Esta pesquisa estudou o método de realcalinização química (RAQ), através da absorção e difusão de soluções alcalinas na superfície do concreto carbonatado. Neste estudo foram utilizadas três espécies químicas para obtenção das soluções alcalinas: carbonato de sódio, hidróxido de potássio, e hidróxido de cálcio. Para avaliar a eficácia desta nova técnica de reabilitação, foram realizadas medidas de profundidade de carbonatação e de realcalinização, medidas eletroquímicas de potencial de corrosão e de espectroscopia de impedância eletroquímica (EIE) para a verificação do estado da armadura, ensaios de imersão, absorção e ascensão capilar em concretos de referência, carbonatados e realcalinizados. Em razão da falta de conhecimento sobre a eficácia da técnica de realcalinização eletroquímica (RAE) em relação à repassivação da armadura, em paralelo foi realizado o estudo da repassivação das armaduras na RAE. Em relação à durabilidade da técnica, foi avaliada a resistência do concreto recuperado quando submetido a um novo ciclo de carbonatação acelerada, analisando as novas profundidades de carbonatação para cada solução alcalina estudada. Na repassivação da armadura com a técnica de RAE, a solução de carbonato de sódio proporcionou valores de potencial de corrosão mais eletropositivos do que a solução de KOH, e gráficos de EIE similares aos obtidos com a solução de KOH. Na RAQ, a solução de KOH foi mais eficiente, sendo os resultados de potencial de corrosão similares aos obtidos com a solução de carbonato de sódio, no entanto, com valores de impedância e ângulo de fase superiores aos obtidos com carbonato de sódio. A solução de hidróxido de cálcio foi a que obteve os melhores valores de potencial de corrosão, proporcionando às barras valores mais eletropositivos do que antes da carbonatação. No entanto, a RAQ utilizando a solução de hidróxido de cálcio não propiciou a realcalinização do cobrimento do concreto, devendo então ser melhor estudada e, até que sua eficácia seja melhor entendida, sua aplicação deve ser vista com ressalvas. Ao final dos experimentos foi possível verificar que a RAQ aumentou bastante a durabilidade do cobrimento do concreto quando submetido a um novo ciclo de carbonatação acelerada. Enquanto os corpos-de-prova de referência ao final dos 45 dias de ensaio de carbonatação acelerada foram quase que totalmente carbonatados, os corpos-de-prova realcalinizados com as soluções de carbonato de sódio e hidróxido de potássio não apresentavam qualquer indício de carbonatação. / This research studied the method of chemical realkalisation (CRA), through the absorption and diffusion of alkalis in the carbonated concrete surface, as a new technique of rehabilitation. The experimental program was conducted in three set of concrete specimens: reference, carbonated and CRA treated. The CRA method was studied with three types of alkaline solutions: sodium carbonate, potassium hydroxide and calcium hydroxide. To evaluate the effectiveness of CRA treatment was carried out measures of depths of carbonation and realkalisation; electrochemical measurements of potential and electrochemical impedance spectroscopy (EIS) to verify the condition of steel bars; immersion, absorption and capillary tests. Besides these tests, the study of repassivation in corroded steel bars when applied the technique of electrochemical realkalisation (ERA) was also performed in parallel, since their effectiveness is considered unclear in various studies regarding the durability of the technique. The concrete treated with CRA method was submitted to a new accelerated carbonation cycle, and new measurements of carbonation depth were made for each alkaline solution applied. The repassivates reinforcements with ERA technique showed that the sodium carbonate solution provided corrosion potential values more electropositive than the KOH solution, and EIS graphics are similar those obtained with the KOH solution. In CRA technique, the KOH solution was more efficient, and the results of corrosion potential are similar those obtained with the sodium carbonate solution, however, with the results of impedance and phase angle higher than for sodium carbonate solution. The calcium hydroxide solution showed the best results of corrosion potential, providing bars more electropositive than before carbonation. However, the calcium hydroxide solution not provided the concrete realkalisation, and this alkaline solution should be more studied. Their implementation must be viewed with exceptions until its effectiveness has been proved. At the end of durability experiments was possible to verify that the CRA greatly increased the concrete durability when subjected to a new accelerated carbonation cycle. After 45 days of testing, the reference concrete specimens were almost totally carbonated. Therefore, the concrete specimens realkalised with sodium carbonate and potassium hydroxide solutions were no carbonation indication.

