

Xiaojuan Hao

CSIRO Manufacturing, Clayton, Victoria, Australia

One of the driving forces behind the recent interest in living free radical procedures, such as Atom Transfer

Radical Polymerization (ATRP) and Reversible Addition–Fragmentation chain Transfer (RAFT) polymerization,

is the realization that these novel techniques bring an unprecedented opportunity to design and control

macromolecular architectures under mild reaction conditions.1–2 The stability and chemical versatility inherent in

RAFT agents make RAFT-based procedures highly attractive for the preparation of well-defined polymers with

specific polymer architectures. RAFT based polymers are cost-intensive (due to the high cost of RAFT agent

preparation) and thus may be not yet favorable for common industrial use, however, it may be ideal for making

high value products particularly for bio-applications. This presentation will focus on investigation of (1) RAFT

polymers modified gold nanoparticles for medical imaging; (2) RAFT polymer-antibody-drug bioconjugates for

cancer treatment.

S-61

Polymer-based Composite Thermal Interface Materials

Liangliang Li

School of Materials Science and Engineering, Tsinghua University

Due to the rapid development of electronic devices, heat dissipation has become a critical problem that affects the

device performance and reliability, especially in high power devices such as high-power LED, Laser, and IGBT

[1,2]. Thermal interface materials (TIMs) are used to conduct the heat generated by power devices to the heat sink.

Polymer-based TIM is widely-used due to its insulating properties, however, the low thermal conductivity of

polymer such as 0.1-0.3 W/(mK) limits the efficiency of heat dissipation, and thus polymer-based TIM can not

meet the requirement of fast heat conduction for state-of-the-art electronic products. In this presentation, several

kinds of polymer-based TIMs containing irregular AlN or spherical Al2O3 powders were synthesized [1,2]. The

thermal conductivity was increased by more than ten times with proper surface treatment of ceramic powders,

while their insulating properties were maintained. The viscosity of ceramic/polymer composite was greatly

reduced by surface treatment; therefore, the filler loading was enhanced. With optimal conditions, the thermal

conductivity of polymer-based composite TIM reached 2.7 W/(mK) and the dielectric strength was more than 10

kV/mm. In addition, the thermal and insulating properties of the polymer-based composite TIM maintained the

same after thermal cycling testing, indicating a good reliability for use in power devices. The experimental data

show that polymer-based TIMs can be obtained by making ceramic/polymer composites.

References:

29

1. H.Yu,L.Li*,et al,Thermal and insulating properties of epoxy/aluminum nitride composites used for thermal

interface material, Journal of Applied Polymer Science, vol. 124, 669-677, 2012.

2. H.Yu,L.Li*,et al,Viscosity and thermal conductivity of alumina microball/epoxy composites, 2011 International

Conference on Electronic Packaging Technology and High Density Packaging, 387-390, 2011.

S-62

Study on the foam properties of poly(buytlene succinate) ionomers

Shuidong Zhang, Peng Wang, Yue xu, Xiangfang Peng

College of Mechanical and Automotive, South China University of Technology, Guangdong Guangzhou 510640

Poly(butylene succinate) (PBS) is regarded as one of the most promising biodegradable polymers due to the

excellent mechanical properties, thermal stability, and thermo-process. However, due to its low melt viscosity,

PBS microcellular foam is difficult to fabricate by using supercritical CO2 foaming. To improve its viscoelasticity

and foamability, PBS was modified through ionizing in this paper. The segmented PBS urethane ionenes (PBSUI)

containing secondary amine cation were synthesized by chain extension reaction of dihydroxyl terminated

poly(butylene succinate) and diethanolamine hydrochloride (DEAH) in the presence of hexamethylene

diisocyanate(HDI). Then the PBSUI foams were fabricated by supercritical CO2 in a rapid depressururization

process via batch foaming method. Rotational rheometer and XRD were used to characterize the rheological and

crystalline properties of PBSUI. The results revealed that the melt viscosity and relaxation time of PBSUI

increased with the rise of urethane ionic group content, while both the degree of crystallinity and spherulitic

diameter of foaming PBSUI and unfoaming PBSUI decreased. The results of SEM demonstrated that the foam

shape of PBSUI transform from circle into polygon with increasing urethane ionic group content. Moreover, both

the cell density and expansion volume ratio increased, while the average cell diameter, the cell wall thickness and

the cell opening ratio decreased when the urethane ionic group content increased from 1% to 5%(wt). PBSUI

foam with 3% urethane ionic group could achieve micro cell, the average cell diameter was 2.05 um, the cell

density was 1.73×1010 cells/cm3 and the expansion volume ratio was more than 10.0. The results illuminated that

when urethane ionic group was introduced into PBS, PBSU microcellular foam was successfully prepared by

supercritical carbon dioxide. The reason was attributed that physical crosslinking and heterogeneous nucleation

effect caused by ion clusters aggregation could increased significantly the PBSU foaming performance.

Keywords: Poly(buytlene succinate), Ionomer, Supercritical foaming, Ion clusters aggregation, Microcellular

morphology.

S-63

Polybutadiene–Poly(styrene-co-4-vinylpyridine)-Based Supra- molecular Shape Memory Elastomers Using

Metal Coordination Interactions

Fang Xie1, R.A.Weiss2, JinsongLeng3, YanjuLiu1

1. Department of Astronautical Science and Mechanics, Harbin Institute of Technology, Harbin 150001, China

2. Department of Polymer Engineering, The University of Akron, Akron, OH 44325, USA

3. enterfor Composite Materials and Structures, Harbin Institute of Technology, Harbin 150080, China

A shape memory polymer (SMP) is a smart polymeric material that can recover its original shape from a

temporary shape when exposed to an external stimulus. The theory and experimental studies of SMP shows

profound theory and practical significances. A transition metal coordinated shape memory elastomer was

investigatedin the terms of synthesis mechanism, formability,micro morphology,thermal properties, mechanical

30

propertiesand shape memory behaviors in this paper. The microstructure and chemical composition of shape

memory elastomer were characterized by small angle X-ray scattering analysis and Fourier transform infrared

spectroscopy. The mechanical properties of these materials were studied by rheological analysis, dynamic

mechanical analysis, and tensile test. The thermal performance of these materials were investigated by differential

scanning calorimetry and thermogravimetric analysis. The shape memory performance of these materials were

investigated by bent-unfold and stretch-shrink test, respectively. The supramolecular shape memory elastomer was

designed and synthesized using a blend of functionalized polybutadiene oligomers and functionalized

poly(styrene-co-vinyl pyridine)(PSVP) where a physically crosslinked network was produced by a transition

metal complex between Zn2+ ions from carboxylatedtelechelic polybutadiene and the pyridine group of the PSVP.

The elastomer had reasonably good formability and was thermoplastic. The shape memory elastomer exhibited

good shape memory properties for large deformations. The shape fixing and recovery efficiencies were as high as

95% and 81%, respectively for the first shape memory cycle, and were 93% ±0.7% and 97%±1% respectively in

the following seven cycles. In addition, the shape memory elastomer showed excellent triple-shape memory effect,

which is applicable to variable deformations, inclouding stretching, twisting and rolling.

S-64

Influence of Disulfide Bond Content on the Healing Ability of Self-Healing Polyurethanes

Yurun Xu, Dajun Chen

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science a

nd Engineering, Donghua University

Self-healing polymers that can recover from mechanical injury autonomously have attracted great research interes

ts recently. Disulfide bond which can initiate chain exchange reaction upon heating can be utilized to introduce sel

f-healing ability to polymers. In this work, self-healing polyurethanes based on polytetramethylene ether glycol (P

TMG), hexamethylene diisocyanate(HDI) and 2-hydroxyethyl disulfide were synthesized. The influences of disulf

ide bond content on mechanical properties and self-healing ability were evaluated. Dynamic mechanical analysis a

nd tensile test were employed to study the influences on mechanical properties. Results showed that the Tg of soft

segment shifted to higher temperature with increasing disulfide bond content. Meanwhile, tensile strength and elo

ngation at break of the samples exhibited a moderate decrease with the increase of disulfide bond content. Self-he

aling test was performed to evaluate the difference of healing ability among the samples. The sample with lowest

disulfide bond content achieved almost fully recovery of the mechanical properties after healing at 80°C.

S-65

Thermal Aging Effects on Fire Performance of the Cross-linked Polyethylene Insulated Cable

Jinmei Li1, Jiaqing Zhang2, Qiang Li3, Zhongjun Shu3

1. University of Science and Technology Beijing

2. State Grid Anhui Electric Power Research Institute

3.Chinese People's Armed Police Academy

To evaluate the combustion performance and insulation failure of the cable in service in the fire, firstly using mod

el 401C thermal aging test box, cone calorimeter and self-developed model SDR-1 cable thermal radiation experi

mental furnace to conduct experimental study on the ignition time, heat release rate and insulation failure paramet

ers (failure time and temperature) of the accelerated thermal aging cable on stimulated fire condition. Research res

ults indicate: (1) thermal aging effect makes the ignition time of cable present the change rule from increasing to d

31

ecreasing. In the early stage of accelerated thermal aging, the ignition time of YJV cable insulating sheath material

is gradually extended; when accelerated aging 15d, the ignition time is extended from 8s of un-aged to 56s. With t

he further aggravating of accelerated thermal aging, the ignition time will be quickly decreased, and keep in a stab

le value soon afterwards. When accelerated aging 45d, the ignition time will be decreased to 30s.(2) The initial pe

ak of combustion heat release rate is from decreasing to increasing, that present a upside-down saddle-shaped cha

nge. When accelerated aging 15d, the initial peak of heat release rate will be decreased from 125 kW/m2 of un-ag

ed to 24 kW/m2. With the further aggravating of accelerated thermal aging, the initial peak of heat release rate wil

l quickly rise again. (3) As for the cable of the same kind, the insulation failure temperature under different high te

mperature is basically constant. With the aggravating of aging, the temperature and time of cable insulation failure

core are all on a declining curve, and the decreasing degree is related with accelerated thermal aging preset stabili

ty and the ambient temperature of the fire stimulated by cable thermal radiation experimental furnace.

