Development of superlattice CrN/NbN coatings for joint replacements deposited by high power impulse magnetron sputtering

The demand for reliable coating on medical implants is ever growing. In this research, enhanced performance of medical implants was achieved by a CrN/NbN coating, utilising nanoscale multilayer/superlattice structure. The advantages of the novel high power impulse magnetron sputtering technology, namely, its unique highly ionised plasma, were exploited to deposit dense and strongly adherent coatings on CoCr implants. Transmission electron microscopy analysis revealed coating superlattice structure with bi-layer thickness of 3.5?nm. CrN/NbN deposited on CoCr samples showed exceptionally high adhesion, critical load values of L_C2?=?50?N in scratch adhesion tests. Nanoindentation tests showed high hardness of 34?GPa and Young’s modulus of 447?GPa. Low coefficient of friction (μ) 0.49 and coating wear coefficient (K _C)?=?4.94?×?10^?16?m³?N^?1?m^?1 were recorded in dry sliding tests. Metal ion release studies showed a reduction in Co, Cr and Mo release at physiological and elevated temperatures (70?°C) to almost undetectable levels (<1?ppb). Rotating beam fatigue testing showed a significant increase in fatigue strength from 349?±?59?MPa (uncoated) to 539?±?59?MPa (coated). In vitro biological testing has been performed in order to assess the safety of the coating in biological environment; cytotoxicity, genotoxicity and sensitisation testing have been performed, all showing no adverse effects.     

Effect of TiO2 nanotube length and lateral tubular spacing on photovoltaic properties of back illuminated dye sensitized solar cell

The main objective of this study is to show the effect of TiO₂ nanotube length, diameter and intertubular lateral spacings on the performance of back illuminated dye sensitized solar cells (DSSCs). The present study shows that processing short TiO₂ nanotubes with good lateral spacings could significantly improve the performance of back illuminated DSSCs. Vertically aligned, uniform sized diameter TiO₂ nanotube arrays of different tube lengths have been fabricated on Ti plates by a controlled anodization technique at different times of 24, 36, 48 and 72?h using ethylene glycol and ammonium fluoride as an electrolyte medium. Scanning electron microscopy (SEM) showed formation of nanotube arrays spread uniformly over a large area. X-ray diffraction (XRD) of TiO₂ nanotube layer revealed the presence of crystalline anatase phases. By employing the TiO₂ nanotube array anodized at 24?h showing a diameter ??80?nm and length ??1·5???m as the photo-anode for back illuminated DSSCs, a full-sun conversion efficiency (??) of 3·5 % was achieved, the highest value reported for this length of nanotubes.     

The microstructure and the mechanical property of AZ91D solidified under GPa-grade high-pressure

High-pressure (2–4?GPa) solidified AZ91D alloy was prepared and the microstructure was investigated by X-ray energy diffraction and scanning electronic microscopy. The room-temperature compression deformation behaviour was also studied. The results showed that the high-pressure solidified AZ91D alloy was composed of nanometre β-Mg₁₇Al₁₂ and equiaxed α-Mg dendrites. The average size of α-Mg grains decreased from 395?±?5?µm (atmosphere pressure) to 12?±?3?µm (4?GPa) and the solubility of Al in α-Mg increased to 6.25?wt-% at 4?GPa. The compression strength of 402?MPa and the relative compression ratio of 27% (4?GPa) were 50% and 93% higher than the original AZ91D. Meanwhile, high pressure can also decreased the corrosion rate from 0.0675?mA/cm² (atmosphere pressure) to 0.0122?mA/cm² (4?GPa).     

Microstructure and mechanical properties of an ultrafine grained Ti5Si3-TiC composite fabricated by spark plasma sintering

The purpose of this study was to investigate mechanical properties, microstructure and sintering behavior of ultrafine grained Ti₅Si₃-TiC composite synthesized by mechanically activated self-propagating high-temperature synthesis method. For this purpose, the composite was sintered at 1450?°C at constant pressure of 50?MPa and reached to 97% of theoretical density by spark plasma sintering technique. The XRD pattern of the sintered sample is composed of the same peaks as the synthesized sample which means that the composite is stable at high temperature. The microstructure analyses illustrate that the composite retained its fine microstructure during the sintering process. The results also show that the amount of C atoms in the structure of titanium silicide slightly increased during the sintering process. The Young’s modulus and nanohardness of the composite reached 281?±?15.5?GPa and 16.6?±?0.8?GPa, respectively. In addition, Vickers indentation test results show that the composite possesses hardness and fracture toughness of 13.2?±?0.6?GPa and 4.7?±?0.1?MPa.m^1/2, respectively. Formation of microstructure with low microcracks and homogenous distribution of TiC through the matrix are responsible for relative high mechanical properties of the composite. The crack deflection is observed as the main toughening mechanism.     

