Fracture Toughness and Thermal Shock Behavior of Silicon Nitride-Boron Nitride Ceramics

Ekkehard H. Lutz" and Michael V. Swain*

Department of Mechanical Engineering, IJniversity of Sydney, Sydney, New South Wales 2006, Australia
Fracture toughness behavior, stress-strain behavior, and flaw resistance of pressureless-sintered Si3N4-BN ceramics are investigated. The results are discussed with respect to the reported thermal shock behavior of these composites. Although the materials behave linear-elastic and exhibit no R-curve behavior, their flaw resistance is different from that of other linear-elastic materials. Whereas the critical thermal shock temperature difference (AT,) is enhanced by adding BN, the content of BN has no influence on the strength loss during severe thermal shocks. [Key words: silicon nitride, boron nitride, fracture toughness, thermal shock, strength.]

I. Introduction composite materials are attracting considerablc interest for a range of diverse applications such as components for automobiles to refractory nozzles, tubes, sliding gates, and break rings for the horizontal continuous casting of steel. The development of such advanced composites has taken place in the last decade although it has been known for a number of dccadcs that the addition of BN to TiBz composites greatly improves the thermal shock resistance for applications such as metal evaporator boats.' In addition, various authors have established that the thermal shock resistance of many materials increases with thc amount of BN added.2-' Microstructural observations of these composites have shown that the role of BN is to increase the amount of fine porosity as well as to enhance microcracking.' The highly anisotropic fracture behavior of the hcxagonal-structured BN flakes, due to the easy cleavage perpendicular to thc c-axis, assists in the formation of microcracks. Excellent examples of such microcracking in a range of BN-containing composites has been presentcd by Sinclair and S i r n m o n ~These authors .~ show that BN cleaves along parallcl planes of thickness down to 0.05 p m , enabling significant dilatant strain to develop within the material. Sinclair and Simmons4 point out that this is due to the large coefficient of thermal expansion ( a ) anisotropy of the BN grains, with a = 40 x lO-'"C-' parallel to the c-axis and <lO-'"C-' perpendicular to the c-axis. The large thermal strains developed upon cooling such a polycrystallinc material are largely accommodated by microcracking of thc BN grains. Such precxisting microcracks also explain the relatively low elastic modulus ( E ) of composite matcrials containing hexagonal BN grains. Traditionally the poor sinterability of BN has meant that hot-pressing techniques had to be used to densify such com-

ILICON NITRIDE-BOKON N I T R I D E (Si,N,-BN)

posites. However, recently a number of groups have overcome this problcm by the blcnding of superfine BN and the addition of liquid-phase sintering aids. These groups have been ablc to densify such composites by pressureless or low-gas-pressure ( 51 MPa) sintering. This fabrication route enablcs more complex practical-shaped objects to be economically produccd. Thermal shock observations of pressurcless-sintcrcd Si3N4BN composites made by a number of groups show very significantly enhanced thcrmal shock temperature diffcrencc (AT,) after strength degradation from plunging heatcd specimens into water.' The results also show that, for AT > AT, up to 900"C, the retained strength of Si3N4materials containing 30 to 40 vol% BN is much higher than thc rctaincd strength of those with only 10 and 20 vol% BN. This might indicate that thc AT, and retaincd strength of Si3N4 is improvcd by adding BN. Detailed fracture mechanics approaches to thermal shock degradation have been proposcd by a number of a ~ t h o r s . ~ . ~ These approachcs arc based upon the application of linearelastic behavior of the material and a critical stress-intensity factor (Kr,)for dcciding about unstable crack propagation and arrest. However, it is well-known that most ceramic materials that exhibit exceptional thcrmal shock resistance exhibit nonlinear stress-strain behavior and a pronounced incrcase in fracture toughness upon crack propagation, i.c., R-curve T h e influence of the R-curve of a matcrial on the flaw damage and rcsultant strength degradation was considered in detail by Cook el ~ f . " and~ Chantikul et al. " for the specific ~ ' case of pointed indentation. These authors found that the cxtent of strength dcgradation was strongly influenced by the microstructure which in turn dctermined the R-curve behavior. They investigatcd a range of AlzOi ceramics varying from single crystals through fine- to coarscr-grained materials. As the grain size increased, the initial strength decreascd. However, increased indentation loads led to a higher rctaincd strength for the coarscr-grained materials for indentation loads exceeding 100 N. The purpose of this paper is to investigate strcss-strain behavior, R-curve bchavior, and flaw rcsistance of prcssurclesssintered Si3N4-BN composites. The results will be used to prcdict the thcrmal shock strength dcgradation of thesc materials for very high AT, >900"C. The anticipated rctained strength will b e compared with t h c measurcd rctaincd strength obtained after a quench test in water which will be conducted for AT = 1200C.
11. Experimental Procedure

