EFFECTS OF SIZE COMBINATION AND CONTACTING STATE OF RAW POWDER PARTICLES ON SPARK PLASMA SINTERED ULTRAFINE CEMENTED CARBIDES

本文采用亚微米WC粉和纳米Co粉、亚微米WC粉和高能球磨后具有纳米晶组织的微米级Co粉这两种具有不同粒径匹配的混合粉末作为原料粉末，利用放电等离子烧结（SPS）技术制备超细晶WC-10Co硬质合金。对不同原料粉末的SPS过程及烧结试样的显微组织和性能进行了系统的对比分析。实验结果表明，以两种混合粉末为原料均获得了平均晶粒尺寸在200nm以下的超细硬质合金材料，其中，采用亚微米WC粉和高能球磨的微米级Co粉利用SPS技术制备的材料相对密度达到98%以上，硬度达到HRA94.5，断裂韧性达到13.50MPa•m1/2，表明具有优良的综合性能。而采用亚微米WC粉和纳米Co粉利用SPS技术制备出的超细晶硬质合金的组织均匀性和性能较差。根据SPS技术的特殊烧结机理，对采用不同粒径匹配和结合状态的WC和Co混合粉末的SPS致密化机制进行了分析。     

原料粉末粒径匹配对放电等离子烧结制备的超细WC-Co硬质合金性能的影响

采用亚微米WC粉和纳米Co粉以及亚微米WC粉和微米Co粉的混合粉末作为原料,利用放电等离子烧结(SPS)技术制备超细晶WC-10Co硬质合金.对比研究表明,以两种混合粉末为原料均获得了平均晶粒尺寸约为200 nm的超细硬质合金材料.其中,采用微米Co粉制备的材料的相对密度达到98.0%以上,硬度HRA达到94.5,断裂韧性达到13.50 MPa·m1/2,具有优良的综合性能;而采用纳米Co粉制备的硬质合金的组织均匀性和性能较差.根据SPS技术的烧结机理,对混合粉末的致密化机制进行了分析.     

水溶化学法制备纳米WC/Co复合粉工艺探索

本文通过实验探索了水溶化学法制备纳米WC/C0复合粉工艺,研究了影响喷雾转换、锻烧、碳化和调碳的工艺因素,找到了满足纳米WC/Co复合粉制备的工艺参数。在Kear等人的经典合成技术中,碳化钨钴纳米复合材料是由喷雾转化水溶液的化学计量量的水溶性钨源和钴源,然后用流化床通氢将钨钴氧化物还原为金属钨和钴,之后在一个充满CO/CO2的气体环境中将金属钨和钴碳化成纳米WUCo复合粉末。本研究不同于Kear等人的处理方法,涉及的WC/C0使用水溶性溶液钨、钴和碳前躯体加工的纳米复合材料,大量的WGCo纳米复合粉体是将钨、钴和碳在分子级水平上混合制备成一个复杂的前驱体粉末的独特方案,前驱体粉末在煅烧炉充满惰性气体约100撕00cC的温度下转化成一个含有W-Co-C-0的预复合粉粉末,随后在碳化炉低于1000℃的温度下碳化。实验表明,水溶化学法生产的纳米WC/Co复合粉较常规方法,具有晶粒细而均匀、流动性好等特点,更适于高性能硬质合金的生产。     

纳米及超细复合粉添加对超粗晶硬质合金晶粒长大的影响及机制

在粗颗粒WC/Co混合粉末中分别添加平均粒径为100、250、400nm的WC-8Co复合粉,经球磨混合压坯后在不同温度进行Ar气保护烧结。针对烧结块体的形貌、晶粒尺寸及其分布进行了研究,并分析了复合粉添加对不同烧结阶段WC晶粒长大的影响机理。研究发现,在WC/Co混合粉中加入纳米和亚微米复合粉末均可制备得到超粗晶硬质合金,且添加纳米复合粉烧结的试样平均晶粒尺寸达到9.3μm。烧结初期,纳米和亚微米复合粉通过增加混合粉末的表面能而有效促进WC晶粒长大;当达到液相烧结温度时,添加纳米复合粉的烧结块体中,由于小晶粒具有更大的溶解驱动力,促使小晶粒溶解并在周围大晶粒表面析出,进一步增大烧结块体的晶粒尺寸;添加亚微米复合粉的块体中,小晶粒WC呈集中分布,使其溶解驱动力较小,且析出主要发生在周围细小晶粒之间,达到溶解析出动态平衡,从而使烧结块体的平均晶粒尺寸增长缓慢。     

