A Novel Method for Direct Synthesis of WC-Co Nanocomposite Powder

In this study, a novel method, termed dielectric-barrier-discharge-plasma (DBDP) assisted ball milling and low-temperature carburization, was used to synthesize WC-Co nanocomposite powder. X-ray diffraction, scanning/transmission electron microscopy, and differential scanning calorimetry were used to characterize the microstructure of powders. Starting from W, Co, and graphite powder mixtures, the DBDP-milled W-C-10Co powder exhibited a flakelike morphology with very fine lamellar structure. The WC-Co composite powder was synthesized at 1273 K (1000 °C), which is much lower than the requisite temperature for the conventional carburizing method. The obtained WC-Co composite powder had a nanocomposite microstructure in which fine WC particles were bounded by homogenously distributed Co phase, and the WC crystals had a slablike morphology with a planar size of about 200 nm and <100-nm thickness. The combinational effect of the milling and the plasma in the DBDP milling caused a unique fine flakelike morphology and high-density interfaces in the W-C-10Co powder mixture, which is responsible for the reduced carburization temperature and the nanocomposite structure of WC-Co powder.     

Effects of Ni60WC25 powder content on the microstructure and wear properties of WC<Subscript>p</Subscript> reinforced surface metal matrix composites

The vacuum evaporative pattern casting technique was used to fabricate WC_p reinforced surface metal matrix composites in order to study the effects of Ni60WC25 powder content on the microstructure and wear properties of it. The results showed that the Ni60WC25 powders weakened the stability of WC particles and reacted with metal matrix at the interfacial regions in the composite. Diffusion kinetics and Gibbs free energy were calculated from the interactions between WC particles and matrix. It was found that adding 35 vol% Ni60WC25 alloy powder to composites led to the formation of Fe₃W₃C phases and complete dissolution of WC particles. The wear properties of composites with different Ni60WC25 alloy powder content were tested by the MLD-10 type tester. WC particles and Fe₃W₃C phases could protect the matrix and the matrix could support WC particles and Fe₃W₃C phases during wear processing.     

WC粉中聚集体成因分析

对ＷＣ粉中聚集体的成因进行了试验研究。结果表明：保证原料氧化钨相成分单一和性能稳定是生产粒度均匀、聚团少的优质ＷＣ粉的前提;若普通蓝钨中平杂其他相,尤其是ＷＯ２．７２相,则生产的Ｗ粉、ＷＣ粉中容易产生聚集体;ＷＣ中Ｆｅ含量的增加会使ＷＣ粉聚集程度明显增加,而且,同一种原料,不同工艺生产的Ｗ粉、ＷＣ粉的聚集体也不同,用普通蓝钨常规氢还原生产细Ｗ粉时,聚团现象无法避免。但在后续工序能基本得到打散,若碳     

Effects of wet and dry milling conditions on properties of mechanically alloyed and sintered W–C and W–B4C–C composites

Abstract

Tungsten based W–1C and W–2B₄C–1C (wt-%) powders synthesised by mechanical alloying (MA) for milling durations of 10, 20 and 30 h, in wet (ethanol) and dry conditions, were characterised. X-ray fluorescence spectroscopy investigations revealed Co contamination which increased with increasing milling time during wet milling. X-ray diffraction investigations revealed the presence of W and WC phases in all powders, Co₃C intermetallic in the wet milled W–1C powders and W₂B intermetallic phase in both wet and dry milled W–2B₄C–1C powders. As blended and MA processed powders were consolidated into green compacts by uniaxial cold pressing at 500 MPa and solid phase sintered at 1680°C under hydrogen and argon atmospheres for 1 h. X-ray diffraction investigations revealed the presence of W₂C intermetallic phase in sintered composites produced from both wet and dry milled W–1C powders and the W₂B intermetallic phase in sintered material from the wet milled W–2B₄C–1C powder. Sintered composites from wet milled powders showed relative densities >91%, with the maximum density of 99·5% measured for the sintered 30 h wet milled W–2B₄C–1C composites. Microhardness values for the wet milled W–1C and W–2B₄C–1C composites were 2–2·5 times higher than those for dry milled composite powders. A maximum hardness value of 23·7±2·1 GPa was measured for the sintered W–2B₄C–1C composite wet milled for 20 h.     

