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Ultrasonic characterization of the curing process of hydroxyapatite-modified bone cement.

Ultrasonic parameters such as velocity of sound and broad-band ultrasonic attenuation (BUA) are sensitive to changes in the viscoelastic properties of a material. Bone cement undergoes changes is these properties as it cures. By monitoring the propagation of ultrasonic pulses through a sample of curing bone cement, the curing reaction of polymethylmethacrylate-based (PMMA) bone cement was investigated for hydroxyapatite (HA) concentrations of 0, 10, and 30% (by weight). As the material hardens, the velocity of sound increases by 70%. BUA shows a large peak at the midpoint of the velocity transition. These data are used to compare the cure time and cure duration for PMMA bone cement mixed with hydroxyapatite particles. Measurements of the final sound velocity and BUA were also performed to investigate the mechanical properties of the fully cured cement, and to compare to compression testing data. This is the first time the curing process of bone cement has been investigated as a function of hydroxyapatite concentration. Results indicate that the cure time is not significantly affected by the addition of HA particles, and that both velocity of sound and BUA are sensitive to the curing process.

Bone Cements↗

Improvement of the long-term adhesive strength between metal stem and polymethylmethacrylate bone cement by a silica/silane interlayer system.

A loss of adhesive strength between metal stem and bone cement is clinically found to be a serious problem in total hip arthroplasty and causes many operative revisions. The objective of this study was to improve the long-term adhesive strength at this interface. A new silica/silane interlayer coating system is introduced. The layers are designed to bond the metal stem surface to the polymethylmethacrylate bone cement marginally leakage free. In vitro tensile tests were performed on specimens of TiAl6V4 and CoCrMo that were cemented by pairs with different bone cements with and without the new coating system. The specimens were stored in isotonic saline solution up to 150 days. The adhesive strength decreased about 75% within 30 days of storage on specimens of both metal alloys that were conventionally cemented without the new interlayer system. With the new coating, the high initial adhesive strength (40-50 MPa) could be stabilized for TiAl6V4 over 150 days. For the same 150-day storage period, the adhesive strength of the coated CoCrMo alloy still decreased but the decrease was only half that experienced by the uncoated CoCrMo. The loss of adhesive strength on CoCrMo specimens could be reduced if the metal surface was activated by a plasma treatment. The new coating interface system could help to considerably reduce revision operations caused by debonding effects at the interface metal/polymethylmethacrylate bone cement.

Adhesiveness↗

Kinetic study of citric acid influence on calcium phosphate bone cements as water-reducing agent.

Most of the research performed on calcium phosphate bone cements (CPBCs) has dealt with the improvement of bone cement formulations for new, demanding bone-filling applications. In particular, the development of injectable bone cements is of real interest for the biomedical community. The aim of this work was to study the effect of citric acid on the injectability and the setting properties of alpha-tricalcium phosphate-based cements. A comparative kinetic study was performed on cements with and without citric acid relating the hardening curves and the hydration rates using a mathematical approach. Citric acid behaved as a fluidificant during the first stages of the cement mixing. The dissolution-precipitation reactions of the alpha-tricalcium phosphate were retarded with the addition of citric acid and the compressive strength at saturation increased. In conclusion, citric acid can behave as a water-reducing admixture.

Bone Cements↗

New acrylic bone cements conjugated to vitamin E: curing parameters, properties, and biocompatibility.

Acrylic bone cement formulations with antioxidant character were prepared by incorporation of a methacrylic monomer derived from vitamin E (MVE). Increasing concentrations of this monomer provided decreasing peak temperature values, ranging from 62 to 36 degrees C, and increasing setting time with values between 17 and 25 min. Mechanical properties were evaluated by compression and tension tests. Compressive strength of the new formulations were superior to 70 MPa in all cases. The cement containing 25 wt % MVE, however, showed a significant decrease in tensile properties. Biocompatibility of the new formulations was studied in vitro. The analysis of the effect of leachables from cements into the media showed continued cell proliferation and cell viability with a significant increase for the cement containing 15 wt % MVE. This formulation also showed a significant increase in cellular proliferation over a period of 7 days as indicated by the Alamar Blue test. The cells were able to differentiate and express phenotypical markers in presence of all materials. A significant increase in alkaline phosphatase activity was observed on the cements prepared in presence of 15-25 wt % MVE compared with PMMA. Morphological assessment showed that the human osteoblast (HOB) cells were able to adhere, retain their morphology, and proliferate on all the cements.

