新型Pr基大块非晶及其特性研究

用铜模吸铸法获得了直径为5mm的一种新的Pr基大块非晶.与以往其他稀土-过渡金属(RE-TM)大块非晶不同的是，这种新的Pr基大块非晶具有明显的玻璃转变和稳定的过冷液相区，且其玻璃转变温度在目前已知的大块非晶中是最低的，T_g=409K.研究了该大块非晶的玻璃转变动力学，并给出了Kauzmann温度T_k、Vogel-Fulcher温度T⁰_g及脆性参数m等重要参数. 关键词： 大块非晶 玻璃转变 脆性参数m     

Thermodynamical properties of Zr-based bulk metallic glasses

The temperature dependence of Gibb's free energy difference (ΔG), entropy difference (ΔS) and enthalpy difference (ΔH) between the undercooled melt and the corresponding equilibrium solid phases of bulk metallic glass (BMG) forming melts has been proved to be very useful in the study of their thermodynamical behavior. The present study is made by calculating ΔG, ΔS and ΔH in the entire temperature range T_m (melting temperature) to T_g (glass transition temperature) for three Zr-based samples of BMGs: Zr₅₇Cu_15.4Ni_12.6Al₁₀Nb₅, Zr_41.2Ti_13.8Ni₁₀Cu_12.5Be_22.5 and Zr_58.5Cu_15.6Ni_12.8Al_10.3Nb_2.8. The study is made on the basis of Taylor's series expansion and a comparative study is also performed between the present result and the result obtained in the framework of expansions proposed by earlier workers, and also with the experimental results. An attempt has also been made to study the glass forming ability for BMGs.     

Physical ageing in Se94Sn6 glass induced by gamma irradiation

A differential scanning calorimeter (DSC) has been used to monitor the influence of high-energy Co⁶⁰ gamma-irradiation on physical ageing in Se₉₆Sn₄ glass. It is observed that the relaxation process in the studied glass is slow after 1 and 3 years of natural storage, and can be highly accelerated by γ-irradiation. The glass transition temperature T_g and the endothermic peak area, which is directly related to the relaxation enthalpy Δh, were found to exhibit a remarkable change after irradiation and also during an additional natural storage for 6 months and 1 year of the irradiated Se₉₆Sn₄ glass. T_g value of γ-irradiated glass increases by 12 K; meanwhile, that of additional 6-months- and 1-year-stored glass T_g increases by 19 and 20 K in comparison to its counterpart of 1-year-aged non-irradiated sample. The same trend is also observed for Δh, which becomes 2.33, 3.61 and 3.65 times that of the 1-year-aged non-irradiated case, respectively, for γ-irradiated, additional 6-months- and 1-year-stored glass. These indications reveal that γ-irradiation activates the relaxation of the glass towards a state thermodynamically close to the equilibrium super-cooled liquid state.     

Long-Term Thermal Stability of Binary Cu50.3Zr49.7 Bulk Metallic Glass

We investigate the kinetics and thermal stability of a simple Cu50.3Zr49.7 binary bulk metallic glass （BMG）. The long-term thermal stability of CU50.3Zr49.7 BMG is evaluated by a newly developed method from an extension of Vogel- Fulcher-Tammann analysis. The method has been proven to be valid in CU50.3Zr49.7 or even other BMGs.     

Cu-Zr-Ti系Cu基块体非晶合金的形成和成分优化

利用与团簇相关的变电子浓度判据研究了过渡金属Cu-Zr-Ti系中Cu基块体非晶合金的形成区域和成分特征.据此判据在Cu-Zr-Ti系相图中确定出三条特殊的成分线，(Cu_9／13Zr_4／13)_100-xTi_x，(Cu_0.618Zr_0.382)_100-xTi_x和(Cu_0.56Zr_0.44)关键词： 块体非晶合金 Cu-Zr-Ti合金 原子团簇 电子浓度     

The glassy state of the amorphous V2O5–NiO–TeO2 samples

The glass transition temperature dependence to heating rate and therefore the activation energy (ΔH^?) of the glass transition of (60-x)V₂O₅–xNiO–40TeO₂ oxide glasses with 0≤x≤20 (in mol%) were investigated at heating rates φ (=3 6, 9, 10 and 12 K/min) using differential scanning calorimetry (DSC). The heating rate dependence of T_g was used to investigate the applicability of different theoretical models describing the glass transition. Using the application of Moynihan and Kissinger et al. models to the present data, different values of (ΔH^?) at each different heating-rate regions were obtained. The fragility parameter (m=ΔH^?/R T_g) was ∼24.98 for x=10 mol%, suggesting that this glass may be considered as a rather strong glass (fragility index m∼>20 is an indication of fragile glass). Also the compositional dependence of T_g and ΔH^? was investigated.     

