Effect of nanoparticle dispersion on glass transition in thin films of polymer nanocomposites

We present spectroscopic ellipsometry measurements on thin films of polymer nanocomposites consisting of gold nanoparticles embedded in poly(styrene). The temperature dependence of thickness variation is used to estimate the glass transition temperature, T(g). In these thin films we find a significant dependence of T(g) on the nature of dispersion of the embedded nanoparticles. Our work thus highlights the crucial role played by the particle polymer interface morphology in determining the glass transition in particular and thermo-mechanical properties of such nanocomposite films.

Pressure Dependence of Glass Transition in As2Te3 Glass

Amorphous solids prepared from their melt state exhibit glass transition phenomenon upon heating. Viscosity, specific heat, and thermal expansion coefficient of the amorphous solids show rapid changes at the glass transition temperature (T-g). Generally, application of high pressure increases the T-g and this increase (a positive dT(g)/dP) has been understood adequately with free volume and entropy models which are purely thermodynamic in origin. In this study, the electrical resistivity of semiconducting As2Te3 glass at high pressures as a function of temperature has been measured in a Bridgman anvil apparatus. Electrical resistivity showed a pronounced change at T-g. The T-g estimated from the slope change in the resistivity-temperature plot shows a decreasing trend (negative dT(g)/dP). The dT(g)/dP was found to be -2.36 degrees C/kbar for a linear fit and -2.99 degrees C/kbar for a polynomial fit in the pressure range 1 bar to 9 kbar. Chalcogenide glasses like Se, As2Se3, and As30Se30Te40 show a positive dT(g)/dP which is very well understood in terms of the thermodynamic models. The negative dT(g)/dP (which is generally uncommon in liquids) observed for As2Te3 glass is against the predictions of the thermodynamic models. The Adam-Gibbs model of viscosity suggests a direct relationship between the isothermal pressure derivative of viscosity and the relaxational expansion coefficient. When the sign of the thermal expansion coefficient is negative, dT(g)/dP = Delta k/Delta alpha will be less than zero, which can result in a negative dT(g)/dP. In general, chalcogenides rich in tellurium show a negative thermal expansion coefficient (NTE) in the supercooled and stable liquid states. Hence, the negative dT(g)/dP observed in this study can be understood on the basis of the Adams-Gibbs model. An electronic model proposed by deNeufville and Rockstad finds a linear relation between T-g and the optical band gap (E-g for covalent semiconducting glasses when they are grouped according to their average coordination number. The electrical band gap (Delta E) of As2Te3 glass decreases with pressure. The optical and electrical band gaps are related as Delta E-g = 2 Delta E; thus, a negative dT(g)/dP is expected when As2Te3 glass is subjected to high pressures. In this sense, As2Te3 is a unique glass where its variation of T-g with pressure can be understood by both electronic and thermodynamic models.

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.

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.

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.

MOLECULAR-WEIGHT DEPENDENCE OF THE GLASS-TRANSITION OF CYCLIC POLYSTYRENE

The glass transition temperature (T(g)) of cyclic polystyrene was measured by differential scanning calorimetry. There was a marked difference in the glass transition behaviour between cyclic and linear polystyrene. In the low molecular weight region (M(n) < 5 x 10(3)), the T(g) of the cyclic polystyrene increased with decreasing M(n), contrary to that of linear polystyrene. With M(n) higher than 5 x 10(3), the T(g) of cyclic polystyrene increased with increasing M(n). The T(g) of cyclic and linear polystyrene approached the same constant value when the M(n) was high enough (M(n) > 10(5)). Combining the results of specific volume, it is believed that the variation of T(g) with molecular weight does not depend only on free volume effects but that configurational entropy is also an important factor.

Degradation of poly-L-lactide. Part2 : increased temperature accelerated degradation

Poly-L-lactide (PLLA) is one of the most significant members of a group of polymers regarded as bioresorbable. The degradation of PLLA proceeds through hydrolysis of the ester linkages in the polymer's backbone; however, the time for the complete resorption of orthopaedic devices manufactured from PLLA is known to be in excess of five years in a normal physiological environment. To evaluate the degradation of PLLA in an accelerated time period, PLLA pellets were processed by compression moulding into tensile test specimens, prior to being sterilized by ethylene oxide gas (EtO) and degraded in a phosphate-buffered solution (PBS) at both 50°C and 70°C. On retrieval, at predetermined time intervals, procedures were used to evaluate the material's molecular weight, crystallinity, mechanical strength, and thermal properties. The results from this study suggest that at both 50°C and 70°C, degradation proceeds by a very similar mechanism to that observed at 37°C in vitro and in vivo. The degradation models developed also confirmed the dependence of mass loss, melting temperature, and glass transition temperature (Tg) on the polymer's molecular weight throughout degradation. Although increased temperature appears to be a suitable method for accelerating the degradation of PLLA, relative to its physiological degradation rate, concerns still remain over the validity of testing above the polymer's Tg and the significance of autocatalysis at increased temperatures.

Effect of relaxation on pressure sensitivity index in a Zr-based metallic glass

Shear-banding features of as-cast and annealed Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass were investigated through Rockwell indentation tests. Isothermal annealing of the as-cast samples was conducted at temperatures below its glass transition temperature, Tg. The exothermal enthalpy during continuous heating below Tg decreases with increasing annealing temperature, indicating the gradual reduction of free-volume upon annealing. The observation on the morphology of shear-banding pattern around the indents implies a reduced shear bands activity in the annealed samples. The included angles (2θ) between two families of shear bands emanating from the edge of Rockwell indent decrease from 88° for the as-cast sample to 79° for the sample annealed at 633 K for 1 h, indicating a pressure sensitive plasticity. By Mohr–Coulomb criterion, the pressure sensitive index can be obtained on the basis of the measured 2θ, which increases with increasing annealing temperature, indicating an increase of “atomistic friction” due to the reduction of the free volume upon annealing.

