机械合金化结合放电等离子烧结技术制备热电材料的研究进展

近年来,热电材料研究取得重要突破,不仅传统Bi₂Te₃、PbTe基热电材料性能得到提升,同时还发现一批新型高性能热电材料,如SnSe、GeTe等。热电材料性能的提升不仅取决于材料成分、结构及缺陷,还与制备工艺密不可分。机械合金化（mechanical alloying,MA）结合放电等离子体烧结（spark plasma sintering,SPS）的粉末冶金技术是制备热电材料的重要方法,该方法简单、高效,获得的晶粒尺寸较小,同时可以引入纳米结构和缺陷,有助于降低晶格热导率,获得高热电性能。此外,基于机械合金化结合放电等离子体烧结技术制备出的块体材料具有更优的力学性能,可以有效地增强热电器件的使用寿命。本文介绍了机械合金化与放电等离子体烧结方法制备热电材料的基本原理和关键影响因素,并概述了利用该方法制备的碲化物、硫化物和硒化物基热电材料的研究进展。     

Thermoelectric Properties of CexCo4Sb12 Prepared by MA-SPS

Starting with elementary powders, thermoelectric materials CexCo4Sb12 were prepared by mechanical alloying and spark plasma sintering (MA-SPS). XRD analyses reveal that the expected major phase, named skutterudite was formed in MA process and was kept after SPS. The thermoelectric properties of MA-SPS samples including resistivity, Seebeck coefficient, power factor, thermal conductivity and the dimensionless figure of merit (ZT) were studied by varying Ce content and temperature. Depending on Ce levels, both P and N types of thermoelectric semiconductors were obtained. MA-SPS sintered Ce1.0Co4Sb12 exhibits the highest ZT in the range of 100-500℃ and the maximum ZT is found at x=1.0 and 400℃.     

Influence of zirconium addition on the microstructure,thermodynamic stability,thermal stability and mechanical properties of mechanical alloyed spark plasma sintered (MA-SPS) FeCoCrNi high entropy alloy

ABSTRACT

Equiatomic FeCoCrNi (Zr₀) and non-equiatomic FeCoCrNiZr_0.4 (Zr_0.4) high-entropy alloys (HEAs) were synthesised by mechanical alloying and spark plasma sintering. XRD analysis verified the formation of FCC and BCC solid solution phases in both alloys after 30?h of ball milling. While the SPS FeCoCrNi alloy contains both FCC and BCC solid solution phases, the FeCoCrNiZr_0.4 presents an FCC solid solution. The thermodynamic analysis showed that FeCoCrNiZr_0.4 is more stable with respect to the FeCoCrNi alloy. The phase stability of FeCoCrNiZr_0.4 was revealed up to ～800°C. The shear strength and hardness of the FeCoCrNi HEA improved with Zr addition. Failure analysis of the shear punch tested samples revealed a ductile fracture with dimple structure for FeCoCrNi and a brittle fracture with a smooth featureless surface for FeCoCrNiZr_0.4.     

Preparation of TiAl15Si15 intermetallic alloy by mechanical alloying and the spark plasma sintering method

This work is devoted to the preparation of alloys based on intermetallic compounds in the Ti–Al–Si system by powder metallurgy using mechanical alloying and the spark plasma sintering (SPS) method. The aim was to describe the formation of intermetallic phases during mechanical alloying of TiAl15Si15 (wt-%) alloy and to consolidate the powder prepared by optimised conditions. Phase composition, microstructure and hardness of compacted alloy were determined. Four hours of mechanical alloying is sufficient time for preparation of pure elements free material composed only of intermetallic phases. After consolidation, the TiAl15Si15 alloy has a homogeneous structure composed of silicide (Ti₅Si₃) in aluminide (TiAl) matrix. The hardness of the material reaches 865?±?42 HV 5.     

放电等离子烧结金属多孔材料研究现状

金属多孔材料是一种新兴功能材料,具有良好的渗透性、规则的孔道结构、独特的力学、吸附及光电性能等诸多优点。利用放电等离子烧结技术(spark plasma sintering,SPS)制备金属多孔材料具有升温速度快,高效干洁等优点。本文简述了放电等离子烧结技术在材料制备中的应用,讨论了放电等离子烧结参数对金属多孔材料的影响,并对放电等离子烧结制备金属多孔材料的应用现状及前景做出了展望。     

TiC含量对WC-8Co超细晶硬质合金力学性能和微观组织的影响

采用放电等离子烧结技术制取不同TiC含量的WC-8Co硬质合金。分析了TiC含量对WC-8Co基硬质合金刀具材料的致密度、力学性能和微观组织的影响。实验结果表明,随着TiC含量增加,WC-8Co硬质合金常温综合力学性能先提高后降低,添加5%(质量分数)TiC的WC-8Co硬质合金具有较好的综合力学性能。当烧结温度和压力分别为1 250℃、50 MPa时,WC-5TiC-8Co硬质合金材料致密度、维氏硬度、断裂韧性以及室温下的抗弯强度分别达到98.85%、19.49 GPa、9.46 MPa·m^1/2和1 893 MPa。硬质合金致密化烧结曲线和组织显微形貌的分析结果表明,随着TiC含量增加,硬质合金的致密化烧结的起始温度向更低的温度偏移,Co相流动性变差,从而导致致密化烧结条件变差。试样中孔隙增多,是硬质合金维氏硬度和力学性能下降的主要原因。     