K.T. Fdber-contributing

editoi

Manuscript No. 197044. Received December 28, IYYO; approved August

19, 1991,

The work of H. E. Lutz was supported by Deutsche Forschungsgemeinschaft, Bonn, FKG, under Contract No. Iu 416/1-1. *Member, American Ceramic Society.

The tcsts were conductcd on pressureless-sintered Si3N, composites containing 10, 20, 30, and 40 wt% BN (Kawasaki Steel, Tokyo, Japan). Fabrication condition, microstructure, and mechanical propcrties of thcse materials are dcscribed in detail by Isomura et af.' To avoid complicated and long descriptions Si3N4plus 10, 20, 30, and 40 voM BN will be labeled SNBIO, SNB20, SNB30, and SNB40, respectively.
67

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Vol. 75, No. 1

The KR-curve cxperimcnts wcre performed using compact tension (CT) tests. The C T samples had thc dimensions 25 to 27 mm x 32 mm x 5.2 to 6.2 mm. Onc sidc of each test piece was polished. The samples werc prccracked by starting the cracks from a chevronlike prenotch. Whcn sharp, straightthrough cracks werc achieved, the specimens wcrc renotchcd to a point as near as possible behind thc crack fronts. The notch depth: sample width ratio (a,,: w) was choscn to be 0.51 to 0.61. The samples were loaded using a crosshead specd of 10 pm/min. Thc crack propagation was measured directly using a traveling microscopc. The K R - v -I ues wcre calculated on 'I thc basis of the load ( P ) , the rclative crack length (a/w), thc sample thickness (b),and the appropriate Y-function, namclyI4 P K H = Y(a/w)bw' ' for a/w
5

The flaw resistance, KR-curvebehavior, and thermal shock behavior are shown in Fig. 2. The logarithm of the retained strength of as-indented specimens is plotted vcrsus the logarithm of the indentation load (Fig. 2(A)). All materials show a similar behavior. T h c strength rcduction is quite low for indentation loads up to 100 N, but is apparently more pronounced for higher loads with a final slope of the curves closer to the anticipated value of - 1/3. All SNB composites cxhibit flat KR-curves with their toughness decrcasing with increasing BN content (Fig. 2(B)). A thermal shock of AT = 1200C into water at room tcmperature rcsults in a strength loss of 56% to 66% (Fig. 2(C)). The rctaincd strcngth of the SNB ceramics subjected to such sevcre thermal shock declines in proportion to their initial strength as the BN content increases (Table I).
IV. Discussion

0.85 with [0.886

2 + a/w Y(a/w) = (1 - a/w)'

+ 4 . 6 4 ~ /-~ 1 3 . 3 2 ( ~ / ~ ) '
(2)

+ 1 4 . 7 2 ( ~ / ~ -' S.~(U/W)'] )

Stress-strain tests werc performed in three-point bending (span of 29.5/7.9 mm) using beams with dimensions of 5.2 to 6.2 mm x 2.5 to 3.1 mm x 32 mm. Thc strain was measured by strain gauges attached to the tensile surface of the samples. The flaw resistancc tests werc conducted on beams of the above dimensions using the indentation-strength-in-bending (ISB) method." One side of each sample was indented using various loads between 10 and 1000 N. The rctained strength was measured in four-point bending (span of 18/6 mm). Some additional thermal shock tcsts wcre conducted to complement thc manufacturers reported data by mcasuring the rctained bcnding strcngth after quenching samplcs from 1220C into 20C water.
111.

