Mei Wei

Sintering effects on the strength of hydroxyapatite.

Mechanisms underlying temperature-strength interrelations for dense (> 95% dense, pores closed) hydroxyapatite (HAp) were investigated by comparative assessment of temperature effects on tensile strength, Weibull modulus, apparent density, decomposition (HAp:tricalcium phosphate ratio), dehydroxylation and microstructure. Significant dehydroxylation occurred above approximately 800 degrees C. Strength peaked at approximately 80 MPa just before the attainment of closed porosity (approximately 95% dense). For higher temperatures (closed porosity), the strength dropped sharply to approximately 60 MPa due to the closure of dehydroxylation pathways, and then stabilized at approximately 60 MPa. At very high temperatures (> 1350 degrees C), the strength dropped catastrophically to approximately 10 MPa corresponding to the decomposition of HAp to tricalcium phosphate and the associated sudden release of the remaining bonded water.

Electrophoretic deposition of hydroxyapatite coatings on metal substrates : A nanoparticulate dual-coating approach

Hydroxyapatite coatings can be readily deposited on metal substrates by electrophoretic deposition. However, subsequent sintering is highly problematic owing to the fact that temperatures in excess of 1100°C are required for commercial hydroxyapatite powders to achieve high density. Such temperatures damage the metal and induce metal-catalysed decomposition of the hydroxyapatite. Furthermore, the firing shrinkage of the hydroxyapatite coating on a constraining metal substrate leads to severe cracking. The present study has overcome these problems using a novel approach: the use of aged nanoparticulate hydroxyapatite sols (lower sintering temperature) and a dual coating strategy that overcomes the cracking problem. Dual layers of uncalcined hydroxyapatite (HAp) powder were electrophoretically coated on Ti, Ti6Al4V and 316L stainless steel metal substrates, sintered at 875–1000°C, and characterised by SEM and XRD, and interfacial shear strength measurement. Dual coatings on stainless steel had an average high bond strength (about 23 MPa), and dual coatings on titanium and titanium alloy had moderate strengths (about 14 and 11 MPa, respectively), in comparison with the measured shear strength of bone (35 MPa). SEM and XRD demonstrated that the second layer blended seamlessly with the first and filled the cracks in the first. The superior result on stainless steel is attributed to a more appropriate thermal expansion match with hydroxyapatite, the thinner oxide layer, or a combination of these factors.

Interfacial bond strength of electrophoretically deposited hydroxyapatite coatings on metals.

Hydroxyapatite (HAp) coatings were deposited onto substrates of metal biomaterials (Ti, Ti6Al4V, and 316L stainless steel) by electrophoretic deposition (EPD). Only ultra-high surface area HAp powder, prepared by the metathesis method 10Ca(NO3)2 + 6(NH4)2HPO4 + 8NH4OH), could produce dense coatings when sintered at 875–1000°C. Single EPD coatings cracked during sintering owing to the 15–18% sintering shrinkage, but the HAp did not decompose. The use of dual coatings (coat, sinter, coat, sinter) resolved the cracking problem. Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) inspection revealed that the second coating filled in the “valleys” in the cracks of the first coating. The interfacial shear strength of the dual coatings was found, by ASTM F1044-87, to be ∼12 MPa on a titanium substrate and ∼22 MPa on 316L stainless steel, comparing quite favorably with the 34 MPa benchmark (the shear strength of bovine cortical bone was found to be 34 MPa). Stainless steel gave the better result since α-316L (20.5 μm mK-1) > α-HAp (∼14 μm mK-1), resulting in residual compressive stresses in the coating, whereas α-titanium (∼10.3 μm mK-1) < α-HAp, resulting in residual tensile stresses in the coating.

