Chemical composition, microstructure and sintering temperature modifications on mechanical properties of TiC-based cermet – A review

Accepted Manuscript Chemical Composition, Microstructure And Sintering Temperature Modifications On Mechanical Properties Of Tic-Based Cermet– A Review Mariyam Jameelah Ghazali PII: DOI: Reference:

S0261-3069(14)00869-3 http://dx.doi.org/10.1016/j.matdes.2014.10.081 JMAD 6940

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Materials and Design

Received Date: Accepted Date:

12 June 2014 28 October 2014

Please cite this article as: Ghazali, M.J., Chemical Composition, Microstructure And Sintering Temperature Modifications On Mechanical Properties Of Tic-Based Cermet– A Review, Materials and Design (2014), doi: http:// dx.doi.org/10.1016/j.matdes.2014.10.081

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TITLE PAGE CHEMICAL COMPOSITION, MICROSTRUCTURE AND SINTERING TEMPERATURE MODIFICATIONS ON MECHANICAL PROPERTIES OF TiC-BASED CERMET– A REVIEW

CORRESPONDING AUTHOR: Mariyam Jameelah Ghazali

FULL MAILING ADDRESS:

Dept. of Mechanical & Materials Engineering, Faculty of Engineering & Built Environment, National University of Malaysia (UKM) , 43600 UKM, Bangi, Selangor, Malaysia TELEPHONE: +603-89216418 FAX: +603-89259659 E-MAIL: [email protected]

or

[email protected]

Highlights • • • • •

Composition, grain size and sintering temperature are vital in TiC-based cermets. Nano-TiN plays important role in increasing the performance of the cermets. Decrease of core-rim thickness improves mechanical properties in the cermets Increase in carbide stoichiometry in Ti(CN) decreases the wear rate. Increase of sintering temperature above 1430 °C, the decomposition of TiN occurs.



CHEMICAL COMPOSITION, MICROSTRUCTURE AND SINTERING TEMPERATURE MODIFICATIONS ON MECHANICAL PROPERTIES OF TiC-BASED CERMET – A REVIEW

A. Rajabia,M. J. Ghazalib,* , A. R. Daudb a,b

Department of Mechanical and Material Engineering, Faculty of Engineering & Built Environment Universiti Kebangsaan Malaysia, 43600 Bangi, UKM, Malaysia

b

School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, UKM, Malaysia

Abstract Cermets, particularly those based on TiC, are receiving considerable attention because of their unique properties, including high hardness and resistance to thermal deformation. However, TiCbased cermets lack sufficient toughness. To improve the performance of these cermets, numerous studies have been conducted to determine the factors that can be manipulated to improve their toughness. However, the results of these studies vary. This paper summarizes the studies to improve cermet design via chemical compositions and microstructures. Critical issues including the effects of grain size and sintering temperature on the mechanical properties (i.e., toughness, hardness, and wear resistance) of TiC-based cermets are also discussed.

Keywords: Cermets; TiC; TiN; Sintering; Mechanical properties

1.0

Introduction

Since 1927, various materials have been investigated to improve tool life and mechanical properties of cermets and cutting tools that are extensively utilized; roughly two billion-dollar allotment in semi-finishing and finishing works have been allotted for polymers, ferrous alloys, nonferrous

alloys, and advanced materials such as intermetallics and composites [1–3]. Cermets present beneficial resistance to oxidation throughout metal machining and build up edge formation towing to their good chemical stability and high-temperature hardness [4–6]. In general, cermets include two different phases (i.e., ceramic and metal binder). The ceramic parts retain the high hardness and cutting ability, but the softer phase (binder) can deform and absorb energy [7–9]. The ceramics are compounds of carbon, nitrogen, oxide, boron, and silicon with metals such as tungsten, titanium, tantalum, niobium, aluminum, and molybdenum [4, 10-12]. Among those, carbides are very stiff and have high melting temperature, ranging from 2000 °C to 4000 °C, and their hardness is second to that of diamond, which is the hardest known material [13–15]. Thus, titanium carbide (TiC), with a cubic structure similar to that of NaCl, has been considered as one of the most significant metal carbides for manufacturing a new generation of cermets. Such cermets may be endowed with intrinsic properties of TiC, namely, low density (4.93 g/cm3), low friction coefficient, thermal stability, high solvency with other carbides, high melting point (3067 °C), high elastic modulus (410 GPa to 450 GPa), high thermal conductivity (30×106 S/cm), as well as higher thermodynamic stability and hardness than WC (33% more than WC) [16–20]. Conventional cermets (WC-Co) are tough and hard; however, these materials possess poor oxidation resistance and plastic deformation at high temperature, which prohibit their application at elevated temperatures [21–24]. As a result, a growing interest has been given to the use of TiCbased cermets because of their several advantages [4, 25]. However, using TiC-based cermets in its early stage is not advisable because of their inherent brittleness at low temperature [26, 27]. Thus, scholars have attempted to improve the mechanical properties of TiC-based cermets [24, 28, 29]. In general, the mechanical properties of cermets depend on chemical composition and sintering temperature [30–32]. Thus, the present study aimed to summarize the current state of knowledge

concerning the effects of chemical composition, microstructure, and sintering temperature on the mechanical properties of TiC-based cermets.

