Characteristic and microstructure of the microarc oxidized TiO2-based film containing P before and after chemical- and heat treatment

Chemical- and heat treatment was performed to modify the surface of the microarc oxidized TiO₂-based (TOB) film containing P to produce nano-scale compounds containing Na, Ti and O elements. In the TOB film, anatase and rutile nanocrystals were randomly distributed in P-doped matrix. On the surface of the chemically treated TOB (C-TOB) film, amorphous titanium oxide containing Na shows nano-scale ribbonlike morphology. Na, Ti and O show uniform distribution in the outer layer of the C-TOB film along surface depth. Chemical treatment did not alter the surface roughness of the TOB film obviously; however, it improved its hydrophilic property. Heat treatment has no influence on the chemical states of Ti, Na and O, as well as wetting ability, elemental composition and atomic concentration in the outer layer of the C-TOB film. However, the phase compositions and surface morphology of the C-TOB film after heat treatment are dependent on the heat treatment temperature.     

Chemical treatment of TiO2-based coatings formed by plasma electrolytic oxidation in electrolyte containing nano-HA, calcium salts and phosphates for biomedical applications

TiO₂-based coatings were formed on titanium alloy by plasma electrolytic oxidation (PEO) in an electrolyte containing nano-HA, calcium salts and phosphates. Bioactive surface was formed after chemical treatment (NaOH aqueous solution) of the PEO coating. The surface of the PEO coating was mainly composed of Ti, O, Ca and P showing anatase and rutile; while that of the chemically treated PEO (CT-PEO) coating mainly contains Ti, O, Ca and Na showing anatase, rutile and amorphous phase. And the chemically treated surface exhibits dissolution of P and introduction of Na during the chemical treatment process. The chemical treatment has no effect on the chemical states of Ca and Ti of the PEO coating. In addition, the surface constituents of the CT-PEO coating show a uniform distribution near its surface with increasing depth. When incubated in a simulated body fluid for 7 and 14 days, the PEO coating does not exhibit apatite-forming ability; however, apatite was successfully deposited on the CT-PEO coating after 7 days probably due to the formation of hydroxyl functionalized surface, enhancing the heterogeneous nucleation of apatite. The addition of nano-HA in the electrolyte has effects on the surface character and apatite-forming ability of the PEO coating; however, it has no obvious influence on those of the CT-PEO coatings.     

Characteristic of microarc oxidized coatings on titanium alloy formed in electrolytes containing chelate complex and nano-HA

Microarc oxidized (MAO) TiO₂-based coatings containing Ca and P on titanium alloy were formed in electrolytes containing nano-hydroxyapatite (nano-HA), calcium and phosphate salts. The effects of HA concentration on the thickness, micropore size and number of the MAO coatings were not pronounced. However, the surfaces of the MAO coatings become rough and the crystallinity of anatase increases with increasing HA concentration. In addition, the Ca and P concentrations on the surfaces of the MAO coatings decrease, since the chelate complex of CaY²⁻ (Y = [₂(OOC)NCH₂CH₂N(COO)₂]⁴⁻) and phosphate ions are hindered to be incorporated into the MAO coatings by HA. In vitro experiments indicate that the apatite-forming abilities of the MAO coatings decrease with increasing HA concentration. Furthermore, with increasing HA concentration, the solubility of Ca and P of the MAO coatings decreases, which could lower the supersaturation of the SBF with respect to apatite near the surfaces of the MAO coatings, further leading to the decreased apatite-forming ability. The results indicate that the HA addition in the electrolytes has an important effect on the structure and in vitro bioactivity of the MAO coatings.     

