Effect of carbon source on the carbothermal reduction nitridation for synthesis of (Ti, W, Mo, V)(C, N) nanocrystalline powders

The effect of carbon source on the carbothermal reduction-nitridation during synthesizing (Ti, W, Mo, V)(C, N) nanocrystalline powders was investigated. For a systematic comparison, activated carbon, graphite and two kinds of carbon black powder were used as reducing agents in this study. Ultrafine (Ti, W, Mo, V)(C, N) powders with a particle size of ~ 200-500 nm have been produced at 1450 °C for 2 h by using nanosized carbon black source with small particle size. The presence of phases in the reaction products was characterized with X-ray diffraction (XRD) and the microstructure of carbon source powders and final products was studied by scanning electron microscopy (SEM). The results show that the formation of the Ti(C, N) phase is strongly dependent on the particle size of carbon source powders, and the synthesizing temperature of the Ti(C, N) phase decreases significantly from 1750 °C to 1300 °C by using nanosized carbon black, as compared with micron graphite. In addition, activated carbon with a particle size of 5-50 μm does not favor the dissolution of tungsten or molybdenum carbides into Ti(C, N) despite its large specific surface area.     

Synthesis of ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders by low-energy milling and subsequent carbothermal reduction–nitridation reaction

Ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders with globular-like particles of 50–300 nm were synthesized at static nitrogen pressure from oxides by a simple and cost-effective route which combines traditional low-energy milling plus carbothermal reduction–nitridation (CRN) techniques. Reaction path of the (Ti, W, Mo, V)(C, N)–Ni system was discussed by X-ray diffraction (XRD) and thermogravimetry–differential scanning calorimetry (TG–DSC), and microstructure of the milled powders and final products was studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. The results show that CRN reaction has been enhanced by nano-TiO₂ and nano-carbon powders. Thus, the preparation of (Ti, 15W, 5Mo, 0.2V)(C, N)–20Ni is at only 1300 °C for 1 h. During synthesizing reaction, Ni solid solution phase forms at about 700 °C and reduction–carbonization of WO₂ and MoO₂ occurs below 900 °C. The reactions of TiO₂ → Ti₃O₅, Ti₃O₅ → Ti(C, O) and Ti(C, O) → Ti(C, N) take place at about 930 °C, 1203 °C and 1244 °C, respectively.     

Effect of partial substitution of Cr for Ni on densification behavior, microstructure evolution and mechanical properties of Ti(C,N)-Ni-based cermets

Four cermets of composition TiC-10TiN-16Mo-6.5WC-0.8C-0.6Cr₃C₂-(32 − x)Ni-xCr (x = 0, 3.2, 6.4 and 9.6 wt%) were prepared, to investigate the effect of the partial substitution of Cr for Ni on densification behavior, microstructure evolution and mechanical properties of Ti(C,N)-Ni-based cermets. The partial substitution of Cr for Ni decreased full densification temperature, and the higher the content of Cr additive was, the lower full densification temperature was. The partial substitution of Cr for Ni had no significant effect of the formation of Mo₂C and Ti(C,N) and the dissolution of WC, and however, it had a significant effect on the dissolution of Mo₂C. Cr in Ni-based binder phase diffused into undissolved Mo₂C to form (Mo,Cr)₂C above 1000 °C at 6.4-9.6 wt% Cr additive, and a small amount of (Mo,Cr)₂C did not dissolve after sintering at 1410 °C for 1 h at 9.6 wt% Cr additive. In the final microstructure, Cr content in Ni-based binder phase increased with increasing the content of Cr additive, and however, regardless of the content of Cr additive, coarse Ti(C,N) grains generally consisted of black core, white inner rim and grey outer rim, and fine Ti(C,N) grains generally consisted of white core and grey rim. The partial substitution of Cr for Ni increased hardness and decreased transverse rupture strength (TRS). Ni-based binder phase became hard with increasing the content of Cr additive, therefore resulting in the increase of hardness and the decrease of TRS. TRS was fairly low at 9.6 wt% Cr additive, which was mainly attributed hardening of Ni-based binder phase and undissolved (Mo,Cr)₂C.     

Synthesis of (Ti,W, Mo,V)(C,N) nanocomposite powder from novel precursors

(Ti, W, Mo, V)(C, N) nanocomposite powders with globular-like particle of ∼10–100 nm were synthesized by a novel method, namely carbothermal reduction–nitridation (CRN) of complex oxide–carbon mixture, which was made initially from salt solution containing titanium, tungsten, molybdenum, vanadium and carbon elements by air drying and subsequent calcining at 300 °C for 0.5 h. Phase composition of reaction products was discussed by X-ray diffraction (XRD), and microstructure of the calcined powders and final products was studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. The results show that the synthesizing temperature of (Ti, W, Mo, V)(C, N) powders was reduced greatly by the novel precursor method. Thus, the preparation of (Ti, 15W, 5Mo, 0.2V)(C, N) is at only 1200 °C for 2 h. The lowering of synthesizing temperature is mainly due to the homogeneous chemical composition of the complex oxide–carbon mixture and its unusual honeycombed structure.     