2.0

Chemical Composition

2.1

TiN

The use of TiN is constantly developing because of its prominent physical and chemical properties, such as high melting temperature (2927 °C), relatively low oxidation, and low friction coefficient. TiN can be utilized as hard coating and an essential material for cermet and cutting tools owing to its high wear resistance [33–35]. Since 1970, several studies have been conducted to improve the toughness of TiC-based cermets by modifying their microstructure and grain size [36, 37]. Changing the chemical composition of TiN is a crucial strategy, and TiN has been considered more than other elements. The hardness of TiN is much less than that of TiC (TiC=32 GPa; TiN=20 GPa); thus, TiN can effectively improve the toughness of TiC. However, the hardness and Young’s modulus of TiC are reduced, as shown in Table 1 [38, 39]. Another important issue to be noted is the quantity of TiN added in the TiC-based cermets. Moskowitz et al. [40] demonstrated that the maximum tool life value (TiC-TiN-22.5Ni-10Mo10VC) is achieved when the R=TiN/(TiN+TiC) ratio is approximately 4 to 5, as illustrated in Fig. 1, because of grain refinement and dissolution of Mo in binder phase, which leads to solid solution hardening. In this case, the fracture toughness (KIC) is decreased when R > 5, resulting in a decreased tool life because of the formation of finer grains. Although the effect of R ratio [TiN/(TiN+TiC)] on mechanical properties of the cermets was investigated [40], the main reason of the decrease in grain size is not significantly considered. As described in several studies [41–43],

typical microstructures of TiC-based cermets involve a rim that encompassed the whole core, as shown in Fig. 2. In general, dissolution and re-precipitation of the metallic carbide (Ti, W, Mo, Ta) on the cores in the binder phase results in rim formation [41]. Due to the complexity of the core– rim formation of the cermets, a fair assessment of the formation mechanisms remain a difficult task [38]. Recently, many studies have been conducted to understand the mechanisms of core–rim formation in cermets. Solid solution of rim, such as that in Ti(CN), can be made through partial replacement of C atoms with N because TiN decomposes at elevated temperature [42, 43]. In this case, a dissolution–reprecipitation process is limited due to the declining amount of TiC that is dissolving in the liquid phase, which results in decrease in grains and moderate rims. As Ling et al. [42] observed that the average grain size of the cermets decreases from 1.44 μm to 0.78 μm with increasing TiN addition from 0 to 37 wt.%, as shown in Fig. 3; however, this finding is controversial. How rim thickness can be hindered by existence of TiN particles in the cermets at during sintering has not been elucidated. Liang [42] found that N in the cermets can act as an obstacle that is capable of preventing the diffusion of Mo into rim at temperatures above 900 °C; hence, this process can be effectively employed to decrease rim thickness. If these conditions are met, then the toughness of the cermets can be improved, probably because of tensile stress reduction at the core–rim interface [43]. Tensile stress promotes crack propagation within a core– rim interface, leading to a decline in toughness [44]. Previous studies [36, 45, 46] observed that microstructures with coarse grains provide higher KIC than finer grains, in which the transcrystalline fracture of the coarse grains offer a higher bonding force than the intergranular fracture of fine grains. In general, the finer grains of alloys assist in the increase in hardness, resulting in a decline in KIC, as described by the following equation [47, 48]. KIC = 2.15 × 106

× H -1. 5

(1)

