Comparative Study of Wear Resistance of Cemented Carbides WC-Ni-Al and WC-Co Subjected to Micro-Scale Abrasive TestAbstract
The combination of tungsten carbide (WC) and cobalt forms the most common cemented carbide on the market, as it is one of the most widely used materials industrially due to its excellent combination of properties. However, the search for a substitute binder is motivated by cobalt's high cost, toxicity, and low corrosion resistance. In this scenario, nickel (Ni) has stood out for meeting the necessary requirements and offering good corrosion resistance. However, its product presents a loss in mechanical properties. To improve these properties, the addition of alloying elements, such as aluminum (Al), was studied. This work aims to compare the micro-abrasive wear resistance of WC-Co and WC-Ni-Al cemented carbide. The micro-scale abrasion tests were carried out in a test rig with fixed-ball configuration, AISI 52100 steel ball and abrasive slurry composed of water and silicon carbide (SiC). The volume loss of the samples was the parameter used to determine micro-abrasive wear resistance. The samples were characterized before and after testing using scanning electron microscopy to identify the predominant wear mechanisms. WC-Ni-Al cemented carbide presented a microstructure similar to WC-Co, but pores and binder islands were observed. The micro-scale tests showed that WC-Ni-Al cemented carbide, despite its higher porosity, presented superior micro-abrasive wear resistance than WC-Co cemented carbide, indicating that the addition of Al contributed significantly to the increased wear resistance of this cemented carbide. This result also demonstrates the feasibility of using WC-Ni-Al cemented carbide as a substitute for WC-Co in applications involving abrasive wear.
Keywords:
Abrasive particle size distribution; Ball material; Binder islands; Cemented carbides; Cross-sectional profiles; Grooving; Micro-abrasive; Micro-scale; Micro-rolling abrasion; Particle pull-out; Rolling; Wear modes; Wear resistance; Wear test
1. Introduction
Abrasive wear is one of the major causes of equipment damage in the mining, cement, and coal industries. To mitigate this damage, the search for materials with higher wear resistance, corrosion resistance, and cost-effectiveness has increased considerably. In this regard, cemented carbide has stood out due to its excellent combination of hot hardness and toughness1,2.
Moreover, this characteristic of cemented carbide, combined with its relatively low cost, makes it an ideal material for applications such as mining and oil drilling bits, mechanical forming dies, as well as various other components that require good resistance3-7
The abrasive wear behavior of cemented carbide is directly and primarily related to its chemical composition and microstructure. Therefore, and depending on each specific application, its properties can be adjusted according to its binder content, initial WC particle size, use of grain growth inhibitors, etc. The abrasive wear resistance of this material generally increases with the reduction in binder content and the decrease in WC particle size8.
The most widely used industrial cemented carbide employs cobalt (Co) as the binder phase due to its high wettability with WC (the carbide phase), ensuring good mechanical properties. However, because of its low corrosion resistance, scarcity, high cost, and toxicity, an alternative binder phase has been researched7,9,10
Among the binder phases investigated, nickel has proven to be the most suitable replacement for cobalt. However, since this element dissolves smaller amounts of W and C than cobalt during the sintering stage, cemented carbides with pure Ni binder exhibit inferior mechanical properties, especially hot hardness. For this reason, the addition of small fractions of solid solution-forming elements to nickel, such as Al, Ti, Nb, Cr, etc., are often used to promote the hardening of the Ni binder in WC-Ni cemented carbides, providing a better combination of hardness and ductility4,5,11-14. It is important to emphasize that the solid solution-hardened nickel binder phase, although more ductile than cobalt, can reduce the loss of carbide phase (WC) particles during the abrasive wear process.
Therefore, this study aims to investigate the influence of microstructure on the micro-abrasive wear resistance of WC-Ni-Al carbide and WC-Co cemented carbide produced by conventional powder metallurgy, as well as to compare the performance of both materials in order to identify which of these will present better performance
2. Experimental Procedure
2.1. Production of cemented carbides
The weight compositions and hardness of the studied cemented carbides are presented in Table 1.