纳米Ti(C,N)增强Ti(C,N)基金属陶瓷的研究

采用纳米Ti(C，N)粉末制备Ti(C，N)基金属陶瓷，研究了纳米粉末对金属陶瓷组织及性能的影响。结果表明，粉末冶金过程中，纳米Ti(C，N)粉末易于在粘结相中扩散与溶解及沿晶界分布，降低了硬质相在粘结相中的溶解度，抑制了晶粒长大，提高了材料的红硬性能。抗弯强度与晶粒尺寸满足于Hall-Perch公式，5wt％～l0wt％的纳米粉末加入量可使金属陶瓷的抗弯强度和切削性能得到较大的提高，但硬度变化不大。切削磨损主要表现为磨粒磨损和轻微的粘着磨损，磨痕细小均匀。     

Ti(C,N)_w/Ti(C,N)基金属陶瓷的组织与力学性能研究

采用Ti(C,N)晶须和颗粒复合粉末(Ti(C,N)w+Ti(C,N)p)制备Ti(C,N)w/Ti(C,N)基金属陶瓷。研究了复合粉末对金属陶瓷组织及性能的影响。结果表明,Ti(C,N)w的加入,金属陶瓷的各项力学性能都得到了提高。组织表现为环形相结构特征,与Ti(C,N)基金属陶瓷相比,双层环形相结构所占比例增大,且尺寸加厚。烧结组织中Ti(C,N)w的长径比大于临界长径比,在强化金属陶瓷方面起着重要的作用。环形相使Ti(C,N)w与基体界面结合紧密,增韧机制主要表现为裂纹桥联和裂纹偏转,拔出效应不明显。     

Effects of molybdenum on the microstructure and mechanical properties of Ti（C,N）-based cermets with low Ni

The effects of Mo on the microstructure and mechanical properties of Ti（C,N）-based cermets with low Ni have been studied systematically. Different contents of Mo （4-12 wt.%） were added into Tl（C,N）-based cermets. Specimens were fabricated by conventional powder metallurgy and vacuum sintered at temperatures of 1440, 1450, and 1460℃ individually. The microstructure and fracture morphology were investigated by scanning electron microscope, and the mechanical properties such as transverse strength and hardness were measured. The results show that the microstructure is uniform and the thickness of rim phase is moderate when the content of Mo is 8 wt.%; the mechanical properties of the specimens sintered at 1450℃ are better than those sintered at 1440 and 1460℃. The integrated properties of transverse strength and hardness are the best when the content of Mo is 8 wt.% and the sintering temperature is 1450℃.     

Effect of secondary carbides addition on the microstructure and mechanical properties of (Ti, W, Mo, V)(C, N)-based cermets

(Ti, W, Mo, V)(C, N)-based cermets were prepared by mixing Mo₂C, WC and TaC with ultrafine (Ti, W, Mo, V)(C, N) powders, and then processed via a conventional P/M technique. The effect of Mo₂C, WC and TaC on the microstructure and mechanical properties of (Ti, W, Mo, V)(C, N)-8 wt.% Ni-7 wt.% Co systems was investigated. The Mo₂C content was varied from 0 to 10 wt.% and additive WC or TaC was added at a level of 5 wt.% with Mo₂C addition. The results show that the densification of (Ti, W, Mo, V)(C, N)-8 wt.% Ni-7 wt.% Co cermets was improved significantly by the addition of Mo₂C. With the increase of Mo₂C content, there is a coarsening tendency in the microstructure of (Ti, 20W, 15Mo, 0.2V)(C, N)-8Ni-7Co system, but the refinement for (Ti, 15W, 5Mo, 0.2V)(C, N)-8Ni-7Co. TaC addition decreases the density of (Ti, 15W, 5Mo, 0.2V)(C, N)-10Mo₂C-8Ni-7Co cermet and thus weakens its bending strength. (Ti, 15W, 5Mo, 0.2V)(C, N)-10Mo₂C-5WC-8Ni-7Co cermet has optimal mechanical properties: bending strength of 1999 MPa, hardness (H_v) of 1677 MPa and toughness of 9.95 MPa m^1/2 respectively by adding WC, which is due to its ultrafine and weak core/rim structure.     

