Hydroxyapatite is a biocompatible material that is extensively used in the replacement and regeneration of bone material. In nature, nanostructured hydroxyapatite is the main component present in hard body tissues. Hence, the state of the art in nanotechnology can be exploited to synthesize nanophase hydroxyapatite that has similar properties with natural hydroxyapatite. Sustainable methods to mass-produce synthetic hydroxyapatite nanoparticles are being developed to meet the increasing demand for these materials and to further develop the progress made in hard tissue regeneration, especially for orthopedic and dental applications. This article reviews the current developments in nanophase hydroxyapatite through various manufacturing techniques and modifications.
Due to similarity in composition to the mineral component of bones and human hard tissues, hydroxyapatite with chemical formula Ca10(PO4)6(OH)2 has been widely used in medical field. Both chicken and duck eggshells are mainly composed of calcium carbonate. An attempt has been made to fabricate nanohydroxyapatite (nHA) by chicken (CES) and duck eggshells (DES) as calcium carbonate source (CaCO3). CES and DES were reacted with diammonium hydrogen [(NH4)2HPO4] solution and subjected to microwave heating at 15 mins. Under the effect of microwave irradiation, nHA was produced directly in the solution and involved in crystallographic transformation. Sample characterization was done using by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM).
This study is focused on finite element analysis of a model comprising femur into which a femoral component of a total hip replacement was implanted. The considered prosthesis is fabricated from a functionally graded material (FGM) comprising a layer of a titanium alloy bonded to a layer of hydroxyapatite. The elastic modulus of the FGM was adjusted in the radial, longitudinal, and longitudinal-radial directions by altering the volume fraction gradient exponent. Four cases were studied, involving two different methods of anchoring the prosthesis to the spongy bone and two cases of applied loading. The results revealed that the FG prostheses provoked more SED to the bone. The FG prostheses carried less stress, while more stress was induced to the bone and cement. Meanwhile, less shear interface stress was stimulated to the prosthesis-bone interface in the noncemented FG prostheses. The cement-bone interface carried more stress compared to the prosthesis-cement interface. Stair climbing induced more harmful effects to the implanted femur components compared to the normal walking by causing more stress. Therefore, stress shielding, developed stresses, and interface stresses in the THR components could be adjusted through the controlling stiffness of the FG prosthesis by managing volume fraction gradient exponent.
The present study investigates the chemical composition, solubility, and physical and mechanical properties of carbonate hydroxyapatite (CO3Ap) and silicon-substituted carbonate hydroxyapatite (Si-CO3Ap) which have been prepared by a simple precipitation method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence (XRF) spectroscopy, and inductively coupled plasma (ICP) techniques were used to characterize the formation of CO3Ap and Si-CO3Ap. The results revealed that the silicate (SiO4(4-)) and carbonate (CO3(2-)) ions competed to occupy the phosphate (PO4(3-)) site and also entered simultaneously into the hydroxyapatite structure. The Si-substituted CO3Ap reduced the powder crystallinity and promoted ion release which resulted in a better solubility compared to that of Si-free CO3Ap. The mean particle size of Si-CO3Ap was much finer than that of CO3Ap. At 750°C heat-treatment temperature, the diametral tensile strengths (DTS) of Si-CO3Ap and CO3Ap were about 10.8 ± 0.3 and 11.8 ± 0.4 MPa, respectively.
Ultrahigh-molecular-weight polyethylene/high-density polyethylene (UHMWPE/HDPE) blends prepared using polyethylene glycol PEG as the processing aid and hydroxyapatite (HA) as the reinforcing filler were found to be highly processable using conventional melt blending technique. It was demonstrated that PEG reduced the melt viscosity of UHMWPE/HDPE blend significantly, thus improving the extrudability. The mechanical and bioactive properties were improved with incorporation of HA. Inclusion of HA from 10 to 50 phr resulted in a progressive increase in flexural strength and modulus of the composites. The strength increment is due to the improvement on surface contact between the irregular shape of HA and polymer matrix by formation of mechanical interlock. The HA particles were homogenously distributed even at higher percentage showed improvement in wetting ability between the polymer matrix and HA. The inclusion of HA enhanced the bioactivity properties of the composite by the formation of calcium phosphate (Ca-P) precipitates on the composite surface as proven from SEM and XRD analysis.
