International Journal of Fracture 59: 361-375, 1993. ~ 1993 K luwer Academic Publishers. Printed in the Netherlands. 361 Nonsingular toughening and R-curve behavior in nominally pure alumina G.B. MAY, 1 K.E. PERRY, 2 J.L. SHULL, 3 J.S. EPSTEIN, 4 H. OKADA, 5 C. SCOTT 6 and S.N. ATLURI 7 Department of Mechanical Engineering. University of Washington, Seattle, WA 98195 USA; ZDepartment of Process and Mechanical Engineering, University of Strathclyde, Strathclyde G1 1X J, Scotland, UK; 3Department of Materials Science, University of Illinois, Urbana-Champaign, IL 61801, USA; 4Fracture Behavior Section, Idaho National Engineering Laboratory, Idaho Falls, P.O. Box 1625. Idaho 83415-2218 USA; SVehicle Research Lab., Nissan Motor Co., I, Natsushima-cho, Yokuska, 237, Japan; 6Lighting Products Div., General Electric Corp., Cleveland, Ohio 44112, USA; 7Computational Modelling and Infrastructure Rehabilitation Center, Georgia Institute of Technology, Atlanta, Georgia 30332-0356 USA. Received 10 December 1991; accepted in revised form 25 September 1992 Abstract. Moire interferometry is employed to study toughening in medium to large grain size nominally pure alumina. The fracture scale length, which is characterized by the grain size of the alumina, is systematically varied from 35 to 102 p,m. R curves are derived from bulk mode I compliance calculations for the differing grain sizes and from the near tip moire fringes. The level of material toughening that arises from the nonsingular processes of crack bridging and grain boundary friction are found by comparing the bulk and near tip moire R curves. 1. Introduction R curve testing is well established in the metallic fracture community [1] for plane stress fracture. For metals, the principal mechanism of energy dissipation is dislocation damage. For monolithic non-transforming ceramics, the mechanisms of subcritical crack growth or R curve behavior are known to be sensitive to size scale(s) local to the crack tip [2, 3, 4, 5, 6, 7, 8, 9]. In particular, grain bridging, microcracking, and crack deflection and accompanying friction processes operate on a local scale to affect the overall R curve behavior of the ceramic. However, the above reports infer the local toughening mechanisms from bulk sample measurements with some qualitative microscopic studies. We wish to report in detail our recent experimental findings regarding the explicit toughening mechanisms that account, for in some instances, the bulk rising R curve behavior in alumina [5, 6, 7, 8, 9]. Pursuant to this goal, we have employed a unique high compliance, low load capacity, miniature load frame to obtain bulk compliance R curves via direct pin loading of the alumina samples. During the same experiment we have also employed high sensitivity moire interferometry local to the growing crack tip in order to obtain directly the energy to fracture that the crack tip by itself experiences. In order to study the effect of grain size as a controlling size scale on the overall R curve behavior, we have carefully fabricated heats of nominally pure alumina with 35, 47, 60, 74, 75 and 102 micron grain sizes. For the differing alumina grain sizes, we will compare the two measurements, moire displacement derived and bulk compliance derived energies of fracture, with micrographs of the growing crack, to infer the explicit mechanisms of toughening in nominally pure medium to large grained alumina. 362 G.B. M a y et al. 2. Materials The nominally pure A1203 under study is produced by General Electric under the brand name Lucalox. This material is doped with ~ 500ppm of MgO as a grain stabilizer. Other impurities from the raw alum-derived powder, such as potassium and calcium, are boiled out of the material during sintering in a dry hydrogen environment between 1870 and 1890°C. The chemical analysis of the pre-sintered product is given in Table I using Inductively Coupled Plasma (ICP) Spectroscopy Analysis. The raw material is extruded and sintered to 12mm square bar stock of variable length. Single-pass sintering for 3 to 4 h produces a uniform grain structure with grains in the 30 ~tm size range. Figure 1 is a micrograph of Lucalox from a Table I. Impurity analysis and concentration for pre-sintered Lucalox via inductively coupled plasma spectroscopy analysis Element ppm* B 2.0--3.0 ND-4.0 1.0-4.0 70.0 0.6 ND-2.0 30.0 52.0 ND-2.0 1.0 500t Ca Fe K Li Mn Na Si V Zr MgO * p p m = parts per million. N D = not detectable. t