Acrylates↗

Tobramycin-containing bone cement and systemic cefazolin in a one-stage revision. Treatment of infection in a rabbit model.

The efficacy of tobramycin-containing bone cement with that of systemic cefazolin for treatment of infection in a one-stage revision model is compared. In addition, the value of detecting bacterial DNA after antibiotic treatment was investigated. An implant was inserted into the right tibia of rabbits after inoculation with Staphylococcus aureus. At 28 days, the implant was removed. Subsequently, either plain bone cement with or without systemic administration of cefazolin, or tobramycin-containing bone cement was injected into the medullary canal. The tibiae were cultured 14 days after revision (Day 42), and showed a significant decrease in bacterial counts for both antibiotic groups compared with the control group (p</=0.05). The rate of infection in the tobramycin-cement group was slightly higher (2/9) than in the cefazolin group (0/8), although the difference was not significant. Persistence of bacterial DNA after antibiotic treatment may be the result of delayed clearance of DNA and not a sign of active infection. This animal model shows that in a one-stage revision tobramycin-containing bone cement can reduce size and rate of infection, although systemic cefazolin may be more efficacious. Therefore, the use of antibiotic-containing bone cement combined with systemic antibiotic might provide optimal treatment.

Animals↗

PMMA-based bioactive cement: effect of glass bead filler content and histological change with time.

A new bioactive bone cement (designated GBC), which is a polymethyl methacrylate (PMMA)-based composite consisting of bioactive glass beads as an inorganic filler and high molecular-weight PMMA as an organic matrix, has been developed. The purpose of the present study was to evaluate the effect of the filler content on the mechanical properties and osteoconductivity of GBC, to decide the most suitable filler proportion, and to evaluate the degree of cement degradation with time. The bioactive beads, consisting of MgO-CaO-SiO(2)-P(2)O(5)-CaF(2) glass, were added to the cement in various proportions (40-70 wt %). The bending strength of GBC did not differ among the proportions (approximately 136 MPa), but the elastic modulus of bending of GBC increased as the glass bead filler content increased (approximately 4.1-7.2 GPa). The all types of GBC were packed into the intramedullary canals of rat tibiae to evaluate osteoconductivity, as determined by an affinity index calculated as the length of bone in direct contact with the cement surface expressed as a percentage of the total length of the cement surface. Rats were sacrificed at 4, 8, 25, and 39 weeks after implantation, and the affinity index was calculated for each type of GBC at each time point. Histologically, new bone had formed along the surface of all types of GBC within 4 weeks, even in GBC containing only 40 wt % of glass beads. The affinity indices of GBC tended to increase as the proportion of glass bead filler increased and as the implantation period increased. In GBC containing 60 or 70 wt % of glass beads, significant rapid increases in the affinity indices were found from 4 to 8 weeks, and the high values (approximately 70%) were maintained up to 39 weeks. A sign of glass bead degradation was observed at the bone-cement interface in the rat tibiae at 39 weeks. We conclude that, when mechanical properties and osteoconductivity are both taken into consideration, GBC containing 60 or 70 wt % of glass beads is the most suitable formulation, but that further studies are needed to investigate and overcome the degradation.

Animals↗

Fracture characteristics of acrylic bone cements. I. Fracture toughness.

The vital first phase of the overall materials study to protract the life of the total joint replacements is the identification of the fracture toughness and fatigue properties of bone cements. Information gained from fatigue testing, performed in a manner which simmulates in vivo conditions, and fracture toughness, which is a measure of the propensity of a crack to propagate, is the first step towards the prediction of the life of the total joint replacement. This study is concerned with the fracture toughness of Zimmer and Simplex-P cold-curing bone cements. Following cement fabrication conditions which closely approximate clinical procedures, fracture toughness testing was conducted on cement specimens which were immersed in bovine serum at 37 degrees C in order to simulate in vivo conditions. In addition, a similar study was completed on specimens, tested in air at ambient temperature for purposes of comparison. Results of this procedure, when analyzed by a Student's t-test at the 95% confidence level with eight degrees of freedom, indicate that both Zimmer and Simplex-P exhibit a higher fracture toughness in the simulated physiological environment. In order to determine whether the addition of barium sulfate to these cements compromises the fracture toughness, the above described testing rationale was repeated, indicating the existence of a complicated relationship between the different testing environments and barium sulfate. The importance of these results lies in the fact that an increased fracture toughness indicates that a cement will inherently exhibit a greater degree of resistance to the propagation of cracks, which could contribute to the ultimate failure of the total joint replacement.

