Deposition of calcium phosphate coatings with defined chemical properties using the electrostatic spray deposition technique

The electrostatic spray deposition (ESD) technique was used for biomedical purposes in order to deposit calcium phosphate (CaP) coatings onto titanium substrates. The relationship between various deposition parameters and the chemical properties of deposited coatings was investigated in order to be able to deposit CaP coatings with tailored chemical characteristics.The results showed that the chemical properties of the coatings were determined by both physical, apparatus-related factors and chemical, solution-related parameters. By varying the processing parameters of the technique, several crystal phases and phase mixtures were obtained, ranging from carbonate-free phases such as meta- and pyrophosphates, monetite and various tricalcium phosphates to carbonate-containing phases such as various carbonate apatites and calcite. On the basis of these results, a chemical mechanism of coating formation was proposed. Essentially, the deposition of the various crystal phases was the result of an acid–base reaction between basic CO₃²⁻ groups (originating from solvent decomposition reactions) and acidic HPO₄²⁻ groups from an intermediate monetite (CaHPO₄) phase of the CaP precipitate. The amount of carbonate incorporation (ranging from 0 to 15 wt%) determined the crystal and molecular structure of the deposited coatings.     

Electrochemical and structural evaluation of functionally graded bioglass-apatite composites electrophoretically deposited onto Ti6Al4V alloy

Titanium and its alloys are widely used as materials for implants, owing to their corrosion resistance, mechanical properties and excellent biocompatibility. However, clinical experience has shown that they are susceptible to localised corrosion in the human body causing the release of metal ions into the tissues surrounding the implants. Several incidences of clinical failures of such devices have demanded the application of biocompatible and corrosion resistant coatings and surface modification of the alloys. Coating metallic implants with bioactive materials is necessary to establish good interfacial bonds between the metal substrate and the bone. Hence, this work aimed at developing a bioglass-apatite (BG-HAP) graded coating on Ti6Al4V titanium alloy through electrophoretic deposition (EPD) technique. The coatings were characterized for their properties such as structural, electrochemical and mechanical stability. The electrochemical corrosion parameters such as corrosion potential (E_corr) (open circuit potential) and corrosion current density (I_corr) evaluated in simulated body fluid (SBF) have shown significant shifts towards noble direction for the graded bioglass-apatite coated specimens in comparison with uncoated Ti6Al4V alloy. Electrochemical impedance spectroscopic investigations revealed higher polarisation resistance and lower capacitance values for the coated specimens, evidencing the stable nature of the formed coatings. The results obtained in the present work demonstrate the suitability of the electrophoretic technique for the preparation of graded coating on Ti6Al4V substrates.     

Incorporation of ZnO–ZrO2 nanoparticles into TiO2 coatings obtained by PEO on Ti–6Al–4V substrate and evaluation of its corrosion behavior,microstructural and antibacterial effects exposed to SBF solution

In this research, Plasma Electrolytic Oxidation technique was used to incorporate ZnO–ZrO₂ nanoparticles into TiO₂ ceramic coating on Ti6–Al–4V using sodium phosphate as an electrolyte. The effect of adding these nanoparticles on corrosion, morphology, wettability and antibacterial properties in the simulated body fluid (SBF) solution was investigated. The results indicated nanoparticles modified the microstructure of coating, which increased corrosion resistance 12 times higher than that of substrate. Besides, ZrO₂ nanoparticles had the most significant effect on increasing the contact angle. In addition, due to the compatibility of zirconium and zinc oxides with human body environment, the antibacterial properties of coatings were significantly improved.     

Development of Hydrothermally Synthesized Hydroxyapatite Coatings on Metallic Substrates and Weibull's Reliability Analysis of its Shear Strength

Hydroxyapatite (HA) and Mg‐substituted HA coatings were synthesized on Mg‐9Al‐1Zn and Ti‐6Al‐4V by the hydrothermal process. Grazing‐incidence X‐ray diffractograms showed the formation of calcium–magnesium–phosphate is resulted from the substitution of Mg²⁺‐ions into HA crystal. The chemical state of Mg²⁺‐ions in Mg‐substituted HA coatings was examined by X‐ray photoelectron spectroscopy. The shear test results showed the Mg‐substituted HA coatings deposited on Mg‐9Al‐1Zn have higher shear strength than those coatings on Ti‐6Al‐4V. The Weibull model provided a powerful statistical method for assessing failure mechanism of hydrothermal coatings, which is attributed to a wear‐out failure model with a Weibull modulus m > 3.     