Un-sintered state but is boiled off after 15 successive firings 200 ppm. Fig. 1. Thermally etched Lucalox, 200X. Nonsingular toughening and R-curve behavior 363 single sintering pass that has been thermally etched at 1600°C for 4 h in argon. To obtain grain sizes ranging from 35 to 102 ~m, samples were given 1, 3, 5, 7, 9, or 15 sintering passes; measured grain sizes are given in Table II. ICP was not performed on the final sintered product. Figure 2 is a white light transmission micrograph of the 15-pass Lucalox. The fine traces in Table II. The spatial distribution of microcrack density surrounding the grown crack Specimen Grain size (microns) Microcrack densities 1 Pass 35.6 0.088 0.092 0.088 Tip Wake Far 3 Pass 47.6 0.122 0.119 0.095 Tip Wake Far 5 Pass 60.9 0.136 0.148 0.122 Tip Wake Far 7 Pass 74.0 0.197 0.199 0.166 Tip Wake Far 9 Pass 75.7 0.202 0.190 0.144 Tip Wake Far 15 Pass 102.4 0.291 0.322 0.308 Tip Wake Far Fig. 2. White light transmission micrograph of 100 micron grain size Lucalox detailing microcracks, 500X. 364 G.B. May et al. Fig. 2 show the grain boundary triple point microcracks. The range of processing-induced microcrack density versus grain size may be obtained using the microcrack density approximation given by [10] 37~ - 16E(k)K(k)M(12), (1) where M is the number of crack traces in a 2-D micrograph, (I) is the average microcrack trace size (in this case the assumed grain facet length), E(k) is the complete elliptic integral of the second kind, and K(k) is the complete elliptic integral of the first kind. The as processed microcrack densities are the far field values in Table II. These microcrack densities were obtained by imposing a microscope focal plane grid divided into 5 x 5 squares at 500X over the near tip, wake, and far field regions, then counting the number of traces in the grid, and averaging over 20 readings in each area E11]. The 5 x 5 grid corresponds to an overall region of 244 ~tm x 244 tam directly on the specimen. In theory, according to (1), the microcrack density will level out at a saturation density of ~ or 0.56. Using a 5 MHz transducer in pulse echo mode [12], on the 12mm square sintered bar stock, Young's modulus was determined to be 4 0 G P a and Poisson's ratio 0.23. In theory, Young's modulus should vary with microcrack density; however, the 5 M H z transducer's wavelength within the Lucalox was greater than the microcrack sizes (1(~100 p.m) and hence not affected by the microcrack density variation. Hence only bulk properties were measured. 3. Experimental design The experimental design emphasized two critical aspects, (i) a specimen configuration that would be two dimensional in the damage distribution (minimal thickness effects on crack growth) and (ii) controlled loading and diagnostics. Each aspect will be discussed separately. 3.1. Specimen design The specimen design chosen was a double cantilever beam (DCB) geometry with a width to thickness ratio approximating generalized plane stress for the specimen overall but not necessarily for the local crack tip fields. The specimen dimensions are given in Fig. 3. The overall specimen dimensions were selected by optimizing the far field asymptotic crack terms to produce straight crack growth [13]. The double cantilever beam geometry measures the effect of crack growth in the presence of a rear tip microcrack or frictional wake zone due to the preexisting crack, unlike the typical bend test which measures only initiation toughness [14]. A crack was introduced into the specimen in three stages. First, a large, 5 mm diameter, rounded diamond saw cut was made to produce the pin contact region. A second cut by a Nonsingular toughening and R-curve behavior -I "- C A BI Th°rme, C eck 365 Specimen Thickness : E All Dimensions In mm Crossed Diffraction Grating 1200 Ymm Lucalox A 19.0 R C 1 0 . 1 7.6 D 12.7 E 2.0 Fig. 3. The double cantilever beam geometry for the Lucalox. vee-sharpened 0.7 mm thick diamond saw extended the notch further into the sample. Finally, a thermal crack was introduced using a mini torch and an acoustic emission transducer to monitor initiation. The thermal crack length was measured using transmissive white light. The crack typically extended 50 lam from the vee notch. The samples were polished in successive stages to a 1 lam finish. 