THE USE OF LIGHT-MICROSCOPY FOR INVESTIGATIONS OF EPITAXIAL-GROWTH OF POLYMERS ON POLYMERIC SUBSTRATES

In order to study the oriented (epitaxial) crystallization of thermoplastic polymers on oriented polymer substrates, generally the transmission electron microscopy (TEM) is used. With this instrument, the crystallized material can easily be resolved and orientation relationships can be monitored by electron diffraction. Disadvantages are the time consuming sample preparations and difficulties in the in-situ observations of the crystallization events, because of the radiation sensitivity of the polymer crystals. It is demonstrated that these disadvantages of the TEM can be eleminated by the use of different methods of light optical contrasts under specific preparation conditions of the samples and that the optical microscopy being a supplementary method to the TEM for investigations of epitaxial crystallization.

MECHANISM OF RADIATION CROSS-LINKING OF POLYMERS AND ITS RELATIONSHIP WITH STRUCTURAL MULTIPLICITY

In an attempt to explore the effect of structural multiplicity of polymers on the mechanism of radiation crosslinking, the adaptability of the Charlesby-Pinner's equation and its various modified versions are examined. It is recognized that both chemical and morphological multiplicity of polymer structure results in the multiplicity of crosslinking mechanism, and that any single equation can only be applicable to a certain step of the whole radiation process.

STRUCTURES AND PROPERTIES OF DIALKYL FUMARATES POLYMERS

Polymers of methyl-iso-propyl fumarate, di-iso-propyl fumarate, di-t-butyl fumarate, di-s-butyl fumarate, di-s-amyl fumarate and di-cyclo-hexyl fumarate were prepared by radical polymerization. The structures of the polymers were examined by H-1-NMR, C-13-NMR and WAXD. Some properties of the polymers, including thermal properties, were examined.

THERMODYNAMICS OF POLY(ETHYLENE OXIDE)-POLY(VINYL ACETATE) BLENDS

Heat-of-mixing data, obtained on blends of poly(ethylene oxide) (PEO) with whole and fractionated poly(vinyl acetate) (PVAc), were used to feed Patterson's theory of polymer-polymer miscibility. Negative values of mixing enthalpy, contact-energy term, interaction'' parameter and excess volume were obtained only for blends with the lowest molecular weight PVAc fraction. These results show that miscibility of PVAc with PEO strongly depends on its molecular weight. The calculated unfavourable excess volume term of the Patterson equation is small in comparison with the absolute value of the interaction term. Therefore, miscibility of PEO and low-molecular-weight PVAc is dictated by the weak specific interactions between different repeat units and by the entropic gain in the mixing process.

STATISTICAL THERMODYNAMICS OF POLYDISPERSE POLYMERS

A statistical thermodynamics theory of polydisperse polymers based on a lattice model of fluids is formulated. Pure polydisperse polymer can be completely characterized by three scale factors and the molecular weight distribution of the system. The equation of state does not satisfy a simple corresponding-states principle, except for a polymer fluid of sufficiently high molecular weight. The relationships between thermal expansion coefficient alpha and isothermal compressibility beta with reduced variables are also predicted.

SEQUENCE STRUCTURE OF ETHYLENE-VINYL SUBSTITUTED COPOLYMER WITH C-13 NMR .4.

The substituent chemical shift (SCS) has been applied to the assignment of the C-13 NMR spectrum of chlorinated polyethylene (CPE). CPE of different chlorine contents has been employed and their sequence structure discussed. The results show that characteristic of CPE with medium chlorine content is the dichloroethane structure in molecular chain. SCS parameters have been obtained from the C-13 NMR spectra. It was found that the effects of chlorine content and temperature on SCS are negligible, but the substituent parameter S1 reduced by 0.39 ppm when C2Cl4 was added to solvent ODCB.

RADIATION EFFECTS ON CRYSTALLINE POLYMERS .1. GAMMA-RADIATION-INDUCED CROSS-LINKING AND STRUCTURAL CHARACTERIZATION OF POLYETHYLENE OXIDE

By using WAXD, DSC and gel fraction determination techniques, the mechanism of radiation crosslinking of polyethylene oxide (PEO) was explored, and the dependence of aggregated state on the chemical reaction and physical structure was also discussed. It was found that just like other semi-crystalline polymers, the state of aggregation of the specimen has a profound influence on the radiation effects on PEO. On the contrary, the crystalline structure of the specimen is severely affected with the increase in radiation dose and eventually amorphortized when subjected to an extremely high radiation dose.

