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。     

再生WC-Co复合粉及高耐磨性硬质合金涂层的制备

以WC-6Co废旧硬质合金块体和Co_3O_4粉末为原料,采用氧化-还原碳化法制备再生WC-12Co复合粉,将复合粉经过造粒和热处理制备再生热喷涂喂料,进而采用超音速火焰喷涂(HVOF)制备再生WC-Co硬质合金涂层,比较再生硬质合金涂层和商业购买热喷涂喂料制备涂层的显微组织、耐磨性及其机制。结果表明:当配碳量为16.70%(质量分数)时,再生复合粉的碳含量适中;制备的再生热喷涂喂料由WC和Co相组成,热喷喂料球形度好,粒径分布均匀,平均粒径为23μm;再生WC-12Co硬质合金涂层的结构致密,WC晶粒尺寸分布均匀。与商业化热喷涂粉制备涂层显微组织和性能相比,再生涂层的磨粒磨损性能明显优于商业喷涂粉制备涂层的,其根本原因是两者的磨损机制不同。     

WC/FeAl金属间化合物基金属陶瓷涂层的冷喷涂制备

采用WC/Fe/Al混合粉末,通过机械合金化制备40v0l％ WC/Fe(Al)固溶体复合粉末,利用冷喷涂沉积涂层并结合热处理原位反应制备了WC/FeAl金属间化合物基金属陶瓷涂层.研究了球磨时间对复合粉末相结构、晶粒尺寸及组织结构的影响,并分析了冷喷涂WC/FeAl金属间化合物基金属陶瓷涂层的组织和显微硬度.结果表明,机械合金化可获得WC陶瓷颗粒呈微/纳米多尺度分布的WC/Fe(Al)金属陶瓷复合粉末,球磨36 h的复合粉末基体相平均晶粒尺寸约为90 nm,冷喷复合涂层组织致密、多尺度WC颗粒在基体中均匀弥散分布,涂层显微硬度约为1060 HV0.3,涂层在650℃热处理后发生Fe(Al)固溶体向FeAl金属间化合物的原位转变,制备出了WC/FeAl金属间化合物基金属陶瓷涂层.     

超细结构WC-η涂层的制备及其耐熔锌腐蚀性能

以钨氧化物、钴氧化物和炭黑为原料,采用创新的原位反应技术快速合成超细WC-η复合粉,在优化的工艺条件下制备复合粉中只含有WC和Co6W6C相,粉末平均粒径为260 nm。复合粉经团聚造粒制备得到具有高致密性和良好流动性的热喷涂粉末,以此粉末作为喂料,利用超音速火焰喷涂技术制备得到超细结构的WC基涂层,其平均显微硬度(HV0.3)达到(14060±340)MPa,孔隙率仅约为0.3%。熔融锌腐蚀结果表明,制备的超细结构WC基涂层具有良好的耐熔锌腐蚀性能,其腐蚀机制主要是锌液沿微裂纹扩散导致涂层自表层向内部出现缓慢的溶解腐蚀,并逐渐形成贯穿性裂纹而引起涂层材料的大块剥落。     

WC晶体结构特征对HVOF喷涂纳米结构WC-CoCr涂层组织及性能的影响

为提高纳米结构WC-CoCr涂层的综合力学性能,采用超音速火焰喷涂（HVOF）工艺制备纳米结构和超细结构WC-CoCr涂层。探讨了不同晶体特征的WC粉末对颗粒飞行和沉积变形过程的脱碳行为、涂层微观组织及力学性能的影响。结果表明：含有高密度位错的超细WC粉末在喷涂过程中发生了严重的氧化脱碳,形成了大量的W₂C相,涂层孔隙率较大,断裂韧性显著降低。而含有显著孪晶的纳米WC颗粒具有抑制WC脱碳和增强涂层断裂韧性的作用,纳米结构涂层呈现低脱碳率、高致密性、高硬度和高断裂韧性的优良综合性能。     

以石墨烯为碳源的硬质合金制备与性能

以N-甲基吡咯烷酮分散的石墨烯代替常规的冶金炭黑作为碳源,采用短流程原位还原碳化反应制备出纳米晶WC-Co复合粉末。采用放电等离子烧结系统对复合粉末进行快速烧结致密化。结果表明,石墨烯作为碳源可显著降低原位还原碳化反应温度,复合粉末粒径细小且分布均匀。得到的超细晶硬质合金块体材料平均晶粒尺寸约为290 nm,HV_(30)硬度值为13.877±0.131 GPa,断裂韧性KIC值为8.3±0.1 MPa·m~(1/2)。通过HRTEM观测表明,试样中WC/WC晶界、WC/Co相界、WC/C相界具有很高的匹配度。     

