两相WC-Ni系硬质合金成份的评估原理

探讨了两相 WC- Ni系硬质合金的成分、相含量同合金密度 d及比饱和磁化强度 4πσ的定量关系 ,并将这些关系归因于γ相 (镍基 Ni- W- C固溶体 )成分 (钨和碳在γ相中的固溶度 )的影响。得到了相应于 WC- Ni系合金材料处于 WC+γ两相区上、下限成分和消磁 (4πσ=0 )成分的密度求值公式。论述了评估两相 WC- Ni系硬质合金成分的原理。     

机械合金化制备W-Ni-Fe纳米-非晶材料

按照80．7W-13．2Ni-6．1Fe的原子分数．采用机械合金化(MA)方法，制备了W-Ni-Fe合金纳米晶和非晶相的混晶结构。结合XRD，利用近似内标法计算了球磨不同时间球磨粉中残留晶体W的体积分数和非晶相中的W含量，并分析了球磨过程中非晶形成的机制。结果表明：随球磨时间的延长，W晶粒不断细化．球磨60h，钨晶粒尺寸可达到10nm-20nm，非晶相的形成过程主要是Ni(Fe)首先溶入W中形成过饱和固溶体，球磨20h后形成W-Ni(Fe)非晶。过饱和固溶体的形成是由于携带较大晶界存储能的小粒子不断溶入W中，计算得到可固溶的临界Ni粒子尺寸约为3nm。由于Fe污染不断溶入W中，在球磨过程中，残留晶体W的体积分数不断减少．而非晶相中的W-Ni(Fe)比例基本保持恒定，为63W-37Ni(Fe)。     

机械合金化制备Ni-W(B)非晶-纳米晶的粉末特性

利用机械合金化(MA)制备了Ni-20.7W和Ni-17.9W-27B(at%)非晶-纳米晶粉末,分别采用扫描电镜(SEM)和X射线衍射(XRD)仪分析了不同球磨时间粉末的微观形貌和结构参数,探讨了B的添加对非晶化过程的影响。研究结果表明:MA过程中,Ni-20.7W样品没有明显发生非晶化,而Ni-17.9W-27B样品在40 h时发生了非晶化,说明B提高了Ni-W合金体系的非晶化形成能力;非晶化过程为W/B首先固溶于Ni中生成Ni(W,B)过饱和固溶体,然后转变为非晶;Ni-20.7W样品球磨30 h后Ni的晶粒尺寸为32.9 nm,晶格畸变为0.48%,而Ni-17.9W-27B样品球磨10 h后的晶粒尺寸为9 nm,晶格畸变为0.62%。     

高能球磨合成W—Ni—Fe纳米复合粉末特性

采用X衍射、BET氮吸附法和DTA差热分析方法对球磨后的90W-7Ni-3Fe(质量百分数）纳米复合粉的组织结构变化、表面特性和热稳定性进行了系统的研究。XRD和DTA的分析结果表明：球磨可以生成纳米复合粉,晶粒内部产生很大的晶格畸变,同时球磨产生的密度和缺陷使原子扩散加快,形成超饱和固溶体、非晶和扩大W在粘结相中的溶解度,BET氮吸附结果证明了球磨使粉末产生微孔,比表面、中孔表面和孔径降低。     

稀土La在纳米晶（W, Ni, Fe, La）复合粉末烧结过程中的作用机理

采用溶胶-喷雾干燥法制备纳米晶(W,Ni,Fe,La)复合粉末,研究了粉末在烧结过程中La对抑制鼓泡和晶粒长大的作用机理,通过XRD与SEM分析了La在烧结过程中的相转变规律和在合金中的存在形式,讨论了稀土La对合金液相烧结过程中扩散的影响。结果表明:稀土La在纳米复合粉末中主要以La2WO6与La4W2O15的形式存在。经液相烧结后,稀土La主要以二次相颗粒的形式分布于粘结相中,生成高温下能稳定存在的La4W2O15相,该相对杂质元素Ca、O具有很好的亲和力,起到晶界净化和晶内净化的作用。同时二次相颗粒存在于粘结相中,抑制了W在粘结相中的扩散,降低了W在粘结相中的溶解度,使得液相烧结溶解-析出过程减慢,从而抑制液相烧结阶段的晶粒长大和鼓泡现象。     