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.     

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     

Large relative cooling power of Gd52.5Co16.5Al31 magnetic bulk metallic glass

The magnetocaloric effect and thermal stability have been investigated on the new bulk metallic glass (BMG) Gd_52.5Co_16.5Al₃₁ alloy. The extent of supercooled liquid region is 70 K, which is wider than that of any other Gd-Co-Al ternary BMGs. The magnetic entropy change (ΔS_M) and relative cooling power (RCP) of 9.8 J/kg K and 9.1×10² J/kg are obtained, respectively, under a field change of 5 T. The large ΔS_M and RCP values make Gd_52.5Co_16.5Al₃₁ BMG attractive potential candidate for the magnetic refrigeration application.     

Structural relaxation investigations of glassy polystyrene by radial distribution functions

The structural relaxation of an atactic polystyrene under sub-T _g annealing at 50°C and at 70°C was investigated by the radial distribution function (RDF) derived from its wide-angle x-ray scattering (WAXS). By recording the changes in RDF (i.e., ΔH(r), where r is the radial distance from an arbitrary reference atom) after it had been annealed for a certain period of days, and taking the integration of ΔAH(r) ²dr, we found that the atom density within structural domains in a size below 15 Å was changed dramatically, but that the tendency leveled off as annealing proceeded. However, the atom density outside the domains is barely changed by sub-T _g annealing. The size of the domain is similar to the statistical segment length reported in the literature. The behavior of the domains—that the segmental relaxation inside the domains in the initial sub-T _g annealing is unconstrained by their neighbors outside the domains—is also similar to the behavior of the statistical segments. The domains are believed to be composed of a statistical segment across the center, which has about 6 styrene repeat units, and 6 equal-distanced parallel segments tangent to the edge of the domain. On the other hand, as the annealing temperature is closer to the glass transition temperature, the frozen unstable chain segments reach equilibrium sooner and with less disturbance in their conformation.     

Influence of stress and temperature on damping behavior of amorphous Pd77.5Cu6.0Si16.5 below Tg

In this work we analyzed the mechanical damping behavior of amorphous Pd_77.5Cu_6.0Si_16.5 below the glass transition temperature (T _g) with creep/recovery measurements. Here a correlation between temperature stimulation and external stress is found in an exponential, multiplicative way. This demonstrates that not only is the yield stress of the material influenced by temperature variation (mechanical melting) but also the secondary relaxation is modified under stress and temperature.     

Effects of Fe doping on ac susceptibility of Pr0.75Na0.25MnO3

Ac susceptibility at low temperatures of Pr_0.75Na_0.25Mn_1-xFe_xO₃ (0 ≤ x ≤ 0.30) is investigated. The peak value of the real component of ac susceptibility χ' at the freezing temperature T_f is suppressed with the increasing frequency. The peak value of χ' shows a linear relation between T_f and the logarithm of the frequency ω. The normalized slope P = ΔT_f/T_fΔlgω, which is much lower than canonical insulating spin glass systems in which 0.06 ≤ P ≤ 0.08. The peak value of the imaginary component of the ac susceptibility χ' at T_f for the x = 0, 0.02, 0.30 samples increases with increasing frequency, suggesting a cluster glass ground state with a coexistence of charge-ordered phase and correlated ferromagnetic clusters in spin glass matrix. The peak value of χ' at T_f for the x = 0.10 sample decreases with increasing frequency, suggesting a phase separation ground state. The peak value of χ' at T_f for the x = 0.05 sample decreases with increasing frequency for ω ≤ 52 Hz and increases subsequently till 701 Hz, and then decreases with further increasing frequency for ω ≥ 1501 Hz. This complex behaviour is ascribed to the competition between the effects of large and little ferromagnetic clusters in the sample. The ground state of x = 0.05 sample is a transition state from cluster glass to phase separation.     

