The Effect of Chemical Composition and Thermal Sprayed Method on the Chromium and Tungsten Carbides Coatings Microstructure

The microstructure, phase consistence and microhardness of thermal sprayed coatings were investigated. The tungsten and chromium carbide coatings and also composite NiCrSiB coating were analyzed. The microstructure of coatings were observed by using optical microscopy (MO), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Almost equiaxial carbide particles settled inside the surrounded material of coating were found. The cracks propagating thorough the particles and along boundaries between the particles and surrounded material were observed. This phenomenon was connected with the porosity of coatings. The decarburization process was detected in coatings by phase composition investigation using X-ray method. The decarburization process was the reason due to which beside initial Cr3C2 the Cr7C3 and Cr23C6 particles were found. In the tungsten coatings beside the initial WC carbides the W2Cones were found.

Electronic structure and catalytic behavior of tungsten carbides

The electronic structure of tungsten carbide was investigated by EHMO semiempirical me- thod.The most stable structure of the carbide was predicted on the basis of binding energy calcula- tions.The W-C bonding is covalent in nature with some charge transfer from the W to the C atoms. The increase in the occupancy of the d shell of the W atoms and the position of the Fermi level may account for the platinum-like catalytic behavior of tungsten carbide.

CUTTING FORCES IN HIGH SPEED TAPPING CAST IRON BY TUNGSTEN CARBIDE TAPS

The engineblock production lines need high speed tapping with tungsten carbide taps. In the tapping process, the machining precision and the tool life of taps are directly influenced by tapping forces. And the parameter optimization of tap structures is also correlated with the variation of tapping forces. Therefore, the study of tapping forces is necessary in developing new style taps. Several experiments about some novel carbide taps are performed on a vertical machining center by a Kistler dynamometer system in blind tapping both gray cast iron and ductile cast iron. And the variations of tapping forces are analyzed in tapping-in and tapping-out periods. It indicates that cutting forces hardly vary with the tap wear in tapping cast iron. Contrarily, tapping forces are closely correlated with the holding method. Besides, it also depends on the helix angle, the flute numbers and the plasticity of the work material to some extent.

FABRICATION OF DLC COATED COBALT-CEMENTED TUNGSTEN CARBIDE MICRO-DRILLS AND THEIR CUTTING PERFORMANCE

In machining the particle reinforced aluminum based composite material with high Si content using the cobalt-cemented tungsten carbide micro cutting tools, diamond like carbon （DLC） films are deposited on cobalt-cemented tungsten carbide micro-drills with two-step pretreatment method. Characteristics of DLC coated tools are investigated in bias-enhanced HFCVD system with the optimized hot filament arrangement. The optimization deposition technology is obtained and the wear mechanism of cutting tools is analyzed. The drilling performance of DLC coated tools is verified by the experiments of cutting particle reinforced aluminum based composite material （Si 15% in volume） compared with uncoated ones. Experimental results show that the two-step pretreatment method is appropriate for complex shaped cemented carbide substrates and ensures the good adhesive strength between the diamond film and the substrate. The cutting performance of DLC coated tool is enhanced 10 times when machining the Si particle reinforced aluminum based metal matrix composite compared with that of uncoated ones under the same cutting conditions.

Synthesis of high-purity ultrafine tungsten and tungsten carbide powders

High-purity ultrafine W or WC powder was prepared via a two-step process composed of the carbothermic pre-reduction of WO2.9 and the following deep reduction with H2 or carbonization with CH4+H2 mixed gases. The effects of C/WO2.9 molar ratio and temperature on phase composition, morphology, particle size, and impurity content of products were investigated. The results revealed that when the C/WO2.9ratio was in the range from 2.1:1 to 2.5:1, the carbothermic pre-reduction products consisted of W and a small amount of WO2. With changing C/WO2.9 ratio from 2.1:1 to 2.5:1, the particle sizes were gradually decreased. In order to prepare ultrafine W or WC powder, a relatively high C/WO2.9 ratio and a lower reaction temperature at this stage were preferred. After the second reaction, the final products of ultrafine W and WC powders with a high purity could be obtained, respectively.

