Enhanced corrosion resistance of Zr coating on biomedical TiNi alloy prepared by plasma immersion ion implantation and deposition

Zirconium film was prepared on TiNi alloy by plasma immersion ion implantation and deposition (PIIID) technique to enhance its corrosion resistance and prolong its working lifetime. The atomic force microscopy (AFM) results show that the film was relatively smooth with the root mean square roughness being 9.166 nm. The X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) results indicate that the implant element of Zr was oxidation partialness. The potentiodynamic polarization measurements in the Hank's solution at 37 °C show that the corrosion resistance of the alloy was improved by the Zr coating film and the atomic absorption spectrometry (AAS) tests also indicate that Ni ion concentration released from the substrate in the Hank's solution after the polarization test was reduced greatly, in comparison to the unmodified TiNi alloy sample.     

Inhomogeneity of calcium phosphate coatings deposited by laser ablation at high deposition rate

Calcium phosphate coatings were deposited with a KrF excimer laser onto titanium alloy to study their homogeneity. Deposition was performed at a high deposition rate under a water vapour atmosphere of 45 Pa and at a substrate temperature of 575 °C. Samples were also submitted to annealing under the same conditions of deposition for different times just after deposition. The effects of the annealing were also investigated. The morphology of the coatings was studied by scanning electron microscopy. Their structure and phase distribution was analysed by X-ray diffractometry and infrared and micro-Raman spectroscopies. Besides the non-uniform thickness, the results reveal an inhomogeneity in the spatial distribution of calcium phosphate phases in the coatings. The phase distribution can be almost completely correlated with the deposition rate. High deposition rates (0.5 nm/pulse) occurring in the centre of deposition results in the formation of amorphous calcium phosphate, while lower deposition rates favour the presence of hydroxyapatite and alpha tricalcium phosphate. At intermediate deposition rates, beta tricalcium phosphate is found, probably because the superimposed effect of energetic particles bombardment. The annealing process promotes the crystallisation of the amorphous material. The importance of the deposition rate in the phases obtained is stated after comparing these results with a previous work where homogeneous hydroxyapatite coatings were obtained under the same conditions of laser fluence, temperature and pressure, but at lower deposition rates. Received: 22 November 2001 / Accepted: 12 March 2002 / Published online: 5 July 2002 RID="*" ID="*"Corresponding author. Fax: +34-93/402-1138, E-mail: jmfernandez@fao.ub.es     

Induction of osteoconductivity by BMP-2 gene modification of mesenchymal stem cells combined with plasma-sprayed hydroxyapatite coating

Success in bone implant depends greatly on the composition and surface features of the implant. The surface-modification measures not only favor the implant's osteoconductivity, but also promote both bone anchoring and biomechanical stability. This paper reports an approach to combine a hydroxyapatite (HA) coated substrate with a cellular vehicle for the delivery of bone morphogenetic protein-2 (BMP-2) synergistically enhancing the osteoconductivity of implant surfaces. We examined the attachment, growth and osteoinductive activity of transfected BMP-producing bone marrow mesenchymal stem cells (BMSCs) on a plasma-sprayed HA coated substrate. It was found that the HA coated substrate could allow the attachment and growth of BMP-2 gene modified BMSCs, and this combined application synergistically enhanced osteconductivity of the substrate surface. This synergistic method may be of osseointegration value in orthopedic and dental implant surgery.     

Attachment, proliferation and differentiation of BMSCs on gas-jet/electrospun nHAP/PHB fibrous scaffolds

In this study, poly(3-hydroxybutyrate) (PHB)-based scaffolds containing nanosized hydroxyapatite (nHAP) were manufactured by gas-jet/electrospinning. The morphologies of the scaffolds were characterized. The effect of the scaffolds on attachment, proliferation and differentiation of the bone marrow stroma cells (BMSCs) were accessed by using scanning electron microscopy (SEM), methylthiazol tetrazolium (MTT) assay and alkaline phosphatase (ALP) activity. The results show that the gas-jet/electrospun scaffolds possess an extracellular matrix-like topography. In vitro studies describe that the scaffolds have positive effects on attachment, proliferation and differentiation of BMSCs in vitro. It can be concluded that the scaffolds combing the unique structural features generated by gas-jet/electrospinning with functional factors, have the potential to be used in bone tissue engineering.     

