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Radio frequency magnetron sputtering of Sr- and Mg-substituted β-tricalcium phosphate: Analysis of the physicochemical properties and deposition rate of coatings
Abstract
The effect of the sputtered target composition on the deposition rate of coatings formed by radio frequency magnetron sputtering (RFMS) is investigated. Strontium substitution in the sputtered β-tricalcium phosphate (β-TCP) target composition increases the coating deposition rate, whereas magnesium substitution decreases the coating deposition rate. Computer modelling shows that both the unit cell volume and bond lengths increase when strontium is introduced into the crystal lattice, whereas the incorporation of magnesium leads to a decrease in these parameters. A correlation between the change in unit cell volume due to magnesium and strontium substitutions, and the coating deposition rate is also determined.
... As a result, it can be seen that the ions substituted for TCP also affect the powder particle size. preferentially substituted for the Ca(4) site of the β-TCP lattice [62]. Therefore, the binding force of the (PO4) 3− band corresponds to the ν3 stretching mode being reduced, and finally moved to a lower wavenumber. ...
... In Figure 7b, the results of the substitution of Sr 2+ ions are shown. As the Sr 2+ is preferentially substituted for the Ca(4) site of TCP, the Ca-O and P-O lengths further increase [62], which increases the Ca2p binding energy. These results are consistent with previously reported literature [66]. ...
β-tricalcium phosphate is a promising bone graft substitute material with biocompatibility and high osteoinductivity. However, research on the ideal degradation and absorption for better clinical application remains a challenge. Now, we focus on modifying physicochemical properties and improving biological properties through essential ion co-substitution (Fe and Sr) in β-TCPs. Fe- and Sr-substituted and Fe/Sr co-substituted β-TCP were synthesized by aqueous co-precipitation with substitution levels ranging from 0.2 to 1.0 mol%. The β-TCP phase was detected by X-ray diffraction and Fourier transform infrared spectroscopy. Changes in Ca–O and P–O bond lengths of the co-substituted samples were observed through X-ray photoelectron spectroscopy. The results of VSM represent the M-H graph having a combination of diamagnetic and ferromagnetic properties. A TRIS–HCl solution immersion test showed that the degradation and resorption functions act synergistically on the surface of the co-substituted sample. Cell adhesion tests demonstrated that Fe enhances the initial adhesion and proliferation behavior of hDPSCs. The present work suggests that Fe and Sr co-substitution in β-TCP can be a candidate for promising bone graft materials in tissue engineering fields. In addition, the possibility of application of hyperthermia for cancer treatment can be expected.
... Além disso, ele acelera o processo de osteogênese e de mineralização, onde seus efeitos in vivo e in vitro têm sido estudados visando a consolidação e a regeneração óssea (Baheiraei et al., 2021;Neves et al., 2017). Kozelskaya et al. (2020) investigaram o efeito das substituições de estrôncio e magnésio na composição de pulverização catódica de β-TCP nas propriedades físico-químicas e na taxa de deposição em revestimentos de fosfato de cálcio. Chegou-se a ...
... Typical coating techniques within this category include electrochemical deposition, plasma spraying, chemical treatment, micro-arc oxidation and physical vapor deposition (PVD). Sputtering is the technique of choice for magnesium [25][26][27] due to the high adhesion strength and uniformity of the coating produced [28,29]. Other coating techniques possess limitations with non-uniformity on complex geometries [22,30], poor adherence [31] and cracking [32] which could potentially drive corrosion. ...
Magnesium orthopaedic fracture fixation devices can potentially provide significant clinical benefits, such as the elimination of secondary surgeries for device removal due to in-vivo resorption and reduced stress shielding due to reduced device stiffness. However, development, approval, and clinical adoption of magnesium devices has been hindered by the excessively high rates of in-vivo corrosion such that the structural integrity of the device can be catastrophically reduced before fracture healing occurs. Coating of devices with calcium phosphate coatings has been shown to significantly reduce corrosion rates, while enhancing osseointegration. However, the adhesion strength between the CaP coatings and magnesium substrates has not been previously investigated. Clinical insertion of fracture fixation devices such as intramedullary nails and k-wires will impose significant shear loading on the coated surface of the implant. If the effective shear strength of the coating-device interface is not sufficiently high, the coating will be damaged and removed during device insertion. In the current study a bespoke experimental-computational approach is developed to provide a new understanding of the relationship between coating thickness, surface roughness, and effective shear strength of the CaP coating- Mg substrate interface. Nine test cases were created by adjusting either the deposition time (3 thickness values) or the surface treatment of the Mg alloy using SiC paper (3 roughness values) and double-lap shear testing was performed for these coating configurations. Strain development in the Mg substrates was monitored using strain gauges, and failure stress was determined for each configuration. Test results revealed that the effective shear strength of the coating-substrate interface is significantly higher for coatings on the rougher substrate surfaces when compared to those on smoother surfaces. Coating thickness was not found to significantly influence the effective shear strength over the range considered in this study (0.37–1.34 μm). Micro-scale finite element models of lap-shear tests were constructed using experimental profilometry data. Simulations of rough coating-substrate interfaces reveal that significant localised compression occurs at the coating-substrate interface in regions of large asperities. A novel cohesive zone formulation has been developed to simulate compression induced shear hardening, and the resultant simulations are found to accurately predict the significantly higher effective shear strength measured experimentally for rougher coatings compared to smoother Mg substrate surfaces.
... RF-MS allows to coat implantable devices with films of uniform thickness [32]. Its deposition rate is strongly influenced by the target density and crystallinity, as was demonstrated during the deposition of Sr and Mg-doped β-TCP [33]. With regard to the coatings' morphology, rough and smooth films can grow on the same substrate by varying the deposition parameters [34]. ...
The deposition of thin films of bioactive materials is the most common approach to improve the bone bonding ability of an implant surface. With this purpose, several wet and plasma assisted deposition methods were proposed in the scientific literature. In this review, we considered films obtained by nanosecond Pulsed Laser Deposition (PLD). Since hydroxyapatite (HA) has composition and structure similar to that of the mineral component of the bone, the initial studies focused on the selection of experimental conditions that would allow the deposition of films that retain HA stoichiometry and crystallinity. However, biological apatite was found to be a poorly crystalline and multi-substituted mineral; consequently, the attention of researchers was oriented towards the deposition of substituted HA, glass (BG), and glass-ceramic (BGC) bioactive materials to exploit the biological relevance of foreign ions and crystallinity. In this work, after a description of the nanosecond ablation and film growth of ceramic materials, we reported studies on the mechanism of HA ablation and deposition, evidencing the peculiarities of PLD. The literature concerning the PLD of ion substituted HA, BG, and BGC was then reviewed and the performances of the coatings were discussed. We concluded by describing the advantages, limitations, and perspectives of PLD for biomedical applications.
... Sr substitution increases the rate of β-TCP RFMS, while Mg has no significant effect on the sputtering rate. We discussed the effect of Sr and Mg substitutions on the β-TCP RFMS rate in more detail in our previous study [22]. For HA-based upper coatings, we observed no significant effect of Sr and Mg substitution on the rate of sputtering. ...
The porous CaP subcoating was formed on the Ti6Al4V titanium alloy substrate by plasma electrolytic oxidation (PEO). Then, upper coatings were formed by radio frequency magnetron sputtering (RFMS) over the PEO subcoating by the sputtering of various CaP powder targets: β-tricalcium phosphate (β-TCP), hydroxyapatite (HA), Mg-substituted β-tricalcium phosphate (Mg-β-TCP) and Mg-substituted hydroxyapatite (Mg-HA), Sr-substituted β-tricalcium phosphate (Sr-β-TCP) and Sr-substituted hydroxyapatite (Sr-HA). The coating surface morphology was studied by scanning electron and atomic force microscopy. The chemical composition was determined by X-ray photoelectron spectroscopy. The phase composition of the coatings was studied by X-ray diffraction analysis. The Young’s modulus of the coatings was studied by nanoindentation test. RF-magnetron sputtering treatment of PEO subcoating resulted in multileveled roughness, increased Ca/P ratio and Young’s modulus and enrichment with Sr and Mg. Sputtering of the upper layer also helped to adjust the coating crystallinity.
... Numerous authors have showed RF magnetron sputtering could be a potentially beneficial technique for applying coatings to future implantable devices [16][17][18][19][20]. Current work has shown that HA coatings are bioactive and exhibit similar properties to bulk materials. ...
