细晶粒Ti（C，N）基金属陶瓷的研究进展

综述了细晶粒Ti（C,N）基金属陶瓷的研究现状,简要分析了原始粉末粒径、烧结工艺、烧结方法对其性能的影响,介绍了几种新的制备方法,指出必须发展新的制备技术,以充分发挥细晶粒金属陶瓷的优越性。     

纳米Ti(C,N)增强Ti(C,N)基金属陶瓷的制备研究

采用Ti(C,N)纳米粉末制备Ti(C,N)基金属陶瓷.研究了烧结温度、保温时间和升温速度等工艺参数对含10wt％纳米粉末的Ti(C,N)基金属陶瓷性能的影响,得到优化烧结工艺为1450℃,保温75min,升温速度3℃/min.用优化工艺制备的Ti(C,N)基金属陶瓷抗弯强度提高了约36.7％,增强机理主要表现为细晶强化、弥散强化和固溶强化.     

Synthesis of titanium-chromium nitride composites by millimeter-wave sintering

New composites of Ti-Cr-N system were synthesized using a high power millimeter-wave heating method. Ti-Cr-N composites were synthesized from the powder mixtures containing metallic Ti and Cr₂N under nitrogen atmosphere by 28 GHz millimeter-wave radiation. The composites consisted of (Ti,Cr)N, Cr₂N with some amount of metallic Cr, and their hardness ranged from 9 GPa to 15 GPa, depending on the nitrogen pressure during sintering. In these composites, quite high oxidation resistance was found from their small weight gains less than 5 g/m² in oxidation experiment in air at 1000 °C for 60 min. It was also indicated that a high pressure nitrogen environment is advantageous for the millimeter-wave syntheses of nitride composites with high oxidation resistance.     

实现Ti(C,N)基金属陶瓷强韧化的技术路径

Ti(C,N)基金属陶瓷因具有高强度、高硬度、耐高温、耐酸碱、耐磨损等优良性能而被广泛应用于刀具、模具等。在高温切削加工时,金属陶瓷刀具不但具有优良的抗粘附性和热稳定性,还拥有比硬质合金刀具更好的高温红硬性、耐磨性和抗氧化性,并且具有自润滑性能。在日本,金属陶瓷刀具的应用占全部刀具的35%以上,欧美等国也达到20%以上,而在我国,金属陶瓷刀具和陶瓷刀具主要依靠进口,金属陶瓷刀具的使用量仅占刀具总量的3%。由此可见,我国金属陶瓷刀具的研发与生产应用远远落后于发达国家。为实现把我国建设成为全球制造业强国的梦想,必须加快我国金属陶瓷刀具研发、生产与推广应用,以改善加工业的加工精度和产品表面光洁度,提高加工业的加工效率,保证制造业零部件的高质量,全面提高我国制造业水平。虽然Ti(C,N)基金属陶瓷刀具比传统的硬质合金刀具有更好的高温红硬性、耐磨性和抗氧化性,但是冲击韧性、断裂强度较差及高温强度不够是其致命的缺点。为此,国内外学者在Ti(C,N)基金属陶瓷的强韧性方面展开大量的研究工作,并取得了一定的研究成果。研究工作主要集中在:(1)陶瓷相与金属相的成分;(2)烧结工艺;(3)引入纳米增强体。近两年来,由于钼、钴的资源短缺与价格上涨,从实际生产成本和高性能等方面考虑,一些学者还对无钼无钴、掺高熵合金Ti(C,N)基金属陶瓷的性能进行了研究。本文采用比较法,对有关Ti(C,N)基金属陶瓷材料强韧化的研究成果进行了分类、归纳与总结,从而得出了影响Ti(C,N)基金属陶瓷材料强韧化的三个因素——组成成分、显微结构和烧结工艺,并就此展开讨论;介绍了当前增强增韧Ti(C,N)基金属陶瓷的三种主要方法——纳米颗粒改性增韧法、晶须增韧法和纤维增韧法;最后提出关于今后Ti(C,N)基金属陶瓷材料的强韧化研究亟待解决的问题与发展方向。     

