Crack initiation processes in acrylic bone cement

` re,4 I. Sinclair2 P. E. Sinnett-Jones,1 M. Browne,1 A. J. Moffat,2 J. R. T. Jeffers,1 N. Saffari,3 J.-Y. Bufe 1 Bioengineering Sciences Research Group, School of Engineering Sciences, Southampton University, Southampton SO17 1BJ, United Kingdom 2 Engineering Materials, School of Engineering Sciences, Southampton University, Southampton SO17 1BJ, United Kingdom 3 Department of Mechanical Engineering, University College London, Torrington Place, London WC1E 7JE, United Kingdom 4 ry, 20 Av. Albert Einstein F-69621, Villeurbanne Cedex, France GEMPPM, INSA Lyon, Bat. St Exupe
Received 14 March 2007; revised 28 November 2007; accepted 18 January 2008 Published online 15 May 2008 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jbm.a.32037 Abstract: A major constraint in improving the understanding of the micromechanics of the fatigue failure process and, hence, in optimizing bone cement performance is found in the uncertainties associated with monitoring the evolution of the internal defects that are believed to dominate in vivo failure. The present study aimed to synthesize high resolution imaging with complementary damage monitoring/detection techniques. As a result, evidence of the chronology of failure has been obtained. The earliest stages of crack initiation have been captured and it is proposed that, in the presence of a pore, crack initiation may occur away from the pore due to the combined inuence of pore morphology and the presence of defects within regions of stress concentration. Furthermore, experimental evidence shows that large agglomerations of BaSO4 are subject to microcracking during fatigue, although in the majority of cases, these are not the primary cause of failure. It is proposed that cracks may then remain contained within the agglomerations because of the clamping effect of the matrix during volumetric shrinkage upon curing. 2008 Wiley Periodicals, Inc. J Biomed Mater Res 89A: 10881097, 2009 Key words: PMMA; synchrotron microtomography; mechanical performance; crack initiation; nondestructive testing and evaluation

INTRODUCTION While the fatigue and fracture properties of acrylic bone cement are recognized as being critical to the in vivo longevity of cemented total joint replacements, uncertainty regarding the underlying micromechanics of failure limits the potential for future optimization of cement material properties.1,2 It is well established that the presence of porosity and/or other defects (e.g. agglomerates of radiopacier phases) may play a role in the fracture process. It has been shown experimentally that the lower the porosity, the better are the quasi-static compressive and exural properties of the cement.36 However, many authors do not specify how this reduction relates to void size, morphology, number or spatial
Correspondence to: M. Browne; e-mail: doctor@soton.ac. uk or I. Sinclair; e-mail: i.sinclair@soton.ac.uk Contract grant sponsor: School of Engineering Sciences, University of Southampton

2008 Wiley Periodicals, Inc.

distribution, while others may only record one of these variables. Further uncertainties are seen in the role of radiopaciers. Radiopacifying agents are typically included in the bone cement mix to make the cement easily distinguishable on clinical X-ray images; examples include the use of BaSO4 or ZrO2 powders, or iodine containing copolymer.79 Results of the studies reviewed by Lewis1 show that radiopacier powders, such as BaSO4, may have a positive effect on the fatigue life of acrylic bone cements although this depends on the size and morphology of the particles.8 Deb and Vazquez10 report detrimental effects on quasi-static mechanical performance with addition of BaSO4 to CMW, a commercially available bone cement, reducing both the ultimate tensile strength and strain to failure of the bone cement, while increasing the tensile modulus. It has been suggested that using nanoparticles of barium sulfate (average diameter 100 nm) as radiopaque ller may lead to a signicant increase in cement fatigue life and a decrease of crack growth rates,11 a result attributed to homogeneous dispersal and absence of BaSO4 agglomerations. Furthermore,

