Ageing exploration of the energy landscape of a glass by the TSDC technique

Different thermal treatments were used in order to follow the structural relaxation of m-toluidine by thermally stimulated depolarization currents (TSDC) in the sub-T _g temperature region. In some of these thermal treatments, the ageing time, t _a, and the probing (or polarization) time, t _P, are varied independently in order to allow a clear understanding of the exploration of the energy landscape which occurs as a consequence of the structural relaxation. The TSDC results show that ageing induces a shift to higher temperatures of the TSDC peaks, in a way similar to that observed in the calorimetric heat capacity overshoot. More importantly, TSDC results show that ageing induces a decrease of the activation energies with regard to the window defined by the probing time and a sharpening of the energy distribution of the modes of motion that are present in the glass, in the studied sub-T _g temperature region.     

Temperature‐Sensitive Amorphous Polyurethanes

Abstract

Shape‐memory polymers based on segmental polyurethanes (PUs) were synthesized from 1,3‐butane diol (1,3‐BD), hexamethylene diisocyanate (HDI), and 4,4′‐diphenylmethane diisocyanate (MDI), and characterized in terms of thermomechanical, dynamic mechanical, rheological, and thermal properties. It was found that soft segments (1,3‐BD and HDI) and hard segments (1,3‐BD and MDI) were well phase mixed to give a single glass transition temperature (T _g) that was easily controlled by hard segment content. With the increase in hard segment content, T _g, melt viscosity, rubbery plateau, modulus, relaxation time, and shape recovery increased, and shape fixability for repeated cycles decreased.     

Temperature dependence of Bi2O3 structural parameters close to the α–δ phase transition

This article presents the results of in situ X-ray powder diffraction, Raman spectroscopy, and electrical impedance spectroscopy of the α-phase of Bi₂O₃, at 0.1 MPa in the temperature range below and above the α–δ-phase transition. This work demonstrated subtle nonlinear temperature variations of the cell parameters, of the hard-mode Raman shift, and of the activation energy of electrical conductivity in the temperature range about 100–120°C below the α–δ phase transition temperature T _Tr ≈ 725°C in Bi₂O₃. At T < 600°C, the linear variation of the inverse dielectric susceptibility (χ ^?1) correlates well with the hard mode frequency shift Δ(ω ²) of Raman A_1g mode as Δ(χ ^?1)/Δ(ω ²) ≈ 5.5 × 10^?7 cm². A structural model describing the mechanism of O^2? anion distribution and electric dipole disordering in the vicinity of T _Tr is discussed.     

Crystallization behaviour in a new multicomponent Ti16.6Zr16.6Hf16.6Ni20Cu20Al10 metallic glass developed by the equiatomic substitution technique

A new amorphous Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ alloy has been developed using the novel equiatomic substitution technique. Melt spinning Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ forms an amorphous phase with a large supercooled liquid region, ΔT=70°C. After isothermal annealing within the supercooled liquid region for 3 h at 470°C, the amorphous alloy crystallizes to form a fine-scale distribution of 2–5 nm nanocrystals, and the supercooled liquid region increases to ΔT=108°C. Atomic-scale compositional analysis of this partially crystalline material using a three-dimensional atom probe (3DAP) is unable to detect any compositional difference between the nanocrystals and the remaining amorphous phase. After annealing for 1 hr at 620°C, the amorphous alloy crystallizes to form 20–50nm equiaxed grains of a hexagonal-type C14 Laves phase with lattice parameters a = 5.2Å and c = 9.0 Å. 3DAP analysis shows that this Laves phase has a composition very close to that of the initial amorphous phase, suggesting that the alloy crystallizes via a polymorphic rather than a primary crystallization mechanism, despite the complexity of the alloy composition.     

