金属玻璃形成液体的热力学特性

通过分析规则熔体的热力学模型，计算了典型金属玻璃的熔体混合焓ΔH^mix和混合熵ΔS^mix.结合临界冷却速率，归纳出典型金属玻璃形成液体的热力学特性,并提出基于原子尺寸、元素组成以及元素之间混合焓等参数的形成大块金属玻璃的成分判定方法.结果表明，当ΔH^mix<-15 kJ·mol^-1且ΔS^mix>0.6 J·K^-1mol^-1时，合金易于形成大块金属玻璃.金属玻璃的临界冷却速率R_c具有明显的尺寸效应，其值与熔体的ΔS^mix值呈指数关系，可以用R_c＝42.24×10⁴exp(-13.91ΔS^mix)+19.66粗略判断.运用该方法成功设计并制备出远离原有Zr基大块金属玻璃形成区域(55at%—65at%Zr)的Zr₄₀Al₁₀Ni₁₅Cu₃₅和四元Fe-B基Fe₅₃Co₅Nd₁₂B₃₀大块金属玻璃. 关键词： 混合焓 混合熵 大块金属玻璃 玻璃形成能力     

Stress relaxation and viscosity of a bulk Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> metallic glass under isochronous heating conditions

Isochronous relaxation of tensile stresses is measured in a bulk Pd₄₀Cu₃₀Ni₁₀P₂₀ metallic glass in the initial state and after certain thermal treatments. The results of measurements are used to find the energy spectrum of irreversible structural relaxation, from which the temperature dependence of shear viscosity is then calculated. This dependence is also found independently from measurements of creep in the same glass. The calculated viscosity is shown to agree well with the experimental data.     

Isothermal kinetics and relaxation recovery of high-frequency shear modulus in the course of structural relaxation of Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> bulk glass

Isothermal kinetics of relaxation of the high-frequency (1.4 MHz) shear modulus during structural relaxation of Pd₄₀Cu₃₀Ni₁₀P₂₀ bulk metallic glass below the glass transition temperature is studied by an in situ method of contactless electromagnetic acoustic transformation. The kinetic law of relaxation is established. It is shown that quenching of aged samples from the supercooled liquid state leads to a decrease in the absolute value of shear modulus to below the initial value; the degree of subsequent isothermal relaxation of the modulus may be several times higher than the initial value. Possible reasons for relaxation and recovery of the shear modulus are considered.     

1at％ Ag替代Zr57Cu20Al10Ni8Ti5金属玻璃中各组元对玻璃形成能力及热稳定性的作用分析

以1at％ Ag元素分别等量替代Zr57Cu20Al10Ni8Ti5金属玻璃的各个组元,利用差示扫描量热升温分析获得不同试样的热力学参数,并结合不同尺寸(Φ8,Φ10,Φ12)吸铸试样的X-射线衍射分析结果,考察、验证元素替代后合金的实际玻璃形成能力及热稳定性的变化规律.经比较发现,Ag替代Ti元素,其玻璃形成能力显著提高(直径实际增大4 mm),同时热稳定性也明显改善,且临界冷却速率也明显降低,而Ag替代其他组元却无明显规律.针对玻璃形成能力的相关数据比较分析表明,本文结果未显示符合其Inoue的尺寸准则,混合焓判据也未显示出明显符合的现象.通过对堆垛密度的计算发现,1 at％ Ag替代Ti元素后使金属玻璃体系内部的堆垛密度增加.通过动力学分析,从晶化激活能、晶化反应速率常数两方面探讨了元素替代对玻璃形成能力和热稳定性的作用机理.     

永磁性大块金属玻璃Nd60Al10Fe20Co10低 温磁性的研究

研究了Nd₆₀Al₁₀Fe₂₀Co₁₀ 大块金属玻璃 磁性随温度的变化关系，结果表明Nd₆₀Al₁₀Fe₂₀Co₁₀ 在室温下 表现为永磁性，随着温 度的降低，矫顽力和磁滞回线形状都有很大的变化.交流磁化率在18 K左右出现尖峰而且峰 值温度随频率变化，表明该大块非晶体系中存在自旋玻璃态. 关键词： 大块金属玻璃 低温磁化率 自旋玻璃     

Deformation behavior of Zr-based bulk metallic glass and composite in the supercooled liquid region

