Insight into silicate-glass corrosion mechanisms

Energy Technology Data Exchange (ETDEWEB)

Cailleteau, C; Angeli, F; Gin, S; Jollivet, P [CEA VALRHO, DEN, Lab Etude Comportement Long Terme, F-30207 Bagnols Sur Ceze, (France); Devreux, F [Ecole Polytech, CNRS, Lab Phys Mat Condensee, F-91128 Palaiseau, (France); Jestin, J [CEA, CNRS, Lab Leon Brillouin, F-91191 Gif Sur Yvette, (France); Spalla, O [CEA, DSM, Lab Interdisciplinaire Org Nanometr et Supramol, F-91191 Gif Sur Yvette, (France)

2008-07-01

The remarkable chemical durability of silicate glass makes it suitable for a wide range of applications. The slowdown of the aqueous glass corrosion kinetics that is frequently observed at long time is generally attributed to chemical affinity effects (saturation of the solution with respect to silica). Here, we demonstrate a new mechanism and highlight the impact of morphological transformations in the alteration layer on the leaching kinetics. A direct correlation between structure and reactivity is revealed by coupling the results of several structure-sensitive experiments with numerical simulations at mesoscopic scale. The sharp drop in the corrosion rate is shown to arise from densification of the outer layers of the alteration film, leading to pore closure. The presence of insoluble elements in the glass can inhibit the film restructuring responsible for this effect. This mechanism may be more broadly applicable to silicate minerals. (authors)

Physical-chemical model for the mechanism of glass corrosion with particular consideration of simulated radioactive waste glasses

International Nuclear Information System (INIS)

Grambow, B.

1985-01-01

A physical-chemical model for the mechanism of glass corrosion is described. This model can be used for predicting, interpreting, and extrapolating experimental results. In static leaching tests the rate of corrosion generally decreases with time. Some authors assume that the surface layer, which grows during the course of the reaction, protects the underlying glass from further attack by the aqueous phase. Other authors assume that the saturation effects in solution are responsible for reducing the rate of the reaction. It is demonstrated within the scope of this work that examples can be found for both concepts; however, transport processes in the surface layer and/or in solution can be excluded as rate-determining processes within a majority of the examined cases. The location of the corrosion reaction is the boundary surface between the surface layer and the not yet attacked glass (transition zone)

Nuclear waste glass corrosion mechanisms

International Nuclear Information System (INIS)

Jantzen, C.M.

1987-04-01

Dissolution of nuclear waste glass occurs by corrosion mechanisms similar to those of other solids, e.g., metallurgical and mineralogic systems. Metallurgical phenomena such as active corrosion, passivation and immunity have been observed to be a function of the glass composition and the solution pH. Hydration thermodynamics was used to quantify the role of glass composition and its effect on the solution pH during dissolution. A wide compositional range of natural, lunar, medieval, and nuclear waste glasses, as well as some glass-ceramics were investigated. The factors observed to affect dissolution in deionized water are pertinent to the dissolution of glass in natural environments such as the groundwaters anticipated to interact with nuclear waste glass in a geologic repository. The effects of imposed pH and oxidation potential (Eh) conditions existing in natural environments on glass dissolution is described in the context of Pourbaix diagrams, pH potential diagrams, for glass

In situ corrosion tests on HLW glass as part of a larger approach

International Nuclear Information System (INIS)

Van Iseghem, P.

1997-01-01

In-situ corrosion tests were performed on various candidate high-level waste glasses in the underground laboratory in clay underneath SCK x CEN. The tests exposed the glass samples directly to the Boom clay rock, for maximum durations of 7.5 years. We succeeded to interpret the corrosion data at 90 deg C in terms of dissolution mechanisms, and we concluded that the glass composition has a determining effect on the corrosion stability. The data from our in-situ tests were of high relevance for estimating the long-term behaviour of the glasses. The long-term in-situ tests provide corrosion data which show different trends than other corrosion tests, e.g. shorter duration tests in Boom clay, or tests in deionized water. The initial dissolution rate using MCC1 test at 90 deg C is about the same for the three glasses discussed, but the longest duration in Boom clay at 90 deg C shows a difference in mass loss of about 25 times. We finally present some ideas on how the corrosion tests can meet the needs, such as the modelling of the glass corrosion or providing input in the performance assessment. (author)

Aqueous corrosion of borosilicate glasses: experiments, modeling and Monte-Carlo simulations

International Nuclear Information System (INIS)

Ledieu, A.

2004-10-01

This work is concerned with the corrosion of borosilicate glasses with variable oxide contents. The originality of this study is the complementary use of experiments and numerical simulations. This study is expected to contribute to a better understanding of the corrosion of nuclear waste confinement glasses. First, the corrosion of glasses containing only silicon, boron and sodium oxides has been studied. The kinetics of leaching show that the rate of leaching and the final degree of corrosion sharply depend on the boron content through a percolation mechanism. For some glass contents and some conditions of leaching, the layer which appears at the glass surface stops the release of soluble species (boron and sodium). This altered layer (also called the gel layer) has been characterized with nuclear magnetic resonance (NMR) and small angle X-ray scattering (SAXS) techniques. Second, additional elements have been included in the glass composition. It appears that calcium, zirconium or aluminum oxides strongly modify the final degree of corrosion so that the percolation properties of the boron sub-network is no more a sufficient explanation to account for the behavior of these glasses. Meanwhile, we have developed a theoretical model, based on the dissolution and the reprecipitation of the silicon. Kinetic Monte Carlo simulations have been used in order to test several concepts such as the boron percolation, the local reactivity of weakly soluble elements and the restructuring of the gel layer. This model has been fully validated by comparison with the results on the three oxide glasses. Then, it has been used as a comprehensive tool to investigate the paradoxical behavior of the aluminum and zirconium glasses: although these elements slow down the corrosion kinetics, they lead to a deeper final degree of corrosion. The main contribution of this work is that the final degree of corrosion of borosilicate glasses results from the competition of two opposite mechanisms

Exploration and Modeling of Structural changes in Waste Glass Under Corrosion

Energy Technology Data Exchange (ETDEWEB)

Pantano, Carlos; Ryan, Joseph; Strachan, Denis

2013-11-10

Vitrification is currently the world-wide treatment of choice for the disposition of high-level nuclear wastes. In glasses, radionuclides are atomistically bonded into the solid, resulting in a highly durable product, with borosilicate glasses exhibiting particularly excellent durability in water. Considering that waste glass is designed to retain the radionuclides within the waste form for long periods, it is important to understand the long-term stability of these materials when they react in the environment, especially in the presence of water. Based on a number of previous studies, there is general consensus regarding the mechanisms controlling the initial rate of nuclear waste glass dissolution. Agreement regarding the cause of the observed decrease in dissolution rate at extended times, however, has been elusive. Two general models have been proposed to explain this behavior, and it has been concluded that both concepts are valid and must be taken into account when considering the decrease in dissolution rate. Furthermore, other processes such as water diffusion, ion exchange, and precipitation of mineral phases onto the glass surface may occur in parallel with dissolution of the glass and can influence long-term performance. Our proposed research will address these issues through a combination of aqueous-phase dissolution/reaction experiments and probing of the resulting surface layers with state-of-the-art analytical methods. These methods include solid-state nuclear magnetic resonance (SSNMR) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The resulting datasets will then be coupled with computational chemistry and reaction-rate modeling to address the most persistent uncertainties in the understanding of glass corrosion, which indeed have limited the performance of the best corrosion models to date. With an improved understanding of corrosion mechanisms, models can be developed and improved that, while still conservative, take advantage of

Enhancement of the glass corrosion in the presence of clay minerals: testing experimental results with an integrated glass dissolution model

International Nuclear Information System (INIS)

Godon, N.; Vernaz, E.Y.

1992-01-01

Recent glass dissolution experiments, conducted at 90 deg C in the presence of potential backfill materials, indicate remarkably faster glass corrosion in the presence of clay, compared to tests where the glass is leached either alone or with alternative backfill materials. This effect correlates with the clay content in the backfill, and may be attributed to the removal of silica from solution. Scorpion, or dissolution with reprecipitation of a silica-rich clay, have been proposed as possible mechanisms for the silica consumption. The results of some experiments have been tested against a glass dissolution model, in which a widely used kinetic equation for glass corrosion is coupled with diffusive silica transport through a single porosity, linearly sorbing medium, which represents the backfilling. Because the glass corrosion rates imposed by the kinetic equation are inversely proportional to the silicic acid concentration of the leachant contacting the glass, the model predicts enhanced glass dissolution if silica is sorbed by the porous medium. The experimental data proved to be consistent with the predicted enhancement of the glass dissolution. Moreover, the model-estimated distribution coefficients for silica sorption (K d ) fall within the range of values extracted from available literature data, thus supporting the hypothesis that the observed high corrosion rates are due to sorption of silica on the clay mineral surfaces. (author)

Corrosion behavior of environmental assessment glass in product consistency tests of extended duration

International Nuclear Information System (INIS)

Bates, J.K.; Buck, E.C.; Ebert, W.L.; Luo, J.S.; Tam, S.W.

1998-01-01

We have conducted static dissolution tests to study the corrosion behavior of the Environmental Assessment (EA) glass, which is the benchmark glass for high-level waste glasses being produced at US Department of Energy facilities. These tests were conducted to evaluate the behavior of the EA glass under the same long-term and accelerated test conditions that are being used to evaluate the corrosion of waste glasses. Tests were conducted at 90 C in a tuff groundwater solution at glass surface area/solution volume (WV) ratios of about 2000 and 20,000 m -1 . The glass dissolved at three distinct dissolution rates in tests conducted at 2000 m -1 . Based on the release of boron, dissolution within the first seven days occurred at a rate of about 0.65 g/(m 2 · d). The rate between seven and 70 days decreased to 0.009 g/(m 2 · d). An increase in the dissolution rate occurred at longer times after the precipitation of zeolite phases analcime, gmelinite, and an aluminum silicate base. The dissolution rate after phase formation was about 0.18 g/(m 2 · d). The formation of the same zeolite alteration phases occurred after about 20 days in tests at 20,000 m - . The average dissolution rate over the first 20 days was 0.5 g/(m 2 · d) and the rate after phase formation was about 0.20 g/(m 2 · d). An intermediate stage with a lower rate was not observed in tests at 20,000 m -1 . The corrosion behavior of EA glass is similar to that observed for other high-level waste glasses reacted under the same test conditions. The dissolution rate of EA glass is higher than that of other high-level waste glasses both in 7-day tests and after alteration phases form

Waste glass corrosion modeling: Comparison with experimental results

International Nuclear Information System (INIS)

Bourcier, W.L.

1994-01-01

Models for borosilicate glass dissolution must account for the processes of (1) kinetically-controlled network dissolution, (2) precipitation of secondary phases, (3) ion exchange, (4) rate-limiting diffusive transport of silica through a hydrous surface reaction layer, and (5) specific glass surface interactions with dissolved cations and anions. Current long-term corrosion models for borosilicate glass employ a rate equation consistent with transition state theory embodied in a geochemical reaction-path modeling program that calculates aqueous phase speciation and mineral precipitation/dissolution. These models are currently under development. Future experimental and modeling work to better quantify the rate-controlling processes and validate these models are necessary before the models can be used in repository performance assessment calculations

Stress corrosion in a borosilicate glass nuclear wasteform

International Nuclear Information System (INIS)

Ringwood, A.E.; Willis, P.

1984-01-01

The authors discuss a typical borosilicate glass wasteform which, when exposed to water vapour and water for limited periods, exhibits evidence of stress corrosion cracking arising from the interaction of polar OH groups with stressed glass surfaces. Glass wasteforms may experience similar stress corrosion cracking when buried in a geological repository and exposed to groundwaters over an extended period. This would increase the effective surface areas available for leaching by groundwater and could decrease the lifetime of the wasteform. Conventional leach-testing methods are insensitive to the longer-term effects of stress corrosion cracking. It is suggested that specific fracture-mechanics tests designed to evaluate susceptibility to stress corrosion cracking should be used when evaluating the wasteforms for high-level nuclear wastes. (author)

Corrosion effects on soda lime glass

NARCIS (Netherlands)

Veer, F.A.; Rodichev, Y.M.

2010-01-01

Although soda lime glass is the most common used transparent material in architecture, little is known about the corrosion effects on long term strength and the interaction between corrosion and defects. Extensive testing on soda lime bars under different environmental conditions and different

Aqueous corrosion of borosilicate glasses. Nature and properties of alteration layers

International Nuclear Information System (INIS)

Trotignon, Laurent

1990-01-01

This research thesis addresses physical and chemical processes which occur during aqueous corrosion of silicates, and the study of the properties of their interfaces with solutions, and thus issues related to the fate of high activity nuclear wastes which are embedded in a vitreous matrix as the potential release of radionuclides towards the environment then depends on the glass parcel behaviour submitted to chemical attacks which could alter it, notably by aqueous corrosion. The objective is then to model the dissolution of nuclear glass over long periods of time, and to predict the behaviour of radionuclides. The author compared the corrosion and alteration layers of gradually more complex borosilicate glasses, from a ternary sodium borosilicate glass to a simulated nuclear glass (the French reference glass R7T7). Complexity is increased by adding oxides. After some theoretical recalls on the structure and corrosion of borosilicate glasses, the author presents the studied materials, the corrosion experiments, and analytical techniques used to study alteration layers. The mechanism of formation of altered layers is studied based on corrosion experiments performed at 90 C on the whole set of glasses. Alteration layers formed on corroded glasses are studied and compared by using various techniques: electronic microscopy, high energy ion beams, spectroscopy, infrared, photo-electron spectroscopy. Implications for underground storage of nuclear glasses are discussed

Dissolution rates of DWPF glasses from long-term PCT

International Nuclear Information System (INIS)

Ebert, W.L.; Tam, S.W.

1996-01-01

We have characterized the corrosion behavior of several Defense Waste Processing Facility (DWPF) reference waste glasses by conducting static dissolution tests with crushed glasses. Glass dissolution rates were calculated from measured B concentrations in tests conducted for up to five years. The dissolution rates of all glasses increased significantly after certain alteration phases precipitated. Calculation of the dissolution rates was complicated by the decrease in the available surface area as the glass dissolves. We took the loss of surface area into account by modeling the particles to be spheres, then extracting from the short-term test results the dissolution rate corresponding to a linear decrease in the radius of spherical particles. The measured extent of dissolution in tests conducted for longer times was less than predicted with this linear dissolution model. This indicates that advanced stages of corrosion are affected by another process besides dissolution, which we believe to be associated with a decrease in the precipitation rate of the alteration phases. These results show that the dissolution rate measured soon after the formation of certain alteration phases provides an upper limit for the long-term dissolution rate, and can be used to determine a bounding value for the source term for radionuclide release from waste glasses. The long-term dissolution rates measured in tests at 20,000 per m at 90 degrees C in tuff groundwater at pH values near 12 for the Environmental Assessment glass and glasses made with SRL 131 and SRL 202 frits, respectively

Silicate glasses corrosion. Texture analysis of the corrosion layer

International Nuclear Information System (INIS)

Portal, Sabine

2001-01-01

We have studied the kinetic and the texture evolution of the corroded layer that forms on glass surfaces exposed to acidic solutions. The corroded layer is depleted in alkali cations and is produced by an ion exchange mechanism. It is porous and shows a lower refractive index than the one of the bulk glass. Spectroscopic ellipsometry allows determining the thickness of the layer and its refractive index. Several other techniques have been developed for characterizing the corrosion behaviour of glass surfaces: porosity is thus investigated by adsorption-desorption of nitrogen; the thickness and the composition of the layer are studied by secondary ion mass spectroscopy (S.I.M.S.); sodium concentration in the solution has been analyzed by atomic absorption. This study shows the importance of leaching conditions and glass preparation. The type of drying employed is susceptible to modify the texture and the structure of the layer. The layers produced in the early stages of the leaching process are not easily detectable. The different results lead however to the same conclusion: after a strong increase of porosity, a densification of the layer is observed with increasing time. The evolution of the layer texture could therefore modify the kinetic of the glass corrosion. (author) [fr

Corrosion of synthesized glasses and glazes as analogs for nuclear waste glass degradation

International Nuclear Information System (INIS)

Vandiver, P.B.

1994-01-01

Synthesized glasses provide an opportunity to study natural corrosion processes which are intermediate in time span between geological examples of natural glasses, such as obsidians and tektites, and relatively short term laboratory tests lasting a few hours to several decades. In addition, synthesized glasses can usually be tracked to particular archaeological find sites with known dates of production and often burial. Environmental conditions are routinely measured at archaeological sites as a part of the excavation-process, such that information is available on the yearly cycling of temperature and relative humidity, sometimes at the depth at which the artifact was found. Whether the artifacts were excavated in an air enclosure, such as a tomb, or in the soil can also be reconstructed, such that one can determine whether aqueous or atmospheric corrosion was involved in the degradation process. For instance, so-called open-quotes Roman glassclose quotes may span a time period of production of 800 years and a geographical range from Germany to North Africa and from Britain to Afghanistan. One example is the storage during World War II of glass from the British Museum in underground metro stations. Some of these glasses have been in collections for over 100 years. Thus, populations of glasses can be chosen for experimentation which compare variations in bulk composition, dopants, microstructure, heat treatment, ground vs. fire polished surfaces, aqueous vs. atmospheric corrosion, geographic, geological as well as recent storage conditions. Glasses in museums are generally considered to have had their corrosion arrested and be stable because changes in visual appearance are not obvious. However, if we attempt to measure the range of surface water content in these glasses using Fourier transform infrared analysis, a considerable variability is found, as shown

Corrosion mechanisms of containment glasses for fission products

International Nuclear Information System (INIS)

Nogues, J.L.

1984-01-01

After a review of nuclear energy production and waste vitrification principles, the aqueous corrosion mechanisms of the containment glasses and the various parameters affecting the corrosion are studied: effects of glass composition, temperature, lixiviation agent pH, lixiviation duration and mode. Conventional mass loss measurement and solution analyses are coupled to sophisticated surface analysis techniques. The hydrolyzed layer formation and the solubility limits are discussed. 87 figs., 30 tabs., 144 refs

The effect of corrosion on stained glass windows

Directory of Open Access Journals (Sweden)

Laissner, Johanna

1996-06-01

Full Text Available Stained glass windows belong to the most important cultural heritage of Europe. Within the last decades a disastrous deterioration took place. The wonderful stained glass windows and their glass paintings as pieces of art are acutely menaced by environmental corrosive influences. This corrosion process is a very complex reaction which is not only influenced by temperature and humidity changes but also by gaseous pollutants like sulfur dioxide, nitrogen oxides or ozone, by dust and air, microorganisms as well as synergetic interactions. Strongly affected by these environmental attacks are medieval stained glasses due to their chemical composition. They have a low content in silica and high contents of modifier ions (e.g. potassium and calcium. The corrosion phenomena can range from predominantly pitting on the surface to the formation of thick corrosion crusts which are turning the panel opaque and thus reducing strongly the transparency of the windows. In order to set up a conservation and restoration concept, it is necessary to know about the environmental conditions to which the stained glass windows are exposed. For this purpose very corrosion sensitive model glasses (so called glass sensors were developed which have a similar chemical composition as historic stained glasses. They exhibit the same corrosion reactions but react much faster, and are now widely used to estimate corrosive stresses on stained glass windows to give basic information about the corrosive impacts which work on the historic glasses. In this paper principle corrosion mechanisms of stained glass windows and their enhancing factors are discussed. For the evaluation of the environmental impact, the application of glass sensors is demonstrated.

Las vidrieras coloreadas pertenecen al legado cultural más importante de Europa. En las últimas décadas se ha producido en ellas un desastroso deterioro. Las maravillosas vidrieras coloreadas y sus policromías est

High-level waste borosilicate glass: A compendium of corrosion characteristics. Volume 2

International Nuclear Information System (INIS)

Cunnane, J.C.

1994-03-01

The objective of this document is to summarize scientific information pertinent to evaluating the extent to which high-level waste borosilicate glass corrosion and the associated radionuclide release processes are understood for the range of environmental conditions to which waste glass may be exposed in service. Alteration processes occurring within the bulk of the glass (e.g., devitrification and radiation-induced changes) are discussed insofar as they affect glass corrosion.This document is organized into three volumes. Volumes I and II represent a tiered set of information intended for somewhat different audiences. Volume I is intended to provide an overview of waste glass corrosion, and Volume 11 is intended to provide additional experimental details on experimental factors that influence waste glass corrosion. Volume III contains a bibliography of glass corrosion studies, including studies that are not cited in Volumes I and II. Volume I is intended for managers, decision makers, and modelers, the combined set of Volumes I, II, and III is intended for scientists and engineers working in the field of high-level waste

High-level waste borosilicate glass: A compendium of corrosion characteristics. Volume 2

Energy Technology Data Exchange (ETDEWEB)

Cunnane, J.C. [comp.; Bates, J.K.; Bradley, C.R. [Argonne National Lab., IL (United States)] [and others

1994-03-01

The objective of this document is to summarize scientific information pertinent to evaluating the extent to which high-level waste borosilicate glass corrosion and the associated radionuclide release processes are understood for the range of environmental conditions to which waste glass may be exposed in service. Alteration processes occurring within the bulk of the glass (e.g., devitrification and radiation-induced changes) are discussed insofar as they affect glass corrosion.This document is organized into three volumes. Volumes I and II represent a tiered set of information intended for somewhat different audiences. Volume I is intended to provide an overview of waste glass corrosion, and Volume 11 is intended to provide additional experimental details on experimental factors that influence waste glass corrosion. Volume III contains a bibliography of glass corrosion studies, including studies that are not cited in Volumes I and II. Volume I is intended for managers, decision makers, and modelers, the combined set of Volumes I, II, and III is intended for scientists and engineers working in the field of high-level waste.

Autoadaptive Emailtest AZ90 for corrosion monitoring of glass-lined reactors

International Nuclear Information System (INIS)

Jean-Marie, H.

1993-01-01

In the Chemical and Pharmaceutical Industry, glass-lined vessels often contain very corrosive and harmful products. To prevent major problems such as batch contamination, leakages or explosions, it is important to detect as soon as possible a failure of the glass-lining. The well-known electrolytic method of detection has been improved by using a permanent comparison of a reference current passing between these electrodes and a defect in the glass-lining. This is made possible with the microprocessorized glass-guard to detect a leak rate independent of the product conductivity, to be self monitoring and to give an evaluation of the conductivity

High-level waste borosilicate glass: A compendium of corrosion characteristics. Volume 3

International Nuclear Information System (INIS)

Cunnane, J.C.

1994-03-01

The objective of this document is to summarize scientific information pertinent to evaluating the extent to which high-level waste borosilicate glass corrosion and the associated radionuclide release processes are understood for the range of environmental conditions to which waste glass may be exposed in service. Alteration processes occurring within the bulk of the glass (e.g., devitrification and radiation-induced changes) are discussed insofar as they affect glass corrosion. Volume III contains a bibliography of glass corrosion studies, including studies that are not cited in Volumes I and II

High-level waste borosilicate glass: A compendium of corrosion characteristics. Volume 3

Energy Technology Data Exchange (ETDEWEB)

Cunnane, J.C. [comp.; Bates, J.K.; Bradley, C.R. [Argonne National Lab., IL (United States)] [and others

1994-03-01

The objective of this document is to summarize scientific information pertinent to evaluating the extent to which high-level waste borosilicate glass corrosion and the associated radionuclide release processes are understood for the range of environmental conditions to which waste glass may be exposed in service. Alteration processes occurring within the bulk of the glass (e.g., devitrification and radiation-induced changes) are discussed insofar as they affect glass corrosion. Volume III contains a bibliography of glass corrosion studies, including studies that are not cited in Volumes I and II.

Corrosion resistant metallic glasses for biosensing applications

Science.gov (United States)

Sagasti, Ariane; Lopes, Ana Catarina; Lasheras, Andoni; Palomares, Verónica; Carrizo, Javier; Gutierrez, Jon; Barandiaran, J. Manuel

2018-04-01

We report the fabrication by melt spinning, the magnetic and magnetoelastic characterization and corrosion behaviour study (by potentiodynamic methods) of an Fe-based, Fe-Ni-Cr-Si-B metallic glass to be used as resonant platform for biological and chemical detection purposes. The same study has been performed in Fe-Co-Si-B (with excellent magnetoelastic properties) and Fe-Ni-B (with good corrosion properties due to the substitution of Co by Ni) composition amorphous alloys. The well-known, commercial metallic glass with high corrosion resistance Metglas 2826MB®(Fe40Ni38Mo4B18), widely used for such biological and chemical detection purposes, has been also fully characterized and used as reference. For our Fe-Ni-Cr-Si-B alloy, we have measured values of magnetization (1.22 T), magnetostriction (11.5 ppm) and ΔE effect (6.8 %) values, as well as corrosion potential (-0.25 V), current density (2.54 A/m2), and polarization resistance (56.22 Ω.cm2) that make this composition very promising for the desired biosensing applications. The obtained parameters from our exhaustive characterization are compared with the values obtained for the other different composition metallic glasses and discussed in terms of Ni and Cr content.

