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Journal

J. Am. Ceram. Soc., 81 [7] 174348 (1998)

Reinforcement of Hydroxyapatite Bioceramic by Addition of Ni3Al and Al2O3


Je-Won Choi, Young-Min Kong, and Hyoun-Ee Kim*
Department of Inorganic Materials Engineering, Seoul National University, Seoul, 151-742, Korea

In-Seop Lee
Research Center of Orthopaedic and Rehabilitation Engineering, Inchon, 403-120, Korea

The effects of Ni3Al and Al2O3 additions on the mechanical properties of hydroxyapatite (HAp) were investigated. The addition of Ni3Al particles increased the strength as well as the fracture toughness of HAp. However, the improvements in the properties were limited because of the formation of microcracks around the metal particles. The microcracks were formed because of the large difference in the coefficients of thermal expansion between HAp and Ni3Al, and because of the relatively large size of Ni3Al particles (20 m). The addition of submicrometer Al2O3 powder was also effective in increasing the mechanical properties. The flexural strength and the fracture toughness were increased from about 100 MPa and 0.7 MPam1/2, respectively, to 200 MPa and 1.5 MPam1/2 by the addition of 20 vol% Al2O3. When Ni3Al and Al2O3 were added together, the fracture toughness was further increased to 2.3 MPam1/2. This increase in the fracture toughness was attributed to the synergistic effect of matrix strengthening and crack interactions with the metal particles. I. Introduction

YDROXYAPATITE (HAp: Ca10(PO4)6(OH)2) is one of the most attractive materials for human hard tissue implants because of its close resemblance to bones and teeth.1 Actually, HAp is almost identical to the mineral found in human bone tissue, both chemically and crystallographically.2 TEM lattice image analyses illustrate a nearly perfect epitaxial alignment of growing bone crystallites with HAp crystals in an implant.3 Despite its excellent biocompatibility, the applications of HAp are limited to non-load-bearing implants, such as inner-ear bones or filler materials, because of its poor mechanical properties, and consequent lack of reliability.4 Coating metallic implants, such as stainless steel, CoCr alloy, or Ti-based materials, with HAp powder is one option to circumvent this problem. However, large differences in the coefficient of thermal expansion (CTE) and other physical properties between metals and HAp limit the effectiveness of this approach.5 There have been many investigations to improve the mechanical properties of dense HAp. The effects of the starting powder, and processing parameters, such as sintering temperature, time, and atmosphere, on the densification behavior and the mechanical properties have been studied extensively.614 Despite valuable scientific findings, the improvements in the

D. J. Greencontributing editor

Manuscript No. 191053. Received April 29, 1997; approved October 21, 1997. Supported by the Korea Science and Engineering Foundation (KOSEF) through the Center for Interface Science and Engineering of Materials at the Korea Advanced Institute of Science and Technology (KAIST). *Member, American Ceramic Society.

mechanical properties of monolithic HAp are not yet satisfactory. Significant enhancements in strength and fracture toughness of HAp reportedly have been achieved by making composite materials, using various types of second phases, such as polymers, metals, and ceramics, as reinforcing agents.1529 A composite material consisting of HAp and a polymer such as polyethylene has been shown to exhibit improved fracture toughness and strain-to-failure compared to monolithic HAp.16 However, the strength is less than 30 MPa, restricting the application of the composite to only special cases. Even though most metals (including CoCr and Ti-based alloys) are not suitable as a reinforcement because of excessive reactions with HAp, some metals, such as stainless steel in the form of chopped fiber, have been found to be effective in increasing the strength and the fracture toughness of HAp.18 However, excessive addition of metals might reduce the biocompatibility of the material. Ceramics have also been found to be effective reinforcing agents for HAp. When partially stabilized ZrO2 is added, both the strength and the fracture toughness are increased.19,20 However, special precautions need to be taken to avoid deleterious reactions between HAp and ZrO2 during the fabrication process. Addition of Al2O3 platelets or powder increases the strength and the fracture toughness of the material; however, a large difference in the CTE between HAp and Al2O3 limits further improvements.2124 Glasses with various compositions have been effective mainly in increasing the strength rather than the fracture toughness of HAp.2529 For both monolithic and composite materials of HAp, wide ranges of strength and fracture toughness values have been reported. One of the main reasons for this scatter in data is presumably the employment of different testing techniques by different researchers. For example, for strength measurements, three-point bending or biaxial testing has been used in most cases. However, despite the merit of simplicity, the three-point bending test generally yields somewhat higher values than other test methods because of the small maximally stressed area. On the other hand, the biaxial test requires many precautions for accurate strength measurements.30 In the case of fracture toughness, the single-edge-notched-beam (SENB) or direct-indentation (DI) method has been employed in many cases. However, the SENB method, when the specimen is not precracked, yields different fracture toughness values depending on the geometry of the crack tip. The DI method is generally regarded as the least reliable method because of the difficulties in crack length measurement in addition to its inherent uncertainties involved in developing the formula.31 In the present study, we investigated the effects of concurrent addition of Ni3Al metallic particles and fine Al2O3 powder on the mechanical properties of HAp. The Ni3Al was selected because of its chemical inertness and high fracture toughness,32 and Al2O3 was chosen to increase the matrix strength. The addition of Al2O3 was also expected to be effective in reducing the difference in thermal expansion between the matrix and Ni3Al. We were a little concerned about the biocompatibility of
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Ni3Al. However, the biocompatibility of Ni3Al is expected to be different from that of Ni, as is the case for Al2O3 and Al. Currently we are carrying out tests to determine the biocompatibility of Ni3Al, and the results will be reported separately. The strength and the fracture toughness of HAp containing various amounts of Ni3Al and Al2O3 were measured by the four-point flexure test and the indentation-strength method,33 respectively. Factors determining these mechanical properties were identified based on SEM observations, XRD analyses, and CTE measurements of the composites. II. Experimental Procedure

