Pressure-dependent glass-transition temperatures of poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) blends

The pressure-dependent glass-transition temperatures (T-g's) of poly(methyl methacrylate) (PMMA)/poly(styrene-co-acrylonitrile) (SAN) blends were determined by pressure-volume-temperature (PVT) dilatometry via an isobaric cooling procedure. The Gordon-Taylor and Fox equations were used to evaluate the relationships between the T-g's and compositions of the PMMA/SAN system at different pressures. The relationships were well fitted by the Gordon-Taylor equation, and the experimental data for T-g positively deviated from the values calculated with the Fox equation. Also, the influence of the cooling rate (during the PVT measurements) on T-g was examined.

The glass transition temperatures of PS/PPO blends: Couchman volume-based equation and its verification

The glass transition temperatures (T-g) of PS/PPO blends with different compositions were studied under various pressures by means of a PVT-100 analyzer. A general relation of T-g and pressure of the PS/PPO system was deduced by fitting the experimental T-g's. Couchman volume-based equation was testified with the aid of those data. It was found that the experimental T-g's do not obey the Couchman equation of glass transition temperature based on thermodynamic theory. According to our studies, the major reason of the deviation is caused by the neglect of DeltaV(mix). (C) 2001 Published by Elsevier Science Ltd.

Study on the two class glass transition and ion transport of a comb polymer electrolyte

The thermal behaviour and ion-transport properties of a comb polymer electrolyte CP350/LiSCN based on methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains were studied by means of DSC and ac impedance method. The two glass transition temperatures which can be attributed to side chains and main chains respectively were found to increase with increasing salt concentration. Conductivities which displayed non-Arrhenius behaviour were analyzed by using Vogel-Tammann-Fulcher equation and interpreted on the basis of the configurational entropy model derived by Gibbs and coworkers. The optimum ionic conductivity at 25 degrees C achieved was 2.19x10(-5)S/cm.

Glass transition and crystallization process of hard magnetic bulk Nd60Al10Fe20Co10 metallic glass

Glass transition and crystallization process of bulk Nd60Al10Fe20Co10 metallic glass were investigated by means of dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and scanning electronic microscopy (SEM). It is shown that the glass transition and onset crystallization temperature determined by DMTA at a heating rate of 0.167 K/s are 480 and 588 K respectively. The crystallization process of the metallic glass is concluded as follows: amorphous alpha-->alpha' + metastable FeNdAl novel phase -->alpha' + primary delta phase-->primary delta phase + eutectic delta phase Nd3Al phase + Nd3Co phase. The appearance of hard magnetism in this alloy is ascribed to the presence of amorphous phase with highly relaxed structure. The hard magnetism disappeared after the eutectic crystallization of amorphous phase.

Kinetics of Glass Transition and Crystallization in Carbon Nanotube Reinforced Mg-Cu-Gd Bulk Metallic Glass

Mg65 Cu25 Gdlo bulk metallic glass and its carbon nanotube reinforced composite were prepared. Differential scanning calorimeter (DSC) was used to investigate the kinetics of glass transition and crystallization processes. The influence of CNTs addition to the glass matrix on the glass transition and crystallization kinetics was studied. It is shown that the kinetic effect on glass transition and crystallization are preserved for both the monothetic glass and its glass composite. Adding CNTs in to the glass matrix reduces the influence of the heating rate on the crystallization process. In addition, the CNTs increase the energetic barrier for the glass transition. This results in the decrease of GFA . The mechanism of the GFA decrease was also discussed.

Stability of ZrTiCuNiBe Bulk Metallic Glass Upon Isothermal Annealing Near the Glass Transition Temperature

The stability of Zr41Ti14Cu12.5Ni10Be22.5 bulk metallic glass (BMG) upon isothermal annealing near the glass transition temperature has been investigated by using x-ray diffraction, differential scanning calorimetry, and the pulse echo overlap method. The density, elastic constants, and thermodynamic parameters as well as their annealing time dependence have been determined. The microstructural and properties changes of the annealed BMG were checked by acoustic measurement. Obvious structural and property changes were observed with prolonged annealing of the BMG near the glass transition temperature.

