Effect of Process Conditions on the Synthesis of TiB2/TiC Nanocomposite Powders by Mechanical Alloying

采用机械合金化的方法利用工业纯Ti粉和B4C粉末合成了TiB2/TiC 纳米复合粉末。结果表明,球磨过程中保护气氛的纯度对合金化过程有着非常重要的影响。在纯氩气保护的情况下球磨5 h,Ti和B4C粉末发生了固相反应,形成了复合TiB2/TiC相,随着球磨时间增加,合成的TiC相的晶粒尺寸减小至10 nm,而TiB2晶粒尺寸略大;如果球磨过程中混入空气,合金化产物中将会出现大量的TiN和TiO     

球磨工艺对原位合成纳米级TiB的影响

球磨工艺对球磨粉末及其烧结组织的微观结构和形态都有重要的影响。本实验采用低能和高能球磨两种方式对Ti-Al-0.2B wt.%合金粉末进行球磨,研究球磨过程中粉末组织和形态的变化,并将球磨后的粉末进行热压烧结,研究不同球磨方式对烧结组织中原位合成TiB增强相形态的影响。研究结果表明：低能球磨过程中粉末颗粒间有机械合金化发生,其烧结组织中生成的TiB为细长态,在基体中分布均匀,没有联结的粗晶或成簇生长现象。对于高能球磨,粉末颗粒细化效果明显,颗粒平均尺寸降至1 μm,球磨过程中除了机械合金化还形成了Ti(Al)过饱和固溶体,并在球磨后期形成了非晶结构。经高能球磨的粉末烧结后,组织中生成了均匀分布的纳米级TiB晶须。     

Synthesis and grain growth kinetics of in-situ FeAl matrix nanocomposites （ Ⅱ ）： Structural evolution and grain growth kinetics of mechanically alloyed Fe-Al-Ti-B composite powder during heat treatment

Morphological changes, structural evolutions and grain growth kinetics of mechanically alloyed（MAed） Fe50Al50, Fe42.5Al42.5Ti5B10 and Fe35Al35Ti10B20 （mole fraction, %） powders were investigated by XRD and SEM, when being isothermally annealed at 1 073-1 373 K. The effect of different Ti and B addition on the grain growth of FeAI phase was also discussed. The results show that the nanocrystalline FeAI and in-situ TiB2/FeAl nanocomposite powders can be synthesized by subsequent heat treatment. Besides the relaxation of crystal defects and lattice stress, the transformation from Fe-based solid solution into B2-FeAl and TiB2 occurs upon heating of the MA-processed alloys. Although the grain growth takes place, the grain sizes of both FeAl and TiB2 are still in nanometer scale. The activation energies for the nanocrystalline FeAl growth in the three alloys are calculated to be 534.9, 525.6 and 1 069.6 kJ/mol respectively, according to kinetics theory of nanocrystalline growth. Alloys with different TiB2 contents exhibit unequal thermal stability. The presence of higher content TiB2 plays significant role in the impediment of grain growth.     

Synthesis and grain growth kinetics of in-situ FeAl matrix nanocomposites (Ⅱ): Structural evolution and grain growth kinetics of mechanically alloyed Fe-Al-Ti-B composite powder during heat treatment

Morphological changes, structural evolutions and grain growth kinetics of mechanically alloyed(MAed) Fe50Al50, Fe42.5Al42.5Ti5B10 and Fe35Al35Ti10B20 (mole fraction, %) powders were investigated by XRD and SEM, when being isothermally annealed at 1 073-1 373 K. The effect of different Ti and B addition on the grain growth of FeAl phase was also discussed. The results show that the nanocrystalline FeAl and in-situ TiB2/FeAl nanocomposite powders can be synthesized by subsequent heat treatment. Besides the relaxation of crystal defects and lattice stress, the transformation from Fe-based solid solution into B2-FeAl and TiB2 occurs upon heating of the MA-processed alloys. Although the grain growth takes place, the grain sizes of both FeAl and TiB2 are still in nanometer scale. The activation energies for the nanocrystalline FeAl growth in the three alloys are calculated to be 534.9, 525.6 and 1 069.6 kJ/mol respectively, according to kinetics theory of nanocrystalline growth. Alloys with different TiB2 contents exhibit unequal thermal stability. The presence of higher content TiB2 plays significant role in the impediment of grain growth.     

