Composite Bone Cement Research Articles

Influence of two changes in the composition of an acrylic bone cement on its handling, thermal, physical, and mechanical properties

This study is a contribution to the growing body of work on the influence of changes in the composition of an acrylic bone cement on various properties of the curing and cured material. The focus is on one commercially-available acrylic bone cement brand, Surgical Simplex P, and three variants of it and a series of properties, namely, setting time, maximum exotherm temperature, activation energy and frequency factor for the polymerization reaction, diffusion coefficient for the uptake of phosphate buffered saline, at 37 degrees C, ultimate compressive strength (UCS), plane-strain fracture toughness, fatigue life (under fully-reversed tension-compression stress), hardness (H) and elastic modulus (both determined using quasi-static nanoindentation), and the variation of the storage and loss moduli with frequency of the applied force in a dynamic nanoindentation test. It was found that (a) a 68% reduction in the volume of the activator, N,N dimethyl-4-toluidine, relative to the total volume of the liquid monomer (the amounts of all the constituents in the powder and of the hydroquinone in the liquid monomer remaining unchanged) led to, for example, a significant decrease in the rate of the polymerization reaction, at 37 degrees C (c') and a significant increase in H; and (b) the elimination of the pre-polymerized poly (methyl methacrylate) beads in the powder (the amounts of all the other powder constituents and those of the liquid monomer remaining unchanged) led to, for example, a significant drop in c' and a significant increase in UCS. Thus, these findings suggest a strategy for optimizing the composition of an acrylic bone cement.

Long‐term variations in mechanical properties and in vivo degradability of CPC/PLGA composite

A new type of bone cement composite was successfully achieved by mixing degradable biosecure polylactic-co-glycolic acid (PLGA) fibers with high initial strength calcium phosphate cement (CPC). Its higher initial strength was mainly responsible for the in situ reinforcing effect of residual tetra-calcium phosphate monoxide (r-TTCP) particles reported in our previous work. So this bone cement composite containing fibers and the controlling group could be termed as CPC/PLGA composite and pure CPC or fiber-free group, respectively. In this study, we had investigated mechanical properties and microstructures of the CPC/PLGA composite immersed in 0.9% saline solution for different time and its in vivo degradation behaviors after implanting in rabbit muscle and femur bone, respectively. Results showed that the incorporation of the degradable fibers not only greatly increased the initial toughness and flexural strength of the CPC/PLGA composite but also significantly improved its later osteo-conduction as well as degradation rate. The rabbit muscle implant tests showed that the weight loss ratio of the CPC/PLGA composite increased by 41.03% as compared to the pure CPC. And the rabbit femur implant tests showed that the composite exhibits outstanding biocompatibility and bioactivity and more excellent osteoconduction and degradability than the pure CPC.

The Effect of Lif-Maleic Acid Added Calcium Aluminate Bone Cement and Ca-PMMA Composite Bone Cement on Bone Regeneration in Rat Calvarial Defects

The purpose of this study was to evaluate histologically the effect of LiF-maleic acid added calcium aluminate (LM-CA) bone cement and calcium aluminate-polymethylmethacrylate (CA-PMMA) composite bone cement on bone regeneration in rat calvarial defect. After calvarial defects in 8 mm in diameter were created, three groups of 10 animals, a total of 30, each either received LM-CA bone cement, CA-PMMA composite bone cement or a sham-surgery control. Histologic analysis was done at 2 weeks and 8 weeks of healing periods. We concluded that LM-CA bone cement can be used as a bioactive bone graft material due to ability of bonding to the existing bone and CA-PMMA can be used as a graft material for augmentation of bone-volume due to dimensional stability.

Bone-Bonding Strength of a New Composite Bone Cement

A composite bone cement designated G2B1 that contains β tricalcium phosphate particles was developed as a bone substitute for percutaneous transpedicular vertebroplasty. In this study, both G2B1 and commercial PMMA bone cement (CMW1) were implanted into proximal tibiae of rabbits with a metal frame fixed on it, and their bone-bonding strengths were evaluated at 4, 8, 12 and 16 weeks after implantation using a detaching test. Some of the specimens were evaluated histologically using Giemsa surface staining and scanning electron microscopy (SEM). It was found that the bone-bonding strength of G2B1 was significantly higher than that of CMW1 at each time point, and significantly increased from 4 weeks to 8 and 12 weeks, while it decreased significantly from 12 weeks to 16 weeks. Giemsa surface staining and SEM showed that G2B1 contacted bone directly without intervening soft tissue in the specimens at each time point, while there was always a soft tissue layer between CMW1 and bone. The results indicate that G2B1 has excellent bioactivity.

