Bioactive coating on titanium implants modified by Nd:YVO4 laser

Apatite coating was applied on titanium surfaces modified by Nd:YVO₄ laser ablations with different energy densities (fluency) at ambient pressure and atmosphere. The apatites were deposited by biomimetic method using a simulated body fluid solution that simulates the salt concentration of bodily fluids. The titanium surfaces submitted to the fast melting and solidification processes (ablation) were immersed in the simulated body fluid solution for four days. The samples were divided into two groups, one underwent heat treatment at 600 °C and the other dried at 37 °C. For the samples treated thermally the diffractograms showed the formation of a phase mixture, with the presence of the hydroxyapatite, tricalcium phosphate, calcium deficient hydroxyapatite, carbonated hydroxyapatite and octacalcium phosphate phases. For the samples dried only the formation of the octacalcium phosphate and hydroxyapatite phases was verified. The infrared spectra show bands relative to chemical bonds confirmed by the diffraction analyses. The coating of both the samples with and without heat treatment present dense morphology and made up of a clustering of spherical particles ranging from 5 to 20 μm. Based on the results we infer that the modification of implant surfaces employing laser ablations leads to the formation of oxides that help the formation of hydroxyapatite without the need of a heat treatment.     

Influence of surface topography and pore architecture of alkali-treated titanium on in vitro apatite deposition

Alkali-treated titanium surfaces have earlier shown to induce bone-like apatite deposition. In the present study, the effect of surface topography of two-dimensional and pore architecture of three-dimensional alkali-treated titanium substrates on the in vitro bioactivity was investigated. Titanium plates with a surface roughness of R_a = 0.13 μm, 0.56 μm, 0.83 μm, and 3.63 μm were prepared by Al₂O₃ grit-blasting. Simple tetragonal and face-centered Ti6Al4V scaffolds with spatial gaps of 450-1100 μm and 200-700 μm, respectively, were fabricated by a three-dimensional fiber deposition (3DFD) technique. After alkali treatment, the titanium plates with a surface roughness of R_a = 0.56 μm were completely covered with hydroxyapatite globules after 7 days in simulated body fluid (SBF), while the coverage of the samples with other surface roughness values remained incomplete. Similarly, face-centered Ti₆Al₄ scaffolds with spatial gaps of 200-700 μm exhibited a full surface coverage after 21 days in SBF, while simple tetragonal scaffolds with spatial gaps of 450-1100 μm were only covered for 45-65%. This indicates the importance of surface topography and pore architecture for in vitro bioactivity.     

Assessment of strength properties of cemented paste backfill by ultrasonic pulse velocity test

Ultrasonic pulse velocity (UPV) test is one of the most popular non-destructive techniques used in the assessment of the mechanical properties of concrete or rock materials. In this study, the effects of binder type/dosage, water to cement ratio (w/c) and fines content (<20 μm) of the tailings on ultrasonic pulse velocity (UPV) of cemented paste backfill (CPB) samples were investigated and correlated with the corresponding unconfined compressive strength (UCS) data. A total of 96 CPB samples prepared at different mixture properties were subjected to the UPV and UCS tests at 7, 14, 28 and 56-days of curing periods. UPV and UCS of CPB samples of ordinary Portland cement (CEM I 42.5 R) and sulphate resistant cement (SRC 32.5) initially increased rapidly, but, slowed down after 14 days. However, UPV and UCS of CPB samples of the blast furnace slag cement (CEM III/A 42.5 N) steadily increased between 7 and 56 days. Increasing binder dosage or reducing w/c ratio and fines content (<20 μm) increased the UCS and UPV of CPB samples. UPV was found to be particularly sensitive to fines content. UCS data were correlated with the corresponding UPV data. A linear relation appeared to exist between the UCS and UPV of CPB samples. These findings have demonstrated that the UPV test can be reliably used for the estimation of the strength of CPB samples.     

