Formation of Grain Boundaries in Liquid-Phase-Sintered WC–Co Alloys

The origin of WC/WC grain boundaries in liquid-phase-sintered WC–Co alloys has been investigated in a WC–Mo₂C–Co model system using coarse WC polygrain powder. The evolution of grain shape during liquid phase sintering was able to be identified by observing a growth layer that contained Mo. During liquid phase sintering, most of the grain boundaries in the powder were penetrated by a Co liquid but some of them were not. Electron backscattered diffraction analysis confirmed that some boundaries in the powder, in particular, Σ2 twist boundaries and Σ97 special boundaries, remained intact during liquid phase sintering. These experimental results confirm that the grain boundaries of WC grains in liquid-phase-sintered WC–Co alloys originated from those present in the starting powder.     

A New Route for the Synthesis of Tungsten Carbide–Cobalt Nanocomposites

Synthesis of WC–Co nanocomposites generally involves gas-phase carburization. A novel approach in which a polymer precursor such as polyacrylonitrile serves as an in situ carbon source has been developed. The WC–Co nanocomposites formed are characterized by X-ray powder diffraction and electron microscopy. Nearly phase pure WC–Co nanocomposites with a particle size of 50–80 nm have been obtained. The phase purity of the products is strongly influenced by the synthesis and processing conditions such as the firing temperature, time, and atmosphere.     

Development of WC–ZrO2 Nanocomposites by Spark Plasma Sintering

In the present work, we report the processing of ultrahard tungsten carbide (WC) nanocomposites with 6 wt% zirconia additions. The densification is conducted by the spark plasma sintering (SPS) technique in a vacuum. Fully dense materials are obtained after SPS at 1300°C for 5 min. The sinterability and mechanical properties of the WC–6 wt% ZrO₂ materials are compared with the conventional WC–6 wt% Co materials. Because of the high heating rate, lower sintering temperature, and short holding time involved in SPS, extremely fine zirconia particles (∼100 nm) and submicrometer WC grains are retained in the WC–ZrO₂ nanostructured composites. Independent of the processing route (SPS or pressureless sintering in a vacuum), superior hardness (21–24 GPa) is obtained with the newly developed WC–ZrO₂ materials compared with that of the WC–Co materials (15–17 GPa). This extremely high hardness of the novel WC–ZrO₂ composites is expected to lead to significantly higher abrasive-wear resistance.     

Compaction as a Critical Factor for Success in the Sintering of Ultra-Fine WC–Co Powders

Heat treatment of ultra-fine WC–13Co powders was carried out prior to cold compaction, in an attempt to improve the sintered density. The findings indicate that a preheat treatment of ultra-fine or nano-sized powders significantly improves the densification process. This study showed that a low compacting pressure, <200 MPa, can be effectively used through this technique to retain ultra-fine structure. The densification behavior of preheated powder was compared with the samples prepared by a conventional technique and explained with size distribution, standard deviation, and surface effect.     

Structural Analysis on Planar Defects Formed in WC Platelets in Ti-Doped WC–Co

Platelet-reinforced WC–Co alloys are processed by liquid-phase sintering from very fine-grained WC powders in the presence of small amounts of TiC. Large and flat WC grains develop in the material. The microstructure of these platelets is investigated by high-resolution electron microscopy in order to obtain information on their formation mechanism. Inside the grains, an extended defect parallel to the basal plane is observed. It can be described by a pair of stacking faults with a shear vector equal to 1/3 〈0-110〉 occurring in two successive (0001) planes. At the level of the faults, the plane spacing is slightly reduced. The defect area is similar to a thin cubic layer about 0.5 nm thick at the interior of the platelet. The enhanced grain growth of the platelets is likely related to the presence of the defect area.     

Microstructure and Abrasive Wear of Binderless Carbides

The microstructure and the abrasive wear characteristics of two binderless carbides (WC–Mo₂C and WC–TiC–TaC) have been studied. The microstructural analysis identified differences in the amount of mixing between the γ-phase and WC. Mo₂C and WC showed a large tendency to form mixed carbides, whereas WC and TiC did not. In both materials grain boundary segregation of metallic species was found. Compared with alumina ceramics and WC–6 wt% Co the WC–Mo₂C material showed the lowest abrasion rate and WC–TiC–TaC an intermediate. The wear mechanism was surprisingly ductile for WC–Mo₂C, whereas WC–TiC–TaC suffered from grain pullout of TiC.     

