Exothermal characteristics and release of residual monomers from fiber-reinforced oligomer-modified acrylic bone cement

The aim of this study is to determine the peak temperature of polymerization, the setting time and the release of residual monomers of a modified acrylic bone cement. Palacos R, a commercial bone cement, is used as the main component. The cement is modified by adding short glass fibers and resorbable oligomer fillers, and an additional cross-linking monomer. The test specimens are classified according to the composition of the bone cement matrix (i.e., oligomer-filler, glass-fiber reinforcement, and/or cross-linking monomer). The exothermal characteristics during autopolymerization are analyzed using a transducer connected with a computer. The quantities of residual monomers were analyzed from different test groups using high performance liquid chromatography (HPLC). The DeltaT value for the oligomer filler and the glass-fiber-containing acrylic bone cement is lower than that for the unmodified bone cement (2.1 +/- 0.8 vs. 23.5 +/- 4.2 degrees C). The addition of a cross-linking monomer, EGDMA, shortens the setting time of the autopolymerization of the unmodified bone cement (7.1 +/- 0.9 min vs. 3.3 +/- 0.3 min). The quantity of the residual monomers released is higher in the modified bone cement than that in the unmodified cement. The cement that contains glass fibers and oligomer fillers has a considerably lower exothermal peak, whereas the total quantity of residual monomers released is increased.     

Mechanical behaviour of a new acrylic radiopaque iodine-containing bone cement

In total hip replacement, fixation of a prosthesis is in most cases obtained by the application of methacrylic bone cements. Most of the commercially available bone cements contain barium sulphate or zirconium dioxide as radiopacifier. As is shown in the literature, the presence of these inorganic particles can be unfavourable in terms of mechanical and biological properties. Here, we describe a new type of bone cement, where X-ray contrast is obtained via the introduction of an iodine-containing methacrylate copolymer; a copolymer of methylmethacrylate and 2-[4-iodobenzoyl]-oxo-ethylmethacrylate (4-IEMA) is added to the powder component of the cement. The properties of the new I-containing bone cement (I-cement) are compared to those of a commercially available bone cement, with barium sulphate as radiopacifier (B-cement). The composition of the I-cement is adjusted such that similar handling properties and radiopacity as for the commercial cement are obtained. In view of the mechanical properties, it can be stated that the intrinsic mechanical behaviour of the I-cement, as revealed from compression tests, is superior to that of B-cement. Concerning the fatigue behaviour it can be concluded that, though B-cement has a slightly higher fatigue crack propagation resistance than I-cement, the fatigue life of vacuum-mixed I-cement is significantly better than that of B-cement. This is explained by the presence of BaSO4 clumps in the commercial cement; these act as crack initiation sites. The mechanical properties (especially fatigue resistance) of the new I-cement warrant its further development toward clinical application.     

Mechanical properties of bone cement: a review

Many authors have examined the mechanical properties of bone cement and the various factors that affect its mechanical behavior. This article presents a comprehensive survey on the reported mechanical properties of bone cement. Variables that influence the mechanical properties, such as handling characteristics, strain rate, loading modes, additives, porosity, blood inclusion, in vivo environment, temperature, etc. have also been reviewed. The importance of specifying these variables in reporting test results on the mechanical properties of bone cement is pointed out. Previous attempts to improve the mechanical properties of bone cement are also summarized. Future research areas important for fully characterizing the physical properties of PMMA are also suggested.     

Influence of the activator in an acrylic bone cement on an array of cement properties

In all but one of the acrylic bone cement brands used in cemented arthroplasties, N,N-dimethyl-4-toluidine (DMPT) serves as the activator of the polymerization reaction. However, many concerns have been raised about this activator, all related to its toxicity. Thus, various workers have assessed a number of alternative activators, with two examples being N,N-dimethylamino-4-benzyl laurate (DMAL) and N,N-dimethylamino-4-benzyl oleate (DMAO). The results of limited characterization of cements that contain DMAL or DMAO have been reported in the literature. The present work is a comprehensive comparison of cements that contain one of these three activators, in which the values of a large array of their properties were determined. These properties range from the setting time and maximum exotherm temperature of the curing cement to the variation of the loss elastic modulus of the cured cement with frequency of the applied indenting force in dynamic nanoindentation tests. The present results, taken in conjunction with those presented in previous reports by the present authors and co-workers on other properties of these cements, indicate that both DMAL and DMPT are suitable alternatives to DMPT.     