Dimensionality-dependent photocatalytic activity of TiO2-based nanostructures: nanosheets with a superior catalytic property

TiO₂-based nanostructures usually possess excellent photochemical properties. However, the relationship between their dimensionality and photocatalytic activity was rarely investigated. In this study, a series of TiO₂-based nanostructures in various dimensionalities (such as nanosheets, nanotubes) were obtained by hydrothermal treatment of P25, and the process of structural evolution was also systematically investigated by TEM, BET, Raman, and XRD analysis. Much higher rate constant (3.7 × 10^?2 min^?1) for the degradation of rhodamine B was found for nanosheets, comparing with those of three-dimensional P25 nanoparticles (0.59 × 10^?2 min^?1) and one-dimensional nanotubes (0.85 × 10^?2 min^?1). It is found that the hydrothermally prepared TiO₂-based nanosheets possess small thickness (ca. 5 nm) and plentiful surface hydroxyl groups, and the reason why TiO₂-based nanosheets possess superior photocatalytic activity is also discussed in detail from the microstructure and surface chemical states. In addition, TiO₂-based nanosheets exhibit good reusability in the cyclic experiments, implying a potential application for photocatalytic degradation of organic pollutants.     

Rutile TiO<Subscript>2</Subscript> films as electron transport layer in inverted organic solar cell

Titanium dioxide (TiO₂) thin films were prepared by sol–gel spin coating method and deposited on ITO-coated glass substrates. The effects of different heat treatment annealing temperatures on the phase composition of TiO₂ films and its effect on the optical band gap, morphological, structural as well as using these layers in P3HT:PCBM-based organic solar cell were examined. The results show the presence of rutile phases in the TiO₂ films which were heat-treated for 2 h at different temperatures (200, 300, 400, 500 and 600 °C). The optical properties of the TiO₂ films have altered by temperature with a slight decrease in the transmittance intensity in the visible region with increasing the temperature. The optical band gap values were found to be in the range of 3.28–3.59 eV for the forbidden direct electronic transition and 3.40–3.79 eV for the allowed direct transition. TiO₂ layers were used as electron transport layer in inverted organic solar cells and resulted in a power conversion efficiency of 1.59% with short circuit current density of 6.64 mA cm^?2 for TiO₂ layer heat-treated at 600 °C.     

Electrodeposition of dicalcium phosphate dihydrate coatings on stainless steel substrates

Cathodic reduction of an aqueous solution containing dissolved calcium and phosphate ions results in the deposition of micrometer thick CaHPO₄·2H₂O (dicalcium phosphate dihydrate) coatings on stainless steel substrates. The coating obtained at a low deposition current (8 mA cm^???2) comprises lath-like crystallites oriented along 020. The 020 crystal planes are non-polar and have a low surface energy. At a high deposition current (12 mA cm^???2), platelets oriented along 121? are deposited. CaHPO₄·2H₂O is an important precursor to the nucleation of hydroxyapatite, the inorganic component of bones. Differently oriented CaHPO₄·2H₂O coatings transform to hydroxyapatite with different kinetics, the transformation being more facile when the coating is oriented along 121?. These observations have implications for the development of electrodeposited biocompatible coatings for metal endoprostheses for medical applications.     

Investigation of superhydrophilic mechanism of titania nano layer thin film—Silica and indium oxide dopant effect

In this paper, TiO₂?CSiO₂?CIn₂O₃ nano layer thin films were deposited on glass substrate using sol?Cgel dip coating method. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and water contact angle measurements were used to evaluate chemical structure, surface composition, hydroxyl group contents and superhydrophilicity of titania films. FTIR result indicated that Si?CO?CSi, Si?CO?CTi and Ti?CO?CTi bands formed in TiO₂?CSiO₂?CIn₂O₃ sample. According to XPS, the hydroxyl content for TiO₂, TiO₂?CSiO₂ and TiO₂?CSiO₂?CIn₂O₃ films was calculated as 11·6, 17·1 and 20·7%, respectively. The water contact angle measurements indicated that silica and indium oxide dopant improved the superhydrophilicity of titania nano film surface especially in a dark place. The enhanced superhydrophilicity can be related to the generation of surface acidity on the titania nano film surfaces. In the present state, superhydrophilicity is induced by the simultaneous presence of both Lewis and Bronsted sites.     