Ti-6Al-4V anterior cervical plates (ACP) are used in spinal fusion surgeries to fixate cervical vertebrae during graft adhesion. However, documented cases of implant failure and the potential for ACP corrosion raise concerns regarding any degradation of material resulting from extended implantation. In addition, abrasion during implantation may damage a section of the protective oxide layer, potentially exposing surrounding tissues to the harmful effects of bare titanium, aluminum, and vanadium. Thermal oxidation has been shown to improve corrosion-resistance and wear-resistance, depending on temperature and time. To quantify the attributes of the thermally grown oxide layer, Ti-6Al-4V coupons underwent thermal oxidation treatments in an atmosphere environment at 600 and 675 ˚C for 1, 4, 8, and 16 hours. Two sample types were produced: non-abraded and abraded. Non-abraded samples underwent potentiodynamic polarization according to ASTM F2129, which included open circuit potential tests. Open circuit potentials (EOC) increased with increasing treatment time, indicating that longer treatment time resulted in thicker oxides. All samples treated at 675˚C displayed higher EOC than samples treated at 600˚C, indicating an increase in oxide thickness with higher temperature. During the first hour of treatment at 675˚C, the rate of oxide growth was greater than the rate of oxide growth of all samples treated at 600˚C. Samples treated at 600˚C for 4 and 8 hours displayed pitting during potentiodynamic polarization, but all other samples withstood the applied potentials and surfaces were further passivated. To simulate damage during surgery, a single abrasion was made across samples in the abraded group with a diamond-tip indenter under a load of 471g at 4.4 mm/s. Abraded samples were subjected to potential-step tests to assess repassivation ability after abrasion. All samples displayed repassivation ability, except for the sample treated at 600˚C for 4 hours. Surface roughness was measured with atomic force microscopy before and after thermal oxidation treatments. Lower surface roughness was desired to discourage osseointegration, or the growth of bone cells. No isothermal surface roughness trends were observed, as high surface roughness outliers were seen in samples treated at 675˚C for 8 hours and 600˚C for 4 hours. Rockwell hardness and Vickers microhardness were also measured to assess bulk changes in mechanical properties and hardness of the oxidized surfaces. No statistical change was seen in Rockwell hardness. Vickers hardness increased with increasing temperature and time, with the exception of the sample treated at 600˚C for 4 hours. Metallography of the thermally oxidized samples was analyzed to determine if a change in microstructure had occurred due to thermal processing. No major change in grain size or the amount of alpha and beta grains was seen in samples treated at 600˚C, but samples treated for extended times at 675˚C showed equiaxed enlarged alpha grains and a reduction in beta grains. The breakdown of samples treated at 600˚C exemplified possible differences in the alpha-beta oxide behavior during thermal oxidation and corrosion. Outlying surface roughness and microhardness values related to the thermal oxidation treatments and resulting oxide structure. Due to delamination of oxides grown at 675˚C for 4, 8, and 16 hours, the treatment parameters would not be effective in the ACP application. Therefore, through corrosion resistance, repassivation ability, low surface roughness, increased microhardness, and no microstructural change, thermal oxidation treatments at 600˚C for more than 16 hours, and 675˚C for 1 hour or less would be suitable treatments for anterior cervical plates.