Synthesis and characterization of hydroxyapatite, fluoride-substituted hydroxyapatite and fluorapatite

Powders of hydroxyapatite (HA), partially fluoride-substituted hydroxyapatite (fHA), and fluorapatite (FA) were synthesized in house using optimum methods to achieve relatively pure powders. These powders were assessed by the commonly used bulk techniques of X-ray diffraction (XRD), Fourier transform infra-red (FTIR) and FT-Raman spectroscopies, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and F-selective electrode. In addition, the current study has employed transmission electron microscopy (TEM), involving morphological observation, electron diffraction and energy-dispersive X-ray spectrometry (EDX), as an effective analytical technique to evaluate the powders at a microscopic level. The HA and fHA particles were elongated platelets about 20×60 nm in size, while FA particles were over twice this size. Calcination of the HA and fHA powders at 1000 °C for 1 h resulted in increased grain size and crystallinity. The calcined fHA material appeared to possess a crystal structure intermediate between HA and FA, as evidenced by the (3 0 0) peak shift in XRD, as well as by the position of the hydroxyl bands in the FTIR spectra. This result was consistent with electron diffraction of individual particles. Small levels of impurities in some of the powders were identified by EDX and electron diffraction, and the carbonate content was detected by FTIR. The use of TEM in conjunction with the bulk techniques has allowed a more thorough assessment of the apatites, and has enabled the constituents in these closely related apatite powders to be identified.

In vitro cell performance on hydroxyapatite particles/poly(L-lactic acid) nanofibrous scaffolds with an excellent particle along nanofiber orientation.

Highly porous hydroxyapatite (HA)/poly(L-lactide) (PLLA) nanofibrous scaffolds were prepared by incorporating needle-shaped nano- or micro-sized HA particles into PLLA nanofibers using electrospinning. The scaffolds had random or aligned fibrous assemblies and both types of HA particles were perfectly oriented along the fiber long axes. The biocompatibility and cell signaling properties of these scaffolds were evaluated by in vitro culture of rat osteosarcoma ROS17/2.8 cells on the scaffold surface. Cell morphology, viability and alkaline phosphatase (ALP) activity on each scaffold were examined at different time points. The HA/PLLA scaffolds exhibited higher cell viability and ALP activity than a pure PLLA scaffold. In addition, micro-sized HA particles supported cell proliferation and differentiation better than nano-sized ones in random scaffolds through a 10 day culture period and in aligned scaffolds at an early culture stage. The fibrous assembly of the scaffold had a pronounced impact on the morphology of the cells in direct contact with the scaffold surface, but not on cell proliferation and differentiation. Thus, HA/PLLA nanofibrous scaffolds could be good candidates for bone tissue engineering.

Fabrication and characterization of biomimetic collagen–apatite scaffolds with tunable structures for bone tissue engineering

The objective of the current study is to prepare a biomimetic collagen-apatite scaffold for improved bone repair and regeneration. A novel bottom-up approach has been developed, which combines a biomimetic self-assembly method with a controllable freeze-casting technology. In this study, the mineralized collagen fibers were generated using a simple one-step co-precipitation method which involved collagen self-assembly and in situ apatite precipitation in a collagen-containing modified simulated body fluid (m-SBF). The precipitates were then subjected to controllable freeze casting, forming scaffolds with either an isotropic equiaxed structure or a unidirectional lamellar structure. These scaffolds were comprised of collagen fibers and poorly crystalline bone-like carbonated apatite nanoparticles. The mineral content in the scaffold could be tailored in the range 0-54wt.% by simply adjusting the collagen content in the m-SBF. Further, the mechanisms of the formation of both the equiaxed and the lamellar scaffolds were investigated, and freezing regimes for equiaxed and lamellar solidification were established. Finally, the bone-forming capability of such prepared scaffolds was evaluated in vivo in a mouse calvarial defect model. It was confirmed that the scaffolds well support new bone formation.

Apatite-forming ability of CaO-containing titania.