CRACK INITIATION PROCESSES IN ACRYLIC BONE CEMENT

1089

results reported by Molino and Topoleski12 for a standard BaSO4-lled commercial bone cement suggest that voids associated with the BaSO4 particles in the matrix could act to blunt the propagating crack. In addition, it was believed that preferential crack growth through the inter-bead matrix occurs, possibly due to the weakening of the matrix in the presence of BaSO4 particles since the propensity for failure to occur through the matrix was not seen for the radiolucent cement. These observations are speculative and have yet to be quantied or micromechanically modeled. If preferential interbead failure occurs, a longer crack path suggests an overall slower crack growth rate in radiopacied cement. Conversely, fractographic analyses of acrylic cement specimens, under both in vivo and in vitro loading conditions, have shown that agglomeration of radiopaque particles is directly associated with fatigue failure initiation.13,14 Monitoring the evolution of internal defects under both fabrication and service loads would allow the assessment of their contribution to nal failure. Synchrotron microtomography has been shown to achieve high resolution 3D images of acrylic bone cement specimens, overcoming the limitations of other fatigue analysis techniques, such as surface examination or indirect signal analysis.15 Detailed assessment of fatigue damage processes in in-vitro fatigue test specimens have been analyzed.2,16 However, the uncertain nature of locating and imaging fatigue cracks and other defects identies the need for the synthesis of tomographic imaging with prior damage monitoring techniques to locate defect populations and their evolution under load. This may be achieved via an amalgamation of nondestructive techniques: the combined use of acoustic emission (AE) and ultrasound (US) scans may enable regions of interest for detailed X-ray scanning to be accurately identied and subsequently extracted. Nondestructive testing and evaluation (NDTE) may enable the location and characterization of aws within a specimen using noninvasive techniques in such a way that does not permanently affect the functionality of the component, material, or structure (i.e. no damage is incurred). Such techniques have been utilized to monitor damage accumulation in bone cement. For example, dye penetrant examination enabled Murphy and Prendergast16 to investigate the nonlinear stress-dependent nature of fatigue damage accumulation in acrylic bone cement; however, limitations included the need to stop the test to take measurements and the omission of BaSO4 from the cement used in order to allow visualization of the penetrant through the specimens (i.e. the test material was not a true clinical cement). More effective may be the use of AE which enables structural degradation within a component/material to be

monitored passively in real time.17 In a recent review by Browne et al.17 and work performed by Roques et al.18 and Jeffers et al.13 it has been demonstrated that, through AE, it is possible to distinguish between different failure processes and to locate damage sites. Furthermore, AE has the potential to monitor microcrack formation in the cement mantle in vitro for cemented femoral stems during fatigue loading19 and has been used in orthopaedics to predict the probability of bone rupture in patients.20 More recently, successful correlation between AE signals and US images has allowed the progression of delamination in a cement/metal interface construct to be monitored. Damage mechanisms could be identied and the methodology was proposed as a possible tool for the preclinical assessment of total hip joint replacements.21 The present study aims to demonstrate the combined use of ultrasonic and in situ AE techniques during fatigue testing and the potential for detailed micromechanical failure characterization via high resolution synchrotron tomography. While the synthesis of damage monitoring methods is a goal in itself (exploiting the advantages of different approaches) it must be noted that synchrotron tomographic assessment is necessarily limited by beam time access. The use of conventional laboratory damage assessment therefore offers the opportunity to make efcient, strategic use of synchrotron time. While the number of specimens that can be scanned is still limited, regions of interest can be selected for greatest insight into the failure process. Concurrently, as a result of NDTE work, the study enhances the knowledge of the role of defects and microstructure in the fatigue of bone cement.

MATERIALS AND METHODS Specimen preparation and testing

Mixing of CMW-1 Radiopaque acrylic bone cement (DePuy-CMW, Blackpool, UK) was performed at room temperature, as per manufacturers instructions, utilizing the VacuMix1 vacuum mixing system (DePuy-CMW). Specimens were subsequently aged in Ringers solution at 378C for a minimum of 14 days. Fatigue testing of ve specimens was performed in load control, at a frequency of 5 Hz and a peak stress level of 7 MPa under a cyclic sinusoidal load, at an R-ratio of 0.1. Of the ve specimens, three failed to break after the run-out period of 3 3 106 cycles (failures corresponded to 3 3 105 and 3 3 106 cycles) and as such, ultrasonic images were obtained of the damaged regions of these unbroken specimens after fatigue testing in order to capture the evolution of failure processes. Note that the damaged regions were identied from the AE results (see below).
Journal of Biomedical Materials Research Part A

1090

SINNETT-JONES ET AL.