Microstructure and osteoblast response of gradient bioceramic coating on titanium alloy fabricated by laser cladding

To construct a bioactive interface between metal implant and the surrounding bone tissue, the gradient calcium phosphate bioceramic coating on titanium alloy (Ti-6Al-4V) was designed and fabricated by laser cladding. The results demonstrated that the gradient bioceramic coating was metallurgically bonded to the titanium alloy substrate. The appearance of hydroxyapatite and β-tricalcium phosphate indicated that the bioactive phases were synthesized on the surface of coating. The microhardness gradually decreased from the coating to substrate, which could help stress relaxation between coating and bone tissue. Furthermore, the methyl thiazolyl tetrazolium (MTT) assay of cell proliferation revealed that the laser-cladded bioceramic coating had more favorable osteoblast response compared with the surface of untreated titanium alloy substrate.     

Controlling cell-material interactions with polymer nanocomposites by use of surface modifying additives

Polymer nanocomposites (NC) are fabricated by incorporating well dispersed nanoscale particles within a polymer matrix. This study focuses on elastomeric polyurethane (PU) based nanocomposites, containing organically modified silicates (OMS), as bioactive materials. Nanocomposites incorporating chlorhexidine diacetate as an organic modifier (OM) were demonstrated to be antibacterial with a dose dependence related to both the silicate loading and the loading of OM. When the non-antibacterial OM dodecylamine was used, both cell and platelet adhesion were decreased on the nanocomposite surface. These results suggest that OM is released from the polymer and can impact on cell behaviour at the interface. Nanocomposites have potential use as bioactive materials in a range of biomedical applications.     

Preparation and characterization of the sol-gel nano-bioactive glasses modified by the coupling agent gamma-aminopropyltriethoxysilane

The sol-gel derived bioactive glasses (SBG) have been used in bone-tissue engineering because of their excellent biocompatibility and osteoconductivity. In this study, nano-SBG was successfully achieved through a wet mechanical grinding technique, and to further improve its dispersibility and cells proliferation, a silane coupling agent was coupled onto the surface of nano-SBG. Gamma-aminopropyltriethoxysilane (APTES) was used to the surface modification of the nano-SBG (60 mol%SiO₂, 36 mol%CaO, 4 mol%P₂O₅) by a wet-chemical method in a dynamic inert nitrogen atmosphere. The surface properties of the biomaterials before and after modification were characterized and compared using FTIR and XPS. The characteristic peaks in FTIR spectra indicated that -CH₂CH₃ and -NH₂ groups appeared on the surface of modified nano-SBG, and also, XPS spectra analysis revealed that nitrogen element was detected and carbon concentration increased on the surface of nano-SBG after modification. The above analysis proved that the desired groups of APTES had been covalently bonded onto the surface of nano-SBG.     

Cellular reactions of osteoblast-like cells to a novel nanocomposite membrane for guided bone regeneration

This study investigated the bioactivity and biocompatibility of hydroxyapatite nanoparticles (n-HA)/Polyamide-66 (PA66) nanocomposite membrane and expanded-polytetrafluoroethylene (e-PTFE) membrane (as control) to MG63 osteoblast-like cells. The attachment and proliferation of the cells on the porous surface of nHA/PA66 membrane and the surface of e-PTFE membrane were evaluated by scanning electron microscope (SEM) observation and the MTT assay. The bioactivity of the cells on the surface of the two membranes was evaluated by testing cell viability and alkaline phosphatase (ALP) activities. The results suggested that the bioresponse of MG63 osteoblast-like cells on the porous surface of nHA/PA66 membrane was better than the bioresponse on the opposite surface of e-PTFE membrane. Because of a better cell attachment manner, there is a potential utilization of the guided bone regeneration (GBR) membrane to substitute nHA/PA66 membrane for e-PTFE membrane.     

Synthesis and bioactivity of highly ordered TiO2 nanotube arrays

The highly ordered TiO₂ nanotube arrays were fabricated by potentiostatic anodization of Ti foils in fluorinated dimethyl sulfoxide (DMSO). TiO₂ nanotube arrays are formed using a 40 V anodization potential for 24 h, with a length of 12 μm, diameter of 170 nm and aspect ration of about 70. The as-prepared nanotubes are amorphous, but can be crystallized as the heat treatment temperature increases. Anatase phase appears at a temperature of about 300 °C, then transforms to rutile phase at about 600 °C. After heat treatment at 500 °C and soaking in SBF for 14d, a thick apatite layer of about 13 μm covers the whole surface of TiO₂ nanotube arrays, indicating their excellent in vitro bioactivity, which is mainly attributed to their high specific surface area and the anatase phase.     