Microstructures of mechanically activated Ti-46at.% Al powders and spark plasma sintered ultrafine TiAl alloy

Powder of Ti-46at.%Al was synthesized through mechanical activation (MA) for different milling times, and the 16 h MAed powder was sintered by using a spark plasma sintering (SPS) process at different sintering temperatures. The XRD profiles showed that the MAed Ti-46at%Al powder for 12,16, and 20 h contained initial α-Ti and Al phases, and that the SPSed TiAl alloys contained the gamma TiAl and α2-Ti3Al phases. The TEM showed two different types of regions in the 16 h MAed Ti-46at.%Al powder. One type consisted of only Al with a grain size about 80 nm, and the other type a mixture of Al and Ti with a grain size of 30 nm. According to the optical micrographs of MA-SPSed samples, the alloys sintered at higher temperatures showed a coarser microstructure. In the case of the 1473 K sintering, typical duplex structures ((α2 + γ) lamella and γ phases) with interlamellar spacings of 50-400 nm and the grain size either less man 100 nm, or 1000 nm were observed.     

Microstructures of mechanically activated Ti-46at.%Al powders and spark plasma sintered ultrafine TiAl alloy

Powder of Ti-46at.%Al was synthesized through mechanical activation (MA) for different milling times, and the 16 h MAed powder was sintered by using a spark plasma sintering (SPS) process at different sintering temperatures. The XRD profiles showed that the MAed Ti-46at%Al powder for 12,16, and 20 h contained initial α-Ti and Al phases, and that the SPSed TiAl alloys contained the gamma TiAl and α2-Ti3Al phases. The TEM showed two different types of regions in the 16 h MAed Ti-46at.%Al powder. One type consisted of only Al with a grain size about 80 nm, and the other type a mixture of Al and Ti with a grain size of 30 nm. According to the optical micrographs of MA-SPSed samples, the alloys sintered at higher temperatures showed a coarser microstructure. In the case of the 1473 K sintering, typical duplex structures ((α2 γ) lamella and γ phases) with interlamellar spacings of 50-400 nm and the grain size either less man 100 nm, or 1000 nm were observed.     

不同SPS烧结温度Ti-45Al-5.5(Cr,Nb,B,Ta)合金的显微组织及力学性能(英文)

采用高能球磨和放电等离子烧结(SPS)技术,制备成分为Ti-45Al-5.5(Cr,Nb,B,Ta)的TiAl合金块体,随后对TiAl合金进行热处理。研究在不同SPS烧结温度下制备的TiAl合金经过热处理后的显微组织和力学性能。结果表明:高能球磨后的合金粉末形状不规则,粉末颗粒尺寸大约为几十微米。XRD分析表明,机械球磨后的粉末由TiAl和Ti3Al两相组成;烧结后的Ti-45Al-5.5(Cr,Nb,B,Ta)合金块体主要是TiAl相,以及少量的Ti3Al和TiB2相。当烧结温度为900°C和1000°C时,合金的显微组织为双相结构,并伴随有一些细小的等轴γ晶粒和细小的针状TiB2相。当烧结温度从900°C上升到1000°C时,Ti-45Al-5.5(Cr,Nb,B,Ta)合金的显微硬度变化不大,抗压强度从1812MPa提高到2275MPa,压缩率从22.66%增加到25.59%,合金的断裂方式为穿晶断裂。     