Correlation between microstructure and properties of biocomposite coatings

A SiO₂–CaO–Na₂O (SCN) based bioactive glass was used to prepare glass–matrix/Ti particle composite coatings (SCNT). The coatings were obtained by vacuum plasma spray (VPS) on Ti–6Al–4V substrates. Two different deposition methods have been compared: (a) VPS of powders obtained by ball milling of sintered composites; (b) in situ plasma spray of mixed titanium and glass powders. For comparative purposes, pure SCN glass coatings were produced. The coating morphology and microstructure were observed by optical and scanning electron microscopy, compositional analyses by energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD). Comparative mechanical tests were carried out by shear tests and by Vickers indentations at the interface between the substrate and the coatings. The bioactivity of glass- and composite coatings was investigated in vitro by soaking them in a simulated body fluid (SBF) with the same ion concentration of the human plasma. All the layers retain their starting composition. The composite coatings obtained by VPS of the powdered presintered composites showed a better mechanical behaviour with respect both to the composite coatings obtained by the in situ method and to the pure glass coatings. Both the glass- and the two kind of composite coatings revealed to be bioactive by the growth of a thick apatite layer after 30 days of soaking in SBF. The electrochemical behaviour of the SCNT coatings was evaluated by means of potentiodynamic anodic polarization curves and free corrosion potential measurements in Ringer solution at 25 °C. For comparative purposes the same analyses were performed on analogous bioactive glass-matrix/Ti particle composite coated samples, based on the system TiO₂–SiO₂–CaO–B₂O₃ (TSCB), and obtained both by the in situ and by presintering method as well. The results of the electrochemical tests showed a better corrosion behaviour of the samples coated by VPS of powdered sintered composites with respect to those coated by in situ VPS composites.     

Stress–corrosion cracking by indentation techniques of a glass coating on Ti6Al4V for biomedical applications

The fixation of bone replacement implants to the hosting tissue can be improved if the implants have a bioactive surface that can precipitate hydroxyapatite in vivo. Titanium alloys, despite their desirable mechanical and nontoxic properties, are not bioactive and do not bond directly to the bone. One of the ways to change a bioinert metallic surface such as a titanium alloy is to coat it with a bioactive material. This work presents the microstructural and stress–corrosion cracking characterization of two glass coatings on Ti6Al4V with different SiO₂ contents (61% and 64%). These coatings belong to the SiO₂–CaO–MgO–Na₂O–K₂O–P₂O₅ system and they were obtained by a simple enamelling technique. They will be used as the first layer of a bioactive multilayer system which will have an outer layer with a lower SiO₂ content in order to ensure the surface bioactivity. Microstructural characterization performed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) shows that the coating porosity is clearly influenced by the firing time because of the longer extension of the reaction between Ti and SiO₂. The X-ray diffraction (XRD) integration method shows that the amount of crystalline phase (2.4CaO 0.6Na₂O P₂O₅) percentage is between 3 vol.% and 16 vol.%. After acid etching, a microstructure with clear boundaries is observed which is the result of the sintered glass particles separation. Stress–corrosion cracking was evaluated using Vickers and Hertzian (spherical) indentation, showing that both coatings are sensitive to subcritical crack growth, and that the coating with the lower silica content is more sensitive to stress–corrosion cracking. These two results are related with the larger residual stresses due to the thermal expansion mismatch. Finally, the stress–corrosion ring cracking behavior by Hertzian indentation is rationalized from the linear-elastic fracture mechanics framework.     