After that, combined with the thermogravimentry analysis experiment of YJV cable sheath material and insulation

material, analyze the combustion performance and insulation failure rule of the cable under the effect of thermal a

ging. The result indicates: (1) In the early stage of aging, the main reason for the extended ignition time and decre

asing peak of heat release rate of the cable is that the addictives including the lubricant (for example paraffin), pla

sticizer and anti-oxygen, etc. in the cable sheath material with the accelerated thermal aging are gradually resolvin

g and volatilizing in advance; with the aggravating of thermal aging, labile materials with low heating value will b

e exhausted, while the thermal stability of insulation sheath material will decrease, and its corresponding ignition t

ime will start to shorten and initial peak of heat release rate will start to rise.(2) The insulation failure temperature

of the cable is related with the decomposition temperature of insulation materials of the cable by heating. In each a

ging stage, the decomposition temperatures of insulation materials by heating are all lower than the insulation fail

ure temperature of the cable (inner core) for about 10℃. The reason for the insulation failure of the cable is that th

e ambient heat, under the thermal transmission effect, finally gives rise to the decomposition by heating of internal

insulation materials of the cable through sheath materials.

At last, analyze the feasibility of the common-used thermal aging affecting the estimation method in the cable fire

performance evaluation. The result indicates: (1) Based on the DSC method of Arrhenius equation, it can effective

ly evaluate the combustion heat release rate of the cable in the fire. However, as for the large-scale fire with ambie

nt radiation intensity 75kW/m2, adopt DSC method to evaluate might causes big error. (2) Adopting the time-temp

erature superposition method based on the elongation at break and retention rate of cable insulation materials can

achieve the life curve of cable sample aging with better linear relation, which is applicable to the insulation failure

evaluation of the cable in service in the fire.

Figure 1 a. Illustration of the fabrication process; b. SEM images of the surface morphologies under the heating

32

stimulation; The photographs of the circuit connecting with the samples in the state of cracked and healed.

Key words: self-healable; shape memory; conductive; carbon nanotubes; composites.

S-66

Controllable Shape Memory Behavior Actuated by Selective Stimuli

Wenbing Li1, Yanju Liu2, and Jinsong Leng1

1. Centre for Composite Materials and Structures, Harbin Institute of Technology (HIT), No. 2

2. YiKuang Street, PO Box 3011, Harbin 150080, PR China.

3. Department of Astronautical Science and Mechanics, Harbin Institute of Technology (HIT),Harbin 150080, PR

China.

In this paper, one type of multistage styrene-based shape memory polymer (SSMP) was fabricated, unlike

traditional shape memory polymers (SMPs), including SSMP matrix filled with multiwalled carbon nanotubes

(SSMP-CNT) region and SSMP matrix filled with Fe3O4 nanoparticles (SSMP-Fe3O4) region which were

separated by the neat SSMP region. The results of differential scanning calorimetry (DSC) and dynamic

mechanical analysis (DMA) demonstrated that all the three SSMP materials possessed two well-separated

transitions, which were subsequently used for the fixing/recovery of two temporary shapes (triple-shape memory

effect) in each region. Furthermore, the unique selective actuation functionality was demonstrated. Due to the

selective remote heating properties of Fe3O4 (30 kHz alternating magnetic field) and CNT (13.56 MHz

radiofrequency) nanoparticles, well-controlled multiple shape recoveries of the multistage material were achieved

by performing selective stimuli. This proposed approach of selective actuations was presented as a versatile

method to increase the potential applications of this multistage material in designing optimal functional

stimuli-responsive material systems for target applications.

S-67

Highly efficient flame retardant polyurethane foam with alginate/clay aerogel coating

Hongbing Chen1, Peng Shen1, Mingjun Chen2, Haibo Zhao3

1. Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621000, China

2. School of Science (Sichuan), Xihua University, Chengdu 610039, China

3. Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621000, China

Highly efficient flame retardant polyurethane foams with alginate/clay aerogel coatings were fabricated using a

freeze-drying method. The microstructure and the interaction of the samples were characterized with scanning

electron microscopy (SEM) and optical microscope (OM). The results show that PU foam has a porous structure

with pore size of several hundred microns, and that of aerogel ranges from 10 to 30 microns. PU foam matrix and

the aerogel coatings have strong interaction, due to the infusion of aerogel into the porous structure of the foam

and the tension generating during freeze-drying process. Both PU foam and the aerogel have good thermal

stability, with onset decomposition temperature above 240 °C. Combustion parameters, including LOI, TTI, HRR,

TSR, FIGRA, CO and CO2, all indicate significantly reduced fire risk. THR of all the samples maintained except

A5C10-1.5mm, indicating the flame retardant mechanism is to decrease flame spread rate by forming heat,

oxygen and smoke barrier, but not reducing fuel content. This facile and inexpensive post-treatment of PU foam

enlarges its application with requirement of fire safety.

33

Poster

S-P01

Improved Thermal and Mechanical Properties through Controlled Molecular Network in Multi-functional

Epoxy Resins

Chengjun Liu1, Miqiu Kong1, Yajiang Huang2, Guangxian Li1

School of Aeronautics and Astronautics, Sichuan University, Chengdu 610065, PRC1, College of Polymer

Science and Engineering, State Key Laboratory of Polymer Materials Engineering of China, Sichuan University,

Chengdu 610065, PRC2

Epoxy resins are widely used as the matrix material of high performance polymer composites, but it is brittle

because of highly cross-linked molecular network. The objective of this study is to investigate the effects of

controlled molecular network on the thermal and mechanical properties of epoxy resins. Epoxy polymer network

is controlled by two-step polymerization. Epoxy resin is pre-mixed with ionic liquid, then the pre-reacted epoxy

network is added into epoxy with curing agent, and finally the mixture is cured again. It is found that the

properties of the resulting epoxy network are promoted in various ways. The toughness of epoxy resin is improved

by controlling the epoxy network without sacrificing the modulus and strength. This is attributed to the existence

of highly cross-linked epoxy-ionic liquid networks with high resistance to fracture. Moreover, thermal stability

and heat resistance of epoxy resin are also improved, possibly due to the more complete epoxy network promoted

by the ionic liquid.

S-P02

Role of aging time in photo-oxidative degradation of polyolefins subjected to tensile stress

Qiang Liu1, Heng Yang1, Miqiu Kong2, Yajiang Huang1

1. College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering of China,

Sichuan University

2. School of Aeronautics and Astronautics, Sichuan University

The photooxidation behavior of high density polyethylene (HDPE) subjected to uniaxial tensile stress was

investigated. The injection bars of HDPE were used, and the irradiation intensity as well as temperature was

carefully controlled. Fourier transform infrared spectroscopy (FTIR) was employed to gain insight into the change

of molecular structure. Differential scanning calorimetry (DSC) was used to characterize the melt and

crystallization behavior of aged HDPE. The morphology of HDPE before and after exposure was observed by

scanning electron microscope (SEM). It was found that HDPE suffered serious degradation with increasing aging

time. Yellowing became obvious and oxidation products (such as carbonyl, vinyl and secondary alcohol) was

found to accumulate gradually. Crystallinity increased because of chain scission during aging. It was surprising to

find that uniaxial stress played different roles in different aging times. In view of carbonyl index (CI), stress

speeded up aging rate in the beginning. Later, stress prohibited HDPE from degradation. Stress initially

accelerated circular arc crack in the traverse direction but it hindered the nucleation rate of crack. As a result, the

crack density decreased. On the contrary, crack initiation and growth parallel to flow line was favorable in all

conditions. All these findings implied that the morphology evolution process of stressed HDPE bars affected

degradation process. A conclusion can be drawn that stress enhanced oxidation rate and extent in the beginning

and prevented it latterly during aging. The mechanism of crack formation and growth was discussed and the effect

of stress on surface morphology was analyzed in terms of stress level, surface morphology and photooxidation

behavior of HDPE.