Photochemical deposition of platinum on titanium dioxide–tungsten trioxide nanocomposites: an efficient photocatalyst under visible light irradiation

Highly ordered titanium dioxide–tungsten trioxide nanotubular composites (TiO₂–WO₃) were fabricated on titanium sheets by electrochemical anodizing. Platinum nanoparticles have been successfully deposited onto TiO₂–WO₃ nanotubes by UV light photoreduction method. In this work, X-ray diffraction, field emission scanning electron microscope, ultraviolet–visible spectroscopy and energy dispersive X-ray spectrometer methods were adopted to characterize the samples. The degradation of methylene blue (MB) was used as a model reaction to evaluate the photocatalytic activity of the obtained samples. After irradiated under visible light for 60 min, the degradation rate of MB solution on unmodified TiO₂–WO₃ and Pt/TiO₂–WO₃ reached 77 and 93 %, respectively. Under the same condition, no obvious photodegradation of MB was found for bare TiO₂ (T). Kinetic research showed that photodegradation process followed the first-order reaction; the apparent reaction rate constant of Pt/TiO₂–WO₃-1 was 4.56 × 10^?2 min^?1 which is approximately 1.75 times higher than that on the unmodified TiO₂–WO₃. This work provides an insight into designing and synthesizing new TiO₂–WO₃ nanotubes based hybrid materials for effective visible light-activated photocatalysis.     

Biomineralization capability of adherent bio-glass films prepared by magnetron sputtering

Radiofrequency magnetron sputtering deposition at low temperature (150°C) was used to deposit bioactive glass coatings onto titanium substrates. Three different working atmospheres were used: Ar 100%, Ar + 7%O₂, and Ar + 20%O₂. The preliminary adhesion tests (pull-out) produced excellent adhesion values (~75 MPa) for the as-deposited bio-glass films. Bioactivity tests in simulated body fluid were carried out for 30 days. SEM–EDS, XRD and FTIR measurements were performed. The tests clearly showed strong bioactive features for all the prepared films. The best biomineralization capability, expressed by the thickest chemically grown carbonated hydroxyapatite layer, was obtained for the bio-glass coating sputtered in a reactive atmosphere with 7% O₂.     

Microstructure,electrical and humidity sensing properties of TiO<Subscript>2</Subscript>/polyaniline nanocomposite films prepared by sol–gel spin coating technique

High sensitive resistive type humidity sensor based titanium oxide/polyaniline (TiO₂/PANI) nanocomposite thin films prepared by a sol–gel spin coating technique on an alumina substrate. The resultant nanocomposites were characterized by using X-ray diffraction (XRD), Field emission electron microscopy, Fourier transform infrared spectroscopy (FTIR), UV–Vis absorbance and energy dispersive spectra analysis. In the XRD patterns of both pure and TiO₂/PANI composite confirms the deposition of PANI on TiO₂ and the average size of the composite particle was found to be 32 nm. Large number of nano grain surface being covered by PANI, which agrees very well with the results obtained by XRD studies. FTIR and UV–Vis spectra reveal that the PANI component undergoes an electronic structure modification as a result of the TiO₂ and PANI interaction. The room temperature resistivity was found to be for TiO₂ and TiO₂/PANI nanocomposite films 1.42?×?10⁶ and 2.56?×?10³ Ω cm respectively. The obtained TiO₂/PANI nanocomposites sensor exhibited higher humidity sensing performance such as high sensitivity, fast response (20 s) and recovery time (15 s) and high stability.     