Acrylates↗

Porous acrylic cement.

The use of acrylic bone cement has a number of shortcomings, viz., high curing temperatures that can cause thermal necrosis, release of toxic monomer, and a less than perfect cement-to-bone bond. However, by modifying the cement composition through the addition of a soluble, nontoxic filler such as sucrose or tricalcium phosphate which does not impair the workability of the material during surgery, a significant improvement in the performance of the cement can be achieved. Because the filler replaces part of the acrylic components, less heat is generated during curing while the filler itself acts as a heat sink. Also, less monomer, proportional to the amount replaced by the filler, diffuses from the implant site. Upon elution of the filler, a porous cement will be obtained provided that a critical minimum percentage loading is exceeded so that the filler crystals will make physical contact with each other. The value of this percentage depends on both crystal modification and size. In the 125-175 micron sucrose crystal size range, the critical minimum percentage lies in the range of 20-28 wt% loading. Above 30%, the interconnecting pore size increases sharply to a value which allows good tissue ingrowth into the pores. The introduction of filler and pores causes a drop in strength, but the diametral tensile strength of modified cement containing up to 40% pores and sucrose lies between .7 and 1.5 kg/mm2, respectively, which is still in the same range as that of bone.

Acrylic Resins↗

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.

Bone Cements↗

Bone-particle-impregnated bone cement: an in vivo weight-bearing study.

To evaluate an experimental inorganic-bone-particle-impregnated bone cement, canine hip prostheses were implanted in dogs using a regular bone cement on one side and the experimental bone cement on the other. In a preliminary feasibility study, bone ingrowth into the resorbed bone-particle spaces was established 3 months after implantation in three dogs. In a more detailed study, twenty-eight (28) dogs were divided in four groups to delineate the effects of time on the phenomena of bony ingrowth. One month after implantation, active bone ingrowth into the bone cement was obvious. By 3 months postimplantation, the ingrowth appeared to have traversed the thickness of the bone-particle-impregnated cement. By the fifth month, most of the interconnected inorganic bone particles were replaced by new bone. At the end of a year, the ingrown bone was mature and negligible new bone activity was present. Biomechanical pushout tests closely corroborated the histologic observations. The maximum shear strength of the cement/bone interface of the experimental side reached 3.6 times that of the control side at 5 months postimplantation. No further improvements were seen at 12 months postimplantation. A viable bone/cement interface may result in a better orthopedic implant fixation system by combining the advantages of both cement for immediate rigidity and biological ingrowth for longterm stability.

Animals↗

The periapical tissue reactions to a calcium phosphate cement in the teeth of monkeys.

A calcium phosphate cement, Grossman sealer, and Sargenti N2 were compared under conditions where root canals of monkey incisors were deliberately overfilled and the apical tissue responses were evaluated histologically. The periapical tissues exposed to Sargenti N2 revealed severe irritation at all times through the 6-month experimental period. The reactions to Grossman sealer were milder but persisted throughout the observation period. The calcium-phosphate-cement treated animals showed mild tissue irritation after 1 month, but thereafter the adverse tissue reactions were minimal. New bone formation adjacent to the cement was also observed. These results point to the possibility that calcium phosphate cement might be used in simplified endodontic procedures. The compatibility of calcium phosphate cement with the periapical tissue suggests that the cement may have other applications in dentistry and medicine.

Animals↗

Adhesive bone cement containing hydroxyapatite particle as bone compatible filler.

Acrylic bone cement containing hydroxyapatite (HA) as a filler was developed using 4-methacryloyloxyethyl trimellitate anhydride (4-META) to promote adhesion both to bone and HA. The mechanical strengths of the cement did not decrease significantly with increasing HA in the cement by 4-META. However, strengths decreased with increasing HA content in the absence of 4-META. Scanning electron micrographic examination of fractured surfaces of the cement clearly showed that the HA particles adhered to the matrix resin when 4-META was added. Thus, it was important to maintain the original mechanical strengths for 4-META. The HA particles along the surface increased with increased HA content in the cement. The cement adhered to bone with a tensile bond strength was higher than 10 MPa.