Corrosion resistant metallic glasses for biosensing applications

Directory of Open Access Journals (Sweden)

Ariane Sagasti

2018-04-01

Full Text Available We report the fabrication by melt spinning, the magnetic and magnetoelastic characterization and corrosion behaviour study (by potentiodynamic methods of an Fe-based, Fe-Ni-Cr-Si-B metallic glass to be used as resonant platform for biological and chemical detection purposes. The same study has been performed in Fe-Co-Si-B (with excellent magnetoelastic properties and Fe-Ni-B (with good corrosion properties due to the substitution of Co by Ni composition amorphous alloys. The well-known, commercial metallic glass with high corrosion resistance Metglas 2826MB®(Fe40Ni38Mo4B18, widely used for such biological and chemical detection purposes, has been also fully characterized and used as reference. For our Fe-Ni-Cr-Si-B alloy, we have measured values of magnetization (1.22 T, magnetostriction (11.5 ppm and ΔE effect (6.8 % values, as well as corrosion potential (-0.25 V, current density (2.54 A/m2, and polarization resistance (56.22 Ω.cm2 that make this composition very promising for the desired biosensing applications. The obtained parameters from our exhaustive characterization are compared with the values obtained for the other different composition metallic glasses and discussed in terms of Ni and Cr content.

Comparison of the corrosion behaviors of the glass-bonded sodalite ceramic waste form and reference HLW glasses

International Nuclear Information System (INIS)

Ebert, W. L.; Lewis, M. A.

1999-01-01

A glass-bonded sodalite ceramic waste form is being developed for the long-term immobilization of salt wastes that are generated during spent nuclear fuel conditioning activities. A durable waste form is prepared by hot isostatic pressing (HIP) a mixture of salt-loaded zeolite powders and glass frit. A mechanistic description of the corrosion processes is being developed to support qualification of the CWF for disposal. The initial set of characterization tests included two standard tests that have been used extensively to study the corrosion behavior of high level waste (HLW) glasses: the Material Characterization Center-1 (MCC-1) Test and the Product Consistency Test (PCT). Direct comparison of the results of tests with the reference CWF and HLW glasses indicate that the corrosion behaviors of the CWF and HLW glasses are very similar

Aqueous Corrosion Rates for Waste Package Materials

Energy Technology Data Exchange (ETDEWEB)

S. Arthur

2004-10-08

The purpose of this analysis, as directed by ''Technical Work Plan for: Regulatory Integration Modeling and Analysis of the Waste Form and Waste Package'' (BSC 2004 [DIRS 171583]), is to compile applicable corrosion data from the literature (journal articles, engineering documents, materials handbooks, or standards, and national laboratory reports), evaluate the quality of these data, and use these to perform statistical analyses and distributions for aqueous corrosion rates of waste package materials. The purpose of this report is not to describe the performance of engineered barriers for the TSPA-LA. Instead, the analysis provides simple statistics on aqueous corrosion rates of steels and alloys. These rates are limited by various aqueous parameters such as temperature (up to 100 C), water type (i.e., fresh versus saline), and pH. Corrosion data of materials at pH extremes (below 4 and above 9) are not included in this analysis, as materials commonly display different corrosion behaviors under these conditions. The exception is highly corrosion-resistant materials (Inconel Alloys) for which rate data from corrosion tests at a pH of approximately 3 were included. The waste package materials investigated are those from the long and short 5-DHLW waste packages, 2-MCO/2-DHLW waste package, and the 21-PWR commercial waste package. This analysis also contains rate data for some of the materials present inside the fuel canisters for the following fuel types: U-Mo (Fermi U-10%Mo), MOX (FFTF), Thorium Carbide and Th/U Carbide (Fort Saint Vrain [FSVR]), Th/U Oxide (Shippingport LWBR), U-metal (N Reactor), Intact U-Oxide (Shippingport PWR, Commercial), aluminum-based, and U-Zr-H (TRIGA). Analysis of corrosion rates for Alloy 22, spent nuclear fuel, defense high level waste (DHLW) glass, and Titanium Grade 7 can be found in other analysis or model reports.

Aqueous Corrosion Rates for Waste Package Materials

International Nuclear Information System (INIS)

Arthur, S.

2004-01-01

The purpose of this analysis, as directed by ''Technical Work Plan for: Regulatory Integration Modeling and Analysis of the Waste Form and Waste Package'' (BSC 2004 [DIRS 171583]), is to compile applicable corrosion data from the literature (journal articles, engineering documents, materials handbooks, or standards, and national laboratory reports), evaluate the quality of these data, and use these to perform statistical analyses and distributions for aqueous corrosion rates of waste package materials. The purpose of this report is not to describe the performance of engineered barriers for the TSPA-LA. Instead, the analysis provides simple statistics on aqueous corrosion rates of steels and alloys. These rates are limited by various aqueous parameters such as temperature (up to 100 C), water type (i.e., fresh versus saline), and pH. Corrosion data of materials at pH extremes (below 4 and above 9) are not included in this analysis, as materials commonly display different corrosion behaviors under these conditions. The exception is highly corrosion-resistant materials (Inconel Alloys) for which rate data from corrosion tests at a pH of approximately 3 were included. The waste package materials investigated are those from the long and short 5-DHLW waste packages, 2-MCO/2-DHLW waste package, and the 21-PWR commercial waste package. This analysis also contains rate data for some of the materials present inside the fuel canisters for the following fuel types: U-Mo (Fermi U-10%Mo), MOX (FFTF), Thorium Carbide and Th/U Carbide (Fort Saint Vrain [FSVR]), Th/U Oxide (Shippingport LWBR), U-metal (N Reactor), Intact U-Oxide (Shippingport PWR, Commercial), aluminum-based, and U-Zr-H (TRIGA). Analysis of corrosion rates for Alloy 22, spent nuclear fuel, defense high level waste (DHLW) glass, and Titanium Grade 7 can be found in other analysis or model reports

Determination of the corrosion mechanisms of high level waste containing glass

International Nuclear Information System (INIS)

Conradt, R.; Roggendorf, H.

1985-01-01

The purpose of the reported work was to determine the corrosion behaviour of the inactive HLW glass SM 58 LW 11 in Q-solution at temperatures up to 200 0 C and elevated pressures up to 13 MPa. In particular, a parametric study on the effects of time, temperature, pressure, crystallization, metallic impurities a.o. was performed. Further tests helped to identify the rate determining steps in the entire process and the most likely long-term corrosion law. (orig./RB)

Rhyolitic glasses as natural analogues of nuclear waste glasses: behaviour of an Icelandic glass upon natural aqueous corrosion

International Nuclear Information System (INIS)

Magonthier, M.-C.; Petit, J.-C.; Dran, J.-C.

1992-01-01

A detailed study of the altered rims present in narrow fissures of a 52 ka-old Icelandic obsidian reveals the behaviour of transition and heavy elements, as well as the mechanism and kinetics of alteration, during glass/solution interaction. These complex altered rims are alkali depleted and consist of alternating layers of Fe-rich aluminosilicate and aluminium thihydroxide. The elemental partitioning observed on this naturally corroded obsidian is supported by laboratory experiments performed on the same glass, the elemental accumulation being explained by the formation of a hydrosilicate. A good correlation exists between the thickness of the altered rims and that calculated from the amounts of Fe and Ti accumulated locally. Thus, immobile elements can be used reliably as indices of the extent of alteration because only near-equilibrium conditions occur. The good agreement between the experimental hydration rate of obsidians and the progress of natural corrosion, leads to the assumption that ion diffusion is the long-term controlling mechanism of corrosion. Such an assumption is supported by the particular distribution of the immobile elements which is due to ion diffusion and coprecipitation processes (self-organization genesis). These observations have implications for nuclear waste disposal topics and support the validity of obsidians as analogues of nuclear waste glasses with respect to some local environmental constraints induced by waste packaging and disposal. (author)

Corrosion of inconel in high-temperature borosilicate glass melts containing simulant nuclear waste

Science.gov (United States)

Mao, Xianhe; Yuan, Xiaoning; Brigden, Clive T.; Tao, Jun; Hyatt, Neil C.; Miekina, Michal

2017-10-01

The corrosion behaviors of Inconel 601 in the borosilicate glass (MW glass) containing 25 wt.% of simulant Magnox waste, and in ZnO, Mn2O3 and Fe2O3 modified Mg/Ca borosilicate glasses (MZMF and CZMF glasses) containing 15 wt.% of simulant POCO waste, were evaluated by dimensional changes, the formation of internal defects and changes in alloy composition near corrosion surfaces. In all three kinds of glass melts, Cr at the inconel surface forms a protective Cr2O3 scale between the metal surface and the glass, and alumina precipitates penetrate from the metal surface or formed in-situ. The corrosion depths of inconel 601 in MW waste glass melt are greater than those in the other two glass melts. In MW glass, the Cr2O3 layer between inconel and glass is fragmented because of the reaction between MgO and Cr2O3, which forms the crystal phase MgCr2O4. In MZMF and CZMF waste glasses the layers are continuous and a thin (Zn, Fe, Ni, B)-containing layer forms on the surface of the chromium oxide layer and prevents Cr2O3 from reacting with MgO or other constituents. MgCr2O4 was observed in the XRD analysis of the bulk MW waste glass after the corrosion test, and ZrSiO4 in the MZMF waste glass, and ZrSiO4 and CaMoO4 in the CZMF waste glass.

Corrosion of glass-bonded sodalite as a function of pH and temperature

International Nuclear Information System (INIS)

Morss, L. R.; Stanley, M.; Tatko, C.; Ebert, W. L.

1999-01-01

This paper reports the results of corrosion tests with monoliths of sodalite, binder glass, and glass-bonded sodalite, a ceramic waste form (CWF) that is being developed to immobilize radioactive electrorefiner salt used to condition spent sodium-bonded nuclear fuel. These tests were performed with dilute pH-buffered solutions in the pH range of 5-10 at temperatures of 70 and 90 C. The pH dependence of the forward dissolution rates of the CWF and its components have been determined. The pH dependence of the dissolution rates of sodalite, binder glass, and glass-bonded sodalite are similar to the pH dependence of dissolution rate of borosilicate nuclear waste glasses, with a negative pH dependence in the acidic region and a positive pH dependence in the basic region. Our results on the forward dissolution rates and their temperature and pH dependence will be used as components of a waste form degradation model to predict the long-term behavior of the CWF in a nuclear waste repository

Basaltic glasses from Iceland and the deep sea: Natural analogues to borosilicate nuclear waste-form glass

International Nuclear Information System (INIS)

Jercinovic, M.J.; Ewing, R.C.

1987-12-01

The report provides a detailed analysis of the alteration process and products for natural basaltic glasses. Information of specific applicability to the JSS project include: * The identification of typical alteration products which should be expected during the long-term corrosion process of low-silica glasses. The leached layers contain a relatively high proportion of crystalline phases, mostly in the form of smectite-type clays. Channels through the layer provide immediate access of solutions to the fresh glass/alteration layer interface. Thus, glasses are not 'protected' from further corrosion by the surface layer. * Corrosion proceeds with two rates - an initial rate in silica-undersaturated environments and a long-term rate in silica-saturated environments. This demonstrates that there is no unexpected change in corrosion rate over long periods of time. The long-term corrosion rate is consistent with that of borosilicate glasses. * Precipitation of silica-containing phases can result in increased alteration of the glass as manifested by greater alteration layer thicknesses. This emphasizes the importance of being able to predict which phases form during the reaction sequence. * For natural basaltic glasses the flow rate of water and surface area of exposed glass are critical parameters in minimizing glass alteration over long periods of time. The long-term stability of basalt glasses is enhanced when silica concentrations in solution are increased. In summary, there is considerable agreement between corrosion phenomena observed for borosilicate glasses in the laboratory and those observed for natural basalt glasses of great age. (With 121 refs.) (authors)

Influence of gel morphology on the corrosion kinetics of borosilicate glass: calcium and zirconium effect

International Nuclear Information System (INIS)

Cailleteau, C.

2008-12-01

This study is related to the question of the long-term behaviour of the nuclear waste confinement glass. A glass alteration layer (known as the 'gel'), formed at the glass surface in contact with water, can limit the exchanges between the glass and the solution. We studied five oxide based glasses SiO 2 -B 2 O 3 -Na 2 O-CaO-ZrO 2 . Two series of glasses were synthesized by substituting CaO for Na 2 O and ZrO 2 for SiO 2 . The leaching showed that the presence of Ca improves the reticulation of the vitreous network, inducing a decrease in the final degree of corrosion and the presence of Zr prevents the hydrolysis of silicon, which leads to a decrease of the initial dissolution rate. However, the introduction of Zr delays the drop of the alteration rate and leads to an increase in the alteration degree. In order to explain this unexpected behaviour, the gel morphology was investigated by small angle X-ray scattering. These experiments showed that the restructuring of porous network during the glass alteration process is limited by the increase of the Zr-content. Then, the restructuring of gel is at the origin of the major drop in the alteration rate observed for the low Zr-content glasses. Besides, both time-of-flight secondary-ion mass spectroscopy (ToF-SIMS) that provides an evaluation of extraneous element penetration into the gel pores and neutron scattering with index matching showed that the porosity closed during the corrosion in the glass without zirconia, but remained open in the high Zr-content glasses. These experiments, associated to simulations by a Monte Carlo method, establish a relationship between the morphologic transformations of gel and the alteration kinetics. (author)

Performance of surrogate high-level waste glass in the presence of iron corrosion products

International Nuclear Information System (INIS)

Jain, V.; Pan, Y.M.

2004-01-01

Radionuclide release from a waste package (WP) is a series of processes that depend upon the composition and flux of groundwater contacting the waste-forms (WF); the corrosion rate of WP containers and internal components made of Alloy 22, 316L SS, 304L SS and carbon steel; the dissolution rate of high-level radioactive waste (HLW) glass and spent nuclear fuel (SNF); the solubility of radionuclides; and the retention of radionuclides in secondary mineral phases. In this study, forward reaction rate measurements were made on a surrogate HLW glass in the presence of FeCl 3 species. Results indicate that the forward reaction rate increases with an increase in the FeCl 3 concentration. The addition of FeCl 3 causes the drop in the pH due to hydrolysis of Fe 3+ ions in the solution. Results based on the radionuclide concentrations and dissolution rates for HLW glass and SNF indicate that the contribution from glass is similar to SNF at 75 deg C. (authors)

Chemistry of glass corrosion in high saline brines

International Nuclear Information System (INIS)

Grambow, B.; Mueller, R.

1990-01-01

Corrosion data obtained in laboratory tests can be used for the performance assessment of nuclear waste glasses in a repository if the data are quantitatively described in the frame of a geochemical model. Experimental data were obtained for conventional pH values corrected for liquid junction, amorphous silica solubility and glass corrosion in concentrated salt brines. The data were interpreted with a geochemical model. The brine chemistry was described with the Pitzer formalism using a data base which allows calculation of brine compositions in equilibrium with salt minerals at temperatures up to 200C. In MgCl 2 dominated brines Mg silicates form and due to the consumption of Mg the pH decreases with proceeding reaction. A constant pH (about 4) and composition of alteration products is achieved, when the alkali release from the glass balances the Mg consumption. The low pH results in high release of rare earth elements REE (rare earth elements) and U from the glass. In the NaCl dominated brine MgCl 2 becomes exhausted by Mg silicate formation. As long as there is still Mg left in solution the pH decreases. After exhaustion of Mg the pH rises with the alkali release from the glass and analcime is formed

Stress-corrosion mechanisms in silicate glasses

International Nuclear Information System (INIS)

Ciccotti, Matteo

2009-01-01

The present review is intended to revisit the advances and debates in the comprehension of the mechanisms of subcritical crack propagation in silicate glasses almost a century after its initial developments. Glass has inspired the initial insights of Griffith into the origin of brittleness and the ensuing development of modern fracture mechanics. Yet, through the decades the real nature of the fundamental mechanisms of crack propagation in glass has escaped a clear comprehension which could gather general agreement on subtle problems such as the role of plasticity, the role of the glass composition, the environmental condition at the crack tip and its relation to the complex mechanisms of corrosion and leaching. The different processes are analysed here with a special focus on their relevant space and time scales in order to question their domain of action and their contribution in both the kinetic laws and the energetic aspects.

Corrosion behaviour of the WAK-HLW glass

International Nuclear Information System (INIS)

Grambow, B.; Luckscheiter, B.; Nesovic, M.

1997-01-01

Sorption studies were performed on corrosion products from the glass GP WAK1 formed over a period of 40 days in deionized water at 80 C and S/V=1000 m -1 . After 40 days the pH of the solution was adjusted to various preselected values in the pH range 2-10. The pH was kept constant during the experiments by daily addition of either HNO 3 or NaOH. The sorption experiments were run at ambient temperature and 80 C for up to 10 days using various starting concentrations of Eu, Th and U. Sorption isotherms of Eu, Th and U(VI) on corrosion products were determined in deionized water, in NaCl-rich and MgCl 2 -rich solution. Presently, data of the sorption studies in deionized water are available.Furthermore the investigations of the pH dependence of saturation concentration of silica and of the release of various glass constituent of the glass GP WAK1 were continued with studies in the MgCl 2 -rich solution 1 at 80 C. Results of these studies (30 days) are given in terms of normalized elemental mass losses. (MM)

Glass corrosion in natural environments

Science.gov (United States)

Thorpe, Arthur N.; Barkatt, Aaron

1992-01-01

Experiments carried out during the progress period are summarized. Experiments carried out involving glass samples exposed to solutions of Tris have shown the appearance of 'spikes' upon monitoring glass dissolution as a function of time. The periodic 'spikes' observed in Tris-based media were interpreted in terms of cracking due to excessive stress in the surface region of the glass. Studies of the interactions of silicate glasses with metal ions in buffered media were extended to systems containing Al. Caps buffer was used to establish the pH. The procedures used are described and the results are given. Preliminary studies were initiated as to the feasibility of adding a slowly dissolving solid compound of the additive to the glass-water system to maintain a supply of dissolved additive. It appears that several magnesium compounds have a suitable combination of solubility and affinity towards silicate glass surfaces to have a pronounced retarding effect on the extraction of uranium from the glass. These preliminary findings raise the possibility that introducing a magnesium source into geologic repositories for nuclear waste glass in the form of a sparingly soluble Mg-based backfill material may cause a substantial reduction in the extent of long-term glass corrosion. The studies described also provide mechanistic understanding of the roles of various metal solutes in the leachant. Such understanding forms the basis for developing long-term predictions of nuclear waste glass durability under repository conditions. From what is known about natural highly reduced glasses such as tektites, it is clear that iron is dissolved as ferrous iron with little or no ferric iron. The reducing conditions were high enough to cause metallic iron to exsolve out of the glass in the form of submicroscopic spherules. As the nuclear waste glass is much less reduced, a study was initiated on other natural glasses in addition to the nuclear waste glass. Extensive measurements were

Aqueous corrosion of silicate glasses. Analogy between volcanic glasses and the French nuclear waste glass R7T7

International Nuclear Information System (INIS)

Goldschmidt, F.

1991-01-01

The behaviour of borosilicate glasses upon aqueous corrosion is controlled for long periods of time (>10,000 years) by processes which are not directly accessible by means of laboratory experiments. The analogical approach consists here to compare leaching performances between the french nuclear waste glass R7T7 and natural volcanic glasses, basaltic and rhyolitic ones. The three glasses were leached in the same conditions; open system, 90 deg C, initial pH of 9.7. Basaltic and R7T7 glasses having the same kinetic of dissolution, the basaltic glass was chosen as the best analogue. (author). refs., figs., tabs

Development of models and online diagnostic monitors of the high-temperature corrosion of refractories in oxy/fuel glass furnaces : final project report.

Energy Technology Data Exchange (ETDEWEB)

Griffiths, Stewart K.; Gupta, Amul (Monofrax Inc., Falconer, NY); Walsh, Peter M.; Rice, Steven F.; Velez, Mariano (University of Missouri, Rolla, MO); Allendorf, Mark D.; Pecoraro, George A. (PPG Industries, Inc., Pittsburgh, PA); Nilson, Robert H.; Wolfe, H. Edward (ANH Refractories, Pittsburgh, PA); Yang, Nancy Y. C.; Bugeat, Benjamin () American Air Liquide, Countryside, IL); Spear, Karl E. (Pennsylvania State University, University Park, PA); Marin, Ovidiu () American Air Liquide, Countryside, IL); Ghani, M. Usman (American Air Liquide, Countryside, IL)

2005-02-01

This report summarizes the results of a five-year effort to understand the mechanisms and develop models that predict the corrosion of refractories in oxygen-fuel glass-melting furnaces. Thermodynamic data for the Si-O-(Na or K) and Al-O-(Na or K) systems are reported, allowing equilibrium calculations to be performed to evaluate corrosion of silica- and alumina-based refractories under typical furnace operating conditions. A detailed analysis of processes contributing to corrosion is also presented. Using this analysis, a model of the corrosion process was developed and used to predict corrosion rates in an actual industrial glass furnace. The rate-limiting process is most likely the transport of NaOH(gas) through the mass-transport boundary layer from the furnace atmosphere to the crown surface. Corrosion rates predicted on this basis are in better agreement with observation than those produced by any other mechanism, although the absolute values are highly sensitive to the crown temperature and the NaOH(gas) concentration at equilibrium and at the edge of the boundary layer. Finally, the project explored the development of excimer laser induced fragmentation (ELIF) fluorescence spectroscopy for the detection of gas-phase alkali hydroxides (e.g., NaOH) that are predicted to be the key species causing accelerated corrosion in these furnaces. The development of ELIF and the construction of field-portable instrumentation for glass furnace applications are reported and the method is shown to be effective in industrial settings.

Aqueous corrosion mechanisms of the nuclear glass R7T7. Experimental approach. Kinetics and thermodynamic simulation

International Nuclear Information System (INIS)

Advocat, T.

1991-01-01

An inactive borosilicate glass made of about 30 oxides is studied. The composition was developed by the CEA for encapsulation of calcinated fission product solutions from reprocessing. Hydration energy of glass is first calculated for 8 glasses and results are compared to experimental data. Dissolution of R7T7 glass is examined at 90 0 C in a large range of pH and S/V ratios (glass surface/solution volume). In dilute media (S/V = 0.1 cm -1 ) dissolution is selective at acid pH and stoichiometric at basic pH. In alkaline media dissolution rate increases with pH. Corrosion products, generally amorphous or badly crystallized are observed on glass surface. For high S/V ratios (4, 20, 80 and 200 cm -1 ) the very low dissolution rate is explained by saturation. Orthosilic acid controls corrosion kinetics. A kinetic equation is proposed taking into account pH, S/V ratio and dissolved silica concentration. Geochemical consequences of R7T7 dissolution are modelled at 100 0 C and 90 0 C. Affinity of dissolution reaction depends upon many factors (pH, silica concentration, nature and crystallinity of secondary phases. Reaction affinity is not constant for the long-term [fr

Long term corrosion behavior of the WAK-HLW glass in salt solutions

International Nuclear Information System (INIS)

Luckscheiter, B.; Nesovic, M.