BLENDS OF POLY[3,3-BIS(CHLOROMETHYL)OXETANE] WITH POLY(VINYL ACETATE) .1. THERMAL AND MECHANICAL-PROPERTIES

Blends of poly[3,3-bis(chloromethyl)oxetane] (Penton) with poly(vinyl acetate) were prepared. Compatibility, morphology, thermal behavior, and mechanical properties of blends with various compositions were studied using differential scanning calorimetry (DSC), dynamic mechanical measurements (DMA), tensile tests, and scanning electron microscopy (SEM). DMA study showed that the blends have two glass transition temperatures (T(g)). The T(g) of the PVAc rich phase shifts significantly to lower temperatures with increasing Penton content, suggesting that a considerable amount of Penton dissolves in the PVAc rich phase, but that the Penton rich phase contains little PVAc. The Penton/PVAc blends are partially compatible. DSC results suggest that PVAc can act as a beta-nucleator for Penton in the blend. Marked negative deviations from simple additivity were observed for the tensile strength at break over the entire composition range. The Young's modulus curve appeared to be S-shaped, implying that the blends are heterogeneous and have a two-phase structure. This was confirmed by SEM observations.

ISOPOLYMOLYBDIC ACID-POLY(4-VINYL)PYRIDINE FILM MODIFIED ELECTRODE

Electrochemical polymerization of 4-vinylpyridine produced a uniform poly(4-vinyl)pyridine(PVP) film on the glassy carbon (GC) electrode surface. The isopolymolybdic acid-PVP film-modified electrode was prepared by soaking the PVP/GC electrode in the 0.05 M H2SO4 aqueous solution containing 0.005 M isopolymolybdic acid (H4Mo8O26). The latter (catalyst) is incorporated and held in the PVP film electrostatically. The electrochemical behavior and electrocatalytic properties of this H4Mo8O26-PVP/GC electrode was described. The results indicate that this modified electrode has good stability and electrocatalytic activity on the reduction of chlorate and bromate ions in aqueous solution. The catalytic process is regarded as an EC mechanism.

MUTUAL ENTANGLEMENTS IN POLY(VINYL ACETATE) POLY(METHYL ACRYLATE) INTERPENETRATING POLYMER NETWORKS

An equation has been derived for the equilibrium swelling of sequential interpenetrating polymer networks (IPNs), which exhibit a single glass transition temperature and the two components are considered to be compatible. The properties of the equilibrium swelling and elastic modulus of sequential poly(vinyl acetate)/poly(methyl acrylate) IPNs have been discussed according to the derived equation and the Siegfried-Thomas-Sperling formula of the elastic modulus for homo IPNs. In both fully swollen and bulk states, there was favourable evidence for added physical crosslinks in poly(vinyl acetate)/poly(methyl acrylate) IPNs. The Binder-Frisch theory is also discussed.

INSITU CONDUCTIVITY ELECTROCHEMISTRY OF CONDUCTIVE POLYMERS - POLY(3-METHYLTHIOPHENE) AND POLYTHIOPHENE

In situ monitoring of conductivity and potential response of conductive polymers during electrochemical process had been described. A renewable carbon fibre array ring-glassy carbon disk electrode was used for this purpose. Poly(3-methylthiophene) and polythiophene were investigated with this method, and some 5 orders in magnitude of conductivity changes were observed during the electrochemical redox process.

RADIATION-INDUCED CROSS-LINKING OF AROMATIC POLYMERS WITH A CARDO GROUP

The effects of irradiation on some members of the family of aromatic polymers with a cardo group, such as polyetherketone with a cardo group (PEK-C) and polyethersulfone with a cardo group (PES-C), were studied. It was found that PEK-C and PES-C can be crosslinked by irradiation under vacuum. Moreover, it was also found that the intensity of the shake-up peak of x-ray photoelectron spectroscopy (XPS) for PEK-C and PES-C varies with irradiation dose. Gelation doses (Rg) of PEK-C and PES-C were estimated from the XPS shake-up peak.

DYNAMIC SCALING OF THE STRUCTURE-FUNCTION FOR SPINODAL DECOMPOSITION IN CRITICAL AND NONCRITICAL MIXTURES OF POLY(VINYL ACETATE) POLY(METHYL METHACRYLATE)

The dynamics of phase separation in a binary polymer blend of poly(vinyl acetate) with poly(methyl methacrylate) was investigated by using a time-resolved light-scattering technique. In the later stages of spinodal decomposition, a simple dynamic scaling law was found for the scattering function S(q, t)(S(q, t) approximately I(q, t)): S(q, t)q(m)-3 S approximately (q/q(m)). The scaling function determined experimentally was in good agreement with that predicted by Furukawa, S approximately (X) approximately X2/(3 + X8) for critical concentration, and approximately in agreement with that predicted by Furukawa, S approximately (X) approximately X2/(3 + X6) for non-critical mixtures. The light-scattering invariant shows that the later stages of the spinodal decomposition were undergoing domain ripening.

A NEW ISOTHERMAL EQUATION OF STATE FOR POLYMERS

A new isothermal equation of state for polymers in the solid and the liquid is given by P = B(T, 0)/(n - m){[V(T, 0)/V(T, P)]n + 1 - [V(T, 0)/V(T, P)]m + 1} where n = 6.14 and m = 1.16 are general constant's for polymer systems. Comparison of the equation with experimental data is made for six polymers at different temperatures and pressures. The results predict that the equation of state describes the isothermal compression behaviour of polymers in the glass and the melt states, except at the transition temperature.