It was recently shown that titanium metal and its alloys spontaneously form a bonelike apatite layer on their surfaces in the living body and bond to the bone through the apatite layer, when the sodium ions are incorporated into titanium oxide layer of their surfaces by chemical and heat treatments. It is expected that their apatite-forming ability, and hence their bone-bonding ability, could be enhanced, if the calcium ions are incorporated into their surface titanium oxide layers instead of the sodium ions, because the calcium ions released from their surface layers can increase the ionic activity product of the apatite of the surrounding fluid more effectively than the sodium ions. In the present study, in order to investigate the effect of incorporation of the calcium ions into the titanium oxide layer on its apatite-forming ability, apatite-forming abilities of titania gels which have different CaO contents and subjected to different heat treatments were examined in a simulated body fluid with ion concentrations nearly equal to those of the human blood plasma. It was found that CaO-containing gels do not form the apatite on their surfaces as far as they take an amorphous phase in spite of the fact that they release larger amounts of the calcium ions with increasing CaO contents of the gels. They form the apatite when they take an anatase-like structure even though they do not contain CaO. These results indicate that a specific structure of the titanium oxide is more important for the apatite nucleation than the magnitude of the ionic activity products of the apatite in the surrounding fluid.

Controlling the biodegradation rate of magnesium using biomimetic apatite coating

Magnesium is light, biocompatible and has similar mechanical properties to natural bone, so it has the potential to be used as a biodegradable material for orthopedic applications. However, pure magnesium severely corrodes in a physiological environment, which may result in fracture prior to substantial tissue healing. Hydroxyapatite (HA) is the main composition of natural bone. It has excellent bioactivity and osteoconductivity. In this study, HA coating with two different thicknesses was applied onto the surface of pure magnesium substrates using a biomimetic technique. The corrosion rate of the surface-treated substrates was tested. It was found that both types of coatings substantially slowed down the corrosion of the substrate, and the dual coating was more effective than the single coating in hindering the degradation of the substrate. Thus, the corrosion rate of magnesium implants can be closely tailored by adjusting apatite coating thickness and thereby monitoring the release of magnesium ions into the body.

The effect of temperature and initial pH on biomimetic apatite coating

Bone-like apatite coatings were prepared using a biomimetic method in a simulated body fluid (SBF). The effect of initial pH values and immersing temperatures on biomimetic apatite coating formation was studied. Three different temperatures were used in this study: 24 (room temperature), 40, and 60 degrees C. At each temperature, SBF solutions with three different initial pHs were chosen: low, medium, and high. The total inorganic carbon (TIC) content and pH-time profile of each coating system were recorded during the coating formation. The apatite coatings were characterized using X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), and Fourier transform infra-red (FTIR). It has been found that SBF temperature has a great effect on the bicarbonate decomposition rate. The bicarbonate ions tend to decompose faster as the temperature increases. The decomposition of bicarbonate ions results in a pH increase in the SBF. With different initial SBF pHs, the decomposition of different amounts of bicarbonate ions is required to reach the critical pH range of apatite formation. With different amounts of bicarbonate ions in the SBF, the surface morphology of the biomimetic apatite coating formed is different. Therefore, the initial pH of the SBF solution plays a vital role in controlling the surface morphology of the biomimetic apatite coating. Also, it was found that as the SBF temperature increased, the critical pH range at which biomimetic apatite coating forms decreased. The critical pH range for the SBF prepared at 24, 40, and 60 degrees C was 6.65-6.71, 6.55-6.65, and 6.24-6.42, respectively.

Apatite formation on alkaline-treated dense TiO2 coatings deposited using the solution precursor plasma spray process.

A dense titania (TiO2) coating was deposited from an ethanol-based solution containing titanium isopropoxide using the solution precursor plasma spray (SPPS) process. XRD and Raman spectrum analyses confirmed that the coating is exclusively composed of rutile TiO2. SEM micrographs show the as-sprayed coating is dense with a uniform thickness and there are no coarse splat boundaries. The as-sprayed coating was chemically treated in 5M NaOH solution at 80 degrees C for 48 h. The bioactivity of as-sprayed and alkaline-treated coatings was investigated by immersing the coatings in simulated body fluid (SBF) for 14-28 days, respectively. After 28 days immersion, there is a complete layer of carbonate-containing apatite formed on the alkaline-treated TiO2 coating surface, but none formed on the as-sprayed coating.