The starting powders were commercial Ca10(PO4)6(OH)2 (Alfa Aesar Co, Ward Hill, MA) with 3440% Ca, Ni3Al with a composition of Ni, 20 at.% Al, 8 at.% Cr (IC-218, from Oak Ridge National Laboratory, TN), and Al2O3 without MgO (ERC-DBM, Reynolds Metals Co., Bauxite, AK). Average particle sizes of HAp and Al2O3 were less than 1 m and that of Ni3Al was about 20 m. The powders were mixed by ball milling in distilled water for 24 h with alumina balls as media. The slurry was dried by evaporating the water on a hot plate while stirring vigorously. The powder mixtures were hotpressed in a graphite die between 1100 and 1200C for 1 h in flowing Ar atmosphere with an applied pressure of 20 MPa. Microstructures of the hot-pressed specimens were observed with an SEM after etching the polished surfaces with 10% lactic acid (CH3CHOHCOOH) for 30 s. The composition and the CTE of the composite materials were determined with an X-ray diffractometer and a dilatometer, respectively. The CTE of the materials containing Ni3Al particles were monitored in flowing N2 gas to prevent the oxidation of metal particles, while those of other specimens were monitored in air. The elastic moduli of selected specimens were measured by the sonic resonance method.34 Flexural strengths were measured at room temperature in air with a crosshead speed of 0.5 mm/min by a four-point bend test with outer and inner spans of 20 and 10 mm, respectively. Test specimens with dimensions of 2.7 mm 4.0 mm 25 mm were cut and machined from hot-pressed disks. All of the specimen surfaces were ground with a 800-grit diamond wheel and tensile surfaces were polished with diamond slurries (1 m finish). Edges were chamfered to eliminate machining flaws that could act as fracture origins. The fracture toughness was determined by the indentation-strength method suggested by Chantikul et al.33 After indenting with a Vickers indentor at the center of the flexure bars with an applied load of 9.8 or 49 N, the fracture stresses were measured by the four-point bending configuration. For each set of conditions, 5 to 10 specimens were tested for both strength and fracture toughness measurements. III. Results and Discussion

Fig. 1. Flexural strength of the hydroxyapatite (HAp) containing different amounts of Ni3Al particles hot-pressed at 1100C for 1 h. Error bars represent 1 standard deviation.

by the formation of microcracks around Ni3Al particles. Generally, the CTEs of ceramics are smaller than those of metals. However, the CTE of HAp is much larger than that of most ceramics,35 and in this case, it is higher than that of Ni3Al. When the CTE of a second phase particle is different from that of the matrix, a tangential stress, , is developed around the spherical particle due to the CTE difference () as follows:36 1 1 + m 1 2p = T + 2 2Em Ep

R r

(1)

where T is the difference between the sintering temperature and room temperature, Em and Ep are the elastic moduli of the matrix and the second phase particle, respectively, and is Poissons ratio. R and r represent the radius of the second phase particle and the distance from the center of the particle, respectively. Using the measured values of Em 108 GPa, CTE of HAp (HAp) 16.9 106/C, CTE of Ni3Al (Ni3Al)

