International Journal of Refractory Metals & Hard Materials 23 (2005) 391397 www.elsevier.

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Characterization and wear behavior of modied silicon nitride

E. Carrasquero
a

a,*

, A. Bellosi b, M.H. Staia

School of Metallurgy and Materials Science, Central University of Venezuela, Apartado 49141, Caracas 1042-A, Venezuela b IRTEC-CNR, Research Institute for Ceramics Technology, Via Granarolo 64-48018 Faenza, Italy Received 11 November 2004; accepted 30 June 2005

Abstract Silicon nitride-based materials are applied to many tribological components because of their superior thermal and mechanical properties and corrosion resistance. The purpose of this study is to investigate the wear performance of modied silicon nitride which contained 3 wt.% La2O3 and 3 wt.% Y2O3. The relationships between microstructure and mechanical properties have been also addressed. Vickers microhardness and toughness were measured, the later being determined by means of the direct crack measurement method (DCM). Scanning electron microscopy technique (SEM) coupled with energy dispersive X-ray spectroscopy (EDS) was used for the morphological characterization of the samples as well as for the characterization of the wear scars. Wear properties were studied under a load of 10 N by using the ball-on-disk tribometer. AISI 52100 steel balls and balls of WC + 6% Co (6 mm diameter) were used as static counterparts, respectively. Steady state friction coecients of 0.66 and 0.62 were measured for the tribological pairs WC + 6 % Co/Si3N4 and AISI 52100/Si3N4, respectively. The wear mechanism was determined in each case, and comparison between the wear performance of the traditional and modied silicon nitride is also presented. 2005 Elsevier Ltd. All rights reserved.
Keywords: Silicon nitride; Sintering additives; Sliding wear

1. Introduction Silicon nitride ceramics are gaining recognition in the market as triboelements such as ball bearing, seal, tool dies, and engine parts. Si3N4 materials have lower density and thermal expansion than metals, and their mechanical stability and corrosion resistance over a wide range of temperature are superior to those of several other high-strength ceramic materials. Dense Si3N4 based materials can be fabricated by the use of additives to provide a liquid phase which allows sintering. However, the liquid phase promotes the formation of intergranular phases, which inuence the mechanical and physical properties, depending on their composition, amount and distribution. In order to provide adeCorresponding author. E-mail addresses: carrasqe@ucv.ve (E. Carrasquero), bellosi@ irtec1.istec.cnr.it (A. Bellosi), mstaia@reacciun.ve (M.H. Staia). 0263-4368/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.ijrmhm.2005.06.004
*

quate properties, several investigations have been focused on the control of the microstructure (grain size and shape, intergranular phase in terms of amount, distribution and composition) through the production of ne and pure powders, the design of the sintering aids systems and the development of both controlled powder processing and densication procedures [15]. The use of rare-earth oxide additives as a mean able to provide a liquid medium for sintering is therefore required in order to obtain a high-density Si3N4. Some metal oxides such as MgO, Al2O3, Y2O3, Re2O3 have been used as sintering additives for this purpose. The liquid formed via the chemical reactions between these additives and the initial powder could enhance the diusivity of the atoms during sintering. The starting composition, i.e. the type and the amount of the sintering aids, is a key factor in determining the characteristics of the grain boundary phase, i.e. refractoriness, crystallinity, etc., which in turn, determines all the mechanical and