A Zr-based bulk metallic glass (BMG) with a composition of (Zr₇₅Cu₂₅)_78.5Ta₄Ni₁₀Al_7.5 and a bulk metallic glass matrix composite (BMGC) with a composition of (Zr₇₅Cu₂₅)_74.5Ta₈Ni₁₀Al_7.5 have been prepared by copper-mold casting. The compressive deformation behavior of the BMG and BMGC was investigated in the supercooled region at different temperatures and various strain rates ranging from 8×10⁻⁴ s⁻¹ to 8×10⁻² s⁻¹. It was found that both the strain rate and test temperature significantly affect the deformation behavior of the two alloys. The deformation follows Newtonian flow at low strain rates but non-Newtonian flow at high strain rates. The deformation mechanism for the two kinds of alloys was discussed in terms of the transition state theory. Supported by the National Natural Science Foundation of China (grant Nos. 50471060 and 50635020)     

Thermal equation of state of goethite (α-FeOOH)

ABSTRACT

The pressure–volume–temperature (P–V–T) equation of state (EoS) of natural goethite (α-FeOOH) has been determined by an X-ray diffraction study using synchrotron radiation. Fitting the volume data to the third-order Birch–Murnaghan EoS yielded an isothermal bulk modulus, B₀ of 85.9(15)?GPa, and a pressure derivative of the bulk modulus, B′, of 12.6(8). The temperature derivative of the bulk modulus, (?B/?T)_P, was –0.022(9)?GPa?K^?1. The thermal expansion coefficient α₀ was determined to be 4.0(5)?×?10^?5?K^?1.     

Low-temperature elastic experiments on glasses at very low frequencies

The Grüneisen parameter and the low-frequency elastic loss of vitreous silica, PMMA, and of the metallic glasses PdSiCu, PdZr, and CuZr have been measured between 0.4 K and 6 K using an elasto-caloric technique. The absorption measurements between 5·10^–3 Hz and 30 Hz give further support for the tunneling model in a hitherto poorly investigated domain of relaxation times. New features of the low-temperature behaviour of glasses are a long-time creep and an absorption peak of the metallic glass PdZr nearT _c.Dedicated to K. Dransfeld on the occasion of his 60th birthday     

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.     

Formation,thermal stability and mechanical properties of Ti<Subscript>42.5</Subscript>Zr<Subscript>7.5</Subscript>Cu<Subscript>40</Subscript>Ni<Subscript>5</Subscript>Sn<Subscript>5</Subscript> bulk metallic glass

Ti_42.5Zr_7.5Cu₄₀Ni₅Sn₅ bulk metallic glass with a critical diameter of 4 mm was fabricated by the conventional copper mould casting method. The supercooled liquid region ΔT _x, reduced glass transition temperature T _rg, γ parameter, and δ parameter of the alloy were measured to be 63.9 K, 0.561, 0.393, and 1.400, respectively, implying that the alloy has an excellent glass-forming ability. The bulk metallic glass exhibits high compressive fracture strength of 2162 MPa with distinct plastic strain of 0.9%. The fracture surface consists mainly of vein-like patterns, typical of bulk glassy alloys. Supported by the Program for New Century Excellent Talents in University of China and the National Natural Science Foundation of China (NSFC)(Grant No. 50771040)     

溶胶-凝胶法制备PbS量子点玻璃的研究

采用溶胶-凝胶法合成了半导体PbS量子点掺杂的Na₂O-B₂O₃-SiO₂玻璃,研究了不同热处理工艺对玻璃结构的影响,利用多种表征手段研究了量子点掺杂玻璃中的微晶结构及其光学性能.孔径分析结果表明随着热处理温度的升高玻璃内部孔径不断减小,最终孔结构几乎完全消失;红外光谱分析表明玻璃网络结构在较低温度下己经形成,随温度的升高不断密实化; X射线光电子能谱证明了玻璃中存在PbS,高分辨透射电镜表征了玻璃基质中掺杂的微晶结构是PbS,统计计算表明,玻璃中微晶的平均粒径尺寸为3.5nm;吸收光谱分析发现,微晶掺杂玻璃的吸收边界较PbS的块体材料发生了明显的蓝移,产生了量子尺寸效应;通过Z扫描技术测得其非线性折射率γ为-2.03×10^-14cm²/GW. 关键词： PbS量子点 半导体 非线性光学效应 溶胶-凝胶法     