Glass transition and free volume behaviour of poly(acrylonitrile)/LiCF3SO3 polymer-in-salt electrolytes compared to poly(ether urethane)/LiClO4 solid polymer electrolytes

Measurements of the glass transition temperature (T_g) and free volume behaviour of poly(acrylonitrile) (PAN) and PAN/lithium triflate (LiTf), with varying salt composition from 10 to 66 wt% LiTf, were made by positron annihilation lifetime spectroscopy (PALS). Addition of salt from 10 to 45 wt% LiTf resulted in an increase in the mean free volume cavity size at room temperature (r.t.) as measured by the orthoPositronium (oPs) pickoff lifetime, τ₃, with little change in relative concentration of free volume sites as measured by oPs pickoff intensity, I₃. The region from 45 to 66 wt% salt displayed no variation in relative free volume cavity size and concentration. This salt concentration range (45 wt%<[LiTf]<66 wt%) corresponds to a region of high ionic conductivity of order 10⁻⁵ to 10⁻⁶ S cm⁻¹ at T_g as measured by PALS. A percolation phenomenon is postulated to describe conduction in this composition region. Salt addition was shown to lower the T_g as measured by PALS; T_g was 115°C for PAN and 85°C for PAN/66 wt% LiTf. The T_g and free volume behaviour of this polymer-in-salt electrolyte (PISE) was compared to a poly(ether urethane)/LiClO₄ where the polymer is the major component, i.e. traditional solid polymer electrolyte (SPE). In contrast to the PISE, the T_g of the SPE was shown to increase with increasing salt concentration from 5.3 to 15.9 wt%. The relative free volume cavity size and concentration at r.t. were shown to decrease with increasing salt concentration. Ionic conductivity in this SPE was of order 10⁻⁵ S cm⁻¹ at r.t., which is over 60°C above T_g, 10⁻⁸ S cm⁻¹ at 25°C above T_g, and conductivity was not measurable at T_g.

Glass transition and degree of conversion of a light-cured orthodontic composite

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Collapse and Color Changes in Grapefruit Juice Powder as Affected by Water Activity, Glass Transition, and Addition of Carbohydrate Polymers

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Glass transition in DNA from molecular dynamics simulations.

Molecular dynamics simulations of the oligonucleotide duplex d(CGCGCG)2 in aqueous solution are used to investigate the glass transition phenomenon. The simulations were performed at temperatures in the 20 K to 340 K range. The mean square atomic fluctuations showed that the behavior of the oligonucleotide duplex was harmonic at low temperatures. A glass transition temperature at 223 K to 234 K was inferred for the oligonucleotide duplex, which is in agreement with experimental observations. The largest number of hydrogen bounds between the polar atoms of the oligonucleotide duplex and the water molecules was obtained at the glass transition temperature. With increasing temperature we observed a decrease in the average lifetime of the hydrogen bonds to water molecules.

The old problems of glass and the glass transition, and the many new twists.

In this paper I review the ways in which the glassy state is obtained both in nature and in materials science and highlight a "new twist"--the recent recognition of polymorphism within the glassy state. The formation of glass by continuous cooling (viscous slowdown) is then examined, the strong/fragile liquids classification is reviewed, and a new twist-the possibility that the slowdown is a result of an avoided critical point-is noted. The three canonical characteristics of relaxing liquids are correlated through the fragility. As a further new twist, the conversion of strong liquids to fragile liquids by pressure-induced coordination number increases is demonstrated. It is then shown that, for comparable systems, it is possible to have the same conversion accomplished via a first-order transition within the liquid state during quenching. This occurs in the systems in which "polyamorphism" (polymorphism in the glassy state) is observed, and the whole phenomenology is accounted for by Poole's bond-modified van der Waals model. The sudden loss of some liquid degrees of freedom through such weak first-order transitions is then related to the polyamorphic transition between native and denatured hydrated proteins, since the latter are also glass-forming systems--water-plasticized, hydrogen bond-cross-linked chain polymers (and single molecule glass formers). The circle is closed with a final new twist by noting that a short time scale phenomenon much studied by protein physicists-namely, the onset of a sharp change in d/dT ( is the Debye-Waller factor)--is general for glass-forming liquids, including computer-simulated strong and fragile ionic liquids, and is closely correlated with the experimental glass transition temperature. The latter thus originates in strong anharmonicity in certain components of the vibrational density of states, which permits the system to access the multiple minima of its configuration space. The connection between the anharmonicity in these modes, vibrational localization, the Kauzmann temperature, and the fragility of the liquid is proposed as the key problem in glass science.

Glass transition behaviour of fructose

The glass transition temperature and the second transition (the endothermic change between the glass transition and melting temperatures) of fructose were studied. The thermal history strongly affected both transitions of fructose. Storage for 10 days at 22degreesC increased the dynamic glass transition temperature from 16 to 25degreesC and decreased the second transition of fructose from 110 to 98degreesC in the first differential scanning calorimetric (DSC) scan. The amplitude of the second transition increased slightly with storage time and reached 260% of the first transition for vacuum oven dried samples. The effect of thermal history on the glass transition temperature of fructose can be removed by scanning the sample in a DSC to 130degreesC. The effects of water content, glucose and sucrose on the two transitions were also investigated.