Synthesis of bioactive PMMA bone cement via modification with methacryloxypropyltri- methoxysilane and calcium acetate

Bone cement consisting of polymethylmethacrylate (PMMA) powder and methylmethacrylate (MMA) liquid is clinically used for fixation of implants such as artificial hip joints. However, it does not show bone-bonding ability, i.e., bioactivity. The lack of bioactivity would be one of factors which cause loosening between the cement and the implant. The present authors recently showed the potential of bioactive PMMA-based bone cement through modification with γ -methacryloxypropyltrimethoxysilane (MPS) and calcium acetate. In this study, the effects of the kinds of PMMA powder on setting time, apatite formation and compressive strength were investigated in a simulated body fluid (Kokubo solution). The cement modified with calcium acetate calcined at 220 ^∘C could set within 15 min when the PMMA powder had an average molecular weight of 100,000 or less. The addition of calcium acetate calcined at 120 ^∘C in the PMMA powder required a much longer period for setting. The modified cements formed an apatite layer after soaking in the Kokubo solution within 1 day for cement starting from PMMA powder with a molecular weight of 100,000 or less. Compressive strengths of the modified cements were more than 70 MPa for cements starting from 100,000 and 56,000 in molecular weight. After soaking in Kokubo solution for 7 days, the modified cement consisting of PMMA powder of 100,000 in molecular weight showed a smaller decrease in compressive strength than that consisting of 56,000 in molecular weight. These results indicate that bioactive PMMA cement can be produced with appropriate setting time and mechanical strength when PMMA powders with a suitable molecular weight are used. Such a type of design of bioactive PMMA bone cement leads to a novel development of bioactive material for bone substitutes.     

Relationship between apatite-forming ability and mechanical properties of bioactive PMMA-based bone cement modified with calcium salts and alkoxysilane

Polymethylmethacrylate (PMMA)-based bone cement is used for the fixation of artificial joints in orthopaedics. However, the fixation is liable to loosen in the body, because the cement does not bond to living bone. So-called bioactive ceramics bond directly to living bone through the apatite layer formed on their surfaces in the body. We previously revealed that modification using γ-methacryloxypropyltrimethoxysilane (MPS) and water-soluble calcium salts such as calcium acetate and calcium hydroxide was effective for providing the PMMA-based bone cement with apatite-forming ability in a simulated body fluid (SBF, Kokubo solution) that closely reproduces the body environment. However, the effect of the chemical reaction forming the apatite on the mechanical properties of the cements has not been clarified. The present work aimed to investigate this issue from the viewpoint of the interface structure between the apatite and the cement. The surface of the cement modified with calcium acetate and MPS was fully covered with newly formed apatite after soaking in Kokubo solution within 7 days, while half of the surface area of the cement modified with calcium hydroxide and MPS was covered with the apatite. The bending strength of the modified cements decreased after soaking in Kokubo solution. Porous structure was observed in the region about 50–100 μm in depth from the top surface because of release of the Ca²⁺ ions by both modified cements after soaking in Kokubo solution. The decrease in bending strength of the modified cements could be attributed to the formation of the pores. In addition, the pores on the top surfaces of the cements were filled with the newly formed apatite. The apatite formation would be effective not only for bioactivity but also for decreasing the reduction of mechanical strength.     

Development of bioactive PMMA-based cement by modification with alkoxysilane and calcium salt

Poly (methyl methacylate) (PMMA) bone cement is one of the popular bone-repairing materials for fixation of artificial hip joints. Significant problems on the PMMA bone cement are caused by loosening at the interface between bone and the cement, since the cement does not show bone-bonding, i.e. bioactivity. Development of PMMA bone cement capable of bone-bonding has been therefore long desired. The prerequisite for an artificial material to show bone-bonding is the formation of a biologically active bone-like apatite layer on its surface when implanted in the body. The same type of apatite formation can be observed on bioactive materials even in a simulated body fluid (Kokubo solution) with ion concentrations nearly equal to those of human blood plasma. Fundamental researches for bioactive glasses and glass-ceramics revealed that the apatite deposition is initiated by release of Ca2+ ions from the material into the body fluid, and by catalytic effect of Si-OH groups formed on the surface of the material. These findings lead an idea that novel bioactive cement can be designed by incorporation of Si-OH groups and Ca2+ ion into PMMA bone cement. In the present study, PMMA bone cement is modified with 20 mass % of various kinds of alkoxysilanes and calcium salts, and its apatite-forming ability was evaluated in Kokubo solution. The apatite formation was observed on the surface of the modified cements containing 20 mass % of CaCl2, irrespective of the kind of the examined alkoxysilane. On the other hand, the apatite formation was observed on the cement containing CaCl2, Ca(CH3COO)2 or Ca(OH)2, but not on the cement containing CaCO3 or beta-Ca3(PO4)2, even when the cement contains 3-methacryloxypropyltrimethoxysilane (MPS). The results indicate that modification with alkoxysilane and calcium salts showing high water-solubility is effective for providing PMMA bone cement with bioactivity.     

