Pd20Pt20Cu20Ni20P20 高熵金属玻璃的热稳定性和热塑成形性

采用差示扫描量热法、X射线衍射和热力学分析研究了Pd₂₀Pt₂₀Cu₂₀Ni₂₀P₂₀高熵金属玻璃（HEMG）的热稳定性和热力学性能。结果表明,与其他经典贵金属基金属玻璃相比,Pd₂₀Pt₂₀Cu₂₀Ni₂₀P₂₀ HEMG具有相当的性能和鲜明的特点。     

过冷液态Zr48Cu36Ag8Al8块体非晶合金的相分离及组织演变

本文通过x射线衍射(XRD)、差示扫描量热法(DSC)和透射电子显微镜(TEM)研究了退火温度对Zr₄₈Cu₃₆Ag₈Al₈金属玻璃微观结构演化的影响。结果表明,快速凝固获得的样品为典型的非晶态结构。当样品在703K保温20分钟时,均一的非晶基体相分离成两种非晶合金,即,发生相分离。由于相分离结构与非晶基体在等温退火过程是竞争的关系,这个结构很容易向晶化态进行转变,形成AlZr₂ AlAg₃相。Zr₄₈Cu₃₆Ag₈Al₈金属玻璃的微观结构在过冷液相区等温退火过程中经历了的局部结构转变,相分离以及纳米晶转变,这个过程意味着Zr₄₈Cu₃₆Ag₈Al₈金属玻璃的微观结构对退火温度十分敏感。此外,相分离的形成可以加速纳米晶的形成。     

Cu添加对La0.7Ce0.3Fe11.54-xCuxMn0.16Si1.3合金及其氢化物磁性能的影响

La(Fe, Si)₁₃系合金是具有一级相变大磁热效应的磁制冷合金,被认为是极具应用前景的磁热效应材料之一。本文采用高频感应悬浮炉制备了添加不同Cu元素比例的La_0.7Ce_0.3Fe_11.54-xCu_xMn_0.16Si_1.3(x=0, 0.05, 0.1, 0.15)合金。并利用粉末XRD衍射仪,扫描电镜(SEM)对合金的相组成、微观组织结构进行了研究,采用多功能振动样品磁强计VersaLab对合金的磁性能进行了分析。添加Cu元素后,合金的居里温度提高,但氢化后添加Cu的合金居里温度反而偏低。随着Cu元素提高磁热性能下降,但La_0.7Ce_0.3Fe_11.44Cu_0.1Mn_0.16Si_1.3H_1.68合金的最大等温磁熵变仍高达8.5 J/kg.K(0 ~ 2 T),相对制冷能力RCP提高(118 J/kg),磁滞明显降低。     

一种具有良好直流叠加特性的Fe95Si1B2P0.5Cu1.5磁粉芯

：本文采用片状Fe₉₅Si₁B₂P_0.5Cu_1.5合金粉体替代球形Fe-6.5%Si合金粉体,制备了FeSi系金属磁粉芯,研究了合金粉及磁粉芯的制备,退火温度和成型压力对磁粉芯的软磁性能的影响情况。研究结果表明,Fe₉₅Si₁B₂P_0.5Cu_1.5磁粉芯的磁导率在1~200kHz频率范围内具有良好的频率稳定性,经450℃×1h退火处理后,磁粉芯内部残余内应力得到充分的释放,其有效磁导率μe得到大幅的提升,成型压力为1.74GPa时,最大值达到53。随着外加直流磁场强度的逐渐变大,磁粉芯的磁导率逐渐下降,当外加直流磁场强度H=50Oe时,有效磁导率μe维持在70%以上,当H继续增大到130Oe时,μe仍大于20,表明磁粉芯具有良好的直流叠加特性。     

