SPS烧结W-10Ti合金的组织和性能

采用放电等离子烧结(SPS)技术制备了W-10Ti合金。通过扫描电镜和能谱分析了合金的微观组织,利用Den Broeder方法计算了合金的互扩散系数,测试了合金的密度和显微硬度,并与真空烧结的合金进行了对比。结果表明:与真空烧结相比,SPS烧结的合金组织均匀,富钛相少且细小,W在富钛相中的固溶度和Ti在富钨相中的固溶度都有所增加,且Ti在富钨相中的固溶度增加得更多。W-Ti合金的互扩散系数与W的摩尔浓度有一定的依赖关系,随着W摩尔浓度的升高呈先减小后增大趋势,SPS烧结的合金互扩散系数比真空烧结高出2个数量级。SPS法制备的W-Ti合金相对密度为96.1%,显微硬度HV0.05为5.21 GPa。     

Effects of sintering temperature on fine-grained tungsten heavy alloy produced by high-energy ball milling assisted spark plasma sintering

Fine-grained tungsten heavy alloys (WHAs) were successfully produced using the high-energy ball milling assisted spark plasma sintering (SPS) method. The effects of increasing sintering temperatures on the microstructure and mechanical properties of the alloy were studied in detail. The hardness of the alloy was found to continuously decrease from 79.3 to 63.8 HRA. In contrast, the bending strength continuously increased from 353.6 to 954.5 MPa. W grain size increased with increased sintering temperature. The temperature ranges from 1000 to 1100 °C and 1150 to 1200 °C were a period of rapid growth of W grain. According to the color change in the scanning electron microscope (SEM) image, the W alloy microstructure were classified into white W grains, off-white W-rich particles, dark grey matrix γ-(Ni, Fe, W), as well as pitch-black W- and O-rich particles. The bending fracture of the alloy mainly displays the features of intergranular fracture. The microporosity of different sizes was distributed on the bending fracture, and grew with increased sintering temperature.     

Spark plasma sintering of W-10Ti high-purity sputtering target: Densification mechanism and microstructure evolution

The densification mechanism and microstructure evolution of W-10Ti sputtering target prepared by spark plasma sintering (SPS) method at a temperature ranges from 900 to 1600 °C, with dwelling time of 6 min and fixed pressure of 30 MPa were investigated. Densification occurs mainly at low temperatures (900 to 1300 °C), while grain growth occurs at high temperatures (1400 to 1600 °C). The creep model has been used to reveal the densification process. The effective stress exponent n is calculated systematically, which indicates that the densification process is mainly due to the particle rearrangement (n < 1), grain boundary diffusion (n = 1–2), and dislocation climbing (n = 3.77 or 4.14). In addition, the apparent activation energy Q_d is calculated to be 119.30 and 271.79 kJ/mol when the effective stress exponent n is equal to 1 and 2, respectively. It is also found that the microstructure of W-10Ti alloys is greatly affected by the sintering temperatures. The solution between W and Ti significantly improves with the increase of the sintering temperature. The solubility of W in βTi(W) exceeded the eutectoid point (28.97 wt% W) and the eutectoid structure (βW(Ti) + αTi) forms in cooling process when the temperature is up to 1300 °C. With the temperature increasing to 1500 °C, the composition of the βTi(W) phase is located in the miscibility gap of the (βTi(W), βW(Ti)) system, which tends to decompose in to βTi(W) and βW(Ti) phases.     

A study of new phase of elongated shape in granular structure of WС-(Ti,W)С-Со cemented carbide after its solid-phase annealing

