Implant related infection is one of the key concerns in total joint hip arthroplasties. In order to reduce bacterial adhesion, silver (Ag) / silver oxide (Ag2O) doping was used in plasma sprayed hydroxyapatite (HA) coating on titanium substrate. HA powder was doped with 2.0, 4.0 and 6.0 wt% Ag, heat treated at 800 °C and used for plasma spray coating using a 30 kW plasma spray system, equipped with supersonic nozzle. Application of supersonic plasma nozzle significantly reduced phase decomposition and amorphous phase formation in the HA coatings as evident by X-ray diffraction (XRD) study and Fourier transformed infrared spectroscopic (FTIR) analysis. Adhesive bond strength of more than 15 MPa ensured the mechanical integrity of the coatings. Resistance against bacterial adhesion of the coatings was determined by challenging them against Pseudomonas Aeruginosa (PAO1). Live/Dead staining of the adherent bacteria on the coating surfaces indicated a significant reduction in bacterial adhesion due to the presence of Ag. In vitro cell-material interactions and alkaline phosphatase (ALP) protein expressions were evaluated by culturing human fetal osteoblast cells (hFOB). Present results suggest that the plasma sprayed HA coatings doped with an optimum amount of Ag can have excellent antimicrobial property without altering mechanical property of the Ag doped HA coatings.
HA coating; Plasma Spray; Pseudomonas Aeruginosa; biocompatibility
Infection in primary total joint prostheses is estimated to occur in up to 3% of all surgeries. As a measure to improve the antimicrobial properties of implant materials, silver (Ag) was incorporated into plasma sprayed hydroxyapatite (HA) coatings. To offset potential cytotoxic effects of Ag in the coatings, strontium (Sr) was also added as a binary dopant. HA powder were doped with 2.0 wt% Ag2O, 1.0 wt% SrO and the powder was then heat treated at 800° C. Titanium substrates were coated using a 30 kW plasma spray system equipped with a supersonic nozzle. X-ray diffraction (XRD) confirmed the phase purity and high crystallinity of the coatings. Samples were evaluated for mechanical stability by adhesive bond strength testing. Results show that the addition of dopants did not affect the overall bond strength of the coatings. The antibacterial efficacies of the coatings were tested against Pseudomonas aeruginosa. Samples that contained the Ag2O dopant were found to be highly effective against the bacterial colonization. In vitro cell-material interactions using human fetal osteoblast (hFOB) cells were characterized by 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay for cell viability, field emission scanning electron microscopy (FESEM) for cell morphology and confocal imaging for the important differentiation marker alkaline phosphatase (ALP). Our results showed evidence of cytotoxic effects in the Ag-HA coatings, characterized by poor cellular morphology and cell death and nearly complete impediment of functional ALP activity. The addition of SrO to Ag-HA coatings was able to effectively offset these negative effects and improve the performance when compared to pure HA coated samples.
hydroxyapatite; coating; antibacterial; silver; strontium
Functionally graded coatings (FGCs) of bioactive glass on titanium alloy (Ti6Al4V) were fabricated by the enameling technique. These innovative coatings may be an alternative to plasma-sprayed, hydroxyapatite-coated implants. Previously we determined that a preconditioning treatment in simulated body fluid (SBF) helped to stabilize FGCs (Foppiano, S., et al., Acta Biomater, 2006; 2(2):133-42). The primary goal of this work was to assess the in vitro cytocompatibility of preconditioned FGCs with MC3T3-E1.4 mouse pre-osteoblastic cells. We evaluated cell adhesion, proliferation and mineralization on FGCs in comparison to uncoated Ti6Al4V and tissue culture polystyrene (TCPS). No difference in cell adhesion was identified, whereas proliferation was significantly different on all materials, being highest on FGCs followed by TCPS and Ti6Al4V. Qualitative and quantitative mineralization assays indicated that mineralization occurred on all materials. The amount of inorganic phosphate released by the mineralizing layers was significantly different, being highest on TCPS, followed by FGC and uncoated Ti6Al4V. The secondary objective of this work was to assess the ability of the FGCs to affect gene expression, indirectly, by means of their dissolution products, which was assessed by real-time reverse-transcription polymerase chain reaction. The FGC dissolution products induced a 2-fold increase in the expression of Runx-2, and a 20% decrease in the expression of collagen type 1 with respect to TCPS extract. These genes are regulators of osteoblast differentiation and mineralization, respectively. The findings of this study indicate that preconditioned FGCs are cytocompatible and suggest that future work may allow composition changes to induce preferred gene expression.