3.2. Specimen loading and diagnostics Rather than the traditional wedge opening technique for high compliance crack loading, the crack mouth was opened by two contacting inner load pins (0.8 mm diameter) connected to the load train so that the loads could be measured directly. This method is in contrast to the wedge loading which produces friction at the wedge/crack mouth contact region, invalidating any load measurement. The load frame is shown in Fig. 4. The outer frame was machined from a single piece of aluminum stock. The crack mouth opening was fixeddisplacement and controlled by a differential micrometer with a resolution of 0.2 p.m. The actual load was monitored by a calibration bar of aluminum in the load train with a capacitance transducer (Capacitec model HPB-75 transducer and 4100S amplifier/clock) to monitor gage length separation. The load transducer sensitivity was 100 g. This form of load transducer does not sacrifice critical overall frame stiffness as does a typical low load transducer, which consists of a flexible bar with a strain gage. A 450 kHz resonant transducer was fixed behind the specimen opposite the crack. The acoustic emission (A/E) activity was monitored on a 500 MHz bandwidth scope, permitting feedback to the load operator for control of stable crack growth. Straight cracks were grown stably in excess of 5 mm in the sample (1-2 mm thick) using this combination of frame and acoustic emission. Finally, 12001/mm crossed diffraction gratings were applied directly to the specimen surface in the region where crack growth was expected. A three-mirror system [15] was employed with a multiplication of 2 for an in-plane displacement sensitivity of 0.4 ~tm. Both X and Y displacement fields were recorded on 100 × 125 mm Kodak TMAX 400 ASA film at 514 nm, 0.25 W illumination with a ~ second shutter speed. Displacement moire interferograms were taken after the crack growth had been arrested by reducing the load until all A/E activity ceased. 366 G.B. May et al. J~. 40 crn I Coarse Adjt Load Screw Micrometer Load Screw Fi,q. 4. The single piece load frame. 4. Data reduction The energy to fracture as a function of crack growth was obtained by two methods. The first method used bulk mode I compliance calculations for the DCB specimen [16]. The DCB specimen employed used a three-stage sl,3: and not a single slot of one thickness as found in Tada [16]. A boundary element analysis performed for the actual specimen yielded a K differing from [16] by 6 percent overall. The second method employed fitted the moire fringes with an assumed L E F M mixed mode displacement field. The method was first used by Barker [17] for mode I loading. An extension to mixed mode fields was given by Chona [18]. Because the displacement field is inherently mixed mode (due to grain boundary deflection), the method was developed in full for this work. The local L E F M mixed mode eigenfunction expansion is given as U,(r, O) :- [KIFI(O) + KnH,(O)]r½ + ~ [A,F,(O) + BnHn(O)]r2, (2) n=2 where i = 1, 2 for the X(U) and Y(V) displacements respectively. The crack tip moire field is given as Ui(r, 0). One then simply performs a least squares fit to the right hand expansion, adding terms until the rms error decreases and the values of K~ and K , stabilize. The fit is over deterministic as more data points are collected than unknowns. It is noted that our digitizing procedure utilized the entire frontal moire region which is basically a square starting at the crack tip and extending out to the free specimen boundaries and hence is influenced by the overall plane stress crack tip solution which was utilized in (2). Nonsingular toughening and R-curve behavior 367 5. Results The Lucalox K~c, measured as a function of the fracture energy versus grain size, is plotted in Fig. 5. This K~c variation as a function of grain size has also been shown by Evans et al. [14] and is attributed to the hexagonal close pack structure of the alumina, which yields high anisotropy and residual stresses at the grain boundaries. Figure 5 shows that the fracture size scale is controlled by the grain size. A critical aspect of microcracking theories is that upon unloading residual strains exist [4, 14] near the traction free boundary of the crack due to volume expansion effects and the inherent residual stresses at the grain boundaries (Fig. 6). If this residual strain effect exists, there should be a gradation of microcracking density around the crack as shown in Fig. 7. Table II gives the spatial variation of microcrack density as a function of the grain size for the Lucalox specimens tested. Interestingly, the microcrack density does not fully saturate to the value of 9 . Figure 8 shows the Y displacement field for an elastic traction-free crack with no residual stresses at the crack faces. The traction free face characteristics manifest themselves in that the Y fringes ++ 4 KIC (MPa (rn)112) 0 + + 3 [ " 20 I + • ,,i 40 , 60 , , I I S0 100 J i 120 Grain Size, Microns Fi9. 