Characterization of new biodegradable bone cement compositions based on functional polysuccinates and methacrylic anhydride

New biodegradable poly(3-allyloxy-1,2-propylene)succinate-based materials were obtained by cross-linking poly(3-allyloxy-1,2-propylene)succinate (PSAGE) with methyl methacrylate (MMA) and methacrylic anhydride (MAAH). The aim of this study was to examine the influence of MAAH/MMA ratio and incorporation of biphasic calcium phosphate (BCP) filler on the maximum curing temperature, setting time, compressive strength and modulus of the cured materials, as well as on their hydrolytic degradation. The latter was characterized by determination of the weight loss and observation of changes in samples morphology by SEM. The maximum temperature during cross-linking was found to decrease with increasing MAAH content. The setting time was affected strongly by the concentration of double bonds and was rapidly shortened with its increase. The compressive strength and compressive modulus values increased with increasing MAAH/MMA ratio. Moreover, addition of bioactive mineral filler (BCP) improves significantly mechanical properties of these materials. On the other hand, it slows down their hydrolytic degradation.

The in vitro bioactivity of two novel hydrophilic, partially degradable bone cements

Composite bone cements were prepared with bioactive glasses (MgO–SiO 2–3CaO · P 2O 5) of different reactivities. The matrix of these so-called hydrophilic, partially degradable and bioactive cements was composed of a starch/cellulose acetate blend and poly(2-hydroxyethyl methacrylate). The addition of 30 wt.% of glasses to this system made them bioactive in acellular medium: a dense apatite layer formed on the surface after 7 days of immersion in simulated body fluid. This was demonstrated both by microscopic and infrared spectroscopic techniques. The composition of the glass and, consequently, its structure was found to have important effects on the rate of the apatite formation. The combination of reactivity obtained by one formulation with the hydrophilic and degradable character of these cements makes them a very promising alternative to conventional acrylic bone cements, by allowing a better stabilization of the implant and a stronger adhesion to the bone.

Characterization of a novel calcium phosphate composite bone cement: Flow, setting, and aging properties

The flow, setting, and aging characteristics of a newly developed calcium phosphate/calcium aluminate composite orthopaedic cement were studied. The effect of vibration on the flow of the cement paste was studied and found to greatly enhance placement. The setting times of this cement were dependent on temperature and decreased with increasing temperatures. At 37 degrees C, the working and setting times were 6.3 +/- 0.3 and 12.8 +/- 0.4 minutes, respectively. Hydration and conversion of the cement phases continued while specimens were stored under simulated, physiological conditions. A cumulative increase in mass of 8.23 +/- 0.65% was observed over a 14 month test period. During this time, the cement was found to expand slightly, 0.71 +/- 0.39%. X-ray diffraction was used to characterize the crystalline phases present during hydration and conversion. The calcium aluminate in the cement hydrated and formed calcium aluminate chloride hydrates, while no changes were observed in the beta-tricalcium phosphate during the testing period.

Influence of changes in the composition of an acrylic bone cement on its polymerization kinetics

It has been suggested in the literature that a lower polymerization rate of an acrylic bone cement is favorable for the in vivo longevity of a cemented arthroplasty. The present work was a study of the influence of three changes in the composition of an acrylic bone cement (when taken separately) on the cement polymerization rate at 37 degrees C (assumed to be the temperature in the bone bed during a cemented arthroplasty) [k']. The changes were the amount of copolymer as a proportion of the total powder weight (in cements in which there is a copolymer in the powder), the amount of DMPT as a proportion of the total volume of the liquid monomer, and the accelerator. k' was calculated using values of the activation energy and the frequency factor (assuming the polymerization reaction is Arrhenius in nature) that were computed from measurements made using the nonisothermal mode of differential scanning calorimetry. Statistical analysis (one-way ANOVA, with Bonferroni correction, and factorial ANOVA) of the k' values showed that the change in accelerator had a significant influence on k'. The importance of this finding, together with results from two relevant literature reports, is discussed within the context of the use of modified bone cements in cemented arthroplasties.