The sintering behaviour of a commercial HA and synthesized HA was investigated over the temperature range of 700 degrees C to 1400 degrees C in terms of phase stability, bulk density, Young's modulus and Vickers hardness. In the present research, a wet chemical precipitation reaction was successfully employed to synthesize a submicron, highly crystalline, high purity and single phase stoichiometric HA powder that is highly sinteractive particularly at low temperature regimes below 1100 degrees C. It has been revealed that the sinterability of the synthesized HA was significantly greater than that of the commercial HA. The temperature for the onset of sintering and the temperature required to achieve densities above 98% of theoretical value were approximately 150 degrees C lower for the synthesized HA than the equivalent commercial HA. Nevertheless, decomposition of HA phase upon sintering was not observed in the present work for both powders.
In this study, porous hydroxyapatite (HA) samples were fabricated via sponge techniques with the aid of sago as part of the binder mixture. Development processes for the production of porous bone graft substitutes are studied using polyurethane sponge. To obtain the optimum amount of binder for successful fabrication of porous HA were done. Initially, porous HA powder was synthesized using calcium hydroxide and orthorphosphoric acid. Meanwhile, sago was mixed with PVA in a certain ratio to be used as binder for preparing the porous HA. After a series of investigative tests were conducted to characterize the sintered samples, the use of the sago and polymeric mixture was found to successfully aid the fabrication of porous HA samples. In this investigation, comparison of physical and mechanical characteristics between samples prepared using difference techniques was made.
A novel hydrothermal process has been developed various hydroxyapatite(HA) powder. The HA powder was investigated in different calcination temperatures over the range of 200 degrees C-800 degrees C. TG/DTA and XRD analysis revealed that at temperatures of 700-800 degrees C the decomposition processes and phase changes took place. It is due to the appearance of TCP phase substituting the HA phase. FESEM observation showed that the produced hydroxyapatite powder was extraordinarily fine with nanosize primary particles and almost evenly spherical in shaped. Its high purity proved that the powder fulfills medical requirement.
The sintering behaviour of synthesized HA powder that was calcined at various temperatures ranging from 700 degrees C to 1000 degrees C was investigated in terms of phase stability, bulk density, Young's modulus and Vickers hardness. The calcination treatment resulted in higher crystallinity of the starting HA powder. Decomposition of HA phase to form secondary phases was not observed in all the calcined powders. The results also indicated that powder calcination (up to 900 degrees C) prior to sintering has negligible effect on the sinterability of the HA compacts. However, powder calcined at 1000 degrees C was found to be detrimental to the properties of sintered hydroxyapatite bioceramics.
The effect of Manganese (Mn) addition on the Vickers hardness and relative density of nanocrystalline hydroxyapatite (HA) dense bodies were studied. The starting Mn doped HA powders was synthesized via sol-gel method with Mn concentration varies from 2 mol% up to 15 mol% Mn. The Mn doped HA disc samples were prepared by uniaxial pressing at 200MPa and subsequently sintered at 1300 degrees C. Characterization was carried out where appropriate to determine the phases present, bulk density, Vickers hardness of the various content of Mn doped HA dense bodies. The addition of Mn was observed to influence the color appearance of the powders and dense bodies as well. Higher Mn concentration resulted in dark grey powders. It was also found that the hardness and relative density of the material increased as the Mn content increased and influenced by the crystallinity of the prepared Mn doped HA powders.
Various materials have been used as scaffolds to suit different demands in tissue engineering. One of the most important criteria is that the scaffold must be biocompatible. This study was carried out to investigate the potential of HA or TCP/HA scaffold seeded with osteogenic induced sheep marrow cells (SMCs) for bone tissue engineering.
The complex architecture of the cortical part of the bovine-femur was examined to develop potential tissue engineering (TE) scaffolds. Weight-change and X-ray diffraction (XRD) results show that significant phase transformation and morphology conversion of the bone occur at 500-750°C and 750-900°C, respectively. Another breakthrough finding was achieved by determining a sintering condition for the nucleation of hydroxyapatite crystal from bovine bone via XRD technique. Scanning electron microscopy results of morphological growth suggests that the concentration of polymer fibrils increases (or decreases, in case of apatite crystals) from the distal to proximal end of the femur. Energy-dispersive analysis of X-ray, Fourier transform infrared, micro-computer tomography, and mechanical studies of the actual composition also strongly support our microscopic results and firmly indicate the functionally graded material properties of bovine-femur. Bones sintered at 900 and 1000°C show potential properties for soft and hard TE applications, respectively.
