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.

Niobium treated by Plasma Electrolytic Oxidation with calcium and phosphorus electrolytes.

Niobium plates were electrochemically treated by Plasma Electrolytic Oxidation (PEO) with electrolytes containing phosphorous and/or calcium. Three different electrolyte and experimental parameters were used forming three different surfaces. Film morphology, thickness, and chemical composition were analyzed by scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). A profilometer and the sessile drop technique measured the average surfaces roughness (Ra) and contact angles respectively. X-ray diffraction technique (XRD) analyzed the oxide crystallinity, and scratch tests evaluated the film adhesion. All oxidized surfaces presented pores, without observed cracks. Comparing the different experimental conditions, films obtained with phosphoric acid (P100) show superficial pores, phosphorus incorporation, high hydrophilicity, non-crystalline oxide formation, and good scratch resistance. Films treated with calcium acetate electrolyte (Ca100), compared to P100 exhibit smaller size pores and film thickness, smaller hydrophilicity, and lower scratch resistance. They also demonstrated higher oxide crystallinity, calcium incorporation, and pores interconnections. When the PEO was executed with a blended electrolyte containing calcium acetate and phosphoric acid (Ca50P50) the formed films presented the highest thickness, high phosphorus incorporation, and the lowest contact angle compared with other films. In addition, the pores size, the scratch resistance, calcium incorporation, and oxide crystallinity present intermediate values compared to P100 and Ca100 films. Film crystallinity seems to be influenced by calcium incorporation, whereas, hydrophilicity is phosphorus amount dependent. The pores amount and their interconnections reduced the scratch resistance. Surface features obtained in this work are largely mentioned as positive characteristics for osseointegration processes.

Apatite grown in niobium by two-step plasma electrolytic oxidation.

Plasma electrolytic oxidation (PEO) of niobium plates were done electrochemically in two steps with electrolytes containing phosphorous and calcium being observed the formation of crystalline apatite. All samples were submitted to a first step of PEO using an electrolyte containing phosphate ions. The second oxidization step was made using three different electrolytes. Some samples were oxidized by PEO in electrolyte containing calcium, while in other samples it was used two mixtures of phosphoric acid and calcium acetate monohydrate solutions. Three different surface layers were obtained. The morphology and chemical composition of the films were analyzed by scanning electronic microscopy (SEM), and energy dispersive spectroscopy (EDS) respectively. It was observed that all samples submitted to two-step oxidation shown porous surface and a calcium and phosphorus rich layer. Average surface roughness (Ra) was measured by a profilometer remaining in the sub-micrometric range. The contact angle by sessile drop technique, using 1µL of distilled water was performed with an optical goniometer. It was verified a higher hydrophilicity in all surfaces compared to the polished niobium. Orthorhombic Nb2O5 was identified by XRD in the oxide layer. Crystalline apatite was identified by XRD in surfaces after the second oxidation made with the Ca-rich electrolyte and a mixture of an electrolyte richer in Ca compared to P. These results indicate that a two-step oxidized niobium surface present great features for applications in the osseointegration processes: favorable chemical composition that increase the biocompatibility, the formation of crystalline niobium pentoxide (orthorhombic), high hydrophilicity and formation of crystalline calcium phosphate (apatite) under adequate electrolyte composition.

New method of plasma immersion ion implantation and also deposition of industrial components using tubular fixture and plasma generated inside the tube by high voltage pulses.

A new method of Plasma Immersion Ion Implantation (PIII) and deposition (PIII and D) for treating industrial components in the batch mode has been developed. A metal tubular fixture is used to allocate the components inside, around, and along the tube, exposing only the parts of each component that are to be ion implanted to the plasma. Hollow cathode-like plasma is generated only inside the tube filled with the desired gas, by applying high negative voltage pulses to the hollow cylindrical fixture which is insulated from the vacuum chamber walls. This is a very convenient method of batch processing of industrial parts by ion implantation, in which a large number of small to medium sized components can be treated by PIII and PIII and D, very quickly, efficiently, and also at low cost.

Mechanical properties of the bond interface associated with ND: YAG laser / Propriedades mecanicas da interface adesiva associada ao laser de ND: YAG

This study evaluated the hardness and modulus of elasticity of the dentin bond interface using total-etch(Single Bond /SB) and self-etch (Clearfil SE Bond/CSEB) adhesives associated with Nd:YAG Laser irradiation through the unpolymerized adhesives. Material and Methods: The occlusal surfaces of 12 human third molars were ground until superficial dentin was exposed. A standardized circular cavity was performed on the occlusal surface. Specimens were sectioned in the mesio-distal direction, and the 24 hemi-crowns were divided into four groups: Group SB/Control - SB + polymerization; GroupSB/Laser - SB + Nd:YAG laser (174.16J/cm2/60s/noncontact)+ polymerization; Group CSEB/Control – CSEB +polymerization; Group CSEB/Laser - CSEB + Nd:YAG laser(174.16J/cm2/cm2/60s/non-contact) + polymerization. Composite were placed in the cavities and polymerized. The specimens were immersed in distilled water and stored in an oven at 37ºC for 24h and then submitted to nanoindentation in a Nano Indenter® XP appliance. Results: The results were submitted to ANOVA, Tukey’stest and Student’s-t test (p < 0.05). Conclusion: It was concluded that the application of the Nd:YAG laser inboth adhesive systems did not changed the hybrid layer hardness; however, it increases the modulus of elasticityin the hybrid layer for both adhesives tested and it may bepreserves the integrity of the adhesive interface and its durability. Clinical relevance: The application of Nd:YA Glaser prior to photopolymerization of adhesive systems can increase the modulus of elasticity in the hybrid layerand may contribute to stress distribution in the adhesive interface during the polymerization preserving the integrity of the adhesive interface and its durability...