Highly porous titanium (Ti) scaffolds with bioactive microporous hydroxyapatite/TiO2 hybrid coating layer

Highly porous Ti scaffolds with a bioactive microporous hydroxyapatite (HA)/TiO₂ hybrid coating layer were fabricated using the sponge replication process and micro-arc oxidation (MAO) treatment to produce the porous Ti scaffold and hybrid coating layer, respectively. In particular, the morphology and chemical composition of the hybrid coating layer were controlled by carrying out the MAO treatment in electrolyte solutions containing various concentrations of HA, ranging from 0 to 30 wt.%. The fabricated sample showed high porosity of approximately 70 vol.% with interconnected pores and reasonably high compressive strength of 18 ± 0.3 MPa. Furthermore, the surfaces could be coated successfully with a bioactive microporous HA/TiO₂ hybrid layer. The amount of HA particles in the hybrid coating layer increased with increasing HA content in the electrolyte solution, while preserving the microporous morphology. This hybrid coating improved the osteoblastic activity of the porous Ti scaffolds significantly.     

Tuning the mechanical properties of composites from elastomeric to rigid thermoplastic by controlled addition of carbon nanotubes

A commercial thermoplastic polyurethane is identified for which the addition of nanotubes dramatically improves its mechanical properties. Increasing the nanotube content from 0% to 40% results in an increase in modulus, Y, (0.4–2.2 GPa) and stress at 3% strain, σ_{? = 3%}, (10–50 MPa), no significant change in ultimate tensile strength, σ_B, (≈50 MPa) and decreases in strain at break, ?_B, (555–3%) and toughness, T, (177–1 MJ m^?3). This variation in properties spans the range from compliant and ductile, like an elastomer, at low mass fractions to stiff and brittle, like a rigid thermoplastic, at high nanotube content. For mid‐range nanotube contents (≈15%) the material behaves like a rigid thermoplastic with large ductility: Y = 1.5 GPa, σ_{? = 3%} = 36 MPa, σ_B = 55 MPa, ?_B = 100% and T = 50 MJ m^?3. Analysis suggests that soft polyurethane segments are immobilized by adsorption onto the nanotubes, resulting in large changes in mechanical properties.     

Effects of High Pressure on the Physical Properties of MgB2

The synthesis of MgB₂-based materials under high pressure gave the possibility to suppress the evaporation of magnesium and to obtain near theoretically dense nanograined structures with high superconducting, thermal conducting, and mechanical characteristics: critical current densities of 1.8?C1.0×10⁶ A/cm² in the self-field and 10³ A/cm² in a magnetic field of 8 T at 20 K, 5?C3×10⁵ A/cm² in self-field at 30 K, the corresponding critical fields being H _c2=15 T at 22 K and irreversible fields H _irr=13 T at 20 K, and H _irr=3.5 T at 30 K, thermal conduction of 53±2 W/(m?K), the Vickers hardness H _V =10.12±0.2 GPa under a load of 148.8 N and the fracture toughness K _1C =7.6±2.0 MPa?m^0.5 under the same load, the Young modulus E=213 GPa. Estimation of quenching current and AC losses allowed the conclusion that high-pressure-prepared materials are promising for application in transformer-type fault current limiters working at 20?C30 K.     

One-step synthesis of petal-like apatite/titania composite coating on a titanium by micro-arc oxidation

Petal-like apatite/titania (TiO₂) coating was prepared on commercially pure titanium (Ti) by micro-arc oxidation in electrolyte containing calcium and phosphate for the first time. The surface morphology, crystalline structure, chemical composition and binding state of the apatite/TiO₂ composite coating were characterized. The coating consists of a double-layer (apatite layer and TiO₂ layer) structure. The average thickness of the inner TiO₂ layer and the outer apatite layer is about 6 μm and 16 μm respectively. The outer apatite layer is porous and exhibits petal-like pattern. The apatite layer consists of hydroxyapatite (HA) and carbonate-apatite and the inner TiO₂ layer consists of anatase and rutile.     

Room temperature elastic moduli and Vickers hardness of hot-pressed LLZO cubic garnet

Cubic garnet Li_6.24La₃Zr₂Al_0.24O_11.98 (LLZO) is a candidate material for use as an electrolyte in Li–Air and Li–S batteries. The use of LLZO in practical devices will require LLZO to have good mechanical integrity in terms of scratch resistance (hardness) and an adequate stiffness (elastic modulus). In this paper, the powders were fabricated by powder processing of cast ingots. All specimens were then densified via hot pressing. The room temperature elastic moduli (Young’s modulus, shear modulus, bulk modulus, and Poisson’s ratio) and hardness were measured by resonant ultrasound spectroscopy, and Vickers indentation, respectively. For volume fraction porosity, P, the Young’s modulus was 149.8?±?0.4?GPa (P?=?0.03) and 132.6?±?0.2?GPa (P?=?0.06). The mean Vickers hardness was 6.3?±?0.3?GPa for P?=?0.03 and 5.2?±?0.4 for P?=?0.06.     

