Novel tricalcium silicate/monocalcium phosphate monohydrate composite bone cement

In this paper, we obtained a novel bone cement composed of tricalcium silicate (Ca(3)SiO(5); C(3)S) and monocalcium phosphate monohydrate (MCPM). The weight ratio of MCPM in the cement is 0, 10, 20, and 30%. The initial setting time was dramatically reduced from 90 min to 30 min as the content of MCPM reached 20%. The workable paste with a liquid/powder (L/P) ratio of 0.8 mL/g could be injected for 2-20 min (nozzle diameter 2.0 mm). The pH variation of the composite cement in simulated body environment was obviously lowered. The compressive strength of the composite cement after setting for 4-28 days was slightly lower than that of the tricalcium silicate paste. The in vitro bioactivity was investigated by soaking in simulated body fluid for 7 days. The result showed that the novel bone cement had good bioactivity and could degrade in tris-(hydroxymethyl)-aminomethane-hydrochloric-acid (Tris-HCl) solution. Our result indicated that the Ca(3)SiO(5)/MCPM paste had good hydraulic properties, bioactivity, and degradability. The novel bone cement could be a potential candidate as bone substitute.     

Calcium phosphate cements: study of the beta-tricalcium phosphate--monocalcium phosphate system

The possibility of making cements based on beta-tricalcium phosphate (beta-TCP), a promising bone graft material, was investigated. Upon admixture with water, beta-TCP/monocalcium phosphate monohydrate (MCPM) mixtures were found to set and harden like conventional hydraulic cements. Beta-TCP powders with larger particle size, obtained by sintering at higher temperatures, increased the ultimate strength of the cement. Results show that setting occurs after dissolution of MCPM, as a result of the precipitation of dicalcium phosphate dihydrate (DCPD) in the paste. The ultimate tensile strength of the hardened cement is proportional to the amount of DCPD formed. Upon ageing above 40 degrees C, DCPD transforms progressively into anhydrous dicalcium phosphate (DCP), thereby decreasing the strength. Ageing of the pastes in 100% r.h. results in a decay of the mechanical properties. This can be ascribed to an intergranular dissolution of the beta-TCP aggregates as a result of the pH lowering brought about by the MCPM to DCPD conversion.     

Strontium modified biocements with zero order release kinetics

Strontium-substituted beta-TCP with the general formula Ca((3-x))Sr(x)(PO(4))(2) (0相似文献   

Thermal reactions of brushite cements

The thermal reactions of a brushite cement made of beta-tricalcium phosphate (beta-TCP), monocalcium phosphate monohydrate (MCPM), and an aqueous solution were followed in situ with an isothermal calorimeter at 37 degrees C. The investigated parameters were the beta-TCP/MCPM weight ratio, the liquid-to-powder ratio, the synthesis route and milling duration of the beta-TCP powder, as well as the presence of sulfate, citrate, and pyrophosphate ions in the mixing liquid. The thermograms were complex, particularly for mixtures containing an excess of MCPM or additives in the mixing solution. Results suggested that the endothermic MCPM dissolution and the highly exothermic beta-TCP dissolution occurred simultaneously, thereby leading to the formation of a large exothermic peak at early reaction time. Both reactions were followed by the exothermic crystallization of brushite and in the presence of an excess of MCPM by the endothermic crystallization of monetite. Additives generally widened the main exothermic reaction peak, or in some cases with pyrophosphate ions postponed the main exothermic peak at late reaction time. Generally, the results could be well explained and understood based on thermodynamic and solubility data.     

Vertical bone augmentation with granulated brushite cement set in glycolic acid

Brushite cements are a biocompatible materials that are resorbed in vivo. A new cement composed of a mixture of monocalcium phosphate (MCP) and beta-tricalcium phosphate (beta-TCP) that sets using glycolic acid (GA) was synthesized and characterized. After setting, the cement composition, derived from X-ray diffraction, was 83 wt % brushite and 17 wt % beta-TCP with an average brushite crystal size of about 2.6 +/- 1.4 microm. The cement has a diametral tensile strength of 2.9 +/- 0.7 MPa. Granules prepared from the set-cement were used as grafting material in bone defects on rabbit calvaria for evaluating in vivo its bone regeneration capacity. Considerable cement resorption, improvement in the bone mineral density, and bone neoformation was observed after 4 weeks of the granules' implantation.     

