纳米多晶体的热力学函数及其在相变热力学中的应用

以往关于纳米材料热力学的研究，绝大多数以界面的热力学函数表征整体纳米材料的热力学性质，这种近似处理，对于尺寸超过几十纳米的较粗纳米材料，在相变热力学中对特征转变温度和临界尺寸等重要参量的预测，将导致很大误差. 应用“界面膨胀模型”和普适状态方程，研究了纳米晶界的热力学特性，进一步发展了纳米晶整体材料热力学函数的计算模型，给出了单相纳米多晶体的焓、熵和吉布斯自由能随界面过剩体积、温度，以及晶粒尺寸发生变化的明确表达式. 以Co纳米晶为例，分析了界面与整体纳米多晶体热力学函数的差异，确定了相变温度与晶粒尺寸的依赖关系，以及一定温度下可能发生相变的临界尺寸. 关键词： 纳米多晶体 热力学函数 相变热力学     

亚稳相的纳米尺度稳定化:热力学模型与实验研究

建立了亚稳相合金的热力学模型,描述亚稳相的各种热力学物理量及其随成分、温度、晶粒尺寸等因素的变化.结合模型计算和系列实验,揭示了亚稳相的热力学性质、变化特征及其纳米尺度效应.以亚稳相SmCo₇合金为例,定量研究了亚稳相以单相形式稳定存在的条件及失稳发生的相分解行为.研究结果对亚稳相合金应用过程中相稳定性和相变的调控具有定量化指导意义.     

铁基非晶的低频脉冲磁场处理效应

对非晶合金Fe₇₈ Si₉ B₁₃进行了低频脉冲磁场处理，用穆斯堡尔谱学、透射电 镜等方法观察处理试样的微观结构变化.研究发现，当脉冲频率20—25Hz,磁场16—32kA/m,作用时间≤2min，合金发生了纳米晶化，纳米相岐睩e(Si)晶粒尺寸为10nm. 而且，在低频脉冲磁场处理过程中，非晶试样的温升≤20℃. 关键词： 非晶态合金 脉冲磁场处理 纳米晶化     

Fe-Cu-Si-B纳米晶合金的结构与性能

利用非晶晶化法制备了(Fe_0.99Cu_0.01)₇₈Si₉B₁₃纳米晶合金。发现其显微硬度H_v与晶粒尺寸d之间基本服从Hall-Petch关系。利用M?ssbauer谱研究了晶粒尺寸为30nm的材料中类金属原子的分布及其对晶化相电子结构的影响。 关键词：     

纳米尺度下Sm-Co合金体系中相组成与相稳定性的研究

建立了纳米晶合金相的热力学模型,可定量描述纳米尺度下合金体系中化合物相的热力学性质,并预测合金相的稳定性及其转变规律.利用该模型全面计算了纳米晶Sm-Co合金体系中各化合物相在不同晶粒尺寸下的摩尔吉布斯自由能随温度的变化关系,预测了纳米尺度下Sm-Co合金体系中各物相的相对稳定性及转变规律.模型预测结果示出,在室温附近,随着纳米晶粒尺寸的减小,某些纳米晶合金相的摩尔吉布斯自由能将由负值变为正值,预示着将向其他更稳定的纳米晶合金相转变,这是与传统粗晶材料中合金相的稳定性仅依赖于温度条件而完全不同的纳米晶合金 关键词： 纳米晶材料热力学 Sm-Co合金 相稳定性 相变     

晶体相场法模拟纳米晶材料反霍尔-佩奇效应的微观变形机理

采用晶体相场模型模拟获得了平均晶粒尺寸从11.61–31.32 nm的纳米晶组织, 研究了单向拉伸过程纳米晶组织的强化规律的微观变形机理. 模拟结果表明: 晶粒转动、晶界迁移等晶间变形行为是纳米晶材料的主要微观变形方式, 纳米晶尺寸减小, 有利于晶粒转动, 使屈服强度降低, 显示出反霍尔-佩奇效应.当纳米晶较小时, 变形量超过屈服点达到4%, 位错运动开启, 其对变形的直接贡献有限, 主要通过改变晶界结构而影响变形行为, 位错运动破坏三叉晶界, 引发晶界弯曲, 促进晶界迁移. 随纳米晶增大, 晶粒转动困难, 出现晶界锯齿化并发射位错的现象. 关键词： 晶体相场 纳米晶 反霍尔-佩奇效应 微观变形     