Cement from magnesium substituted hydroxyapatite

Brushite cement may be used as a bone graft material and is more soluble than apatite in physiological conditions. Consequently it is considerably more resorbable in vivo than apatite forming cements. Brushite cement formation has previously been reported by our group following the mixture of nanocrystalline hydroxyapatite and phosphoric acid. In this study, brushite cement was formed from the reaction of nanocrystalline magnesium-substituted hydroxyapatite with phosphoric acid in an attempt to produce a magnesium substituted brushite cement. The presence of magnesium was shown to have a strong effect on cement composition and strength. Additionally the presence of magnesium in brushite cement was found to reduce the extent of brushite hydrolysis resulting in the formation of HA. By incorporating magnesium ions in the apatite reactant structure the concentration of magnesium ions in the liquid phase of the cement was controlled by the dissolution rate of the apatite. This approach may be used to supply other ions to cement systems during setting as a means to manipulate the clinical performance and characteristics of brushite cements.     

Bone cements and fillers: A review

Charnley [1] developed the first bone cement in the 1960s using poly(methyl methacrylate) (PMMA), which remains the most widely used material for fixation of orthopaedic joint replacements. In the field of dentistry, zinc polycarboxylate and glass polyalkenoate cements received major research interest from the 1970s to the present day. The discovery of a well-integrated intermediate layer between bone and many bioactive ceramic phases from the calcium–phosphate system, such as hydroxyapatite (HA), resulted in the development of new cements incorporating such phases. These investigations ranged from the development of castable bioactive materials to modified bioactive composites. This paper attempts to give a broad overview of the many different types of cements that have being developed in the past and those which are being researched at the present time. It has lead to a set of fundamental design criteria that should be considered prior to the development of a cement for use as a bone cement or in applications requiring a bone substitute.     

Fracture toughness of acrylic bone cements

Clinical experience has shown that fracture of PMMA-based bone cements is a significant factor in the failure of orthopaedic joint replacements. Earlier studies of the fracture toughness properties of bone cement have been limited to relatively large test specimens — ASTM standard test methods require the use of specimens with dimensions considerably larger that those associated with bone cement in clinical use. In this study, a miniature short-rod specimen was used to measure the fracture toughness (K _IC) or two bone cements (Simplex-P and Zimmer LVC). The dimension of our mini specimens approaches the cross-section of bone cements as usedin vivo. The short-rod elastic-plastic fracture toughness test method introduced by Barker was utilized to ascertain the effect of specimen preparation and ageing in distilled water on fracture toughness. Our study indicated that slow hand-mixed specimens possess comparable fracture toughness to centrifuged specimens. After ageing in water, however, centrifuged and slow hand-mixed specimens are more fracture resistant than specimens prepared by mixing the cement quickly. An optimum void content for the bone cements studied was suggested by the experimental results; for Simplex-P bone cement it appeared to be less than 1.6% whereas it was between 1.6 and 3.6% for Zimmer LVC cement. Simplex-P bone cement also showed superior fracture toughness compared to Zimmer LVC cement after storage in water for 60 days at 37° C.     

Composition and properties of silver-containing calcium carbonate–calcium phosphate bone cement

The introduction of silver, either in the liquid phase (as silver nitrate solution: Ag(L)) or in the solid phase (as silver phosphate salt: Ag(S)) of calcium carbonate–calcium phosphate (CaCO₃–CaP) bone cement, its influence on the composition of the set cement (C-Ag(L) and C-Ag(S) cements with a Ca/Ag atomic ratio equal to 10.3) and its biological properties were investigated. The fine characterisation of the chemical setting of silver-doped and reference cements was performed using FTIR spectroscopy. We showed that the formation of apatite was enhanced from the first hours of maturation of C-Ag(L) cement in comparison with the reference cement, whereas a longer period of maturation (about 10 h) was required to observe this increase for C-Ag(S) cement, although in both cases, silver was present in the set cements mainly as silver phosphate. The role of silver nitrate on the setting chemical reaction is discussed and a chemical scheme is proposed. Antibacterial activity tests (S. aureus and S. epidermidis) and in vitro cytotoxicity tests (human bone marrow stromal cells (HBMSC)) showed that silver-loaded CaCO₃–CaP cements had antibacterial properties (anti-adhesion and anti-biofilm formation) without a toxic effect on HBMSC cells, making C-Ag(S) cement a promising candidate for the prevention of bone implant-associated infections.     