Acrylic Resins↗

Effect of particle size of metastable calcium phosphates on mechanical strength of a novel self-setting bioactive calcium phosphate cement.

Resistance to compressive strength after setting of the calcium phosphate cement consisting of tetracalcium phosphate (TECP), dicalcium phosphate dihydrate (DCPD), and 40 wt/wt% of a synthetic hydroxyapatite (HAP) was tested. An equimolar mixture of the calcium phosphate powder containing DCPD (particle diameter [D] 0.52-3.33 microns) and TECP (D, 1.1-13.1 microns) transformed into HAP at 37 degrees C, 100% RH after being mixed with 25 mM phosphoric acid. X-ray diffraction suggested that the cement containing fine particles of DCPD and TECP completely transformed to HAP, but that mixtures containing larger particles did not. Because particle size of both DCPD and TECP affected the compressive strength of the cement, the crystal growth of HAP during cement formation depended on the specific surface area (Sw) of the raw materials. The crystallite size of transformed HAP was estimated based on X-ray diffraction peaks at 25.8 and 32.8 degrees attributable to the 002 and 300 planes. The crystalline size attributable to the 300 plane decreased with increasing Sw, but that attributable to the 002 plane showed no significant relationship. The compressive strength of the cement after hardening increased with an increase of its Sw. This suggested that the harder calcium phosphate cement was (derived) from the smaller particle size of the raw materials.

Bone Cements↗

The effects of centrifugation and titanium fiber reinforcement on fatigue failure mechanisms in poly(methyl methacrylate) bone cement.

The contributions to fatigue resistance in poly(methyl methacrylate) bone cement (PMMA) by centrifugation and titanium fiber addition were studied. Three modified bone cements were tested: porosity reduced cement (C-PMMA); titanium (Ti) fiber-reinforced cement (R-PMMA), using a novel method to incorporate fibers; and porosity reduced and Ti fiber-reinforced cement (C-R-PMMA). Specimens of untreated bone cement (PMMA) were included as controls. Non-notched and notched specimens were cyclically loaded in fully reversed bending. For the non-notched specimens, at all stress levels, C-R-PMMA had significantly greater fatigue life than either C-PMMA or R-PMMA (except C-PMMA at 30 MPa). R-PMMA had lower fatigue life than the control at 30 MPa (nominal maximum stress), but higher fatigue life at 20 and 15 MPa. At both 20 and 15 MPa, there was no statistical difference between the fatigue lives of C-PMMA and R-PMMA. Fractography revealed that, at 30 MPa, characteristics of rapid fracture predominated. At 20 and 15 MPa, in contrast, almost the entire fracture surface showed the characteristic fatigue morphology, indicating that subcritical crack growth was predominant. For the notched specimens, C-PMMA showed greater life than PMMA at the highest stress intensity, but the lifetimes converged with decreasing stress intensity. In contrast, the life-times for PMMA and R-PMMA diverged with decreasing stress intensity. The effect of centrifugation appeared to be strongest at higher stress intensities, and diminished with decreasing stress intensity. The reinforcing effect of Ti fiber addition increased the notched fatigue life at high initial stress intensities, and the reinforcing effect increased with decreased stress intensity.(ABSTRACT TRUNCATED AT 250 WORDS)

Biocompatible Materials↗

Fiber-enriched double-setting calcium phosphate bone cement.

Calcium phosphate bone cements are useful in orthopedics and traumatology, their main advantages being their biocompatibility and bioactivity, which render bone tissue osteoconductive, providing in situ hardening and easy handling. However, their low mechanical strength, which, in the best of cases, is equal to the trabecular bone, and their very low toughness are disadvantages. Calcium phosphate cement compositions with mechanical properties more closely resembling those of human bone would broaden the range of applications, which is currently limited to sites subjected to low loads. This study investigated the influence of added polypropylene, nylon, and carbon fibers on the mechanical properties of double setting alpha-tricalcium phosphate-based cement, using calcium phosphate cement added to an in situ polymerizable acrylamide-based system recently developed by the authors. Although the addition of fibers was found to reduce the compression strength of the double-setting calcium phosphate cement because of increased porosity, it strongly increased the cement's toughness (J(IC)) and tensile strength. The composites developed in this work, therefore, have a potential application in shapes subjected to flexure.