原位合成复合粉制备超细WC-Co硬质合金

以偏钨酸铵、可溶钴盐、可溶碳源为原料,经喷雾转化、煅烧、低温还原碳化制备超细晶WC-Co复合粉;采用同样成分配比及工艺,在煅烧后增加短时球磨工艺,制备出另一种超细晶WC-Co复合粉;分别以2种复合粉为原料,用放电等离子直接烧结制备超细WC-Co硬质合金。采用SEM、XRD、钴磁仪、矫顽磁力计、维氏硬度计等对复合粉形貌、合金显微组织与性能进行表征分析。结果表明,未短时球磨的粉末呈现出球形结构,WC颗粒被Co相粘结在一起,可观察到烧结颈并有异常长大晶粒,经过短时球磨工序制备的粉末为分散颗粒,2种粉末中Co相同时以fcc与hcp的结构存在,粉末WC晶粒尺寸约为0.26μm;未短时球磨的粉末制备的合金存在少量孔隙,致密度较低,有异常长大晶粒。短时球磨能有效提高粉末颗粒的分散性,减少烧结体中的显微组织缺陷,制备的合金综合性能得到提高。     

超细/纳米结构WC-10Co-4Cr涂层的透射电镜表征与性能分析

利用真空原位还原碳化反应合成超细/纳米WC-Co复合粉末,通过添加一定量Cr获得WC-10Co-4Cr复合粉末,经团聚造粒获得喷涂用复合粉末喂料,采用超音速火焰(HVOF)喷涂系统制备出超细/纳米结构的WC-10Co-4Cr涂层。利用X射线衍射仪,扫描电子显微镜和透射电子显微镜对涂层的物相、显微组织结构、元素分布特征等进行了系统表征,并对涂层耐磨性、耐蚀性进行了测试分析。结果表明:基于原位反应合成WC-Co复合粉制备的超细/纳米结构WC-10Co-4Cr涂层具有较好的耐磨性和耐腐蚀性。涂层以WC为主相,含有非晶结构的粘结相Co(Cr),同时存在少量六方晶体结构的W_2C相和非晶复相W_2C+Co(Cr)。对涂层中元素Co和Cr的分布进行了量化分析,得到其从WC晶粒到相界到共晶区再到Co区的变化规律。结合WC-10Co-4Cr复合粉末和超音速火焰喷涂工艺的特点,阐释了Cr在WC-10Co-4Cr涂层分布状态的形成原因,并讨论了对涂层性能的影响。     

超细碳化钨粉末特性对金刚石锯片刀头显微结构的影响

采用超细WC粉末和工业级的Sn、Ni、Co、Cu粉末以及金刚石为原料，经真空烧结后制备成金刚石锯片刀头。用扫描电镜（SEM）观察了WC粉末和合金的形貌，用能量散射谱（EDS）测试了合金的微区成分分布。研究结果表明，超细WC粉末的添加能改善Sn-Ni-Co-Cu结合金刚石锯片刀头的显微结构，超细WC含量的增加有利于材料晶粒的细化和强度提高，Cu是烧结中产生液相和使成分偏析的重要影响因素，Co对晶粒异常生长影响很大，Sn的添加有利于晶粒的细化。     

原位合成WC-6Co复合粉末制备超细YG6硬质合金

将原位合成WC-6Co复合粉末采用干袋式冷等静压压制成型(压制压力1×10~8 Pa、保压时间15 s),将压制好的坯料采用低压烧结炉烧结(烧结温度1360℃、烧结时间40 min、加压5 MPa、保温保压时间20 min),烧结制备超细YG6硬质合金,对合金的形貌、金相组织及物理力学性能进行分析。结果表明:原位合成WC-6Co复合粉末制备的超细YG6硬质合金,晶粒异常长大,WC平均晶粒尺寸为0.8μm,硬度HV_(30)为(21500±100) MPa,较传统超细YG6X硬度高。再将WC-6Co复合粉末采用滚动湿磨、压力式喷雾干燥、掺成型剂、挤压成型、低压烧结等工序制备超细YG6硬质合金,研究不同晶粒长大抑制剂配比、球磨时间、挤压压力、烧结温度对合金性能的影响。结果表明:添加0.3%VC、0.8%Cr_3C_2(质量分数),湿磨48 h,挤压压力24 MPa,烧结温度1340℃,制备的超细YG6硬质合金WC晶粒均匀,无异常长大的WC晶粒,WC平均晶粒度尺寸0.4μm,呈多边形,外形较圆。强度、硬度最高,抗弯强度TRS为(2250±20) MPa、硬度HV30为(22600±100) MPa。断口形貌为沿晶断裂,沿WC与WC晶界断裂或WC与Co晶界断裂。     

