含板状WC晶粒硬质合金的强韧化机制研究

通过加入2.5%板状WC晶种,制备含板状WC晶粒硬质合金,研究其强韧化机制。结果表明:WC晶粒的各向异性和形状改变诱导的Hall-Petch硬化是硬质合金硬度增加的主要原因。加入板状晶种后,裂纹在扩展过程中出现了明显的穿晶断裂和Co相桥接,增加了裂纹偏转,硬质合金的抗弯强度大大提高。不同Co含量和初始WC粉体粒度制备的含板状WC晶粒硬质合金,穿晶断裂、Co相桥接和裂纹偏转对抗弯强度增加的贡献不同。     

Effects of Ni addition and cyclic sintering on microstructure and mechanical properties of coarse grained WC–10Co cemented carbides

Coarse grained WC–10(Co, Ni) cemented carbides with different Ni contents were fabricated by sintering-HIP and cyclic sintering at 1450 °C. The effects of Ni addition and cyclic sintering on the microstructures, magnetic behavior and mechanical properties of coarse grained WC–10(Co, Ni) cemented carbides have been investigated using scanning electron microscope (SEM), magnetic performances tests and mechanical properties tests, respectively. The results showed that the mean grain size of hardmetals increases from 3.8 μm to 5.78 μm, and the shape factor Pwc decreases from 0.72 to 0.54, with the Ni content increases from 0 to 6 wt.%. Moreover, the W solubility reaches the highest value of 10.33 wt.% when the Ni content is 2 wt.%. The hardness and transverse rupture strength of WC–8Co–2Ni are 1105 HV₃₀ and 2778 MPa, respectively. The cyclic sintering is conducive to increase the WC grain size of WC–10(Co, Ni) and improves the transverse rupture strength of WC–10Co without compromising the hardness of alloys.     

Effects of submicron WC addition on structures,kinetics and mechanical properties of functionally graded cemented carbides with coarse grains

Functionally graded cemented carbides (FGCCs) were prepared by pre-sintering and carburizing of carbon-deficient WC–Co cemented carbides. Submicron WC powder with different contents was added in FGCCs with coarse grains to study the influences of microstructures, kinetics and mechanical properties. The results show that the addition of submicron WC can increase the thickness of the gradient layer, and improve the carburizing rate in FGCCs. The average grain size becomes finer with the content of submicron WC increasing. The FGCCs with the addition of submicron WC has a higher grain growth rate, and the grain growth kinetics is proposed to be diffusion-controlled. Meanwhile, a simplified equation for estimating the final average grain size of FGCCs is provided. The hardness and the transverse rupture strength of FGCCs can be efficiently improved by the addition of submicron WC due to the fine microstructures and thick gradient layer.     

细WC配比对非均匀YG20C合金性能的影响

研究了碳化钨粗颗细粒搭配对YG20C合金的力学性能与组织结构的影响,即在WC颗粒平均粒径为25μm的合金中,加入不同比例的平均粒径为2.0μm的WC颗粒,构成非均匀晶粒硬质合金。结果表明,非均匀YG20C合金的硬度和抗弯强度随着细晶粒碳化钨含量的增加都是先升高再降低。当细颗粒碳化钨比例为20%(文中含量均为质量分数)时,YG20C合金的综合力学性能最好,硬度和抗弯强度都达到"双高",其值分别为HRA83.5和2 800 MPa,比均匀YG20C合金的硬度和抗弯强度分别提高HRA1.2和400 MPa。并且非均匀YG20C合金的冲压使用效果最佳。     

W+Co+C(碳黑)制备板状晶硬质合金及其性能研究

采用经球磨扁平化处理的W粉末为原料,添加适量Co、C(碳黑)、成型剂及纳米W粉制备板状晶硬质合金,研究了烧结温度、时间和添加纳米W粉,对板状晶硬质合金显微组织结构和性能的影响。结果表明,球磨预处理中颗粒W粉末可获得扁平化程度高的薄片状W粉末,以其为原料制备的WC-12%Co(质量分数)板状晶合金相对密度达97%,合金硬度呈现出明显的各向异性;添加纳米W粉或提高烧结温度、延长烧结时间,均有利于压坯烧结收缩致密化,生成更多的板状WC晶粒。     

WO3添加量对超粗硬质合金微观结构及性能影响*

本文以WC、WO₃、Co、C为原料,通过原位细晶溶解-析出长大法制备了超粗硬质合金,并分析了不同WO₃添加量对合金微观结构及性能影响规律。结果表明：初始粉末中加入的WO₃和C在烧结过程中将发生原位一步还原碳化反应转化为高活性的细WC,促进溶解-析出长大现象,使超粗硬质合金WC平均晶粒度随着WO₃含量增加而增大。同时,WO₃添加能够减少粗WC晶粒微观缺陷和曲边的阶梯状表面,平直化晶粒边界,使其形貌趋于形成完整的三角棱柱体,其(0 0 0 1)晶面占比高,能够有效提高合金硬度,阻碍裂纹扩展,增加钴相韧性断裂比例。当WO₃添加量为4.20wt.%时,制备的超粗硬质合金具有最大的硬度(1085kgf/mm₂⁾和抗弯强度(2692MPa)。     