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physical properties of the material. Besides, the addition of sintering aids is a crucial step during its processing [3 10]. Additives with low melting point eutectics (i.e. MgO) as well as the presence of impurities could favor the development of an equiaxed morphologies for the b-Si3N4, whereas the presence of rare-earth oxides (i.e. Y2O3, La2O3, Yb2O3) could contribute to the development of an elongated grain structures, due to the fact that a high-temperature of the liquidus line and, consequently, a higher viscosity, decrease the diusion rates promoting a textured grain growth. Considerable advantage can be gained using chemical methods to produce additives which are nely and homogeneously distributed at the nanoscale level on the surface of the silicon nitride powder. In this way, by coating the powder, the distribution and the microchemistry of the intergranular phase could be easily controlled, and that contribute to an appreciable improvement of the mechanical properties of the material, such as strength and toughness [4,10,11]. Few studies correlate the wear resistance to the microstructure of bulk silicon nitride [1524]. However, these studies have been focused mainly on the relationships between the sliding condition (sliding speed, load, temperature and atmosphere) and the tribological performance of the Si3N4 [17,18,23]. However, the reported relationships between wear resistance and microstructure are often contradictory. For example, Wang and Mao [15] underlined that elongated grains not only improve both fracture toughness and strength due to the crack deection process, but they also improve the wear resistance as result of the pullout mechanism of the grains. On the contrary, Zutshi et al. [16] found that the pullout mechanism cause third-body wear and this mechanism is enhanced when both the aspect ratio and the grain size increase. When the wear tests were carried out on a hot pressed silicon nitride containing lanthania and yttria, as sintering aids, Gomes et al. [24] found that cracking occurs when the pullout mechanism initiates below the surface and propagates assisted by fatigue, in a mixed intergranular/transgranular mode leading to microscale delamination and fragmentation. In this work, sliding wear resistance tests were carried out on a hot pressed silicon nitride samples containing lanthania and yttria, as sintering aids, introduced by employing a chemical method, since it was shown in the literature [4,11,12] that the selected additive system is particularly suitable in providing self-reinforcing microstructures, improving both high-temperature strength and oxidation resistance.

tion of 3 wt.% La2O3 + 3 wt.% Y2O3. Sintering aids were introduced by chemical co-precipitation from the nitrate solutions. The powder mixture was hot pressed under vacuum at 1850 C, using 30 MPa for 30 min. Details on the processing procedures have been presented in previous papers [4,11]. The microstructure was examined on polished and plasma etched surface parallel and normal to the hot pressing direction. The mean grain size, thickness, length and aspect ratio of the silicon nitride grains were also evaluated. X-ray diffraction allowed the determination of the crystalline phases which were present, as well as the orientation of the b-Si3N4 grains. In order to evaluate the degree of the recrystallization of the secondary phases, annealing tests were performed at 1400 C for 6 h in a owing nitrogen atmosphere. The direct crack measurement (DCM) method was employed for the determination of the fracture toughness, KIC, by means of Vickers indentation at a load of 98.1 N in a Zwick hardness tester. The fracture toughness of the material was derived from a semi-empirical equation proposed in the literature by Anstis et al. [14], by considering the radial-median crack indentation fracture model. The microstructural characteristics and the mechanical properties of the hot pressed material are presented in Table 1. A tribometer (CSEM, Switzerland), under ball-ondisc conguration, was employed to investigate the sliding wear behavior of the samples. The static partners were AISI 52100 steel and balls of WC + 6% Co (6 mm diameter), respectively were loaded with a normal force of 10 N. The sliding velocity used during the tests was of 0.1 m/s for a sliding distance of 1000 m. The experiments were performed in air, without lubrication, at a temperature of 24 1 C and a relative humidity of 55 2%. The radius of the traveling circle of the ball on the disc was of 10 mm. A standard procedure [13] was employed to calculate the wear volume of the balls by assuming that a at wear scar was produced. The wear rate constant, K, was calculated from the equation which results from the adhesive theory of wear [25], in which the volume of the worn samples is proportional to the applied normal load and total sliding distance: K V mm3 N1 m1 SL 1

where V is the worn volume of the ball or disc (mm3), S is the sliding distance (m) and L is the normal load applied (N). The worn volume of the disc was calculated as: V A t Lw 2 where At represents the cross section area of the wear scar produced on the disc and Lw corresponds to the length of the wear scar. The surface topography of the wear scars was analyzed by using the Zygo NewView 200 optical

2. Experimental details A fully dense silicon nitride was produced starting from a commercial Si3N4 (UBE SNE10) with the addi-