1998-01-01

The corrosion behavior of the HLW glass GP WAK1 containing simulated HLW oxides from the WAK reprocessing plant in Karlsruhe is investigated in long-term corrosion experiments at high S/V ratios in two reference brines at 110 and 190 C. In case of the MgCl 2 -rich solution the leachate becomes increasingly acid with reaction time up to a final pH of about 3.5 at 190 C. In the NaCl-rich solution the pH rises to about 8.5 after one year of reaction. The release of soluble elements in MgCl 2 solution, under Si-saturated conditions, is proportional to the surface area of the sample and the release increases at 190 C according to a t 1/2 rate law. This time dependence may be an indication of diffusion controlled matrix dissolution. However, at 110 C the release of the mobile elements cannot be described by a t 1/2 rate law as the time exponents are much lower than 0.5. This difference in corrosion behavior may be explained by the higher pH of about 5 at 110 C. In case of NaCl solution under alkaline conditions, the release of soluble elements is not proportional to the surface area of the sample and it increases with time exponents much lower than 0.5. After one year of reaction at 190 C a sharp increase of the release values of some elements was observed. This increase might be explained by the high pH of the solution attained after one year. The corrosion mechanism in NaCl solution, as well as in MgCl 2 solution at 110 C, has not yet been explained. By corrosion experiments in water at constant pH values between 2 and 10, it could be shown that the time exponents of the release of Li and B decrease with increasing pH of the solution. This result can explain qualitatively the differences found in the corrosion behavior of the glass under the various conditions

Bioactive glass-ceramic coating for enhancing the in vitro corrosion resistance of biodegradable Mg alloy

Energy Technology Data Exchange (ETDEWEB)

Ye Xinyu [Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin 300072 (China); Cai Shu, E-mail: caishu@tju.edu.cn [Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin 300072 (China); Dou Ying [Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin 300072 (China); Xu Guohua [Shanghai Changzheng Hospital, Shanghai 200003 (China); Huang Kai; Ren Mengguo; Wang Xuexin [Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin 300072 (China)

2012-10-15

Highlights: Black-Right-Pointing-Pointer Sol-gel derived 45S5 glass-ceramic coating was prepared on Mg alloy substrate. Black-Right-Pointing-Pointer The corrosion resistance of glass-ceramic coated Mg alloy was markedly improved. Black-Right-Pointing-Pointer The corrosion behavior of the coated sample varied due to the cracking of coating. - Abstract: In this work, a bioactive 45S5 glass-ceramic coating was synthesized on magnesium (Mg) alloy substrate by using a sol-gel dip-coating method, to improve the initial corrosion resistance of AZ31 Mg alloy. The surface morphology and phase composition of the glass-ceramic coating were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The coating composed of amorphous phase and crystalline phase Na{sub 2}Ca{sub 2}Si{sub 3}O{sub 9}, with the thickness of {approx}1.0 {mu}m, exhibited a uniform and crack-free surface morphology. The corrosion behavior of the uncoated and coated Mg alloy substrates was investigated by the electrochemical measurements and immersion tests in simulated body fluid (SBF). Potentiodynamic polarization tests recorded an increase of potential (E{sub corr}) form -1.60 V to -1.48 V, and a reduction of corrosion current density (i{sub corr}) from 4.48 {mu}A cm{sup -2} to 0.16 {mu}A cm{sup -2}, due to the protection provided by the glass-ceramic coating. Immersion tests also showed the markedly improved corrosion resistance of the coated sample over the immersion period of 7 days. Moreover, after 14 days of immersion in SBF, the corrosion resistance of the coated sample declined due to the cracking of the glass-ceramic coating, which was confirmed by electrochemical impedance spectroscopy (EIS) analysis. The results suggested that the 45S5 glass-ceramic coated Mg alloy could provide a suitable corrosion behavior for use as degradable implants.

Corrosion mechanism and bioactivity of borate glasses analogue to Hench’s bioglass

Directory of Open Access Journals (Sweden)

Mona A. Ouis

2012-09-01

Full Text Available Bioactive borate glasses (from the system Na2O-CaO-B2O3-P2O5 and corresponding glass-ceramics as a new class of scaffold material were prepared by full replacement of SiO2 with B2O3 in Hench patented bioactive glass. The prepared samples were investigated by differential thermal analysis (DTA, Fourier transform infrared (FTIR spectroscopy and X-ray diffraction (XRD analysis. The DTA data were used to find out the proper heat treatment temperatures for preparation of the appropriate glass-ceramics with high crystallinity. The prepared crystalline glass-ceramics derivatives were examined by XRD to identify the crystalline phases that were precipitated during controlled thermal treatment. The FTIR spectroscopy was used to justify the formation of hydroxyapatite as an indication of the bioactivity potential or activity of the studied ternary borate glasses or corresponding glass-ceramics after immersion in aqueous phosphate solution. The corrosion results are interpreted on the basis of suggested recent views on the corrosion mechanism of such modified borate glasses in relation to their composition and constitution.

High-level waste glass compendium; what it tells us concerning the durability of borosilicate waste glass

International Nuclear Information System (INIS)

Cunnane, J.C.; Allison, J.

1993-01-01

Facilities for vitrification of high-level nuclear waste in the United States are scheduled for startup in the next few years. It is, therefore, appropriate to examine the current scientific basis for understanding the corrosion of high-level waste borosilicate glass for the range of service conditions to which the glass products from these facilities may be exposed. To this end, a document has been prepared which compiles worldwide information on borosilicate waste glass corrosion. Based on the content of this document, the acceptability of canistered waste glass for geological disposal is addressed. Waste glass corrosion in a geologic repository may be due to groundwater and/or water vapor contact. The important processes that determine the glass corrosion kinetics under these conditions are discussed based on experimental evidence from laboratory testing. Testing data together with understanding of the long-term corrosion kinetics are used to estimate radionuclide release rates. These rates are discussed in terms of regulatory performance standards

Glass Dissolution Parameters: Update for Entsorgungsnachweis

International Nuclear Information System (INIS)

Curti, E.

2003-11-01

This document provides updated long-term corrosion rates for borosilicate glasses used in Switzerland as a matrix for high-level radioactive waste. The new rates are based on long-term leaching experiments conducted at PSI and are corroborated by recent investigations. The asymptotic rates have been determined through weighted linear regressions of the normalised mass losses, directly calculated from B and Li concentrations in the leaching solutions. Special attention was given to the determination of the analytical uncertainty of the mass losses. The sensitivity of the corrosion rates to analytical uncertainties and to other criteria (e.g. the choice of data points for the regressions) was also studied. A major finding was that the uncertainty of the corrosion rate mainly depends on the uncertainty of the specific glass surface area. The reference rates proposed for safety assessment calculations are 1.5 mg m -2 d -1 for BNFL glasses and 0.2 mg m -2 d -1 for Cogema glasses. The relevance of the proposed corrosion rates for repository conditions is shown based on the analysis of processes and parameters currently known to affect the long-term kinetics of silicate glasses. Specifically, recent studies indicate that potentially detrimental effects, notably the removal of silica from solution through adsorption on clay minerals, are transitory and will not affect the long-term corrosion rate of the Swiss reference glasses. Iron corrosion products are also known to bind silica, but present data are not sufficient to quantify their influence on the long-term rate. (author)

Aqueous corrosion of borosilicate glasses: experiments, modeling and Monte-Carlo simulations; Alteration par l'eau des verres borosilicates: experiences, modelisation et simulations Monte-Carlo

Energy Technology Data Exchange (ETDEWEB)

Ledieu, A

2004-10-01

This work is concerned with the corrosion of borosilicate glasses with variable oxide contents. The originality of this study is the complementary use of experiments and numerical simulations. This study is expected to contribute to a better understanding of the corrosion of nuclear waste confinement glasses. First, the corrosion of glasses containing only silicon, boron and sodium oxides has been studied. The kinetics of leaching show that the rate of leaching and the final degree of corrosion sharply depend on the boron content through a percolation mechanism. For some glass contents and some conditions of leaching, the layer which appears at the glass surface stops the release of soluble species (boron and sodium). This altered layer (also called the gel layer) has been characterized with nuclear magnetic resonance (NMR) and small angle X-ray scattering (SAXS) techniques. Second, additional elements have been included in the glass composition. It appears that calcium, zirconium or aluminum oxides strongly modify the final degree of corrosion so that the percolation properties of the boron sub-network is no more a sufficient explanation to account for the behavior of these glasses. Meanwhile, we have developed a theoretical model, based on the dissolution and the reprecipitation of the silicon. Kinetic Monte Carlo simulations have been used in order to test several concepts such as the boron percolation, the local reactivity of weakly soluble elements and the restructuring of the gel layer. This model has been fully validated by comparison with the results on the three oxide glasses. Then, it has been used as a comprehensive tool to investigate the paradoxical behavior of the aluminum and zirconium glasses: although these elements slow down the corrosion kinetics, they lead to a deeper final degree of corrosion. The main contribution of this work is that the final degree of corrosion of borosilicate glasses results from the competition of two opposite mechanisms

Effect of lead species on the durability of simulated nuclear waste glass

International Nuclear Information System (INIS)

Kuchinski, F.A.

1987-01-01

It has been shown that the incorporation of lead metal into the corrosion environment reduces the leaching rate of nuclear waste glasses. The present study evaluated the effects of lead metal, oxides, alloys, glasses and soluble species on the corrosion rate of a waste glass. The inherent durability of nuclear waste glasses comes from the about due to the insoluble surface film developed during corrosion. This surface film, enriched with iron, aluminum and calcium acts as a diffusion barrier to further corrosion. Except for PbO 2 , all lead species inhibited glass corrosion due to the formation of a surface film enriched in lead. No corroded glass layer was observed below the lead surface layer. Also, no glass corrosion products were found on the lead surface, except for small amounts of silicon. The transport and deposition of lead on the glass surface appears to be the key factors in preventing glass corrosion. At high glass surface area to volume ratios, the glass corroded considerably at short times since the dissolved lead source could not coat the entire glass surface rapidly enough to prevent continued corrosion. Also, experimental solution values did not agree with thermodynamics model predictions. This suggests that kinetic factors, namely diffusion barriers, are controlling the glass corrosion rate

REACTION PRODUCTS AND CORROSION OF MOLYBDENUM ELECTRODE IN GLASS MELT CONTAINING ANTIMONY OXIDES AND SODIUM SULFATE

Directory of Open Access Journals (Sweden)

JIŘÍ MATĚJ

2012-09-01

Full Text Available The products on the interface of a molybdenum electrode and glass melt were investigated primarily at 1400°C in three model glass melts without ingredients, with 1 % Sb2O3 and with 1 % Sb2O3 and 0.5 % SO3 (wt. %, both under and without load by alternating current. Corrosion of the molybdenum electrode in glass melt without AC load is higher by one order of magnitude if antimony oxides are present. The corrosion continues to increase if sulfate is present in addition to antimony oxides. Isolated antimony droplets largely occur on the electrode-glass melt interface, and numerous droplets are also dissipated in the surrounding glass if only antimony oxides are present in the glass melt. A comparatively continuous layer of antimony occurs on the interface if SO3 is also present, antimony being always in contact with molybdenum sulfide. Almost no antimony droplets are dissipated in the glass melt. The total amount of precipitated antimony also increases. The presence of sulfide on the interface likely facilitates antimony precipitation. The reaction of molybdenum with antimony oxides is inhibited in sites covered by an antimony layer. The composition of sulfide layers formed at 1400°C approximates that of Mo2S3. At 1100°C, the sulfide composition approximates that of MoS4. Corrosion multiplies in the glass melt without additions through the effect of AC current, most molybdenum being separated in the form of metallic particles. Corrosion also increases in the glass melt containing antimony oxides. This is due to increased corrosion in the neighborhood of the separated antimony droplets. This mechanism also results in the loosening of molybdenum particles. The amount of precipitated antimony also increases through the effect of the AC current. AC exerts no appreciable effect on either corrosion, the character of the electrode-glass interface, or antimony precipitation in the glass melt containing SO3.

Comprehension and modelling of chromia-forming alloys corrosion mechanisms in nuclear glasses

International Nuclear Information System (INIS)

Schmucker, Eric

2016-01-01

Nuclear wastes management consists in the confinement of the radioactive wastes in a glass matrix. This is made by inductive melting in a hot crucible at an operating temperature around 1150 C. These crucibles are constituted of nickel based superalloys with high chromium content. They are submitted to a harsh corrosion by the molten glass, eventually leading to their replacement. The protection of the crucible against corrosion is best provided by the establishment of a protective chromium oxide layer at the surface of the alloy. A binary chromia-forming alloy (Ni-30Cr) is studied in this work. Three different binary and ternary glass compositions are chosen in order to understand the influence of the glass basicity and glass viscosity on the corrosion kinetics. Besides, the de-correlation of the formation and dissolution kinetics of the oxide layer allows the modelling of the overall oxide growth in the molten glass. For that purpose, the oxide formation kinetics in molten glass media is assimilated to the oxidation kinetics of the alloy in gaseous media with oxygen partial pressure that are representative of the redox properties of the glasses. Studies of the oxidation kinetics and of the diffusion mechanisms have shown that the oxidation kinetics is independent on the oxygen pressure in the range of 10"-"1"3 up to 10"-"3 atm O_2 at 1150 C. The present work has shown that the dissolution kinetics of the oxide layer is governed by the diffusion of Cr(III) in the glass melt. This dissolution kinetics has been evaluated from the diffusion coefficient and the solubility limit of Cr(III) in the glass. Finally, the overall growth kinetics of the Cr_2O_3 layer in the glass has been successfully modelled for each glass, thanks to the knowledge of (i) the solubility limit of Cr(III), (ii) its diffusion coefficient in the glasses and (iii) the oxidation kinetics of the alloy. The presented model also allows quantifying the influence of each of these parameters on the

Aqueous corrosion of french R7T7 nuclear waste glass: selective then congruent dissolution by pH increase

International Nuclear Information System (INIS)

Advocat, T.; Vernaz, E.; Crovisier, J.L.

1991-01-01

A study of the corrosion of a borosilicate nuclear glass shows the strong effect of the pH on the dissolution mechanism. Acidic media lead to selective extraction of the glass modifier elements (Li, Na, Ca) as well as B, while dissolution is congruent under alkaline conditions. The silica dissolution rate significantly increases with increasing pH [fr

Aqueous corrosion of borosilicate glasses: experiments, modeling and Monte-Carlo simulations; Alteration par l'eau des verres borosilicates: experiences, modelisation et simulations Monte-Carlo

Energy Technology Data Exchange (ETDEWEB)

Ledieu, A

2004-10-01

This work is concerned with the corrosion of borosilicate glasses with variable oxide contents. The originality of this study is the complementary use of experiments and numerical simulations. This study is expected to contribute to a better understanding of the corrosion of nuclear waste confinement glasses. First, the corrosion of glasses containing only silicon, boron and sodium oxides has been studied. The kinetics of leaching show that the rate of leaching and the final degree of corrosion sharply depend on the boron content through a percolation mechanism. For some glass contents and some conditions of leaching, the layer which appears at the glass surface stops the release of soluble species (boron and sodium). This altered layer (also called the gel layer) has been characterized with nuclear magnetic resonance (NMR) and small angle X-ray scattering (SAXS) techniques. Second, additional elements have been included in the glass composition. It appears that calcium, zirconium or aluminum oxides strongly modify the final degree of corrosion so that the percolation properties of the boron sub-network is no more a sufficient explanation to account for the behavior of these glasses. Meanwhile, we have developed a theoretical model, based on the dissolution and the reprecipitation of the silicon. Kinetic Monte Carlo simulations have been used in order to test several concepts such as the boron percolation, the local reactivity of weakly soluble elements and the restructuring of the gel layer. This model has been fully validated by comparison with the results on the three oxide glasses. Then, it has been used as a comprehensive tool to investigate the paradoxical behavior of the aluminum and zirconium glasses: although these elements slow down the corrosion kinetics, they lead to a deeper final degree of corrosion. The main contribution of this work is that the final degree of corrosion of borosilicate glasses results from the competition of two opposite mechanisms

Bioactive glass-ceramic coating for enhancing the in vitro corrosion resistance of biodegradable Mg alloy

Science.gov (United States)

Ye, Xinyu; Cai, Shu; Dou, Ying; Xu, Guohua; Huang, Kai; Ren, Mengguo; Wang, Xuexin

2012-10-01

In this work, a bioactive 45S5 glass-ceramic coating was synthesized on magnesium (Mg) alloy substrate by using a sol-gel dip-coating method, to improve the initial corrosion resistance of AZ31 Mg alloy. The surface morphology and phase composition of the glass-ceramic coating were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The coating composed of amorphous phase and crystalline phase Na2Ca2Si3O9, with the thickness of ∼1.0 μm, exhibited a uniform and crack-free surface morphology. The corrosion behavior of the uncoated and coated Mg alloy substrates was investigated by the electrochemical measurements and immersion tests in simulated body fluid (SBF). Potentiodynamic polarization tests recorded an increase of potential (Ecorr) form -1.60 V to -1.48 V, and a reduction of corrosion current density (icorr) from 4.48 μA cm-2 to 0.16 μA cm-2, due to the protection provided by the glass-ceramic coating. Immersion tests also showed the markedly improved corrosion resistance of the coated sample over the immersion period of 7 days. Moreover, after 14 days of immersion in SBF, the corrosion resistance of the coated sample declined due to the cracking of the glass-ceramic coating, which was confirmed by electrochemical impedance spectroscopy (EIS) analysis. The results suggested that the 45S5 glass-ceramic coated Mg alloy could provide a suitable corrosion behavior for use as degradable implants.

High-level waste borosilicate glass a compendium of corrosion characteristics. Volume 1

International Nuclear Information System (INIS)

Cunnane, J.C.

1994-03-01

Current plans call for the United States Department of Energy (DOE) to start up facilities for vitrification of high-level radioactive waste (HLW) stored in tanks at the Savannah River Site, Aiken, South Carolina, in 1995; West Valley Demonstration Project, West Valley, New York, in 1996; and at the Hanford Site, Richland, Washington, after the year 2000. The product from these facilities will be canistered HLW borosilicate glass, which will be stored, transported, and eventually disposed of in a geologic repository. The behavior of this glass waste product, under the range of likely service conditions, is the subject of considerable scientific and public interest. Over the past few decades, a large body of scientific information on borosilicate waste glass has been generated worldwide. The intent of this document is to consolidate information pertaining to our current understanding of waste glass corrosion behavior and radionuclide release. The objective, scope, and organization of the document are discussed in Section 1.1, and an overview of borosilicate glass corrosion is provided in Section 1.2. The history of glass as a waste form and the international experience with waste glass are summarized in Sections 1.3 and 1.4, respectively

Research and development on is process components for hydrogen production. (2) Corrosion resistance of glass lining in high temperature sulfuric acid

International Nuclear Information System (INIS)

Tanaka, Nobuyuki; Iwatsuki, Jin; Kubo, Shinji; Terada, Atsuhiko; Onuki, Kaoru

2009-01-01

Japan Atomic Energy Agency has been conducting a research and development on hydrogen production system using High Temperature Gas-Cooled Reactor. As a part of this effort, thermochemical water-splitting cycle featuring iodine- and sulfur-compounds (IS process) is under development considering its potential of large-scale economical hydrogen production. The IS process constitutes very severe environments on the materials of construction because of the corrosive nature of process chemicals, especially of the high temperature acidic solution of sulfuric acid and hydriodic acid dissolving iodine. Therefore, selection of the corrosion-resistant materials and development of the components has been studied as a crucial subject of the process development. This paper discusses corrosion resistance of commercially available glass-lining material in high temperature sulfuric acid. Corrosion resistance of a soda glass used for glass-lining was examined by immersion tests. The experiments were performed in 47-90wt% sulfuric acids at temperatures of up to 400degC and for the maximum immersion time of 100 hours using an autoclave designed for the concerned tests. In every condition tested, no indication of localized corrosion such as defect formation or pitting corrosion was observed. Also, the corrosion rates decreased with the progress of immersion, and were low enough (≅0.1 mm/year) after 60-90 hours of immersion probably due to formation of a silica rich surface. (author)

R7T7 nuclear waste glass behavior in moist clay: role of the clay mass/glass surface area ratio

International Nuclear Information System (INIS)

Godon, N.; Vernaz, E.

1989-01-01

R7T7 glass alteration was investigated in the presence of various moist clays. In contact with smectite 4a, selected in France as a potential engineered barrier material, the glass was significantly corroded: after 6 months the glass corrosion rate was practically the same as the initial alteration rate in double-distilled water. Substantially lower alteration was observed in contact with bentonite 6 activated by sodium carbonate. Smectite 4a consumes silicon released by glass corrosion, and thus retards the rise to high silicon concentrations in solution at which the glass corrosion rate diminishes. Glass can therefore in some cases be altered as much in moist clay as in water with high renewal rates. Other experiments with smaller quantities of smectite 4a showed that the phenomenon becomes less important in time: its duration is proportional to the ratio between the clay mass (C) and the glass surface area (SA). Comparing the results of studies at different C/SA ratios indicates that low glass corrosion rates are obtained more slowly at higher C/SA ratios. Tests with 239 Pu-doped R7T7 glass also showed that the radionuclide retention factor in the alteration film at the glass surface is only 6, compared with a factor of nearly 50 in double-distilled water

Corrosion of ancient glass beads found in Southern Thailand

International Nuclear Information System (INIS)

Won-in, K; Thongkam, Y; Intarasiri, S; Kamwanna, T; Dararutana, P

2012-01-01

Glass has been used as ornaments and decorations in Thailand for several hundred years. The archaeological resources suggested that the ancient glass beads excavated in southern Thailand were made more than 1300 years ago. Initial findings revealed that there were number of difference in shade between the glass beads of difference colors. Energy dispersive X-ray spectrometer (EDS) system attached with scanning electron microscope (SEM) and particle-induced X-ray emission spectroscopy (PIXE) were firstly used to study the surface corrosion of the samples. SEM micrographs showed more corroded and flaked microstructure. These were contributed to the interaction of both the ground water and its dissolved chemical compounds.

Improvement of corrosion resistance in NaOH solution and glass forming ability of as-cast Mg-based bulk metallic glasses by microalloying

Directory of Open Access Journals (Sweden)

Peng Hao

2011-02-01

Full Text Available The influences of the addition of Ag on the glass forming ability (GFA and corrosion behavior were investigated in the Mg-Ni-based alloy system by X-ray diffraction (XRD and electrochemical polarization in 0.1 mol/L NaOH solution. Results shows that the GFA of the Mg-Ni-based BMGs can be improved dramatically by the addition of an appropriate amount of Ag; and the addition element Ag can improve the corrosion resistance of Mg-Ni-based bulk metallic glass. The large difference in atomic size and large negative mixing enthalpy in alloy system can contribute to the high GFA. The addition element Ag improves the forming speed and the stability of the passive film, which is helpful to decrease the passivation current density and to improve the corrosion resistance of Mg-Ni-based bulk metallic glass.

Corrosion mechanisms and behaviour of actinides in the 'R7T7' nuclear glass

International Nuclear Information System (INIS)

Fillet, Sylvie

1987-01-01

This research thesis reports the study of aqueous corrosion of the R7T7 nuclear glass and of the identified corrosion mechanisms in conditions of static lixiviation which are close to that expected during long term storage in a geological environment. More specifically, this work aims at assessing the durability of this glass which has been selected for the vitrification of solutions from pressurized water reactors. The main glass alteration phenomena have been studied. The first part addresses the study of the alteration of the glassy matrix, and aims at identifying corrosion mechanisms in various lixiviation conditions (high temperature, saturation). The second part addresses the action of different materials present in the environment on the glassy matrix by simulating as well as possible a storage case. Based on the obtained results, a mathematical model is developed to predict the glass behaviour on the long term. Finally, the glass confinement power with respect to actinides is studied [fr

The applicability of alkaline-resistant glass fiber in cement mortar of road pavement: Corrosion mechanism and performance analysis

Directory of Open Access Journals (Sweden)

Qin Xiaochun

2017-11-01

Full Text Available The main technical requirements of road pavement concrete are high flexural strength and fatigue durability. Adding glass fiber into concrete could greatly increase flexural strength and wearing resistance of concrete. However, glass fiber has the great potential of corrosion during the cement hydration, which will directly affect the long-term performance and strength stability. In this paper, accelerated corrosion experiments have been done to find out the corrosion mechanism and property of alkali-resistant glass fiber in cement mortar. The applicability and practicability of alkaline-resistant glass fiber in road concrete have been illustrated in the analysis of flexural strength changing trend of cement mortar mixed with different proportions of activated additives to protect the corrosion of glass fiber by cement mortar. The results have shown that a 30% addition of fly ash or 10% addition of silica fume to cement matrix could effectively improve the corrosion resistance of alkali-resistant glass fiber. The optimal mixing amount of alkali-resistant glass fiber should be about 1.0 kg/m3 in consideration of ensuring the compressive strength of reinforced concrete in road pavement. The closest-packing method has been adopted in the mixture ratio design of alkali-resistant glass fiber reinforced concrete, not only to reduce the alkalinity of the cement matrix through large amount addition of activated additives but also to greatly enhance the flexural performance of concrete with the split pressure ratio improvement of 12.5–16.7%. The results suggested a prosperous application prospect for alkaline-resistant glass fiber reinforced concrete in road pavement.

Nanoscale Characterization of Glass Flake Filled Vinyl Ester Anti-Corrosion Coatings

Directory of Open Access Journals (Sweden)

Salim Barbhuiya

2017-08-01

Full Text Available Vinyl ester is a thermoset matrix resin that is widely used in the coating industry. The presence of glass flakes further enhances the anti-corrosion performance of this coating. This paper reports the nanoscaled characterization of glass flake filled vinyl ester anti-corrosion coatings on mild steel. Bond strength properties of one uncoated and four coated samples with different thicknesses (300, 600, 900 and 1200 μm were studied using nanoscratch technique and ASTM Standard Test. It was found that the bond strength of coating with thickness 900 μm was the highest. The frequency distributions of elastic modulus on coating with 900 μm thickness determined using nanoindentation indicated that only 20–25% of the coating is composed of glass flakes and the balance is vinyl ester matrix. The critical depth at which the material is subject to failure due to external load and abrasion, was found to be around 100 nm.