where H, E, and KIC are the hardness, Young’s modulus, and fracture toughness, respectively. By contrast, Sun et al. [49] observed an increase in toughness in WC-11Co cermets with the formation of fine grains, which may be induced by increasing the density. The formation of finer grains results in a decline in pore size and an increase in fracture toughness. Such changes can be explained by the existence of cracks that can be easily propagated from pores during fracture process [50, 51]. A brief comparison demonstrates that poor densification can be derived from large particles, whereas high densification is obtained by nano-grains to create large surface area– grain boundary [52–54]. Consistent to this, the physical–mechanical properties of materials with the same chemical composition can be improved using nano-grains [55–58]. This hypothesis can be approved by the Hall–Patch relationship [59, 60]. Previous studies [32, 61] showed that the presence of nano-TiN (~10 wt.%) in TiC cermets provides higher fracture toughness and transverse rupture strength (TRS) than that of WC-Co cermets (Table 2). Such improvement is believed to be due to the existence of nano-TiN in grain boundary that acts as an obstacle for grain growth; nanoTiN do not dissolve in the sintering process completely and do not diffuse into the ceramic hard phase. Moreover, nano-TiN sharply hinders the coalescence of TiC grains when distributed between TiC particles (Fig. 4), resulting in disrupted motion of dislocations. Thus, grain size reduction (refinement) in the cermets can improve mechanical properties such as TRS, based on Hall–Petch formula [62]. A previous study [32] indicated that intergranular fracture (along the grain boundaries) is usually the dominant failure mode. Thus, crack propagation can be limited by nanoparticles of TiN that are distributed in grain boundaries of TiC [63]. The main reason for the occurrence of such phenomenon is that cracks growing along the TiC/TiNnano need more energy to propagate, resulting in improved mechanical properties. Therefore, the distribution of TiN nanoparticles between TiC particles or inlayed between particles can be a significant factor [32,

61]. In addition, Han et al. [32, 61] indicated that some added TiN nanoparticles (<80 nm) might be entrapped within TiC grains, whereas nanoparticles with sizes ranging from 50 nm to100 nm are distributed at the ceramic grain boundaries, forming an intra/inter-type microstructure, as shown in Fig. 5.Micropits are also found because of breakage of TiN nanoparticles during milling.

2.1.1

Effects on Wear Resistance

Fig. 6 displays the chipping and flank edge occurring at the tip of the cermets. The crater wear zone between these two features is wider in WC-Co cermet than that in the TiC-TiN cermet. The formation of the thermal cracks is not destructive in TiC–TiN cermets [61], which may be induced by higher thermal conductivity of TiN, leading to an increase in thermal shock resistance of the cermets [67, 68]. This improvement is also due to the fact that low thermal conductivity in cutting tools favors local overheating and results in formation of microcracks and failure [66, 69]. Consequently, an increase in heat conductivity is considered an important factor in controlling microcracks [70–72]. The effect of chemical composition of TiC-based cermets on flank wear is illustrated in Fig. 7 and Table 3. The tests were conducted under the same conditions: cutting speed (VC=200m/min), feed rate (ƒ=0.5mm/r), and depth of cutting (ap=0.5mm). As shown in Fig. 7, an increase in the wear resistance for TiC-based cermets is accompanied by existence of nano-TiN. These results are in accordance with those reported by Han et Al. [61], in which they found an increase of tool life by approximately 15 times than that of WC-Co cermets by incorporating 10 wt.% nano TiN in TiCbased cermets at 294 mm/min cutting speed. However, tool life of the cermets depends on cutting speed, and its value can be decreased as cutting speed is increased.

Despite the unique features of nanomaterials, some scholars [73, 74] reported that the development trend of nanoparticles is sometimes inadequate. This phenomenon can be related to pores existence in the cermets, resulting in decrease of density and fracture toughness of the cermets as shown in the Fig. 8. However, the main reason of pore formation is not sufficiently dealt with [63]. Moreover, nanoparticles can be contaminated by oxygen [23, 75, 76], mainly because of the increase in surface area and surface energy of nanoparticles, which can be a result of oxygen absorption [77, 78]. Table 4 shows that the oxygen quantity in nanoparticles is higher than the micropowders. Thus, when the amount of added nanopowders is too high, the surface energy of the solids decreases, thereby enhancing the wetting angle, as described by Eq. (2) [73, 79]. Cosθ =

(2)

where γsv, γsl, and γlv are the surface energy of the solid, solid–liquid interfacial energy, and surface energy of the liquid, respectively [79]. Equation (2) also shows that the wetting of ceramic particles with binder decreases as the wetting angle increases becaus of the oxidation of nanoparticles, thereby resulting in low density for sintered cermets. Under this condition, lack of wettability in the two phases (ceramic and binder) creates a clear trend toward decreasing the mechanical properties [79–81]. Fig. 9 shows the variation in bending strength of TiC-based cermets and Fe-TiC composite with the nano-TiN content. The figure also shows that bending strength decreases when the added nano-TiN exceeds 6 wt.%, which corresponds to increase of oxygen contamination of nano-TiN; studies are being conducted to solve this problem. Using a vacuum heat treatment at 1200 °C for 1 h, the quantity of oxygen can be considerably decreased from 6.64 wt.% to 1.18 wt.% (i.e., about 82%) in the nano-TiN powder [82].

