Silicon-substituted hydroxyapatite composite coating by using vacuum-plasma spraying and its interaction with human serum albumin

The incorporation of silicon can improve the bioactivity of hydroxyapatite (HA). Silicon-substituted HA (Ca₁₀(PO₄)_6−x (SiO₄) _x (OH)_2−x , Si-HA) composite coatings on a bioactive titanium substrate were prepared by using a vacuum-plasma spraying method. The surface structure was characterized by using XRD, SEM, XRF, EDS and FTIR. The bond strength of the coating was investigated and XRD patterns showed that Ti/Si-HA coatings were similar to patterns seen for HA. The only different XRD pattern was a slight trend toward a smaller angle direction with an increase in the molar ratio of silicon. FTIR spectra showed that the most notable effect of silicon substitution was that –OH group decreased as the silicon content increased. XRD and EDS elemental analysis indicated that the content of silicon in the coating was consistent with the silicon-substituted hydroxyapatite used in spraying. A bioactive TiO₂ coating was formed on an etched surface of Ti, and the etching might improve the bond strength of the coatings. The interaction of the Ti/Si-HA coating with human serum albumin (HSA) was much greater than that of the Ti/HA coating. This might suggest that the incorporation of silicon in HA can lead to significant improvements in the bioactive performance of HA.     

An interfacial study of sol-gel-derived magnesium apatite coatings on Ti6Al4V substrates

Magnesium apatite coatings on Ti6Al4V substrate were synthesized by the sol-gel dip-coating method. Magnesium was incorporated in the coating according to the formula (Ca_10−xMg_x)(PO₄)₆(OH)₂, where x = 0, 0.50, 1.00, 1.50 and 2.00. Approximately 2-μm-thick apatite coatings were derived after five cycles of dip-drawing-drying-firing process. A transitional region (R_t) was formed between substrate and coating during the firing process. Adhesion tests show that the adhesion strength between substrate and apatite coating is enhanced by the incorporation of magnesium in the coating. The quantity of magnesium incorporated appeared to correspond to the Mg-Ti-O chemical bonds formed in the transitional region, which contributed to the adhesion strength of the coatings.     

Processing, physico-chemical characterisation and in vitro evaluation of silicon containing β-tricalcium phosphate ceramics

For bone grafting applications, the elaboration of silicon containing beta-tricalcium phosphate (β-TCP) was studied. The synthesis was performed using a wet precipitation method according to the hypothetical theoretical formula Ca_3 − x(PO₄)_2 − 2x(SiO₄)_x. Two silicon loaded materials (0.46 wt.% and 0.95 wt.%) were investigated and compared to a pure β-TCP. The maturation time of the synthesis required in order to obtain β-TCP decreased with the amount of silicon. Only restrictive synthesis conditions allow preparing silicon containing β-TCP with controlled composition. To obtain dense ceramics, the sintering behaviour of the powders was evaluated. The addition of silicon slowed the densification process and decreased the grain size of the dense ceramics. Rietveld refinement may indicate a partial incorporation of silicon in the β-TCP lattice. X-ray photoelectron spectroscopy and transmission electron microscopy analyses revealed that the remaining silicon formed amorphous clusters of silicon rich phase. The in vitro biological behaviour was investigated with MC3T3-E1 osteoblast-like cells. After the addition of silicon, the ceramics remained cytocompatible, highlighting the high potential of silicon containing β-TCP as optimised bone graft material.     

