金属玻璃Ni30Zr70的动态粘度和稳态粘度

本文测量了金属玻璃Ni₃₀Zr₇₀的动态粘度和稳态粘度,结果表明,由于结构弛豫的影响,动态粘度随升温速率的减小而线性增加,在玻璃转变温度T_g以下,动态粘度与温度的关系可以用Arrhenius方程进行描述,稳态粘度与温度的依赖关系满足Fulcher-Vogel方程。从4种不同升温速率的高温(结晶开始温度T_x)动态粘度值,给出金属玻璃Ni₃₀Zr₇₀的平衡粘度。在630—670K     

Kinetics of isothermal nucleation in a supercooled iron melt

An isothermal kinetic diagram for the beginning of homogeneous nucleation is constructed using the molecular-dynamics model of an instantaneously supercooled iron melt near the icosahedral percolation transition temperature identified with the glass transition temperature T _g . This diagram is compared with the theoretical one calculated using quantitative information obtained by analyzing the kinetics of the initial stage of growth of supercritical nuclei at temperatures higher than T _g . A satisfactory coincidence of the theoretical curve with computer simulation data at temperatures higher than T _g and substantial disagreement with these data below T _g , where crystallization is necessarily preceded by the formation of an icosahedral percolation cluster, demonstrate the substantive influence of an icosahedral substructure on the nucleation rate predicted by the classical theory.     

Temperature dependence of the fundamental absorption edge in CuGaSe2

The temperature dependence of the fundamental absorption edge in CuGaSe₂ single crystals was determined in the temperature range from 15 to 300 K. Above about 120 K the gap energy changes linearly with temperature with dE_g/dT = ? (2.1 ± 0.1) eV K^?1. The downshift in dE_g/dT of the I–III–VI₂ compounds compared to their II–VI analogs is discussed accounting for the p-d hybridization of the uppermost valence band.     

The magnetic field dependence of the structural transition temperature in La3S4 and La3Se4

The magnetic field dependence of the structural transition temperature T_m from the cubic to the tetragonal phase has been determined for single crystals of La₃S₄ and La₃Se₄. The observed field dependence of T_m can be accounted for by the band Jahn-Teller model of the coupling of an e_g-band to the shear mode of the cubic lattice without invoking any coupling to acoustic or optical phonons.     

Thermal Behaviors of Confined Triphenylmethyl Chloride Crystals in Various Molecular Weight Polystyrene

The thermal behaviors of polystyrene (PS)/triphenylmethyl chloride (TPCM) blends with different polymer molecular weights were investigated through differential scanning colorimetry (DSC). It was shown that when solvent content was lower than a critical composition, there was only a single amorphous phase in the blends. With increasing polymer concentration, both T_g and T_m could be detected in DSC curves, revealing that the blends were heterogeneous. The constant T_g of the amorphous phase indicated that the composition of the amorphous phase in the blends did not depend on the solvent concentration, and the T_m depression with decreasing PS content showed the decrease of TPCM crystallite size owing to geometric constraint by the polymer chains. On the basis of the Flory–Huggins theory, the interaction parameters between PS and TPCM in the blends were obtained; they showed that the PS/TPCM blends were not thermodynamically miscible with low polymer content. The Hoffmann-Weeks equation indicated that the crystals corresponding to the lower melting point were unstable. The unstable crystals in the blends were located in the interfacial regions between the crystalline solvent molecules and the amorphous phase. The heat capacity of the blends confirmed the geometric constraint on the crystallization of TPCM in the blends.     

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.     

Large‐Scale Fluctuation Behavior Prior to the Crystallization of Poly(ethylene terephthalate) Glass: A Small‐Angle Light Scattering Study

The crystallization processes of amorphous, glassy‐state poly(ethylene terephthalate) (PET) at two temperatures, a low temperature near T _g where PET has a slow crystallization speed and a middle temperature (about 55°C above T _g ) where PET crystallization is rapid, were monitored in situ by a time‐resolved small‐angle light scattering (SALS) device. It was found that large‐scale fluctuations happened prior to the crystallization at both temperatures, but the kind of fluctuation had a temperature dependence: at the middle temperature, pure density fluctuation took place during the induction period, whereas at low temperature, both density fluctuation and orientation fluctuation occurred, but the latter was the dominant factor. Analyses of the kinetics of these two kinds of fluctuation processes demonstrated that the spinodal decomposition (SD) type of phase‐separation character was undistinguishable in the SALS scale, while the nucleation‐growth (NG) type of phase behavior could describe the scattering results as well.     

