Effects of fatigue loading and PMMA precoating on the adhesion and subcritical debonding of prosthetic-PMMA interfaces

Kevin L. Ohashi,1 Reinhold H. Dauskardt2 1 Department of Mechanical Engineering, Division of Biomechanical Engineering, and 2Department of Materials Science and Engineering, Stanford University, Stanford, California 94305-2205
Received 11 August 1999; revised 25 October 1999; accepted 3 December 1999 Abstract: Debonding of clinically relevant CoCrMopolymethylmethacrylate (PMMA) interfaces is shown to occur subcritically under fatigue loading, implying that debonding may occur at loads much lower than those required for catastrophic failure. Interface fracture mechanics samples containing precoated and uncoated grit-blasted CoCrMo substrates and a PMMA layer were constructed and quantitatively evaluated in terms of their critical interface adhesion and subcritical debond behavior. The precoat surfaces had markedly enhanced adhesion and fatigue resistance in both air and simulated physiological environmental conditions compared to the uncoated samples. Constraint of the PMMA layer does not significantly affect the debond process for thickness between 2- and 5-mm. In addition, wear particles were collected and shown to be consistent with particle sizes reported in vivo and are on the scale of the metal surface roughness. Life prediction methods using the subcritical debond-growth data are discussed. 2000 John Wiley & Sons, Inc. J Biomed Mater Res, 51, 172183, 2000. Key words: adhesion; subcritical debonding; fatigue; polymethylmethacrylate; total joint replacements

INTRODUCTION Debonding and failure of the prosthetic-polymethylmethacrylate (PMMA) interface has been implicated as a primary cause of loosening in cemented femoral components.1,2 Debonding has been shown to result in substantial increases in stress levels in the PMMA bone cement mantle,3,4 leading to extensive cracking of the PMMA and premature failure of cemented systems. Several histomorphological studies support this scenario in the presence of a structurally intact bonePMMA interface.5,6 In contrast to the bonded interfaces described above, an alternative approach has been to employ unbonded interfaces using smooth polished prosthetic surfaces. However, contemporary debates on the advantages of unbonded compared to bonded prosthetic surfaces have yet to

No benefit of any kind will be received either directly or indirectly by the authors. Correspondence to: R. H. Dauskardt; e-mail: dauskardt@ stanford.edu Contract grant sponsor: Whitaker Foundation Support from: Charles Lee Powell Foundation
2000 John Wiley & Sons, Inc.

define a clear recommendation for the optimal interface.79 In the present study, we were interested in the debonding mechanics of bonded interfaces; unbonded interfaces to smooth polished prosthetic surfaces were not considered. One technique that has emerged to increase the strength of the prostheticPMMA interface is precoating of the implant surface with a thin PMMA layer (3050 m) before surgery.10,11 Such precoating can be accomplished at elevated temperatures where the lower viscosity of PMMA allows for more intimate contact between the polymer and metal surface. PMMAmetal contact at the atomic level (<10) allows for the possibility of strong intermolecular bonding across the interface, increased mechanical interdigitation, and reduced interfacial flaw populations (e.g., porosity, contamination). Such intimate contact is difficult to achieve in situ during surgery where contamination of the implant surface and the high viscosity of the PMMA leads to low wettability of the metal surface. However, to date, there exists little quantitative understanding of the adhesive properties of these interfaces and the micromechanics which determine the debond resistance behavior. In a previous study, we used an interface fracture mechanics approach to characterize the debond be-

