Search

Two types of synthetic carbonate apatite [potassium-containing carbonate apatite (CAK) and sodium-containing carbonate apatite (CANa)] were prepared and characterized by thermogravimetric analysis, X-ray diffraction analysis (XRD) and Fourier transform infrared spectroscopy. The chemical formulas of carbonate apatite were determined to be Ca 9.36 K 0.12 (PO 4 ) 5.12 (CO 3 ) 0.88 (OH) 1.73 and Ca 8.72 Na 1.33 (PO 4 ) 4.96 (CO 3 ) 1.04 (OH) 1.80 , respectively. Thermogravimetric analysis showed that the final weight loss at 1,200°C reached about 11.2% for CAK and 13.9% for CANa. Carbonate loss gradually occurred above 150°C and continued to 1,200°C. The crystallinity of the apatite phase was found to be much improved between 800 and 850°C for CAK and 750 and 800°C for CANa, where rapid carbonate loss occurred. A small amount of CaO formed above 900°C. For CANa, NaCaPO 4 also formed above 700°C in both apatites. Although the lattice parameters of the carbonate apatites varied with temperature, the final a and c lattice parameters attained constant values of 0.9421 and 0.6881 nm.

Appropriate setting time is an important parameter that determines the effectiveness of apatite cement (AC) for clinical application, given the issues of crystalline inflammatory response phenomena if AC fails to set. To this end, the present study analyzes the effects of the method of apatite seed crystals addition on the setting reaction of α-tricalcium phosphate (α-TCP) based AC. Two ACs, both consisting of α-TCP and calcium deficient hydroxyapatite (cdHAp), were analyzed in this study. In one AC, cdHAp was added externally to α-TCP and this AC was abbreviated as AC(EA). In the other AC, α-TCP was partially hydrolyzed to form cdHAp on the surface of α-TCP. This AC was referred to as AC(PH). Results indicate a decrease in the setting time of both ACs with the addition of cdHAp. Among them, for the given amount of added cdHAp, AC(PH) showed relatively shorter setting time than AC(EA). Besides, the mechanical strength of the set AC(PH) was also higher than that of set AC(EA). These properties of AC(PH) were attributed to the predominant crystal growth of cdHAp in the vicinity of the α-TCP particle surface. Accordingly, it can be concluded that the partial hydrolysis of α-TCP may be a better approach to add low crystalline cdHAp onto α-TCP based AC.

The objective of this study was to fabricate a type of bone cement that could fully transform to carbonate apatite (CO3Ap) in physiological conditions. A combination of calcium carbonate (CaCO3) and dicalcium phosphate anhydrous was chosen as the powder phase and mixed with one of three kinds of sodium phosphate solutions: NaH2PO4, Na2HPO4, or Na3PO4. The cement that fully transformed to CO3Ap was fabricated using vaterite, instead of calcite, as a CaCO3 source. Their stability in aqueous solutions was different, regardless of the type of sodium phosphate solution. Rate of transformation to CO3Ap in descending order was Na3PO4>Na2HPO4>NaH2PO4. Transformation rate could be affected by the pH of solution. Results of this study showed that it was advantageous to use vaterite to fabricate CO3Ap-forming cement.

Carbonate apatite (CO3Ap), fabricated by dissolution-precipitation reaction based on an appropriate precursor, is expected to be replaced by bone according to bone remodeling cycle. One of the precursor candidates is gypsum because it shows self-setting ability, which then enables it to be shaped and molded. The aim of this study, therefore, was to fabricate CO3Ap blocks from set gypsum. Set gypsum was immersed in a mixed solution of 0.4 mol/L disodium hydrogen phosphate (Na2HPO4) and 0.4 mol/L sodium hydrogen carbonate (NaHCO3) at 80-200°C for 6-48 h. Powder X-ray diffraction patterns and Fourier transform infrared spectra showed that CO3Ap block was fabricated by dissolution-precipitation reaction in Na2HPO4-NaHCO3 solution using set gypsum in 48 h when the temperature was 100°C or higher. Conversion rate to CO3Ap increased with treatment temperature. CO3Ap block containing a larger amount of carbonate was obtained when treated at lower temperature.

Sr-containing carbonate apatite (SrCAp) specimens of varied Sr contents, ranging from 0 to 13.3 mol%, were prepared through a phosphate treatment of set gypsum-and-carbonate mixture at 100°C for 7 days. Effects of Sr content in SrCAp on microstructure, osteoblast-like cell (MC3T3-E1) attachment and proliferation, and alkaline phosphatase (ALP) activity were evaluated. Sr(2+) ion substituted Ca(2+) ion in the apatite lattice. Carbonate content was about 9-13.6 wt%, increasing in content level as Sr content increased. Sr addition benefited cell attachment but had no significant influence on cell proliferation, although the latter was inhibited at the highest Sr content. ALP activity reached a peak in specimen containing 3.4 mol% of Sr. The present study revealed that SrCAp is a promising candidate for use as a bone substitute material with good resorbabilty and osteoconductivity.