Figure 1. Fatigue test specimen (150 3 30 3 3.5 mm3; gauge section 12 3 12 mm2) highlighting orientation of x, y and z directions and position of AE sensors (*).

location in three dimensions. The ultrasonic imaging system used employed a three-axis scanning rig with a broadband Panametrics V312 focused transducer having a center frequency of 10 MHz and a focal length of 12.7 mm. The focal spot size for subsurface imaging in PMMA cement was 98 lm. The transducer was excited with a Panametrics 5601T broadband pulser-receiver. The signal from the transducer was captured with a LeCroy 9300 digital oscilloscope. Further explanation regarding the ultrasound technique is given by Briggs.22

For the work reported in the present investigation, two in vitro specimen types were used: fatigued and nonfatigued. The latter specimens acted as a control, prepared, and aged in the same manner as the fatigue specimens, and subsequently sectioned as required for synchrotron microtomography. The combined AE and US results allowed 1 mm 3 1 mm 3 12 mm sections to be extracted (for high resolution tomographic imaging) across the gauge length from the damaged regions using a Buehler isomet 4000 diamond saw. Low cutting speeds, low feed rates, and generous water lubrication were used to ensure specimen integrity. The prepared specimens were then subjected to tomographic imaging (see below).

X-ray tomography
High resolution X-ray tomography scans (effective isotropic voxel size of 0.7 lm) were performed on the 1 mm 3 1 mm 3 12 mm sections, at the European Synchrotron Research Facility (ESRF, Grenoble), on beamline ID19. The energy was set at 20.5 keV, with an individual projection exposure time of 0.5 s. One thousand and ve hundred radiographs were recorded using a high performance CCD camera for a 1808 rotation of the specimen. A camera distance of 62 mm was set to achieve phase contrast imaging in the edge detection regime. A full description of a typical experimental set-up is given by Ludwig et al.23; however, specic experimental variables were set according to previous experiments performed by Sinnett-Jones et al.15 Reconstructed volumes were analyzed using a commercially available software package (VGStudio Max 1.2; Volume Graphics GmbH, Heidelberg, Germany).

Acoustic emission and ultrasound

When failure processes occur in a material, energy is typically released in the form of compression waves. Piezoelectric sensors attached to the surface of the specimen can be used to detect these waves. Using type M31 AE sensors (Vallen Z-series, 3 mm diameter, bandwidth 100 kHz to 1 MHz), established AE damage monitoring techniques13 were employed during fatigue testing. Two AE sensors were attached centrally across the gauge length, 30 mm apart, using a thermoplastic adhesive (see Fig. 1); these were connected to a preamplier with a bandpass lter (100 kHz to 1 MHz) and a 40 dB gain. AE parameters for each acoustic event, such as number of counts (i.e. number of threshold crossings), peak amplitude, rise time, duration, and energy (as seen in Fig. 2), were recorded throughout the experiment. The lower bound threshold was set at 40 dB ensuring that no signal data were recorded from background noise (e.g. electrical and mechanical noise from the hydraulic testing machine). All data were processed via an AMSY4 panel (Vallen Systeme GmbH, Munich) and displayed using Vallen Visual AE (R2004.0625) software. In one of the unbroken specimens, signicant fatigue damage was identied to have occurred (by AE) with testing then being stopped before nal failure (at 3 million cycles); in this instance, the fatigue life was taken as a runout although the point of stopping the test was within the range of scatter of fatigue life results typically found for this material and production method.13 The gauge length was then scanned with ultrasonic imaging systems to ascertain regions of damage. The use of just two AE sensors only allows location of damage in the x-direction of the specimen (see Fig. 1), while additional ultrasonic scanning, both across and through the specimen, enables damage
Journal of Biomedical Materials Research Part A

RESULTS Acoustic emission and ultrasound Previous work has shown that the AE technique can passively monitor failure in real time.17,18 Figure 3 shows that damage accumulation appeared to occur as a discontinuous process (as seen by bursts

Figure 2. Schematic of an AE signal and associated parameters on a plot of voltage versus time.