以石墨烯为碳源的硬质合金制备与性能研究

以N-甲基吡咯烷酮分散的石墨烯代替常规的冶金炭黑作为碳源,采用短流程原位还原碳化反应制备出纳米晶WC-Co复合粉末,石墨烯作为碳源可显著降低原位还原碳化反应温度,复合粉末粒径细小且分布均匀。采用放电等离子烧结系统对复合粉末进行快速烧结致密化,得到平均晶粒尺寸为~290nm的超细晶硬质合金块体材料,具有硬度值HV30为1387.7±13.1kg/mm2,断裂韧性KIC值为8.3±0.1MPa?m1/2的良好力学性能,通过HRTEM观测得到试样中WC/WC晶界、WC/Co相界、WC/C相界具有很高的匹配度。     

复合添加晶粒长大抑制剂对WC-12Co超细晶硬质合金涂层性能的影响

利用真空原位还原碳化反应合成超细WC-12Co复合粉末,通过复合添加不同含量的晶粒长大抑制剂VC和Cr_3C_2,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WC-12Co涂层。利用X射线衍射和扫描电镜对涂层的物相、显微组织结构等进行了系统表征,并对涂层耐磨性进行了测试分析。结果表明:WC-12Co涂层中WC晶粒的平均尺寸,随着晶粒长大抑制剂的增加而减小,且抑制剂的添加使涂层的摩擦系数降低;当复合添加抑制剂总含量(质量分数)为1.0%时,WC-12Co涂层的显微硬度(HV_(0.3))达到最大值13 670 MPa,且涂层的磨损速率最低;随抑制剂含量进一步增加,WC-12Co涂层的显微硬度逐渐降低,磨损速率增加,涂层的耐磨性降低。     

粉末结构对冷喷涂纳米结构WC-Co沉积行为的影响

纳米结构WC-Co具有比常规WC-Co更高的硬度,因此受到了广泛关注.冷喷涂制备纳米结构WC-Co涂层过程中,因粒子温度低于熔点,沉积过程需要依靠WC-Co粒子的塑性变形,然而WC-Co粒子变形能力有限,使得WC-Co涂层难以实现有效沉积.文中从粉末结构角度出发,选用3种不同孔隙结构的WC-12Co粉末,运用扫描电镜研究不同结构WC-12Co单个粒子在基体上的沉积行为,分析了3种粉末在相同喷涂工艺参数下沉积的涂层的组织结构.研究发现,定点喷涂容易实现,沉积的WC-12Co沉积层组织结构致密,硬度接近块材,为粉末的连续沉积制备涂层提供了可能.涂层的连续沉积需要粉末和基体材料均产生一定的变形,具有一定孔隙结构的纳米结构WC-Co粉末,因其多孔结构促进了粉末拟变形的发生,适合于冷喷涂制备纳米结构WC-Co涂层.     

粉末结构对HVOF喷涂WC-Co涂层组织性能的影响

选用4种不同WC尺度的WC-12Co粉末作为初始喂料,通过超音速火焰喷涂系统(HVOF)制备了涂层。考察了不同粉末结构对涂层沉积过程的脱碳行为和涂层组织性能的影响。结果表明:WC颗粒尺寸减小加剧了涂层脱碳行为,涂层中W2C含量增加,粘结相非晶化现象明显,涂层硬度增加,但是当WC颗粒尺寸减小到纳米尺度时,韧性下降。双峰结构涂层表现出最好的韧性同时兼备较高的硬度。     

Effect of Particle and Carbide Grain Sizes on a HVOAF WC-Co-Cr Coating for the Future Application on Internal Surfaces: Microstructure and Wear

The use of nanoscale WC grain or finer feedstock particles is a possible method of improving the performance of WC-Co-Cr coatings. Finer powders are being pursued for the development of coating internal surfaces, as less thermal energy is required to melt the finer powder compared to coarse powders, permitting spraying at smaller standoff distances. Three WC-10Co-4Cr coatings, with two different powder particle sizes and two different carbide grain sizes, were sprayed using a high velocity oxy-air fuel (HVOAF) thermal spray system developed by Castolin Eutectic-Monitor Coatings Ltd., UK. Powder and coating microstructures were characterized using XRD and SEM. Fracture toughness and dry sliding wear performance at three loads were investigated using a ball-on-disk tribometer with a WC-Co counterbody. It was found that the finer powder produced the coating with the highest microhardness, but its fracture toughness was reduced due to increased decarburization compared to the other powders. The sprayed nanostructured powder had the lowest microhardness and fracture toughness of all materials tested. Unlubricated sliding wear testing at the lowest load showed the nanostructured coating performed best; however, at the highest load this coating showed the highest specific wear rates with the other two powders performing to a similar, better standard.     