5. The variation of K with grain size for the Lucalox. Microcrack Saturated Stress / / Unloading / P "---] Residual 'Strain Fig. 6. Hysteresis generated by microcracking, Fig. 7. Predicted microcracking densification at a crack tip, The theoretical saturation limit is ~ . 368 G.B. M a y et al. I I J GratingDirecUon,0.4 micronsper Y fringe I Steel ' I Y X I 50 mm Fig. 8. Linear elastic Y field displacement fringes. approach the crack face at 90°. The perpendicular nature of the Y fringes at the crack face indicate that the derivative of the Y fringes, in the Y direction, yield no strain and hence no Y stress consistent with the traction free crack face. Figures 9a and b show the displacement fields for the 35 and 47 ~tm grain size samples. The Y displacement field in this case approaches the crack face with a strong gradient unlike Fig. 8. This strong shear gradient of the Y displacement ResidualDisplacement~ ' (a) ffl GratingDirection, 0.4 micronsper Y fringe Y f Figs. 9. Y displacement fields for the (a) 35. (b) 47, (c) 74 and (d) 102 lam grain size Lucalox. Nonsingular toughening and R-curve behavior 369 fringes reveals compressive residual stresses approaching the crack face for the 35 I.tm grains (Fig. 9a). Figure 9a contains an added frequency mismatch to improve the spatial resolution [153. Figures 9c and d show the moire Y field for the 74 and 102 gm grain size Lucalox. In both cases, no residual wake effect is evident. However, highly local mixed mode effects at the crack tip are revealed by the asymmetry of the crack tip Y displacement field in that the fringes on either side of the crack face do not meet. This local mixed mode effect in a bulk mode I test is due to crack deflection at the grain boundaries, which are inherently weak [14] from the thermal mis-match and grain anisotropy at this large grain size. Micrographs of the 35, 47 and 75 gm grain size Lucalox after thermal etching (Figs. 10a, b and c) show the deflection and bridging. At the 102 gm grain size, the boundaries were so weak that the grains literally pulled out. Figure 11 gives the bulk R curve data of the Lucalox samples as a function of grain size. Figures 12a-e show the moire data R curves versus the bulk values. It should be noted that total energy (plane stress) is plotted (K~ + K~). Figures 13a and b detail the moire derived K1 and K2 R curves for the 60 and 102 gm grain size Lucalox. The Kn in Figs. 13a and b is on the order of 10 percent due to crack deflection at grain boundaries. As expected, the moire extracted energy value is considerably lower than that of the bulk and more consistent with the intrinsic fracture toughness without rear tip bridging or friction. The bulk R curve reflects the cumulative effect of the crack bridging and friction, which increases with crack length. Figs. lOa, b and c. Transmission micrographs of the 35, 47 and 74 gm grain Lucalox, 400X. 370 G.B. M a y et al. Figs. lOa, b and c.--contd. Nonsingular toughenin9 and R-curve behavior I0 r,O M h:&roll 47 Mic#pn 74 Micron • *" 371 O A M ~ 8 O ~, A~, ~ £ O • 6 ~4 0 0 .... *I • ..:, .¢ A3s Micron • eee 102 Micron i .... i .... i .... i .... i .... 0 I 2 3 4 An ( r a m ) Fig. 11. R curve behavior of the Lucalox as a function of grain compliance size from measurement. 120 30 0 • G (Jim 2) Compliance O (Jim2) Moire O • 25 G (Jim 2) ComplhlnC! O (Jim 2) Moire IO0 I 0 0 80 20 O O rl • E •A 0 D D r~ m c3 [] 60 • t~ (3 [] O L"I rl 47 mlcton Alumlnl 40 20 3$MlcronAlumlnl , j , , i .... i .... 0,5 i .... I i .... 1,5 t .... 2 , , i • 2.5 l . . . . I . . . . ! 0.5 I . . . . J 1.S . . . . I 2 A a (ram) . . . . 2.5 I . . . . 3 | l i i i 3.5 Aa ( r a m ) Fig. 12a. The local and bulk R curves for the 35 ~tm grain size alumina. Fig. 12b. The local versus bulk R curves for the 47 lain grain size alumina. 100 13 • 120 D • O (J/m:) ColnplJance G (J/m2) Moire G (J/m:1) Moire G (J/m 3) Compliance IOO ++ 6O II0 (3 O o 13 11 4o o 0 0 60 Mlcro+1 Alllllrllrll 0 4o O 0 n 20 2o I 0 . . . . l o.s . . . . l I . . . . I . . . . I l~Sa ( m m )2 . . . . I 2.5 . . . . I 3 • i i . . . . I :),s J . . . . i t 2 . . . , I 3 ?4 MJC;'OrlAIundnll . . . . 