XPS Characterization of TiO2 Nanotubes Growth on the Surface of the Ti15Zr15Mo Alloy for Biomedical Applications.

Ti15Zr15Mo (TMZ alloy) has been studied in recent years for biomedical applications, mainly due to phase beta formation. From the surface modification, it is possible to associate the volume and surface properties with a better biomedical response. This study aimed to evaluate the possibility of using anodization to obtain TiO2 nanotubes due to the presence of valve-type metal (Zr) in their composition. X-ray photoelectron spectroscopy (XPS) was performed to determine the surface chemical composition in both after-processing conditions (passive layer) and after-processing plus anodization (TiO2 nanotube growth). The anodization resulted in nanotubes with diameters and thicknesses of 126 ± 35 and 1294 ± 193 nm, respectively, and predominated anatase phase. Compared to the passive layer of titanium, which is less than ~10 nm, the oxide layer formed was continuous and thicker. High-resolution spectra revealed that the oxide layer of the element alloys contained different oxidation states. The major phase in all depths for the nanotube samples was TiO2. While the stable form of each oxide was found to predominate on the surface, the inner part of the oxide layer consisted of suboxides and metallic forms. This composition included different oxidation states of the substrate elements Ti, Zr, and Mo.

TiO2NTs bio-inspired coatings: revisiting electrochemical, morphological, structural, and mechanical properties.

By altering some synthesis variables, the morphology and structural properties of anodic TiO2nanotube arrays (TiO2NTs) can be tailored to a specific application. This study aims to investigate the effect of electrolyte-containing ions from human plasma and annealing temperature on structural, morphological, and mechanical parameters of TiO2NTs films, targeting its potential biomedical applications. Bio-inspired TiO2NTs were grown from Ticpand its Ti6Al4V alloy by potentiostatic anodization in the recently developed SBF-based electrolyte, maintained at 10 °C and 40 °C. The thermal investigation was performed by TGA/DSC and used to define the phase transition temperatures used for annealing (450 °C and 650 °C). Morphological and structural parameters were evaluated by FE-SEM, XRD, contact angle measurements, and nanoindentation. Results show that self-organized as-formed TiO2NTs were grown under all synthesis conditions with different wettability profiles for each substrate group. At 450 °C annealing temperature, the beginning of nanostructures collapse starts, becoming evident at 650 °C. The nanoindentation characterization reveals that both electrolyte and thermal annealing exhibited low effects on the hardness and Young's modulus. The tailoring of specific properties by different synthesis conditions could allow the individualization of treatments and better performancein vivo.

The Use of Anodic Oxides in Practical and Sustainable Devices for Energy Conversion and Storage.

This review addresses the main contributions of anodic oxide films synthesized and designed to overcome the current limitations of practical applications in energy conversion and storage devices. We present some strategies adopted to improve the efficiency, stability, and overall performance of these sustainable technologies operating via photo, photoelectrochemical, and electrochemical processes. The facile and scalable synthesis with strict control of the properties combined with the low-cost, high surface area, chemical stability, and unidirectional orientation of these nanostructures make the anodized oxides attractive for these applications. Assuming different functionalities, TiO2-NT is the widely explored anodic oxide in dye-sensitized solar cells, PEC water-splitting systems, fuel cells, supercapacitors, and batteries. However, other nanostructured anodic films based on WO3, CuxO, ZnO, NiO, SnO, Fe2O3, ZrO2, Nb2O5, and Ta2O5 are also explored and act as the respective active layers in several devices. The use of AAO as a structural material to guide the synthesis is also reported. Although in the development stage, the proof-of-concept of these devices demonstrates the feasibility of using the anodic oxide as a component and opens up new perspectives for the industrial and commercial utilization of these technologies.

Evaluation of annealed titanium oxide nanotubes on titanium: From surface characterization to in vivo assays.

The entire route from anodic oxidation and surface characterization, including in vitro experiments and finally in vivo osseointegration assays were performed with the aim to evaluate nanotubular and crystalline annealed titanium oxides as a suitable surface for grade 2 titanium permanent implants. Polished titanium (T0) was compared with anodized surfaces obtained in acidic media with fluoride, leading to an ordered nanotubular structure of titanium oxide on the metal surface, characterized by tube diameter of 89 ± 24 nm (Tnts). Samples were thermally treated in air (TntsTT) to increase the anatase crystalline phase on nanotubes, with minor alteration of the structure. Corrosion tests were performed to evaluate the electrochemical response after 1, 14, and 28 days of immersion in simulated body fluid. Based on the in vitro results, heat-treated titanium nanotubes (TntsTT) were selected as a promissory candidate to continue with the osseointegration in vivo assays. The in vivo results showed no major improvement in the osseointegration process when compared with untreated Ti after 30 days of implantation and there also was a lower increase in the development of new osseous tissue.