冲击加载下Zr51Ti5Ni10Cu25Al9金属玻璃的塑性行为

进行了10—27 GPa应力范围内Zr₅₁Ti₅Ni₁₀Cu₂₅Al₉金属玻璃的平面冲击实验以研究其高压-高应变率加载下的塑性行为.由样品自由面粒子速度剖面的分析获得了冲击加载过程的轴向应力,并通过轴向应力与静水压线的比较获得剪应力.实验结果表明,尽管存在明显的松弛效应,但Zr基金属玻璃的Hugoniot弹性极限随着冲击应力的增加而增加.然而,塑性波阵面上的剪应力则显示先硬化而后软化现象,而且软化的幅度随冲击应力的增加而增加.冲击加载下Zr基金属玻璃的上述剪应力变化特征与分子动力学模拟结果比较一致,但与压剪实验结果和一维应力冲击实验结果明显不同.     

Vortex pinning in YBa2Cu3O7?x films

Evidence that pinning on linear or planar defects dominates the vortex dynamics in YBa₂Cu₃O_7−x (YBCO) films is provided by complex impedance measurements at temperature 8 K<T<T _c and magnetic field 0<B<6 T. Below the vortex lattice melting transition B_g(T) but above a threshold field B_p≈8(1-T/T _c ) T, the inductance of vortices increases as B², much less rapidly than predicted for collective pinning of vortices by point defects. Above the vortex melting line, critical scaling persists over the region B_g(T<B<B^*(T) where the vortex correlation length ξ exceeds a characteristic length scale ξ^*≡ξ(B=B^*)≈450?. The value of ξ^* is not sensitive to Al-doping in the Cu sites in the lattice and is close to the size of twin domains in the film. The nature of the observed crossovers is discussed in terms of available theoretical models for a glass-liquid transition at B_g.     

DSC and elastic moduli studies on tellurite-vanadate glasses containing antimony oxide

xSb₂O₃-40TeO₂-(60 − x) V₂O₅ glasses with 0 ≤ x ≤ 10 (in mol%) have been prepared by rapid- melt quenching method. DSC curves of these ternary glasses have been investigated. The glass transition properties that have been measured and reported in this paper, include the glass transition temperature (T _g ), glass transition width (ΔT _g ), heat capacity change at glass transition (ΔC _P ) and fragility (F). Thermal stability, Poisson’s ratio, fragility and glass forming tendency of these glasses have been estimated, to determine relationship between chemical composition and the thermal stability or to interpret the structure of glass. In addition, Makishima and Makenzie’s theory was applied for determination of Young’s modulus, bulk modulus and shear modulus, indicating a strong relation between elastic properties and structure of glass. Generally, results of this work show that glass with x = 0 has the highest shear, bulk and Young’s moduli which make it as suitable candidate for the manufacture of strong glass fibers in technological applications; but it should be mentioned that glass with x = 8 has higher handling temperature and super resistance against thermal attack.     

Glass transition and dynamics of single and stacked thin films of poly(2-chlorostyrene)

The glass transition temperature and the dynamics of the α-process have been investigated using dielectric relaxation spectroscopy for single and stacked thin films of poly(2-chlorostyrene) (P2CS). The stacked film consists of 10 layers of single thin films with thickness of 12 nm or 18 nm. The glass transition temperature T _g of the single thin films of P2CS is found to decrease with decreasing film thickness in a similar way as observed for polystyrene thin films. The magnitude of the depression of T _g for the stacked thin films is larger than that of the single thin films with corresponding thickness. The depression of the temperature at which the dielectric loss shows a peak due to the α-process at a given frequency, T _α, is larger than that of the single thin films, although the magnitude is smaller than that of T _g . Annealing at a high temperature could cause the T _g and T _α of the stacked thin films to approach the values of the bulk system.     