Cell adhesion; cell proliferation; cell differentiation; cytocompatibility
In this work, the preparation and characterization of silver doped hydroxyapatite thin films were reported and their antimicrobial activity was characterized. Silver doped hydroxyapatite (Ag:HAp) thin films coatings substrate was prepared on commercially pure Si disks by sol-gel method. The silver doped hydroxyapatite thin films were characterized by various techniques such as Scanning electron microscopy (SEM) with energy Dispersive X-ray attachment (X-EDS), Fourier transform infrared spectroscopy (FT-IR), and glow discharge optical emission spectroscopy (GDOES). These techniques have permitted the structural and chemical characterisation of the silver doped hydroxyapatite thin films. The antimicrobial effect of the Ag:HAp thin films on Escherichia coli and Staphylococcus aureus bacteria was then investigated. This is the first study on the antimicrobial effect of Ag:HAp thin films obtained by sol-gel method. The results of this study have shown that the Ag:HAp thin films with xAg = 0.5 are effective against E. coli and S. aureus after 24 h.
Ultra smooth nanostructured diamond (USND) coatings were deposited by microwave plasma chemical vapor deposition (MPCVD) technique using He/H2/CH4/N2 gas mixture. The RMS surface roughness as low as 4 nm (2 micron square area) and grain size of 5–6 nm diamond coatings were achieved on medical grade titanium alloy. Previously it was demonstrated that the C2 species in the plasma is responsible for the production of nanocrystalline diamond coatings in the Ar/H2/CH4 gas mixture. In this work we have found that CN species is responsible for the production of USND coatings in He/H2/CH4/N2 plasma. It was found that diamond coatings deposited with higher CN species concentration (normalized by Balmer Hα line) in the plasma produced smoother and highly nanostructured diamond coatings. The correlation between CN/Hα ratios with the coating roughness and grain size were also confirmed with different set of gas flows/plasma parameters. It is suggested that the presence of CN species could be responsible for producing nanocrystallinity in the growth of USND coatings using He/H2/CH4/N2 gas mixture. The RMS roughness of 4 nm and grain size of 5–6 nm were calculated from the deposited diamond coatings using the gas mixture which produced the highest CN/Hα species in the plasma. Wear tests were performed on the OrthoPOD®, a six station pin-on-disk apparatus with ultra-high molecular weight polyethylene (UHMWPE) pins articulating on USND disks and CoCrMo alloy disk. Wear of the UHMWPE was found to be lower for the polyethylene on USND than that of polyethylene on CoCrMo alloy.
Nanostructure; diamond films; plasma CVD; wear
This paper reports the improvement in the sensing performance of nanocrystalline SnO2-based liquid petroleum gas (LPG) sensors by doping with fluorine (F). Un-doped and F-doped tin oxide films were prepared on glass substrates by the dip-coating technique using a layer-by-layer deposition cycle (alternating between dip-coating a thin layer followed by a drying in air after each new layer). The results showed that this technique is superior to the conventional technique for both improving the film thickness uniformity and film transparency. The effect of F concentration on the structural, surface morphological and LPG sensing properties of the SnO2 films was investigated. Atomic Force Microscopy (AFM) and X-ray diffraction pattern measurements showed that the obtained thin films are nanocrystalline SnO2 with nanoscale-textured surfaces. Gas sensing characteristics (sensor response and response/recovery time) of the SnO2:F sensors based on a planar interdigital structure were investigated at different operating temperatures and at different LPG concentrations. The addition of fluorine to SnO2 was found to be advantageous for efficient detection of LPG gases, e.g., F-doped sensors are more stable at a low operating temperature (300 °C) with higher sensor response and faster response/recovery time, compared to un-doped sensor materials. The sensors based on SnO2:F films could detect LPG even at a low level of 25% LEL, showing the possibility of using this transparent material for LPG leak detection.