Evaluation of colloidal silica suspension as efficient additive for improving physicochemical and in vitro biological properties of calcium sulfate-based nanocomposite bone cement

In the present study new calcium sulfate-based nanocomposite bone cement with improved physicochemical and biological properties was developed. The powder component of the cement consists of 60 wt% α-calcium sulfate hemihydrate and 40 wt% biomimetically synthesized apatite, while the liquid component consists of an aqueous colloidal silica suspension (20 wt%). In this study, the above mentioned powder phase was mixed with distilled water to prepare a calcium sulfate/nanoapatite composite without any additive. Structural properties, setting time, compressive strength, in vitro bioactivity and cellular properties of the cements were investigated by appropriate techniques. From X-ray diffractometer analysis, except gypsum and apatite, no further phases were found in both silica-containing and silica-free cements. The results showed that both setting time and compressive strength of the calcium sulfate/nanoapatite cement improved by using colloidal silica suspension as cement liquid. Meanwhile, the condensed phase produced from the polymerization process of colloidal silica filled the micropores of the microstructure and covered rodlike gypsum crystals and thus controlled cement disintegration in simulated body fluid. Additionally, formation of apatite layer was favored on the surfaces of the new cement while no apatite precipitation was observed for the cement prepared by distilled water. In this study, it was also revealed that the number of viable osteosarcoma cells cultured with extracts of both cements were comparable, while silica-containing cement increased alkaline phosphatase activity of the cells. These results suggest that the developed cement may be a suitable bone filling material after well passing of the corresponding in vivo tests.     

Influence of strontium for calcium substitution in bioactive glasses on degradation,ion release and apatite formation

Bioactive glasses are able to bond to bone through the formation of hydroxy-carbonate apatite in body fluids while strontium (Sr)-releasing bioactive glasses are of interest for patients suffering from osteoporosis, as Sr was shown to increase bone formation both in vitro and in vivo. A melt-derived glass series (SiO₂–P₂O₅–CaO–Na₂O) with 0–100% of calcium (Ca) replaced by Sr on a molar base was prepared. pH change, ion release and apatite formation during immersion of glass powder in simulated body fluid and Tris buffer at 37°C over up to 8 h were investigated and showed that substituting Sr for Ca increased glass dissolution and ion release, an effect owing to an expansion of the glass network caused by the larger ionic radius of Sr ions compared with Ca. Sr release increased linearly with Sr substitution, and apatite formation was enhanced significantly in the fully Sr-substituted glass, which allowed for enhanced osteoblast attachment as well as proliferation and control of osteoblast and osteoclast activity as shown previously. Studying the composition–structure–property relationship in bioactive glasses enables us to successfully design next-generation biomaterials that combine the bone regenerative properties of bioactive glasses with the release of therapeutically active Sr ions.     

Comparison of an experimental bone cement with surgical Simplex<Superscript>®</Superscript> P,Spineplex<Superscript>®</Superscript> and Cortoss<Superscript>®</Superscript>

Conventional polymethylmethacrylate (PMMA) cements and more recently Bisphenol-a-glycidyl dimethacrylate (BIS-GMA) composite cements are employed in procedures such as vertebroplasty. Unfortunately, such materials have inherent drawbacks including, a high curing exotherm, the incorporation of toxic components in their formulations, and critically, exhibit a modulus mismatch between cement and bone. The literature suggests that aluminium free, zinc based glass polyalkenoate cements (Zn-GPC) may be suitable alternative materials for consideration in such applications as vertebroplasty. This paper, examines one formulation of Zn-GPC and compares its strengths, modulus, and biocompatibility with three commercially available bone cements, Spineplex, Simplex P and Cortoss. The setting times indicate that the current formulation of Zn-GPC sets in a time unsuitable for clinical deployment. However during setting, the peak exotherm was recorded to be 33 degrees C, the lowest of all cements examined, and well below the threshold level for tissue necrosis to occur. The data obtained from mechanical testing shows the Zn-GPC has strengths of 63 MPa in compression and 30 MPa in biaxial flexure. Importantly these strengths remain stable with maturation; similar long term stability was exhibited by both Spineplex and Simplex P. Conversely, the strengths of Cortoss were observed to rapidly diminish with time, a cause for clinical concern. In addition to strengths, the modulus of each material was determined. Only the Zn-GPC exhibited a modulus similar to vertebral trabecular bone, with all commercial materials exhibiting excessively high moduli. Such data indicates that the use of Zn-GPC may reduce adjacent fractures. The final investigation used the well established simulated body fluid (SBF) method to examine the ability of each material to bond with bone. The results indicate that the Zn-GPC is capable of producing a bone like apatite layer at its surface within 24 h which increased in coverage and density up to 7 days. Conversely, Spineplex, and Simplex P exhibit no apatite layer formation, while Cortoss exhibits only minimal formation of an apatite layer after 7 days incubation in SBF. This paper shows that Zn-GPC, with optimised setting times, are suitable candidate materials for further development as bone cements.     