铁基纳米晶合金介观结构的等效RLC并联模型

根据实验研究成果提出纳米晶合金软磁性能受其介观结构影响的观点，建立了Fe基纳米晶合金的球状介观结构模型，分别求出只有交变磁场或交变磁场和静磁场作用时纳米晶粒球的频率函数——D函数.分析表明，两种D函数都是复变函数，其实部Re(D)为纳米晶电感性质和电容性质的反映，虚部Im(D)为纳米晶电阻性质的反映，据此建立了Fe基纳米晶合金介观结构的等效RLC并联模型.由该模型求得合金产生极值巨磁电阻的条件为v_extGMI=v|_Re(D)=0，决定因素有μ,σ,ω,R和H_ex及微观磁结构. 关键词： Fe基纳米晶合金 等效RLC并联模型 球状介观结构模型 频率函数     

晶粒易轴取向度对纳米晶永磁Pr2Fe14B磁性的影响

构造了立方和不规则形状晶粒的各向异性纳米晶单相Pr₂Fe₁₄B磁体 .利用微磁学的有限元法，模拟计算了样品的磁滞回线.计算结果表明，随着磁体晶粒易轴取向度的变差， 磁体的剩磁、矫顽力均随之下降.不同晶粒尺寸的纳米晶单相Pr₂Fe_{14B磁体，其磁 性能随取向度的变化快慢不同，原因在于磁体中的晶间交换作用 (IGEC) 的强弱不同.随着 晶粒取向度的提高，纳米晶单相磁体的矫顽力逐渐增加，这完全不同于烧结磁体. 关键词： 纳米晶磁体 矫顽力 剩磁}     

Fe基纳米晶合金晶粒尺寸反常变化的物理机制

晶粒尺寸在很大程度上决定了Fe基纳米晶合金的磁学性能,其随退火温度变化的物理机理是纳米晶领域重要的研究内容.研究了初始晶化温度与二次晶化温度之间退火1 h Fe基纳米晶合金晶粒尺寸随退火温度的变化,并建立了相应的模型.利用提出的模型分析了该温度范围内Fe基纳米晶合金晶粒尺寸随退火温度升高先减小后增大的物理机制. 研究发现,在初始晶化温度与二次晶化温度之间等时退火,当退火温度约为Fe基纳米晶合金熔点的0.6倍时其晶粒尺寸最小.在研究的温度区间内,理论研究结果与实验符合得较好. 本研究提供了一种快速获得小晶粒尺寸纳米晶合金的方法.     

频率对纳米晶软磁合金磁性能影响的理论解释

根据原子力显微镜（AFM）对Fe基纳米晶Fe_735Cu₁Nb_{3< /sub>Si135B9合金薄带的介观结构的研究结果，提出了解释纳米晶软磁合金磁性能的理论模型——柱、球混合模型，并成功地解释了频率对纳米晶软磁合金磁性能的影响，所得理论体现了Herzer理论和纪松理论的特点，并弥补了它们的不足，同时提出了纳米晶粒电导率σ、磁导率μ对合金磁性有影响的观点. 关键词： 铁基纳米晶合金 模型 频率 软磁性能}     

Highly anisotropic resin-bonded magnets processed with surfactant-coated SmCo5 nanocrystalline powders

Highly anisotropic SmCo₅ nanocrystalline powders with grain size in the range 5-20 nm were processed through surfactant and magnetic field-assisted milling. The SmCo₅ nanocrystalline powders so obtained by this method possess unusual characteristics such as reduction in particle size, platelet-structure and high remanence values. A possible mechanism for achieving remanence enhancement with the surfactant-coated SmCo₅ powders has been discussed. Besides, the resin-bonded magnets processed with the surfactant-coated SmCo₅ powders showed relatively higher density, induction remanence and energy product with strong anisotropic behavior than those of the magnets processed with the conventionally milled SmCo₅ powders. Maximum values of H_ci (16 kOe), B_r (4.66 kG) and (BH)_max (5.5 MG Oe) were achieved for the resin-bonded magnets processed with the surfactant-coated powders.     