F-doped tin oxide films; dip-coating technique; liquid petroleum gas (LPG) sensors
This paper reports preparation of a highly crystalline nano hydroxyapatite (HA) coating on commercially pure titanium (Cp-Ti) using inductively coupled radio frequency (RF) plasma spray and their in vitro and in vivo biological response. HA coatings were prepared on Ti using normal and supersonic plasma nozzles at different plate powers and working distances. X-ray diffraction (XRD) and Fourier transformed infrared spectroscopic (FTIR) analysis show that the normal plasma nozzle lead to increased phase decomposition, high amorphous calcium phosphate (ACP) phase formation, and severe dehydroxylation of HA. In contrast, coatings prepared using supersonic nozzle retained the crystallinity and phase purity of HA due to relatively short exposure time of HA particles in the plasma. In addition, these coatings exhibited a microstructure that varied from porous and glassy structure at the coating-substrate interface to dense HA at the top surface. The microstructural analysis showed that the coating was made of multigrain HA particles of ~200 nm in size, which consisted of recrystallized HA grains in the size range of 15– 20 nm. Apart from the type of nozzle, working distance was also found to have a strong influence on the HA phase decomposition, while plate power had little influence. Depending on the plasma processing conditions, a coating thickness between 300 and 400 μm was achieved where the adhesive bond strengths were found to be between 4.8 MPa to 24 MPa. The cytotoxicity of HA coatings was examined by culturing human fetal osteoblast cells (hFOB) on coated surfaces. In vivo studies, using the cortical defect model in rat femur, evaluated the histological response of the HA coatings prepared with supersonic nozzle. After 2 weeks of implantation, osteoid formation was evident on the HA coated implant surface, which could indicate early implant- tissue integration in vivo.
Nano HA coatings; Induction plasma spray; Mechanical properties; In vitro studies; Histology
Titanium is widely used in biomedical materials, particularly in dental implants, because of its excellent biocompatibility and mechanical characteristics. However, titanium implant failures still remain in some cases, varying with implantation sites and patients. Improving its overall performance is a major focus of dental implant research. Equal-channel angular pressing (ECAP) can result in ultrafine-grained titanium with superior mechanical properties and better biocompatibility, which significantly benefits dental implants, and without any harmful alloying elements. Lanthanum (La) can inhibit the acidogenicity of dental plaque and La-containing hydroxyapatite (La-HA) possesses a series of attractive properties, in contrast to La-free HA. Micro-arc oxidation (MAO) is a promising technology that can produce porous and firmly adherent hydroxyapatite (HA) coatings on titanium substrates. Therefore, we hypothesize that porous La-containing hydroxyapatite coatings with different La content (0.89%, 1.3% and 1.79%) can be prepared on ultrafine-grained (~200–400 nm) titanium by ECAP and MAO in electrolytic solution containing 0.2 mol/L calcium acetate, 0.02 mol/L β-glycerol phosphate disodium salt pentahydrate (β-GP), and lanthanum nitrate with different concentrations to further improve the overall performance of titanium, which are expected to have great potential in medical applications as a dental implant.
