In this paper, the fracture toughness KIc of near-nano and nanostructured WC-Co cemented carbides by Vickers indentation fracture toughness (VIF) was investigated. The aim was to research the type of cracking occurring in near-nano and nano-grained WC-Co cemented carbides with respect to the Co content and, consequently, to evaluate the appropriateness of different models for the fracture toughness calculation. The mixtures with different binder content—4, 6, and 9 wt. % Co—were consolidated by sintering in a hydrogen atmosphere. Vickers indentation using a test force of 294 N was used for the determination of fracture toughness. The type of crack that occurred as a consequence of the applied load on the corners of the Vickers indentations was analysed with optical microscopy before and after repolishing the samples. Different crack models, Palmqvist and radial-median, were applied for the calculation of KIc. Instrumented indentation testing was used to determine the modulus of elasticity of the consolidated samples. From the research it was found that near-nano and nanostructured cemented carbides with 9 and 6 wt. % Co do not exhibit median cracking and the indenter cracks remain radial in nature, while near-nano and nanostructured cemented carbides with 4 wt. % Co exhibit both radial and median cracking. Accordingly, it was concluded that the critical amount of the binder phase in near-nano and nanostructured WC-Co at which the crack changes its geometry from Palmqvist to radial-median is around 4 wt. % Co. Comparing different models it was found that KIc values are not consistent and differ for each method used. Models from Exner crack resistance for the Palmqvist crack showed good agreement. Radial-median crack models showed significant KIc deviations for the same testing conditions for all samples.
The influence of grain growth inhibitors and powder size on the microstructure and mechanical properties of ultrafine and nanostructured cemented carbides was researched. Three different WC powders, with an addition of different type and content of grain growth inhibitors GGIs, VC and Cr3C2 and with dBET grain sizes in the range from 95 to 150 nm were selected as starting powders. Four different mixtures with 6 and 9 wt. % Co were prepared. The consolidated samples are characterized by different microstructural and mechanical properties with respect to the characteristics of starting powders. Increased sintering temperatures led to microstructural irregularities in the form of a discontinuous WC growth, carbide agglomerates and abnormal grain growth as a consequence of coalescence via grain boundary elimination. The addition of 0.45% Cr3C2 contributed to microstructure homogeneity, reduced discontinuous and continuous grain growth, and increased Vickers hardness by approximately 70 HV and fracture toughness by approximately 0.15 MN/m3/2. The reduction of the starting powder to a real nanosize of 95 nm resulted in lower densities, and significant hardness increase, with a simultaneously small increase in fracture toughness. The consolidation of real nanopowders (dBET < 100 nm) solely by conventional sintering in hydrogen without isostatic pressing is not preferred.
In recent years, coated cemented carbides have often been the first choice for a wide variety of tool inserts and applications. Its success as a cutting tool material arises from the unique combination of wear resistance and toughness, and its ability to be formed into complex shapes. The structure obtained by sintering nanoparticle powders provides a significant improvement in product properties, such as higher cutting speeds, lower tool tolerances, and longer service life. In this study, a multi-layered gradient coating, deposited on nanostructured cemented carbides by plasma-assisted chemical vapor deposition (PACVD) was investigated with emphasis on its wear and exploitation properties. TiBN coating was deposited on nanostructured cemented carbide samples with the addition of 5 wt% Co, 10 wt% Co and 15 wt% Co. The samples were consolidated by one cycle hot isostatic pressing (HIP) technique. Complex architecture built of TiN and TiB2 gradient multilayer sequence block was deposited on each type of substrate. Wear resistance of the obtained samples was determined by erosion wear testing and dry sliding wear testing (ball-on-flat test). The friction coefficients of ~0.22 obtained for coated samples by the ball-on-flat test show a decrease in friction when compared to uncoated samples values of ~0.32. The absence of coating rupture was confirmed by wear track depth measurements showing a wear trace depth of ~1.2 μm. Exploitation properties i.e., tool life determination of samples was obtained using single-point turning tool test and compared to commercial cutting tool insert type K10 tested under the same conditions. All the conducted tests show excellent wear and exploitation properties of the newly developed TiBN coating under chosen conditions, including cutting speed, vc = 200 m/min, depth of cut, ap = 1 mm, and feed, fn = 0.2 mm. Coated WC-Co samples with 15 wt% Co, having withstood 15 min of machining with flank wear trace size less than 0.3 mm, suggest significant improvement when compared to trace size of 0.56 mm obtained for K10 commercial cutting insert.
In this paper, the electrochemical corrosion resistance of near-nano and nanostructured WC-Co cemented carbides was investigated. WC powders with an average grain size dBET in the range from 95 nm to 150 nm and with an addition of vanadium carbide (VC) and chromium carbide Cr3C2 as grain growth inhibitors were used as starting powders. The mixtures with 6 wt. % and 9 wt. % Co were consolidated by two different processes; sintering in hydrogen atmosphere and the sinter-HIP process. WC-Co samples were researched by direct current and alternating current techniques in the solution of 3.5% NaCl at room temperature. Corrosion parameters such as corrosion potential (Ecorr), corrosion current density (jcorr) and polarization resistance (Rp) were determined by electrochemical techniques. From the conducted research, it was found that the consolidation processes and microstructural characteristics—grain growth inhibitors, grain size of the starting WC powders and η-phase—influenced the electrochemical corrosion resistance. η-phase enhanced the formation of a passive layer on the samples’ surfaces, thereby reducing the tendency of the sample dissolution and increasing the stability of oxides forming therewith a passive layer on the sample surface.
The advantages of nanostructured cemented carbides are a uniform, homogenous microstructure and superior, high uniform mechanical properties, which makes them the best choice for wear-resistant applications. Wear-resistant applications in the chemical and petroleum industry, besides mechanical properties, require corrosion resistance of the parts. Co as a binder is not an optimal solution due to selective dissolution in an acidic environment. Thus, the development of cemented carbides with alternative binders to increase the corrosion resistance but still retaining mechanical properties is of common interest. Starting mixtures with WC powder, grain growth inhibitors GGIs; VC and Cr3C2, and an identical binder amount of 11-wt.% were prepared. GGIs were added to retain the size of the starting WC powder in the sintered samples. The parameters of the powder metallurgy process were adapted, and samples have been successfully consolidated. A very fine homogeneous microstructure with relatively uniform grain-size distribution and without microstructural defects in the form of carbide agglomerates and abnormal grain growth was achieved for both Ni-bonded and Co-bonded samples. Achieved mechanical properties, Vickers hardness, and Palmqvist toughness, of Ni-bonded near-nanostructured cemented carbides are slightly lower but still comparable to Co-bonded nanostructured cemented carbides. Two samples of each grade were researched by different electrochemical direct current corrosion techniques. The open circuit potential Ecorr, the linear polarisation resistance (LPR), the Tafel extrapolation method, and the electrochemical impedance spectroscopy (EIS) at room temperature in the solution of 3.5% NaCl. From the carried research, it was found that chemical composition of the binder significantly influenced the electrochemical corrosion resistance. Better corrosion resistance was observed for Ni-bonded samples compared to Co-bonded samples. The corrosion rate of Ni-bonded cemented carbides is approximately four times lower compared to Co-bonded cemented carbides.