Bioactive glass thin films deposited by magnetron sputtering technique: The role of working pressure

Bioglass coatings were prepared by radio frequency magnetron sputtering deposition at low temperature (150 °C) onto silicon substrates. The influence of argon pressure values used during deposition (0.2 Pa, 0.3 Pa and 0.4 Pa) on the short-range structure and biomineralization potential of the bioglass coatings was studied. The biomineralization capability was evaluated after 30 days of immersion in simulated body fluid. SEM-EDS, XRD and FTIR measurements were performed. The tests clearly showed strong biomineralization features for the bioglass films. The thickness of the chemically grown hydroxyapatite layers was more than twice greater for the BG films deposited at the highest working pressure, in comparison to those grown on the films obtained at lower working pressures. The paper attempts to explain this experimental fact based on structural and compositional considerations.     

Investigation of the surface reactivity of a sol-gel derived glass in the ternary system SiO2-CaO-P2O5

A new glass formulation, with the molar composition 60% SiO₂-35% CaO-5% P₂O₅, was synthesized using the sol-gel process, for applications as biomaterial in orthopaedic or maxillo facial surgery. Pellets, made of glass powder, were uniaxially compacted and soaked in simulated body fluid (SBF) for up to 7 days at 37 °C to evaluate glass bioactivity. Ionic exchanges at the interface glass-SBF were evaluated by studying evolutions of calcium, phosphorus and silicon concentrations in SBF using ICP-OES. Changes in glass surface, and the formation of crystalline phases were analyzed using XRD, SEM, EDS and FTIR methods.Results form ICP-OES showed a high reactivity of the glass surface with a very high and continuous release of calcium, a limited glass dissolution and an uptake of phosphorous from SBF. Results from both FTIR and XRD analysis indicated that the glass surface was progressively covered by two different phases: CaCO₃ as calcite and a carbonated apatite layer. The formation of these phases, following two different schemas, was observed after 2 h of immersion and confirmed after 7 days. SEM micrographs and EDS analysis demonstrated that the main phase, a carbonated apatite, was present as micro-spheroids and the secondary phase, calcite, was materialized by agglomerates which have diameters up to 10-15 μm. These results are in accordance with a bioactive feature of the glass studied.     

The role of target-to-substrate distance on the DC magnetron sputtered zirconia thin films’ bioactivity

Zirconium dioxide thin films were deposited on 316L-stainless steel type substrates using DC unbalanced magnetron sputtering. The process parameter of this work was the target-to-substrate distance (d_t-s), which was varied from 60 to 120 mm. The crystal structure and surface topography of zirconium dioxide thin films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). The results demonstrate that all of the ZrO₂ thin films are composed monoclinic phase. The film sputtered at short d_t-s (60 mm) shows a rather heterogeneous, uneven surface. The grain size, roughness, and thickness of thin films were decreased by increasing d_t-s. The bioactivity was assessed by investigating the formation of hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) on the thin film surface soaked in simulated body fluids (SBF) for 7 days. XRD and scanning electron microscopy (SEM) were used to verify the formation of apatite layers on the samples. Bone-like apatites were formed on the surface of the ZrO₂ thin film in SBF immersion experiments. A nanocrystalline hydroxyapatite (HA) with a particle size of 2-4 μm was deposited. Higher crystallinity of HA on the surface was observed when the distance d_t-s increased to more than 80 mm. Therefore, it seems that a d_t-s greater than 80 mm is an important sputtering condition for inducing HA on the zirconia film.     

Characterization and corrosion behavior of hydroxyapatite/zirconia composite coating on NiTi fabricated by electrochemical deposition

NiTi alloy is used as biomaterial due to its unique properties, but the high content of Ni (about 50 at.%) in biomedical NiTi is concerned. Hydroxyapatite and hydroxyapatite/zirconia composite coatings were directly electrodeposited on NiTi alloy surface. The coated samples were characterized using X-ray diffraction, scanning electron microscopy, infrared spectroscopy, bonding strength test, polarization and EIS. Results showed that when ZrO₂ was added into the electrolyte, morphology of HAP was changed from thin flake-flower-like crystals to needle-flower-like crystals, and coating was denser. Besides, HAP crystal grains in the coating were preferentially arranged in the [0 0 1] direction. Addition of ZrO₂ could improve the bonding strength between the coating and the substrate. Corrosion resistance of NiTi in the simulated body fluid at 37 °C was significantly improved by almost 60 times by electrodeposition of the hydroxyapatite/zirconia composite coating.     