Interfacial microstructure and mechanical properties of tungsten carbide brazed joints using Ag-Cu-Zn + Ni/Mn filler alloy

WC-Co hard metal was furnace brazed by Ag-Cu-Zn+Ni/Mn filler alloy using a tube furnace under high-purity argon at730°C.The influence of brazing time and gap size of joints was studied.The results revealed the maximum shear strength of(156±7)MPa for samples with150μm gap size at a holding time15min.The characterization and microstructure of the brazed joints were characterized by SEM,EDS and XRD.The results showed that increasing the time from5to15min could provide a better chance for the liquid interlayer to flow towards the base metal.However,the formation of some metallic phases such as Mn3W3C at brazing time longer than15min resulted in decreased shear strength of the joint.

Solvent-Free Synthesis of Ultrafine Tungsten Carbide Nanoparticles-Decorated Carbon Nanosheets for Microwave Absorption

Carbides/carbon composites are emerging as a new kind of binary dielectric systems with good microwave absorption performance.Herein,we obtain a series of tungsten carbide/carbon composites through a simple solvent-free strategy,where the solid mixture of dicyandiamide(DCA)and ammonium metatungstate(AM)is employed as the precursor.Ultrafine cubic WC1-x nanoparticles(3-4 nm)are in situ generated and uniformly dispersed on carbon nanosheets.This configuration overcomes some disadvantages of conventional carbides/carbon composites and is greatly helpful for electromagnetic dissipation.It is found that the weight ratio of DCA to AM can regulate chemical composition of these composites,while less impact on the average size of WC1-x nanoparticles.With the increase in carbon nanosheets,the relative complex permittivity and dielectric loss ability are constantly enhanced through conductive loss and polarization relaxation.The different dielectric properties endow these composites with distinguishable attenuation ability and impedance matching.When DCA/AM weight ratio is 6.0,the optimized composite can produce good microwave absorption performance,whose strongest reflection loss intensity reaches up to-55.6 dB at 17.5 GHz and qualified absorption bandwidth covers 3.6-18.0 GHz by manipulating the thickness from 1.0 to 5.0 mm.Such a performance is superior to many conventional carbides/carbon composites.

Effect of deposition temperature on properties of boron-doped diamond films on tungsten carbide substrate

Boron-doped diamond(BDD)films were deposited on the tungsten carbide substrates at different substrate temperatures ranging from 450 to 850°C by hot filament chemical vapor deposition(HFCVD)method.The effect of deposition temperature on the properties of the boron-doped diamond films on tungsten carbide substrate was investigated.It is found that boron doping obviously enhances the growth rate of diamond films.A relatively high growth rate of 544 nm/h was obtained for the BDD film deposited on the tungsten carbide at 650°C.The added boron-containing precursor gas apparently reduced activation energy of film growth to be 53.1 kJ/mol,thus accelerated the rate of deposition chemical reaction.Moreover,Raman and XRD analysis showed that heavy boron doping(750 and 850°C)deteriorated the diamond crystallinity and produced a high defect density in the BDD films.Overall,600-700°C is found to be an optimum substrate temperature range for depositing BDD films on tungsten carbide substrate.

Preparation of nano-sized tungsten carbide via fluidized bed

Ultrafine or nano-sized of tungsten carbide(WC)is the key material to prepare ultrafine grained cemented carbides.In this paper,nano-sized WC powders were directly prepared by using industrial nano-needle violet tungsten oxide(WO2.72)as the raw material,a fluidized bed as the reactor,and CO as the carbonization gas.The relationship between particle sizes and reaction temperatures,residence times,atmospheres has been investigated systematically.In addition,the physical–chemical indexes(such as residual oxygen,total carbon and free carbon)of the products were measured.The results indicated that the particle size of WC increased with the increase of temperature from 800 to 950°C.As the residence time increased,the particle size decreased gradually,and then increased due to slight sintering.The introduction of hydrogen reduced the carbonization rate,and is not beneficial to obtaining nano-sized WC.Products that satisfy the standard were obtained when WO2.72 reacted with CO at 850°C,900°C and 950°C for 3.0 h,2.5 h and 2.0 h,respectively.The particle sizes of the three samples calculated from the specific surface area were 46.4 nm,53.2 nm and 52.1 nm,respectively.

