钼合金Si-Cr-Ti-SiC-MnO2涂层的制备与组织性能

目的提高钼合金表面红外辐射性能与高温抗氧化性能。方法将40%Si、20%Cr、5%Ti、5%SiC、30%Mn O_2五种粉末与酒精、粘结剂按比例混合,经高能球磨6 h后制得均匀悬浮的料浆。采用浸涂工艺对预处理的钼合金试样进行料浆涂覆,在1450℃真空烧结0.5 h后制得黑色涂层试样。通过1550℃高温静态氧化试验和高温粒子薄片红外光谱综合实验系统,分别评价涂层抗氧化性能和红外辐射性能,并通过扫描电镜(SEM)、能谱分析(EDS)、X射线衍射仪(XRD)对涂层氧化前后的形貌与组织结构进行分析。结果钼合金Si-Cr-Ti-SiC-Mn O_2涂层在700、900℃的法向发射率分别达0.85、0.88,在1550℃高温有氧环境下的静态抗氧化寿命达7 h。原始涂层呈四层复合梯度结构,由外到内分别为SiO_2+Mn3O_4+M5Si3(M指Mo、Cr、Ti)、M5Si3+Mo Si2+SiC+Mn3O_4、Mo Si2、Mo5Si3。高温氧化后,涂层四层复合结构由外到内转变为SiO_2+(Cr,Ti)5Si3+Mn Cr2O_4+Mn3O_4、M5Si3+SiC+Mn Cr2O_4+Mn3O_4、Mo Si2、M5Si3。高温氧化过程中,MSi2高硅化物层逐渐转变为M5Si3低硅化物层,涂层表面形成含Mn Cr2O_4尖晶石相和复合硅化物的致密SiO_2玻璃膜。结论 Si-Cr-Ti-SiC-Mn O_2涂层可有效提高钼合金基体的红外辐射性能和高温抗氧化性能,复合硅化物与硅锰复杂氧化物具有良好的抗氧化性能、高辐射性能和自愈合性能。     

铌-硅基自生复合材料的新发展

铌 -硅基自生复合材料是一种颇具潜力的高温 (>115 0℃ )结构材料 ,它可用作先进的涡轮叶片材料。这些复合体包含由Nb固溶体增韧的Nb5Si3 ,Nb3 Si型硅化物 ,并含有高Cr、Ti、Hf、B和Al等合金元素。对复合材料的室温断裂韧性和高温蠕变强度有良好的作用 ,如加入Cr和B有利于产生稳定Laves相和铌硼硅化物T2 相等 ,从而提高抗氧化性能。铌和铌 -硅化物复合材料相平衡的基础是Nb -Si相图靠近富Nb一边有一共晶点(Nb3 Si和Nb)。由Si含量为 10 %～ 2 5 %(原子分数　下同 )的Nb -Si二元系制备Nb -Nb3 Si和Nb -Nb5Si3 复合材料。由二元亚…     

合金化和热处理对难熔金属硅化物基合金组织和性能影响的研究现状

综述了合金化和热处理对硅化物基合金组织和性能的影响。在铌硅化物基合金中添加Mo，W或Al后，电弧熔炼态组织中的硅化物相为βNb5Si3；添加Cr或者V后，硅化物相为αNb5Si3：加入Ti后，硅化物相是Nb3Si。添加Ti，Hf和B可提高铌硅化物基合金的室温断裂韧性，添加W或Mo后合金的高温强度显著提高，而添加Cr，Al和Ti明显改善其高温抗氧化性能。在MoSi2中加入W，Nb和Ge等合金化元素后分别形成（Mo，W）Si2，（Mo，Nb）Si2或Mo（Si，Ge）2等硅化物，但在钼硅化物基合金中添加B后生成α—Mo，Mo3Si和T2相（MoSiB2），并且T2相所占的体积百分比与B的含量成正比。α-Mo相的含量对合金的断裂韧性和抗氧化性有重要影响。Nb或Mo的硅化物基合金的热处理温度都比较高，经过再结晶退火后合金中的组成相及其所占的体积百分比均发生变化，并且组织粗化，但分布更加均匀，从而对力学性能有显著的影响。     

β相区热变形诱导TiC/Ti复合材料硅化物析出行为

本实验对5vol.%TiCp/近α钛复合材料进行了β相区的热物理模拟试验,研究了复合材料热变形过程中硅化物的析出行为和β相变形机理。变形后的室温组织中主要由片层α相和破碎的TiCp组成,通过透射电子显微镜(TEM)确定组织中存在(Ti,Zr)6Si3型硅化物,尺寸为350-600nm。硅化物的含量随着温度升高和应变速率增加而减少。此外,根据室温α相重构了β母晶粒。TiCp沿β晶界分布,通过提供形核位点和阻碍位错运动,促进了β相动态再结晶过程。热变形过程中的应变积累和TiCp附近形成的高密度位错诱导和促进了硅化物析出。     

