Studies on a novel bioactive glass and composite coating with hydroxyapatite on titanium based alloys: Effect of γ-sterilization on coating

A novel silicate based bioactive glass coating composition containing B₂O₃ and TiO₂ having matching thermal properties with that of Ti₆Al₄ V implants was developed and characterized. A conventional vitreous enamelling technique was used for coating small flat surface and curved surface of small rods. Hydroxyapatite (HAp) micro and nano-crystalline particles were used to prepare bioactive glass-HAp composite coating. Scratch testing was used to study the coating adhesion and its fracture behaviour under simulated conditions. As observed from scratch testing results, adhesion strength of the coating improved from 21 N normal load to 27 N and 32 N on addition of micro-HAp and nano HAp powder, respectively, to bioactive glass matrix. Further, sterilization of the coated samples with 25 kGy gamma irradiation substantially enhanced the adhesion of glass coating and HAp-composite coating.     

Fabrication and characterization of in-situ duplex plasma-treated nanocrystalline Ti/AlTiN coatings

Plasma nitriding and plasma-assisted PVD duplex treatment was adopted to improve the load-bearing capacity, fatigue resistance and adhesion of the AlTiN coating. Ion etch-cleaning was applied for better adhesion before plasma nitriding. After plasma nitriding Ti interlayer was in-situ deposited by high power impulse magnetron sputtering (HIPIMS), followed by the AlTiN coating through in-situ deposition by advanced plasma-assisted arc (APA-Arc). The microstructure and properties of the duplex-treated coating were carefully characterized and analyzed. The results show that the thicknesses of the nitriding zone, the γ′-Fe₄N compound layer, the Ti interlayer and the AlTiN top layer with nanocrystalline microstructures are about 60 μm, 2–3 μm, 100 nm and 6.1 μm, respectively. The nitriding rate is about 30 μm/h and the AlTiN coating deposition rate reaches 6.1 μm/h. The interfacial adhesion of the Ti/AlTiN coating is well enhanced by ion etch-cleaning and a Ti interlayer, and the load-bearing capacity is also improved by duplex treatment. In addition, the instinct hardness of the Ti/AlTiN coating reaches 3368HV_0.05 while the wear rate coefficient of 5.394×10⁻⁸ mm⁻³/Nm is sufficiently low. The Ti/AlTiN coating, which possesses a high corrosion potential (E_corr=−104.6 mV) and a low corrosion current density (i_corr=4.769 μA/cm²), shows highly protective efficiency to the substrate.     

Thickness-dependent phase evolution and bonding strength of SiC ceramics joints with active Ti interlayer

A robust solid state diffusion joining technique for SiC ceramics was designed with a thickness-controlled Ti interlayer formed by physical vapor deposition and joined by electric field-assisted sintering technology. The interface reaction and phase revolution process were investigated in terms of the equilibrium phase diagram and the concentration-dependent potential diagram of the Ti-Si-C ternary system. Interestingly, under the same joining conditions (fixed temperature and annealing duration), the thickness of the Ti interlayer determined the concentration and distribution of the Si and C reactants in the resulting joint layer, and the respective diffusion distance of Si and C into the Ti interlayer differentiated dramatically during the short joining process (only 5 min). In the case of a 100 nm Ti coating as an interlayer, the C concentration in the joint layer was saturated quickly, which benefited the formation of a TiC phase and subsequent Ti₃SiC₂ phase. The SiC ceramics were successfully joined at a low temperature of 1000 °C with a flexural strength of 168.2 MPa, which satisfies applications in corrosive environments. When the Ti thickness was increased to 1 μm, Si atoms diffused easily through the diluted Ti-C alloy (a dense TiC phase was not formed), and the Ti₅Si₃ brittle phase formed preferentially. These findings highlight the importance of the diffusion kinetics of the reactants on the final composition in the solid state reaction, particularly in the joining technique for covalent SiC ceramics.     

Composition,structure and mechanical properties of the titanium surface after induction heat treatment followed by modification with hydroxyapatite nanoparticles

Coatings of titania (TiO₂) and "titania–hydroxyapatite" were prepared by oxidation of commercially pure titanium VT1-00 using induction heat treatment (IHT), followed by modification with colloidal hydroxyapatite (HAp) nanoparticles. The IHT treatment was performed at temperatures within 600–1200 °C for 300 s. According to the results of scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray fluorescent analysis (EDX), nanoindentation and in vitro testing, titania coatings of high morphological heterogeneity, and high mechanical properties and biocompatibility were formed on the titanium surface after IHT. The coatings were found to consist of nano- and submicron crystals of oval, needle-like, plate and prismatic shapes. A subsequent modification with HAp nanoparticles of the coated titanium substrate leads to accelerated formation of mechanically strong oxidebioceramic composite coatings. It was established that the porous oxide coatings modified with nanoparticles of HAp that were formed at temperatures from 800 to 1000 °C and holding for at least 30 s had a high biocompatibility.     