Texture of altered layers issued from glass corrosion

International Nuclear Information System (INIS)

Phalippou, J.; Woignier, Th.; Ayral, A.

1997-01-01

The layers which develop at the glass surface subjected to water corrosion depend on a collection of interacting parameters. Such a material can be studied using techniques which have been previously demonstrated as suitable for gels. A detailed description of the behaviour of gels under measurements is given. Investigations show that to really know the texture both mechanical properties and permeability must be known. Different experiments are reported. They give a rough estimate of the altered layer texture. Results coming from different techniques are compared and in a few cases are used to estimate additional textural information. Finally we put an insight into the nature and consequently to the texture evolution of the layer as the corrosion proceeds. (authors)

A review on pipeline corrosion, in-line inspection (ILI), and corrosion growth rate models

International Nuclear Information System (INIS)

Vanaei, H.R.; Eslami, A.; Egbewande, A.

2017-01-01

Pipelines are the very important energy transmission systems. Over time, pipelines can corrode. While corrosion could be detected by in-line inspection (ILI) tools, corrosion growth rate prediction in pipelines is usually done through corrosion rate models. For pipeline integrity management and planning selecting the proper corrosion ILI tool and also corrosion growth rate model is important and can lead to significant savings and safer pipe operation. In this paper common forms of pipeline corrosion, state of the art ILI tools, and also corrosion growth rate models are reviewed. The common forms of pipeline corrosion introduced in this paper are Uniform/General Corrosion, Pitting Corrosion, Cavitation and Erosion Corrosion, Stray Current Corrosion, Micro-Bacterial Influenced Corrosion (MIC). The ILI corrosion detection tools assessed in this study are Magnetic Flux Leakage (MFL), Circumferential MFL, Tri-axial MFL, and Ultrasonic Wall Measurement (UT). The corrosion growth rate models considered in this study are single-value corrosion rate model, linear corrosion growth rate model, non-linear corrosion growth rate model, Monte-Carlo method, Markov model, TD-GEVD, TI-GEVD model, Gamma Process, and BMWD model. Strengths and limitations of ILI detection tools, and also corrosion predictive models with some practical examples are discussed. This paper could be useful for those whom are supporting pipeline integrity management and planning. - Highlights: • Different forms of pipeline corrosion are explained. • Common In-Line Inspection (ILI) tools and corrosion growth rate models are introduced. • Strength and limitations of corrosion growth rate models/ILI tools are discussed. • For pipeline integrity management programs using more than one corrosion growth rate model/ILI tool is suggested.

Recent progress to understand stress corrosion cracking in sodium borosilicate glasses: linking the chemical composition to structural, physical and fracture properties

Science.gov (United States)

Rountree, Cindy L.

2017-08-01

This topical review is dedicated to understanding stress corrosion cracking in oxide glasses and specifically the SiO_2{\\text-B_2O_3{\\text-}Na_2O} (SBN) ternary glass systems. Many review papers already exist on the topic of stress corrosion cracking in complex oxide glasses or overly simplified glasses (pure silica). These papers look at how systematically controlling environmental factors (pH, temperature...) alter stress corrosion cracking, while maintaining the same type of glass sample. Many questions still exist, including: What sets the environmental limit? What sets the velocity versus stress intensity factor in the slow stress corrosion regime (Region I)? Can researchers optimize these two effects to enhance a glass’ resistance to failure? To help answer these questions, this review takes a different approach. It looks at how systemically controlling the glass’ chemical composition alters the structure and physical properties. These changes are then compared and contrasted to the fracture toughness and the stress corrosion cracking properties. By taking this holistic approach, researchers can begin to understand the controlling factors in stress corrosion cracking and how to optimize glasses via the initial chemical composition.

Laboratory testing of LITCO glasses

International Nuclear Information System (INIS)

Ellison, A.; Wolf, S.; Buck, E.; Luo, J.S.; Dietz, N.; Bates, J.K.; Ebert, W.L.

1995-01-01

The purpose of this program is to measure, the intermediate and long-term durability of glasses developed by Lockheed Idaho Technology Co. (LITCO) for the immobilization of calcined radioactive wastes. The objective is to use accelerated corrosion tests as an aid in developing durable waste form compositions. This is a report of tests performed on two LITCO glass compositions, Formula 127 and Formula 532. The main avenue for release of radionuclides into the environment in a geologic repository is the reaction of a waste glass with ground water, which alters the glass and releases its components into solution. These stages in glass corrosion are analyzed by using accelerated laboratory tests in which the ratio of sample surface area to solution volume, SA/V, is varied. At low SA/V, the solution concentrations of glass corrosion products remain low and the reaction approaches the forward rate. At higher SA/V the solution approaches saturation levels for glass corrosion products. At very high SA/V the solution is rapidly saturated in glass corrosion products and secondary crystalline phases precipitate. Tests at very high SA/V provide information about the composition of the solution at saturation or, when no solution is recovered, the identities and the order of appearance of secondary crystalline phases. Tests were applied to Formula 127 and Formula 532 glasses to provide information about the interim and long-term stages in glass corrosion

Glass containing radioactive nuclear waste

International Nuclear Information System (INIS)

Boatner, L.A.; Sales, B.C.

1985-01-01

Lead-iron phosphate glasses containing a high level of Fe 2 O 3 for use as a storage medium for high-level-radioactive nuclear waste. By combining lead-iron phosphate glass with various types of simulated high-level nuclear waste, a highly corrosion resistant, homogeneous, easily processed glass can be formed. For corroding solutions at 90 C, with solution pH values in the range between 5 and 9, the corrosion rate of the lead-iron phosphate nuclear waste glass is at least 10 2 to 10 3 times lower than the corrosion rate of a comparable borosilicate nuclear waste glass. The presence of Fe 2 O 3 in forming the lead-iron phosphate glass is critical. Lead-iron phosphate nuclear waste glass can be prepared at temperatures as low as 800 C, since they exhibit very low melt viscosities in the 800 to 1050 C temperature range. These waste-loaded glasses do not readily devitrify at temperatures as high as 550 C and are not adversely affected by large doses of gamma radiation in H 2 O at 135 C. The lead-iron phosphate waste glasses can be prepared with minimal modification of the technology developed for processing borosilicate glass nuclear waste forms. (author)

Thermodynamic and structural models compared with the initial dissolution rates of SON glass samples

International Nuclear Information System (INIS)

Tovena, I.; Advocat, T.; Ghaleb, D.; Vernaz, E.

1993-01-01

The experimentally determined initial dissolution rate R 0 of nuclear glass was correlated with thermodynamic parameters and structural parameters. The initial corrosion rates of six ''R7T7'' glass samples measured at 100 deg C in a Soxhlet device were correlated with the glass free hydration energy and the glass formation enthalpy. These correlations were then tested with a group of 26 SON glasses selected for their wide diversity of compositions. The thermodynamic models provided a satisfactory approximation of the initial dissolution rate determined under Soxhlet conditions for SON glass samples that include up to 15 wt% of boron and some alumina. Conversely, these models are inaccurate if the boron concentration exceeds 15 wt% and the glass contains no alumina. Possible correlations between R 0 and structural parameters, such as the boron coordination number and the number of nonbridging oxygen atoms, were also investigated. The authors show that R 0 varies inversely with the number of 4-coordinate boron atoms; conversely, the results do not substantiate published reports of a correlation between R 0 and the number of nonbridging oxygen atoms. (authors). 13 refs., 2 figs., 4 tabs

Rutherford backscattering investigation of the corrosion of borosilicate glass

International Nuclear Information System (INIS)

Sales, B.C.; Boatner, L.A.; Naramoto, H.; White, C.W.

1981-10-01

The RBS spectra from Frit 21 borosilicate glasses doped with 5 wt % UO 2 , SrO, or Cs 2 O show that: during the initial stages of leaching (0 to 3 h) there is a substantial (300 to 500%) enhancement in the concentration of U, Sr, Ca, and Ti in the outer surface layer and that this enhancement is accompanied by a large depletion of Na, Si, and Cs; and upon further leaching under static conditions (24 h) the leached surface layer composition is indistinguishable from the unleached surface. Other borosilicate glasses such as PNL 76-68 may eventually show the same behavior if the final equilibrium pH value is greater than 9. The technique of Rutherford backscattering depth profile analysis can be a powerful tool for investigating the initial stages of glass corrosion

Development of Copper Corrosion Products and Relation between Surface Appearance and Corrosion Rate

International Nuclear Information System (INIS)

Lan, Tran Thi Ngoc; Binh, Nguyen Thi Thanh; Tru, Nguyen Nhi; Yoshino, Tsujino; Yasuki, Maeda

2008-01-01

Copper was exposed unsheltered and sheltered in four humid tropical sites, representing urban, urban-industrial, urban-marine and rural environments. The corrosion rates and the sequence of corrosion product formation are presented and discussed in relation with climatic and atmospheric pollution parameters. Chemical compositions of corrosion products were found to depend on environments and duration of exposure. In all environments, cuprite was the predominating corrosion product that formed first and continuously increased during the exposure. Among the sulphur-containing corrosion products, posnjakite and brochantite were more frequently found and the first formed earlier. Nantokite was the most common chlorine-containing products for most cases, except the high-chloride environment, where atacamite was detected instead. The corrosion rate of copper was well indicated by the colour of patina. The red-purple colour corresponded to the high corrosion rate and the greenish grey colour corresponded to the low corrosion rate. Corrosion rate of sheltered copper in urban-marine environment increased with the exposure time

Corrosion Rate Monitoring in District Heating Systems

DEFF Research Database (Denmark)

Hilbert, Lisbeth Rischel; Nielsen, Lars Vendelbo; Andersen, A.

2005-01-01

be applicable, and if on-line monitoring could improve the quality control. Water quality monitoring was applied as well as corrosion rate monitoring with linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS), electrical resistance (ER) technique, mass loss and a crevice corrosion......Quality control in district heating systems to keep uniform corrosion rates low and localized corrosion minimal is based on water quality control. Side-stream units equipped with carbon steel probes for online monitoring were mounted in district heating plants to investigate which techniques would...... cell for localized corrosion risk estimation. Important variations in corrosion rate due to changes in make-up water quality were detected with the continuous monitoring provided by ER and crevice cell, while LPR gave unreliable corrosion rates. The acquisition time of two-three days for EIS...

Monitoring corrosion rates and localised corrosion in low conductivity water

DEFF Research Database (Denmark)

Hilbert, Lisbeth Rischel

2006-01-01

Monitoring of low corrosion rates and localised corrosion in a media with low conductivity is a challenge. In municipal district heating, quality control may be improved by implementing on-line corrosion monitoring if a suitable technique can be identified to measure both uniform and localised...... corrosion. Electrochemical techniques (LPR, EIS, crevice corrosion current) as well as direct measurement techniques (high-sensitive electrical resistance, weight loss) have been applied in operating plants. Changes in the corrosion processes are best monitored in non-aggressive, low conductivity media...

First multi-scale investigation of an iron corrosion products/glass interface on an archaeological analogue

Energy Technology Data Exchange (ETDEWEB)

Michelin, A.; Neff, D.; Dillmann, Ph. [CEA Saclay, Lab. Pierre Sue, UMR 9956 CEA/CNRS, 91 - Gif-sur-Yvette (France); Michelin, A.; Gin, St. [CEA Marcoule, Lab. d' Etudes du Comportement a Long Terme des Materiaux de Conditionnement 30 (France); Robinet, L. [Synchrotron SOLEIL, IPANEMA, 91 - Gif-sur-Yvette (France)

2009-07-01

Full text of publication follows: In the context of nuclear waste storage, the French approach is to cast the high-level radioactive waste into a stable form and to bury them into a deep geological repository. This conditioning is based on a multi-barrier concept (glass matrix, steel container, overpack and geological barrier) and must ensure the durable confinement of radionuclides. But laboratory experiments do not permit to predict directly the behaviour of these materials over typically a million-year timescale and the extrapolation of short-term laboratory data to long time periods remains problematic. Part of the validation of the predictive models relies on natural and archaeological analogues. For that reason, blast furnace slags originating from a 16. century iron-making site (Glinet, Normandy) are studied. This material is composed of opaque glass containing cast iron balls. Thus, it represents a good analogue for long-term prediction of glass/iron alteration behaviour. Moreover, these artefacts were buried several centuries in a fine characterized anoxic environment which is the subject of field investigations. The aim of this study is to characterize interfacial zones using microbeam techniques (EDS/WDS for elemental information, EDS/TEM microanalysis, {mu}Raman, {mu}XAS under synchrotron radiation for structural analyses). First of all, corrosion products around cast iron balls have been identified as siderite (FeCO{sub 3}) and iron hydroxycarbonate (Fe{sub 2}(OH){sub 2}CO{sub 3}) using {mu}Raman and EDS microanalysis. Then the interface glass/corrosion products has been studied with the same techniques. A signal variation on Raman spectra is observed along the interface and EDS-SEM microanalysis points out a calcium depletion. It means that mass transfer exists between glass and iron-rich phases and this leads to the development of an altered zone of glass. However, this interface seems to be too thin for the resolution of these techniques. That

In-situ investigations of corrosion processes on glass and metal surfaces by scanning probe microscopy (SPM)

International Nuclear Information System (INIS)

Nicolussi-Leck, G.

1996-09-01

The corrosion of potash-lime-silica glass was observed in-situ by AFM (atomic force microscopy) for the first time. The topographic changes with time due to the interaction of a replica glass with the ambient atmosphere were studied. A comparison of dynamic mode AFM and static mode AFM has demonstrated their potential for the investigation of soft, sensitive specimens. A combination of both methods yielded a correlation between structural changes during the corrosion process and different corrosion products on glass. The activation of surface reactions by the tip touching the surface could be observed with dynamic mode AFM. In-situ sample preparation and introduction of a defined atmosphere consisting of nitrogen with adjustable amounts of relative humidity and varying contents of SO 2 and NO 2 allowed model studies of the atmospheric corrosion. A replica glass with medieval composition was used in order to investigate the impact of the above described conditions. Besides the influence of the relative humidity the effects of SO 2 and NO 2 as well as their, synergistic effects could be studied. The evaluation of the phase signal in dynamic mode AFM in addition to the topographic information allowed the identification of humid domains in and on corrosion products, respectively. The observed contrast and thus the adhesion forces, are mainly related to the different water coverage of the surface regions or the hydroscopic properties, respectively. Furthermore, the topographic changes of copper-nickel, and palladium surfaces exposed to humidified nitrogen with SO 2 have been observed in-situ. Contrary to the assumption of the metal surfaces being covered by a homogeneous layer of corrosion products, distinct clusters of products could be observed. In case of different kinds of products these clusters were arranged adjacent to each other rather than in different stacked layers. (author)

Corrosion study of resorbable Ca60Mg15Zn25 bulk metallic glasses in physiological fluids

Directory of Open Access Journals (Sweden)

Rafał Babilas

2017-10-01

Full Text Available The corrosion activity of amorphous plates of Ca60Mg15Zn25 alloy was investigated. The biocompatible elements were selected for the alloy composition. The electrochemical corrosion and immersion tests were carried out in a multi-electrolyte fluid and Ringer's solution. Better corrosion behavior was observed for the samples tested in a multi-electrolyte fluid despite the active dissolution of Ca and Mg in Ringer's solution. The experimental results indicated that reducing concentration of NaCl from 8.6 g/dm3 for Ringer's solution to 5.75 g/dm3 caused the decrease of the corrosion rate. The volume of the hydrogen evolved after 480 min in Ringer's solution (40.1 ml/cm2 was higher in comparison with that obtained in a multi-electrolyte fluid (24.4 ml/cm2. The values of open-circuit potential (EOCP for the Ca60Mg15Zn25 glass after 1 h incubation in Ringer's solution and a multi-electrolyte fluid were determined to be −1553 and −1536 mV vs. a saturated calomel electrode (SCE. The electrochemical measurements indicated a shift of the corrosion current density (jcorr from 1062 μA/cm2 for the sample tested in Ringer's solution to 788 μA/cm2 for the specimen immersed in a multi-electrolyte fluid. The corrosion products analysis was conducted by using the X-ray photoelectron spectroscopy (XPS. The corrosion products were identified to be CaCO3, Mg(OH2, CaO, MgO and ZnO. The mechanism of corrosion process was proposed and described based on the microscopic observations. The X-ray diffraction and Fourier transform infrared spectroscopy (FTIR also indicated that Ca(OH2, CaCO3, Zn(OH2 and Ca(Zn(OH32·2H2O mainly formed on the surface of the studied alloy. Keywords: Ca-based metallic glasses, X-ray photoelectron spectroscopy, FTIR spectroscopy, X-ray diffraction, Corrosion resistance, Hydrogen evaluation

The role of nuclear analytical techniques in the study of aqueous corrosion of glasses

International Nuclear Information System (INIS)

Trocellier, P.

1984-01-01

Direct observation of resonant nuclear reactions, backscattering spectrometry and X ray microanalysis with a nuclear microprobe were used to determine elementary depth profiles in the near surface region of leached glasses. Some computing programs required to interpretate the analytical information detected were built. Experimental conditions to characterize glass samples without secondary effects were defined; and the influence of some leaching parameters was studied to describe the first stages of aqueous corrosion of borosilicate glasses [fr

Glass as a waste form for the immobilization of plutonium

International Nuclear Information System (INIS)

Bates, J.K.; Ellison, A.J.G.; Emery, J.W.; Hoh, J.C.

1995-01-01

Several alternatives for disposal of surplus plutonium are being considered. One method is incorporating Pu into glass and in this paper we discuss the development and corrosion behavior of an alkali-tin-silicate glass and update results in testing Pu doped Defense Waste Processing Facility (DWPF) reference glasses. The alkali-tin-silicate glass was engineered to accommodate a high Pu loading and to be durable under conditions likely to accelerate glass reaction. The glass dissolves about 7 wt% Pu together with the neutron absorber Gd, and under test conditions expected to accelerate the glass reaction with water, is resistant to corrosion. The Pu and the Gd are released from the glass at nearly the same rate in static corrosion tests in water, and are not segregated into surface alteration phases when the glass is reacted in water vapor. Similar results for the behavior of Pu and Gd are found for the DWPF reference glasses, although the long-term rate of reaction for the reference glasses is more rapid than for the alkali-tin-silicate glass

Fatigue and corrosion of a Pd-based bulk metallic glass in various environments

Energy Technology Data Exchange (ETDEWEB)

Watanabe, L.Y. [East Los Angeles College, Monterey Park, CA 91754 (United States); Roberts, S.N. [Keck Laboratory of Materials Science, California Institute of Technology, Pasadena, CA 91125 (United States); Baca, N. [Department of Chemistry and Biochemistry, California State University Northridge, Northridge, CA 91330 (United States); Wiest, A. [Naval Surface Warfare Center, Norco, CA (United States); Garrett, S.J. [Department of Chemistry and Biochemistry, California State University Northridge, Northridge, CA 91330 (United States); Conner, R.D., E-mail: rdconner@csun.edu [Department of Manufacturing Systems Engineering and Management, California State University Northridge, 18111 Nordhoff St., Mail Code 8295, Northridge, CA 91330 (United States)

2013-10-15

Bulk metallic glasses (BMGs) possess attractive properties for biomedical applications, including high strength, hardness and corrosion resistance, and low elastic modulus. In this study, we conduct rotating beam fatigue tests on Pd{sub 43}Ni{sub 10}Cu{sub 27}P{sub 20} bulk metallic glass in air and Eagle's medium (EM) and measure the corrosive resistance of the alloy by submersion in acidic and basic electrolytes. Fatigue results are compared to those of commonly used biometals in EM. Rotating beam fatigue tests conducted in air and in Eagle's medium show no deterioration in fatigue properties in this potentially corrosive environment out to 10{sup 7} cycles. A specimen size effect is revealed when comparing fatigue results to those of a similar alloy of larger minimum dimensions. Corrosion tests show that the alloy is not affected by highly basic (NaOH) or saline (NaCl) solutions, nor in EM, and is affected by chlorinated acidic solutions (HCl) to a lesser extent than other commonly used biometals. Corrosion in HCl initiates with selective leaching of late transition metals, followed by dissolution of Pd. - Highlights: • Fatigue limit of 600 MPa with no deterioration when exposed to Eagle's medium. • Fatigue shows sample size effect. • Pd-based BMG is unaffected by saline or strong basic solutions. • Pd-based BMG is substantially more resistant to chlorinated acids than CoCrMo, 316 L Stainless, or Ti6Al4V alloys. • Corrosion shows selective leaching of late transition metals, followed by Pd and P.

Radiation effects in moist-air systems and the influence of radiolytic product formation on nuclear waste glass corrosion

International Nuclear Information System (INIS)

Wronkiewicz, D.J.; Bates, J.K.; Buck, E.C.; Hoh, J.C.; Emery, J.W.; Wang, L.M.

1997-07-01

Ionizing radiation may affect the performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water to produce a variety of radiolytic products. Tests were conducted to examine the effects of radiolysis under high gas/liquid ratios. Results indicate that nitrate is the predominant radiolytic product produced following both gamma and alpha radiation exposure, with lesser amounts of nitrite and carboxylic acids. The formation of nitrogen acids during exposure to long-lived, alpha-particle-emitting transuranic elements indicates that these acids may play a role in influencing nuclear waste form reactions in a long-term unsaturated disposal scenario. Experiments were also conducted with samples that simulate the composition of Savannah River Plant nuclear waste glasses. Radiolytic product formation in batch tests (340 m -1 , 90 C) resulted in a small increase in the release rates of many glass components, such as alkali and alkaline earth elements, although silicon and uranium release rates were slightly reduced indicating an overall beneficial effect of radiation on waste form stability. The radiolytic acids increased the rate of ion exchange between the glass and the thin film of condensate, resulting in accelerated corrosion rates for the glass. The paragenetic sequence of alteration phases formed on both the irradiated and nonirradiated glass samples reacted in the vapor hydration tests matches closely with those developed during volcanic glass alteration in naturally occurring saline-alkaline lake systems. This correspondence suggests that the high temperatures used in these tests have not changed the underlying glass reaction mechanism relate to that which controls glass reactions under ambient surficial conditions

Radiation effects in moist-air systems and the influence of radiolytic product formation on nuclear waste glass corrosion

Energy Technology Data Exchange (ETDEWEB)

Wronkiewicz, D.J.; Bates, J.K.; Buck, E.C.; Hoh, J.C.; Emery, J.W. [Argonne National Lab., IL (United States). Chemical Technology Div.; Wang, L.M. [Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Geology

1997-07-01

Ionizing radiation may affect the performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water to produce a variety of radiolytic products. Tests were conducted to examine the effects of radiolysis under high gas/liquid ratios. Results indicate that nitrate is the predominant radiolytic product produced following both gamma and alpha radiation exposure, with lesser amounts of nitrite and carboxylic acids. The formation of nitrogen acids during exposure to long-lived, alpha-particle-emitting transuranic elements indicates that these acids may play a role in influencing nuclear waste form reactions in a long-term unsaturated disposal scenario. Experiments were also conducted with samples that simulate the composition of Savannah River Plant nuclear waste glasses. Radiolytic product formation in batch tests (340 m{sup {minus}1}, 90 C) resulted in a small increase in the release rates of many glass components, such as alkali and alkaline earth elements, although silicon and uranium release rates were slightly reduced indicating an overall beneficial effect of radiation on waste form stability. The radiolytic acids increased the rate of ion exchange between the glass and the thin film of condensate, resulting in accelerated corrosion rates for the glass. The paragenetic sequence of alteration phases formed on both the irradiated and nonirradiated glass samples reacted in the vapor hydration tests matches closely with those developed during volcanic glass alteration in naturally occurring saline-alkaline lake systems. This correspondence suggests that the high temperatures used in these tests have not changed the underlying glass reaction mechanism relate to that which controls glass reactions under ambient surficial conditions.

Mechanisms and kinetics laws of inactive R7T7 reference glass dissolution in water at 90 deg C: initial dissolution rate measurements

International Nuclear Information System (INIS)

Advocat, T.; Ghaleb, D.; Vernaz, E.