Quantification of MgO surface excess on the SnO2 nanoparticles and relationship with nanostability and growth

In this work, we experimentally showed that the spontaneous segregation of MgO as surface excess in MgO doped SnO₂ nanoparticles plays an important role in the system's energetics and stability. Using X-ray fluorescence in specially treated samples, we quantitatively determined the fraction of MgO forming surface excess when doping SnO₂ with several different concentrations and established a relationship between this amount and the surface energy of the nanoparticles using the Gibbs approach. We concluded that the amount of Mg ions on the surface was directly related to the nanoparticles total free energy, in a sense that the dopant will always spontaneously distribute itself to minimize it if enough diffusion is provided. Because we were dealing with nanosized particles, the effect of MgO on the surface was particularly important and has a direct effect on the equilibrium particle size (nanoparticle stability), such that the lower the surface energy is, the smaller the particle sizes are, evidencing and quantifying the thermodynamic basis of using additives to control SnO₂ nanoparticles stability.     

Effect of cooperative nanograin boundary sliding and migration on dislocation emission from a blunt nanocrack tip in nanocrystalline materials

Theoretical model is suggested that describes the effects of the cooperative nanograin boundary sliding and stress-driven nanograin boundary migration (CNGBSM) process on the lattice dislocation emission from an elliptically blunt nanocrack tip in deformed nanocrystalline materials. Within the model, CNGBSM deformation near the tip of growing nanocrack carries plastic flow, produces two dipoles of disclination defects and creates high local stresses in nanocrystalline materials. By using the complex variable method, the complex form expression of dislocation force is derived, and critical stress intensity factors for the first lattice dislocation emission are obtained under mode I and mode II loading conditions, respectively. The combined effects of the geometric features and strengths of CNGBSM deformation, nanocrack blunting and length on critical SIFs for dislocation emission depend upon nanograin size and material parameters in a typical situation where nanocrack blunting and growth processes are controlled by dislocation emission from nanocrack tips. It is theoretically shown that the cooperative CNGBSM deformation and nanocrack blunting have great influence on dislocation emission from blunt nanocrack tip.     

Effect of grain size dispersion on the strength and plasticity of nanocrystalline metals

The effect of the dispersion of the grain size distribution on the yield stress, ultimate stress, and uniform strain of nanocrystalline metals is analyzed theoretically. It is shown that, as the grain size dispersion increases, the degree of grain boundary hardening (Hall-Petch effect) of nanocrystalline materials decreases, the onset of the grain boundary softening (inverse Hall-Petch effect) shifts to smaller nanograin sizes, and the uniform strain at which necking occurs increases.     

Microstructural evolution and thermal stability of Fe–Zr metastable alloys developed by mechanical alloying followed by annealing

The effect of Zr (up to 1 at.%) addition on the formation of Fe–Zr metastable alloys and their thermal stability were investigated for their possible nuclear applications. Fe–xZr (x = 0.25, 0.5, 1%) alloys were synthesised by mechanical alloying under a high-purity argon atmosphere using stainless steel grinding media in a SPEX 8000M high energy mill. The milling was conducted for 20 h with a ball-to-powder weight ratio of 10:1. The formation of metastable solid solutions after milling was confirmed from the change in the Gibbs free energy analysis as per Miedema’s model. The microstructural characterisation was carried out by analysis of X-ray diffraction, atomic force microscopy and transmission electron microscopy. The effect of Zr on the thermal stability of Fe–Zr alloys was investigated by extensive annealing experiments followed by microstructural analysis and microhardness measurements. The stabilisation was found to occur at 800 °C and thereafter, no significant change in the crystallite size was observed for the samples annealed between 800 and 1200 °C. The supersaturated solid solution, especially 1% Zr alloy, found to be highly stable up to 800 °C and the microhardness value of the same measured to be as high as 8.8 GPa corresponding to a crystallite size of 57 nm. The stabilisation effect has been discussed in the light of both the thermodynamic and kinetic mechanisms and the grain size stabilisation is attributed to the grain boundary segregation of Zr atoms and/or Zener pinning by nanoscale precipitation of the Fe₂Zr phase.     