Femoroplasty – augmentation of the proximal femur with a composite bone cement – feasibility, biomechanical properties and osteosynthesis potential

Background Analogous to vertebroplasty, cement-augmentation of the proximal femur (“femoroplasty”) could reinforce osteoporotic bones. This study was to evaluate (i) the feasibility of femoroplasty with a composite cement (Cortoss™), (ii) its influence on femoral strength by mechanical testing and (iii) the feasibility of stable osteosynthesis of the augmented fractured bones. Methods Nine human cadaveric femora were augmented with a composite bone cement, the surface heat generation monitored, and then tested biomechanically against their native contralateral control to determine fracture strength. Subsequently, thirteen reinforced and fractured femora were osteosynthetized by different implants and tested against their osteosynthetisized, non-augmented contralateral control. Findings Cement could be injected easily, with a moderate temperature rise. A positive correlation between BMD and fracture load and a significant increase in fracture load (+43%) of the augmented femora compared to their native controls (6324 N and 4430 N, respectively) as well as a significant increase in energy-to-failure (+187%, 86 N m and 30 N m, respectively) was found. Osteosynthesis was possible in cement-augmented femora. Osteosynthetisized femora showed equivalent strength to the intact controls. Interpretation Augmentation of the proximal femur with composite bone cement could be of use in prophylaxis of fractures in osteoporotic femurs. Osteosynthesis of the fractured augmented bones is a challenging procedure but has a good chance to restore strength.

Development of a degradable cement of calcium phosphate and calcium sulfate composite for bone reconstruction

A new type of composite bone cement was prepared and investigated by adding calcium sulfate (CS) to calcium phosphate cement (CPC). This composite cement can be handled as a paste and easily shaped into any contour, which can set within 5–20 min, the setting time largely depending on the liquid–solid (L/S) ratio; adding CS to CPC had little effect on the setting time of the composite cements. No obvious temperature increase and pH change were observed during setting and immersion in simulated body fluid (SBF). The compressive strength of the cement decreased with an increase in the content of CS. The degradation rate of the composite cements increased with time when the CS content was more than 20 wt%. Calcium deficient apatite could form on the surface of the composite cement because the release of calcium into SBF from the dissolution of CS and the apatite of the cement induced the new apatite formation; increasing the content of CS in the composite could improve the bioactivity of the composite cements. The results suggested that composite cement has a reasonable setting time, excellent degradability and suitable mechanical strength and bioactivity, which shows promising prospects for development as a clinical cement.

Influence of two changes in the composition of an acrylic bone cement on some of its properties: the case of Surgical Simplex® P

Influence of two changes in the composition of an acrylic bone cement on some of its properties: the case of Surgical Simplex® P

Synthesis and Characterization of Fumarate Copolyesters for Use in Bioresorbable Bone Cement Compositions

Unsaturated amorphous copolyesters of varied composition were prepared by transesterification copolymerization of diethyl fumarate, and two diols, 1,2‐propanediol and 2‐methyl‐1,3‐propanediol. The copolyesters were characterized by IR, 1H‐ and 13C‐NMR, GPC, DSC, and TGA. The glass transition is changing with composition from 0°C to 19°C as the content of 1,2‐propanediol residue in the copolyester increases. The copolyester structure and composition have an impact on the compressive strength and hydrolytic stability of the composites prepared by crosslinking the fumarate double bonds with N‐vinyl pyrrolidone in the presence of inorganic filler, calcium sulfate dihydrate, with the addition of a radical initiator, benzoyl peroxide, at ambient temperatures.

The biocompatibility and osteoconductivity of a cement containing β–TCP for use in vertebroplasty

A new composite bone cement designated "G2B1" was developed for percutaneous transpedicular vertebroplasty. G2B1 contains beta tricalcium phosphate particles and methylmethacrylate-methylacrylate copolymer as the powder components, and methylmethacrylate, urethane dimethacrylate, and tetrahydrofurfuryl methacrylate as the liquid components. Biocompatibility and osteoconductivity were evaluated using scanning electron microscopy, contact microradiography, and Giemsa surface staining 4, 8, 12, 26, and 52 weeks after implantation into rat tibiae. To evaluate osteoconductivity, affinity indices (%) were calculated. Scanning electron microscopy and contact microradiography revealed that bone contact with G2B1 was attained within 4 weeks (affinity index: 50.2 +/- 11.8 at 4 weeks) and at most of the margin within 26 weeks (affinity index: 87.4 +/- 7.2 at 26 weeks). Specifically, G2B1 contacted bone via a wide calcium-phosphate-rich layer, and its degradation started within 8 weeks, mainly in the marginal area. Giemsa surface staining showed that there was almost no inflammatory reaction around the G2B1. These results indicate that G2B1 is a biocompatible and osteoconductive bone cement.