1993-02-01

The initial dissolution rate of inactive R7T7 reference glass was measured at 90 deg C in dilute aqueous solutions first at unspecified pH, then with imposed pH values. In distilled water, R7T7 glass corrosion initially involved preferential extraction of boron and network modifier elements (Li, Na, Ca) as long as the solution pH remained acid. When the solution pH became alkaline, glass dissolution was stoichiometric. These two mechanisms were confirmed by dissolution tests in aqueous solutions at imposed pH values under acid and alkaline conditions. The initial dissolution rate r 0 in mole.cm -3 .s -1 also increased significantly in alkaline media when the pH of the aqueous phase increased: in slightly acid media, selective glass dissolution formed a residual, de-alkalinized, hydrated glass that was characterized by transmission electron microscopy and secondary ion mass spectrometry. Under steady-state dissolution conditions, the initial glass corrosion rate (in mole.cm -3 .s -1 ) was: in acid and alkaline media, amorphous and crystallized alteration products formed after complete dissolution of the silicated glass network. The first products formed consisted mainly of Zr, Rare Earths, Fe and Al. (author). 67 refs., 29 figs., 26 tabs., 21 plates

Colloid formation during waste glass corrosion

International Nuclear Information System (INIS)

Mertz, C.J.; Buck, E.C.; Fortner, J.A.; Bates, J.K.

1996-01-01

The long-term behavior of nuclear waste glass in a geologic repository may require a technical consideration of the role of colloids in the release and transport of radionuclides. The neglect of colloidal properties in assessing the near- and far-field migration behavior of actinides may lead to significant underestimates and poor predictions of biosphere exposure from high-level waste (HLW) disposal. Existing data on colloid-facilitated transport suggests that radionuclide migration may be enhanced, but the importance of colloids is not adequately assessed. Indeed, the occurrence of radionuclide transport, attributed to colloidal species, has been reported at Mortandad Canyon, Los Alamos and at the Nevada Test Site; both unsaturated regions are similar to the proposed HLW repository at Yucca Mountain. Although some developments have been made on understanding the transport characteristics of colloids, the characterization of colloids generated from the corrosion of the waste form has been limited. Colloids are known to incorporate radionuclides either from hydrolysis of dissolved species (real colloids) or from adsorption of dissolved species onto existing groundwater colloids (pseudocolloids); however, these colloids may be considered secondary and solubility limited when compared to the colloids generated during glass alteration

Corrosion of 15th and early 16th century stained glass from the monastery of Batalha studied with external ion beam

Energy Technology Data Exchange (ETDEWEB)

Vilarigues, M., E-mail: mgv@fct.unl.pt [Dep. de Conservacao e Restauro and Centro do Vidro e da Ceramica para as Artes, FCT-UNL, Quinta da Torre, 2829-516 Caparica (Portugal); Redol, P. [Dep. de Conservacao e Restauro and Centro do Vidro e da Ceramica para as Artes, FCT-UNL, Quinta da Torre, 2829-516 Caparica (Portugal); Monastery of Batalha, P-2440 (Portugal); Machado, A. [Dep. de Conservacao e Restauro and Centro do Vidro e da Ceramica para as Artes, FCT-UNL, Quinta da Torre, 2829-516 Caparica (Portugal); Rodrigues, P.A.; Alves, L.C.; Silva, R.C. da [Dep. Fisica, LFI, ITN, E.N.10, 2686-953 Sacavem (Portugal)

2011-02-15

This paper reports the study of corrosion in two stained glass panels from the south aisle of Sta. Maria da Vitoria monastery, at Batalha (Portugal), one depicting the Last Supper (dated from 1508), and the other one showing a saint (c. 1450). These panels exhibit extensive corrosion with darkening phenomena that are an impediment to their correct visualization, a source of major concern both to conservators and curators. By using external micro-beam Particle Induced X-ray Emission (PIXE) and Particle Induced Gamma Emission (PIGE) spectrometry, the elemental compositions of large fragments were obtained, enabling the selection of representative corroded areas, from which elemental distribution maps were produced by scanning. Calcium and potassium rich structures were found - at the surface and inside cavities in the glass - that were identified as oxalates and carbonates, by Raman microscopy and micro-FTIR. The dark spots present in the glass surfaces were found to be Zn and Pb rich. These findings indicate that the corrosion observed was due not only to reactions with atmospheric water and CO{sub 2} but also with the oxalic acid secreted by micro-organisms. Furthermore, it did not result from reactions with atmospheric SO{sub 2} or acid rain. The information obtained is relevant for a better understanding of the corrosion processes and products formed on the surface of these panels and therefore for the proper planning of much needed adequate conservation-restoration actions and appropriate display conditions. - Research Highlights: {yields} Corrosion and darkening of stained glasses is of concern to conservators and curators. {yields} A multi-technique approach is of relevance to study stained glass corrosion. {yields} External beam PIXE-PIGE provide valuable insight on stained glass corrosion.

Improvement of bio-corrosion resistance for Ti42Zr40Si15Ta3 metallic glasses in simulated body fluid by annealing within supercooled liquid region.

Science.gov (United States)

Huang, C H; Lai, J J; Wei, T Y; Chen, Y H; Wang, X; Kuan, S Y; Huang, J C

2015-01-01

The effects of the nanocrystalline phases on the bio-corrosion behavior of highly bio-friendly Ti42Zr40Si15Ta3 metallic glasses in simulated body fluid were investigated, and the findings are compared with our previous observations from the Zr53Cu30Ni9Al8 metallic glasses. The Ti42Zr40Si15Ta3 metallic glasses were annealed at temperatures above the glass transition temperature, Tg, with different time periods to result in different degrees of α-Ti nano-phases in the amorphous matrix. The nanocrystallized Ti42Zr40Si15Ta3 metallic glasses containing corrosion resistant α-Ti phases exhibited more promising bio-corrosion resistance, due to the superior pitting resistance. This is distinctly different from the previous case of the Zr53Cu30Ni9Al8 metallic glasses with the reactive Zr2Cu phases inducing serious galvanic corrosion and lower bio-corrosion resistance. Thus, whether the fully amorphous or partially crystallized metallic glass would exhibit better bio-corrosion resistance, the answer would depend on the crystallized phase nature. Copyright © 2015 Elsevier B.V. All rights reserved.

Corrosion rate of steel in concrete - Evaluation of confinement techniques for on-site corrosion rate

DEFF Research Database (Denmark)

Nygaard, Peter Vagn; Geiker, Mette Rica; Elsener, Bernhard

2009-01-01

Earlier on-site investigations and laboratory studies have shown that varying corrosion rates are obtained when different commercially available instruments are used. The different confinement techniques, rather than the different electrochemical techniques used in the instruments, are considered...... to be the main reason for the discrepancies. This paper presents a method for the quantitative assessment of confinement techniques based on monitoring the operation of the corrosion rate instrument and the current distribution between the electrode assembly on the concrete surface and a segmented reinforcement...... bar embedded in the concrete. The applicability of the method was demonstrated on two commercially available corrosion rate instruments based on different confinement techniques. The method provided an explanation of the differences in performance of the two instruments. Correlated measurements...

Corrosion testing of a plutonium-loaded lanthanide borosilicate glass made with Frit B.

Energy Technology Data Exchange (ETDEWEB)

Ebert, W. L.; Chemical Engineering

2006-09-30

Laboratory tests were conducted with a lanthanide borosilicate (LaBS) glass made with Frit B and added PuO2 (the glass is referred to herein as Pu LaBS-B glass) to measure the dependence of the glass dissolution rate on pH and temperature. These results are compared with the dependencies used in the Defense HLW Glass Degradation Model that was developed to account for HLW glasses in total system performance assessment (TSPA) calculations for the Yucca Mountain repository to determine if that model can also be used to represent the release of radionuclides from disposed Pu LaBS glass by using either the same parameter values that are used for HLW glasses or parameter values specific for Pu LaBS glass. Tests were conducted by immersing monolithic specimens of Pu LaBS-B glass in six solutions that imposed pH values between about pH 3.5 and pH 11, and then measuring the amounts of glass components released into solution. Tests were conducted at 40, 70, and 90 C for 1, 2, 3, 4, and 5 days at low glass-surface-area-to-solution volume ratios. As intended, these test conditions maintained sufficiently dilute solutions that the impacts of solution feedback effects on the dissolution rates were negligible in most tests. The glass dissolution rates were determined from the concentrations of Si and B measured in the test solutions. The dissolution rates determined from the releases of Si and B were consistent with the 'V' shaped pH dependence that is commonly seen for borosilicate glasses and is included in the Defense HLW Glass Degradation Model. The rate equation in that model (using the coefficients determined for HLW glasses) provides values that are higher than the Pu LaBS-B glass dissolution rates that were measured over the range of pH and temperature values that were studied (i.e., an upper bound). Separate coefficients for the rate expression in acidic and alkaline solutions were also determined from the test results to model Pu LaBS-B glass dissolution

The Corrosion Inhibition Characteristics of Sodium Nitrite Using an On-line Corrosion Rate Measurement System

International Nuclear Information System (INIS)

Park, Mal-Yong; Kang, Dae-Jin; Moon, Jeon-Soo

2015-01-01

An on-line corrosion rate measurement system was developed using a personal computer, a data acquisition board and program, and a 2-electrode corrosion probe. Reliability of the developed system was confirmed with through comparison test. With this system, the effect of sodium nitrite (NaNO 2 ) as a corrosion inhibitor were studied on iron and aluminum brass that were immersed in sodium chloride (NaCl) solution. Corrosion rate was measured based on the linear polarization resistance method. The corrosion rates of aluminum brass and iron in 1% NaCl solutions were measured to be 0.290 mm per year (mmpy) and 0.2134 mmpy, respectively. With the addition of 200 ppm of NO 2 - , the corrosion rates decreased to 0.0470 mmpy and 0.0254 mmpy. The addition of NO 2 - caused a decrease in corrosion rates of both aluminum brass and iron, yet the NO 2 - acted as a more effective corrosion inhibitor for iron. than aluminum brass

Thermodynamic and structural models compared with the initial dissolution rates of open-quotes SONclose quotes glass samples

International Nuclear Information System (INIS)

Tovena, I.; Advocat, T.; Ghaleb, D.; Vernaz, E.; Larche, F.

1994-01-01

The experimentally determined initial dissolution rate R 0 of nuclear glass was correlated with thermodynamic parameters and structural parameters. The initial corrosion rates of six open-quotes R7T7close quotes glass samples measured at 100 degrees C in a Soxhlet device were correlated with the glass free hydration energy and the glass formation enthalpy. These correlations were then tested with a group of 26 SON glasses selected for their wide diversity of compositions. The thermodynamic models provided a satisfactory approximation of the initial dissolution rate determined under Soxhlet conditions for SON glass samples that include up to 15 wt% of boron and some alumina. Conversely, these models are inaccurate if the boron concentration exceeds 15 wt% and the glass contains no alumina. Possible correlations between R 0 and structural parameters, such as the boron coordination number and the number of nonbridging oxygen atoms, were also investigated. The authors show that R 0 varies inversely with the number of 4-coordinate boron atoms; conversely, the results do not substantiate published reports of a correlation between R 0 and the number of nonbridging oxygen atoms

Designing new biocompatible glass-forming Ti75-x Zr10 Nbx Si15 (x = 0, 15) alloys: corrosion, passivity, and apatite formation.

Science.gov (United States)

Abdi, Somayeh; Oswald, Steffen; Gostin, Petre Flaviu; Helth, Arne; Sort, Jordi; Baró, Maria Dolors; Calin, Mariana; Schultz, Ludwig; Eckert, Jürgen; Gebert, Annett

2016-01-01

Glass-forming Ti-based alloys are considered as potential new materials for implant applications. Ti75 Zr10 Si15 and Ti60 Zr10 Nb15 Si15 alloys (free of cytotoxic elements) can be produced as melt-spun ribbons with glassy matrix and embedded single β-type nanocrystals. The corrosion and passivation behavior of these alloys in their homogenized melt-spun states have been investigated in Ringer solution at 37°C in comparison to their cast multiphase crystalline counterparts and to cp-Ti and β-type Ti-40Nb. All tested materials showed very low corrosion rates as expressed in corrosion current densities icorr  alloys passive states in a wide potential range. This corresponds to low passive current densities ipass  = 2 ± 1 µA/cm(2) based on the growth of oxide films with thickness d alloys is beneficial for stable surface passivity. The addition of Nb does not only improve the glass-forming ability and the mechanical properties but also supports a high pitting resistance even at extreme anodic polarization up to 4V versus SCE were oxide thickness values of d ∼35 nm are reached. With regard to the corrosion properties, the Nb-containing nearly single-phase glassy alloy can compete with the β-type Ti-40Nb alloy. SBF tests confirmed the ability for formation of hydroxyapatite on the melt-spun alloy surfaces. All these properties recommend the new glass-forming alloys for application as wear- and corrosion-resistant coating materials for implants. © 2015 Wiley Periodicals, Inc.

Engineering Glass Passivation Layers -Model Results

Energy Technology Data Exchange (ETDEWEB)

Skorski, Daniel C.; Ryan, Joseph V.; Strachan, Denis M.; Lepry, William C.

2011-08-08

The immobilization of radioactive waste into glass waste forms is a baseline process of nuclear waste management not only in the United States, but worldwide. The rate of radionuclide release from these glasses is a critical measure of the quality of the waste form. Over long-term tests and using extrapolations of ancient analogues, it has been shown that well designed glasses exhibit a dissolution rate that quickly decreases to a slow residual rate for the lifetime of the glass. The mechanistic cause of this decreased corrosion rate is a subject of debate, with one of the major theories suggesting that the decrease is caused by the formation of corrosion products in such a manner as to present a diffusion barrier on the surface of the glass. Although there is much evidence of this type of mechanism, there has been no attempt to engineer the effect to maximize the passivating qualities of the corrosion products. This study represents the first attempt to engineer the creation of passivating phases on the surface of glasses. Our approach utilizes interactions between the dissolving glass and elements from the disposal environment to create impermeable capping layers. By drawing from other corrosion studies in areas where passivation layers have been successfully engineered to protect the bulk material, we present here a report on mineral phases that are likely have a morphological tendency to encrust the surface of the glass. Our modeling has focused on using the AFCI glass system in a carbonate, sulfate, and phosphate rich environment. We evaluate the minerals predicted to form to determine the likelihood of the formation of a protective layer on the surface of the glass. We have also modeled individual ions in solutions vs. pH and the addition of aluminum and silicon. These results allow us to understand the pH and ion concentration dependence of mineral formation. We have determined that iron minerals are likely to form a complete incrustation layer and we plan

The role of natural glasses as analogues in projecting the long-term alteration of high-level nuclear waste glasses: Part 1

International Nuclear Information System (INIS)

Mazer, J.J.

1993-01-01

The common observation of glasses persisting in natural environments for long periods of time (up to tens of millions of years) provides compelling evidence that these materials can be kinetically stable in a variety of subsurface environments. This paper reviews how natural and historical synthesized glasses can be employed as natural analogues for understanding and projecting the long-term alteration of high-level nuclear waste glasses. The corrosion of basaltic glass results in many of the same alteration features found in laboratory testing of the corrosion of high-level radioactive waste glasses. Evidence has also been found indicating similarities in the rate controlling processes, such as the effects of silica concentration on corrosion in groundwater and in laboratory leachates. Naturally altered rhyolitic glasses and tektites provide additional evidence that can be used to constrain estimates of long-term waste glass alteration. When reacted under conditions where water is plentiful, the corrosion for these glasses is dominated by network hydrolysis, while the corrosion is dominated by molecular water diffusion and secondary mineral formation under conditions where water contact is intermittent or where water is relatively scarce. Synthesized glasses that have been naturally altered result in alkali-depleted alteration features that are similar to those found for natural glasses and for nuclear waste glasses. The characteristics of these alteration features appear to be dependent on the alteration conditions which affect the dominant reaction processes during weathering. In all cases, care must be taken to ensure that the information being provided by natural analogues is related to nuclear waste glass corrosion in a clear and meaningful way

Studies on the long-term characteristics of HLW glass under ultimate storage conditions

International Nuclear Information System (INIS)

Roggendorf, H.; Conradt, R.; Ostertag, R.

1987-01-01

This interim report deals with first results of corrosion investigations of HLW simulation glass (COGEMA glass SON 68) in quinary salt solutions of different concentrations; the aim of these investigations was to find out about the corrosion mechanism at the surface of the glass and the quantitative registration of the corrosion products. It became obvious that the surface layers developed can be easily removed and that a determination of weight losses becomes possible thereby. The corrosion rates for a test period of 30 days were determined. (RB) [de

Lead iron phosphate glass as a containment medium for disposal of high-level nuclear waste

International Nuclear Information System (INIS)

Boatner, L.A.; Sales, B.C.

1989-01-01

This patent describes lead-iron phosphate glasses containing a high level of Fe 2 O 3 for use as a storage medium for high-level radioactive nuclear waste. By combining lead-iron phosphate glass with various types of simulated high-level nuclear waste, a highly corrosion resistant, homogeneous, easily processed glass can be formed. For corroding solutions at 90 0 C, with solution pH values in the range between 5 and 9, the corrosion rate of the lead-iron phosphate nuclear waste glass is at least 10 2 to 10 3 times lower than the corrosion rate of a comparable borosilicate nuclear waste glass. The presence of Fe 2 O 3 in forming the lead-iron phosphate glass is critical. The lead-iron phosphate waste glasses can be prepared with minimal modification of the technology developed for processing borosilicate glass nuclear wasteforms

The Effects of Corrosive Chemicals on Corrosion Rate of Steel Reinforcement Bars: II. Swamp Sludges

Directory of Open Access Journals (Sweden)

Henki Ashadi

2010-10-01

Full Text Available A polluted environment will influence the building age. The objective of this research was to find out the influence of corrosive chemicals within the sludge swamp area with the corrosion rate of steel concrete. Corrosion in steel concrete usually occur in acid area which contain of SO42-, Cl- and NO3-. The research treatment used by emerging ST 37 andST 60 within 60 days in 'polluted' sludge swamp area. Three variation of 'polluted' swamp sludge were made by increasing the concentration a corrosive unsure up to 1X, 5X and 10X. The corrosion rate measured by using an Immersion Method. The result of Immersion test showed that sulphate had a greatest influence to corrosion rate of ST 37 and ST 60 and followed by chloride and nitrate. Corrosion rate value for ST 37 was 17.58 mpy and for ST 60 was 12.47 mpy.

Exposure testing of fasteners in preservative treated wood: Gravimetric corrosion rates and corrosion product analyses

Energy Technology Data Exchange (ETDEWEB)

Zelinka, Samuel L., E-mail: szelinka@fs.fed.u [USDA Forest Products Laboratory, One Gifford Pinchot Drive, Madison, WI 53726 (United States); Sichel, Rebecca J. [College of Engineering, University of Wisconsin, Madison, WI 53706 (United States); Stone, Donald S. [Department of Materials Science and Engineering, College of Engineering, University of Wisconsin, Madison, WI 53706 (United States)

2010-12-15

Research highlights: {yields} The composition of the corrosion products was similar for the nail head and shank. {yields} Reduced copper was not detected on any of the fasteners. {yields} Measured corrosion rates were between 1 and 35 {mu}m year{sup -1}. - Abstract: Research was conducted to determine the corrosion rates of metals in preservative treated wood and also understand the mechanism of metal corrosion in treated wood. Steel and hot-dip galvanized steel fasteners were embedded in wood treated with one of six preservative treatments and exposed to 27 {sup o}C at 100% relative humidity for 1 year. The corrosion rate was determined gravimetrically and the corrosion products were analyzed with scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. Although the accepted mechanism of corrosion in treated wood involves the reduction of cupric ions from the wood preservative, no reduced copper was found on the corrosion surfaces. The galvanized corrosion products contained sulfates, whereas the steel corrosion products consisted of iron oxides and hydroxides. The possible implications and limitations of this research on fasteners used in building applications are discussed.

Solution exchange corrosion testing with the glass-zeolite ceramic waste form in demineralized water at 900C

International Nuclear Information System (INIS)

Simpson, L. J.

1998-01-01

A ceramic waste form of glass-bonded zeolite is being developed for the long-term disposition of fission products and transuranic elements in wastes from the U.S. Department of Energy's spent nuclear fuel conditioning activities. Solution exchange corrosion tests were performed on the ceramic waste form and its potential base constituents of glass, zeolite 5A, and sodalite as part of an effort to qualify the ceramic waste form for acceptance into the Civilian Radioactive Waste Management System. Solution exchange tests were performed at 90 C by replacing 80 to 90% of the leachate with fresh demineralized water after set time intervals. The results from these tests provide information about corrosion mechanisms and the ability of the ceramic waste form and its constituent materials to retain waste components. The results from solution exchange tests indicate that radionuclides will be preferentially retained in the zeolites without the glass matrix and in the ceramic waste form, with respect to cations like Li, K, and Na. Release results have been compared for simulated waste from candidate ceramic waste forms with zeolite 5A and its constituent materials to determine the corrosion behavior of each component

Phase formation during corrosion experiments with two simulated borosilicate nuclear waste glasses

International Nuclear Information System (INIS)

Haaker, R.F.

1985-10-01

Corrosion products resulting from the reaction of simulated high-level radioactive waste glasses with various solutions have been identified. At 200degC, in saturated NaCl, a degree of reaction of 10 g C31-3 glass or 2.6 g SON 68 glass per liter of solution was obtained. Analcime, vermiculite (a phyllosilicate) and a 2:1 zinc silicate are the major silica containing alteration products for the C31-3 glass. Analcime was the only silicate alteration product which could be identified for SON 68 glass. C31-3 glass appeared to be less reactive with a quinary brine containing Mg ++ than with NaCl. With the quinary brine, montmorillonite (a phyllosilicate) was the predominant silica containing alteration product. Hydrotalcite (a Mg-Al hydroxysulfate) and montmorillonite were the major Al-containing phases. A phyllosilicate, probably montmorillonite, was observed to form during the reaction of SON 68 glass with quinary brine. With either glass, modified NaCl brines which contained small amounts of MgCl 2 seem to have the effect of decreasing the amount of analcime and increasing the amount of phyllosilicate which is formed. In the case of C31-3 glass, there is approximately enough Mg, Al and Zn to precipitate most of the leached Si; measured Si concentrations remain well below that expected for amorphous silica. SON 68 glass has less Zn, Al and Mg than C31-3 glass and much higher Si concentrations of the leachates. (orig./RB)

Corrosion of K-3 glass-contact refractory in sodium-rich aluminosilicate melts

International Nuclear Information System (INIS)

Lu, X.D.; Gan, H.; Buechele, A.C.; Pegg, I.L.

1999-01-01

The corrosion of the glass-contact refractory Monofrax K-3 in two sodium-rich aluminosilicate melts has been studied at 1,208 and 1,283 C using a modified ASTM procedure with constant agitation of the melt by air bubbling. The results for the monolithic refractory indicate a fast initial stage involving phase dissolution and transformation and a later passivated stage in which the surface of the refractory has been substantially modified. The composition of the stable spinel phase in the altered layer on monolithic coupons of K-3 is almost identical to the equilibrium composition bracketed by the dissolution of powdered K-3 into under-saturated melts on the other. The temperature and melt shear viscosity were found to have significant effects on the rates of K-3 dissolution and transformation

The dissolution behavior of borosilicate glasses in far-from equilibrium conditions

Science.gov (United States)

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin P.; Ryan, Joseph V.; Asmussen, R. Matthew

2018-04-01

An area of agreement in the waste glass corrosion community is that, at far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this work is to study the effects of temperature and pH on the dissolution rate of three model nuclear waste glasses (SON68, ISG, AFCI). The dissolution rate data are then used to parameterize a kinetic rate model based on Transition State Theory that has been developed to model glass corrosion behavior in dilute conditions. To do this, experiments were conducted at temperatures of 23, 40, 70, and 90 °C and pH (22 °C) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies though quantifiable differences exist. The glass dissolution rates were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), with which a robust uncertainty analysis is performed. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, a mathematical description of the effect of glass composition on the rate parameter values should be possible. This would allow for the possibility of calculating the forward dissolution rate of glass based solely on composition. In addition, the method of determination of parameter uncertainty and correlation provides a framework for other rate models that describe the dissolution rates of other amorphous and crystalline materials in a wide range of chemical conditions. The higher level of uncertainty analysis would provide

Affinity functions for modeling glass dissolution rates

Energy Technology Data Exchange (ETDEWEB)

Bourcier, W.L. [Lawrence Livermore National Lab., CA (United States)

1997-07-01

Glass dissolution rates decrease dramatically as glass approach ''saturation'' with respect to the leachate solution. Most repository sites are chosen where water fluxes are minimal, and therefore the waste glass is most likely to dissolve under conditions close to ''saturation''. The key term in the rate expression used to predict glass dissolution rates close to ''saturation'' is the affinity term, which accounts for saturation effects on dissolution rates. Interpretations of recent experimental data on the dissolution behaviour of silicate glasses and silicate minerals indicate the following: 1) simple affinity control does not explain the observed dissolution rate for silicate minerals or glasses; 2) dissolution rates can be significantly modified by dissolved cations even under conditions far from saturation where the affinity term is near unity; 3) the effects of dissolved species such as Al and Si on the dissolution rate vary with pH, temperature, and saturation state; and 4) as temperature is increased, the effect of both pH and temperature on glass and mineral dissolution rates decrease, which strongly suggests a switch in rate control from surface reaction-based to diffusion control. Borosilicate glass dissolution models need to be upgraded to account for these recent experimental observations. (A.C.)