Ti(C,N)基金属陶瓷烧结过程的冶金基础及其显微组织特征Ⅱ芯-环结构的形成机理及烧结过程中的脱气演化

综述了Ti(C,N)基金属陶瓷烧结过程中的冶金反应规律.介绍和分析了Ti(C,N)基金属陶瓷典型芯-环结构组织的形成过程和机理,以及烧结过程的脱气现象和规律.     

碳纳米管增韧超细Ti(C|N)基金属陶瓷

Ti(C,N)基金属陶瓷的低韧性限制了其广泛应用于切削刀具领域。为探究碳纳米管对超细Ti(C,N)基金属陶瓷断裂韧性的影响,采用化学镀工艺在碳纳米管表面镀Ni,采用粉末冶金法真空烧结制备了不同碳纳米管含量的超细Ti(C,N)基金属陶瓷。研究了不同含量镀镍和未镀镍的碳纳米管对Ti(C,N)金属陶瓷组织和断裂韧性的影响。扫描电镜照片表明 , 添加CNTs后,组织中出现无芯晶粒及微孔洞。压痕法测试断裂韧性的结果表明,纳米管的加入使超细Ti(C,N)金属陶瓷的断裂韧性提高 29. 4 %～62. 7 % , 碳纳米管增韧机制为裂纹偏转和桥接增韧、无芯晶粒增韧及微孔洞增韧。此外,随着碳纳米管含量的增加,超细CNTs/Ti(C,N)金属陶瓷复合材料的相对密度和硬度均有轻微下降。添加镀镍和未镀镍碳纳米管对超细Ti(C,N)金属陶瓷都具有很好的增韧作用。     

搅拌球磨制备亚微米晶粒Ti(C,N)基金属陶瓷

用搅拌球磨方法制备了亚微米TiC-TiN-WC-Mo-Ni-C金属陶瓷复合粉，并烧结成亚微米晶粒Ti(C,N）基金属陶瓷；研究了原始粉末粒度，磨球大小，球磨时间对复合粉粒度的影响，研究了球磨过程中氧和铁元素对粉末的污染情况；并对烧结合金的组织，性能进行了分析，表明亚微米晶粒Ti(C,N）金属陶瓷的性能优良。     

功能梯度Ti(C, N)基金属陶瓷制备技术

通过真空液相烧结制备出Ti(C,N)基金属陶瓷基体,并对基体表面进行双辉等离子渗碳处理。运用扫描电子显微镜(SEM) 、电子探针(EPMA)、X射线衍射(XRD)等分析手段对渗碳前后材料的显微组织形貌、成分分布以及物相组成进行分析。结果表明,双辉等离子渗碳后金属陶瓷表面富Ti、Mo、W、C、N元素,贫Ni。渗碳过程中表层高的碳活度驱使内部的Ti、Mo、W元素向外迁移,从而迫使Ni向内迁移。渗碳后,材料表层富硬质相,近表层富粘结相。渗碳处理使试样表层硬度得到提高,对横向断裂强度影响不大。     

Ti(C,N)基金属陶瓷烧结过程的冶金基础及其显微组织特征Ⅰ烧结过程的冶金基础

综述了Ti(C,N)基金属陶瓷烧结过程中的冶金基础.涉及烧结冶金过程中的几个重要的基础问题:Ti(C,N)的稳定性,粘结相同硬质相的润湿性,碳、氮化合物在粘结上中的溶解度及其选择溶解性.     

超细/纳米粉末改进Ti(C,N)基金属陶瓷性能研究进展

综述了近几年超细或纳米粉末改进Ti(C,N)基金属陶瓷性能的方法,简要分析了含超细或纳米粉末Ti(C,N)基金属陶瓷的致密化问题.总结了真空烧结 热等静压处理和放电等离子烧结的特点,并分析了微波烧结和等离子活化烧结制备Ti(C,N)基金属陶瓷的可能性.     