2.2 Ti(CN) Ti(CN) can be far better than TiN because of its high microhardness as well as the presence of carbon that serves as a lubricant may enhance the cutting tool speed and service life [83]. Nitrogen assists in increasing the coefficient of thermal expansion (CTE), which is directly related to the inherent properties of TiN (Fig. 10) [84]. In fact, Ti(CN) includes privileged characteristics to both TiC and TiN, as shown in Table 5. These unique properties make Ti(CN) one of the advanced ceramic-based composites employed in several applications such as electrical and electronics, automotive, composites, refractory industries, and cutting tools with much lower friction coefficient [39, 85, 86]. In addition, lack of built-up edges, scaling, crescent depression, and formation of oxidation layers during machining are another benefits of Ti(CN)-based in comparison to the TiC cermets [87, 88]. Other advantages include high microhardness, TRS, and thermal conductivity (Table 6), resulting in better machining of high hardness/strength of materials [39, 67, 68]. Thus, Ti(CN)-based cermets are good candidate for milling and rough machining of steelworks and hard materials, as supported by the following two reasons. First, surface finishing, dimensional accuracy in work pieces, and resistance to chipping are more desirable in Ti(CN)based cermets than in WC-Co cermets [40, 89]. Second, the mechanical–physical properties, such as microhardness and density of Ti(CN) cermets are higher than TiC/TiN cermets [90, 91]. Ti(CN) has a common structure, that is, sodium chloride structure, wherein carbon atoms on the TiC superlattice can be replaced by nitrogen atoms in any proportions that means C for TiC or N for TiN-filed edges of face-centered cubic, while Ti atoms occupied (0.5,0,0) position of the superlattice, as shown schematically in Fig. 11 [67, 92]. Thus, a continuous series of solid solutions Ti(C1−x, Nx)(0 ≤ x ≤ 1) can be achieved, in which the physical–mechanical properties would change with an increasing amount of nitrogen and carbon, as listed in Table 7.

The desired mechanical properties (fracture toughness and TRS) are related to Ti(C0.5N0.5) composition. This phenomenon can be explained from the fracture surfaces, as depicted in Fig. 12, indicating that Ti(C0.5 N 0.5) microstructure is finer than other compositions. Furthermore, the effect of stoichiometry on wear behavior and coefficient friction of the TiCN is shown in Fig. 13. For different stoichiometries of the TiCxN1−x a moderate decrease in wear rate and coefficient friction is accompanied by an increase in amount of carbon [93, 94]. Therefore, increasing the stoichiometry of the carbide increases hardness values, as shown in Table 7. For this similar result, Zhan et al. [95] explained that the decrease of C/N ratio results in decreasing mechanical properties of the cermets because of TiN decomposition at high temperature. An example of this finding is illustrated in flank-worn SEM images in Fig. 14, which shows an improvement in wear resistance achieved by increasing C/N. Weight loss of the cermets can be inversely proportional to the bulk hardness based on Archard’s law [96–98]. The variation of TRS of Ti(CN) cermets with different nano-TiC and TiN additions is illustrated in Fig. 15. Table 4 shows chemical compositions of sintered Ti(CN) cermets (33 wt.% TiC–10 wt.% TiN–32 wt.% Ni–16 wt.% Mo–6.9 wt.% WC–1.5 wt.% C–0.6 wt.% Cr3 C2) using two different methods; vacuum furnace and spark plasma sintering (SPS). Weight ratios of nano-TiC to microTiC and that of nano TiN to TiN micro-TiN are 0%:100%, 20%:80%, 60%:40%, and 100%:0%, respectively. As can be seen from Fig. 15, a significant increase in TRS is observed in sintered samples in vacuum furnace, when the weight ratio of nanopowder to micropowder reaches 0.2. However, the cermet with greater content of nanoceramic powders shows a different trend; indicating that the contaminated nano-particles are still stable [79]. By contrast, Zheng et al. [23] indicated that the change in TRS of cermets is relatively small and, there is a peak when the quantity of the ratio is 1. This trend may indicate that oxygen contamination could be declined

during SPS method because of detached oxide layers on the particle surface, resulting in improved TRS.