Glass Transition and Thermal Stability of Hard Magnetic Bulk NdAlFeCo Metallic Glass

Glass transition and thermal stability of bulk Nd60Al10Fe20Co10 metallic glass were investigated by means of dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The glass transition temperature, not revealed by DSC, is alternatively determined by DMTA via storage modulus E' and loss modulus E" measurement to be 498 K at a heating rate of 0.167 K s (-1). The calculated reduced glass transition temperature (T-g/T-m) is 0.63. The large value of T-g/T-m of this alloy is consistent with its good glass-forming ability. The crystallization process of the metallic glass is concluded as follows: amorphous --> amorphous + metastable FeNdAl phase --> amorphous + primary delta-FeNdAl phase --> primary delta-phase + eutectic delta-phase + Nd3Al + Nd3Co. The appearance of hard magnetism in this alloy is ascribed to the presence of amorphous phase with highly relaxed structure. The hard magnetism disappeared after the eutectic crystallization of the amorphous phase. (C) 2002 Elsevier Science B.V. All rights reserved.

Influence of intermolecular entanglements on the glass transition and structural relaxation behaviors of macromolecules. 2. Polystyrene and phenolphthalein poly(ether sulfone)

The effect of entanglements on the glass transition and structural relaxation behaviors has been studied for polystyrene (PS) and phenolphthalein poly(ether sulfone) (PES-C) samples by fast evaporation of the solution of concentrations varying from above the overlapping concentration to far below it, and compared to the results we have studied previously in PC. It has been found that for all the polymers we have studied, in the concentrated solution region, the T-g of the samples obtained from solution are independent of the change of concentration and are very close to that of normal bulk samples, whereas in the dilute solution region the T-g of the samples decrease with the logarithm of decreasing concentration. The critical concentrations that divide the two distinct regions for the three polymers are 0.9% g/mL for PC, 0.1% g/mL for PS, and 1% g/mL for PES-C. The decrease of T-g of the samples is interpreted by the decrease of intermolecular entanglements as the isolation of polymer chains, and the entanglement of polymer chains restrained the mobility of the segments. The structural relaxation behavior of the polymers is also found to be different from that of normal bulk samples. The enthalpies of single-chain samples are lower than that of the bulk ones, which correspond to the lower glass transition temperature; the peaks are lower and broader, and the relaxed enthalpy is much lower as compared to that of bulk samples. In the three polymers we have studied, the influence of change of entanglements on both the decrease in glass transition temperature and relaxed enthalpy is the most significant for PS and the least for PES-C. It is indicated that the interactions in the flexible polymers are weak; thus, the restraint of the entanglements on the mobility of the segments plays a more important role in the flexible polymers, and the change of entanglement in the flexible polymers has a more significant influence on the physical properties.

Influence of entanglements an the glass transition and structural relaxation behaviors of macromolecules. 1. Polycarbonate

We obtained the single-chain polycarbonate sample, by a new fast evaporation method and found that the polycarbonate sample obtained by this method is completely amorphous, while the polycarbonate sample obtained by other methods all have a certain degree of crystallinity. The glass transition temperature (T-g) of the sample decreases with the decreasing of concentration when the concentration of the prepared solution is below the critical value. The critical concentration we obtained from the T-g dependence of concentration is 0.9% g/mL and is in accord with that obtained by viscometry and light scattering methods directly from the solution. The structural relaxation behavior is found also different from that of a normal bulk sample of polycarbonate. The enthalpic peak of the single-chain sample is lower: than that of the bulk one, which corresponds to the lower glass transition temperature. The peak of the single-chain sample is lower and broader, and the relaxed enthalpy is much lower compared with that of the bulk sample. These results have been explained in terms of the effect of entanglement on the mobility of the segments in polymer and the compact conformation in the single-chain sample.

Phase transition temperatures of side chain liquid crystal polymer from molecular dynamics simulation

In this paper, phase transition temperatures of side chain liquid crystal polymer were predicted by molecular dynamics simulation. We analyzed the change of energy and the degree of similarity(S) with the temperature varying. The simulated phase transition temperatures agree with the experimental values in a proper deviation.

Effects of molecular weight and interaction parameter on the glass transition temperature of polystyrene mixtures and its blends with polystyrene/poly(2,6-dimethyl-p-phenylene oxide)

The glass transition temperature (T-g) of mixtures of polystyrene (PS) with different molecular weight and of blends of poly(2,6-dimethyl-p-phenylene oxide) (PPO) and polystyrene with different molecular weight (DMWPS) was studied by a DSC method. For the whole range of composition, the curves of T-g vs composition obtained by experiment were compared with predictions from the Fox, Gordon-Taylor, Couchman and Lu-Weiss, equations. It was found that the experimental results were not in agreement with those from the Fox, Gordon-TayIor and Couchman equations for the binary mixtures of DMWPS, where the interaction parameter chi was approximately zero. However, for the blends PPO/DMWPS (chi < 0), with an increase of molecular weight of PS, it was shown that the experimental results fitted well with those obtained from the Couchman, Gordon-Taylor and Fox equations, respectively. Furthermore, the Gordon-Taylor equation was nearly identical to the Lu-Weiss equation when \chi\ was not very large. Further, the dependence of the change of heat capacity associated with the glass transition (Delta C-p) on the molecular weight of PS was investigated and an empirical equation was presented. (C) 1997 Elsevier Science Ltd.

