A novel high-viscosity, two-solution acrylic bone cement: effect of chemical composition on properties.

Solutions of poly(methyl methacrylate) (PMMA) powder predissolved in methyl methacrylate (MMA) have been developed as an alternative to current powder/liquid bone cements. They utilize the same addition polymerization chemistry as commercial cements, but in mixing and delivering via a closed system, porosity is eliminated and the dependence of material properties on the surgical technique is decreased. Twelve different sets of compositions were prepared, with two solutions of constant polymer-to-monomer ratio (80 g of PMMA/100 mL of MMA) and all combinations of four benzoyl peroxide (BPO) initiator levels added to the first solution and three N, N-dimethyl-p-toluidine (DMPT) activator levels added to the second. These compositions were tested, along with Simplex-P bone cement, for effects of BPO and DMPT concentrations on polymerization exotherm, setting time, flexural strength, modulus, and maximum strain. The results show that each of these dependent variables was affected significantly by the individual concentrations of BPO and DMPT and their interactions. The flexural strength, modulus, and polymerization exotherm reached their maximums at about a 1:1 molar ratio of BPO to DMPT. Most compositions had exotherms, setting times, and maximum strains within the range of commercial cements and flexural strengths and moduli up to 54 and 43% higher than Simplex-P, respectively.     

Relationship between fracture toughness and impact strength of acrylic bone cement

This work involved determining the fracture toughness, KIc (in MPa(square root)m) (using rectangular compact tension specimens) and impact strength, IS (in kJ/m2) (Charpy type specimens) of Surgical Simplex P and three variants of Palacos R acrylic bone cements. The best fit to these results yielded a power relationship KIc = 0.795(IS)0.59. The usefulness of this relationship is detailed, especially for the purpose of performing quality control checks on bone cements.     

Effect of lithotriptor treatment on the fracture toughness of acrylic bone cement.

Extracorporeal shock wave lithotripsy (ESWL) has now been established as an efficacious non-invasive modality for the management of renal calculi and has shown promise for management of other types of stone, as well. Following on from these successes, ESWL has recently been proposed for use in the preliminary stages of revision of cemented total hip joint replacements as a means of breaking up the cement mantle. It is useful, therefore, to examine the effect of shock waves on pertinent mechanical properties of the cement. This study utilizes the chevron-notch short-rod specimen and a commercially available test system to obtain the values of one such property, namely fracture toughness, of Palacos Radiopaque bone cement before and after treatment with shock waves delivered from a lithotriptor. The fracture toughness drops by about 14% following the shock wave treatment, thus confirming the possibility that ESWL can be used, as indicated earlier, in revision arthroplasty.     

Effect of loading rate on the apparent fracture toughness of acrylic bone cement

In this study, a determination is made of the effect of loading rate, v (0.1 mm min(-1) versus 1.0 mm min(-1) versus 10 mm min(-1)) on the value of the plane strain fracture toughness, K(Ic), of three commercial formulations of acrylic bone cement (Osteopal), CMW3, and Copal), that are characterized as "low-", "medium-", and "high-" viscosity brands, respectively). For all formulations, K(Ic) increases with increase in v. However, while this trend is statistically significant for CMW3 and Copal, this is not so for Osteopal. The CMW3 and Copal results are explained in terms of changes of the molecular relaxation transitions in the cement and the thermal state at the crack tip of the test specimen. Two implications of the findings are discussed. In the case of Osteopal, a recommendation for further study is made.     

Quantitative analysis of monomer vapor release from two-solution bone cement by using a novel FTIR technique

Methyl methacrylate monomer can evaporate from bone cement to reach cytotoxic levels of concentrations in the implant bed of total joint prosthesis. Therefore, this study was performed by using a novel Fourier transform infrared spectroscopy method to quantify the release of monomer vapor from experimental two-solution bone cement in vitro during polymerization, to examine the effect of surface area versus cement mass, and to explore the effect of initiation chemistry. The results revealed that monomer vapor release is a surface phenomenon. In addition, initiation chemistry plays a major role in controlling the reaction time, and therefore heat concentration and dissipation, which resulted in a higher absorbance peak as initiation chemicals concentration increased. It was concluded that using the FTIR to monitor MMA vapors is an effective technique to obtain quantitative information about monomer vapor release from bone cements during polymerization and provides insight on the polymerization kinetics of two-solution acrylic bone cement.     