E. Carrasquero et al. / International Journal of Refractory Metals & Hard Materials 23 (2005) 391397 Table 1 Microstructural features and mechanical properties of the hot pressed material Residual a-Si3N4 (%) 15
a

393

I200/I002 b-Si3N4 parall.a 1.9

Aspect ratio 9.8 2.0

Mean grain size (lm) 0.33 0.08

k 201200 C 106 C1 4.02

E (GPa) 325

HV (GPa) 18.1 0.5

KIC (MPa m1/2) 5.5 0.1

r (Mpa) RT 941 84 1000 C 927 52 1200 C 968 30 1400 C 761 32

Value of the random orientation: 6.6.

prolometer and the scanning electron microscopy technique (SEM). The wear scars produced on both samples and balls were analyzed by using SEM with an EDX attachment in order to determine the dominant wear mechanism and the surface degradation process. Prior to the SEM examination, the silicon nitrides discs were gold coated for improved conductivity.

3. Results and discussion 3.1. Microstructural characteristics The results from the microstructural characterization of the Si3N4 samples (Fig. 1a and b) show the polished and the plasma etched surface normal and parallel to the hot pressing direction of the silicon nitride under study. As it can be observed from Fig. 1a, the material presented a coarser microstructure with elongated grains Si3N4 and interlocked b-Si3N4, originating the so called self-reinforced microstructure [4]. The elongated grains align their basal planes in the direction parallel to that of the direction of the applied pressure as it is shown in Fig. 1b. Theoretical considerations of the Si3N4 crystal structure revealed a higher stability of the prismatic planes of the hexagonal shaped grains compared to the basal planes. However, it was shown that the growth rate of basal planes is much higher than the one corresponding to the prismatic planes producing, therefore, a needle-like grain morphology. The difference in growth rates could be related to the Si3N4 crystal structure, and it was attributed to an energeti-

cally more favourable attachment of a surface nucleus on a basal plane [26]. A very strong preferred orientation of the b-Si3N4 grains, indicated by the low value of the relationship I(200)/I(002), has been detected by X-ray diraction studies carried out in this work, whose results are reported in Table 1, which corroborate the microstructural features shown in Fig. 1. It was also reported, that the nearly one-dimensional growth parallel to the crystallographic c-axis has induced an in situ whisker reinforcement mechanism, so that Si3N4 ceramics exhibit a higher fracture toughness than other unreinforced structural ceramics [27]. It was also determined the presence of small amounts of a-Si3N4 and only traces of La and Y crystalline phases were detected. After the annealing tests, La- and Y-silicon oxi-nitrides and Y-silicates were identied from the XRD patterns. Fig. 1b shows a distribution of ne, nearly equiaxed grains of 0.33 0.08 lm diameter, which is clearly dierent from the microstructure presented in Fig. 1a. These results are similar to those found by Zutshi et al. [16], who determined that a much slower growth rate occurred in the direction of the grain thickness. The grain boundaries and their features represent another important factor, which will inuence the mechanical properties of the bulk material. The coarser the microstructure is, the larger are the glassy pockets which are present at the triple grain junctions and, the thicker is the glassy phase between the grains. It was shown [4] that if the triple points are considered as weak microstructural points, failure can originate there and then advance along the grain boundaries layer.

Fig. 1. SEM micrographs of the plasma etched surfaces: (a) normal to the hot pressing direction and (b) parallel to the hot pressing direction.