2.3

Carbon

A large number of potential applications of carbon that motivated researchers to study its effect on the properties of cermets. According to earlier studies, carbon can change the mechanical properties of cermets [100–102]. Therefore, the importance of carbon has attracted interest to obtain desired qualifications caused by oxygen reduction. The reaction rate between carbon and oxygen increased moderately with the increase in temperature during sintering. Ettmayer et al. [103] illustrated that the maximum value of CO released is achieved at 1100 °C, but decreased slowly because of oxygen depletion, as shown in Fig. 16. The exact reaction sequence is still under debate. Chen et al. [104] observed that the first pick of CO related to reaction of the surface of the binder phase particles around 600–700 °C. Oxygen reaction in ceramic particles is accompanied with the formation of main CO peak at around 1100–1250 °C. The small CO peak located at around 1250–1300 °C is attributed to the action of liquid phase and reduction of particles ceramic, which is consistent with the observation of Zhu et al. [105]. They reported that the reduction reaction is significantly performed at 1100 °C to 1300 °C is due to the rapid decrease in oxygen content of Ti(CN) cermets. Considering all of the mentioned facts, carbon may have some different effects (positive or negative) on the mechanical properties of cermets. Fig. 17 shows the variation of TRS with carbon content for different TiC-based cermets and Ti(CN). However, the absolute value cannot be compared because of different chemical composition and particles sizes. The investigators found that an increase in TRS can be noticed when the carbon content of the cermet is increased. This effect can be attributed to improve of wettability in binder with ceramic phase

because of the carbon reaction with oxygen-contaminated nanoparticles, and lower solid solubility of alloy elements in the binder phase, as a result of the formation of carbides through reaction alloy element with carbon addition [106–108]. However, increasing the carbon content in cermets possesses limitation when dealing with the mechanical properties. For example, the TRS for TiC10%TiN-15%WC-20%Co is considered minimum when the added carbon exceeds 1.5 wt.% because of the presence of pores, which may be explained by the following criteria: (I) The main source of pores maybe related to the release of trapped gas because of a reduction reaction during sintering temperature [101, 109, 110]. (II) At the final stage of solidification, a part of the binder phase has the lowest melting point because of segregation phenomenon, leading to a rich carbon. Therefore, no existing supplier supports the shrinkage at this condition [111, 112]. (III) In addition, high carbon content (more than 2.5%, 1.5%, and 2.0% for cermets, Ti(C,N)-15%Ni-15Mo%15%WC,

33%TiC-10%TiN-32%Ni-16%Mo-WC,

and

TiC-10%TiN-15%WC-20%Co,

respectively) may generate graphite formation and a decrease in the mechanical properties, particularly along the ceramic particle boundaries (Fig. 18a) [113]. Characterization by EDX spectroscopy confirmed the presence of graphite phase, as observed in Fig. 18b. This phase can promote crack propagations because of the relatively low strength of graphites[114, 115]. As indicated in Fig. 18c, cracks are easily propagated when graphite precipitation occurs at grain boundaries. These results are in accordance with the investigation of Seo et al. [101], who have studied the effect of carbon on mechanical properties of Ti(CN) cermets. They showed that carbon excess can assist in the formation of pores and graphite phase, resulting in a decrease in hardness and fracture toughness (Fig. 19).

3.0

Sintering

Most TiC-based cermets are synthesized via hot pressing (HP) and vacuum furnace (VF) depending on specific requirements for practical applications [116, 117]. However, there are disadvantages that limit the performance of cermets, hence, the application areas for HP are particularly for maintenance costs and design flexibility [118, 119]. Comprehensive knowledge has been acquired for sintering TiC-based cermets at different temperatures. Wang [120] showed that the mechanical properties (i.e., hardness and TRS) of TiC– TiN cermets depend on sintering temperature. The chemical composition of cermets are TiC13%TiN-13%Ni-Mo2C (Mo2C/TiC:1/4), which were milled for 24 h. The green samples were pressed at 149 MPa and sintered in vacuum (10−4torr). Fig. 20a shows the variations of the hardness of the cermets with TiN content and sintering temperature. The explanation is that the solubility of TiC in TiN is anticipated according to phase diagram of TiC-TiN [121]. Hardness can be decreased with an increase in TiN and sintering temperature towing to the reaction of TiN with TiC during sintering, resulting in the formation of Ti(CN) solid solution; thus, the hardness of this element is lower than that of the TiC phase [93, 122]. Fig. 20b displays the variations in TRS of the cermets in relation to the sintering temperature during the sintering process. The TRS value exhibits a tendency to increase as the sintering temperature rises between 1400 and 1460 °C, as shown in Fig. 20b. This phenomenon can be attributed to the formation of more Ti(CN) at 1460 °C than at 1400 °C. Ti(CN) is produced by a substitutional mechanism, where C atoms replace N atoms. Therefore, a higher sintering temperature is expected to produce more Ti(CN). Thus, the cermet TRS exhibits the maximum value when sintering temperature reaches 1460 °C. Higher TRS value is derived from higher sintering temperature, and its performance is more inferior at 1520 °C compared with that at other temperatures. This phenomenon may be due

