Journal

J. Am. Ceram. Soc., 93 [5] 14611466 (2010) DOI: 10.1111/j.1551-2916.2010.03614.x r 2010 The American Ceramic Society

Fabrication of Silicon Nitride Nanoceramics and their Tribological Properties

Jae-Hee Kim, B. Venkata Manoj Kumar, and Seong-Hyeon Hong*,w
Department of Materials Science and Engineering and Research Institute of Advanced Materials (RIAM), Seoul National University, Seoul 151-744, Korea

Hai-Doo Kim
Korea Institute of Materials Science, Changwon, Gyeongnam 641-010, Korea

Si2N2O secondary phase-free, fully dense nano-Si3N4 ceramics ( ! 97% of theoretical density) were developed by combining carbothermal reduction treatment and spark plasma sintering (SPS), and their tribological properties were investigated by subjecting to self-mated sliding under unlubricated conditions. Commercially available Si3N4 nanopowder was used as a starting material and phenolic resin was used for carbothermal reduction, which was conducted at 14501C for 10 h. Fully densied Si2N2O phase-free Si3N4 ceramics with a wide range of grain size from 90 nm to 1.5 lm were fabricated by varying SPS temperature from 15501 to 17501C. The microstructure of the developed Si3N4 ceramics was changed from nano equi-axed at 15501C to large elongated bimodal grain morphology at 17001 or 17501C. The frictional behavior was not dependent on the microstructure, but the wear rate was strongly inuenced such that it decreased by an order of magnitude (from 9.7 105 to 0.88 105 mm3/N . m) with decreasing grain size. The dominant wear mechanism was changed from the delamination of tribochemical layer for the ceramics with nano equi-axed grain microstructure to the fracture and grain pull-out for the ceramics with duplex microstructure.

I. Introduction
ILICON nitride is a potential material for a variety of structural applications such as reciprocating engine components and turbocharger rotors, cutting tools, and ball bearings, because of its unique combination of mechanical properties like high hardness, moderate fracture toughness, and superior wear resistance with high chemical stability.1,2 Accordingly, extensive research has been conducted toward understanding the wear properties of such a highly important ceramic material in different environments.311 Friction varied in the wide range from 0.2 to 0.8 and wear rate varied from 104 to 108 mm3/N m based on the experimental and material parameters.311 It is widely reported that the complex behavior of friction and wear can be described by several mechanisms of material removal such as tribochemical reactions, plastic deformation, microfracture, and oxidation.1216 Many factors such as temperature, humidity, environment, sliding speed, contact load, lubrication, chemical composition, and microstructural characteristics strongly inuence the propensity of several wear mechanisms.5,13

Recently, there has been signicant research to rene the grain size of polycrystalline ceramics to ultra-ne and nanometer ranges with the anticipation of improving mechanical properties of the developed ceramics.1720 However, the reported studies about tribological performance of monolithic Si3N4 ceramics were limited to ultra-ne grain size (300 nm),21 while no information is available for the sliding wear properties of nanocrystalline ceramics, probably owing to processing difculties.22,23 Hot isostatic pressing (HIP), spark plasma sintering (SPS), and hot pressing (HP) methods were recently explored to prepare nanograined Si3N4 ceramics, but the average grain size was limited to B200 nm.2426 Li et al.,27 densied amorphous silicon nitride nanopowders without additives under ultrahigh pressure, but a rapid grain growth occurred during crystallization or sintering process leading to a grain size of 4160 nm. Recently, two approaches have produced the fully dense Si3N4 nanoceramics with grain size of o100 nm; high-energy mechanical milling followed by SPS28 and two-step sintering with primary phase eld change by addition of Y2O3.29 The key factors are the suppression of grain growth through a rapid consolidation such as SPS or two-step sintering and preparation of nanosized Si3N4 powder. The Si3N4 nanopowder generally contains a signicant amount of oxygen, which results in the secondary crystalline Si2N2O phase in the sintered body. The presence of Si2N2O in Si3N4 could be detrimental to mechanical, thermal and tribological properties due to large agglomeration of nanocrystalline grains and high temperature instability.21 In this study, Si2N2O secondary phase-free, fully dense nanoSi3N4 ceramics were fabricated using a commercially available Si3N4 nanosized powder and the inuence of microstructural characteristics on the tribological properties was investigated. For this, a combined processing method was used, i.e., carbothermal reduction treatment (CRT) to remove the excess oxygen and avoid the Si2N2O phase formation, followed by SPS to achieve a rapid consolidation with limited grain growth. The friction and wear properties were evaluated against commercially available Si3N4 ball when subjected to unidirectional sliding in unlubricated testing conditions.