纳米晶Mo-Cu复合粉末烧结行为的研究

采用溶胶-喷雾干燥-煅烧-氢气还原的方法制备了纳米晶Mo-18Cu、Mo-30Cu、Mo-40Cu复合粉末,研究了纳米晶Mo-Cu粉末的烧结行为以及Cu含量对致密化的影响.结果表明,纳米晶Mo-Cu复合粉末致密化程度高,速度快,在1050～1200 ℃烧结,Mo-30Cu和Mo-40Cu的相对密度可达98%以上,且合金晶粒细小,而Mo-18Cu在1350 ℃以上烧结,相对密度也可达98%以上,但晶粒聚集长大到5 μm左右.研究发现Mo-Cu复合粉末形成了亚稳态的超饱和Mo(Cu)固溶体,随着烧结温度的升高,Cu相逐渐从亚稳态的超饱和Mo(Cu)固溶体颗粒中析出.     

镧和钇对氢气还原(W,Ni,Fe)复合氧化物粉末的影响

以喷雾干燥法制备的(W,Ni,Fe)复合氧化物粉末为原料,在700℃、保温90 min的条件下进行还原,研究了镧和钇对氢气还原(W,Ni,Fe)复合氧化物粉末的影响.采用XRD、高倍TEM和SEM分别对还原后的复合粉末进行了物相分析、晶粒尺寸计算和形貌观察,并对还原后复合粉末的Fsss粒度、比表面进行了测定与分析.研究结果表明:不加稀土元素时,还原粉末由钨和γ-(Ni,Fe)两相组成,添加一定量的镧或钇后,还原粉末中分别出现了新相La(Ni0.75W0.25)O3或Y(Ni0.75W0.25)O3;未添加稀土元素时,颗粒为球形,添加一定量的稀土元素时,颗粒变为近球形或多面体,并随着稀土元素含量的增加,稀土元素对颗粒形貌的影响增大;当90W-7Ni-3Fe复合粉末中的稀土元素含量为0～0.8%时,随着稀土元素含量的增加,粉末dBET粒度、Fsss粒度和晶粒尺寸均显著降低,且粉末的分散性也明显提高;当添加相同含量的稀土元素时,对粉末性能影响程度的大小顺序是钇＞La-Y(混合稀土)＞镧.     

线能量密度对电子束增材制造W-Ni-Fe合金致密化过程的影响

采用粉床型电子束增材制造技术制备了90W-7Ni-3Fe高比重钨基合金,研究了不同的线能量密度对合金的显微组织及致密化过程的影响。结果表明:电子束增材制造成形的90W-7Ni-3Fe合金的组织由W颗粒和Ni-Fe固溶体粘结相组成,粘结相内溶解了一定量的W,随着线能量密度的增大,粘结相的含量及其内部W的含量增大;在不同的线能量密度下合金的致密化过程略有不同:在低的线能量密度下(0. 24 J/mm),合金的致密化过程主要是钨颗粒的粘结,随着线能量密度的升高(0. 3～0. 75 J/mm),出现了W颗粒的重排和W在Ni-Fe固溶体里的溶解-析出,随着能量密度继续增大(1. 0 J/mm),出现了一定量的钨颗粒的熔化和低熔点元素Ni、Fe的挥发,且随着钨在粘结相中的含量升高,合金的固溶强化作用增强,显微硬度相应提高。     

80W-10Ta-7Ni-3Fe高密度合金研究

用金相显微镜，扫描电镜，X射线衍射及密度测定，研究了90W-7Ni-3Fe和80W-10Ta-7Ni-3Fe2种成分合金。结果表明，含Ta合金在1400℃烧结时密度可达96.3％，合金密度随烧结温度提高而增加，在1460℃时密度达到最大；Ta原子固溶到硬质相W和粘结相中，使得合金硬度明显提高；含Ta合金断口形貌中，粘结相呈沿晶断裂、W晶粒穿晶断裂及其脱出具有相当比例；Ta粉末粒度对合金力学性能、微观组织及断裂方式均产生显著影响。     

高能球磨制备Fe-Cu纳米晶过饱和固溶体

对Fe-20at%Cu合金粉末进行了高能球磨,并利用XRD对Fe-Cu二元合金粉末在球磨过程中的物相变化进行了分析。结果表明,球磨30 h后形成了Fe(Cu)纳米晶过饱和固溶体。热力学计算分析指出,Fe-Cu二元系不具有形成过饱和固溶体的热力学驱动力。高能球磨在Fe-Cu二元互不溶体系中扩展固溶度的驱动力是动力学驱动。在随后的退火过程中,纳米晶过饱和固溶体发生分解。     

Fabrication of nano-crystalline W-Ni-Fe alloy with Mo and rare earth element additives

