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Effect of WC content on ultrasonic properties, thermal and electrical conductivity of WC–Co–Ni–Cr composites

  • Vildan Özkan Bilici EMAIL logo
Published/Copyright: September 26, 2022

Abstract

This study focused on the effect of WC on the ultrasonic properties, thermal and electrical conductivity of WC–Co–Ni–Cr composites. The samples were produced by powder metallurgy method for microstructural, physical, and ultrasonic characterization. Pulse-echo, hot disk, and four probe methods were used to evaluate the ultrasonic properties, thermal and electrical conductivity of WC–Co–Ni–Cr composites with different WC contents, respectively. Experimental results show that thermal conductivity and electrical conductivity of WC–Co–Ni–Cr composites increase linearly with increasing WC content and then decrease rapidly. The reason for this rapid decrease is expressed in the fact that the structure becomes more ceramic as the WC additive ratio increases. The same situation was observed in ultrasonic measurements. As the amount of WC particles in the sample increased, longitudinal and shear wave velocity, attenuation values, and elastic modulus increased.

1 Introduction

The powder metallurgy industry is growing rapidly due to increasing demand for pure metals to high-performance composites, thermal management materials, hard metals, and other cemented carbide tools and components [1,2,3]. These materials show not only good electrical, magnetic, and thermal properties but also good mechanical properties. Therefore, WC–Co composite material is still an ideal option in these fields. The hard metals obtained when the impact toughness of metals (Co) and the high hardness and wear resistance specific to ceramics (WC) are combined have taken their place as materials that are constantly sought and used in applications such as rock drilling, cutter-scrapers, mining, and metalworking. Cobalt as a cemented carbide binder is predominant in this field due to its unique features [4,5,6]. A lot of research has been performed on probable successful alternative connectors to cobalt that can be used with WC. Nickel which is another iron group was thought to be an ideal alternative due to the oxidation susceptibility of iron [7,8,9,10,11]. Moreover, by adding some sintering materials like Fe, Co, Ni, Pd, Zn, Cr, Mo, and Cu in WC ceramic powder, ternary or tetra compound composite materials can be formed in order to activate solid phase sintering and consolidate the structure. The added materials are formed compounds to affect self-diffusion and inter-diffusion between WC and Co, Cr, Ni atoms [12,13,14,15,16].

Recently, some researchers have studied to measure the variation of thermal conductivity with some parameters such as the temperature of multicomponent metallic alloys [17,18,19,20,21,22].

The main objective in the determination of material properties by ultrasonic techniques is to carefully record and examine the propagation properties and changes of ultrasonic waves in the material. By measuring the changes in the propagation velocity of the waves in the material and the attenuation coefficients, information about the internal structure, mechanical properties, stresses, and density of the material can be obtained [23,24,25]. In the study conducted by Gaafar et al., the longitudinal and transverse ultrasonic wave velocities of Cu x Ag1−x InTe2 ( 0 x 1 ) , quaternary compounds were determined using pulse echo technique. Furthermore, Gaafar et al. have observed that these compounds become closely packed and more rigid with the substitution of Cu instead of Ag [26]. A theoretical model providing the relationship between ultrasonic wave velocity and microstructure has been proposed by Lu and Liaw [27]. Erol et al. calculated the elastic modulus values of the composites prepared at different temperatures using the ultrasonic pulse-echo method and examined the relationship between this ultrasonic parameter (E (GPa)) and its physical and mechanical properties [28]. Bilici Özkan and Kaya synthesized polyPNPMMA-TiO2 as a new derivative nanocomposite considering the possibility of using polymer/nanocomposites in the material industry. The relationship between the microstructure of the polymer nanocomposite, which changes with the reinforcement, and the ultrasonic analysis was investigated. The accuracy of the results of the ultrasonic analysis was also confirmed by the measured mechanical properties [29]. The reason for choosing the PM technique is that it offers a significant advantage in the interaction of microstructural parameters with each other. The aim of this study is to establish a correlation between the microstructural, physical, and ultrasonic properties of the new composite material obtained by doping different ratios of Co, Ni, and Cr metal binders from WC-based cemented carbides, resulting from variations depending on WC content and sintering temperature. In addition, there is a relationship between thermal and electrical conductivity at high temperatures, and it has been observed that microstructure organization is important in heat transfer and solidification process parameters.