Catalytic effect of cobalt on the carburization kinetics of tungsten

The kinetics of the gas-phase carburization of tungsten by methane were studied and found to be controlled by two surface reactions and a later diffusion limiting reaction. The two surface reactions were found to produce the compounds W₂C and W₂C-WC respectively. The diffusion limiting reaction produced only WC. Extensive carburization caused cracking of the tungsten material. Cobalt was found to form a thin film on each tungsten surface which was easily converted to eta-phase (Co₃W₃C) when carburization began. A model was proposed and kinetic equations were developed which predict the rate of reaction for both cylinders and powders. The reaction rate curves for the uncatalyzed reaction using the same equations was also developed. CHARLES F. DAVIDSON, formerly with Fansteel Research Center, Salt Lake City, Utah     

Control of surface carburization and improvement of dynamic fracture behavior in tungsten heavy alloys

A carburization technique using a Cr powder layer has been developed to control the diffusion depth of carbon in W-Ni-Fe heavy alloys. The aged heavy alloy samples were covered with a Cr powder layer of about 1-mm thickness and then packed with carbon black powder. The packed samples were heat-treated at 1150 °C for 10 minutes in H₂ and then for 50 minutes in N₂. The carburization treatment resulted in the formation of Cr₇C₃ and Fe₃W₃C around the tungsten grains from the sample surface with a thickness of 40 to 50 μm. This carburized layer was much thinner than that formed without a Cr powder layer under the same experimental conditions. With the surface carburization, the surface hardness increased by ∼75 pct, from 508 to 888 VHN, and the impact energy decreased by ∼31 pct, from 123 to 85 J. After the carburization treatment, the main fracture behavior in a dynamic torsional test changed from smearing of the matrix to cleavage of the tungsten grains. A high-speed impact test showed that the surface carburization of penetrators induced the formation of many cracks around the penetrator surface, enhanced the self-sharpening, and improved the penetration performance. It appears that the developed technique provides an easy method of carburization without serious deterioration of the toughness of the material.     

A Morphological Study of the Carburization/Reduction of Tungsten Oxides with Carbon Monoxide

Thermogravimetry, X-ray diffraction analysis and scanning electron microscopy have been used to study the gas phase carburization/reduction by CO of WO₃, W₁₈O₄₉ and WO₂ over the temperature range 600 to 1100°C. The lower oxides W₁₈O₄₉ and WO₂ were produced by controlled reduction of WO₃ in H₂-H₂O mixtures. A wide range of particle morphologies and sizes have been obtained for the WC product and these have been related to the roles played by the lower oxides. The total carbon content of the carburized products is shown to be dependent upon both the temperature and time of processing.     

烧结方法对WC-Co硬质合金性能的影响

以原位还原碳化反应法制备的超细WC-Co复合粉为原料,分别采用放电等离子烧结、低压烧结和真空烧结工艺获得块体硬质合金,系统研究烧结方法对合金的显微组织、密度及力学性能的影响。结果表明:放电等离子烧结的合金中,主相为WC和Co,有少量η相(Co6W6C),低压烧结和真空烧结获得的合金中物相为WC和Co;所用3种不同的烧结方法均能获得细晶块体硬质合金,其中放电等离子烧结的晶粒最细为0.35μm;低压烧结合金具有优异的综合性能,HV30为15 121 MPa,断裂韧性为13.6 MPa.m1/2,横向断裂强度为4 210 MPa。     