Effect of triphenyl bismuth on glass transition temperature and residual monomer content of acrylic bone cements

Self-curing acrylic bone cements are widely used in the fixation of prosthetic implants in orthopaedic surgery. Commercial bone cements are rendered radiopaque by the addition of heavy metal salts of barium and zirconia. The addition of barium sulphate adversely affects the mechanical strength and fracture toughness of bone cement and despite the fact that it has low solubility in water; its slow release and subsequent toxicity have caused concern. In an earlier study triphenyl bismuth (TPB) was found to be a viable alternative as a radiopaque agent in acrylic bone cements, which provided enhanced homogeneity. In this study we report the effect of the inclusion of TPB on the thermal properties of PMMA-based bone cements using both conventional DSC and Modulated Temperature DSC. Furthermore, analysis of the residual monomer contents is reported analysed by NMR spectroscopy in order to ascertain the influence of TPB on the polymerisation reaction. The glass transition temperature (Tg) determined by DSC showed that the values decreased with the addition of increasing amounts of TPB through both blending and dissolution methods; however, the method of incorporating TPB did not influence Tg. The magnitude of reduction was dependent of the amount of TPB and was greatest in the case of highest concentration of TPB used. A TPB melting peak was observed in the 25 wt% TPBBC, suggesting a limit to the solubility of TPB. The residual monomer analysis showed that at 10 and 15% by weight of TPB in the cement caused no significant changes in the residual monomer content but 25 wt% of TPB exhibited a significantly higher residual monomer content.     

Effect of triphenyl bismuth on glass transition temperature and residual monomer content of acrylic bone cements

Self-curing acrylic bone cements are widely used in the fixation of prosthetic implants in orthopaedic surgery. Commercial bone cements are rendered radiopaque by the addition of heavy metal salts of barium and zirconia. The addition of barium sulphate adversely affects the mechanical strength and fracture toughness of bone cement and despite the fact that it has low solubility in water; its slow release and subsequent toxicity have caused concern. In an earlier study triphenyl bismuth (TPB) was found to be a viable alternative as a radiopaque agent in acrylic bone cements, which provided enhanced homogeneity. In this study we report the effect of the inclusion of TPB on the thermal properties of PMMA-based bone cements using both conventional DSC and Modulated Temperature DSC. Furthermore, analysis of the residual monomer contents is reported analysed by NMR spectroscopy in order to ascertain the influence of TPB on the polymerisation reaction. The glass transition temperature (T _g) determined by DSC showed that the values decreased with the addition of increasing amounts of TPB through both blending and dissolution methods; however, the method of incorporating TPB did not influence T _g. The magnitude of reduction was dependent of the amount of TPB and was greatest in the case of highest concentration of TPB used. A TPB melting peak was observed in the 25 wt% TPBBC, suggesting a limit to the solubility of TPB. The residual monomer analysis showed that at 10 and 15% by weight of TPB in the cement caused no significant changes in the residual monomer content but 25 wt% of TPB exhibited a significantly higher residual monomer content.     

Relative influence of composition and viscosity of acrylic bone cement on its apparent fracture toughness

The composition and viscosity of an acrylic bone cement have both been identified in the literature as being parameters that affect the mechanical properties of the material and, by extension, the in vivo longevity of cemented arthroplasties. The objective of the present study was to determine the relative influence of these parameters on a key cement mechanical property; namely, its fracture toughness. Two sets of cements were selected purposefully to allow the study objective to be achieved. Thus, one set comprised two cements with very similar compositions but very different viscosities (Cemex RX, a medium-viscosity brand, and Cemex Isoplastic, a high-viscosity brand) while the other set comprised two cements with similar viscosities but with many differences in composition (Cemex Isoplastic and CMW 1). Values of the fracture toughness (as determined using chevron-notched short rod specimens) [K(ISR)] obtained for Cemex RX and Cemex Isoplastic were 1.83 +/- 0.12 and 1.85 +/- 0.12 MPa square root(m), respectively, with the difference not being statistically significant. The K(ISR) values obtained for Cemex Isoplastic and CMW 1 were 1.85 +/- 0.12 and 1.64 +/- 0.18 MPa square root(m), respectively, with the difference being statistically significant. Thus, the influence of cement composition on its K(ISR) is more marked relative to the influence of cement viscosity. Explanations of this finding are offered, together with comments on the implications of the results for the in vivo longevity of cemented arthroplasties.     

The fracture toughness of titanium-fiber-reinforced bone cement.