The materials tested in this study were produced in a previous work11 to evaluate the quality of the proposed substitution. The hardness values obtained for the produced materials fall within a range consistent with the literature15-17.
The cemented carbides were produced by conventional powder metallurgy. Powders of tungsten carbide, carbonyl Ni powder, and 99% pure AlN, each with an average particle size of 2.5 µm, were used as starting materials. The initial powders were milled in a conventional ball mill at a rotation speed of 50 rpm for 80 hours. After milling, 1.5 wt.% of paraffin was added to the mixtures to improve compaction. The compaction was then carried out in a stainless-steel die at 130 MPa for 3 minutes. Next, the green compacts were pre-sintered in a pure hydrogen atmosphere at 750 °C for 30 minutes to remove the paraffin. Finally, sintering was performed in a high-vacuum furnace (2 to 6 × 10−5 bar) at 1,460 °C for 1 hour. The alloys were ground and polished using abrasive papers and diamond paste.
2.2. Microstructural Characterization
The samples were etched with Murakami’s chemical reagent for 15 seconds to enhance microstructural visualization. Microstructural characterization was carried out both before (with and without the chemical etching) and after the micro-abrasive wear tests, employing optical microscopy, scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). Prior to testing, SEM analyses were performed. After testing, optical observations were conducted using the microscope integrated into the micro-scale test rig to visualize and measure the resulting wear crater. Subsequently, the crater surface was examined by SEM. All SEM analyses were conducted using a ZEISS EVO MA 15 microscope, equipped with a Bruker xFlash 360 EDS detector.
2.3. Micro-scale test conduction
The micro-scale tests were carried out using a TE 66 test rig (Plint and Partners, Wokingham, UK) constructed according to the fixed sphere tribological configuration, as shown in Figure 1.
The mechanism uses a sphere that comes into contact with the abrasive solution and the sample. The sphere used is AISI 52100 martensitic steel with a hardness of 798 ± 69 HV and a diameter of 25.392 ± 0.001 mm. The test creates wear tracks on the sphere used, which are influenced by the topography of the counter-body and the wear behavior of the particles. The sphere was conditioned in a water-sand solution before the experiment began, and subsequent conditioning was performed after every three tests. This methodology is necessary to ensure surface wear that maintains the spherical geometry, minimizing the effects related to the counter body's topography18,19.
The abrasive used to produce the slurry for the tests was Silicon Carbide Powder (SiC), provided by Logitech ind, code 0CON-001, 1000 Grit, with an average particle size of 5 μm and hexagonal crystalline structure, knoop100 hardness of 2480 HK0.1, dark gray color, pH 6.8, block shape with sharp edges and conchoidal fracture. The SiC abrasive particles were analyzed and are identified in Figure 2. In (a), characterization by SEM in secondary electron mode was used to evaluate the particle morphology, while in (b) the particle size distribution was obtained; this condition is important for understanding the behavior observed in micro-abrasive wear20,21.
The selection of parameters was based on the studies conducted by Trezona et al.22, in order to ensure the occurrence of the three-body wear mechanism, which is more representative of typical industrial conditions. Table 2 presents the parameters used in the micro-scale tests.
The rotational speed and number of revolutions of the ball were controlled using the software Compend 2000 V2.23. The test was initiated by securing the ball and the specimen in the sample holder. Then, the system was positioned and balanced with a counterweight (0.2 N in this equipment), followed by the application of a working load of 0.25 N as a dead weight on the test tribosystem. The tests were stopped at 100, 400, 900, 1,900, 2,900, and 3,900 revolutions, totaling 311.21 m of sliding distance in six interruptions to measure the diameter of the generated wear crater.
These interruptions were performed to monitor the wear progression in each cemented carbide studied. Using an illumination system, the microscope integrated into the equipment, and the software Infinity Capture® versions 4 and Infinity Analyzer®-v.4, it was possible to measure the wear crater diameter perpendicular to the ball’s rotation direction. The wear crater profiles were traced using a Mahr laser profilometer, model Perthometer Concept.