In vitro effect of magnesium inclusion in sol-gel derived apatite

Magnesium-containing apatite coatings were prepared on Ti6Al4V substrates by sol-gel dip coating method. Standard simulated body fluid (SBF) was used to evaluate the bioactivity of the coatings. A series of the coatings according to the composition (Ca_10−xMg_x)(PO₄)₆(OH)₂, where x = 0 to 2, is synthesized and immersed in the standard SBF for periods of 7 to 35 days for direct deposition of apatite layer from the SBF solution. Scanning electron microscopy (SEM) was used to examine the morphology changes of the SBF apatite layer that occurred during in vitro immersion. X-ray diffractometry, Fourier Transformation Infra-Red Spectroscopy and X-ray Photoelectron Spectroscopy were used to analyse the phases, chemical groups and composition of the sol-gel coating. Results show that as the sol-gel coating contains magnesium, this promotes deposition of apatite layer from SBF. As x ≤ 1, SBF immersion gives rise to a dense apatite layer. However, as x ? 1, selected dissolution of the deposited layer takes place, which results in serious pitting on the surface. Also, Mg ions from the dissolution of the sol-gel coating during immersion in the SBF apparently played a role in the subsequent deposition of apatite o the coating, evidence of Mg was found in the apatite layer.     

Surface microstructure and cell biocompatibility of silicon-substituted hydroxyapatite coating on titanium substrate prepared by a biomimetic process

Silicon-substituted hydroxyapatite (Si-HA) coatings with 0.14 to 1.14 at.% Si on pure titanium were prepared by a biomimetic process. The microstructure characterization and the cell compatibility of the Si-HA coatings were studied in comparison with that of hydroxyapatite (HA) coating prepared in the same way. The prepared Si-HA coatings and HA coating were only partially crystallized or in nano-scaled crystals. The introduction of Si element in HA significantly reduced P and Ca content, but densified the coating. The atom ratio of Ca to (P + Si) in the Si-HA coatings was in a range of 1.61–1.73, increasing slightly with an increase in the Si content. FTIR results displayed that Si entered HA in a form of SiO₄ unit by substituting for PO₄ unit. The cell attachment test showed that the HA and Si-HA coatings exhibited better cell response than the uncoated titanium, but no difference was observed in the cell response between the HA coating and the Si-HA coatings. Both the HA coating and the Si-HA coatings demonstrated a significantly higher cell growth rate than the uncoated pure titanium (p < 0.05) in all incubation periods while the Si-HA coating exhibited a significantly higher cell growth rate than the HA coating (p < 0.05). Si-HA with 0.42 at.% Si presented the best cell biocompatibility in all of the incubation periods. It was suggested that the synthesis mode of HA and Si-HA coatings in a simulated body environment in the biomimetic process contribute significantly to good cell biocompatibility.     

Pulsed laser deposition of silicon-substituted hydroxyapatite coatings

Thin films of Si-substituted hydroxyapatite (Si-HA) were deposited on Si and Ti substrates by pulsed laser deposition (PLD), in the presence of a water vapour atmosphere. The PLD ablation targets were made with different mixtures of commercial carbonated HA and Si powder, in order to produce the Si-HA thin films. The physicochemical properties of the coatings and the incorporation of the Si into the HA structure was studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Si atoms were successfully incorporated into the HA structure, and were found to be in the form of SiO₄⁴⁻ groups, principally displacing carbonate groups off the HA structure.     

Synthesis and photoluminescence of Ca-(Sn,Ti)-Si-O compounds

The phase relation of the compounds prepared in the CaO-SnO₂-SiO₂ system at 1673 K and in the CaO-TiO₂-SiO₂ system at 1573 K was investigated in order to explore new Ti⁴⁺-activated stannate phosphors. Solid solutions of Ca(Sn_1−xTi_x)SiO₅ and Ca₃(Sn_1−yTi_y)Si₂O₉ were synthesized at x = 0-1.0 and y = 0-0.10, respectively, and their crystal structures were analyzed by powder X-ray diffraction. Photoluminescence of these solid solutions was observed in a broad range of a visible light wavelength region under ultraviolet (UV) light excitation. The peaks of the emission band of Ca(Sn_0.97Ti_0.03)SiO₅ and Ca₃(Sn_0.925Ti_0.075)Si₂O₉ were at 510 nm under excitation of 252 nm and at 534 nm under excitation of 258 nm, respectively. The absorption edges estimated by the diffuse reflectance spectra were at 300 nm (4.1 eV) for CaSnSiO₅ and at 270 nm (4.6 eV) for Ca₃SnSi₂O₉, suggesting that the excitation levels in Ca(Sn_1−xTi_x)SiO₅ were above the band gap of the host, although the levels in Ca₃(Sn_1−yTi_y)Si₂O₉ were within the band gap and near the conduction band edge.     