Fracture of the poly(methyl methacrylate) bone cement mantle can lead to the loosening and ultimate failure of cemented total joint prostheses. The addition of fibers to the bone cement increases fracture resistance and may reduce, if not eliminate, in vivo fracturing. This study discusses the effect of incorporating titanium (Ti) fibers on fracture toughness. Essential characteristics of the composite bone cement included a homogeneous and uniform fiber distribution, and a minimal increase in apparent viscosity of the polymerizing cement. Ti fiber contents of 1%, 2%, and 5% by volume increased the fracture toughness over non-reinforced bone cement by up to 56%. Bone cements of two different viscosities were used as matrix material, but when reinforced with the same fiber type and content, they showed no difference in fracture toughness. Four different fiber aspect ratios (68, 125, 227, 417) were tested. At 5% fiber content, there was no statistically significant dependence of fracture toughness on fiber aspect ratio. Scanning electron microscopy revealed important toughening mechanisms such as fiber/matrix debonding, local fracture path alteration, and ductile fiber deformation and fracture. Fiber fracture was evidence that the critical fiber length was exceeded. The surfaces of the Ti fibers were rough and irregular, indicating that a high degree of mechanical interlock between matrix and fiber was likely. The energy absorption contribution of plastic deformation and ductile fracture is absent in brittle fibers, like carbon, but is a distinction of the Ti fibers used in this study.     

Effect of mixing method and storage temperature of cement constituents on the fatigue and porosity of acrylic bone cement.

The influence of the storage temperature of the cement constituents prior to mixing (21 vs. 4 degrees C) and the mixing method (hand mixing vs. vacuum mixing) on the uniaxial tension-compression fatigue performance and porosity of Palacos R acrylic bone cement was studied. The fatigue results were analyzed using the three-parameter Weibull equation. The fatigue performance was expressed as an index I, which was defined as the product of the Weibull characteristic fatigue life and the square root of the Weibull slope. Statistical analyses of these results show that although the mixing method (for a given storage temperature) exerts a significant influence on the fatigue performance and areal porosity, the effect of storage temperature (for a given mixing method) on either of these parameters is not significant.     

Effect of test frequency on the in vitro fatigue life of acrylic bone cement

The goal of the present work was to test the hypothesis that test frequency, f, does not have a statistically significant effect on the in vitro fatigue life of an acrylic bone cement. Uniaxial constant-amplitude tension-compression fatigue tests were conducted on 12 sets of cements, covering three formulations with three very different viscosities, two different methods of mixing the cement constituents, and two values of f (1 and 10 Hz). The test results (number of fatigue stress cycles, N(f)) were analyzed using the linearized form of the three-parameter Weibull equation, allowing the values of the Weibull mean (N(WM)) to be determined for each set. Statistical analysis of the lnN(f) data, together with an examination of the N(WM) estimates, showed support for the hypothesis over the range of f used. The principal use and explanation of the present finding are presented.     

Effect of fabrication pressure on the fatigue performance of Cemex XL acrylic bone cement

During a cemented arthroplasty, the prepared polymerizing dough of acrylic bone cement is subjected to pressurization in a number of ways; first, during delivery into the freshly prepared bone bed, second, during packing in that bed (either digitally or with the aid of a mechanical device), and, third, during the insertion of the prosthesis. Only a few studies have reported on the influence of the level of pressurization experienced during these events (which, depending on the cementing technique used, has been put at between 8 and 273 kPa) on various properties of the cement. That was the focus of the present study, in which the fully reversed tension-compression (+/-15 MPa; 5 Hz) fatigue lives (expressed as number of cycles to fracture, N(f)) of rectangular cross-sectioned "dog-bone" specimens (Type V, per ASTM D 638) fabricated from Cemex XL cement, at pressure applied continuously to the cement dough during curing in the specimen mold, p=75,150, and 300 kPa, were determined. The N(f) results were analyzed using the linearized transformation of the three-parameter Weibull relationship to obtain estimates of the Weibull mean, N(WM), which was taken to be the index of fatigue performance of the specimen set. Over the range of p studied, N(WM) increased as p increased (for example, from 329,118 cycles when p was 75 kPa to 388,496 cycles when p was 300 kPa); however, the increase was not significant over any pair of p increment steps (Mann-Whitney U-test; alpha<0.05).     