In vitro biological performance of nano-particles on the surface of hydroxyapatite coatings

The biocompatibility of a kind of heat-treated bilayer hydroxyapatite (HA) coatings with nano-particles was investigated, mainly in terms of the immersion in simulated body fluid (SBF) and osteoblast adhesion. Scanning electron microscopy (SEM) was used to observe the morphology of coatings and cellular adhesion. The phases present in the coatings were determined by X-ray diffraction (XRD). Calcium ion (Ca²⁺) concentration in SBF was measured by Atomic absorption spectrophotometer. The results show nano-HA heat-treated at 650 °C for 0.5 h (BBCs) is comparatively stable during immersion in SBF and favor of the adhesion of osteoblasts. Cellular filopodia adhere firmly to the nano-particles and stretch in various direction.     

Sub-gigahertz laser resonant ultrasound spectroscopy for the evaluation of elastic properties of micrometric fibers

The cross-section eigenmodes of micrometric cylinders were measured in the range of several tens of MHz to about 0.5 GHz. The vibrations were excited using subnanosecond laser pulses. The cross-section eigenmodes were simulated using finite element modeling in a 2D geometry. Using the method of resonant ultrasound spectroscopy, the vibration spectrum of an aluminum wire of diameter 33μm served to determine Young’s modulus and Poisson’s ratio with a precision of 0.7% and 0.3%, respectively. The calculated and measured frequencies of cross-section eigenmodes were fitted with a precision better than 0.5% in the 50–500 MHz range.     

Evolution of magnetic and microstructural properties of thick sputtered NdFeB films with processing temperature

Ta (100 nm)/NdFeB (5 μm)/Ta (100 nm) films have been deposited onto Si substrates using triode sputtering (deposition rate ∼18 μm/h). A 2-step procedure was used: deposition at temperatures up to 400 °C followed by ex-situ annealing at higher temperatures. Post-deposition annealing temperatures above 650 °C are needed to develop high values of coercivity. The duration of the annealing time is more critical in anisotropic samples deposited onto heated substrates than in isotropic samples deposited at lower temperatures. For a given set of annealing conditions (750 °C/10′), high heating rates (?2000 °C/h) favour high coercivity in both isotropic and anisotropic films. The shape and size of Nd₂Fe₁₄B grains depend strongly on the heating rate.     

Bioactivity of SiO2-CaO-P2O5-Na2O glasses containing zinc-iron oxide

Glasses with composition x(ZnO,Fe₂O₃)(65 − x)SiO₂20(CaO,P₂O₅)15Na₂O (6 ≤ x ≤ 21 mol%) were prepared by melt-quenching technique. Bioactivity of the glasses was investigated in vitro by examining apatite formation on the surface of glasses treated in acellular simulated body fluid (SBF) with ion concentrations nearly equal to those in human blood plasma. Formation of bioactive apatite layer on the samples treated in SBF was confirmed by using Fourier transform infrared reflection (FTIR) spectroscopy, grazing incidence X-ray diffraction (GI-XRD) and scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer. Development of an apatite structure on the surface of the SBF treated glass samples as functions of composition and time could be established using the GI-XRD data. FTIR spectra of the glasses treated in SBF show features at characteristic vibration frequencies of apatite after 1-day of immersion in SBF. SEM observations revealed that the spherical particles formed on the glass surface were made of calcium and phosphorus with the Ca/P molar ratio being close to 1.67, corresponding to the value in crystalline apatite. Increase in bioactivity with increasing zinc-iron oxide content was observed. The results have been used to understand the evolution of the apatite surface layer as a function of glass composition and immersion time in SBF.     