1 . . . . 4 ~a I m m l Fig. 12c. The local and bulk R curves for the 60 !am grain size alumina. Fig. 12d. The local and bulk R curves for the 74 pm grain size alumina. G.B. M a y et al. 372 25 rl O (J/hi l ) Compliance O (J/m ;/) Moire 20 15 O •o D Q lO 13 D 102 Micron Alumina . , , i . . . . 03 I I . . . . i . . . . 1 .S I . . . . 2 ~a ( r a m ) i . . . . i 2,5 . . . . 3 n . . , , 3.5 Fig. 12e. The local and bulk R curves for the 102 lam grain size alumina. • • • • KI K2 4" 4 60 M i c r o n Moire K 1 lind K 2 =f 3.5. 3.5- 3" 3- 2.5- 2.S- I.S" I.S, KI Ki :102 MIcron kto~l K I and Klt o o 1- o o ILS0 0,S~ o :::::::::::::::::::::::::::::::::: O.S 1 los 2 2.5 0,::: 3 0.5 3,S Aa(mm) Fig. 13a. The moire derived K~ and K, R curve for the 60 lam grain Lucalox. ::::I::::I::::: 1 1.5 ..... 2 ::::,::::' 2.5 3 I:::: 3.5 Aa(mm) Fig. 13b. The moire derived K~ and KII R curve for the 102 ~tm grain Lucalox. 6. Discussion 6.1. Load frame effects The micrographs in Fig. 10 showed extensive crack deflection and friction between the deflected crack path(s). We did not find any evidence of intact crack bridges behind the tip, even for the 47 to 74 lam range where the rising R curve usually is attributed to this effect [8]. We attribute this lack of intact bridging to two features of our experiment, (i) very thin samples, 10 to 30 grains thick depending on the grain size, which ensured through - thickness crack growth, and (ii) a loading system that was extremely sensitive i.e. using a differential micrometer for opening the crack combined with an acoustic emission feedback to the load operator to control the rate of loading or unloading. Nonsingular toughening and R-curve behavior 373 One could increase the load and hear A/E without seeing any crack growth in the moire interferograms (under a magnification of 40). Thus, when the crack was observed to grow in the interferograms, we were assured that the crack front was through the entire specimen thickness. As the crack advanced, as observed in the moire interferograms, or when the A/E activity occurred at a higher rate, the load was decreased until the A/E ceased entirely. This was the load at which K was obtained for the R curve. 6.2. Bulk R curves Three classes of bulk R curves are shown in Fig. 11. The R curve for the 35 jam grains, the R curves for the 47-74 jam grains and finally the R curve for the 102 jam grains. Each will be discussed separately. For the 35 jam grain size, Fig. 11 shows that the R curve stabilizes and correspondingly a wake or residual compressive zone is evident in the moire displacement fields (Fig. 9a). The wake zone or residual stress zone height of Fig. 9a does not change during steady state growth, nor is there any indication of microcracking change from Table II. This constant zone height in Fig. 9a corresponds to the stabilized portion of the R curve in Fig. 11. The stable R curve and constant wake zone height are analogous to a plane stress test for metals where the R curve levels with the steady state plastic zone height during propagation. Between 47 and 74 jam grain sizes as shown in Table II indicate that microcracking occurs but not up to the theoretical density of ~ . It should be noted that in counting microcrack density some error may be present in distinguishing between a grain boundary triple point microcrack and spurious grain cracking from rear tip bridging. A continuum damage wake zone is not dominant in the corresponding moire displacements (Figs. 9b and c). An important added effect is that crack deflection does become dominant as evidenced in the moire interferograms (Figs. 9b and c) and the micrographs (Figs. 10b and c). This deflection causes non-steady state friction and local mixed mode shear behavior which is evidenced in the asymmetry of the interferograms (Figs. 9b and c). The result is that the toughening mechanism is discrete in nature and not steady state. The R curve for this class of grain sizes in Fig. 11 does not stabilize. At the 102 jam grain size, microcracking occurs extensively due to the residual stress weakened grain boundaries, Table II. The 102 jam R curve of Fig. 11 does stabilize but at a lower value than the R curve for the 35 jam grain size Lucalox. The stabilization occurs because the extremely weak grain boundaries 1-14] open fully, minimizing contact friction between the deflected crack faces. 