Effect of cold-setting calcium- and magnesium phosphate matrices on protein expression in osteoblastic cells

Bone loss due to accidents or tissue diseases requires replacement of the structure by either autografts, allografts, or artificial materials. Reactive cements, which are based on calcium phosphate chemistry, are commonly used in nonload bearing areas such as the craniofacial region. Some of these materials are resorbed by the host under physiological conditions and replaced by bone. The aim of this study was to test different calcium and magnesium cement composites in vitro for their use as bone substitution material. Phase composition of calcium deficient hydroxyapatite (Ca(9) (PO(4) )(5) HPO(4) OH), brushite (CaHPO(4) ·2H(2) O), and struvite (MgNH(4) PO(4) ·6H(2) O) specimens has been determined by means of X-ray diffraction, and compressive strength was measured. Cell growth and activity of osteoblastic cells (MG 63) on the different surfaces was determined, and the expression of bone marker proteins was analyzed by western blotting. Cell activity normalized to cell number revealed higher activity of the osteoblasts on brushite and struvite when compared to hydroxyapatite and also the expression of osteoblastic marker proteins was highest on brushite scaffolds. While brushite sets under acidic conditions, formation of struvite occurs under physiological pH, similar to hydroxyapatite cements, providing the possibility of additional modifications with proteins or other active components.     

An improvement in sintering property of beta-tricalcium phosphate by addition of calcium pyrophosphate.

The sintering behavior of calcium pyrophosphate (CPP, Ca2P2O7)-doped beta-tricalcium phosphate [TCP, Ca3(PO4)2], prepared by solid state reaction, was investigated in-situ, using dilatometry. Pure beta-TCP undergoes phase transition to alpha-TCP at about 1200 degrees C; hence pure beta-TCP ceramics should be sintered bclow 1200 degrees C. Pure beta-TCP sintered body can achieve a relative density of only 86% when sintered at 1150 degrees C. However, the addition of CPP in the range of 0.5-3 wt% delays phasc transition of beta-TCP and enables sintering of beta-TCP at 1200 degrees C without a phase transformation to alpha-TCP. Due to this effect of CPP added to TCP, CPP-doped beta-TCP ceramics with relative density over 95% could be obtained when sintered at 1200 degrees C for 2 h.     

Characterization of chlorhexidine-releasing, fast-setting, brushite bone cements

The effect of antibacterial chlorhexidine diacetate powder (CHX) on the setting kinetics of a brushite-forming beta-tricalcium phosphate/monocalcium phosphate monohydrate (beta-TCP/MCPM) cement was monitored using attenuated total reflection Fourier transform infrared spectroscopy. The final composition of the set cement with up to 12 wt.% CHX content before and after submersion in water for 24h, the kinetics of chlorhexidine release and the total sample mass change in water over four weeks was monitored using Raman mapping, UV spectroscopy and gravimetry, respectively. Below 9 wt.%, CHX content had no significant effect on brushite formation rate at 37 degrees C, but at 12 wt.% the half-life of the reaction decreased by one-third. Raman mapping confirmed that brushite was the main inorganic component of the set cements irrespective of CHX content, both before and after submersion in water. The CHX could be detected largely as discrete solid particles but could also be observed partially dispersed throughout the pores of the set cement. The percentage of CHX release was found to follow Fick's law of diffusion, being independent of its initial concentration, proportional to the square root of time and, with 1mm thick specimens, 60% was released at 24h. Total set cement mass loss rate was not significantly affected by CHX content. On average, cements exhibited a loss of 7 wt.% assigned largely to surface phosphate particle loss within the initial 8h followed by 0.36 wt.% per day.     