Second-order optical nonlinearity in thermally poled Pyrex borosilicate glass

The thermal poling method was utilized to create second-order optical nonlinearity in Pyrex borosilicate glass. The distribution and amplitude of the induced nonlinearity were characterized with second harmonic microscopy. The induced optical nonlinearity was found in a thin layer around 1.9 μm under the anode surface with a magnitude as high as 0.24 pm/V, comparable to that observed in fused silica samples. SEM observation of the cross-section of the poled glass region, after it had been etched in diluted hydrofluoric acid for several minutes, revealed an etched trench, ∼1.8 μm under the anode edge and ∼0.3 μm in width; while in post-annealed samples, no such etched trench could be observed. The effect of poling voltage on the magnitude of the induced nonlinearity was also studied, where the results showed that higher poling voltage resulted in higher nonlinearity with a threshold of ∼0.9 kV.     

Influence of the calcium phosphate content of the target on the phase composition and deposition rate of sputtered films

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.     

Bioglass thin films for biomimetic implants

Pulsed laser deposition (PLD) method was used to obtain bioglass (BG) thin film coatings on titanium substrates. An UV excimer laser KrF* (λ = 248 nm, τ = 25 ns) was used for the multi-pulse irradiation of the BG targets with 57 or 61 wt.% SiO₂ content (and Na₂O-K₂O-CaO-MgO-P₂O₅ oxides). The depositions were performed in oxygen atmosphere at 13 Pa and for substrates temperature of 400 °C. The PLD films displayed typical BG of 2-5 μm particulates nucleated on the film surface or embedded in. The PLD films stoichiometry was found to be the same as the targets. XRD spectra have shown, the glass coatings obtained, had an amorphous structure. One set of samples, deposited in the same conditions, were dipped in simulated body fluids (SBFs) and subsequently extracted one by one after several time intervals 1, 3, 7, 14 and 21 days. After washing in deionized water and drying, the surface morphology of the samples and theirs composition were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), IR spectroscopy (FTIR) and energy dispersive X-ray analysis (EDX). After 3-7 days the Si content substantially decreases in the coatings and PO₄³⁻ maxima start to increase in FTIR spectra. The XRD spectra also confirm this evolution. After 14-21 days the XRD peaks show a crystallized fraction of the carbonated hydroxyapatite (HAP). The SEM micrographs show also significant changes of the films surface morphology. The coalescence of the BG droplets can be seen. The dissolution and growth processes could be assigned to the ionic exchange between BG and SBFs.     

Influences of Bi2O3 additive on the microstructure, permeability, and power loss characteristics of Ni-Zn ferrites

Nickel-zinc ferrite materials containing different Bi₂O₃ concentrations have been prepared by the conventional ceramic technique. Micrographs have clearly revealed that the Bi₂O₃ additive promoted grain growth. When the Bi₂O₃ content reached 0.15 wt%, a dual microstructure with both small grains (<5 μm) and some extremely large grains (>50 μm) appeared. With higher Bi₂O₃ content, the samples exhibited a very large average grain size of more than 30 μm. The initial permeability gradually decreased with increasing Bi₂O₃ content. When the Bi₂O₃ content exceeded 0.15 wt%, the permeability gradually decreased with frequency due to the low-frequency resonance induced by the large grain size. Neither the sintering density nor the saturation magnetization was obviously influenced by the Bi₂O₃ content or microstructure of the samples. However, power loss (Pcv) characteristics were evidently influenced. At low flux density, the sample with 0.10 wt% Bi₂O₃, which was characterized by an average grain size of 3-4 μm and few closed pores, displayed the lowest Pcv, irrespective of frequency. When the flux density was equal to or greater than the critical value of 40 mT, the sample with 0.20 wt% Bi₂O₃, which had the largest average grain size, displayed the lowest Pcv.     