Characterisation of CorGlaes<Superscript>®</Superscript> Pure 107 fibres for biomedical applications

A degradable ultraphosphate (55?mol?% P₂O₅) quinternary phosphate glass composition has been characterised in terms of its chemical, mechanical and degradation properties both as a bulk material and after drawing into fibres. This glass formulation displayed a large processing window simplifying fibre drawing. The fibres displayed stiffness and strength of 65.5?±?20.8?GPa and 426±143 MPa. While amorphous discs of the glass displayed a linear dissolution rate of 0.004?mg cm^?2?h^?1 at 37?°C, in a static solution with a reduction in media pH. Once drawn into fibres, the dissolution process dropped the pH to <2 in distilled water, phosphate buffer saline and corrected-simulated body fluid, displaying an autocatalytic effect with >90?% mass loss in 4 days, about seven times faster than anticipated for this solution rate. Only cell culture media was able to buffer the pH taking over a week for full fibre dissolution, however, still four times faster dissolution rate than as a bulk material. However, at early times the development of a HCA layer was seen indicating potential bioactivity. Thus, although initial analysis indicated potential orthopaedic implant applications, autocatalysis leads to accelerating degradation in vitro.     

Enhancement of photoelectrochemical performance of CdSe sensitized seeded TiO<Subscript>2</Subscript> films

In this work, we highlight the effect of TiO₂ seed layer (SL) on the photoelectrochemical performances of CdSe/TiO₂ photoanodes (PAs). TiO₂ thin films were prepared by spin coating starting from a sol gel solution containing TiO₂ nanopowder, then sensitized with electrodeposited CdSe nanoparticles. Structural, optical and photoelectrochemical properties of the CdSe/TiO₂ PAs with and without the SL were investigated. Charge accumulation processes and charge transfer characteristics were identified by electrochemical impedance spectroscopy. The introduction of the compact TiO₂ SL was found to significantly increase the electron transport. The photocurrent density produced by the CdSe/TiO₂/SL PA reached 0.95 mA/cm², about two times higher than that performed by the CdSe/TiO₂ PAs. This enhancement might be attributed to a substantial decrease of the leakage current induced by a better crystallization of TiO₂ thin films as well as a higher sensitizing effect of the CdSe nanoparticles.     

The key factor for fabricating through-hole TiO2 nanotube arrays: a fluoride-rich layer between Ti substrate and nanotubes

Through-hole TiO₂ nanotube arrays (THTNA) are fabricated successfully by applying a large-voltage pulse (ΔV ≥ 40 V) at the end of anodization, and a mechanism is proposed that the fluoride-rich layer (FRL) between Ti substrate and nanotubes is the key factor for fabricating THTNA. In order to confirm the mechanism, the effects of temperature of voltage pulse on the morphology of the bottom of TiO₂ nanotubes are explored. The results show the inner diameter of the bottom became larger with the temperature increasing due to the wall thickness of bottom of TiO₂ nanotubes decreased and assisted by the increased fluorine content of the bottom, which is strong evidence for the mechanism proposed. What is more, the inner diameter of the bottom of THTNA can be manipulated via this novel mechanism.     

Charge transfer enhancement of TiO2/perovskite interface in perovskite solar cells

In the conventional perovskite solar cells (PSCs) structure, TiO₂ is the most commonly used electron transport layer (ETL) as it has good energy-level matching with perovskite layer. However, oxygen vacancy defects will appear when TiO₂ is exposed to ultraviolet light for a long time, which would reduce its carrier extraction ability. Here, we report a simple and effective interface engineering method for TiO₂ ETL to achieve a highly efficient PSCs. An ultra-thin [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) layer is used to modify the mesoporous TiO₂/perovskite layer interface. The PCBM effectively passivates defects on the TiO₂ surface, promotes the extraction of electrons, and improves the quality of the perovskite film. Finally, a high efficiency of 16.4% was achieved for the modified device, much higher than 13.5% of the reference devices. After storing for 12 days in an atmosphere with an air humidity of 30?±?5%, the efficiency of the PSCs maintains more than 60% of its initial level. This strategy is beneficial to enhance the efficiency and working stability of PSCs.