铈浓度对ZrH1.8 微弧氧化膜层阻氢性能的影响

利用微弧氧化技术在电解液中加入不同含量的铈,制备了阻氢性能良好的二氧化铈稳定氧化锆（ceria-stabilized zirconia, CSZ）陶瓷膜。利用涂层测厚仪、涂层附着力自动划痕仪、扫描电子显微镜、X射线能谱仪、X射线衍射仪、X射线光电子能谱仪和真空脱氢实验对膜层的厚度、结合力、形貌、相结构、元素化学价态和膜层的阻氢性能进行了测试和表征。结果表明：CSZ陶瓷膜主要由单斜相氧化锆（m-ZrO₂）、四方相氧化锆（t-ZrO₂）和t-Zr_0.82Ce_0.18O₂组成。随铈浓度的增加,膜层厚度逐渐增加。当铈浓度为9mol%时,陶瓷膜厚度为135.5 μm,结合力为52.46 N,膜层具有优异的阻氢性能,阻氢渗透因子为19。铈的加入抑制了t-ZrO₂向m-ZrO₂的相转变,促进了高温稳定t-ZrO₂的生成。     

纳米BaTiO3复合Cu1.8S块体的热电性能和力学性能研究

Cu_1.8S作为一种P型半导体热电材料,具有环境友好、原料丰富、价格低廉等优点而受到广泛关注。本研究采用机械合金化(Mechanical Alloying, MA)结合放电等离子烧结(Spark Plasma Sintering, SPS)工艺制备了一系列Cu_1.8S-x wt%BaTiO₃ (x =0,0.075,0.1,0.15,0.2)块体材料,研究了复合纳米BaTiO₃对Cu_1.8S的相结构、微观形貌、热电性能及力学性能的影响。结果表明,纳米BaTiO₃的加入不影响Cu_1.8S的相结构、晶胞参数和载流子浓度;纳米BaTiO₃均匀分布在Cu_1.8S基体的晶界处产生钉扎效应进而细化晶粒并产生气孔。Cu_1.8S-0.2 wt%BaTiO₃样品在773 K时获得最低的热导率2.2 Wm^_-1K^_-1,所有样品的ZT值基本保持不变约0.39 (773 K)。同时Cu_1.8S-x wt%BaTiO₃块体样品的维氏硬度由82 (x = 0)增加到87 (x = 0.2)。本研究表明在Cu_1.8S中复合纳米BaTiO₃可以在不影响材料热电性能的前提下有效提升块体样品的力学性能,为后续Cu-S体系热电性能和力学性能的协同提升提供了思路,有利于制备高机械性能且稳定耐用的Cu-S体系的热电器件。     

内生型(Ti0.474Zr0.34Cu0.06Be0.126)100 - x Fe x (x=0, 2)金属玻璃基复合材料的动态力学行为

为了解内生β-Ti相的Zr/Ti基金属玻璃复合材料的动态力学性能和热力学稳定性,采用力学弛豫谱研究了(Ti_0.474Zr_0.34- Cu_0.06Be_0.126)_100-xFe_x（x=0,2）金属玻璃复合材料。通过引入Fe元素,提高了β-Ti相的稳定性。此外,还发现了一个异常的内耗峰,这是由于在亚稳的β-Ti相中析出ω-Ti所引起的。在玻璃化转变温度T_g以下,由于相变和非晶基体部分结晶的耦合效应,2种金属玻璃复合材料的储能模量均表现出异常过冲行为。所得结果为更好地理解内生亚稳β-Ti型金属玻璃复合材料的复杂动态力学弛豫行为提供了借鉴。     

