梯度硬质合金梯度层形成的计算机模拟及验证

结合相图热力学计算,使用DICTRA软件计算模拟Co-W-Ti-C-N、Co-W-Ti-Nb-C-N和Co-W-Ti-Ta-C-N体系梯度硬质合金梯度层形成过程,对比计算模拟和实测的梯度硬质合金中Co含量的距离变化曲线。通过分析各相体积分数及组元成分随距离的分布研究烧结时间、烧结温度、Co含量和Ti含量对梯度层厚度的影响。结果表明:计算模拟与实验数据吻合较好。延长烧结时间、升高烧结温度和增加Co含量均会促进梯度层厚度的增加,而增加Ti含量则会抑制梯度层厚度的增加。     

立方相成分对梯度合金结构的影响——理论计算及实验研究

通过理论计算和实验研究了x(Ti)/x(Ta+Nb)比值对梯度层厚度、表层化学成分分布的影响。利用DICTRA扩散动力学软件对合金表层各相含量以及各组元成分随距离的分布进行了计算机模拟;采用SEM观察梯度层的显微结构,利用EDS对不同成分合金进行了合金表面组元成分分布测定。结合理论计算与实验结果,分析了烧结过程中尤其是固相烧结阶段N分解程度对梯度厚度的影响,以及立方相成分对梯度厚度、表层化学成分分布的影响。计算结果和实验结果表现出良好的一致性。计算结果表明其它成分一定时,梯度厚度随着x(Ti)/x(Ta+Nb)比例的升高而下降;实验结果显示N含量相同时,x(Ti)/x(Ta+Nb)比例越高,烧结过程中N损失越大;梯度层内液相含量随着x(Ti)/x(Ta+Nb)比例增大而升高,同时,梯度层毗邻区Co含量及Ti含量受梯度层厚度及立方相成分的影响。     

烧结碳势对梯度硬质合金组织结构的影响

结合热力学计算,通过两次烧结法,先在含氮气氛下预烧结,然后在不同碳势的气氛下梯度烧结,分别制备了WC-Ti(C,N)-7.5%Co、WC-Ti(C,N)-10%Co、WC-Ti(C,N)-7.5%Co-3%Nb和WC-Ti(C,N)-10%Co-3%Ta共4组成分的梯度硬质合金。通过对其成分分布和微观组织结构的表征,研究了烧结碳势对不同组分的梯度硬质合金基体合金表面无立方相层厚度的影响。结果表明:烧结碳气氛与合金碳势差较大时能形成表面无立方相层,烧结气氛的碳势越高,表面无立方相层越薄;在气氛与合金碳势差过小时不形成梯度,而是形成均质结构;Co含量提高,更容易形成梯度,表面无立方相层加厚;加入了Ta或Nb之后,立方相增多,梯度形成效果更明显,但无立方相层变薄。     

真空-压力两步烧结制备的表层脱立方相梯度硬质合金的组织与性能

本文通过真空-压力两步烧结制备了脱立方相梯度硬质合金,并对材料的组织和性能做了研究。研究发现,相比于一步真空烧结制备的脱立方相梯度硬质合金,真空-压力两步烧结制备的梯度硬质合金脱立方相层更厚,合金内部的立方相晶粒尺寸更大。梯度硬质合金脱立方相层中的平均WC晶粒尺寸比内部的更大,这与脱立方相层中Co含量更高以及内部含Ti立方相的存在有关。梯度硬质合金中过渡层的微观硬度高于合金内部,而脱立方相层的硬度最低,微观硬度变化与Co、Ti等元素含量变化紧密相关。压力烧结对表面脱立方相层的致密化作用明显,使得脱立方相层的孔隙减少,梯度合金相对密度达到99.6%。脱立方相层厚度增加和孔隙缺陷减少促进了梯度硬质合金横向断裂强度的提高。     

烧结温度对梯度硬质合金表层组织结构和力学性能的影响

梯度硬质合金表层组织结构的变化直接影响着CVD涂层硬质合金刀具的加工性能,而烧结温度的变化将显著影响梯度硬质合金表层和芯部组织结构。本文研究了1 410、1 440℃和1 460℃3种烧结温度对梯度硬质合金表层（0～100μm）组织结构和力学性能的影响规律。采用SEM和EBSD对梯度硬质合金表层组织结构、梯度区和合金芯部粒度进行了分析,研究了不同温度下表层组织结构的变化对梯度硬质合金抗弯强度和显微硬度的影响。结果表明：随着温度升高,表面Co含量明显下降,梯度层厚度增加。合金硬质相（WC和立方固溶体相）晶粒度随烧结温度升高而明显长大,梯度区内WC晶粒度大于芯部WC晶粒度,并且二者差异随烧结温度的升高而加大,芯部立方固溶体的生长速度高于WC。随烧结温度的升高,合金的磁力下降了10.3%,合金的断裂韧性和抗弯强度分别提高了8.5%和7.7%,相比去除梯度层试样,3个烧结温度下保留梯度层合金试样的抗弯强度提高了7.6%～9.8%。从表面至芯部合金的显微硬度先降低至最低点后逐渐上升至接近芯部硬度,梯度层内HV最低点约为芯部HV的87%。随烧结温度的升高,梯度区和芯部的HV都呈现下降趋势。     