este estudo avaliou a dureza e o módulo de elasticidade da interface adesiva a dentina usando adesivo convencional (Sinngle Bond /SB) e adesivo autocondicionante (Clearfil SE Bond/CSEB) associados com irradiação do Laser Nd:YAH sobre os adesivos não polimerizados. Material e Métodos: As superfícies oclusais de 12 terceiros molares humanos foram desgastadas ate exposição de dentina superficial plana. Cavidades circulares padronizadas foram realizadas na superficie oclusal. Os espécimes foram seccionados no sentido mesio-distal, e as 24 hemicoroas foram divididas em quatro grupos: Grupo SB/Controle - SB + fotopolimerização; Grupo SB/Laser- SB + Laser Nd:YAG (174,16J/cm2/60s/não-contato)+ fotopolimerização; Grupo CSEB/Controle – CSEB +fotopolimerização; Grupo CSEB/Laser - CSEB + LaserNd:YAG (174.16J/cm2/cm2/60s/ não-contato) +fotopolimerização. Restaurações de resina composta foram realizadas nas cavidades e fotopolimerizadas. Os espécimes foram armazenados em água destilada a 37 ºC por 24 h e submetidas a nanoindentação no aparelho Nano Indenter® XP. Resultados: Os resultados foram submetidos ao ANOVA, seguidos dos testes de Tukey e T-Student (p < 0,05). Conclusão:Foi concluído que a aplicação do Laser de Nd:YAG nos adesivos não alterou a dureza da camada híbrida;entretanto, aumentou o módulo de elasticidade de ambos os adesivos testados e talvez preserve a integridade da interface adesiva e sua durabilidade...

Effect of the regional variability of dentinal substrate and modes of application of adhesive systems on the mechanical properties of the adhesive layer.

AIM: This study assessed the effect of the dentin depth and the application mode on the hardness and elastic modulus of the adhesive layer. MATERIALS AND METHODS: Occlusal surfaces of 48 caries-free human third molars were removed, at two levels: Superficial and deep dentin. For each type of surface, the test specimens were randomly divided into groups which underwent the application: A conventional two-step adhesive system (Adper™ Single Bond [SB]) and self-etch adhesives system (Adper™ SE Plus [SE] and AdheSE(®) [AD]). The adhesives applied were active or passive. Composite build-ups were constructed incrementally. The teeth were sectioned, embedded, and polished. The nanoindentation test was performed in the adhesive layer. The results were analyzed by ANOVA and Tukey tests. RESULTS: In the adhesive layer, the higher hardness (0.307 ± 0.006 GPa) and elastic modulus (4.796 ± 0.165 GPa) of SE were obtained in superficial dentin in passive application. The elastic modulus of SE (4.115 ± 0.098 GPa) was lowest in active application in superficial dentin. The active application significantly increased the hardness of the SB in the deep dentin (0.011 ± 0.314 GPa) compared the superficial dentin (0.280 ± 0.010 GPa). For the AD, only the mode of application was statistically significant (P=0.0041) for the hardness, active application (0.289 ± 0.015 GPa) being higher than passive application (0.261 ± 0.013 GPa) (P=0.0042) in deep dentin. CONCLUSION: The experimental results reveal that the mechanical properties were influenced for the application mode of adhesive systems and dentin depth.

Nanomechanical and nanotribological properties of bioactive titanium surfaces prepared by alkali treatment.

Alkali-heat treatment (AHT) is a simple and practical method to make titanium surfaces bioactive. Hydroxyapatite nucleates on Ti when in contact with body fluids due to the presence of a thin sodium titanate film produced by the AHT. This method was proposed more than a decade ago and it has been widely investigated at varied scopes. However, there is still little information about the mechanical properties of this film. In this work, the tribo-mechanical behavior of films produced by alkali treatment (AT) and AHT on Ti is investigated using instrumented indentation technique. The films were also characterized by TF-XRD, SEM, EDS and in vitro bioactivity tests. Analytical methods were employed to obtain the mechanical properties of the film from instrumented indentation data. The heat treatment subsequent to the alkaline processing increased the film elastic modulus from 1.7 GPa to 2.8 GPa, the hardness from 12 MPa to 20 MPa and the critical load for scratch test from 1.5 mN to 5.5 mN. Despite the overall improvement in the film bioactivity and tribo-mechanical behavior, the AHT elastic modulus is only 2% of the pristine Ti whereas hardness is less than 1%. This information must be considered for implant design purposes.