Development of a New Composite Bone Cement as a Bone Substitute for Vertebroplasty

A new composite bone cement designated ‘G2B1’ was developed for percutaneous transpedicular vertebroplasty. G2B1 contains beta tricalcium phosphate particles and methylmethacrylate –methylacrylate copolymer as the powder components, and methylmethacrylate, urethane dimethacrylate, and tetrahydrofurfuryl methacrylate as the liquid components. Osteoconductivity and histological changes with time were evaluated using scanning electron microscopy, contact microradiography, and Giemsa surface staining 4, 8, 12, 26, and 52 weeks after implantation into rat tibiae. To evaluate osteoconductivity, affinity indices (%) were calculated. Scanning electron microscopy and contact microradiography revealed that bone contact with G2B1 was attained within 4 weeks (affinity index: 50.2 ± 11.8 at 4 weeks) and at most of the margin within 26 weeks (affinity index: 87.4 ± 7.2 at 26 weeks). Giemsa surface staining showed that there was almost no inflammatory reaction around the G2B1. These results indicate that G2B1 is a biocompatible and highly osteoconductive bone cement.

Controlled release of gentamicin from calcium phosphate—poly(lactic acid-co-glycolic acid) composite bone cement

Modification of a self setting bone cement with biodegradable microspheres to achieve controlled local release of antibiotics without compromising mechanical properties was investigated. Different biodegradable microsphere batches were prepared from poly(lactic-co-glycolic acid) (PLGA) using a spray-drying technique to encapsulate gentamicin crobefate varying PLGA composition and drug loading. Microsphere properties such as surface morphology, particle size and antibiotic drug release profiles were characterized. Microspheres were mixed with an apatitic calcium phosphate bone cement to generate an antibiotic drug delivery system for treatment of bone defects. All batches of cement/microsphere composites showed an unchanged compressive strength of 60MPa and no increase in setting time. Antibiotic release increased with increasing drug loading of the microspheres up to 30% (w/w). Drug burst of gentamicin crobefate in the microspheres was abolished in cement/microsphere composites yielding nearly zero order release profiles. Modification of calcium phosphate cements using biodegradable microspheres proved to be an efficient drug delivery system allowing a broad range of 10–30% drug loading with uncompromised mechanical properties.

Optimisation of the composition of an acrylic bone cement: application to relative amounts of the initiator and the activator/co-initiator in Surgical Simplex®P

In cemented arthroplasties, the two-part self-curing acrylic bone cement is currently the only material used for anchoring the total joint replacement to the contiguous bone. In virtually all commercially available formulations of this cement, the agents used for the initiation and activation/co-initiation of the radical polymerisation reaction are benzoyl peroxide (BPO) and N, N dimethyl-para-toluidine (DMPT), respectively. There are no reports in the open literature on the rationale for the amounts of these and other constituents in the formulations of the cement. Given the concerns that have been raised in the literature regarding the effect of residual DMPT on the body, it is important to keep the starting amounts of BPO and DMPT as high and as low, respectively, as possible. In the present work, the focus is on the relative amounts of these two agents in the case of one widely used commercial formulation, Surgical Simplex(R) P. Thirty variants of this cement were formulated, covering three concentrations of the co-polymer/BPO (75%, 80%, and 85% of the mass of the powder) and DMPT amounts (ranging from 0.8 %v/v to 2.4% v/v.) The setting time (t(set)), the peak temperature reached during the cement polymerisation process (T(max)), and the ultimate compressive strength (UCS) of each of the formulations were determined in accordance with procedures specified in ISO 5833. A critical examination of all the results indicated that the optimum ratio of the concentration of the initiator (BPO embedded in the PMMA-sytrene co-polymer) to that of the activator/co-initiator (DMPT) in Surgical Simplex(R) P is 57.14 (80%w/w co-polymer + BPO per 1.4%v/v DMPT). The mean values of t(set), T(max), and UCS of this optimum formulation were determined to be 12.30 min, 68 degrees C, and 101 MPa, respectively, all of which are within the limits specified in ISO 5833. The commercially available formulation of this cement contains 2.5%v/v DMPT, while the optimum formulation, as found in the present work, has 44% less DMPT, which may translate to a smaller amount of residual DMPT that is available for elution into the periprosthetic tissue in a cemented arthroplasty, over the in vivo life of the joint replacement.