CRACK INITIATION PROCESSES IN ACRYLIC BONE CEMENT

1091

Figure 3. Typical AE damage (measured as duration) recorded as a function of location (x 5 0 cm at Sensor 1) and time. [Color gure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

of activity between periods of inactivity); data recorded enabled damage locations to be predicted as shown by the graph in Figure 4b where high levels of damage are represented by a greater number of hits (i.e. damage events located by both sensors). Ultrasonic scanning [Fig. 4(a)] conrmed the location of possible defects associated with the measured AE activity for those locations [Fig. 4(b)]. Two main regions of interest were identied as points X1 and X2 on Figure 4(a); these two regions showed greatest AE activity, recorded as number of hits (i.e. located events) on Figure 4(b). The high levels of AE activity recorded in the same plane as points X1 and X2 in the US image are consistent with crack initiation and/or propagation. Of the ve specimens that were tested in fatigue, the specimen associated with Figure 4 will be the focus of much of the subsequent discussion as this appeared to best capture the initial stages of failure: AE signals suggested that initial fatigue damage had occurred, but no large cracks should have been present (indicated by absence of any high energy and duration events). This was subsequently conrmed by US measurements. The large area and intensity of ultrasound recorded for region X1 suggests that the defect observed is due to the presence of a large void. Using US, defect dimensions cannot be measured to a high enough accuracy to ensure subsequent precise sectioning. This, in addition to material loss due to the blade thickness during sectioning, would reduce the chances of imaging cracks associated with X1 that appeared greater in diameter than the specimen size needed for tomographic imaging (to give the desired resolution of 0.7 lm). As such, subsequent

Figure 4. Correlation of (a) ultrasonic and (b) acoustic emission data for region of high AE activity, near Sensor 2. The pixel color corresponds to the peak ultrasound signal within a time gate. (Note that both US scales have been normalized with respect to maximum pixel amplitude over each trace). [Color gure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

investigation concentrated on capturing the region surrounding X2, the whole of which could be captured in one extracted specimen.

Figure 5. Through thickness ultrasound image showing damage across gauge length. Pixel color corresponds to the ultrasound signal amplitude over the entire trace. (Note that both US scales have been normalized with respect to maximum pixel amplitude over each trace). [Color gure can be viewed in the online issue, which is available at www.interscience.wiley.com.]
Journal of Biomedical Materials Research Part A

1092

SINNETT-JONES ET AL.

Figure 6. Radiograph taken using synchrotron radiation of region X2 showing areas of porosity (thin arrows) and agglomerations of barium sulphate (thick arrows).

Tomographic imaging The information gained by US (including throughthickness scanning, as seen in Figure 5) allowed successful extraction of specimens for tomographic imaging. Figure 6 shows a simple projection radiograph taken of the extracted specimen containing region X2: the regions outlined in black and identied by the thin arrows are porosities, while the

darker regions, identied by the thick arrows, are agglomerations of barium sulfate, as also seen in Figure 7. As stated in our previous report,15 the synchrotron tomography images clearly identied prepolymerized PMMA beads in a barium sulfate-lled matrix with porosity clearly dened by the phase contrast effect. The larger pore, seen in Figure 6, and its location within the original specimen, is shown in 3D in Figure 8. The Sum along ray24 rendering in Figure 9 gains a clear image of the pore structure, characterized by imprints of prepolymerized PMMA beads protruding into the pore; in addition, the location of a small agglomerate of barium sulfate near the pore edge is identied by the white arrow. (Note that a 2D projection is produced where grey levels are given by the sum of the voxel opacity running along the imaging direction). In region X2, the smallest isolated crack event observed and imaged is shown in Figure 10 by the black arrow and corresponds to the earliest stages of failure. Also identied (white arrow) is the small agglomerate of barium sulfate at the pore edge, as previously highlighted in Figure 9, although no signicant cracking has appeared to have occurred from this particular agglomerate. A selection of tomographic slices are shown in Figure 11, while 3D segmentation allows the crack and pore edge to be extracted and imaged together in 3D (Fig. 12). The observed crack is particularly seen to be discontinuous from the pore along its length; i.e. has no contact with the pore. Further investigation of the region surrounding the crack shows that cracking occurred close to a ridge/notch, in the pore morphology, formed by the alignment and intersection of several prepolymerized beads, perpendicular to the applied stress. The crack (Fig. 11) did not form at the root of this stress concentrating feature, but would appear to be linked to a small BaSO4rich region of matrix, as circled in Figure 11(b,c),

Figure 7. Tomographic reconstructed 2D sections of fatigue specimens of CMW-1 cement identifying defects: (a) porosity and (b) barium sulfate agglomerates, in specimens extracted from damaged region X2.
Journal of Biomedical Materials Research Part A