合金成分及熔炼工艺对多元铌基超高温合金组织的影响

采用真空自耗电弧熔炼和真空非自耗电弧熔炼2种工艺熔炼了4种不同成分的多元铌基超高温合金,研究了合金成分及熔炼工艺对组织的影响规律.结果表明:4种成分的合金均由初生Nb基固溶体枝晶或初生(Nb,x)5Si3(x代表Ti, Cr和Hf元素)块和板条以及Nbss/(Nb,x)5Si3共晶团组成.随着Si含量的升高,组织中Nbss/(Nb,x)5Si3共晶团的含量增多且初生相也从Nbss枝晶转变为(Nb,x)5Si3块或板条.铌硅化物相为γ-(Nb,x)5Si3及β-(Nb,x)5Si3.大块或板条状硅化物内有微裂纹出现.     

Si对高Nb-TiAl合金组织及室温拉伸性能的影响

研究硅化物(Nb5Si3相)析出对高Nb-TiAl合金组织及室温拉伸性能的影响.实验结果表明,硅化物脱溶析出温度在1000~1200℃之间,析出物位于片层团晶界处、b(B2)相偏析处以及片层之间.添加Si元素后,合金室温拉伸性能有所增加.因为Nb5Si3相的形成使得b(B2)相稳定元素Nb含量下降,导致脆性相b(B2)相体积减少.但是,含Si高Nb-TiAl合金经过热处理后,室温拉伸性能随热处理温度提高而逐步降低.因为沿片层析出的硅化物会导致裂纹沿片层产生与增殖,而且应力会导致硅化物进一步析出,加速裂纹扩展.而且,Si的加入会导致γ相区扩大,在1280~1300℃之间形成γ单相区.硅化物析出在片层边界处,会导致块状γ+b(B2)相组织,脆化晶界;而硅化物析出在片层内部会导致二次γ板条形成,割裂了初始片层组织.     

近α-Ti合金Ti_3Si相电子衍射分析

在近α-Ti合金中加入适量的Si,能提高其高温强度。Si与Ti、Zr形成细小的硅化物相,分布于α相的内部和边界,起到强化作用。我们曾用电子衍射方法,对几种含Si的钛合金的弥散相进行分析。结果,除了(Ti,Zr)_5Si_3和Zr_5Si_3两种六方晶格的硅化物相外,许多含硅的钦合金也存在四方晶格的TiSi相。     

TC4合金表面Zr增效硅化物涂层的组织结构及韧性

采用扩散共渗的方法在TC4合金表面制备了Zr增效的硅化物涂层,研究了涂层的组织形成机制和韧性。结果表明,所制备的涂层具有多层结构,由外向内分别由(Ti,X)Si_2(X代表Zr、Al和V)外层、TiSi中间层和Ti_5Si_4+Ti_5Si_3内层组成。涂层的形成主要受Si向基体合金内的扩散控制,Zr在渗包内的卤化物气相分压虽然较Si的高,但扩散速率较慢,在涂层内的含量较低。与TC4合金表面单一硅化物涂层相比,Zr增效硅化物涂层具有更优良的韧性。     

Zr-Si合金的显微组织与力学性能

选用真空钨极纽扣熔炼炉制备Zr-xSi(x=0,2,3.3,4,7 mass%)合金。采用光学显微镜(OM),X-射线衍射仪(XRD),扫描电镜(SEM)对合金退火态的显微结构进行研究。结果表明:铸态纯Zr的物相为α相,添加Si元素后,合金中出现了Zr5Si3和Zr_2Si相的衍射峰,当Si含量为7%时,可明显看到Zr_2Si相的衍射峰强度增加;四边形块状、长条状为初生的硅化物Zr5Si3,颗粒状化合物为Zr_2Si,随着Si含量增多,硅化物的数量也明显增多;当Si含量为4%时,四边形块状的Zr5Si3相及颗粒状的Zr_2Si分布均匀。力学性能及断口研究表明:铸态Zr-4Si合金的抗压强度最高,约1154 MPa,屈服强度为845 MPa,伸长率为10.3%,展示了良好的综合性能;合金断口中的裂纹被清楚的观察到,且为脆性断裂,表明塑性较低。     