Numerical study of pile-up in bulk metallic glass during spherical indentation

Pile-up around indenter is usually observed during instrumented indentation tests on bulk metallic glass. Neglecting the pile-up effect may lead to errors in evaluating hardness, Young’s modulus, stress-strain response, etc. Finite element analysis was employed to implement numerical simulation of spherical indentation tests on bulk metallic glass. A new model was proposed to describe the pile-up effect. By using this new model, the contact radius and hardness of Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass were obtained under several different indenter loads with pile-up, and the results agree well with the data generated by numerical simulation. Supported by the National Natural Science Foundation of China (Grant Nos 10725211, 10721202 and 10472119) and the Key Project of Chinese Academy of Sciences (Grant Nos KJCX2-YW-M04 and KJCX-SW-L08)     

Diffusion of titanium atoms in Ni-Si-B metallic glass

The diffusion ot Ti atoms in the Ni₇₇Si₃B₂₀ metallic glass was studied by the Auger electron spectroscopy. The temperature dependence of the diffusion coefficient obeys the Arrhenius relation with the activation energyE=1·7 eV and the pre-exponential factorD ₀=0·86 × ×10^–4 m² s^–1. Possible mechanisms of the atomic transport in metallic glasses are discussedThe authors wish to thank Dr. P. Duhaj for providing the metallic glass samples.     

Measuring surface and bulk relaxation in glassy polymers

We present a comprehensive study of gold nanoparticle embedding into polystyrene (PS) surfaces at temperatures ranging from T _g + 8 K to T _g − 83 K and times as long as 10⁵ minutes. This range in times and temperatures allows the first concurrent observation of and differentiation between surface and bulk behavior in the 20nm region nearest the free surface of the polymer film. Of particular importance is the temperature region near the bulk glass transition temperature where both surface and bulk processes can be measured. The results indicate that for the case of PS, enhanced surface mobility only exists at temperatures near or below the bulk T _g value. The surface relaxation times are only weakly temperature dependent and near T _g , the enhanced mobility extends less than 10nm into the bulk of the film. The results suggest that both the concept of a “surface glass transition” and the use of glass transition temperatures to measure local mobility near interfaces may not universally apply to all polymers. The results can also be used to make a quantitative connection to molecular dynamics simulations of polymer films and surfaces.     

Solutions for the T = 0 quantum spin glass transition in a metallic model with spin-charge coupling

We solve several low temperature problems of an infinite range metallic spin glass model. A compensation problem of T 0 divergencies is solved for the free energy which helped to extract the quantum critical behaviour of the spin glass order parameters as a function of δJ = J – J_c (T = 0). The critical value J_c(T = 0) = 3/16p_F^?1 of the frustrated spin coupling J, which separates spin glass from nonmagnetic (spin liquid) phase, is determined exactly in the static saddle point solution for a semielliptic metallic band model in terms of the density of states at the Fermi level. In addition to the replica-overlap order parameter 〈Q^ab〉, a ≠ b, the diagonal 〈Q^aa〉 is confirmed as order parameter by the result 〈Q^aa〉 _SP ～ (δJ)^β, β = 1, and its susceptibility χ^aaaa ～(-δJ)^?γ with γ = 1/2 at T = 0. The value for γ agrees with the one for the transverse field Ising spin glass. The low γ decay of 〈Q^aa〉, ～ T is obtained exactly in the whole quantum disordered phase including the critical value.     

Fe-B-Y-Nb bulk metallic glasses in relation to clusters

Bulk metallic glass formations in the Fe-B-Y-Nb quaternary alloy system were investigated by using the cluster line rule in combination with the minor alloying principle. The Fe-B-Y ternary system was selected as the basic system and the intersections of cluster lines were taken as the basic ternary compositions. The basic compositions were further alloyed with minor amounts of Nb. After 3–5 at.% Nb was added, the basic composition Fe_68.6B_25.7Y_5.7, which was developed from the most densely packed cluster Fe₈B₃, formed 3 mm bulk metallic glasses. These quaternary bulk metallic glasses (Fe_68.6B_25.7Y_5.7)_100−x Nb _x (x = 3–5 at.%) are expressed approximately with a unified simple composition formula: (Fe₈B₃)₁(Y, Nb)₁. The (Fe_68.6B_25.7Y_5.7)₉₇Nb₃ bulk metallic glass has the largest glass forming ability with the following characteristic parameters T _g = 907 K, T _x = 1006 K, T _g/T _l = 0.644, γ = 0.434, and longness t = 22 mm. The combination of the cluster line rule and the minor-alloying principle is a promising new route towards the quantitative composition design of multi-component metallic glasses. Supported by the National Natural Science Foundation of China (Grant Nos. 50671018, 50631010 and 50401020) and the National Basic Research Program of China (Grant No. 2007CB613902)     