喷雾干燥-直接碳化法制备WC-Co复合粉末

在高性能WC-Co的制备中,WC与Co均匀混合和C含量的严格控制具有重要意义。以偏钨酸铵、乙酸钴、重铬酸铵和炭黑为原料,通过喷雾干燥和直接还原碳化法制备WC-Co复合粉末,然后在钼丝炉中通入氢气对前驱体进行还原碳化制备WC-Co复合粉末。对制备好的WC-Co进行总碳含量测定,用X射线衍射进行相分析。研究了喷雾法制备WC复合粉末形貌粒度及碳化温度、碳化时间、配碳量对WC-Co粉末总碳量的影响。结果表明:WC复合粉末为球形粉末,平均颗粒度为50μm;当碳化温度在950℃、碳化时间为3.5h、配碳量为9%时,所得WC-Co复合粉末中WC与Co达到均匀的分布,且其实际总碳含量达到理论总碳量5.79%。     

Physicochemical interaction and structure development during the formation of metal gas-transfer coatings on diamond (review). 1. Kinetics

Work devoted to studying the phase composition and thickness of chromium, titanium, molybdenum, vanadium, and tungsten coatings which form on diamond powder during vacuum annealing of this powder mixed with chromium powder or oxidized powders of Ti, Mo, V, and W is analyzed. Coatings consist of metal (Cr, Ti, Mo, V, W) and carbide (Cr₇C₃, Cr₃C₂, TiC, -Mo₂C, V₂C, VC, W₂C, WC) phases. Diffusion of carbon during coating growth with increased metallizing time and temperature causes carbidization of chromium, titanium, and vanadium (it causes a reduction in the content of metal phase and an increase in carbide phases is coatings), growth of higher carbides (Cr₃C₂, VC, WC) at the expense of lower carbides (Cr₇C₃, V₂C, W₂C), and filling of carbon vacancies in the lattices of TiC and VC. Saturation of coatings with carbides correlates with the temperature-time range in which a further increase in coating weight slows down.Translated from Poroshkovaya Metallurgiya, No. 7(355), pp. 34–40, July, 1992.     

A study of microstructures of tungsten carbide powder

X-ray diffraction profiles were obtained from eight process variants of tungsten carbide (WC) powders in both the unmilled and heavily milled conditions. From these X-ray profiles, coherent domain size and microstrain were determined. This study indicated that the degree of crystalline imperfections in the unmilled WC powder decreased with increasing reaction temperatures,i.e., the reduction and carburization temperatures. Additionally, the morphology of the WC particles was examined using SEM. The particle morphology evaluated by SEM and the degree of crystalline imperfection obtained by X-ray profile analysis are in good agreement. The behavior of the WC powder during wet milling is closely related to the perfection of the powder.     

Features of the effect of nanodispersed additives on the sintering process and properties of powdered cobalt alloys

Some questions on the development of the cobalt-based composite material dispersion-hardened by nanoparticles using powder metallurgy are considered. The powders of WC, ZrO₂, and Al₂O₃ are used as nanoparticles that harden the Co matrix. The nanoparticles are mixed with cobalt powder of extra fine grade Co in a centrifugal planetary mill. It is shown that the treatment according to the suggested mode ensures a uniform distribution of nanoparticles throughout the volume of the Co powder, which is also retained after hot pressing. The obtained dispersion-hardened Co alloy possesses high indices of mechanical and tribological properties. For example, the wear resistance of the samples of optimum composition increases by a factor of six, while the bending strength increases by 25%.     

Characterization of the W2C phase formed during the high velocity oxygen fuel spraying of a WC + 12 pct Co powder

A variety of experimental techniques have been used to study a WC-12 pct Co powder and the coatings produced by high velocity oxygen fuel (HVOF) spraying of the powder onto a steel substrate. Many of the structural characteristics of the powder were also found in the coating. However, when the metallic matrix of the powder was melted during thermal spraying, the carbides were partially dissolved and a very heterogeneous liquid phase was produced in which the W/C ratio varied from about 1 to 4. These variations have been linked with oxidation of the liquid phase during spraying. The factors influencing the formation of W₂C in the coating have been identified as (1) an in situ transformation of WC into W₂C maintaining the original WC faceted morphology and (2) the precipitation of W₂C from the W-rich liquid phase matrix as the coating cools. A cobalt containing carbide of the M₆C-M₁₂C type has also precipitated from the liquid phase when the W/C and W/Co ratios were high. deceased.     