Dental Implants; Dentistry; Hydroxyapatites; Titanium
The structure and phase evolution of nanocrystalline Ce1−xLnxO2−x/2−δ (Ln = Yb, Lu, x = 0 − 1) oxides upon heating in H2 was studied for the first time. Up to 950 °C the samples were single-phase, with structure changing smoothly with x from fluorite type (F) to bixbyite type (C). For the Lu-doped samples heated at 1100 °C in the air and H2, phase separation into coexisting F- and C-type structures was observed for ~0.40 < x < ~0.70 and ~0.25 < x < ~0.70, respectively. It was found also that addition of Lu3+ and Yb3+ strongly hinders the crystallite growth of ceria during heat treatment at 800 and 950 °C in both atmospheres. Valency of Ce and Yb in Ce0.1Lu0.9O1.55−δ and Ce0.95Yb0.05O1.975−δ samples heated at 1100 °C was studied by XANES and magnetic measurements. In the former Ce was dominated by Ce4+, with small contribution of Ce3+ after heating in H2. In the latter, Yb existed exclusively as 3+ in both O2 and H2.
Nanocrystalline ceria based oxide; CeO2–Lu2O3; CeO2–Yb2O3; Crystallite growth; Hydrogen; TEM; XANES; EBSD; Magnetic susceptibility
Improved methods to increase surface hardness of metallic biomedical implants are being developed in an effort to minimize the formation of wear debris particles that cause local pain and inflammation. However, for many implant surface treatments, there is a risk of film delamination due to the mismatch of mechanical properties between the hard surface and the softer underlying metal. In this article, we describe the surface modification of titanium alloy (Ti-6Al-4V), using microwave plasma chemical vapor deposition to induce titanium nitride formation by nitrogen diffusion. The result is a gradual transition from a titanium nitride surface to the bulk titanium alloy, without a sharp interface that could otherwise lead to delamination. We demonstrate that vitronectin adsorption, as well as the adhesion and spreading of human mesenchymal stem cells to plasma-nitrided titanium is equivalent to that of Ti-6Al-4V, while hardness is improved 3- to 4-fold. These in vitro results suggest that the plasma nitriding technique has the potential to reduce wear, and the resulting debris particle release, of biomedical implants without compromising osseointegration; thus, minimizing the possibility of implant loosening over time.
titanium nitride; chemical vapor deposition; mesenchymal stem cells; osseointegration; vitronectin
Synthesis of nanosized particle of Ag-doped hydroxyapatite with antibacterial properties is in the great interest in the development of new biomedical applications. In this article, we propose a method for synthesized the Ag-doped nanocrystalline hydroxyapatite. A silver-doped nanocrystalline hydroxyapatite was synthesized at 100°C in deionized water. Other phase or impurities were not observed. Silver-doped hydroxyapatite nanoparticles (Ag:HAp) were performed by setting the atomic ratio of Ag/[Ag + Ca] at 20% and [Ca + Ag]/P as 1.67. The X-ray diffraction studies demonstrate that powders made by co-precipitation at 100°C exhibit the apatite characteristics with good crystal structure and no new phase or impurity is found. The scanning electron microscopy (SEM) observations suggest that these materials present a little different morphology, which reveals a homogeneous aspect of the synthesized particles for all samples. The presence of calcium (Ca), phosphor (P), oxygen (O), and silver (Ag) in the Ag:HAp is confirmed by energy dispersive X-ray (EDAX) analysis. FT-IR and FT-Raman spectroscopies revealed that the presence of the various vibrational modes corresponds to phosphates and hydroxyl groups. The strain of Staphylococcus aureus was used to evaluate the antibacterial activity of the Ca10-xAgx(PO4)6(OH)2 (x = 0 and 0.2). In vitro bacterial adhesion study indicated a significant difference between HAp (x = 0) and Ag:HAp (x = 0.2). The Ag:Hap nanopowder showed higher inhibition.
Many techniques for the surface modification of titanium and its alloys have been proposed from the viewpoint of improving bioactivity. This paper contains an overview of surface treatment methods, including coating with hydroxyapatite (HAp), an osteoconductive compound. There are two types of coating methods: pyroprocessing and hydroprocessing. In this paper, hydroprocessing for coating on the titanium substrate with HAp, carbonate apatite (CO3–Ap), a CO3–Ap/CaCO3 composite, HAp/collagen, and a HAp/gelatin composite is outlined. Moreover, evaluation by implantation of surface-modified samples in rat tibiae is described.
