The formation of ring-banded spherulites of poly(epsilon-caprolactone) in its miscible mixtures with poly(styrene-co-acrylonitrile)

Ring-banded spherulites in polymer blends of poly(epsilon-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) were investigated by optical microscopy equipped with a digital image analysis system. PCL/SAN blends exhibit not only spherulites with a Maltese cross, but also distinct extinction rings. The periodic distance of rings changes with blend ratio and crystallization temperature and was plotted as a function of the undercooling and overall mobility of the mixtures, respectively. It was found that the overall mobility of chain segments in the mixtures could be mainly attributed to the origin of the formation of ring-banded spherulites. It was believed that for the first time a quantitative experimental result was obtained about the relationship of periodic distance of rings and the overall mobility of the mixtures. This relationship may be useful to explain the formation mechanism of ring-banded spherulites in polymer blends or even in homopolymers in the future. (C) 1977 Elsevier Science Ltd.

Synthesis, characterization and ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Three comb polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 were synthesized and characterized, and the ionic conductivity of CP/salt complexes is reported. The conductivity of these complexes was about 10(-5)-10(-6) S cm(-1) at room temperature. The conductivity, which displayed non-Arrhenius behaviour, was analysed using the Vogel-Tammann-Fulcher equation. The conductivity maxima appear at lower salt concentration, when CP has longer side chains. Infrared (i.r.) was used to study the cation-polymer interaction. I.r. results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring. (C) 1997 Elsevier Science Ltd.

Ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. CP/salt complexes showed conductivity up to 10(-5)Scm(-1) at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Synthesis and ionic conductivity studies of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type-O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with LiNO3 to form an amorphous polymer electrolyte. CP/salt complexes showed conductivity up to 10(-5) S/cm at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Comb polymer electrolytes - Ionic conductivity and cation-polymer interaction

Three comb polymers(CP) with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 were prepared from methyl vinyl ether/maleic anhydride alternating copolymer. Homogeneous amorphous polymer electrolytes were made from CP and LiCF3SO3 or LiClO4 by solvent-casting method, and their conductivities were measured as a function of temperature and salt concentration. The conductivity which displayed non-Arrhenius behaviour was analyzed using the Vogel-Tammann-Fulcher equation. The conductivity maximum appears at lower salt concentration when CP has longer side chains. XPS was used to study the cation-polymer interaction.

Phase behavior in mixtures of a homopolymer and a block copolymer .4. SALS and SAXS studies

Phase behavior of blends of poly(vinyl methyl ether) (PVME) with four styrene-butadienestyrene (SBS) triblock copolymers, being of various molecular weights, architecture, and compositions, was investigated by small-angle light scattering. Small-angle X-ray scattering investigation was accomplished for one blend. Low critical solution temperature (LCST) and a unique phase behavior, resembling upper critical solution temperature (UCST), were observed. It was found that the architecture of the copolymer greatly influenced the phase behavior of the blends. Random phase approximation theory was used to calculate the spinodal phase transition curves of the ABA/C and BAB/C systems; LCST and resembling UCST phase behavior were observed as the parameters of the system changed. Qualitatively, the experimental and the theoretical results are consistent with each other. (C) 1996 John Wiley & Sons, Inc.

PHASE-BEHAVIOR IN MIXTURES OF A HOMOPOLYMER AND A BLOCK-COPOLYMER .1. FTIR AND DSC STUDIES

Miscibility in blends of three styrene-butadiene-styrene and one styrene-isoprene-styrene triblock copolymers containing 28%, 30%, 48%, and 14% by weight of polystyrene, respectively, with poly(vinyl methyl ether) (PVME) were investigated by FTIR spectroscopy and differential scanning calorimetry (DSC). It was found from the optical clarity and the glass transition temperature behavior that the blends show miscibility for each kind of triblock copolymers below a certain concentration of PVME. The concentration range to show miscibility becomes wider as the polystyrene content and molecular weight of PS segment in the triblock copolymers increase. From the FTIR results, the relative peak intensity of the 1100 cm-1 region due to COCH3 band of PVME and peak position of 698 cm-1 region due to phenyl ring are sensitive to the miscibility of SBS(SIS)/PVME blends. The results show that the miscibility in SBS(SIS)/PVME blends is greatly affected by the composition of the copolymers and the polystyrene content in the triblock copolymers. Molecular weights of polystyrene segments have also affected the miscibility of the blends. (C) 1995 John Wiley & Sons, Inc.

CRYSTALLIZATION KINETICS OF MIXTURES OF POLY(EPSILON-CAPROLACTONE) AND POLY(STYRENE-CO-ACRYLONITRILE)

The crystallization kinetics in mixtures of poly(epsilon-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) has been investigated as the function of composition and crystallization temperature. The isothermal growth rates of PCL spherulites decrease with increasing concentration of SAN. Because of the miscibility of PCL/SAN mixtures, the radial growth rates of the spherulites are described by a kinetic equation including the interaction parameter and the free energy for the formation of crystal nuclei. The interaction parameter obtained from the fitting of the kinetic equation with experimental data is in good agreement with that obtained from melting point depression. Folding surface free energies decrease with the increase of SAN concentration. In light of these results, it is suggested that, for the PCL/SAN mixtures, the noncrystallizable SAN polymer reduces the mobility of crystallizable PCL polymer so that the growth rates decrease with the increase of noncrystallizable component fraction.

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.