34

Keywords: photooxidation, stress, high density polythene, crack, surface morphology, crystal form

S-P03

Elongation Thinning and Morphology Deformation of Nanoparticle-filled Immiscible Blends in

Elongational Flow

Miqiu Kong1, Yajiang Huang2, Qi Yang2, Guangxian Li2

1. School of Aeronautics and Astronautics, Sichuan University

2. College of polymer science and engineering, State key laboratory of polymer materials engineering of China,

Sichuan University

Elongational flow is dominant in polymer melt processing, but under elongational flow how nanoparticles affect

the morphology and rheology of blends is still unclear. For this reason, a model polypropylene/polystyrene (PP/PS)

blend filled with nanoparticles with different surface chemistries is performed in simple elongational flow. An

obvious “elongation thinning” behavior is observed in blends with high nanoparticle loadings (≥3 vol.%) at high

strain rates, where the nanoparticle network formed is destroyed. More notable elongational thinning behavior is

found in blends with hydrophilic silica than with hydrophobic silica due to stronger interactions between

hydrophilic silica networks. Moreover, upon adding hydrophilic silica, the elongation deformation of droplets is

almost unaltered at lower loadings but nearly inhibited at higher loadings. This is ascribed to the substantially

enhanced viscoelasticity of PS matrix by high loadings of hydrophilic silica apart from the reduced interfacial

tension. In contrast, hydrophobic silica significantly boosts the elongation deformation of droplets because of the

improved interfacial properties due to the preferential distribution of hydrophobic silica at the interface.

S-P04

Synergistic toughening of high-performance trifunctional epoxy resin by poly(ether sulfone) and silica

nanoparticles

Xin Xu, Bing Tang, Miqiu Kong, Guangling Chen, Qi Yang, Yajiang Huang

College of polymer science and engineering, Sichuan University, Chengdu 610065, China

The higher crosslinking density of polyfunctional epoxies endows them with better thermal and mechanical

properties but also lower ductility than traditional bifunctional epoxies. Here, we demonstrated that a noticeable

toughening of trifunctional epoxy (TDE85) could be accomplished by adding poly(ether sulfone) (PES) and

hydrophilic fumed silica (A200) nanoparticles simultaneously. The optimum composition was found to be

TDE85:PES:A200=100:5:0.3. The tensile strength and strain at breakup of modified epoxy was improved by

38.1% and 29.4% at most, respectively, without significantly sacrificing their modulus and thermal properties. The

critical stress intensity factor (KIc) and the critical strain energy release rate (GIc) increased by 65% and 186%,

respectively. Scanning electron microscopy (SEM) demonstrated that modified epoxies exhibited desirable ductile

fracture behavior. The mechanism for the notable enhancement in the toughness of trifunctional epoxy was

interpreted by the synergism between PES and silica nanoparticles which possess diverse toughening mechanisms.

S-P05

Cellulose Triacetate Aerogels with Ultralow Densities

Yu Fang, Xuan Luo, Shufan Chen


A novel and facile method which needs only several steps of dissolution, gelation and supercritical carbon dioxide

35

(ScCO2) drying has been developed to fabricate ultralow density cellulose triacetate (TAC) aerogels. In this

method, by using dioxane as solvents and isopropanol as nonsolvent, regeneration and solvent exchange are not

necessary according to the phase separation and heat-induced gelation and the good solubility of

dioxane/isopropanol in ScCO2, and thus leading to more efficient synthesis and better quality of aerogels in terms

of less shrinkage and breakage. The relationship between theoretical density and the actual density of the TAC

aerogel is discussed, and the actual density of aerogels could be well tuned in the range between 5 mg/cm3 and 50

mg/cm3. These nanostructured TAC aerogels were characterized using scanning electron microscopy (SEM) and

nitrogen adsorption. All the prepared aerogels have showed both a nanostructured solid network and a nanoporous

network together with specific fiber sizes about 30 nm. So the fiber thickness and pore sizes are much lower than

that of the normal porous polymer materials. The specific surface area of areogels with different density ranges

from 229 m2/g to 958 m2/g measured by nitrogen adsorption tests. The porosity of all these aerogels is higher

than 96%.

S-P06

A New Strategy for Synthesis of Fluorinated Polyurethanes Based on the Xanthate-Mediated

Living/Controlled Radical Copolymerization of Chlorotrifluoroethylene and Butyl Vinyl Ether

Pucheng Wang1,Ruke Bai2

1. Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621000,

People’s Republic of China

2. CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of

Science and Technology of China, Hefei 230026, People’s Republic of China

In this contribution, we report RAFT/MADIX copolymerization of chlorotrifluoroethylene (CTFE) and butyl

vinyl ether (BVE) using S-benzyl O-ethyl dithiocarbonate (BEDTC) as the chain transfer agent at a moderate

condition without using cobalt-60 source. The results indicate that the process has the features of living/controlled

free radical polymerization. The molecular weights of the obtained copolymers increase linearly with the

monomer conversion and the molecular weight distributions are narrow. Moreover, a linear relationship between

ln([M]0/[M]) and the polymerization time exists. Using the obtained polymer as a macro-CTA, a block copolymer

was prepared by chain extension polymerization of vinyl acetate and a fluorinated amphiphilic polymer has been

obtained via basic methanolysis. After that, we successfully prepared a novel fluorinated polyurethane with

isophorone diisocyanate (IPDI) as the cross-linking agent, which can be used as a new promising coating and

other materials.

S-P07

Synthesis of Donor-Acceptor Paired Acrylic Copolymers

Haibin Hu1, Hai Deng1

1. Department of Macromolecular Science, Fudan University

2. State Key Laboratory of Molecular Engineering of Polymers, Fudan University

The copolymer properties are mostly determined by the monomer unit structure. Recent years, sequence

controlled polymerization has attracted much attention due to the unique microstructure of resulting

polymers.1-13 It had been reported that small molecules with donor and acceptor moiety formed alternating

structure via inter-molecular interaction and hydrogen bonding,14 which could be used as an alternative route to

design monomer pairs for potential sequence controlled polymers.

36

In this study, acrylic monomers with donor (such as pyrene) or acceptor (such as naphthalimide) moiety were

synthesized. The interaction between different monomers via donor-acceptor and hydrogen bonding was

investigated. After mixing equal molar ratio monomers together, obvious change of chemical shift in proton

nuclear magnetic resonance (1H NMR) was observed, indicating that monomer pairs formed. Radical

polymerization of monomer pairs was carried out. The resulted copolymers were analyzed by nuclear magnetic

resonance (NMR) and infra-red spectrum (IR).

S-P08

Novel microcellular polyurethane foam prepared by supercritical carbon dioxide

Junsong Li1, Xia Liao1, Qi Yang1, Guangxian Li1, Qianping Ran2

1. College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan

University, Chengdu

2. State Key Laboratory of High Performance Civil Engineering Materials, Jiangsu Bote New Materials Co., Ltd.,

Nanjing

This study aims to develop novel microcellular polyurethane foam (millable polyurethane foam, MPF) using

supercritical carbon dioxide as physical blowing agent. The raw millable polyurethane, silica nanoparticles,

dicumyl peroxide and stearic acid were mixed to make sure that the silica nanoparticles were well dispersed in the

polyurethane matrix, and the polyurethane compounds were pre-cured with hot press. Then the polyurethane

sheets were exposed to the supercritical carbon dioxide in the high pressure vessel and foamed by releasing the

pressure rapidly. At last, the foams were post-cured in a heated oven. In order to obtain stable cell structure the

optimal pre-curing time and silica nanoparticles content were first determined. Furthermore, the foam structure of

MPF was regulated by varying the saturation temperature and pressure. The compressive hysteresis of MPF was

better that that of millable polyurethane elastomer (MPU), which showed that the energy absorption of

polyurethane elastomer was enhanced after the introduction of microcells. The tensile strength of MPF decreased

with an increase of the cell diameter. In addition, it was found that the tensile strength and the cell diameter

displayed a power-law function relationship. The bigger cell size and the broader cell size distribution led to the

reduced elongation at break.

S-P09

Fabrication of high Z metals doped low density polymer foam shells

Xuan Luo, Yu Fang, Shufan Chen, Ruizhuang Yang, Qinjun Zhang, Chuanqun Huang, Ting Shao

Research Center of Laser Fusion, China Academy of Engineering Physics

Low-density polymer foam shell doped with high Z metal is a very attractive target material used for the high-gain

direct drive ignition experiments and the future inertial fusion energy (IFE) program. Many methods have been

used to dope metal into foam shell, such as atomic layer deposition technology (ALD), organic metal precursor,

nano metallic particle, etc. This paper reports an in-situ doped method which contains solution adsorption process

and high temperature reduction reaction of metallic salt. The control conditions of metal morphology have been

discussed in detail. The characterization results of foam shell microstructure show that the metallic particles have

been uniformly distributed into framework of foam shell. With this doped method, many high Z metals have been

conveniently introduced into foam shell, such as Ag, Au, Cu, etc.

S-P10

37

The Study of Blending Modification of PEBAX/BaSO4 for Invasive Medical Devices

Zhaomin Li, Shu Zhu, Muhuo Yu

Key Laboratory of Shanghai City for lightweight composites, State Key Laboratory for Modification of Chemical

Fibers and Polymer Materials, Donghua University, Shanghai 201620, China

Polyether block amide (PEBAX)/BaSO4 composite is widely used in the invasive medical devices, such as

Cardiovascular Devices, Endovascular Devices, Electrophysiological Devices, Neurovascular Devices,

Angiographic Guidewire, Angiographic Catheter and so on. In this paper, the PEBAX/BaSO4 composites are

obtained through adding different ratios of BaSO4 into PEBAX by twin-screw extrusion process. The influences

of BaSO4 on the structure, radiopaque and mechanical properties of PEBAX/BaSO4 are studied. We applied

mechanical properties testing, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA),

dynamic thermo mechanical analysis (DMA) to evaluate the tensile properties, thermal properties and dynamic

mechanical properties of PEBAX/BaSO4 composites. The SEM results indicate that BaSO4 can be distributed

homogeneously into PEBAX. While with the increasing of the content of BaSO4, the tensile stress and storage

modulus of the composites will increase and the elongation will decrease. In addition, the radiopaque properties

will also increase. These results have been applied in developing relevant products of Shanghai Microport

Medical (Group) Co., Ltd.