Preparation of freestanding and crack-free titania–silica aerogels and their performance for gas phase,photocatalytic oxidation of VOCs

Freestanding and crack-free titania–silica aerogels with high titanium content (i.e., Ti/Si = 1) were successfully prepared by adjusting the hydrolysis of the two alkoxide precursors to a comparable rate during the sol–gel processing. Two titania–silica aerogels were prepared by ethanol and CO₂ supercritical drying methods. Well-dispersed, nanometer-sized anatase crystal domains (ca. 10 nm) were crystallized by high temperature, ethanol supercritical drying. The crystalline domains were solidly anchored to the aerogel network by Ti–O–Si bonds. Titania–silica aerogels prepared by CO₂ supercritical drying method were devoid of TiO₂ crystals. A molecular-level mixing was achieved and anatase TiO₂ was only crystallized with difficulty by high temperature calcination (1073 K). Both aerogels were mesoporous and displayed similar open pore structure that is readily accessible to reactant molecules. However, only the titania–silica aerogel with anatase TiO₂ prepared by ethanol supercritical drying was active for the gas phase, photocatalytic oxidation of volatile organic compounds (i.e., isopropanol and trichloroethylene). Catalysts prepared from Degussa P25 TiO₂ displayed lower activity under similar reaction conditions.     

Preparation of dense β-CaSiO3 ceramic with high mechanical strength and HAp formation ability in simulated body fluid

In present study, dense CaSiO₃ (CS) ceramics have been fabricated through spark plasma sintering (SPS) technique using β-CS powder prepared by chemical precipitation method. The β-CS ceramic sintered at 950 °C has a relative density of about 95% and shows a fine microstructure with an average grain size of 0.6 μm, thus expresses good bending strength of about 294 MPa. The simulated body fluid (SBF) immersion tests show that the dense β-CS ceramic has a high hydroxyapatite (HAp) formation rate on its surface. The HAp layer formed on the CS ceramic surface has a granular structure consisting of silkworm-like HAp grains, and the thickness of HAp and Si-rich layer are 70 and 120 μm, respectively.     

Flash joining of CVD-SiC coated Cf/SiC composites with a Ti interlayer

Flash joining of CVD-SiC coated C_f/SiC samples with a Ti interlayer was achieved using a Spark Plasma Sintering machine. The influence of different heating powers and discharge times were investigated. The sample flash joined at a maximum heating power of 2.2 kW (peak electric current of 370 A) within 7 s showed the highest apparent shear strength of 31.4 MPa, which corresponds to the interlaminar shear strength of the composites. A maximum joining temperature of ∼1237 °C was reached during the flash joining. An extremely rapid heating rate of 9600 °C/min combined with a very short processing time hindered any reaction between the CVD-SiC coating and the Ti interlayer. The formation of a metallic joint (Ti based) in the absence of any detectable reaction phase is proposed as a new joining mechanism. For a conventionally joined SPS sample, the formation of titanium silicide phases inhibited the formation of a bond.     

Polyimide/nano-TiO2 hybrid films having benzoxazole pendent groups: In situ sol–gel preparation and evaluation of properties

Polyimide/titania (PI/TiO₂) nanocomposite films have been successfully fabricated through the in situ formation of TiO₂ within a PI matrix via sol–gel method. Poly(amic acid) (PAA), which is the precursor of PI, was successfully synthesized by mixing pyromellitic dianhydride (PMDA), with equimolar amount of a diamine monomer having a pendent benzoxazole unit and two flexible ether linkages in N,N-dimethylformamide (DMF) solvent. Tetraethyl orthotitanate [Ti(OEt)₄] and acetylacetone were then added to the resulted PAA. After imidization at high temperature, PI/TiO₂ hybrid films were formed. The structure and morphology of the hybrid nanocomposites with different titania contents (0 wt%, 5 wt%, 10 wt%, and 15 wt%) were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and transmission electron microscopy. The results indicate that the TiO₂ nanoparticles were homogeneously dispersed in the hybrid films. The thermogravimetric analysis of nanocomposites confirms the improvement in the thermal stability with the increase in the percentage of titania nanoparticle. Transmission electron microscopy showed that the nanoparticles with an average diameter of 25–40 nm were dispersed in the polymer matrix.     

