ABSTRACT Among titanium alloys with non-toxic elements, the Ti-25Nb-25Ta alloy has good elastic behavior for applications in osseous implants, biocompatibility, and excellent corrosion resistance. The present study aimed to better the biocompatibility characteristics of Ti-25Nb-25Ta alloy modifying its surface through Plasma Electrolytic Oxidation (PEO) treatment. The formed oxide coating is amorphous and composed of two distinct porous formations: smaller hole-shaped pores and larger volcano-like pores. The regions with the formation of smaller pores and in the hole shaped presented the highest atomic percentage of the chemical element phosphorus. Nanoindentation tests have shown that the hardness of the Ti-25Nb-25Ta alloy is slightly lower than the commercially pure grade 2 titanium (a material used as reference), while elastic modulus measurements of Ti-25Nb-25Ta presented more suitable values for implant application (lower values when compared with titanium reference). After PEO treatment there were significant mechanical surface improvements (increased fairly surface hardness and decreased elastic modulus) for application in osseous tissue. Despite the Ti-25Nb-25Ta alloy presented excellent characteristics for applications in hard biological tissues, the PEO treatment better its features.

The present study produced binary titanium-niobium alloys Ti-xNb with high niobium percentage (x = 50, 80 e 90 wt.%) aiming to apply it as a base material in osseous implant devices. The produced TiNb alloys presented a cubic crystalline phase, lower corrosion rate than titanium, lower elastic modulus values, and superior cellular viability than titanium and niobium. The Ti50Nb alloy among all analyzed metallic substrates showed the best values of elastic modulus, corrosion properties, wettability, and cellular viability. Thus, this work suggests a Ti/Nb ratio close to 1 (Ti50Nb) displays optimum characteristics to apply in orthopedic devices.

This work aims to investigate the role of epoxy addition in high density polyethylene (HDPE) matrix. The block copolymer polyethylene-b-poly (ethylene glycol) (PEG-co-PE) was used as a compatibilizer. The samples were obtained by melt mixing using a torque rheometer. Instrumental nanoindentation was used to determine Young's modulus and nanohardness, thermal properties were analyzed by differential scanning calorimetry (DSC) and phase morphology was investigated through transmission and scanning electronic microscopy. The epoxy addition increased HDPE crystallinity by 13% and Young's modulus by 8%. The addition of PEG-co-PE decreased the size of dispersed phase by approximately 50% and improved phase adhesion and homogeneity compared to the blends without block copolymer. The experimental results were compared to numerical results obtained from the use of the homogenization by asymptotic expansion approach. The numerical results presented a fair agreement to the experimental values.

ABSTRACT In this paper, nanocomposites with multiwalled carbon nanotubes (MWCNT) or graphene nanosheets were prepared using a high density polyethylene (HDPE) matrix. Two different processes were employed: a solution method and a melt mixing method. The crystallinity index of the HDPE showed similar levels in nanocomposites after the addition of carbon nanotubes. It can be seen that the preparation process modified the degree of crystallinity of the HDPE matrix with graphene nanosheets. Nanocomposites prepared by the solution method showed a decrease in the crystallinity index. The addition of carbon nanotubes led to an increase of Young's Modulus with an increase in the MWCNT quantity, regardless of the preparation process used, with a 22.8 % increase for composites with 0.5 wt% of CNTs. The nanocomposites with graphene nanosheets exhibited a different behavior with each mixing method. Nanocomposites prepared by the solution method showed a higher Young's Modulus than those prepared by melt mixing. Results of transmission electronic microscopy and field emission scanning electronic microscopy indicated homogeneous dispersion for carbon nanotubes in melt mixing. Graphene nanocomposites showed some agglomerates, with smaller platelets in the nanocomposites prepared by solution mixing compared to that prepared by the melt mixing.

In this work, nanocomposites with simultaneous dispersion of carbon nanotubes and clays in a high density polyethylene (HDPE) matrix were prepared. Two different processes of preparation were employed: solution or melt intercalation. Two different montmorillonite clays were used separately: a natural (MMT-Na) or an organoclay (MMT-30B) and it was used multiwalled carbon nanotubes (MWCNT). Thermal properties were evaluated by DSC and TGA, mechanical properties were evaluated by nanoindentetion and morphology was investigated by transmission electronic microscopy (TEM). Alterations of 20% in crystallinity were detected, increases in Young´s modulus up to 12% were observed and up to 20% of increase was observed in Oliver-Pharr hardness. It is possible to explain part of those results based on the state of dispersion observed in our TEM results.