Influence of mixing techniques on the physical properties of acrylic bone cement

Palacos R bone cement was prepared using three commercially available mixing techniques, first generation, second generation and third generation, to determine the mechanical properties and porosity contents of the bone cement. The compressive strengths, bending strengths and flexural moduli were expressed as a function of void content. The volume of pores within the cement structure was found to be a contributing factor to the physical properties of acrylic bone cement. The lower the volume of voids in the cement the better the compressive and flexural properties, hence stronger bone cement. It was found that the best results were obtained from cement that had been mixed using the Mitab Optivac or Summit HiVac Syringe systems at a reduced pressure level of between -72 and -86 kPa below atmospheric pressure, resulting in cement of porosity 1.44-3.17%; compressive strength 74-81 MPa; flexural modulus 2.54-2.60 GPa; and flexural strength 65-73 MPa.     

Mixing of acrylic bone cement: effect of oxygen on setting properties

The present study investigates the effect of different mixing methods on the setting properties of bone cement. It was found that vacuum mixing decreased the setting time of the bone cement by nearly 2 min (10%), compared to mixing in air. Two additional experiments, in which the bone cement powders were purged with argon or oxygen, and mixed with the methyl methacrylate monomer, revealed that oxygen concentrations in the bone cement had a great effect on the setting time. The setting time increases significantly as the oxygen concentration increases, which suggests that the decrease in the setting time by vacuum mixing may be attributed to the lower oxygen levels present in the mixer. No significant effect was observed on dough time or maximum exothermic temperature by varying oxygen concentrations in the bone cement mixer.     

Elastic and ultimate properties of acrylic bone cement reinforced with ultra-high-molecular-weight polyethylene fibers

A study of the fracture behavior of poly-(methyl methacrylate) (PMMA) bone cement reinforced with short ultra-high-molecular-weight polyethylene (Spectra 900) fibers is presented. Linear elastic and nonlinear elastic fracture mechanics results indicate that a significant reinforcing effect is obtained at fiber contents as low as 1% by weight, but beyond that concentration a plateau value is reached and the fracture toughness becomes insensitive to fiber content. The flexural strength and modulus are apparently not improved by the incorporation of polyethylene fibers in the acrylic cement, probably because of the presence of voids, the poor mixing practice and the weakness of the fiber/matrix interfacial bond. The present polyethylene/PMMA composite presents several advantages as compared to other composite cements, but overall the mechanical performance of this system resembles that of Kevlar 29/PMMA cement, with a few differences. Scanning electron microscopy reveals characteristic micromechanisms of energy absorption in Spectra 900/PMMA bone cement. A scheme for the strength of random fiber-reinforced composites, which is a simple extension of the Kelly and Tyson model for the strength of unidirectional composites, is presented and discussed. Young's modulus and the fracture toughness results are discussed in the framework of existing theories. More fundamental modeling treatments are needed in terms of fracture micromechanisms to understand and optimize the various mechanical properties with respect to structural parameters and cement preparation technique.     

Crack initiation processes in acrylic bone cement

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 influence of pore morphology and the presence of defects within regions of stress concentration. Furthermore, experimental evidence shows that large agglomerations of BaSO(4) 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.     

Degree of polymerization of acrylic bone cement.

Self-curing powder-liquid admixed acrylic systems are used for internal fixation fo total hip and total knee prostheses. Gel permeation chromatography revealed that the polymer chain length distributions of set cements were basically unaffected by their curing pressures. However, a decrease of approximately 11% in porosity coupled with a measured increase in mechanical strengths could be induced through the use of high curing pressures well beyond those attainable by the surgeon in the current arthroplasties. The conclusion of the investigation was that, to improve such cements, attention should be focused on elimination of porosity rather than attempting to produce higher degree of polymerization.     