Disposition of actinides released from high-level waste glass

International Nuclear Information System (INIS)

Ebert, W.L.; Bates, J.K.; Buck, E.C.; Gong, M.; Wolf, S.F.

1994-01-01

The disposition of actinide elements released from high-level waste glasses into a tuff groundwater in laboratory tests at 90 degrees C at various glass surface area/leachant volume ratios (S/V) between dissolved, suspended, and sorbed fractions has been measured. While the maximum release of actinides is controlled by the corrosion rate of the glass matrix, their solubility and sorption behavior affects the amounts present in potentially mobile phases. Actinide solubilities are affected by the solution pH and the presence of complexants released from the glass, such as sulfate, phosphate, and chloride, radiolytic products, such as nitrate and nitrite, and carbonate. Sorption onto inorganic colloids formed during lass corrosion may increase the amounts of actinides in solution, although subsequent sedimentation of these colloids under static conditions leads to a significant reduction in the amount of actinides in solution. The solution chemistry and observed actinide behavior depend on the S/V of the test. Tests at high S/V lead to higher pH values, greater complexant concentrations, and generate colloids more quickly than tests at low S/V. The S/V also affects the rate of glass corrosion

Corrosion resistance and in-vitro bioactivity of BaO containing Na2O-CaO-P2O5 phosphate glass-ceramic coating prepared on 316 L, duplex stainless steel 2205 and Ti6Al4V

Science.gov (United States)

Edathazhe, Akhila B.; Shashikala, H. D.

2018-03-01

The phosphate glass with composition 11Na2O-15BaO-29CaO-45P2O5 was coated on biomedical implant materials such as stainless steel 316 L, duplex stainless steel (DSS) 2205 and Ti6Al4V alloy by thermal enamelling method. The structural properties and composition of glass coated substrates were studied by x-ray diffraction (XRD), Scanning electron microscopy (SEM) and Energy dispersive x-ray spectroscopy (EDS) analysis. The coatings were partially crystalline in nature with porous structure and pore size varied from micro to nanometer range. The polarization curve was obtained for uncoated and coated substrates from electrochemical corrosion test which was conducted at 37 °C in Hank’s balanced salt solution (HBSS). The corrosion resistance of 316 L substrate increased after coating, whereas it decreased in case of DSS 2205 and Ti6Al4V. The XRD and SEM/EDS studies indicated the bioactive hydroxyapatite (HAp) layer formation on all the coated surfaces after electrochemical corrosion test, which improved the corrosion resistance. The observed electrochemical corrosion behavior can be explained based on protective HAp layer formation, composition and diffusion of ions on glass coated surfaces. The in-vitro bioactivity test was carried out at 37 °C in HBS solution for 14 days under static conditions for uncoated and coated substrates. pH and ion release rate measurements from the coated samples were conducted to substantiate the electrochemical corrosion test. The lower ion release rates of Na+ and Ca2+ from coated 316 L supported its higher electrochemical corrosion resistance among coated samples. Among the uncoated substrates, DSS showed higher electrochemical corrosion resistance. Amorphous calcium-phosphate (ACP) layer formation on all the coated substrates after in-vitro bioactivity test was confirmed by XRD, SEM/EDS and ion release measurements. The present work is a comparative study of corrosion resistance and bioactivity of glass coated and uncoated

The Effects of Corrosive Chemicals on Corrosion Rate of Steel Reinforcement Bars: I. Swamp Water

Directory of Open Access Journals (Sweden)

Sulistyoweni Widanarko

2010-10-01

Full Text Available Most of infrastructures using steel concrete to reinforce the strength of concrete. Steel concrete is so vulnerable to chemical compounds that can cause corrosion. It can happen due to the presence of chemical compounds in acid environment in low pH level. These chemical compounds are SO42-, Cl-, NO3-. There are many swamp area in Indonesia. The acid contents and the concentration of ion sulphate, chlorides, and nitrate are higher in the swamp water than in the ground water .The objective of this research was to find out the influence of corrosive chemicals in the swamp water to the steel concrete corrosion rate. There were two treatment used: (1 emerging ST 37 and ST 60 within 60 days in the 'polluted' swamp water, (2 moving the ST 37 up and down periodically in the ' polluted' swamp water. Three variation of 'polluted' swamp water were made by increasing the concentration of corrosive chemical up to 1X, 5X and 10X respectively. The corrosion rate was measured by using an Immersion Method. The result of Immersion test showed that chloride had the greatest influence to corrosion rate of ST 37 and ST 60 and followed by sulphate and Nitrate. Corrosion rate value for ST 37 is 24.29 mpy and for ST 60 is 22.76 mpy. By moving the sample up and down, the corrosion rate of ST 37 increase up to 37.59 mpy, and chloride still having the greatest influence, followed by sulphate and nitrate.

Amorphous Metallic Alloys: Pathways for Enhanced Wear and Corrosion Resistance

Science.gov (United States)

Aditya, Ayyagari; Felix Wu, H.; Arora, Harpreet; Mukherjee, Sundeep

2017-11-01

Amorphous metallic alloys are widely used in bulk form and as coatings for their desirable corrosion and wear behavior. Nevertheless, the effects of heat treatment and thermal cycling on these surface properties are not well understood. In this study, the corrosion and wear behavior of two Zr-based bulk metallic glasses were evaluated in as-cast and thermally relaxed states. Significant improvement in wear rate, friction coefficient, and corrosion penetration rate was seen for both alloys after thermal relaxation. A fully amorphous structure was retained with thermal relaxation below the glass transition. There was an increase in surface hardness and elastic modulus for both alloys after relaxation. The improvement in surface properties was explained based on annihilation of free volume.

Cooling Rates of Lunar Volcanic Glass Beads

Science.gov (United States)

Hui, Hejiu; Hess, Kai-Uwe; Zhang, Youxue; Peslier, Anne; Lange, Rebecca; Dingwell, Donald; Neal, Clive

2016-01-01

It is widely accepted that the Apollo 15 green and Apollo 17 orange glass beads are of volcanic origin. The diffusion profiles of volatiles in these glass beads are believed to be due to degassing during eruption (Saal et al., 2008). The degree of degassing depends on the initial temperature and cooling rate. Therefore, the estimations of volatiles in parental magmas of lunar pyroclastic deposits depend on melt cooling rates. Furthermore, lunar glass beads may have cooled in volcanic environments on the moon. Therefore, the cooling rates may be used to assess the atmospheric condition in an early moon, when volcanic activities were common. The cooling rates of glasses can be inferred from direct heat capacity measurements on the glasses themselves (Wilding et al., 1995, 1996a,b). This method does not require knowledge of glass cooling environments and has been applied to calculate the cooling rates of natural silicate glasses formed in different terrestrial environments. We have carried out heat capacity measurements on hand-picked lunar glass beads using a Netzsch DSC 404C Pegasus differential scanning calorimeter at University of Munich. Our preliminary results suggest that the cooling rate of Apollo 17 orange glass beads may be 12 K/min, based on the correlation between temperature of the heat capacity curve peak in the glass transition range and glass cooling rate. The results imply that the parental magmas of lunar pyroclastic deposits may have contained more water initially than the early estimations (Saal et al., 2008), which used higher cooling rates, 60-180 K/min in the modeling. Furthermore, lunar volcanic glass beads could have been cooled in a hot gaseous medium released from volcanic eruptions, not during free flight. Therefore, our results may shed light on atmospheric condition in an early moon.

Effects of B Addition on Glass Formation, Mechanical Properties and Corrosion Resistance of the Zr66.7- x Ni33.3B x ( x = 0, 1, 3, and 5 at.%) Metallic Glasses

Science.gov (United States)

Xu, Jing; Niu, Jiazheng; Zhang, Zitang; Ge, Wenjuan; Shang, Caiyun; Wang, Yan

2016-02-01

The effects of B addition on glass formation, mechanical properties and electrochemical corrosion of Zr66.7- x Ni33.3B x ( x = 0, 1, 3, and 5 at.%) glassy ribbons have been investigated. The results reveal that the B addition can improve the glass forming ability and obviously raise the thermal stability of the Zr-Ni-B metallic glasses. The 1 at.% B addition exhibits the most positive effect on enhancing the microhardness of Vickers-type (HV) by 13.83%. In addition, Zr63.7Ni33.3B3 possesses the best plasticity in the nanoindentation test. The electrochemical test and microstructural observation show that the moderate B addition effectively enhances the corrosion resistance of the Zr-Ni-B metallic glasses in different solutions. The 3 at.% B addition is beneficial to improve the corrosion resistance in the 0.5 M NaCl solution. But in the 1 M HCl and 2 M NaOH solutions, the better effect is induced by the 1 and 5 at.% B addition. Moreover, the Zr-Ni-B metallic glasses exhibit active dissolution behavior in the chloride- and hydrogen-containing solutions, but passivation occurs in the 2 M NaOH solution.

Deformation behavior, corrosion resistance, and cytotoxicity of Ni-free Zr-based bulk metallic glasses.

Science.gov (United States)

Liu, L; Qiu, C L; Chen, Q; Chan, K C; Zhang, S M

2008-07-01

Two Ni-free bulk metallic glasses (BMGs) of Zr(60)Nb(5)Cu(22.5)Pd(5)Al(7.5) and Zr(60)Nb(5)Cu(20)Fe(5)Al(10) were successfully prepared by arc-melting and copper mold casting. The thermal stability and crystallization were studied using differential scanning calorimetry. It demonstrates that the two BMGs exhibit very good glass forming ability with a wide supercooled liquid region. A multi-step process of crystallization with a preferential formation of quasicrystals occurred in both BMGs under continuous heating. The deformation behavior of the two BMGs was investigated using quasi-static compression testing. It reveals that the BMGs exhibit not only superior strength but also an extended plasticity. Corrosion behaviors of the BMGs were investigated in phosphate buffered solution by electrochemical polarization. The result shows that the two BMGs exhibit excellent corrosion resistance characterized by low corrosion current densities and wide passive regions. X-ray photoelectron spectroscopy analysis revealed that the passive film formed after anodic polarization was highly enriched in zirconium, niobium, and aluminum oxides. This is attributed to the excellent corrosion resistance. Additionally, the potential cytotoxicity of the two Ni-free BMGs was evaluated through cell culture for 1 week followed by 3-(4,5-Dimethylthiazol-2-yl-)-2,5-diphenyltetrazolium bromide assay and SEM observation. The results indicate that the two Ni-free BMGs exhibit as good biocompatibility as Ti-6Al-4V alloy, and thus show a promising potential for biomedical applications. (c) 2007 Wiley Periodicals, Inc.

Cheap non-toxic non-corrosive method of glass cleaning evaluated by contact angle, AFM, and SEM-EDX measurements.

Science.gov (United States)

Dey, Tania; Naughton, Daragh

2017-05-01

Glass surface cleaning is the very first step in advanced coating deposition and it also finds use in conserving museum objects. However, most of the wet chemical methods of glass cleaning use toxic and corrosive chemicals like concentrated sulfuric acid (H 2 SO 4 ), piranha (a mixture of concentrated sulfuric acid and 30% hydrogen peroxide), and hydrogen fluoride (HF). On the other hand, most of the dry cleaning techniques like UV-ozone, plasma, and laser treatment require costly instruments. In this report, five eco-friendly wet chemical methods of glass cleaning were evaluated in terms of contact angle (measured by optical tensiometer), nano-scale surface roughness (measured by atomic force microscopy or AFM), and elemental composition (measured by energy dispersive x-ray spectroscopy or SEM-EDX). These glass cleaning methods are devoid of harsh chemicals and costly equipment, hence can be applied in situ in close proximity with plantation such as greenhouse or upon subtle objects such as museum artifacts. Out of these five methods, three methods are based on the chemical principle of chelation. It was found that the citric acid cleaning method gave the greatest change in contact angle within the hydrophilic regime (14.25° for new glass) indicating effective cleansing and the least surface roughness (0.178 nm for new glass) indicating no corrosive effect. One of the glass sample showed unique features which were traced backed to the history of the glass usage.

Water leaching of borosilicate glasses: experiments, modeling and Monte Carlo simulations

International Nuclear Information System (INIS)

Ledieu, A.

2004-10-01

This work is concerned with the corrosion of borosilicate glasses with variable oxide contents. The originality of this study is the complementary use of experiments and numerical simulations. This study is expected to contribute to a better understanding of the corrosion of nuclear waste confinement glasses. First, the corrosion of glasses containing only silicon, boron and sodium oxides has been studied. The kinetics of leaching show that the rate of leaching and the final degree of corrosion sharply depend on the boron content through a percolation mechanism. For some glass contents and some conditions of leaching, the layer which appears at the glass surface stops the release of soluble species (boron and sodium). This altered layer (also called the gel layer) has been characterized with nuclear magnetic resonance (NMR) and small angle X-ray scattering (SAXS) techniques. Second, additional elements have been included in the glass composition. It appears that calcium, zirconium or aluminum oxides strongly modify the final degree of corrosion so that the percolation properties of the boron sub-network is no more a sufficient explanation to account for the behavior of these glasses. Meanwhile, we have developed a theoretical model, based on the dissolution and the reprecipitation of the silicon. Kinetic Monte Carlo simulations have been used in order to test several concepts such as the boron percolation, the local reactivity of weakly soluble elements and the restructuring of the gel layer. This model has been fully validated by comparison with the results on the three oxide glasses. Then, it has been used as a comprehensive tool to investigate the paradoxical behavior of the aluminum and zirconium glasses: although these elements slow down the corrosion kinetics, they lead to a deeper final degree of corrosion. The main contribution of this work is that the final degree of corrosion of borosilicate glasses results from the competition of two opposite mechanisms

Prediction of corrosion rates of water distribution pipelines according to aggressive corrosive water in Korea.

Science.gov (United States)

Chung, W S; Yu, M J; Lee, H D

2004-01-01

The drinking water network serving Korea has been used for almost 100 years. Therefore, pipelines have suffered various degrees of deterioration due to aggressive environments. The pipe breaks were caused by in-external corrosion, water hammer, surface loading, etc. In this paper, we focused on describing corrosion status in water distribution pipes in Korea and reviewing some methods to predict corrosion rates. Results indicate that corrosive water of lakes was more aggressive than river water and the winter was more aggressive compared to other seasons. The roughness growth rates of Dongbok lake showed 0.23 mm/year. The high variation of corrosion rates is controlled by the aging pipes and smaller diameter. Also the phenolphthalein test on a cementitious core of cement mortar lined ductile cast iron pipe indicated the pipes over 15 years old had lost 50-100% of their lime active cross sectional area.

Corrosion of Metal Inclusions In Bulk Vitrification Waste Packages

Energy Technology Data Exchange (ETDEWEB)

Bacon, Diana H.; Pierce, Eric M.; Wellman, Dawn M.; Strachan, Denis M.; Josephson, Gary B.

2006-07-31

The primary purpose of the work reported here is to analyze the potential effect of the release of technetium (Tc) from metal inclusions in bulk vitrification waste packages once they are placed in the Integrated Disposal Facility (IDF). As part of the strategy for immobilizing waste from the underground tanks at Hanford, selected wastes will be immobilized using bulk vitrification. During analyses of the glass produced in engineering-scale tests, metal inclusions were found in the glass product. This report contains the results from experiments designed to quantify the corrosion rates of metal inclusions found in the glass product from AMEC Test ES-32B and simulations designed to compare the rate of Tc release from the metal inclusions to the release of Tc from glass produced with the bulk vitrification process. In the simulations, the Tc in the metal inclusions was assumed to be released congruently during metal corrosion as soluble TcO4-. The experimental results and modeling calculations show that the metal corrosion rate will, under all conceivable conditions at the IDF, be dominated by the presence of the passivating layer and corrosion products on the metal particles. As a result, the release of Tc from the metal particles at the surfaces of fractures in the glass releases at a rate similar to the Tc present as a soluble salt. The release of the remaining Tc in the metal is controlled by the dissolution of the glass matrix. To summarize, the release of 99Tc from the BV glass within precipitated Fe is directly proportional to the diameter of the Fe particles and to the amount of precipitated Fe. However, the main contribution to the Tc release from the iron particles is over the same time period as the release of the soluble Tc salt. For the base case used in this study (0.48 mass% of 0.5 mm diameter metal particles homogeneously distributed in the BV glass), the release of 99Tc from the metal is approximately the same as the release from 0.3 mass% soluble Tc

Effect of Flow Velocity on Corrosion Rate and Corrosion Protection Current of Marine Material

Energy Technology Data Exchange (ETDEWEB)

Lee, Seong Jong [Kunsan National University, Kunsan (Korea, Republic of); Han, Min Su; Jang, Seok Ki; Kim, Seong Jong [Mokpo National Maritime University, Mokpo (Korea, Republic of)

2015-10-15

In spite of highly advanced paint coating techniques, corrosion damage of marine metal and alloys increase more and more due to inherent micro-cracks and porosities in coatings formed during the coating process. Furthermore, flowing seawater conditions promote the breakdown of the protective oxide of the materials introducing more oxygen into marine environments, leading to the acceleration of corrosion. Various corrosion protection methods are available to prevent steel from marine corrosion. Cathodic protection is one of the useful corrosion protection methods by which the potential of the corroded metal is intentionally lowered to an immune state having the advantage of providing additional protection barriers to steel exposed to aqueous corrosion or soil corrosion, in addition to the coating. In the present investigation, the effect of flow velocity was examined for the determination of the optimum corrosion protection current density in cathodic protection as well as the corrosion rate of the steel. It is demonstrated from the result that the material corrosion under dynamic flowing conditions seems more prone to corrosion than under static conditions.

CORROSION RATE OF STEELS DX51D AND S220GD IN DIFFERENT CORROSION ENVIRONMENT

Directory of Open Access Journals (Sweden)

Alina Crina CIUBOTARIU

2016-06-01

Full Text Available Corrosion in the marine environment is an important issue because the costs causes by marine corrosion increased year upon year. It is necessary a correctly approach to materials selection, protection and corrosion control to reduce this burden of wasted materials, wasted energy and wasted money. Many different types of corrosion attack can be observed to structures, ships and other equipment used in sea water service. Shipping containers are exposed to various corrosive mediums like as airborne salt, industrial pollutants, rain and saltwater. Transport damage during loading onto and unloading off trucks, train beds and ships breaches the paint coating which further contributes to corrosion. The result is shortened container life and high costs for container repair or replacement. The paper intends to evaluate, by gravimetric method, the corrosion rate and corrosion penetration rate of two types of carbon steel DX51D and S220GD. Carbon steel DX51D and hot-dip galvanized steel S220GD are used in marine and industrial applications for buildings cargo vessels, container ships and oil tankers. For testing it was used different corrosive environments: 5% NaOH solution; 5% HCL solution and 0.5M NaCl solution. The samples were immersed in 400mL of testing solution for exposure period of 28 days. Periodically at 3 days, 7 days, 14 days, 21 days and 28 days was measured de mass loss and evaluate the corrosion rate and corrosion stability coefficient. The steel DX51D was stable in 5% NaOH solution for 28 days, the values of corrosion stability coefficient was 7 after 3 days and 6 after 28 days of immersion in corrosive medium. In 5% HCL solution steels DX51D and S220GD was completely corroded in 21 days with a corrosion stability coefficient equal with 9 for 7 days and 8 for 21 days of immersion in corrosive solution. It was observed a good resistance for 3 days in 0.5M NaCl solution with a corrosion stability coefficient equal with 5, but after that

Strain rate effects in stress corrosion cracking

Energy Technology Data Exchange (ETDEWEB)

Parkins, R.N. (Newcastle upon Tyne Univ. (UK). Dept. of Metallurgy and Engineering Materials)

1990-03-01

Slow strain rate testing (SSRT) was initially developed as a rapid, ad hoc laboratory method for assessing the propensity for metals an environments to promote stress corrosion cracking. It is now clear, however, that there are good theoretical reasons why strain rate, as opposed to stress per se, will often be the controlling parameter in determining whether or not cracks are nucleated and, if so, are propagated. The synergistic effects of the time dependence of corrosion-related reactions and microplastic strain provide the basis for mechanistic understanding of stress corrosion cracking in high-pressure pipelines and other structures. However, while this may be readily comprehended in the context of laboratory slow strain tests, its extension to service situations may be less apparent. Laboratory work involving realistic stressing conditions, including low-frequency cyclic loading, shows that strain or creep rates give good correlation with thresholds for cracking and with crack growth kinetics.

Influence of temperature on corrosion rate and porosity of corrosion products of carbon steel in anoxic bentonite environment

International Nuclear Information System (INIS)

Stoulil, J.; Kaňok, J.; Kouřil, M.; Parschová, H.; Novák, P.

2013-01-01

Highlights: •The corrosion rate is not significantly dependent on temperature. •Corrosion products at higher temperatures have different color. •Corrosion products at higher temperatures are more compact. •The change in corrosion products nature is reversible. -- Abstract: The study focuses on the porosity of layers of corrosion products and its impact on corrosion rate of carbon steel in moist bentonite. Measurements were performed in an aggressive Czech type of bentonite – Rokle B75 at temperatures of 90 and 40 °C. Aggressiveness of B75 bentonite consists in low content of chlorides. Presence of chlorides in pore solution allows formation of more protective magnetite. The evaluation was made by electrochemical techniques (red/ox potential, open circuit potential, linear polarization resistance, impedance spectroscopy) and resistometric sensor measurements. The result imply that the higher the temperature the more compact is the layer of corrosion products that slightly decelerates corrosion rate compared to the state at 40 °C. The state of corrosion products at both temperatures is reversible

Influence of temperature on corrosion rate and porosity of corrosion products of carbon steel in anoxic bentonite environment

Energy Technology Data Exchange (ETDEWEB)

Stoulil, J., E-mail: jan.stoulil@vscht.cz [Department of Metals and Corrosion Engineering, Institute of Chemical Technology, Prague (Czech Republic); Kaňok, J.; Kouřil, M. [Department of Metals and Corrosion Engineering, Institute of Chemical Technology, Prague (Czech Republic); Parschová, H. [Department of Power Engineering, Institute of Chemical Technology, Prague (Czech Republic); Novák, P. [Department of Metals and Corrosion Engineering, Institute of Chemical Technology, Prague (Czech Republic)

2013-11-15

Highlights: •The corrosion rate is not significantly dependent on temperature. •Corrosion products at higher temperatures have different color. •Corrosion products at higher temperatures are more compact. •The change in corrosion products nature is reversible. -- Abstract: The study focuses on the porosity of layers of corrosion products and its impact on corrosion rate of carbon steel in moist bentonite. Measurements were performed in an aggressive Czech type of bentonite – Rokle B75 at temperatures of 90 and 40 °C. Aggressiveness of B75 bentonite consists in low content of chlorides. Presence of chlorides in pore solution allows formation of more protective magnetite. The evaluation was made by electrochemical techniques (red/ox potential, open circuit potential, linear polarization resistance, impedance spectroscopy) and resistometric sensor measurements. The result imply that the higher the temperature the more compact is the layer of corrosion products that slightly decelerates corrosion rate compared to the state at 40 °C. The state of corrosion products at both temperatures is reversible.

Investigation of corrosion experienced in a spray calciner/ceramic melter vitrification system

International Nuclear Information System (INIS)

Dierks, R.D.; Mellinger, G.B.; Miller, F.A.; Nelson, T.A.; Bjorklund, W.J.