Extension of hydrophilicity stability by reactive plasma treatment and wet storage on TiO2 nanotube surfaces for biomedical implant applications.

Micro and nanoscale changes allow the optimization of physico-chemical properties of titanium implant surfaces. Recently UV and plasma treatments have allowed surface hydrophilicity to take increased prominence; however, this beneficial effect is short-lived. The aim of this study is to investigate methodologies post-anodizing treatment to generate and maintain high surface hydrophilicity along with high biocompatibility. Anodized surfaces were characterized regarding physical-chemical properties. Then, surface wettability with nanomorphology was evaluated at different times and with distinct post-treatments: as deposited, with a reactive plasma and UV-light post-treatment, stored in air or deionized (DI) water. Adhesion, alkaline phosphatase (ALP) activity and bone cell viability tests were executed after the incremental treatments. The anodizing process generated a surface with TiO2 nanotubes morphology and micro-roughness. Plasma-treated surfaces resulted in the most hydrophilic samples and this property was maintained for a longer period when those were stored in DI water (angle variation of 7° to 12° in 21 days). Furthermore, plasma post-treatment changed the titanium surface crystalline phase from amorphous to anatase. Anodized surfaces modified by reactive plasma and stored in DI water suggest better hydrophilicity stability, biocompatibility, ALP activity and achievement of crystalline phase alteration, indicating future potential use on biomedical implants.

Effect of anodized zirconium implants on early osseointegration process in adult rats: a histological and histomorphometric study.

Since surface plays a key role in bioactivity, the response of the host to the biomaterial will determine the success or failure of the prosthesis. The purpose of this study is to make an exhaustive analysis of the histological and histochemical characteristics of new bone tissue around Zr implants anodized at 60 V (Zr60) supported by histomorphometric methods in a rat model. Fibrous tissue was observed around the control implants (Zr0) and osteoblasts were identified on the trabeculae close to the implantation site that showed typical cytological characteristics of active secretory cells, regardless of the surface condition. The histomorphometrical analysis revealed a significant increase in cancellous bone volume, trabecular thickness and in trabecular number together with a decrease in trabecular separation facing Zr60. TRAP staining showed that there was a relative increase in the number of osteoclasts for Zr60. In addition, a larger number of osteoclast with a greater number of nuclei were detected in the tibiae for Zr60. This research demonstrated that the new bone microarchitecture in contact with Zr60 is able to improve the early stages of the osseointegration process and consequently the primary stability of implants which is a crucial factor to reduce recovery time for patients.

Optimization of the Anodization Processing for Aluminum Oxide Gate Dielectrics in ZnO Thin Film Transistors by Multivariate Analysis.

The present study reports a two-level multivariate analysis to optimize the production of anodized aluminum oxide (Al2O3) dielectric films for zinc oxide thin-film transistors (TFTs). Fourteen performance parameters were measured and analysis of variance (ANOVA) of the combined responses has been applied to identify how the Al2O3 dielectric fabrication process influences the electrical properties of the TFTs. Using this approach, the levels for the manufacturing factors to achieve optimal overall device performance have been identified and ranked. The cross-checked analysis of the TFT performance parameters demonstrated that the appropriate control of the anodization process can have a higher impact on TFT performance than the use of traditional methods of surface treatment of the dielectric layer. Flexible electronics applications are expected to grow substantially over the next 10 years. Given the complexity and challenges of new flexible electronics components, this "multivariate" approach could be adopted more widely by the industry to improve the reliability and performance of such devices.

Electrochemical dopamine sensor using a nanoporous gold microelectrode: a proof-of-concept study for the detection of dopamine release by scanning electrochemical microscopy.