Simulated glass-forming polymer melts: Glass transition temperature and elastic constants of the glassy state

By means of molecular-dynamics simulation we study a flexible and a semiflexible bead-spring model for a polymer melt on cooling through the glass transition. Results for the glass transition temperature T _g and for the elastic properties of the glassy state are presented. We find that T _g increases with chain length N and is for all N larger for the semiflexible model. The N dependence of T _g is compared to experimental results from the literature. Furthermore, we characterize the polymer glass below T _g via its elastic properties, i.e., via the Lamé coefficients λ and μ. The Lamé coefficients are determined from the fluctuation formalism which allows to split λ and μ into affine (Born term) and nonaffine (fluctuation term) contributions. We find that the fluctuation term represents a substantial correction to the Born term. Since the Born terms for λ and μ are identical, the fluctuation terms are responsible for the different temperature dependence of the Lamé coefficients. While λ decreases linearly on approaching T _g from below, the shear modulus μ displays a much stronger decrease near T _g. From the present simulation data it is not possible to decide whether μ takes a finite value at T _g, as would be expected from mode-coupling theory, or vanishes continuously, as suggested by recent work from replica theory.     

Viscosity of strong and fragile glass-forming liquids investigated by means of principal component analysis

The Vogel—Fulcher-Tammann-Hesse (VFTH) equation has been the most widespread tool for describing the temperature dependence with viscosity for strong, moderate and fragile glass-forming liquids. In this work, the VFTH equation was applied over a wide temperature range (between the glass transition temperature, T_g, and the melting point, T_m) for 38 oxide glasses, considering simple, binary and ternary compositions of silicate and borate systems. The Levenberg-Marquart non-linear fitting procedure was used to assess VFTH viscosity parameters B and T₀, maintaining A=−5 fixed (in Pa·s) to reduce the number of adjustable parameters. Regarding this restriction, the VFTH formula has shown to adjust very well to experimental data in a wide temperature range. Previous assertions revealed that there is statistical correlation between B and T₀. Principal component analysis (PCA) was used in the present study to verify the correlation between the B and T₀ parameters [J. F. Mano, E. Pereira, J. Phys. Chem. A 108 (2004) 10824], as well as between T_g and T_m. In brief, PCA is a mathematical method aimed at reorganizing information from data sets. The results have shown that it is possible to map either borate (and almost fragile) or silicate (usually strong up to near fragile) systems. As a statistical tool, PCA justifies the use of B, T₀ and T_g as the main parameters for the fragility indexes m=d(log₁₀η)/d(T_g/T)|_T=Tg and D=B/T₀, where η is the viscosity and T the absolute temperature.     

Melting and Recrystallization of Nylon-6,10 Thin Films

The melting and recrystallization of nylon-6,10 thin films immersed in an aqueous solution of calcium chloride were investigated by DSC measurements. The crystal length, ζ, was determined as a function of the melting peak temperature, T _m . The end surface free energy of nylon-6,10 crystals used for the ζ–T _m conversion was derived thermodynamically. For films of 0.01 mm thickness, the original length of ζ (=7.6 structural units) at T _m decreased step by step with increasing immersion time by the length near the structural unit (2.24 nm) per step. However, the suppression of the recrystallization after melting of the original crystals formed during the first cooling by the adsorbed calcium ions did not occur completely, even for films immersed for 30～60 min at 50°C.     

Temperature dependence of liquid viscosity

Least squares programs were used to evaluate the correlation between recent experimental results and theoretical, semi-theoretical, or empirical relations between liquid viscosity and temperature. It was found that none of these describes the experimental dependence in the whole range of temperature. A new dependence based on the free volume concept and cell-hole liquid theory is proposed. The theory permits linearization of the viscosity-temperature data in the range (T_i, T_i+1), where the T_i's are the liquid-liquid transition temperatures. It was demonstrated that these transitions, both in small molecular and in polymeric liquids, occur in discrete steps: T_i = a_iT_g, where T_g is the glass transition temperature and the a_i's are numerical parameters. Not all the transitions T_i were apparent in all liquids. Transition T₂ = 1.26T_g was observed for most polymeric liquids. On the basis of thermal analysis it was demonstrated that the T_i's coincide with the temperatures at which small changes in the apparent specific heat were detected. These temperatures can be assigned to the maximum rate of crystallization and melting temperatures of the metastable and stable crystalline forms.     

