Nicotinic acid as a nontoxic corrosion inhibitor for hot dipped Zn and Zn-Al alloy coatings on steels in diluted hydrochloric acid

The inhibition effect of nicotinic acid for corrosion of hot dipped Zn and Zn-Al alloy coatings in diluted hydrochloric acid was investigated using quantum chemistry analysis, weight loss test, electrochemical measurement, and scanning electronic microscope (SEM) analysis. Quantum chemistry calculation results showed that nicotinic acid possessed planar structure with a number of active centers, and the populations of the Mulliken charge, the highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) were found mainly focused around oxygen and nitrogen atoms, and the cyclic of the benzene as well. The results of weight loss test and electrochemical measurement indicated that inhibition efficiency (IE%) increased with inhibitor concentration, and the highest inhibition efficiency was up to 96.7%. The corrosion inhibition of these coatings was discussed in terms of blocking the electrode reaction by adsorption of the molecules at the active centers on the electrode surface. It was found that the adsorption of nicotinic acid on coating surface followed Langmuir adsorption isotherm with single molecular layer, and nicotinic acid adsorbed on the coating surface probably by chemisorption. Nicotinic acid, therefore, can act as a good nontoxic corrosion inhibitor for hot dipped Zn and Zn-Al alloy coatings in diluted hydrochloric acid solution. (c) 2007 Elsevier Ltd. All rights reserved.

Experimental and theoretical investigation of the adsorption behaviour of new triazole derivatives as inhibitors for mild steel corrosion in acid media

Three triazole derivatives (4-chloro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (CATM), 4-methoxyl-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (MATM) and 4-fluoro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (FATM)) have been synthesized as new inhibitors for the corrosion of mild steel in acid media. The inhibition efficiencies of these inhibitors were evaluated by means of weight loss and electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and polarization curves. Then the surface morphology was studied by scanning electron microscopy (SEM). The adsorption of triazole derivatives is found to obey Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The relationship between molecular structure of these compounds and their inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were computed. (c) 2007 Elsevier Ltd. All rights reserved.

Some new triazole derivatives as inhibitors for mild steel corrosion in acidic medium

Two triazole derivatives, 3,4-dichloro-acetophenone-O-1'-(1',3',4'-triazolyl)-methaneoxime (4-DTM) and 2,5-dichloro-acetophenone-O-1'-(1',3',4'-triazolyl)-methaneoxime (5-DTM) were synthesized, and the inhibition effects for mild steel in 1 M HCl solutions were investigated by weight loss measurements, electrochemical tests and scanning electronic microscopy (SEM). The weight loss measurements showed that these compounds have excellent inhibiting effect at a concentration of 1.0 x 10(-3) M. The potentiodynamic polarization experiment revealed that the triazole derivatives are inhibitors of mixed-type and electrochemical impedance spectroscopy (EIS) confirmed that changes in the impedance parameters (R-ct and C-dl) are due to surface adsorption. The inhibition efficiencies obtained from weight loss measurements and electrochemical tests were in good agreement. Adsorption followed the Langmuir isotherm with negative values of the free energy of adsorption Delta G(ads)(o). The thermodynamic parameters of adsorption were determined and are discussed. Results show that both 4-DTM and 5-DTM are good inhibitors for mild steel in acid media.

Electrochemical and quantum chemical study of purines as corrosion inhibitors for mild steel in 1 M HCl solution

The purines and its derivatives, such as, guanine, adenine, 2,6-diaminopurine, 6-thioguanine and 2,6-dithiopurine, were investigated as corrosion inhibitors for mild steel in 1 M HCl solution by weight loss measurements, electrochemical tests and quantum chemical calculations. The polarization curves of mild steel in the hydrochloric acid solutions of the purines showed that both cathodic and anodic processes of steel corrosion were suppressed. The Nyquist plots of impedance expressed mainly as a depressed capacitive loop with different compounds and concentrations. For all these purines, the inhibition efficiency increased by increasing the inhibitor concentration, and the inhibition efficiency orders are 2,6-dithiopurine > 6-thioguanine > 2,6-diaminopurine > adenine > guanine with the highest inhibiting efficiency of 88.0% for 10(-3) M 2,6-dithiopurine. The optimized structures of purines, the Mulliken charges, molecular orbital densities and relevant parameters were calculated by quantum chemical calculations. The quantum chemical calculation results inferred that the adsorption belong to physical adsorption, which might arise from the pi stacking between the pi electron of the purines and the metal surface. (C) 2008 Elsevier Ltd. All rights reserved.