Cements from nanocrystalline hydroxyapatite

Calcium phosphate cements are used as bone substitute materials because they may be moulded to fill a void or defect in bone and are osteoconductive. Although apatite cements are stronger than brushite cements, they are potentially less resorbable in vivo. Brushite cements are three-component systems whereby phosphate ions and water react with a soluble calcium phosphate to form brushite (CaHPO4 x 2H2O). Previously reported brushite cement formulations set following the mixture of a calcium phosphate, such as beta-tricalcium phosphate (beta-TCP), with an acidic component such as H3PO4 or monocalcium phosphate monohydrate (MCPM). Due to its low solubility, hydroxyapatite (HA) is yet to be reported as a reactive component in calcium phosphate cement systems. Here we report a new cement system setting to form a matrix consisting predominantly of brushite following the mixture of phosphoric acid with nanocrystalline HA. As a result of the relative ease with which ionic substitutions may be made in apatite this route may offer a novel way to control cement composition or setting characteristics. Since kinetic solubility is dependent on particle size and precipitation temperature is known to affect precipitated HA crystal size, the phase composition and mechanical properties of cements made from HA precipitated at temperatures between 4 and 60 degrees C were investigated.     

Alpha-TCP improves the apatite-formation ability of calcium-silicate hydraulic cement soaked in phosphate solutions

The in vitro apatite-forming ability of experimental calcium-silicate hydraulic cements designed for dentistry was investigated.Two cements containing di- and tricalcium-silicate (wTC and wTC-TCP, i.e. wTC added with alpha-TCP) were soaked in different phosphate-containing solutions, namely Dulbecco's Phosphate Buffered Saline (DPBS) or Hank's Balanced Salt Solution (HBSS), at 37 °C and investigated over time (from 24 h to 6 months) by SEM/EDX, micro-Raman and ATR-FTIR.The early formation (24 h) of an aragonite/calcite layer onto both cements in both media was observed. Calcium phosphate deposits precipitated within 1–3 days in DPBS; spherical particles (spherulites) of apatite appeared after 3–7 days. wTC-TCP cement showed earlier, thicker and more homogeneous calcium phosphate deposits than wTC.In HBSS calcite deposits were mainly noticed, while phosphate bands appeared only after 7 days; the presence of globular deposits after 14–28 days was mostly detected on wTC-TCP.After 6 months, an approx. 900 micron carbonated apatite layer formed in DPBS whilst a 150–350 micron thick calcite/apatite layer generated in HBSS. Also in HBSS the carbonated apatite coating was earlier and thicker on wTC-TCP than wTC.Calcium-silicate cements showed the formation of a bone-like apatite layer, depending on the medium composition and ageing time. The addition of alpha-TCP increases the apatite-forming ability of calcium-silicate cements.Calcium-silicate hydraulic cements doped with alfa-TCP represent attractive materials to improve apical bone healing.     

Injectable acrylic bone cements for vertebroplasty based on a radiopaque hydroxyapatite. Formulation and rheological behaviour

The utilization of injectable acrylic bone cement is crucial to the outcome of vertebroplasty and kyphoplasty. However, only a few cements that are in clinical use today are formulated specifically for use in these procedures and even these formulations are not regarded as “ideal” injectable bone cements. The aim of this work is to prepare bioactive bone cements by adding strontium hydroxyapatite (SrHA) to a cement formulation based on polymethylmethacrylate. Thus, the cement combines the immediate mechanical support given by the setting of the acrylic matrix with optimum radiopacity and bioactivity due to the incorporation of the SrHA. Formulations of bioactive cement were prepared with 10 and 20 wt% of SrHA as synthesised and after a surface treatment with the monomer. Cements loaded with treated particles showed an enhancement of their handling properties, and hence, an improvement on their rheological behaviour, injectabilities and compressive parameters. Further experiments were also carried out to determine their bioactivity and biocompatibility and results appear in other publication.     