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havior of various clinically relevant prostheticPMMA interfaces quantitatively under monotonic loading conditions. 12 It was demonstrated that interface debond resistance is a strong function of surface preparation and debond loading mode. In addition, interfaces exhibited resistance curve (R-curve) behavior, indicating an increasing resistance to debonding with initial debond extension. Such behavior was rationalized in terms of debond surface interactions that act behind the debond tip and shield the debond tip from the applied debond driving force. However, only critical debond resistance values of the interfaces were investigated. Of perhaps greater importance is an understanding of delayed failure mechanisms and associated lifetimes of cemented structures.13 Subcritical debonding associated with mechanisms of cyclic fatigue crack growth are particularly relevant considering that these systems will experience over 1,000,000 physiological loading cycles per year, and are expected to survive a minimum of 1015 years. In these terms, it is critical to understand the progressive debonding of prostheticPMMA interfaces. Similar to other bulk polymer material systems, under fatigue loading conditions, crack growth is expected to occur at stresses well below those required for catastrophic failure.1316 Such subcritical debonding is driven by residual stresses at the interface and alternating physiological loads on the system. Subcritical debonding along the interface and cracking through the PMMA may be affected by timedependent mechanisms involving temperature (creep), physiologic environment (stress corrosion or plasticizing effects on the PMMA), and mechanical fatigue. Therefore, determination of the long-term reliability of these prostheticpolymer interfaces must be addressed in terms of the above time-dependent failure mechanisms. To date, information about the subcritical debond-growth behavior at or near to these interfaces is almost completely lacking. The intent of this study was therefore to characterize the adhesion and the subcritical debond behavior of a grit-blasted CoCrMo metalPMMA interface with and without a PMMA precoat. Adhesion was determined from the debond fracture R-curve behavior measured under monotonic loads and reported in terms of the energy required to initiate debonding, Go, and the steady-state interfacial fracture energy, Gss, taken from the plateau of the R-curve. Subcritical debond behavior was determined in terms of debond growth per cycle, da/dN, as a function of applied debond driving energy, G. Salient interface debond parameters which include surface morphology, surface precoating, cement layer thickness, physiological environmental conditions, and debond length were investigated. Implications for progressive debonding under physiological loads in vivo and design consid-

erations for engineering interfaces to promote adhesion and fatigue resistance are discussed.

METHODS AND MATERIALS Materials

Interfaces were formed between clinically relevant CoCrMo prosthetic surface morphologies (Zimmer, Warsaw, IN) and PMMA (Dough Type; Zimmer) bone cement. The metal surface morphology used was a 60-grit alumina oxide grit-blasted CoCrMo substrate. The study was divided into two groups. A control group was prepared from an uncoated grit-blasted surface, and another group of samples of the same grit-blasted surface with a thin precoated layer (3050 m) of PMMA. Each group consisted of 10 samples and was first evaluated in ambient air (25C, 45% RH), then in physiological environment (37C, Ringers). Profile and topographical views of these surfaces are shown in Figure 1. Bonding between the metallic substrate and PMMA was performed under controlled conditions in a Delrin mold at room temperature (25C, 45% RH). The PMMA bone cement was hand mixed for 1.5 min in a commercial vacuum mixing kit (2.53.0 kPa; Zimmer), then transferred into a cement injection syringe (Zimmer) and injected into the Delrin mold containing a CoCrMo substrate. A mold cap was placed on top of the cement and weighted to induce a cement pressure of 0.13 MPa. Samples were cured in the mold before final preparation and testing. All edges of the specimens were carefully polished to allow for optimal optical viewing of the debond during testing.

Interface fracture mechanics

The interface debond resistance was characterized using a sandwiched double-cantilever beam (DCB) fracture mechan-

Figure 1. Scanning electron micrographs of the profile and topographical views of the (a) grit-blasted and (b) polymethylmethacrylate-precoated surfaces.

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ics sample configuration (Fig. 2). For each sample, the metal substrate had a thickness, b = 10 mm, height, h = 5 mm, and a total length, l = 70 mm. The sandwiched PMMA layer had thicknesses, hPMMA, of 2 and 5 mm, representative of actual clinical applications.17 Debond growth was initiated by cutting a wedge-shaped starter notch along the interface using a diamond wafer blade (blade thickness = 0.5 mm). A 0.5- to 1.0-mm long precrack was grown into the notch under cyclic loading conditions. Interface debond energy or toughness was measured in terms of the strain energy release rate, GR(a), as a function of debond (crack) extension, a, using the following sample dependent relations for the DCB sample18: GI = C= k= 12P2a2
2 3 E 1B h1

zone (176 m was selected in the present study; this value is representative of the largest size of the plastic zone that was estimated from the fracture experiments). was taken as the thickness of the PMMA layer. For the present samples, tip varies between 2.8 to 1.0 for the 2- and 5-mm PMMA layer thicknesses, from which it is apparent that the GII contribution will be small. In fact, numerical studies of sandwiched DCB samples with similar elastic property mismatch and layer thickness by Ozdil and Carlsson indicates that the GII contribution is typically <5%.23 Equation (1) can therefore be employed for debonding of sandwiched layers with only a small error for a relatively wide range of layer thicknesses.