Osseointegration of 2 different types of calcium phosphate materials: ceramics and ionic cements

Different kinds of calcium phosphate biomaterials can be used as bone substitutes. Ceramics are constituted by HA or TCP grains linked by grain boundaries. Their porosity depends on the powder characteristics and the sintering temperature. It can be very low with a pore size inferior to one micron. The setting of calcium phosphate hydraulic cements results from the precipitation of a calcium phosphate phase different from the one in suspension in the paste. The strength of the cement is given by the entanglement of the growing mineral crystals. Calcium phosphate hydraulic cements and ceramics have very different physico-chemical characteristics. We have studied the histological integration of both kinds of material. The first material was constituted by macroporous ceramics composed of 75% HA and 25% beta-TCP, the cement was made of beta-TCP grains dispersed in a DCPD matrix. The sequence of events which leads to the ceramic integration is always the same: a/ ingrowth of a loose connective tissue; b/ osteoblast differentiation from fibroblast-like cells of the connective tissue in close proximity to the implant surface; c/ osteoid synthesis at the ceramic surface toward the pore center; d/ remodeling of the immature bone and the ceramic itself. The cement is differently integrated. The osteoblasts differentiate at some distance from the implant and there is a trabeculae ingrowth toward the material. CONCLUSIONS: The early stages of both materials osteointegration are different. The integration is centrifugal for ceramics and centripetal for the cement.     

硅酸钙-磷酸盐复合骨水泥的制备及其性能研究

分别以α-磷酸三钙（α—TCP）、磷酸四钙（TTCP）为基本原料，添加羟基磷灰石（HAP）、磷酸氢钙（DCPD）、碳酸钙（CaCO2）、氧化钙（CaO）等其它辅料，并与一定量的无定形硅酸钙（CaSiO3）进行复合，确定了钙磷比均为1．50的六种骨水泥配方，对其基本性能进行了研究。对固化骨水泥样品进行了Ringer’S模拟液浸泡实验，研究了浸泡液pH值、样品的抗压强度随浸泡时间的变化。结果表明：调和液0．25MK2HPO4／KH2PO4和无定形CaSiO3对骨水泥有促凝作用，缩短骨水泥的终凝时间，其中初凝时间为4～5．5min，终凝时间为18～19．5min；同时添加适量无定形CaSiO3可以显著提高骨水泥的抗压强度，其中添加适量无定形CaSiO3的以α—TCP为主要原料的骨水泥Ringer’s模拟液浸泡两周后抗压强度可达45．3MPa。     

Bone repair in radii and tibias of rabbits with phosphorylated chitosan reinforced calcium phosphate cements

Biocompatibility of two calcium phosphate cements (CPCs), reinforced with phosphorylated chitosan (P-chitosan), was investigated in rabbits in present study. The two CPCs are monocalcium phosphate monohydrate (MPCM) with calcium oxide (CaO) in 1 M phosphate buffer (i.e. MCPM/CaO/1 M phosphate buffer cement, CPC-I) and dicalcium phosphate dihydrate (DCPD) with calcium hydroxide [Ca(OH)2] in 1 M Na2HPO4 solution (i.e. DCPD/Ca(OH)2/1 M Na2HPO4 cement, CPC-II). Different amount of P-chitosan was added to the liquid phase before the power phase was mixed with the liquid phase. The MCPM/CaO/1 M phosphate buffer/P-chitosan cements (P-CPC-I) with neutral pH were filled into the holey defects of rabbit tibias. While the DCPD/Ca(OH)2/1 M Na2HPO4/P-chitosan cements (P-CPC-II) shaped as prehardened cylinders were implanted into rabbit radial defects. After operation, the two serial groups and CPC-II controls were observed for 1, 4, 12 and 22 weeks, respectively. Histological and histomorphological studies proved that P-chitosan containing cements are biocompatible, bioabsorbable and osteoinductive. The biodegradation rate has a negative relationship with the P-chitosan content. Progressive substitution took place at the interface of implants and host bones. No adverse effects were found in tissues around the bone defects. Thus, they could be used as bone substitutes in clinic.     