To compare the effect of bovine bone derived porous hydroxyapatite (BDHA) scaffold on proliferation and osteogenic differentiation of human bone marrow-derived mesenchymal stromal cells (hMSCs) compared with commercial hydroxyapatite (CHA) scaffold.
The combination of metallic bio-inert material, stainless-steel 316L (SS316L) and a bio-active material, hydroxyapatite (HA) can produce a composite which has superior properties for orthopaedic applications. The main objective of this study is to investigate the effects of sintering temperature and holding time on the physical and mechanical properties of the sintered part. 50wt.% SS316L and 50wt.% HA were mixed with a binder system of palm stearin (PS) and polyethylene (PE) at 61 vol.% powder loading. Rheological properties show a pseudo-plastic behaviour of the feedstock, where viscosity decreases with increasing shear rate. The feedstock was injection moulded into a tensile bar shape while thermal debinding was carried out at 320°C and 500°C. The brown parts were sintered at 1000, 1100, 1200 and 1300°C, with three different sintering times of 1, 3 and 5 hours in the furnace. It was found that the highest sintered density measured was 95.61% of the theoretical density. In addition, the highest hardness and Young's modulus measured were 150.45 HV and 52.61 GPa respectively, which are higher than those of human bone. The lowest percentage of carbon content was 0.022wt.% given by the sample sintered at 1300°C for 1 hour. Therefore, SS316L/HA composite with good mechanical and physical properties was successfully produced through the PIM process.
A hydroxyapatite scaffold is a suitable biomaterial for bone tissue engineering due to its chemical component which mimics native bone. Electronic states which present on the surface of hydroxyapatite have the potential to be used to promote the adsorption or transduction of biomolecules such as protein or DNA. This study aimed to compare the morphology and bioactivity of sinter and nonsinter marine-based hydroxyapatite scaffolds. Field emission scanning electron microscopy (FESEM) and micro-computed tomography (microCT) were used to characterize the morphology of both scaffolds. Scaffolds were co-cultured with 5 × 104/cm2 of MC3T3-E1 preosteoblast cells for 7, 14, and 21 days. FESEM was used to observe the cell morphology, and MTT and alkaline phosphatase (ALP) assays were conducted to determine the cell viability and differentiation capacity of cells on both scaffolds. Real-time polymerase chain reaction (rtPCR) was used to identify the expression of osteoblast markers. The sinter scaffold had a porous microstructure with the presence of interconnected pores as compared with the nonsinter scaffold. This sinter scaffold also significantly supported viability and differentiation of the MC3T3-E1 preosteoblast cells (p < 0.05). The marked expression of Col1α1 and osteocalcin (OCN) osteoblast markers were also observed after 14 days of incubation (p < 0.05). The sinter scaffold supported attachment, viability, and differentiation of preosteoblast cells. Hence, sinter hydroxyapatite scaffold from nacreous layer is a promising biomaterial for bone tissue engineering.
The present study addressed the synthesis of a bi-layered nanostructured fluorine-doped hydroxyapatite (nFHA)/polycaprolactone (PCL) coating on Mg-2Zn-3Ce alloy via a combination of electrodeposition (ED) and dip-coating methods. The nFHA/PCL composite coating is composed of a thick (70-80 μm) and porous layer of PCL that uniformly covered the thin nFHA film (8-10 μm) with nanoneedle-like microstructure and crystallite size of around 70-90 nm. Electrochemical measurements showed that the nFHA/PCL composite coating presented a high corrosion resistance (R(p)=2.9×10(3) kΩ cm(2)) and provided sufficient protection for a Mg substrate against galvanic corrosion. The mechanical integrity of the nFHA/PCL composite coatings immersed in SBF for 10 days showed higher compressive strength (34% higher) compared with the uncoated samples, indicating that composite coatings can delay the loss of compressive strength of the Mg alloy. The nFHA/PCL coating indicted better bonding strength (6.9 MPa) compared to PCL coating (2.2 MPa). Immersion tests showed that nFHA/PCL composite-coated alloy experienced much milder corrosion attack and more nucleation sites for apatite compared with the PCL coated and uncoated samples. The bi-layered nFHA/PCL coating can be a good alternative method for the control of corrosion degradation of biodegradable Mg alloy for implant applications.