Nanoporous gold (NPG) structures were prepared on the surface of a gold microelectrode (Au-µE) by an anodization-reduction method. Cyclic voltammetry and field emission scanning electron microscopy were used to study the electrochemical properties and the morphology of the nanostructured film. Voltammetry showed an improved sensitivity for dopamine (DA) oxidation at this microelectrode when compared to a bare gold microelectrode, with a peak near 0.2 V (vs. Ag/AgCl) at a scan rate of 0.1 V s-1. This is due to the increased surface area and roughness. Square wave voltammetry shows a response that is linear in the 0.1-10 µmol L-1 DA concentration range, with a 30 nmol L-1 detection limit and a sensitivity of 1.18 mA (µmol L-1)-1 cm-2. The sensor is not interfered by ascorbic acid. The reproducibility, repeatability, long-term stability and real sample analysis (spiked urine) were assessed, and acceptable performance was achieved. The "proof-of-concept" detection of dopamine release was demonstrated by using scanning electrochemical microscopy (SECM) with the aim of future applications for single cell analysis. Graphical abstract A reproducible electrochemical approach was proposed to fabricate an NPG-microelectrode for DA detection, with enhanced sensitivity and selectivity. Besides, a proof-of-concept detection of DA release was also demonstrated by using SECM.

Abordagem regenerativa do osso alveolar pósextração com o uso da folha laminada de titânio anodizado ­ Titânio Seal® / Bone regenerative post extraction approach using anodized titanium foil - Titanium Seal®

O objetivo deste trabalho foi relatar o uso da folha laminada de titânio, Titânio Seal®, em sítios pós-extração sem fechamento primário do rebordo, discutindo os efeitos da anodização no processo regenerativo do osso alveolar. Após verificação da fratura radicular, uma instrumentação transalveolar foi executada de modo a diminuir as interferências da anatomia da crista do rebordo na estabilidade da broca durante a fresagem para o implante. Na sequência da exodontia minimamente traumática, foram instalados o implante, a matriz mineralizada bovina e a folha laminada de titânio anodizada. A anodização é um tratamento superficial feito através do processo de descarga eletroquímica que converte o óxido de titânio amorfo em anatase, camada que aumenta a adesão de osteoblastos e fibroblastos e diminui o crescimento de bactérias específicas bucais. Os acompanhamentos demonstraram um eficiente selamento do rebordo, com vantajosa formação tecidual (AU).

The aim of this article was to report the use of titanium foil, Titanio Seal®, at post extraction sites without primary closure of the ridge, discussing the effects of anodization on the regenerative process of alveolar bone. After verifying the root fracture, a transalveolar instrumentation was performed in order to reduce the interference of the ridge crest anatomy in the drill stability during the preparation for the implant. Following the minimally traumatic extraction, the implant, the bovine mineralized matrix, and the anodized titanium foil were installed. Anodizing is a surface treatment made through the electrochemical discharge process that converts the amorphous titanium oxide into anatase, a layer that increases the adhesion of osteoblasts and fibroblasts and decreases the growth of specific buccal bacteria. The accompaniments demonstrated an efficient sealing of the ridge, with an advantageous tissue formation (AU).

Self-Organized TiO2-MnO2 Nanotube Arrays for Efficient Photocatalytic Degradation of Toluene.

Vertically oriented, self-organized TiO2-MnO2 nanotube arrays were successfully obtained by one-step anodic oxidation of Ti-Mn alloys in an ethylene glycol-based electrolyte. The as-prepared samples were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), UV-Vis absorption, photoluminescence spectroscopy, X-ray diffraction (XRD), and micro-Raman spectroscopy. The effect of the applied potential (30-50 V), manganese content in the alloy (5-15 wt. %) and water content in the electrolyte (2-10 vol. %) on the morphology and photocatalytic properties was investigated for the first time. The photoactivity was assessed in the toluene removal reaction under visible light, using low-powered LEDs as an irradiation source (λmax = 465 nm). Morphology analysis showed that samples consisted of auto-aligned nanotubes over the surface of the alloy, their dimensions were: diameter = 76-118 nm, length = 1.0-3.4 µm and wall thickness = 8-11 nm. It was found that the increase in the applied potential led to increase the dimensions while the increase in the content of manganese in the alloy brought to shorter nanotubes. Notably, all samples were photoactive under the influence of visible light and the highest degradation achieved after 60 min of irradiation was 43%. The excitation mechanism of TiO2-MnO2 NTs under visible light was presented, pointing out the importance of MnO2 species for the generation of e- and h⁺.

Improved in vitro angiogenic behavior on anodized titanium dioxide nanotubes.