II. Experimental Procedures

A commercially available nano-Si3N4 powder containing 6 wt% Y2O3 and 3 wt% Al2O3 (PCT6Y3A, Plasma and Ceramic Technology, Salaspils, Latvia) was used as a starting material. The specic surface area was 70 m2/g and average particle size was 30 nm.29 For carbothermal reduction, Si3N4 powder was mixed with 10 wt% phenolic resin (B5 wt% C, Kangnam Chemical Co., Seoul, Korea) by ball milling in acetone using Si3N4 ball and polythene jar. After drying in an oven, the powder was uniaxially pressed into pellets of 10 mm in diameter and then cold isostatically pressed at 150 MPa. The powder compact was heat treated at 14501C for 10 h in N2 owing atmosphere. For

K.-H. Zum Gahrcontributing editor

Manuscript No. 26593. Received July 24, 2009; approved December 19, 2009. This study was supported by a grant from the Fundamental R&D Program for Core Technology of Materials funded by the Ministry of Knowledge Economy, Republic of Korea. *Member, The American Ceramic Society. w Author to whom correspondence should be addressed. e-mail: shhong@snu.ac.kr

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: -Si3N4

SPS, the carbothermally reduced compact was placed into a 10 mm graphite die and an electric current of B1500 A was applied under a pressure of B30 MPa in N2 owing atmosphere. The heating rate was 1001C/min, and the sintering temperature ranged from 15501 to 17501C for 520 min. The apparent density of the sintered specimens was measured using the Archemedes method in water. Microstructure of the samples was examined using a eld emission scanning electron microscope (FE-SEM 7401F, JEOL, Tokyo, Japan) after plasma etching using O2-CF4 gas (80:20 in vol%). The average grain size was estimated using a conventional linear intercept method and Image Pro software (Media Cybernetics, Image-Pro Plus, Bethesda, MD). The elastic modulus (E) was determined by an ultrasonic pulse-echo testing (Tektronix TDS-220, Tektronix Inc., Beaverton, OR). Vickers Hardness (Mituyoto, Kawasaki, Japan) was measured at 1 kg load for 15 s, while fracture toughness was estimated from the crack length measurements based on Anstiss formula after indenting at 10 kg load for 15 s.30 A unidirectional ball-on-disk tribometer was used to evaluate the friction and wear characteristics of sintered specimens in ambient conditions (201751C and 45%710% RH). The detailed description of the tribometer can be found elsewhere.31 Si3N4 balls (hardness: 13 GPa, surface roughness (Ra): 38 nm, SBB Tech. Co., Suwon, Korea) of 6.35 mm diameter were used as the counterbody materials. Both Si3N4 ball and sintered pellets were ultrasonically cleaned with acetone before wear testing. Si3N4 balls were xed in the ball holder so as to make a track diameter of 6 mm from the central axis and the tests were conducted at a xed rotational speed of 1500 rpm (linear speed of 0.47 m/s) for 15 min (total sliding distance of 424 m). The sliding tests were carried out at a 5 N load that resulted in a maximum Hertzian contact stress (initial) of B1.2 GPa. During the test runs, frictional forces were recorded using an electronic sensor to generate the real time coefcient of friction (COF) data. Each experiment was repeated three times and the average values are reported. In order to understand the wear mechanism and to determine the track width, a detailed microstructural characterization of the as-worn surfaces was conducted using SEM (JSM 5600, JEOL) or FE-SEM. Surface proles of the worn surfaces were acquired using an alpha-step prolometer (Model No. 500, KLA-Tencor, Milpitas, CA) to measure the depth of the wear tracks. The wear track width and depth were further used in computing the wear volume (and subsequently wear rate) according to following relations: Vd 2p r w d WR Vd P s (1) (2)

(E) Intensity (a.u.)

s : Si2N2O s s

(D) s

s s

ss

(C) (B) (A) 20 25 30 35 40

2
Fig. 1. XRD patterns of the developed Si3N4 ceramics spark plasma sintered at (A) 15501C for 5 min, (B) 16501C for 5 min, (C) 17501C for 20 min, (D) 15501C for 5 min without carbothermal reduction treatment, and (E) carbothermally reduced powder at 14501C for 10 h using carbon nanopowder.

the wear rate in (mm3/N m), P is the normal load (N), s is the total sliding distance (m).

