Kinetics and mechanism of hot corrosion of γ-Y 2Si 2O 7 in thin-film Na 2SO 4 molten salt

γ-Y 2Si 2O 7 is a promising candidate material both for hightemperature structural applications and as an environmental/thermal barrier coating material due to its unique properties such as high melting point, machinability, thermal stability, low linear thermal expansion coefficient (3.9×10 -6/K, 200°-1300°C), and low thermal conductivity (<3.0 W/ṁK above 300°C). The hot corrosion behavior of γ-Y 2Si 2O 7 in thin-film molten Na 2SO 4 at 850°-1000°C for 20 h in flowing air was investigated using a thermogravimetric analyzer (TGA) and a mass spectrometer (MS). γ-Y 2Si 2O 7 exhibited good resistance against Na 2SO 4 molten salt. The kinetic curves were well fitted by a paralinear equation: the linear part was caused by the evaporation of Na2SO4 and the parabolic part came from gas products evolved from the hotcorrosion reaction. A thin silica film formed under the corrosion scale was the key factor for retarding the hot corrosion. The apparent activation energy for the corrosion of γ-Y 2Si 2O 7 in Na 2SO 4 molten salt with flowing air was evaluated to be 255 kJ/mol.

Problems associated with the over protection of fishing trawlers against sea water corrosion and fouling

Some presently used anti-fouling materials contain metals and other compounds, which are toxic in the environment. Coating products are not always stable, and there is a resulting pollution hazard. In particular if surfaces are poorly prepared and manufactures' instructions are not closely followed the application of anti-fouling substances becomes pointless and dangerous. In addition the salinity, constant biological activity and suspended particles make seawater a highly corrosive material in its own right.

Effects of sulfate-reducing bacteria on the corrosion behavior of carbon steel

The influences of the growing process of sulfate-reducing bacteria (SRB) in seawater system on the medium state and corrosion behavior of carbon steel were studied by detecting solution state parameters and using corrosion electrochemical methods. The growing process of SRB in the seawater shows the three stages of growing, death and residual phases. The solution state parameters of the concentration of sulfide, the pH value and the redox potential changed during the three stages of the SRB growing process. And the corrosion rate of D36 carbon steel was accelerated during the growing phase and stable during the death and residual phases. The results indicate that the medium state and the corrosion rate of the steel do not depend on the number of active SRB, but depend on the accumulation of the metabolism products of SRB. (c) 2007 Elsevier Ltd. All rights reserved.

Software Products for Modelling and Simulation in Materials Science

Models and software products have been developed for modelling, simulation and prediction of different correlations in materials science, including 1. the correlation between processing parameters and properties in titanium alloys and ?-titanium aluminides; 2. time–temperature–transformation (TTT) diagrams for titanium alloys; 3. corrosion resistance of titanium alloys; 4. surface hardness and microhardness profile of nitrocarburised layers; 5. fatigue stress life (S–N) diagrams for Ti–6Al–4V alloys. The programs are based on trained artificial neural networks. For each particular case appropriate combination of inputs and outputs is chosen. Very good performances of the models are achieved. Graphical user interfaces (GUI) are created for easy use of the models. In addition interactive text versions are developed. The models designed are combined and integrated in software package that is built up on a modular fashion. The software products are available in versions for different platforms including Windows 95/98/2000/NT, UNIX and Apple Macintosh. Description of the software products is given, to demonstrate that they are convenient and powerful tools for practical applications in solving various problems in materials science. Examples for optimisation of the alloy compositions, processing parameters and working conditions are illustrated. An option for use of the software in materials selection procedure is described.

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.

A study of slag corrosion of oxides and oxide-carbon refractories during steel refining