The effect of the addition of an ionic dopant to calcium phosphates for biomedical applications requires specific research due to the essential roles played in such processes. In the present study, the mechanical and biological properties of Ni-doped hydroxyapatite (HA) and Ni-doped HA mixed with graphene nanoplatelets (GNPs) were evaluated. Ni (3wt.% and 6wt.%)-doped HA was synthesized using a continuous precipitation method and calcined at 900°C for 1h. The GNP (0.5-2wt.%)-reinforced 6% Ni-doped HA (Ni6) composite was prepared using rotary ball milling for 15h. The sintering process was performed using hot isostatic pressing at processing conditions of 1150°C and 160MPa with a 1-h holding time. The results indicated that the phase compositions and structural features of the products were noticeably affected by the Ni and GNPs. The mechanical properties of Ni6 and 1.5Ni6 were increased by 55% and 75% in hardness, 59% and 163% in fracture toughness and 120% and 85% in elastic modulus compared with monolithic HA, respectively. The in-vitro biological behavior was investigated using h-FOB osteoblast cells in 1, 3 and 5days of culture. Based on the osteoblast results, the cytotoxicity of the products was indeed affected by the Ni doping. In addition, the effect of GNPs on the growth and proliferation of osteoblast cells was investigated in Ni6 composites containing different ratios of GNPs, where 1.5wt.% was the optimum value.
In this study, HA is superplastically embedded into Titanium substrate and the sample is subsequently deformed superplastically until 70% deformation degree. The former process is termed as superplastic embedment (SPE) while the later as superplastic deformation (SPD). After the SPE, HA is successfully embedded into the substrate, forming a layer with a thickness of about 249 nm. After the SPD the embedded HA layer thickness decreases to 111 nm. The SPD sample is then immersed in simulated body fluid (SBF) to evaluate its biological properties. A newly grown apatite is formed as a result of the immersion and the HA layer thickness increases with immersion time. The cohesion and adhesion strength within the HA coating and coating-substrate interface of the SPD samples before and after immersion in the SBF is evaluated through the nanoscratch test technique. The results indicate that the HA layer after SPD is still strong even though after being exposed in SBF environment for quite some time. The study suggests that the superplastically embedded HA nanolayer is still intact mechanically and functioning appropriately as biological activity base even after the SPD process.
Hydroxyapatite (HA) coated implant is more susceptible to bacterial infection as the micro-structure surface which is beneficial for osseointegration, could also become a reservoir for bacterial colonisation. The aim of this study was to introduce the antibacterial effect of silver (Ag) to the biomineralised HA by utilising a polydopamine film as an intermediate layer for Ag and HA immobilisation. Sufficient catechol groups in polydopamine were required to bind chemically stainless steel 316 L, Ag and HA elements. Different amounts of Ag nanoparticles were metallised on the polydopamine grafted stainless steel by varying the immersion time in silver nitrate solution from 12 to 24 h. Another polydopamine layer was then formed on the metallised film, followed by surface biomineralisation in 1.5 Simulated Body Fluid (SBF) solution for 3 days. Several characterisation techniques including X-Ray Photoelectron Spectroscopy, Atomic Force Microscopy, Scanning Electron Microscopy and Contact Angle showed that Ag nanoparticles and HA agglomerations were successfully immobilised on the polydopamine film through an element reduction process. The Ag metallisation at 24 h has killed the viable bacteria with 97.88% of bactericidal ratio. The Ag was ionised up to 7 days which is crucial to prevent bacterial infection during the first stage of implant restoration. The aged functionalised films were considered stable due to less alteration of its chemical composition, surface roughness and wettability properties. The ability of the functionalised film to coat complex and micro scale metal make it suitable for dental and orthopaedic implants application.
We have successfully used continuous microwave flow synthesis (CMFS) technique for the template free synthesis of mesoporous hydroxyapatite. The continuous microwave flow reactor consisted of a modified 2.45GHz household microwave, peristaltic pumps and a Teflon coil. This cost effective and efficient system was exploited to produce semi-crystalline phase pure nano-sized hydroxyapatite. Effect of microwave power, retention time and the concentration of reactants on the phase purity, degree of crystallinity and surface area of the final product was studied in detail. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used to study the phase purity and composition of the product, while transmission electron microscopy (TEM) was used to study the effect of process parameters on the morphology of hydroxyapatite. The TEM analysis confirmed the formation of spherical particles at low microwave power; however the morphology of the particles changed to mesoporous needle and rod-like structure upon exposing the reaction mixture to higher microwave power and longer retention time inside the microwave. The in-vitro ion dissolution behavior of the as synthesized hydroxyapatite was studied by determining the amount of Ca(2+) ion released in SBF solution.