Amorphous germanium II. Structural properties

The coherent X-ray scattering for momentum transfer, k, between 0·025 and 15·0 Å^?1 has been measured for a series of sputtered amorphous Ge films prepared at various substrate temperatures, T _s, between 0 and 350°C. Differences in the radial distribution function (RDF) of films of different T _s have been determined by an accurate differential scattering technique. The small angle scattering (SAS) of the films is less than 100 electron units for k < 1 Å^?1. From a combination of SAS, RDF and scanning electron microscope studies, it is concluded that an observed increase in film density with increasing T _s occurs through a reduction in the number of voids about 7 Å or less in diameter. No variation of bond length with T _s is found. With increasing T _s, there is an increase in first and second-neighbour coordination and a reduction in bond angle distortion.

The rate of change of coordination, C, with density, ρ₀, is found to be d ln C/d ln ρ₀ = 0·6±0·2. Using a new, general theory of the dependence of the RDF on the dihedral angle distribution, P(θ), it is shown that with increasing T _s there is an increased probability of dihedral angles corresponding to the staggered configuration. For all films, the experimental RDF between r = 4·5 and 6·2 Å agrees with a nearly random P(θ) distribution. Comparison of experimental RDF's of crystalline and amorphous Ge indicates the static distortion of the first-neighbour bond length has a standard deviation of only about 0·04 Å.     

Effects of gas temperature on optical and transport properties of a-Si:H films deposited by PECVD

Effects of silane temperature (T _g) before glow-discharge on the optical and transport properties of hydrogenated amorphous silicon (a-Si:H) thin films were investigated. The optical measurements show that the refractive index increases with increasing T _g. The transport characterizations show that when T _g increases, the dark conductivity increases. However, the temperature coefficient of resistance decreases. In addition, after holding at 130°C for 20 h, the resistance variation, ΔR/R, of the films deposited at T _g = room temperature (10.8%) is much larger than those deposited at silane temperatures of 80°C (3%) and 160°C (2%). This can be attributed to different rates of defect creation in a-Si:H films caused by various T _g.     

An apparent double glass transition in semicrystalline polymers

Thermal expansion and/or specific heat and/or dynamic mechanical loss data reveal the presence of two glass-like transitions in bulk crystallized polyethylene, polypropylene, polybutene-1, polypentene-1, cis-and trans-polyisoprene (natural), poly-4-methylpentene-1, isotactic polystyrene, poly(vinyl alcohol), nylon 6, the oxide polymers ?(CH₂)_nO?, with n = 1 to 4, polyethylene terephthalate, polyvinylidene fluoride, polyacrylonitrile, and polyvinylidene chloride. We designate the lower of these as T_g(L), which appears identical with the conventional T_g at zero crystallinity. The higher one, designated as T_g(U), is strongly increased with increasing levels of cystallinity. The differnece ΔT_g = T_g(U) ? T_g(L) tends to approach zero as the fractional crystallinity, X, approaches zero. For a X of 0.5 [Ptilde] 0.1, ΔT_g is about 50°C and T_g(U)/T_g(L) is about 1.2 with temperatures in °K. The increases in coefficient of thermal expansion, (Δα)_L and (Δα)_U, at these two transitions seem to depend on crystallinity and morphology in the expected manner for polyethylene and polypropylene: for × = 0.5–0.7, (Δα)_U is stronger than (Δα)_L; for X χ 0, (Δα)_L is stronger than (Δα)_U. Such data are not available for the other listed polymers. Some atactic polymers, poly-4-methylpentene-1, and polystyrene also seem to have a double T_g, the upper of which we tentatively ascribe to the presence of Geil-Yeh types of local order. Since polyethylene, polyvinylidene fluoride, and polyvinylidene chloride exhibit the apparent double T_g, tacticity, per se, is not necessary to produce it. Special care must be exercised to distinguish T_g(U) from the crystalline phase α_c relaxation occurring at temperature T_c. It is shown that T_c for well-annealed crystalline material tends to occur at about 0.83 to 0.85 T_M where T_M is the crystalline melting point in °K. Hence T_c is very close to the temperature at which rate of bulk crystallization is a maximum. While the phenomenon of a double T_g seems clear, its origin is in doubt. We suggest that T_g(L) and T_g(U) arise from tkie presence of different types of amorphous material. For example, polymer molecules not incorporated in the crystallites and/or cilia might give rise to T_g(L). Morphological entities under greater restraint, such as tie molecules or loose loops, might give rise to T_g(U). Conversely, pseudocrystalline structures (smectic or nematic) might be responsible for T_g(U), at least in polypropylene, poly-4-methylpentene-1, and possibly in some nylons.