A Review on Binderless Tungsten Carbide: Development and Application

WC-Co alloys have enjoyed great practical significance owing to their excellent properties during the past decades.Despite the advantages,however,recently there have been concerns about the challenges associated with the use of Co,i.e.price instability,toxicity and properties degeneration,which necessitates the fabrication of binderless tungsten carbide(BTC).On the other hand,BTC or BTC composites,none of them,to date has been commercialized and produced on an industrial scale,but only used to a limited extent for specialized applications,such as mechanical seals undergoing high burthen as well as high temperature electrical contacts.There are two challenges in developing BTC:fully densifying the sintered body together with achieving a high toughness.Thus,this review applies towards comprehensively summarize the current knowledge of sintering behavior,microstructure,and mechanical properties of BTC,highlighting the densification improving strategies as well as toughening methods,so as to provide reference for those who would like to enhance the performance of BTC with better reliability advancing them to further wide applications and prepare the material in a way that is environment friendly,harmless to human health and low in production cost.This paper shows that the fabrication of highly dense and high-performance BTC is economically and technically feasible.The properties of BTC can be tailored by judiciously selecting the chemical composition coupled with taking into careful account the effects of processing techniques and parameters.

Effect of process parameters on induction plasma reactive deposition of tungsten carbide from tungsten metal powder

Tungsten carbide deposit was made directly from tungsten metal powder through the reaction with methane in radio frequency induction plasma. Effect of major process parameters on the induction plasma reactive deposition of tungsten carbide was studied by optical microscopy, scanning electron microscopy, X ray diffraction analysis, water displacement method, and microhardness test. The results show that methane flow rate, powder feed rate, particle size, reaction chamber pressure and deposition distance have significant influences on the phase composition, density, and microhardness of the deposit. Extra carbon is necessary to ensure the complete conversion of tungsten metal into the carbide.

INDUCTION PLASMA REACTIVE DEPOSITION OF TUNGSTEN CARBIDE FROM TUNGSTEN METAL POWDER

Experimental results on the primary carburization reaction between the tungsten powder and methane in the induction plasma, and the secondary carburization of the deposit on substrate at high temperature are reported. Optical microscopy and scanning electron microscopy were used to examine the microstructures of starting tungsten powder, carburized powder, and deposit. X-ray diffraction analysis, thermal gravimetric analysis and microhardness measurement were used to characterize the structures and properties of the powder and the deposit. It is found that the primary carburization reaction in the induction plasma starts from the surface of tungsten particles when the particles are melted. Tungsten particles are partially carburized inside the reactive plasma. Complete carburization is achieved through the secondary carburization reaction of the deposit on substrate at high temperature.

Synthesis of nanosized tungsten carbide from phenol formaldehyde resin coated precursors

Nanosized tungsten carbide was synthesized from phenol formaldehyde resin （PF） coated tungsten precursors. The process has three steps in which nanosized tungsten particles were first coated with PF, then the precursors were carburized at 950℃, and finally the carburized powders were treated in flowing wet hydrogen atmosphere at 940℃ to remove the uncombined carbon. The obtained powders were characterized using X-ray diffraction analysis （XRD）, field-emission scanning electron microscopy （FESEM）, small angle X-ray scattering （SAXS）, and combustion-gas-volume method. The results indicated that single-phase WC could be synthesized using excessive PF as carburizer at a much lower temperature compared with using mixed carbon black. After wet hydrogen treating, the mean size of the obtained WC particles was 94.5 nm and the total carbon content was 6.18 wt.%.

Plasma Enhanced Chemical Vapor Deposition Nanocrystalline Tungsten Carbide Thin Film and Its Electro-catalytic Activity

Nanocrystalline tungsten carbide thin films were fabricated on graphite substrates by plasma enhanced chemical vapor deposition （PECVD） at H2 and Ar atmosphere, using WF6 and CH4 as precursors. The crystal phase, structure and chemical components of the films were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and energy-dispersive spectrometer （EDS）, respectively. The results show that the film prepared at CH4/WF6 concentration ratio of 20 and at 800℃ is composed of spherical particles with a diameter of 20-35 nm. Electrochemical investigations show that the electrochemical real surface area of electrode of the film is large, and the electrode of the film exhibits higher electro-catalytic activity in the reaction of methanol oxidation. The designated constant current of the film catalyst is 123.6 mA/cm^2 in the mixture solution of H2SO4 and CH3OH at the concentration of 0.5 and 2.0 mol/L at 70℃, and the designated constant potential is only 0.306 V （vs SCE）.