(1) Effect of Ni3 Al Addition The strength of HAp was influenced by the addition of Ni3Al particles, as shown in Fig. 1. The flexural strength of pure HAp hot-pressed at 1100C for 1 h was 100 MPa. When 10 vol% Ni3Al was added to HAp and hot-pressed under the same conditions, the strength increased to 120 MPa. However, further additions of Ni3Al particles reduced the strength to the level of pure HAp. The densities of all specimens were higher than 97% of theoretical. X-ray diffraction patterns of pure HAp and HAp with 10 vol% Ni3Al after hot pressing under the same conditions are shown in Figs. 2(A) and (B), respectively. As seen in these patterns, no new phase was detected by the XRD analyses, implying that there was no significant chemical reaction between HAp and Ni3Al. The observed slight increase and subsequent decrease in strength with Ni3Al content were believed to be due to two competing processes: strengthening by Ni3Al and weakening

Fig. 2. X-ray diffraction patterns of (A) pure HAp, (B) HAp with 10 vol% Ni3Al hot-pressed at 1100C, and (C) HAp with 20 vol% Al2O3 hot-pressed at 1200C: () HAp, () Ni3Al, () Al2O3, and () -TCP.

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10.5 106/C, published values32,37 of Ep 200 GPa, Poissons ratios of 0.3 for both materials, and T 1000C, the residual stress at the interface was calculated to be about 350 MPa in tension, which is much higher than the tensile strength of the HAp matrix. For cracks to develop around the particles, an energy-balance criterion should be satisfied along with the above stress criterion. In other words, cracks are developed only when the energy of the system is lowered by crack formation. The stored energy inside and around a second phase particle is proportional to the volume of the particle. Therefore, cracks are developed only when the particles are larger than a certain critical size.36,38 When the polished surface of hot-pressed HAp with 10 vol% Ni3Al was chemically etched with 10% lactic acid, radial cracks around the Ni3Al particles were observed, as shown in Fig. 3, implying that both the stress criterion and the energybalance criterion for crack development were satisfied. This micrograph also shows a diffusion layer in the metal particles where traces of Ca and P were detected by EDS analyses. The formation of microcracks was confirmed by CTE measurements for the composite materials. The CTEs of the specimens with different amounts of Ni3Al, measured at temperatures between 25 and 1000C, are shown in Fig. 4. For an isotropic composite with components 1 and 2 without any microcracks, the CTE of the composite (c) may be estimated using Turners law as follows:39 1K1V1 + 2K2V2 c = K1V1 + K2V2 (2)

Fig. 4. Coefficients of thermal expansion of HAp composites with various amounts of Ni3Al, showing significant deviation from the calculated values.

where K1 and V1 represent the bulk modulus and the volume fraction, respectively, of component 1. However, when there are microcracks in the composite, the apparent CTE becomes lower, especially at low temperature, because of the closure and opening of the microcracks during heating and cooling, respectively.39 Figure 4 illustrates a significant deviation of the CTE from the theoretical value, implying the formation of microcracks in the composite materials. Therefore, the increase in strength by the addition of 10 vol% Ni3Al was due to the dominance of the strengthening effect despite the formation of microcracks. However, when the amount of Ni3Al was increased to 20 vol% or higher, the effect of microcracking became dominant, reducing the strength of the materials. (2) Effect of Al2O3 Addition The difference in CTE between HAp and Al2O3 (Al2O3 9 106/C) is even larger than in the case of HAp and Ni3Al. Therefore, according to Eq. (1), higher tensile stress is expected to develop in the matrix around Al2O3 particles than

around Ni3Al. However, the average particle size of Al2O3 was 0.5 m, while that of Ni3Al was 20 m, and the energy stored around an Al2O3 particle was several orders of magnitude smaller than in the case of Ni3Al. Therefore, the formation of microcracks around Al2O3 particles is not likely. The CTE of specimens with various amounts of Al2O3 is shown in Fig. 5. Unlike the case of Ni3Al additions, the CTE of HAp with Al2O3 specimens followed the calculated values, implying no formation of microcracks in the materials. The strength of HAp was significantly improved by the addition of Al2O3, as shown in Fig. 6. The strength of pure HAp hot-pressed at 1150C was 100 MPa. The strength increased to 170 MPa when 15 vol% Al2O3 was added and processed under the same conditions. When hot-pressed at 1200C, a higher strength of 200 MPa was obtained. However, with further additions of Al2O3, the level of increase in strength was reduced, presumably because of the insufficient densification of the specimens. Hot-pressing at temperatures higher than 1200C was also not desirable because of the decomposition of HAp to form -tricalcium phosphate, as illustrated in Fig. 2(C). The microstructure and the average grain size of the materials were

Fig. 3. SEM micrograph of the HAp specimen with 10 vol% Ni3Al, showing the radial cracks around the Ni3Al particles.

Fig. 5. Coefficients of thermal expansion of HAp composite with various amounts of Al2O3.

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Fig. 6. Flexural strength of HAp composite with various amounts of Al2O3 hot-pressed at 1150 and 1200C for 1 h. Error bars represent 1 standard deviation.