硬质相粒度对Ti（C,N）基金属陶瓷断裂韧性的影响

用压痕法测定了具有不同粒度硬质相的Ti(C,N)基金属陶瓷的断裂韧度,结果发现,当成分和制备工艺不变时,Ti(C,N)基金属陶瓷的断裂韧性随硬质相粒度的增大而减小,进一步分析表明,当Ti(C,N)颗粒较粗时,极易发生穿晶断裂,并且裂纹连续穿晶扩展时亦不会发生显著的偏转或分叉,金属陶瓷呈现较强的脆性断裂特征,而当Ti(C,N)颗粒较细时穿晶断裂几率大大减小,裂纹较易沿Ti(C,N)颗粒与粘结相的界面扩展,导致脆性断裂现象减少和裂纹偏转而增韧。产生上述现象的主要原因与Ti(C,N)晶体的结构有关,面心立方结构的Ti(C,N)晶体中可能存在多个潜在的滑移面和滑移系,裂纹从一个Ti(C,N)颗粒扩展至另一个Ti(C,N)颗粒时很容易形成取向有利。     

纳米增强金属陶瓷的组织及热冲击性能

为了进一步提高金属陶瓷的力学性能及其刀具的高速切削性能, 研究了纳米增强金属陶瓷的显微组织特征和热冲击性能。扫描电镜和透射电镜分析表明: 组织中陶瓷相呈现典型的芯2壳结构特征; 芯为TiC 或Ti (C ,N) , 而壳则为( Ti ,Mo ,W) (C ,N) 固溶体。纳米增强金属陶瓷机制为细晶强化、弥散强化和固溶强化。热冲击实验表明: 随着热循环的进行, 材料中孔洞的数量、孔洞的尺寸以及微裂纹的尺寸随之增大; 同时, 热循环过程中出现的表面氧化、裂纹长大、偏转以及桥接现象也很显著。与常规Ti (C ,N) 金属陶瓷相比, 纳米增强金属陶瓷的抗热冲击性能明显提高。      

Effect of Ni powder characteristics on the consolidation of ultrafine TiMoCN cermets by means of SPS and HIP technologies

Fully dense titanium carbonitride cermets have been consolidated from Ti(C,N)–Ni–Mo₂C–TiAl₃ powder mixtures either by spark plasma sintering or hot isostatic pressing techniques. Carbonyl Ni powders enhance the densification of the cermets produced by SPS (spark plasma sintering), a phenomenon likely related to a more efficient dissolution of Mo₂C additions and the possible precipitation of α″ phase. Both SPS and HIP (hot isostatic pressing) processes lead to materials with a bimodal Ti(C,N) grain size distribution containing a considerable fraction of nanometric grains. Unlike SPS, HIP induces significant graphite precipitation which could be explained by the destabilization of the carbonitride phase under high isostatic pressures at high temperature. Optimized compositions processed by SPS exhibit a combination of hardness and toughness close to the range covered by ultrafine WC–Co hardmetals of similar binder contents.     

Ti(C,N)/AlCoCrFeNi金属陶瓷烧结过程中的粘结相表面富集行为研究

通过分析合金表面形貌以及表面物相,研究了新型Ti(C,N)/AlCoCrFeNi金属陶瓷烧结过程中粘结相的表面富集行为。结果表明,在1 300℃下烧结60min后,合金烧结体表面发生了明显的富集,并形成了第三相,即类似M_6C结构的缺碳相(η)。该现象的产生主要归因于烧结过程中,表面脱碳形成了表面和内部的碳浓度差、固溶体浓度差以及温度差,促使金属元素钨、钽、钛、钼以扩散的方式向内迁移,表面的低碳造成合金的共晶温度提高,表面的液相量减少从而产生负压张力,导致内部的液相向表面迁移。另外,由于合金微观组织中体积含量不同的粘结相区域产生压力差,导致在烧结过程中富钨区的粘结相倾向于向液相量低的贫钨区迁移,使得金属粘结相逐渐向表面迁移、渗透,富集于表面。     