The results of the investigations by scanning electron microscopy, Auger spectroscopy and X-ray diffraction of the structure of Т5К10 cemented carbide (WC-(Ti,W)C-10Co group) sintered at 1520 °C before and after its additional heat treatment in vacuum at 1200 °C for 7 h are presented. It was shown that in addition to faceted WC grains, globular (Ti,W)C (γ-phase) grains of equilibrium (ratio Ti:W ~ 1:3) chemical composition for sintering temperature 1520 °C and Co-based layers, new inclusions of elongated shape up to 30 μm wide and up to 200 μm long were revealed in the structure. They are distributed stochastic both singly and in the form of clusters. The new phase contains the chemical elements W, Ti, C in the ratio (wt%) of the average values as 6.26:9.39:84.35, which is described by the stoichiometric formula W_2.3TiС_2.6. In contrast to the cubic cell of (Ti,W)C solid solution, the new phase has a hexagonal GaSe type crystal cell (quality H) with parameters a = 3.750 nm and c = 15.950 nm. On the surfaces of the new phase there are dispersed grains WС and (Ti,W)С solid solution, the sizes of which are 3–6 times smaller than the sizes of similar grains of the basic structure. The content (4.77%) of C in the dispersed grains of WC and in the same grains of the main structure is less than the calculated one. The cobalt phase in the adjacent surface of the new phase of the basic structure is superseded by W (3.57%) and C (0.85%).The formation of a new phase W_2.3ТіС_2.6 elongated shape in the structure of the T5K10 cemented carbide for the above annealing conditions cannot be explained by the basics of modern material science of its production.     

Effect of pre-alloyed raw materials on the microstructure of a (Ti,W)(C,N)–Co cermet

Four alloys manufactured from different combinations of powders (TiC + TiN + WC; Ti(C,N) + WC; (Ti,W)C + TiN and (Ti,W)(C,N)) were studied using X-ray diffractometry, optical microscopy (OM), scanning electron microscopy (SEM) and analytical electron microscopy (AEM). The alloy manufactured from binary powders had a smaller grain size and a more inhomogeneous microstructure than the other alloys. The alloys manufactured with WC contained an inner rim around Ti(C,N) cores, as well as W-rich cores. Thermodynamic calculations suggest that these are formed during solid-state sintering at 900°C in a low nitrogen activity. The outer rim had a composition that is in good agreement with calculations of the equilibrium during liquid phase sintering at 1450°C.     

Quantitative analysis of the effect of heat treatment on microstructural evolution and microhardness of an isothermally forged Ti–22Al–25Nb (at.%) orthorhombic alloy

The microstructural features of the 980 °C isothermally forged Ti–22Al–25Nb (at.%) orthorhombic alloy during heat treatment were quantitatively investigated. The volume fraction of the O phase precipitates, the width and length of the lath O phase, and the diameter of equiaxed grains at different heat treatment temperatures were measured using an image analysis software. Quantitative relationships among heat treatment temperature, microstructure parameters, and microhardness were established. The relationship between microstructure parameters and microhardness was analyzed with a multiple regression analysis technique. The results indicate that the microstructure of this alloy is mainly depended on the heat treatment schedule. Only equiaxed O/α₂ grains and B2 matrix existed when the samples were solution-treated above 980 °C, while equiaxed α₂ grains, rim O around α₂, and equiaxed/lath O could be obtained after the samples were solution treated below 980 °C. The width of lath and acicular O phases, and volume fraction of total precipitates could be controlled in the range of 0.37–0.88 μm, 0.09–0.48 μm and 10.91–60.18%, respectively. Experimental and statistical analysis showed a linear relationship between the microstructure parameters and microhardness.     

Effect of carbon content and cooling mode on the microstructure and properties of Ti(C,N)-based cermets

Ti(C,N)-based cermets were prepared by vacuum liquid sintering. The effects of carbon content as well as cooling mode on the microstructure, magnetic and mechanical properties of the cermets were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and vibrating sample magnetometer (VSM). Hardness and transverse rupture strength (TRS) were also measured. The grains of Ti(C,N)-based cermets became finer and solid solubility of titanium, molybdenum, tungsten in binder phases decreased with increasing carbon content. The thickness of the rim phases increased when the cermet was annealed at 1360 °C for 30 min during cooling, which resulted in the decrease of the hardness and the transverse rupture strength (TRS). On the other hand, the magnetic saturation of Ti(C,N)-based cermets increased with increasing carbon content, which was due to the decrease of the solid solution of alloy elements in binder phases.     