Preparation,scratch adhesion and anti-corrosion performance of TiO2-MgO-BHA coating on Ti6Al4V implant by plasma electrolytic oxidation technique

Bovine hydroxyapatite (BHA) (from cortical bone), was selected as the main electrolyte for plasma electrolytic oxidation (PEO) on Ti6Al4V implant. The prepared PEO coatings were examined by X-ray diffraction, field emission scanning electron microscope and energy-dispersive X-ray spectroscopy. The surface roughness, adhesion strength, wettability, surface energy and corrosion behaviour of the film were also investigated. The results show that the oxide layer (26 μm) formation on the Ti6Al4V was rough and porous. The micro-pores were filled with anatase TiO₂, cubic MgO and hexagonal BHA particles. The porous structures and the compound particles were mainly composed of Mg, O, Ca, P, Ti, Na and Al. Unlike previous coatings produced from calcium and phosphorus inorganic solutions, the coating formation from a newly developed bovine bone-derived HA electrolyte revealed an additional MgO phase in the coating layer. Moreover, higher amount of single phase hexagonal crystalline BHA phase with a Ca/P ratio of 1.1 was achieved with a single PEO process. A film-to-substrate adhesion strength of 1862.24 mN and scratch hardness of about 4.1 GPa was achieved from this method. The TiO₂/MgO/BHA film exhibited better wettability, higher surface energy and superior corrosion resistance compared to the bare Ti6Al4V substrate.     

Influence of CaO<Subscript>2</Subscript> additives on the properties of Fe–WB-based composite lining deposited by centrifugal SHS on the inner surface of steel pipe

Influence of calcium peroxide (CaO₂) additives on the characteristics and properties of composite coatings deposited by centrifugal SHS was investigated. Microstructure and composition of deposited coatings were characterized by SEM, EDX, XRD, and mechanical testing. The additives of CaO₂ and Al were found to markedly improve the properties of deposited composite coatings. Under optimized conditions, the deposited coatings exhibited rather smooth surface, good adhesive strength, and reasonable micro-hardness.     

Mechanical behavior of YSZ coatings co-deposited with Al and Ag on AISI 316L via RF sputtering

This article presents nanohardness, coefficient of friction (COF), and wear of Yttria-stabilized zirconia coatings (YSZ) deposited on 316L steel substrates and co-deposited with Al and Ag. YSZ coatings were deposited via RF sputtering reactive phase technique. It is widely known that the RF sputtering technique produces stoichiometric coatings with high homogeneity and density. The average thickness of the coatings was 200 nm, and the X-ray diffraction study (XRD) showed the formation of alumina alpha (α-Al₂O₃) and metallic silver in the YSZ coatings deposited with Al and Ag, respectively. The mechanical properties were evaluated by means of nanoindentation, and the wear resistance was studied with pin-on-disk technique. The addition of Ag to the YSZ coatings led to decreased hardness, while the YSZ coatings deposited with Al presented an increased hardness. Finally, YSZ coatings deposited with aluminum and silver had the lowest friction coefficient, while Ag-YSZ coatings had a COF very similar to that obtained in YSZ coatings. The wear resistance test showed that YSZ coatings deposited with Al had lower volume loss compared to YSZ coatings deposited with Ag. The wear mechanism in the deposited coatings is analyzed.     

A novel apatite-inspired Sr5(PO4)2SiO4 plasma-sprayed coating on Ti alloy promoting biomineralization,osteogenesis and angiogenesis

Osteoconductive, osteoinductive, anti-infection, and controlled ionic release properties are crucial for the long-term clinical success of orthopedic and dental metallic implants. In this study, we have successfully synthesized apatite chemical structure mimic Sr₅(PO₄)₂SiO₄ (SPS) nanopowder by sol-gel method to be used as a novel bioactive ceramics coatings on medical-grade titanium alloy by plasma-spray deposition technique. The deposited SPS coatings were analytically characterized by XRD and SEM-EDS analysis and confirmed that the coating possessed a pure crystalline phase of SPS without any other secondary phases, and exhibited a sharp needle-like morphology with the existence of Sr, P, O, Si elements. The cross-sectional view proved that the deposition of dense SPS layer with a thickness of 116 μm. The in vitro ionic dissolution behavior of SPS coatings was detected by ICP-OES analysis and confirmed their controlled releasing profile of ions such as Sr (120–55 ppm) and Si (0.14–9.86 ppm). In vitro biomineralization study demonstrated that the SPS coatings were remarkably encouraged the ball likes apatite crystals growth on their surface with a Ca/P ratio (1.677) similar to natural bone minerals. The SPS coatings exhibited notable cellular interactions with human umbilical card-derived mesenchymal stem cells (HUMSCs) in terms of cell proliferation, early-stage differentiation, and calcium nodule accumulation in ECM, also the osteogenic differentiation was found to be prominent for SPS coated Ti64 than sandblasted Ti64. Furthermore, the angiogenic property of SPS coated Ti64 was evaluated by Human umbilical vein endothelial cells (HUVECs) and confirmed their tremendous cell viability with non-toxicity and nominal angiogenic differentiation. Therefore, our study proved that the apatite-inspired SPS bioactive ceramics coatings could improve the biofunctional activities of orthopedic and dental implants for their better clinical success.     