S-P11

Study on the effects of poly(ethylene glycol) segment on physical and chemical properties of poly(ether ester)

elastomers

Qiushu Xu, Lian Tang, Chaosheng Wang, Biao Wang, Huaping Wang

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science

and Engineering, Donghua University

Poly(ether ester) elastomer, a segmented copolymers, recently has attracted a wide attention for its unique

properties such as elasticity, low temperature impact resistance and chemistry resistance. In this work, a range of

poly(ether ester) elastomer were synthesized via a two-step polymerization method using poly(ethylene

terephthalate) (PET) as rigid segment and poly(ethylene glycol) (PEG) as flexible segment. The effects of the

molecular weight (1000 - 8000 g/mol) and the weight ratios with PET (30/100 - 70/100) of PEG segments on the

performance of prepared copolymers were investaged. The chemical structure, thermal properties and hydrophilic

performance of the copolymers were respectively evaluated by Fourier transform infrared spectroscopy (FTIR),

1H-nuclear magnetic resonance (1H-NMR), thermogravimetric analysis (TGA), differential scanning calorimeter

(DSC), contact angle (CA) and water absorption test. The obtained results revealed that increasing the molecular

weight or content of PEG segment enhanced the hydrophilic performance of the copolymers and reversely

reduced its thermal stability and crystallization behavior. Additionally, the reaction rate of PEG during the

polymerization was caculated by the oligomers content of the copolymer with Soxhlet extraction as the oligomers

consisted of the majority of unreacted PEG. It was found that the increase of the molecular weight or content of

PEG significantly reducd the intrinsic viscosity of the copolymers before and after soxhlet extraction. The

reactivity of PEG in the polycondensation process weakened when its molecular weight was above 4000 or weight

ratio with PET was higher than 50/100, subsequently affecting the block ratios of PEG/PET in the resulting

poly(ether ester) elastomers.

S-P12

38

Thermal-infrared reflective properties of perylene derivatives

Jianliang Xie, Wenle Liu, Yunfeng Liu, Bo Peng, Shuai Jian, Longjiang Deng

State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and

Technology of China, Chengdu 610054, China

Thermal-infrared reflecting pigments offer the potential as infrared camouflaged coatings. Perylene-based

pigments exhibit excellent reflecting properties in the thermal-infrared region. Some works have reported the

reflect properties of in the 3,4,9,10-perylenebis(dicarboximide)(PCI) molecule and PCI derivatives the 8-14μm in

experiments and theory. However, the effect of molecular dipole moment on the thermal-infrared reflecting

properties is still not clear.

Herein, we have synthesized three different black pure PCI compounds, and established the relationship between

the molecular dipole moment and the reflectance using the method of B3LYP/6-31G(d,p) of the GAUSSIAN09

computer program.

Thus, to achieve high reflectance in 8-14μm, it is necessary to design sufficient asymmetry molecular structure

with big dipole moment. Our results should be useful in the design of novel perylene-based molecules for

applications in the field of infrared camouflage.

S-P13

Construction of photonic crystal microcapsules with tunable density

Chun Yang1, Xuan Luo1, Ting Shao1, Xiaodong Jiang1, Linhong Cao2

1. Research Center of Laser Fusion，China Academy of Engineering Physices

2. Southwest University of science and Technology

Ordered porous microspheres are generated through a combined technique of microfluidic and

photopolymerization. The process of microcapsules preparation is as follow: firstly, the double emulsion drops,

which compose of water in the inner drop surrounded by a cinnamene styrene oil drop, are produced by co-axial

capillaries. And then, photonic crystal spheres are fabricated by the photopolymerization of the double emulsion

drops. After the process of etching by HF and freeze drying, the order porous microspheres are obtained. This

versatile route allows the fine tuning of density by template size or flow rates of diverse phase. The diameter and

wall thickness of the double emulsion droplets are measured by optical microscope. The distribution of silica in

the composite microspheres shell structure is measured by Scanning Electron Microscope and Transmission

Electron Microscope. The characteristic spectral lines of the composite microspheres are obtained by infrared

spectrum and compared with the silica and polystyrene lines. The results show that the microspheres are highly

ordered porous materials with ultra-low density, which has a good potential application as optical components and

catalyzer.

S-P14

Dual-responsive, robust and recyclable hydrogels for environmental pollution remediation

Man Zhang, Changsheng Zhao

Sichuan University

High strength hydrogels with soft and wet properties have attracted much attention due to their great potential

applications in various fields. Although the mechanical performance of hydrogels can be achieved by means of

physical and chemical cross-linking approaches, multi-responsiveness and reversibility of tough hydrogels are

39

rarely targeted. Herein, we prepared a novel family of multi-responsive, robust, and reversible hydrogels by a

combination of dipole-dipole, hydrogen bonding interaction and slightly chemical cross-linking of random

copolymers of acrylonitrile, sodium allylsulfonate and itaconic acid. Reversible gel-sol transition was achieved by

the flexible conversion of the dipole-dipole interactions between acrylonitrile-acrylonitrile and

acrylonitrile-sodium thiocyanate, and the hydrogels could freely form desired shapes. The dipole-dipole and

hydrogen bonding interactions improved the mechanical strength of the hydrogels with a compressive stress of

2.38 MPa. Meanwhile, the hydrogels sustained cyclic compressive tests with 60% strain, exhibited excellent

elastic property. The hydrogels were sensitive to ionic strength and pH, and could keep their perfect spherical

structures without any obvious cracks even after immersing in strong ionic strength solution for several reversible

cycles. Furthermore, the hydrogels were recycled and regenerated for environmental pollution remediation, and

the adsorption amounts reached above 250 mg g-1 after each desorption, indicating that their potential to be

applied in water treatments and other related fields.

S-P15

Influence of [6, 6]-phenyl-C61-butyric acid isopropyl ester (PCBM) on glass transition temperature (Tg) of

photorefractive composite

Baili Chen, Shufan Chen, Xuan Luo, Yu Fang, Qingjun Zhuang, Weidong Wu

Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900, China

2, 5-dimethyl-(4-p-nitrophenylazo) phenetole (DMNPAPE) was synthesized. And its structure was confirmed with

UV-vis spectrum, FT-IR spectrum and 1H NMR. The photorefractive composite consist of 33 wt % poly

(N-vinycarbazole) (PVK), 50 wt % 2, 5-dimethyl-(4-p-nitrophenylazo) phenetole (DMNPAPE) and 16 wt % ethyl

carbazole (ECZ) doped with x wt % (<1 wt%) PCBM was fabricated. The influence of PCBM on the glass

transition temperature (Tg) of the photorefractive composite was studied using a differential scanning calorimetric

(DSC) method. The active energy of glass transition (Eg) was evaluated by Kissinger’s and Moynihan’s relation.

The analysis results indicate that the transition region shifts to higher temperatures with the increasing heating rate,

and PCBM content (below 1.0 wt %) can influence Tg of PVK - based PR composite polymers. The Tg first

increase and then went down with the PCBM content (below 1.0 wt %) increasing. The possible cause of the

influence of PCBM on Tg was proposed.

S-P16

Study on the dielectric properties of epoxy/anhydride system during eleven months storing

Chunmiao Han, Kang Peng, Liu Yang, Zhibin Zeng

Institute of Electronic Engineering, China Academy of Engineering Physics

The change of dielectric properties of epoxy/anhydride systems during eleven months storing was investigated in

this paper. Test systems were bisphenol A epoxy cured by different content of methyl-hexahydrophthalic

anhydride with a slow cooling process across Tg range included in their curing procedure to reduce residual stress.

The results showed all the systems’ dielectric constant and dielectric loss angle tangent had a trend of down then

up. The decreasing amplitudes were about 3.6% and 10% respectively. Possible explanations for these

phenomenons were proposed, and then some preliminary investigations were carried out like DSC and IR.

Understand the change of dielectric properties during natural storing is quite important for epoxy’s insulation

application. The results obtained in this paper also mean that proper control in sample preparation and the choice

of test time point are quite necessary for epoxy’s dielectric properties comparation and accelerated aging

40

investigation.

S-P17

Polyethersulfone/ poly (sodium acrylate) hybrid particles for the removal of environmental toxins

Zhenqiang Shi

College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan

University, Chengdu 610065, China

In this study, polyethersulfone (PES)/ poly (sodium acrylate) (PSA) hybrid particles for the removal of

environmental toxins were prepared by in situ cross-linked polymerization coupled with a liquid-liquid phase

separation technique. The particles were characterized by Fourier transform infrared spectroscopy (FTIR),

thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Batch experiments were carried out

to study the adsorption capability of the particles, the initial concentration and pH value of the solution could

affect the adsorption process obviously. In addition, adsorption kinetic and adsorption isotherm models were used

to analyze the adsorption process of Cu2+. The modified PES particles showed high adsorption capability for

Cu2+ and methylene blue (MB), and a hybrid particle column experiment was further carried out with excellent

toxin removal ability. The results indicated that the hybrid particles had great potential for wastewater treatment.