钼表面包埋渗法制备(Ti, Mo)Si2/MoSi2 涂层及其在1200 ℃周期性氧化环境下的氧化行为

利用连续沉积的包埋渗法,在钼表面制备了(Ti,Mo)Si₂/MoSi₂复合涂层。利用X射线衍射、扫描电子显微镜、能谱仪和热力学计算对涂层进行了表征与反应机理分析。结果表明,共沉积法无法实现Ti的有效沉积。先渗Ti、再渗Si的两步沉积工艺能有效制备Ti改性硅化物涂层。涂层分为3层,最外层为(Ti,Mo)Si₂三元化合物层,次外层为MoSi₂层,次外层与基体间为Mo₅Si₃过渡层。渗硅温度对涂层结构无明显影响。Ti改性硅化物涂层的生长速率略低于单一渗硅涂层的生长速率。(Ti,Mo)Si₂/MoSi₂复合涂层的形成由Ti、Si内扩散控制。Ti元素集中在涂层表层,Si元素通过(Ti,Mo)Si₂化合物层与基体作用形成MoSi₂层和Mo₅Si₃过渡层。渗Ti过程中,埋渗料间反应会引入游离态铝氟化物AlF₃。在随后的渗硅过程中,游离态Al以Al₃Mo的形式在(Ti,Mo)Si₂层中靠近MoSi₂层的上界面处析出。在1200 ℃周期性氧化过程中,(Ti,Mo)Si₂/MoSi₂复合涂层持续循环氧化180 h后未出现明显失重。(Ti,Mo)Si₂层氧化形成的SiO₂与TiO₂致密复合氧化层能填充涂层表面裂纹,持续阻碍氧扩散,因此其在周期性氧化环境下的抗氧化性能显著优于单一渗硅涂层。     

复合粘结La0.8Ce0.2Fe11.7- x Mn x Si1.3H1.8 磁工质的磁性能

采用中频感应炉制备La_0.8Ce_0.2Fe_11.7-xMn_xSi_1.3母合金并退火,将合金饱和氢化后破碎成粉末。通过环氧树脂粘结,将居里温度T_C间隔为5 K的多种La_0.8Ce_0.2Fe_11.7-xMn_xSi_1.3H_1.8（x=0.23,0.26,0.29,0.32,质量分数,%）合金粉末进行混合粘结,提高合金的磁熵半峰宽。用VersaLab和绝热温变直接测量仪测试粘结样品的磁性能。结果表明,与单一成分粘结样品相比,混合粘结样品的最大等温磁熵变有所降低,磁熵半峰宽以及相对制冷能力有所提高。含4种成分的混合粘结样品的相对制冷能力可以达到139.2 J/kg。     

TiZrNiCu钎焊Si3N4-MoSi2复合陶瓷与Nb接头组织与力学性能

采用高温活性钎料TiZrNiCu对Si₃N₄-MoSi₂复合陶瓷和金属Nb进行真空钎焊试验,研究了其典型界面组织组成及形成机理,分析了钎焊温度和保温时间对钎焊接头界面组织及力学性能的影响规律。结果表明,接头典型界面结构为Nb/β-Ti/(Ti. Zr)₂(Cu, Ni)+β-Ti+(Ti, Zr)₅Si₃/TiN+(Ti, Zr)₅Si₃+MoSi₂/Si₃N₄-MoSi₂。钎焊温度和保温时间主要通过控制Si₃N₄-MoSi₂复合陶瓷母材中Si原子向钎料中扩散程度,来影响钎缝中(Ti, Zr)₅Si₃化合物的数量及分布,进而影响钎焊接头的抗剪强度。在920 ℃/10 min的工艺参数下,Si₃N₄-MoSi₂/Nb接头的室温抗剪强度最高达到112 MPa,选择最优参数条件下的Nb/Si₃N₄-MoSi₂钎焊接头在500 ℃和600 ℃条件下进行高温剪切实验,其高温抗剪强度分别达到123 MPa和131 MPa。     

Electron irradiation induced phase transformation in Zr66.7Cu33.3 and Zr66.7Pd33.3 metallic glass

Crystallization and phase selection in Zr_66.7Cu_33.3 and Zr_66.7Pd_33.3 metallic glass during thermal annealing and electron irradiation were examined. During thermal annealing an equilibrium C11_b–Zr₂Cu phase directly precipitated in the amorphous phase of Zr_66.7Cu_33.3 metallic glass while a thermal equilibrium C11_b–Zr₂Pd phase formed after icosahedral quasi-crystalline phase precipitation in Zr_66.7Pd_33.3 metallic glass. The amorphous phase was not stable under electron irradiation and metastable crystalline phases with face-centered cubic-based structure formed in both kinds of metallic glass by electron irradiation induced crystallization. The unique phase selection in electron irradiation induced crystallization is due to a change in the phase stability of crystal, quasi-crystal and amorphous phase under electron irradiation.     