2.4. Calculation of worn volume
The wear volume of each cemented carbide was calculated using the equation below, in accordance with the standard22,23:
Where:
V is the wear volume (mm3);
b is the crater diameter (mm);
R is the radius of the sphere (mm).
3. Results and Discussions
3.1. Microstructural characterization of cemented carbides prior to testing
Figure 3 and Figure 4 reveal the microstructures of the WC-Co cemented carbide before and after chemical etching, respectively. In Figure 3, small pores uniformly distributed throughout the matrix can be observed. A homogeneous distribution of the binder phase (bright spots) with some regions of binder accumulation (binder islands) is also evident. Both features are attributed to the excellent wettability of cobalt with the carbide phase. After chemical etching (Figure 4), the faceted WC grains (light) embedded in the cobalt metallic matrix (dark) become clearly visible
Micrograph of WC-Co cemented carbide before chemical etching, showing the uniform distribution of the binder and small pores.
Figures 5 and 6 show the microstructures of the WC-Ni-Al cemented carbide before and after chemical etching, respectively. Unlike what was observed for WC-Co cemented carbide, Figure 5 reveals a less uniform distribution of the binder during sintering, leading to the formation of binder islands and the presence of larger pores. This is attributed to the lower wettability of Ni with the carbide phase and the shorter duration of the binder in the liquid state in this cemented carbide. However, although the binder islands in the microstructure tend to reduce the mechanical properties, they may contribute to increasing the toughness of the composite and help prevent the pull-out of carbide particles during abrasive wear. After etching (Figure 6), the presence of larger WC particles is clearly observed, due to more pronounced grain growth in the WC-Ni-Al cemented carbide.
Micrograph of WC-Ni-Al cemented carbide before chemical etching, showing binder islands and pores larger than those observed in WC-Co cemented carbide.
Micrograph of WC-Ni-Al cemented carbide after chemical etching, showing larger and more polygonal WC particles than those observed in WC-Co cemented carbide.
3.2. Tests results
To evaluate the micro-abrasive wear resistance of WC-Ni-Al cemented carbide and compare it with that of conventional WC-Co cemented carbide, the materials were subjected to the test under the same conditions. The crater diameter was measured by optical microscopy, and the volume of material lost was calculated using Equation 1 throughout the test. The calculations of lost volume, a calculated mean, and standard deviation for each interruption distance can be seen in Table 3 for the WC-Ni-Al sample and in Table 4 for the WC-Co sample. Figure 7 show the test evolution for the two tested materials.
Figure 8 shows the average wear volume loss of each cemented carbide throughout the test interruptions. It can be observed that during the initial stage (interruptions 1 and 2), there is an abrupt increase in the worn volume due to the greater removal of wear particles (debris) that constitute the tribological pair. With continued sliding, an almost linear relationship (steady state) between the wear volume and the sliding distance traveled by the rotating sphere is reached, indicating the presence of the three-body wear mechanism, in which the removed wear particles remain in the crater, resulting in the formation of a tribo-layer8.
It can also be observed that the WC-Ni-Al cemented carbide exhibited significantly higher micro-abrasive wear resistance than the conventional WC-Co cemented carbide. A possible explanation for this behavior is that the more ductile Ni-Al binder undergoes a greater amount of plastic micro-deformation than the cobalt binder during micro-abrasive wear. These plastic micro-deformations, in turn, provide greater stress relief between the carbide phase and the binder, preventing the abrupt pullout of the WC carbide phase from the matrix and reducing the action of more severe wear mechanisms such as micro-machining11,24
Another possible explanation for the higher abrasive wear resistance of the WC-Ni-Al cemented carbide, despite its coarser porosity, is the presence of binder islands. Due to hardness differences, the binder phase wears faster than the carbide phase25. Since these binder islands (binder accumulations) are thicker and provide a larger average free path between the WC particles, the pullout of WC particles only occurs when these islands are removed by abrasive particles, producing deeper grooves26. Finally, another factor that may have contributed to the higher wear resistance of the WC-Ni-Al cemented carbide is the greater grain growth of the WC particles during sintering. These larger WC particles, besides restricting abrasive particle access to the binder phase, tend to be more resistant to pullout by smaller abrasive particles26,27
3.3. Wear mechanisms
All tests show the same wear mechanisms in the crater for each material. Thus, Figure 9a shows the crater produced in the WC-Co sample, test 3, which showed the lowest wear resistance, therefore, among the tests, this was the most severe, with a final diameter of 1509 µm. The surface of the craters analyzed shows grooves (Figure 9b) and indentations along the surface, including inside the grooves, reinforcing the predominance of grooving, rolling, and micro-rolling mechanisms. The rounding of the WC particles (Figure 9d) confirms the action of micro-polishing. In addition, it is possible to note points of WC particle pull-out, favored by the preferential removal of the binder, although not in a generalized manner, by the smaller and more intense abrasive particles, attributed to their greater volumetric fraction.