BACKGROUND: Neovascularization over dental implants is an imperative requisite to achieve successful osseointegration onto implanted materials. The aim of this study was to investigate the effects on in vitro angiogenesis of anodized 70 nm diameter TiO2 nanotubes (NTs) on Ti6Al4V alloy synthesized and disinfected by means of a novel, facile, antibacterial and cost-effective method using super oxidized water (SOW). We also evaluated the role of the surface roughness and chemical composition of materials of materials on angiogenesis. METHODS: The Ti6Al4V alloy and a commercially pure Ti were anodized using a solution constituted by SOW and fluoride as electrolyte. An acid-etched Ti6Al4V was evaluated to compare the effect of micro-surface roughness. Mirror-polished materials were used as control. Morphology, roughness, chemistry and wettability were assessed by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy, atomic force microscopy, energy dispersive X-ray spectroscopy (EDX) and using a professional digital camera. Bovine coronary artery endothelial cells (BCAECs) were seeded over the experimental surfaces for several incubation times. Cellular adhesion, proliferation and monolayer formation were evaluated by means of SEM. BCAEC viability, actin stress fibers and vinculin cellular organization, as well as the angiogenic receptors vascular endothelial growth factor 2 (VEGFR2) and endothelial nitric oxide synthase (eNOS) were measured using fluorescence microscopy. RESULTS: The anodization process significantly increased the roughness, wettability and thickness of the oxidized coating. EDX analysis demonstrated an increased oxygen (O) and decreased carbon (C) content on the NTs of both materials. Endothelial behavior was solidly supported and improved by the NTs (without significant differences between Ti and alloy), showing that endothelial viability, adhesion, proliferation, actin arrangement with vinculin expression and monolayer development were evidently stimulated on the nanostructured surface, also leading to increased activation of VEGFR2 and eNOS on Ti6Al4V-NTs compared to the control Ti6Al4V alloy. Although the rougher alloy promoted BCAECs viability and proliferation, filopodia formation was poor. CONCLUSION: The in vitro results suggest that 70 nm diameter NTs manufactured by anodization and cleaned using SOW promotes in vitro endothelial activity, which may improve in vivo angiogenesis supporting a faster clinical osseointegration process.

Bone response to a Ca- and P-enriched titanium surface obtained by anodization

This study evaluated bone response to a Ca- and P- enriched titanium (Ti) surface treated by a multiphase anodic spark deposition coating (BSP-AK). Two mongrel dogs received bilateral implantation of 3 Ti cylinders (4.1 x 12 mm) in the humerus, being either BSP-AK treated or untreated (machined - control). At 8 weeks postimplantation, bone fragments containing the implants were harvested and processed for histologic and histomorphometric analyses. Bone formation was observed in cortical area and towards the medullary canal associated to approximately 1/3 of implant extension. In most cases, in the medullary area, collagen fiber bundles were detected adjacent and oriented parallel to Ti surfaces. Such connective tissue formation exhibited focal areas of mineralized matrix lined by active osteoblasts. The mean percentages of bone-to-implant contact were 2.3 (0.0-7.2 range) for BSP-AK and 0.4 (0.0-1.3 range) for control. Although the Mann-Whitney test did not detect statistically significant differences between groups, these results indicate a trend of BSP-AK treated surfaces to support contact osteogenesis in an experimental model that produces low bone-to-implant contact values.

O objetivo desse estudo foi avaliar a resposta do tecido ósseo à superfície de titânio (Ti) enriquecida com Ca e P obtida por anodização (BSP-AK). Três cilindros de Ti (4,1 x 12 mm) BSP-AK ou usinado (controle) foram implantados bilateralmente nos úmeros de dois cães de raça indefinida. Oito semanas após a implantação, os fragmentos ósseos contendo os implantes foram removidos e processados para análises histológica e histomorfométrica. A formação óssea foi observada na região cortical e no canal medular até aproximadamente um terço da extensão do implante. Na maioria dos casos, feixes de fibras colágenas dispostos paralelamente à superfície do implante foram observados na região medular. Nessa região observaram-se também áreas focais de formação de matriz mineralizada e osteoblastos ativos. Os implantes do grupo BSP-AK apresentaram média de contato osso-implante 2,3 por cento, com medidas variando de 0,0 a 7,2 por cento e os do grupo controle tiveram média 0,4 por cento, com medidas variando de 0,0 a 1,3 por cento. Apesar do teste de Mann-Whitney não mostrar diferença estatisticamente significante entre os grupos, nossos resultados indicaram uma tendência para a ocorrência de osteogênese de contato na superfície BSP-AK em um modelo experimental que resulta em baixos valores de contato osso-implante.