Investigation on bio-mineralization of melt and sol-gel derived bioactive glasses

The bio-mineralization properties of the melt-derived bioactive glass 45S5 and the sol-gel derived bioactive glasses 58S and 77S were investigated and compared using in vitro test combined with BET, XRD, FTIR and SEM techniques. It was found that the surfaces of the three bioactive glasses could be mineralized by immersion in a simulated body fluid (SBF) at 37 °C for several hours. The bio-mineralized products on the surfaces of the bioactive glasses were apatite microcrystals with a low crystallinity, but the composition and morphologies of the apatite microcrystals on three glasses were different.     

Bioactivity of Mg-ion-implanted zirconia and titanium

Titanium and zirconia are bioinert materials lacking bioactivity. In this work, surface modification of the two typical biomaterials is conducted by Mg-ion-implantation using a MEVVA ion source in an attempt to increase their bioactivity. Mg ions were implanted into zirconia and titanium with fluences ranging from 1 × 10¹⁷ to 3 × 10¹⁷ ions/cm² at 40 keV. The Mg-implanted samples, as well as control (unimplanted) samples, were immersed in SBF for 7 days and then removed to identify the presence of calcium and phosphate (Ca-P) coatings and to characterize their morphology and structure by SEM, XRD, and FT-IR. SEM observations confirm that globular aggregates are formed on the surfaces of the Mg-implanted zirconia and titanium while no precipitates are observed on the control samples. XRD and FT-IR analyses reveal that the deposits are carbonated hydroxyapatite (HAp). Our experimental results demonstrate that Mg-implantation improves the bioactivity of zirconia and titanium. Further, it is found that the degree of bioactivity is adjustable by the ion dose. Mechanisms are proposed to interpret the improvement of bioactivity as a result of Mg implantation and the difference in bioactivity between zirconia and titanium.     

Improving the bioactivity of NiTi shape memory alloy by heat and alkali treatment

TiO₂ films were formed on an NiTi alloy surface by heat treatment in air at 600 °C. Heat treated NiTi shape memory alloys were subsequently alkali treated with 1 M, 3 M and 5 M NaOH solutions respectively, to improve their bioactivity. Then treated NiTi samples were soaked in 1.5SBF to evaluate their in vitro performance. The results showed that the 3 M NaOH treatment is the most appropriate method. A large amount of apatite formed within 1 day's soaking in 1.5SBF, after 7 day's soaking TiO₂/HA composite layer formed on the NiTi surface. SEM, XRD, FT-IR and TEM results showed that the morphology and microstructure are similar to the human bone apatite.     

Effects of anodizing conditions on bond strength of anodically oxidized film to titanium substrate

The bond strength of the oxide film to the titanium substrate and its inherent structural characteristics are very important preconditions for the success of titanium implants. The purpose of this study was to evaluate the micro-morphologies, crystalline structures, and bond strengths of the anodically oxidized films formed on titanium with the variation of electrolytes and applied current densities. In contrast to the specimens produced using sulfuric acid as the electrolyte, those produced using phosphoric acid showed quite different shapes and densities of the pores as the applied current densities were varied. The oxide films anodized in sulfuric acid consisted of anatase and rutile TiO₂, whileTiP₂O₇ was predominantly formed on the Ti surfaces anodized using phosphoric acid as the electrolyte. The oxide films, which did not experience spark deposition showed amorphous shape and their bond strengths were significantly lower than those of the other groups (p < 0.05). Those specimens which experienced initial spark deposition with a low current condition showed the highest bond strengths (34.2 MPa) within each electrolyte sub-set. The growing rates of the oxide film thicknesses in relation to the electric current changes varied according to the type of electrolyte, and the oxide film thickness influenced the bond strength.     

Characterization and human gingival fibroblasts biocompatibility of hydroxyapatite/PMMA nanocomposites for provisional dental implant restoration

The aim of this study was to determine nHA/PMMA composites (H/P) in an optimal ratio with improved cytocompatibility as well as valid physical properties for provisional dental implant restoration. 20 wt.%, 30 wt.%, 40 wt.% and 50 wt.% H/P were developed and characterized using XPS, bending strength test and SEM. Human gingival fibroblasts cultured in extracts or directly on sample discs were investigated by fluorescent staining and MTT assay. Chemical integration in nHA/PMMA interface was indicated by XPS. Typical fusiform cells with adhesion spots were detected on H/P discs. MTT results also indicated higher cell viability in 30 wt.% and 40 wt.% H/P discs (P < 0.05). We conclude that nHA addition to PMMA enhances cytocompatibility and the optimal nHA/PMMA ratio for provisional fixed crowns (PFC) is 0.4:1.     