S-P18

An antireflection method for fluorinated ethylene propylene (FEP) film which may be used as the short

pulse laser debris shields

Shufan Chen, Chuanqun Huang, Xuan Luo, Yu Fang, Baili Chen, Weidong Wu

Research Center of Laser Fusion, China Academy of Engineering Physics

Debris mitigation is a major challenge for all high-peak-power lasers system; the impulsive debris will pollute and

damage the optical element and diagnostic facility. Thus, fabrication of special polymer films to protect from

target debris is significant. Fluoride polymers representative of the fluorinated ethylene propylene (FEP) have

excellent ultraviolet-visible transmission, laser induced damage threshold and mechanical properties, and stand a

good chance to be used as the debris shields. However, it was found in our previous research work that the light

transmittance of FEP is still lower than fused silica glass, and the transmittance of FEP need to be improved

before it is really used in the laser field. The difficulty is obvious for modify and anti-reflexion on inactive

fluoride polymers is very hard. But if the antireflection method for FEP can be exploited and applied in large

acreage, it will be meaningful for saving cost and improving efficiency. In view of above reasons, we proposed a

sol-gel coating method which can implement large acreage antireflection for FEP film and investigated the optical

properties of antireflection FEP film. Through an oxygen gas plasma processing, the interface interaction between

silica sol and the FEP film can be improved. Through regulate the structure of silica gels and coating technique,

transmittance of specific and single wavelengthfull can be improved to higher than 97%. This cladding

antireflection film has considerable applications in the high-peak-power laser field.

S-P19

The effect of quartz/epoxy composite charred on electricity properties under outer heating source

Yongqiang Zhang, Li Zhang, Chunyan Wang, Fuli Tan

Institute of Fluid Physics, CAEP

41

In order to study the electricity properties and analyze radar wave transmitting characteristic of quartz/epoxy

under thermal environment, the charring damage experiments of quartz/epoxy composite irradiated by CW laser

regarded as the outer heating source were done. By the high Q cavity methods testing, the dielectric constant and

dielectric loss tangential value of charred materials are higher than initial material。Based on the infrared spectrum

analysis, XRD and the thermal analysis of quartz fiber and epoxy, because the epoxy resin is high polymer organic

material, it will occur heat decomposition with temperature rising, the bond of molecular constitution breakdown.

The carbon black is generated, which is graphitized with temperature sustained rising because the diffraction peak

of graphite was found. Thus, the conduction capability of charred material is higher, and the charred material is

continuous state. Thus, quartz/epoxy composite irradiated by CW laser produces charring layer, which is higher

absorption capacity for radar wave, and the scatter capability is also higher for radar wave because of rough

surface, the radar wave transmitting capacity of quartz/epoxy composite irradiated by CW laser will be affected.

S-P20

The Synthesis, Structure and Properties of Terpolymer of Ethylene/Propylene/ω-bromo-α-olefins Catalyzed

by Titanium Complex

Jing Wang, Lei He, Runcong Zhang, Qigu Huang, Wantai Yang

Beijing University of Chemical Technology

Objective: Polyolefin product has wide application range because of its stable performance of chemistry and

physics along with its long service life. However, the lack of polar groups limited its application in the areas

where adhesion, processability, and compatibility with other polymers. In these decades, introducing polar

functional groups into polyolefin has been given much attention. In this study, we synthesized

high-molecular-weight terpolymers of ethylene and propylene with ω-bromo-α-olefins by non-metallocene

catalyst and investigated their stress-strain behavior, which was not reported before.

Methods: A novel multi-chelated non-metallocene catalyst was synthesized and used as the precursor for

terpolymerization of ethylene and propylene with ω-bromo-α-olefins, methylaluminoxane (MAO) as a cocatalyst.

The new terpolymers were determined by 1H NMR, 13C NMR, FT-IR, DSC and GPC. Furthermore, the

stress-strain behavior was measured with ASTMD1708 microtensile specimens cut from the films.

Results: The catalytic activity was as high as 6.21×105 gP (molTi)1 h1 for terpolymerization of ethylene and

propylene with 11-bromo-1-undecylene catalyzed by titanium complex. The insertion ratio of

11-bromo-1-undecylene was up to 2.49 mol%. With the incorporation of ω-bromo-α-olefins increasing, the

melting point of terpolymer decreased and plasticity of polymers became weak. Molecular weight distribution of

ethylene/propylene/ω-bromo-α-olefins terpolymer was slightly broader than ethylene/propylene copolymer. There

was an peak at 598.02 cm-1 which represented absorption peak of bromine showing in FT-IR spectra, declaring

11-bromo-1-undecylene was inserted into PEPBr.

The PE and PEPBr 1.90 showed a highly localized yield, which is the typical behavior of stiff-plastic materials,

forming of a neck and an extended region of cold drawing. With 11-bromo-1-undecylene content increasing to

2.38%, PEPBr 2.38 showed a week yield and tended to deforming in a manner characteristic of thermoplastic

materials, and the stress decreased from 33.1 MPa to 12.0 MPa. Furthermore, PEPBr 1.90 and PEPBr 2.38 can be

stretched up to 921% and 850% of the strain at room temperature.

Conclusion: The terpolymers of ethylene and propylene with ω-bromo-α-olefins were efficiently prepared by

titanium complex, MAO as a cocatalyst. The catalytic activity was as high as 6.21×105 gP (molTi)1 h1. The

insertion ratio of 11-bromo-1-undecylene was up to 2.49 mol%, which can be determined by 1H NMR and 13C

NMR. From 13C NMR spectrum, we can also analyze that the ω-bromo-α-olefins tends to participate in

42

copolymerization not homopolymerization. Furthermore, with insertion of ω-bromo-α-olefins into the terpolymer

chains increasing, the highly localized yield became weak, resulting in the property of polymers from stiff-plastic

to thermoplastic gradually.

S-P21

Effect of Long-Chain Branching Structure on the Cell Morphology of Poly(lactide acid) Foamed by

Supercritical Carbon Dioxide

Shaojie Li1, Guangjian He2, Xia Liao1, Chul B. Park3, Qi Yang1,Guangxian Li1

1. State Key Laboratory of Polymer Materials Engineering of China, College of polymer science and engineering,

Sichuan University

2. Key Laboratory of Polymer Processing Engineering ,National Engineering Research of Novel Equipment for

Polymer Processing, South China University of Technology

3. University of Toroto

Due to its poor melt strength and shear-insensitive melt viscosity, the application of PLA is limited, especially in

high temperature foaming. The introduction of long-chain branching structure is one of the best ways to solve this

problem. As a novel method, UV-induced reaction extrusion was proved an efficient way to prepare long-chain

branched PLA (LCB-PLA) without employing a peroxide initiator in our previous work. Thus, in this work, the

LCB-PLA prepared via UV-induced reaction extrusion with trimethylolpropane triacrylate (TMPTA) was foamed

by supercritical CO2 at high temperature to show the effect of long-chain branching on the foaming behavior of

PLA. The results shown that when foamed at 142 oC under 12 MPa and 150 oC under 8 MPa, the linear PLA and

LCB-PLA with 0.5 wt% TMPTA performed micro-cells, while the LCB-PLA with more TMPTA shown

nano-cells. With increasing temperature and pressure, although only micro-cells were observed, the shape of cells

changed from ellipse to circular with the increasing TMPTA content. All these results are due to the stronger

matrix strength and higher nucleation potential of LCB-PLA which could be proved by high-pressure rheometer

and high-pressure DSC. The LCB-PLA shown higher viscosity and storage modulus under high-pressure, which

were related to its high matrix strength. The high-pressure DSC data shown that the melt point of LCB-PLA under

12 MPa was about 142 oC to 146 oC, and it increased with increasing TMPTA content. The simulation of foaming

process at 150 oC under 12 MPa shown that the crystals may form during cooling and foaming, and the

crystallinity increased from 10.71% to 43.36% from linear PLA to LCB-PLA with 2 wt% TMPTA. The crystals

would strengthen the cell walls, thus prevent the collapse of bubbles. These results indicate that the long-chain

branching structure could improve the processing property of PLA, thus widen its application.

