BRITTLE-DUCTILE TRANSITION OF POLYMERS AND ITS PERCOLATION MODEL

The brittle-ductile transition (BDT) of particlc toughened polymers was extensively studied in terms ofmorphology, strain rate, and temperature. The calculation results showed that both the critical interparticle distance (ID_c) andthe brittle-ductile transition temperature (T_(BD)) of polymers were a function of strain rate. The ID_c reduced nonlinearly withincreasing strain rate, whereas T_(BD) increased considerably with increasing strain rate. The effects of temperature andplasticizer concentration on BDT were discussed using a percolation model. The results were in agreement with theexperiments.     

THE EFFECT OF MATRIX TOUGHNESS ON THE BRITTLE-DUCTILE TRANSITION OF HDPE/CaCO_3 BLENDS

The effects of HDPE matrix toughness on the brittle-ductile transition of HDPE/CaCO_3blends are investigated. Not all HDPE can be toughened by CaCO_3 particles. The ability of thematrix to yield plays a fundamental role in determing whether HDPE can be toughened or not.There exists a critical matrix toughness (I_(sc)≈45J/m) below which HDPE can not be toughenedobservably by CaCO_3 particle at given average size, and above which the critical matrix ligamentthickness (τ_?) is proportional to matrix impact strength.     

MIXED EXCITATION IN ELECTROLUMINESENCE*

Anong the present three types of electric field-induced luminescence we noticed similarities between the inorganicand organic materials in electric field intensity. In this high electric field range SiO_2 has three functons: acceleration,excitation and multiplication of electrons. Based on the acceleration effect, cathodoluminescence-like emission of organicmolecules and polymers was found. By using the three functions of SiO_2 or II-VI compounds and the heterojunction ofinorganic and organic material we realized different variants of mixed excitation in electroluminescence.     

TRANSIMIDIZATION IN THERMOPLASTIC POLYIMIDES*

In order to improve the processibility in thermoplastic polyimides, a new method, termed the"reactive plasticizer" approach, has been proposed. This method uses a small amount (5～15 mol%) of a lessactivated, weak nucleophilic diamine co-monomer as a "reactive plasticizer" to obtain copolyimide resinswhich possess relatively low viscosity at low temperatures and can be readily processed through the autoclavecycle at low pressures. During a high temperature treatment, the reactive plasticizers join the reaction to formhigh molecular weight copolyimides, and the preferred material properties are thus achieved. The mosteffective reactive plasticizer is aromatic heterocyclic diamines, such as 2, 6-diaminopyridine diamine (DAP),and the transimidization involved with a reactive plasticizer has been proposed to play a major role for thesuccess of this approach. In order to understand the transimidization mechanism, three steps have been takenin this research: first, a copolyimide system of 50% of DAP and 50% 1, 4 -bis [4-aminophenoxy] benzenediamine (DODA) with 100% of 2, 2'-bis[4-(3, 4-dicarboxyphenoxy)phenyl] propane dianhydride (Ultem~(R)DA) is prepared. Second, several specifically designed polyimide mixture systems were used, and they consistof two homopolyimides: one is Ultem~(R) DA-DODA, and the other is Ultem~(R) DA-DAP. The third step is toinvestigate two mixture systems in which Ultem~(R) DA-DODA is mixed with DAP monomer solution andUltem~(R) DA-DAP is mixed with DODA monomer solution. For all systems, with increasing degree oftransimidization upon heat-treatment, the chain structures of the mixtures and their thermal and dynamicmechanical transition behaviors are investigated via one-dimensional and two-dimensional nuclear magneticresonance, differential scanning calorimetry, and dynamic mechanical analysis experiments. Experimentalresults indicate that in the mixture of two homopolyimides, transimidization takes place much moreefficiently in solution than in the melt. For the two mixtures with monomer solutions, the transimidizationcan only be found in the mixture of Ultem~(R) DAP/DODA system in p-chlorophenol, and this process does noteffectively occur in the Ultem~(R) DODA/DAP system in p-chlorophenol, indicating that free DODA canefficiently attack the imide linkage of Ultem~(R) DA-DAP. The final product resulting from the transimidizationin the mixtures is a random copolyimide with a major population of DAP as end groups for the copolymersystem.     