The use of ceramic material as refractories in the manufacturing industry is a common practice worldwide. During usage, for example in the production of steel, these materials do experience severe working conditions including high temperatures, low pressures and corrosive environments. This results in lowered service lives and high consumptions of these materials. This, in turn, affects the productivity of the whole steel plant and thereby the cost. In order to investigate how the service life can be improved, studies have been carried out for refractories used in the inner lining of the steel ladles. More specifically, from the slag zone, where the corrosion is most severe. By combining thermodynamic simulations, plant trails and post-mortem studies of the refractories after service, vital information about the behaviour of the slagline refractories during steel refining and the causes of the accelerated wear in this ladle area has been achieved. The results from these studies show that the wear of the slagline refractories of the ladle is initiated at the preheating station, through reduction-oxidation reactions. The degree of the decarburization process is mostly dependent on the preheating fuel or the environment. For refractories without antioxidants, refractory decarburization is slower when coal gas is used in ladle preheating than when a mixture of oil and air is used. In addition, ladle preheating of the refractories without antioxidants leads to direct wear of the slagline refractories. This is due to the total loss of the matrix strength, which results in a sand-like product. Thermal chemical changes that take place in the slagline refractories are due to the MgO-C reaction as well as the formation of liquid phases from impurity oxides. In addition, the decrease in the system pressure during steel refining makes the MgO-C reaction take place at the steel refining temperatures. This reduces the refractory’s resistance to corrosion. This is a serious problem for both the magnesia-carbon and dolomite-carbon refractories. The studies of the reactions between the slagline refractories and the different slag compositions showed that slags rich in iron oxide lead mostly to the oxidation of carbon/graphite in the carbon-containing refractories. This leads to an increased porosity and wettability and therefore an enhanced penetration of slag into the refractory structure. If the slag contains high contents of alumina and or silica (such as the steel refining slag), reactions between the slag components and the dolomite-carbon refractory are promoted. This leads to the formation of low-temperature melting phases such as calcium-aluminates and silicates. The state of these reaction products during steel refining leads to an accelerated wear of the dolomite-carbon refractory. The main products of the reactions between the magnesia-carbon refractory and the steel refining slag are MgAl2O4 spinels, and calcium-aluminates, and silicates. Due to the good refractory properties of MgAl2O4 spinels, the slag corrosion resistance of the magnesiacarbon refractory is promoted.

Study on the initial stages of water corrosion of fluorozirconate glasses

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, ZBLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)) was investigated using X-ray photoelectron spectroscopy (XPS), grazing-incidence small angle X-ray scattering (GISAXS), X-ray reflectivity (XRR) and scanning electron microscopy (SEM). After a short exposure period (25 min) of the glass surface to deionized water the XPS data indicate an increase of the oxygen content accompanied by a decrease of fluorine concentration. The analysis of the chemical bonding structure identified the predominant surface reaction products as zirconium hydroxyfluoride and oxyfluoride species. The second most abundant glass component, bariumfluoride, remains almost unaffected by oxygen, while sodium fluoride is completely removed from the attacked surface region. The detected structural and compositional changes are related to the selective dissolution of the glass components leading to the formation of a new surface phase. This process is accompanied by a visible surface roughening caused by reprecipitated species, observed by SEM. The modification of the glass surface is responsible for an increase of the GISAXS intensity. The scattering was attributed to nanovoids formed at the surface region of the glass with an average size of 2.4 +/- 0.05 nm. (C) 2004 Elsevier B.V. All rights reserved.

Corrosion and tribocorrosion behaviour of Al-Si-Cu-Mg alloy and its composites reinforced with B4C particles in 0.05M NaCl solution

The corrosion behaviour of metal matrix composites (MMCs) is strictly linked with the presence of heterogeneities such as reinforcement phase, microcrevices, porosity, secondary phase precipitates, and interaction products. Most of the literature related to corrosion behaviour of aluminium matrix composites (AMCs) is focused on SiC reinforced AMCs. On the other hand, there is very limited information available in the literature related to the tribocorrosion behaviour of AMCs. Therefore, the present work aims to investigate corrosion and tribocorrosion behaviour of Al-Si-Cu-Mg alloy matrix composites reinforced with B4C particulates. Corrosion behaviour of 15 and 19% (vol) B4C reinforced Al-Si-Cu-Mg matrix composites and the base alloy was investigated in 0.05M NaCl solution by performing immersion tests and potentiodynamic polarisation tests. Tribocorrosion behaviour of Al-Si-Cu-Mg alloy and its composites were also investigated in 0.05M NaCl solution. The tests were carried out against alumina ball using a reciprocating ball-on-plate tribometer. Electrochemical measurements were performed before, during, and after the sliding tests together with the recording of the tangential force. Results suggest that particle addition did not affect significantly the tendency of corrosion of Al-Si-Cu-Mg alloy without mechanical interactions. During the tribocorrosion tests, the counter material was found to slide mainly on the B4C particles, which protected the matrix alloy from severe wear damage. Furthermore, the wear debris were accumulated on the worn surfaces and entrapped between the reinforcing particles. Therefore, the tendency of corrosion and the corrosion rate decreased in Al-Si-Cu-Mg matrix B4C reinforced composites during the sliding in 0.05M NaCl solution. © 2013 Elsevier B.V.