Kinetics of crystallization process for Pd-based bulk metallic glasses

The crystallization behavior of Pd₇₉Cu₆Si₁₀P₅ and Pd₇₉Cu₄Au₂Si₁₀P₅ bulk metallic alloys was studied using differential scanning calorimeter (DSC) under different heating conditions. Under isochronal heating, the onset temperatures of the glass transition and crystallization for these glasses exhibited strong heating-rate dependence. The activation energies for the glass transition and crystallization were determined, based on the Kissinger plots, to be 540 and 452 kJ/mol, respectively, for Pd₇₉Cu₆Si₁₀P₅ glassy alloy, and 640 and 318 kJ/mol, respectively, for Pd₇₉Cu₄Au₂Si₁₀P₅ glassy alloy. The isothermal kinetics was modeled by the Johnson–Mehl–Avrami equation. For the Pd₇₉Cu₆Si₁₀P₅ glassy alloy the Avrami exponent was mostly in the range from 2.23 to 2.52, which indicated a decreasing nucleation rate and a diffusion-controlled three-dimensional growth. For the Pd₇₉Cu₄Au₂Si₁₀P₅ glassy alloy the Avrami exponent was in the range between 2.42 and 2.76, which indicated an increasing nucleation rate and a diffusion-controlled three-dimensional growth.     

The influence of structural peculiarities of rapidly quenched bands of the Fe76.1Cu1.0Nb3.0Si13.0B6.1 alloy on their electrochemical behavior

X-ray diffraction analysis, auger spectroscopy and electrochemical measurement showed that, by varying the temperature of starting melt, it is possible to change the surface crystallization degree of quenched metallic glass of the Fe_76.1Cu_1.0Nb_3.0Si_13.8B_6.1 composition, while the presence of crystallites of an ordered α-Fe(Si) solid solution and the air-oxide film formed during the quenching of bands allows improving their corrosion-electrochemical characteristics.     

Thermal behaviour of Pd40Cu30Ni10P20 bulk metallic glass

The thermal behaviour of differently milled Pd₄₀Cu₃₀Ni₁₀P₂₀ bulk metallic glass through the glass transition has been investigated by in situ high-energy synchrotron X-ray diffraction. Repeated heating and cooling were performed between the glassy and the supercooled liquid state. The changes in positions and intensities of the first and second diffraction maxima of the as-milled powder indicate irreversible changes during first heating up to the glass transition temperature T_g due to structural relaxation. After annealing, reversible structural changes with temperature are observed upon heating and cooling in the glassy phase, and in the supercooled liquid state respectively. The shift in the position of the first maximum scales approximately with the linear thermal expansion for the glassy state; however, this relation does not hold for the supercooled liquid. The structural transition from the glass to the supercooled liquid at the glass transition temperature is reflected by the intensity of the diffraction maxima and by a reversed temperature dependence of the position of the second diffuse maximum below and above T_g. The changes of the glass structure for the decrease of free volume by annealing are found to be different from those observed for the reversible volume expansion or shrinkage by varying the temperature. Therefore, the shift of the first diffuse maximum position of bulk metallic glasses cannot be used as a measure of the change in free volume.     

Thermodynamic properties of the Pd77.5Cu6Si16.5 undercooled liquid

Proper understanding of glass formation implies the knowledge of the thermodynamics of the undercooled melts. Specifically, high values of the excess specific heat of the liquid are expected for good glass-formers. Extending the work of Gillessen and Herlach [F. Gillessen, D.M. Herlach, J. Non-Cryst. Solids 117–118 (1990) 555–558], we re-propose a calculation of the temperature dependence of entropy difference between amorphous-liquid and crystal states.An amorphous Pd_77.5Cu₆Si_16.5 alloy has been produced by injection casting in a cylindrical copper mould. DSC measurements in the liquid, amorphous and crystalline states were performed with samples sliced from the cylinder to determine the heat of fusion, of crystallization and the difference in specific heat capacity between amorphous-liquid and crystal phases. These thermodynamic quantities are used to calculate the thermodynamic functions of the liquid-glass with reference to the equilibrium crystal mixture. The data are compared to those of other bulk glass-formers in terms of fragility plots.     