2 Experimental procedure

2.1 Measurement of ultrasonic properties

The study of some properties related to ultrasonic wave propagation in composites, alloys, and metal-based materials gives information about the microstructural, mechanical, and physical properties of the materials. The composite’s longitudinal ultrasonic velocities have been measured using a pulse-echo method with an Olympus Panametrics-NDT Model 5800 Computer Controlled Pulse/Receiver. Two-channel Rigol brand DS1102E 100 MHz digital oscilloscope with pulser/receiver was used for ultrasound measurements. The ultrasonic pulse-echo system in this study consisted of an ultrasonic Olympus brand pulser–receiver, a transducer, an oscilloscope, and a computer, as shown in Figure 1. All devices used before measuring were calibrated. In the pulse-echo method, piezoelectric ultrasonic transducers were used. Piezoelectric ultrasonic transducers, which have the ability to detect all kinds of shape defects without the mechanical movement of the probe, are widely used in the medical or industrial field thanks to these capabilities. Since the piezoelectric effect is bidirectional, the transducers can generate ultrasonic signals from electrical energy as well as convert the sound wave into an electrical signal, so the waves passing through the material are reflected from the back side and converted into electronic signals by the same piezoelectric element [30,31,32,33].

Figure 1 
                  Schematic diagram of the experimental setup for ultrasonic properties of composite samples by the ultrasonic pulse-echo method.
Figure 1

Schematic diagram of the experimental setup for ultrasonic properties of composite samples by the ultrasonic pulse-echo method.

The direction of oscillation depends on the orientation of the piezo-electric crystal which produces longitudinal or shear (transverse) waves of the probe. In a longitudinal wave, the distortion is parallel to the traveling direction, while in a shear wave, the distortion is perpendicular to the traveling direction [34]. The pulse-echo ultrasonic velocity (V) can be calculated from the measured time also called the time of flight ( t ) , between two back wall echoes [35]

(1) V = 2 S t .

For each sample, the ultrasonic velocity measurement values were repeated six times and the average velocity value was calculated. The densities of composite samples were measured with the Archimedes principle, and ultrasonic velocities were used to calculate the elastic modulus. Standard velocity–elasticity relationships can be used considering that the internal structures of the samples used in this study are done by equation (2).

(2) E = ρ V s 2 3 V l 2 4 V s 2 V l 2 V s 2 ,

where V s is the shear wave velocity (m/s), V l is the longitudinal wave velocity (m/s), ρ is the bulk density, and E is the elastic modulus (GPa) [36,37]. The ultrasonic attenuation measurement has previously been studied by several researchers [38,39,40,41]. To measure the number of dB or loss, the amplitudes of the backwall echoes were used according to this equation [42]:

(3) Number of dB = 20 log A 1 A 2 or α = 1 d 20 log A 1 A 2 ,

where α is the attenuation coefficient in Nepers per unit length and A 1 and A 2 are the first two successive amplitudes of the reflected ultrasonic wave within the material’s boundary.

2.2 Measurement of the thermal conductivity

Different researchers attempted to determine the thermal conductivity for solid and liquid phases in different materials. One of the commonly used techniques for measuring the thermal conductivity of solids is the hot disk method. In this study, the Hot Disk Thermal Constants Analyzer model TPS 2500 utilizes a sensor element in the shape of a double spiral. Hot disk sensors made by spiral nickel wire through hot disk measurement shown in Figure 2 were sandwiched between two half-metal blocks. The hot disk sensor method has been used to measure the thermal conductivity of solids for pure materials, composites, and alloys [43,44,45,46,47].

Figure 2 
                  Schematic diagram of the hot-disk method.
Figure 2

Schematic diagram of the hot-disk method.