In recent years, it has been found that small weight percent additions of silicon to HA can be used to enhance the initial response between bone tissue and HA. A large amount of research has been concerned with bulk materials, however, only recently has the attention moved to the use of these doped materials as coatings. This paper focusses on the development of a co-RF and pulsed DC magnetron sputtering methodology to produce a high percentage Si containing HA (SiHA) thin films (from 1.8 to 13.4 wt.%; one of the highest recorded in the literature to date). As deposited thin films were found to be amorphous, but crystallised at different annealing temperatures employed, dependent on silicon content, which also lowered surface energy profiles destabilising the films. X-ray photoelectron spectroscopy (XPS) was used to explore the structure of silicon within the films which were found to be in a polymeric (SiO 2 ; Q 4) state. However, after annealing, the films transformed to a SiO 4 4− , Q 0 , state, indicating that silicon had substituted into the HA lattice at higher concentrations than previously reported. A loss of hydroxyl groups and the maintenance of a single-phase HA crystal structure further provided evidence for silicon substitution. Furthermore, a human osteoblast cell (HOB) model was used to explore the in vitro cellular response. The cells appeared to prefer the HA surfaces compared to SiHA surfaces, which was thought to be due to the higher solubility of SiHA surfaces inhibiting protein mediated cell attachment. The extent of this effect was found to be dependent on film crystallinity and silicon content.
RANQUE-HILSCH VORTEX TUBE: ANALYSIS OF ITS HISTORICAL EVOLUTION AND
RECENT NUMERICAL MODELS
This research aims to present the geometry and operational parameters of the Ranque-Hilsch vortex tube, in addition to the numerical models used and investigations throughout its history. Therefore, it was possible to know the state-of�the-art of the RHVT, the numerical models applied recently for its study and conclude that little has evolved in its physical concept, since its invention, in 1934, by Georges Joseph Ranque.
This work is dedicated to studying of the properties of the calcium phosphate (CaP) coatings deposited on Ti substrates by radio-frequency magnetron sputtering (RFMS) of three hydroxyapatite-based powder targets: pure hydroxyapatite (HA), Mg-substituted HA (Mg-HA, Mg = 0.93 ± 0.13 at.%) and Sr-substituted HA (Sr-HA, Sr ∼ 0.47 at.%). The influence of ionic substitutions in the structure of the sputtered targets on the surface morphology, physicochemical properties of the coatings and their wettability were studied. It is revealed that Mg and Sr ionic substitutions in the crystal lattice of HA at these concentrations don’t affect deposition rate, however, it influences morphology, wettability and elemental and phase composition of deposited coatings.
The adsorption/desorption behavior, conformational and orientational changes of proteins on the surface of biomaterials are the significant parameters for understanding how biomaterials perform their biological functions. In this study, for the first time, the interactions between BMP-7 and β-TCP (001) surface models with different ion-rich terminations (Ca-rich and P-rich) were investigated by molecular dynamic simulation (MD) and steered molecular dynamic simulation (SMD). The results indicated that BMP-7 preferentially interacts with both Ca-rich and P-rich β-TCP (001) surfaces at its wrist epitope residues with certain conformational changes, which led to more exposure of BMP-7 knuckle epitope residues to the environment and facilitation for binding to the type II receptor. Compared to the P-rich surface, it speculated that the Ca-rich surface was more conducive to BMP-7 signal transduction since the upright orientation of the protein adsorption would lead to smaller hindrance for receptor binding. This study provided more atomistic and molecular informations for better understanding the process of Ca-P surfaces affecting BMP-7 biological properties and further interpreted the osteoinductive mechanism from the perspective of growth factor adsorption. Moreover, the docking screening method adopted in this study is of guiding significance to the design and development of bioactive materials.
Coatings based on ion-substituted calcium phosphate (Ca-P) have attracted great attention in the scientific community over the past decade for the development of biomedical applications. Among such Ca-P based structures, hydroxyapatite (HA) has shown significant influence on cell behaviors including cell proliferation, adhesion, and differentiation. These cell behaviors determine the osseointegration between the implant and host bone and the biocompatibility of implants. This review presents a critical analysis on the physical vapor deposition magnetron sputtering (PVDMS) technique that has been used for ion-substituted Ca-P based coatings on implants materials. The effect of PVDMS processing parameters such as discharge power, bias voltage, deposition time, substrate temperature, and post-heat treatment on the surface properties of ion-substituted Ca-P coatings is elucidated. Moreover, the advantages, short comings and future research directions of Ca-P coatings by PVDMS have been comprehensively analyzed. It is revealed that the topography and surface chemistry of amorphous HA coatings influence the cell behavior, and ion-substituted HA coatings significantly increase cell attachment but may result in a cytotoxic effect that reduces the growth of the cells attached to the coating surface areas. Meanwhile, low-crystalline HA coatings exhibit lower rates of osteogenic cell proliferation as compared to highly crystalline HA coatings developed on Ti based surfaces. PVDMS allows a close reproduction of bioapatite characteristics with high adhesion strength and substitution of therapeutic ions. It can also be used for processing nanostructured Ca-P coatings on polymeric biomaterials and biodegradable metals and alloys with enhanced corrosion resistance and biocompatibility. Statement of Significance: Recent studies have utilized the physical vapor deposition magnetron sputtering (PVDMS) for the deposition of Ca-P and ion-substituted Ca-P thin film coatings on orthopedic and dental implants. This review explains the effect of PVDMS processing parameters, such as discharge power, bias voltage, deposition time, substrate temperature, and post-heat treatment, on the surface morphology and crystal structure of ion-substituted Ca-P and ion-substituted Ca-P thin coatings. It is revealed that coating thickness, surface morphology and crystal structure of ion-substituted Ca-P coatings via PVDMS directly affect the biocompatibility and cell responses of such structures. The cell responses determine the osseointegration between the implant and host bone and eventually the success of the implants.
The use of lignocellulosic remnants of the açaí agro-business will benefit the environment with a precursor material for biomedical applications. Nanocellulose (NC) allows the biomimetic growth of biphasic ceramics on its surface, with characteristics compatible with bone tissue, including bioactive properties and biocompatibility. In this study, the composites were obtained from açaí tegument (Euterpe Oleracea Mart.) NC using acid hydrolysis. The characterization performed by scanning electron microscopy showed the characteristic crystals of hydroxyapatite (HA) and calcium triphosphate (β-TCP) based on the results of X-ray diffraction, with the peak at 22°, showing the NC nucleation of HA and peak at 17° showing tricalcium phosphate (β-TCP). Fourier transform infrared spectroscopy confirmed the presence of O-H at 3400 cm−1 and C-H at 2900 cm−1, which is characteristic of cellulose; peaks were also observed at 1609 cm−1, verifying the reduction in lignin content. Groups PO4−3 at approximately 1070 cm−1, P-OH at 910–1040 cm−1, and HCO3− at 2450 cm−1 confirmed the formation of HA and β-TCP. The zeta potential had a range of −11 ± 23.8 mV related to particle size, which had a range of 164.2 × 10−9–4748 × 10−9 m.
Calcium phosphate (CaP) bioceramics are widely used in the field of bone regeneration, both in orthopedics and in dentistry, due to their good biocompatibility, osseointegration and osteoconduction. The aim of this article is to review the history, structure, properties and clinical applications of these materials, whether they are in the form of bone cements, paste, scaffolds, or coatings. Major analytical techniques for characterization of CaPs, in vitro and in vivo tests, and the requirements of the US Food and Drug Administration (FDA) and international standards from CaP coatings on orthopedic and dental endosseous implants, are also summarized, along with the possible effect of sterilization on these materials. CaP coating technologies are summarized, with a focus on electrochemical processes. Theories on the formation of transient precursor phases in biomineralization, the dissolution and reprecipitation as bone of CaPs are discussed. A wide variety of CaPs are presented, from the individual phases to nano-CaP, biphasic and triphasic CaP formulations, composite CaP coatings and cements, functionally graded materials (FGMs), and antibacterial CaPs. We conclude by foreseeing the future of CaPs.