Thermophysics characteristics and densification of powder metallurgy composites

Abstract

An analytical densification model describing the final stages of hot pressing and sintering has been developed and found to be consistent with empirical findings. The behaviour of composite powders for the matrices of diamond tools has been studied under hot pressing conditions. Differential scanning calorimetry was used to determine the heat capacity at constant pressure C _p of pure Co, 663Cu, and composite iron- and cobalt based powders (also containing WC, Ni and 663Cu). The relationship between C _p and composite densification has been analysed, and it has been found that optimised rare earth additions to the iron based composite powders can produce C _p characteristics close or equivalent to that of pure Co powders. This modified composite powder has been used to hot press diamond drill and saw bits that show good properties. Employing a densification regime guided by the dynamic model has been found radically to improve stability in service (bend strength, hardness, impact, ductility and porosity).     

紫钨喷雾干燥-直接碳化法制备纳米WC-Co复合粉

以WC-6%Co为基本成分,计算原料紫钨、醋酸钴、有机碳及超纯炭黑配料量,称量后加入装有适量纯水的可倾斜式滚动球磨机,湿磨混匀12 h,形成复合盐料浆,然后充分搅拌,进行喷雾干燥后制备的前驱体粉末粒度在10¹00μm,平均粒度为50μm。将喷雾干燥好的粉末装舟(200 g),推入高温钼丝炉中,通入氢气,还原碳化温度950℃,时间30min制备的纳米WC-Co复合粉,粉末粒度分布窄,颗粒粒度在5100μm,平均粒度为50μm。将喷雾干燥好的粉末装舟(200 g),推入高温钼丝炉中,通入氢气,还原碳化温度950℃,时间30min制备的纳米WC-Co复合粉,粉末粒度分布窄,颗粒粒度在5⁴5μm,平均粒度为23.38μm。SEM、BET结果表明WC晶粒度在300 nm左右,由扫描电镜(SEM)、X光微区分析(EDS)及元素面分布图得到,W、Co、C分布均匀、Co相均匀包覆在WC晶粒周围,不存在成分偏析。XRD的半高宽窄,晶粒细小;物相纯净,无η相。     

Improving the wear resistance of hard-alloy rolling disks by pulsed-plasma treatment

Pulsed-plasma surface treatment of VK20 hard-alloy (WC + 20% Co) components changes the crystallite size by 10–20% and enriches the binding metal Co with complex carbides of type W₆Co₆C and W₃Co₃C and nonequilibrium carbides of composition W₂C, WC_1-x, and W₆C_2.54. The internal stress (compression) reaches 800 N/mm². Industrial tests show that pulsed-plasma treatment increases the wear resistance of the working surface of VK 20 hard-alloy (WC + 20% Co) rollers (rolling disks) by a factor of 2–4.     

Near-nanostructured WC-18 pct Co coatings with low amounts of non-WC carbide phase: Part I. Synthesis and characterization

Near-nanostructured WC-18 pct Co coatings, with low amounts of non-WC carbide phases, have been synthesized using high velocity oxygen fuel (HVOF) thermal spraying under spraying conditions of varying fuel chemistry, fuel-oxygen ratio, and powder particle size. The results show that the temperature the particles experience during spraying depends on the preceding parameters. Compared to available published results on WC-Co system coatings, nanostructured WC-18 pct Co coatings, synthesized in these experiments, contain very low amounts of non-WC carbide phase (less than 10 pct vol). This is comparable to that of the conventional WC-12 pct Co coating, prepared in the present study for comparison purposes. Regardless of whether the binder phase in the agglomerated feedstock powder particles melt or not, the WC particles do not appear to experience significant growth as a result of the spraying. The size of WC particles remains in the 200 to 500 nm range, consistent with that present in the feedstock powder. The as-received near-nanostructured WC-18 pct Co feedstock powder exhibits morphological characteristics that lead to low amounts of non-WC carbide phases in the coatings. The microstructure and phase constitution of the coatings depend on particle size of the feedstock powder and flame characteristics of the fuels during spraying. A higher particle temperature causes more decomposition of the WC phase but reduces porosity in the coatings, this occurs with higher flame temperature and smaller particle sizes. Propylene fuel produces less decomposition of the WC phase despite the higher flame temperature and, thus, provides the best combination of dense coating with low amount of non-WC phase.     