烧结温度对(Ti, W, Mo, Nb)(C, N)-(Co, Ni)金属陶瓷组织结构和性能的影响

本文以(Ti,W,Mo,Nb)(C,N)-(Co,Ni)基金属陶瓷材料为研究对象,研究烧结温度对金属陶瓷的成分、微观组织和力学性能的影响,初步探讨成分、微观组织与材料强度的关系。研究结果表明：烧结温度对(Ti,W,Mo,Nb)(C,N)-(Co,Ni)基金属陶瓷组织特征有显著的影响;合金的总碳(Ct%)随着烧结温度的提高而降低,当烧结温度达到1490℃时,合金总碳的急剧降低,导致合金组织中出现脱碳相(η相),从而使得合金的硬度(HV₃₀) 、断裂韧性(KIC)和抗弯强度(TRS)降低;1470℃烧结温度下,(Ti,W,Mo,Nb)(C,N)-(Co,Ni)基金属陶瓷合金的硬度(HV₃₀) 、断裂韧性(KIC)和抗弯强度(TRS)的匹配最佳,表现为在实际应用工况下的综合切削性能最优。     

Phase equilibria in the Co-rich Co-Al-W-Ti quaternary system

We determined phase equilibria in the Co-rich Co-Al-W-Ti quaternary system at a temperature range between 900 °C and 1200 °C with a close attention to the thermodynamic stability of the γ′-Co₃(Al, W, Ti) (L1₂) phase, based on micro-structure observation and electron microprobe analysis on bulk alloy samples heat-treated for periods up to 2000 h. In the quaternary system the single phase field of γ′ extends from the Co-Ti binary edge to a composition of Co-5Al-8.5W-8Ti (in at.%) at 900 °C. At the tip of the single phase field, the γ′ phase is in equilibrium with the γ-Co (A1), Co₂AlTi (L2₁) and Co₃W (D0₁₉) phases. The constructed vertical section of phase diagram between Co-9.4Al-9.6W and Co-16.5Ti indicates that there is a narrow composition range around Co-4.5Al-5.4W-7.5Ti in which the γ single phase field exists at high temperatures above 1200 °C and two-phase of γ+γ′ is thermodynamically stable at low temperatures below 1100 °C.     

Spark plasma sintering of TiC particle-reinforced molybdenum composites

In order to improve the recrystallization resistance and the mechanical properties of molybdenum, TiC particle-reinforcement composites were sintered by SPS. Powders with TiC contents between 6 and 25 vol.% were prepared by high energy ball milling. All powders were sintered both at 1600 and 1800 °C, some of sintered composites were annealed in hydrogen for 10 h at 1100 up to 1500 °C. The powders and the composites were investigated by scanning electron microscopy and XRD. The microhardness and the density of composites were measured, and the densification behavior was investigated. It turns out that SPS produces Mo–TiC composites, with relative densities higher than 97%.The densification behavior and the microhardness of all bulk specimens depend on both the ball milling conditions of powder preparation and the TiC content. The highest microhardness was obtained in composites containing 25 vol.% TiC sintered from the strongest milled powders. The TiC particles prevent recrystallization and grain growth of molybdenum during sintering and also during annealing up to 10 h at 1300 °C. Interdiffusion between molybdenum and carbide particles leads to a solid solution transition zone consisting of (Ti_1 −x Mo_x)C_y carbide. This diffusion zone improves the bonding between molybdenum matrix and TiC particles. A new phase, the hexagonal Mo₂C carbide, was detected by XRD measurements after sintering. Obviously, this phase precipitates during cooling from sintering temperature, if (Ti_1 −x Mo_x)C_y or molybdenum, are supersaturated with carbon.     

Fabrication of W-20wt.%Ti alloy by pressureless sintering at low temperature

A powder metallurgical technology of low temperature and pressureless is used to fabricate a W-20wt.%Ti alloy using milled TiH₂ powders and micro-sized W powders. The microstructure of the milled TiH₂ powders and the bulk W–Ti alloy were studied. It is indicated that TiH₂ nanoparticles with the size of 8 to 15 nm were obtained after milling for 48 h and the decomposition temperature decreased from 520.2 °C to 395.5 °C. The W-20wt.%Ti alloy prepared at 1200 °C for 80 min had a relative density of 97.8% which was composed of α-Ti, W and β(W/Ti) solid solution. A preparation mechanism of the W–Ti alloy is also proposed based on the experimental results.     