A MONTE CARLO STUDY OF THE GLASS TRANSITION OF POLYMETHYLENE*

By this Monte Carlo simulation we studied the glass transition of polymethylene using themodified bond-fluctuation model combined with considering the rotational-isomeric state model. Theconfigurational properties in the polymethylene (PM) melts, such as the mean length, the mean energy perbond and the mean square radius of gyration were monitored. We found that the chains cannot be in theequilibrium states after a very long time when the temperature of the dense PM chains decreases to 120 K. Asthe melt vitrifies, these quantities gradually become independent of temperature in a narrow range. The glasstransition temperature T_g depends upon the chain length of PM chains, and extrapolation to (CH_2)_∞givesT_g~∞=212 K. The dynamics in the PM melts was also studied. It was found that the diffusion coefficients canbe described by the Vogel-Fulcher law and the Vogel-Fulcher temperature T_0 is 124 K. This method may beused to investigate the glass transition of other real polymer chains.     

A NEURAL NETWORK STUDY ON GLASS TRANSITION TEMPERATURE OF POLYMERS

In this paper, an atificial neural network model is adopted to study the glass transition temperature of polymers. Inour artificial neural networks, the input nodes are the characteristic ratio C_∞, the average molecular weigh M_e betweenentanglement points and the molecular weigh M_(mon) of repeating unit. The output node is the glass transition temperature T_g,and the number of the hidden layer is 6. We found that the artificial neural network simulations are accurate in predicting theoutcome for polymers for which it is not trained. The maximum relative error for predicting of the glass transitiontemperature is 3.47%, and the overall average error is only 2.27%. Artificial neural networks may provide some new ideas toinvestigate other properties of the polymers.     

MORPHOLOGICAL TRANSITION BETWEEN VESICLES AND TUBULES FOR A GLYCOPOLYMER-CONTAINING AMPHIPHILIC DIBLOCK COPOLYMER IN AQUEOUS SOLUTIONS*

The morphological transition of molecular assemblies in aqueous solutions for a new amphiphilic diblockcopolymer induced by changing the initial solvent conditions was studied by transmission electron microscopy (TEM). Thecopolymer was polystyrene(77)-b-poly [2 -(β-D-glucopyranosyloxy) ethyl acrylate (6)] (PSt_(77)-b-PGEA_6) and the solvent was amixture of DMF and THF. PSt_(77)-b-PGEA_6 yields vesicles and tubules when it is initially dissolved in THF and DMFrespectively. The morphological transition between vesicles and tubules can be achieved by simply varying the amounts ofTHF and DMF, or changing the temperature at which the aggregates were prepared.     

STUDIES ON CRITICAL CONCENTRATION OF LIQUID CRYSTALLINE ETHYLCELLULOSE

Critical concentrations of lyotropic liquid crystalline ethylcellulose in more than tensolvents were determined using both Abbe refractometer and polarized microscopy. Criti-cal concentration C_(crit) of forming liquid crystal phase decreased with increasing solubilityparameter δ of solvent until approaching the δ of polymer. Although the alcohols usedas solvents had the same variation rule, the critical concentration values of their solutionswere much higher, due to their excessive large hydrogen bond component of δ. The experi-ments of using mixed solvents which showed good linear relation between C_(crit) and δ alsoproved this rule. A technique of Transmission Optical Analysis was first used to estimatethe concentration dependence of critical phase transition temperature T_(crit) of EC, and aT-C phase diagram could be drawn.     

POLYMER CHAIN DIFFUSION AT A TEMPERATURE BELOW ITS BULK GLASS TRANSITION TEMPERATURE

In this study, it was examined whether the dynamics of polymer chains at a surface is different from that in thebulk, and if so, to what extent they differ in terms of surface glass transition temperature and diffusion coefficient. Obtainedresults clearly indicate that surface chains can travel for a relatively large distance in comparison with the characteristiclength scale of usual segmental motion even at a temperature below its bulk glass transition temperature, T_g~b. This isconsistent with our previous results that the surface glass transition temperature is much lower than the corresponding T_g~b.Also, it was experimentally revealed that there was a gradient of molecular motion in the surface region.     