Figure 10a shows the crater of the WC-Ni-Al cemented carbide, test 3, with a diameter of 1227 µm, showing greater wear resistance compared to WC-Co. In this sample, there are slightly pronounced grooves (Figure 10b) with microindentations (Figure 10c), in addition to indentations along the surface, suggesting the action of rolling and micro-rolling mechanisms, and little grooving, concentrating wear on the surface of the hard particles and also resulting in a relatively uniform wear condition. The surface has a smooth appearance with rounding of the hard particles, attributed to micro-polishing. Indentations arise when abrasive particles act with localized load without slippage, generating plastic deformations that only contribute to volume loss when simultaneous28. In contrast to WC-Co, wear in WC-Ni-Al is not as evident, with preferential binder removal and no evidence of WC particle pull-out, suggesting that the toughness of the Ni-Al binder favored their retention in the matrix for a longer time.
Similarly, both samples exhibit the same wear mechanisms. The evident rounding of the hard particles observed in the WC-Ni-Al cemented carbide reinforces that wear occurred directly on them, facilitated by their larger relative size and shorter distance between particles (shorter mean free path), in addition to low porosity, conditions attributed to aluminum reinforcement. Although wear of the binder phase occurred at low intensity, this composite has the ability to retain its hard particles more efficiently when compared to WC-Co.
As shown in the performance test of cemented carbides along the sliding distances, it is possible to note that the WC-Ni-Al samples, even in average performance, always stand out when compared to the WC-Co samples.
Figure 11 and Figure 12 shows the cross-sectional profiles of representative wear craters for the WC-Co and WC-Ni-Al cemented carbides, respectively. As observed, the craters exhibit slight roughness beyond the cratered area, a phenomenon (scuffing) that can lead to errors in measuring the crater diameter. However, in this study, the tests demonstrated consistent and predictable behavior regarding this phenomenon, allowing errors to be minimized through the easy identification of the false edge. Both cemented carbides present a spherical-cap profile corresponding to the shape of the test ball, indicating a relatively smooth transition of micro-wear between the hard particles and the binder phase. This similar behavior in both cemented carbides can be attributed to their very close coefficients of friction, given their similar microstructures and the absence of material accumulation at the crater edges (pile-up). This results in a more uniform three-body wear system with lower contact pressure.
From the figures, roughness peaks can also be observed along the entire curvature of the crater, with slightly more pronounced characteristics at the edges. This may indicate the location and depth of micro-grooves. Such peaks were also observed in previous studies by Cozza29 and Esteves20 and correspond to the surface roughness formed by abrasive wear.
The wear profile of the WC-Co cemented carbide exhibits similar roughness peaks across the entire sample profile, with relatively low amplitude compared with the WC-Ni-Al cemented carbide (Figure 10), which shows well-pronounced roughness peaks throughout the sample, with the highest intensities preferentially concentrated at the right edge. This can provide insights into groove depth and help explain the superior wear resistance of this material, highlighting that the enhanced toughness of the composite and its ability to retain WC particles within the structure may promote particle guidance. According to Cozza30, at a certain stage of the wear process, the abrasive paste particles begin to follow preferential trajectories, ceasing interaction between the ball and the sample, which leads to direct contact and the formation of higher-amplitude peaks (ridge).