化学包裹粉工艺制备粗晶粒WC-Co硬质合金

以费氏粒度为8.06μm的WC粉与Co(NO3)2·6H2O为原料,采用N(CH2CH2OH)3(TEA)为还原剂制备WC-12%Co(质量分数)包裹粉,以包裹粉为原料制备WC-12%Co硬质合金。采用扫描电镜观察包裹粉与合金中WC晶粒的立体形貌,采用X射线衍射仪分析粉末的物相组成,采用比表面积分析仪分析TEA还原产物多孔泡沫Co的比表面积,采用金相显微镜观察合金的组织结构。结果表明:包裹粉中Co为纯fcc高温相结构,呈多孔泡沫状纳米组装结构形式包裹在WC粉末表面;WC-12%Co合金组织结构均匀,平均晶粒度为4.8μm,WC晶粒结晶完整、呈规则多面体形状。     

放电等离子烧结制备超细WC基硬质合金

采用纳米碳化钒(V8C7)粉末作为晶粒抑制剂及放电等离子烧结(SPS)方式制备超细WC基硬质合金.X射线衍射结果表明:超细WC基硬质合金主要由WC和Co3C两相组成,随着温度的升高,WC的衍射峰逐渐向小角度偏移.扫描电镜结果表明:SPS和纳米V8C7粉末对超细WC基硬质合金的微观组织具有重要影响.SPS使超细WC基硬质合金在较低温度下(1200℃)实现致密化;纳米V8C7粉末可以有效抑制超细WC基硬质合金中WC的晶粒长大,1200℃时WC的晶粒尺寸约500 nm.力学性能结果表明:1200℃时超细WC基硬质合金具有较高的性能(相对密度99.5%,洛氏硬度93.2,断裂韧性12.5 MPa·m1/2).     

High temperature wear resistance and thermal fatigue behavior of Stellite-6/WC coatings produced by laser cladding with Co-coated WC powder

The Stellite-6/WC composite coatings were produced on AISI H13 hot work tool steel by laser cladding with mixture of Co-coated WC (WC-12Co) particles and Stellite-6 powder. The phase composition, microstructural characterization, high temperature wear resistance and thermal fatigue behavior of Stellite-6/WC coatings were investigated and compared with the properties of the coatings produced from mixture of WC particles and Stellite-6 powder. The results showed that using the WC-12Co particles alleviated the decomposition of WC and resulted in the weaker intensity of W₂C, CoC_x and Co₆W₆C peaks in the X-Ray Diffraction (XRD) patterns. Compared with using the WC particles directly as the coating material, using the WC-12Co particles could further improve the wear resistance of coatings according to the relative lower width and depth of wear scars at the same WC content. In addition, fewer fatigue cracks were observed on the surface of coatings made by adding WC-12Co particles under the same thermal fatigue conditions, which indicates that using WC-12Co is beneficial to extend the life of Stellite-6/WC coatings.     

Effects of mechanical milling on the carbothermal reduction of oxide of WC/Co hardmetal scrap

The effects of mechanical milling on the carbothermal reduction of oxidized WC/Co hardmetal scrap with solid carbon were examined. Mixed powders were manufactured by milling the WC/Co hard metal scrap oxide and carbon powder in either a tumbler-ball mill or a planetary-ball mill. The milling type affected the carbothermal reduction of the oxide owing to the differing collision energies (mechanical milling energies) in the mills. The hardmetal scrap oxide powder (WO₃, CoWO₄) milled at high energy was more greatly reduced and at a lower temperature than that milled at lower mechanical energy. The formation of WC by the carburization reaction with solid carbon reached completion at a lower temperature after higher-energy milling than after lower-energy milling. The WC/Co composite particles synthesized by the combined oxidationmechanical milling-carbothermal reduction process were smaller when the initial powder was milled at higher mechanical energy.     

Parametric study on a coaxial multi-material powder flow in laser-based powder deposition process

The manner with which the composite powder particles injected into the laser formed molten pool decides the deposition quality in a typical laser-based powder deposition of composite material. Since, the morphology and physical properties of nickel (Ni) and tungsten carbide (WC) are different their powder flow characteristics such as the powder particles stream structure, maximum concentration at the converging spot, and the powder particles velocity are noticeably different. In the current study, a computational fluid dynamics (CFD) based powder flow model is established to characterize the coaxial powder flow behavior of Ni–WC composite powders. The key powder flow characteristics such as the stand-off distance, the diameter of the powder stream at the stand-off distance, and the velocity of the powder particles are measured using three different vision based techniques. Both the numerical and experimental results reveal the exact stand-off distance where the substrate needs to be placed, the diameter of the concentration spot of powder at the stand-off distance, and a combination of suitable nozzle angle, diameter, and carrier gas flow rate to obtain a maximum powder concentration at the stand-off distance with a stable composite powder flow.     