Fig. 8. Flexural strength of HAp composites containing 5 vol% Ni3Al and various amounts of Al2O3. Error bars represent 1 standard deviation.

not found to have been much altered by Al2O3 addition. Therefore, the observed increase in strength by Al2O3 addition is probably due to the formation of a strong bond between HAp and Al2O3 without microcracks. (3) Concurrent Addition of Ni3 Al and Al2O3 When the submicrometer-sized Al2O3 powder was added to HAp, the CTE of the materials decreased following Turners law,39 as shown in Fig. 5. Therefore, if Ni3Al particles are added to a matrix composed of HAp and Al2O3, the difference in the CTE between the Ni3Al particles and the matrix is reduced remarkably. When Ni3Al was added to a matrix composed of HAp and 20 vol% Al2O3, the maximum residual stress at the interface was estimated, using Eq. (1), to be 175 MPa in tension. The strength of the matrix is also in that range (Fig. 6). Therefore, the formation of microcracks around metal particles was not expected, and this was confirmed by SEM observation, as shown in Fig. 7. The strength data of HAp composite materials containing 5 vol% Ni3Al and various amounts of Al2O3 are shown in Fig. 8. The strength increased with the amount of Al2O3. However, compared to the case of solely Al2O3 additions (Fig. 6), the

level of increase was slightly reduced by the addition of Ni3Al particles, presumably because of the tensile residual stress in the matrix. The fracture toughness of the materials was strongly influenced by the addition of Ni3Al and/or Al2O3 particles. The fracture toughness was determined by the indentation-strength method using the following equation:33
KIC = R

E H

18

P1 33 4

(3)

where P and are the indentation load and the fracture stress of the indented specimen, respectively, and R is a geometric factor with a value of 0.62. The fracture toughness of pure HAp was less than 1 MPam1/2, which is well known to be one of the biggest obstacles for wider applications of this material.1 By additions of 5 and 10 vol% Ni3Al particles, the fracture toughness increased to 1.1 and 1.3 MPam1/2, respectively, as illustrated in Fig. 9. Further addition of the intermetallic was not beneficial for the fracture toughness, again because of the formation of microcracks in the specimens. When 20 vol% Al2O3

Fig. 7. SEM micrograph of polished surface of HAp composite containing 20 vol% Al2O3 and 10 vol% Ni3Al showing no radial cracks around Ni3Al particles.

Fig. 9. Fracture toughness of the HAp composites with various amounts of Ni3Al and Al2O3. Error bars represent 1 standard deviation.

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Fig. 10. SEM micrograph showing the crack path around the Ni3Al particle in HAp composite containing 5 vol% Ni3Al and 20 vol% Al2O3.

was added, the fracture toughness improved to 1.5 MPam1/2. Therefore, the addition of Al2O3 is an effective method to increase the strength and the fracture toughness of HAp at the same time. The highest fracture toughness in the present research was obtained when 20 vol% Al2O3 and 5 vol% Ni3Al were added together. It was 2.3 MPam1/2, which is about 3 times higher than the fracture toughness of pure HAp. The increase in fracture toughness by the addition of Ni3Al is attributed to the inhibition of crack propagation with the tough metal particles.40 However, the formation of microcracks around the Ni3Al particles limited the toughening effect. On the other hand, an increase in the fracture toughness as well as the flexural strength by Al2O3 additions was deemed to be due to the formation of strong bonds between HAp and Al2O3 without microcracks. When Ni3Al particles were added to a composite matrix of HAp and Al2O3, the difference in CTE was reduced remarkably, and the formation of microcracks around the metal particles was suppressed. Therefore, the fracture toughness of HAp increased remarkably through the synergistic effects of matrix strengthening by Al2O3, and crack deflection by metal particles.40 Figure 10 clearly illustrates that a crack has propagated around the Ni3Al particle in the HAp specimen containing 5 and 20 vol% Ni3Al and Al2O3, respectively. IV. Conclusions

The strength and the fracture toughness of HAp were improved significantly by the addition of Ni3Al and Al2O3 together. When only Ni3Al was added, the improvement in the mechanical properties was minimal because of the formation of microcracks around the metal particles. On the other hand, the addition of fine Al2O3 powders was effective in increasing the strength rather than the fracture toughness of HAp. By concurrent addition of Ni3Al and Al2O3, both the strength and the fracture toughness were substantially improved up to 200 MPa and 2.3 MPam1/2, respectively. The increase in the fracture toughness is attributed to the synergistic effect of matrix strengthening and crack deflection. Acknowledgments:
We thank A. J. Moorhead, at Oak Ridge National Laboratory, for supplying the Ni3Al powder, Prof. Y. Kim, at Chonnam National University, for measuring the elastic modulus, and Director H. W. Lee, at Metatech Co., Ltd., for financial support.

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