Corrosion Resistance of MgZn Alloy Covered by Chitosan-Based Coatings

Chitosan coatings are deposited on the surface of Mg20Zn magnesium alloy by means of the spin coating technique. Their structure was investigated using Fourier Transform Infrared Spectroscopy (FTIR) an X-ray photoelectron spectroscopy (XPS). The surface morphology of the magnesium alloy substrate and chitosan coatings was determined using Scanning Electron Microscope (FE-SEM) analysis. Corrosion tests (linear sweep voltamperometry and chronoamperometry) were performed on uncoated and coated magnesium alloy in the Hank’s solution. In both cases, the hydrogen evolution method was used to calculate the corrosion rate after 7-days immersion in the Hank’s solution at 37 °C. It was found that the corrosion rate is 3.2 mm/year and 1.2 mm/year for uncoated and coated substrates, respectively. High corrosion resistance of Mg20Zn alloy covered by multilayer coating (CaP coating + chitosan water glass) is caused by formation of CaSiO₃ and Ca₃(PO₄)₂ compounds on its surface.     

Anticorrosive coatings containing modified phosphates

The aim of this paper was to prepare and to compare anticorrosion efficiency of various types of pigments based on phosphates. Their exact composition was defined by X-ray diffraction analysis and their structure by scanning electron microscopy (SEM). Commercially available zinc phosphate was used as a standard. Pigments were prepared in three different ways and they were dispersed in the solution of epoxy medium-molecular resin. Paints were formulated with 10% PVC (pigment volume concentration). Anticorrosion efficiency of coatings was tested by three direct cyclic corrosion tests. These pigments seem to be a good alternative for corrosion protection. AlPO₄/Al(PO₃)₃, prepared according to process No. 1, showed very good results in all prepared pigments.     

Wear-resistant Ti–Al–Ni–C–N coatings produced by magnetron sputtering of SHS-targets in the DC and HIPIMS modes

The hard wear-resistant nanocomposite Ti–Al–Ni–C–N coatings were deposited by direct current magnetron sputtering (DCMS) and high power impulse magnetron sputtering (HIPIMS) in the Ar, Ar+15%N_2, and Ar+25%N₂ atmospheres. The structure of coatings was analyzed using the X-ray diffraction analysis, glow discharge optical emission spectroscopy, and scanning electron microscopy. Mechanical and tribological properties were measured using the nanoindentation and scratch testing as well as by tribological testing using the “pin-on-disc” scheme. Electrochemical corrosion resistance and oxidation resistance of coatings were investigated. The results suggest that the coatings are based on the FCC phases TiCN and Ni₃Al with crystallites size ~3 and ~15 nm, correspondingly. DCMS coatings with optimal composition were characterized by hardness 34 GPa, stable friction coefficient <0.26 and wear rate <5 × 10^-6 mm³N^-1m^-1. Application of HIPIMS mode allowed the increase of adhesion strength, tribological properties and corrosion resistance of coatings.     

Deposition behavior and characteristics of hydroxyapatite coatings on Al2O3, Ti,and Ti6Al4V formed by a chemical bath method

A simple chemical bath method was used to deposit hydroxyapatite (HA) coatings on Al₂O₃, Ti, and Ti6Al4V substrates at ambient pressure by heating to 65–95 °C in an aqueous solution prepared with Ca(NO₃)₂·4H₂O, KH₂PO₄, KOH, and EDTA. The deposition behavior, morphology, thickness, and phase of the coatings were investigated using scanning electron microscopy and X-ray diffractometry. The bonding strength of the coatings was measured using an epoxy resin method. The HA coatings deposited on the three kinds of substrates were fairly dense and uniform and exhibited good crystallinity without any additional heat treatment. A coating thickness of 1–1.8 μm was obtained for the samples coated once. By repeating the coating process three times, the thickness could be increased to 4.5 μm on the Al₂O₃ substrate. The bonding strength of these coatings was 18 MPa.     