合金化元素对纳米晶铝合金热稳定性的影响

为研究加入Fe和Ti扩散系数有限的元素对纳米晶铝合金热稳定性的影响,制备Al?10％Fe(质量分数)和Al?10％Fe?5％Ti(质量分数)合金.将初始混合粉末在真空下球磨100 h,用高频感应加热烧结系统将球磨后的粉末制备成块体样品.采用X射线衍射仪、维氏显微硬度仪、场发射扫描电子显微镜和透射电子显微镜对球磨后的粉末...     

Vacuum sintering of WC-8 wt.% Co hardmetals from WC powders with different dispersity

The effect of sintering temperature and particle size of tungsten carbide WC on phase composition, density and microstructure of hardmetals WC-8 wt.% Co has been studied using X-ray diffraction, scanning electron microscopy and density measurements. The sintering temperature has been varied in the range from 800 to 1600 °C. The coarse-grained WC powder with an average particle size of 6 μm, submicrocrystalline WC powder with an average particle size of 150 nm and two nanocrystalline WC powders with average sizes of particles 60 and 20 nm produced by a plasma-chemical synthesis and high-energy ball milling, respectively, have been used for synthesis of hardmetals. It is established that ternary Co₆W₆C carbide phase is the first to form as a result of sintering of the starting powder mixture. At sintering temperature of 1100-1300 °C, this phase reacts with carbon to form Co₃W₃C phase. A cubic solid solution of tungsten carbide in cobalt, β-Co(WC), is formed along with ternary carbide phases at sintering temperature above 1000 °C. Dependences of density and microhardness of sintering hardmetals on sintering temperature are found. The use of nanocrystalline WC powders is shown to reduce the optimal sintering temperature of the WC-Co hardmetals by about 100 °C.     

等离子电火花烧结TiAl-Nb复合材料的显微组织与断裂韧性(英文)

将钛铝预合金粉末和铌粉按照摩尔比9:1混合均匀,再采用等离子电火花烧结技术在1250°C、50MPa下烧结5min制备细晶钛铝基复合材料。采用X射线衍射、电子扫描、透射以及电子探针探讨烧结样品中显微组织、相成分的分布及晶粒度。结果表明:合金的显微组织主要由大量的层片γ相、O相、Nbss(Nb固溶相)以及B2相组成;室温烧结样品的断裂韧性高达28.7MPa·m1/2,韧性铌固溶相在裂纹尖端以塑性延伸的方式吸收断裂能,从而提高了合金的断裂韧性;B2相以也会促进裂纹的侨联和分叉。对合金各相的显微硬度也进行了测试。     

Precipitation in Fe–15Cr–1Nb alloys after oxygenation

The effect of O on the phase relations at 950 °C in Fe–15Cr–1Nb alloys is experimentally investigated. Fe–15Cr–1Nb alloys are oxygenated by subjecting high-purity Fe–15Cr–1Nb to an O atmosphere at 600 °C. Both the high-purity and the oxygenated Fe–15Cr–1Nb alloys are heat treated for up to 500 h at 950 °C, quenched and investigated by scanning electron microscopy, transmission electron microscopy and electron probe microanalysis. The results show that Fe₂Nb is in equilibrium with α (Fe, Cr) with 0.29 at.% Nb in solid solution in the pure Fe–15Cr–1Nb alloy. The presence of a small amount of O induces the precipitation of a Fe₆Nb₆O_x phase with a cubic crystal structure and lattice parameter 1.13 nm, thereby decreasing the Nb in solid solution in α (Fe, Cr) with increasing O content.     

