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.     

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.     

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...     

Microstructure and properties of sintered tungsten heavy alloys

The microstructure and properties of liquid-phase sintered tungsten heavy alloys were studied. The structure and segregation of the impurity elements at the interfacial boundaries were examined using scanning electron microscopy (SEM) and fine-probe energy dispersive spectroscopy (EDS) microanalysis. Test results of mechanical properties are presented and correlated with fracture behavior of the liquid-phase sintered tungsten alloys. It was found that the Fe-Ni-W alloy exhibits superior properties as compared with the Cu-Ni-W alloy. The detection of copper was found across tungsten grains and matrix that could be associated with inferior properties of the Cu-Ni-W alloy as compared to the Fe-Ni-W alloy. Although the fracture was predominantly brittle in both alloys, complex fracture modes seem to be operative due to the composite microstructure of the alloys. Evidence of microsegregation was observed that also contributed primarily to the brittle failure in the alloys. The impurity elements, such as sulfur and phosphorus, were detected at the tungsten matrix and tungsten-tungsten particle boundaries.     

The effects of ball-milling treatment on the densification behavior of ultra-fine tungsten powder

Ultra-fine tungsten powder with a BET particle size of 210 nm was synthesized by sol spray drying, calcination and subsequent hydrogen reduction process. Then this powder was treated by ball-milling, the characteristic changes of this powder before and after milling were investigated. Then the sintering densification behavior of these powders with different ball-milling time (0 h, 5 h, 10 h) were also studied. The results show that ball-milling treatment greatly activates the sintering process of ultra-fine tungsten powder. The relative density of the powder ball-milled for 10 h could reach 97.3% of theoretical density (TD) when sintered at 1900 °C for 2 h, which is 600 °C lower than the required temperature of the traditional micro-scaled powder sintered for the same density. At the same time, ball-milling treatment could substantially reduce the onset temperature of sintering as well as recrystallization, and bulk tungsten materials with more uniform and finer microstructure and much better mechanical properties (hardness) could be obtained.     

Effect of size and shape of tungsten particles on penetration performance in tungsten heavy alloys

The effects of the size and shape of tungsten particles on dynamic torsional properties in tungsten heavy alloys were investigated. Dynamic torsional tests were conducted on seven tungsten alloy specimens, four of which were fabricated by repeated sintering, using a torsional Kolsky bar, and then the test results were comparedvia microstructure, mechanical properties, adiabatic shear banding, and deformation and fracture mode. The size of tungsten particles and their hardness were increased with the increasing of the sintering temperature and time, thereby deteriorating the fracture toughness. The dynamic torsional test results indicated that a cleavage fracture occurred predominantly with little shear deformation in the specimens whose tungsten particles were coarse and irregularly shaped whereas shear deformation was concentrated into the center of the gage section in the conventionally fabricated specimens. The deformation and fracture behavior of the specimens having coarse tungsten particles correlated well with the observation of thein situ fracture test results,i.e., cleavage crack initiation and propagation. These findings suggested that there would be an appropriate tungsten particle size condition in the penetration performance since the cleavage fracture mode would be beneficial for the self-sharpening of tungsten heavy alloys.     

An investigation on the solid state sintering of mechanically alloyed nano-structured 90W–Ni–Fe tungsten heavy alloy

In this study, 90W–7Ni–3Fe heavy alloy was investigated for its microstructure development, mechanical properties and fracture behavior after solid state sintering. The nano-sized powders were synthesized by mechanical alloying (MA). The microstructure of solid state sintered heavy alloys consisted of tungsten matrix. The average tungsten grain size in the range of 1.7–3.0 μm was obtained. It was found that the grain size largely affected the mechanical properties. Tensile strength more than 1200 MPa was achieved at a sintering temperature of 1350 °C. Fracture mechanisms based on microscopical observations on the fracture surfaces were studied. Matrix failure, tungsten-intergranular cleavage and tungsten–matrix interfacial separation were found to be the possible failure mechanisms.     

机械合金化和添加微量Y2O3对制备细晶钨合金

采用机械合金化、添加微量Y2O3和冷等静压、液相烧结工艺制备Ф25mm的晶粒度为3～4μm的细晶93W-4.9Ni-2.1Fe(质量分数%,下同)合金棒材,研究粉末机械合金化、添加微量Y2O3、烧结温度和保温时间对合金棒材烧结致密化和显微组织的影响。结果表明:在1480℃液相烧结时钨晶粒发生明显球化,在此温度下降低保温时间对控制钨晶粒长大有较大影响,保温时间为30min时,钨晶粒尺寸为5～8μm;保温时间为60min时,钨晶粒为8～10μm。添加微量稀土氧化物Y2O3可以进一步有效地抑制晶粒的长大,降低合金的钨晶粒尺寸和提高组织均匀性,在1480℃烧结60min时,钨晶粒为3～4μm,而且晶粒尺寸分布更均匀。     