The in vitro and in vivo performance of hydroxyapatite (HAp) coatings can be modified by the addition of different trace ions, such as silicon (Si), lithium (Li), magnesium (Mg), zinc (Zn) or strontium (Sr) into the HAp lattice, to more closely mirror the complex chemistry of human bone. To date, most of the work in the literature has considered single ion-substituted materials and coatings, with limited reports on co-substituted calcium phosphate systems. The aim of this study was to investigate the potential of radio frequency magnetron sputtering to deposit Sr and Zn co-substituted HAp coatings using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The FTIR and XPS results highlight that all of the Sr, Zn and Sr-Zn co-substituted surfaces produced are all dehydroxylated and are calcium deficient. All of the coatings contained HPO4²⁻ groups, however; only the pure HAp coating and the Sr substituted HAp coating contained additional CO3²⁻ groups. The XRD results highlight that none of the coatings produced in this study contain any other impurity CaP phases, showing peaks corresponding to that of ICDD file #01-072-1243 for HAp, albeit shifted to lower 2θ values due to the incorporation of Sr into the HAp lattice for Ca (in the Sr and Sr-Zn co-substituted surfaces only). Therefore, the results here clearly show that RF magnetron sputtering offers a simple means to deliver Sr and Zn co-substituted HAp coatings with enhanced surface properties.
Graphical Abstract
(a) XRD patterns for RF magnetron sputter deposited hydroxyapatite coatings and (b)-(d) for Sr, Zn and Sr-Zn co-substituted coatings, respectively. The XPS spectra in (b) confirms the presence of a HA sputter deposited coating as opposed to (c) XPS spectra for a Sr-Zn co-substituted sputter deposited coating. Open image in new window
Statement of significance:
Nowadays, BCPs are definitely considered as the gold standard of bone substitutes in bone reconstructive surgery. Among the numerous clinical studies in literature demonstrating the performance of BCP, Passuti et al and Randsford et al studies largely contributed to the emergence of the BCPs. It could be interesting to come back to the main events that made their success and could explain their large adhesion from scientists to clinicians. This paper aims to review the most significant biological responses reported in the last 30 years, of these BCP-based materials. We also discuss about their exciting future applications as osteoconductive scaffold for delivering various bioactive molecules or bone cells in bone tissue engineering and regenerative medicine.
β-tricalcium phosphate (β-TCP) has a fast rate of bioabsorption, and has been used clinically as bioabsorbant ceramics that is absorbed in vivo and gradually replaced by newly formed bone. Here, we focus on various metal ions with regards to their solid solution substitution in β-TCP, and explain the effects of ion substitution in β-TCP on properties such as structural stability and solubility from a crystal chemistry viewpoint. We also discuss the possibility of metal-ion-subsituted β-TCP materials as hard tissue replacements.
This review summarizes recent and very recent work on preparing substituted hydroxyapatites. Ease of atomic doping or substitution in apatite opens this mineral up for a wide range of biomedical applications. It can be used for repairing and replacing diseased and damaged parts of musculoskeletal systems, and also as a drug or gene delivery agent, as a bioactive coating on metallic osseous implants, biomagnetic particles and fluorescent markers. First, the physicochemical properties of bioapatites are described and discussed. Then a general summary on substitution reaction for hydroxyapatite is made. Special attention is paid to describing anionic, cationic and multisubstituted hydroxyapatites used for various biomedical applications. Finally, conclusions are drawn and future perspectives are discussed.
β-Tricalcium phosphate bioceramics with small, close to bone-like amounts of Mg (up to 1 wt.%) were obtained by modified precipitation method and following sintering. The effect of small amounts of Mg on the thermal stability, microstructure and sintering behavior of β-tricalcium phosphate bioceramics was evaluated. Addition of small amounts of Mg can induce a remarkable effect on the physic-chemical properties of β-TCP and therefore the chemical composition of the starting materials should be controlled.
A radio-frequency magnetron sputtering technique operating in right-angle geometry (RAMS) with high plasma confinement was revised to produce thin films (15–570 nm) of fluorine-substituted hydroxyapatite, FHA, adapted to be used as nano-coatings for biomedical implants. An electron temperature of Teff ≈ 9.0 eV and a plasma electron density of 1.2 × 1015 m− 3 assured the nucleation of an amorphous fluorine-substituted hydroxyapatite phase on Si and Ti surfaces. With the aid of a Langmuir probe, the RAMS plasma energy was tuned to control the coating stoichiometry and the ratio between the crystalline and amorphous phases. The energy delivered over time from the bombardment of ions and electrons transformed the amorphous calcium phosphate phase into crystalline fluorine-substituted hydroxyapatite. The crystalline films were obtained at room temperature. The partial substitution of OH− for F− in the HA structure was confirmed by X-ray diffraction using synchrotron radiation in grazing-incidence mode, X-ray photoelectron spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy. High-resolution transmission electron microscopy carried out on cross-section film samples prepared by a focused ion beam (FIB) technique revealed that the film ultrastructure was composed of columnar crystals oriented perpendicularly to the substrate surface. The crystals were connected to the substrate surface by ordered nanolayers, indicating the existence of a continuous binding between the two materials. This work demonstrates that the RAMS technique is able to produce FHA nano-coatings with controlled chemical compositions and structures on metallic implants for clinical applications.
PURPOSE
The purpose of this study was to evaluate the properties of a porous zirconia scaffold coated with bioactive materials and compare the in vitro cellular behavior of MC3T3-E1 preosteoblastic cells to titanium and zirconia disks and porous zirconia scaffolds.
MATERIALS AND METHODS
Titanium and zirconia disks were prepared. A porous zirconia scaffold was fabricated with an open cell polyurethane disk foam template. The porous zirconia scaffolds were coated with β-TCP, HA and a compound of β-TCP and HA (BCP). The characteristics of the specimens were evaluated using scanning electron microscopy (SEM), energy dispersive x-ray spectrometer (EDX), and x-ray diffractometry (XRD). The dissolution tests were analyzed by an inductively coupled plasma spectrometer (ICP). The osteogenic effect of MC3T3-E1 cells was assessed via cell counting and reverse transcriptase-polymerase chain reaction (RT-PCR).
RESULTS
The EDX profiles showed the substrate of zirconia, which was surrounded by the Ca-P layer. In the dissolution test, dissolved Ca2+ ions were observed in the following decreasing order; β-TCP > BCP > HA (P<.05). In the cellular experiments, the cell proliferation on titanium disks appeared significantly lower in comparison to the other groups after 5 days (P<.05). The zirconia scaffolds had greater values than the zirconia disks (P<.05). The mRNA level of osteocalcin was highest on the non-coated zirconia scaffolds after 7 days.
CONCLUSION
Zirconia had greater osteoblast cell activity than titanium. The interconnecting pores of the zirconia scaffolds showed enhanced proliferation and cell differentiation. The activity of osteoblast was more affected by microstructure than by coating materials.
Biphasic calcium phosphate bioceramics composed of hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP) have relevant properties as synthetic bone grafts, such as tunable resorption, bioactivity, and intrinsic osteoinduction. However, they have some limitations associated to their condition of high-temperature ceramics. In this work self-setting Biphasic Calcium Phosphate Cements (BCPCs) with different HA/β-TCP ratios were obtained from self-setting α-TCP/β-TCP pastes. The strategy used allowed synthesizing BCPCs with modulated composition, compressive strength, and specific surface area. Due to its higher solubility, α-TCP was fully hydrolyzed to a calcium-deficient HA (CDHA), whereas β-TCP remained unreacted and completely embedded in the CDHA matrix. Increasing amounts of the non-reacting β-TCP phase resulted in a linear decrease of the compressive strength, in association to the decreasing amount of precipitated HA crystals, which are responsible for the mechanical consolidation of apatitic cements. Ca2+ release and degradation in acidic medium was similar in all the BCPCs within the timeframe studied, although differences might be expected in longer term studies once β-TCP, the more soluble phase was exposed to the surrounding media.
Calcium carbonate has evoked interest owing to its use as a biomaterial, and for its potential in biomineralization. Three polymorphs of calcium carbonate, i.e. calcite, aragonite, and vaterite were synthesized. Three conventional bulk analysis techniques, Fourier transform infrared (FTIR), X-ray diffraction (XRD), and SEM, were used to confirm the crystal phase of each polymorphic calcium carbonate. Two surface analysis techniques, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS), were used to differentiate the surfaces of these three polymorphs of calcium carbonate. XPS results clearly demonstrate that the surfaces of these three polymorphs are different as seen in the Ca(2p) and O(1s) core-level spectra. The different atomic arrangement in the crystal lattice, which provides for a different chemical environment, can explain this surface difference. Principal component analysis (PCA) was used to analyze the TOF-SIMS data. Three polymorphs of calcium carbonate cluster into three different groups by PCA scores. This suggests that surface analysis techniques are as powerful as conventional bulk analysis to discriminate calcium carbonate polymorphs. Copyright © 2008 John Wiley & Sons, Ltd.