渗硅制备6．5％Si硅钢表面Fe-Si过渡梯度层的特性

在KCl-NaCl-NaF-(SiO2)熔盐体系中,以含硅3%(质量分数)的硅钢为阴极,石墨为阳极,将电沉积硅和在硅钢基体上渗硅同时进行,制备了Fe-Si梯度层,并对梯度层的特性进行了分析.结果表明:梯度层中硅含量呈3种不同的变化规律,在靠近试样表而的部分,硅含量沿深度下降率较大;在梯度层中间部分,硅含量基本保持不变;在梯度层靠近基体一侧,硅含量的下降率介于前两者之间;梯度层中,以Fe3Si、FeSi、Fe5Si3和Fe构成的厚度占整个梯度层厚度的比率最大;梯度层沿基体一侧向表而的物质组成变化规律为Fe3Si+FeSi+Fe→Fe3Si+FeSi+Fe5Si3+Fe→Fesi,且各物质的量随硅含量的变化而变化;温度对梯度层中各物质含量的变化规律影响不大.     

金属多孔材料梯度层最佳厚度的研究

用离心沉积工艺在粗孔基体材料上制备孔径梯度变化的膜层(简称梯度层),研究复合材料的过滤性能与梯度层的粉末粒度、厚度之间的关系.结果表明,为获得复合材料的最佳过滤性能,梯度层的粉末粒度必须小于基体的中流量平均孔径.随着梯度层厚度的增加,复合材料的透过性能下降,过滤精度提高.为了得到二者的最佳配合,存在着梯度层的最佳匹配厚度,这一厚度与梯度层粉末粒度呈线性关系,且基体的中流量平均孔径值是该直线的截距.     

具有梯度结构的涂层硬质合金刀片

研究了Co和Ti(CN)含量对梯度硬质合金的力学性能、梯度结构的影响.测试了梯度硬质合金刀片的切削性能.结果表明:随着合金钴含量的增多,合金梯度层厚度增厚,梯度结构越明显;合金的强度提高,磁饱和提高,磁力、硬度和密度减小.随着合金Ti(CN)含量的增多,合金梯度层厚度有变薄的趋势;随合金的硬度提高,合金的强度和密度减小.切削试验表明:具有梯度结构涂层硬质合金刀片的切削性能比无梯度结构涂层硬质合金刀片的切削性能优良.达到同一磨损高度hB=0.15 mm时,前者的切削寿命较后者提高了近一倍.同时随着合金钴含量的增多,硬质合金刀片的切削性能提高.     

功能梯度硬质合金球齿的研制

作者对含 η相的烧结体的碳含量、其高温渗碳时间、温度以及烧结体本身尺寸大小对无 η相区的厚度和钴梯度形成的影响进行研究。结果表明 :烧结体的碳含量必须足够低 ,才能使烧结体中间形成富钴层 ;提高渗碳温度有利于液相钴向烧结体内部迁移 ;对尺寸大小不同的烧结体 ,应选择不同的渗碳时间     

渗硅制备Mo-MoSi_2梯度材料层的特性

以Mo为基体,利用KCl-NaCl-NaF-(SiO2)熔盐体系电沉积出的硅作为渗硅硅源,电沉积硅和在Mo基体上渗硅同时进行,制备Mo-MoSi2梯度材料.以实验结果和理论计算为依据,对梯度层的特性进行了分析.结果表明:梯度层硅含量呈3种不同的变化规律,在靠近试样表面部分,硅含量沿深度下降率较大,在梯度层中间部分,硅含量基本保持不变,在梯度层靠近Mo一侧.硅含量的下降率介于前两者之间;梯度层中,以Mo、Mo3Si、Mo5Si3 3种物质构成的厚度占整个梯度层的比重最大;梯度层沿Mo基体一侧向表面的物质组成变化规律为:Mo→Mo5Si3+Mo3Si+Mo→Mo5Si3+MoSi2→MoSi2,并且各物质所占的比重随硅含量的变化而变化.     