Increase of the final setting time of brushite cements by using chondroitin 4-sulfate and silica gel

Chondroitin 4-sulfate (C4S) is a bioactive glycosaminoglycan with inductive properties in bone and tissue regeneration. Dicalcium phosphate dehydrate cements (known as brushite) are biocompatible and resorbable materials used in bone and dental surgery. In this study we analyzed the effect of C4S on the setting of a calcium phosphate cement and the properties of the resulting material. Brushite based cement powder was synthesised by mixing monocalcium phosphate with β-tricalcium phosphate and sodium pyrophosphate. When the concentration of C4S, in the liquid added to the cement powder, was between 1 and 8% the cement final setting time increases. Furthermore, the cement diametral tensile strength remains unaffected when solutions with concentrations of C4S below 5% were used, but decreases at higher C4S concentrations. Calorimetric analysis showed that the cements prepared with C4S alone and in combination with silica gel have a greater content of hydrated water. We concluded from our study that the addition of small amounts of C4S increases the cement setting time without affecting its diametral tensile strength and at the same time improves the cement’s hydrophilicity.     

Bioactive sol–gel glass added ionomer cement for the regeneration of tooth structure

Dental cements including the glass ionomer cement (GIC) have found widespread use in restoring tooth structures. In this study, a sol-gel derived glass (SG) with a bioactive composition (70SiO(2) . 25CaO . 5P(2)O(5)) was added to the commercial GIC (GC, Fuji I) to improve the bioactivity and tooth regeneration capability. The SG powders prepared with sizes in the range of a few micrometers were mixed with GIC at SG/GC ratios of 10 and 30 wt%. The setting time, diametral tensile strength, and in vitro bioactivity of the GC-SG cements were examined. The setting time of the GC-SG cements increased with increasing amount of SG. However, the addition of SG did not significantly alter the diametral tensile strength of the GC. GC-SG induced the precipitation of an apatite bone-mineral phase on the surface after immersion in a simulated body fluid (SBF), showing in vitro bone bioactivity. However, no mineral induction in SBF was observed in the commercial GIC after the immersion. The in vitro cell assay confirmed that the GC-SG samples produced higher cell viability than the GC sample with cell culturing for up to 7 days.     

Evaluation of two novel aluminum-free,zinc-based glass polyalkenoate cements as alternatives to PMMA bone cement for use in vertebroplasty and balloon kyphoplasty

Vertebroplasty (VP) and balloon kyphoplasty (BKP) are now widely used for treating patients in whom the pain due to vertebral compression fractures is severe and has proved to be refractory to conservative treatment. These procedures involve percutaneous delivery of a bolus of an injectable bone cement either directly to the fractured vertebral body, VB (VP) or to a void created in it by an inflatable bone tamp (BKP). Thus, the cement is a vital component of both procedures. In the vast majority of VPs and BKPs, a poly(methyl methacrylate) (PMMA) bone cement is used. This material has many shortcomings, notably lack of bioactivity and very limited resorbability. Thus, there is room for alternative cements. We report here on two variants of a novel, bioactive, Al-free, Zn-based glass polyalkenoate cement (Zn-GPC), and how their properties compare to those of an injectable PMMA bone cement (SIMPL) that is widely used in VP and BKP. The properties determined were injectability, radiopacity, uniaxial compressive strength, and biaxial flexural modulus. In addition, we compared the compression fatigue lives of a validated synthetic osteoporotic VB model (a polyurethane foam cube with an 8 mm-diameter through-thickness cylindrical hole), at 0–2300 N and 3 Hz, when the hole was filled with each of the three cements. A critical review of the results suggests that the performance of each of the Zn-GPCs is comparable to that of SIMPL; thus, the former cements merit further study with a view to being alternatives to an injectable PMMA cement for use in VP and BKP.     