A DYNAMIC MECHANICAL ANALYSIS STUDY OF THE TRANSITION BEHAVIOUR OF I-PP/EPDM BLENDS

The transition behaviour of the blends of isotactic polypropylene (i-PP) with ethylene-propylene terpolymer (EPDM) containing 42 wt% propylene was investigated by dynamic mechanical analysis technique (DMA). Owing to its high propylene content, EPDM is compatible with i-PP to some degree. The interaction between the two components was strengthened. As expected, for partially compatible system the glass transition temperature of i-PP in the blends shifted to lower temperature. It was found that there existed two transitions, αEPDM and βEPDM, for the EPDM used in this work. The former was considered to be the glass transition of the random chain segments of EPDM, while the latter the local motion of the long ethylene sequences in EPDM. The unusual transition behaviour of αEPDM in the blends was explained in terms of the greater thermal expansion of EPDM and the compatibility of the two components. On the other hand, the βEPDM changed with the composition of the blends in a regular manner.     

DYNAMIC MECHANICAL RESPONSE OF CRAZES IN POLYSTYRENE

Dynamic mechanical analysis was used to study the mechanical properties and microstructureof crazes in polystyrene produced in air or in methanol at different temperatures. A new loss peakwas found at about 82℃,which is assigned to glass transition peak of craze fibrils. The decreaseof glass transition temperature of polymer in craze fibrils is due to the high values of surface tovolume ratio. The glass transition temperature ratio of craze fibrils to bulk material (T_g~l /Tg) hasbeen expressed as a function of the fibrils diameter (d). From T_g~l of craze fibrils,the value of fibrildiameter can be calculated. Annealing the crazed specimen at room temperature makes the fibrilsplastically deform and cause the fibrils to thin slightly,whereas annealing the crazed specimen atthe temperature near T_g of the craze fibrils makes the fibrils bundle together.     

ELECTRORHEOLOGICAL PROPERTIES OF POLYANILINE/PUMICE COMPOSITE SUSPENSIONS

Electrorheological （ER） properties of polyaniline （PAni）, pumice and polyaniline/pumice composites （PAPC） were investigated. Polyaniline and PAni/pumice composite were prepared by oxidative polymerization. PAni/pumice particlesbased ER suspensions were prepared in silicone oil （SO）, and their ER behavior was investigated as a function of shear rate, electric field strength, concentration and temperature. Sedimentation stabilities of suspensions were determined. It has been found that ER activity of all the suspensions increases with increasing electric field strength, concentration and decreasing shear rate. It has shown that the suspensions have a typical shear thinning non-Newtonian viscoelastic behavior. Yield stress of composite suspensions increased linearly with increasing applied electric field strength and with concentrations of the particles. The effect of high temperature on ER activity of purrfice/silicone oil systems was also investigated.     

MESO-STRUCTURED POLYMERIC HYDROGELS

Meso-structured (opal and inverse opal) polymeric hydrogels of varied morphology and composition wereprepared by using two methods: post-modification of the template-synthesized structured polymers and template-polymerization of functional monomers. A polyacrylic acid based inverse opal hydrogel was chosen to demonstrate its fastpH response by changing color, which is important in designing tunable photonic crystals. Template effects of the hydrogelson controlling structure of the template-synthesized inorganic materials were discussed. The catalytic effect of acid groups inthe templates was emphasized for a preferential formation of TiO_2 in the region containing acid groups, which allowedduplicating inorganic colloidal crytals from colloidal crystal hydrogels (or macroporous products from macroporoushydrogels) via one step duplication.     

POLYELEOSTEARIC ACID VESICLES

α-Eleostearic acid and β-eleostearic acid formed vesicles in aqueous medium when an ethanol solution of eleostearic acid was injected rapidly into a vigorously vortexed aqueous phase. Formation of the vesicles was demonstrated by electron microscopic observation and bromothymol blue encapsulation experiments. Polymerizations of the eleostearic acids in the formed vesicles carried out by UV irradiation produced poly-α-eleostearic acid and poly-β-eleostearic acid vesicles.     

RADIATION-INDUCED EMULSION POLYMERIZATION OF STYRENE IN SOAP-FREE SYSTEM

Radiation-induced emulsion polymerization of styrene in soap-free system has beenstudied and the monodisperse polystyrene lattices were obtained. Both its purity and emulsionconversion are better than that of chemically initiated polymers.     