Three kinds of nano-crystalline high density alloys (86W-7Ni-3Fe-4Mo, 90W-4Ni-2Fe-4Mo and 90W4Ni-2Fe-3.8Mo-0.2RE) were fabricated by a technique combining lower temperature vacuum sintering with highenergy ball milling mechanical alloying. The crystalline size and microstructures of the specimens sintered at different sintering temperatures were examined by X-ray diffraction(XRD) and scanning electron microscope(SEM). The results show that the optimal sintering temperature of 86W-7Ni-3Fe-4Mo, 90W-4Ni-2Fe-4Mo and 90W-4Ni-2Fe-3.8Mo-0.2RE alloys are 1 300 - 1 350℃. When they are sintered at 1 300℃ for 75 min， the hardness of three kinds of specimens can reach above HRC30, the relative density can reach above 96%, and 90W-4Ni-2Fe-3.8Mo-0.2RE alloy possesses the best integrated properties, its hardness is HRC35 and its relative density is 98%.     

Microstructure and properties of liquid-phase sintered tungsten heavy alloys by using ultra-fine tungsten powders

The microstructure and properties of liquid-phase sintered 93W-4.9Ni-2.1Fe tungsten heavy alloys using ultra-fine tungsten powders (medium particle size of 700 nm) and original tungsten powders (medium particle size of 3um) were investigated respectively. Commercial tungsten powders (original tungsten powders) were mechanically milled in a high-energy attritor mill for 35 h. Ultra-fine tungsten powders and commercial Ni, Fe powders were consolidated into green compacts by using CIP method and liquid-phase sintering at 1465℃ for 30 rain in the dissociated ammonia atmosphere. Liquid-phase sintered tungsten heavy alloys using ultra-fine tungsten powders exhibit full densification (above 99% in relative density) and higher strength and elongation compared with conventional liquidphase sintered alloys using original tungsten powders due to lower sintering temperature at 1465℃ and short sintering time. The mechanical properties of sintered tungsten heavy alloy are found to be mainly dependent on the particles size of raw tungsten powders and liquid-phase sintering temperature.     

Microstructural control of and mechanical properties of mechanically alloyed tungsten heavy alloys

93W-5.6Ni-l.4Fe tungsten heavy alloys with controlled microstructures were fabricated by mechanically alloying of elemental powders of tungsten, nickel and iron by two different process routes. One was the full mechanical alloying of blended powders with a composition of 93W-5.6Ni-l.4Fe, and the other was the partial mechanical alloying of blended powders with a composition of 30W-56Ni-14Fe followed by blending with tungsten powders to form a final composition of 93W-5.6Ni-l.4Fe. The raw powders were consolidated by die compaction followed by solid state sintering at 1300°C for 1 hour in a hydrogen atmosphere. The solid state sintered tungsten heavy alloys were subsequently liquid phase sintered at 1445∼1485°C for 4-90 min. The two-step sintered tungsten heavy alloy using mechanically alloyed 93W-5.6Ni-l.4Fe powders showed tungsten particles of about 6-15 μm much finer than those of 40 um in a conventional liquid phase sintered tungsten heavy alloy. An inhomogeneous distribution of the solid solution matrix phase was obtained in the two-step sintered tungsten heavy alloy using partially mechanically alloyed powders. The two-step sintered tungsten heavy alloy using mechanically alloyed 93W-5.6Ni-l.4Fe powders showed larger elongation of 16% than that of 1% in the solid state sintered tungsten heavy alloy due to the increase in matrix volume fraction and decrease in W/W contiguity. Dynamic torsional tests of the two-step sintered tungsten heavy alloys showed reduced shear strain at maximum shear stress than did the sintered tungsten heavy alloys using the conventional liquid phase sintering.     

Densification behavior of nanocrystalline W–Ni–Fe composite powders prepared by sol-spray drying and hydrogen reduction process

This paper studied the densification behavior of nanocrystalline composite powders of 93W–4.9Ni–2.1Fe (wt.%) and 93W–4.9Ni–2.1Fe–0.03Y synthesized by sol-spray drying and hydrogen reduction process. The X-ray diffraction (XRD) analysis showed that γ-(Ni, Fe) phase was formed in the final obtained powders. Powders morphology characterized by scanning electron microscope (SEM) showed that the 93W–4.9Ni–2.1Fe nanocrystalline composite powders exhibited larger agglomeration and grain size compared with the 93W–4.9Ni–2.1Fe–0.03Y nanocrystalline composite powders. Both kinds of green compacts can obtain full density if sintered at 1410 °C for 1 h. When sintering temperature was above 1410 °C, the sintering density for both compacts decreased rapidly. In addition, the sintering density, densification rate and grain coarsening rate of 93W–4.9Ni–2.1Fe compacts were higher than those of 93W–4.9Ni–2.1Fe–0.03Y. The effect of trace yttrium on the densification behavior of nanocrystalline composite powders was also discussed.     