CRACK INITIATION PROCESSES IN ACRYLIC BONE CEMENT

1093

Figure 8. (a) 3D reconstruction of largest pore found in region X2 and (b) corresponding ultrasound image. [Color gure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

immediately ahead of the ridge (protruding from the top of the pore in the images). Of all the specimens radiographed, some four cracks were identied in this same size regime (<50 lm) that were seen to be discontinuous with their associated pore, and occurred in the BaSO4-containing matrix; in two more cases, it was unclear if the crack was or was not continuous with its local pore. A further number of small cracks were also seen that were clearly continuous with local porosity, but these were associated with complex groups of cracks, that were not thought to be independent initiation sites. The region encompassing X1 in Figure 4 revealed numerous large BaSO4 agglomerations (diameter

> 20 lm). Of the 24 agglomerates clearly imaged, 71% demonstrated the presence of cracks as seen in Figure 13. Similar agglomerations were carefully assessed in the control specimen (nonfatigue loaded). For the control specimen, only 2 out of 42 BaSO4 agglomerates (4.5%) were found to contain prior microcracks, suggesting that the cracks predominantly arose from the cement specimen testing.

DISCUSSION Fatigue crack initiation It is evident that pore shape is geometrically determined by the surrounding beads of prepolymerized PMMA. Murphy and Prendergast16,25 reported the tendency of cracks to initiate in the notch between adjacent beads which is necessarily in the BaSO4 lled matrix; this tendency was conrmed in images taken using synchrotron tomography by SinnettJones et al.15 In the current work, the very earliest stages of crack growth have been captured in partic-

Figure 9. 3D tomographic image of pore in region X2; white arrow identies small barium sulfate agglomerate near the surface.

Figure 10. Tomographic section of fatigue crack initiation site (black arrow) in the vicinity of a pore. Small agglomerate of barium sulfate also imaged at pore edge (white arrow).
Journal of Biomedical Materials Research Part A

1094

SINNETT-JONES ET AL.

Figure 11. A series of tomographic slices through the cross-section of a fatigue crack initiated in the vicinity of a pore in CMW-1 bone cement demonstrating the discontinuous nature of the crack and the presence of a barium sulfate-rich region at the crack edge (circled in (b) and (c)).

ular. Through our current extensive observations, it was conrmed that small cracks associated with porosity have not been seen in the control specimens; therefore, the crack shown in Figure 10 is not considered to be an artifact. Fatigue cracks from voids have been widely reported2,3,5,6,13,14,26 but because of limitations experienced using conventional observation methods it is impossible to capture the very early stages of interaction observed here. As reported by Molino and Topoleski,12 limited bonding between the BaSO4 particles and the matrix may facilitate debonding and void formation between the BaSO4 and the surrounding matrix and is visualized via SEM of fractured specimens (see Fig. 14). Analysis of the matrix region close to the crack in Figure 10 conrmed the presence of small voids adjacent to a cluster of BaSO4 particles, as previously seen by Topoleski et al.14 who suggested that the presence of these BaSO4-associated voids could promote crack propagation. However, it may

also be possible that crack initiation may occur due to microvoid formation/coalescence in the region surrounding the BaSO4 particles which, as they are in close proximity to a pore, are within a region of amplied stress. The various small cracks that were seen to be discontinuous with their neighboring porosity may then be attributed to such decohesion and crack growth from matrix BaSO4 particles. A schematic representation of this is shown in Figure 15, which is closely analogous to a mechanism pro` re et al.27 for pore-initiated fatigue posed by Bufe cracking in cast Al-Si alloy specimens; these often contain pores of similar shape to voids typically seen in fabricated acrylic bone cement specimens. In the case of cast Al-Si alloy specimens, the pores are geometrically hindered by the solidifying dendrites and the Si eutectic particles lie along the grain boundaries that stem from the convex part of the pore. ` re et al.27 note that decohesion was driven by Bufe the stress/strain mismatch between the aluminium matrix and Si particles (due to the differing elastic and plastic compliances of the phases), particularly in close proximity to the convex part of a void. The bone cement and the Al-Si alloy are analogous in that the secondary phase containing part of the microstructure will necessarily lie at the most convex/small local radius regions of the pores that are present. It may be seen in the 3D reconstruction of Figure 12 that the crack is closely correlated with a ridge in the side of the pore formed by the surrounding beads; the ridge is approximately perpendicular to the load direction, consistent with an enhanced stress concentration effect. Hence, as previ` re et al.,27 it may be the comously noted by Bufe bined inuence of pore stress concentrators and the stress/strain mismatch between the constituent