S-P22

Enhancing electrical conductivity of rubber composites by constructing interconnected network of

self-assembled graphene with latex mixing

Kaiye Zhang, Yanhu Zhan, Hesheng Xia

Sichuan University

Graphene (GE) combines the extraordinary electrical conductivity of carbon nanotubes and the excellent gas

barrier properties of the layered structure of clays, together with its intrinsic high mechanical strength, and it is

hopeful to be the best nanofiller for polymers. Despite that a range of rubber/GE composites were successfully

prepared. The construction of a GE network in a polymer matrix is still a big challenge. we report a newly

developed approach, i.e. self-assembly in latex, to obtain highly stretchable , electrically conductive and water

43

vapor barrier vulcanized rubber composites with a conductive segregated graphene network. GE platelets are

assembled on the surface of the rubber latex particles with a size of several hundred nanometers to form the

prototype of the GE network. After static hot pressing and vulcanization of the coagulated solid GE/NR mixture

from NR latex containing sulfur and other additives, the crosslinked GE/NR composites with a conductive

segregated network of GE were prepared. The formation of a GE network significantly enhances the electrical

conductivity and reduces the electrical percolation threshold of the composites. The composite exhibits a

percolation threshold of 0.62vol% and a conductivity of 0.03 S/m at a content of 1.78vol%, which is 5 orders of

magnitude higher than that of the composites made by conventional methods. In addition, the vulcanized GE/NR

composites with a conductive segregated network have excellent water vapor barrier properties and good

mechanical properties. Our approach can be easily extended to other rubber and elastomer materials. The obtained

rubber/graphene composites with the combination of multiple functions have potential applications in stretchable

conductors, conductive seals, electromagnetic shielding and package materials.

S-P23

Kinetics of Nucleation and Growth of Form II to I Polymorphic Transition in Polybutene-1 as Revealed by

Stepwise Annealing

Yongna Qiao, Yongfeng Men


Academy of Sciencess, University of Chinese Academy of Sciences, Renmin Street 5625, 130022 Changchun, P.R.

China

Kinetics of II to I polymorphic transformation in isotactic polybutene-1 (PB-1) and its annealing temperature and

time dependencies have been investigated by means of differential scanning calorimetry (DSC) and in-situ wide

angle X-ray diffraction (WAXD) techniques. The PB-1 samples were isothermally crystallized into metastable

form II crystalline modification and annealed at a lower temperature (Tl) followed by annealing at a higher

temperature (Th) or annealed at a single temperature (Ts) to promote polymorphic transition from form II to I.

This solid-to-solid phase transition is shown to be a two-step process including nucleation and growth suggested

by the result that more form I was obtained after being annealed at Tl and Th than annealed at Ts for same period.

Annealing at Tl benefits nucleation due to internal stress induced by difference of thermal expansion coefficient

between the amorphous and crystalline phases, while annealing at Th is beneficial to growth owing to rapid

segmental diffusion. At a given annealing time at Tl (tl) and at Th (th), and fixing one of temperatures between Tl

and Th, it shows a maximum in the transformation-temperature profile that can be correlated with the optimal

temperature for nucleation or growth. The phase transition was efficiently accelerated with the increase of lamellar

thickness, and appears a linearly relationship. Our results decomposed the polymorphic transition into nucleation

and growth for the first time and provided a simple and effective way for rapid transition of form II to I in PB-1.

Keywords: poly(1-butene), polymorphic transition, kinetics.

S-P24

Synthesis, functionalization and application of hyperbranched polypropylene oxide(PPOX)

Guangcheng Shan1, Shishan Wu1, Qianping Ran2

1. School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, P. R. China;

2. State Key Laboratory of High Performance Civil Engineering Materials, Jiangsu Sobute New Material Co. Ltd.,

Nanjing 211103, P. R. China

44

Hyperbranched polymer, which performs high reactivity, low viscosity and good dispersion, is a kind of polymer

with high degree of branching. The hyperbranched polymer can be synthesized under control and has applications

in many fields [1-7]. In this paper, hyperbranched polypropylene oxide (PPOX) is prepared using

trimethylolpropane (TMP), glycidol (G), CH3OK and diethylene glycol dimethyl ether. Factors, such as

n[G]/n[TMP] ratio, n[CH3OK]/n[TMP] ratio, the content of G and the reaction time and so on, have great

influence on the molecular weight and distribution of PPOX. The molecular weight of PPOX increases with the

improving ratio of n[G]/n[TMP], the decreasing ratio of n[CH3OK]/n[TMP] as well as prolonging the reaction

time, however, the distribution of molecular weight becomes narrow (before the two) or wide. By increasing

concentration of G, the molecular weight of PPOX first increases and then decreases, and its distribution becomes

narrow (Table 1-4). The hydroxyls of PPOX are sulfated with sulphur trioxide/pyridine system and SPPOX is

gained. SPPOX is competent dispersant for Al2O3 aqueous suspensions.

S-P25

Electric Heating Behavior of Flexible Graphene/Natural Rubber Conductor*

Yanhu Zhan1, Yanyan Meng1, Hesheng Xia2

1. School of Materials Science and Engineering, Liaocheng University, Liaocheng 252000, China. E-mail:

[email protected]

2. State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute, Sichuan University,


The graphene (GE)/natural rubber (NR) composites (RGE) with a conductive segregated network (RGES) are

prepared by latex mixing. Results show that the RGES composite with GE content of 10 phr (RGES-10) exhibits

excellent electrical conductivity of 2.7 S/m and good flexibility. RGES-10 composite possesses excellent heat

propagation with a uniform temperature distribution. The steady-state temperature of the RGES-10 increases from

57 to 152 oC as the applied voltage increases from 10 to 20 V. The steady-state temperature of RGES-10 prepared

by latex approach is ~3 times higher than that of the GE/polymer for the input voltage of 20 V.

S-P26

Hyperbranched azobenzene: A new dye intermediate with circle structure and polyfunctional groups

Lei Xu, Xizhi Jiang, Yongfu Zhao, Liru Xia

Institute of Agricultural facilities and equipment, Jiangsu Academy of Agricultural Sciences, Zhongling Street

No.50, Nanjing, China

In this paper, the synthesis and characterization of a new azobenzene intermediate is reported. Hyperbranched

polyorganosiloxane modified azobenzene was prepared and analyzed by FTIR, UV-vis, 1H NMR and 29Si NMR.

A circle structure azobenzene with various polyfunctional groups was introduced in this paper.

Because of their potential applications in separation, biosensor, chemical storage and transport, drug delivery,

polymer nanoparticles with response to environmental stimuli have attracted much attention. The

stimuli-responsive behaviors of polymer nanoparticles strongly depend on the external chemical and physical

stimuli, such as ionic strength, light, electric and magnetic field, temperature and pH. Because of the easy-control,

light-response is becoming of special importance to polymer nanoparticles in the application fields of drug

delivery and photo sensor. To obtain the polymer nanopaticles response to light, a variety of light-responsive

moieties are introduced into the polymers which construct polymer nanoparticles. Among these light-responsive

moieties, azobenzene group is most studied due to its well-known reversible isomerization from trans- to cis-

45

configuration upon irradiation. However, it is worthy of note that most of them were constructed from linear block

copolymers. Recently, hyperbranched polymers with a three-dimensional dendritic architecture have attracted

much new attention as building matrices for supramolecular self-assembly. Compared with linear polymers,

hyperbranched polymers have shown some advantages for construction of self-assemblies such as a large

population of terminal functional groups, globular architectures, better solubility and lower viscosity. Additionally

and importantly, these obtained self-assemblies have demonstrated some unique characteristics, including

morphology varieties, self-assembly mechanism, unusual mechanical property, excellent template ability and

smart responsibility.

Published only

Effects of beta-nucleating agent on impact property and crystallization behavior of PPR

Yaxin Gu1, Hongmei Wang1, Genhua Liu1, Yunxue Liu1, Jianfeng Gui2

1. Shenyang Jianzhu University, shenyang

2. Easy Great Plastic Technology Co Ltd, Fushun

By adding different contents of beta-nucleating agent (rare earth WBG-2 and amide TMB-5) into polypropylene

random copolymer (PPR)，the PPR composite materials (PPR/WBG-2 and PPR/TMB-5) were prepared. The

influence rules of impact performance at room temperature and low temperature and crystallization property of

different beta-nucleating agent in PPR were analyzed by differential scanning calorimeter，polarizing microscope，

and so on.The results show that compared with pure PPR materials beta-nucleating agent WBG-2 and TMB-5

improved the impact strength of PPR，and the impact performance of PPR/WBG-2 is better than that of

PPR/TMB-5 under room temperature and low temperature range from -25℃ to 0℃. The room temperature and

low temperature impact strength of PPR reaches best when the addition of beta-nucleating agent is 0. 1%；The

beta-nucleating agent raise the crystallization temperature of PPR. And after adding the same mass fraction of

WBG-2 and TMB-5 respectively，the content of beta-crystal of PPR/WBG-2 is higher. The influence of

crystallization behavior consistent with its changes in impact strength.

Molecular Weight and Distribution of Ultra High Molecular Weight Poly (p-phenyleneterephalamide)

Haijuan Kong1, Minglin Qin2, Muhuo Yu2, Xiaoma Ding2, Yao Wu2

1. Shanghai University Of Engineering Science

2. Donghua University

The measurement of molecular weight (Mw) and distribution for ultra high molecular weight poly

(p-phenyleneterephalamide) (UHMWPPTA) is still a great challenge, because it is hardly dissolved in organic

solvents normally to determine its Mw by gel permeation chromatography (GPC). In this paper, n-alkylated

PPTAs with different molecular weight (including SHMWPPTA) were prepared by n-alkylation method with

different length of alkyl side chains. The n-alkylated PPTAs can be dissolved in organic solvents such as

tetrahydrofuran (THF).The longer the alkyl side chains, the solubility is better. The molecular weight and

distribution of n-alkylated PPTAs were characterized by GPC with THF as eluent (MWGPC) and the Mw of

PPTA were measured in concentrated sulfuric acid by intrinsic viscosity measurement.The results showed a good

linear relationship between them for PPTA with molecular weight from 10900 to 60800,which imply that

molecular weight of SHMWPPTA could be measured by the GPC measurement of n-alkylation of PPTA.