亚微米WC添加对超音速火焰喷涂WC–Co涂层磨损性能影响

采用湿法球磨将亚微米WC（~300 nm）和WC–12Co粉末混合均匀并使亚微米WC均匀粘附于WC–12Co粉末的表面,采用超音速火焰喷涂方法（HVOF）在304不锈钢基体表面制备WC和WC–12Co的WC–Co复合涂层,研究亚微米WC的添加对涂层相组成、显微硬度、耐磨性能和表面形貌的影响。利用X射线衍射分析涂层相组成,压痕法测试涂层的显微硬度,通过往复式摩擦磨损实验测试磨损性能,扫描电子显微镜（SEM）对涂层磨损表面和断面进行微观形貌观察,并分析涂层的磨损过程和机制。结果表明,添加质量分数5%的亚微米WC颗粒显著提高了涂层的显微硬度（16.3%）;增强了涂层的耐磨性,磨损率从6.09×10-7 mm3/Nm减小到5.15×10-7 mm3/Nm（减小13.8%）;亚微米WC颗粒喷涂后在涂层中保持了WC相,并主要存在于WC–Co扁平粒子界面和孔隙。基于涂层中扁平粒子的结合特性与磨损失效特征,建立强化模型,分析亚微米WC颗粒对涂层扁平粒子界面的强化机制。     

Cold Spray Deposition of Ni and WC-Reinforced Ni Matrix Composite Coatings

Ni-WC composites are ideal protective coatings against wear and are often fabricated using laser cladding and thermal spray processes, but the high temperatures of these processes result in decarburization, which deteriorates the performance of the coating. Cold spray has the potential to deposit Ni-WC composite coatings and retain the composition of the initial WC feedstock. However, the insignificant plastic deformation of hard WC particles makes it difficult to build up a high WC content coating by cold spray. By using three different WC powder sizes, the effect of feedstock powder size on WC retention was tested. To improve WC retention, a WC/Ni composite powder in mixture with Ni was also sprayed. Microstructural characterization, including the deformed structure of Ni splats, retention, distribution, and fragmentation of WC, was performed by scanning electron microscopy. An improvement in WC retention was achieved using finer WC particles. Significant improvement in WC particles retention was achieved using WC/Ni composite powder, with the WC content in the coating being close to that of the feedstock.     

WC-Co复合粉形貌遗传特性及粒度分布研究

以偏钨酸铵、可溶钴盐、有机碳为原料,经喷雾转化、煅烧、低温还原碳化制备WC-Co复合粉。对前驱体、复合粉物相组成、WC晶粒度、微观形貌、平均粒度及分布进行研究。结果表明:复合粉由WC和Co两相组成,WC晶粒度约为60 nm;前驱体粉末呈空壳球形结构,部分颗粒破裂;经煅烧后,形貌未发生明显变化;再经还原碳化处理,颗粒表面产生大量孔隙,形貌与前驱体相似,具有很好的形貌结构遗传特性;复合粉平均粒度比前驱体略有减小且粒度分布更窄;溶液浓度、给料速度越大,离心转速越小,则平均粒度越大;进气温度对粒度影响很小。     

超音速火焰喷涂低碳WC/12Co涂层的组织及性能研究

采用离心雾化干燥法制得团聚颗粒,经连续高温烧结成两种不同松装密度的热喷涂粉末。采用以C3H8/O2为燃料的超音速火焰喷涂（HVOF）工艺制备了WC/12Co涂层。对粉末及涂层做了显微组织观察和XRD分析,测定了涂层的厚度、显微硬度和粉末沉积效率。结果表明,在1120℃、1180℃烧结的粉末中主要有WC和W6Co6C,但无Co相;涂层有脱碳,有Co6W6C相,但未出现单质Co。涂层组织均匀致密,沉积效率可达65%。     

Synthesis of WC-Co composite powders with two-step carbonization and sintering performance study

In this study, WC-Co composite powder was synthesized by two-step carbonization method using W, Co and C as raw materials. X-ray diffraction (XRD) showed that the η phase (Co₆W₆C) was kept at 1100 °C for 1 h under vacuum, and it could be completely carbonized into WC-Co composite powders. The surface morphology of WC-Co composite powders was analyzed by scanning electron microscope (SEM). The effects of η phase and second phase (W phase) on WC morphology and Co phase distribution were investigated. Electron backscattered diffraction (EBSD) was used to analyze WC-10 wt% Co cemented carbide particle distribution. Comparison of transverse rupture strength, hardness and fracture toughness of two kinds of WC-10 wt% Co cemented carbides synthesized by WC-Co composite powders + WC and WC + Co respectively, the cemented carbide of composite powders + WC increases the fracture toughness from 11.4 ± 0.3 MPa·m^1/2 to 12.4 ± 0.3 MPa·m^1/2.