Resistance of nanocrystalline vis-à-vis microcrystalline Fe–Cr alloys to environmental degradation and challenges to their synthesis

This paper presents a hypothesis and its experimental validation that a nanostructure can bring about dramatic improvements in the oxidation/corrosion resistance of iron–chromium alloys. More specifically, a nanocrystalline Fe–10 wt% Cr alloy was found to undergo oxidation at a rate that was an order of magnitude lower than its microcrystalline counterpart. Importantly, the oxidation resistance of nanocrystalline Fe–10 wt% Cr alloy was comparable with that of the common corrosion-resistant microcrystalline stainless steels (having 18–20 wt% chromium). The findings have the potential of leading to the next generation of oxidation-resistant alloys. However, due to poor thermal stability of nanocrystalline structure, synthesis/processing of such alloys is a challenge. Discs of nanocrystalline Fe–10% Cr alloy were produced by ball-milling of Fe and Cr powders and compaction of the powder without considerable grain growth by processing within a suitable time–temperature window. The paper also presents a theoretical treatise to arrive at the minimum chromium content required for establishing a protective layer of chromium oxide in an Fe–Cr alloy of a given nanometric grain size.     

Grain growth process of two-phase nanocrystalline soft magnetic materials

In order to clarify the origin of the high thermal stability of the microstructure in bcc-Fe/amorphous two-phase nanocrystalline soft magnetic materials, we have investigated the changes in the magnetic and microstructural properties upon isothermal annealing at 898 K for an Fe₈₉Zr₇B₃Cu₁ alloy by means of transmission electron microscopy, Mössbauer spectroscopy and DC magnetometry. The mean grain size was found to remain almost unchanged at the early stage of annealing. However, rapid grain coarsening was evident at an annealing time of 7.2 ks where the intergranular amorphous phase begins to crystallize into Fe₂₃Zr₆. The grain growth process with a kinetic exponent of 1.6 is observed for the growth process beyond this annealing time, reflecting the disappearance of the intergranular amorphous phase. Our results confirm that the thermal stability of the bcc-Fe/amorphous two-phase nanocrystalline soft magnetic alloys is governed by the residual amorphous phase.     

Estimation of critical grain size at different temperatures and thermodynamic stability of γ→α in NC Fe by QDA and EOS methods

Thermodynamic properties of Nanocrystalline (NC) materials are essentially different from the conventional coarse-grained materials (with the same chemical composition). The role of grain boundary is very important in the characterization of thermodynamic functions and thermal properties of NC materials when the grain size is less than 100 nm. Therefore, the traditional thermodynamics being applied for coarse-grained materials is not applicable for NC materials. In this study, Quasiharmonic Debye Approximation (QDA) and Equation of State (EOS) methods are used to calculate the Gibbs free energy in NC Fe. Since the Gibbs free energy for Fe, predicted by EOS and QDA methods, is inaccurate (especially at temperatures higher than the ambient temperature), a term called as ΔG^Excess is proposed to modify the results. Thus, the Modified QDA (MQDA) and Modified EOS (MEOS) methods are introduced for this purpose. Thereafter, the change in the Gibbs free energy for γ-Fe to α-Fe phase transformation (ΔG^γ→α) via the grain size is calculated by MQDA and MEOS methods. The results obtained by the two methods are also compared and discussed. Finally, the critical grain size, at which ΔG^γ→α=0, can be estimated at different temperatures, is found to increase with increasing temperature.