Sol–gel preparation of titania multilayer membrane for photocatalytic applications

The main goal of the present study is to prepare a titania membrane with high permeability and photocatalytic activity for environmental applications. In this investigation a mesoporous titania multilayer membrane on alumina substrate is successfully fabricated via the sol–gel processing method. The prepared titania polymeric sol for the membrane top layer has an average particle size of 11.7 nm with a narrow distribution. The resulting TiO₂ multilayer membrane exhibits homogeneity with no cracks or pinholes, small pore size (4 nm), large specific surface area (83 m²/g), and small crystallite size (10.3 nm).The permeability and photocatalytic properties of the titania membrane were measured. The photoactivity of the titania membrane was examined to be 41.9% after 9 h UV irradiation based on methyl orange degradation. This measurement indicates high photocatalytic activity per unit mass of the catalyst. Through multilayer coating procedure, the photocatalytic activity of the membrane improved by 60% without sacrificing the membrane permeation. The prepared TiO₂ photocatalytic membrane has a great potential in developing high efficient water treatment and reuse systems due to its multifunctional capability such as decomposition of organic pollutants and physical separation of contaminants.     

Densification behavior and properties of alumina–chrome ceramics: Effect of TiO2

Highly dense alumina–chrome bodies with low porosity are usually used as corrosion and thermal resistant refractories. Alumina–chrome refractory with molar ratio 1:1 was developed using chemical grade hydrated alumina and chromium (III) oxide by conventional sintering route. Batch materials were attrition milled, isostatically pressed and sintered in the temperature range from 1000 °C to 1700 °C with 2 h soaking at peak temperature. Phase development of the sintered materials with temperature was studied by X-ray diffraction. Sintering temperature, sintering condition and addition of sintering aid (TiO₂) have immense effect on the densification of the alumina–chrome refractory. Highly dense alumina–chrome refractory with almost nil apparent porosity was developed at 1500 °C in reducing atmosphere. Flexural strength of the sintered materials at room temperature and at 1200 °C was also measured. 1 wt% TiO₂ gives the optimum result with respect to densification and flexural strength.     

The role of titania on the microstructure,biocorrosion and mechanical properties of Mg/HA-based nanocomposites for potential application in bone repair

Bone defects are very challenging in orthopedic practice. The ideal bone grafts should provide mechanical support and enhance the bone healing. Biodegradable magnesium (Mg)–based alloys demonstrate good biocompatibility and osteoconductive properties, which are promising biomaterials for bone substitutes. However, the high rate of their biodegradation in human body environment is still challenging. For this scope, synthesis Mg-based composites with bioceramic additives such as HA and titania (TiO₂) is a routine to solve this problem. The aim of this study was to evaluate the effect of addition TiO₂ nanopowders on the corrosion behavior and mechanical properties of Mg/HA-based nanocomposites fabricated using a milling-pressing-sintering technique for medical applications. The microstructure of Mg/HA/TiO₂ nanocomposites, in vitro degradation and biological properties including in vitro cytocompatibility were investigated. The corrosion resistance of Mg/HA-based nanocomposites was significantly improved by addition 15 wt% of TiO₂ and decrease HA amount to 5 wt% this was inferred from the lower corrosion current; 4.8 µA/cm² versus 285.3 µA/cm² for the Mg/27.5 wt%HA, the higher corrosion potential; −1255.7 versus −1487.3 mV_SCE, the larger polarization resistance; 11.86 versus 0.25 kΩ cm² and the significantly lower corrosion rate; 0.1 versus 4.28 mm/yr. Compressive failure strain significantly increased from 1.7% in Mg/27.5HA to 8.1% in Mg/5HA/15TiO₂ (wt%). The Mg/5HA/15TiO₂ (wt%) nanocomposite possessed high corrosion resistance, cytocompatibility and mechanical properties and can be considered as a promising material for implant applications.     

Preparation,characterization and photocatalytic activity of a novel nanostructure composite film derived from nanopowder TiO2 and sol–gel process using organic dispersant