III. Results and Discussion

XRD patterns of the developed Si3N4 specimens sintered at various temperatures are shown in Fig. 1. For comparison, the pattern of the sintered sample without a CRT was included where a signicant amount of Si2N2O second phase was found (Fig. 1(D)), which can be attributed to the presence of a large amount of oxygen in the starting powder.32 With carbothermal reduction, Si2N2O phase almost completely disappeared and a nearly single phase b-Si3N4 ceramics was obtained irrespective of sintering temperature (Figs. 1(A)(C)). A carbon nanopowder (average particle size: 30 nm, Aldrich, Milwaukee, WI) was also used for the carbothermal reduction, but Si2N2O phase still existed after carbothermal reduction (Fig. 1(E)) and SPS, possibly due to an inhomogeneous mixing between nanopowders during ball milling. Thus, phenolic resin was very effective to remove the oxygen in the starting powder and to fabricate the Si2N2O phase-free Si3N4 ceramics. The apparent density and average grain size of the developed Si3N4 ceramics are shown in Table I, and the representative

where Vd is the wear volume of disk (mm3), r, w, and d are the radius, width, and depth of wear track, respectively (mm), WR is

Table I. Microstructural, Physical, and Mechanical Properties of Developed Si3N4 Ceramics

Grain size (nm) Sintering conditions (1C-min) Apparent density (g/cm3) [% of theoretical] Linear intercept Image analyzer Elastic modulus (GPa) HV1 (GPa) KIC (MPa m1/2)

1550-5 1600-5 1650-5 1650-20 1700-10 1750-20

w

3.18 [97] 3.18 [97] 3.20 [98] 3.21 [98] 3.21 [98] 3.22 [99]

90 117 140 157 207 241

85 (242w) 102 (272) 114 (341) 176 (641) 215 (863) 262 (1082)

269 270 280 280 277 277

13.5 13.6 13.2 12.6 12.6 12.8

2.5 3.0 3.4 3.9 3.6 4.5

Average length of top 10% elongated grains.

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Fabrication of Silicon Nitride Nanoceramics and their Tribological Properties

0.8 (A)

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Coefficient of friction

0.6

0.4

0.2

0.0 1550-5 1600-5 1650-5 1650-20 1700-10 1750-20 Temperature-time (C-min) 1 m

1.5x104 Wear rate (mm3/Nm) 1.2x104 9.0x105 6.0x105 3.0x105

(B)

Si2N2O - Containing

Si2N2O - Free

(B)

0.0

1550-5 1600-5 1650-5 1650-20 1700-10 1750-20 Temperature - time (C-min)

Fig. 3. (A) Average coefcient of friction and (B) wear rate of the developed Si3N4 ceramics (disk specimens) as a function of sintering conditions. For reference, wear rates of Si2N2O-containing Si3N4 ceramics (disk specimens) fabricated without carbothermal reduction treatment are included in (B).

1 m

(C)

1 m
Fig. 2. Field emission scanning electron microscopic micrographs of the polished and etched surfaces of the developed Si3N4 ceramics spark plasma sintered at (A) 15501C for 5 min (B) 16501C for 5 min, and (C) 17501C for 20 min.

microstructures are presented in Fig. 2. A nearly full densication (! 97% of theoretical density) was successfully achieved by SPS and the apparent density slightly increased with sintering temperature and time. A relatively uniform nanograined microstructure with an average grain size of B90 nm was developed at 15501C (Fig. 2(A)). Consistent with the previous report,25 SPS was effective in reducing sintering temperature, sintering time, and grain size. With increasing sintering temperature and time, elongated grains appeared in the nano equi-axed matrix grains and average grain size increased (Fig. 2(B)). The specimen sintered at 17501C for 20 min exhibited a typical bimodal Si3N4