Microstructure and mechanical properties of functionally gradient cemented carbides fabricated by microwave heating nitriding sintering

A new method is presented for the fast preparation of functionally graded cemented carbide materials by microwave heating nitriding sintering. The influence of composition and sintering temperature on the mechanical properties, microstructure, and phase composition of the materials was studied. Results showed that functionally graded cemented carbides with the desired mechanical properties can be obtained rapidly by microwave heating nitriding sintering. A gradient layer with a Ti(C, N)-enriched surface layer, and underneath a Co-enriched layer formed on the top of the hard alloy substrate. The nitriding process had little effect on the microstructure of the matrix. A lower surface roughness, and the similar layer thickness as seen in conventional heating nitriding was obtained by microwave heating nitriding sintering in a short period of time. The thickness of the gradient layer increased with increasing temperature. The high Ti content in the raw material was beneficial to the formation of the gradient layer; however, the Co content had little effect on the gradient layer thickness when it increased from 6% to 10%.     

Fabrication of WC-Co/(Ti,W)C graded cemented carbide by spark plasma sintering

The WC-Co/(Ti, W)C graded cemented carbide was prepared by spark plasma sintering. The substrate is WC-8Co, and the hard layer is (Ti, W)C solid-solution. The effects of sintering temperature and holding time on the microstructure and properties of graded cemented carbide were analyzed. The hard layer is mainly formed by dissolving WC in the Co-phase and then by solid-solution reaction with TiC. As the sintering temperature increases, the migration rate of WC increases. When the holding time is 5 min, the thickness and the W content of the (Ti, W)C solid-solution hard layer increases with the increasing of sintering temperature. The thickness of the (Ti, W)C solid-solution can reach 51 ± 2 μm at the sintering temperature of 1700 °C for the holding time of 5 min. The hardness of hard layer surface increases first and then decreases with the increasing of sintering temperature. The Vickers hardness is the highest at 1600 °C, which can reach HV_0.221.53GPa. As the holding time increases, the thickness of the solid-solution hard layer increases, but the rate of growth decreases. As the thickness increases, the difference in the W element concentration between the solid-solutions of the same pitch decreases along the layer depth direction, and W element concentration in the entire hard layer increases. The oxidation behavior of graded cemented carbide at 400 °C and 600 °C was investigated. The (Ti, W)C hard layer has superior oxidation resistance relative to the WC-Co substrate.     

初始成分对梯度硬质合金微观组织及脱β层厚度的影响

采用普通市售中颗粒Ti(C,N)粉末,以一步烧结法制备脱β层梯度硬质合金;利用显微组织分析和图像分析等手段,研究合金初始成分对其微观组织及脱β层厚度的影响规律。结果表明:当Ti(C,N)含量低于1.6%(质量分数)时,随着Ti(C,N)含量的增加,脱β层厚度明显增大,而当Ti(C,N)含量超过1.6%时,脱β层厚度呈缓慢缩小的趋势;随着钴含量的增加,脱β层的厚度迅速增大,但当钴含量达到10%(质量分数)左右时,在脱β层与芯部的界面处钴相聚集现象严重;总碳含量为6.51%(质量分数)的合金中WC晶粒度较大且呈规则的多边形,在1 450℃、2 h梯度烧结工艺下制备的脱β层厚度可达38μm左右,而总碳含量为6.23%的合金中WC晶粒度较小且呈等轴化趋势,同时脱β层的厚度仅为17μm左右。     

Fracture toughness of coated TiCN–WC–Co cermets with graded composition

Mixed TiCN–WC–Co cermets are developed to improve at the same time toughness and resistance to deformation of materials for cutting tool applications. Moreover, graded materials joining optimum properties according to the functional part of the tool are elaborated. To this end, TiCN–WC–Co cermets are interesting because they develop a WC–Co layer at the surface during the sintering. This tough layer at the surface limits the crack propagation that can lead to the rupture of the tool. Such materials show a good resistance to the deformation in the bulk and a good toughness at the surface, where the cracks are initiated upon machining. Cutting tools are often coated by CVD to improve the wear resistance. This paper proposes a method to measure the toughness K_IC at high temperature by using this CVD coating for initial crack formation. The coating thickness is the precrack length of traditional K_IC measurements. Samples are fractured by three point bend tests. The rupture stress is measured by Weibull statistics. This method is particularly interesting for graded structure materials where the influence of surface layers on toughness must be estimated. The comparison between cermets with and without WC–Co layer shows an improvement of 28% of the toughness when the layer is present. The possible bias of internal stresses on the results is discussed.     