Analysis of the shelf life of a two-solution bone cement

Two-solution bone cement consists of methyl methacrylate monomer and poly(methyl methacrylate) polymer dissolved together to yield a viscous solution. Two solutions are used such that the initiator, benzoyl peroxide (BPO), is placed in one solution and the activator, N,N, dimethyl-para-toluidine, is placed in the other. This approach to bone cement provides for a simplified use during surgery and eliminates some of the sources of porosity formation. However, the BPO-containing solution cement will spontaneously polymerize over time and will limit the useful shelf life of this component of the system. The activator-containing component is much more stable and is not as susceptible to spontaneous polymerization. In making two-solution cements, it is envisioned that antibiotics may be incorporated and that the polymer may be sterilized using gamma(gamma)-irradiation. Therefore, this study investigated the shelf life of the initiator-containing solution bone cement and studied the effects of initiator concentration, gamma-irradiation, gentamicin addition, and the role of storage temperature. Isothermal differential scanning calorimetry (Iso-DSC) techniques were used to monitor the polymerization of BPO-containing solutions. It was found that the shelf life was highly temperature dependent and followed an Arrhenius expression where refrigeration storage (4 degrees C) yielded approximately a 12-month storage time, while 70 degrees C storage results in setting in about 5-7 min. gamma-irradiation and gentamicin addition did not significantly affect the shelf life. Initiator concentration affected storage time with higher levels resulting in shorter shelf life.     

Effect of test specimen cross-sectional shape on the in vitro fatigue life of acrylic bone cement

Constant-amplitude uniaxial tension-compression fatigue tests were conducted on specimens fabricated from 12 sets of acrylic bone cements, covering cement formulations with three different viscosities (so-called "high-", "medium-" and "low-viscosity" varieties), two different methods of mixing the cement constituents (so-called "hand-" and "vacuum-mixed" methods) and two test specimen shapes (rectangular-cross-sectioned or "flat" and circular-cross-sectioned or "round"). The test results-namely, the number of fatigue stress cycles, N(f)-were analyzed using the linearized transformation of the three-parameter Weibull relationship, allowing the values of the Weibull mean, N(WM), to be determined for each set. Values ranged from 14,300 to 1,284,331 for the round specimen sets and from 2898 to 72,960 for the flat specimen sets. Statistical analysis of the ln N(f) data, together with an examination of the N(WM) values, showed that, for any combination of cement formulation and mixing method, round specimens had significantly longer fatigue lives compared to flat ones. These results are explained in terms of two factors. The first is the smaller surface area of the waisted zone in the round specimens compared to that in the flat specimens (nominal value of 157mm(2) versus nominal value of 185mm(2)), leading to the possibility of fewer crack initiation sites on the round specimens compared to the flat ones. Secondly, it is postulated that the crystallinity of the round specimens was higher than that of the flat ones, a consequence of the significantly lower measured residual liquid monomer contents of the former compared to the latter (3.40+/-1.28wt%/wt compared to 3.81+/-1.48wt%/wt). The significance of the present finding is that it indicates that, for a set of bone cement formulation and experimental conditions, discriminating fatigue test results are more likely to be obtained if flat, rather than round, test specimens are used.     

Effect of two variables on the fatigue performance of acrylic bone cement: mixing method and viscosity

The goal of the present work was to establish the relative influence of one exogenous variable versus one endogenous variable on the fully-reversed tension-compression fatigue performance of bone cement. The method used to mix the cement constituents was the exogenous variable, while the viscosity of the mixed cement dough was the endogenous variable. Two commercial cement formulations (Palacos R and Osteopal) and two cement mixing methods (hand mixing and vacuum mixing) were used. It was found that for a given mixing method, cement viscosity exerts a marginal influence on fatigue performance. On the other hand, for a given cement formulation, vacuum mixing led to a statistically significant improvement in fatigue performance. The present results demonstrate the superior influence of mixing method over cement viscosity.     

Effect of porosity and environment on the mechanical behavior of acrylic bone cement modified with acrylonitrile-butadiene-styrene particles: I. Fracture toughness.

The elastomeric copolymer acrylonitrile-butadiene-styrene (ABS) was added to a conventional acrylic bone cement matrix. The results obtained show that although strength and stiffness decreased with an increasing second phase volume fraction, ductility and toughness both increased. The crack propagation became stable for specimens containing over a 5% volume fraction of the second phase. The fracture toughness increased up to 60% when the amount of ABS reached 20% (v/v). For larger amounts linear elastic fracture mechanics techniques could not be used properly. The effects of porosity and environmental conditions on the mechanical behavior were also studied. The mechanisms that control the fracture process were investigated by means of scanning electron microscopy.     