Ni3Al添加量对WC-Co硬质合金中WC晶粒形状的影响

采用粉末冶金制备技术,以粗WC粉末、Co粉和WC＋Ni3Al预合金粉末为原料制备出WC-40vol％（Co—Ni,Al）硬质合金。利用扫描电镜和透射电镜研究了不同NbAl含量对WC-40vol％（Co—Ni3Al）硬质合金中WC晶粒形状的影响规律。结果表明：W在Co粘结相中的固溶度接近25．4wt％,而W在Ni,Al粘结相中的固溶度接近9．5wt％,随着NbAl含量的增加,粘结相对W的固溶度减小,合金中的WC晶粒圆钝和细小;WC晶粒表面上出现明显的台阶。相应的,延长烧结时间,WC—Co—Ni3Al硬质合金具有与WC—Co硬质合金相同的WC生长行为,WC-40vol％（Co—Ni3Al）硬质合金中的WC晶粒表面上的台阶处出现明显的刻面。     

Effect of Cu on the microstructures and properties of WC-6Co cemented carbides fabricated by SPS

The aim of this work is to study the effect of Cu on sintering temperature, densification, microstructure and mechanical properties of WC-6Co cemented carbides fabricated by spark plasma sintering (SPS). Fine grained WC powders with an average size of 1.2 μm, were investigated. Microstructures, hardness, fracture toughness and wear resistance of WC-6(Co/Cu) cemented carbides were measured and observed using SEM, mechanical property test. The results show that the sintering temperature of WC-6Co cemented carbides can be decreased obviously with Cu added; addition of Cu reduced grain size to 0.85 μm, but led to lower density. The adding amount of Cu should be controlled within a certain range, and the samples adding the appropriate proportion of Cu can obtain higher hardness and wear resistance.     

Effect of Mo2C additions on the properties of SPS manufactured WC–TiC–Ni cemented carbides

The effect of spark plasma sintering (SPS) on the microstructure and mechanical properties of WC–Co and WC–Ni cemented carbides was studied, and compared to WC–Co produced by liquid phase sintering (LPS). There were finer WC grains with larger Co pools in the spark plasma sintered WC–Co, resulting in higher hardness and slightly lower fracture toughness than the liquid phase sintered WC–Co. The influence of the addition of 0.5–5 wt.%Mo₂C to WC-based cemented carbide containing 6.25 wt.%TiC and 9.3 wt.%Ni prepared by SPS was also studied. This addition improved the wettability between WC and Ni and lead to the improvements of microstructures, resulting in good combinations of hardness, fracture toughness and modulus of elasticity that were comparable to WC–Co based cemented carbides.     

烧结温度对含钽双晶硬质合金组织和性能的影响

同时采用不同粒度WC原料制备WC-TaC-Co硬质合金,并在不同的温度下进行烧结。研究表明:合金主要由两相组成,晶粒大小相间。所测硬度、密度和矫顽磁力随温度升高先升后降,抗弯强度随烧结温度升高而略有升高,但变化不明显。烧结温度为1450℃保温1.5h时,合金的综合性能达到最优,维氏硬度(HV30)为1668.8,抗弯强度为988MPa,密度为14.87g/cm3,矫顽磁力为15.2kA/m,此时Ta元素对WC晶粒的抑制效果最佳,晶粒尺寸达到0.75μm±0.33μm。     

Wear-resistance and hardness: Are they directly related for nanostructured hard materials?

The major challenge in the field of cemented carbides and other hard materials is to obtain their better combination of hardness, wear-resistance and fracture toughness. It is well known that the dependence of abrasion wear on fracture toughness for WC–Co cemented carbides is represented by a relatively narrow band and it is hardly possible to “break away” out from it by the use of conventional approaches based on varying the WC mean grain size and Co content. Also, it is well known that the wear-resistance of conventional cemented carbides depends mainly on their hardness. The major objective of this paper is to establish what will happen with the wear-resistance of hard materials as a result of their nanostructuring when the hardness is nearly the same as for conventional WC–Co cemented carbides. The results obtained provide clear evidence that, if one enters the region of nanostructured materials with the mean grain size of less than 10 nm, traditional wisdom indicating that the wear-resistance is directly related to the hardness appears not to be valid. In some cases of such nanostructured materials, it can be possible to achieve the dramatically improved wear-resistance compared to that of conventional WC–Co cemented carbides at nearly the same level of hardness and fracture toughness. The abovementioned is based on considering hard nanomaterials of the following four types: (1) WC–Co cemented carbides with nanograin reinforced binder, (2) near-nano WC–Co cemented carbides, (3) cemented carbides of the W–C–Cr–Si–Fe system for hard-facing having a nanostructured Fe-based binder, and (4) CVD hard materials consisting of nanostructured W₂C grains embedded in a tungsten metal binder.     