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     

Microstructure and mechanical properties of the TiZrNbMoTa refractory high-entropy alloy produced by mechanical alloying and spark plasma sintering

The equiatomic refractory high entropy alloy (HEA) TiZrNbMoTa was investigated. The alloyed powders with face-centered cubic (FCC) structured solid solution phase were prepared by mechanical alloying (MA) and then sintered by spark plasma sintering (SPS) at 1300, 1400, 1500, and 1600 °C. The microstructure and mechanical properties of the bulk alloy were investigated. The body-centered cubic (BCC) structured solid solution phase and the ZrO₂ phase precipitated from the FCC structured solid solution phase during cool-down from sintering. The highest compression fracture strength (3759 MPa) and fracture strain (12.1%) were obtained in the refractory HEA sintered at 1400 °C. The grain boundary strengthening, precipitation strengthening, solid solution strengthening, transformation-induced plastic (TRIP) effect, and toughening effect of the ZrO₂ phase are the important factors for the high strength and ducitily of the refractory HEA prepared in this study.     

Experimental investigation of phase equilibria and microstructure in the Co–Ti–V ternary system

The phase equilibria in the Co–Ti–V ternary system have been investigated by means of optical microscopy (OM), electron probe microanalyzer (EPMA), differential scanning calorimetry (DSC), field emission scanning electron microscope (SEM) and X-ray diffraction (XRD). The mechanical properties were measured by compressive tests. Four isothermal sections of the Co–Ti–V ternary system at 800 °C, 1000 °C, 1100 °C and 1200 °C were experimentally established. The results show that: (1) there is no ternary compound in this system; (2) the CoTi₂ phase and Co₃Ti phase stabilized by the V addition; (3) a large solubility of Ti in the σ-Co₂V₃ phase was observed at all isothermal sections of 800 °C, 1000 °C, 1100 °C and 1200 °C; (4) The alloy with the distribution of fine cuboidal Co₃Ti (L1₂) in (αCo) phase was observed. (5) The compressive strength of Co_77.29Ti_5.83V_16.88 (at.%) alloy at room temperature was measured to be about 1985 MPa. The newly determined phase equilibria in this system will provide useful information for the development of Co-based and Ti-based materials.     

纳米TiN复合Ti(C,N)基金属陶瓷烧结过程中的相演变

本文采用XRD与SEM对纳米复合Ti(C,N)基金属陶瓷烧结过程中的相演变进行了研究,结果发现:对于缺碳体系,Mo在800℃即可以夺取TiC中的C,生成Mo2C;1 000℃时开始生成Ni2(Mo,W,Ti)4C相,其含量在1 250℃时达到最大,随着温度的进一步升高而部分分解并进入Ti(C,N)晶格,生成非化学计量的(Ti,Mo,W)(C,N),导致Ti(C,N)的相对含量升高,晶格常数减少。纳米TiN与亚微米TiN相比并没有显示出更高的烧结活性。当添加适量的C时,纳米TiN复合的Ti(C,N)基金属陶瓷与同一体系的亚微米金属陶瓷烧结过程中的相变规律基本相同。     

Rapid Synthesis of V-4Cr-4Ti Alloy/Composite by Field Assisted Sintering Technique

The present investigation deals with synthesis and characterization of V-4Cr-4Ti composite/alloy from unmilled and mechanically alloyed powders. Starting powders were sintered by field assisted sintering technique with varying process parameters viz., temperature, holding time, etc. Both powder and sintered samples were subjected to microstructural and morphological characterization by using scanning electron microscopy and phase analysis was done with the help of X-ray diffraction. Field assisted sintering of unmilled and milled powders has resulted in V-4Cr-4Ti composite and single phase V-4Cr-4Ti alloy. Differential thermal analysis was performed in powder samples to identify the recovery and recrystallization regimes of starting powders. Activation energy of the starting powder was calculated by Kissinger analysis. Field assisted sintering of mechanically alloyed powders resulted in nanostructured single phase V-4Cr-4Ti alloy whereas sintering of unmilled powders resulted in V-4Cr-4Ti composite. X-ray diffraction analysis confirms nanostructured single phase V-4Cr-4Ti alloy after field assisted sintering of milled powders. For identical sintering condition, unmilled V-4Cr-4Ti powders have consumed 75% more current than milled powders. Role of particle size, shape and their distribution on the densification behavior of V-4Cr-4Ti powders are also discussed. Interstitial contamination in the sintered samples were studied using electron probe micro-analysis. Microhardness experiments were done on the sintered samples and their corresponding Hall-Pitch plots were deduced.