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3.2. Mechanical properties The values of the properties shown in Table 1 highlight that this material presents a unique combination of properties like hardness, Youngs modulus, toughness and strength. The toughening eect is a result from the enhanced brous microstructure. Several reinforcement mechanisms were found to act against the crack propagation, due to the typical self reinforcing microstructure: crack deection, bridging, branching and debonding [4]. The excellent strength at both room and high-temperature reveal the suitability of the composition and processing conditions which were chosen in order to design and control the microstructure. It was found [4,11] that the strength at high-temperature is related to the degree of softening and stability of the phases situated at the grain boundary. Therefore, the strength of 761 MPa achieved at a temperature of 1400 C could be mainly attributable to the highly refractory grain boundary phases originated as result to the chemical process employed for the addition of the sintering aids to the starting silicon nitride powders. This strength value represents a relative small reduction (18%) when compared to the strength value obtained at room temperature for the same system. 3.3. Tribological behavior The surface roughness average (Ra) of the sample was of 0.13 0.01 lm. Table 2 shows the results obtained from the wear tests for two of the tribological pairs under study and the variation of the friction coecient with the sliding distance is presented in Fig. 2. Dierences in the friction coecients values were observed in the running-in period (less than 200 m of the sliding distance), due to the initial interactions between the asperities of the tribological pairs, their chemical nature and the value of the Hertzian contact pressure. The Hertzian contact pressure was calculated from the mechanical properties of the materials involved in the contact and values of 1.7 GPa and 2.3 GPa were found for the Si3N4/AISI 52100 and Si3N4/WC6% Co pairs, respectively. However, the form of the friction curve had the same trend for all the tests, i.e. starting at a relatively low level of friction coecient value, increasing to a peak and then achieving a steady state value, which was uctuatTable 2 Wear test results Tribological pair Average friction coecient (lav) 0.62 0.06 0.65 0.05 Wear volume, ball V (mm3) Wear volume, disc V (mm3) Wear constants K 107 (mm3 m1 N1) Ball Si3N4/AISI 52100 Si3N4/WC6% Co 7.4E3 1.4E3 5.8E3 82.6E3 7.4 0.14 1.4 0.02 Disc 5.8 0.11 82.6 1.65

Fig. 2. Variation of the friction coecient against the sliding distance for the tribological pairs under study.

ing for both contacts, around 0.62 and 0.68, respectively. Similar values were reported by other researchers when analogue wear testing conditions were employed [17,18]. The scanning electron micrograph presented in Fig. 3a shows the morphology of the worn surface of the Si3N4 disc in contact with the AISI 52100. The debris generated during the test have been deposited on both sides of the wear track. The magnied view, presented in Fig. 3b, shows that the wear track appears rather smooth and, as expected, there are still some patches of the transferred steel lm from the ball to silicon nitride surface due to the high dierences in the hardness values between the mating pair, but most of the steel lm was detached from the sliding surface as result of the fatigue process, which takes place during the test. EDX analysis of the debris has conrmed the presence of Fe and O mainly, indicating that the typical adhesive and abrasive sliding wear mechanism was found for the steel ball in contact with a harder Si3N4 disc material. The scanning electron micrographs shown in Fig. 4a and b, which represent the morphologies of the worn silicon nitride disc in contact with the WCCo ball, indicate that a much more severe damage took place. A higher amount of silicon nitride debris was formed and an abrasive wear mechanism took place on both surfaces, as a consequence of the contact between the

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Fig. 3. SEM micrographs showing the morphology of the worn surface corresponding to the tribological pair Si3N4 disc/AISI 52100 steel ball: (a) wear scar and (b) detail of the wear scar (back scattering mode).

disc (HVSi3N4 = 18 GPa) with a slightly harder material (HVWCCo = 2022 GPa). The EDS analysis of debris has indicated the presence of WC particles besides the silicon nitride particles corroborating, thus, the abrasion of both surfaces. Wear scar topographies and surface proles for silicon nitride discs are shown in Fig. 5. The 3D proles conrm the material transfer from the ball to the surface. As it can be seen, the worn surfaces for the tribological pair Si3N4/WC6% Co (Fig. 5b) were much wider and deeper than those produced for the tribological pairs Si3N4/AISI 52100 (Fig. 5a), indicating clearly that the latter has superior sliding wear resistance under the experimental conditions carried out in this investigation. The values of the wear constants determined for the tribological pairs Si3N4/AISI 52100 and Si3N4/WC6% Co, respectively are reported in Table 2. The wear constant of the silicon nitride disc, k, in contact with the 52100 steel ball is 1400% smaller than that corresponding to the silicon nitride disc which was in contact with the WC6% Co ball. The table also reports the values corresponding to the wear constants of the balls, indi-