On the disappearance of Mo2C during low-temperature sintering of Ti(C,N)-Mo2C-Ni cermets

In order to seek a better understanding of the mechanisms leading to the disappearance of Mo₂C during the sintering of Ti(C,N)-based cermets at or below 1200 °C, the sintering reactions occurring in ternary phase mixtures Ti(C,N)-Mo₂C-Ni and their associated binary counterparts Ni-Mo₂C, Ti(C,N)-Mo₂C and Ni-Ti(C,N) at 1200 °C were investigated by X-ray diffraction analysis. It was shown that the decrease and disappearance of Mo₂C during the sintering of Ti(C,N)-MoC-Ni cermet composites at or below 1200 °C are dictated by the relative amount of Mo₂ to Ni, through enhanced dissolution of Mo₂C in Ni by the presence of Ti(C,N). The reprecipitation of (Ti,Mo)(C,N) onto Ti(C,N) grains does not occur to a large extent under these conditions. On average, when the ratio of Mo₂C to Ni is below or around 0.3, all of the Mo₂C phases present in the Ti(C,N)-Mo₂C-Ni alloys can be dissolved in Ni after 1 h at 1200 °C. However, when the ratio is well over 0.3, only partial dissolution of Mo₂C can be observed even when the alloys are sintered at 1200 °C for 10 h. Both Mo₂C and Ti(C,N) can be dissolved in Ni in the solid state, but the dissolution of Mo₂C in Ni in the Ti(C,N)-Mo₂C-Ni alloys is enhanced by the presence of Ti(C,N), hence N, compared to the dissolution of Mo₂C in the Ni-Mo₂C alloys. Negligible phase interactions are detected between Ti(C,N) and Mo₂C when sintered at 1200 °C for up to 5 h, either with or without Ni presence.     

Microstructure development during sintering and heat-treatment of cemented carbides and cermets

WC based cemented carbides and Ti(C, N) based cermets are used in cutting tool applications. They are produced by liquid phase sintering, but much of the microstructure is formed already during solid state sintering, before the eutectic temperature has been reached. Changes in the microstructure during the sintering process have been followed with microscopy and microanalysis, in particular SEM and TEM including energy filtered transmission electron microscopy (EFTEM). It was found that part of the hard phases are dissolved in the solid binder, transported by diffusion and re-precipitated onto undissolved hard grains with a composition given by the equilibrium conditions (“inner rim”). For vacuum sintering of nitrogen containing materials, this means a low nitrogen activity due to the open porosity at this stage. After the liquid has formed, further dissolution and re-precipitation occur, but now the porosity is closed so the “outer rim” is formed with the nitrogen activity of the material. The solid solution of the binder (often by tungsten) is determined primarily by the carbon activity in the liquid phase. During cooling after sintering, tungsten and other metals dissolved in the binder re-precipitate onto hard grains so that depleted zones around these are formed, whereas dissolved carbon and nitrogen have time to leave the binder almost completely. Sintering or post-sintering heat-treatment of nitrogen containing materials in an atmosphere with a lower or higher nitrogen activity than in the material results in the formation of surface zones with a composition different from the bulk (“gradient sintering”). In the former case, a tough zone enriched in binder and depleted of cubic carbides is created, which is beneficial if the material is going to be coated with a wear resistant layer. In the latter case a hard surface zone rich in cubic carbo-nitrides and depleted of WC and binder may be obtained, improving the wear resistance of the material.     