to TiN decomposition, that is, denitrification (2TiN=2Ti+N2). The generated N2 gas results in internal pores, thereby decreasing the mechanical properties of cermets. Evidence shows the decomposition of TiN during high-temperature sintering is greater than that of 1400 °C [50, 123, 124]. These values are in good agreement with those reported previously [125]. They indicated that porosities at the grains could be detected by SEM due to TiN decomposition (Fig. 21). Comprehensive studies have been performed by Yan et al. [123] to obtain additional details about TiN decomposition. They demonstrated that the mechanical properties (i.e., hardness and TRS) in Ti(CN) cermets have a similar trend with that of the variation in sintering temperature, as depicted in Fig. 22. TRS and hardness increase with the increase in sintering temperature, reaching a maximum value at 1430 °C, but decrease with a further increase in sintering temperature. Decomposition of TiN occurs when the sintering temperature is higher than 1430 °C. Recently, Li et al. [109] reported that the density of Ti(CN)-based cermets increased sharply when the sintering temperature reaches approximately 1450 °C because of melting of metal binders, which can improve wettability for binder and ceramic particles (Fig. 23). Furthermore, the increase in TRS can be attributed to the dissolution of heavy elements, such as W, Mo, and Ta in the binder, causing a solution hardening.

4.0

Conclusions

Recent investigations on the improvement of TiC-based cermets are summarized in this review to evaluate the different research results. The high hardness of TiC has been well known to increase the mechanical properties of cermets, except for toughness. The studies in this review showed that chemical composition, grain size, microstructure, and sintering temperature are key factors for

increasing toughness in TiC-based cermets. Among the different elements, TiN is more crucial in improving the toughness of cermets because of low hardness and similar crystal structure. The use of nano-TiN is believed to have an effect in increasing the performance of cermets. The advantages of using nano-TiN in cermets include high densification, control of grain growth, lack of easy motion of dislocations, and control over micro-crack propagation during wear. Using nanoparticles can pose some negative consequences, which can be induced by contamination of nanoparticles with oxygen. Under this condition, the mechanical properties of cermets decrease with the decline in wettability between nanoparticles and binder. The limitation may be improved by using vacuum heat treatment. Previous studies have presented that microstructure of the cermets included binder and grains because most of them have a typical core–rim structure, in which the rim is formed during sintering process via dissolution–reprecipitation. The increase in rim thickness can be a result of decreasing mechanical properties of the cermets because of the existence of tensile stress at the core–rim interface. Therefore, rim thickness has been moderated with the use of TiN. In fact, released N from decomposition TiN during sintering act as barrier of diffusion of elements, such as Mo, into rim above 900 °C. The increase in carbide stoichiometry in the Ti(CN), such as Ti(C0.7N0.3), decreases the wear rate because of its high hardness. However, the best toughness is achieved at Ti(C0.5N0.5). In general, the increase in sintering temperature can be noted because of relatively high rate of Ti(CN) solid solution. Increasing the sintering temperature to just above 1430 °C results in the decomposition of TiN. Moreover, the formation of porosities because of TiN decomposition favors to the decrease in mechanical proprieties.

In the last 10 years, a strong interest for TiC-based cermets motivated researchers to produce cermets with higher toughness without losing too much of their other properties. These properties make such cermets as adequate candidate for WC-Co cermets. Therefore, the trend of developing TiC-based cermets is still motivated by its potential use as a source of a kind of tool wear and numerous engineering applications. Further studies are necessary to fabricate novel materials consisting of characterization TiC/TiCN with excellent performance and ideal durability for use in more demanding applications.

Acknowledgement Financial support from FRGS, Govt. of Malaysia (Grant No. UKM-KK-03-FRGS 0120-2010) to conduct the study is gratefully acknowledged.

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List of Figure Captions Fig. 1.Tool life of AISI 4140 steel at 158 m/ min as a function of TiN-to(TiC+TiN) ratio at sintering temperature of 1400 (o), 1475 (●), and 1550 °C ( ) [40]

Fig.2. FE-SEM image of sintered cermet by SPS at 1718 K [32]

Fig. 3 SEM micrographs of polished specimens: (a) 0wt%TiN (b) 7.5wt%TiN (c) 22.5wt%TiN and (d) 37.5wt%TiN [42]

Fig.4. TEM micrographs showing TiN nano particles distributed at the interface of TiC/TiC grains (a[66]), (b [32]) and (c[47]).

Fig.5. FE-SEM image of cermet etched by nitric acid solution (0.1 mol/l) at 298 K (a) [32] and (b) [61].

Fig. 6. SEM micrographs of the frontal view of the flank wear from (a) (TiC-10% nano TiN) and( b) (WC-8%Co), after 30 min milling [61]

Fig. 7. Cutting performance of different cutting tools [6] (1-3 details are in Table 3).