Research on Diamond Enhanced Tungsten Carbide Composite Button

At the present, the cutters used in button bits and rock bits are mainly cobalt tungsten carbide in our country. Because of its low abrasive resistance, the bit service life and drilling efficiency was very low when the hard and extremely hard formations were being drilled. Owing to its high abrasive resistance, the diamond composite material is widely used in drilling operations. However, its toughness against impact is too low to be used in percussion drilling, only can it be used in rotary drilling. In order to solve the problems encountered by DTH hammer in hard rock drilling, make bit life longer, increase rate of penetration and decrease drilling cost, a new type diamond enhanced tungsten carbide composite button with high abrasive resistance and high toughness against impact, which may be used in percussion drilling, has been developed. The key problems to make the button are to improve the thermal stability of diamond, to increase the welding strength between diamond and cemented tungsten carbide, and to lower the sintering temperature of tungsten carbide. All these problems have been solved effectively by pretreatment of diamond, low temperature activation hot-press sintering and high sintering pressure. (1) To plate tungsten on the surface of diamond. Diamond suffers easily from erosion in the environment of high temperature containing oxygen and iron family elements. There is very high energy between the interface of diamond and bonding metal and so the metallurgical bond can’t form at the interface between diamond and bond metal. This will lower greatly the bending strength and the toughness against impact of diamond enhanced tungsten carbide composite button. In order to improve thermal stability of diamond and increase the bonding strength of the interface between diamond and bond metal, to plate tungsten on the surface of diamond by vacuum vapor deposit is adopted. (2) To lower the sintering temperature by adding nickel, phosphorus and boron etc into conventional mixed powder. In general, the sintering temperature of cemented tungsten carbide is more than 1 350 ℃ in which diamond will suffer from serious heat erosion, so the sintering temperature must be lowered. To add nickel, phosphorus and boron etc into cobalt-base bond whose melting point is more than 1 350 ℃ will lower the sintering temperature to about 1 050 ℃. To add phosphorus can lower the temperature of liquid phase occurring and promote the densification of matrix alloy in advance because the co-crystallization temperature of Ni-P and Co-P is 880 ℃ and 1 020 ℃ respectively. The proper adding amount of nickel, phosphorus and boron etc is a key problem. To substitute nickel for partial cobalt can improve the toughness against impact of diamond enhanced tungsten carbide composite button and lower the sintering temperature. To add boron is helpful for sintering and improving the toughness against impact of diamond enhanced tungsten carbide composite button. (3) To increase the sintering press. Under the same sintering temperature, to improve the sintering press can improve the density and strength of sintering products. In this study to increase the sintering press 35 MPa in the usual conditions to 50～60 MPa in sintering diamond enhanced tungsten carbide button by adopting ceramic material as pressing rod has improved the sintering quality effectively. The properties of the button have been measured under lab conditions. The testing results show that its hardness is more than HRA86 and that its abrasiveness resistance is 100 times more than conventional cemented tungsten carbide, and its toughness against impact is more than 100J. All these data theoretically show that the button has very good mechanical properties that can meet the need of percussion drilling, and can solve the problems encountered with button bit of conventional cemented tungsten carbide.

Study on in-situ WC particles/tungsten wire reinforced iron matrix composites under electromagnetic field

By applying electromagnetic field to a system consisting of tungsten wires and grey cast iron melt,the grey cast iron matrix composite reinforced by either in-situ WC particles or the combination ofin-situ WC particles and the residual tungsten wire was obtained.By means of differential thermal analysis(DTA),the pouring temperature ofiron melt was determined at 1,573 K.The microstructures of the composites were analyzed by using of X-ray diffraction(XRD),scanning electron microscopy(SEM) equipped with an energy dispersive spectrum(EDS) and pin-on-disc abrasive wear test.The obtained results indicated that,with the enhancing frequency of electromagnetic field,the amount ofin-situ WC particles gradually increases,leading to continuous decrease of the residual tungsten wires.When the electromagnetic field frequency was up to 4 kHz,tungsten wires reacted completely with carbon atoms in grey cast iron melt,forming WC particals.The electromagnetic field appeared to accelerate the elemental diffusion in the melt,to help relatively quick formation of a series of small FeW-C ternary zones and to improve the kinetic condition ofin-situ WC fabrication.As compared with the composite prepared without the electromagnetic field,the composite fabricated at 4 kHz presented good wear resistance.