自蔓延高温合成非化学计量碳化钛基金属陶瓷

以Ｔｉ粉和冶金碳黑为原料，Ｃ／Ｔｉ（原子比）配料为０．１２～０．５０时，经ＳＨＳ－准热等静压获得了非化学计量碳化钛基金属陶瓷。研究表明：金属陶瓷由非化学计量碳化钛和α－Ｔｉ相组成，随着Ｃ／Ｔｉ增大，金属陶瓷中α－Ｔｉ相比例减少，碳化物晶粒尺寸增大，金属陶瓷的抗弯强度降低而硬度升高。     

Sintering of Ti(C,N)-Based Cermets: The Role of Compaction

Different compaction processes were employed in studying the effect of green state on the sintering of TiC-TiN-Ni-Mo₂C and Ti(C_0.3N_0.)-Ni-Mo₂C cermets. Specimens were uniaxially pressed and some being subsequently compacted by cold isostatic pressing. Liquid and solid phase sintering was carried out in nitrogen atmosphere. Green state porosity, pore size distributions, as sintered morphologies, micro-hardness and microstructural development were characterized. Mercury porosimetry measurements indicate that with increasing compacting pressure, large pores are eliminated and the pore size distribution curves shift towards smaller pores. Higher compaction load also leads to decrease in average pore size and a wider pore size distribution. It was found that the Ti(CN)-based cermets are superior than the (TiC-TiN)-based cermet. Cermets with carbowax additives are better sintered than those without the wax. The two-stage consolidation (diepressing + CIP) results in better sintering properties than die-pressing alone.     

Effect of nanocrystalline binder on the microstructure and mechanical properties of ultrafine Ti(CN) cermets

The influence of highly deformed nanocrystalline binder ingredient on the overall microstructure and mechanical properties of ultrafine grade Ti(C_0.5N_0.5) cermet was investigated. Nanocrystalline Ni and Ni-aluminides viz. NiAl and Ni₃Al, synthesized by mechanical milling/alloying, were blended to the cermet powder prior to sintering. The mechanically milled nano-Ni contained a mixture of f.c.c. and hexagonal Ni phases. The cermet with nanocrystalline Ni showed a considerably improved microstructure over cermets with commercial coarse grade Ni and exhibits a high Vickers hardness of 16.1 GPa, along with a good fracture toughness value of 9 MPa m^1/2. However, no significant change in the mechanical properties could be detected in the case of nanocrystalline NiAl and Ni₃Al binder addition. The enhanced properties of the cermets containing nano-Ni were attributed to the finer particle size of the hard phase after sintering along with improved particle size distribution caused by rapid dissolution, which prevents excessive coalescence of the hard particles. On the other hand, the presence of high porosity in the cermets containing nano-NiAl and -Ni₃Al apparently nullified any such enhancement.     

硬质相粒度对金属陶瓷断裂韧性的影响

用压痕法测定了具有不同粒度硬质相的Ti(C,N)基和WC基金属陶瓷的断裂韧性,结果发现,Ti(C,N)基金属陶瓷的断裂韧性随硬质相粒度的增大而减小,而WC基金属陶瓷的断裂韧性随硬质相粒度的增大而增大。产生上述现象的主要原因与硬质相的晶体结构有关:在室温条件下,面心立方结构的Ti(C,N)晶体中可能存在｛110｝<11 0>和｛111｝<11 0>两个滑移族(含18个独立滑移系);裂纹从一个Ti(C,N)颗粒扩展至另一个Ti(C,N)颗粒时很容易形成取向有利。当Ti(C,N)颗粒较粗时,极易发生穿晶断裂,并且裂纹连续穿晶扩展时亦不会发生显著的偏转或分叉,Ti(C,N)呈现较强的脆性断裂特征。而密排六方结构的WC晶体只有｛101 0｝<112 3>一个滑移族(含4个独立的滑移系);由于取向不利,裂纹难以连续穿晶扩展,且随WC粒度的增大,其对裂纹的偏转和分叉作用增强,从而导致断裂面表面积增大而增韧。