2.3 Measurement of the electrical conductivity

The electrical conductivity is highest in pure metals, lower in the case of alloys and composites, and also in semimetals and semiconductors. Electrical conductivity is defined as a measure of a material’s ability to conduct an electric current. It is one of the primary physical properties of materials such as thermal conductivity, specific heat, and thermal expansion [48].

In the present work, Keithley 2601A System Source Meter four-point probe method has been used to measure electrical conductivity (Figure 3) [49].

Figure 3 
                  Keithley 2601A System Sourcemeter four-point probe setup and schematic representation.
Figure 3

Keithley 2601A System Sourcemeter four-point probe setup and schematic representation.

2.4 Sample preparation and metallographic characterization

Composite samples were produced from tungsten carbide (WC), cobalt (Co), nickel (Ni), and chromium (Cr) matrix powders by the conventional powder metallurgy (PM) method. In the production of composites, cobalt (Co) powder of 99.5% purity, chromium (Cr) powder, 99% purity, and nickel (Ni) powder of 99.8% purity were used as metal powder, and the grain size of all powders was −325 mesh. Tungsten carbide (WC) powder of 99.5% purity and grain size of less than 1 micron was used. All these powders used in composite production were supplied by Alfa Easer. In the study, the composition (wt%) and codes of the selected WC–Co–Ni–Cr composites are given in Table 1. The powders taken in determined amounts were mixed in the mixer rotating at 20 dv/min speed for 24 h in order to obtain a homogeneous mixture. All the powders were placed in a mold of 15 mm diameter and 5 mm height and pressed using a hydraulic press at a pressure of 305.9 kg/cm2 at room temperature. Sintering was carried out at 1,000°C in an Argon atmosphere for 2 h, allowing them to cool naturally. Scanning electron microscopic (SEM) images of the samples were taken, and EDX analyses were carried out by SEM (LEO 1430 VP equipped with RONTEC EDX). SEM images and EDX analysis of WC–Co–Ni–Cr powders, which yielded the best results in terms of mechanical strength in sintered samples during operation, are shown in Figures 4 and 5, respectively.

Table 1

Composition (wt%) and codes of selected WC–Co–Ni–Cr composites

Codes WC Co Ni Cr
C1 40 18 36 6
C2 50 15 30 5
C3 60 12 24 4
C4 70 9 18 3
C5 80 6 12 2
C6 90 3 6 1
Figure 4 
                  SEM Images of (a) C1, (b) C2, (c) C3, (d) C4, (e) C5, and (f) C6 samples.
Figure 4

SEM Images of (a) C1, (b) C2, (c) C3, (d) C4, (e) C5, and (f) C6 samples.

Figure 5 
                  EDX spectrum of (a) C3 and (b) C6 composites at 1,000°C.
Figure 5

EDX spectrum of (a) C3 and (b) C6 composites at 1,000°C.

3 Results

In this study, first, it was aimed to investigate the changes in thermal conductivity and electrical conductivity of WC–Co–Ni–Cr composite samples, which contain WC particles in weights from 40% up to 90% that were produced via the powder metallurgy method, with respect to their reinforcement percentages. Second, the relationship between WC ratios ranging from 40 to 90% with respect to reinforcement percentages and ultrasonic properties (such as longitudinal and shear attenuation values, longitudinal and shear velocity values, and elastic modulus) was investigated. Ultrasonic properties, thermal conductivity, and electrical conductivity values for WC–Co–Ni–Cr composite samples are given in Table 2. As also seen in Table 2, it was observed that thermal conductivity and electrical conductivity have increased approximately with an increase in the WC ratio.