机械合金化制备纳米晶Ti-6Al-4V合金

采用机械合金化制备Ti-6Al-4V粉末。结果表明:采用机械合金化可以制备纳米晶Ti-6Al-4V合金粉,其反应机理以扩散为主,该固态反应是缺陷能和碰撞能共同作用的结果;随球磨时间延长,部分V固溶于Ti中形成置换固溶体Ti(V),球磨过程中没有中间相生成。球磨40 h后都能获得纳米晶,60 h的粉末为纳米晶和非晶的混合物,晶粒尺寸小于60 nm;60 h后晶粒尺寸变化缓慢。球磨后Ti、Al、V的原子比近似为90:6:4,与Ti-6Al-4V元素成分一致。     

高能球磨制备Al3Ti/Al块体纳米晶复合材料

通过对Al Ti系和Al TiO2 系进行高能球磨和压制烧结制备了固态原位反应生成的纳米晶块体Al3Ti/Al复合材料。研究表明 :Al Ti合金系高能球磨后 ,各组元晶粒得到细化 ,并且Ti在Al中发生了强制超饱和固溶 ,烧结时原位反应形成纳米晶Al3Ti/Al复合材料 ;而Al TiO2 反应体系高能球磨仅发生组分晶粒细化 ,烧结时TiO2 部分还原并和Al原位反应生成纳米晶 (Ti2 O3 Al3Ti) /Al复合材料。     

高能球磨制备Al-Pb-Si-Sn-Cu纳米晶粉末的特性

通过机械合金化制备了Al-15％Pb-4％Si-1％Sn-1．5％Cu(质量分数)纳米晶粉末。采用X射线衍射(XRD)，扫描电镜(SEM)和透射电镜(TEM)对不同球磨时间的混合粉末的组织结构、晶粒大小、微观形貌以及颗粒中化学成分分布情况进行了研究。结果表明混合粉末经过球磨后形成了纳米晶，其组织非常均匀。球磨对Pb的作用效果明显大于对Al的作用效果，经过40h球磨后Pb粒子达到40nm，而Al在球磨60h后晶粒为65nm；经球磨后，Cu和Si固溶于Al的晶格中，而Sn则固溶于Pb晶格中，并且Al和Pb发生了互溶，形成了Pb(Al）超饱和固溶体；在球磨过程中硬度高的脆性粒子Si难于完全实现合金化。     

原位TiB2/Fe3Al基纳米复合材料的合成及其晶粒生长动力学(Ⅰ)--Fe-Al-Ti-B四元粉体的机械合金化

研究了机械合金化过程中Fe-Al-Ti-B四元粉体的结构演变,讨论了其合金化机制.研究表明,Fe-Al-Ti-B四元粉体的机械合金化通过Al、Ti、B原子向Fe晶格中扩散形成Fe（Al,Ti,B）过饱和固溶体.在机械合金化的早期（＜10h）,形成包覆结构的复合颗粒,合金化尚未进行.在机械合金化的中期（10-60h）,首先形成具有几个同心圆环结构的复合颗粒,然后环状结构消失,同时Fe（Al,Ti,B）晶格常数迅速增加,但成分均匀化过程缓慢.在机械合金化的后期（60-80h）,主要发生复合颗粒内部的成分均匀化过程,球磨80h后,复合颗粒内部各组元的成分已经非常均匀.Fe（Al,Ti,B）晶粒细小（6.8nm）,晶格畸变严重,具有近似非晶态的结构.由于Ti、B元素的添加,Fe-Al-Ti-B四元粉体晶粒细化速率更快,但合金化速率明显降低.     

Synthesis and grain growth kinetics of in-situ FeAl matrix nanocomposites（ Ⅰ ）： Mechanical alloying of Fe-A1-Ti-B composite powder

Three nanocrystalline alloys, FesoAlso, Fe42.5Al42.5Ti5B10 and Fe35Al35Ti10B20 （molar fraction, %）, were synthesized from elemental powders by high-energy ball milling. The structural evolutions and morphological changes of the milled powders were characterized by X-ray diffractometry（XRD）, transmission electron microscopy（TEM） and scanning electron microscopy（SEM）. The effects of different Ti, B additions on the structure and phase transformation in these alloys were also discussed. It is observed that the diffusion of AI, Ti, B atoms into Fe lattice occurs during milling, leading to the formation of a BCC phase identified as Fe（Al） or Fe（Al, Ti, B） supersaturated solid solution. Fe-based solid solution with nanocrystalline structure is observed to be present as the only phase in all the alloy compositions after milling. Furthermore, the contents of Ti, B affect the formation of mechanical alloying products, changes in the lattice parameter as well as the grain size.     