Figure 12. 3D reconstructed tomographic image of (a) the extracted pore edge and initiating crack (white arrow) and (b) the location of the crack initiating at an apex formed by four prepolymerized PMMA beads. These images demonstrate the structure of the pore in the locality of the crack, the absence of any point of contact between the pore and the crack, and the direction of the crack perpendicular to the applied stress (r). [Color gure can be viewed in the online issue, which is available at www.interscience.wiley.com.]
Journal of Biomedical Materials Research Part A

CRACK INITIATION PROCESSES IN ACRYLIC BONE CEMENT

1095

Figure 13. Tomographic slice taken of a cross-section through a large agglomeration of barium sulfate demonstrating the presence of cracking as a result of fatigue.

phases (PMMA and BaSO4 in this case) that may control damage initiation.

Figure 15. Schematic 2D illustration showing a typical arrangement of PMMA beads with respect to a void within acrylic bone cement. A series of microvoids existing in a region of high stress near a convex part of the void is believed to be the cause of crack initiation, roughly perpendicular to the applied stress (r), which subsequently propagates towards the larger void. Matrix material is not shown.

Microcracking of barium sulfate agglomerates As previously noted, disagreement exists over the effect of BaSO4 particles on the mechanical properties of acrylic bone cement. Comparing the fatigued specimen with the control specimen, it was observed that many of the hits recorded, via AE, from region X1 may have originated from the cracking observed within the large agglomeration of BaSO4. Fatigue testing of the same material at a maximum applied stress level of 15 MPa, performed by Jeffers et al.,13 found clear evidence of failure in one specimen from a batch of ve due to a large agglomeration of BaSO4 (see Fig. 16); all other fracture surfaces were the result of porosity. The specimen in question failed after 444,905 cycles; of the ve specimens

tested, this specimen performed the best (i.e. greatest number of cycles to failure). These combined results suggest that, in the absence of critical porosity or other major defects, large agglomerates of barium sulfate can cause fatigue failure and are therefore detrimental to the mechanical properties of bone cement. This is consistent with the use of nano-sized particles of barium sulfate that are reported to improve the mechanical properties of bone cement via a uniform dispersal of radiopaque particles throughout the matrix.11,28 Prior to fatigue testing, it has been established that, in the majority of cases, no microcracking exists within these agglomerations; however, it is seen via CT that these agglomerations readily crack under load but

Figure 14. Scanning electron micrograph showing the static fracture surface of a CMW-1 fatigue specimen demonstrating limited bonding between the matrix and the barium sulfate particles.

Figure 16. Scanning electron micrograph of fatigue failure of CMW-1 bone cement specimen,13 due to the presence of a large barium sulfate agglomerate (maximum applied stress of 15 MPa; failure after 444,905 stress cycles).
Journal of Biomedical Materials Research Part A

1096

SINNETT-JONES ET AL.

are not the primary cause of failure. As such, a competition between initiation processes would appear to exist, where BaSO4 agglomerates and pores of similar length scales (100200 lm, see Figs. 12 and 13) can promote failure. However, there is initially very slow or arrested crack growth occurring within the BaSO4 agglomerates, limiting their damage potential. As a relatively stiff (cf. PMMA) and poorly bonded phase, this effect is perhaps surprising. In the rst instance, it is suggested that the BaSO4 agglomerates may experience clamping forces due to polymerization and/or thermal shrinkage of the matrix during processing. A simple estimate of the initial magnitude of these clamping stresses may be made using Eshelbys equivalent inclusion methods.29 Specically, the stiffness parameters and the coefcients of thermal expansion of PMMA and BaSO4 are known and can then be used to estimate the equivalent parameters for a matrix of PMMA containing 3 vol % BaSO4 (i.e. representative of the bulk of the cement), and a particle of 90 vol % BaSO4 in PMMA (i.e. representative of an agglomerate). It is then possible to estimate the clamping stresses generated in a spherical body of agglomerate material within the matrix for a temperature drop of 308C, i.e. representing a drop from a peak curing temperature of 708C down to body temperature. An internal clamping stress >50 MPa is predicted within the BaSO4 agglomerates for these conditions, which would then be expected to have a signicant inuence on mechanical behavior, compared to the applied stress of 7 MPa and the tensile strength of CMW-1 (45 MPa). It should be recognized that this clamping stress estimate will undoubtedly be an upper bound value as stresses of this order would undergo creep relaxation during cooling and subsequent thermal exposure30,31the limiting factor in the level of clamping would then be the matrix strength. Overall, it may still be seen that thermal contraction is sufcient to generate appreciable clamping stresses, consistent with the observed delay and/or arrest of cracking within the agglomerates. However, if porosity levels within a given test specimen or component are sub-critical for crack initiation, or if larger stresses are applied, then these agglomerate microcracks may eventually propagate into the matrix and prepolymerized beads, leading to nal failure of the specimen. CONCLUSIONS A methodology has been presented for the combined use of nondestructive techniques in order to determine the location of cracks/defects within acrylic bone cement specimens, subjected to cyclical loading, prior to high resolution tomographic imagJournal of Biomedical Materials Research Part A