Surface modification enables the creation of bioactive implants using traditional material substrates without altering the mechanical properties of the bulk material. For applications such as bone plates and stents, it is desirable to modify the surface of metal alloy substrates to facilitate cellular attachment, proliferation, and possibly differentiation. In this work we present a general strategy for altering the surface chemistry of nickel-titanium shape memory alloy (NiTi) in order to covalently attach self-assembled peptide amphiphile (PA) nanofibers with bioactive functions. Bioactivity in the systems studied here includes biological adhesion and proliferation of osteoblast and endothelial cell types. The optimized surface treatment creates a uniform TiO2 layer with low levels of Ni on the NiTi surface, which is subsequently covered with an aminopropylsilane coating using a novel, lower temperature vapor deposition method. This method produces an aminated surface suitable for covalent attachment of PA molecules containing terminal carboxylic acid groups. The functionalized NiTi surfaces have been characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and atomic force microscopy (AFM). These techniques offer evidence that the treated metal surfaces consist primarily of TiO2 with very little Ni, and also confirm the presence of the aminopropylsilane overlayer. Self-assembled PA nanofibers presenting the biological peptide adhesion sequence Arg-Gly-Asp-Ser are capable of covalently anchoring to the treated substrate, as demonstrated by spectrofluorimetry and AFM. Cell culture and scanning electron microscopy (SEM) demonstrate cellular adhesion, spreading, and proliferation on these functionalized metal surfaces. Furthermore, these experiments demonstrate that covalent attachment is crucial for creating robust PA nanofiber coatings, leading to confluent cell monolayers.
Peptide amphiphile nanofibers; self-assembly; titanium; nickel-titanium APTES; biofunctionalization; MC3T3-E1; CPAE; covalent attachment
Chromium and ruthenium-doped zinc oxide (ZnO:Cr) and (ZnO:Ru) thin solid films were deposited on soda-lime glass substrates by the sol-gel dip-coating method. A 0.6 M solution of zinc acetate dihydrate dissolved in 2-methoxyethanol and monoethanolamine was used as basic solution. Chromium (III) acetylacetonate and Ruthenium (III) trichloride were used as doping sources. The Ru incorporation and its distribution profile into the films were proved by the SIMS technique. The morphology and structure of the films were studied by SEM microscopy and X-ray diffraction measurements, respectively. The SEM images show porous surfaces covered by small grains with different grain size, depending on the doping element, and the immersions number into the doping solutions. The sensing properties of ZnO:Cr and ZnO:Ru films in a propane (C3H8) atmosphere, as a function of the immersions number in the doping solution, have been studied in the present work. The highest sensitivity values were obtained for films doped from five immersions, 5.8 and 900, for ZnO:Cr and ZnO:Ru films, respectively. In order to evidence the catalytic effect of the chromium (Cr) and ruthenium (Ru), the sensing characteristics of undoped ZnO films are reported as well.
zinc oxide; thin solid films; sol-gel; 07.07.Df; 73.61.–r; 52.77.Fv; 81.15.Rs
This study was designed to investigate bone remodelling around the cup in cementless THA. Previous studies indicate an advantage of better sealing of the bone-prosthesis interface by HA/TCP coating of implants, inhibiting polyethylene-induced osteolysis. One hundred patients gave informed consent to participate in a controlled randomized study between porous coated Trilogy versus Trilogy Calcicoat (HA/TCP coated). The cup was inserted in press-fit fixation. The femoral component was a cementless porous coated titanium alloy stem (Bi-Metric), with a modular 28-mm CrCo head. The Harris Hip Score (HHS) and bone mineral density (BMD) determined by DEXA scanning were used to study the effect. Measurements revealed no difference between the two groups after 3 years either in the clinical outcome or in terms of periprosthetic bone density. Patients with a body mass index above normal regained more bone mineral than patients with normal weight. This finding supports the assumption that load is beneficial to bone remodelling.