Bioactivity and cytocompatibility of dicalcium phosphate/poly (amino acid) biocomposite with degradability

A bioactive composite of dicalcium phosphate (DCP) and poly (amino acid) (PAA) was fabricated, and the in vitro bioactivity, degradability, and cellular responses to the DCP/PAA composite (DPC) were investigated as compared to PAA. Apatite formation on DPC surfaces occurred after immersion into simulated body fluid (SBF) for 7 days, but not on the surface of PAA. The weight loss ratio of DPC could reach 18.6 ± 0.3 wt% after soaking into phosphate buffered saline (PBS) for 2 months, which was higher than PAA (11.0 ± 0.2 wt%). Cell attachment and proliferation of MG-63 cells on DPC was obviously higher than on PAA. Moreover, the cells spread and formed confluent layer on the DPC surfaces. The alkaline phosphatase activity (ALP) of the cells on DPC was significantly greater than PAA at day 5 and day 7. The results suggested that introducing DCP into PAA makes the composite bioactive and more degradable, and meanwhile enhances osteoblast-like cells attach, proliferation and osteogenic differentiation.     

Variation of microstructure with carbonation in lime and blended pastes

Carbonation, as a reaction of the curing process of both, cement and lime binders, modifies the microstructure. Several microstructure properties, namely porosity, pore size distribution, surface fractal dimension, and specific surface area have been investigated in this study to describe the effect of carbonation on microstructure. Both carbonated and non-carbonated pastes of lime and blended pastes of lime and cement having varying water/binder (W/B) ratios are studied. Results show that carbonation decreases the porosity, but not with the same intensity in all pore size ranges. The highest modification is between 0.03 μm and 0.01 μm in lime pastes and between 0.2 μm and 0.02 μm in 50% lime pastes, while in 80% lime pastes the modification is very small. It is also observed that carbonation is a function of the binder composition but not of the W/B ratio. Moreover, surface fractal dimension decreases during the carbonation process, while the specific surface area varies depending of the binder composition.     

Low temperature perovskite phase formation in PCT 90/10 system by modified chemical route

Perovskite phase development study of PCT 90/10 system was carried out. Modified chemical technique was used for synthesis. Single perovskite phase with a polycrystalline tetragonal structure was obtained in PCT 90/10 ceramic system at 600 °C processing temperature. Dense packing of grains with average grain size ∼1 μm was observed in PCT 90/10 ceramic samples. Curie transition temperature (T_c) of PCT 90/10 ceramic samples was found to be ∼180 °C with diffuse phase transition.     

Synthesis of zinc oxide nanosheet thin films and their improved field emission and photoluminescence properties by annealing processing

ZnO nanosheet thin films have been synthesized through a solvothermal route. These obtained nanosheets disperse quasi-vertically and homogenously on the copper substrates and range in thickness from 80 nm to 250 nm. The as-grown nanosheet thin films were then annealed in the oxygen-presented atmosphere. Field emission plots indicate that the value of turn-on field is reduced from 2.86 V/μm to 1.52 V/μm and the corresponding value of threshold field decreases from 7.19 V/μm to 4.45 V/μm after annealing processing. Room temperature photoluminescence spectrum from the sample annealed at 850 °C in almost pure oxygen atmosphere shows only UV emission and a blue shift while the visible light band is unobservable compared with those of the other two samples, indicating that the crystalline quality of the obtained zinc oxide nanosheet thin films is greatly improved through annealing treatment. This solution approach combined with annealing treatment can, therefore, be regarded as a convenient route to fabricate high-quality crystalline ZnO nanomaterials.     

Influence of particle size and compaction pressure on the magnetic properties of iron-phenolic soft magnetic composites

This paper investigates the effect of particle size and compaction pressure on the magnetic properties of iron-phenolic soft magnetic composites (50 Hz-1000 kHz). The results showed that the optimum amount of phenolic resin to attain maximum permeability and minimum loss factor at 10 kHz is 0.7 wt% for samples containing iron powder with average particle size ∼150 μm compacted at 800 MPa. In accordance with this resin content, at high frequencies (>300 kHz), the sample with lower particle size ∼10 μm exhibits higher magnetic permeability, higher operating frequencies and lower imaginary part of permeability. With increase in the compaction pressure, specific resistivity decreases and imaginary and real parts of permeability increase at low frequencies.