Spherical carbonate apatite (CO3Ap) microspheres approximately 1 mm in diameter were fabricated by granulation of calcium hydroxide around a core followed by carbonation and phosphatization through dissolution-precipitation reaction. CO3Ap microspheres with high uniformity could not be achieved without using a core. Solid CO3Ap microspheres were obtained using a calcite core whereas hollow CO3Ap microspheres were obtained using a NaCl core. The obtained microsphere was identified as B-type CO3Ap by Fourier transform infrared analysis and the carbonate content was approximately 7-8 wt% regardless of the type of core used for sample preparation. The mechanical strength of both the solid and hollow CO3Ap microspheres was sufficient for practical use as a bone substitute.

To understand the feasibility of calcium (Ca) modification of type 316L stainless steel (316L SS) surface using hydrothermal treatment, 316L SS plates were treated hydrothermally in calcium chloride (CaCl(2)) solution. X-ray photoelectron spectroscopic analysis revealed that the surface of 316L SS plate was modified with Ca after hydrothermal treatment at 200°C. And the immobilized Ca increased with CaCl(2) concentration. However no Ca-modification was occurred for 316L SS plates treated at 100°C. When Ca-modified 316L SS plate was immersed in simulated body fluid (SBF) with ion concentrations nearly equal to those of human blood plasma, low crystalline apatite was precipitated on its surface whereas no precipitate was observed on non Ca-modified 316L SS. The results obtained in the present study indicated that hydrothermal treatment at 200°C in CaCl(2) solution is useful for Ca-modification of 316L SS, and Ca-modification plays important role for apatite precipitation in SBF.

Carbonate apatite (CO(3)Ap) foam may be an ideal bone substitute as it is sidelined to cancellous bone with respect to its chemical composition and structure. However, CO(3)Ap foam fabricated using α-tricalcium phosphate foam showed limited mechanical strength. In the present study, feasibility of the fabrication of calcite which could be a precursor of CO(3)Ap was studied. Calcite foam was successfully fabricated by the so-called "ceramic foam" method using calcium hydroxide coated polyurethane foam under CO(2)+O(2) atmosphere. Then the calcite foam was immersed in Na(2)HPO(4) aqueous solution for phase transformation based on dissolution-precipitation reaction. When CaO-free calcite foam was immersed in Na(2)HPO(4) solution, low-crystalline CO(3)Ap foam with 93-96% porosity and fully interconnected porous structure was fabricated. The compressive strength of the foam was 25.6 ± 6 kPa. In light of these results, we concluded that the properties of the precursor foam were key factors for the fabrication of CO(3)Ap foams.

In this study, we investigated a novel method for fabrication of carbonate apatite block without ionic movement between precursor and solution by using precursor that includes all constituent ions of carbonate apatite. A powder mixture prepared from dicalcium phosphate anhydrous and calcite at appropriate Ca/P ratios (1.5, 1.67, and 1.8) was used as starting material. For preparation of specimens, the slurry made from the powder mixture and distilled water was packed in a split stainless steel mold and heat - treated, ranging from 60 degrees C to 100 degrees C up to 48 hours at 100% humidity. It appeared that carbonate apatite could be obtained above 70 degrees C and monophasic carbonate apatite could be obtained from the powder mixture at Ca/P ratio of 1.67. Carbonate content of the specimen was about 5-7%. Diametral tensile strength of the carbonate apatite blocks slightly decreased with increasing treatment temperature. The decrease in diametral tensile strength is thought to be related to the crystal size of the carbonate apatite formed.

The effect of temperature on crystallinity of carbonate apatite (CAp) foam prepared from alpha-tricalcium phosphate (alpha-TCP) foam by hydrothermal treatment was investigated in the present study. The alpha-TCP foams were prepared through a conventional sintering method using polyurethane foam as template. Then, the resultant alpha-TCP foams were hydrothermally treated with Na2CO3 aqueous solution at 100 degrees C, 150 degrees C and 200 degrees C for 72 h. After hydrothermal treatment, the cancellous bone-like macroporous structure of the alpha-TCP foams was maintained. However, microscopic morphology of the foams' frame significantly changed after the 72 h treatment period. The smooth surface of alpha-TCP foam disappeared and the whole surface was covered with plate-like deposits. The plate-like deposits treated at 150 degrees C and 200 degrees C had smooth surface while those treated at 100 degrees C were constructed from spherical particles of approximately 200 nm in diameter. The results of X-ray diffraction and Fourier transform infrared analysis showed that alpha-TCP was completely converted to CAp and the crystallinity of CAp prepared at 100 degrees C was significantly lower than those prepared at 150 degrees C and 200 degrees C. Hydrothermal treatment of alpha-TCP foam at 100 degrees C allowed the formation of low-crystalline CAp foam but complete conversion needs a longer treatment period.