1980-08-01

After periodic testing of a large-scale spray calciner/ceramic melter vitrification system over a 2-yr period, sufficient corrosion was noted on various parts of the vitrification system to warrant its disassembly and inspection. A majority of the 316 SS sintered metal filters on the spray calciner were damaged by chemical corrosion and/or high temperature oxidation. Inconel-601 portions of the melter lid were attacked by chlorides and sulfates which volatilized from the molten glass. The refractory blocks, making up the walls of the melter, were attacked by the waste glass. This attack was occurring when operating temperatures were >1200 0 C. The melter floor was protected by a sludge layer and showed no corrosion. Corrosion to the Inconel-690 electrodes was minimal, and no corrosion was noted in the offgas treatment system downstream of the sintered metal filters. It is believed that most of the melter corrosion occurred during one specific operating period when the melter was operated at high temperatures in an attempt to overcome glass foaming behavior. These high temperatures resulted in a significant release of volatile elements from the molten glass, and also created a situation where the glass was very fluid and convective, which increased the corrosion rate of the refractories. Specific corrosion to the calciner components cannot be proven to have occurred during a specific time period, but the mechanisms of attack were all accelerated under the high-temperature conditions that were experienced with the melter. A review of the materials of construction has been made, and it is concluded that with controlled operating conditions and better protection of some materials of construction corrosion of these systems will not cause problems. Other melter systems operating under similar strenuous conditions have shown a service life of 3 yr

Reaction products and corrosion of molybdenum electrode in glass melt containing antimony oxides and sodium sulfate

Czech Academy of Sciences Publication Activity Database

Matěj, J.; Langrová, Anna

2012-01-01

Roč. 56, č. 3 (2012), s. 280-285 ISSN 0862-5468 Institutional support: RVO:67985831 Keywords : antimony oxides * corrosion * glass melt * Molybdenum electrode * sulfate Subject RIV: DD - Geochemistry Impact factor: 0.418, year: 2012 http://www.ceramics-silikaty.cz/2012/pdf/2012_03_280.pdf

Glass dissolution rate measurement and calculation revisited

Energy Technology Data Exchange (ETDEWEB)

Fournier, Maxime, E-mail: maxime.fournier@cea.fr [CEA, DEN, DTCD, SECM, F-30207, Bagnols sur Cèze (France); Ull, Aurélien; Nicoleau, Elodie [CEA, DEN, DTCD, SECM, F-30207, Bagnols sur Cèze (France); Inagaki, Yaohiro [Department of Applied Quantum Physics & Nuclear Engineering, Kyushu University, Fukuoka, 819-0395 (Japan); Odorico, Michaël [ICSM-UMR5257 CEA/CNRS/UM2/ENSCM, Site de Marcoule, BP17171, F-30207, Bagnols sur Cèze (France); Frugier, Pierre; Gin, Stéphane [CEA, DEN, DTCD, SECM, F-30207, Bagnols sur Cèze (France)

2016-08-01

Aqueous dissolution rate measurements of nuclear glasses are a key step in the long-term behavior study of such waste forms. These rates are routinely normalized to the glass surface area in contact with solution, and experiments are very often carried out using crushed materials. Various methods have been implemented to determine the surface area of such glass powders, leading to differing values, with the notion of the reactive surface area of crushed glass remaining vague. In this study, around forty initial dissolution rate measurements were conducted following static and flow rate (SPFT, MCFT) measurement protocols at 90 °C, pH 10. The international reference glass (ISG), in the forms of powders with different particle sizes and polished monoliths, and soda-lime glass beads were examined. Although crushed glass grains clearly cannot be assimilated with spheres, it is when using the samples geometric surface (S{sub geo}) that the rates measured on powders are closest to those found for monoliths. Overestimation of the reactive surface when using the BET model (S{sub BET}) may be due to small physical features at the atomic scale—contributing to BET surface area but not to AFM surface area. Such features are very small compared with the thickness of water ingress in glass (a few hundred nanometers) and should not be considered in rate calculations. With a S{sub BET}/S{sub geo} ratio of 2.5 ± 0.2 for ISG powders, it is shown here that rates measured on powders and normalized to S{sub geo} should be divided by 1.3 and rates normalized to S{sub BET} should be multiplied by 1.9 in order to be compared with rates measured on a monolith. The use of glass beads indicates that the geometric surface gives a good estimation of glass reactive surface if sample geometry can be precisely described. Although data clearly shows the repeatability of measurements, results must be given with a high uncertainty of approximately ±25%. - Highlights: • Initial dissolution

High temperature corrosion in straw-fired power plants: Influence of steam/metal temperature on corrosion rates for TP347H

DEFF Research Database (Denmark)

Montgomery, Melanie; Biede, O; Larsen, OH

2002-01-01

The corrosion in straw-fired boilers has been investigated at various straw-fired power plants in Denmark. Water/air-cooled probes, a test superheater and test sections removed from the actual superheater have been utilised to characterise corrosion and corrosion rates. This paper describes...... the corrosion rates measured for the TP347H type steel. The corrosion morphology at high temperature consists of grain boundary attack and selective attack of chromium. The corrosion rate increases with calculated metal temperature (based on steam temperature), however there is great variation within....... The difference in the results could be traced back to a lower flue gas temperature on one side of the boiler. Although metal temperature is the most important parameter with respect to corrosion rate, flue gas temperature also plays an important role. Efforts to quantify the effect of flue gas temperature...

Long-term modeling of glass waste in portland cement- and clay-based matrices

International Nuclear Information System (INIS)

Stockman, H.W.; Nagy, K.L.; Morris, C.E.

1995-12-01

A set of ''templates'' was developed for modeling waste glass interactions with cement-based and clay-based matrices. The templates consist of a modified thermodynamic database, and input files for the EQ3/6 reaction path code, containing embedded rate models and compositions for waste glass, cement, and several pozzolanic materials. Significant modifications were made in the thermodynamic data for Th, Pb, Ra, Ba, cement phases, and aqueous silica species. It was found that the cement-containing matrices could increase glass corrosion rates by several orders of magnitude (over matrixless or clay matrix systems), but they also offered the lowest overall solubility for Pb, Ra, Th and U. Addition of pozzolans to cement decreased calculated glass corrosion rates by up to a factor of 30. It is shown that with current modeling capabilities, the ''affinity effect'' cannot be trusted to passivate glass if nuclei are available for precipitation of secondary phases that reduce silica activity

Leaching behavior of microtektite glass compositions in sea water and the effect of precipitation on glass leaching

International Nuclear Information System (INIS)

1991-01-01

In the present study it was attempted to account for the slow corrosion rates of microtektite glass in nature by comparing the leach rates of synthetic microtektite glass samples in deionized water and in sea-water, respectively. In order to obtain systematic data about leachant composition effects, leach tests were also carried out with synthetic leachant compositions enriched with respect to silica or depleted with respect to certain major components of sea-water (Mg, Ca). 47 refs., 1 fig., 5 tabs

Study on the formation of heterogeneous structures in leached layers during the corrosion process of glass

Directory of Open Access Journals (Sweden)

Willemien Anaf

2010-11-01

Full Text Available Le verre, corrodé dans des conditions naturelles, montre souvent des hétérogénéités dans la couche lixiviée, comme une structure lamellaire ou des inclusions de MnO2 ou Ca3(PO42. La formation de ces hétérogénéités n’est pas encore bien comprise. Des structures de ce type ont été produites artificiellement en laboratoire en immergeant des échantillons de verre dans des solutions riches en métaux. Les résultats expérimentaux ont été comparés avec des théories décrivant la corrosion du verre.Glass that corrodes under natural conditions often shows heterogeneities in the leached layer, such as a lamellar structure or inclusions of MnO2 or Ca3(PO42. The formation of these heterogeneities is still not well understood. By means of experiments under laboratory conditions, our aim was to artificially generate specific structures. Therefore, glass samples were immersed in metal-rich solutions. The experimental results were compared with theories describing glass corrosion from a molecular point of view.

Nuclear waste under glass, further discussion

Science.gov (United States)

O'Keefe, J. A.; Barkatt, A.; Glass, B. P.; Alterescu, S.

J. J. Crovisier and J. Honnorez [1988] discuss an article by W. W. Maggs, “Mg May Protect Waste Under Glass” [Maggs, 1988] summarizing work by A. Barkatt (Catholic University, Washington, D.C.), B. P. Glass (University of Delaware, Newark), and S. Alterescu and J. A. O'Keefe (NASA/GSFC, Greenbelt, Md.). We found that seawater is orders of magnitude less corrosive t h an fresh water in attacking tektite glass; traced the protective effect to the presence of magnesium, at a level of about 1.3 g/L in seawater; and suggested that the effect might be useful in protecting nuclear waste glasses from corrosion.Crovisier and Honnorez first make the point that the rate of corrosion of glass is, in principle, a function of the ratio of surface area 5 to the effective volume V. This concept, which is usually discussed in American literature under the name of S/V effects, is discussed by Crovisier and Honnorez in terms of the “permeability of the environment.” These effects have been carefully considered throughout our work (see, for example, Barkatt et al. [19867rsqb;). It turns out that in the sea the effective S/V is so small that the effects referred to by Crovisier and Honnorez can be ignored.

Linear free energy relationships in glass corrosion

International Nuclear Information System (INIS)

Abrajano, T.A. Jr.; Bates, J.K.; Bohlke, J.K.

1988-01-01

Various theoretical models that have been proposed to correlate glass durability to their composition for a wide variety of silicate, borosilicate, and aluminosilicate glasses are examined. Comparisons are made between the predictions of these models and those of an empirical formulation extracted from existing data in the present work. The empirical approach provides independent confirmation of the relative accuracy of the silica release rate predictions of the different theoretical models in static leaching systems. Extension of the empirical approach used in this work are discussed. 23 refs., 2 figs., 1 tab

Lead iron phosphate glass as a containment medium for disposal of high-level nuclear waste

Science.gov (United States)

Boatner, Lynn A.; Sales, Brian C.

1989-01-01

Lead-iron phosphate glasses containing a high level of Fe.sub.2 O.sub.3 for use as a storage medium for high-level radioactive nuclear waste. By combining lead-iron phosphate glass with various types of simulated high-level nuclear waste, a highly corrosion resistant, homogeneous, easily processed glass can be formed. For corroding solutions at 90.degree. C., with solution pH values in the range between 5 and 9, the corrosion rate of the lead-iron phosphate nuclear waste glass is at least 10.sup.2 to 10.sup.3 times lower than the corrosion rate of a comparable borosilicate nuclear waste glass. The presence of Fe.sub.2 O.sub.3 in forming the lead-iron phosphate glass is critical. Lead-iron phosphate nuclear waste glass can be prepared at temperatures as low as 800.degree. C., since they exhibit very low melt viscosities in the 800.degree. to 1050.degree. C. temperature range. These waste-loaded glasses do not readily devitrify at temperatures as high as 550.degree. C. and are not adversely affected by large doses of gamma radiation in H.sub.2 O at 135.degree. C. The lead-iron phosphate waste glasses can be prepared with minimal modification of the technology developed for processing borosilicate glass nuclear wasteforms.

Glass composition and solution speciation effects on stage III dissolution

International Nuclear Information System (INIS)

Trivelpiece, Cory L.; Rice, Jarret A.; Pantano, Carlo G.

2017-01-01

To understand and mitigate the onset of Stage III corrosion of multicomponent oxides waste glasses. Stage III refers to a resumption of the high initial rate of glass dissolution in some glass samples that have otherwise exhibited dissolution at the much lower residual rate for a long time (Stage II). Although the onset of Stage III is known to occur concurrently with the precipitation of particular alteration products, the root cause of the transition is still unknown. Certain glass compositions (notably AFCI) and high pH environmental conditions are also associated with this observed transition.

Glass composition and solution speciation effects on stage III dissolution

Energy Technology Data Exchange (ETDEWEB)

Trivelpiece, Cory L. [Pennsylvania State Univ., University Park, PA (United States); Rice, Jarret A. [Pennsylvania State Univ., University Park, PA (United States); Pantano, Carlo G. [Pennsylvania State Univ., University Park, PA (United States)

2017-10-03

To understand and mitigate the onset of Stage III corrosion of multicomponent oxides waste glasses. Stage III refers to a resumption of the high initial rate of glass dissolution in some glass samples that have otherwise exhibited dissolution at the much lower residual rate for a long time (Stage II). Although the onset of Stage III is known to occur concurrently with the precipitation of particular alteration products, the root cause of the transition is still unknown. Certain glass compositions (notably AFCI) and high pH environmental conditions are also associated with this observed transition.

Laboratory testing of glasses for Lockheed Idaho Technology Company: Final report

International Nuclear Information System (INIS)

Ellison, A.J.G.; Buck, E.C.; Dietz, N.L.; Ebert, W.L.; Luo, J.S.; Wolf, S.F.; Bates, J.K.

1997-06-01

Tests have been conducted at Argonne National Laboratory (ANL) in support of the efforts of Lockheed Idaho Technology Company (LITCO) to vitrify high-level waste calcines. Tests were conducted with three classes of LITCO glass formulations: Formula 127 (fluorine-bearing), Formula 532 (fluorine-free), and 630 series (both single- and mixed-alkali) glasses. The test matrices included, as appropriate, the Product Consistency Test Method B (PCT-B), the Materials Characterization Center Test 1 (MCC-1), and the Argonne vapor hydration test (VHT). Test durations ranged from 7 to 183 d. In 7-d PCT-Bs, normalized mass losses of major glass-forming elements for the LITCO glasses are similar to, or lower than, normalized mass losses obtained for other domestic candidate waste glasses. Formula 532 glasses form zeolite alteration phases relatively early in their reaction with water. The formation of those phases increased the dissolution rate. In contrast, the Formula 127 glass is highly durable and forms alteration phases only after prolonged exposure to water in tests with very high surface area to volume ratios; these alteration phases have a relatively small effect on the rate of glass corrosion. No alteration phases formed within the maximum test duration of 183 d in PCT-Bs with the 630 series glasses. The corrosion behavior of the mixed-alkali 630 series glasses is similar to that of 630 series glasses containing sodium alone. In VHTs, both single- and mixed-alkali glasses form zeolite phases that increase the rate of glass reaction. The original 630 series glasses and those based on a revised surrogate calcine formulation react at the same rate in PCT-Bs and form the same major alteration phases in VHTs

First-order dissolution rate law and the role of surface layers in glass performance assessment

Science.gov (United States)

Grambow, B.; Müller, R.

2001-09-01

potential mechanical destruction it will be reformed instantaneously. The same is true for radiation damage. The dissolution of silica from the surface in this concept is considered as rate limiting for the release of soluble elements from the glass. After surface stabilization by local solid/solution equilibrium the release of soluble radionuclides continues with lower rates, but this is considered as resulting from parallel leaching mechanism. In fact, the deconvolutions of the overall leach mechanism into individual parallel and sequential rate limiting steps (not necessarily elementary reactions) is fundamental to this concept. In concept (2) surface stability as well as surface morphology are fundamental. A fracture in the protective surface would increase glass corrosion. The protective effect is based on the low diffusivities of radionuclides and other glass constituents in this layer. However, a true relation between layer thickness and rates is seldom observed. Diffusion coefficients are considered to vary with time as well as with the surface area to solution volume S/ V ratio. Sometimes, extremely low diffusivities in extremely thin layers are invoked to explain experimental data. The two concepts are not so different from each other and one is tempted to think of a problem of semantics. In fact, there are two alternative ways by which the protective layer concept can be coupled to the saturation concept: (a) the layer may be formed by solubility effects as proposed in [loc.cit] and/or (b) the layer plays the role of a silica diffusion barrier limiting glass dissolution rates according to the first-order rate law at the interface between the pristine glass and the surface layer. However, the mathematical models based on these conceptual models yield quite different long-term predictions, even though the models may equally well fit a given set of experimental data. The models are also different with respect to the number of interrelated parameters. In the case of

Long term behaviour of glass and steel in interaction with argillites in deep geological conditions

International Nuclear Information System (INIS)

Bildstein, O.; Lartigue, J.E.; Devallois, V.; Pointeau, V.; Trotignon, L.; Michau, N.; Cochepin, B.; Munier, I.

2010-01-01

Document available in extended abstract form only. The concept developed in France for the disposal of vitrified high level waste in deep geological repository includes the containment in steel canisters, designed to prevent contact between glass and water and to maintain mechanical stability, and the confinement at ca. 500 m into an argillaceous host rock. After canister disposal and repository closure, the site will progressively re-saturate in non-isothermal conditions and the alteration of the different materials will start: corrosion of the canisters, degradation of concrete plugs, and ultimately, the alteration of glass waste. These perturbations will affect the properties of the different materials present in the near field and the lifetime of the glass matrix. Several scenarios are investigated which all involve (1) the geochemical interactions between iron and clay-rich materials, and (2) the alteration of glass in the presence of corrosion products. The evolution of the near field system is complex since geochemical and transport processes are highly coupled. Steel corrosion and glass alteration produce an increase of pH which in turn affects the rate of glass dissolution. The concentration of dissolved silica is also one key to the rate of glass alteration and, along with the concentration of other elements such as iron and aluminum, it determines the nature of steel corrosion and clay alteration products. These interactions may also lead to partial dissolution of the initial clay minerals potentially affecting the overall confinement properties such as swelling and capacity to exchange cations. Coupled reaction-transport simulations with the Crunch code was used to assess the impact of steel corrosion and glass alteration phases in the presence of corrosion products (CP), looking at mass transfer for chemical elements, especially iron and silicon, pH, porosity change. A first set of calculations based on a reference case in isothermal conditions (90 deg

Simulation of Self-Irradiation of High-Sodium Content Nuclear Waste Glasses

International Nuclear Information System (INIS)

Pankov, Alexey S.; Ojovan, Michael I.; Batyukhnova, Olga G.; Lee, William E.

2007-01-01

Alkali-borosilicate glasses are widely used in nuclear industry as a matrix for immobilisation of hazardous radioactive wastes. Durability or corrosion resistance of these glasses is one of key parameters in waste storage and disposal safety. It is influenced by many factors such as composition of glass and surrounding media, temperature, time and so on. As these glasses contain radioactive elements most of their properties including corrosion resistance are also impacted by self-irradiation. The effect of external gamma-irradiation on the short-term (up to 27 days) dissolution of waste borosilicate glasses at moderate temperatures (30 deg. to 60 deg. C) was studied. The glasses studied were Magnox Waste glass used for immobilisation of HLW in UK, and K-26 glass used in Russia for ILW immobilisation. Glass samples were irradiated under γ-source (Co-60) up to doses 1 and 11 MGy. Normalised rates of elemental release and activation energy of release were measured for Na, Li, Ca, Mg, B, Si and Mo before and after irradiation. Irradiation up to 1 MGy results in increase of leaching rate of almost all elements from both MW and K-26 with the exception of Na release from MW glass. Further irradiation up to a dose of 11 MGy leads to the decrease of elemental release rates to nearly initial value. Another effect of irradiation is increase of activation energies of elemental release. (authors)

Preliminary experiments to simulate glass/electrode interactions within a Joule Ceramic Melter

International Nuclear Information System (INIS)

Dalton, J.T.; Paige, E.L.; Sutcliffe, P.W.

1986-01-01

Preliminary isothermal corrosion tests have been made on Inconel 690 coupon samples immersed in Harvest II M9 glass with and without excess additions of Li 2 O (1.5%) and RuO 2 (20%) together with TeO 2 (2%) at 1200 0 C for periods up to 100 hours. Inconel 690 corrosion and the products and ruthenium redox conditions within the glass approximate to those observed in the 1/3rd scale Joule Ceramic Melter operations. Corrosion takes place by an oxidation mechanism to form a chromium-rich surface oxide, and dissolution of this surface oxide by the surrounding glass. Additions of excess Li 2 O increase the corrosion rate of Inconel 690, whereas RuO 2 + TeO 2 are neutral. The latter however have a marked effect in lowering the room temperature resistivity by at least 5 orders of magnitude even though relatively small fraction of the RuO 2 precipitates were reduced to ruthenium metal. (author)

Corrosion rate transients observed by linear polarization techniques at Zr-1%Nb alloy

International Nuclear Information System (INIS)

Beran, J.; Cerny, K.

1997-01-01

Momentary corrosion rate of Zr-1%Nb alloy during nonisothermal autoclave experiments at temperature up to 328 deg. C in various solutions was determined by T/R p values (T - absolute temperature, R p - polarization resistance), multiplied by temperature independent conversion factor. This factor was found by comparison of conventional corrosion loss evaluation with electrochemical measurements. Corrosion rate transients in boric acid solutions and in lithium hydroxide differed significantly. Great differences were also found in stabilized corrosion rates at the end of experiments. Temperature irregularities caused considerable changes in corrosion rate. (author). 5 refs, 5 figs, 1 tab

Corrosion rate transients observed by linear polarization techniques at Zr-1%Nb alloy

Energy Technology Data Exchange (ETDEWEB)

Beran, J; Cerny, K [ZJS SKODA plc., Pelzen (Czech Republic)

1997-02-01

Momentary corrosion rate of Zr-1%Nb alloy during nonisothermal autoclave experiments at temperature up to 328 deg. C in various solutions was determined by T/R{sub p} values (T - absolute temperature, R{sub p}- polarization resistance), multiplied by temperature independent conversion factor. This factor was found by comparison of conventional corrosion loss evaluation with electrochemical measurements. Corrosion rate transients in boric acid solutions and in lithium hydroxide differed significantly. Great differences were also found in stabilized corrosion rates at the end of experiments. Temperature irregularities caused considerable changes in corrosion rate. (author). 5 refs, 5 figs, 1 tab.

A statistical approach to determine the effects of nuclear glass components on the short and long term glass alteration

International Nuclear Information System (INIS)

Advocat, Th.; Tovena, I.; Vernaz, E.; Larche, F.; Phan Tan Luu, R.

1997-01-01

The experimentation plan methodology may be a powerful tool to design statistical models able to calculate quantitative leach rates as a function of glass compositions. The investigation discussed here implemented an experimentation plan methodology covering a wide range of glass composition variations with two major objectives: - identify the effects of the main component oxides of R7T7 glass (SiO 2 , B 2 O 3 , Al 2 O 3 , Na 2 O+Li 2 O, additive oxides, Fission Products oxides, actinide oxides) on the dissolution rates far and close to equilibrium; - and develop a statistical model relating the measured initial dissolution rate with the selected oxide compositions. A second-degree silica-based model was developed to express the initial dissolution rates at 100 deg C according to the oxide weight percentage of 6 major oxides or oxide groups. The model is qualified by comparison with independent experimental results. For the short term, far from saturation conditions (confined media), plotting the effects of the oxides clearly showed that SiO 2 , Al 2 O 3 and the additive oxides enhanced glass durability at 100 deg C, while B 2 O 3 and Na 2 O+Li 2 O diminished the initial corrosion resistance. For the long term, plotting the effects of the oxides showed that additive oxides, Al 2 O 3 and SiO 2 enhanced glass durability at 90 deg C, in that order, while Na 2 O+Li 2 O still diminished the corrosion resistance. The fission products and actinide oxides and ZrO 2 have apparently a slight beneficial effect on the glass durability, under saturation conditions (long term). (author)

The borosilicate glass for 'PAMELA'

International Nuclear Information System (INIS)

Schiewer, E.

1986-01-01

The low enriched waste concentrate (LEWC) stored at Mol, Belgium, will be solidified in the vitrification plant 'PAMELA'. An alkali-borosilicate glass was developed by the Hahn-Meitner-Institut, Berlin, which dissolves (11 +- 3)wt% waste oxides while providing sufficient flexibility for changes in the process parameters. The development of the glass labelled SM513LW11 is described. Important properties of the glass melt (viscosity, resistivity, formation of yellow phase) and of the glass (corrosion in aqueous solutions, crystallization) are reported. The corrosion data of this glass are similar to those of other HLW-glasses. Less than five wt% of crystalline material are produced upon cooling of large glass blocks. Crystallization does not affect the chemical durability. (Auth.)

Effect of alteration phase formation on the glass dissolution rate

International Nuclear Information System (INIS)

Ebert, W.L.

1997-01-01

The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. While simulations have predicted the accelerating effect of formation of certain phases, the phases predicted to form in computer simulations are usually different than those observed to form in experiments. This is because kinetically favored phases form first in experiments, while simulations predict the thermodynamically favored phases. Static dissolution tests with crushed glass have been used to measure the glass dissolution rate after alteration phases form. Because glass dissolution rates are calculated on a per area basis, an important effect in tests conducted with crushed glass is the decrease in the surface area of glass that is available for reaction as the glass dissolves. This loss of surface area must be taken into account when calculating the dissolution rate. The phases that form and their effect on the dissolution rate are probably related to the glass composition. The impact of phase formation on the glass dissolution rate also varies according to the solubility products of the alteration phases and how the orthocilicic acid activity is affected. Insight into the relationship between the glass dissolution rate, solution chemistry and alteration phase formation is provided by the results of accelerated dissolution tests

Effect of alteration phase formation on the glass dissolution rate

Energy Technology Data Exchange (ETDEWEB)

Ebert, W L [Argonne National Laboratory, Chemical Technology Div. (United States)

1997-07-01

The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. While simulations have predicted the accelerating effect of formation of certain phases, the phases predicted to form in computer simulations are usually different than those observed to form in experiments. This is because kinetically favored phases form first in experiments, while simulations predict the thermodynamically favored phases. Static dissolution tests with crushed glass have been used to measure the glass dissolution rate after alteration phases form. Because glass dissolution rates are calculated on a per area basis, an important effect in tests conducted with crushed glass is the decrease in the surface area of glass that is available for reaction as the glass dissolves. This loss of surface area must be taken into account when calculating the dissolution rate. The phases that form and their effect on the dissolution rate are probably related to the glass composition. The impact of phase formation on the glass dissolution rate also varies according to the solubility products of the alteration phases and how the orthocilicic acid activity is affected. Insight into the relationship between the glass dissolution rate, solution chemistry and alteration phase formation is provided by the results of accelerated dissolution tests.