A partially fluorine substituted hydroxyapatite- (FHA-) coated Mg-Zn alloy was prepared to investigate the interfacial behavior of degradable Mg-based biomaterials with degradable bioactive coatings in a cell culture environment. Peaks from the results of X-ray diffraction (XRD) were characterized and compared before and after cell culture. It was found that Ca-P, including poorly crystalline ion-substituted Ca-deficient HA (CDHA), was formed in greater amounts on the interface of coated samples compared with the uncoated ones. A thermodynamic mechanism for Ca-P formation on biodegradable Mg alloys in a cell culture environment is proposed. Combined with improved cell calcification, the-FHA coated Mg alloys have the ability to promote CDHA formation, as expected thermodynamically. It is suggested that the specific cell culture environment and the bone-like FHA coatings together facilitate the observed behavior. Moreover, cell culture environment probably increased the biomineralization to a detectable level by affecting the kinetics of apatite formation.
Our primary aim was to compare the long‐term survivorship rates and the rates of successful osseointegration between two different types of uncemented acetabular components.
Two types of alloys have primarily been used for the manufacture of the uncemented acetabular components: titanium‐based and cobalt‐based alloys. A titanium‐based alloy appears to be more effective with regard to interface stress transfer to the host bone because of its lower elastic modulus relative to a cobalt‐based alloy. This supposed mechanical advantage of a titanium‐based alloy component motivated this comparative study.
Two uncemented acetabular components, a porous‐coated acetabulum and a Plasmacup®, were compared with a focus on long‐term prosthesis survivorship and the development of acetabular osseointegration. Five radiographic signs of osseointegration were evaluated at the last follow‐up appointment: (1) absence of radiolucent lines, (2) presence of a superolateral buttress, (3) medial stress‐shielding, (4) radial trabeculae, and (5) an inferomedial buttress. We considered the presence of any three of these radiographic signs, in the absence of acetabular dislocation or symptoms, to be indicative of successful acetabular osseointegration.
Among 70 patients implanted with the porous‐coated acetabulum, 80% achieved osseointegration over a mean follow‐up time of 11.9 years versus 75.3% of the 73 patients who received a Plasmacup insert over a mean of 10.7 years. Prosthesis survivorship rates were not different between the two groups. Revision surgery due to mild or severe acetabular osteolysis, polyethylene wear, and aseptic loosening occurred in eight patients (11.4%) with a PCA versus nine (12.3%) with a Plasmacup.
We conclude that, during the first ten years after surgery, there is no significant difference between these two types of uncemented cups with regard to either prosthesis survivorship or successful osseointegration.
Hip; Arthroplasty; Comparative study; Osseointegration; Porous‐coated acetabulum; Plasmacup®
Osteomyelitis therapy is a long-term and inconvenient procedure for a patient. Antibiotic-loaded bone cements are both a complementary and alternative treatment option to intravenous antibiotic therapy for the treatment of osteomyelitis. In the current study, the biphasic calcium phosphate cement (CPC), called α-TCP/HAP (α-tricalcium phosphate/hydroxyapatite) biphasic cement, was prepared as an antibiotics carrier for osteomyelitis. The developed biphasic cement with a microstructure of α-TCP surrounding the HAP has a fast setting time which will fulfill the clinical demand. The X-ray diffraction and Fourier transform infrared spectrometry analyses showed the final phase to be HAP, the basic bone mineral, after setting for a period of time. Scanning electron microscopy revealed a porous structure with particle sizes of a few micrometers. The addition of gentamicin in α-TCP/HAP would delay the transition of α-TCP but would not change the final-phase HAP. The gentamicin-loaded α-TCP/HAP supplies high doses of the antibiotic during the initial 24 hours when they are soaked in phosphate buffer solution (PBS). Thereafter, a slower drug release is produced, supplying minimum inhibitory concentration until the end of the experiment (30 days). Studies of growth inhibition of Staphylococcus aureus and Pseudomonas aeruginosa in culture indicated that gentamicin released after 30 days from α-TCP/HAP biphasic cement retained antibacterial activity.