cating that the wear constant for the steel ball is approximately one order of magnitude higher than the wear constant of the WCCo ball. It has to be reminded that, during the sliding wear experiments, the normal load was applied on a plane normal to the hot pressing direction, i.e. perpendicular to the plane shown in Fig. 1a. For this condition, it is expected that silicon nitride samples will exhibit a smaller wear resistance than when the load will be applied on the surface parallel to the hot pressing direction, according to the results reported by dierent researchers [23,28] when studying the inuence of the b-Si3N4 grains orientation with respect to the sliding direction. Nakamura et al. [23] indicated that the highest wear resistance could be obtained when the load was applied in a plane normal to the Si3N4 grain alignment, and this behavior could be attributable to the inhibition of crack propagation along the sliding surface by the stacked elongated grains which were normal to the sliding surface. However, the silicon nitride samples have shown an appreciable wear resistance with k values between 106 and 107 mm3 m1 N1 and this performance could be attributed, therefore, to the microstuctural characteristics of the samples under study,

Fig. 4. SEM micrographs showing the morphology of the worn surface corresponding to the tribological pair Si3N4 disc/WC6% Co ball: (a) wear scar and (b) detail of the wear scar.

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Fig. 5. Surface topography and prole of the wear scars for the: (a) Si3N4 disc against AISI 52100 steel ball and (b) Si3N4 disc against WC6% Co ball.

where the self reinforced microstructure, with dierently grain orientation, hinders the propagation of cracks and contributes to the in situ toughening of the material.

tion of the Research Institute for Ceramics Technology, Faenza, Italy.

References 4. Conclusions The present study highlighted that the wear mechanism of the silicon nitride discs occurs mainly by an abrasion mechanism, when sliding wear tests were carried out by using 52100 steel and WCCo balls, respectively. The wear constant of the silicon nitride disc, k, in contact with the 52100 steel ball is 1400% smaller than that corresponding to the silicon nitride disc in contact with the WC6% Co ball. For the conditions tested, the silicon nitride presented a high wear resistance and could be recommended for several wear protection applications. This performance could be attributed to the microstuctural characteristics of the silicon nitride samples, where the self reinforced microstructure, with dierently grain orientation, hinders the propagation of cracks and contributes to the in situ toughening of the material. Acknowledgements The authors would like to acknowledge the nancial support received from the Venezuelan National Fund for Scientic and Technological Research (FONACIT) through the project S1-2002000475 and the collabora[1] Wotting G, Ziegler G. Inuence of powder properties and processing conditions on microstructure and mechanical properties of sintered Si3N4. Ceram Int 1984;10(1):18. [2] Kleebe HJ, Ziegler G. Inuence of crystalline secondary phases on densication of reaction-bonded silicon nitride during post sintering under increased nitrogen pressure. J Am Ceram Soc 1989;72:2314. [3] Galassi C, Biasini V, Bellosi A. Eect of powder characteristics and mixing processes on the microstructure and properties of silicon nitride. Process Adv Mater 1993;3:153. [4] Bellosi A, Monteverde F, Babini GN. Inuence of powder treatment methods on sintering, microstructure and properties of Si3N4-based materials. Engineering ceramics96. Higher reliability through processing, vol. 25. Dordrecht: Kluwer Academic Publishers; 1996. p. 197. [5] Shaw TM, Pethica BA. Preparation and sintering of homogeneous silicon nitride green compacts. J Am Ceram Soc 1986;69(2): 88. [6] Kim JS, Shubert H, Petzow G. Sintering of Si3N4 with Y2O3 and Al2O3 added by co-precipitation. J Eur Ceram Soc 1989;5:311. [7] Wang CM, Riley FL. Alumina coating of silicon nitride powder. Am Ceram Soc Bull 1992;10:83. [8] Joshi PN, McCauley RA. Metal-organic surfactants as sintering aids for silicon nitride in an aqueous medium. J Am Ceram Soc 1994;77:2926. [9] Schmidt H, Nabert G, Ziegler G, Gorezki H. Characterization and surface chemistry of uncoated and coated silicon nitride powders. J Eur Ceram Soc 1995;15:667. [10] Kleebe HJ, Braue W, Schmidt H, Pezzotti G, Ziegler G. Transmission electron microscopy of microstructures in ceramic materials. J Eur Ceram Soc 1996;16:339.

