Key Engineering Materials Vols. 309-311

Abstract: Organic polymers with ability of apatite formation in body environment are expected as novel bone substitutes having not only bone-bonding ability, i.e. bioactivity, but also mechanical performance analogous to natural bone. Several metal oxides have been found to be effective for the apatite deposition in body environment. In addition, release of calcium ions from the materials significantly enhances it. In this study, we attempted to synthesize bioactive organic-inorganic hybrids from poly(vinyl alcohol) (PVA) by incorporation of titanium oxide or zirconium oxide as well as calcium salt. Ability of apatite formation on the hybrids was examined in vitro using simulated body fluid (SBF, Kokubo solution). Apatite deposition was observed to occur on the surfaces of PVA/titanium oxide hybrids in SBF, when their compositions were appropriately controlled.

Abstract: An injectable bone substitute (IBS) made of a suspension of Calcium phosphate ceramic was used to filled dental root canal after removing of canal pulp. The aim of this study was to verify the ability of calcium phosphate ceramic suspension to fill the apical zone of teeth ex vivo (n=40) and in vivo in a sheep model (n=8). The results showed that injection is possible with a good level of BCP granules at the end of the root dental canal with extracted tooth. In vivo, the presence of blood pressure due to the pulpectomy is a negative parameter to allow a good filling. The scanning electron microscopy revealed mineral formation at the apex level with mineral tissue conduction between the BCP granules but only one tooth showed a good apical filling with a good sealing. The sealing of the apex seems to depend of the amount of BCP granules. Other experiments with other animal models closer to a Human model have to be performed before human trials.

Abstract: We have reported that CaSiO3 ceramics show very fast bone-like apatite formation in simulated body fluid (SBF). However, CaSiO3 ceramics have disadvantages in their mechanical properties and shapability. It is therefore more effective to develop composites of CaSiO3 particles dispersed in a matrix of polymer or metal. Such composites are usually prepared by homogeneously blending the ceramic powder with the matrix component. This method is, however, ineffective for the preparation of biocompatible polymers or metals because only the surfaces containing accidentally-exposed ceramic particles play a role in generating apatite in SBF. It is therefore necessary to add a large volume of ceramic powder and also to abrade the surface to expose more of the ceramic particles. In this study, CaSiO3/high-density polyethylene (HDPE) composites were prepared by hot-pressing to introduce surface CaSiO3 particles and their biocompatibilities were evaluated under in vitro conditions using SBF. CaSiO3 powders were spread on a HDPE plate and hot-pressed at 140oC and 4.9-14.7 MPa for 2 min. The composite sample (about 10×10×1 mm3 in size) was immersed in 30ml SBF (sample/solution ratio of 2.5 g/l) at 36.5oC. After 14 days soaking, the apatite product particles covered most of the composite surface and formed apatite layers. Bone-like apatite particles were formed only on the surface regions containing exposed CaSiO3 particles but no apatite was formed on the CaSiO3 particles buried in the HDPE matrix. The results show that this surface deposition method is very effective in developing biocompatibility in the composites using very small amounts of CaSiO3 powder (about <1 %v) compared with results reported for hydroxyapatite and AW glass-ceramic powders (requiring about 40 %v). It is also found that the inhomogeneous state of the CaSiO3 particles in the surface of the present composites strongly influences their biocompatibility. It will be necessary to improve the homogeneity of CaSiO3 dispersion in the surface of the composites to achieve a more uniform surface apatite layer.

Abstract: A composite hydrogel with interpenetrating network structure was prepared via in-situ synthesis of calcium phosphates during the physical-chemical crosslinking of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA). The hydrogel water content was tested. Fourier transform infrared absorption spectrum (FT-IR), X-ray diffraction and scanning electron microscopy were employed to evaluate the characteristics of the composite hydrogel. The results showed that the composite hydrogel had high water content and that the inorganic phase was poorly crystalline calcium phosphates. FT-IR confirmed that the interpenetrating network structure was formed between PVA and PAA. The chemical interactions between inorganic and organic phases were further investigated and discussed. The composite hydrogel with an interpenetrating network achieved using the present novel method could be a promising material for tissue engineering.

Abstract: Silk fibroin (SF) films containing 5wt% of CaCl2 were prepared by a cast-film method from the degummed SF and then immersed into the simulated body fluid (SBF) to deposit hydroxyapatite (HAp) crystals. The multilayer film of HAp and SF (5-layers), and pure SF film (4-layers) were prepared by a thermo-compression method at 130 °C and 3MPa for 4min. The ratio of β-sheet structure against other structures in both samples showed almost same value of 55.8% and 55.1%. The swelling ratio and in vitro biodegradation were examined by incubating in phosphate-buffered saline (PBS) with and without protease XIV for 1 to 14 days. The changes of sample weight and its tensile strength were investigated. The multilayer film showed slower biodegradation and higher mechanical strength compared with pure SF film.

Abstract: A composite material consisting of cellulose and HAp was prepared using coagulation of a native cellulose suspension. Composite tapes with a HAp content below 50 vol.% exhibit a gradient of filler particles across the cross-section of the sample due to gravity force that causes sedimentation of HAp, as long as the viscosity of the suspension is below a critical level during the coagulation process. According to gravimetric and solution analysis as well as SEM, the filler content influences the amount and uniformity of HCA precipitated in the surface of the tape. With increasing content of filler in the cellulose matrix, the apatite growth from SBF is promoted, due to a higher amount of HAp particles that serve as nucleation sites.

Abstract: By electrophoretic deposition, wollastonite particles were deposited in pores of porous ultrahigh molecular weight polyethylene (UHMWPE). The UHMWPE-wollastonite composite thus fabricated was soaked in a simulated body fluid. As a result, apatite was formed inside the pores as well as on the surface of the UHMWPE-wollastonite composite. The formed apatite showed high adhesive strength to the composite.

Abstract: An ethylene-vinyl alcohol copolymer (EVOH) film with a laminin–apatite composite layer on its surface showed improved adhesion and compatibility to living epithelial tissue compared to untreated EVOH film. This result can be attributed to the good biocompatibility of apatite and the cell-adhesion activity of the laminin on the EVOH surface. This composite material, consisting of laminin, apatite, and EVOH, is considered a promising material for skin terminals to prevent epidermal downgrowth.

Abstract: An organic/inorganic composite hydrogel route was used to prepare collagen-calcium phosphate hybrids with high mechanical strengths, via in-situ mineral synthesis during collagen fibrillogenesis followed by dehydration. An array of characterization techniques including X-ray diffraction and Fourier transform infrared spectroscopy analyses confirmed that the final products are analogous to natural bone. A three-point bending strength of 70 MPa, much higher than the values reported in the literature, was recorded in the present case, due to the three dimensional network structure achieved between inorganic and organic phases. This innovative method provides an efficient route to produce bone grafts with the desirable mechanical properties which are dependent upon the actual inorganic/organic ratio and water content.

Abstract: Microfracture process during bending tests of alumina ceramics used for artificial joints was evaluated by acoustic emission (AE) technique. Four-point bending tests were carried out in air, refined water, physiological saline and simulated body fluid. AE behavior during bending test inhibited the rapid increasing point of AE events and energy prior to the final unstable fracture. It was understood that the bending stress at the increasing point corresponds to the critical stress for maincrack formation. The critical stress was affected by water in environments more strongly than fracture strength. Consequently, it was suggested that the characterization of maincrack formation is essential for the long-term reliability assessment of load-bearing bioceramics.