The effect of chemical treatment on apatite-forming ability of the macroporous zirconia films formed by micro-arc oxidation

Macroporous and nano-crystalline zirconia film was prepared by micro-arc oxidation (MAO) of zirconium, and the effect of chemical treatment in H₂SO₄ or NaOH aqueous solutions on the microstructure and apatite-forming ability of the film was investigated. Compared with the MAO film, the chemically treated films do not exhibit apparent changes in phase component, morphology and grain size, however, have more abundant basic Zr-OH groups. The films treated with H₂SO₄ and NaOH solutions can induce apatite formation on their surfaces in simulated body fluids (SBF) within 1 day, whereas no apatite was detected on the untreated ZrO₂ surface by 30 days. It is believed that the enhanced apatite-forming ability of the chemically treated ZrO₂ films is related to the abundant basic Zr-OH groups on their surface.     

Preparation and antibacterial effect of plasma sprayed wollastonite coatings loading silver

In this work, the plasma sprayed wollastonite coating was soaked in 5 wt% AgNO₃ solution at room temperature to load silver for improving its antibacterial effect. The surface characteristics of the silver-loaded coating were investigated by SEM, EDS and XRD. The release rate of silver from the coating was measured by ICP-OES in deionized water. The osteotoxicity of the silver-loaded coating was evaluated by in vitro cell culturing test. The antibacterial activity against Staphylococcus aureus was examined by Zone of Inhibition test. The results showed that the loaded silver reacted with the wollastonite coating to form silver silicate, which ensured a sustained release of silver in deionized water for as long as 50 days. The antibacterial activity and cell culturing tests confirmed that the silver released from silver-loaded wollastonite coating had strong inhibition against the growth of S. aureus, while they did not exhibit any adverse effects on the osteoblasts proliferation.     

Application of positron annihilation spectroscopy on the ion implantation damaged Fe-Cr alloys

Four different Fe-Cr binary alloys with Cr content 2.5-11 wt% were studied in details using various methods. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were applied to obtain basic information, required for standard positron annihilation lifetime spectroscopy (PALS) spectra analysis. Additionally, PALS measurements were performed on as-received state as well as on helium implanted specimens. The He implantation was proposed for simulation of radiation damage and obtain high doses even in near surface areas (up to 1 μm). The implantation was based on the SRIM code simulation and next DPA calculations. Final concentration of vacancy type defects were calculated for 250 keV He²⁺ beam and the maximum was determined in 600 μm depth. Such specimens are very suitable for positron beam study of vacancy type defect mobility as a result of thermal treatment, which will be performed simultaneously in the future.     

Influence of zinc ion implantation on surface nanomechanical performance and corrosion resistance of biomedical magnesium-calcium alloys

It is believed that magnesium and its alloys may find applications in biomedical fields as implants, bone fixation devices, and tissue engineering scaffolds. However, their corrosion rate must be controlled. In this study, biomedical magnesium-calcium (Mg-Ca) alloys were ion-implanted with zinc. The surface nanomechanical performance and corrosion behavior of the ion-implanted Mg-Ca alloys are determined. The results show that zinc ion implantation at a dose of 0.9 × 10¹⁷ ions/cm² significantly improves the surface hardness and modulus. However, the results on corrosion resistance reveal that zinc ion implantation degrades the corrosion behavior of Mg-Ca alloys. Thus, zinc is not a favorable element for the ion implantation treatment of biomedical Mg-Ca alloys.     

Electrochemical oxidation of La2CuO4 thin films grown by molecular beam epitaxy

Thin insulating and c-axis oriented films of La₂CuO₄ are grown using a molecular beam epitaxy technique. Subsequently, these films are oxidized electrochemically using a 1N KOH solution. This approach is used to induce superconductivity, leading to a maximum T_c0 of 31 K,, measured both resistively and inductively. The surface morphology, lattice constants and the resistivity before and after the electrochemical treatment are compared.     

Thin zirconium nitride films prepared by plasma-enhanced CVD

Thin films of zirconium nitride have been deposited at temperatures as low as 573 K by PECVD using tetrakis(diethylamido)zirconium, Zr[N(C₂H₅)₂]₄ as precursor. The influence of the various experimental parameters on film properties and deposition rates has been studied. Under most experimental conditions hard coatings of good adherence and low carbon contamination resulted.