Esta pesquisa estudou o método de realcalinização química (RAQ), através da absorção e difusão de soluções alcalinas na superfície do concreto carbonatado. Neste estudo foram utilizadas três espécies químicas para obtenção das soluções alcalinas: carbonato de sódio, hidróxido de potássio, e hidróxido de cálcio. Para avaliar a eficácia desta nova técnica de reabilitação, foram realizadas medidas de profundidade de carbonatação e de realcalinização, medidas eletroquímicas de potencial de corrosão e de espectroscopia de impedância eletroquímica (EIE) para a verificação do estado da armadura, ensaios de imersão, absorção e ascensão capilar em concretos de referência, carbonatados e realcalinizados. Em razão da falta de conhecimento sobre a eficácia da técnica de realcalinização eletroquímica (RAE) em relação à repassivação da armadura, em paralelo foi realizado o estudo da repassivação das armaduras na RAE. Em relação à durabilidade da técnica, foi avaliada a resistência do concreto recuperado quando submetido a um novo ciclo de carbonatação acelerada, analisando as novas profundidades de carbonatação para cada solução alcalina estudada. Na repassivação da armadura com a técnica de RAE, a solução de carbonato de sódio proporcionou valores de potencial de corrosão mais eletropositivos do que a solução de KOH, e gráficos de EIE similares aos obtidos com a solução de KOH. Na RAQ, a solução de KOH foi mais eficiente, sendo os resultados de potencial de corrosão similares aos obtidos com a solução de carbonato de sódio, no entanto, com valores de impedância e ângulo de fase superiores aos obtidos com carbonato de sódio. A solução de hidróxido de cálcio foi a que obteve os melhores valores de potencial de corrosão, proporcionando às barras valores mais eletropositivos do que antes da carbonatação. No entanto, a RAQ utilizando a solução de hidróxido de cálcio não propiciou a realcalinização do cobrimento do concreto, devendo então ser melhor estudada e, até que sua eficácia seja melhor entendida, sua aplicação deve ser vista com ressalvas. Ao final dos experimentos foi possível verificar que a RAQ aumentou bastante a durabilidade do cobrimento do concreto quando submetido a um novo ciclo de carbonatação acelerada. Enquanto os corpos-de-prova de referência ao final dos 45 dias de ensaio de carbonatação acelerada foram quase que totalmente carbonatados, os corpos-de-prova realcalinizados com as soluções de carbonato de sódio e hidróxido de potássio não apresentavam qualquer indício de carbonatação. / This research studied the method of chemical realkalisation (CRA), through the absorption and diffusion of alkalis in the carbonated concrete surface, as a new technique of rehabilitation. The experimental program was conducted in three set of concrete specimens: reference, carbonated and CRA treated. The CRA method was studied with three types of alkaline solutions: sodium carbonate, potassium hydroxide and calcium hydroxide. To evaluate the effectiveness of CRA treatment was carried out measures of depths of carbonation and realkalisation; electrochemical measurements of potential and electrochemical impedance spectroscopy (EIS) to verify the condition of steel bars; immersion, absorption and capillary tests. Besides these tests, the study of repassivation in corroded steel bars when applied the technique of electrochemical realkalisation (ERA) was also performed in parallel, since their effectiveness is considered unclear in various studies regarding the durability of the technique. The concrete treated with CRA method was submitted to a new accelerated carbonation cycle, and new measurements of carbonation depth were made for each alkaline solution applied. The repassivates reinforcements with ERA technique showed that the sodium carbonate solution provided corrosion potential values more electropositive than the KOH solution, and EIS graphics are similar those obtained with the KOH solution. In CRA technique, the KOH solution was more efficient, and the results of corrosion potential are similar those obtained with the sodium carbonate solution, however, with the results of impedance and phase angle higher than for sodium carbonate solution. The calcium hydroxide solution showed the best results of corrosion potential, providing bars more electropositive than before carbonation. However, the calcium hydroxide solution not provided the concrete realkalisation, and this alkaline solution should be more studied. Their implementation must be viewed with exceptions until its effectiveness has been proved. At the end of durability experiments was possible to verify that the CRA greatly increased the concrete durability when subjected to a new accelerated carbonation cycle. After 45 days of testing, the reference concrete specimens were almost totally carbonated. Therefore, the concrete specimens realkalised with sodium carbonate and potassium hydroxide solutions were no carbonation indication.