Structural and electrical properties of Ce0.75(Gd0.95−xSrxCa0.05)0.25O2−δ thick film electrolyte

The effects of Sr doping on the electrical properties of Ce_0.75(Gd_0.95−xSr_xCa_0.05)_0.25O_2−δ (x = 0, 0.01, 0.02, 0.03, 0.04, 0.05 mol%) electrolytes thick films were investigated. The samples sintered at 1400 °C for 8 h. X-ray diffraction (XRD) showed typical XRD patterns of a cubic fluorite structure, and the ionic conductivity was examined by AC impedance spectroscopy. From the experimental results, it was observed that Ce_0.75(Gd_0.95−xSr_xCa_0.05)_0.25O_2−δ (x = 0.04 mol%) electrolytes thick film have higher conductivity and minimum activation energy at 600 °C. This is explained in terms of the increased in the oxygen vacancy concentration at the grain boundary.     

Effects of argon and oxygen flow rate on water vapor barrier properties of silicon oxide coatings deposited on polyethylene terephthalate by plasma enhanced chemical vapor deposition

Plasma polymer coatings were deposited from hexamethyldisiloxane on polyethylene terephthalate (PET) substrates while varying the operating conditions, such as the Ar and O₂ flow rates, at a fixed radio frequency power of 300 W. The water vapor transmission rate (WVTR) of the untreated PET was 54.56 g/m²/day and was decreased after depositing the silicon oxide (SiO_x) coatings. The minimum WVTR, 0.47 g/m²/day, was observed at Ar and O₂ flow rates of 4 and 20 sccm, respectively, with a coating thickness of 415.44 nm. The intensity of the peaks for the Si-O-Si bending at 800-820 cm^− 1 and Si-O-Si stretching at 1000-1150 cm^− 1 varied depending on the Ar and O₂ flow rates. The contact angle of the SiO_x coated PET increased as the Ar flow rate was increased from 2 to 8 sccm at a fixed O₂ flow rate of 20 sccm. It decreased gradually as the oxygen flow rate increased from 12 to 28 sccm at a fixed Ar carrier gas flow rate. The examination by atomic force microscopy revealed a correlation of the SiO_x morphology and the water vapor barrier performance with the Ar and O₂ flow rates. The roughness of the deposited coatings increased when either the O₂ or Ar flow rate was increased.     

Synthesis and electrical properties of scheelite Ca1−xSmxMoO4+δ solid electrolyte ceramics

Scheelite-type Ca_1−xSm_xMoO_4+δ electrolyte powders were prepared by the sol-gel auto-combustion process. The crystal structure of the samples was determined by employing the techniques of X-ray diffraction (XRD). According to the XRD analysis, the formed continuous series of Ca_1−xSm_xMoO_4+δ (0 ≤ x ≤ 0.3) solid solutions had the structure of tetragonal scheelite, and the lattice parameters increased with increasing x in the Sm-substituted system. Results of sinterability and electrochemical testing revealed that the performances of Sm-doped calcium molybdate were superior to that of pure CaMoO₄. Ca_1−xSm_xMoO_4+δ ceramics show higher sinterability, and the Ca_0.8Sm_0.2MoO_4+δ sample with 98.7% of the theoretical density were obtained after being sintered at 1250 °C for 4 h. The conductivity increased with increasing samarium content, and a total conductivity 9.54 × 10⁻³ S cm⁻¹ at 800 °C could be obtained in Ca_0.8Sm_0.2MoO_4+δ sintered at 1250 °C for 4 h.     

