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.     

Effects of sintering conditions on mechanical properties of mechanically alloyed tungsten heavy alloys

The effects of sintering conditions on the microstructural evolution and mechanical properties of mechanically alloyed tungsten heavy alloys were investigated. W, Ni and Fe powders were mechanically alloyed in a tumbler ball mill at a milling speed of 75 rpm, ball-to-powder ratio of 20∶1 and ball filling ratio of 15%. The mechanically alloyed powders were compacted and solid-state sintered at a temperature of 1300°C for 1 hour in a hydrogen atmosphere. The solid-state sintered tungsten heavy alloy was subsequently liquid-phase sintered at 1470°C with varying sintering times from 4 min to 90 min. The solid-state sintered tungsten heavy alloy showed fine tungsten particles of 3 μm in diameter and high relative density above 99%. The volume fraction of the W-Ni-Fe matrix phase was measured, as 11% and tungsten/tungsten contiguity was 0.74 in solid-state sintered tungsten heavy alloys. Mechanically alloyed and two-step sintered tungsten heavy alloys showed tungsten particles of 6–15 μm and a volume fraction of the W-Ni-Fe matrix phase of 16% and tungsten/tungsten contiguity of 0.40. The solid-state sintered tungsten heavy alloy exhibited a yield strength of about 1100 MPa due to its finer tungsten particles, while it showed low elongation and impact energy due to its large tungsten/tungsten contiguity. The yield strength of two-step sintered tungsten heavy alloys increased with the decreasing of tungsten particle size and volume fraction of the W-Ni-Fe matrix. This article is based on a presentation made in “The 4th International Conference on Fracture and Strength of Solid”, held at POSTECH, Pohang, Korea, August 16–18, 2000 under the auspices of Far East and Ocean Fracture Society (FEOFS)et al.     

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.     

纳米钨合金粉末的制备技术

钨合金包括W－Ni-Fe,W-Ni-Cu,W-Cu,WC-Co等钨基合金材料。钨合金材料将是21世纪出现的一种多功能高性能的多胜任的新型材料。有杉纳米粉末制备的亚微或微米钨合金块体材料具有非常优越的潜在物理力学性能,用作高性能结构件和高性能电子、微电子等功能材料方面都将具有很大的潜在优势,可以更好地满足高性能新型材料的要求。本文综合近几年来国内外纳米钨合金的研究状况,详细地介绍了有关纳米钨合金粉末的制备技术,预测了今后钨合金材料的研究方向。     

Cu/W-Ni-Co/Ni多中间层的钨/钢扩散连接

采用铜箔/90W-5Ni-5Co(质量分数,%)混合粉末/镍箔复合中间层,在加压5 MPa、连接温度1120℃、保温60 min的工艺条件下,对纯钨(W)和0Cr13Al钢进行了连接。利用SEM、EDS、电子万能试验机及水淬热震实验等手段研究了接头的微观组织、成分分布、断口特征、力学性能及抗热震性能。结果表明,连接接头由钨母材、Cu-Ni-Co合金层、钨基高密度合金层、镍层、钢母材5部分组成。接头中的钨基高密度合金层由90W-5Ni-5Co混合粉末固相烧结生成,其Ni-Co粘结相和钨颗粒相冶金结合且分布均匀。钨基高密度合金层与钨母材以瞬间液相扩散连接机制实现了良好结合。接头剪切强度达到286 MPa,断裂均发生在钨基高密度合金层/镍层结合区域,断口形貌呈现为韧性断裂。经过60次700℃至室温的水淬热震测试,接头无裂纹出现。     

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.     

Milling media and alloying effects on synthesis and characteristics of mechanically alloyed ODS heavy tungsten alloys

Oxide dispersion strengthened (ODS) tungsten heavy alloys produced by mechanical alloying exhibit high creep strength at elevated temperatures and good penetration performance. The effect of process parameters during mechanical alloying is important in determining material properties. In this study, we have examined different grinding media and have varied the composition of alloying elements to investigate their effect on grinding performance and microstructure evolution. The composition of the milled powders can be changed due to the wear of the grinding media and can form different phases, which results in a significant effect on microstructural development and material properties. Our results show that alloys milled by a stainless steel grinding media encourage the formation of iron–tungsten carbides and iron–tungsten intermediate phases, which deteriorate the material densification and ductility. Conversely, the use of a tungsten carbide grinding media leads to an extreme refinement of the milled powders, whereby alloys form a uniform microstructure with a γ(Ni, Fe) phase configuration. This phase provides sufficient binding strength between the tungsten particles, such that the relative density and ductility of the materials were found to have been significantly enhanced.     