Divalent cobalt ions (Co 2+) have been shown to possess the capacity to induce angiogenesis by activating hypoxia inducible factor-1a (HIF-1a) and subsequently inducing the production of vascular endothelial growth factor (VEGF). However, there are few reports about Co-containing biomaterials for inducing in vitro angiogenesis. The aim of the present work was to prepare Co-containing b-tricalcium phosphate (Co-TCP) ceramics with different contents of calcium substituted by cobalt (0, 2, 5 mol%) and to investigate the effect of Co substitution on their physicochemical and biological properties. Co-TCP powders were synthesized by a chemistry precipitation method and Co-TCP ceramics were prepared by sintering the powder compacts. The effect of Co substitution on phase transition and the sintering property of the b-TCP ceramics was investigated. The proliferation and VEGF expression of human bone marrow mesenchymal stem cells (HBMSCs) cultured with both powder extracts and ceramic discs of Co-TCP was further evaluated. The in vitro angiogenesis was evaluated by the tube-like structure formation of human umbilical vein endothelial cells (HUVECs) cultured on ECMatrixÔ in the presence of powder extracts. The results showed that Co substitution suppressed the phase transition from b-to a-TCP. Both the powder extracts and ceramic discs of Co-TCP had generally good cytocompatibility to support HBMSC growth. Importantly, the incorporation of Co into b-TCP greatly stimulated VEGF expression of HBMSCs and Co-TCP showed a significant enhancement of network structure formation of HUVECs compared with pure TCP. Our results suggested that the incorporation of Co into bioceramics is a potential viable way to enhance angiogenic properties of biomaterials. Co-TCP bioceramics may be used for bone tissue regeneration with improved angiogenic capacity.
Strontium doped hydroxyapatite (Sr-doped HA) nanopowder has been synthesized using a sol-gel method. The concentration of strontium was varied at 2, 5, 10 and 15 mol%. The as synthesized powders were calcined at temperatures of 500-900°C. The calcined white Sr-doped HA powders were characterized using differential and thermogravimetric analysis (TG/DTA), field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). Morphological evaluation by FESEM measurement shows that the particles of the Sr-doped HA agglomerates are globular in shape with an average size of 1-2 mm in diameter while the primary particles have a diameter of 30-150 nm in average. The calcined powders contained hydroxyapatite phase only for all doping concentration except for the smallest doping concentration, 2 mol%, where â-TCP appeared as the secondary phase. This indicates that the substitution of Sr atoms for Ca atoms have stabilized the HA phase, leading to the inhibition of the appearance of â-TCP phase upon high temperature calcination. Even, for 2 mol% Sr-doped HA, the appearance of â-TCP peak only started to appear at a temperature as high as of 900°C, compared to non-Sr doping HA which appeared at a temperature below 800°C.
In this study, strontium-doped calcium phosphate coatings were deposited by electrochemical deposition and plasma spray under different process parameters to achieve various coating morphologies. The coating composition was investigated by energy dispersive X-ray spectroscopy and X-ray diffraction. The surface morphologies of the coatings were studied through scanning electron microscopy while the cytocompatibility and bioactivity of the strontium-doped calcium phosphate coatings were evaluated using bone cell culture using MC3T3-E1 osteoblast-like cells. The addition of strontium leads to enhanced proliferation suggesting the possible benefits of strontium incorporation in calcium phosphate coatings. The morphology and composition of deposited coatings showed a strong influence on the growth of cells.
The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blöchl's projector augmented wave (PAW) method is derived. It is shown that the total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addition, critical tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed core all electron methods. These tests include small molecules (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
Biomaterials can be endowed with biologically instructive properties by changing basic parameters such as elasticity and surface texture. However, translation from in vitro proof of concept to clinical application is largely missing. Porous calcium phosphate ceramics are used to treat small bone defects but in general do not induce stem cell differentiation, which is essential for regenerating large bone defects. Here, we prepared calcium phosphate ceramics with varying physicochemical and structural characteristics. Microporosity correlated to their propensity to stimulate osteogenic differentiation of stem cells in vitro and bone induction in vivo. Implantation in a large bone defect in sheep unequivocally demonstrated that osteoinductive ceramics are equally efficient in bone repair as autologous bone grafts. Our results provide proof of concept for the clinical application of "smart" biomaterials.
Magnesium (Mg) and strontium (Sr), which are essential nutrient elements in the natural bone, positively affect the osteogenic activity even in wide ranges of ion concentrations. However, it remains unknown whether magnesium-strontium phosphates [MgxSr3-x(PO4)2] are potential bone grafts for accelerating bone regeneration. Herein, a serial of MgxSr3-x(PO4)2, including Mg3(PO4)2, Mg2Sr(PO4)2, Mg1.5Sr1.5(PO4)2, MgSr2(PO4)2 and Sr3(PO4)2, were synthesized using a solid-state reaction approach. The physicochemical properties and cell behaviors of MgxSr3-x(PO4)2 bioceramics were characterized and compared with the common bone graft β-tricalcium phosphate (β-TCP). The results indicated that various MgxSr3-x(PO4)2 bioceramics differed in compressive strength and in vitro degradation rate. All the MgxSr3-x(PO4)2 bioceramics had excellent biocompatibility. In contrast to β-TCP, the MgxSr3-x(PO4)2 enhanced alkaline phosphatase activity of mouse bone mesenchymal stem cells (mBMSCs), and inhibited osteoclastogenesis-related gene expression of RAW264.7 cells, but did not enhance osteogenesis-related gene expression of mBMSCs which were treated with osteogenesis induction supplements. However, Mg3(PO4)2 stimulated osteogenesis-related gene expression of mBMSCs without the treatment of osteogenesis induction supplements. This work contributes to the design of bone graft and may open a new avenue for the bone regeneration field.
In this study, we examined the effect of β-tricalcium phosphate (β-TCP) coating on alkali-treated CP Grade II titanium surface via RF magnetron sputtering on osteoblast like cell (MC3T3-E1) viability and bone formation in rat tibia. The specimens were divided into three groups; commercially pure titanium (control group), alkali-treated titanium with nanofiber structure (NF group) and β-TCP coating on alkali-treated titanium with nanofiber structure (TNF group). The surface characteristics of specimens were observed under a field emission scanning electron microscope (FE-SEM), and contact angle was measured. The cell viability was assessed in vitro after 1 day, 3 days and 7 days. Implants of 2.0 mm diameter and 5.0 mm length were inserted into the tibia of rats. After 4 wks, the histomorphometric analysis was performed. Group NF and group TNF showed improved hydrophilicity of Ti. Group TNF showed significantly higher cell viability (P < 0.05) after 7 days. The bone to implant contact (BIC) ratio of the control group, NF group, and TNF group were 32.3%, 35.5%, and 63.9%, respectively. The study results suggested that β-TCP coated alkali-treated titanium surface via RF magnetron sputtering might be effective in implant dentistry due to enhanced hydrophilicity, improved cell response, and better osseointegration.
Bone is a composite material composed of collagen and calcium phosphate (CaP) mineral. The collagen gives bone its flexibility while the inorganic material gives bone its resilience. The CaP in bone is similar in composition and structure to the mineral hydroxyapatite (HA) and is bioactive, osteoinductive and osteoconductive. Therefore synthetic versions of bone apatite (BA) have been developed to address the demand for autologous bone graft substitutes. Synthetic HA (s-HA) are stiff and strong, but brittle. These lack of physical attributes limit the use of synthetic apatites in situations where no physical loading of the apatite occurs. s-HA chemical properties differ from BA and thus change the physical and mechanical properties of the material. Consequently, s-HA is more chemically stable than BA and thus its resorption rate is slower than the rate of bone regeneration. One solution to this problem is to introduce a faster resorbing CaP, such as β-tricalcium phosphate (β-TCP), when synthesizing the material creating a biphasic (s-HA and β-TCP) formulation of calcium phosphate (BCP). The focus of this review is to introduce the major differences between BCP and biological apatites and how material scientists have overcome the inadequacies of the synthetic counterparts. Examples of BCP performance in vitro and in vivo following structural and chemical modifications are provided as well as novel ultrastructural data. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2017.