A study of the main oxidation products of natural pyrite by voltammetric and photoelectrochemical responses

(Photo)electrochemical experiments on pyrite electrodes in acetic acid-acetate buffer (pH = 4.5) are conducted to clarify the main oxidation reactions and the nature of the products. Electrochemical reactions in the -0.40 to 1.25 V (SHE) potential range are studied, and the production of iron (III) polysulfide from anodically formed iron oxides and polysulfides is discussed. Charges experimentally obtained are considered for the estimation of the most likely stoichiometry of the metallic polysulfide. The photoselectivity of the pyrite corrosion process indicates that the oxidation reactions of Fe2+ and S-2(2-) an not consecutive. The changes in stoichiometry and/or annihilation of crystalline structure defects are responsible for the observed photosensitivity of pyrite. A description of light effects on the interfacial behaviour and stability of pyrite is presented in terms of conduction and valence band energies, and thermodynamic potentials. (C) 2001 Elsevier Science B.V. All rights reserved.

Evaluation of corrosion resistance and cytotoxicity of electrodeposited gold on various types of intermediate layers

Gold plated surfaces are widely applied in several technical and decorative fields. The two main issues regarding the discussion on the field of precious metal coatings concern the increase in the use of thinner gold layers and 'Ni free' substrates. In order to ensure the quality of the final products, the effects of the plated surfaces on their performance require thorough and accurate research. In this paper, the corrosion resistance of gold plated nickel, copper and bronze was investigated by electrochemical methods specifically potentiodynamic polarisation and electrochemical impedance spectroscopy in phosphate buffered saline. The cytotoxicity of the gold plated substrates was also evaluated and compared. The results showed that the substrate related to the best corrosion resistance and cytotoxicity among the tested ones was bronze, and the one with the lowest performance was nickel.

Polymer controlled mineralization of zinc phosphate hydrates and applications in corrosion protection, catalysis and biomedicine

