Mechancial properties of amorphous alloys: In the framework of the microstructure heterogeneity
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摘要: 非晶合金弛豫/晶化、玻璃转变、塑性变形等热力学和动力学行为都与其固有的结构非均匀性密切相关. 但是, 由于淹没在亚稳的长程无序结构中, 探究非晶合金的结构非均匀性十分困难. 尤其, 非晶合金微观结构非均匀性与其力学性能之间的本征关联是一个亟待解决的重要科学问题. 本文基于多尺度时空下的力学激励阐述非晶合金微观结构非均匀性特征与演化规律. 从实验、理论和数值模拟方面出发, 梳理了非晶合金微观结构非均匀性与弛豫机制和力学行为之间的关联. 最后, 针对非晶合金微观结构非均匀性与其物理/力学性能研究的方向提出了建议和展望.Abstract: The intrinsic structural heterogeneities of amorphous alloys are closely related to the thermodynamics and dynamical behavior, such as relaxation/crystallization, glass transition phenomenon and plastic deformation. However, the structural information is submerged into the meta-stable disordered long-range structure, which made it very difficult to explore the structural heterogeneities of amorphous alloys. Specificlly, the correlation between the microstructural heterogeneity and mechanical properties of amorphous alloys is one of important scientific issues. The current paper reviews the structural heterogeneity of dynamics into the amorphous alloys from the time-scale point of view and inspected the relaxation of structure with various spatial scales. From the perspective of experimental results, theoretical analysis and numerical simulations, the correlation between heterogeneous structure and the dynamic relaxations, deformation mechanisms, mechanical properties and dynamic characteristics were discussed. Finally, we discuss the further development of structural heterogeneity of amorphous alloys.
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图 2 均值聚类分析表征弹性微观结构非均匀性: (a) ~ (c)模量图的示例三色表示, 其中像素根据模量 (蓝色为软区, 绿色为中间区, 黄色为硬区) 分组, 图像(a)表示铸态样品的中心位置, (b)为样品退火后的中心位置, (c)180 W激光脉冲处理的样品; (d) ~ (f)反卷积直方图, 显示了三种结构
${{E}}_{\mathrm{r}}^{\mathrm{{'}}}$ 分布 (Tsai et al. 2017)
图 3 (a)超淬火, 部分弛豫和高度弛豫样品的纳米压痕力−深度曲线; (b)纳米压痕硬度和模量与结构非均匀性的特征长度关系; (c)超淬火样品和高度弛豫样品的压痕形貌 (Zhu et al. 2018)
图 4 利用原子电子断层扫描技术观测到非晶固体中的三维原子结构, 1 Å = 0.1 nm (Yang et al. 2021)
图 5 (a)Voronoi多面体结构, (b)中心原子的Voronoi指数 (Cheng & Ma 2011), (c) Cu64Zr36非晶合金中以Cu原子为中心的多面体含量随温度的演变 (Cheng et al. 2009)
图 6 CuZr非晶合金在分子动力学模拟和实验中的结构特征: (a)压应变为1%时的原子应变分布; (b)图(a)中的局域结构放大图; (c)高分辨透射电镜下的显微结构; (d)密度分布图 (Feng et al. 2016)
图 8 (a) Cu50Zr50非晶合金的局域事件激活能的空间分布特点; (b)体系中某个Zr原子沿不同方向激活1000次的激活能分布; (c) ~ (e)体系中原子的激活能分布谱 (Wei et al. 2019)
图 10 非晶合金中二维剪切转变区示意图 (Argon 1979)