Formation, sintering, and electrical conductivity of (Nd1−xCax)CrO3 (0≤x≤0.25) using citric acid as a gelling agent

In Ca²⁺-substituted NdCrO₃, single-phase perovskite compounds (Nd_1−xCa_x)CrO₃, where x=0-0.25, have been formed by a citric acid processing. (Nd_1−xCa_x)CrO₃ powders consisting of submicrometer-size particles are sinterable; dense materials can be fabricated by sintering for 2 h at 1700°C under atmospheric pressure. The relative densities, grain sizes, and electrical conductivities increase with increased Ca²⁺ content. (Nd_0.75Ca_0.25)CrO₃ materials show an excellent electrical conductivity of 1.9×10 S m⁻¹ at 1000°C.     

La and Ca co-doped ceria-based electrolyte materials for IT-SOFCs

Co-doped ceria-based electrolytes of Ce_1−xLa_x−yCa_yO_2−δ, wherein x = 0.15 and 0.20, 0 ≤ y ≤ x, were sintered from powders obtained by solid state reaction method. The phase identification, thermal expansion and ionic conductivities of samples were studied by X-ray diffraction (XRD), dilatometry and AC impedance spectroscopy (IS). Results showed that the samples of co-doping with La and Ca can significantly increase the ionic conductivity and lower activation energies compared with those of the singly doped ones in the temperature range of 500-800 °C. The ionic conductivities of co-doping samples decrease with Ca content. Although both systems reached the optimum ionic conductivity at y = 0.05, Ce_0.85La_0.15−yCa_yO_2−δ exhibits better electrical performance. The results also showed that all the synthesized samples were fluorite-type ceria-based solid solutions. The thermal expansion was linear for all the samples.     

Influence of anionic vacancies on the ionic conductivity of silicated rare earth apatites

Oxyapatites are very promising materials in terms of ionic conductivity. They can be considered as a potential electrolyte for Solid Oxide Fuel Cells (SOFC). Doped silicated rare earth apatites with formula La_9.33−xCa_x(SiO₄)₆O_2−x/2 (0 ≤ x ≤ 1) have been prepared by solid state reaction at high temperature in order to determine the influence of anionic vacancies on the electrical properties of the material. The incorporation of calcium in the structure has been checked by characterizations of the powders (X-ray diffraction, helium pycnometry). The cell parameters of the hexagonal apatite were refined. Samples were sintered at 1550 °C. Electrical properties of each composition have been studied between 280 and 620 °C by the complex impedance method. The evolution of the bulk conductivity and of the activation energy with the substituting ratio gives information on the conductivity mechanism in these materials. An improvement of ionic conductivity about one order of magnitude has been observed for low calcium substitution ratios.     

Novel Dy-doped Ca2Gd8(SiO4)6O2 white light phosphors for Hg-free lamps application

The luminescent properties of Ca₂Gd_8(1−x)(SiO₄)₆O₂:xDy³⁺ (1% ≤ x ≤ 5%) powder crystals with oxyapatite structure were investigated under vacuum ultraviolet excitation. In the excitation spectrum, the peaks at 166 nm and 191 nm of the vacuum ultraviolet region can be assigned to the O²⁻ → Gd³⁺, and O²⁻ → Dy³⁺ charge transfer band respectively, which is consistent with the theoretical calculated value using Jφrgensen's empirical formula. While the peaks at 183 nm and 289 nm are attributed to the f-d spin-allowed transitions and the f-d spin-forbidden transitions of Dy³⁺ in the host lattice with Dorenbos's expression. According to the emission spectra, all the samples exhibited excellent white emission under 172 nm excitation and the best calculated chromaticity coordinate was 0.335, 0.338, which indicates that the Ca₂Gd₈(SiO₄)₆O₂:Dy³⁺ phosphor could be considered as a potential candidate for Hg-free lamps application.     