ing. Such a methodology increases the probability of capturing crack initiation and furthering the micromechanical understanding of crack formation and propagation. Also, the resultant reduction in scanning time needed to nd defects/cracks means more effective use of beam time is achieved. While the work has made specic efforts to increase the efciency in locating such very early, small cracking events by synchrotron CT, the numbers of samples is of necessity small, which is therefore a limitation of the work. It is noted however that nding these internal failure events in a real bone cement (i.e. not a model system) is fundamentally difcult and has not been reported elsewhere: furthermore, no conict is found between the failure processes observed in the present samples and those assessed by more conventional methods (e.g. surface microscopy via SEM and/or optical microscopy) in previous studies. A novel mechanism of crack initiation has been proposed, where porosity and local BaSO4 distribution are seen to act together in the cement matrix rather than directly from pore surfaces. While pores may remain critical to crack formation; the potential for microstructural control of initiation is identied. In addition, it has been seen that in large agglomerates of BaSO4, microcracking is a direct result of fatigue and, in some instances, can lead to failure. The frequent incidence of crack arrest or decay within agglomerates is noted and attributed to microstructural residual stresses associated with the cement curing process. This nding highlights the future potential benets of incorporating more strongly adhered, ne and/or uniformly dispersed particles of a radiopacier within the cement powder, in agreement with the ndings of Bellare et al.11 for example.
The authors acknowledge DePuy CMW, Blackpool, UK, for the supply of CMW-1 radiopaque acrylic bone cement, and extended gratitude is owed to the staff on ID19 at ESRF for their support and technical expertise.

References
1. Lewis G. Fatigue testing and performance of acrylic bonecement materials: State-of-the-art review. J Biomed Mater Res Part B: Appl Biomater 2003;66:457486. 2. Topoleski LDT, Ducheyne P, Cuckler JM. Microstructural pathway of fracture in poly(methyl methacrylate) bonecement. Biomaterials 1993;14:11651172. 3. Dunne NJ, Orr JF. Inuence of mixing techniques on the physical properties of acrylic bone cement. Biomaterials 2001;22:18191826. 4. Dunne NJ, Orr JF, Mushipe MT, Eveleigh RJ. The relationship between porosity and fatigue characteristics of bone cements. Biomaterials 2003;24:239245. 5. Klein RW, Scott CP, Higham PA. The strength of acrylic bone cement cured under thumb pressure. Biomaterials 2004;25: 943947.