The aim of this research is to observe the physicochemical characterization and evaluate the biocompatibility of the HA/β-TCP biphasic calcium phosphate ceramics (BCP) produced from fish bones. In addition, the mechanism of the formation of BCP after calcination of fish bones was discussed. Three kinds of fish bones (Salmo salar, Anoplopoma fimbria and Sardine) were prepared and calcined for one hour at different temperatures ranging from 600 °C to 1100 °C in a muffle furnace. The calcined bones were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (GTA), inductively coupled plasma optical atom emissions spectroscopy (ICP-OES), X-ray fluorescence (XRF) and scanning electron microscopy (SEM). The in vitro cytotoxicity assessment was used to evaluate the biocompatibility of the biphasic ceramics. BCP materials were produced from all kinds of fish bones by calcination above 700 °C, the carbonated hydroxyapatite and multiple trace element were also found in the calcined bones. With the increase of temperature, the ratio of HA/β-TCP varied and the major organic components were progressively removed. The carbonated hydroxyapatite disappeared when temperature rises above 900 °C. Rising temperature also caused crystal growth that eventually gave rise to the increase of the BCP grain size and influenced the mesoporous structure. The BCP materials were confirmed to have no obvious cytotoxicity to mesenchymal stem cells (MSC) in the in vitro cytotoxicity assessment. Calcium-deficient hydroxyapatite(CDHA) may make up the major inorganic constituent of fish bones that could decompose to HA and β-TCP when calcined above 700 °C.800°C-900°C is considered to be the optimal temperature to fabricate BCP materials which contain more β-TCP,carbonated hydroxyapatite and retain distinct mesoporous structure while has good biocompatibility. With the unique composition and structure, these three kinds of fish-bone-derived BCP materials can be further applied to fabricate bioceramic scaffolds for biomedical applications.
One of the main critical aspects behind the failure or success of an implant resides in its ability to fast bond with the surrounding bone. To boost osseointegration, the ideal implant material should exhibit composition and structure similar to those of biological apatite. To this aim, the most common approach is to coat the implant surface with a coating of hydroxyapatite (HA), resembling the main component of mineralized tissues. However, bone apatite is a non-stoichiometric, multi-substituted poorly-crystalline apatite, containing significant amounts of foreign ions, with high biological relevance. Ion-substituted HAs can be deposited by so called “wet methods”, which are however poorly reproducible and hardly industrially feasible; at the same time bioactive coatings realized by plasma assisted method, interesting for industrial applications, are generally made of stoichiometric (i.e. un-substituted) HA.
The growing evidence of the beneficial role of strontium in bone has increased the interest of developing strontium-containing biomaterials for medical applications, and specifically biocompatible coatings that can be deposited on metallic implants to benefit from their load-bearing capabilities. In this work, strontium-substituted hydroxyapatite (Sr-HA) coatings have been fabricated by pulsed laser deposition (PLD) from initial targets obtained after mixing and compacting commercial HA and SrCO3 powders in different proportions. The films thus fabricated were then structurally, morphologically and chemically characterized using scanning electron microscopy, optical profilometry, X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy. The macroscopic morphology of the films presented in all cases equivalent spherical shaped aggregates of typical calcium phosphate coatings. The results reveal, however, the incorporation of Sr2+ and carbonate groups in the coatings as a function of the SrCO3 content in the ablation target, being the incorporation of Sr2+ a linear phenomenon that is accompanied by a similarly linear withdrawal of Ca2+. The role of Sr2+ in the modification of the HA structure and a possible mechanism of substitution of Sr2+ atoms in place of Ca2+ atoms are discussed.
Silicon-doped hydroxyapatite-based (Si-HA) coatings were deposited via radio frequency (RF) magnetron sputtering on the surface of titanium that was treated with a pulsed electron beam. This study aimed to evaluate the effect of Si doping on the structure and mechanical properties of thin HA films. The content of the silicon was 1.2 and 4.6 at.% for the coatings prepared using the Si-HA precursor powders with a chemical formula Ca10(PO4)6 − x(SiO4)x(OH)2 − x where, x = 0.5 and 1.72. Pure HA (Ca10(PO4)6(OH)2) coatings were deposited for comparison. The as-deposited films were analysed with respect to their composition, state of chemical binding and microstructure using XPS, FTIR, XRD, and SEM. We hypothesized that the addition of Si would affect the mechanical features of the coatings due to microstructure changes. The effect of the introduction of Si on the nanohardness and the Young's modulus as well as the adhesion strength and scratch resistance of the HA coating was investigated using nanohardness testing and a scratch test, respectively. Examination of the coating microstructure using SEM and AFM revealed that Si doping influenced the surface morphology and led to a smaller grain size. The tendency to form an amorphous structure also increased with an increase in the Si content. A monotonous decrease in both the nanohardness and the elastic modulus was observed with an increase in the Si content. A maximum nanohardness of ~ 7 GPa was obtained for the Si-free HA coating, whereas the hardness decreased to ~ 4.3 GPa for the films with a Si content of 1.2 at.%. The addition of 4.6 at.% Si to the HA coating resulted in a reduction in the elastic modulus, whereas the nanohardness was very similar to that of the uncoated substrate. The adhesion behaviour of the coatings demonstrated different responses. In the case of pure HA coatings, failure occurred due to the low cohesion of the coating, whereas the crystalline Si-HA coatings with a Si content of 1.2 at.% deformed plastically without crack formation and without detaching from the titanium substrate, which resulted in a greater coating stability.
First-principles calculations were carried out to reveal local atomic arrangements and thermodynamic stability of substitutional divalent cations of Mg(2+), Zn(2+), Sr(2+) and Ba(2+) in tricalcium phosphates (TCP). There are two modifications of α-TCP and β-TCP, and a number of inequivalent Ca sites are present in the crystal structures. It was found that each divalent cation has energetically preferential Ca sites for substitution. For instance, Mg(2+) and Zn(2+) favor the substitution at the Ca-5 site of β-TCP while Sr(2+) and Ba(2+) tend to occupy Ca-3 and Ca-4 in the β-type crystal structure. The calculated site preference of these cations was in reasonable agreement with available experimental data. Moreover, it was found that these cations have negative formation energies at specific Ca sites especially in β-TCP, indicating the stabilization of the β phase.
Copyright © 2015. Published by Elsevier Ltd.
Mg-substituted hydroxyapatite made up of needle-like and plate-like particles containing different amounts of Mg (between 0.21 wt% and 2.11 wt%) were prepared via wet chemical precipitation method of a homogenous suspension of Mg(OH)(2)/Ca(OH)(2) and an aqueous solution of H3PO4. According to the data of Brunauer Emmett Teller method and field emission scanning electron microscopy, high specific surface area Mg-substituted hydroxyapatite was obtained. Specific surface area of as-synthesized powders increased from 94.9 m(2) g(-1) to 104.3 m(2) g(-1) with increasing concentration of Mg up to 0.64 wt%. Fourier transform infrared spectroscopy, X-ray powder diffraction, differential thermal analysis, and heating microscopy, were used to evaluate thermal stability and sintering behavior of synthesis products. Increase in concentration of Mg in synthesis products (>= 0.83 wt%) promoted decomposition of Mg-substituted hydroxyapatite to Mg-substituted beta-tricalcium phosphate after thermal treatment.
Strontium substituted hydroxyapatite (SrHA) coatings have received a lot of interest recently as strontium (Sr) has been shown to have the dual benefit of promoting bone formation and reducing bone resorption, in vivo. In this work, SrHA coatings were deposited onto polycrystalline titanium surfaces using radio frequency (RF) magnetron co-sputtering and compared to those deposited from HA alone. In particular, the influence of different levels of Sr-substitution of the sputtering targets (5 and 13 % Sr-substituted HA targets) on the properties of the deposited coatings produced at a low discharge power level (150 W) were investigated using FTIR, XPS, XRD, ToFSIMS and AFM techniques (both before and after annealing at 500 °C). The results show that Sr could be successfully incorporated into the HA lattice to form SrHA coatings and that they contained no other impurities. However, the coating produced from the 13 % Sr-substituted target had a higher Ca + Sr/P ratio (1.95 ± 0.14) and Sr content when compared to the coating produced from the 5 % Sr-substituted target (1.58 ± 0.20). The deposition rate also decreased with increasing Sr content of the sputtering targets. Furthermore, as the Sr content of the coatings increased, so did the preferred 002 orientation of the coating along with increased surface roughness and heterogeneity of the surface features. Therefore, this study has shown that RF magnetron sputtering offers a means to control attendant properties of Sr-substituted HA, such as the crystallinity, stoichiometry, phase purity and surface topography.