Statistical distribution of the fatigue strength of porous bone cement

This paper reports on the damaging effects of different percentage porosities on the fatigue life of acrylic bone cement as used in the fixation of orthopaedic implants. Both hand-mixed (HM) and vacuum-mixed (VM) specimens containing different levels of porosity were fatigue tested to failure. A negative correlation between porosity level and fatigue life was demonstrated for both techniques. Considerable scatter was present in the data. Using the pore size distributions for HM and VM cement virtual HM and VM specimens were created containing various levels of porosity. Incorporating the effect of pore size and pore clustering quantified previously using the theory of critical distances a fatigue life prediction could be obtained for the virtual specimens. The virtual data agreed strongly with the experimental findings, predicting the correlation and more significantly the scatter in the experimental results. Using the virtual porosity failure model, it was demonstrated that given a constant porosity the fatigue life can vary by over an order of magnitude in both HM and VM cement. This suggests that not only porosity level but pore size distribution is extremely important in controlling the fatigue life of bone cement. It was verified that pore clustering and pore size are the major contributors to failure in HM and VM cement respectively. Furthermore, given the beneficial effects of porosity it has been proposed that an even distribution of small pores would provide an optimal bone cement mantle. Using the virtual model, it was determined that neither technique was capable of achieving such a distribution indicating a need for a new more reliable technique. The TCD based virtual porosity failure model should prove to be a powerful tool in the design of such a technique.     

Effects of the initial temperature of acrylic bone cement liquid monomer on the properties of the stem-cement interface and cement polymerization

It has been shown that preheating the femoral stem prior to insertion minimizes interfacial porosity at the stem-cement interface. In this study, the effects of methylmethacrylate monomer temperature prior to mixing on the properties of stem-cement interface and cement polymerization were evaluated for 4 degrees C, room temperature, and 37 degrees C using a test model and cementing techniques that simulated a clinical situation. The nature and extent of interfacial porosity of stem-cement interface was quantified, the static shear strength of the stem-cement interface determined, and the time and temperature of polymerization at the cement-bone interface were measured. Compared to RT monomer, preheating monomer to 37 degrees C produced higher polymerization temperatures and greater initial interfacial shear strength with an unchanged amount of interfacial porosity. Precooling monomer to 4 degrees C produced lower polymerization temperatures and decreased initial interfacial shear strength, with the amount of interfacial porosity unchanged compared to the RT group. Although clinical techniques of preheating or precooling bone cement have some effects on the properties of the stem-cement interface and cement polymerization, they do not appear to enhance implant fixation.     

Correlation between impact strength and fracture toughness of PMMA-based bone cements

The thrust of the work involved determining the impact strength, IS (in kJ m(-2)) [using non-ASTM-sized Charpy-type specimens and an in-house impact tester] and fracture toughness, K1c (in MPa square root(m)) [using ASTM-sized rectangular compact tension specimens] of Surgical Simplex P and three variants of Palacos R acrylic bone cements. The attractions and drawbacks of this method for determining IS are detailed. The best fit to the K1c and IS results yielded a power relationship K1c = 0.795(IS)(0.59). The usefulness and limitations of this relationship are detailed.     

Fatigue and fracture toughness of acrylic bone cements modified with long-chain amine activators

The composition of acrylic bone cement has been identified as one of the important parameters affecting its mechanical properties and may, in turn, ultimately influence the longevity of a cemented arthroplasty. Our aim in this study was to determine the influence of change of one compositional variable, the activator, on the fatigue performance and fracture toughness of specimens of the fully cured cement. To that end, three sets of cements were prepared, containing either the conventional activator, 4-N,N dimethyl p-toluidine (DMPT), or novel ones that are tertiary amines based on long-chain fatty acids, that is, 4-N,N dimethylaminobenzyl oleate (DMAO) and 4-N,N dimethylaminobenzyl laurate (DMAL). In the fatigue tests, the specimens were subjected to tension-tension loading, and the results (number of cycles to failure, Nf) were analyzed using the linearized form of the three-parameter Weibull equation. The fracture toughness (KIc) tests were conducted with rectangular compact tension specimens. All fracture surfaces were subsequently examined with scanning electron microscopy. We found that the Weibull mean fatigue lives for specimens fabricated using the DMPT, DMAL, and DMAO containing cements were 272,823, 453,551, and 583,396 cycles, respectively. The corresponding values for KIc were 1.94 +/- 0.05, 2.06 +/- 0.09, and 2.00 +/- 0.07 MPa radical m, respectively. Statistical analyses showed that for both the DMAL- and DMAO-containing cements, the mean values of Nf were significantly higher compared to the corresponding value for the DMPT-containing cement (Mann-Whitney test; alpha < 0.10). This result is attributed to the higher molecular weights of the former cements compared to the latter. The same trend was found for the mean KIc values (Mann-Whitney test; alpha < 0.05), with the trend being explained in terms of the differences seen in the crack morphologies. These results thus demonstrate that these novel amines are viable alternatives to DMPT for incorporation into acrylic bone cement formulations in the future.