Results

The stress-strain behavior of the Si7N4-BN materials is illustrated in Fig. l. All materials exhibit an almost ideal linear elastic behavior with a small deviation prior to failure. From the linear portion of such curves thc elastic modulus is dctcrmined and found to agree with dynamic resonancc measurements of the E modulus as listcd in Tablc 1.

Thc results obtained in this study confirm and extend the obscrvations of Isomura et al.' It has becn shown that the elastic modulus and strcngth follow the same trend as previously reported. Estimates of the elastic modulus from straingauged-flcxurc and dynamic-resonancc methods are in good agrcemcnt. However, this work shows that the stress-strain curve is almost lincar to failure with thc inelastic component of thc strain at failure accounting to less than 0.01%. The material behaves very differently from othcr extremely thermal shock resistant materials. Very large differences in the fracture toughness are determined depending on thc techniquc of measurement. The more rcliablc C T technique gives almost constant valucs over crack extcnsions of 6 to 7 mm of stable crack extension. Again it had becn anticipated that some R-curvc behavior may have been observed duc to possible crack-tip shielding effects such as microcracking or crack-tip bridging. The present observations suggcst that if there is an R-curve present then its range is very small (5100 pm). Thc fracture toughness as measured by thc C T technique decreascs almost linearly with thc E modulus. In addition, both K Rand E , and thc energy release rate, G = K:,/[E(l - v2)], dccreasc almost linearly with increasing porosity of thc SNB mixtures (Tablc I). The fracture toughness measured by the retained strength (alt) after indentation with different loads ( P I )can be interprettcd as exhibiting R-curve behavior. For the failure of a brittle material from a mcchanically introduced flaw of sizc c under uniform applied stress a'!,the net stress-intensity factor is the sum of K , and K,, the components for uniform applied strcss and for localizcd loading, namely, K = xP,/c'\' + $gdc"2

(3)

where x = [ ( E / H ) ' " (Refs. 15 and 16) is a numerical constant depending on the contact geornctry and the elasticiplastic propertics of the material, and [ is a material-indcpendent constant for Vickers-produced radial cracks. $ is a numerical crack gcometry parametcr (e.g., T I ' * for an embedded linear crack and 2/7r'" for an embedded circular crack). An expression for the ISB toughness can be dcrived from Eq. (3) in the formI7

Hence, the retained strength ( ceramics in gcneral obeys the law

( T ~ P=' constant ~
0

of brittle non-R-curve
(5)

0.05

0.1

0.15

Strain, %
Fig. 1.
Stress-strain behavior of S N B ceramics.

The toughness value obtained from ISB tests using Eq. (4) is, in other words, constant and independent of the indentation load. A plot of log (rl( vs log P, should give a straight line cxhibiting the characteristic slope of -1/3. The flaw resistance curves in Fig. 2 are, however, significantly flatter.

January 1992

Fructure Toughness and Thermal Shock Behavior of SiiN,-BN Cerarnic.s

Table I.
Pruperty

69

Properties of Si3N4-BN Materials

SNBIO
SNB2O
L

SN B30

SNL340

Porosity (95) Poisson's ratio, v Thermal expansion coefficient, a ( ~ 1 0"C') - ~ E-modulus (GPa)" Toughncss, K R (MPa. m1'2) Bending strength, u n(MPa) 2(c/br)'!i2=K R / u B(ml'?) G = K /[E(1 - v) (J/m') '] R' = c ~ e ( l- v2)/Ea ('C) Critical temperature diffcrence, AT, ("C) Retained strength for AT = 1200C (MPa) "Iwrnura el u l '

0.21" 3.4" 127/150* 2.4 212/360* 0.01 1 47 470/550" 650" 72

18"

26" 0.18" 3.2" 60/58.9 " 1.2 89/200" 0.013 25 450/850* 700" 39

34" 0.13" 3.1" 42134.1 * 0.9 64/90* 0.014 20 48O/1120* KO0* 26

3x* 0.13" 2.7" 23/ 17.1 " 0.55 48/70" 0.01 1

13

76011280" 850%
19

Assuming that K,, equals the average KR-curvevalue, it is possible to calculate thc anticipated flaw resistancc curves for the SNB materials on the basis of Eq. (4). The resulting theoretical curves with slopc -1/3 are shown in Fig. 2(A) as dotted lines. It is apparent that, indepcndcnt of the used indentation load, KI, obtained by the ISB method greatly overestimates the measured KR-curve. A possible explanation for this significant difference may be the reduction in residual strcss about the indentation impression due to thc porosity and, hence. a reduction of x. Upon indentation the region beneath the contact area is expectcd to dcnsify. An SEM observation of the deformation zone beneath a 100-kg indentation