A novel sol–gel-derived titanium dioxide nanostructure composite has been prepared by spin-coating and investigated for the purpose of producing films. The processing of the composite sol–gel photocatalysts involved utilizing of precalcinated nanopowder titanium dioxide as filler mixed with sol and heat treated. The sol solution was prepared by adding titanium tetra isopropoxide (Ti(OPr)₄ or TTP) to a mixture of ethanol and HCl 35.5% (mole ratio TTP:HCl:EtOH:H₂O = 1:1.1:10:10), then a solution of 2 wt% methylcellulose was added and stirred at room temperature. Precalcinated TiO₂ nanopowder was dispersed in the sol and the prepared mixture was deposited on the microscope glass slide by spin-coating. The inhomogeneity problem in preparation of composite film which causes peeling off and cracking after calcination due to the shrinkage of the films with thermal treatment were overcome by using methylcellulose (MC) as a dispersant. The composite heat treated at approximately 500 °C has the greatest hardness value. Surface morphology of composite deposits by scanning electron microscopy (SEM) showed remarkable increase in the composite surface area. Evaluation of the adhesion and bonding strength between the coating and substrate was carried out by the scratch test technique. The minimum load which caused the complete coating removal, for composite thick film was 200 g/mm² which indicates a strong bond to the substrate. Photocatalytic activity of the composite film was evaluated through the degradation of a textile dye, Light Yellow X6G (C.I. Reactive Yellow 2) as a model pollutant and were compared with those of similar composite thick film without MC, thin film of TiO₂ and TiO₂ nanopowder. The results show that the photocatalytic activity and stability of the composite films are higher than those of nanopowder TiO₂. However, a remarkable increase in the composite surface and good mechanical integrity make this composite film a viable alternative for commercial applications.     

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.     

Effect of TiO2 doping on the characteristics of macroporous Al2O3/TiO2 membrane supports

A cost-effective tubular macroporous ceramic support consisting of alumina and titania was prepared by extrusion and subsequent heat treatment. An Al₂O₃/TiO₂ composite support with high porosity (41.4%), an average pore size of 6.8 μm and sufficient mechanical strength (32.7 MPa) was obtained after sintering at 1400 °C. The formation mechanism of this support as investigated with X-ray micromapping, SEM and XRD indicated that the appearance of Al₂TiO₅ plays a key role in the fabrication of high performance composite membrane supports at relatively low temperature. The amount of Al₂TiO₅ present in the composite has a strong impact on the properties of supports, especially with regard to the mechanical strength. A composite of 85 wt.% Al₂O₃/15 wt.% TiO₂ sintered at 1400 °C for 2 h exhibited both high permeability (pure water flux of 45 m³ m^?2 h^?1 bar^?1), together with an excellent corrosive resistance towards hot NaOH and HNO₃ solutions.     

Comparison of the anti-coking performance of CVD TiN,TiO2 and TiC coatings for hydrocarbon fuel pyrolysis

Previous work has shown that both TiN and TiO₂ coatings can inhibit the metallic catalytic coking effectively, but both of them have their own shortage. In this work, TiC coating was prepared on the surface of SS304 tube using TiCl₄-CH₄-H₂ by CVD method. Its morphology, elemental composition, thickness and oxidation resistance were characterized by SEM, EDX, metalloscopy and TPO tests, respectively. The results show that CVD TiC coating is gray, homogeneous, and dense without cracks or holes. The TiC coating presents a cuboid particle structure with the sizes of about 1.0 µm for the cuboid crystals, and the Ti/C ratio close to 1:1, while the average thickness is about 11.62 µm. TPO results show that the TiC coating begins to react with O₂ and release CO₂ at about 810 °C. Compared with the TiN coating (The initial oxidation temperature of TiN is about 350 °C), the oxidation resistance of TiC coating is improved substantially. As a conclusion, the high oxidation resistance order is TiO₂ coating>TiC coating>TiN coating. Furthermore, the temperature programmed cracking of RP-3 Chinese jet fuel was employed to compare the anti-coking performance of TiN, TiO₂ and TiC coatings. The results show that each of TiN, TiO₂ and TiC coating has obvious anti-coking effect, and the anti-coking performance order is TiN coating=TiC coating>TiO₂ coating.     

An evaluation of plasma-sprayed coatings based on Al2O3 and Al2O3–13 wt.% TiO2 with bond coat on pure titanium substrate

In this study, the effects of bond coat on the properties of Al₂O₃ and Al₂O₃–13 wt.% TiO₂ coatings, which is plasma sprayed onto a commercial pure titanium substrate with and without Ni–5 wt.% Al (METCO 450 NS) as bond coating layer were investigated in terms of microhardness, bonding strength and surface roughness. Optical and scanning electron microscopy (SEM) examinations revealed that there is a uniform coating layer with no spalling and delamination. However, there is a little amount of porosity. The results indicated that the application of bond coat layer in the plasma spraying of Al₂O₃ and Al₂O₃–13 wt.% TiO₂ on pure titanium substrate has increased the hardness and bonding strength of coatings. While the adhesive bonding is dominant without bond coat, the cohesive bonding is dominant with the application of the bond coating layer. It has been observed that percentage of cohesion strength was about three times higher than that of adhesion strength.     