6.3. Moire R curves Interestingly in Fig. 11 where the bulk R curves stabilize at 35 and 102 jam, the moire obtained energy to fracture falls within the bulk data (Figs. 12a and e). (It should be noted that if all the curves were plotted together the overall scatter would be small; however, for clarity these curves have each been plotted separately.) For 35 p.m (Fig. 12a) this implies that bulk toughening from ligament bridging and grain friction are not dominant - the near tip intrinsic toughness values are close to the bulk. For the 102 jam grain size (Fig. 12e), the near tip values again fall within scatter of the bulk. At 102 jam, residual stresses have weakened the boundaries 1-14] so that they separate easily. 374 G.B. May et al. For the intermediate values, 47 to 74 jam (Figs. 12b-d), the moire energy values are essentially level and on the order of the initiation toughness of the single grain. As the moire data was digitized ahead of the crack tip, the rear tip mechanisms of grain boundary friction and ligament bridging which accounts for a large percentage of the energy dissipated during growth are not accounted for in the local K solution, (2). 7. Conclusions Moire interferometry has been used to delineate, quantitatively through the comparison of the moire and bulk R curve data, the amount of toughening in medium to large grain size alumina due to crack bridging and grain boundary frictional sliding. Microcrack toughening does not necessarily operate for these grain sizes. This is to be expected; the size of the singular field that can trigger microcracking is small (100 jam) relative to even the smallest grain size (35 jam) for a continuum average type approximation to occur. At 35 jam there are only 3 grains within the singular field instead of the large number required for continuum type microcracking models. We have shown, by comparing bulk and local moire energy measurements in nominally 2-D samples, that the toughening effects are not associated with the crack tip singularity field and can account for a large percentage of bulk toughening in Lucalox. Our micrographs indicate that frictional sliding takes place along the deflected path. We did not observe intact ligaments or grains behind the tip. We attribute this to our thin samples, which produce a single through-thickness crack, and the high resolution fixed displacement loading coupled with an acoustic emission feedback to fully propagate the crack through the sample thickness. These nonsingular toughening effects are discrete in nature and hence do not yield a steady state R curve effect typical of a crack in a metal during its propagation. The result of this discrete nonsingular toughening is a rising R curve behavior, even after 5mm of growth. Finally, because toughening is due to the nonsingular rear face we postulate that the R curve should differ depending on the overall specimen geometry tested. Future work will continue on the spatial variation of friction or microslip that we have measured along the crack face using moire interferometry to understand its relationship in the overall toughening of a quasi brittle material. Acknowledgments The experimentation phase of this work was supported by the Solid Mechanics Division, Office of Naval Research, Dr. R. Barsoum program manager. The data analysis phase of this research was supported by the U.S. Department of Energy, Office of Energy Research, Office of Basic Energy Sciences, Dr. O. Manley program manager, under DOE contract number DEAC07-76ID01570. Mr. G. Lassahn of the INEL Applied Analysis Unit and Mr. J. Smith of Texas A&M University are gratefully acknowledged for developing the mixed mode moire extraction algorithm. Dr. L. Lott of the INEL is gratefully acknowledged for performing the ultrasonic property measurements. Nonsingular toughening and R-curve behavior 375 References 1. 'Recommended Practice for R Curve Determination', ASTM Annual Book of Standards, Part 10, E561-80, American Society for Testing Materials, Philadelphia, PA (1980). 2. B. Mussier, M. Swain and N. Claussen, Journal of the American Ceramic Society 65, no. 11 (1982) 566-572. 3. A. Evans and K. Faber, Journal of the American Ceramic Society 67, no. 4 (1984) 255-260. 4. J. Hutchinson, Acta Metallurgica 35, no. 7 (1987) 1605-1619. 5. R. Knehans and R. Steinbrech, Journal of Materials Science l (1982) 327-29. 6. R. Knehans and R. Steinbrech, Sci. Ceramics 12 (1983) 613-619. 7. M. 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