The effect of consolidation parameters on the mechanical properties of binderless tungsten carbide

This paper discusses the effect of the process parameters on the mechanical properties of binderless pure tungsten carbide during a GPS (gas protection sintering) process. The result of experiments reveal that the mechanical properties of the material increases with raising the sintering temperature and extending the retention time; however a decreased hardness was observed as a result of abnormal grain growth under higher sintering temperatures. The results of XRD and EDS analyses confirmed the absence of brittle phases such as W₂C or impurity phases in the microstructure. The optimized process parameters for GPS process are identified as: a mean particle size of 1.03 μm, a sintering temperature of 1860 °C and a retention time of 60 min; the resulting mechanical properties are: a relative density of 95.1%, a micro-hardness of 1718 kgf/mm² and a fracture toughness of 5.97 MPa m^1/2. The width of particles size distribution has a significant effect on the density and hardness of the sintered material however the width of particles size distribution is dependent on the original particle size. Finally, ultra-fine particles increase the chance of conglomeration and sub-micron structures. The conglomeration of ultra-fine particles hinders the filling of porosities during sintering and lowers the density and hardness of the material.     

高密度活化钨粉低温烧结近全致密化行为

采用物理化学方法制备超细高密度活化钨粉(W-0.1%Ni复合粉末,质量分数),研究球磨时间对活化钨粉形貌及其物理性能的影响,探讨球磨处理对该高密度活化钨粉烧结致密化行为的影响,并与超细纯钨粉末的烧结致密化行为进行对比。结果表明:微量活化元素镍的添加及球磨处理能明显加速钨粉的低温烧结收缩速率,显著促进钨粉的烧结致密化程度;球磨5 h后,活化钨粉在1 600℃下烧结即可达到近全致密化(致密度为99.4%),此外,镍元素的添加和球磨处理也能显著促进钨晶粒的长大。     

The effect of submicron-sized initial tungsten powders on microstructure and properties of infiltrated W-25 wt.% Cu alloys

In the present work, several W-25 wt% Cu alloys have been prepared through combined processes of high-energy ball-milling, liquid-phase sintering and infiltration, using the precursors of industrial copper powders with an average particle size of 50 μm and tungsten powders with alternative average particle size of 8 μm, 800 nm, 600 nm or 400 nm. Microstructure characteristics, relative density, hardness and electrical conductivity of the WCu alloys were investigated to elucidate the effect of initial particle size of tungsten powders. EBSD was further utilized to reveal the orientation and grain size distribution in the WCu alloys prepared by 8 μm and 400 nm-sized tungsten powders. The results showed that the WCu alloy made by 400 nm-sized tungsten powders exhibited excellent homogeneity for both sintered tungsten powders and grains, together with the highest relative density of 98.9%, the highest hardness of 230 HB, and good electrical conductivity of 48.7% IACS. Moreover, it also showed highly improved arc erosion and mechanical wear resistances.     

高密度合金薄壁构件等离子喷涂成形技术

对喷雾造粒高密度合金粉末进行1 600℃瞬时烧结处理,采用常压氩气保护等离子喷涂成形技术制备了壁厚≤5 mm的零部件,研究真空固相及液相烧结对喷涂成形件显微结构、致密度及力学性能的影响。结果表明:瞬时液相烧结后,喷雾造粒团聚体内的微细球磨粉末由机械混合转变为冶金结合,喷涂沉积率从45%提高至70%以上。等离子喷涂沉积层为层片结构,致密度约88.9%。经1 200和1 300℃真空固相烧结后,沉积层保持原始的层片结构,成形件拉伸强度随致密度升高而增大,其断口呈典型的沿晶断裂形貌,伸长率为零。经1 400℃液相烧结后,成形件仍表现为层片结构及沿晶脆性断裂形貌。经1 465℃烧结后,沉积层由层片结构转变为颗粒结构,成形件致密度显著提高至98.05%;断裂方式以沿晶断裂为主,穿晶断裂为辅;拉伸强度显著增大至567.10 MPa,伸长率达8.65%。     

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%.     