46

Synthesis and Characterization of Triple-color White Hyperbranched Conjugated Polymer with

Phospherescent Iridium(Ⅲ) Complexes as the Cores

Jing Sun1, Tiaomei Zhang1, Weihua Chen1, Hua Wang1, Xinwen Zhang3, Bingshe Xu1

1. Key Laboratory of Interface Science and Engineering in Advanced Materials, Taiyuan University of Technology,

Ministry of Education, Taiyuan 030024, P. R. China

2. Research Center of Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan

030024, P. R. China

3. Institute of Polymer Optoelectronic Materials and Devices, Nanjing Post and Communications University,

Nanjing 510640, P. R. China

Hyperbranched polymers had been widely investigated in the single white conjugated polymers owing to the large

steric hindrance which could effectively suppresses triplet-triplet annihilation and improves energy transfer

efficiency. However, double-color white-light hyperbranched polymers with red phosphorescent cores and blue

fluorescent branches had imbalanced white-light electroluminescent (EL) spectra due to a loss of green emission.

Here, a new kind of single triple-color hyperbranched polymer of PF-BTm-Ir(piq)3n were designed and

synthesized, in which red iridium(Ⅲ) complexes acted as cores, 2-benzothiazole (BT) derivatives acted as green

emission units and blue polyfluorene acted as backbone. These hyperbranched polymers had higher

decomposition temperation (＞400 ℃) and glass-transition temperation (＞130 ℃). At the same time, they had

higher fluorescence quantum efficiency and effective energy transfer process had been realized. They also had the

better film forming properties with better surface morphology. A typical single emitting-layer device with the

configuration of ITO/PEDOT:PSS (40 nm)/ PF-BTm-Ir(piq)3n (80 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm)

were also fabricated. By tuning the content of the three emission units, better EL performance of the

hyperbranched polymers was obtained. When the content of BT was 0.25 mol% and the content of Ir(piq)3 was

0.025 mol%, PF-BT125-Ir(piq)350 exhibited excellent electroluminescent properties with a CIE coordinate of

(0.32, 0.35), a maximum luminance of 3267 cd cm-2 and a maximum luminous efficiency of 1.6 cd A-1.

Compared with double-color hyperbranched polymers, triple-color phosphorescent hyperbranched polymers

exhibited optimized EL performance by the introduction of green fluorescnet units. These results indicated that

triple-color white hyperbranched polymers would be promising candidates for display and solid-state lighting

purpose.

Experimental Study on Effects of External Heat Radiation on Combustion and Toxic Gas Release of Flame

Retardant Cables

Jiaqing Zhang1, Bosi Zhang4, Feng Yuan1, Minghao Fan1, Wei Li1, Liufang Wang1, Shuping Wang1

1. State Grid Anhui Electric Power Research Institute

2. Anhui Province Key Laboratory of Electric Fire and Safety Protection

3. State Grid Labortaory of Fire Protection for Transmission and Distribution Facilities

4. China Institute of Industrial Relations

Understanding fire characteristics of cables are of great significance for improving the electrical power security.

The effects of external heat radiation on combustion characteristics and toxic gas release of flame Retardant

cables, which were XLPE insulated, flame retardant PVC sheathed and steel armoured cables, were investigated

experimentally in the present study. Heat release rate (HRR) curve and ignition time were used to describe the

combustion process, and the toxic gas was represented by the carbon monoxide, which was the most common and

fatal gas production in fires. The flame retardant level was also considered. The combustion characteristics of the

47

Level-C and the Level-A flame retardant cables were explored, respectively.

The cable fire experiments were conducted by the cone calorimeter, and the HRR and CO release rate were

measured. Results showed that HRR and CO release rate have the similar tendency with the external radiation

heat flux in all of the conducted experiments. The HRR and CO release rate had different tendencies with the

external radiation heat flux in the two different level flame retardant cables. For Level-C cables, HRR and CO

release rate in cable fires were increased and the ignition times were decreased with the external radiation heat

flux. It implies that the cable becomes easier to be ignited and has more severe combustion process with the

increasing of external radiation heat flux, even the lowest external radiation heat flux can cause the continual

combustion of cables. The HRR curves had three or two peaks for Level-C cables in the present study. The first

HRR peak corresponded to the ignition of the cable sheath, and the second peak of HRR was formed by the

burning of the insulation and filling material, and the ignition of combustible material unexposed directly to the

radiation source caused the third peak of the HRR. It has been indicated that the three peaks of HRR curve might

overlap from each other. Therefore, it was reasonable to get only two peaks in the measured HRR curve. For

Level-A cables, the HRR and CO release rate showed two-stage variations with the external radiation heat flux.

When the external radiation heat flux was smaller or equal to 35 kW/m2, the HRR and CO release rate in cable

fires stayed at lower level and only had single peak. Since the duration of combustion was very short, we

considered that the cable was not ignited successfully under this condition. When the external radiation heat flux

was larger than or equal to 50 kW/m2, the HRR of fire and CO release rate showed a sudden increase and a

continual rise could be found with the further increase of the external radiation heat flux. For the tests, in which

the Level-A flame retardant cable was ignited, the concentrations of CO were remarkable.

The HRR and CO release rates of cables with different fire retardant levels were investigated experimentally in

the present study. The results showed that the flame retardant cable can also be ignited under large enough

external radiation heat fluxes. In the present study, the Level-C flame retardant cable was ignited by the radiation

heat with 25 kW/m2, and the Level-A flame retardant cable was ignited by the radiation heat with 50 kW/m2.

Beyond the critical ignition value, the larger the external radiation heat flux was, the serious result of cable fire

would be. In the tests with Level-A fire retardant cable, the HRR and CO concentration of the cable shows a sharp

increase, once the external radiation heat flux was larger than the critical ignition value. This phenomenon should

be considered in fire protection of the electrical cables to avoid the burst of flashover in cable channel, since the

indictor was not obvious at the initial stage.

Structure and compressive property of heterocyclic aramid fiber

Yingdeng Song, Bintai Li, Liying Xing

Beijing Institute of Aeronautical Materials

The F-3B is a traded name of a new type of heterocyclic para-aramid fibers.The relationship between structural

parameters and compressive property of F-3B has been investigated compared with the Kevlar-49. The orientation

of chains in crystallite and amorphous phase was characterized by the wide-angle X-ray diffraction (WAXD) and

sonic velocity method, respectively. The shear modulus of F-3B was obtained by theoretical-experimental analysis.

The compressive strength of fibers was obtained using the tensile recoil test. In addition, the effect of structural

parameters on compressive property was discussed in detail. The results showed that the orientation of chains in

crystallite and amorphous phase for F-3B was both higher than for Kevlar-49. However, the intermolecular

interaction of F-3B was weaker than Kevlar-49 based on the values of shear modulus. And the compressive

strength of F-3B and Kevlar-49 was approximate within experimental error. It is suggested that the combination of

orientation parameter and shear modulus results in the approximate compressive strength of F-3B and Kevlar-49.

48

Structure and Properties of Carbon Fibers/PA6 Composites Prepared by a Stacking Fabrics Method

Yufei Hu, Jian Zhang, Biao Wang, Xuena Zhang

Donghua University

PA 6 fabrics, due to the textile structure and rough surface, could improve the uniformity of impregnation and

prevent carbon fibers from slipping during the stacking process, resulting in better mechanical properties of

composites. In this study, PA 6 fabrics were used to prepare CF/PA 6 thermoplastic composites by the stacking

fabrics method. The effects of process conditions on mechanical properties of CF/PA 6 composites were

investigated, including processing temperature, holding time and pressure. The impregnation quality of

composites was characterized mainly through microstructural studies. The microstructure of materials was

associated with density measurements and optical microscopic observation of cross section. The mechanical

properties of composites were evaluated by using a transverse flexure testing facility. Meanwhile, a model based

on Darcy’s Law was developed to simulate the impregnation processes of thermoplastic composites by using

stacking fabrics method. The comparison between the experimental and simulated data showed that the program

was reliable to describe the process.

Morphology and Optical Properties Change of Polycarbonate Weathering in Dry-hot Enviroment

Youji Tao, Yu Shi, Lifen Hu, Ganxin Jie, Xin Liu

State Key Laboratory of Environmental Adaptability for Industrial Products, China National Electric Apparatus

Research Institute Ltd., Co.

Polycarbonate(PC) is a second global demand engineering plastic, widely used in automobiles, trains, electronics,

et al. The resistance of weathering is a key feature when PC used outdoors. In order to study the weathering

behavior of PC, PC was subjected to the typical dry-hot (Turpan and Ruoqiang) climate for natural weathering.

The surface morphology and optical properties of PC were characterized by SEM and color difference

spectrometer, respectively. The weathering behavior between the two test sites was contrasted. The results showed

after exposure for 36 months, PC were dramatically degraded, the surface of PC became yellow and cracks

occurred, the yellow index and crack width increased with weathering time. The degradation in Turpan was more

serious than Ruoqiang. The results indicate among the three main factors (solar irradiance, humidity, temperature)

of environment, the high-level of solar irradiance and temperature can accelerate the degradation of PC.