烧结制备含Ti功能梯度硬质合金的研究进展

随着科学技术的发展,对硬质合金的性能提出了越来越高的要求。功能梯度硬质合金通过赋予材料不同部位以不同的性能,成功应用于现代工业技术领域。本文综述了气氛烧结制备含Ti功能梯度硬质合金的研究进展,分析了国内外对表面梯度层的形成机理、制备工艺、梯度结构特征及切削性能的研究成果,指出加强相关机理研究和实验工艺优化是今后研究工作的重点。     

WC-10%Co超细硬质合金烧结中表面钴聚集的形成

通过分析合金表面形貌、表面物相和表面钴含量,研究了WC-10%Co超细晶粒硬质合金烧结时表面Co聚集的形成过程。结果表明:在1 100℃下烧结50 min后,合金表面出现典型的颈缩和孔隙球化,表面Co含量达54.12%,产生了表面Co聚集;在1 250℃、1 300℃、1 320℃、1 330℃、1 350℃下烧结10 min后,合金表面均未见明显颈缩和孔隙球化,1 320℃下开始在表面大孔隙处产生Co聚集,1 330℃下渗出到表面出现孤岛状表面Co聚集,表面出现Co(hcp)相,Co含量达71.63%,1 350℃下相互串联形成网络状Co聚集层,表面Co(hcp)相增多,Co含量达86.32%;1 350℃下烧结30 min后表面网络状Co聚集层部分消退,显露出Co聚集层下的WC晶粒,表面Co(hcp)相减少,表面Co含量82.81%;1 410℃下烧结50 min后,合金表面网络状Co聚集层明显消退,WC晶粒成片显露出来,表面Co(hcp)相消失,表面Co含量降至61.87%。     

Spark Plasma Sintering of Ultrafine YSZ Reinforced Cu Matrix Functionally Graded Composite

Copper matrix composites have received more attentions as possible candidate for thermal and electrical conductive materials to be used in electrical contact applications. In this study, five-layered Cu/YSZ(yttria-stabilized zirconia) functionally graded material(FGM) and copper matrix composite specimens containing 3 and 5 vol% YSZ particles plus pure Cu specimen were synthesized using powder metallurgy(PM) route and spark plasma sintering(SPS)consolidation process. The microstructural and some physical, mechanical features of all specimens were characterized.Microscopic examinations showed that ultrafine YSZ particles were distributed in the copper matrix almost homogeneously. An appropriate interface was observed at each layer of FGM. The density measurement indicated that the graded structure of the composite could be well densified after the SPS process. The microhardness values of various layers of Cu/YSZ FGM specimen were gradually altered from 56.3(pure copper side) to 75.2 HV(Cu-5 vol% YSZ side). The increase of YSZ content resulted in a decrease in electrical conductivity. Additionally, thermal conductivity of Cu/YSZ FGM specimen [308.0 W/(m K)] was determined to be higher than that of the Cu-5 vol% YSZ composite specimen [260.7 W/(m K)]. Accordingly, it can be concluded that the Cu/YSZ FGM can be a good candidate for the electrical applications, like sliding electrical contacts, where different material characteristics in the same component are required.     

高频磁场下制备表面增强自生梯度复合材料

高频磁场作用下利用电磁相分离工艺成功的制备了Al-Si过共晶合金自生梯度复合材料，通过改变磁场作用时间来控制初生硅的迁移，以使其更好地沿径向成梯度分布。分析了合金组织的形成机理，并测试试样硬度和硅含量的分布。结果表明，试样的心部大部分是共晶组织，硬度为HV100左右，表层区富集了大量的初生硅，硅的含量明显高于合金成分，硬度可以达到HV800，在二者之间形成很好的过渡层，使增强相和基体得到很好的结合。     

WC-Ni增强Fe基梯度涂层的制备及组织性能*

利用等离子熔覆同轴双筒送粉工艺,在Q235基板上制备了多层WC-Ni成分渐变的梯度涂层,结果表明:涂层中WC颗粒大部分被溶解,在随后的快速冷却中,有两类碳化物组织析出,组织特征与WC-Ni的含量有关。当WC-Ni含量小于20%时,析出粗大树枝晶基体混合片层状共晶碳化物组织;当WC-Ni含量大于30%时,析出块状初生碳化物组织。未完全溶解的WC颗粒呈圆角形,并与基体之间形成合金过渡层。梯度涂层中各层间形成了冶金过渡,其主要物相有γ-Fe、WC、Fe3C、Fe3W3C、Cr7C3。涂层的硬度明显高于基体,但受WC的溶解及析出碳化物的大小及分布不均影响,梯度涂层的硬度分布波动起伏较大。     

基体碳含量对梯度结构硬质合金微观结构与性能的影响

Co相梯度结构硬质合金与传统硬质合金(WC-Co)相比具有良好的硬度和韧性组合.本文通过固体渗碳烧结处理制备出了Co相梯度结构硬质合金,研究了贫碳量对固体渗碳后硬质合金中Co相梯度结构、力学性能的影响,探索了Co相梯度结构的形成机制.结果表明,贫碳合金碳含量越低,η相体积分数越大,渗碳时需要消耗更多的活性碳原子,渗碳烧...