Enthalpy recovery of a glass-forming liquid constrained in a nanoporous matrix: Negative pressure effects

The T _g of organic liquids confined to nanoporous matrices and that of thin polymer films can decrease dramatically from the bulk value. One possible explanation for this phenomenon is the development of hydrostatic tension during vitrification under confinement that results in a concomitant increase in the free volume. Here we present experimental evidence and modeling results for ortho-terphenyl (o-TP) confined in pores as small as 11.6 nm that indicate that, although there is an important hydrostatic tension in the liquid in the pores, it does not develop until near the reduced T _g of the constrained material --well below the bulk T _g. Enthalpy recovery for the o-TP in the nanopores exhibits accelerated physical aging relative to the bulk, as well as a leveling off of the fictive temperature at equilibrium values greater than the aging temperature. An adaptation of the structural recovery model that incorporates vitrification under isochoric conditions is able to provide a quantitative explanation for the apparently anomalous aging observed in nanopore confined liquids and in thin polymeric films. The results strongly support the existence of an intrinsic size effect as the cause of the reduced T _g. Received 3 September 2001     

Er3+/Yb3+共掺碲硼硅酸盐玻璃的光谱性质和热稳定性研究

制备了系列Er³⁺/Yb³⁺共掺碲硼硅酸盐玻璃样品(85-x)TeO₂-15B₂O₃-xSiO₂ (TBS x=0,5,10,15,20 mol%).测试和分析了样品的吸收光谱、荧光光谱、能级寿命、红外透射光谱及差热特性.并通过对Er³⁺离子⁴I_13/2→⁴I_15/2跃迁发射谱线的高斯拟合，设计了一个简单的四能级结构估算了Er³⁺离子⁴I_13/2和⁴I_15/2能级在碲硼硅酸盐中的Stark分裂情况.研究表明SiO₂的引入能有效地改善玻璃的热稳定性和光谱性能，玻璃析晶温度T_x与玻璃转变温度T_g之差(ΔT=T_x-T_g)可达178℃，说明碲硼硅酸盐是一种适合于光纤拉制的玻璃基质材料.比较了不同基质玻璃中Er³⁺离子的荧光半高宽和受激发射截面，结果表明TBS玻璃系统具有较好的带宽性能，是一种优良的宽带光纤放大器候选基质材料. 关键词： 碲硼硅酸盐 热稳定性 高斯拟合 -基')" href="#">OH^-基     

Icosahedral medium-range order formed in Mg70Zn30 metallic glass: a larger-scale molecular dynamics simulation

A larger-scale Mg70Zn30 alloy system including 100000 atoms has been simulated by using the molecular dynamics method to investigate the icosahedral medium-range order (IMRO) formed in the Mg70Zn30 metallic glass. It is found that the simulated pair distribution function of Mg70Zn30 metallic glass is in good agreement with the experimental results. The glass transition temperature Tg is near 450 K under the cooling rate of 1×1012 K/s. The icosahedral local structures play a critical role in the formation of metallic glass, and they are the dominant local configurations in the Mg70Zn30 metallic glass. The IMRO in the Mg70Zn30 metallic glass is characterized by certain types of extended icosahedral clusters combined by intercross-sharing atoms in the form of chains or dendrites. The size distributions of these IMRO clusters present a magic number sequence of 19, 23, 25, 27, 29, 31, 33, 35, 37, 39,. . . , and the magic clusters can be classified into three types according to their compactness. The IMRO clusters grow rapidly in a low-dimensional way with cooling, but this growth is limited near Tg.     

Evidence of an intermediate phase in ternary Ge<Subscript>7</Subscript>Se<Subscript>93-x</Subscript>Sb<Subscript>x</Subscript> glasses

The compositional dependence of thermal properties, such as glass transition temperature (T_g), non-reversing enthalpy change (ΔH_NR) and the specific heat capacity change (ΔC_p) of melt quenched Ge₇Se_93-xSb_x (21 ≤ x ≤ 31) glasses, has been studied using alternating differential scanning calorimetry (ADSC) which is analogous to modulated differential scanning calorimetry (MDSC). The glass transition temperature, T_g, which is a measure of global connectivity of the glass, has been found to increase with the addition of Sb. In addition, a change in slope has been observed in the composition dependence of T_g at an average coordination 〈r〉 = 2.40. The experimentally observed compositional variation of glass transition temperature, has been compared with the theoretical predictions from the stochastic agglomeration theory (SAT) and has been found to be consistent. Further, a narrow thermally reversing window is seen in the compositional variation of the relaxation enthalpy (ΔH_NR), which is centered around 〈r〉 = 2.40. The change in specific heat capacity (ΔC_p) at T_g is also found to exhibit a distinct minima at 〈r〉 = 2.40, suggesting that the structural rearrangements for the liquid in the glass transition region are minimized around 〈r〉 = 2.4.