The bioactivity of hydroxyapatite (HA) coatings can be modified by the addition of different ions, such as silicon (Si), lithium (Li), magnesium (Mg), zinc (Zn) or strontium (Sr) into the HA lattice. Of the ions listed here, strontium substituted hydroxyapatite (SrHA) coatings have received a lot of interest recently as Sr has been shown to promote osteoblast proliferation and differentiation, and reduce osteodast activity. In this study, SrHA coatings were deposited onto titanium substrates using radio frequency (RF) magnetron co-sputtering (and compared to those surfaces deposited from HA alone). FTIR, XPS, XRD, and SEM techniques were used to analyse the different coatings produced, whereby different combinations of pure HA and 13% Sr-substituted HA targets were investigated. The results highlight that Sr could be successfully incorporated into the HA lattice to form SrHA coatings. It was observed that as the number of SrHA sputtering targets in the study were increased (increasing Sr content), the deposition rate decreased. It was also shown that as the Sr content of the coatings increased, so did the degree of preferred 002 orientation of the coating (along with obvious changes in the surface morphology). This study has shown that RF magnetron sputtering (specifically co-sputtering), offers an appropriate methodology to control the surface properties of Sr-substituted HA, such as the crystallinity, stoichiometry, phase purity and surface morphology.
The use of porous titanium-based implant materials for bone contact has been gaining ground in recent years. Selective laser melting (SLM) is a rapid prototyping method by which porous implants with highly defined external dimensions and internal architecture can be produced. The coating of porous implants produced by SLM with ceramic layers based on calcium phosphate (CaP) remains relatively unexplored, as does the doping of such coatings with magnesium (Mg) to promote bone formation. In this study, Mg-doped coatings of the CaP types octacalcium phosphate and hydroxyapatite (HA) were deposited on such porous implants using the pulsed laser deposition method. The coated implants were subsequently implanted in a rabbit femoral defect model for 6 months. Uncoated implants served as a reference material. Bone–implant contact and bone volume in the region of interest were evaluated by histopathological techniques using a tri-chromatographic Masson–Goldner staining method and by microcomputed tomography (µCT) analysis of the volume of interest in the vicinity of implants. Histopathological analysis revealed that all implant types integrated directly with surrounding bone with ingrowth of newly formed bone into the pores of the implants. Biocompatibility of all implant types was demonstrated by the absence of inflammatory infiltration by mononuclear cells (lymphocytes), neutrophils, and eosinophils. No osteoclastic or foreign body reaction was observed in the vicinity of the implants. µCT analysis revealed a significant increase in bone volume for implants coated with Mg-doped HA compared to uncoated implants. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2014.
Sr-substituted hydroxyapatite thin films were prepared by sputtering technique from mixture targets of hydroxyapatite (HA) and strontium apatite (SrAp). The HA and SrAp powders were mixed at 0-100% Sr/(Sr+Ca) target ratios. The coated films were recrystallized by a hydrothermal treatment to reduce film dissolution. The films were then characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectrometry (ICP). The osteocompatiblity of the films was also evaluated by the size of the bone formation area in osteoblast cells.In the XRD patterns, peaks shifted to lower 2θ values with increasing Sr/(Sr+Ca) target ratios, which indicated Sr incorporation into the HA lattice. In the SEM observation of the hydrothermally treated films, the surface was covered with globular particles, and the size of the globular particles increased from Sr0 to Sr40, and then the size decreased from Sr60 to Sr100. The ICP analysis showed that the Sr/(Sr+Ca) film ratios were almost the same as the target ratios. In the cell culture, the bone formation area on the Sr-substituted HA films increased with increasing Sr concentration, and saturated at Sr60.
To obtain an Sr-substituted hydroxyapatite thin film, sputter-coating was performed on a cellulose filter acting as a substrate from the mixture target of hydroxyapatite (HA) and strontium-apatite (SrAp) at an Ar pressure of 0.5–5.0 Pa. The ratio of the SrAp in the mixture target was varied from 25% to 100%. After coating, the films were heated at 700 °C to remove the cellulose filter substrate, and the crystalline phases were identified by X-ray diffraction (XRD). The sputter-coated film was identified as the Sr-substituted β-tri-calcium phosphate (TCP) and the Sr-substituted β-calcium pyrophosphate (CPP) as well as the Sr-substituted HA. The weight ratio of the Sr-substituted HA decreased with increasing Ar pressure or with an increasing ratio of SrAp to HA in the target. The average Sr/(Ca + Sr) molar ratio in the film was 1.9%–3.5% slightly lower than the initial SrAp ratio of the target, and the ratio was not influenced by the Ar pressure. In the (Sr + Ca)/P ratio, the ratio decreased while increasing the SrAp ratio in the target.
The phase evolution of magnesium incorporated hydroxyapatite/β-tricalcium phosphate (HA/β-TCP) ceramics of high purity prepared by solid-state reaction was investigated with the aid of x-ray diffraction and infrared spectroscopy (IR) in transmittance mode analysis. The dependence of the microstructure on the phase evolution of biphasic ceramics during natural sintering was also investigated as a function of Mg content. When sintered at 1100 °C, Mg is preferentially incorporated into the β-TCP phase rather than the HA phase. This Mg incorporation into the β-TCP effectively suppresses the phase transition from β- to α-TCP. With increasing sintering temperature, the solubility limit of the Mg in the β-TCP decreases and Mg starts to be either incorporated into the HA phase or segregated as free MgO. The decreased Mg content in the β-TCP facilitates the phase transition from β- into α-TCP, at 1300 °C or higher. Different processing methods on Mg addition show that the retarded phase transition from β- to α-TCP is the inherent property of Mg-doped HA/TCP. The variations in processing parameters mainly affect the microstructure instead of the phase evolution, leading to highly densified HA/β-TCP ceramics.
The effects on solubility of the substitution of monovalent metal ions (Li+, Na+, and K+ ions) at the Ca sites in beta-tricalcium phosphate (beta-TCP) were investigated by immersion of beta-TCP powder doped with metal ions in saline, and the dissolution mechanisms of these samples were inferred from the results of dissolution tests and from observations of the crystal structures. beta-TCP powder doped with Li+, Na+, and K+ ions (Li-TCP, Na-TCP, and K-TCP) had a lower solubility than pure beta-TCP powder, and the solubility decreased with an increase in the amount of metal ions. This decrease in solubility can be attributed to an improvement in crystal structure stabilization upon the substitution of monovalent metal ions at the Ca(4) sites and vacancies in beta-TCP, and the resultant occupancy of Ca2+ and metal ions at all Ca sites in the beta-TCP structure. However, the dissolution behavior of Li-TCP differed from that of Na-TCP and K-TCP because the atomic arrangement between the Li(4) sites and oxygen was less stable than that between the Na(4) or K(4) sites and oxygen. In addition, the solubility of beta-TCP doped with divalent metal ions was lower than that of beta-TCP doped with monovalent metal ions because the structural stability of beta-TCP doped with divalent metal ions was higher than that of beta-TCP doped with monovalent metal ions. These results show that the solubility and dissolution mechanisms of beta-TCP doped with metal ions were significantly influenced by the crystal structure stabilization and atomic arrangement of doped beta-TCP.
Calcium phosphate was coated from tetracalcium phosphate (TTCP), hydroxyapatite (HA), β-tricalcium phosphate (TCP), β-calcium pyrophosphate (CPP), and β-calcium metaphosphate (CMP) powder targets using radio frequency magnetron sputtering. The composition of the crystal phase of the coated films was changed, depending on the target materials, and the Ca/P molar ratios of the films varied from 0.74 to 2.54, increasing with the Ca/P molar ratio of the target. The solubility of the target, determined using a microwave-induced plasma-mass spectrometer was: TTCP≈β-CMP>β-TCP>β-CPP>HA, and the deposition rate from each target showed a similar order to the solubility: TTCP≈β-CMP>β-TCP>β-CPP≈HA.