Calcium phosphates of biological importance based coatings deposited on Ti-15Mo alloy modified by laser beam irradiation for dental and orthopedic applications

Ti-15Mo alloy samples were irradiated by pulsed Yb:YAG pulsed laser beam under air and atmospheric pressure. Sequentially, calcium phosphate coatings were deposited on the irradiated surfaces by the biomimetic method. The formation of calcium phosphates (CaP) under biological medium and SBF (Synthetic/Simulated Body Fluid) occurs in the presence of Ca²⁺ and PO₄^3- ions, as well as ions such as: Mg^2+, HCO₃^-, K⁺ and Na⁺, which facilitates the mimicking of the biological process. The biomimetic calcium phosphates-based surfaces were submitted to heat treatment conditions at 350?°C and 600?°C. The present study correlates four conditions of fluency (1.91, 3.17, 4.16 and 5.54?J/cm², respectively) as established have a sufficient energy to promote ablation on the laser beam irradiated surfaces. Likewise, it has been demonstrated the processes of fusion and fast solidification from the laser beam irradiation, under ambient atmosphere, inducing the formation of stoichiometric (TiO₂₎ and non-stoichiometric titanium oxides (TiO, Ti₃O, Ti₃O₅ and Ti₆O) with different oxide percentages depending on the fluency applied. Besides that, laser modification has allowed a clean and reproducible process, providing no traces of contamination, an important feature for clinical applications. The morphological and physico-chemical analysis indicated the formation of a multiphase coatings depending on the heat treatment temperature performed to 350?°C (ACP1–2, CDHA, HA phases) and 600?°C (CDHA, HA and β-TCP phases). It is worth noting multiphasic bioceramic systems has been gaining attention for biomedical applications. The laser beam irradiation associated to bioactive coatings of calcium phosphates of biological interest have shown to be promising and economically feasible for use in clinical applications.     

Characterization and corrosion behavior of plasma sprayed calcium silicate reinforced hydroxyapatite composite coatings for medical implant applications

Titanium and its alloys are widely used for medical implant applications, but their corrosion in the physiological environment leads to the discharge of metal ions, which can trigger severe health issues. In the present study, calcium silicate reinforced hydroxyapatite (HA-CS) coatings were deposited on the Ti6Al4V substrate by using atmospheric plasma spray (APS) process with an aim to improve the corrosion resistance and bioactivity. The coatings were prepared by varying the weight percentage (wt %) of calcium silicate (CS) reinforcement in hydroxyapatite (HA) as Ha/x CS (x = 0, 10, 20 wt %). The SEM analysis of the pure HA coating revealed the presence of surface microcracks, whereas HA-CS coatings displayed the crack-free surface morphology. The corrosion investigation revealed that with the progressive increment of CS content in HA coating, the corrosion resistance of HA-CS coatings improved. In addition, surface roughness, porosity, microhardness and crystallinity increased with the increase of CS content in HA. The findings of this study indicate that the development of plasma sprayed HA-CS coatings is a promising approach to improve the performance of Ti6Al4V alloy for medical implant applications.     

Coupling sol-gel with electrospray deposition: Towards nanotextured bioactive glass coatings

For the first time, the sol-gel method was coupled with electrostatic spray deposition (ESD) to fabricate nanotextured bioactive glass (BG) coatings with a controlled microstructure in a one-pot-process. Three BG compositions belonging to the SiO₂-CaO-P₂O₅ system (S85, S75, and S58) were homogeneously deposited on metallic Ti6Al4V substrates starting from the atomization of precursor solutions. All coatings displayed an amorphous character, as confirmed by XRD. A wide variety of innovative BG morphologies were obtained, tuning the key parameters of ESD, leading from highly porous coral-like to compact reticular-type coatings. The bioactivity, in terms of apatite formation, of as-deposited coatings was tested by immersion in simulated body fluid solution. Textural properties were found to play an important impact in its biological performance. Highly porous ESD-coatings exhibited remarkable bioactivity for S75 and S58 compositions, compared with more compacted ones of equal formulations. S85 composition was found extremely reactive regardless of the coating microstructure.     