microstructure (Fig. 2(C)) and some of elongated grains were B1.5 mm long with an aspect ratio of B7. The average grain size of top 10% elongated grains was estimated to B1mm, but there were many nanoequiaxed matrix grains remained and the overall average grain size was estimated to be B250 nm (Table I). The elastic modulus of the developed Si3N4 ceramics varied in the narrow range of 270280 GPa (Table I). The hardness slightly improved from 13 to 14 GPa, whereas the fracture toughness signicantly reduced from 4.0 to 2.8 MPa m1/2 with decreasing grain size. It was reported that Si3N4 ceramics with micrometer/submicrometer grain size had a modulus of 250300 GPa, a hardness of 1416 GPa and a fracture toughness of 36 MPa m1/2.1,2 The frictional behavior of Si3N4 ceramics was assessed on the basis of the continuous measurement of the frictional force during the test duration. All the specimens exhibited an almost identical evolution of COF with time. The general observation was that COF increased to B0.5 during initial 100 s (runningin-period) and thereafter maintained a steady state. The average steady state COF varied from 0.43 to 0.57 in the investigated range of grain size (Fig. 3(A)). Thus, the inuence of grain size on the frictional behavior of Si3N4 ceramics appears to be minimal. The variation of the calculated wear rates of the developed Si3N4 ceramics is shown in Fig. 3(B). The experimentally determined wear rate varied in the range of 105104 mm3/N m and it decreased by an order of magnitude with decreasing grain size. Thus, a maximum wear rate of 9.7 105 mm3/N m was recorded for the specimen sintered at 17501C for 20 min and a minimum wear rate of 0.88 105 mm3/N m was estimated for the specimen sintered at 15501C for 5 min. The grain size dependence of wear rate (Hall Petch-type relation) could not be determined quantitatively in this study due to the elongated

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5 m (C) (D)

5 m

5 m (E)

5 m

1 m

5 m
Fig. 4. Scanning electron microscopic micrographs of worn surface for the specimens spark plasma sintered at (A) 15501C for 5 min, (B) 16001C for 5 min, (C) 16501C for 5 min, (D) 17001C for 10 min, and (E) 17501C for 20 min. Inset of (E) shows cylindrical debris particles.

grains, but it can be stated that the wear resistance of Si3N4 ceramics can be signicantly improved by reducing the grain size. The bimodal grain structure increased the fracture toughness of the ceramics, while it was not benecial to improve the wear resistance.10 The wear volume of balls was measured according to ASTM method33 and the estimated wear rates were found to decrease with increase in sintering temperature (not shown as gure). A maximum wear rate of 4 105 mm3/N m was obtained for the ball slid against specimen sintered at low temperature of 15501C, while a minimum wear rate of 0.5B1.0 105 mm3/N m was recorded when slid against specimen sintered at high temperatures of 1650117501C. In addition, the wear rates of Si2N2O-containing Si3N4 ceramics fabricated without CRT were two or three times higher than that of Si2N2O-free ceramics at the same sintering conditions (Fig. 3(B)). Thus, the elimination of Si2N2O phase was benecial in improving the wear resistance of Si3N4 ceramics probably due to the removal of the mechanically inferior phase and the reduction of stress from thermal mismatch with the surrounding matrix.21

The dominant mechanisms of material removal during sliding of Si2N2O phase-free Si3N4 ceramics were elucidated using SEM analysis of worn surfaces (Fig. 4). The worn surface of the specimen sintered at 15501C, consisting of equi-axed nanocrystalline grains, was mostly covered with several smooth layers (Fig. 4(A)). These layers were deformed and often contained microcracks. This was almost same in the specimen sintered at 16001C with increased smearing of the tribolayers (Fig. 4(B)). It is widely accepted that the wear of silicon nitride in moderate/ high humid conditions is essentially accompanied by the humidity-driven tribo-reaction to form the soft and friable layer of hydroxilated silicon oxide.1216,34 As the present study was also conducted in laboratory air with a relative humidity of 45%710%, it is reasonable to assume that the observed layers were also resultant of tribochemical reaction products. The removal of such layers (Figs. 4(A) and (B)) indicates the delamination35 for the specimens of equi-axed nano/ne silicon nitride. The microcracking in the tribochemical layer increased in the specimen sintered at 16501C (Fig. 4(C)), but a distinct