THE RING-BANDED SPHERULITE STRUCTURE OF POLY(EPSILON-CAPROLACTONE) IN ITS MISCIBLE MIXTURES WITH POLY(STYRENE-CO-ACRYLONITRILE)

The structure of the PCL spherulite in poly(epsilon-caprolactone)/poly(styrene-co-acrylonitrile) (PCL/SAN) blends was investigated by optical microscopy and small angle light scattering. The spherulite structure with a Maltese cross has been observed in pure PCL. Similar PCL/SAN blends exhibited not only spherulites with a Maltese cross, but also distinct extinction rings. The H(v) light scattering pattern especially caused diffraction rings in PCL/SAN blends but not in pure PCL. The spherical symmetry of spherulite PCL becomes more incomplete and the twist of the lamella becomes more irregular with increasing SAN content. It is found that the spherulite structure of PCL/SAN blends is dependent on the crystallization temperature and the concentration of SAN in PCL/SAN blends.

Preparation and Tribological Studies of Stearic Acid Self-Assembled Monolayers on Polymer-Coated Silicon Surface

We present a good alternative method to improve the tribological properties of polymer films by chemisorbing a long-chain monolayer on the functional polymer surface. Thus, a novel self-assembled monolayer is successfully prepared on a silicon substrate coated with amino-group-containing polyethyleneimine (PEI) by the chemical adsorption of stearic acid (STA) molecules. The formation and structure of the STA-PEI film are characterized by means of contact-angle measurement and ellipsometric thickness measurement, and of Fourier transformation infrared spectrometric and atomic force microscopic analyses. The micro- and macro-tribological properties of the STA-PEI film are investigated on an atomic force microscope (AFM) and a unidirectional tribometer, respectively. It has been found that the STA monolayer about 2.1-nm thick is produced on the PEI coating by the chemical reaction between the amino groups in the PEI and the carboxyl group in the STA molecules to form a covalent amide bond in the presence of N,N'-dicyclohexylcarbodiimide (DCCD) as a dehydrating regent. By introducing the STA monolayer, the hydrophilic PEI polymer surface becomes hydrophobic with a water contact angle to be about 105degrees. Study of the time dependence of the film formation shows that the adsorption of PEI is fast, whereas at least 24 h is needed to generate the saturated STA monolayer. Whereas the PEI coating has relatively high adhesion, friction, and poor anti-wear ability, the STA-PEI film possesses good adhesive resistance and high load-carrying capacity and anti-wear ability, which could be attributed to the chemical structure of the STA-PEI thin film. It is assumed that the hydrogen bonds between the molecules of the STA-PEI film act to stabilize the film and can be restored after breaking during sliding. Thus, the self-assembled STA-PEI thin film might find promising application in the lubrication of micro-electromechanical systems (MEMS).

The damage evaluation of rigid particle filled polymer

In this paper, the rigid particle filled polymer is studied in the hope to understand the real damage mechanisms. Two damage parameters were introduced and measured. One is the macro-damage of the materials calculated from the modulus measured, another is micro-damage describing the interfacial debonding or the percentage of the particle debonded from the matrix. The damage rate of the macro damage decreases, while the micro damage increases with the applied stress.

Deformation and Failure of Polymer Bonded Explosives under Diametric Compression Test

The tensile deformation and failure of polymer bonded explosives (PBXs), a particulate composite, is studied in this paper. Two HMX-based PBXs with different binder were selected for study. A diametric compression test, in which a disc-shaped specimen is loaded diametrically, was chosen to generate tensile failure in the materials. The quasi-static tensile properties and the tensile creep properties were studied by using conventional displacement transducers to measure the lateral strain along the horizontal diameter. The whole-field in-plane creep deformation was measured by using the technique of high resolution moire´ interferometry. Real time microscopic examination was conducted to monitor the process of deformation and failure of PBXs by using a scanning electron microscope equipped with a loading stage. A manifold method (MM) was used to simulate the deformation and failure of PBX samples under the diametric compression test, including the crack initiation, crack propagation and final cleavage fracture. The mechanisms of deformation and failure of PBXs under diametric compression were analyzed. The diametric compression test and the techniques developed in this research have proven to be applicable to the study of tensile properties of PBXs.

Designing Of Partial Similarity Models And Evaluation Method In Polymer Flooding Experiment

Based on the scaling criteria of polymer flooding reservoir obtained in our previous work in which the gravity and capillary forces, compressibility, non-Newtonian behavior, absorption, dispersion, and diffusion are considered, eight partial similarity models are designed. A new numerical approach of sensitivity analysis is suggested to quantify the dominance degree of relaxed dimensionless parameters for partial similarity model. The sensitivity factor quantifying the dominance degree of relaxed dimensionless parameter is defined. By solving the dimensionless governing equations including all dimensionless parameters, the sensitivity factor of each relaxed dimensionless parameter is calculated for each partial similarity model; thus, the dominance degree of the relaxed one is quantitatively determined. Based on the sensitivity analysis, the effect coefficient of partial similarity model is defined as the summation of product of sensitivity factor of relaxed dimensionless parameter and its relative relaxation quantity. The effect coefficient is used as a criterion to evaluate each partial similarity model. Then the partial similarity model with the smallest effect coefficient can be singled out to approximate to the prototype. Results show that the precision of partial similarity model is not only determined by the number of satisfied dimensionless parameters but also the relative relaxation quantity of the relaxed ones.