Electrochemical and thermodynamic investigation of diniconazole and triadimefon as corrosion inhibitors for copper in synthetic seawater

This paper presents the investigation of diniconzole and triadimefon as chemical corrosion inhibitors for freshly polished copper in synthetic seawater (3.5% NaCl solution). Determination of weight loss, polarization curves, electrochemical impedance spectroscopy (EIS), and SEM, were performed to analyze the inhibiting performance of these compounds. Polarization curves show that they act as mixed-type inhibitors. EIS indicates that an adsorption film of the inhibitors is formed on copper surface. The highest values of inhibition efficiency are respectively, 99.2% and 97.3% at 100 mg/L concentration. Thermodynamic calculation suggests that chemisorptions between the compounds and copper are accordance with Langmuir adsorption isotherm. (C) 2010 Elsevier Ltd. All rights reserved.

Hydrogen permeation behavior and corrosion monitoring atmospheric of steel in cyclic wet-dry environment

Hydrogen permeation of 16Mn steel under a cyclic wet-dry condition was investigated by Devanathan-Stachurski's electrolytic cell with a membrane covered on the exit side by a nickel layer and the weight loss was measured for each wet-dry cycle. The results show that hydrogen permeation current change with different atmospheric environment: distilled water, seawater, and seawater containing 100 ppm H2S. The results show that seawater can induce an increase in the hydrogen permeation current due to the hydrolyzation reaction. And after the increase, equilibrium is reached due to the equilibrium of hydrolyzation reaction effect and the block of the rust layer. On the other hand, H2S contamination also can induce an increase in the maximum hydrogen permeation current due to the hydrolyzation reaction. And H2S contamination delays the time that hydrogen permeation is detected because of the formation of the FeS(1-x) film. The FeS(1-x) film can block the absorption of hydrogen onto the specimen surface. The surface potential change and the pH change of the metal surface control the hydrogen permeation current. And a clear linear correlation exists between the quantities of hydrogen permeated through the 16Mn steel and the weight loss. Based on the linear correlation, we monitored the corrosion rate by monitoring the hydrogen permeation current by a sensor outside. Good coherences were shown between results in laboratory and outside.

Durability and water absorption properties of surface treated concretes

Durability of concrete can be improved by applying surface treatments. Pore-lining treatments prevent or delay the ingress of water-borne salts while allowing vapour transfer across the concrete surface. The most common pore-liners are silanes and siloxanes; both reported to give good results. One area of concern, however, is variability in effectiveness of the treatment. This variability may be due to inconsistent coverage or extreme drying conditions. With care these can be controlled but another source of variability which is difficult to control is the moisture profile within the concrete at the time of application of the treatment. This paper describes a test programme to assess the sensitivity of three different surface treatments to moisture gradient in the concrete at the time of application of treatment. The test programme included durability parameters such as chloride ingress, corrosion due to chloride ingress, freeze-thaw salt scaling resistance. Water absorption (sorptivity) of treated and untreated concretes was also measured with a non-distructive test technique called Autoclam with the aim of determining if the Autoclam sorptivity test can be used to assess the effectiveness of surface treatments. Using these results it is possible to avoid, or allow for, moisture conditions which would adversely affect the success of a pore-liner. However there are advantages in specifying an expected performance of the surface treatment rather than specifying the conditions in which it must be placed. By this method a treatment would have to achieve a specified value of sorptivity or a specified reduction in sorptivity. Failure to do so would be an objective basis on which to make a decision of whether or not to reject the treatment. The Autoclam is a device capable of measuring sorptivity values down to the range typical of surface treated concrete. The paper assesses if the device can be used to discriminate between acceptable treatment and unsatisfactory treatments.

Effect of post-weld heat-treatment on the oxide film and corrosion behaviour of laser-welded shape memory NiTi wires

Post-weld heat-treatment (PWHT) was applied to NiTi weldments to improve the corrosion behaviour by modifying the microstructure and surface composition. The surface oxide film on the weldments is principally TiO2, together with some Ti, TiO, and Ti2O3. The surface Ti/Ni ratio of the weldments after PWHT is increased. The oxide film formed in Hanks’ solution is thicker on the weldments after PWHT. The pitting resistance of the weldments is increased by PWHT. The galvanic effect in the weldments is very small. The weldment with PWHT at 350 °C shows the best corrosion resistance among other heat-treated weldments in this study.