Effect of carbon content on microstructure and mechanical properties of WC-10Co cemented carbides with plate-like WC grain

Four sets of WC-10Co cemented carbides with different carbon content were prepared by adding the ultrafine WC powders as seeds during the in-situ sintering reaction among W, Co and C. The effect of carbon content on microstructure and mechanical properties were studied. The results show that the microstructure, phase composition and mechanical properties of WC-10Co cemented carbides with plate-like WC grains were seriously affected by the carbon content. The fast growth of WC grains with high carbon content could proceed the prismatic plane preferentially along the <1 0 $1(-)$ 0> directions, resulting in the high content of plate-like WC grains. The density increased with the increment of the carbon content and reached the maximum value, then, followed by a decline. The hardness and the transverse rupture strength of the alloy in the two-phase zone with carbon content of 5.91 wt% reached the maximum value. The existence of plate-like WC grains could impede the propagation of the cracks due to the decrease of the weakest carbide regions and the increase of the basal facets of broken WC crystals. In this case, more fracture energy was required to crack propagation and further improved the transverse rupture strength. Additionally, the plate-like WC was benefit to reduce the wear volume and bring about a better wear resistance. Thus, the alloy with the appropriate proportion of carbon content can obtain higher mechanical properties and wear resistance.     

Role of Vanadium Carbide Additive during Sintering of WC–Co: Mechanism of Grain Growth Inhibition

In a WC–Co specimen, the shape of WC crystals was a triangular prism with truncated corners. When VC was added to inhibit grain growth, the crystal shape changed to a triangular prism without truncation. This shape change was related to the variation of edge energy, which has a significant influence on the coarsening process of WC grains.     

Modeling the Influence of Orientation Texture on the Strength of WC–Co Composites

Two-dimensional finite element simulations were used to study the effects of orientation texture on the transverse rupture strengths of WC–Co composites. The model incorporates observed microstructural geometries, anisotropic thermal and elastic properties, and a fracture criterion that reproduces the strengths of known specimens. The results show that the greatest potential for increasing the strength occurs when the [001] axes of the carbide grains are orientated perpendicular to the sample loading direction. Furthermore, the strength increases in proportion to the degree of texture, and the texture-derived strength enhancement is greater in microstructures with a larger contiguity.     

Strength and Toughness Degradation of Tungsten Carbide–Cobalt Due to Thermal Shock

WC–Co composites are widely used as cutting or drilling tools because of their high hardness, strength, and fracture toughness. The working temperature is generally in the range of 300° to 700°C, so thermal shock fracture of WC–Co can occur if the parts are suddenly cooled. In this study, changes in fracture strength and fracture toughness after thermal shock were observed.     

Surface Integrity Effects on the Fracture Resistance of Electrical-Discharge-Machined WC–Co Cemented Carbides

The flexural strength evolution for two WC–16 vol% Co cemented carbides, with different mean carbide size, subjected to sequential and upgrading electrical-discharge machining (EDM) is studied. It is compared with the fracture behavior exhibited by a reference surface finish condition, attained through conventional mechanical grinding and polishing using diamond as abrasive. Considering that rupture is related to existing defects, either introduced during sample elaboration or induced by machining, a detailed fractographic examination by scanning electron microscopy is conducted to discern fracture origins. The experimental findings indicate that the flexural strength of WC–Co hardmetals may be strongly affected by EDM, depending on the correlation existing between natural defects, as given by particular microstructural parameters, and EDM-induced flaws. An analysis of the results using a linear–elastic fracture mechanics approach permits one to establish a clear connection between surface integrity and fracture resistance. Quantitative discrepancies between the estimated and the experimentally measured critical flaw sizes for all the EDM-related grades are rationalized through the existence of local residual tensile stresses of considerable magnitude at the shaped surface. Release of these stresses through final mechanical and annealing treatments is pointed out as a quite effective alternative for improving the fracture behavior of WC–Co cemented carbides shaped by EDM.     