Neste trabalho são estudados os efeitos da adição de nanotubos de carbono de parede múltipla (NCPM) em uma matriz de Poli(L-ácido láctico) (PLLA). Foras avaliadas duas rotas distintas de dispersão dos NCPM, uma utilizando agitação mecânica em solvente e a outra utilizando sonificação de alta energia em solvente. As propriedades mecânicas destes nanocompósitos foram avaliadas utilizando nanoindentação e microdureza vickers. Através da calorimetria exploratória diferencial foram determinadas as propriedades térmicas dos nanocompósitos (Tg, Tc, Tm e cristalinidade) obtidas. Por último, as propriedades tribológicas foram determinadas através de ensaios de deslizamento do tipo pino sobre disco, onde foram utilizadas diferentes cargas normais. As propriedades mecânicas e térmicas não foram significativamente afetadas pela adição do nanotubos, o que não se repetiu nas propriedades tribológicas, onde tanto o método de dispersão quanto a concentração de NCPM afetaram as propriedades. A micrografia das trilhas de desgaste sugere ainda que o mecanismo atuante foi modificado com a incorporação dos nanotubos, o mesmo pode ter acontecido nas amostras sonificadas.

This work studied the effects of the addition of Multiwalled Carbon Nanotubes (MWCNT) to a PLLA matrix. Two distinct methods of preparation were employed: a combination of a solvent/ mechanical stirring and a combination of a solvent/high energy sonication. The mechanical properties of the nanocomposites were determined by nanoindentation and by the Vickers hardness test. Thermal properties of the nanocomposites (Tg, Tc, Tm and crystallinity degree) were determined by DSC. The tribological properties of the nanocomposites were determined by using a pin-on-disc apparatus. Mechanical and thermal properties did not present significant alterations, although tribological properties presented significant changes caused by the method of preparation and different loads. SEM images indicated that the wear mechanism was changed by the addition of MWCNT.

This work aims to characterize the phases, thickness, hardness and hardness profiles of the nitride layers formed on the CA-6NM martensitic stainless steel which was plasma nitrided in gas mixtures containing different nitrogen amounts. Nitriding was performed at 500 ºC temperature, and 532 Pa (4 Torr) pressure, for gas mixtures of 5% N2 + 95% H2, 10% N2 + 90% H2, and 20% N2 + 80% H2, and 2 hours nitriding time. A 6 hours nitriding time condition for gas mixture of 5% N2 + 95% H2 was also studied. Nitrided samples results were compared with non-nitrided condition. Thickness and microstructure of the nitrided layers were characterized by optical microscopy (OM), using Villela and Nital etchants, and the phases were identified by X-ray diffraction. Hardness profiles and hardness measured on surface steel were determined using Vickers hardness and nanoindentation tester, respectively. It was verified that nitrided layer produced in CA-6NM martensitc stainless steel is constituted of compound layer, being that formation of the diffusion zone was not observed for the studied conditions. The higher the nitrogen amounts in gas mixture the higher is the thickness of the nitrided layer and the probability to form different nitride phases, in the case γ'-Fe4N, ε-Fe2-3N and CrN phases. Intrinsic hardness of the nitrided layers produced in the CA-6NM stainless steel is about 12-14 GPa (~1200-1400 HV).

The corrosion properties of a 22.5 wt. (%) Cr duplex stainless steel were investigated after long-term aging of 3000, 5000 and 7000 hours at 300 and 400 ºC. The corrosion resistance was measured based on mass loss in a FeCl3 10 wt. (%) solution and electrochemical measurements in a 0.1 M H2SO4 solution. The results indicate that the corrosion resistance decreased steadily up to 5000 hours of aging. However, the samples subjected to 7000 hours of aging showed better corrosion resistance than those aged for 3000 and 5000 hours. This effect is attributed to the phase transformation that occurs during aging, a finding which was confirmed by hardness, transmission electron microscopy and X-ray photoelectron spectroscopy measurements.

RESUMO Esse trabalho apresenta um estudo da dureza e do mee austenita-γ da liga inoxidável à base de ferro com efeito de memória de forma. Utilizando indentação instrumentada, foi possível determinar a dureza e o módulo de elasticidade das fases austenita-γ e martensita-ε separadamente. A fase martensítica apresentou uma dureza de 7,0 GPa, enquanto que a dureza da fase austenítica foi de 3,0 GPa. Os valores de módulo de elasticidade foram 202 e 137 GPa, para as fases martensita e austenita, respectivamente.

ABSTRACT This work presents a hardness study and elastic modulus for the ε-martensite and γ-austenite phases of an iron based shape memory alloy. Using instrumented indentation, it was possible to determine the hardness and elasticity modulus of these phases separately. The martensitic phase presented a hardness of 7.0 GPa and the austenitic phase presented a hardness of 3.0 GPa. The elastic modulus values were 202 and 137 GPa for the martensitic and austenitic phases, respectively.