Microstructure and properties of ultra-fine tungsten heavy alloys prepared by mechanical alloying and electric current activated sintering

The microstructure and properties of the 93W-4Ni-2Co-1Fe(mass fraction,%) tungsten heavy alloys prepared by mechanical alloying and electric current activated sintering from mixed elemental powders were investigated.After 15 h milling,the average W grain size in the powders is decreased to 120 nm.For the powders milled for 15 h,the density,hardness and transverse rupture strength of the alloys sintered only by an intensive pulse electric current are the maximum.When the total sintering time keeps constant,t...     

Grain refinement of W-Ni-Fe heavy alloys by tantalum element adding

90W-TNi-3Fe and (90-x)W-xTa-7Ni-3Fe (x= 1,3,5,7,10) specimens were attained by liquid phase sintering. A model describing the process of liquid forming and spreading was proposed to point out the differences between alloys doped with tantalum and traditional tungsten heavy alloys. Tantalum priority of entering matrix and a relative high solubility in liquid matrix depress tungsten solubility in liquid matrix, which decreases kinetic rate constant K and consequently results in the reduction of W grain size. The grain refinement is influenced by Ta content and becomes more obvious when Ta content is over 5%. The sample with less than 3%Ta has dominant W and matrix phases. While besides W and matrix phases, intermetallic phases emerge in 85W-5Tai-TNi-3Fe sample. Ta is superfluous and forms a new tantalum phase when more than 7% Ta is added into alloys.     

Sintering of a nano-crystalline tungsten heavy alloy powder

A nano-crystalline Tungsten heavy alloy powder was obtained by mechanical alloying of elemental powders in a jar mill with a high ball to powder ratio. The chemical composition of the primary powder was 93 W-4.9Ni-2.1Fe (wt%). The mechanically alloyed powder had 22 nm sized tungsten crystallites distributed in an amorphous nickel base phase. Mechanical alloying reduced particle size of powders and also yielded to more uniform particles size distribution. Sintering behavior and microstructural development of that powder were studied and compared with a conventionally mixed powder. Mechanically stored energy and better distribution of primary elements in Nano-crystalline powder had decreased motivation energy of sintering and that powders showed more densification at relatively lower sintering temperatures. Sintering at low temperatures can depress grain growth during sintering and provide desirable properties. A transient intermetallic phase was formed in the nano-crystalline powder during sintering that has not been seen in conventionally mixed powders.     

放电等离子烧结时间对高密度W-7Ni-3Fe合金组织性能的影响

利用放电等离子烧结技术制备高密度W-7Ni-3Fe合金,研究了烧结保温时间对合金致密度、物相、显微组织以及力学性能的影响。结果表明,在1200℃烧结5~14 min后,合金均能实现充分致密化,保温时间对相对密度影响较小。合金中的W晶粒随保温时间的延长开始尺寸变化不大,烧结11 min以上才明显长大,但大多数W晶粒尺寸仍小于5μm。烧结时间超过8min,合金中新出现一种灰色的富W组织。随保温时间延长,合金的洛氏硬度下降不大,然而抗弯强度却明显上升。合金弯曲断口形貌在较短保温时间以沿晶断裂为主,粘结相的延性撕裂和W晶粒的解理断裂随烧结时间延长逐渐增多。     

Properties and microstructural evolution of W-Ni-Fe alloy via microwave sintering

The mechanical properties and microstructure evolution of 93W-4.9Ni-2.1Fe (wt.%) alloys were investigated via microwave sintering. The microwave sintering promoted the dissolution and diffusion of tungsten atoms in the matrix phase and strengthened sintering activity. With the increase of microwave sintering temperature, pores in the alloy were reduced and gradually eliminated, tungsten grains coarsened, the distribution of tungsten grains and matrix phase became more homogeneous, and the fracture mode transformed from intergranular fracture to tungsten transgranular cleavage fracture, respectively. The W-matrix interfacial bond strength of 93W-4.9Ni-2.1Fe was enhanced and the mechanical properties were significantly improved with the increase of sintering temperature.