Processing of ZrC–Mo Cermets for High Temperature Applications, Part II: Pressureless Sintering and Mechanical Properties

Pressureless sintering of ZrC–Mo cermets was investigated in a He/H₂ atmosphere and under vacuum. A large density increase was observed for specimens with >20 vol% Mo after heating at 2150°C for 60 min in a He/H₂ atmosphere. The increase in density was attributed to the formation of Mo₂C during heating and its subsequent eutectic reaction with Mo, which produced rounded ZrC grains in a Mo–Mo₂C matrix. Sintering in vacuum did not produce the same increase in density, due to the lack of Mo₂C formation and subsequent lack of liquid formation, which resulted in a microstructure with irregular ZrC grains with isolated areas of Mo. Mechanical properties testing showed a decrease in Young's modulus with increasing Mo content that was consistent with the models presented. Flexure strength of ZrC–Mo cermets sintered in He/H₂ atmosphere materials increased with increasing Mo content from 320 MPa at 20 vol% Mo to 410 MPa at 40 vol% Mo. Strength was predicted by adapting theories developed previously for WC–Co cermets.     

Preparation of spherical WC-Co powder by spray granulation combined with radio frequency induction plasma spheroidization

In this paper, spray granulation and radio frequency plasma spheroidization were used to obtain spherical WC-Co powder for laser powder bed fusion from mixed WC and Co powder. The effects of solid content and polyvinyl alcohol content of the slurry on granulated powder were studied. Then the spheroidization effects of different granulated WC-Co powders were investigated and compared. Results show that the granulated powder obtained from the slurry with solid content of 65 wt% and polyvinyl alcohol content of 2.5 wt% has the best performance after plasma spheroidization, whose flowability and apparent density are 10.20 s/50g and 6.76 g/cm³, respectively. Moreover, W and C distribute uniformly in the spheroidized WC-Co powder while the Co element is mainly distributed in the gaps of tungsten carbide. It is also noted that W₂C, free carbon and Co₃W₃C appear in the spheroidized WC-Co powders due to the decomposition of WC during the plasma spheroidization process. Furthermore, the decomposition of WC-Co powder particles with smaller size is more serious, which leads to the presence of black and white particles with significantly different carbon content distribution in the spheroidized powder.     

Wear Mechanisms of TiB2 and TiB2–TiSi2 at Fretting Contacts with Steel and WC–6 wt% Co

Unlubricated fretting wear tests on TiB₂ and TiB₂–5 wt% TiSi₂ ceramics against two different mating materials (bearing grade steel and WC–6 wt% Co balls) were performed with a view to understand the counterbody-dependent difference in friction and wear properties. The fretting experiments were conducted systematically by varying load (2–10 N) at an oscillating frequency of 4 Hz and 100 μm linear stroke, for a duration of 100,000 cycles. Adhesion, abrasion, and three-body wear have been observed as mechanisms of material damage for both the TiB₂/steel and TiB₂/WC–Co tribosystems. The third body is predominantly characterized as tribochemical layer for TiB₂/steel and loose wear debris particles for TiB₂/WC–Co tribocouple. An explanation on differences in tribological properties has been provided in reference to the counterbody material as well as microstructure and mechanical properties of flat materials.     

Interface Character Distributions in WC–Co Composites

The geometric and crystallographic characteristics of interfaces in WC–Co composites with a range of grain sizes and carbide volume fractions have been comprehensively characterized. The carbide crystals are most frequently terminated by (0001) and     surfaces. The average number of carbide vertices per grain and the basal-to-prismatic face area ratio of the WC–Co interfaces increase with the carbide volume fraction. The three most frequently occurring WC/WC grain boundaries are 90° twist boundaries about     , 30° twist boundaries about [0001], and asymmetric 90° boundaries about     . The boundary populations do not vary with grain size or carbide volume fraction, suggesting that they are determined by the grain boundary energy anisotropy.     

Influence of carbon structure of the anode on the synthesis of single-walled carbon nanotubes in a carbon arc plasma

Arc plasma evaporation of carbon electrodes doped with various catalysts is one of the most effective methods of single-walled carbon nanotube fabrication. It was found that the reaction yield is strongly influenced not only by the appropriate choice of the catalyst(s), but also by the type of carbon material used for electrode fabrication. Several different carbon powders i.e. graphite powders, glassy carbon and coke, have been tested in order to establish which parameters (primary particle size, granulation, density or conductivity of the electrode) affected the outcome of the reaction the most. The highest yield of single-walled nanotubes was found for anodes fabricated from graphite powders, whilst the electrodes made from glassy carbon or coke yielded significantly smaller amounts of nanotubes. The reaction zone where carbon radicals nucleate (close to the arc gap) was probed by optical absorption spectroscopy. The estimated temperature distributions and contents of C₂ radicals did not depend on the anode characteristics.     