300

i1 0

20
1

100

I000

i
'

P. N

in the SNB20 material is shown in Fig. 3. In general, it is difficult to detect cracks in thesc porous materials and to determinc thcir length. It seems, however, that no well-defined radial cracks have developed from the corncrs of thc impression shown in Fig. 3; rathcr, the size of the cracks only extends slightly beyond thc densified rcgion, from which thc sample has fracturcd. Assuming that thc crack length equals half of the impression diameter, which is 1.0 mm, the calculation of K,,using only the component K , in Eq. (3) with $ = 2/7r'" gives exactly the KH-value of 1.2 MPa.m". This can may indicatc that the contribution of K , to KI, be almost neglectcd in these matcrials. However, it seems likely that the Q term in Eq. (3) is affected by the porosity. Iwasa and Kakiuchi,Ix using thc controlled surface flaw tcchniquc as proposed by Fctrovic et ul." with a 5-kg load Knoop indenter, report K,, values of -5 MPa . rnl" with 20 and 30 vol% BN. Such values are much higher than those measurcd here, and the possible cause of this discrepancy may be due to the difficulty in measuring the initial flaw size. However, thc values reported by lwasa and Kakiuchi" may well be higher because the size of the BN grains that they used was much larger than in this present study, and the samplcs wcre hot-pressed, generating a strong texture in the material. T h e finer-grained and more equiaxed BN grains and more isotropic propcrties associated with pressureless sintcring arc likely to produce materials of lower toughness and absence of R-curve behavior, but highcr strength. Of particular interest in this work i the thcrrnal shock bcs havior of SNB composites. As shown prcviously by Isomura er al., it is possible to prcdict reasonably well the increasc in AT, with increasing BN content on the basis of strength V H , E-modulus, and thermal expansion coefficient ( a )by R ' = ~ e ( - .)/ECY = (1/2)(~/c)"~Kl~(l l - v2)/Ea
(6)

a, mrn

I, 0 'c-

0.8 0.6 0.L 0.2 A

SNB LO

Fig. 2. (A) Flaw resistance, (B) KR-curve behavior, and (C) thermal shock behavior of SNB composites. Broken lines in (A) are thS; anticipated response for t h e various SNB materials using the K data in Table I and Eq. (4). Basis for the overestimation of K,, by using the ISB technique is discussed in the text.

Fig. 3. Vickers indentation of 100-kg load in SNB20. No cracks are observed having developed around the impression.

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Vol. 74, No. 12

For materials such as these that behavc almost clastically and do not exhibit R-curve behavior, it is possible to usc such a simple estirnatc. Since Tablc I shows that K / c L , is almost equal for all S N B composites, both, K R and (rR can bc used for the estimate. The estimation gives lower valucs than thosc calculated by Isomura et a/. but confirms the increasing AT, values with increasing BN content. A comparison of the cstimated values in this work with thc AT, values measured by Isomura et al. shows that AT, has been, in general, undcrestimated. This may indicatc that Eq. (6) is suitable only for qualitative predictions.

V. Conclusion
Pressurcless-sintcrcd Si3N4-BN ceramic composites exhibit increasing porosity and decrcasing strength and Youngs modulus as the BN content increases. Whereas the critical therma1 shock temperature diffcrencc (AT,) is enhanced by adding BN, the contcnt of BN has no influence on the strength loss during severe thermal shocks and strcss-strain and R-curve behavior. All tested materials behave linear-elastically and cxhibit flat R-curves. However, their indentation flaw resistance behavior is uncharacteristic for linear-elastic matcrials which show no R-curve behavior.
Acknowledgment: The authors
t h a n k Kawasaki Stccl. Tokyo, Japan. for its assistance in supplying the matcrials used in this study.

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