Microstructural evolution and characteristics during sintering of submicron Ti(C,N)-based cermet

1　INTRODUCTIONThebasiccompositionofTi(C ,N ) basedcer metsisTi(C ,N)andNi.IthasbeenknownthattheadditionofMoorMo2 Cisnecessarytoensuregoodwettability[1] ,andWCorothercarbidesareoftenaddedtoimprovetheplasticityofhardgrainsandhothardnessofthecermets[2 ] .Ti(C ,N) basedcermetsconsistmainlyofcarbonitride grainsandmetalbinder.The“core rim”structurewithinthehardgrainsisthetypicalmicrostructureofcermets .Thecarbonitride phaseenrichedMoandW (therimphase)hasbeenfoundtosurroundthe Ti(C ,…     

Influence of preparation process on sintering behavior and mechanical properties of ultrafine grained Ti（C, N）-based cermets

The influences of forming and sintering processes on distortion, cracking as well as mechanical properties of sintered bodies of ultrafine grained Ti（C, N）-based cermets were investigated. The results show that lubricant is indispensable to fabrication of ultrafine Ti（C, N）-based cermets, however, with low binder content in powder mixture, the lubrication action of paraffin is attenuated. A appropriate level of 2% （mass fraction） paraffin is determined for a cermet with binder content of 36% （mass fraction）. It is also found that the influence of compaction pressure on distortion and cracking of sintered bodies presents a complex relationship. A relatively lower or higher compaction pressure, less than 100 MPa and more than 400 MPa respectively, favors uniform density distribution in green compact. The heating rate of sintering should be strictly controlled. Too fast heating rate results in enclosed pores to burst and forms large size pores in sintering body. A heating rate of 3 ℃/min is recommended.     

Mo_2C对Ti(C,N)基金属陶瓷腐蚀性能的影响

通过静态浸泡腐蚀和动电位极化两种方法,研究了Mo2C对Ti(C,N)基金属陶瓷在NaOH溶液中腐蚀性能的影响。实验结果表明:Ti(C,N)基金属陶瓷的耐蚀性明显优于WC-Co硬质合金;添加Mo2C可以大幅度提高Ti(C,N)基金属陶瓷的机械性能,硬度从91.2到94.0 HRA和抗弯强度从930到1 350 MPa,但会降低金属陶瓷的耐蚀性能;由于Mo2C的加入,会使金属陶瓷的动电位极化曲线出现两个钝化区,但是两个钝化区域的电流均未达到真正的钝化电流(10-5A/cm2),因而这些钝化现象均为伪钝化;在经动电位极化后的试样表面,粘结相Ni和白色的内环相均会被腐蚀,其中内环相为富Mo的(Mo,Ti)(C,N)固溶体,其耐腐蚀性较未溶的Ti(C,N)芯更差。随着Mo2C添加量的提高,内环形相的厚度随之会增加,从而降低了Ti(C,N)基金属陶瓷的耐蚀性能。     

Mo含量对Ti(C,N)基金属陶瓷组织和性能的影响

Ti(C,N)基金属陶瓷是一种新型工具材料,在高速切削刀具中得到广泛应用。本文介绍了金属陶瓷中Mo或Mo2C的作用,并综述了国内外关于Mo或Mo2C对Ti(C,N)基金属陶瓷显微组织和性能的影响。     

TiC粉末粒度对Ti（C,N）基金属陶瓷组织及性能的影响

通过采用真空烧结工艺的粉末冶金法制备了两组不同TiC粒度的Ti（C,N）基金属陶瓷材料。采用XRD、SEM、EDS研究了相结构和显微组织,测定了室温力学性能。结果表明,用纳米TiC粉末制备的金属陶瓷组织细小均匀,抗弯强度、硬度均较高,分别达1021.5 MPa和17.7 GPa（HV10）。     

Effect of VC addition on the microstructure and properties of Ti（C,N）-based nano cermets

In this paper, Ti(C,N)-based nano cermets were prepared by nano particles, and the effect of VC addition on the microstructure and properties of Ti(C,N)-based nano cermets was investigated. The results showed that there existed black-core grayish-rim structure as well as gray-core grayish-rim structure in VC-doped Ti(C,N)-based nano cermets. With the increase of VC addition, the number of gray cores increased, the lattice parameter of Ti(C,N) phase increased, the grain size decreased, the hardness and fracture toughness of Ti(C,N)-based nano cermets were enhanced, and nearly full densification could be achieved. However, excessive addition of VC to 1 wt% resulted in slight decrease in hardness and fracture toughness. Some deep dimples were found in the fracture surface of cermets with VC addition, which corresponded to ductile fracture.     

Effect of hot isostatic pressing nitrogen on the microstructure and properties of a Ti（C, N）-based cermet

The high-temperature, high-pressure hot isostatic pressing technology was used for depositing hard coatings on Ti（C, N）-based cermets. The rnicrostructure and properties of the sample were investigated using optical microscopy, scan- ning electron microscopy, X-ray diffraction, electron probe microanalysis, and microhardness tester. The results showed that the rich titanium and nitrogen in surface zone were induced by the heat treatment. The high nitrogen activity of the surface region was the driving force for outward transport of titanium and inward transport of tungsten in the cobalt binder. The toughness and hardness were improved and a hardness gradient was formed. It is the high-temperature, high-pressure N2 that enables closure of holes, thereby alleviating defects and prolonging tool life.     