Impact and dynamic deformation behavior of mechanically alloyed tungsten heavy alloy

93W-5.6Ni-l.4Fe tungsten heavy alloy was fabricated by mechanical alloying process using elemental powders of tungsten, nickel and iron, followed by sintering at temperatures of 1445~1485°C under hydrogen atmosphere. The tungsten heavy alloy sintered using mechanically alloyed powders showed finer tungsten particles about 5~18 μm with high density above 99% at shorter sintering time than that fabricated by conventional liquid-phase sintering process. Charpy impact energy of mechanically alloyed tungsten heavy alloy increased with increasing the matrix volume fraction and with decreasing the W/W contiguity. The high strain rate dynamic deformation behavior of tungsten heavy alloys using torsional Kolsky bar test exhibited different fracture modes dependent on microstructure. While the brittle intergranular fracture mode was dominant when the tungsten particles were contiguously interconnected in tungsten heavy alloys solid-state sintered below 1460°C, the ductile shear fracture mode was dominant when the tungsten particles were surrounded by ductile matrix phase in tungsten heavy alloys liquid-phase sintered above 1460°C.     

Ta，b和MoTi50Ni20Cu25Sn5非晶合金玻璃形成能力的影响

利用旋转铜辊急冷法和铜模铸造法制备非晶合金薄带或圆棒，并采用X衍射仪(XRD)、差示扫描量热仪(DSC)和差示热分析仪(DTA)研究了Ta，Nb和Mo对Ti50Ni20Cu25Sn5非晶合金玻璃形成能力(GFA)的影响。结果表明，Ta的添加提高了Ti50Ni20Cu25Sn5合金的GFA，Mo的添加降低了该合金的GFA，Nb的添加剂对该合金的GFA没有明显的影响；含Ta合金具有超过60K的宽过冷液态区(△Tx)，且其约化玻璃转变温度因子(Tg／Tm)大于含Nb合金和含Mo合金；采用常规铜模铸造法制备出了直径为lmm的(Ti0.5Ni0.2Cu0.25Sn0.05)98Ta2和(Ti0.5Ni0.2Cu0.5Sn0.05)96Ta4块状非晶圆棒；(Ti0.5Ni0.2Cu0.25Sn0.05)98Ta2块状非晶圆棒的Tg，△Tx和Tg／Tm分别为678K，84K和0．60，而(Ti0.5Ni0.2Cu0.25Sn0.05)96Ta4块状非晶圆棒的Tg，△Tx和Tg／Tm分别为680K，70K和0．60。     

高密度钨合金性能的计算机数值模拟研究──钨含量对合金性能的影响

提出了一个钨合金的组织结构模型,在一定的假设条件下用有限元方法和计算机数值模拟研究了钨合金力学性能和钨含量的关系。结果表明;随钨含量增加,合金屈服强度提高,但弹性变形量和延伸率均降低。当钨含量＜85％（质量分数,下同）时,合金抗拉强度随钨含量增加而增加;当钨含量＞85％时,合金抗拉强度随钨含量增加而降低,在钨含量为85％附近达到最大值。在低钨含量合金中（＜90％）,高应力主要集中在钨颗粒中,随钨含量增加,粘结相中应力水平降低;在高钨含量合金中钨颗粒和粘结相中应力水平基本相同,随钨含量增加,粘结相中应力水平增加。     

The effect of phosphorus addition on the corrosion behavior of ARC-MELTED Ni10TaP alloys in 12 M HCl