Self-setting properties and in vitro bioactivity of Ca2SiO4/CaSO4.1/2H2O composite bone cement

In this study, a biphasic injectable bone substitute based on beta-dicalcium silicate (Ca(2)SiO(4)) and plaster of Paris (CaSO(4).1/2H(2)O) is presented, and its behavior as cement was studied and compared to that of pure Ca(2)SiO(4) paste. The results demonstrated that the setting time of the workable Ca(2)SiO(4)/CaSO(4).1/2H(2)O pastes was only 15 min, which was significantly reduced as compared to that of the Ca(2)SiO(4) paste (100 min), and the composite showed higher short- and long-term mechanical strength (3.25 and 37.2 MPa, respectively) than those of the Ca(2)SiO(4) paste (0.2 and 24.6 MPa). Similar to the pure Ca(2)SiO(4) paste, the composite paste could induce apatite formation in simulated body fluid within a short period and degrade in Ringer's solution. Moreover, the degradation rate could be adjusted by modifying the content of the plaster within the composite cement. These results suggested that the addition of the plaster significantly improved the self-setting properties of the Ca(2)SiO(4) paste, and the bioactive composite cement could be a prospective candidate for further investigation as self-setting tissue-repairing substitute.     

Effects of incorporating nanosized calcium phosphate particles on properties of whisker-reinforced dental composites

Clinical data indicate that secondary caries and restoration fracture are the most common problems facing tooth restorations. Our ultimate goal was to develop mechanically-strong and caries-inhibiting dental composites. The specific goal of this pilot study was to understand the relationships between composite properties and the ratio of reinforcement filler/releasing filler. Nanoparticles of monocalcium phosphate monohydrate (MCPM) were synthesized and incorporated into a dental resin for the first time. Silicon carbide whiskers were fused with silica nanoparticles and mixed with the MCPM particles at MCPM/whisker mass ratios of 1:0, 2:1, 1:1, 1:2, and 0:1. The composites were immersed for 1-56 days to measure Ca and PO4 release. When the MCPM/whisker ratio was changed from 0:1 to 1:2, the composite flexural strength (mean +/- SD; n = 5) decreased from 174 +/- 26 MPa to 138 +/- 9 MPa (p < 0.05). A commercial nonreleasing composite had a strength of 112 +/- 14 MPa. When the MCPM/whisker ratio was changed from 1:2 to 1:1, the Ca concentration at 56 days increased from 0.77 +/- 0.04 mmol/L to 1.74 +/- 0.06 mmol/L (p < 0.05). The corresponding PO4 concentration increased from 3.88 +/- 0.21 mmol/L to 9.95 +/- 0.69 mmol/L (p < 0.05). Relationships were established between the amount of release and the MCPM volume fraction v(MCPM) in the resin: [Ca]= 42.9 v(MCPM) (2.7), and [PO4] = 48.7 v(MCPM) (1.4). In summary, the method of combining nanosized releasing fillers with reinforcing fillers yielded Ca- and PO4-releasing composites with mechanical properties matching or exceeding a commercial stress-bearing, nonreleasing composite. This method may be applicable to the use of other Ca-PO4 fillers in developing composites with high stress-bearing and caries-preventing capabilities, a combination not yet available in any dental materials.     