Microtomography assessment of failure in acrylic bone cement

Micromechanical studies of fatigue and fracture processes in acrylic bone cement have been limited to surface examination techniques and indirect signal analysis. Observations may then be mechanically unrepresentative and/or affected by the presence of the free surface. To overcome such limiting factors the present study has utilised synchrotron X-ray microtomography for the observation of internal defects and failure processes that occurred within a commercial bone cement during loading. The high resolution and the edge detection capability (via phase contrast imaging) have enabled clear microstructural imaging of both strongly and weakly absorbing features, with an effective isotropic voxel size of 0.7 microm. Detailed assessment of fatigue damage processes in in vitro fatigue test specimens is also achieved. Present observations confirm a link with macroscopic failure and the presence of larger voids, at which crack initiation may be linked to the mechanical stress concentration set up by adjacent beads at pore surfaces. This study does not particularly support the suggested propensity for failure to occur via the inter-bead matrix; however crack deflections at matrix/bead interfaces and the incidence of crack arrest within beads do imply locally increased resistance to failure and potential improvements in global crack growth resistance via crack tip shielding.     

The effect of the monomer-to-powder ratio on the material properties of acrylic bone cement

The procedure percutaneous vertebroplasty consists of injecting polymethylmethacrylate cement into vertebral bodies for the treatment of osteoporotic compression fractures and tumors of the spine. Clinicians practicing vertebroplasty commonly alter the mixture of monomer-to-powder recommended by the manufacturer in an effort to decrease viscosity and increase the working time. The purpose of the current study was to measure the effect of varying the monomer-to-powder ratio on the compressive material properties (compressive modulus, yield stress, and ultimate compressive strength) of the cement Simplex P (Stryker-Howmedica-Osteonics, Rutherford, NJ). Cylindrical specimens were prepared using monomer-to-powder ratios of 0.45 to 1.00 mL/g and tested in compression. Peak compressive material properties occurred at the mixture ratio recommended by the manufacturer (0.5 mL/g) but decreased as the ratio of monomer to powder was increased. The material properties of specimens cured for 1 hour were significantly less than those for specimens cured for 24 hours. The monomer-to-powder ratio affects the compressive material properties of cement. The clinical significance of these results with respect to vertebroplasty is yet to be determined.     

Slow crack growth in acrylic bone cement.

Slow crack growth in Perspex acrylic sheet (PMMA) and Simplex acrylic bone cement in air and water has been studied from a fracture mechanics viewpoint. It has been found that the crack velocity, V, for each material depends upon the intensification of stress at the tip of the crack. Experimental measurements have been made of V as a function of the stress intensity factor, K, at the crack tip, and a derived V, K relationship has been used to predict the times-to-failure of components made from PMMA and Simplex cement. Direct measurements of time-to-failure for PMMA have shown that the predicted values give a conservative estimate of the structural lifetime of the material.     

A proposed specification for acrylic bone cement.

A proposed specification covering handling characteristics and physical and chemical properties of bone cement composed primarily of methyl methacrylate has been prepared on the basis of data from the authors' studies and from various other sources. Under handling characteristics, requirements included relate to dough, handling and setting time, proper plasticity for insertion and temperature rise on setting. Mechanical properties specified include compressive strength and indentation and recovery characteristics. Maximum limits are proposed for water sorption and solubility. Suggested packaging requirements are also included.     