The synthesis of five different Sr2+- and Mg2+-co-substituted β-tricalcium phosphate (β-TCP) has been obtained by heating the calcium-deficient apatites above 800°C. With the investigated concentrations of Sr2+ and Mg2+ from the present study, no additional phases other than β-TCP have been detected. The synthesized powders have been characterized by X-ray diffraction, Fourier transform infrared spectrometry, elemental analysis and Rietveld refinement studies. The co-substitution of Sr2+ and Mg2+ in the β-TCP has resulted in the formation of crystalline β-TCP at hexagonal setting (space group R3c). The reduction of lattice a- and c-axis parameters with the combined substitution of Sr2+ and Mg2+ in the β-TCP has been found evident from the present results. Sr2+ has been found occupying the Ca(1,2,3,4) sites and Mg2+ was found at the sixfold coordinated Ca(5) site of β-TCP structure.
Biologically important α- and β-tricalcium phosphates (TCPs) have been investigated using ab initio density functional calculations. α- and β-TCP have particularly large unit cells amounting to 312 and 273 atoms, respectively. The relationship between α-TCP and its three subcells, as well as the influence of the distribution of the Ca vacancies apparently existing in β-TCP have been studied. The calculated structural parameters for all the TCP phases, are in substantial agreement with experiment. The Ca-O distance varies continuously, while the P-O bonds distribute over a very narrow range. Oxygens hold the majority of the bonding electrons which reflects the ionic nature of the α and β phases. The results suggest that β-TCP is more stable than the α phase, and that β-TCP with uniformly distributed Ca vacancies is the most stable structure. The three 1/3 α-TCP subcells relax to similar structures, and we found that the full α-TCP cell and its subcells have very similar stability, electronic and structural properties, suggesting that the subcell can be a good approximation for studying α-TCP.
Hydroxyapatite and magnesium modified hydroxyapatite were deposited on nitrited Ti6Al4V substrates by use of pulsed laser deposition technique. Three target materials consisting of non-modified and magnesium modified hydroxyapatite with Mg content of 0.6wt.% and 1.8wt.% were ablated using an ArF excimer laser. The obtained coatings were analyzed using X-ray diffraction, FTIR and AFM methods in order to determine the influence of magnesium on their phase and chemical composition, crystallinity, surface morphology and biological properties. Doping with low concentration of Mg does not significantly influence the HA morphology but improves osteoblast adhesion as compared to pure HA.
An approach for electronic structure calculations is described that generalizes both the pseudopotential method and the linear augmented-plane-wave (LAPW) method in a natural way. The method allows high-quality first-principles molecular-dynamics calculations to be performed using the original fictitious Lagrangian approach of Car and Parrinello. Like the LAPW method it can be used to treat first-row and transition-metal elements with affordable effort and provides access to the full wave function. The augmentation procedure is generalized in that partial-wave expansions are not determined by the value and the derivative of the envelope function at some muffin-tin radius, but rather by the overlap with localized projector functions. The pseudopotential approach based on generalized separable pseudopotentials can be regained by a simple approximation.
Four calcium phosphate ceramic coatings, the less soluble hydroxyapatite (HA) coating, the more soluble β-tricalcium phosphate (β-TCP) coating, and two biphasic calcium phosphate (BCP) coatings with HA/β-TCP ratios of 70/30 and 30/70 were fabricated by spraying each corresponding powder onto a titanium substrate at room temperature (RT) in a vacuum, in order to investigate the effect of the HA/β-TCP ratio on the dissolution behavior and the cellular responses of the coating. No secondary phases, except for HA and β-TCP, were observed for the coatings in the X-ray diffraction results. The coating compositions were almost the same as those of the starting powders because the coating was conducted at RT. Microscopic examination of the coatings revealed crack-free and dense microstructures. The BCP coatings exhibited dissolution rates intermediate between those of the pure HA and β-TCP coatings. The dissolution rate of the coatings was largely dependent on their HA/β-TCP ratio. The cell proliferation and differentiation results indicated that the cellular responses of the coatings were not proportional to their dissolution rates. The 3HA–7TCP (HA/β-TCP ratio of 30/70) coating exhibited an optimal dissolution rate for excellent biological performance.
Hydroxyapatite [Ca10(PO4)6(OH)2], (HA) is similar in composition to bone mineral and has been found to promote new bone formation when implanted in a skeletal
defect. However, its use in biomedical applications is limited by its relatively slow rate of biological interaction, and
there is also a requirement to improve the success rate of HA implants in younger active patients, particularly where implants
will be in place long-term. The addition of silicon (Si) into HA has been demonstrated to enhance the speed, and quality of
the bone repair process. This paper describes the synthesis and detailed characterisation of nanocrystalline silicon-substituted
hydroxyapatite (SiHA) thin coatings applied to a titanium substrate via a magnetron co-sputtering process. Amorphous SiHA
coatings (∼1μm thick) with varying Si content up to 4.9wt% were produced before being transformed into crystalline films
by heat-treatment. The crystalline coating was characterised by X-ray diffraction (XRD) and infrared (IR) analysis, and confirmed
to be a single-phase apatite. The substitution of Si into HA resulted in an increase in both the a- and c-axes of the unit cell parameters, but a decrease in the crystallite size, with increasing Si substitution. This substitution
also caused a decrease in the intensities of both the O–H and P–O bands in the IR spectra. Hence, these findings confirmed
that the crystal structure of HA was altered with Si substitution. In vitro cell culture work showed that these SiHA thin coatings exhibited enhanced bioactivity and biofunctionality. An increase in
the attachment and growth of human osteoblast-like (HOB) cells on these coatings was observed throughout the culture period,
with the formation of extracellular matrix. In addition, confocal microscopy revealed that HOBs developed mature cytoskeletons
with clear evidence of actin stress fibres, along with defined cell nuclei.
X-ray diffraction and infrared absorption analyses have been carried out on zinc-substituted and strontium-substituted β-tricalcium phosphate prepared by solid-state reaction. Zinc can substitute calcium up to 20 atom %, inducing a nonlinear variation of the lattice constants and an increase in degeneracy of the PO43â infrared absorption bands. On the other hand, up to 80 atom % of strontium can enter into the crystal structure of β-tricalcium phosphate, causing a linear enlargement of the unit cell, in agreement with its greater ionic radius compared to that of calcium. Furthermore, strontium incorporation provokes the shift of the PO43â absorption bands toward lower frequencies. On the basis of the data previously obtained on magnesium-substituted β-tricalcium phosphate, the different behaviours exhibited by zinc and strontium could be attributed to a different distribution into the cationic sites of the β-tricalcium phosphate structure. The results allow us to relate the effect of bivalent i
Bone substitute materials are required to support the remodeling process, which consists of osteoclastic resorption and osteoblastic synthesis. Osteoclasts, the bone-resorbing cells, generate from differentiation of hemopoietic mononuclear cells. In the present study, we have evaluated the effects of 1.0 wt % strontium (Sr) and 1.0 wt % magnesium (Mg) doping in beta-tricalcium phosphate (β-TCP) on the differentiation of mononuclear cells into osteoclast-like cells and its resorptive activity. In vitro osteoclast-like cell formation, adhesion, and resorption were studied using osteoclast precursor RAW 264.7 cell, supplemented with receptor activator of nuclear factor κβ ligand (RANKL). Osteoclast-like cell formation was noticed on pure and Sr-doped β-TCP samples at day 8, which was absent on Mg-doped β-TCP samples indicating decrease in initial osteoclast differentiation due to Mg doping. After 21 days of culture, osteoclast-like cell formation was evident on all samples with osteoclastic markers such as actin ring, multiple nuclei, and presence of vitronectin receptor α(v)β(3) integrin. After osteoclast differentiation, all substrates showed osteoclast-like cell-mediated degradation, however, significantly restricted for Mg-doped β-TCP samples. Our present results indicated that substrate chemistry controlled osteoclast differentiation and resorptive activity, which can be used in designing TCP-based resorbable bone substitutes with controlled degradation properties.