Energy model for the Zr-based metallic glass alloy melt with clusters

An energy model for the melt of bulk metallic glass (BMG) with clusters was established, the Gibbs free energy and interfacial energy for the Zr-Al-Ni ternary alloy melt with Zr2Ni clusters were calculated, and the effects of the clusters on the Gibbs free energy, interfacial energy and nucleation rate were analyzed. The results showed that the existence of the clusters in the Zr-Al-Ni ternary alloy melt enables the Gibbs free energy to decrease in the composition range where bulk metallic glass forms easily, makes the interfacial energy increase and changes the distribution of the interfacial energy with the alloy composition. Because of the clusters in the melt, the Gibbs free energy of the Zr66Al8Ni26 alloy melt decreases about 0.3-1 kJ/mol and the interfacial energy between the melt and crystal nucleus increases about 0.016 J/m2. The nucleation rate of the undercooled Zr66Al8Ni26 alloy melt decreases evidently under the influence of the clusters on Gibbs free energy and the interfacial energy, and the maximum of the nucleation rate in the melt with the Zr2Ni clusters is only about 107 mol-1·s-1.     

High-pressure in-situ X-ray diffraction and Raman spectroscopy of Ca2AlFeO5 brownmillerite

The behavior of Ca₂AlFeO₅ brownmillerite was studied by in situ synchrotron X-ray diffraction and Raman spectroscopy at 300?K with pressures up to 26.5 and 32.1 GPa, respectively. A reversible structural phase transition was observed. The P–V data were fitted by a third-order Birch–Murnaghan equation of state, and the isothermal bulk modulus was obtained as K₀?=?181.9(76) GPa with K₀′_?=?4.4(17). If K₀′ was fixed to 4, K₀ was obtained as 183.8(20) GPa. Ca₂AlFeO₅ brownmillerite shows an axial elastic anisotropy since the b-axis is more compressible than a- and c-axis. Combined with previous results, the isothermal bulk modulus and axial compressibility of Ca₂AlFeO₅ brownmillerite increase with more Al incorporated in the structure. The Raman spectra of Ca₂AlFeO₅ brownmillerite were analyzed and the pressure coefficients vary from 2.23 to 4.90?cm^?1/GPa. The isothermal mode Grüneisen parameters range from 0.83 to 1.77 and the thermal Grüneisen parameter is determined as 1.08(11).     

Initial stages in the decay of the amorphous phase in the bulk metallic glass Zr-Cu-Ti

Using methods of x-ray diffraction analysis, differential scanning calorimetry, dilatometry, and transmission electron microscopy, we have investigated the initial stages of decay of the amorphous phase in a bulk metallic glass based on zirconium. We found that crystallization of the bulk metallic glass proceeds in several stages, where in the first stage the bulk conversion effect is equal to more than 1.6%, or about 80% of the total bulk crystallization effect. We showed that the first stage of decay of the amorphous phase in the bulk metallic glass Zr₂₉Ti₁₁Cu₆₀ leads to the formation of a nanocrystalline structure with a grain size of 1–5 nm. We have analyzed the change in the shape of the diffraction maximum during the formation of the very fine nanocrystalline structure. Fiz. Tverd. Tela (St. Petersburg) 41, 1129–1133 (July 1999)     

On the nature of the Kaiser effect in metallic glasses

The Kaiser effect was observed in the measurement of acoustic emission (AE) during the course of uniaxial compression of the bulk samples of metallic glasses Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 and Zr_52.5Ti₅Cu_17.9Ni_14.6Be_22.5. The field-ion microscopy study of bulk Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 shows that this glass has a polycluster structure. This fact allows one to reveal the nature of AE appearing during the course of deformation of metallic glasses and to interpret the observed Kaiser effect. The dislocations generated at the intercluster boundaries and moving through the glass bulk are the sources of AE.