机械合金化及热处理对TiH2-Ni粉末结构和形貌的影响（英文）

研究机械合金化及热处理对TiH2-Ni粉末的结构和形貌的影响。在初始球磨阶段,Ni(Ti)固溶体形成。当球磨至60h时,非晶结构的TiH2-Ni粉末形成,粉末中还包含少量的纳米晶TiH2相,粉末内元素分布均匀。球磨60h的粉末经693K热处理,发生了非晶化反应;经1073K短时间热处理后,非晶相结晶,形成Ti2Ni、TiNi和TiNi3相;在相同热处理温度下进一步延长热处理时间可使富镍相析出以及在3种Ti-Ni相之间发生相转变。     

粉末冶金碳化物强化铌合金组织演变及其力学行为

采用机械球磨与热压烧结相结合的粉末冶金法对不同球磨时间Nb-35Ti-6Al-5Cr-8V-5C合金的粉末变形行为,微观组织结构和力学行为进行研究。结果表明:随着球磨时间的增加,Nb-35Ti-6Al-5Cr-8V-5C复合粉末中的块状金属颗粒首先变形为片状后在碰撞挤压作用下破碎成絮状,TiC粉末均匀的分布于片状金属粉末表面;Nb-35Ti-6Al-5Cr-8V-5C合金由Nbss和(Nb,Ti)C两相构成,各合金碳化物体积分数均为11%左右,Ti元素主要分布于Nbss晶界和碳化物内,Al、Cr、V元素主要分布于Nbss晶粒内,Nbss和(Nb,Ti)C相尺寸均随球磨时间增加而尺寸减小;Nbss晶粒细化及强化相碳化物弥散化导致合金的室温压缩力学性能和塑性变形能力显著提高,压缩变形后合金Nbss与碳化物具有良好的界面结合能力,但是碳化物内部存在明显的近似平行分布的裂纹;数据对比表明,粉末冶金法制备Nb-35Ti-6Al-5Cr-8V-5C合金的力学性能优于电弧熔炼法。     

球磨纳米TiO2的结构转变

采用X射线衍射研究锐钛矿型纳米TiO2在高能球磨过程中及球磨后的纳米TiO2在退火过程中的结构变化。结果表现在室温常压下高能球磨诱发锐钛矿相转变为金红石相和S相。随着退火温度升高，球磨纳米TiO2粉末的晶粒逐渐长大，锐钛矿相逐渐转变为金红石相，而S相并不直接转变为金红石相而是先转变为锐钛矿相，然后由锐钛矿相转变为金红石相。与未球磨的纳米TiO2相比，高能球磨导致的晶粒细化，显微畸变以及晶格缺陷密度的增加而引起的额外储能使球磨后纳米TiO2的锐钛矿相-金红石相转变温度明显降低。     

机械合金化制备Ti(Al,C)复合粉末组织结构研究

目的通过原位合成技术获得Ti(Al,C)复合粉末。方法在不同球磨时间条件下,采用机械合金化方法制备Ti(Al,C)复合粉末,其中Ti粉和Al粉的摩尔比为1:1。采用扫描电子显微镜(SEM)以及X-射线衍射仪(XRD)分析球磨后粉末的显微组织结构及物相,研究不同球磨时间对制备Ti(Al,C)复合粉末物相演变、组织结构及粒子间界面结合状态的影响。结果在球磨过程中,球磨时间越长,粉体的粒径越小,当球磨时间增长到一定程度时,延展性好的Al粉颗粒发生扁平化且其表面积不断增大,使得碎化后的Ti粉颗粒不断嵌入至Al粉颗粒中,最终形成Ti(Al)固溶体。同时根据XRD分析发现,随着球磨时间的延长,Ti(Al,C)复合粉末中的Al峰逐渐减小,说明Al不断固溶到Ti中,形成了一定量的Ti(Al)固溶体。结论通过机械球磨技术在球磨一定时间后可原位合成Ti(Al)固溶体,这说明随着Ti与Al之间的相互扩散,有利于形成Ti(Al)固溶体。     