3k 0.25 E 1B 4E1 E 2w1

1+

2 Ch0.25 1

h1 E 1 1 + + 2 0.5 a 8 C h1 1

h1 a
2

(1)

Interface fatigue debond testing methods

Debond-growth rates (da/dN) of the CoCrMoPMMA interfaces were determined under cyclic fatigue loading in general accordance with the current ASTM Standard E64788 for Measurement of Fatigue Crack-Growth Rates24 and modified cyclic fatigue procedures for low-toughness materials.13,2527 The fatigue tests were performed using a highresolution, computer-controlled, electro-servo-hydraulic testing system (MTS 810 load frame with 458 controller and Crackwatch fatigue-crack software control). The specimens were cyclically loaded at a sinusoidal frequency of 20 Hz under automated load-shedding schemes to obtain growth rates over a wide spectrum from 1011 to 106 m/cycle. A nominal load ratio, R (= Pmin/Pmax) = 0.1 was employed. Debond lengths were monitored in situ to a resolution of better than 2 m using D.C. electrical-potential measurements across Ni-Cr metal foil bonded to the specimen surfaces and periodically confirmed using a high-resolution optical microscope attached to a precision translation stage mounted to the mechanical test system. Current leakage in conducting aqueous environments was negligible as the electrical conductivity of the Ni-Cr metal foil was five orders of magnitude larger, and the gage and leads were insulated with a thin layer of polyurethane (M-Coat A; Measurements Group, Raleigh, N.C.). The fatigue threshold value, GTH, was approached by varying the applied loads such that the instantaneous value of G changed according to the equation: G = Go exp[2C(a ao)] (3)

E 2 2h1 + 4E 1t1 1

where P is the applied load, a the debond length, w the beam width, h1 the half-beam height, B the beam thickness, and E1 elastic modulus [E1/(1 12)] in plane strain, with Poissons ratio 1, respectively. 1 is the shear modulus of the elastic beams, and k is the total foundation modulus which is a function of h1, B, and E1, and the elastic properties, E2 and thickness t of the polymer layer (Youngs modulus: EPMMA = 2.1 GPa, ECo-Cr-Mo = 214 GPa; Poissons ratio: PMMA = 0.35, Co-Cr-Mo = 0.30). (Note that whereas the PMMA is inherently a viscoelastic material, previous work has shown that over the loading times of interest in the present work, it may be treated as a linearly elastic solid.13) The elastic property mismatch across the polymermetal interface results in a mixed mode-loading condition characterized by a phase angle at the debond tip, tip12,19: tip = tip + ln(x/) + (, ) (2) where the far-field applied phase angle, 0, and the Dundurs parameters and are measures of the mismatch in the tensile and bulk modulus across the interface.20 The bimaterial constant, , and phase shift, , depend only on and as defined elsewhere19,21 (,) was determined by extrapolation to be 1322 and was computed to be 0.073. x is an arbitrary length scale chosen to represent a relevant microstructural dimension such as the size of the plastic

where ao and Go are the initial values of the crack length, a, and applied debond energy range, G, and C is the normalized G gradient set to 0.1 mm1 of crack extension. GTH is a debond initiation criterion where the debond is assumed dormant when subjected to loading less than GTH.

Interface fracture resistance testing methods

Figure 2. Schematic representation of the sandwiched double cantilever beam fracture mechanics sample configuration. The phase angle of loading, tip, varied from 2.8 to 1.0 depending on polymethylmethacrylate layer thickness. Following completion of the fatigue debond tests when the debond-growth rate was at near-threshold levels, the interface fracture resistance was determined by montonically increasing the load under displacement control at a rate

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of 5.0 104 mm/s to generate an R-curve, G(a). Interface fracture energies, G(a), were determined as a function of debond length, a, and are presented as a function of the debond extension, a, using Equation (1). The initiation value, Go, was determined from the applied load at which initial debond propagation from the fatigue precrack was detected and the steady-state value, Gss, from the plateau of the R-curve. The fracture resistance of the interface measured under monotonic loads was also indicated on the fatigue debond-growth plots in terms of an equivalent Gc at which Gmax is equal to the steady-state plateau value of the R-curve, Gss, given in terms of the load ratio, R, as: Gc = Gss (1 R2) (4)

GR(a) in ambient air conditions (25C, 45% RH) for the PMMA precoat and uncoated grit-blast surface preparations are shown in Figure 3(a). Stable debonding was obtained over debond extensions, a, of up to 5 mm with no clear indication of initial rising R-curve behavior. The observed fluctuations in GR(a) are assumed to be associated with variations in the interface morphology. Similar debond initiation, G o , and steady-state, Gss, values of the precoated PMMA surface were significantly elevated compared to those of the uncoated grit-blasted surface (Table I). No significant differences were observed when the polymer layer thickness was increased from 2- and 5-mm. How-

Environmental conditions
Baseline interface debond resistance and fatigue debondgrowth testing was performed in ambient temperature air (25C, 45% RH). To assess the effects of physiological environment on debond growth, the same samples were placed in an environmental chamber containing Ringers solution (H2O, NaCl, KCl, and CaCl2 mixture, pH 7.4) at physiological temperature (37C). All Ringers samples were fully submerged and precracked in physiologic environment and allowed to equillibrate to physiologic conditions for a minimum of 24 h before testing. Additional solution was added periodically to the environmental chamber to replenish losses from evaporation.