Fig.8 Effect of TiN nanoparticles on (a) density and (b) fracture toughness KIC [63] Fig. 9. The influence of nano TiN addition on bendng strength (a) TiC-based cermet [60], (b) Fe-TiC [73]

Fig. 10. Temperature-dependent molar linear thermal expansion coefficients for the various Ti(C1−x Nx ) [84]. Fig.11.Illustration of lattice structure of TiC or TiN crystal [67] Fig.12. Fracture surfaces of Ti(C, N) based materials observed by SEM. (a) Ti(C0.3N0.7) (b) Ti(C0.5N0.5) and (c) Ti(C0.7N0.3) [90] Fig.13. Dependence of friction and wear coefficients versus the stoichiometry of the TiCx N1−x hard phase [93]

Fig.14. Flank worn micrographs of TiCN matrix cermets: (a) TiC 0.5 N 0.5 and (b) TiC0.4N0.6 [99] 

Fig.15. The influence of different nano TiC and TiN additions on TRS

Fig.16. Schematic diagram of the released CO [103]

Fig.17.The effect of carbon content on transverse rupture strength ,(a) Ti(C,N)-15%Ni-15Mo%15%WC [108], (b) 33%TiC-10%TiN-32%Ni-16%Mo-WC [107], (c) TiC-10%TiN-15%WC20%Co [112].

Fig.18. (a) Graphite precipitation [112], (b) EDX of graphite precipitation and (c) the rupture mode of crack through grains of high carbon content cermets (3.5 wt %C) [108].

Fig 19. Hardness and fracture toughness of various carbon after sintering for (Ti0.7W0.3)Cx–Ni [101]

Fig.20. The effect of sintering temperature on (a) hardness and (b) transverse rupture strength TiCTiN ceremts [120].

Fig.21. SEM micrograph of TiC0.8N0.2 showing entrapped porosity in the grains [125]. 

Fig.22. Mechanical properties of Ti(CN) based cerements. Transverse rupture strength and hardness with different sintering temperature [123].

Fig.23. The bending strength and density of Ti(CN) based cermets [109]  



Fig. 1.Tool life of AISI 4140 steel at 158 m/ min as a function of TiN-to(TiC+TiN) ratio at sintering temperature of 1400 (o), 1475 (●), and 1550 °C ( ) [40] 

            



Fig.2. FE-SEM image of sintered cermet by SPS at 1718 K [32]   

             



Fig. 3 SEM micrographs of polished specimens: (a) 0wt%TiN (b) 7.5wt%TiN (c) 22.5wt%TiN and (d) 37.5wt%TiN [42]           

 



Fig.4. TEM micrographs showing TiN nano particles distributed at the interface of TiC/TiC grains (a[66]), (b [32]) and (c[47]).

Fig.5. FE-SEM image of cermet etched by nitric acid solution (0.1 mol/l) at 298 K (a) [32] and (b) [61].

Fig. 6. SEM micrographs of the frontal view of the flank wear from (a) (TiC-10% nano TiN) and( b) (WC-8%Co), after 30 min milling [61]

Fig. 7. Cutting performance of different cutting tools [6] (1-3 details are in Table 3).

Fig.8 Effect of TiN nanoparticles on (a) density and (b) fracture toughness KIC [63]

 



Fig. 9. The influence of nano TiN addition on bendng strength (a) TiC-based cermet [60], (b) Fe-TiC [73]

               



Fig. 10. Temperature-dependent molar linear thermal expansion coefficients for the various Ti(C1−x Nx ) [84].

Fig.11.Illustration of lattice structure of TiC or TiN crystal [67]

Fig.12. Fracture surfaces of Ti(C, N) based materials observed by SEM. (a) Ti(C0.3N0.7) (b) Ti(C0.5N0.5) and (c) Ti(C0.7N0.3) [90]

Fig.13. Dependence of friction and wear coefficients versus the stoichiometry of the TiCx N1−x hard phase [93]

        

  



Fig.14. Flank worn micrographs of TiCN matrix cermets: (a) TiC 0.5 N 0.5 and (b) TiC0.4N0.6 [99]           



Fig.15. The influence of different nano TiC and TiN additions on TRS

    



Fig.16. Schematic diagram of the released CO [103]                

 



Fig.17.The effect of carbon content on transverse rupture strength ,(a) Ti(C,N)-15%Ni-15Mo%15%WC [108], (b) 33%TiC-10%TiN-32%Ni-16%Mo-WC [107], (c) TiC-10%TiN-15%WC20%Co [112].       