Pulsed electric current sintered Fe3Al bonded WC composites

WC based composites with 5, 10 and 20 vol.% Fe₃Al binder were consolidated via pulsed electric current sintering (PECS) in the solid state for 4 min at 1200 °C under a pressure of 90 MPa. Microstructural analysis revealed a homogeneous Fe₃Al binder distribution, ultrafine WC grains and dispersed Al₂O₃ particle clusters. The WC-5 vol.% Fe₃Al composite combines an excellent Vickers hardness of 25.6 GPa with very high Young’s modulus of 693 GPa, a fracture toughness of 7.6 MPa m^1/2 and flexural strength of 1000 MPa. With increasing Fe₃Al binder content, the hardness and stiffness decreased linearly to 19.9 and 539 GPa, respectively with increasing binder content up to 20 vol.%, while the fracture toughness and flexural strength were hardly influenced by the binder content. Compared to WC–Co cemented carbides processed under exactly the same conditions, the WC–Fe₃Al composites exhibit a substantially higher hardness and Young’s modulus.     

Mechanical properties of WC–10Co cemented carbides sintered from nanocrystalline spray conversion processed powders

Mechanical properties and microstructures of nanocrystalline WC–10Co cemented carbides were investigated. The nanocrystalline WC–10Co cemented carbide powders were manufactured by reduction and carbonization of the nanocrystalline precursor powders which were prepared by spray drying process of solution containing ammonia meta-tungstate (AMT) and cobalt nitrate. The WC powders were about 100 nm in diameter mixed homogeneously with Co binder phase and were sintered at 1375 °C under a pressure of 1 mTorr. In order to compare the microstructures and mechanical properties with those of nanocrystalline WC–10Co, commercial WC powders in a diameter range of 0.57–4 μm were mixed with Co powders, and were sintered at the same conditions as those of nanocrystalline powders. TaC, Cr₃C₂ and VC of varying amount were added into nanocrystalline WC–10Co cemented carbides as grain growth inhibitors. To investigate the microstructure of Co binder phase in the WC–10Co cemented carbides, Co–W–C alloy was fabricated at the temperature of sintering process for the WC–10Co cemented carbides. The hardness of WC–10Co cemented carbides increased with decreasing WC grain size following a Hall–Petch-type relationship. The fracture toughness of WC–10Co cemented carbides increases with increasing HCP/FCC ratio of Co binder phase by HCP/FCC phase transformation.     

烧结过程中WC晶粒形貌的变化

采用粉末冶金工艺烧结了纯WC,制备了WC-10%Co硬质合金,利用JSM5600LV扫描电镜观察不同烧结温度下制备的试样WC颗粒/晶粒形貌。结果表明:纯WC进行烧结时,烧结过程中在表面张力的作用下,系统向能量最低趋势发展,WC晶粒保持球形或类球形;在有钴的存在下,界面张力状态发生了改变,为了达到系统的稳定状态,WC/Co接触界面向平直化发展,烧结温度达到共晶温度之后,在溶解-析出机理的作用下,WC晶粒有选择性长大,形状更加规则化,最终导致WC/Co界面平直。     

板状WC晶种加入对硬质合金性能的影响

通过加入板状WC晶种制备含板状WC晶粒的WC-10%Co和WC-20%Co硬质合金,研究了加入板状WC晶种对两种硬质合金显微组织和性能的影响。结果表明,加入板状WC晶种后硬质合金中的WC晶粒具有明显的板状特征,WC-20%Co中的板状WC晶粒比WC-10%Co多且尺寸大。少量晶种的加入对WC-10%Co和WC-20%Co硬质合金密度基本无影响,但两者的硬度和抗弯强度都有所增加,特别是抗弯强度分别提高了12%和11%。     

Consolidation and properties of ultrafine binderless cemented carbide by spark plasma sintering

Owing to the absence of metal binder, binderless cemented carbides have higher wear, corrosion, and oxidation resistance. WC-0.3VC-0.5Cr3C2 powders with an average particle size of 200nm and a little amount of active element were consolidated by spark plasma sintering. The sintered microstructure revealed that the average WC grain size was 0.24μm, which was almost consistent with the initial fine powder. The results of XRD showed that W2C phase was formed. Nearly complete densification of ultrafine binderless cemented carbide was achieved by sintering at 1400℃ for 120s under 50MPa. The resulting hardness and the fracture toughness were 28.18 GPa and 6.05MPa·m1/2, respectively.     