Fractography
The resulting fracture surfaces were examined using a scanning electron microscope (Hitachi S-2500; Hitachi, Tokyo, Japan). A thin gold-palladium layer (510 nm) was sputtered onto the fracture surface to prevent material degradation and reduce charge build up on the surface. Regions of low and high debond extension rates along with monotonic fast fracture regions of the fracture surfaces were examined for each specimen. X-ray photoelectron spectroscopy (Surface Science Laboratories, Mountain View, CA) scans were performed on unbonded CoCrMo surfaces and the mating fracture surfaces of debonded samples.

Statistical analysis
One-tail analysis of variance was used to determine whether statistically significant differences (p < .05) existed between the mean values of Go, Gss, GTH, and Gc for the different experimental conditions.

RESULTS Interface fracture resistance Characteristic debond curves (R curves) showing the interface debond resistance (interface adhesion),
Figure 3. (a) Debond resistance curves showing the interface debond resistance, G(a), as a function of debond extension, (a), and (b) subcritical fatigue debond growth, da/ dN, behavior as a function of surface morphology and polymethylmethacrylate layer thickness.

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TABLE I Characteristic Interface Values

Fatigue (Air) Adhesion (Air) Gc (J/m2) Ro (m)* Go (J/M2) 4.6 1.2 14.0 7.2 33.1 0.2 33.3 0.3 68.7 4.7 80.2 3.9 88.1 7.6 127.6 3.5 818.1 24.4 1368.5 29.2 13.9 33.0 79.4 126.3 1354.8 1.3 9 19 25 508 18.4 2.0 23.9 7.3 55.2 12.4 50.1 14.7 89.4 6.0 77.4 6.6 82.4 23.2 187.6 27.8 184.0 39.8 640.1 20.3 2.5 1.3 10.1 0.9 18.5 5.3 31.3 1.0 249.7 7.9 Gss (J/m2) 89.3 102.3 208.1 199.8 556.9 32 27 50 57 209 Threshold Gc (J/m2) Ro (m)* GTH (J/m2) High GR G (J/m2) Threshold GTH (J/m2) Adhesion (Ringers, 37C) Fatigue (Ringers, 37C) High GR G (J/m2) 6.0 2.3 31.5 5.7 97.4 8.1 80.1 3.2 832.8 13.5

Interface/Layer Thickness

Go (J/M2)

Gss (J/m2)

GB/PMMA (2 mm) GB/PMMA (5 mm) PCPMMA (2 mm) PC/PMMA (5 mm) Bulk PMMA

113.0 9.9 94.5 2.0 178.8 8.7 202.5 2.2 147.7 21.1

90.2 7.9 103.3 4.1 210.2 8.1 201.8 2.6 562.5 14.7

*Plastic zone size estimate for interfaces: Ro =

2 31 ys PMMA 2

1 .

GoEPMMA

Plastic zone size estimate for bulk materials: rp = 21

2 2 ys PMMA

1 .

GssEPMMA

High debond growth rate (GR) value, Gc, defined by Gss [see Eq. (4)].

OHASHI AND DAUSKARDT

ever, as noted above there was statistical significance between Go and Gss values of the PMMA precoat compared to the uncoated grit-blasted samples for the 2-mm (p < .05) and 5-mm (p < .05) layers. The effect of physiological environment (37C, Ringers) on the interface debond resistance is shown in Figures 4(a) and 5(a). For both the precoated and uncoated sample sets with either the 2- or 5-mm polymer layer thickness, significant decreases (p < .05) in Go and Gss values were observed. Specifically, decreases in the steady-state debond resistance, Gss, of up to 62% for the precoat samples and up to 84% for the uncoated grit-blasted samples were observed after

Figure 4. (a) Debond resistance curves showing the interface debond resistance, G(a), as a function of debond extension, (a), and (b) subcritical fatigue debond growth, da/ dN, behavior as a function of surface morphology and enviromental conditions for the 2-mm layer thickness sample.