Data available in the literature do not permit making a definite choice between different possible origins of the apparent double glass transition. Indeed, the origin may vary from polymer to polymer.     

电子型掺杂高温超导体La2-xCexCuO4飞秒时间分辨动力学研究

利用飞秒时间分辨光抽运探测技术研究了电子型掺杂La_2-xCe_xCuO₄(LCCO)高温超导材料的准粒子超快动力学过程.得到低温(T<0.7T_c)、转变温度附近(0.7T_c≤T≤T_c)和高温(T>T_c)三个温区内的动力学行为.研究发 关键词： 电子型掺杂高温超导体 飞秒时间分辨 准粒子 声子瓶颈     

Nuclear spin lattice relaxation and electric field gradient in liquid indium

We have measured the nuclear spin lattice relaxation time in liquid indium from 130°C to 300°C to be: 1/T ₁=(1.98 × 0.0082T) × 10³ sec^-1. The relaxation rate consists of two significant parts: (1/T ₁) _K from the nuclear magnetic hyperfine interaction, and (1/T ₁) _Q from the nuclear quadrupole interaction. We calculate (1/T ₁) _K from the the modified Korringa relation using a correction factor of order unity for electron-electron interactions. The hyperfine term is linear in T and accounts for the second term in 1/T ₁. Within experimental error the remaining rate, (1/T ₁) _Q , is temperature independent, and theoretically varies as the product of the square of the electric field gradient, q, and τ_c, a typical time between field gradient fluctuations. Making use of the x-ray RDF, we construct a simple model for liquid indium and calculate the ionic and electronic contributions, q _I and q _E, to the electric field gradient, to be q _I=1.4 × 10²⁴/cm³ and q _E=8.5 × 10²⁴/cm³. The calculation of q _E assumes covalent bonding between nearest neighbours. Taking q _I and q _E to be of opposite sign, we find that the correlation time τ_c is 1.6 × 10^-13 sec. When we further identify τ _c with the correlation time for diffusion in a three-dimensional random walk, we are able to calculate the r.m.s. jump distance, Δr _D, involved in self-diffusion, Δr _D=0.38 Å. This value is consistent with the x-ray peak width of 0.38 Å which we used earlier to calculate the electric field gradient.     

Scattering studies from polymer blends

An ultraquenching technique was used to prepare thin (ca. 1000 Å) amorphous films of polypivalolactone and poly(4-methyl-pentene-1). These films were characterized by electron microscopy, electron diffraction, and dynamic mechanical analysis. Other ultraquenched films of these polymers were crystallized by annealing for various times in the vicinity of their glass transition temperatures. Electron microscopy and electron diffraction were used to follow the reorganization of their structures.

Evidence for a double T_g in polypivalolactone (PPVL) was found, with crystallization of annealed, ultraquenched films occurring just above T_g (L) = 270°K. A T_g (U) = 340°K was noted. When the disordered glass was annealed above T_g (L), polypivalolactone crystallized into the a crystal form, which is composed of antiparallel chain segments, suggesting a chain-folded crystallization mechanism.

Poly(4-methyl-pentene-1) (P4MP1) gave evidence for T_g (L) = 220°K and T_g (U) = 325°K by dynamic mechanical analysis. However, morphology and electron diffraction showed that significant crystallization of ultraquenched polymer did not occur until T_g (U) was reached. X-ray data also supported this conclusion, which is explained by the lower density of the crystal phase of P4MP1 (compared to amorphous material) below 320°K. Long-term annealing of films at T_g (U) resulted in the formation of single-crystal structures, again indicative of a mechanism of chain-folded crystallization from the glass.     