The corrosion resistance of arc-melted Ni10TaP alloys containing 0, 10 and 20 at% phosphorus in 12 M HCl solution at 30 °C was investigated. The alloys containing 0 and 10 at% phosphorus suffer severe corrosion. The addition of 20 at% phosphorus to crystalline Ni10Ta alloy results in a three-orders-of-magnitude decrease in the corrosion rate. The open circuit potentials of the Ni10Ta alloys containing 0 and 10 at% phosphorus stay almost constant in the active region of nickel, while the open circuit potential of the Ni10Ta20P alloy increases almost linearly in the initial 2 h. The Ni10Ta alloy consists of intermetallic Ni₈Ta and immersion in 12 M HCl results in faceting dissolution. Ni10Ta10P alloy is composed of major Ni₈Ta and Ni₃P phases and minor Ni₂Ta and Ni₂P phases. Immersion of Ni10Ta10P alloy leads to preferential dissolution of the Ni₈Ta phase and to continuous thickening of the corrosion product film consisting mostly of tantalum as cations. Ni 10Ta20P alloy consists of Ni₂Ta, Ni₃P, Ni₂P and NiP phases. Immersion of Ni10Ta20P alloy gives rise to initial increase in elemental phosphorus on the surface as a result of selective dissolution of nickel and selective oxidation of tantalum. The formation of elemental phosphorus with a high cathodic activity is responsible for the initial ennoblement of the open circuit potential and for the formation of the passive film in which tantalum is highly concentrated. The higher corrosion resistance of Ni10Ta20P alloy than Ni10Ta10P alloy is attributable to the formation of the Ni₂Ta phase with a higher tantalum content than the Ni₈Ta phase which is the readily corroded major intermetallic phase in the Ni10Ta10P alloy.     

COMPUTER NUMERICAL SIMULATION OF MECHANICAL PROPERTIES OF TUNGSTEN HEAVY ALLOYS

１ＩＮＴＲＯＤＵＣＴＩＯＮＴｕｎｇｓｔｅｎｈｅａｖｙａｌｏｙｓａｒｅｄｕａｌｐｈａｓｅｃｏｍｐｏｓｉｔｅｓｐｒｏｄｕｃｅｄｂｙｌｉｑｕｉｄｐｈａｓｅｓｉｎｔｅｒｉｎｇｏｆａｍｉｘｔｕｒｅｏｆ８０％～９７％ｔｕｎｇｓｔｅｎａｎｄａｓｍａｌａｍｏｕｎｔ...     

退火温度对挤压态细晶钨合金性能及组织演变的影响

采用稀土微合金化和液相强化烧结技术制备细晶93W-4.9Ni-2.1Fe+0.03%Y合金。研究在快速热挤压形变强化后,时效热处理对挤压态细晶93W-4.9Ni-2.1Fe+0.03%Y合金显微硬度和组织演变的影响,并与相应条件的传统钨合金进行对比。结果表明,随着退火温度的升高,2种钨合金钨相的显微硬度大大降低。EDS分析表明,随着退火温度的升高,钨合金粘结相中钨含量逐渐增加,其中细晶钨合金经过1200 ℃退火处理后,粘结相钨含量高达26.11%,而传统钨合金在1350 ℃退火处理后含量最高,达到28.14%。显微组织观察表明,退火有利于降低W-W连接度和细化钨颗粒;与传统钨合金相比,高温退火后,细晶钨合金的粘结相体积比更高且分布更为均匀     

Tensile behavior change depending on the varying tungsten content of W–Ni–Fe alloys

Tungsten heavy alloys (WHAs) are metal–metal composites consisting of nearly pure spherical tungsten particles embedded in a Ni–Fe–W or Ni–Co–W or Ni–Cu–W ductile matrix. In this dual phase alloy, there are several complicated relations between the ductile matrix and hard tungsten particles. The aim of this research was to examine the effect of varying tungsten content on the microstructure and mechanical properties of tungsten heavy alloys. The microstructural parameters (grain size, connectivity, contiguity and solid volume fraction) were measured and were found to have a significant effect on the mechanical properties of tungsten-based heavy alloys. The result shows that the binding strength between the W and the matrix phase has a major influence on the ductility of tungsten-based alloys. The larger this binding force is, the better the ductility is.     