纳米晶W粉和W-Ni-Fe预合金粉的制备

采用高能球磨法制备纳米晶W粉和W-Ni-Fe预合金粉，研究了不同的球磨材质包括硬质合金球(CCB)、钨球(TAB)和球磨转速、球料比及球磨时间等条件对球磨后粉末性能的影响。利用XRD，TEM和EDX分析球磨后粉末的晶粒尺寸、晶格畸变、形貌、结构变化及颗粒成分变化。结果表明：高能球磨法可制得10nm～80nm的W粉和W-Ni-Fe预合金粉，纳米级颗粒含量达80％以上。相同材质的钨球制得的纳米粉末综合性能较好。球磨过程中，粉末保持颗粒状结构，纳米级粉末颗粒形状最终趋于等轴化。     

Structure and properties of composites prepared from partially amorphous ZrCuNiTi and nanocrystalline silver

Alloys of composition Zr40Cu40Ni10Ti10 and Zr48,5Cu32.5Ni9Ti10 (in at.%) were ball milled for 40 h starting from elemental powders or melt spun from cast ingots. In both cases amorphous structure was obtained, however in the case of ribbons, larger crystals of Cu₁₀Zr₇ or Ni₇Zr₂ phases of size of a few hundred nm were observed. In the case of milled alloys much finer intermetallic phases such as Zr₂Cu or Cu₁₀Zr₇ were identified within the amorphous matrix using X-ray diffraction or HRTEM. In both alloys DSC studies have shown higher crystallization temperature for the powder, than for the ribbon. It was explained by a different structure of preexisting intermetallic nuclei crystallizing in milled powders. The milled amorphous powder was also used as a matrix for composites containing 20% or 50% of nanocrystalline silver powder, prepared from silver powder by ball milling. The composites hot pressed at the same temperature as the amorphous samples show in some places very narrow transition phase enriched in silver containing also other elements of the amorphous phase. Composites containing more silver show lower hardness and strength, but exhibit a few percent of plastic deformation in the compression test. Scanning electron studies of deformed composite samples show crack initiation within the amorphous phase, not at the components interfaces.     

机械合金化制备Ni-Ti合金粉末

研究了在机械合金化制备Ni粉和Ti粉并将之混合的过程中,球磨工艺,即球磨时间和球磨转速对粉末粒度的影响,并对粉末进行了XRD相分析.结果表明,以260r/min转速球磨60 h可以合成Ni-Ti非晶粉末,在氩气保护下于530℃×30 min退火可使Ni-Ti非晶粉末晶化.     

Microstructural evolution of mechanically alloyed Mo–Si–B–Zr–Y powders

Elemental powder mixtures with compositions of Mo–13.8Si, Mo–20B and Mo–12Si–10B–3Zr–0.3Y (at.%) were respectively milled in a high energy planetary ball mill at a speed of 500 rpm. Microstructural evolution of powder particles during milling processes was evaluated. The results show that B can hardly be dissolved into Mo under present milling conditions and the additions of B and Si both accelerate the refining rate of Mo crystallites. For Mo–12Si–10B–3Zr–0.3Y system, the morphology and internal structure of powder particles change significantly with milling time. After 40 h of milling, an almost strain-free super-saturated molybdenum solid solution with a grain size of about 6.5 nm forms. The grain refinement mechanism and dissolution kinetics of solute atoms are highlighted. Both thermodynamic calculation and experimental results reveal that for the present alloy composition it is more favorable to form solid solution than amorphous phase.