Sintering and mechanical properties of cemented carbides based on tungsten carbide and multicomponent metallic alloys

Abstract

Cemented carbides are composite materials used in a wide variety of applications requiring the right combination of mechanical strength and wear resistance under harsh environments (i.e. metal cutting and shaping, civil engineering, mining, valves for the chemical industry, etc). The most common compositions comprise tungsten carbide grains bonded with a cobalt based metallic matrix. The reason is twofold. On the one hand, WC-Co materials are relatively easy to sinter to full density state with the adequate processing methodology and, on the other, a wide range of useful properties can be obtained by changing the WC grain size and the WC/Co ratio. Nevertheless, the use and availability of cobalt are presently jeopardized by both its new classification as toxic substance (REACH regulations) and the growing demand of this metal for making Li-ion batteries for electrical vehicles. The present thesis is focused on studying the sintering behavior and mechanical properties of WC-metal systems in which pure cobalt is replaced by different combinations of metals. Two promising candidates have been found: WC-NiCoCrTiAl cemented carbides These materials were designed starting from WC-NiCoCr compositions with a Ni/Co ratio equal to one. The main challenge was to increase the hardness of these compositions since it is too low compared with that of WC-Co grades. This was achieved firstly by alloying the binder phase with aluminum and, afterwards, inducing gamma prime precipitation by aging treatments. Two different aluminum containing compounds were investigated in order to avoid catastrophic oxidation of aluminum during PM processing: AlN and TiAl3. The latter produced the best results concerning sinterability and precipitation hardening effects. WC-Ni-Co-Cr-Ti-Al materials were obtained in fully dense form by using HIP after sintering technique, a process compatible with industrial processing technologies like Sinter HIP. Aging experiments show that hardness peaks occur at lower temperatures as the Al content of the binder phase increases. Apart from hardness, transverse rupture strength (TRS) was also measured in selected WC-NiCoCrTiAl compositions in both as-HIPed and solution-aged conditions. Results are only 15% lower than those reported for WC-Co materials with similar WC grain sizes and WC/metal ratios. These results also suggest that, like in as-cast Ni superalloys, the properties of the binder phase would be retained at temperatures below those used in aging treatments. WC-FeNiCoCr cemented carbides WC-Fe-Ni-Co-Cr compositions were designed following an alternative approach. In this case, the aim was to obtain a metallic binder with no precipitation of free carbon or any secondary carbide (including those of chromium). This was achieved by starting from WC-Fe-Ni-Co-Cr3C2 powder mixtures with a constant proportion between Fe, Ni and Co equal to 40/40/20. Chromium and carbon contents have been modified in order to find the upper and lower bounds defining the “so-called” carbon windows. In addition, shrinkage kinetics have been thoroughly studied in order to define a robust sintering process for both coarse and submicron WC powders. Results of calorimetric experiments have been used to improve the description of the W-C-Fe-Ni-Co quinary system for 40Fe-40Ni-20Co composition by means of ThermoCalc® software. In this case, mechanical tests confirmed that the values of hardness and transverse rupture strength are within tolerances of those reported for WC-Co grades with similar binder contents and WC grain sizes, provided that precipitation of undesired phases is avoided.