For a better understanding of the active wear mechanisms in cemented carbides, an EDS characterization was performed. The images obtained in backscattered electron mode (BSD) allowed the distinction of the different phases present in the wear crater region, as shown in Figure 13. Thus, it was possible to qualitatively identify the distribution of WC-rich phases, which are predominantly present in the region, as well as the binder phase, frequently observed at the particle boundaries. The elemental mapping by EDS, as shown in Figure 14 and Figure 15, reveals the elemental distribution (W, C, Co, Ni, and Al) in the analyzed region. The maps indicate that the elements are well distributed across the surface and remain consistent after the test, also reinforcing the solid presence and dispersion of the binder phase over the surface even after the micro-abrasive test, while distinguishing possible regions where its partial or preferential removal occurs. The presence of SiC contamination resulting from the test was not ruled out; however, for the purpose of evaluating the distinction between phases and constituents, there is no significant interference. The quantitative results obtained by EDS were also used to estimate the local elemental percentage, as presented in Table 5.
Comparative analysis of the chemical composition of wear craters in WC-Co and WC-Ni-Al cemented carbides.
A line scan analysis, shown in Figure 16 and Figure 17, was necessary to evaluate compositional variation (see Table 6) and to verify the consistency, continuity, segregation, or preferential removal of the binder along a surface segment after the micro-abrasive process. The obtained profiles, together with the associated elemental contents, provided evidence of the binder removal mechanism and the exposure of WC grains. When analyzed together for the different materials, these mechanisms indicate that the presence, distribution, and integrity of the binder phase directly influence the resistance to micro-abrasion.
In both tested materials, the binder behavior was similar, remaining on the surface. The superior performance of the nickel-based alloy compared to the cobalt-based alloy may be related to the reinforcement provided by aluminum and the more consistent encapsulation of WC particles, which enabled greater resistance over longer sliding distances when subjected to the test.
4. Conclusions
This study evaluated the performance of a nickel-based cemented carbide and compared its resistance to micro-abrasive wear with that of a conventional cobalt-based cemented carbide. The objective was also to evaluate the feasibility of using nickel-bonded cemented carbide as a substitute for conventional cemented carbide in applications involving abrasive wear.
The WC-Ni-Al cemented carbide exhibited significantly higher resistance to micro-abrasive wear compared to conventional WC-Co cemented carbide. This can be attributed to the reinforcement promoted by aluminum on the nickel binder, thus providing greater resultant toughness for the Ni-Al binder composite, and also to the presence of binder islands, which contributed to minimizing the pullout of WC particles (hard phase) and consequently avoided the occurrence of more severe wear mechanisms, such as micro-machining, during the tests. In addition, another factor that may have contributed to the higher wear resistance of the WC-Ni-Al cemented carbide was the greater WC grain growth obtained during the sintering of this material. In contrast, a greater pullout of WC particles was observed in the WC-Co cemented carbide. This condition may be associated not only with a higher volumetric fraction of cobalt in the composite but also with a greater distribution of binder layers surrounding the WC particles in thin layers, which increases material loss through the preferential path of abrasive particles, removing these thin layers and consequently causing the loss of WC particles.
The predominant wear mechanisms in both cemented carbides were the same, with individual variations in severity, namely rolling, grooving, promoting micro-machining and micro-polishing, binder removal, and particle pullout due to binder loss. The WC-Ni-Al sample stood out for exhibiting ridings of high amplitude and yet still achieving higher wear resistance than WC-Co (which has a highly resistant structure), in addition to the little evidence of particle pullout, suggesting that the WC particles remained firmly embedded and absorbed the entire load that promotes wear.
5. Data Availability
The dataset supporting the results of this study is not publicly available.
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Edited by
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Associate Editor:
Ana Sofia de Oliveira.
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Editor-in-Chief:
Luiz Antonio Pessan.