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Figure 5. (a) Debond resistance curves showing the interface debond resistance, G(a), as a function of debond extension, (a), and (b) subcritical fatigue debond growth, da/ dN, behavior as a function of surface morphology and environmental conditions for the 5-mm layer thickness sample.

exposed to physiological environment (Table I). Therefore, whereas precoating was observed to enhance both the initiation and steady-state interface adhesion values compared to the uncoated surfaces, a significant deterioration of the interface adhesion was observed in all samples exposed to physiological environment.

tions are plotted in terms of debond-growth per cycle, da/dN (m/cycle), as a function of the applied debond energy range, G (J/m2) in Figures 3(b), 4(b), and 5(b). To the best of our knowledge, these represents the first reported cyclic fatigue debond propagation behavior for clinically relevant CoCrMoPMMA interfaces. Stable debond extension rates ranged over six orders of magnitude, from 106 to 1011 m/cycle. The growth-rate curves were sigmoidal in shape, similar to behavior in bulk polymers and metals.1316 Similar to trends observed in the adhesion values, the entire fatigue debond curves for the PMMA-precoated surfaces were shifted to higher values, evidenced by significantly higher fatigue threshold values (GTH = 55 and 50 J/m2 for the 2- and 5-mm layers, respectively), compared to the uncoated grit-blasted samples (18 and 24 J/m2 for the 2- and 5-mm layers, respectively). At the highest growth rates measured, values of G were found to be significantly higher for the precoated surfaces (188 and 184 J/m2 for the 2- and 5-mm layers, respectively) compared to the uncoated grit-blasted samples (77 and 82 J/m2 for the 2- and 5-mm layers, respectively). Therefore, Gmax (1.01 G) values of the fatigue loading cycle at the highest growth rates corresponded well with the measured steady-state adhesion values, Gss (Table I). Fatigue debond-growth data measured in physiological compared to air environments showed substantially decreased fatigue resistance for all samples [Figs. 4(b) and 5(b)], shown by shifts in the entire subcritical debond curves to lower values of G. GTH values were reduced in the Ringers solution by 62% (2-mm layer) and 48% (5-mm layer) compared to 86% (2-mm layer) and 58% (5-mm layer) for the uncoated grit-blasted surfaces (Table I). Fracture behavior of the PMMA bulk polymer in air and physiological environments is compared to the 2-mm PMMA precoat interface samples in Figure 6. The effects of physiological environment on the bulk polymer was markedly different compared to that observed for the CoCrMoPMMA interface. In bulk PMMA, the physiological environment acts as a plasticizing agent,13 increasing the fracture resistance under both monotonic and cyclic fatigue loads. In marked contrast, exposure of the CoCrMoPMMA interface to physiological environment had the opposite effect.

Fractography Scanning electron microscopy and X-ray photoelectron spectroscopy of the debond fracture surfaces revealed primarily adhesive failure between the PMMA and metal substrates for both the PMMA-precoated and uncoated grit-blasted surfaces. However, PMMA

Interface fatigue debond-growth Characteristic fatigue debond extension behavior of the PMMA precoat and grit-blasted surface prepara-

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DISCUSSION Debonds along CoCrMoPMMA interfaces are shown to grow subcritically under fatigue loading, implying that debonding of this interface may occur at loads much lower than those required for catastrophic failure. Whereas previous investigations have only reported critical debond values,12,2931 this study includes the important effect of salient interface parameters such as initial surface morphology (roughness), surface precoating, cement layer thickness, physiological environment, and debond length on both critical fracture resistance and subcritical debondgrowth rate behavior. Understanding the fatigue debonding behavior in particular is a prerequisite for improved lifetime predictions of cemented systems under alternating physiological loads and provides a quantitative basis for designing interfaces with improved long-term reliability. When bonded interfaces are desired, numerous techniques to improve interfacial adhesion have been experimentally evaluated, including the effects of surface morphology, cement type, cement preparation, PMMA precoating, and chemical modification of surfaces (e.g., silanization).1012,30,3236 In the present study, PMMA precoating was shown to enhance the debond resistance significantly even under cyclic fatigue loading and in the presence of physiological environment compared to the uncoated surfaces. The increased resistance is thought to arise principally from an increase in contact at molecular length scales established between the PMMA and CoCrMo surfaces. Such intimate contact is difficult to achieve during surgery when contamination of the implant surface (e.g., oxide formation, biological debris) and high viscosity of the PMMA gives rise to the formation of flaws (e.g., porosity) at the interface, acting as a weak boundary layer.37 Other debond initiation sites may include BaSO4 particles, unreacted polymer, residual monomer, and biological debris. These problems are all reduced by precoating at elevated temperature, as evidenced by the improved adhesion and subcritical debond resistance. Finally, bulk PMMA bonding to the precoated PMMA has been shown to be strongly cohesive,11 and failure of the PMMA precoat and bulk PMMA was not observed in the present study (Fig. 7). From a clinical standpoint, evaluation of interface debonding in physiological environment is critical to understanding the micromechanisms of failure in vivo. A number of studies on other adhesive joint systems have shown that water is one of the most hostile environments for interfaces with metal substrates. Critical fracture values have been shown to deteriorate upon exposure to moist environment.38,39 CoCrMo PMMA interfaces are not exceptions to this general trend. As demonstrated in the present study, resistance to debonding under both monotonic and cyclic