Ti(C,N)复合膜和TiN/Ti(C,N)多层膜组织和显微硬度

采用非平衡反应磁控溅射的方法在Si(100)基片上沉积Ti(C,N)复合膜和不同调制周期、调制比的TiN/Ti(C,N)纳米多层薄膜。薄膜的微观结构和力学性能采用X射线衍射仪(XRD)、显微硬度计进行表征。结果表明,Ti(C,N)复合膜的微观结构和力学性能与掺入C的含量有关;TiN/Ti(C,N)纳米多层膜的微观结构和力学性能与调制周期和调制比有关,其显微硬度在一定的调制周期和调制比范围内出现了超硬现象。Ti(C,N)、TiN/Ti(C,N)均为δ-NaCl面心立方结构;Ti(C,N)复合膜显微硬度提高是因为固溶强化,TiN/Ti(C,N)纳米多层膜硬度的提高主要是共格外延生长在界面处产生的交变应力场。     

原始粉末粒度对Ti(C,N)基金属陶瓷组织性能的影响

采用粉末冶金方法制得四组不同粒度组合的Co-WC-Ti(C,N)金属陶瓷材料。对其室温力学性能进行测量,并采用XRD,SEM,EDX等方法对材料的相结构,显微组织等进行分析。研究表明,主要硬质相粒度的改变使相结构出现了一定程度的变化;以亚微米TiC为原始粉末细化了金属陶瓷组织中的晶粒;以纳米TiN为原始粉末使得晶粒大小趋向一致,分布均匀,并在一定程度上细化了晶粒;当TiC、TiN原始粉末分别为亚微米、纳米尺寸时,材料的综合力学性能最好。     

VC/Cr3C2对Ti(C,N)基金属陶瓷微观组织和力学性能的影响

研究VC/Cr3C2对Ti(C,N)基金属陶瓷微观组织和力学性能的影响.利用光学显微镜、X射线衍射仪和扫描电镜结合能谱仪研究微观组织.测试横向断裂强度、硬度和断裂韧性等力学性能.结果表明:微观组织中存在“黑芯-灰壳”和“白芯-灰壳”结构;由于添加VC/Cr3C2,硬质相晶粒变细,添加0.75VC/0.25Cr3C2的金属陶瓷晶粒细化最明显;黑芯随着VC添加量的增加而变细,壳随着Cr3C2添加量的减少而变厚;孔隙率随着VC/Cr3C2中VC的量增加而增大;横向断裂强度和硬度均升高,并且均在添加0.25VC/0.75Cr3C2时达到最大值;按适当的VC和Cr3C2添加量比例添加VC/Cr3C2可以有效地使断裂韧性升高,并在添加0.5VC/0.5Cr3C2时取得最大值.     

Ti(C,N)基金属陶瓷的芯-壳显微结构与性能研究

以TiC、TiN为原料,Ni、Co为粘结剂,WC、Mo2C、TaC、C、Cr3C2为添加剂,采用真空热压烧结工艺制备Ti(C,N)基金属陶瓷材料。借助于SEM、EDS和XRD分别分析其显微结构、组成和物相,并测试其性能。结果表明:按配方(质量分数,%):TiC:41.2,TiN:10,Ni:7,Co:7,Mo2C:12,WC:15,TaC:6,Cr2C3:0.8,C:1配料,在1450℃,30MPa热压制得的试样晶粒细小,具有完整的芯-壳显微结构。其主要性能为:相对密度99.12%,维氏硬度22.74GPa,断裂韧性10.1MPa·m1/2,抗弯强度1192.83MPa。     

Ni-Ti合金对Ti(C,N)基金属陶瓷组织和性能的影响

采用粉末冶金方法真空烧结制备了添加Ni-Ti形状记忆合金的Ti(C,N)-Co系金属陶瓷,研究了Ni-Ti合金对Ti(C,N)基金属陶瓷显微组织和力学性能的影响。结果表明:未加Ni-Ti合金的Ti(C,N)基金属陶瓷的显微组织表现为经典的黑芯-灰壳组织,陶瓷相多为球形;而加入Ni-Ti后的金属陶瓷随着Ni-Ti加入量的增多,组织逐渐细化,出现了多边形的陶瓷相,陶瓷相与粘结相的界面呈现直线关系。同时,金属陶瓷的抗弯强度和断裂韧性随着Ni-Ti合金加入量的增多有明显的提高,而硬度基本保持不变;Ni-Ti合金的加入量为15wt%时金属陶瓷获得最好的力学性能。