The pure calcite surface was examined using techniques sensitive to the near-surface (XPS and LEED) immediately after fracture in ultra-high vacuum (10−10 mbar) and then following exposure to various atmospheres and aqueous solutions that were free of trace metals. These spectroscopic techniques allow molecular-level observations that offer the possibility of gaining more insight into geochemical processes elucidated from macroscopic solution studies.Several absolute electron binding energies for the atoms in calcite were redetermined with XPS using the gold dot method. The results are for C1s, 347.7 and for and , respectively, and for O1s. Photoelectron energy shifts from main peak positions suggest that immediately after fracture in ultra-high vacuum, bond reconfiguration leads to the formation of carbide-like bonds between Ca and C at the surface. Calcite that has been exposed to water, even as vapour from the atmosphere, shows binding energy shifts that indicate the presence of and S · CaOH where S · represents the calcite surface. Surface hydration is also supported, independently, by the XPS peak intensity ratios and is consistent with adsorption theory derived from macroscopic solution studies. The modified oxygen Auger parameter, α′, (using O1s and O(KVV)), was found to be 1043.9 eV for all samples of calcite tested, whether powder or cleaved from Iceland Spar, clean or contaminated by adventitious carbon, freshly fractured, or exposed briefly to water, or in the process of dissolution or precipitation. LEED patterns of the {101} cleavage surface of samples that were freshly fractured in air and that were exposed to dissolving or precipitating solutions showed that the top few atomic layers exhibit long range order. Lattice spacings at the surface are statistically identical to those of bulk calcite, though some surface CO3 groups may be rotated relative to the bulk structure.This work provides direct, molecular-level evidence for the processes of reconfiguration and hydration at the calcite surface. These results provide a basis for future spectroscopic studies of trace metal adsorption on calcite and subsequent solid-solution formation.
The use of strontium-containing hydroxyapatite (Sr-HA) as a biomaterial has been reported recently. In vitro and in vivo studies have shown that Sr-HA promotes osteoblast response and stimulates new bone formation. In order to extend its usage to major load-bearing applications, such as artificial hip replacement, it has been proposed that the material could be used in the form of a coating on implant surfaces. This paper reports a preliminary study of biocompatibility of plasma sprayed Sr-HA coatings on a metallic substrate. Coatings of Sr-HA containing 10 mol% Sr2+ was produced on titanium alloy substrates. The coating exhibited good bonding with the substrate. The bioactivity of Sr-HA coating was evaluated in vitro by immersion in simulated body fluid (SBF). After immersion in SBF, Sr-HA coating exhibited great ability to induce apatite precipitation on its surface. The possible effects of cell–materials interactions of Sr-HA coating were examined by culturing osteoprecursor cells (OPC1) on coating surfaces. The effect of Sr-HA was also compared to a hydroxyapatite (HA) coating, which is widely used in orthopedics and dentistry. The results indicated that Sr-HA coating had good biocompatibility with human osteoblasts. OPC1 cells survived and proliferated well on the surface of coating. Sr-HA coating promoted OPC1 cells attachment, and more local contacts were produced on the surface. The presence of Sr stimulated OPC1 cell differentiation and ALP expression. No deleterious effect on ECM formation and mineralization was found with Sr-HA coating. The results indicated that Sr-HA coating had good mechanical properties and bioactivity in vitro.
The crystal structure of sintered β-tricalcium phosphate, Ca3(PO4)2, was refined using a high-resolution neutron powder diffraction data and the Rietveld method. This material was confirmed to have a rhombohedral structure (space group R3c, Z=21). Unit-cell parameters with higher precision (a=b=10.4352(2) Å, c=37.4029(5) Å, α=β=90°, and γ=120° in the hexagonal setting) and positional parameters for oxygen with equal precision were obtained by the neutron powder diffraction technique, compared with the single-crystal X-ray diffraction data by Dickens et al. (J. Solid State Chem. 10 (1974) 232). The site Ca(4) with atomic coordinates [0.0, 0.0, −0.0851(6)] was confirmed to be very different from the other four Ca sites: The position Ca(4) is three-fold coordinated with oxygen atoms, and has lower occupancy factor of 0.43(4), and a higher isotropic thermal parameter. On the contrary, each of the Ca(1), Ca(2), Ca(3), and Ca(5) is fully occupied by one Ca atom and these positions are coordinated with seven, eight, eight, and six oxygen atoms, respectively. The bond valence sums of Ca(4) and Ca(5) are lower (0.7) and higher (2.7), respectively, than the others (1.8–2.1).
Biocompatible layers of hydroxyapatite and fluorhydroxyapatite were grown on Ti substrates by means of dip-coating into sol–gel. In order to improve the adhesion of apatite-based coatings, the substrates were a priori covered with calcium titanate. Therefore, the hydroxyapatite, fluorhydroxyapatite and CaTiO3 coatings were produced and analysed. The chemical composition of the coatings (CaTiO3, CaTiO3+hydroxyapatite, and CaTiO3+fluorhydroxyapatite) was studied by using X-ray photoelectron spectroscopy (XPS). The data of quantitative XPS analysis displayed the different features (cleanness, homogeneity, etc.) of CaTiO3, hydroxyapatite, and fluorhydroxyapatite films after the growth and after the treatment in vitro.
We present a detailed description and comparison of algorithms for performing ab-initio quantum-mechanical calculations using pseudopotentials and a plane-wave basis set. We will discuss: (a) partial occupancies within the framework of the linear tetrahedron method and the finite temperature density-functional theory, (b) iterative methods for the diagonalization of the Kohn-Sham Hamiltonian and a discussion of an efficient iterative method based on the ideas of Pulay's residual minimization, which is close to an order N-atoms(2) scaling even for relatively large systems, (c) efficient Broyden-like and Pulay-like mixing methods for the charge density including a new special 'preconditioning' optimized for a plane-wave basis set, (d) conjugate gradient methods for minimizing the electronic free energy with respect to all degrees of freedom simultaneously. We have implemented these algorithms within a powerful package called VAMP (Vienna ab-initio molecular-dynamics package), The program and the techniques have been used successfully for a large number of different systems (liquid and amorphous semiconductors, liquid simple and transition metals, metallic and semi-conducting surfaces, phonons in simple metals, transition metals and semiconductors) and turned out to be very reliable.
This study aimed to investigate the formation and properties of magnesium substituted tricalcium phosphate containing various amounts of Mg2+ and Ca2+ ions (β-TCMP), isostructural with β- Mg 2+ ions (β-Ca3 (PO4)2. Beta-TCP and β-TCMP were prepared by a solid-state reaction, then calcination at 900°C for 2hr, and finally sintered at 1100°C for 2hr. The incorporation of Mg was reflected in the shift in the x-ray diffraction peaks due to partial Mg-for-Ca substitution in tricalcium phosphate, causing a contraction in the unit cell dimension. Unit cell parameters ao and co, and molar volume Vo decrease linearly for atomic ratios Mg2+/ Mg2++Ca2+ varying from 0 to 10 mol%.. The morphology and chemical composition were analyzed semiquantitatively using X-ray diffraction analysis (XRD), thermogravimetric analysis (TGA), differential thermal analysis (DTA), scanning electron microscopy (SEM) and infrared spectroscopy (IR). The dissolution behaviour of Mg-substituted samples was tested in distilled water, at pH=6.1. Results demonstrated that Mg2+ ions can easily substitute for Ca2+ ions in the TCP lattice. Increasing the Mg content from 0 to 10%m reduces the dissolution rate of Mg-TCP samples.
In this work, an improved version of the radio frequency magnetron sputtering (RF-MS) technique was used to prepare highly adherent B-type carbonated hydroxylapatite (B-CHA) thin films. Fourier transform infrared spectroscopy (FTIR) and grazing incidence X-ray diffraction studies proved that the coatings maintained the composition and revealed the polycrystalline structure of HA. Scanning electron microscopy analysis showed that the CHA films are rough and exhibit a homogeneous microstructure. Energy-dispersive X-ray spectroscopy (EDX) mapping demonstrated a uniform distribution of the Ca and P cations while a Ca/P ratio of 1.8 was found. In addition, the FTIR experiments showed a remarkable reproducibility of the nanostructures. Human mesenchymal stem cells (hMSCs), in vitro differentiated osteoblasts, and explanted bone cells were grown over the surface of CHA coatings for periods between a few hours and 21 days. Osteoprogenitor cells maintained viability and characteristic morphology after adhesion on CHA coatings. Ki67-positive osteoblasts were the evidence of cell proliferation events. Cells showed positive staining for markers of osteoblast phenotype such as collagen type I, bone sialoprotein and osteonectin. Our data showed the formation of mineralized foci by differentiation of hMSCs to human primary osteoblasts after cultivation in osteogenic media on RF-sputtered films. The results demonstrate the capacity of B-type CHA coating to support MSCs adhesion and osteogenic differentiation ability.