烧结温度对内燃机用TiZrVMo高熔合金组织和力学性能的影响

运用放电等离子烧结方法(SPS)制备TiZrVMo合金,并通过控制不同的烧结温度获得了不同力学特性与组织结构的试样。测试结果表明,对合金烧结处理后其基体中形成了包含BCC与FCC两种晶体结构,BCC组织形成了比FCC组织更高的衍射峰。当烧结温度增加后,晶粒尺寸呈现增大的现象,塑性先增大后降低。经过1100℃烧结得到的试样压缩屈服强度为1501.4MPa,塑性应变31.4%。随着烧结温度的增加,屈服强度先减少后增加,塑性应变先增大后减小。当烧结温度上升后,合金材料从准脆性断裂逐渐转变为微孔聚集型断裂,之后形成了大尺寸晶粒并发生沿晶断裂的现象,呈现脆性解理断裂的特点。     

放电等离子烧结的超细纯碳化钨的组织与性能

利用放电等离子烧结技术得到了近全致密的无粘结相超细纯碳化钨材料。烧结前后平均粒径达200nm的超细组织基本维持不变。该材料的硬度明显超过了常规的碳化钨基硬质合金，可以用作优异的硬质材料。     

烧结温度与混粉比例对双尺度钛合金组织与性能的影响

采用高能球磨-放电等离子烧结技术制备具有双尺度显微组织的Ti-6Al-4V合金,并研究烧结温度和加入未球磨粉末的比例对烧结试样显微组织及力学性能的影响。实验结果表明:当球磨时间为6 h时,由于球磨粉末内部的应变量不均匀,球磨粉末烧结试样的显微组织均由粗晶网篮组织和细晶等轴组织组成。随烧结温度升高,烧结试样的密度逐渐提高,细晶区的晶粒尺寸逐渐增大,材料强度呈先上升后下降的趋势。在球磨粉末中加入一定比例的未球磨粉末可显著提高烧结材料的塑性,并且保持较高的强度。当球磨粉末与未球磨粉末按质量比4:1混合、SPS烧结温度为850℃、保温时间为4min时,烧结材料相对密度达到99.0%,细晶区晶粒尺寸为1~2μm,烧结试样获得最佳强度-塑性组合,其拉伸屈服强度为1012 MPa,断裂强度为1056 MPa,伸长率为10%。     

High-entropy alloys fabricated via powder metallurgy. A critical review

High-entropy alloys (HEAs) have attracted a great deal of interest over the last 14 years. One reason for this level of interest is related to these alloys breaking the alloying principles that have been applied for many centuries. Thus, HEAs usually possess a single phase (contrary to expectations according to the composition of the alloy) and exhibit a high level of performance in different properties related to many developing areas in industry. Despite this significant interest, most HEAs have been developed via ingot metallurgy. More recently, powder metallurgy (PM) has appeared as an interesting alternative for further developing this family of alloys to possibly widen the field of nanostructures in HEAs and improve some capabilities of these alloys. In this paper, PM methods applied to HEAs are reviewed, and some possible ways to develop the use of powders as raw materials are introduced.     

Preparation and Mechanical Properties of Misch Metal Based Bulk Metallic Glasses

Bulk metallic glasses(BMGs)have been devel-oped in many alloy systems during past decade.Among these systems,rare-earth(RE)metal-basedBMGs are ones of those found earliest and with betterglass forming ability(GFA).For example,La-basedBMGs were the first a…     

合金元素对机械合金化和放电等离子烧结Ti-Nb基合金显微组织的影响

β-Ti型结构的钛基材料在生物材料领域具有广泛的应用前景。本文采用机械合金化法和放电等离子烧结制备β-Ti型Ti-Nb基合金,研究不同Nb,Fe含量对合金显微组织及力学性能的影响。利用扫描电镜(SEM)、X射线衍射仪(XRD)和透射电镜(TEM)等手段分析合金的显微组织变化情况。结果表明:机械合金化过程中,粉末的平均粒度减小,当球磨时间超过60 h时粉末易发生团聚。当球磨转速为300 r/min,球料比为12:1,Ti和Nb的质量分数分别为64%和24%时,球磨100 h后制备的粉体材料中具有一定体积的非晶相。该粉末在1 000℃下通过放电等离子烧结(SPS)制备具有均匀细小的球状晶粒组织的Ti-Nb合金,其强度、伸长率和弹性模量分别为2 180MPa,6.7%和55 GPa。通过控制Nb,Fe的含量,可以促进β-Ti相形成,获得高强度和低杨氏模量的Ti-Nb合金。     