New developments of antimicrobial implant surfaces doped with copper (Cu) ions may minimize the risk of implant-associated infections. However, experimental evaluation of the Cu release is influenced by various test parameters. The aim of our study was to evaluate the Cu release characteristics in vitro according to the storage fluid and surface roughness. Plasma immersion ion implantation of Cu (Cu-PIII) and pulsed magnetron sputtering process of a titanium copper film (Ti-Cu) were applied to titanium alloy (Ti6Al4V) samples with different surface finishing of the implant material (polished, hydroxyapatite and corundum blasted). The samples were submersed into either double-distilled water, human serum, or cell culture medium. Subsequently, the Cu concentration in the supernatant was measured using atomic absorption spectrometry. The test fluid as well as the surface roughness can alter the Cu release significantly, whereby the highest Cu release was determined for samples with corundum-blasted surfaces stored in cell medium.
Magnesium alloys as biodegradable metal implants in orthopaedic research received a lot of interest in recent years. They have attractive biological properties including being essential to human metabolism, biocompatibility, and biodegradability. However, magnesium can corrode too rapidly in the high-chloride environment of the physiological system, loosing mechanical integrity before the tissue has sufficiently healed. Hydroxyapatite (HAp) coating was proposed to decrease the corrosion rate and improve the bioactivity of magnesium alloy. Apatite has been cathodically deposited on the surface of Mg alloy from solution that composed of 3 mM Ca(H2PO4)2 and 7 mM CaCl2 at various applied potentials. The growing of HAp was confirmed on the surface of the coatings after immersion in SBF solution for 7 days. The coating obtained at −1.4 V showed higher corrosion resistance with bioactive behaviors.
Novel Ca-Si-Ti-based sphene (CaTiSiO5) ceramics possess excellent chemical stability and cytocompatibility. The aim of this study was to prepare sphene coating on titanium alloy (Ti-6Al-4V) for orthopaedic applications using the plasma spray method. The phase composition, surface and interface microstructure, coating thickness, surface roughness and bonding strength of the plasma-sprayed sphene coating were analysed using X-ray diffraction, scanning electron microscopy, atomic force microscopy and the standard mechanical testing of the American Society for Testing and Materials, respectively. The results indicated that sphene coating was obtained with a uniform and dense microstructure at the interface of the Ti-6Al-4V surface and the thickness and surface roughness of the coating were approximately 150 and 10 μm, respectively. Plasma-sprayed sphene coating on Ti-6Al-4V possessed a significantly improved bonding strength and chemical stability compared with plasma-sprayed hydroxyapatite (HAp) coating. Plasma-sprayed sphene coating supported human osteoblast-like cell (HOB) attachment and significantly enhanced HOB proliferation and differentiation compared with plasma-sprayed HAp coating and uncoated Ti-6Al-4V. Taken together, plasma-sprayed sphene coating on Ti-6Al-4V possessed excellent bonding strength, chemical stability and cellular bioactivity, indicating its potential application for orthopaedic implants.
plasma spraying; surface modification; sphene; osteoblasts; titanium alloy
The aim of the present study was to prepare hydroxyapatite (HA) and then characterize its effect on bone integration in a rabbit tibial defect model. The bone formation with different designs of HA was compared and the bony integration of several graft materials was investigated qualitatively by radiologic and histologic study.
Ten rabbits were included in this study; two holes were drilled bilaterally across the near cortex and the four holes in each rabbit were divided into four treatment groups (HAP, hydroxyapatite powder; HAC, hydroxyapatite cylinder; HA/TCP, hydroxyapatite/tri-calcium phosphate cylinder, and titanium cylinder). The volume of bone ingrowth and the change of bone mineral density were statistically calculated by computed tomography five times for each treatment group at 0, 2, 4, 6, and 8 weeks after grafting. Histologic analysis was performed at 8 weeks after grafting.