Bone consists of a mineral phase (carbonate apatite) and an organic phase (principally collagen). Cancellous bone is characterized by interconnecting porosity necessary for tissue ingrowth and nourishment of bone cells. The purpose of the present study was to fabricate macroporous carbonate apatite (CAP) blocks with interconnecting porosity as potential bone substitute biomaterials by hydrothermal conversion of alpha-TCP foam in carbonate solution. The fabrication of the macroporous CAP was accomplished in two steps: (1) preparation of alpha-TCP foams using polyurethane foams as templates, and (2) hydrothermal conversion at 200 degrees C of alpha-TCP foam in the presence of ammonium carbonate solutions of different concentrations. The maximum carbonate content of the resultant CAP foam was approximately 7.4 wt %. The mean porosity of the CAP foam was as high as 93 vol %. The macroporous CAP blocks or granules prepared in this manner has properties similar to that of bone in mineral composition and in having interconnecting macroporosity necessary for osteoconductivity and tissue ingrowth. On the basis of composition and interconnecting macroporosity, the CAP foam materials could be ideal biomaterials for bone repair and as scaffolds for tissue engineering., (2008 Wiley Periodicals, Inc.)

B-type carbonate apatite (CO3Ap) block may be an ideal artificial bone substitute because it is closer in chemical composition to bone mineral. In the present study, the feasibility to fabricate CO3Ap blocks was investigated using compositional transformation, which was based on the dissolution-precipitation reaction of a gypsum-calcite composite with free-molding behavior. For the compositional change, or phosphorization, gypsum-calcite composites of varying CaCO3 contents were immersed in 1 mol/L (NH4)3PO4 aqueous solution at 100 degrees C for 24 hours. No macroscopic changes were found after the treatment, whereas microscopic change was observed at SEM level. X-ray diffraction, Fourier transform infrared spectroscopy and CHN analysis indicated that the composites were B-type CO3Ap containing approximately 6-7 wt% of CO3, a value similar to that of biological bone apatite. Diametral tensile strength of the CO3Ap block was approximately 1-3 MPa. Based on the results obtained, it was therefore concluded that gypsum-calcite was a good candidate for the fabrication of CO3Ap blocks, coupled with the advantage that the composite can be molded to any shape by virtue of the setting property of gypsum.

Effects of liquid phase on the basic properties of alpha-tricalcuim phosphate (alpha-TCP)-based cement, BIOPEX, were investigated by employing three liquid phases: distilled water, neutral sodium hydrogen phosphate solution, and succinic acid disodium salt solution containing sodium salt of chondroitin sulfate. When mixed with neutral sodium hydrogen phosphate or succinic acid disodium salt solution, the initial setting times of the cement were 19.4 +/- 0.55 and 11.8 +/- 0.45 minutes respectively. These setting times were much shorter than that of distilled water, 88.4 +/- 0.55 minutes. Formation of needle-like crystals typical of apatite was much faster when neutral sodium hydrogen phosphate solution was used, as compared to distilled water or succinic acid disodium salt solution. Moreover, at 24 hours after mixing, the largest amount of apatite was formed when neutral sodium hydrogen phosphate solution was used, whereas use of succinic acid resulted in the least. On the final mechanical strength of the cement, that yielded with neutral sodium hydrogen phosphate solution was the highest. In contrast, lower mechanical strength was observed--especially at the initial stage--when succinic acid sodium salt was used. It was thus concluded that alpha-TCP-based cement allowed accelerated transformation to apatite, and that higher mechanical strength since the initial stage was achieved when neutral sodium hydrogen phosphate solution was used as the liquid phase.

Apatite cement (AC) can be injected through syringe and forms apatite mass. Therefore, AC is very useful for a minimally invasive surgical operation aimed for the reconstruction of bone defects. However, injectability of current AC is not satisfactory for its clinical use. In this investigation, therefore, spherical tetracalcium phosphate (s-TTCP) was prepared with plasma melting method and its effect on injectability were evaluated as well as other basic properties of AC. We found much better handling property and injectability when we used s-TTCP as a component of AC (s-AC). For example, cement spread area used as an index of consistency of the s-AC paste was 512 mm2 whereas that of ordinary AC with irregular TTCP (i-AC) was 158 mm2 when powder to liquid mixing ratio was 2.5. However, diametral tensile strength of set s-AC (1.4 MPa) was significantly lower than that of set i-AC (10.7 MPa) when the powder to liquid ratio was 4.0. X-ray powder diffraction analysis revealed limited formation of apatite in the case of s-AC. Although there are some drawbacks, we feel the use of spherical particle is very useful to improve the injectability of AC. Therefore, it is important to find suitable method to prepare spherical powder as the component of AC.

Biopex sets upon mixing with its liquid phase due to chelate reaction between sodium succinate and calcium phosphate, then gradually transforms to apatite. As a result of apatite formation, set Biopex shows excellent tissue responses and good osteoconductivity. However, Biopex would be washed out when the paste is exposed to body fluid before its setting reaction. Washed out cement causes an inflammatory response. In this investigation, therefore, sodium alginate was added to the liquid phase of Biopex and its effects on washout properties and transformation to apatite were studied. We found that cement remaining ratio, an index of the anti-washout property, of the Biopex increased by increasing the amounts of added sodium alginate to reach 100% when the liquid phase of Biopex contained 0.6% or more sodium alginate. Biopex gradually transformed to apatite regardless of the amount of added sodium alginate at least when the concentration of the sodium alginate in the liquid phase was 1.0% or less. It is concluded therefore, that addition of sodium alginate is very useful for Biopex to acquire the anti-washout property.