Structural investigations of detonation-deposited tungsten carbide-cobalt coatings

Conclusions The phase composition of detonation-deposited VK type coatings differs from that of the starting mixtures. A deposited layer contains about 40–50% of the tungsten carbide WC present in the starting mixture, metallic tungsten and cobalt, the intermetallic compounds Co₇W₆ and Co₃W, traces of W₂C, and a small amount of complex carbides. The amount and particle size of the tungsten carbide in a coating are determined by the particle size distribution of the powder being deposited and detonation process parameters. Our investigations have shown that the optimum powder particle size range for the process of detonation deposition of hard-metal mixtures may be taken to be 5–40 m. During detonation deposition under the conditions investigated the usual hard-metal structure and composition are not obtained. Most of the starting tungsten carbide decomposes with the formation of tungsten and cobalt intermetallic compounds. Attempts should now be made to improve deposition conditions so as to increase the phase and structural homogeneity of layers being deposited. In coatings deposited by an optimum method the ductile Co binder will be present in an amount close to that in a sintered VK type hard metal. The fracture of coatings and basis metal on the antivibration shelves of compressor blades has a fatigue character. Crack initiation takes place in the surface and inner layers of detonation-deposited coatings as a result of their considerable brittleness, which is due to the presence of metastable intermetallic phases as well as of defects in the form of pores and blowholes.Translated from Poroshkovaya Metallurgiya, No. 10(238), pp. 24–29, October, 1982.     

The Corrosion and Wear Performance of Microcrystalline WC-10Co-4Cr and Near-Nanocrystalline WC-17Co High Velocity Oxy-Fuel Sprayed Coatings on Steel Substrate

The study of near-nanocrystalline cermet composite coating was performed by depositing near-nanocrystalline WC-17Co powder using the high velocity oxy-fuel spraying technique. The WC-17Co powder consists of a core with an engineered near-nano-scale WC dispersion with a mean grain size 427 nm. The powder particle contains 6 wt pct of the ductile phase Co matrix mixed into the core to ensure that the reinforcing ceramic phase WC material is discontinuous to limit debridement during wear, while the remainder of the binding phase (11 wt pct) is applied as a coating on the powder particle to improve the ductility. The tribological properties of the coating, in terms of corrosion resistance, microhardness, and sliding abrasive wear, were studied and compared with those of an industrially standard microcrystalline WC-10Co-4Cr coating with a WC mean grain size 3 μm. Results indicated that the WC-17Co coating had superior wear and corrosion resistance compared to the WC-10Co-4Cr coating. The engineered WC-17Co powder with a duplex Co layer had prevented significant decarburization of the WC dispersion in the coating, thereby reducing the intersplat microporosity necessary for initiating microgalvanic cells. The improved wear resistance was attributed to the higher hardness value of the near-nanocrystalline WC-17Co coating.     

RF-PCVD法碳化钨纳米粉的制备

以WCl6+H2+C2H2为反应体系,采用高频等离子化学气相沉积法(RF-PCVD)制备了纳米级碳化钨(WC)粉体,用HRTEM(高分辨率透射显微镜)、XRD(X光衍射)表征了WC粉体的形貌和物相组成,粉体为以WC为主体、W2C和WC1-X的多相共存的混合体,微粒呈近球形与少量棱柱形混合体,粒径范围为50￣100nm,平均粒径为70nm。