Table 2

Ultrasonic, thermal, and electrical properties of WC–Co–Ni–Cr composite samples

Composites Ultrasonic longitudinal velocity (m/s) Ultrasonic shear velocity (m/s) Ultrasonic longitudinal attenuation (dB) Ultrasonic shear attenuation (dB) Elastic modulus (GPa) Thermal conductivity (W/Km) Electrical conductivity (σ) (×1010/Ω m) Density (g/cm3)
C1 3,428 2,461 0.4569 1.0036 81.28 7.296 7.131 6.93
C2 3527.2 2542.8 0.3638 0.7748 89.29 8.758 7.713 7.20
C3 3,924 2655.3 0.3023 0.5819 109.41 9.151 8.289 7.20
C4 4591.7 2838.3 0.2886 0.4906 145.82 9.554 8.516 7.60
C5 4,294 2,519 0.5672 0.9685 123.29 7.391 7.431 7.85
C6 3943.5 2358 0.8145 1.0022 104.61 6.120 7.326 7.70

Figures 6 and 7 show thermal conductivity and electrical conductivity graphics of composites which were formed with different WC additive amounts. It was observed that there are similar changes in the thermal and electrical conductivity values. The changes in physical properties above could be explained by the following:

  1. It is clearly seen that the curve can be considered in three stages. At stage I, when the WC rate increases from 40 to 50% in WC–Co–Ni–Cr composite, there is an increase in thermal and electrical conductivity. When WC additive content is 50%, the thermal conductivity and electrical conductivity increase to 8.758 Wm−1 K−1 and 7.713 × 1010(Ωm)−1, respectively. With the regular increase of WC additive, the thermal conductivity of WC–Co–Ni–Cr composite continues to increase drastically to 9.554 Wm−1 K−1 at stage II and the electrical conductivity increase in the same way to 8.516 × 1010(Ωm)−1. At stage III, both thermal conductivity and electrical conductivity decrease rapidly.

  2. Specific properties of materials are related to other properties. For example, physical properties have an effect on mechanical properties directly. Specific properties stand out according to the function of the material within the structure. It is known that ceramic has low electrical and heat conductivity. Accordingly, we can state the reason for the rapid decrease at stage III such that as the WC admixture rate increase, the structure becomes more and more ceramic. The electrical conduction depends on the formation of the conducting pathway [50]. Bigg [51] observed that the thermal conductivity of the composites depended on not the pathway characteristic but the material’s integral characteristic. The increase in the magnitude of the powder boundary (Figure 4e and f) of the C5 and C6 composites has a disadvantage for electron and phonon transmission. Previously, the conductivity increasing due to the formation of the network structure has been reported in refs. [52,53,54,55,56]. This could be mainly due to the contribution of the connected network structure, and it was found that the interface plays an important role in thermal conductivity [57,58]. When the content of the C1, C2, C3, and C4 composite powder exceeds 80 and 90 wt%, the magnitude of the powder boundary of the WCCoNiCr composites increases.

  3. WCCoNiCr composites were characterized using energy-dispersive X-ray spectroscopy (EDX) analysis. As can be seen from the analysis results, there exists oxidation in the sintering process forming the oxygen peak which can be confirmed using EDX spectrum in Figure 5b. The existence of oxygen in the structure prevents heat flow as a barrier and thus decreases the transmission of free electrons and scattering of phonons. As a result, thermal and electrical conductivity decreases because free electron and phonon conduction in metals, alloys, and composites are impressed by components in the structure.

Figure 6 
               Variations of thermal conductivity with the composition of WC for WC–Co–Ni–Cr composites.
Figure 6

Variations of thermal conductivity with the composition of WC for WC–Co–Ni–Cr composites.

Figure 7 
               Variations of electrical conductivity with the composition of WC for WC–Co–Ni–Cr composites.
Figure 7

Variations of electrical conductivity with the composition of WC for WC–Co–Ni–Cr composites.