Mechanical properties of WC–Co coatings with different decarburization levels

In this study, two kinds of WC–Co coatings with different decarburization levels were deposited by high-velocity oxy-fuel(HVOF) spraying using the ultrafine WC–Co composite powder and commercial micronsized powder, respectively. The hardness and elastic modulus were measured on the top surface and cross sections of the prepared coatings by the nanoindentation method. The results show that the ultrafine-structured coating has much higher density and inhibited decarburization than the conventional coating, which thus results in higher hardness and elastic modulus values than the micronsized coating. The wear resistance of thermal-sprayed cermet coatings greatly depends on the cross-sectional hardness and elastic modulus which reflects the bond strength between splats to some extent. Based on the analysis, a better understanding of the microstructure and properties in cermet coating materials was obtained.     

Selection criteria for wear resistant powder coatings under extreme erosive wear conditions

Wear-resistant thermal spray coatings for sliding wear are hard but brittle (such as carbide and oxide based coatings), which makes them useless under impact loading conditions and sensitive to fatigue. Under extreme conditions of erosive wear (impact loading, high hardness of abrasives, and high velocity of abradant particles), composite coatings ensure optimal properties of hardness and toughness. The article describes tungsten carbide-cobalt (WC-Co) systems and self-fluxing alloys, containing tungsten carbide based hardmetal particles [NiCrSiB-(WC-Co)] deposited by the detonation gun, continuous detonation spraying, and spray fusion processes. Different powder compositions and processes were studied, and the effect of the coating structure and wear parameters on the wear resistance of coatings are evaluated. The dependence of the wear resistance of sprayed and fused coatings on their hardness is discussed, and hardness criteria for coating selection are proposed. The so-called “double cemented” structure of WC-Co based hardmetal or metal matrix composite coatings, as compared with a simple cobalt matrix containing particles of WC, was found optimal. Structural criteria for coating selection are provided. To assist the end user in selecting an optimal deposition method and materials, coating selection diagrams of wear resistance versus hardness are given. This paper also discusses the cost-effectiveness of coatings in the application areas that are more sensitive to cost, and composite coatings based on recycled materials are offered.     

粉末原料粒径对WC-17Co涂层性能的影响

本文利用超音速火焰喷涂技术喷涂四种不同粒径的WC-17Co粉末,评价粉末粒径对涂层机械性能和抗磨粒磨损性能的影响。结果表明,粉末的粒径越小,在超音速焰流作用下获得的速度和温度越高,形成的涂层越致密,颗粒间的粘接强度越高,同时涂层的显微硬度也越高。WC-17Co粉末的粒径越小,获得涂层的孔隙直径越小,颗粒间的粘接缺陷越少,因此涂层的抗磨粒磨损性能越好。但是当WC-17Co粉末的粒径过于微小时,涂层的断裂韧性将受到影响。在本文研究的四种粒径分布的WC-17Co粉末中,中间粒径且分布范围集中的粉末制得的涂层兼具良好的机械性能和抗磨粒磨损性能。     

不同粉末超音速火焰喷涂WC-10%Co4%Cr涂层的性能

对两种(粉末A、粉末B)及其按一定比例混合(粉末C)的WC-10%Co4%Cr的粉末特性进行了表征,以这三种粉末为原料,利用空气助燃的超音速火焰喷涂(HVAF,High Velocity AirFuel)制备了WC-10%Co4%Cr涂层,着重研究喷涂粉末粒径、WC颗粒大小等对涂层的喷涂沉积率、硬度、韧性、结合强度和耐腐蚀等综合性能的影响。研究结果表明:A粉末喷涂沉积率高且价格较低;B粉末制备的涂层具有较高的硬度和韧性等,综合性能更优,但价格较高;混合粉末C喷涂沉积率较高,涂层的硬度、韧性和抗中性盐雾腐蚀等综合性能优良,具有较高的性价比。     

Development of WC-Co Coatings Deposited by Warm Spray Process

The high-velocity oxy-fuel (HVOF) process is commonly used to deposit WC-Co coatings. There are some problems with this process; especially the decomposition and decarburization of WC during spraying make a coating brittle. To suppress such degradation, the warm spray (WS) process was applied to deposit WC-Co coatings, which is capable of controlling the flame temperature in the range of 500-2000 °C. The microstructure and phases of the deposited coatings were characterized by using SEM and XRD, and the mechanical properties such as hardness, fracture toughness, and wear properties were also investigated. WS process successfully suppressed the formation of the detrimental phases such as W₂C and W, which are usually observed in HVOF coatings. The WS coatings showed the similar trend of the hardness variation for Co content with a sintered bulk material. Improvement of toughness and wear behavior was also observed in WS coatings.     