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)。     

Effect of tungsten content on microstructure and quasi-static tensile fracture characteristics of rapidly hot-extruded W-Ni-Fe alloys

Tungsten heavy alloys (WHAs) with three different compositions (90W-7Ni-3Fe, 93W-4.9Ni-2.1Fe and 95W-3.5Ni-1.5Fe, wt.%) were heavily deformed by one-pass rapid hot extrusion at 1100 °C with an extrusion speed of ~ 100 mm/s and an extrusion ratio of ~ 3.33:1. The influence of tungsten content on the microstructure and tensile fracture characteristics of the as-extruded alloys was investigated in detail. The results show that the tungsten particles in the as-extruded 95W have the largest shape factor compared to the as-extruded 90W and 93W alloys and this implies that the tungsten particles in the as-extruded 95W alloy were subjected to the heaviest plastic deformation. In addition, ultimate tensile strength (UTS) and hardness (HRC) are significantly improved after rapid hot extrusion. The as-extruded 95W alloy processes the highest strength (1455 MPa) and hardness (HRC40) but the lowest elongation (5%), followed by the as-extruded 93W (UTS1390MPa; HRC39; 7%) and 90W alloys (UTS1260MPa; HRC36; 10%). The fracture morphology shows the distinct fracture features between the as-sintered alloys and the as-extruded alloys. For the as-sintered alloys, the fracture modes are various while transgranular cleavage of tungsten particles is the main characteristic in the as-extruded alloy. Meanwhile, the fracture modes of the three as-extruded alloys vary slightly with the tungsten content. TEM bright field images indicate that many lath-like subgrains with the width of 150-500 nm are present in the three as-extruded alloys, particularly in the as-extruded 93W and 95W alloys. Furthermore, the dislocations are absent in the γ-(Ni, Fe) phase. This means that dynamic recovery-recrystallization process took place during rapid hot extrusion.     

W-Ni-Fe系机械合金化过程中的相变及热力学和动力学研究

W,Ni,Fe粉末按照91.16W6.56Ni2.28Fe的成分配比进行机械合金化(MA)。用XRD确定物相,用TEM(JEM-2000CX型)观察微观形貌和显微结构。并对机械合金化粉末的物相、颗粒尺寸、晶格畸变作了分析讨论。MA可以使W-Ni-Fe系形成纳米晶超饱和固溶体和非晶。参照Miedema半经验理论模型,计算了该合金系的相变驱动力,热力学分析指出该合金系不存在发生非晶化反应的化学驱动力。应用固态反应模型解释了MA过程非晶形成的热力学可能性,在MA过程中,非晶的形成并不绝对要求体系ΔHmix<<0和DB>>DA     

Microstructure Limitations of High Tungsten Content Heavy Alloys

Tungsten heavy alloys are two phase composites that are useful for several applications requiring high densities, such as radiation shields, counterbalance weights, and projectiles. This paper focuses on the density, strength and ductility variations at high tungsten concentrations (90 to 99.5 wt.% W). Fundamental relations are developed between properties, processing and micro-structure versus the tungsten content. At high tungsten levels, the strength and ductility are limited by the sintered microstructure. Furthermore, the high tungsten content heavy alloys are susceptible to impurity segregation to the tungsten-matrix interface. As a consequence, the mechanical behavior of high tungsten content alloys are sensitive to processing conditions.     

注射成形高密度合金的变形控制

研究了注射成形高密度合金的变形行为和变形控制。实验表明,在液相烧结过程中,由于重力作用导致粘性流动,合金试样发生变形。对W含量较高的合金,采用二步烧结工艺可以有效地控制变形。在此工艺中,压坯首先在粘结相熔点以下温度烧结,形成W连通骨架,然后在高于粘结相熔点以上的温度下烧结较短时间以达到全致密;对于W含量较低的高密度合金,将原始混合粉末采用机械合金化,然后再进行固相烧结,可以得到性能很高的无变形的合金。     

Performance of powder-injection-molded W-4.9Ni-2.1Fe components

A 93 wt% W heavy alloy was injection molded into standard tensile test specimens and kinetic energy penetrators. Due to the relatively high activation energy of flow (124 kJ/mol), the rheological behavior of the molten feedstock was very susceptible to temperature variation. Using die sets with constant-volume die cavities, the tensile test specimens could be formed within a wide working window, whereas the penetrator could not be molded without defects because of different jetting phenomena during molding. The penetrator could be molded successfully using a die set whose die cavity progressively expanded during molding. The parts thus formed could subsequently be processed into intact components with full density and low carbon contents (<100 ppm). Their mechanical properties were comparable to or better than those of conventionally processed tungsten heavy alloys. Additional penetration test results indicated that powder injection molding was a viable route for processing high-performance tungsten heavy alloys.