Enthalpy Relaxation Study of Poly(Vinyl Chloride) Films Based on the Time-Temperature Superposition Principle

Abstract

In the enthalpy relaxation of poly(vinyl chloride), a decrease in enthalpy upon the isothermal ageing was measured using the differential scanning calorimetry method as a function of ageing time (t_A) and ageing temperature. The range of the ageing temperature was from 56?°C (T_g ? 25?°C) to 72?°C (T_g ? 9?°C) where T_g denotes the glass transition temperature. The limiting value of the decrease in enthalpy was determined by applying a stretched exponential function to the measured enthalpy data. The relaxation function (?) was derived from the measured enthalpy and the construction of a master curve was tried by shifting the ? ? t_A curves of the respective ageing temperatures horizontally. Although there was no agreement between the shift factors (a_T) and the relaxation times of the ? ? t_A curves, the superposition was successfully constructed and the a_T values obtained for the poly(vinyl chloride) sample were found to be comparable to those reported for viscoelastic experiments over a broad temperature range above and below T_g carried out for different polymers. The origin of the decrease in enthalpy was briefly discussed in terms of the chain dynamics in the isothermal condition.     

Dynamic light scattering in solid polymers

The viscosity of an amorphous polymeric solid above its glass transition [T _g (T,P)] increases as the temperature of the solid is decreased or the pressure is increased. Under changes in temperature or pressure, molecular subunits in the polymeric solid undergo configurational changes. Such changes or relaxations have a distribution of relaxation strengths and times. As the solid is cooled or as the hydrostatic pressure on the solid is increased, the relaxation strengths increase and the relaxation times increase. These changes in relaxation or dynamic properties are very dramatic as the empirical T _g is approached. Near T _g the polymeric solid is no longer in volume equilibrium; continued cooling or pressuring at a time rate faster than the average relaxation time will produce a polymeric glass. This glass is a nonequilibrium, amorphous solid. If the glass is held at a fixed temperature and pressure very close to, but below, T _g , the volume of the glass will be observed to relax to its equilibrium value. For temperatures and pressures well below T _g , equilibrium is a much more conjectural concept since the relaxation times become extremely long. It has been proposed^1,2 that there is a characteristic temperature T _g at which an amorphous polymer undergoes a second-order transition to an equilibrium glass with zero configurational entropy (i.e., a noncrystallizable solid).     

μ+SR in amorphous spin glasses Pd75Fe5Si20 and Pd75Fe5P20

The zero-field muon spin relaxation functionG _zz (t) has been measured as a function of reduced temperaturet=T/T _g in the amorphous metallic spin glasses Pd₇₅Fe₅Si₂₀ and Pd₇₅Fe₅P₂₀. The results are in qualitative agreement with earlier measurements on dilute alloy spin glasses, including an onset of static order belowT _g and a [t/(t-1)]² dependence of the correlation time τ_c aboveT _g. Both samples have the same τ_c (t) aboveT _g and almost identical static width Δ_S→Δ_o?43 μS^?1) asT»0, but thet-dependence of Δ_s nearT _g differs markedly.     

Amorphous linear polyethylene: Annealing effects

The effect of annealing amorphous linear polyethylene films prepared by an improved ultraquenching technique at temperatures just below and above a dynamic mechanical relaxation peak (torsion braid) observed at ∽190K has been characterized by electron microscopy and torsion braid analysis. Based on the results described, this peak is believed related to the lower glass transition temperature T_g(L), the T_g of wholly amorphous linear polyethylene, whereas the β peak at 260K is T_g (upper). Annealing just below T_g (L) results in a growth in size of the nodules observed in the as-quenched samples, whereas annealing above T_g (L) can result in the growth of single crystal-like structures, spherulites, and shish-kebobs. Storage of the crystallized samples at room temperatures results in a decrease in size of the relaxation peak during subsequent torsion braid spectroscopy measurements. The results indicate significant amounts of molecular motion can occur during crystallization even at T_g.     