Powder/processing/structure relationships in WC-Co thermal spray coatings: A review of the published literature

Thermally sprayed coatings based on tungsten carbide are widely used but not yet fully understood, particularly with regard to the chemical, microstructural, and phase changes that occur during spraying and their influence on properties such as wear resistance. The available literature on thermally sprayed WC-Co coatings is considerable, but it is generally difficult to synthesize all of the findings to obtain a comprehensive understanding of the subject. This is due to the many different starting powders, spray system types, spray parameters, and other variables that influence the coating structures and cause difficulties when comparing results from different workers. The purpose of this review is to identify broad trends in the powder/processing/structure relationships of WC-Co coatings, classified according to powder type and spray method. Detailed comparisons of coating microstructures, powder phase compositions and coating phase compositions as reported by different researchers are given in tabular form and discussed. The emphasis is on the phase changes that occur during spraying. This review concerns only WC-12% Co and WC-17% Co coatings, and contrasts the coatings obtained from the cast and crushed, sintered and crushed, and agglomerated and densified powder types. Properties such as hardness, wear, or corrosion resistance are not reviewed here.     

Effect of Feedstock Size and its Distribution on the Properties of Detonation Sprayed Coatings

The detonation spraying is one of the most promising thermal spray variants for depositing wear and corrosion resistant coatings. The ceramic (Al₂O₃), metallic (Ni-20 wt%Cr) , and cermets (WC-12 wt%Co) powders that are commercially available were separated into coarser and finer size ranges with relatively narrow size distribution by employing centrifugal air classifier. The coatings were deposited using detonation spray technique. The effect of particle size and its distribution on the coating properties were examined. The surface roughness and porosity increased with increasing powder particle size for all the coatings consistently. The feedstock size was also found to influence the phase composition of Al₂O₃ and WC-Co coatings; however does not influence the phase composition of Ni-Cr coatings. The associated phase change and %porosity of the coatings imparted considerable variation in the coating hardness, fracture toughness, and wear properties. The fine and narrow size range WC-Co coating exhibited superior wear resistance. The coarse and narrow size distribution Al₂O₃ coating exhibited better performance under abrasion and sliding wear modes however under erosion wear mode the as-received Al₂O₃ coating exhibited better performance. In the case of metallic (Ni-Cr) coatings, the coatings deposited using coarser powder exhibited marginally lower-wear rate under abrasion and sliding wear modes. However, under erosion wear mode, the coating deposited using finer particle size exhibited considerably lower-wear rate.     

Effect of flame conditions on abrasive wear performance of HVOF sprayed nanostructured WC-12Co coatings

Nanostructured WC-12Co coatings were deposited by high velocity oxy-fuel (HVOF) spraying with an agglomerated powder. The effect of flame conditions on the microstructure of the nanostructured coatings was investigated. The wear properties of the coatings were characterized using a dry rubber-wheel wear test. The results show that the nanostructured WC-Co coatings consist of WC, W2C, W and an amorphous binder phase. The microstructure of the coating is significantly influenced by the ratio of oxygen flow to fuel flow. Under the lower ratio of oxygen/fuel flow, the nanostructured coating presents a relative dense microstructure and severe decarburization of WC phase occurs during spraying. With increasing ratio of oxygen/fuel flow, the bonding of WC particles in the coating becomes loose resulting from the original structure of feedstock and the decarburization of WC becomes less owing to limited heating to the powder. Both the decarburization of WC particles in spraying and the bonding among WC particles in the coatings affect the wear performance. The examination of the worn surfaces of the nanostructured coatings reveals that the dominant wear mechanisms would be spalling from the interface of WCCo splats when spray particles undergo a limited melting. While the melting state of the spray particles is improved,the dominant wear mechanisms become the plastic deformation and plowing of the matrix and spalling of WC particles from the matrix.     

Plasma spraying of Wc-Co part II: Experimental study of particle deposition and coating microstructure

WC-Co base wear-resistant coatings deposited by plasma spraying are widely used to enhance component longevity in a variety of wear environments. During spraying of WC-Co, ideally only the cobalt phase should melt and act as a binder for the WC particles. Although it is undesirable to fully melt WC because it can cause decarburization, complete melting of the cobalt phase and its satisfactory flattening on impacting the substrate is necessary to minimize porosity and achieve good substrate/coating adhesion. In this article, the influence of the primary plasma spray variables on the melting characteristics of WC-Co powders is investigated with respect to the microstructure of these coatings. This experimental work complements an analytical study on plasma spraying of WC-Co, and thus, observations are presented to support the predictions of the modeling effort.