Mesoporous TiO2–SiO2 aerogels with hierarchal pore structures

Freestanding blocks of binary oxides, TiO₂–SiO₂ aerogel containing highly ordered mesophase structures were successfully prepared by a new synthesis method involving partial solvent evaporation followed by supercritical extraction and drying. The new method allows the routine preparation of large, crack-free aerogels of high titanium content (i.e., Ti/Si ? 0.75 or up to 50 wt.% Ti), ordered mesopores (i.e., 2–20 nm), large surface area (i.e., 400–900 m² g^?1) and pore volume (i.e., 0.7–2.6 cm³ g^?1). Aerogels with well-ordered mesopores were obtained for Ti/Si atom ratios of 0.04–0.08. The size of ordered mesopore domains decreases with increasing titanium loading, and TS75 aerogels with Ti/Si = 0.75 display discontinuous microdomains of ordered mesoporosity within disordered phases interspersed with crystalline anatase TiO₂. The greater permeability of the TS75 pore network resulted in fifteen times better activity for photocatalytic oxidation of airborne trichloroethylene compared to commercial Degussa P25 TiO₂ and more than twice that TiO₂–SiO₂ aerogel (TS100) of similar titanium loading but with disordered and tortuous pore network.     

Characteristic reaction processes in the system brushite–NaOH solution

The reaction of brushite (CaHPO₄·2H₂O, DCPD) with NaOH solutions ranging in concentration from 0 to 40 mass% were investigated at 25 °C. At low NaOH concentrations below 20 mass%, hydroxyapatite (HAp) formed directly through the reaction (1) DCPD → HAp. At middle concentrations of 20–27 mass%, DCPD changed once into Ca(OH)₂ and then into HAp, i.e., through the consecutive reaction (2) DCPD → Ca(OH)₂ → HAp. At high concentrations above 27 mass%, the consecutive reaction (3) DCPD → HAp → Ca(OH)₂ was concluded. The boundary concentrations, i.e., singular points, between the first/second and the second/third reactions were estimated to be ca. 20 and 27 mass%, respectively. HAp particles obtained were platelet aggregates of very fine HAp microcrystals. The platelet form was compatible to the original platelet DCPD form. HAp samples prepared in this reaction system were structurally low crystalline and compositionally stoichiometric, and had a feature of large heating weight losses below 400 °C.     

TiO2 photocatalysis in cementitious systems: Insights into self-cleaning and depollution chemistry

The present work offers a general overview about application of titanium dioxide (or titania), TiO₂, photocatalysis to concrete technology in relation to enhanced aesthetic durability and depollution properties achieved by implementing TiO₂ into cement. Chemistry of degradation of Rhodamine B (RhB), a red dye used to assess self-cleaning performances of concretes containing TiO₂, as well as oxidation of nitrogen oxides (NOx), gaseous atmospheric pollutants responsible for acid rains and photochemical smog, is investigated using two commercial titania samples in cement and mortar specimens: a microsized, m-TiO₂ (average particle size 153.7 nm ± 48.1 nm) and a nanosized, n-TiO₂ (average particle size 18.4 nm ± 5.0 nm). Experimental data on photocatalytic performances measured for the two samples are discussed in relation to photocatalyst properties and influence of the chemical environment of cement on titania particles. Impacts on applications in construction concrete are also discussed.     

Electrophotocatalytic decolorization of an azo dye on TiO2 self-organized nanotubes in a laboratory scale reactor

It was investigated the feasibility of decolorization of an azo dye (DG 26) using a large scale nanotubular TiO₂ structured electrode in a laboratory photoelectrochemical reactor (0.8 L). Catalyst was grown by anodic oxidation directly on Ti surface and its microstructure and crystalline structure were characterized with SEM and XRD. TiO₂/Ti photoactivity under different anodic polarization values was evaluated via photoelectrochemical tests. The nanostructured TiO₂ was used in a reactor as photo-anode under UV monochromatic irradiation (254 nm) and it was subjected to bias (+ 1.5 V vs. SCE). A comparison with photolysis and photocatalysis processes was carried out under the same operating conditions to evaluate the synergistic action of photocatalysis and TiO₂/Ti electrochemical polarization.Electrophotocatalysis was proven to be more effective than photocatalysis in DG 26 decolorization. Catalyst polarization resulted in synergistic effect on process yields. The complete decolorization of a 40 mg/L solution of DG 26 was achieved in 24 h, without adding chemical reagents, and catalyst durability was demonstrated over 360 h tests. Therefore, the work done is challenging to prove that the process (irradiation + catalyst + polarization) is feasible and effectively up-grading to pilot and demonstrative scale applications after a fluid dynamics optimization of the photoreactor.