Synthesized silicon-substituted hydroxyapatite coating on titanium substrate by electrochemical deposition

Silicon-substituted hydroxyapaptite (Si-HA) coatings were prepared on titanium substrates by electrolytic deposition technique in electrolytes containing Ca²⁺, PO₄ ³⁻ and SiO₃ ²⁻ ions with various SiO₃ ²⁻/(PO₄ ³⁻ + SiO₃ ²⁻) molar ratios(η_si). The deposition was all conducted at a constant voltage of 3.0 V, with titanium substrate as cathode and platinum as anode, for 1 h at 85°C. The coatings thus prepared were characterized with inductively coupled plasma (ICP), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), field-emission-type scanning electron microscope (FSEM). The results show that the silicon amount in the coatings increases linearly to about 0.48 wt% at first with increasing η_si between 0 and 0.03, then increases slowly to about 0.55 wt% between 0.03 and 0.10 and finally maintains almost at a level around 0.55 wt% between 0.10 and 0.30. The tree-like Si-HA crystals are observed in the coatings prepared in the electrolyte of η_si = 0.20. And the presence of silicon in electrolytes decreases the thickness of the coatings, with effect being more significant as η_si increased. Additionally, the substitution of Si causes some OH⁻ loss and changes the lattice parameters of hydroxyapatite (HA).     

Structural and magnetic properties of glass-ceramics containing silver and iron oxide

Glass-ceramics with a nominal composition of 25SiO₂–(50 − x)CaO–15P₂O₅–8Fe₂O₃–2ZnO–xAg (where x = 0, 2 and 4 mol%) have been prepared. Structural features of glass-ceramics have been investigated using X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques. Magnetic properties were studied using vibrating sample magnetometer and Mössbauer spectroscopy. Ca₃(PO₄)₂, hematite and magnetite are formed as major crystalline phases. The microstructure reveals the formation of 25–30 nm size particles. Mössbauer spectroscopy has shown the relaxation of magnetic particles. Saturation magnetization value is increased with an increase of Ag content up to 4 mol%, which has been attributed to the formation of magnetically ordered particles. The antibacterial response was found to depend on Ag ions concentration in the glass matrix and samples with 4 mol% Ag in glass matrix have shown effective antibacterial activity against Escherichia coli.     

Effects of substrate bias voltage and target sputtering power on the structural and tribological properties of carbon nitride coatings

Effects of substrate bias voltage and target sputtering power on the structural and tribological properties of carbon nitride (CN_x) coatings are investigated. CN_x coatings are fabricated by a hybrid coating process with the combination of radio frequency plasma enhanced chemical vapor deposition (RF PECVD) and DC magnetron sputtering at various substrate bias voltage and target sputtering power in the order of −400 V 200 W, −400 V 100 W, −800 V 200 W, and −800 V 100 W. The deposition rate, N/C atomic ratio, and hardness of CN_x coatings as well as friction coefficient of CN_x coating sliding against AISI 52100 pin in N₂ gas stream decrease, while the residual stress of CN_x coatings increases with the increase of substrate bias voltage and the decrease of target sputtering power. The highest hardness measured under single stiffness mode of 15.0 GPa and lowest residual stress of 3.7 GPa of CN_x coatings are obtained at −400 V 200 W, whereas the lowest friction coefficient of 0.12 of CN_x coatings is achieved at −800 V 100 W. Raman and XPS analysis suggest that sp³ carbon bonding decreases and sp² carbon bonding increases with the variations in substrate bias voltage and target sputtering power. Optical images and Raman characterization of worn surfaces confirm that the friction behavior of CN_x coatings is controlled by the directly sliding between CN_x coating and steel pin. Therefore, the reduction of friction coefficient is attributed to the decrease of sp³ carbon bonding in the CN_x coating. It is concluded that substrate bias voltage and target sputtering power are effective parameters for tailoring the structural and tribological properties of CN_x coatings.     