放电等离子烧结法制备金刚石/Cu复合材料

通过真空镀铬对金刚石颗粒进行表面改性,采用放电等离子烧结法(SPS)制备改性金刚石/Cu复合材料;研究金刚石的体积分数、工艺参数以及金刚石颗粒表面改性对复合材料导热性能的影响。结果表明,烧结温度、混料时间以及金刚石颗粒的体积分数都会影响材料的致密度,金刚石颗粒的体积分数还会影响材料的界面热阻,而致密度和界面热阻是影响该复合材料导热性能的2个重要因素;对金刚石颗粒进行真空镀铬表面改性,可改善颗粒与铜基体的润湿性,降低界面热阻。在一定的工艺条件下,镀铬金刚石体积分数为60%时,改性金刚石/Cu复合材料具有很高的致密度,其热导率达到503.9W/(m.K),与未改性的金刚石/Cu复合材料相比,热导率提高近2倍,适合做为高导热电子封装材料。     

放电等离子烧结压力对92WC-8Co纳米硬质合金组织及性能的影响

通过放电等离子烧结技术制备了92WC-8Co纳米硬质合金样品,研究了烧结压力对合金晶粒大小、组织结构、密度和硬度的影响.     

ZnO/Y_2O_3 对氧化铝基陶瓷性能的影响

研究了ZnO/Y_2O_3复合添加剂对75%氧化铝基陶瓷烧结性、体积密度、抗折强度和物相组成的影响. 结果表明: 当ZnO/Y_2O_3为1∶ 0.3时, 在1290 ℃烧结后, 样品的性能可达到: 抗折强度149.9 MPa和体积密度3.16 g·cm~(-3). XRD分析结果表明: ZnO/Y_2O_3不同比例复合时, 锌铝尖晶石相、钙长石相和刚玉相发生了较大变化, 从而影响了材料的性能.     

高Si电工钢铁芯的MA-SPS制备工艺和磁性能研究

以一种新的Fe-Si合金制备工艺为出发点,研究了不同放电等离子体快速烧结工艺(SPS)和Si含量变化对Fe-Si合金材料显微组织与磁性能的影响.结果表明,在烧结温度为1 000℃时制备的Fe-6.5％ Si合金(质量分数,下同)的综合磁性能较好,其在50Hz下的铁损为0.549W/kg,最大磁感应强度为0.124 3T,矫顽力245.6 A/m,磁导率0.338mH/m.另外,材料的最大磁感应强度随Si含量的增加显著增长,1 000Hz下,Fe-10.0％ Si的最大磁感应强度可达到Fe-6.5％ Si合金的5倍左右.     

机械合金化CuRECr合金的显微组织结构及性能分析

利用机械合金化和真空烧结技术制备CuRECr25和CuRECr50合金，讨论了机械合金化不同球磨时间、球料比等工艺参数对合金显微组织结构、物理机械性能，含氧量、含氮量等的影响，并且与CuCr25、CuCr50合金进行了物理机械性能比较。研究结果表明：CuRECr合金组织均匀、细微，具有强度、硬度高等特点，为改进CuCr系电真空接触材料开辟了新途径。     

Microstructure and properties of CrMnFeCoNi high-entropy alloy prepared by mechanical alloying and spark plasma sintering

The equiatomic ratio CrMnFeCoNi high entropy alloy (HEA) was prepared by mechanical alloying (MA) and spark plasma sintering. This paper reports the behaviour of MA, the phase formation, microstructure and mechanical properties of CrMnFeCoNi HEA. With the increase of milling time, solid solution with single FCC phase was gradually formed. The single FCC phase remained as matrix after SPS at 1373?K and 50?MPa. Ultrafine-grained microstructure and good mechanical properties were obtained: At room temperature, the as-sintered bulks exhibit an excellent combination of high compressive strength (2390?MPa) and high fracture strain (47%).     

Preparation of Nanocrystalline 430L Stainless Steel by HEBM and SPS

Preparation of nanocrystalline 430L stainless steel by both high-energy ball milling and spark plasma sintering technique has been investigated. The results have shown that the hardness can be improved markedly with an increase in sintering temperature and holding time. The lower the apparent porosity of nanocrystalline 430L stainless steel, the higher is the Vickers-hardness. The tensile strength reached a maximum value of 713 MPa when the sampie was sintered at 1 173 K for 10 min, and then it evidently decreased with an increase in sintering temperature and holding time because of the growth of crystalline grain.     

致密烧结Ti/Al2O3复合材料

利用放电等离子烧结技术(SPS)制备出相对密度、断裂韧性、弯曲强度分别为99.74%、19.73±0.4MPa·m1/2、1002±12MPa的40vol%Ti/Al2O3复合材料。SEM对复合材料表面形貌观察发现,Ti、Al2O3两相分布均匀,表面无明显气孔存在;断口的SEM和EDS表明,复合材料已形成网络导电结构;复合材料的HREM微观结构分析表明,Al2O3三角晶界处无其它杂质的偏聚,小颗粒的金属Ti富集在Al2O3的三角晶界结合处,界面结合紧密。