Effect of Alkyl Side Chain Length on Relaxation Behaviors in Poly(n-alkyl Acrylates) and Poly(n-alkyl Methacrylates)

Dynamic mechanical analysis (DMA) is used to investigate the effect of alkyl side chain length on the relaxation behavior of poly(n-alkyl acrylates) (PnAA) and poly(n-alkyl methacrylates) (PnAMA) above the glass transition temperature (T_g). Master curves and shift factors (log a_T) were obtained using the time–temperature superposition (TTS) principle. The log a_T curves of PnAA and PnAMA exhibit a dynamic crossover from one Vogel–Fulcher–Tammann–Hesse (VFTH) equation to another above T_g. The corresponding temperature was designated as the dynamic crossover temperature (T_c). It is found that T_c/T_g and the apparent activation energy (E_g) increases, e whereas the fragility index (m) decreases with increasing alkyl side chain length. Further analysis shows that m ∝ T_g, E_g∝ , and E_g∝ m² for both PnAA and PnAMA.     

Surface superconductivity and twinning-plane superconductivity in aluminum

The critical supercooling field H _sc is measured in aluminum single crystals and twinned bicrystals in a temperature range slightly below T _c0 (T _c0 ? 0.055 K < T < T _c0), where T _c0 is the critical superconducting transition temperature. It is found that, even in this small temperature range, the H _sc(H _c) dependence, which is considered to be identical to the H _c3(H _c) dependence for single crystals, is substantially nonlinear. The H _sc(H _c) dependences of the twinned bicrystals and single crystals are shown to be significantly different. The qualitative features of the phase diagram of the twinned aluminum bicrystals coincide with those of the phase diagram of twinning-plane superconductivity obtained earlier for tin in [1]. These findings allow the conclusion that the phenomenon of twinning-plane superconductivity also exists in face-centered cubic crystal lattices.     

Dependence on substrate bias of the effective mass and dingle temperature of electrons in the surface inversion layer of silicon

The amplitude of the quantum oscillations in the magnetoconductance of a silicon inversion layer has been studied as a function of gate voltage V_g, for different values of the temperature T, applied magnetic field strength H and substrate bias V_s. By analyzing the amplitude of the oscillations at fixed V_g and V_g as a function of T and H, the dependence of the cyclotron effective mass m¹ and the Dingle temperature T_D on V_g and V_s can be obtained. The dependence of m¹ on V_g for different values of V_s is compared with the prediction of theory.     

Anisotropy of the hopping conductivity in TlGaSe2 single crystals

The temperature dependences of the conductivities parallel and perpendicular to the layers in layered TlGaSe₂ single crystals are investigated in the temperature range from 10 K to 293 K. It is shown that hopping conduction with a variable hopping length among localized states near the Fermi level takes place in TlGaSe₂ single crystals in the low-temperature range, both along and across the layers. Hopping conduction along the layers begins to prevail over conduction in an allowed band only at very low temperatures (10–30 K), whereas hopping conduction across the layers is observed at fairly high temperatures (T?210 K) and spans a broader temperature range. The density of states near the Fermi level is determined, N _F=1.3×10¹⁹eV·cm³)^?1, along with the energy scatter of these states J=0.011 eV and the hopping lengths at various temperatures. The hopping length R along the layers of TlGaSe₂ single crystals increases from 130 Å to 170 Å as the temperature is lowered from 30 K to 10 K. The temperature dependence of the degree of anisotropy of the conductivity of TlGaSe₂ single crystals is investigated.     

The effect of Bi content on the thermal stability and crystallization of Se–Te chalcogenide glass

Glass formation and devitrification of intermediate alloys in the Se–Te–Bi system were studied by differential scanning calorimetry. A comparison of various simple quantitative methods to assess the level of stability of the glassy materials in the above-mentioned system is presented. All of these methods are based on characteristic temperatures, such as the glass transition temperature, T _g, the onset temperature of crystallization, T _in, the temperature corresponding to the maximum crystallization rate, T _p, or the melting temperature, T _m. In this work, a kinetic parameter, K _r(T), is added to the stability criteria. The thermal stability of several compositions of Se–Te–Bi was evaluated experimentally and correlated with the activation energies of crystallization by this kinetic criterion and compared with those evaluated by other criteria. All the results confirm that the thermal stability decreases with increasing Bi content in this glassy system. The crystallization results are analysed and the activation energy and mechanism of crystallization characterized.     

Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: Novel fluorescence measurements

Fluorescence intensity measurements of chromophore-doped or -labeled polymers have been used for the first time to determine the effects of decreasing film thickness on glass transition temperature, T _g, the relative strength of the glass transition, and the relative rate of physical aging below T _g in supported, ultrathin polymer films. The temperature dependence of fluorescence intensity measured in the glassy state of thin and ultrathin films of pyrene-doped polystyrene (PS), poly(isobutyl methacrylate) (PiBMA), and poly(2-vinylpyridine) (P2VP) differs from that in the rubbery state with a transition at T _g. Positive deviations from bulk T _g are observed in ultrathin PiBMA and P2VP films on silica substrates while substantial negative deviations from bulk T _g are observed in ultrathin PS films on silica substrates. The relative difference in the temperature dependences of fluorescence intensity in the rubbery and glassy states is usually reduced with decreasing film thickness, indicating that the strength of the glass transition is reduced in thinner films. The temperature dependence of fluorescence intensity also provides useful information on effects of processing history as well as on the degree of polymer-substrate interaction. In addition, when used as a polymer label, a mobility-sensitive rotor chromophore is demonstrated to be useful in measuring relative rates of physical aging in films as thin as 10 nm. Received 21 August 2001     

Optoelectronic effects in p-CdGeAs2 single crystals and structures based on them

Spectra of inelastic light scattering by optical phonons in p-CdGeAs₂ single crystals were obtained for the first time. The observed clear polarization dependence and the absence of any appreciable dependence of the intensity and frequency of the observed lines when the sample is swept in ≈300 μm steps indicates these CdGeAs₂ single crystals grown by directional crystallization from a near-stoichiometric flux, are of high quality and homogeneous. The type of symmetry of the observed phonon lines is interpreted and it is shown that the force constants in CdGeAs₂ and CdSnP₂ crystals differ slightly. Temperature dependences of the electrical conductivity and the Hall constant were studied in oriented homogeneous p-CdGeAs₂ single crystals. It was established that the conductivity of these crystals is determined by the deep acceptor level E _A=0.175 eV and has the degree of compensation 0.5–0.6. The temperature dependence of the Hall mobility reflects the competition between impurity and lattice mechanisms of hole scattering. The photosensitivity of In/CdGeAs₂ surface barrier structures reaches 20 μA/W at T=300 K and remains at this level within the fundamental absorption of CdGeAs₂. It is concluded that these structures may be used as wide-band photoconverters for natural light and as selective photoanalyzers for linearly polarized radiation. Fiz. Tverd. Tela (St. Petersburg) 40, 212–216 (February 1998)     

Investigation of phase transition mechanisms of CsH3(SeO3)2 single crystals by observation of nuclear magnetic resonance

The relaxation times of the ¹H and ¹³³Cs nuclei in CsH₃(SeO₃)₂ crystals were investigated using FT NMR. The ¹³³Cs spectrum does change from seven resonance lines to one resonance line near T_m (=350 K). The presence of only one ¹³³Cs signal is due to the liquid state resulting from the melting of the crystal. The variation in the separation of the ¹³³Cs resonance lines with temperature indicates that the EFG at the Cs sites produced by the (SeO₃)²⁻ groups varies with temperature, which in turn means that the atoms neighboring ¹³³Cs are displaced. And, the T₁ for ¹³³Cs is very long and undergoes significant changes near T_m. The change in the temperature dependence of T₁ at T_m for the ¹³³Cs nuclei coincides with the melting temperature. These results are compared with those obtained for MH₃(SeO₃)₂ (M=Na, K, and Cs) crystals.     

X-ray diffraction study of a structural phase transition in (NbSe4)3I

The second-order structural phase transition was observed by X-ray diffraction technique in (NbSe₄)₃I. The transition temperature (T_c) was 274.2 K. No evidence of the formation of the charge-density wave was found out. Temperature dependence of the intensity of (0,5,12) reflection obeys the Landau theory of the second kind of phase transition near T_c. Temperature dependence of the integral breadth of (0,0,12) reflection indicates the effect of the soft-phonon mode below T_c. The existence of the structural phase transition, probably not associated with charge-density-wave formation, suggests the unique nature of (NbSe₄)Z₃I in the new series of compounds (MSe₄)_xI (M=Nb, Ta).