Co-based catalysts from Co/Fe/Al layered double hydroxides for preparation of carbon nanotubes

Carbon nanotubes have been prepared via catalytic chemical vapor deposition of acetylene on a series of catalysts derived from Co/Fe/Al layered double hydroxides (LDHs). The catalytically active cobalt particles were obtained by calcination of LDHs containing cobalt (II) ions followed by reduction. The obtained products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, high-resolution electron microscopy and Raman spectroscopy. The content of Co in the precursors had a distinct effect on the growth of carbon nanotubes. Increasing Co content enhanced the carbon yield, due to good dispersion of a large number of active Co species. This indicated that the agglomeration of metallic Co particles did not take place even at high Co content. Higher Co content led to the formation of carbon nanotubes with smaller diameters and less structural disorder.     

Nylon 11/silica nanocomposite coatings applied by the HVOF process. I. Microstructure and morphology

Nylon 11 coatings filled with nanosized silica and carbon black have been produced using the high velocity oxy‐fuel (HVOF) combustion spray process. The physical properties and microstructure of coatings produced from nylon 11 powders with starting particle sizes of 30 and 60 μm have been evaluated as a function of the filler content, filler chemistry, and processing conditions. The nominal filler content was varied from 5 to 20 vol %. Co‐milling of the nano‐sized fillers with the polymer powders produced an embedded 4–8 μm thick filler layer on the surfaces of the polymer particles. Optimization of the HVOF processing parameters based on an assessment of the degree of splatting of polymer particles was accomplished by varying the jet temperature (via hydrogen/oxygen ratio). Gas mixtures with low hydrogen contents minimized polymer particle degradation. The filler was found to be agglomerated at the splat boundaries in the final coating microstructures. Aggregates of silanated silica and carbon black were of the order of 50 nm in size, whereas the aggregates of untreated silica and hydrophilic silica were of the order of 100 nm. The morphology of the polymer and the microstructure of the coatings depended on the filler surface chemistry and the volume fraction of the filler, as well as the initial nylon 11 particle size. Although all filled coatings had higher crystallinities than pure nylon 11 coatings, coatings produced from a smaller starting polymer particle size exhibited improved spatial distribution of the silica in the matrix and lower crystallinity. In addition, coatings prepared from smaller polymer particles had a higher density and lower porosity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1684–1699, 2000     

Influence of carbon on the synthesis of AlN powder from combustion synthesis precursors

AlN powders were synthesized by carbothermal reduction of combustion synthesis precursors. Water-soluble organics and carbon black were used as carbon sources. The effects of carbon on the synthesis of AlN powders were studied. Results showed that AlN powders were synthesized directly from γ-Al₂O₃ without γ-Al₂O₃ to α-Al₂O₃ phase transition when water-soluble organics were used as carbon sources, and the nitridation of the precursors could be completed at 1400 °C. However, AlN powders were synthesized from the nitridation of α-Al₂O₃ when carbon black was used as carbon source, and the reaction temperature for a complete conversion increased to 1500 °C. The particles of AlN powders synthesized with water-soluble organics was smaller than the particles of AlN powders synthesized with carbon black and their particle size distribution was sharper. The specific surface area of synthesized AlN powders increased with the increase of carbon content in the precursors.     

Microstructures and grain boundaries of cubic boron nitrides

Two types of chemically pristine polycrystalline cubic boron nitrides (c-BN) are sintered at different conditions using the starting cubic and hexagonal BN powders and their microstructures and grain boundaries are investigated systematically by transmission electron microscopy. The two c-BN samples are found to exhibit a number of twins inside their grains and have a similar grain size, despite their huge differences in the grain size of the starting powders and sintering conditions. Twin width for the c-BN sintered from hexagonal BN is significantly smaller than that for the c-BN sintered from c-BN. Grain boundaries in the two samples can be atomically abrupt without any amorphous or secondary layers and oxygen is detected merely at the grain boundaries of the c-BN sintered from the c-BN powders. Such microstructural differences have a direct impact on mechanical behaviors of the c-BN, as the Vickers hardness of the c-BN sintered from hexagonal BN powders is found to be higher than that of the c-BN sintered from the c-BN powders.