ZUSAMMENFASSUNG Die Tauglichkeit von Hybridmaterialien auf der Basis von Zinkphosphathydrat-Zementen zum Einsatz als korrosionshemmende anorganische Pigmente oder zur prothetischen und konservierenden Knochen- und Zahntherapie wird weltweit empirisch seit den neunziger Jahren intensiv erforscht. In der vorliegenden Arbeit wurden zuerst Referenzproben, d.h. alpha-und beta-Hopeite (Abk. a-,b-ZPT) dank eines hydrothermalen Kristallisationsverfahrens in wässerigem Milieu bei 20°C und 90°C hergestellt. Die Kristallstruktur beider Polymorphe des Zinkphosphattetrahydrats Zn3(PO4)2  4 H2O wurde komplett bestimmt. Einkristall-strukturanalyse zeigt, daß der Hauptunterschied zwischen der alpha-und beta-Form des Zinkphosphattetrahydrats in zwei verschiedenen Anordnungen der Wasserstoffbrücken liegt. Die entsprechenden drei- und zweidimensionalen Anordnungen der Wasserstoffbrücken der a-und b-ZPT induzieren jeweils unterschiedliches thermisches Verhalten beim Aufwärmen. Während die alpha-Form ihr Kristallwasser in zwei definierten Stufen verliert, erzeugt die beta-Form instabile Dehydratationsprodukt. Dieses entspricht zwei unabhängigen, aber nebeneinander ablaufenden Dehydratationsmechanismen: (i) bei niedrigen Heizraten einen zweidimensionalen Johnson-Mehl-Avrami (JMA) Mechanismus auf der (011) Ebene, der einerseits bevorzugt an Kristallkanten stattfindet und anderseits von existierenden Kristalldefekten auf Oberflächen gesteuert wird; (ii) bei hohen Heizraten einem zweidimensionalen Diffusionsmechanismus (D2), der zuerst auf der (101) Ebene und dann auf der (110) Ebene erfolgt. Durch die Betrachtung der ZPT Dehydratation als irreversibele heterogene Festkörperstufenreaktion wurde dank eines „ähnlichen Endprodukt“-Protokolls das Dehydratationsphasendiagramm aufgestellt. Es beschreibt die möglichen Zusammenhänge zwischen den verschiedenen Hydratationszuständen und weist auf die Existenz eines Übergangszustandes um 170°C (d.h. Reaktion b-ZPT  a-ZPT) hin. Daneben wurde auch ein gezieltes chemisches Ätzverfahren mit verdünnten H3PO4- und NH3 Lösungen angewendet, um die ersten Stufe des Herauslösens von Zinkphosphat genau zu untersuchen. Allerdings zeigen alpha- und beta-Hopeite charakteristische hexagonale und kubische Ätzgruben, die sich unter kristallographischer Kontrolle verbreitern. Eine zuverlässige Beschreibung der Oberfächenchemie und Topologie konnte nur durch AFM und FFM Experimente erfolgen. Gleichzeitig konnte in dieser Weise die Oberflächendefektdichte und-verteilung und die Volumenauflösungsrate von a-ZPT und b-ZPT bestimmt werden. Auf einem zweiten Weg wurde eine innovative Strategie zur Herstellung von basischen Zinkphosphatpigmenten erster und zweiter Generation (d.h. NaZnPO4  1H2O und Na2ZnPO4(OH)  2H2O) mit dem Einsatz von einerseits oberflächenmodifizierten Polystyrolatices (z.B. produziert durch ein Miniemulsionspolymerisationsverfahren) und anderseits von Dendrimeren auf der Basis von Polyamidoamid (PAMAM) beschritten. Die erhaltene Zeolithstruktur (ZPO) hat in Abhängigkeit von steigendem Natrium und Wassergehalt unterschiedliche kontrollierte Morphologie: hexagonal, würfelförmig, herzförmig, sechsarmige Sterne, lanzettenförmige Dendrite, usw. Zur quantitativen Evaluierung des Polymereinbaus in der Kristallstruktur wurden carboxylierte fluoreszenzmarkierte Latices eingesetzt. Es zeigt sich, daß Polymeradditive nicht nur das Wachstum bis zu 8 µm.min-1 reduzierten. Trotzdem scheint es auch als starker Nukleationsbeschleuniger zu wirken. Dank der Koordinationschemie (d.h. Bildung eines sechszentrigen Komplexes L-COO-Zn-PO4*H2O mit Ligandenaustausch) konnten zwei einfache Mechanismen zur Wirkung von Latexpartikeln bei der ZPO Kristallisation aufgezeigt werden: (i) ein Intrakorona- und (ii) ein Extrakorona-Keimbildungsmechanismus. Weiterhin wurde die Effizienz eines Kurzzeit- und Langzeitkorrosionschutzes durch maßgeschneiderte ZPO/ZPT Pigmente und kontrollierte Freisetzung von Phosphationen in zwei Näherungen des Auslösungsgleichgewichts abgeschätzt: (i) durch eine Auswaschungs-methode (thermodynamischer Prozess) und (ii) durch eine pH-Impulsmethode (kinetischer Prozess. Besonders deutlich wird der Ausflösungs-Fällungsmechanismus (d.h. der Metamorphismus). Die wesentliche Rolle den Natriumionen bei der Korrosionshemmung wird durch ein passendes zusammensetzungsabhängiges Auflösungsmodell (ZAAM) beschrieben, das mit dem Befund des Salzsprühteste und der Feuchtigkeitskammertests konsistent ist. Schließlich zeigt diese Arbeit das herausragende Potential funktionalisierter Latices (Polymer) bei der kontrollierten Mineralisation zur Herstellung maßgeschneiderter Zinkphosphat Materialien. Solche Hybridmaterialien werden dringend in der Entwicklung umweltfreundlicher Korrosionsschutzpigmente sowie in der Dentalmedizin benötigt.

Modelling of corrosion-induced cover cracking in reinforced concrete by an embedded cohesive crack finite element

Corrosion of a reinforcement bar leads to expansive pressure on the surrounding concrete that provokes internal cracking and, eventually, spalling and delamination. Here, an embedded cohesive crack 2D finite element is applied for simulating the cracking process. In addition, four simplified analytical models are introduced for comparative purposes. Under some assumptions about rust properties, corrosion rate, and particularly, the accommodation of oxide products within the open cracks generated in the process, the proposed FE model is able to estimate time to surface cracking quite accurately. Moreover, emerging cracking patterns are in reasonably good agreement with expectations. As a practical case, a prototype application of the model to an actual bridge deck is reported.