E. Carrasquero et al. / International Journal of Refractory Metals & Hard Materials 23 (2005) 391397 [11] Bellosi A, Babini GN. Eect of raw powders on microstructure and properties of Si3N4-based ceramic. Key Eng Mat 1999;161 163:203. [12] Monteverde F, Bellosi A. High oxidation resistance of hot pressed silicon nitride containing yttria and lanthania. J Eur Ceram Soc 1998;18:2313. [13] ASTM G99-03, Standard test method for wear testing with a pinon-disk apparatus. [14] Anstis GR, Chantikul P, Lawn BR, Marshall DB. A critical evaluation of indentation techniques for measuring fractures toughness: Idirect crack measurement. J Am Ceram Soc 1981;64:539. [15] Wang D, Mao Z. Studies on abrasive wear of monolithic silicon nitride and a silicon carbide whiskers-reinforced silicon nitride composite. J Am Ceram Soc 1995;78(10):2705. [16] Zutshi A, Haber RA, Niesz DE, Adams JW, Wachtman JB, Ferber MK, et al. Processing, microstructure, and wear behavior of silicon nitride hot-pressed with alumina and yttria. J Am Ceram Soc 1994;77(4):883. [17] Gee MG, Buttereld D. The combined eect of speed and humidity on the wear and friction of silicon nitride. Wear 1993;162164:234. [18] Liu W, Duda JL, Klaus EE. Wear property of silicon nitride in steel-on-Si3N4 systems. Wear 1996;199:217. [19] Takadoum J, Houmid-Bennani H, Mairey D. The wear characteristics of silicon nitride. J Eur Ceram Soc 1998;18: 553.

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[20] Enomoto Y, Mizuhara K. Characterization of wear behavior of steel and ceramics in the VAMAS round robin tests. Wear 1993;162164:119. [21] Zhao XZ, Liu JJ, Zhu BL, Miao HZ, Luo ZB. Friction and wear of Si3N4 ceramic/stainless steel sliding contact in dry and lubricated conditions. J Mater Eng Perform 1997;6:203. [22] Gomes JR, Miranda AS, Silva RF, Vieira JM. Tribo-oxidational eect on friction and wear behavior of silicon nitride/tool steel and silicon nitride/gray cast iron contacts. J Am Ceram Soc 1999;82(4):953. [23] Nakamura M, Hirao K, Yamauchi Y, Kanzaki S. Tribological properties of unidirectionally aligned silicon nitride. J Am Ceram Soc 2001;82(11):2579. [24] Gomes JR, Osendi MI, Miranzo P, Oliveira FJ, Silva RF. Tribological characteristics of self-mated couples of Si3N4SiC composites in the range 22700 C. Wear 1999;233235:222. [25] Archard J, Hirst W. The wear of metals under unlubricated conditions. Proc Roy Soc A 1956;236:397. [26] Kra mer M, Wittmu ss D, Ku ppers H, Homan MJ, Petzon G. Relations between crystal structure and growth morphology of b-Si3N4. J Cyst Growth 1994;140:157. [27] Homann MJ. Relationship between microstructure and mechanical properties of silicon nitride ceramics. Pure Appl Chem 1995;67:939. [28] Liang YN, Lee SW, Park DS. Eect of whisker distribution and sintering temperature on friction and wear of Si3N4-whiskerreinforced Si3N4-composite. Wear 1999;225229:1327.