碳化钨粗细颗粒搭配对WC—10%Co合金力学性能与组织结构的影响

本实验系统地研究了碳化钨粗颗细粒搭配对WC—10%合金的力学性能与组织结构的影响.优质碳化钨粉,通过空气分级的方法获得三种不同粒度级别的碳化钨.不同粒度级别的碳化钨,以适当的比例搭配和钴粉混合.获得具有“双重晶粒结构”的硬质合金,在凿岩试验中取得了良好的结果.     

Micro characteristics of binder phases in WC–Co cemented carbides with Cr–V and Cr–V–RE additives

Taking the advantage of the large mean free paths of the binder phases, we investigated the effect of Cr–V and Cr–V–RE (RE: rare earth) additives on the micro characteristics of the Co-based binder phases (the Cos) in WC–8.4Co cemented carbides with grain sizes larger than 5 μm and a narrow two-phase carbon window. It included the crystal structure parameters, composition and morphology. To avoid the interference of WC phase on the analysis, a method of selective electrolysis corrosion of WC was employed. Based on the investigation of the residual Co skeletons, the following facts were established: (1) the sole fcc structure; (2) the quite different solution behavior of V and Cr; (3) the significantly suppressed solid solubility of W and significantly increased solid solubility of W + Cr + V (in atomic fraction) and (4) the formation of fine stairs on the surfaces. A strong ability of Cr–V and Cr–V–RE additives in the grain growth inhibition was observed even though an extra coarse WC raw material was used. The relationship among the solid solubility, lattice parameter and strain in/of the Cos, the magnetic saturation and the grain growth inhibition of the alloys were discussed.     

WC-6%Co硬质合金的冲击磨粒磨损性能研究

用MLD-10型动载磨粒磨损试验机研究了不同晶粒度YG6硬质合金的冲击磨粒磨损性能。对试样进行了失重测量,并用FESEM分析磨损试样表面形貌。结果表明,硬质合金的耐磨性能与粘结相自由程、WC晶粒度有关;在本实验条件下,随着WC晶粒度或粘结相自由程增加,合金耐磨性先增加后减小,特定WC晶粒度配比的混晶WC-6%Co合金的抗冲击耐磨性能最好。合金的磨损失效机制也发生了转变:细晶合金主要表现为WC颗粒的剥落;随WC晶粒度增加,合金主要表现为大颗粒WC破碎后脱落。在以SiC为磨料的冲击磨粒磨损试验中,WC-6%Co合金的磨损是以WC颗粒的破碎和碎片脱落为主要的失效机制。     

Wear damage of cemented carbides with different combinations of WC mean grain size and Co content. Part I: ASTM wear tests

In the present work we made and examined cemented carbides characterized by very different WC grain sizes varying from near-nano with a WC mean grain size of about 200 nm to coarse-grain with a WC mean grain size of about 4.5 μm and Co contents varying from 3 to 24 wt.%. The major objective of the present work was to examine the wear damage, wear behavior and wear mechanisms of cemented carbides having nearly the same hardness but greatly varying with respect to their WC grain size and Co content in the high-load ASTM B611 test and low-load G65 test.Both the hardness and resistance to fracture and micro-fatigue of cemented carbides play an important role in the wear damage by use of the high-stress ASTM B611 test when the carbide surface is subjected to alumina particles at high loads. In this case, the wear-resistance increases with increasing the WC mean grain size and decreasing the Co content at nearly the same hardness of the different cemented carbides. The submicron and near-nano cemented carbides are characterized by lower wear-resistance in comparison with the coarse-grain grade due to their reduced fracture toughness, fracture resistance and resistance to micro-fatigue.The Co mean free path in the carbide microstructure plays an important role with respect to wear-resistance in the low-stress ASTM G65 test when the carbide surface is subjected to gentle scratching by abrasive silica particles. The predominant wear of the thick Co interlayers leaving unsupported WC grains plays the decisive role in the wear behavior of the coarse-grain grade resulting in its low wear-resistance. In contrast to the ASTM B611 test the wear rate decreases with decreasing the WC mean grain size and increasing the Co content due to the corresponding reduction of Co mean free path in the carbide microstructure. As a result, the wear-resistance of the near-nano grade in the ASTM G65 test is the best of all in spite of its reduced fracture toughness.Phenomena of micro-fatigue, micro-fracturing and micro-chipping are found to play a decisive role in the wear damage of cemented carbides if they are subjected to abrasion wear, high loads and severe fatigue.