Nesse trabalho, apresentamos a caracterização estrutural de regiões soldadas em aço austenítico AISI-304, que foram submetidas a processo de nitretação a plasma (20%N2 + 80%H2). Posteriormente as amostras foram hidrogenadas catodicamente. As temperaturas de nitretação foram de 400, 500 e 550°C. As regiões da solda e fora da solda hidrogenadas após a nitretação foram comparadas por DRX, microscopia ótica e microscopia eletrônica de varredura (MEV). As fases austenita-γ, martensita-α', martensita-ε, ferrita-α e os nitretos CrN, γ'-Fe4N e e-Fe2+xN foram identificados. As microestruturas de ambas as regiões e da zona termicamente ativada (ZTA) foram similares. Para 400°C, a estequiometria das fases formadas foi diferente das observadas em 500°C e 550°C. Os efeitos provocados pela hidrogenação foram mais acentuados em 550°C, com o arrancamento da camada nitretada.

Structural characterization of weld and outside weld regions of AISI-304 nitrided (20%N + 80%H) and cathodically hydrogenated is presented. Nitriding temperatures were 400, 500 e 550°C. The weld and outside weld regions were compared by XRD, optical microscopy and SEM. The phases γ-austenite, α'-martensite, ε-martensita and α-ferrite and the nitrides: CrN, γ'-Fe4N e e-Fe2+xN were identified. Microstructures of both regions and the thermal active zone were similar. For 400°C the stoichiometry of the formed phases was different from that formed at 500°C and 550°C. Hydrogen effects were more intense for 550°C, due to chipping occurrence.

The effects of Ag addition on some physical properties of YBa2Cu3O7-δ superconductor has been studied. The samples were produced by different routes and characterized by scanning electron microscopy, differential thermal analysis, thermogravimetric analysis, X-ray diffraction and nanoindentation. The superconducting properties were studied by dc magnetization and electrical resistivity measurements. The X-ray patterns revealed that all samples were polycrystalline and corresponded to the orthorhombic YBa2Cu3O7-δ phase. However, for some samples, silver appears to be present within the grains. The superconducting properties were not significantly influenced by Ag addition. Hardness and elastic modulus were also obtained by instrumented indentation. Ag addition was found to be effective in improving the mechanical properties, probably by filling the pores in the grain boundaries. Hardness profiles indicated values between 3.1 and 3.4 GPa at deep tip penetration depths. The highest elastic modulus of 146 GPa was attained for samples prepared using Y2O3, BaCO3, CuO and Ag2O as precursors, while the lowest modulus (125 GPa) was obtained for the pure YBa2Cu3O7-δ sample.

Mechanical and tribological properties os AISI 304 and AISI 316 stainless steels submited to glow discharge ion nitriding are reported.The atmosphere was 20:80 - N2:H2 with substrate temperatures ranging from 300 to 500 °C. Treatment at 300 °C produced expanded austenite (γN) in both steels. Increasing the temperature, the phases γ´-Fe4N and - Fe2+xN were present and the latter is the major phase for AISI 304. At 500 °C, the CrN phase was also identified in both steels. Hardnesses of about 13-14 GPa at near surface regions were obtained in both steels. Moreover, AISI 316 nitrided at 500 °C has the deepest hard layer. Tribological tests showed that wear can be reduced by up to a factor of six after the nitriding processes, even for a working temperature of 300 °C. The profiles during and after nanoscratch tests did not reveal significant differences after nitriding processes in both steels.

The nanoindentation technique allows the determination of mechanical properties at nanometric scale. Hardness (H) and elastic modulus (E) profiles are usually determined by using the Oliver-Pharr method from the load/unload curves. This approach is valid only for flat surfaces, or at least, when a very low degree of asperity is present (lower than 30 nm). The basic statement is the determination of the zero tip-surface contact point. If a rough surface is present, errors can occur in determining this contact point and, as a consequence, the surface hardness and elastic modulus profiles are drastically altered resulting in under evaluated values. Surfaces with different roughness were produced by controlled nitrogen glow discharge process on titanium. The changed nitriding parameters were different N2/H2 atmospheres and temperatures (600 °C-900 °C). The most correct H and E profiles were obtained by using the contact stiffness analysis method, proposed here, that overcomes the surface roughness. The obtained results were compared with available literature data.

Based on the fact that the Ti-6Al-4V alloy has good mechanical properties, excellent resistance to corrosion and also excellent biocompatibility, however with low wear resistance, this work aims to test plasma processes or combination of plasma and ion implantation processes to improve these characteristics. Two types of processing were used: two steps PIII (Plasma Immersion Ion Implantation) combined with PN (Plasma Nitriding) and single step PIII treatment. According to Auger Electron Spectroscopy (AES) results, the best solution was obtained by PIII for 150 minutes resulting in ~ 65 nm of nitrogen implanted layer, while the sample treated with PIII (75 minutes) and PN (75 minutes) reached ~ 35 nm implanted layer. The improvement of surface properties could also be confirmed by the nanoindentation technique, with values of hardness increasing for both processes. AFM (Atomic Force Microscopy) characterization showed that the single step PIII process presented greater efficiency than the duplex process (PIII + PN), probably due to the sputtering occurring during the second step (PN) removing partially the implanted layer of first step (PIII).