退火温度对Zr-3.3Si合金显微组织和力学性能的影响

采用光学显微(OM),X-射线衍射仪(XRD),扫描电镜(SEM)对铸态以及分别在600、700、800和900℃退火处理30 min的Zr-3.3wt%Si合金的显微结构进行了研究。结果表明:铸态Zr-3.3Si合金的相组成主要为α-Zr、Zr5Si3和Zr2Si,合金退火处理后,没有新的衍射峰出现,但衍射峰向高角度有轻微的偏移。在600℃退火时,粗大的四边形Zr5Si3相数量减少,而长条状的硅化物没有明显变化;退火温度为700℃时,四边形硅化物数量增多,尺寸细小、分布均匀;温度继续升高,硅化物的尺寸没有减小,反而增加。力学性能研究表明:在700℃退火时合金的抗压强度和屈服强度最高,分别达到1249 MPa和1094 MPa,硬度值达到最大,约353 HV0.2,但塑性应变是最低的,仅有6.2%。     

Elastic properties and electronic structure of vanadium silicides-a density functional investigation

Vanadium and silicon form several binary compounds; the most well characterized structures have the compositions V:Si = 3:1, 5:3, 6:5, 1:2. Spin-polarized density functional band-structure calculations using the projector augmented wave method have been carried out for the stable binary compounds in the Si–V system. As many rare earth and early transition metals are refractory materials, the study focuses on the ground state structures and their stabilities by determining their elastic properties. The magnetic properties are also investigated because structurally related Si–Mn compounds exhibit magnetism. All the silicides investigated were found to be refractory, hard, metallic materials and no magnetism was found in the ground state structures.     

Overview of magnetoelastic coupling in(Mn,Fe)_2(P,Si)-type magnetocaloric materials

(MnFe)_2(P, Si)-type compounds are, to date, one of the best candidates for magnetic refrigeration and energy conversion applications due to the combination of giant magnetocaloric effect (MCE), tunable working temperature range and low material cost. The giant MCE in the (Mn,Fe)_2(P, Si)-type compounds originates from strong magnetoelastic coupling, where the lattice degrees of freedom and spin degrees of freedom are efficiently coupled. The tunability of the phase transition, in terms of the critical temperature and the character of the phase transition, is essentially attributed to the changes in the magnetoelastic coupling in the (Mn, Fe)_2(P, Si)-type compounds. In this review, not only the fundamentals of the magnetoelastic coupling but also the related practical aspects such as magnetocaloric performance, hysteresis issue and mechanical stability are discussed for the (Mn, Fe)_2(P, Si)-type compounds. Additionally, some future fundamental studies on the MCE as well as possible ways of solving the hysteresis and fracture issues are proposed.     

Electronic struture of titanium silicides

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Reactive growth of niobium silicides in bulk diffusion couples

The diffusion-controlled growth of niobium silicides (NbSi₂ and Nb₅Si₃) was studied in Nb/Si and Nb/NbSi₂ bulk diffusion couples annealed at 1200–1350 °C for 2–24 h. Both compounds were found to grow as parallel layers, according to the parabolic rate law. The concept of the integrated diffusion coefficient is used to describe the growth kinetics of the two silicides. The corresponding activation energy is 263 kJ/mol for Nb₅Si₃ and 304 kJ/mol for NbSi₂. The activation energy (in eV) scales as 0.98T_m(K)/1000 for Nb₅Si₃ and as 1.4T_m(K)/1000 for NbSi₂ in agreement with the general behavior observed for many transition metal silicides. The position of the Kirkendall plane inside the Nb₅Si₃ layer developed in Nb/NbSi₂ couples indicates that, in the present temperature range, the diffusion of Si in Nb₅Si₃ is considerably faster than that of Nb.     

Reactive diffusion in the system vanadium–silicon

The diffusion-controlled growth of vanadium silicides (V₃Si, V₅Si₃, V₆Si₅, VSi₂) was studied on bulk V–Si diffusion couples annealed for 2–36 h at 1150–1390°C. The layer growth kinetics was parabolic for all of the silicides. Only at 1150 and 1200°C was an induction period observed before the formation of a continuous V₆Si₅ layer. The parabolic growth constants of the II kind for the exclusive growth of each silicide from the adjacent phases were calculated from the parabolic constants of the I kind measured on the V–Si diffusion couples. The rate constants of the II kind were in turn related to the diffusion properties of the silicides. As a result, the interdiffusion coefficient, taking into account the diffusion of both elements, was obtained for each phase. The resulting activation energies were 240 kJ mol⁻¹ for V₃Si, 250 kJ mol⁻¹ for V₅Si₃ and 190 kJ mol⁻¹ for VSi₂. The activation energies scale well with the melting point of the compounds. For V₆Si₅, the activation energy is strongly dependent on the set of thermodynamic data used in the calculation owing to the uncertainty in the decomposition temperature of this phase.     