ABSTRACT The Characterization and Analysis of In-vitro and Elevated Temperature Repassivation of Ti-6Al-4V via AFM Techniques Aaron J Guerrero Research in the corrosion of orthopaedic implants is a growing research field where implants have been known to show adverse effects in patients who have encountered the unfortunate dissolution of their implants due to corrosion. Once corrosion begins within the body, many adverse biological reactions can occur such as late on-set infections resulting in severe health complications. The focus of this research is specifically related to the problem of late on-set infections caused by localized corrosion of orthopaedic implants. In medical implants today the most common form of corrosion protection is the implant materials’ ability to impede corrosion through the formation of an oxide layer. This ability to passivate and quickly repassivate a uniform and stable oxide layer dictates how well an orthopaedic implant will survive in-vivo. To better understand the repassivation of orthopaedic implant materials, research was conducted at the nanoscale via atomic force microscopy (AFM) on anodized Ti-6Al-4V. Using an Asylum Research MFP-3DTM AFM and AFM lithography techniques, nano scratch test methods were created simulating in-vitro surface repassivation conditions. These nano-scratches were created and characterized in Hank’s balanced saline solution (HBSS) with the AFM in contact mode at 1 and 3 Hz scan rates. HBSS was used as it best simulates the pH, ionic compounds, and constituents that are commonly found in blood. It was discovered that the AFM was successful in creating in-vitro repassivation conditions. However, the ability of the AFM to successfully observe repassivation was limited by the speed of the AFM scanner. Using the same AFM scratch methods, experiments were performed in air and in-vitro and characterized with AFM conductance measurements at 20, 37, & 45 °C. The conductance measurements were taken using an AFM conductance module and allowed for observations of decreasing current measurements over time. The current data was then used to calculate current density, resistivity, conductance, and electron mobility and compared to similar experiments This study highlights the ability of the AFM to create and characterize repassivation and shows promise in developing further capability to use the AFM for characterization of repassivation on the nanoscale. Keywords: Orthopaedics, late on-set infections, repassivation, AFM, lithography, conductive measurements.

No description available.

Five well-known Zr-based alloys of the systems Zr–Cu–Al–(Ni–Nb, Ni–Ti, Ag) (Cu 5 15.4–36 at.%) with the highest glass-forming ability were comparatively analyzed regarding their pitting corrosion resistance and repassivation ability in a chloride-containing solution. Potentiodynamic polarization measurements were conducted in the neutral 0.01 M Na₂SO₄ 1 0.1 M NaCl electrolyte and local corrosion damages were subsequently investigated with high resolution scanning electron microscopy (HR-SEM) coupled with energy dispersive x-ray spectroscopy (EDX). Both pitting and repassivation potential correlate with the Cu concentration, i.e., those potentials decrease with increasing Cu content. Pit morphology is not composition dependent: while initially hemispherical pits then develop an irregular shape and a porous rim. Corrosion products are rich in Cu, O, and often Cl species. A combination of low Cu and high Nb or Ti contents is most beneficial for a high pitting resistance of Zr-based bulk metallic glasses. The bulk glassy Zr₅₇Cu₁₅.₄Al₁₀Ni₁₂.₆Nb₅ (Vit 106) and Zr₅₂.₅Cu₁₇.₉Al₁₀Ni₁₄.₆Ti₅ (Vit 105) alloys exhibit the highest pitting resistance.