When the ultrasonic properties of the composite samples obtained in this study were examined, using the longitudinal and shear velocity, longitudinal and shear attenuation, and elastic modulus values of samples given in Table 1, calibration curves (longitudinal velocity-WC (%), shear velocity-WC (%), longitudinal attenuation-WC (%), shear attenuation-WC (%), and elastic modulus-WC (%)) were drawn (Figure 8). Ultrasonic longitudinal and shear velocities of WC–Co–Cr–Ni composite samples were measured using the ultrasonic method, and elastic modulus was calculated using equation (2). The results indicate that when the ratio of volume (WC) increases, the elastic modulus, density, longitudinal and shear velocity also increase and then rapidly decrease at 80 and 90% volume ratios. As the volume ratio (WC) increased, ultrasonic longitudinal and shear attenuation values also decreased and then increased sharply (Figure 8). The decrease in physical properties at 80 and 90% volume ratios can be explained as follows:

Figure 8 
               The relationship between the WC (%) values of the samples and (a) ultrasonic wave velocities, (b) ultrasonic attenuation, (c) elastic modulus and (d) density.
Figure 8

The relationship between the WC (%) values of the samples and (a) ultrasonic wave velocities, (b) ultrasonic attenuation, (c) elastic modulus and (d) density.

The high amount of tungsten carbide at 80 and 90% volume ratios enabled the structure to become more ceramicized and made it more fragile. As a result, the structure loses its flexibility. In addition, the fact that the main matrix element is proportionally higher than the added additive elements has reduced their interaction with each other and the porosity between the grain boundaries has increased. In other words, due to the inability of cobalt (Co), nickel (Ni), and chromium (Cr) powder, which are the binding materials in composites, to cover a large amount of tungsten powder sufficiently (not forming a chemical bond), it can be said that the mechanical properties of the sintered composite decrease. In the literature, it has been determined that elements with good ductility such as cobalt, nickel, and chromium increase WC toughness [59]. However, since the nickel, cobalt, and chromium ratios are low, the mechanical properties of the structure have decreased. Due to the fact that the volume ratios of the reinforcement elements are less than tungsten carbide, they could not wet the tungsten carbide grains very well, causing the formation of a porous structure. Accordingly, ultrasonic sound velocities and elastic modulus values have decreased. The scattering of the ultrasonic wave as it passes through a solid generally depends on the size, shape, length, orientation, anisotropy, and chemical structure of the particles. In electrical conductivity, there is a direct proportionality between the number of scattering events and the length of conductivity. This is proof that the results obtained with different physical properties confirm each other. These results are important data for literature as some of previous works done on composite for different purposes [60,61,62,63,64,65,66,67,68,69,70,71].

4 Conclusions

The dense WC–Co–Ni–Cr composite materials are fabricated solid-state sintering by adding different ratios of materials. The SEM images show that WC grains are homogeneously distributed in the Co–Ni–Cr matrix and the combination between WC, Co, Ni, and Cr is enhanced significantly because of making different ratios added. It is observed that the thermal conductivity and electrical conductivity are preserved at good values after the additive is added.

It has been clearly seen with the results obtained those ultrasonic properties are not independent of other physical properties and their relationship with each other. Consequently, ultrasonic properties, thermal and electrical conductivity of WC–Co–Ni–Cr composite samples increased linearly with the increase of WC additive ratio, but decreased to a large extent with the increase of the additive ratio in the C5 and C6 composite composition. The reason for this decrease is that, in short, they are changes in the microstructure. These changes are the further ceramicization of the structure, the increase in porosity due to the decrease in the interaction between the particles, and the defects existing in the structure.


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Acknowledgments

I would like to thank to Prof. Dr. İdris AKYÜZ, (Eskişehir Osmangazi University) and Assoc. Prof. Murat KORU, (Süleyman Demirel University) for their support.

  1. Funding information: There is no external funding to declare.

  2. Conflict of interest: The author declares no conflict of interest.

  3. Data availability statement: Data sharing is not applicable to this article as no new data were created or analyzed in this study.

  4. Ethical approval: The conducted research is not related to either human or animal use.

  5. Declaration: Raw data were generated at Afyon Kocatepe University Technology Research and Application Center (TUAM). Derived data supporting the findings of this study are available from the corresponding author Vildan OZKAN BILICI on request.

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Received: 2022-08-08
Revised: 2022-08-24
Accepted: 2022-08-29
Published Online: 2022-09-26

© 2022 Vildan Özkan Bilici, published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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