Influence of polymeric additives on the biological properties of brushite cements: an experimental study in rabbit

The resorbability and ability of calcium phosphate hydraulic cements to promote new bone formation was investigated in vivo. The effects of two hydrosoluble polymeric additives (hyaluronic acid, and xanthan gum,) on the biological response of two brushite cement formulations (BHC-A vs BHC-B) was investigated. The brushite cements differed in P/Ca (0.71 vs 0.98) and S/Ca (0.10 vs 0.005) atomic ratios and by the presence of calcium sulfate hemihydrate in BHC-A. Polymer-free cements were used as controls. Cement specimens were injected in cylindrical bone defects manually drilled in the distal condyle of rabbit femora. The implants were harvested at 12 and 24 weeks after implantation and subjected to quantitative histomorphometry. The study showed a significantly lower resorption rate for cement BHC-A, which induces the formation of well-mineralized bone in close apposition to the residual material. In contrast, cement BHC-B showed a significant increase of bone formation period and the formation of a thick layer of unmineralized osteoid tissue at the bone/residual cement interface. The presence of xanthan gum made the biological response even worse, particularly in the case of cement BHC-B. The presence of hyaluronic acid has little effect, except for a slight decrease in initial resorption rate, in the case of cement BHC-A.     

Transformation mechanism of different chemically precipitated apatitic precursors into beta-tricalcium phosphate upon calcination

The Ca-deficient apatite (CDHA) was prepared from the precursors of (CH3COO)2Ca x xH2O, Ca(NO3)2 x 4H2O and H3PO4, (NH4)H2PO4 to investigate the transformation mechanism of beta-tricalcium phosphate (beta-TCP). X-ray diffraction analysis shows that the development of beta-TCP is not via direct reaction between Ca and P for all the different combinations between Ca and P precursors. The activation energy of beta-TCP formation with (NH4)H2PO4 as precursor was higher than that with H3PO4. Following the Johnson-Mehl-Avrami equation, the reaction kinetics of beta-TCP phase formation is found one-dimension growth with interface-controlled and diffusion controlled growth depending on the annealing temperature. There exists a transition between 750 degrees C and 825 degrees C, and the transition rate from interface-controlled to diffusion-controlled growth is precursor-dependent.     

Advantages of using glycolic acid as a retardant in a brushite forming cement

In this study we have compared the effect of using acetic, glycolic, and citric acids on the brushite cement setting reaction and the properties of the resultant cement. The cement solid phase was made by mixing beta-tricalcium phosphate (beta-TCP), monocalcium dihydrogen phosphate anhydrate (MCPA), and sodium pyrophosphate, whereas the cement liquid phase consisted of aqueous solutions of carboxy acids at concentrations ranging from 0.5 to 3.5M. Cements were prepared by mixing the solid phase with the liquid phase to form a workable paste. The cement setting time was longer for glycolic and citric acids. The best mechanical properties in dry environments were obtained using glycolic and citric acid liquid phases. In a wet environment at 37 degrees C, the cement set with glycolic acid was the strongest one. Brushite cement diametral tensile strength seems to be affected by the calcium-carboxyl phase produced in the setting reaction. The acceptable setting time and mechanical properties of cements set in glycolic acid solutions are attributed to the additional hydrophilic groups in the carboxylic acid and the low solubility in water of the calcium salt produced in the reaction. Moreover, at high concentrations, carboxylic acids add chemically to the cement matrix becoming reactants themselves.     

Calcium phosphate apatites with variable Ca/P atomic ratio III. Mechanical properties and degradation in solution of hot pressed ceramics.

Calcium deficient hydroxyapatite powders Ca(10-x)(PO4)(6-x)(HPO4)x(OH)(2-x) (0 < or = x < or = 1) were hot pressed to produce dense hydroxyapatite-tricalcium phosphate (HAP/TCP) biphasic materials. Ceramics hot pressed at 1000 degrees C were composed of an homogeneous distribution of the HAP and beta-TCP grains with an average size of 0.2 microm. Grain growth was observed for TCP loading > 70 wt%. The strength exhibited a maximum of sigma(f) = 150 MPa for 90/10 (w/w) HAP/TCP and it dropped for smaller and greater amounts of TCP. This value was twice that of pure HAP. When placed in Ringer's solution, only the surface of biphasic compounds was degraded after 60 days of immersion with a preferential etching of the TCP phase. After hot pressing at 1200 degrees C, grain growth was observed and the mechanical properties were decreased. This was explained by the allotropic transformation alpha/beta of TCP.     