In recent years, the demand for alternatives to fossil fuels has risen dramatically, and ethanol fuel has become an important liquid fuel alternative globally. The most efficient mode of transportation of petroleum-based fuel is via pipelines, and due to the 300% increase in ethanol use in the U.S. in the past decade, a similar method of conveyance must be adopted for ethanol. Low-carbon, low-alloy pipeline steels like X52, X60, and X65 comprise the existing fuel transmission pipeline infrastructure. However, similar carbon steels, used in the ethanol processing and production industry, were found to exhibit stress corrosion cracking (SCC) in ethanol service. Prior work has shown that contaminants absorbed by the ethanol during distillation, processing or transport could be the possible determinants of SCC susceptibility; 200 proof ethanol alone was shown not to cause SCC in laboratory studies. To ensure the safety and integrity of the pipeline system, it was necessary to perform a mechanistic study of SCC of pipeline steel in fuel grade ethanol (FGE). The objective of this work was to determine the environmental factors relating to SCC of X65 steel in fuel grade ethanol (FGE) environments. To accomplish this, a systematic study was done to test effects of FGE feedstock and common contaminants and constituents such as water, chloride, dissolved oxygen, and organic acids on SCC behavior of an X65 pipeline steel. Slow strain rate tests (SSRT) were employed to evaluate and compare specific constituents' effects on crack density, morphology, and severity of SCC of X65 in FGE. SCC did not occur in commercial FGE environments, regardless of the ethanol feedstock. In both FGE and simulated fuel grade ethanol (SFGE), SCC of carbon steel was found to occur at low water contents (below 5 vol%) when chloride was present above a specific threshold quantity. Cl- threshold for SCC varied from 10ppm in FGE to approximately 1 ppm in SFGE. SCC of carbon steel was inhibited when oxygen was removed from solution via N2 purge or pHe was increased by addition of NaOH. During SSRT, in-situ¬ electrochemical measurements showed a significant role of film rupture in the SCC mechanism. Analysis of repassivation kinetics in mechanical scratch tests revealed a large initial anodic dissolution current spike in SCC-causing environments, followed by repassivation indicated by current transient decay. In the deaerated environments, repassivation did not occur, while in alkaline SFGE repassivation was significantly more rapid than in SCC-inducing SFGE. Composition and morphology of the passive film on X65 during static exposure tests was studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results showed stability of an air-formed native oxide under static immersion in neutral (pHe = 5.4) SFGE, and dissolution of the film when pHe was decreased to 4.3. XPS spectra indicated changes in film composition at high pHe (near 13) and in environments lacking sufficient water. In light of all results, a film-rupture anodic-dissolution mechanism is proposed in which local plastic strains facilitates local breakdown of the air-formed oxide film, causing iron to dissolve anodically. During crack propagation anodic dissolution occurs at the crack tip while crack walls repassivate preserving crack geometry and local stress concentration at the tip. It is also proposed that SCC can be mitigated by use of alkaline inhibitors that speed repassivation and promotes formation of a more protective Fe(OH)3 film.

No description available.

No description available.

The corrosion behaviour of cast Al-Mg alloy A535 and its composites containing 10 wt.% and 15 wt.% fly ash, and 10 wt.% hybrid reinforcement (5 wt.% fly ash + 5 wt.% SiC) was investigated using weight-loss and electrochemical corrosion tests, optical microscopy, Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). The tests were conducted in fresh water collected from the South Saskatchewan River and 3.5 wt.% NaCl solution at room temperature. The pH of the salt solution varied from 3 to 9. For comparison, two other aluminum alloys, AA2618 and AA5083-H116, were tested in the same electrolytes. The results of the weight-loss corrosion test showed that unreinforced A535 alloy had a lower corrosion rate in fresh water and seawater environments than the composites at all the tested pH values. The corrosion rate of the composites increased with increasing fly ash content. As expected, the corrosion rates of A535 alloy and the composites tested in fresh water were lower than those in salt solution. The results of the potentiodynamic and cyclic polarization electrochemical tests showed that the corrosion potential (Ecorr) and pitting potential (Epit) of the alloy were more positive than those of the composites. The corrosion and pitting potentials of the composites became more negative (active) with increasing fly ash content. The composites showed more positive (noble) repassivation or protection potential (Erp) than the matrix alloy, with the positivity increasing with fly ash content. Analysis of the electrochemical noise data showed that pitting corrosion was the dominant mode of corrosion for the alloy in 3.5 wt.% NaCl solution. Optical microscopy and SEM revealed that Mg2Si phase and Al-Mg intermetallics corroded preferentially to the matrix. The EDS data indicated that the protective oxide film formed on A535 contained Al2O3 and MgO.