Die Korrosionsbeständigkeit der Silicide der Übergangsmetalle

The corrosion resistance of the silicides of transitional metals The disilicides of Ti, V, Nb, Ta, Cr, Mo and W, as well as Mo₅Si₃, Mo₃Si and W₃Si₂ have, in general, an extremely high resistance to acids. However, the silicides of Mo and W have a low resistance to most acids whilst the remaining silicides have a high resistance to nitric, hydrochloric and sulphuric acid, but a low resistance to hydrofluoric acid, but a low resistance to hydrofluoric acid. Similar conditions are encountered for hydroazoic acid whilst the resistance of all silicides to NaOH is poor. The high resistance to acids is due to the formation of a surface layer rich in SiO₂. To obtain comparable results, the silicides were ground to powder which was then fused in a plasma are into fairly uniform globules.     

Transformations and phase relations in Nb—Ti—Si ternary system at 1373—1473K

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激光熔覆Ni-Si金属硅化物复合材料涂层显微组织与耐蚀性

以Ni,Si,Cr元素粉末为原料 ,利用激光熔覆技术在A3钢表面制得了Ni Si金属硅化物复合材料涂层。分析了该涂层的显微组织 ,采用测定阳极极化曲线的方法评价了该涂层在 0 .5mol/LH2 SO4 及 3 .5 %NaCl水溶液中的耐蚀性能。结果表明 :激光熔覆Ni Si金属硅化物复合材料涂层组织由Ni2 Si初生胞状树枝晶及枝晶间少量FeNi/Ni31Si12 共晶组成 ,涂层表面平整、组织细小、与基体间为完全冶金结合 ;涂层组织显微硬度在HV80 0～ 95 0之间且沿层深分布均匀 ;由于涂层组织组成相Ni2 Si和Ni31Si12 等本身均具有很好的耐蚀性并具有快速凝固细小均匀的显微组织 ,激光熔覆Ni Si金属硅化物复合材料涂层在 0 .5mol/LH2 SO4 及 3.5 %NaCl水溶液中均表现出优良的耐蚀性能。激光熔覆Ni Si金属硅化物复合材料涂层可望成为一种很有发展前景的耐蚀涂层新材料。     

Ir–Nb–Si ternary refractory superalloys with a three-phase fcc/L12/silicide structure for high-temperature applications

Ir–Nb binary alloys doped with silicon have been used in this work to attain a three-phase fcc/L1₂/silicide structure. Typical Ir–Nb binary alloys, including a hypoeutectic Ir–10Nb, an eutectic Ir–16Nb, and a hypereutectic Ir–25Nb, were used as alloy bases, and Ir was further replaced by 5 at% Si. With the addition of Si, the microstructures of the Ir–(10–25)Nb–5Si ternary alloys contained three phases: fcc, L1₂, and compounds of Ir and Si (referred to silicide hereafter). Compressive tests from room temperature to 1500 °C showed that the Ir–10Nb–5Si alloy, with a predominant fcc microstructure, always had the highest deformation hardening rate, strength, and ductility; on the other hand, the Ir–25Nb–5Si alloy showed the worst performance. With the silicide in the microstructures, the damage sustained by the Ir–Nb–Si alloys at both room and high temperatures was dominated by interface debonding, which occurred between the fcc and the silicide or the L1₂ and the silicide. It is believed that the interface debonding is an instinct failure mechanism of Ir-based alloys. Additionally, a strong solid-solution hardening effect of Si acting on the fcc phase was found to occur without loss of ductility. A principle in the composition and microstructure design is proposed in this paper for further development of Ir-based alloys with Si addition. This principle is to saturate the fcc phase with Si and other alloying elements so as to achieve maximum solid-solution hardening and tie-in fine silicides homogenously distributed within the fcc by elimination of the grain boundary concentration of silicides.     

A Review of Metal Silicides for Lithium-Ion Battery Anode Application

Lithium batteries(LIBs) with low capacity graphite anode(～372 mAh g~(-1)) cannot meet the ever-growing demand for new energy electric vehicles and renewable energy storage.It is essential to replace graphite anode with higher capacity anode materials for high-energy density LIBs.Silicon(Si) is well known to be a possible alternative for graphite anode due to its highest capacity(～4200 mAh g~(-1)).Unfortunately,large volume change during lithiation and delithiation has prevented the Si anode from being commercialized.Metal silicides are a promising type of anode materials which can improve cycling stability via the accommodation of volume change by dispersing Si in the metal inactive/active matrix,while maintain greater capacity than graphite.Here,we present a classification of Si alloying with metals in periodic table of elements,review the available literature on metal silicide anodes to outline the progress in improving and understanding the electrochemical performance of various metal silicides,analyze the challenges that remain in using metal silicides,and offer perspectives regarding their future research and development as anode materials for commercial LIBs application.