Research on rare earth and iron-rich diamond-enhanced tungsten carbide composite button

At the present time in china, the binder used in tungsten carbide composite button is mainly cobalt, which is very expensive. In order to solve the problems, a new type of rare earth and iron-rich diamond-enhanced tungsten carbide with high abrasive resistance and high toughness against impact, which realizes to substitute ferrum for cobalt, has been developed. The key problems in making the button are to improve the mechanical properties of matrix and increase the welding strength between the diamond and the matrix. All these problems have been solved effectively by low temperature activation hot-press sintering, doping rare earth lanthanum in matrix and high sintering pressure. The properties of the button have been determined under laboratory conditions. The test results show that its hardness is more than 90 HRA, its abrasive resistance is 39 times more than that of conventional cemented tungsten carbide, and its toughness against impact is more than 200 J. All these data show the button has very good mechanical properties.

Characterization and in-situ formation mechanism of tungsten carbide reinforced Fe-based alloy coating by plasma cladding

The precursor carbonization method was first applied to prepare W–C compound powder to perform the in-situ synthesis of the WC phase in a Fe-based alloy coating. The in-situ formation mechanism during the cladding process is discussed in detail. The results reveal that fine and obtuse WC particles were successfully generated and distributed in Fe-based alloy coating via Fe/W–C compound powders. The WC particles were either surrounded by or were semi-enclosed in blocky M7C3 carbides. Moreover, net-like structures were confirmed as mixtures of M23C6 and α-Fe; these structures were transformed from M7C3. The coarse herringbone M6C carbides did not only derive from the decomposition of M7C3 but also partly originated from the chemical reaction at the α-Fe/M23C6 interface. During the cladding process, the phase evolution of the precipitated carbides was WC → M7C3 → M23C6 ＋ M6C.

Corrosion Behavior of Plasma Transferred Arc Fe-based Coating Reinforced by Spherical Tungsten Carbide in Hydrochloric Acid Solutions

Fe-based coatings reinforced by spherical tungsten carbide were deposited on 304 stainless steel using plasma transferred arc(PTA) technology.The composition and phase microstructure of the coatings were evaluated using scanning electron microscopy(SEM),energy dispersive spectrometer(EDS) and X-ray diffraction(XRD).The corrosion behaviors of the coatings in 0.5 mol/L HCl solution were studied using polarization curve and electrochemical impedance spectroscopy(EIS) measurements.The experimental results shows that the tungsten carbide improves the corrosion resistance of the Fe-based alloy coating,but increase in the mass fraction of tungsten carbide leads to increasing amount of defects of holes and cracks,which results in an adverse effect on the corrosion resistance.The defects are mainly present on the tungsten carbide but also extend to the Fe-based matrix.The tungsten carbide,acting as a cathode,and binding material of Fe-based alloy,acting as an anode,create a galvanic corrosion cell.The binding material is preferentially corroded and causes the degradation of the coating.

Preparation, Characterization and Catalytic Properties of S_2O_8^(2-)/ZrO_2 Supported by Tungsten Carbide

A WC-supported S_2O 2-_8/ZrO_2(PSZ) catalyst was prepared and characterized by means of XRD, BET, FTIR and XPS. The isomerization of n-pentane over the catalyst was investigated as well. The results show that the skeletal isomerization and the crack of n-pentane proceed simultaneously on WC-supported S_2O 2-_8/ZrO_2 catalyst. The addition of tungsten carbide showed a significant enhancement in the activity and stability of the catalyst for n-pentane isomerization. The catalyst showed evidently a better activity than S_2O 2-_8/ZrO_2 supported by Pt and WO_3. The results can be interpreted by the existence of the tungsten oxycarbide compound(WC_xO_y) with carbidic, oxide and acidic sites.