Fabrication of hydroxyapatite and TiO2 nanorods on microarc-oxidized titanium surface using hydrothermal treatment

AC-type microarc oxidation (MAO) and hydrothermal treatment techniques were used to enhance the bioactivity of commercially pure titanium (CP-Ti). The porous TiO₂ layer fabricated by the MAO treatment had a dominant anatase structure and contained Ca and P ions. The MAO-treated specimens were treated hydrothermally to form HAp crystallites on the titanium oxide layer in an alkaline aqueous solution (OH-solution) or phosphorous-containing alkaline solution (POH-solution). A small number of micro-sized hydroxyapatite (HAp) crystallites and a thin layer composed of nano-sized HAps were formed on the Ti-MAO-OH group treated hydrothermally in an OH-solution, whereas a large number of micro-sized HAp crystallites and dense anatase TiO₂ nanorods were formed on the Ti-MAO-POH group treated hydrothermally in a POH-solution. The layer of bone-like apatite that formed on the surface of the POH-treated sample after soaking in a modified simulated body fluid was thicker than that on the OH-treated samples.     

Microstructure and shear fracture characteristics of porous anodic TiO2 layer before and after hot water treatment

Porous TiO₂ layer was fabricated on the surface of commercially pure titanium using an anodic spark oxidation technique for biomedical application, and subsequent hot water treatment was performed to modify the resultant oxide layer. The microstructure features and shear fracture characteristics of anodic oxide layer before and after water treatment were investigated. Results show that before water treatment, the oxide layer exhibited a porous surface with few nanometer features and consisted of poorly crystallized oxides, and an inner layer containing numerous cavities was observed near the oxide-substrate interface. After water treatment, the crystallinity degree of oxide layer was increased significantly and a nanostructured surface layer was obtained. The shear fracture characteristics of oxide layer were greatly influenced by its microstructure features. Before water treatment, the shear fracture took place primarily within the cavity-containing layer, resulting in a pitted fracture surface on the substrate side. However, after water treatment, the shear fracture occurred mainly along the bottom surface of nanostructured surface layer and the shear strength of oxide layer decreased obviously.     

Microstructure and infrared emissivity property of coating containing TiO2 formed on titanium alloy by microarc oxidation

Ceramic coatings containing TiO₂ were formed on Ti6Al2Zr1Mo1V alloy surface by microarc oxidation (MAO) method. The microstructure, phase and chemical composition of the coatings were analyzed by SEM, XRD and EDS techniques. The coating mainly consists of rutile TiO₂ and a small amount of anatase TiO₂. The infrared emissivity values of coated and uncoated titanium samples when exposed to 700 °C were tested. It was found that the coating exhibits a higher infrared emissivity value (about 0.9) in the wavelength range of 8–14 μm than that of the uncoated titanium alloy, although which shows a slight increase from 0.1 to 0.3 with increasing exposure time at 700 °C. The relatively high infrared emissivity value of the MAO coating is possibly attributed to the photon emission from the as formed TiO₂ phase.     

Effect of the heat treatment on the corrosion behaviour of amorphous Fe-Cr-P-C-Si alloy in 0.5 M H2SO4

The effect of the heat treatment on the corrosion behaviour of amorphous Fe₈₅Cr₅P₆C₃Si alloy in 0.5 M H₂SO₄ has been investigated using electrochemical techniques. Heat treatment was carried out at temperatures varying between 250 and 650 °C at different times 30, 60, 120 and 240 min. The evolution of crystallization processes after annealing was identified by differential thermal analysis (DTA) and by X-ray diffraction (XRD). The diagrams obtained by DTA show that the structure of samples treated at high temperature changes towards a crystalline state. This crystallization phenomenon is confirmed by the analysis with the XRD. The results obtained from the polarization curves reveal that for all the studied temperatures of annealing, Fe-Cr-P-C-Si exhibits a phenomenon of passivation without breakdown of passivity. The best corrosion resistance is obtained at the temperature of annealing 350 °C. For an annealing at higher temperatures, Fe₈₅Cr₅P₆C₃Si becomes less corrosion resistant than same amorphous alloy treated with temperatures lower than 350 °C.     