Synthesis and characterization of Ca–Sr–P coating on pure magnesium for biomedical application

There are growing evidences that Sr-containing calcium phosphate biomaterials can promote better osteo-precursor cell attachment and proliferation than pure calcium phosphate biomaterials. In this study, attempts were made to fabricate two kinds of Sr-substituted calcium phosphate (Ca–Sr–P) coatings on pure magnesium in electrolyte solutions with differing amounts of Sr(NO₃)₂ for biomedical application. The surface microstructure, composition and chemistry of the coatings were characterized by Scanning Electron Microscope (SEM), Energy-dispersive X-ray Spectroscopy (EDS), and X-ray Diffractometer (XRD), respectively. In addition, electrochemical and immersion tests were performed to evaluate the corrosion resistance of the Ca–Sr–P coated magnesium in phosphate buffered saline solution (PBS).     

Fabrication of Ni-W-B4C composite coatings and evaluation of its micro-hardness and corrosion resistance properties

Boron carbide (B₄C) particles were embedded in nickel-tungsten (Ni-W) coatings by pulse current electrodeposition technique. Physical properties of the composite coatings were studied by XRD, SEM, EDS and Vickers micro-hardness instrument. Corrosion protection of the deposited films was investigated utilizing potentiodynamic polarization and Electrochemical Impedance Spectroscopy (EIS). Results exhibited that the addition of B₄C nanoparticles into the Ni-W alloy can significantly improve the surface morphology and the micro-hardness of the composite coatings. The corrosion resistance of Ni-W-B₄C nanocomposite is much better than Ni-W alloy deposit, especially when the concentration of B₄C nanoparticles is 2?g/L in plating bath, the obtained Ni-W-B₄C composite coating has the best surface morphology, the highest micro-hardness and the excellent corrosion resistance.     

Electrochemical investigation of chromium nanocarbide coated Ti–6Al–4V and Co–Cr–Mo alloy substrates

This study investigated the electrochemical behavior of chromium nano-carbide cermet coating applied on Ti–6Al–4V and Co–Cr–Mo alloys for potential application as wear and corrosion resistant bearing surfaces. The cermet coating consisted of a highly heterogeneous combination of carbides embedded in a metal matrix. The main factors studied were the effect of substrate (Ti–6Al–4V vs. Co–Cr–Mo), solution conditions (physiological vs. 1 M H₂O₂ of pH 2), time of immersion (1 vs. 24 h) and post coating treatments (passivation and gamma sterilization). The coatings were produced with high velocity oxygen fuel (HVOF) thermal spray technique at atmospheric conditions to a thickness of 250 μm then ground and polished to a finished thickness of 100 μm and gamma sterilized. Native Ti–6Al–4V and Co–Cr–Mo alloys were used as controls. The corrosion behavior was evaluated using potentiodynamic polarization, mechanical abrasion and electrochemical impedance spectroscopy under physiologically representative test solution conditions (phosphate buffered saline, pH 7.4, 37 °C) as well as harsh corrosion environments (pH ～ 2, 1 M H₂O₂, T = 65 °C). Severe environmental conditions were used to assess how susceptible coatings are to conditions that derive from possible crevice-like environments, and the presence of inflammatory species like H₂O₂. SEM analysis was performed on the coating surface and cross-section. The results show that the corrosion current values of the coatings (0.4–4 μA/cm²) were in a range similar to Co–Cr–Mo alloy. The heterogeneous microstructure of the coating influenced the corrosion performance. It was observed that the coating impedances for all groups decreased significantly in aggressive environments compared with neutral and also dropped over exposure time. The low frequency impedances of coatings were lower than controls. Among the coated samples, passivated nanocarbide coating on Co–Cr–Mo alloy displayed the least corrosion resistance. However, all the coated materials demonstrated higher corrosion resistance to mechanical abrasion compared to the native alloys.