Organic silicon powder on properties of flame retardant cable sheath

Wei Tang, XinPeng Hou

Beijing FD Science & Technology Co., Ltd

Low-density polyethylene / ethylene - vinyl acetate / polyolefin elastomer (LDPE/EVA/POE) blends as the main

base, intumescent flame retardant(IFR) ammonium polyphosphate (APP) based flame retardant cable sheathing

flame-retardant treatment, using organic silica fume on the mechanical properties of the composites were

improved. Study on IFR / organic silicon fume on mechanical properties, flame retardancy and smoke effects. The

experimental results show that, With the increase of APP content, marked increase in performance of fire retardant

materials, but the tensile strength and tensile strain at break decreased. Organic silicon fume and APP may

produce better synergy and improve the oxygen index. By density of smoke testing, when flame retardant material

burned, Organic silica fume can reduce the amount of smoke. Scanning electron microscope results showed,

49

Organic silica fume helps flame retardants dispersed in the matrix material, thereby improving the mechanical

properties of flame retardant materials.

Influence of humidity on the weldability of carbon fiber reinforced polyamide 66

Qian Zhi, Zhongxia Liu

Zhengzhou University

The welding of hygroscopic polyamide 66 was more complex than other polymers due to the changing material

properties during the welding process. The influence of moisture level on the weldability of polyamide 66 was

investigated via ultrasonic welding in lap configuration. Results showed that the joint strength decreased

significantly when the workpieces were conditioned with high humid (i.e., 80%, 100%) while the low humid (i.e.,

20%, 40%, 60%) had small effect with the same welding parameters. Microstructure inspection of the fracture

surface of the welded joint illustrated that air bubble distributed in the weld surface. Dynamic thermomechanical

analysis revealed that the storage and loss modulus changed as the humid content increased. With increasing

moisture content, the loss modulus increased which led to more energy converted into viscoelastic heat and

absorbed by the workpiece. However, the joint strength was not comparable to that of the normal welded joints

due to the deteriorated weld microstructure.

Preparation of high toughness poly(vinyl alcohol) hydrogel by soaking in NaCl aqueous solution

Xiancai Jiang1, 2, Yujun Sun1, Nanping Xiang1

1. School of chemical engineering, Fuzhou University, Fuzhou 350118, China

2. Polymer Research Institute of Sichuan University, The State Key Laboratory of Polymer Materials Engineering,


Poly(vinyl alcohol) is one of the synthetic biodegradable polymers which has been produced on a large scale

commercially [1]. Because of its biocompatibility, nontoxicity and rubber-like elasticity, PVA hydrogel has been

widely studied and considered as one of the hydrogels the most suitable for biomedical applicaitons. PVA

hydrogels can be prepared by chemical crosslinking method or repeated freezing/thawing method [2]. In the

chemical crosslinking method various chemical crosslinkers such as glutaraldehyde, boric acid were used to react

with the hydroxyl group of PVA chain. Chemical crosslinked method can provid PVA hydrogel with good

mechanical properties. Compared to the chemical method, PVA hydrogel prepared through repeated

freezing/thawing method could largely retained the biocompatibility and nontoxicity of PVA hydrogel. This is

benefical for the application of PVA hydrogel in medicial and biological field. However, the PVA hydrogel

prepared by the freezing/thawing method show poor mechanical properties. This has limited the application of

PVA hydrogel in many areas such as tissue engineering.

Here we reported a simple way for converting the physically crosslinked hydrogel into the high toughness

hydrogel by soaking in saturated NaCl aqueous solution [3, 4]. This finding is meaningful because in this way the

high tough PVA hydrogel could be prepared at the absence of chemical crosslinking. The high tough PVA

hydrogel would add the new appealing property to this old hydrogel. Firstly, we prepared the physically

cross-linked PVA hydrogel through the freezing/thawing method. Typically, PVA (5 g, 1799 from Sichuan Vinylon

Factory, MW: ~75000 g/mol, >99% hydrolysis) was dissolved in distilled water (35 mL) at 95 oC with strong

stirring; the transparent solution was then casted into a mold of desired dimension and cooled at -20 oC for 3 h,

which was followed by thawing at 30 oC for 6 h . The freezing/thawing process was repeated for twice. Then the

control PVA hydrogel was prepared (as designed as PVA hydrogel). For the preparation of high tough PVA, the

50

control PVA hydrogel was immersed into the saturated NaCl solutions for 10 min (as designed as t-PVA hydrogel).

In the freezing/thawing process, the crystallization of PVA occurs at low temperature resulting to the formation of

crystallites which act as physical cross-links to construct the network in the PVA hydrogel. After two repeated

freezing/thawing processes, the translucent PVA hydrogel was obtained. After immersing in NaCl solution, the

translucent PVA hydrogel turned into opaque and white PVA hydrogel. After immersing in NaCl aqueous solution

for 10 min, the PVA hydrogel became tough and strong. To further quantitatively evaluate the change of the

mechanical properties of PVA hydrogel before and after immersing, the tensile testing and compression test were

performed for the hydrogel. The tensile and compression stress-strain curves of the hydrogels were shown in

Figure 1 and Table 1. As expected, the tensile strength of PVA hydrogel increased from 0.71 MPa to 2.29 MPa

after immersing in NaCl aqueous solution. And correspondingly the elongation at break increased from 470% to

794%. This showed that by immersing in NaCl aqueous solution is an effective way to improve the mechanical

properties of PVA hydrogel and in this simple way super tough PVA hydrogel could be obtained. This is the first

report of the preparation of high-tough PVA hydrogel without the chemcial crosslinking. The compression tests

were also performed and the corresponding data were also shown in Table 1.

Application of Curing Co-agent in In-situ Compatibilized Rubber Powder/Polypropylene Thermoplastic

Elastomer

Peijun Li, Xin Zhao, Weina Bi, Shugao Zhao

Key Laboratory of Rubber-plastics, Ministry of Education, Qingdao university of Science and Technology

In this experiment, effect of curing co-agent type and content on the preparation and properties of rubber powder

(RP) /Polypropylene (PP) blends were studied by utilizing many modern analysis equipment such as differential

scanning calorimetry (DSC), rubber processing analysis (RPA), rotation rheometer and electrical tensile machine.

The results showed that simple blended RP/PP blend cannot be used as thermoplastic elastomer, as the mechanical

properties of as-prepared RP/PP blends were very poor due to the bad compatibility between of RP and PP.

co-agent sulfur and di-(trimethylolpropane triacrylate) (DTMPTA) could initiate crosslinking reaction during the

in-situ compatibilization melt blending of RP/PP, which increased the strength of the molten RP/PP fluids.

Co-agent sulfur had little effect on the tensile properties of RP/PP blends, by contrast, co-agent DTMPTA

improved the tensile properties of RP/PP blends significantly. Under lower blending temperature of 160oC, the

tensile strength and elongation at break of RP/PP blend with 0.375% DTMPTA were 14.7 MPa and 197%

respectively, which indicated that it could be used as thermoplastic elastomer.

Key words: rubber powder; polypropylene; thermoplastic elastomers; co-agent; in-situ compatibilization

Research on Urea-Formaldehyde Microcapsules for Self-Healing Coating

Yang Zhao, Jiyun Liu, Ziteng He, Wei Zhang, Shiyun Dong, Binshi Xu

Science and Technology on Remanufacturing Laboratory, Academy of Armored Forces Engineering, Beijing

100072, China

The self-healing technology with microencapsulated healing agent is a new in-situ remanufacturing

engineering technology with high efficiency and environment-friendly properties. Inspired by biological

systems in which damage triggers an autonomic healing response, the polymer composite material that can

heal itself when cracked has been developed. Due to its in-situ repairing function to the polymer materials of

machinery parts, the self-healing technology processes significant resolved the problems caused by micro

crack failures，has improvde the reliability and stability of weapons, as well as increased the service life of

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equipments. Accordingly, it presents a broad application prospect as one of the advanced technologies for

equipments maintenance and remanufacturing engineering.

Microcapsules were successfully fabricated by one step in-situ polymerization in an oil-in-water emulsion

with urea-formaldehyde resin as the shell material and modified epoxy as core substance. The effect of mass

ratio of the reactants, agitation rate, heating rate and surfactant on the physical properties of microcapsules

are systematically investigated. The physical and chemical properties were investigated by optical

microscopy (OM), scanning electron microscopy (SEM), Fourier-transform infrared spectrometer (FTIR),

laser particle size analyses, and thermogravimetry analysis (TGA). The mechanical property of the

microcapsule was performed by single-capsule compression test. The results indicate that microcapsules

containing epoxy resins can be synthesized successfully by one step in-situ polymerization. Controlled

surface morphology and particle size of microcapsules can be prepared by adjusting the processing parameter.

The synthesized microcapsules exhibit good storage stability, thermal stability and show a certain mechanical

property. The dynamic forming model was proposed with formation process of microcapsule.

Keywords: self-healing; one step in-situ polymerization; microcapsules

S. Polymer Materials and Engineering · S. Polymer Materials and Engineering Organizers: Guangxian...

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Transcript of S. Polymer Materials and Engineering · S. Polymer Materials and Engineering Organizers: Guangxian...