Synthesis and Characterization of Diethyl Fumarate‐1,4‐Cyclohexanedimethanol Polyesters for Use in Bioresorbable Bone Cement Composites

Unsaturated polyesters are prepared by transesterification polymerization of diethyl fumarate and 1,4‐cyclohexanedimethanol. The structure of the polyesters was characterized by FT‐IR and 1H‐ and 13C‐NMR spectroscopy. Semicrystalline morphology of the polymers is suggested by DSC analysis with Tg at 21°C and melting at 140°C. The thermogravimetric analysis indicated that the onset of degradation takes place at 300°C. The polyester's structure has significant impact on the properties of the composites prepared by crosslinking the fumarate double bonds with N‐vinyl pyrrolidone in the presence of an inorganic filler, calcium sulfate dihydrate, with the addition of a radical initiator, benzoyl peroxide, at ambient temperatures. The compressive strength and hydrolytic stability of the cement compositions was correlated with structure of the polyesters.

Apatite formation in composites of α-TCP and degradable polyesters

The objective of this study was to investigate the conversion of α-Ca3(PO4)2 (α-TCP) in composite bone cements based on a water-degradable polyester matrix as a function of the polymer formulation and the α-TCP filler content. Cross-linkable dimethacrylates of ε-caprolactone/D,L-lactide co-polymer or of ε-caprolactone/glycolide co-polymer were mixed with hydroxyethyl-methacrylate, a photo-initiator and α-TCP to obtain composites with a filler content of 80 or 40 wt% α-TCP. The disk shaped composite samples were set by visible light irradiation and immersed in HEPES at 37°C. At selected times the samples were removed from the solution and analysed with X-ray diffractometry and infrared spectroscopy. Conversion of α-TCP into calcium-deficient hydroxy-apatite (CDHAp) was observed for all composites, but the reaction was not completed after 8 weeks immersion. The conversion rate of α-TCP and the crystallinity of the formed apatite apparently were not affected by the type of polyester used, but significantly depended on the α-TCP content of the composites. An increase of the amount of α-TCP in the composite resulted in a slower formation of CDHAp with a higher crystallinity.

Surface and chemical properties of surface-modified UHMWPE powder and mechanical and thermal properties of its impregnated PMMA bone cement V. Effect of silane coupling agent on the surface modification of UHMWPE powder

Conventional poly(methyl methacrylate)(PMMA) bone cement has been widely used as an useful biopolymeric material to fix bone using artificial prostheses. However, many patients had to be reoperated, due to the poor mechanical and thermal properties of conventional PMMA bone cement, which are derived from the presence of unreacted MMA liquid, the shrinkage and bubble formation that occur during the curing process of the bone cement, and the high curing temperature(above 100 °C) which has to be used. In the present study, a composite PMMA bone cement was prepared by impregnating conventional PMMA bone cement with ultra high molecular weight polyethylene(UHMWPE) powder, in order to improve its mechanical and thermal properties. The UHMWPE powder has poor adhesion with other biopolymeric materials due to the inertness of the powder surface. Therefore, the surface of the UHMWPE powder was modified with two kinds of silane coupling agent containing amino groups(3-amino propyltriethoxysilane(TSL 8331®) andN-(2-aminoethyl)-3-(amino propyltrimethoxysilane)(TSL 8340®)), in order to improve its bonding strength with the conventional PMMA bone cement. The tensile strengths of the composite PMMA bone cements containing 3 wt% of the UHMWPE powder surface-modified with various ratios of TSL 8331® and TSL 8340® were similar or a little higher than that of the conventional PMMA bone cement. However, no significant difference in the tensile strengths between the conventional PMMA bone cement and the composite PMMA bone cements could be found. However, the curing temperatures of the composite PMMA bone cements were significantly decreased.

Evaluation of Oligo(ethylene glycol) Dimethacrylates Effects on the Properties of New Biodegradable Bone Cement Compositions

New injectable, in situ curable liquid formulations consisting of biodegradable aliphatic polyester, i.e., poly(3-allyloxy-1,2-propylene)succinate (PSAGE), methyl methacrylate (MMA), and hydrophilic oligo(ethylene glycol) dimethacrylates (OEGDMA) were investigated. The effect of MMA/OEGDMA ratio, OEGDMA molecular weight, i.e., the length of oligooxyethylene fragments, on the maximum curing temperature, setting time, compressive strength and modulus of the cured materials as well as their hydrophilicity were examined. The latter was characterized by determination of equilibrium water content and static water contact angle. The maximum temperature during crosslinking was found to decrease with increasing OEGDMA molecular weight and decreasing MMA/OEGDMA ratio. The setting time was affected strongly by the concentration of double bonds and was rapidly shortened with its increase. The compressive strength and compressive modulus values decreased with increasing OEGDMA molecular weight and decreasing MMA/OEGDMA ratio. Poly(3-allyloxy-1,2-propylene succinate).