Performance of bioactive PMMA-based bone cement under load-bearing conditions: an in vivo evaluation and FE simulation

In the past, bioactive bone cement was investigated in order to improve the durability of cemented arthroplasties by strengthening the bone-cement interface. As direct bone–cement bonding may theoretically lead to higher stresses within the cement, the question arises, whether polymethylmethacrylate features suitable mechanical properties to withstand altered stress conditions? To answer this question, in vivo experiments and finite element simulations were conducted. Twelve rabbits were divided into two groups examining either bioactive polymethylmethacrylate-based cement with unchanged mechanical properties or commercially available polymethylmethacrylate cement. The cements were tested under load-bearing conditions over a period of 7?months, using a spacer prosthesis cemented into the femur. For the finite element analyses, boundary conditions of the rabbit femur were simulated and analyses were performed with respect to different loading scenarios. Calculations of equivalent stress distributions within the cements were applied, with a completely bonded cement surface for the bioactive cement and with a continuously interfering fibrous tissue layer for the reference cement. The bioactive cement revealed good in vivo bioactivity. In the bioactive cement group two failures (33?%), with complete break-out of the prosthesis occurred, while none in the reference group. Finite element analyses of simulated bioactive cement fixation showed an increase in maximal equivalent stress by 49.2 to 109.4?% compared to the simulation of reference cement. The two failures as well as an increase in calculated equivalent stress highlight the importance of fatigue properties of polymethylmethacrylate in general and especially when developing bioactive cements designated for load-bearing conditions.     

Influence of ibuprofen addition on the properties of a bioactive bone cement

Bioactive bone cements can promote bone growth and the formation of a strong chemical bond between the implant and bone tissue increasing the lifetime of the prosthesis. This study aims at synthesizing a new bioactive bone cement with different amounts of ibuprofen (5, 10 and 20 wt%) using a low toxicity activator, and investigating its in vitro release profile. The effect of ibuprofen (IB) on the setting parameters, residual monomer and bioactivity in synthetic plasma was also evaluated. It was verified that the different IB contents do not prevent the growth of calcium phosphate aggregates on composite surfaces, confirming that the cements are potentially bioactive. A relevant advantage of these formulations was a significant improvement in their curing parameters with increasing IB amount, associated to a reduction of the peak temperature and an extension of the setting time. The investigated cements released an average of about 20 % of the total incorporated ibuprofen during 30 days test, with IB20 liberating the highest percentage of drug 20.6 %, and IB10 and IB5, respectively 19.1 and 17.6 %. This behavior was attributed to the low solubility of this drug in aqueous media and was also related with the hydrophobic character of the polymer. Regarding the therapeutic concentration sufficient to suppress inflammation, the cement with 10 % of ibuprofen achieved the required release rate for 1 week and the cement with 20 % for 2 weeks.     

In situ study on the curing process of calcium phosphate bone cement

The aim of this study was to follow the entire curing process of modified alpha-TCP cement, and to explore how the liquid phase affects the curing reaction. Two calcium phosphate bone cements (CPCs) with a variety of aqueous solution were studied for comparison. In situ X-ray diffraction analysis and pH testing were employed to follow the chemical reaction, while quantitative ultrasonic measurement (QUS) was carried out to monitor the physical change. Results showed that CPC powders were completely consumed after 72 h. Two steps were presented in apatite formation. The first step was the precipitation of carbonated hydroxyapatite (CHA), and in the second step, conversion of calcium deficient hydroxyapatite (CDHA) was the dominant reaction. Finally, CPCs were fully converted to apatite except the cement with NaH2PO4 as liquid phase, because acidic environment inhibited the conversion of apatite. The pH increased linearly after mixing, when supersaturation was reached, it decreased to pH approximately 6.0 gradually. Ultrasound measurement indicated that the variation of speed of sound (SOS) was related to both apatite formation and microstructural evolution. Ultrasonic attenuation coefficient (UAC) was able to quantitatively describe the curing process from viscous paste to elastic solid as a function of curing time. Moreover, the curing reaction conformed to classical dissolution-precipitation mechanism.     

Microstructure and chemistry affects apatite nucleation on calcium phosphate bone graft substitutes

The bioactivity of calcium phosphate bone grafts of varying chemistry and strut-porosity was compared by determining the rate of formation of hydroxycarbonate apatite crystals on the material surface after being soaked in simulated body fluid for up to 30 days. Three groups of silicate-substituted hydroxyapatite material were tested, with each group comprising a different quantity of strut-porosity (23, 32, and 46 % volume). A commercially available porous β-tricalcium phosphate bone graft substitute was tested for comparison. Results indicate that strut-porosity of a material affects the potential for formation of a precursor to bone-like apatite and further confirms previous findings that β-tricalcium phosphate is less bioactive than hydroxyapatite.