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change was observed in the appearance of worn surface when the sintering temperature was above 17001C. With the increased tendency of elongated bimodal grain morphology, the worn surfaces of specimens sintered at high temperatures exhibited extensive cracking and grain debonding/fracture (Figs. 4(D) and (E)), resulting in severe wear. The change in the worn surface characteristics was also in agreement with the estimated wear rate (Fig. 3(B)). Furthermore, the appearance of sub-surface was also visible with the severe wear of the contacting surface in the specimen sintered at 17501C (Fig. 4(E)). These characteristics primarily indicate mechanical fracture of the surface. On the other hand, the size and shape of the debris were varied, and the rolled needle-like debris particles of 115 mm length and 0.12 mm diameter were often found in a few portions of the wear track (inset of Fig. 4(E)). The formation of needle-like wear debris particles were considered as a consequence of tribochemical reactions at the interface of various ceramics (both oxides and non-oxides) when they were subjected to wear under humid atmosphere.13,16,36,37 Thus, there occurred a combination of both mechanisms of material removal, tribochemical and fracture with the difference in their extent of domination, similar to the observation of Fischer and Tomizawa.17 However, the absence of any coherent smooth layer in combination with the signicant presence of grain pull-out and fracture necessarily indicates that the mechanical fracture was dominant rather than tribochemical wear for the specimens sintered at 17001 and 17501C. This basically implies the possibility that fracture dominated wear resulted in a number of debris that were often rolled and further glued together by the probable reaction products, when silicon nitride of elongated bimodal grains was slid. Thus, there was a distinct transition of wear from the mild wear for the specimen of equi-axed nanograin morphology due to the delamination of tribochemical layer to the fracture-dominated severe wear for the specimen of large bimodal grain structure. The worn surface characteristics of the counterbody Si3N4 balls are shown in Fig. 5. The ball surface worn against SPS specimen sintered at 15501C revealed the pulled-out ne grain morphology (Fig. 5(A)). With increase in sintering temperature to 17501C, the ball surface showed reduced grain pull-out and compacted layer (Fig. 5(B)). Insets of Figs. 5(A) and (B) illustrate the smaller wear scar diameter on the ball worn against samples sintered at higher temperature, indicating that the wear of Si3N4 ball decreased with increasing sintering temperature. From the above results of wear rate and worn surface morphology of disks and balls, the important characteristics of interface that affects the wear behavior of silicon nitride can be now understood. In general, the wear rate of the silicon nitride disks increased (Fig. 3(B)) and wear rate of balls decreased with increase in sintering temperature (or grain size). The ne equi-axed microstructure with high hardness resulted in easy material removal from the ball counterbody (Fig. 5(A)). The pulled-out grains from ball surface were subjected to oxidation and/or transferred onto the disk surface during sliding. The frictional conditions lead to the compaction of third bodies to form a tribochemical layer at the interface. Thus, material removal occurs mainly by tribochemical wear during sliding of silicon nitride specimens sintered at low sintering temperatures (Figs. 4(A) and (B)). On the other hand, material removal of counterbody decreased (Fig. 5(B)), when specimens sintered at high temperatures were slid owing to their reduced hardness difference. Subsequent reduction of transferred material onto the disk surface decreased the tendency for tribochemical layer formation at the interface and the disk material was mainly removed by the mechanical fracture (Figs. 4(D) and (E)). The inuence of mechanical properties on the wear behavior can be discussed. The high sintering temperature resulted in the microstructure of elongated grains that improved the fracture toughness, owing to the greater tendency for crack bridging and deboning. It is generally reported that wear behavior is closely related to the fracture toughness of brittle materials. However, the results from the present study and other reported studies21,3840 indicate that for many ceramics and ceramic-based

250 m

20 m (B)

250 m

20 m
Fig. 5. Scanning electron microscopic micrographs of worn surface for Si3N4 ball worn against specimens spark plasma sintered at (A) 15501C for 5 min and (B) 17501C for 20 min. Insets of (A) and (B) illustrate the wear scars of the respective ball surfaces.

composites, it is the local short-crack toughness of the materials rather than the bulk or long-crack toughness that is important in determining the wear resistance. The specimens sintered at low temperatures resulted in the ne and equi-axed microstructure possessing slightly high hardness. Also, high surface area of debris resulted in the increased tendency toward tribochemical reactions that led to developing/maintaining the protective layers on surfaces of ceramics consisting of negrained structure.

IV. Conclusions
Powder mixture of b-Si3N46 wt% Y2O33 wt% Al2O3 and 10 wt.% phenolic resin was subjected to carbothermal reduction at 14501C for 10 h, followed by SPS with the sintering temperature ranging from 15501 to 17501C for 5B20 min. (1) Fully densied Si2N2O phase-free Si3N4 ceramics with a wide range of average grain size from 90 to 260 nm were fabricated. (2) Equi-axed nanocrystalline ceramics were obtained after plasma sintering at 15501C for 5 min, while a signicant change in microstructure to the bimodal grain morphology was developed with increasing sintering temperature to 17001 or 17501C. (3) When subjected to self-mated sliding in unlubricated conditions, it was found that the friction behavior was not inuenced by the microstructure, but wear rate varied in the range of 105104 mm3/N m. (4) A superior wear resistance was exhibited by the specimens of nano equi-axed microstructure, while large bimodal grain structure resulted in severe wear. The delamination of tribochemical layer dominated the wear of equi-axed nanocrystalline ceramics, while fracture and pull-out of large elongated grains resulted in high material removal.

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