图 11 非晶态物质在准点缺陷理论框架下的微观变形描述. (a) 初始结构, (b) ~ (d) 为热力耦合激励作用下的激活、扩展和融合行为 (Rinaldi et al. 2011)
图 12 高能量状态流变单元示意图(Wang & Wang 2019)
图 13 在极宽频率域内测得高分子玻璃中的介电损耗谱(弛豫现象) (Lunkenheimer et al. 2000)
图 14 不同温度下Zr基非晶合金损耗模量G''/Gu随频率演化. (a)实线根据KWW模型拟合, (b)实线根据QPD模型拟合, (c)关联因子随温度的演化 (Cheng et al. 2021)
图 15 (a)典型非晶合金体系归一化损耗模量随温度的演化 (Yu et al. 2013), (b)不同初始状态La基非晶合金损耗模量随温度的演化 (Zhao et al. 2014), (c) La基铸态和弛豫态非晶合金内耗随温度的演化 (Zhang et al. 2021b)
图 16 结构非均匀性与β弛豫关联示意图. (a)非晶合金(铸态)的接触共振频率云图, (b) 接触共振频率在(a)的分布, (c) 铸态玻璃能量势垒图, (d) 小能谷跃迁积累为β弛豫, (e)非晶合金(物理老化后)的接触共振频率云图, (f) 接触共振频率在(e)中的分布, (g) 退火后玻璃能量势垒图, (h) β弛豫强度减少 (Wang et al. 2019)
图 17 (a) 典型非晶合金体系快β′弛豫与慢β弛豫激活能之间的关系, (b)“脆性”非晶合金和“韧性”非晶合金微观原子排布示意图 (Wang et al. 2017)
图 18 (a) 不同状态下非晶合金热流随温度的演化, (b) 剔除晶化影响后的热流随温度的演化 (Mitrofanov et al. 2014)
图 19 具有温度依赖性的动力学相关的自由体积分布(左上角). 沿温度升高梯度, 分别为玻色峰、β弛豫峰和α弛豫峰 (Huang et al. 2016)
图 20 (a)部分区域晶化的Pd42.5Ni7.5Cu30P20非晶合金的高分辨电镜图 (Ichitsubo et al. 2005); (b)不同温度下La60Ni15Al25非晶合金的应力松弛曲线, 其中实线为KWW拟合曲线 (Wang et al. 2014); (c)弛豫分布宽度相关指数
$ {\mathrm{\beta }}_{\mathrm{K}\mathrm{W}\mathrm{W}} $ 随温度的演化 (Wang et al. 2014); (d)通过X射线光子关联谱实验测量的Mg65Cu25Y10非晶合金在不同温度下的关联函数和弛豫指数 (Ruta et al. 2012)
图 21 (a) Zr44Ti11Cu10Ni10Be25非晶的应力弛豫曲线, (b)弛豫速率及(c)指数随温度的演化, (d)非晶合金及其高温前驱液体的动力学行为的Arrhenius图 (Luo et al. 2017)
图 22 (a)Cu46Zr46Al8 非晶合金在低温弛豫时的双阶段现象 (Qiao et al. 2016b); (b)应力驱动到热激活应力松弛的转变. 插图显示例如在403 K, 表明松弛机制随应力变化的明显转变 (Qiao et al. 2016b) ; (c) Pd40Ni40P20非晶合金在X射线光子关联谱下的弛豫时间随温度的演化(Zhou et al. 2020); (d)聚合物的焓弛豫时间随温度变化 (Cangialosi et al. 2013)
图 23 (a)由n个Kelvin单元和1个Maxwell单元组成的广义Kelvin模型; (b)不同应力及温度下La56.16Ce14.04Ni19.8Al10非晶合金蠕变过程的弛豫时间分布图谱 (Xu et al. 2020)
图 24 (a) Mg65Cu25Y10和(b) Mg85Cu5Y10非晶合金的弛豫时间谱 (Castellero et al. 2008), (c) La70Cu15Al15 和(d) La70Ni15Al15 非晶合金物理时效后的弛豫时间谱 (Lei et al. 2020), (e) La70Cu15Al15 和(f) La70Ni15Al15在物理时效和低温循环下非晶合金的弛豫时间谱 (Lei et al. 2019a)
图 25 (a)铸态、弛豫态、年轻化样品热流曲线; (b)不同处理方式样品的相对焓变变化; (c)不同冷却速率条件下冷却过程中能量演化 (Sun et al. 2016)
图 26 (a)铸态Zr基非晶合金荷载−深度曲线, (b)铸态及预加载不同时长的非晶合金试样临界剪切应力的累积概率分布, (c)弹性静力压缩2天前后的屈服应力和应力−应变曲线 (Wang et al. 2015c)
图 27 (a)代表性荷载位移曲线, (b)不同结构状态下pop-in事件累计分布函数, (c)
$ \mathrm{l}\mathrm{n}\left[\mathrm{ln}{\left(1-\mathrm{f}\right)}^{-1}\right] $ 与不同结构状态(铸态, 冷轧程度为 80% 和 90%, 退火态)$ {\mathrm{\tau }}_{\mathrm{m}\mathrm{a}\mathrm{x}} $ 分布的线性拟合 (Tao et al. 2021)
图 28 不同年轻化方式的时间尺度(a)与不同年轻化程度的玻色峰演化(b) (Ding et al. 2019)
图 29 结构年轻化和弛豫的能量地形关系图 (Tao et al. 2021)
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