Studies on the two class glass transition and the typical VTF behaviour of an amorphous comb polymer electrolyte

A comb polymer (CP350) with oligo-oxyethylene side chains of the type -(CH2CH2O)(7)CH3 was prepared from methyl vinyl ether/maleic anhydride copolymer and poly(ethylene glycol) methyl ether. The polymer can dissolve LiNO3 salt to form homogeneous amorphous polymer electrolyte. This electrolyte system was first found to have two class glass transitions, and the two T(g)s were observed to increase with increasing salt content. The ionic conduction was measured by using the complex impedance method, and conductivities were investigated as functions of temperature and salt concentration. At 25 degrees C, the ionic conductivity maximum of this system can get to 3.72 X 10(-5) S/cm at the [Li]/ [EO] ratio of 0.057. The appearance of the conductivity maximum has been interpreted as being due to the effect of T-g and the so called physical crosslinks. The temperature dependence of the ionic conductivity displaying non-Arrhenius behaviour can be analyzed using the Vogel-Tammann-Fulcher equation and interpreted on the basis of the configurational entropy model.

Comblike polymer electrolyte with main chain glass transition near room temperature

A new amorphous comblike polymer (CBP) based on methylvinyl ether/maleic anhydride altering copolymer backbone and on oligooxyethylene side chain was synthesized. The dynamic mechanical properties of CBP and its Li salt complexes were investigated by means of DDV-11-EA type viscoelastic spectrometry. Results showed that there were two glass transitions (alpha-transition and beta-transition) in the temperature range from -100 to 100 degrees C. The beta-transition was assigned to oligo-PEO side chains and the temperature of beta-transition increases with increasing Li salt content. The alpha-transition was assigned to the main chain of CBP. The temperature of the alpha-transition (T-alpha) is also dependent upon the Li-salt content, but not monotonic. The value of T-alpha lies between 30-45 degrees C in the Li salt concentration range studied, near room temperature. It was found that the CBP-Li salt complexes showed an unusual dependence of ionic conductivity on Li salt content. There are two peaks in the plot of the ionic conductivity vs. Li salt concentration, which has been ascribed to the movability of the CBP main chain at ambient temperature. The temperature dependence bf the ionic conductivity indicated that the Arrhenius relationship was not obeyed, and the plot of log sigma against 1/(T - T-0) showed the unusual dual VTF behavior when using side chain glass transition temperature (T-beta) as T-0.

Study of semicrystalline-amorphous diblock copolymers .1. Microphase separation, glass transition and crystallization of tetrahydrofuran methyl methacrylate diblock copolymers

The microphase separation, glass transition and crystallization of two series of tetrahydrofuran-methyl methacrylate diblock copolymers (PTHF-b-PMMA), one with a given PTHF block of M(n) = 5100 and the other with a given PTHF block of (M) over bar(n) = 7000, were studied in this present work. In the case of solution-cast materials, the microphase separation of the copolymer takes place first, with crystallization then gradually starting in the formed PTHF microphase. The T-g of the PMMA microphase shows a strong dependence on the molecular weight of the PMMA block, while the T-g of the PTHF microphase shows a strong dependence on the copolymer composition. The non-isothermal crystallization temperature (T-c) of the diblock copolymer decreases rapidly and continuously with the increase in the amorphous PMMA weight fraction; the lowest T-c of the copolymer is ca. 35 K lower than the T-c of the PTHF homopolymer. There also exists a T-c dependence on the molecular weight of the PTHF block. In addition, when the major component of the copolymer is PMMA, a strong dependence of the crystallizability of the copolymer on the molecular weight of the PTHF block is observed; the higher the molecular weight, then the stronger its crystallizability. The melting temperature of the block copolymer is dependent on the copolymer composition and the molecular weight of its crystallizable block. Copyright (C) 1996 Elsevier Science Ltd.