Influences of Contents and Reaction of Carbon and Oxygen on Microstructure and Mechanical Properties of Sintered 93W-4.6Ni-1.9Fe-0.5Co Alloys

采用具有不同碳氧含量的初始粉末,利用真空液相烧结制备93W-4.6Ni-1.9Fe-0.5Co合金试样,研究碳氧含量的变化及其平衡反应对合金力学性能与组织的影响。结果表明,压坯在真空高温烧结过程中,原料自身含有的碳具有较强的脱氧能力,通过碳氧反应可减少合金中的氧、碳含量,阻止氧化物、碳化物夹杂的生成,在钨颗粒与粘接相之间形成牢固的界面。当合金总氧含量低于500μg/g时,合金的力学性能显著提高。     

SYNTHESIS AND SOLID STATE SINTERING OF W-Ni-Fe NANO-COMPOSITE POWDERS

1.IntroductionTungstenheavyalloyisakindoftwo-phasecompositecharacterizedbyhighdensity,highstrengthandgoodductilityl1].Themicrostructureconsistsoftungstengrainsem-beddedinanalloymatrix.FullydenseW-Ni-FeheavyalloysaretypicallyprocessedfromWpowderblendedwithNiandFeelementalpowdersthroughliquid-phasesinteringat15oth155oop.Theliquidinitiallyformsatatemperaturenearl465rol2].Therelativelyhighprocessingtemperatureandlongexposuresresultinacoarsefinalmicrostructure(4O-6opmingrainsize)andprogressivec…     

Effects of sintering temperature and Ni/Fe ratio on ballistic performance of tungsten heavy alloy fragments

The aim of this study was to investigate the effects of the sintering temperature and Ni/Fe ratio on the ballistic performance of liquid-phase sintered tungsten heavy alloys. The powder mixtures were pressed under 300 MPa and sintered at 1460, 1480, and 1500 °C for approximately 30 min in a reducing and protective atmosphere. Ballistic tests were performed by accelerating tungsten heavy alloy fragments with a velocity of ~900 m/s toward a 25 mm-thick Al 6061-T6 target. Simulation studies were performed using the finite-element method to model the deformation of the fragment and the target. The experimental results showed that the highest residual velocity and the best perforation performance for multiple-layered targets were obtained with a 93 W-4.67Ni-2.33Fe alloy sintered at 1480 °C, and the increase in the sintering temperature and plastic deformation of the fragments enhanced the damage on the target during the impact process via hole enlargement on the target. The simulation results showed that the mesh sizes of the fragment and the target affected the modeling of the fragment/target deformation and the residual velocity of the fragment. Additionally, the simulation results showed good correlation with test results with regard to the modeling of the deformation at the impact and rear surfaces of the target during perforation.     

高密度纯钨的低温活化烧结工艺及其致密化行为

采用溶胶喷雾干燥-煅烧-氢热还原法制备了BET粒径为0.21μm的超细纯钨粉末,并利用球磨处理进一步活化粉末。研究了超细纯钨粉末形貌及其性能随球磨时间的变化特征,探索了未球磨、球磨5h及球磨10h3种超细纯钨粉末烧结致密工艺,此外还详细研究了纯钨烧结体组织形貌、晶粒尺寸及显微硬度等性能随烧结温度及球磨时间的变化规律。结果表明,球磨处理对超细纯钨粉末的烧结起到了极大的活化作用,由球磨10h粉末制成的压块在1900℃下烧结2h其致密度即可达97.3%,比传统微米级纯钨粉末制成的压块达到相同烧结致密度的温度降低了600℃以上。同时,球磨处理可以大幅降低钨粉的起始烧结温度和再结晶温度,获得组织更加均匀细小、力学性能(硬度)更加优良的钨烧结体。     

The effects of ball-milling treatment on the densification behavior of ultra-fine tungsten powder

Ultra-fine tungsten powder with a BET particle size of 210 nm was synthesized by sol spray drying, calcination and subsequent hydrogen reduction process. Then this powder was treated by ball-milling, the characteristic changes of this powder before and after milling were investigated. Then the sintering densification behavior of these powders with different ball-milling time (0 h, 5 h, 10 h) were also studied. The results show that ball-milling treatment greatly activates the sintering process of ultra-fine tungsten powder. The relative density of the powder ball-milled for 10 h could reach 97.3% of theoretical density (TD) when sintered at 1900 °C for 2 h, which is 600 °C lower than the required temperature of the traditional micro-scaled powder sintered for the same density. At the same time, ball-milling treatment could substantially reduce the onset temperature of sintering as well as recrystallization, and bulk tungsten materials with more uniform and finer microstructure and much better mechanical properties (hardness) could be obtained.     

Influences of sub-micrometer Ta and Co dopants on microstructure and properties of tungsten heavy alloys

Tungsten heavy alloys are aggregates of particles of tungsten bonded with Ni/Fe or Ni/Cu via liquidphase sintering. The sub-micrometer Ta Co powder was added to this aggregate to strengthen the bonding phase. It is found that the main fracture pattern of the alloys is cleavage of tungsten grains and ductile rupture of bond phase,leading to improved tensile strength and elongation. Dopant Ta can act as grain size inhibitor in tungsten heavy alloys.