Figure 6. (a) Debond resistance curves showing the interface debond resistance, G(a), as a function of debond extension, (a), and (b) subcritical fatigue debond growth, da/ dN, behavior for PMMA precoat/PMMA interface, and bulk polymer samples for comparison.

ligaments were found bonded to the metal surface as shown in Figure 7(c). This is consistent with the formation of a debond bridging zone behind the debond tip, where polymer ligaments may be left behind the debond tip as the debond extends, as previously reported.12 In addition, wear debris at the prosthetic PMMA interface was observed [Fig. 7(a,d)]. These wear particles were present only in the fatigue regions of the debond fracture surface. Particle size analysis indicated values in the range of 0.43 m for the PMMA-precoated, and 0.12 m for the uncoated gritblasted surfaces. The size of the wear particles was consistent with those found clinically.28

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Figure 7. Representative scanning electron micrographs of the fracture behavior along the precoated interface showing (a) PMMA ligament left on the fast fracture surface, and (b) PMMA wear particles in the fatigue region. Micrographs for the uncoated grit-blasted surface show (c) no wear particles left on the fast fracture region, and (d) wear particles in the fatigue region.

loads are significantly reduced in simulated physiological environments (Figs. 4 and 5, and Table I). This is in marked contrast to the enhanced fracture resistance observed when bulk PMMA is exposed to a physiological environment, as shown in Figure 6.13 Such behavior is due to plasticization and crazing of the PMMA, which results in crack tip blunting and relaxation of the crack tip stress fields. Although interface debonding in the presence of physiological environment may involve similar processes of plasticization and crazing in the PMMA, this effect is overwhelmed by the reduction of cohesive strength of the interface that results from the interaction of water molecules with the strained debond tip atomic bonds. In the present work, the location of the debond path was precisely determined using X-ray photoelectron spectroscopy (XPS). Debonding was found to occur at the interface between the PMMA and the metal oxide. The XPS spectra indicating the type of oxide formed on the surface of a fine polished

CoCrMo sample in a moist air environment is shown in Figure 8. Only a Cr-oxide (Cr2O3) was noted, with no evidence of Co or Mo on the surface. The susceptibility of chrome oxides to stress corrosion cracking is unknown, but the interface of these oxides to PMMA which typically involves weak van der Waals chemical bonding may be potential sites for environmental attack.40,41 One measure of the interface susceptibility to stress corrosion cracking may be obtained by considering the thermodynamic work of adhesion in the presence of the environment of interest. The work of adhesion in air, Wa, and the work of adhesion in water, Wal, are given by the well-known Dupre relationships42:
D 0.5 P 0.5 + 2P Wa = 2D a s a s

(5)

P P 0.5 P 0.5 D 0.5 D D 0.5 l P D s l Wal = 2l s a l a l P P 0.5 D D 0.5 + a s + a s (6)

where a, s, and l are the surface free energies of the

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Figure 8. Representative X-ray photoelectron spectroscopy scans of a fine-polished CoCrMo substrate showing (a) chrome-oxide (Cr2O3) binding energy peak identified by the appearance of the characteristic chrome peak measured after sputter etching away the oxide layer off the surface with no evidence of a molybdenum oxide, and (b) no indication of a cobalt oxide binding energy peak.