Microabrasion-corrosion of cast CoCrMo alloy in simulated body fluids

Wear and corrosion of metal-on-metal hip replacements results in wear debris and metal-ion release in vivo, which may subsequently cause pain and hypersensitivity for patients. Retrieved metal-on-metal hip replacements have revealed that two-body sliding wear and three-body abrasive wear are the predominant wear mechanisms. However, there is a lack of understanding of the combined effects of wear/corrosion, especially the effect of abrasion-corrosion.

This study investigates the sliding-corrosion and abrasion-corrosion performance of a cast CoCrMo alloy in simulated hip joint environments using a microabrasion rig integrated with an electrochemical cell. Tests have been conducted in 0.9% NaCl, phosphate buffered saline solution, 25% and 50% bovine serum solutions with 0 or 1 g cm(-3) SiC at 37 degrees C. Experimental results reveal that under abrasion-corrosion test conditions, the presence of proteins increased the total specific wear rate. Conversely, electrochemical noise measurements indicated that the average anodic current levels were appreciably lower for the proteinaceous solutions when compared with the inorganic solutions. A severely deformed nanocrystalline layer was identified immediately below the worn surface for both proteinaceous and inorganic solutions. The layer is formed by a recrystallisation process and/or a strain-induced phase transformation that occurs during microabrasion-corrosion. (C) 2008 Elsevier Ltd. All rights reserved.

Interpretation of electrochemical measurements made during micro-scale abrasion-corrosion

This paper brings together and analyzes recent work based on the interpretation of the electrochemical measurements made on a modified micro-abrasion-corrosion tester used in several research programmes. These programmes investigated the role of abradant size, test solution pH in abrasion-corrosion of biomaterials, the abrasion-corrosion performance of sintered and thermally sprayed tungsten carbide surfaces under downhole drilling environments and the abrasion-corrosion of UNS S32205 duplex stainless steel. Various abrasion tests were conducted under two-body grooving, three-body rolling and mixed grooving-rolling abrasion conditions, with and without abrasives, on cast F75 cobalt-chromium-molybdenum (CoCrMo) alloy in simulated body fluids, 2205 in chloride containing solutions as well as sprayed and sintered tungsten carbide surfaces in simulated downhole fluids. Pre- and post-test inspections based on optical and scanning electron microscopy analysis are used to help interpret the electrochemical response and current noise measurements made in situ during micro-abrasion-corrosion tests. The complex wear and corrosion mechanisms and their dependence on the microstructure and surface composition as a function of the pH, abrasive concentration, size and type are detailed and linked to the electrochemical signals. The electrochemical versus mechanical processes are plotted for different test parameters and this new approach is used to interpret tribo-corrosion test data to give greater insights into different tribo-corrosion systems. Thus new approaches to interpreting in-situ electrochemical responses to surfaces under different abrasive wear rates, different abrasives and liquid environments (pH and NaCl levels) are made. This representation is directly related to the mechano-electrochemical processes on the surface and avoids quantification of numerous synergistic, antagonistic and additive terms associated with repeat experiments. (C) 2010 Elsevier Ltd. All rights reserved.

Micro- and Nano-scale Tribo-Corrosion of Cast CoCrMo

Previous studies have established that some of the wear damage seen on cast CoCrMo joint surface is caused by entrained third-body hard particles. In this study, wet-cell micro-indentation and nano-scratch tests have been carried out with the direct aim of simulating wear damage induced by single abrasive particles entrained between the surfaces of cast CoCrMo hip implants. In situ electrochemical current noise measurements were uniquely performed to detect and study the wear-induced corrosion as well as the repassivation kinetics under the micro-/nano-scale tribological process. A mathematical model has been explored for the CoCrMo repassivation kinetics after surface oxide film rupture. Greater insights into the nature of the CoCrMo micro-/nano-scale wear-corrosion mechanisms and deformation processes are determined, including the identification of slip band formation, matrix/carbide deformation, nanocrystalline structure formation and strain-induced phase transformation. The electrochemical current noise provides evidence of instantaneous transient corrosion activity at the wearing surface resulting from partial oxide rupturing and stripping, concurrent with the indent/scratch.