A microscopy study of the effect of heat treatment on the structure and properties of anodised TiO2 nanotubes

Titanium oxide (TiO₂) nanotubes prepared by anodisation of titanium in an aqueous electrolyte and glycerol have been heat treated in the temperature range 200-600 °C to control the conversion of the amorphous structure to nano-crystalline anatase and rutile. The phase changes have been monitored are observed at lower temperatures (100 °C or more) than previously reported. The sensitivity of the different techniques, each of which depends on the size of the crystalline phase, can explain the discrepancy with previous results. Transmission electron microscopy (TEM) has shown the phase changes which have occurred and which have been reported in an earlier publication; phenomena such as the collapse of the structures are explained. The TEM results are consistent with the Raman and XRD data, apart from the transformation temperatures, and also shed light on the nature of an amorphous phase found on the surfaces of the nanotubes.     

Influence of heat treatment on tribological properties of electroless Ni-P and Ni-P-Al2O3 coatings on Al-Si casting alloy

Evolution of tribological properties of electroless Ni-P and Ni-P-Al₂O₃ coating on an Al-10Si-0.3Mg casting alloy during heat treatment is investigated in this work. The pre-treated substrate was plated using a bath containing nickel hypophosphite, nickel lactate and lactic acid. For preparation of fiber-reinforced coating Al₂O₃ Saffil fibers pre-treated in demineralised water were used. The coated samples were heat treated at 400-550 °C/1-8 h. Tribological properties were studied using the pin-on-disc method. It is found that the best coating performance is obtained using optimal heat treatment regime (400 °C/1 h). Annealing at higher temperatures (450 °C and above) leads to the formation of intermetallic compounds that reduce the coating wear resistance. The reason is that the intermetallic phases adversely affect the coating adherence to the substrate. The analysis of wear tracks proves that abrasion is major wear mechanism, however due to the formed intermetallic sub-layers, partial coating delamination may occur during the pin-on-disc test on the samples annealed at 450 °C and above. It was found that fiber reinforcement reduces this scaling and increases wear resistance of coatings as compared to the non-reinforced Ni-P coatings.     

Synthesis of efficient TiO2-based photocatalysts by phosphate surface modification and the activity-enhanced mechanisms

A simple strategy to greatly increase the thermal stability of nanocrystalline anatase has been put forward to fabricate efficient TiO₂-based photocatalysts under ultraviolet irradiation, via the surface modification with phosphate anions. The results show that the increased anatase thermal stability is attributed to the roles of the phosphate modification effectively inhibiting the contacts among anatase nanocrystals. Compared to un-modified TiO₂, the modified TiO₂ calcined at high temperature (over 700 °C) exhibits much high photocatalytic activity for degrading Rhodamine B (or phenol) solution, even superior to the commercial P25 TiO₂. The activity enhancement is mainly attributed to the increased separation rate of photogenerated charge carriers on the basis of the measurements of steady state- and transient state-surface photovoltage spectroscopy. This work would provide a practical route to reasonably design and synthesize high-performance TiO₂-based nanostructured photocatalysts with high anatase thermal stability.     

Effect of heat treatment on morphology, crystalline structure and photocatalysis properties of TiO2 nanotubes on Ti substrate and freestanding membrane

Highly ordered titanium oxide (TiO₂) nanotubes were prepared by electrolytic anodization of titanium electrodes. Morphological evolution and phase transformations of TiO₂ nanotubes on a Ti substrate and that of freestanding TiO₂ membranes during the calcinations process were studied by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction microscopy. The detailed results and mechanisms on the morphology and crystalline structure were presented. Our results show that a compact layer exists between the tubular layer and Ti substrate at 600 °C, and the length of the nanotubes shortens dramatically at 750 °C. The freestanding membranes have many particles on their tubes during calcinations from 450 to 900 °C. The TiO₂ nanotubes on the Ti substrate transform to rutile crystals at 600 °C, while the freestanding TiO₂ membranes retain an anatase crystal with increasing temperature to 800 °C. The photocatalytic activity of TiO₂ nanotubes on a Ti substrate annealed at different temperatures was investigated by the degradation of methyl orange in aqueous solution under UV light irradiation. Due to the anatase crystals in the tubular layer and rutile crystals in the compact layer, TiO₂ nanotubes annealed at 450 °C with pure anatase crystals have a better photocatalytic activity than those annealed at 600 °C or 750 °C.