PMMA, oxide, and water,43 respectively, and P and D indicate the polar and dispersion force contributions. 2 2 P Using values of D a = 35.9 mJ/m and a = 4.3 mJ/m D 2 P 2 for the PMMA, s = 100 mJ/m and s = 500 mJ/m for a typical metal oxide, and l = 72.2 mJ/m2, D l = 2 = 50.2 mJ/m for water, W and Wal 22.0 mJ/m2 and P l a were estimated to be 213 mJ/m2 and 139 mJ/m2, respectively. We conclude that whereas the interface in air is thermodynamically stable, the change from a positive to a negative value in water indicates that the interface has a propensity to spontaneously debond because it is thermodynamically unstable. It is important to note that these interface work of adhesion values only provide a measure of the adhesive energy associated with chemical bonding at the interface. The macroscopic adhesion values reported in this study include additional energy dissipation processes such as mechanical interlocking and debond tip plasticity that result in significantly higher values than the energy required to separate chemical bonds. However, energy dissipation through these processes are coupled to the intrinsic work of adhesion, as has been discussed in detail elsewhere.4446

In addition to the above thermodynamic arguments, other processes may also contribute to the effect of aqueous environments. For example, considerable capillary pressure may develop in a gas pocket trapped at the crack tip and provide energy to extend the debond.47 Alternatively, under cyclic loading the effects of hydrodynamic pressures developed in a trapped fluid in the wake of a growing fatigue crack has been shown to shield the crack tip from the applied loads and reduce the crack growth rate.48 In the case of some metal oxides such as alumina, exposure of the interface to moist environments results in a number of hydration reactions that degrade the oxide and mechanically weaken the interface.40,49,50 Finally, increasing concentrations of active ions such as sodium and chloride have been shown to result in electrochemical reactions at the polymeroxide interface that lead to premature failure.51,52 In all cases, precoating the metal surfaces, which results in more intimate interfacial contact at the interface, is expected to reduce the effects of environment as the environmental species is sterically hindered from reaching the fracture process zone. A strategy to counteract the effect of environmental degradation on similar polymermetal interface systems has been to employ surface chemistry techniques which use organosilane adhesion promoters to replace the weak chemical bond with a stronger covalent bond.39,53,54 Despite the potential advantages of using chemical surface enhancements, few studies have attempted to used such techniques to improve the interfacial strength of prostheticPMMA systems. In a recent study, the presence of a silane coupling agent was demonstrated to significantly increase the interfacial shear strength of CoCrMoPMMA interfaces in both laboratory air and aqueous saline environments.33,34 In another study, we report that similar chemical modification improves both the adhesion and subcritical debond-growth rate behavior of CoCrMoPMMA interfaces when exposed to physiological environment.35 Methods such as these together with their biocompatibility ramifications must clearly be investigated further to optimize the design of cemented implant systems which are exposed to physiological environment. Another issue that may have significant effect on clinical performance is the effect of cement mantle thickness on the reliability of cemented interfaces. It has been suggested that the optimal cement mantle thickness is 25 mm.17 Apparently, mantles <2 mm thick are subject to cracking and failure in the bulk polymer, whereas mantles >5 mm lead to premature debonding of the interface. In the present study, to assess the effect of elastic constraint on measured adhesion and subcritical debonding behavior, we examined samples with PMMA layer thickness in the range of 25 mm. No significant shifts in adhesion or sub-

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181

critical debond behavior were apparent (Fig. 3), and no changes in the debond path were observed except for the thickest layers where the fracture path occasionally moved from the interface into the polymer layer. These results indicate that constraint of the PMMA layer from the adjacent metal substrates does not appear to significantly affect the debond failure process. It should be noted, however, that the size of the plastic zone developed ahead of the debond tip may be significantly affected by elastic constraint from adjacent elastic substrates as has been observed in other polymermetal systems.26,55 In more recent mechanics models of the plastic energy dissipation associated with interface debonding adjacent to a ductile layer, an important length scale that is related to the size of the plastic zone that would form in a sample of the ductile material is given by45,46: Ro = 1
2

EPMMAGo

2 31 YS PMMA

(7)

where ys(PMMA) is the yield strength of PMMA. Previously reported work using bimaterial samples with identical PMMA to grit-blasted CoCrMo interfaces in which the initial R-curve behavior was carefully monitored indicated Go values of 4 J/m2,12 smaller than the steady-state fracture resistance, Gss, but considerably larger than the work of adhesion values calculated above which do not include mechanical interlocking contributions. Using ys(PMMA) = 30 MPa, the value of Ro was found to be 1.6 m. From preliminary studies of thin precoated interfaces (Go 93 J/m2), we estimate that Ro 26 m. Although detailed model calculations are not available for the present material combinations, predictions for other ductile layer systems show that layers may be considered thick when the thickness is a few times the value of Ro.45,46 Thinner layers curtail the development of the plastic zone and result in lower macroscopic fracture resistance as plastic work contributions are reduced. Clearly, for the samples used in the present study and for clinically relevant situations, the cement layer thickness is significantly larger than Ro and no marked effect of layer thickness is expected. Yet another important issue relevant to the clinical performance of cemented interfaces between hard metallic surfaces and softer polymer layers is the formation of wear debris under fatigue loading. Indeed, the compromise associated with enhancing adhesion with rougher interfaces and the potential for increased polymer wear debris formation has been reported.8,36 This study provided ideal conditions for the collection and analysis of wear particles from the fatigue fracture surfaces (Fig. 7). Careful particle size analysis indicated that the wear particles had a bimodal size distribution with peaks 0.3 and 1 m. These particle