Monitoring the development of microcracks in reinforced concrete caused by sustained loading and chloride induced corrosion

Chloride-induced corrosion of steel in reinforced concrete structures is one of the main problems affecting their durability and it has been studied for decades, but most of them have focused on concrete without cracking or not subjected to any structural load. In fact, concrete structures are subjected to various types of loads, which lead to cracking when the tensile stress in concrete exceeds its tensile strength. Cracking could increase transport properties of concrete and accelerate the ingress of harmful substances (Cl ^-, O₂, H₂ O, CO₂). This could initiate and accelerate different types of deterioration processes in concrete, including corrosion of steel reinforcement. The expansive products generated by the deterioration processes themselves can initiate cracking. The success of concrete patch repairs can also influence microcracking at the interface as well as the patch repair itself. Therefore, monitoring the development of microcracking in reinforced concrete members is extremely useful to assess the defects and deterioration in concrete structures. In this paper, concrete beams made using 4 different mixes were subjected to three levels of sustained lateral loading (0%, 50% and 100% of the load that can induce a crack with width of 0.1mmon the tension surface of beams - F _0.1) and weekly cycles of wetting (1 day)/drying (6 days) with chloride solution. The development of microcracking on the surface of concrete was monitored using the Autoclam Permeability System at every two weeks for 60 weeks. The ultrasonic pulse velocity of the concrete was also measured along the beam by using the indirect method during the test period. The results indicated that the Autoclam Permeability System was able to detect the development of microcracks caused by both sustained loading and chloride induced corrosion of steel in concrete. However, this was not the case with the ultrasonic method used in the work (indirect method applied along the beam); it was sensitive to microcracking caused by sustained loading but not due to corrosion. © 2014 Taylor & Francis Group.

Influence of micro and macro cracks due to sustained loading on chloride-induced corrosion of reinforced concrete beams

Chloride-induced corrosion of steel is one of the most commonly found problems affecting the durability of reinforced concrete structures in both marine environment and where de-icing salt is used in winter. As the significance of micro-cracks on chloride induced corrosion is not well documented, 24 reinforced concrete beams (4 different mixes - one containing Portland cement and another containing 35% ground granulated blastfurnace slag at 0.45 and 0.65 water-binder ratios) were subjected to three levels of sustained lateral loading (0%, 50% and 100% of the load that can induce 0.1 mm wide cracks on the tension surface of beam - F_0.1) in this work. The beams were then subjected to weekly cycles of wetting with 10% NaCl solution for 1 day followed by 6 days of drying at 20 (±1) °C up to an exposure period of 60 weeks. The progress of corrosion of steel was monitored using half-cell potential apparatus and linear polarisation resistance (LPR) test. These results have shown that macro-cracks (at load F_0.1) and micro-cracks (at 50% of F_0.1) greatly accelerated both the initiation and propagation stages of the corrosion of steel in the concrete beams. Lager crack widths for the F_0.1 load cases caused higher corrosion rates initially, but after about 38 weeks of exposure, there was a decrease in the rate of corrosion. However, such trends could not be found in 50% F _0.1 group of beams. The extent of chloride ingress also was influenced by the load level. These findings suggest that the effect of micro-cracking at lower loads are very important for deciding the service life of reinforced concrete structures in chloride exposure environments. © 2014 4th International Conference on the Durability of Concrete Structures.

Electroless nickel composite (Ni-P/SiC) coating - A study on interface and corrosion characteristic

Surface behaviour is of paramount importance as failure and degradation tend to initiate from the surface. Electroless composite coating (NiP/SiC) was developed using SiC as reinforcing particles. As heat treatment plays a vital role in electroless nickel coating owing to the changes in microstructure, phase structure and mechanical properties, an insight at the interface changes in chemistry and micromechanical behaviour was investigated using scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) and microindentation techniques. Corrosion performance was analysed using electrochemical impedance spectroscopy (EIS). Absence of zinc and migration of copper at the interface was detected. Brittleness and microcracks was seen long the interface when indenting at load of 500 gf (Vickers). Corrosion performance is weaker than particles free coating. However, a thin blanket of NiP could enhance the resistance to corrosive medium.

High resolution monitoring of surface morphological change of building limestones in response to simulated salt weathering

A salt weathering simulation using a mix of sodium chloride (5%) and magnesium sulphate (5%) in a salt corrosion cabinet and five granular limestones is described. Progressive surface loss from vertical exposed faces was mapped using a high resolution (sub-millimetre) object scanner (Konica Minolta Vi9i). Patterns of loss are related to surface porosity/permeability measurements obtained using a hand-held gas permeameter. Introduction of this spatial dimension into damage assessment is seen as essential for understanding the initial conditions that allow surface loss to be triggered, and changes in surface characteristics as weathering proceeds which dictate subsequent decay in space and time. Preliminary observations suggest that scanning at this high resolution is particularly valuable in quantifying very subtle trends and distortions that are pre-cursors to material loss, including surface swelling and pore filling.