Effect of surface modification of polymer beads on the mechanical properties of acrylic bone cement

The effect of surface modification of polymer filler on the static mechanical properties of acrylic bone cement was studied. The surface of polymer beads was modified with carboxylic and amino groups by photochemical reaction with azide compounds. Monomer modifiers (maleic anhydride, methacrylic acid and p-aminostyrene) are attached to the functionalized surface of polymer beads. Functional allyl groups, which are capable of the graft polymerisation reaction, are attached to the surface via photochemical reaction with N-(2-nitro-4-azidophenyl)-N-(-propen) amine. This approach to bone cement provides the additional covalent bonds between the polymer beads and the inter-bead matrix. The static mechanical properties of bone cements containing modified polymer beads were investigated and compared with the static mechanical properties of unmodified cements. The absolute values of compressive strength for the modified and unmodified cements were found to be similar. An increase in flexural strength for the modified cements (dry and after water storage) was observed. The structure of the surface functional groups affects the methyl methacrylate grafting resulting in a higher value of flexural strength for the maleic anhydride- and p-aminostyrene-modified cements. The scanning electron microscopy examination of the fracture surface of the cement samples showed an improvement of the adhesion between the beads and the matrix after modification.     

Effect of surface modification of polymer beads on the mechanical properties of acrylic bone cement

The effect of surface modification of polymer filler on the static mechanical properties of acrylic bone cement was studied. The surface of polymer beads was modified with carboxylic and amino groups by photochemical reaction with azide compounds. Monomer modifiers (maleic anhydride, methacrylic acid and p-aminostyrene) are attached to the functionalized surface of polymer beads. Functional allyl groups, which are capable of the graft polymerisation reaction, are attached to the surface via photochemical reaction with N-(2-nitro-4-azidophenyl)-N-(-propen) amine. This approach to bone cement provides the additional covalent bonds between the polymer beads and the inter-bead matrix. The static mechanical properties of bone cements containing modified polymer beads were investigated and compared with the static mechanical properties of unmodified cements. The absolute values of compressive strength for the modified and unmodified cements were found to be similar. An increase in flexural strength for the modified cements (dry and after water storage) was observed. The structure of the surface functional groups affects the methyl methacrylate grafting resulting in a higher value of flexural strength for the maleic anhydride- and p-aminostyrene-modified cements. The scanning electron microscopy examination of the fracture surface of the cement samples showed an improvement of the adhesion between the beads and the matrix after modification.     

Augmentation of acrylic bone cement with multiwall carbon nanotubes

Acrylic bone cement, based on polymethylmethacrylate (PMMA), is a proven polymer having important applications in medicine and dentistry, but this polymer continues to have less than ideal resistance to mechanical fatigue and impact. A variety of materials have been added to bone cement to augment its mechanical strength, but none of these augmentative materials has proven successful. Carbon nanotubes, a new hollow multiwalled tubular material 10-40 nm in diameter, 10-100 microm long, and 50-100 times the strength of steel at 1/6 the weight, have emerged as a viable augmentation candidate because of their large surface area to volume ratio. The objective of this study was to determine if the addition of multiwall carbon nanotubes to bone cement can alter its static or dynamic mechanical properties. Bar-shaped specimens made from six different (0-10% by weight) concentrations of multiwall carbon nanotubes were tested to failure in quasi-static 3-point bending and in 4-point bending fatigue (5 Hz). Analyses of variance and the 3-Parameter Weibull model were used to analyze the material performance data. The 2 wt % MWNT concentration enhanced flexural strength by 12.8% (p=0.003) and produced a 13.1% enhancement in yield stress (p=0.002). Bending modulus increased slightly with the smaller (<5 wt % MWNT) concentrations, but increased 24.1% (p<0.001) in response to the 10 wt % loading. While the 2 wt % loading produced slightly improved quasi-static test results, it was associated with clearly superior fatigue performance (3.3x increase in the Weibull mean fatigue life). Weibull minimum fatigue life (No), Weibull modulus (alpha), and characteristic fatigue life (beta) for bone cement augmented with carbon nanotubes were enhanced versus that observed in the control group. These data unambiguously showed that the bone cement-MWNT polymer system has an enhanced fatigue life compared to "control" bone cement (no added nanotubes). It is concluded that specific multiwall carbon nanotube loadings can favorably improve the mechanical performance of bone cement.     