一种具有优异玻璃形成能力的Zr50Ti5Cu27Ni10Al8大块非晶合金的开发

多组元的Zr基非晶合金成分的复杂性对开发具有优异玻璃形成能力的Zr基非晶合金提出巨大的挑战。另外,大部分Zr基非晶合金含有有毒元素Be或者贵金属。因此,采用一种简单有效的方法开发无毒无贵金属元素的多组元Zr基非晶合金十分必要。本文中采用二元共晶比例法和部分元素替代法快速的开发出了一种新的临界尺寸大于10mm的 Zr50Ti5Cu27Ni10Al8非晶合金。这个非晶合金的热稳定性和硬度也通过原位高温X射线衍射和纳米压痕方法测量得出。     

Ti48Zr20Nb12Cu5Be15 非晶复合材料的内耗行为

对Ti₄₈Zr₂₀Nb₁₂Cu₅Be₁₅非晶复合材料的室温力学性能以及随温度变化的动态力学性能进行了研究。结果表明,该非晶复合材料的室温拉伸强度约为1350 MPa,断裂应变约为0.13。随着温度的升高,该非晶复合材料的整体状态由弹性转变为粘弹性。在准点缺陷模型框架下,引入了诸如损耗因子、相关系数等相关物理参数,全面分析了该非晶复合材料动态力学行为,并且模型的理论曲线与实验数据拟合程度较好。因此,准点缺陷模型可以很好地描述不同温度下的Ti₄₈Zr₂₀Nb₁₂Cu₅Be₁₅非晶复合材料的动态力学行为。     

Zr41Ti14Cu12.5Ni10Be22.5非晶棒料摩擦焊接

设计了一种非晶合金摩擦焊装置,以Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5非晶棒料为研究对象,进行了摩擦焊试验.焊接样品经SEM,XRD,维氏硬度、TEM等检测,结果显示焊接界面无明显未熔合,样品仍然保持非晶态,接头硬度总体增大,接头处出现了纳米晶.采用ANSYS软件对非晶合金摩擦焊的温度场进行仿真.结果表明,在摩擦时间t=0.25s时摩擦界面中心温度超过非晶棒料玻璃转变温度,接触面全部进入过冷液相区,应进行顶锻.仿真结果与摩擦焊试验结果基本吻合,有利于指导焊接试验.     

Magnetic, electrical and plastic properties of Fe76Nb2Si13B9, Fe75Ag1Nb2Si13B9 and Fe75Cu1Nb2Si13B9 amorphous alloys

Influence of 1 h annealing in vacuum on magnetic, electrical and plastic properties of Fe₇₆Nb₂Si₁₃B₉, Fe₇₅Ag₁Nb₂Si₁₃B₉ and Fe₇₅Cu₁Nb₂Si₁₃B₉ melt spun ribbons were carefully investigated. It was shown that in all cases soft magnetic properties can be significantly enhanced by applying 1-h annealing at characteristic temperatures T_op. This optimization annealing causes that permeability increases more than 15-times and magnetic losses (tangent of loss angle) achieves a minimum in relation to the as quenched state. Using structural examinations (X-ray and HRTEM) it was shown that for the Fe₇₅Cu₁Nb₂Si₁₃B₉ alloy the optimized microstructure corresponds to a nanocrystalline αFe(Si) phase whereas in other alloys to a relaxed amorphous phase free of iron nanograins. As a consequence of this fact the Fe₇₆Nb₂Si₁₃B₉ and Fe₇₅Ag₁Nb₂Si₁₃B₉ alloys show higher plasticity in comparison to the nanocrystalline Fe₇₅Cu₁Nb₂Si₁₃B₉ alloy. Temperatures of the first stage of crystallization, and related diffusion parameters were determined using measurements of resistivity versus temperature with different heating rates.