TURNING-OVER OF THE ELECTRIC DIPOLE IN A POLYMER*

The transition from the biexciton to the exciton can turn over the direction of the electric dipole of a polymericmolecule. This turning-over action combined with the photoinduced polarization reversion can be used as a switch. Theswitching speed is governed by the relaxation time of the turning-over process, which can be determined by a dynamicalsimulation.     

STATISTICAL PROPERTIES OF LONG-RANGE CONTACTS IN GLOBULAR PROTEINS

The analysis of residue-residue contacts in protein structures can shed some light on our understanding of the folding and stability of proteins. In this paper, we study the statistical properties of long-range and short-range residue-residue contacts of 91 globular proteins using CSU software and analyze the importance of long-range contacts in globular protein structure. There are many short-range and long-range contacts in globular proteins, and it is found that the average number of long-range contacts per residue is 5.63 and the percentage of residue-residue contacts which are involved in long-range ones is 59.4%. In more detail, the distribution of long-range contacts in different residue intervals is investigated and it is found that the residues occurring in the interval range of 4-10 residues apart in the sequence contribute more long-range contacts to the stability of globular protein. The number of long-range contacts per residue, which is a measure of ability toform residue-residue contacts, is also calculated for 20 different amino acid residues. It is shown that hydrophobic residues (including Leu, Val, Ile, Met, Phe, Tyr, Cys and Trp) having a large number of long-range contacts easily form long-range contacts, while the hydrophilic amino acids (including Ala, Gly, Thr, His, Glu, Gln, Asp, Asn, Lys, Ser, Arg, and Pro) form long-range contacts with more difficulty. The relationship between the Fauchere-Pliska hydrophobicity scale (FPH) and the number of short-range and long-range contacts per residue for 20 amino acid residues is also studied. An approximately linear relationship between the Fauchere-Pliska hydrophobicity scale (FPH) and the number of long-range contacts per residue CL is found and can be expressed as     

RHEOLOGICAL BEHAVIOR OF ERWINIA GUM IN AQUEOUS SOLUTION*

Erwinia (E) gum, an extracellular polysaccharide, is composed of fucose, galatose, glucose andglucuronic acid. Its viscosity behavior was investigated by a low-shear-rate multiball viscometer and arotational viscometer. Its weight-average molecular weight M_w and intrinsic viscosity [η] in 0.2 mol/L NaClaqueous solution were measured by light scattering method at 35℃and viscometry at 25℃and found to be1.06×10~6 g/mol and 1050 mL/g, respectively, and its aggregates in aqueous solution were proved by gelpermeation chromatography (GPC). These results indicated that E gum in water has exceedingly highviscosity and exhibits Binham fluid behavior, owing to its aggregation. The viscosity of E gum decreasedwith increasing temperature, and the turning point appeared at 38℃for dilute solution and 80℃forconcentrated solution suggesting that the aggregates of E gum in water started to disaggregate under thesetemperatures. In addition, the aggregates can be disrupted by adding either acid or base. The experimentalresults indicated that the E gum is a good thickening agent, and its fluid behavior is similar to xanthan.     

CONFINING CONDUCTING POLYANILINE IN A STABLE INORGANIC NETWORK

Water soluble conducting polyaniline with electrical conductivity of 10~(-1)-10~(-2) S/cm was prepared employingdopant induced water solubility technology. The water resistance of the conducting film was significantly improvedemploying sol-gel hybrids method, especially when the conductive polyaniline loading was below 30 wt%. The reason forthe improvement is that the conducting polyaniline chains are confined in a stable inorganic network.     

CORRELATION BETWEEN GLASS TRANSITION OF POLYMERS AND ENERGY OF ROTATIONAL ISOMERIZATION OF MOLECULAR CHAINS

It has been shown that the free volume fraction at T_g is not a universal parameter for linear polymers of different molecular structure. The reason is that the volume expansion at T_g is partially contributed from the change of the numbers of conformations of isolated molecular chains due to internal rotation. In this paper, glassy transformation was connected with internal rotation of isolated molecular chains, and the relationship between free volume fraction of polymers at T_g and energy e of rotational isomerization of isolated molecular chains was formulated, e=-k·T_g·In (△α·T_g/1-△α. T_g). The values of calculated from the above formula are in good agreement with those published in the literatures. Thus, the method described in this paper can be used to estimate a parameter for the flexibility of isolated molecular chains.7