非晶态As-Se二元系短程结构的EXAFS研究

用12kW转靶X射线衍射装置测定了非晶半导体a-As₂Se₃,a-AsSe以及a-As_0.05,Se_0.95的k吸收EXAFS,a-As₂Se₃经T≤T_g(玻璃转变温度)的不同温度处理后,亦进行了测定。由获得的径向结构函数分析表明:尽管a-As₂Se₃的短程结构与晶态c-As₂Se₃十分相似,但经过低于T_g的退火处理后,其径向结构函数发生了一定的变化。熔态淬火制备的a-As₂Se₃块体亦发生结构弛豫。此外,在非晶态As-Se二元系中随As含量的变化,材料的近程结构亦不同。 关键词：     

Calorimetric fragility of maltitol

The heat capacity of maltitol has been measured with an adiabatic calorimeter for the crystal from 100 K to 425 K (T _m = 420 K), for the glass from 249 K to T _g (around 311 K) and for the liquid from T _g to 400 K. The heat of melting is 55.068 kJ/mol. The calorimetric glass transition occurs at about T _g = 311 K with a sudden jump of the heat capacity ΔC _p (T _g ) of about 243.6 J/(K mol). The excess entropy between the undercooled liquid and the crystal was calculated from the heat capacity data and was used to estimate the Kauzmann temperature T _K which was found 50 K below T _g . ΔC _p (T _g ) and T _K for maltitol were compared to other compounds like sugars, polyol and hydrogen bonded liquids. It has been found that the glass former maltitol is a "fragile" liquid on the thermodynamic point of view.     

Physical aging in Zr46.75Ti8.25Cu7.5Ni10Be27.5 typical bulk metallic glass manifested as enthalpy relaxation

Enthalpy recovery is not only an important characteristic of physical aging of glass, but also a good tool to investigate the physical aging. Using differential scanning calorimeter (DSC), the enthalpy recovery of Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5 bulk metallic glass (BMG) was studied. The typical characteristics of enthalpy recovery of glass including the sub-T _g peak and ‘overshot’ were found in BMG. The evolution of the sub-T _g peak and ‘overshot’ were described by the free volume theory and Hodge’s model, respectively. It was found that the former failed to describe the enthalpy recovery in the BMG, while the latter could give a qualitative explanation. In combination with the dynamics in the BMG, the origin of the enthalpy recovery in the BMG was discussed. The results show that BMGs are an ideal material to investigate the physical aging. The further understanding of physical aging of BMGs is useful to clarify the nature of glass and improve the application and device of new types of BMGs. Supported by the National Natural Science Foundation of China (Grant No. 50671118)     

Effects of thermal and mechanical history on the viscoelastic properties of rigid poly(vinyl Chloride)

The effects of processing variables on the solid state properties of rigid PVC were studied by evaluating dynamic mechanical and tensile properties for thin film specimens of two different resins. The dynamic measurements were performed over the temperature range ?1]60 to 85°C, encompassing both the low temperature β transition and above ambient a transition (T_g). Engineering tensile strengths and energies to fracture were obtained at ambient conditions for several rates of elongation. Test specimens were prepared by solvent casting and compression molding techniques and subsequently were subjected to various thermal-mechanical histories. The results obtained were similar for both types of specimens and are described below. The various thermal histories considered include: (1) quick quenching from 225°C (samples referred to as “untreated”); (2) very slow (equilibrium) cooling after annealing at T_g; (3) quick quenching from T_g. In addition, the effects of frozen stresses were examined by systematically varying the stresses imposed on samples during the cooling processes 2 and 3. Increasing the load level imposed on specimens during equilibrium cooling resulted in enhancements of the β transition loss dispersion and tensile yield strength. Changes in loading during process 3, however, had little effect on the cooled specimens. But process 3 does alter the relaxation spectrum below T_g so that additional molecular relaxation is induced between T_β and T_α as much as 45°C below the a transition. The anomalous tan δ dispersions thus produced are accompanied by diminished tensile yield strengths and greatly increased energies to fracture. The most extreme case was encountered for the “untreated” specimens which were rapidly quenched from 225°C. The loss tangent data indicate remarkable differences in the region between T_β and T_α. When comparing the dynamic mechanical data with the fracture energy results for the same samples we note that increases in the intensity of the T < T_g anomalous dispersion correlate with increasing energies to fracture. On the other hand, the β transition intensity does not directly correlate. One molecular model which is consistent with these observations assumes that elongation induces a dilation of the polymer. Since most polymers possess Poisson ratios less than 0.5, the dilation will create extra internal volume (including free volume) in the polymer network. The increase in internal volume as elongation proceeds has the net effect of shifting the conditions of testing toward higher temperatures on a molecular relaxation scale permitting a higher level of molecular mobility at ambient conditions. As a sample continues to elongate one of two consequences is encountered: the imposed deformation cannot be accommodated by the available molecular mobility and the specimen fractures; or the deformation results in dilation to the extent that the response properties are shifted into a region of the relaxation spectrum where molecular mobility is sufficient for the specimen to accommodate the imposed deformation and yielding occurs. Yielding is expected if the effective temperature shifts as far as T_g before the sample fractures. In a case where there are additional molecular relaxation possibilities prior to the a transition, such as those in the anomalous dispersion region between T_β and T_α, sufficient dilation for yielding will be encountered before the normal T_g is reached. The anomalous T < T_g relaxation process thus tends to promote increased elongation and higher energies to fracture in PVC.     