A study of the nanostructure and hardness of electron beam evaporated TiAlBN Coatings

TiAlBN coatings have been deposited by electron beam (EB) evaporation from a single TiAlBN material source onto AISI 316 stainless steel substrates at a temperature of 450 °C and substrate bias of − 100 V. The stoichiometry and nanostructure have been studied by X-ray photoelectron spectroscopy, X-ray diffraction and transmission electron microscopy. The hardness and elastic modulus were determined by nanoindentation. Five coatings have been deposited, three from hot-pressed TiAlBN material and two from hot isostatically pressed (HIPped) material. The coatings deposited from the hot-pressed material exhibited a nanocomposite nc-(Ti,Al)N/a-BN/a-(Ti,Al)B₂ structure, the relative phase fraction being consistent with that predicted by the equilibrium Ti-B-N phase diagram. Nanoindentation hardness values were in the range of 22 to 32 GPa. Using the HIPped material, coating (Ti,Al)B_0.29N_0.46 was found to have a phase composition of 72-79 mol.% nc-(Ti,Al)(N,B)_1 − x+ 21-28 mol.% amorphous titanium boride and a hardness of 32 GPa. The second coating, (Ti,Al)B_0.66N_0.25, was X-ray amorphous with a nitride+boride multiphase composition and a hardness of 26 GPa. The nanostructure and structure-property relationships of all coatings are discussed in detail. Comparisons are made between the single-EB coatings deposited in this work and previously deposited twin-EB coatings. Twin-EB deposition gives rise to lower adatom mobilities, leading to (111) (Ti,Al)N preferential orientation, smaller grain sizes, less dense coatings and lower hardnesses.     

Preparation of Ca-doped LaFeO3 nanopowders in a reverse microemulsion and their visible light photocatalytic activity

Nanoparticles of lanthanum ferrite (LaFeO₃) and calcium-doped LaFeO₃ (La_1−xCa_xFeO₃, x = 0.05-0.20) with perovskite-type structure have been prepared in a reverse microemulsion. Perovskite powder could be obtained at 500 °C for 3 h. The prepared powders were characterized by thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD) and UV-Vis absorption spectroscopy. The visible-light photocatalytic activity of the photocatalysts was tested with methylene blue as an objective decomposition substance using fluorescence light as a visible light resource. The results showed that partial substitution of La³⁺ in LaFeO₃ with Ca²⁺ could decrease the crystalline size, enhance visible light absorption and improve visible light photocatalytic activity.     

Physico-chemical, structural and physical properties of hydrogenated silicon oxinitride films elaborated by pulsed radiofrequency discharge

Films prepared by radiofrequency pulsed plasma enhanced chemical vapor deposition from a mixture of silane (SiH₄) and nitrous oxide (N₂O) were studied. Variation of operating conditions (flow rate, deposition temperature ...) resulted in films with chemical compositions changing from hydrogenated silicon oxynitride (SiO_xN_y:H) to silicon oxide (SiO_x:H). Infrared and Rutherford backscattering spectroscopy studies of the as-deposited films revealed different SiO_x arrangements disturbed by Si-N bonds and H-Si ≡ Si_(3 − x)O_x clusters depending on the substrate temperature and the N₂O/SiH₄ ratio. For films obtained using low N₂O/SiH₄ rations and annealed at temperature higher than 1273 K, Raman spectroscopy and microscopy analyses revealed the presence of silicon nanocrystals embedded in a matrix containing Si, O, and N. Spectroscopic ellipsometry revealed the presence of silicon nanocrystals along with two other amorphous phases (SiO_xN_y and SiO₂) in annealed samples. The electrical characteristics of annealed films obtained from capacitance-voltage measurements indicated a stable charge trapping in ultra-thin SiO_xN_y layers. These preliminary results suggest that Si-nc containing silicon oxynitride layers can be potential candidates to be used in the floating gate fabrication of memory devices.