CRACK INITIATION PROCESSES IN ACRYLIC BONE CEMENT

1097

6. Lewis G. Properties of acrylic bone cement: State of the art review. J Biomed Mater Res 1997;38:155182. 7. Artola A, Gurruchaga M, Vazquez B, San Roman J, Goni I. Elimination of barium sulphate from acrylic bone cements. Use of two iodine-containing monomers. Biomaterials 2003; 24:40714080. 8. Ginebra MP, Albuixech L, Fernandez-Barragan E, Aparicio C, Gil FJ, San Roman J, Vazquez B, Planell JA. Mechanical performance of acrylic bone cements containing different radiopacifying agents. Biomaterials 2002;23:18731882. 9. Kurtz SM, Villarraga ML, Zhao K, Edidin AA. Static and fatigue mechanical behavior of bone cement with elevated barium sulfate content for treatment of vertebral compression fractures. Biomaterials 2005;26:36993712. 10. Deb S, Vazquez B. The effect of cross-linking agents on acrylic bone cements containing radiopaciers. Biomaterials 2001;22:21772181. 11. Bellare A, Fitz W, Gomoll A, Turell MB, Scott R, Thornhill T. Using nanotechnology to improve the performance of acrylic bone cements. Orthop J Harv Med Sch 2002;4:9396. 12. Molino LN, Topoleski LDT. Effect of BaSO4 on the fatigue crack propagation rate of PMMA bone cement. J Biomed Mater Res 1996;31:131137. 13. Jeffers JRT, Browne M, Taylor M. Damage accumulation, fatigue and creep behaviour of vacuum mixed bone cement. Biomaterials 2005;26:55325541. 14. Topoleski LDT, Ducheyne P, Cuckler JM. A fractographic analysis of in vivo poly(methyl methacrylate) bone-cement failure mechanisms. J Biomed Mater Res 1990;24:135 154. ` re J-Y, Sinclair 15. Sinnett-Jones PE, Browne M, Ludwig W, Bufe I. Microtomography assessment of failure in acrylic bone cement. Biomaterials 2005;26:64606466. 16. Murphy BP, Prendergast PJ. The relationship between stress, porosity, and nonlinear damage accumulation in acrylic bone cement. J Biomed Mater Res 2002;59:646654. 17. Browne M, Roques A, Taylor A. The acoustic emission technique in orthopaedicsA review. J Strain Anal Eng Des 2005;40:5979. 18. Roques A, Browne M, Thompson J, Rowland C, Taylor A. Investigation of fatigue crack growth in acrylic bone cement using the acoustic emission technique. Biomaterials 2004;25: 769778.

19. Qi G, Li J, Mann KA, Mouchon WP, Hamstad MA, Salehi A, Whitten SA. 3D real time methodology monitoring cement failures in THA. J Biomed Mater Res Part A 2004;71:391402. 20. Schwalbe HJ, Bamfaste G, Franke RP. Non-destructive and non-invasive observation of friction and wear of human joints and of fracture initiation by acoustic emission. Proc Inst Mech Eng Part H: J Eng Med 1999;213:4148. 21. Browne M, Jeffers JRT, Saffari N. Non-destructive evaluation of cemented metallic implants for pre-clinical prediction of implant loosening. Proc. 19th Conference of the European Society for Biomaterials, Sorrento, Italy; 2005. p T210. 22. Briggs A. Acoustic Microscopy. Oxford: Clarendon Press; 1992. ` re J-Y, Savelli S, Cloetens P. Study of the 23. Ludwig W, Bufe interaction of a short fatigue crack with grain boundaries in a cast Al alloy using X-ray microtomography. Acta Materialia 2003;51:585598. 24. VGStudio Max 1.2 Manual. Volume Graphics GmbH, Heidelberg, Germany. Chapter 4.6.3. 25. Murphy BP, Prendergast PJ. On the magnitude and variability of the fatigue strength of acrylic bone cement. Int J Fatigue 2000;22:855864. 26. Prendergast PJ. The functional performance of orthopaedic bone cement. Key Eng Mater 2001;198/199:291300. ` re J-Y, Savelli S, Jouneau PH, Maire E, Fougieres R. Ex27. Bufe perimental study of porosity and its relation to fatigue mechanisms of model Al-Si7-Mg0.3 cast Al alloys. Mater Sci Eng A Struct Mater: Prop Microstruct Process 2001;316:115126. 28. Fitz W, Gomoll A, Bellare A, Scott R, Thornhill T. High speed mixing of different nanometer barium sulfate in acrylic bone cement and its effect on work of fracture, Trans. 47th Annual Meeting of the Orthopaedic Research Society, San Francisco, California; 2001. p 1035. 29. Clyne TW, Withers PJ. An Introduction to metal matrix composites. Cambridge, UK: Cambridge University Press; 1993. 30. Verdonschot N, Huiskes R. Acrylic cement creeps but does not allow much subsidence of femoral stems. J Bone Joint Surg British Volume 1997;79:665669. 31. Jeffers JRT. In silico simulation of long term cement mantle failure in total hip replacement. PhD thesis: University of Southampton: University of Southampton; 2005.

Journal of Biomedical Materials Research Part A