Characterization of acrylic bone cement using dynamic mechanical analysis

Dynamic mechanical analysis (DMA) was used to characterize the properties of acrylic bone cement with the addition of tricalcium phosphate (TCP), hydroxyethyl methacrylate (HEMA), and ethylene glycol dimethacrylate (EGDMA). The glass transition temperature of acrylic bone cement is >100 degrees C; the cement has a flat modulus response near human body temperature. The height of the damping peak decreases and becomes broader with increasing TCP content. Thus, TCP is incompatibile with acrylic bone cement. When the frequency is changed from high to low, the damping peak shifts to low temperature. The shift in damping peak with frequency indicates that this relaxation is time-dependent. When acrylic bone cement contains TCP with HEMA and EGDMA, the incompatibility between acrylic bone cement and TCP can be ameliorated.     

Biocompatibility of a new radiopaque iodine-containing acrylic bone cement

Radiopacity in the vast majority of the commercially available acrylic bone cements that are used clinically is provided by particles of either BaSO(4) or ZrO(2). Literature reports have shown these agents to have a detrimental effect on some mechanical properties of the cements as well as on its biological response. We, therefore, have developed a new type of bone cement, for which radiopacity results from the presence of an iodine-containing methacrylic copolymer. The focus of the present work was the comparison of the biocompatibility of this new cement and a commercially available cement that contains barium sulfate. In vitro experiments show that both cements are cytocompatible materials, for which no toxic leachables are found. Implantation of the cements in a rabbit for three months resulted in the occasional presence of a thin fibrous tissue at the cement-bone interface, which is common for acrylic bone cements. Consideration of all the results led to the conclusion that the new cement is as biocompatible as the BaSO(4)-containing one.     

Open wedge tibial osteotomy with acrylic bone cement as bone substitute

We studied the results of 245 valgus producing high tibial osteotomies performed with the use of an opening wedge technique and rigid internal fixation followed by early passive and active motion of the knee. Previous studies have used iliac bone grafts or hemicollastasis held by an external fixator for opening the osteotomy. In our series the opening was obtained by a block of cement interposed in the postero-medial part of the osteotomy. This series confirms that the opening wedge osteotomy allows good accuracy for the correction. Ninety-three percent of the knees had a correction adjusted between 180 and 187 degrees for the hip-knee-ankle angle. Survivorship analysis showed an expected rate of survival, with conversion to a total knee on the end point, of 94% at 5 years, 85% at 10 years and 68% at 15 years. Conversion to a total knee arthroplasty was accomplished without difficulty in the patients who had this procedure done. We recommend opening wedge tibial osteotomy with acrylic cement bone cement as bone substitute, rigid internal fixation, and early motion for patients who undergo high tibial osteotomy.     

Bone marrow modified acrylic bone cement for augmentation of osteoporotic cancellous bone

The use of polymethylmethacrylate (PMMA) cement to reinforce fragile or broken vertebral bodies (vertebroplasty) leads to extensive bone stiffening. This might be one reason for fractures at the adjacent vertebrae following this procedure. PMMA with a reduced Young's modulus may be more suitable. The goal of this study was to produce and characterize PMMA bone cements with a reduced Young's modulus by adding bone marrow. Bone cements were produced by combining PMMA with various volume fractions of freshly harvested bone marrow from sheep. Porosity, Young's modulus, yield strength, polymerization temperature, setting time and cement viscosity of different cement modifications were investigated. The samples generated comprised pores with diameters in the range of 30-250 μm leading to porosity up to 51%. Compared to the control cement, Young's modulus and yield strength decreased from 1830 to 740 MPa and from 58 to 23 MPa respectively by adding 7.5 ml bone marrow to 23 ml premixed cement. The polymerization temperature decreased from 61 to 38 °C for cement modification with 7.5 ml of bone marrow. Setting times of the modified cements were lower in comparison to the regular cement (28 min). Setting times increased with higher amounts of added bone marrow from around 16-25 min. The initial viscosities of the modified cements were higher in comparison to the control cement leading to a lower risk of extravasation. The hardening times followed the same trend as the setting times. In conclusion, blending bone marrow with acrylic bone cement seems to be a promising method to increase the compliance of PMMA cement for use in cancellous bone augmentation in osteoporotic patients due to its modified mechanical properties, lower polymerization temperature and elevated initial viscosity.