The HAP group showed the most pronounced effect on the bone ingrowth surface area, which seen at 4, 6, and 8 weeks after graft (p < 0.05). On comparing the change of bone mineral density the bone ingrowth surface area among the 4 groups, there were no statistically significant differences among the groups found for any period (p > 0.05). On histological examination, the HAP group revealed well-recovered cortical bone, but the bone was irregularly thickened and haphazardly admixed with powder. The HAC group showed similar histological features to those of the HA/TCP group; the cortical surface of the newly developed bone was smooth and the bone matrix on the surface of the cylinder was regularly arranged.
We concluded that both the hydroxyapatite powder and cylinder models investigated in our study may be suitable as a bone substitute in the rabbit tibial defect model, but their characteristic properties are quite different. In contrast to hydroxyapatite powder, which showed better results for the bone ingrowth surface, the hydroxyapatite cylinder showed better results for the sustained morphology.
Hydroxyapatite; Tibial defect; Bone union
Biphasic calcium phosphates comprising well-controlled mixtures of nonresorbable hydroxyapatite and other resorbable calcium phosphate phases often exhibit a combination of enhanced bioactivity and mechanical stability that is difficult to achieve in single-phase materials. This makes these biphasic bioceramics promising substrate materials for applications in bone tissue regeneration and repair. In this paper we report the synthesis of highly crystalline, biphasic coatings of hydroxyapatite/tetracalcium phosphate with control over the weight fraction of the constituent phases. The coatings were produced by pulsed laser deposition using ablation targets of pure crystalline hydroxyapatite. The fraction of tetracalcium phosphate phase in the coatings was controlled by varying the substrate temperature and the partial pressure of water vapor in the deposition chamber. A systematic study of phase composition in the hydroxyapatite/tetracalcium phosphate biphasic coatings was performed with X-ray diffraction. Tetracalcium phosphate in the coatings obtained at high substrate temperature is not formed by partial conversion of previously deposited hydroxyapatite. Instead, it is produced by nucleation and growth of tetracalcium phosphate itself from the ablation products of the hydroxyapatite target or by accretion of tetracalcium phosphate grains formed during ablation. This finding was confirmed by formation of calcium oxide, not tetracalcium phosphate, after annealing of pure hydroxyapatite coatings at high temperatures of 700–850 °C.
Bulk ultrafine grained (UFG)/nanocrystal metals possess exceptional strength but normally poor ductility and thermal stability, which hinder their practical applications especially in high-temperature environments. Through microalloying strategy that enables the control of grains and precipitations in nanostructured regime, here we design and successfully produce a highly microstructure-stable UFG Al-Cu-Sc alloy with ~275% increment in ductility and simultaneously ~50% enhancement in yield strength compared with its Sc-free counterpart. Although the precipitations in UFG alloys are usually preferentially occurred at grain boundaries even at room temperature, minor Sc addition into the UFG Al-Cu alloys is found to effectively stabilize the as-processed microstructure, strongly suppress the θ-Al2Cu phase precipitation at grain boundary, and remarkably promote the θ′-Al2Cu nanoparticles dispersed in the grain interior in artificial aging. A similar microalloying strategy is expected to be equally effective for other UFG heat-treatable alloys.
Doping an impure element with a larger atomic volume into crystalline structure of buck crystals is normally blocked because the rigid crystalline structure could not tolerate a larger distortion. However, this difficulty may be weakened for nanocrystalline structures. Diamonds, as well as many semiconductors, have a difficulty in effective doping. Theoretical calculations carried out by DFT indicate that vanadium (V) is a dopant element for the n-type diamond semiconductor, and their several donor state levels are distributed between the conduction band and middle bandgap position in the V-doped band structure of diamond. Experimental investigation of doping vanadium into nanocrystalline diamond films (NDFs) was first attempted by hot filament chemical vapor deposition technique. Acetone/H2 gas mixtures and vanadium oxytripropoxide (VO(OCH2CH2CH3)3) solutions of acetone with V and C elemental ratios of 1:5,000, 1:2,000, and 1:1,000 were used as carbon and vanadium sources, respectively. The resistivity of the V-doped NDFs decreased two orders with the increasing V/C ratios.
Nanocrystalline diamond; Vanadium dopant; Donor state levels; Structural distortion toleration