Theoretical studies of the defect structures and spin Hamiltonian parameters for manganese(II) and nickel(II) doped Zn(en)3(NO3)2 single crystals

The spin Hamiltonian parameters (g factors, hyperfine structure constants and zero-field splittings D and E) and local structures for Mn²⁺ and Ni²⁺ in [Zn(en)₃](NO₃)₂ single crystal are theoretically investigated from the perturbation calculations for trigonally distorted 3d⁵ and trigonally (or orthorhombically) distorted 3d⁸ cluster. The trigonal Mn²⁺ and Ni²⁺ centres are found to undergo the moderate angular variations Δβ of 4.5° and 5.2°, respectively, related to host Zn²⁺ site due to size mismatch. The orthorhombic Ni²⁺ centre shows the relative axial elongation ratio ρ (≈ 2.5%) and the relative perpendicular bond length variation ratio τ (≈0.2%). For Mn²⁺ centre, the contributions to g-shifts Δg_CT (or hyperfine structure constants A_CT and zero-field splitting D_CT) from charge-transfer (CT) mechanism are opposite in sign and five times (or 5% and 8%) in magnitude compared with those from crystal-field (CF) mechanism. For the trigonal Ni²⁺ centre, Δg_CT (or D_CT) are the same (or opposite) in sign and 17% (or 2%) in magnitude related to those from CF mechanism. For the orthorhombic Ni²⁺ centre, Δg_CT and E_CT (or D_CT) are same (or opposite) in sign and 16% and 48% (or 442%) in magnitude with respect to those from the CF mechanism. The signs and magnitudes of the trigonal distortion angles δβ (≈ ?0.3 and 0.4°) related to an ideal octahedron and the local angular variations Δβ related to the host bond angle are suitably illustrated by those of the axial distortion degree (ADD) and the angular variation degree (AVD) of the systems, respectively.     

块体非晶合金的黏度与玻璃形成能力的关系

基于经典结晶理论讨论了非晶合金的晶化动力学因素和晶化热力学因素对玻璃形成能力（GFA）的影响.分析表明,合金的等温转变（TTT）曲线“鼻尖”温度T_n对应的黏度与晶化阻力因子成正比;重新加热时晶化开始温度T_x对应的黏度与晶化驱动力因子成反比.由此得到了新的GFA参数ω₀=（T_g-T₀）/（T_x-T₀）-（T_g-T₀）/（T_n-T₀）,其中T_g为玻璃转变温度,T₀为理想玻璃转变温度.统计结果显示,ω₀与临界冷却速率具有较高的相关性,R²高达09626.进一步分析表明：新提出的ω₀参数可以合理地解释过冷熔体的黏度、脆性、液相稳定性、热稳定性以及T_rg、ΔT_x、γ、γ_m、ΔT_rg、α、β、δ和φ等参数与GFA的关系. 关键词： 块体非晶合金 黏度 脆性 玻璃形成能力