sizes are consistent with the size of wear particles reported from in vivo studies and are also similar in size to the scale of the grit-blasted surface roughness (RMS = 4.2 m). Further studies are required to understand the micromechanisms of wear and the effect of metal surface roughness, loading, and environmental conditions on the resulting wear particles. We note how subcritical debond-growth rate behavior can be employed in life prediction methodologies for cemented joint replacements. Using standard fracture mechanics damage tolerant life prediction procedures, the life of the cemented system is assumed to be determined by the growth of preexisting defects or delaminations at the PMMA metal interface to a critical size. Initiation effects are therefore not considered to contribute significantly to the overall life; in the present applications, this is most likely a realistic assumption given the level of porosity and contamination at the interface. By fitting a powerlaw relationship to the subcritical debonding data (da/dN = CGm) and integrating the resulting equation from some initial debond length, ao, to a final critical length, ac, the lifetime of the system can be predicted. The number of cycles to failure of the system, Nf, can be expressed as: Nf =
m ECoCrMo

m 1CQ
2m m

2m

1
1 am o

1
m1 ac

(8)

where Q is a geometrical factor dependent on the debond location and joint geometry, and is the applied physiological stress range. There are a number of complexities and approximations that must be made to apply the procedure. Estimation of the physiological loads, assuming an initial defect size and the changing phase angle of loading during debond growth, is but a few. To illustrate the method, we estimate the lifetime of a CoCrMo/PMMA interface using Equation (8) and approximate the applied physiological stress range and Q values from previously reported finite element studies.56 As a simplification, a bimaterial cylindrical interface model with a penny-shaped crack was used to approximate the geometric factor Q.57 From simple calculations, the number of years to failure, Nf, is shown to be a strong function of initial flaw size and applied stress (i.e., normal gait to stair climbing) (Fig. 9). More accurate predictions of interface lifetimes will require a detailed finite element model of specific joint geometries, initial debond location and physiological loads. However, as illustrated, this approach offers the potential for a conservative life prediction methodology that is otherwise not currently available. CONCLUSIONS A quantitative method to study the adhesion and subcritical debond behavior of clinically relevant

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OHASHI AND DAUSKARDT

2.

3.

4.

5.

6.

Figure 9. Fatigue lifetime curves computed from Equation (8) for a model uncoated grit-blasted CoCrMo/PMMA interface configuration (C = 2.1 1010; m = 4.6; Q = 0.6; and ac = 100 103 m) are shown to be strongly influenced by increasing physiological loads and initial flaw size. For example, for a flaw size of 4.0 mm under normal walking loads (6.5 MPa), the fatigue lifetime is 14 years; under stairclimbing loads (15 MPa), the lifetime is reduced to 3 days.

7. 8.

9.

10.

CoCrMoPMMA interfaces was used to characterize the effects of PMMA precoating of grit-blasted CoCrMo surfaces. Debond R-curve behavior which measures the macroscopic work of fracture and the resistance to subcritical debonding under tension tension fatigue loading conditions (da/dN vs. G) is reported. The effect of precoating, polymer layer thickness and simulated physiological environmental conditions are described. The steady-state interfacial fracture energy and the fatigue debond-extension threshold, GTH, obtained from the subcritical debond curve under fatigue loading were significantly enhanced with PMMA precoating. No significant differences in interfacial debond behavior was observed for PMMA layer thicknesses of 2- and 5-mm. Exposure to a simulated physiological environment resulted in markedly reduced interface adhesion and subcritical debond-growth behavior for the CoCrMoPMMA interfaces studied. However, by precoating at elevated temperature to establish a more intimate bond at the interfaces, increased environmental resistance of the polymer/metal interface can be achieved. Life prediction methods using the subcritical debond-growth rate data were discussed.
Materials were provided by Zimmer (Warsaw, IN). Particle analysis was performed by the Material Science Department at the Pacific Northwest National Laboratory, Richland, Washington.

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