Biocompatible Materials↗

Resorption patterns of calcium-phosphate cements in bone.

Two calcium phosphate cements, one monophasic and the other biphasic, have been used as bone void filler in a sheep model. The cements were injected into a slot defect in the proximal tibia and into a cylindrical defect in the distal femur. In this study, we focused on the resorption pattern of the two cement formulations and the subsequent biologic reaction. Bone remodeling occurred synchronously with the resorption of the implant material in a creeping substitution process. Cracks and pores in the monophasic cement were filled with osseous tissues. The biphasic cement showed faster resorption of the matrix. The more slowly resorbing granules were surrounded by newly grown bone, thus providing an inverse scaffold for cancellous bone regeneration. In highly loaded areas, the long-term support function of the fixation appears to be critical. Because cortical bridging of the defects was seen in only one case, it can be concluded that calcium-phosphate cements are preferentially suitable as cancellous bone substitute materials.

Animals↗

Ultrastructural study of mineralization of a strontium-containing hydroxyapatite (Sr-HA) cement in vivo.

The purpose of this study was to investigate the mineralization leading to osseointegration of strontium-containing hydroxyapatite (Sr-HA) bioactive bone cement injected into cancellous bone in vivo. Sr-HA cement was injected into the ilium of rabbits for 1, 3, and 6 months. The bone mineralization area was found to be largest at 3 months, then at 1 month, and smallest at 6 months (p < 0.01) measured with tetracycline labeling. Osseointegration of Sr-HA cement was achieved at 3 months as observed by scanning electron microscopy. A high calcium and phosphorus area was observed at the interface of bone-Sr-HA cement determined by energy-dispersive X-ray analysis. Transmission electron microscopy gave evidence of the mechanism of bone formation. Dissolution of Sr-HA into debris by the bone remodeling process was thought to increase the concentration of calcium and phosphorus at the interface of bone-Sr-HA cement and stimulate bone formation. Crystalline Sr-HA formed an amorphous layer and dissolved into the surrounding solution, then apatite crystallites were precipitated and formed new bone at 3 months. This young bone then becomes mature bone, which bonds tightly to the Sr-HA cement with collagen fibers inserted perpendicularly after 6 months.

Animals↗

Physicochemical properties of TTCP/DCPA system cement formed in physiological saline solution and its cytotoxicity.

In this paper, the physicochemical properties and cytotoxicity of calcium phosphate cement (CPC), prepared by mixing cement powders of tetracalcium phosphate (TTCP) and dicalcium phosphate (DCPA) with a cement liquid of physiological saline solution, were investigated. The microstructure evolution of various hardened cement bodies and their hydration crystals as a function of immersion time in similar physiological fluids, physiological saline solution (0.9% NaCl), or simulated body fluids (SBF), were also studied. Results show that the setting time of CPC is in the range of 12-15 min, which meets the clinical application demands. We also found that the mean compressive strength of the CPC samples immersed in SBF for 3 days is 104+/-10 MPa which reaches the transverse compressive strength, 106-133 MPa, of human long bone. The results obtained from both the X-ray powder diffraction analyses (XRD) and scanning electron microscopy (SEM) observations indicated that a reinforcing effect of some remaining TTCP particles in the early stages of immersion is mainly responsible for the increase in the initial strength. Although the CPC failed to keep this high level when immersed for a longer time, the initial reinforcing effect of the remaining TTCP particles provides advantages for clinical applications. This would be effective when the material is loaded at the very beginning of the implantation, especially for the material used as a fixation, which requires a certain initial strength in the early stages of the implantation. The cytotoxicity results showed that the relative growth rate (RGR%) of L929 cells on the CPC samples using physiological saline solution as a cement liquid was slightly superior to that of the samples using the 0.5 mol/L phosphate acid solution as the cement liquid. This was most likely caused by the pH difference between the two CPC samples immersed in a DMEM-BFS medium.

Animals↗