 

 

Fig.18. (a) Graphite precipitation [112], (b) EDX of graphite precipitation and (c) the rupture mode of crack through grains of high carbon content cermets (3.5 wt %C) [108].

Fig 19. Hardness and fracture toughness of various carbon after sintering for (Ti0.7W0.3)Cx–Ni [101]             

  







Fig.20. The effect of sintering temperature on (a) hardness and (b) transverse rupture strength TiCTiN ceremts [120].

Fig.21. SEM micrograph of TiC0.8N0.2 showing entrapped porosity in the grains [125].         

      

 

Fig.22. Mechanical properties of Ti(CN) based cerements. Transverse rupture strength and hardness with different sintering temperature [123].

Fig.23. The bending strength and density of Ti(CN) based ceremts [109]  

List of Tables

Table.1.Physical and mechanical properties for the two compositions [39] Table.2.Mechanical properties for TiC-based ceremts and WC-Co Table.3. Chemical composition of the tested cutter and cutting parameters [6]

Table.4. Mean particles and oxygen content of raw materials Table.5. The properties of TiC and TiN [68] Table.6. Comparison of high-temperature properties of a TiC-cermet and a Ti(C, N)-cermet [67]. Table 7 Mechanical properties of TiC+TiN powders hot pressed 1 hour at 1850 °C [90].

Table.1.Physical and mechanical properties for the two compositions [39] Young’s modulus (GPa) Microhardness (Hv) Toughness (MPa√m) Cermet A: 65TiC-10Mo2C-25Ni

Cermet A Cermet B 370 ± 10 290 ± 10 1510 ± 120 1270 ± 70 6±1 10 ± 1 Cermet B: 55TiC-10TiN-10Mo2C-25Ni

Table.2.Mechanical properties for TiC-based ceremts and WC-Co Composition (wt. %) Hardness T.R.S (MPa) KIC (MP√m)

Ref.

TiC-9.3TiNnm-14WC9.3Ni-7.5Mo2C

-----------------------

1895

12

[32]

TiC-10TiNnm-8Ni

89.7±0.2 (HRA) 1295± 22 (HV)

1898±50

12.0±0.3

[61]

----------------

1192

11.85

[63]

WC-6.5Co

1580 (HV)

----------------

10

[39]

WC-6Co

1660 (HV)

----------------

10.9

[64]

WC-8Co

89 (HRA)

1470

----------------

[65]

TiC-10TiN-20Ni15WC-16Mo2C

1222(HV)

Table.3. Chemical composition of the tested cutter and cutting parameters [6] Chemical composition (wt.%) No.

TiC

WC

TiN

Mo2C

Co

1

0

92

0

0

8

2

15

79

0

0

6

3

39

15

10nm

16

0

Table.4. Mean particles and oxygen content of raw materials TiC TiC TiN TiN Ni Mo WC Cr3C2 nm μm nm μm Particle size 0.1 2.58 0.1 14.89 2.3 2.80 0.72 1.80 (μm) O2 content 2.47 0.77 7.51 0.36 0.22 0.10 0.56 0.14 (mass %) Particle size 0.1 2.88 0.1 1.18 1.7 2.80 0.85 2.77 (μm) 2.47 0.37 7.51 0.33 0.30 0.10 0.21 0.16 O2 content (mass %) Powders

C

Ref.

5.5

[79]

----

[79]

5.5

[23]

----

[23]

Table.5. The properties of TiC and TiN [68] Properties Molecular weight Unit cell parameter (nm) Melt point(K) Density (g/cm3) Thermal conductivity(W.m-1K-1) Modulus of elasticity(GPa)

TiC 59.9 0.4318-0.4328 3340-3530 4.90-4.93 17-24 315-450

TiN 61.9 0.4240-0.4249 3223 5.39-5.44 29 251

Table.6.Comparison of high-temperature properties of a TiC-cermet and a Ti(C, N)-cermet [67]. TRS Thermal conductivity Cermets Microhardness (1000 °C Kgf/mm2)

(900 °C, MPa)

(1000 °C,W.m-1k-1)

TiC-based cermets

500

1050

24.7

TiCN-based cermets

600

1360

42.3

Table 7 Mechanical properties of TiC+TiN powders hot pressed 1 hour at 1850 °C [90].



Composition

KIC (MP√m)

σf (MPa)

Hv 0.3 (kg/mm²)

E (GPa)

Ti (C0.3 N 0.7) Ti(C0.5 N 0.5) Ti(C0.7 N 0.3)

5.4 ± 0.62 6.3 ± 0.03 5.7 ± 0.1

360 ± 30 435 ± 10 330 ± 40

1740 ± 150 2100 ± 165 2120 ± 84

467 473 510