Bone colonization of beta-TCP granules incorporated in brushite cements

Injectable calcium phosphate hydraulic cements are known to have a high clinical potential in bone reconstruction for mini-invasive orthopaedic surgery, interventional radiology, and rheumatology. Previous in vivo experiments in rabbit have shown that the presence of beta-TCP granules in injectable bone cement help maintain the transient biomechanical function of the implanted bone and promote the formation of good-quality new bone. Histomorphometric analysis of two brushite hydraulic cement (BHC) mixtures selected from previous results (referred to in this work as BHC-A and BHC-B) was performed at three postoperative delays (0, 12, and 24 weeks): histomorphometric analysis of bone colonization within beta-TCP shows that, just before implantation, the beta-TCP granule area is significantly higher in BHC-B; the residual granule area decreases steadily over time in BHC-A, whereas it goes through a maximum of 30% at 12 weeks in BHC-B; the residual granule porosity increases steadily up to 35% in BHC-A, whereas it goes through a maximum of 35% at 12 weeks and decreases somewhat until 24 weeks in BHC-B. New bone formation within granules appears higher in BHC-A (58% Area) compared to BHC-B (38% area) at 12 weeks. At 24 weeks bone colonization levels off in both cements at about 50% area. Irrespective of the cement matrix composition, beta-TCP granules contribute actively to the conduction of new bone formation.     

Biologically mediated resorption of brushite cement in vitro

A new calcium phosphate cement is reported, which sets to form a matrix consisting of brushite, dicalcium pyrophosphate dihydrate and an amorphous phase following the mixture of beta-tricalcium phosphate with an aqueous pyrophosphoric acid solution. This reactant combination set within a clinically relevant time-frame (approximately 10 min) and exhibited a higher compressive strength (25 MPa) than previously reported brushite cements. The in vitro degradation of the beta-tricalcium phosphate-pyrophosphoric acid cement was tested in both phosphate buffered saline and bovine serum. The pyrophosphate ion containing cement reported here was found not to be hydrolysed to form hydroxyapatite in vitro like beta-tricalcium phosphate-orthophosphoric acid solution cements. This finding is significant since the formation of hydroxyapatite by hydrolysis is thought to retard in vivo degradation of brushite cements. When aged in bovine serum, the cement lost considerably more mass than when aged in phosphate buffered saline, indicating that proteins, most likely phosphatase enzymes played an important role in the degradation. As pyrophosphate ions are thought to be the source of orthophosphate ions during bone mineralisation, this new class of bone cement offers a route to new degradable synthetic bone grafting materials.     

Combined effect of strontium and pyrophosphate on the properties of brushite cements

In this study we report the synthesis of strontium-containing brushite cement with good cohesion and a diametral tensile strength (DTS) of 5 MPa. The cement powder, composed of β-tricalcium phosphate (β-TCP) and monocalcium phosphate, was adjusted by different concentrations of strontium and pyrophosphate ions. The cement liquid phase was 2 M phosphoric acid solution. The cement cohesion and mechanical properties were measured after being aged in water for 24 h at 37 °C. It was found that at low concentration both strontium and pyrophosphate ions inhibit the cement setting reaction. However, the final setting time was significantly reduced when SrCl₂ increased from 5 to 10 wt.% at pyrophosphate concentrations equal to or higher than 2.16 wt.%. The incorporation of strontium ions did not increase the DTS of brushite cements significantly. In contrast, the addition of pyrophosphate ions did increase the DTS of brushite cements significantly. When both ions were added simultaneously, the brushite cement with a Sr²⁺ content of 5 wt.% had the highest DTS value. Nevertheless, the DTS values of Sr-containing cements were significantly reduced if the pyrophosphate concentration was higher than 2.16 wt.%. The Sr²⁺ ions had a negative effect on brushite cement cohesion, although the solid weight loss started to decrease at Sr²⁺ concentrations higher than 5 wt.%.