Prediction of waste glass melt rates

International Nuclear Information System (INIS)

Lee, L.

1987-01-01

Under contract to the Department of Energy, the Du Pont Company has begun construction of a Defense Waste Processing Facility to immobilize radioactive wastes now stored as liquids at the Department of Energy's Savannah River Plant. The immobilization process solidifies waste sludge by vitrification into a leach-resistant borosilicate glass. Development of this process has been the responsibility of the Savannah River Laboratory. As part of the development, a simple model was developed to predict the melt rates for the waste glass melter. This model is based on an energy balance for the cold cap and gives very good agreement with melt rate data obtained from experimental campaigns in smaller scale waste glass melters

Modelling glass alteration in an altered argillaceous environment

International Nuclear Information System (INIS)

Bildstein, O.; Trotignon, L.; Pozo, C.; Jullien, M.

2007-01-01

The long term behaviour of materials such as glass, steel and clay has been investigated in the context of deep geological disposal of radioactive wastes. The interactions between vitrified wastes, canister corrosion products (CPs) and clay are studied using a modified version of the reaction-transport code Crunch, especially looking at pH changes and possible cementation at the interface with the clayey materials. These perturbations may indeed affect the lifetime of glass matrix in deep repositories, e.g., high pH enhances the rate of glass alteration. This work focuses on the argillite of Bure. The calculations were performed at 323 K with a glass alteration rate switching from a high initial rate to a residual rate according to the sorption capacity of CPs. The time at which this sorption capacity is saturated is crucial to the system in terms of wastes package lifetime. The results show that the glass alteration imposes a high pH value at the interface with CPs and clay: up to a value of 9.2, compared to 7.3 which is the initial pH value in the argillite. Experimental data show that the rate of glass alteration is much higher in such pH conditions. For a R7T7-type glass, the rate is about five times higher at pH 9 than at pH 7. This pH perturbation migrates through the clayey domain as a result of the migration of mobile elements such as boron and sodium, and despite the existence of strong pH buffers in the argillite. The cementation of porosity at the interface between glass and clay is predicted by the model due to the massive precipitation of iron corrosion products and glass alteration products. At this point of the evolution of the system, the pH starts to decrease and the alteration rate of the glass could be significantly reduced. This porosity clogging effect is difficult to confirm by experiments especially since existing data on short term experiments tend to show a pervasive precipitation of silica in the domain instead of a localized precipitation

Mineralogical textural and compositional data on the alteration of basaltic glass from Kilauea, Hawaii to 300 degrees C: Insights to the corrosion of a borosilicate glass waste-form

International Nuclear Information System (INIS)

Smith, D.K.

1990-01-01

Mineralogical, textural and compositional data accompanying greenschist facies metamorphism (to 300 degrees C) of basalts of the East Rift Zone (ERZ), Kilauea, Hawaii may be evaluated relative to published and experimental results for the surface corrosion of borosilicate glass. The ERZ alteration sequence is dominated by intermittent palagonite, interlayered smectite-chlorite, chlorite, and actinolite-epidote-anhydrite. Alteration is best developed in fractures and vesicles where surface reaction layers root on the glass matrix forming rinds in excess of 100 microns thick. Fractures control fluid circulation and the alteration sequence. Proximal to the glass surface, palagonite, Fe-Ti oxides and clays replace fresh glass as the surface reaction layer migrates inwards; away from the surface, amphibole, anhydrite, quartz and calcite crystallize from hydrothermal fluids in contact with the glass. The texture and composition of basaltic glass surfaces are similar to those of a SRL-165 glass leached statically for sixty days at 150 degrees C. While the ERZ reservoir is a complex open system, conservative comparisons between the alteration of ERZ and synthetic borosilicate glass are warranted. 31 refs., 2 figs

A High-Performance Corrosion-Resistant Iron-Based Amorphous Metal - The Effects of Composition, Structure and Environment on Corrosion Resistance

International Nuclear Information System (INIS)

Farmer, J.; Haslam, J.; Day, D.; Lian, T.; Saw, C.; Hailey, P.; Choi, J.S.; Rebak, R.; Yang, N.; Bayles, R.; Aprigliano, L.; Payer, J.; Perepezko, J.; Hildal, K.; Lavernia, E.; Ajdelsztajn, L.; Branagan, D.; Beardsley, B.

2007-01-01

The passive film stability of several Fe-based amorphous metal formulations have been found to be comparable to that of high-performance Ni-based alloys, and superior to that of stainless steels, based on electrochemical measurements of the passive film breakdown potential and general corrosion rates. Chromium (Cr), molybdenum (Mo) and tungsten (W) provide corrosion resistance; boron (B) enables glass formation; and rare earths such as yttrium (Y) lower critical cooling rate (CCR). The high boron content of this particular amorphous metal also makes it an effective neutron absorber, and suitable for criticality control applications, as discussed in companion publications. Corrosion data for SAM2X5 (Fe 49.7 Cr 17.7 Mn 1.9 Mo 7.4 W 1.6 B 15.2 C 3.8 Si 2.4 ) is discussed here. (authors)

Near-field performance assessment for a low-activity waste glass disposal system: laboratory testing to modeling results

International Nuclear Information System (INIS)

McGrail, B.P.; Bacon, D.H.; Icenhower, J.P.; Mann, F.M.; Puigh, R.J.; Schaef, H.T.; Mattigod, S.V.

2001-01-01

Reactive chemical transport simulations of glass corrosion and radionuclide release from a low-activity waste (LAW) disposal system were conducted out to times in excess of 20 000 yr with the subsurface transport over reactive multiphases (STORM) code. Time and spatial dependence of glass corrosion rate, secondary phase formation, pH, and radionuclide concentration were evaluated. The results show low release rates overall for the LAW glasses such that performance objectives for the site will be met by a factor of 20 or more. Parameterization of the computer model was accomplished by combining direct laboratory measurements, literature data (principally thermodynamic data), and parameter estimation methods

Glasses used in the solidification of high level radioactive waste: their behaviour in aqueous solutions

International Nuclear Information System (INIS)

Grauer, R.

1983-02-01

Because of their amorphous structure, glasses are particularly suitable matrixes for the solidification of the mixture of radionuclides included in the high level wastes from reactor fuel reprocessing. They are not sensitive to variations in the fractions present of different waste oxides and are resistent to the effects of irradiation. In particular, borosilicate glasses have been investigated for around 25 years and the vitrification techniques have been tested on the technological scale. The environmental conditions within a final waste repository are expected to be such that the chemical resistance of glasses to attack by groundwaters is of special interest. In the present report the corrosion behaviour is described, with emphasis being placed upon the most significant controlling parameters. Since experimental determination of corrosion rates must be done in relatively short-time experiments, the results of which can depend strongly upon the measurement methods employed, it is necessary to carry out a critical assessment of the techniques commonly used in laboratory work. Experimental results are illustrated by means of selected examples. Particular emphasis is placed upon the effects of increased temperatures and of irradiation. The models which have been proposed for the estimation of the long-term corrosion behaviour of glasses are not yet fully sufficient and improvements are required. Furthermore, the actual corrosion rates which are fed into such models must be replaced by values more appropriate for the actual environmental conditions to which the glasses are most likely to be exposed within high level waste repositories. It should be noted, however, that even with current conservative input data on corrosion rates, typical estimated lifetimes for vitrified waste blocks are of the order of 10 5 years. The report concludes with recommendations concerning the most useful areas for further investigations. (author)

Sensitivity Analysis of Corrosion Rate Prediction Models Utilized for Reinforced Concrete Affected by Chloride

Science.gov (United States)

Siamphukdee, Kanjana; Collins, Frank; Zou, Roger

2013-06-01

Chloride-induced reinforcement corrosion is one of the major causes of premature deterioration in reinforced concrete (RC) structures. Given the high maintenance and replacement costs, accurate modeling of RC deterioration is indispensable for ensuring the optimal allocation of limited economic resources. Since corrosion rate is one of the major factors influencing the rate of deterioration, many predictive models exist. However, because the existing models use very different sets of input parameters, the choice of model for RC deterioration is made difficult. Although the factors affecting corrosion rate are frequently reported in the literature, there is no published quantitative study on the sensitivity of predicted corrosion rate to the various input parameters. This paper presents the results of the sensitivity analysis of the input parameters for nine selected corrosion rate prediction models. Three different methods of analysis are used to determine and compare the sensitivity of corrosion rate to various input parameters: (i) univariate regression analysis, (ii) multivariate regression analysis, and (iii) sensitivity index. The results from the analysis have quantitatively verified that the corrosion rate of steel reinforcement bars in RC structures is highly sensitive to corrosion duration time, concrete resistivity, and concrete chloride content. These important findings establish that future empirical models for predicting corrosion rate of RC should carefully consider and incorporate these input parameters.

The Influence of Cooling Rates on Paleointensity of Volcanic Glasses: an Experimental Approach on Synthetic Glass

Science.gov (United States)

von Aulock, F. W.; Ferk, A.; Leonhardt, R.; Hess, K.-U.; Dingwell, D. B.

2009-04-01

The suitability of volcanic glass for paleointensity determinations has been proposed in many studies throughout the last years. Besides the mainly single domain magnetic remanence carriers and the pristine character of the volcanic glass, this was also reasoned by the possibility to correct paleointensity data for cooling rate dependency using relaxation geospeedometry. This method gives the cooling rate of a glass at the glass transition interval which marks the change of a ductile supercooled liquid to a brittle glass. In this study the cooling rate correction as carried out for example by Leonhardt et al. 2006 is tested on synthetic volcanic glass. In order to obtain a stable multicomponent glass with ideal magnetic properties, a natural phonolithic glass from Tenerife (Spain) was melted to avoid heterogeneity and degassing. Further it was tempered for 5 hours at 900 °C to yield a sufficient concentration of magnetic remanence carriers. To exclude nucleation or crystallisation 7 samples were then heated to about 50 °C above the glass transition temperature at around 720 °C and quenched at different rates from 0.1 to 15 K/min. After carrying out a paleointensity experiment using a modified Thellier method, which incorporated alteration, additivity and tail checks, the dependence of the thermoremance on cooling rate was investigated. Using the original cooling rates we corrected the data and obtained paleointensities of around 46 T, which is a good approximation of the ambient field of 48 T. Taking into account that the uncorrected mean paleointensity is about 57 T, this suggests that cooling rate correction is not only working, but also a necessary tool to yield the true field value. R. Leonhardt , J. Matzka, A.R.L. Nichols , D.B. Dingwell Cooling rate correction of paleointensity determination for volcanic glasses by relaxation geospeedometry; Earth and Planetary Science Letters 243 (2006) 282-292

Modelling the dissolution of borosilicate glasses for radioactive waste disposal with the PHREEQE/GLASSOL code: theory and practice

International Nuclear Information System (INIS)

Curti, E.

1991-02-01

A model describing the corrosion kinetics of silicate glasses has been developed by Grambow in recent years. In this report, the theoretical background of the model is thoroughly discussed, and its practical use demonstrated. The main objectives were: 1) to test the validity of the basic assumptions on which the model relies, and 2) to assess whether it can be applied to the safety analysis of a Swiss final repository for high-level radioactive waste. Transition State Theory, a tool based on quantum mechanical principles, has been used by Grambow to derive a general kinetic equation for the corrosion of silicate glasses. This equation predicts successfully the observed dependence of the corrosion rate on the silicic acid concentration in solution according to a first order kinetics law. However, some parameters required by this equation are determined on the base of questionable assumptions. In particular, the simplistic surface complexation model used for the calculation of the free energy of the glass-water reaction yields, for the protonation of silicon on the glass surface, results which are not consistent with the experimental findings. Further, although the model predicts a unique value, common to all silicate glasses, for the activation energy of the rate-determining elementary reaction, leaching experiments conducted on a wide variety of glasses suggest that this quantity may vary by a factor 2. In its present form, the model is judged to be unsuitable for the safety analysis of the Swiss final repository. The reasons include: 1) the model neglects the potential effects of diffusive transport and silica sorption in a bentonite backfill on the glass corrosion kinetics, 2) the release of radionuclides can be only modelled assuming congruent dissolution, and 3) the magnitude of the final rates of corrosion, the parameter defining the maximal lifetime of the glass matrix, is still not known with sufficient precision. (author) figs., tabs., 27 refs

A statistical approach to determine the effects of nuclear glass components on the short and long term glass alteration

Energy Technology Data Exchange (ETDEWEB)

Advocat, Th; Tovena, I; Vernaz, E [CEA Valrho, Dir. de l' Energie Nucleaire, DEN, 30 - Marcoule (France); Larche, F [Montpellier-2 Univ., 34 (France); Phan Tan Luu, R [Faculte de St Jerome, 13 - Marseille (France)

1997-07-01

The experimentation plan methodology may be a powerful tool to design statistical models able to calculate quantitative leach rates as a function of glass compositions. The investigation discussed here implemented an experimentation plan methodology covering a wide range of glass composition variations with two major objectives: - identify the effects of the main component oxides of R7T7 glass (SiO{sub 2}, B{sub 2}O{sub 3}, Al{sub 2}O{sub 3}, Na{sub 2}O+Li{sub 2}O, additive oxides, Fission Products oxides, actinide oxides) on the dissolution rates far and close to equilibrium; - and develop a statistical model relating the measured initial dissolution rate with the selected oxide compositions. A second-degree silica-based model was developed to express the initial dissolution rates at 100 deg C according to the oxide weight percentage of 6 major oxides or oxide groups. The model is qualified by comparison with independent experimental results. For the short term, far from saturation conditions (confined media), plotting the effects of the oxides clearly showed that SiO{sub 2}, Al{sub 2}O{sub 3} and the additive oxides enhanced glass durability at 100 deg C, while B{sub 2}O{sub 3} and Na{sub 2}O+Li{sub 2}O diminished the initial corrosion resistance. For the long term, plotting the effects of the oxides showed that additive oxides, Al{sub 2}O{sub 3} and SiO{sub 2} enhanced glass durability at 90 deg C, in that order, while Na{sub 2}O+Li{sub 2}O still diminished the corrosion resistance. The fission products and actinide oxides and ZrO{sub 2} have apparently a slight beneficial effect on the glass durability, under saturation conditions (long term). (author)

Exposure testing of fasteners in preservative treated wood : gravimetric corrosion rates and corrosion product analyses

Science.gov (United States)

Samuel L. Zelinka; Rebecca J. Sichel; Donald S. Stone

2010-01-01

Research was conducted to determine the corrosion rates of metals in preservative treated wood and also understand the mechanism of metal corrosion in treated wood. Steel and hot-dip galvanized steel fasteners were embedded in wood treated with one of six preservative treatments and exposed to 27oC at 100% relative humidity for 1 year. The...

Materials corrosion and mitigation strategies for APT: End of year report, FY '96

International Nuclear Information System (INIS)

Lillard, R.S.; Butt, D.P.

1996-01-01

The authors major accomplishment in FY96 was the design and fabrication of the corrosion probes to be used ''In Beam'' during the FY97 irradiation period to begin on February 1, 1997. Never before have corrosion rate measurements been made on-line in such a high radiation environment. To measure corrosion rate as a function of beam time, it is necessary to electrical isolate the corrosion electrode to be examined form the plumbing system. Conventionally, this is accomplished with glass seals. Here irradiation of the glass may cause it to become conductive, rendering the seal useless. To overcome this problem, the corrosion probes to be used in-beam at the spallation neutron cooling water loop at the LANSCE A6 target station were fabricated with ceramic inserts which act as electrical feed-throughs. The corrosion sample is joined to the ceramic by means of a compression seal. The corrosion samples are closed end cylinders, 0.5 inches diameter x 6.25 inch length, that are constructed from Stainless Steel 304L, Stainless Steel 316L, Inconel 718, Tungsten, HT-9, and Tantalum. Because of their specialized nature, InTa Corporation, of Santa Clara, CA was contracted to manufacture these problems. As of November 1, 1996 delivery of these probes has begun and the authors anticipate having all of the probes in hand by Nov. 25

Glass science tutorial: Lecture No. 7, Waste glass technology for Hanford

International Nuclear Information System (INIS)

Kruger, A.A.

1995-07-01

This paper presents the details of the waste glass tutorial session that was held to promote knowledge of waste glass technology and how this can be used at the Hanford Reservation. Topics discussed include: glass properties; statistical approach to glass development; processing properties of nuclear waste glass; glass composition and the effects of composition on durability; model comparisons of free energy of hydration; LLW glass structure; glass crystallization; amorphous phase separation; corrosion of refractories and electrodes in waste glass melters; and glass formulation for maximum waste loading

A finite element modeling method for predicting long term corrosion rates

International Nuclear Information System (INIS)

Fu, J.W.; Chan, S.

1984-01-01

For the analyses of galvanic corrosion, pitting and crevice corrosion, which have been identified as possible corrosion processes for nuclear waste isolation, a finite element method has been developed for the prediction of corrosion rates. The method uses a finite element mesh to model the corrosive environment and the polarization curves of metals are assigned as the boundary conditions to calculate the corrosion cell current distribution. A subroutine is used to calculate the chemical change with time in the crevice or the pit environments. In this paper, the finite element method is described along with experimental confirmation

Effect of alumina on the dissolution rate of glasses

International Nuclear Information System (INIS)

Palavit, G.; Montagne, L.

1997-01-01

Small alumina addition to silicate glasses improves their chemical durability, but a large amount of alumina can also be beneficial to obtain a high dissolution rate. This paper describes the effect of Al 3+ on the early stage of glass alteration, in relation with its coordination in the glass and also with the reactions involved (hydrolysis and ionic exchange). We describe briefly nuclear magnetic resonance tools available to characterize the aluminum environments in the glasses. The rote of alumina on the dissolution rate of phosphate glasses is also discussed in order to show that the effect of Al 3+ is dependant upon the nature of the glass matrix. (author)

FY2016 ILAW Glass Corrosion Testing with the Single-Pass Flow-Through Method

Energy Technology Data Exchange (ETDEWEB)

Neeway, James J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Asmussen, Robert M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Parruzot, Benjamin PG [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cordova, Elsa [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Williams, Benjamin D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Leavy, Ian I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Stephenson, John R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McElroy, Erin M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2017-04-21

The inventory of immobilized low-activity waste (ILAW) produced at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) will be disposed of at the near-surface, on-site Integrated Disposal Facility (IDF). When groundwater comes into contact with the waste form, the glass will corrode and radionuclides will be released into the near-field environment. Because the release of the radionuclides is dependent on the dissolution rate of the glass, it is important that the performance assessment (PA) model accounts for the dissolution rate of the glass as a function of various chemical conditions. To accomplish this, an IDF PA model based on Transition State Theory (TST) can be employed. The model is able to account for changes in temperature, exposed surface area, and pH of the contacting solution as well as the effect of silicon concentrations in solution, specifically the activity of orthosilicic acid (H4SiO4), whose concentration is directly linked to the glass dissolution rate. In addition, the IDF PA model accounts for the alkali-ion exchange process as sodium is leached from the glass and into solution. The effect of temperature, pH, H4SiO4 activity, and the rate of ion-exchange can be parameterized and implemented directly into the PA rate law model. The rate law parameters are derived from laboratory tests with the single-pass flow-through (SPFT) method. To date, rate law parameters have been determined for seven ILAW glass compositions, thus additional rate law parameters on a wider range of compositions will supplement the existing body of data for PA maintenance activities. The data provided in this report can be used by ILAW glass scientists to further the understanding of ILAW glass behavior, by IDF PA modelers to use the rate law parameters in PA modeling efforts, and by Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program.

Evaluation of intergranular corrosion rate and microstructure of forged 316L round bar

International Nuclear Information System (INIS)

Lim, H. K.; Kim, Y. S.

2009-01-01

When austenitic stainless steels are heat treated in the range of 500∼850 .deg. C, the alloys are sensitized due to the formation of chromium carbide at grain boundaries and then intergranular corrosion occurs. This paper aims to evaluate the intergranular corrosion rate and microstructural change of forged 316L stainless steel. To analyze the microstructure by forging conditions, ferrite phase, sigma phase, intergranular precipitation were observed. In order to evaluate the intergranular corrosion rate. Huey test was performed by ASTM A262. On the base of microstructural observation, ferrite and sigma phases were not detected, and also intergranular precipitation was not revealed in optical microscopic observation. By ASTM A262 Practice A, step structure was shown in all forging conditions. Intergranular corrosion rate gradually increased by Huey test periods but average corrosion rate was under 0.03 mm/month

Evaluation of intergranular corrosion rate and microstructure of forged 316L round bar

Energy Technology Data Exchange (ETDEWEB)

Lim, H. K.; Kim, Y. S. [Andong National University, Andong (Korea, Republic of)

2009-12-15

When austenitic stainless steels are heat treated in the range of 500{approx}850 .deg. C, the alloys are sensitized due to the formation of chromium carbide at grain boundaries and then intergranular corrosion occurs. This paper aims to evaluate the intergranular corrosion rate and microstructural change of forged 316L stainless steel. To analyze the microstructure by forging conditions, ferrite phase, sigma phase, intergranular precipitation were observed. In order to evaluate the intergranular corrosion rate. Huey test was performed by ASTM A262. On the base of microstructural observation, ferrite and sigma phases were not detected, and also intergranular precipitation was not revealed in optical microscopic observation. By ASTM A262 Practice A, step structure was shown in all forging conditions. Intergranular corrosion rate gradually increased by Huey test periods but average corrosion rate was under 0.03 mm/month.

Degradation of partially immersed glass: A new perspective

Science.gov (United States)

Chinnam, R. K.; Fossati, P. C. M.; Lee, W. E.

2018-05-01

The International Simple Glass (ISG) is a six-component borosilicate glass which was developed as a reference for international collaborative studies on high level nuclear waste encapsulation. Its corrosion behaviour is typically examined when it is immersed in a leaching solution, or when it is exposed to water vapour. In this study, an alternative situation is considered in which the glass is only partially immersed for 7 weeks at a temperature of 90 °C. In this case, half of the glass sample is directly in the solution itself, and the other half is in contact with a water film formed by condensation of water vapour that evaporated from the solution. This results in a different degradation behaviour compared to standard tests in which the material is fully immersed. In particular, whilst in standard tests the system reaches a steady state with a very low alteration rate thanks to the formation of a protective gel layer, in partially-immersed tests this steady state could not be reached because of the continuous alteration from the condensate water film. The constant input of ions from the emerged part of the sample caused a supersaturation of the solution, which resulted in early precipitation of secondary crystalline phases. This setup mimics storage conditions once small amounts of water have entered a glass waste form containing canister. It offers a more realistic outlook of corrosion mechanisms happening in such situations than standard fully-immersed corrosion tests.

Attenuation of glass dissolution in the presence of natural additives

Energy Technology Data Exchange (ETDEWEB)

Sang, Jing C.; Barkatt, Aaron [Department of Chemistry, The Catholic University of America, Washington, DC (United States); O`Keefe, John A. [National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, MD (United States)

1996-11-01

The dissolution kinetics of silicate glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase are reported. The results demonstrate the possibility of a dramatic decrease in the rate of dissolution of silicate glass in the presence of certain varieties of olivine-based materials. This decrease in dissolution rate was shown to be due to the fact that these additives consist mostly of Mg-based material but also contain minor amounts of Al and Ca. The combined presence of Mg with these minor species affected the corrosion rate of the glass as a whole, including its most soluble components such as boron. This study has potentially important implications to the durability of glasses exposed to natural environments. The results may be relevant to the use of active backfill materials in burial sites for nuclear waste glasses, as well as to better understanding of the environmental degradation of natural and ancient glasses.

Evaluation of the flow-accelerated corrosion downstream of an orifice. 2. Measurement of corrosion rate and evaluation on the effects of the flow field

International Nuclear Information System (INIS)

Nagaya, Yukinori; Utanohara, Yoichi; Nakamura, Akira; Murase, Michio

2008-01-01

In this study, in order to evaluate the effects of flow field on corrosion rate due to flow accelerated corrosion (FAC), a corrosion rate downstream of an orifice was measured using the electric resistance method. The diameter of the pipe is 50 mm and that of the orifice is 24.3 mm, and flow velocity of the experimental loop was set at 5m/s, and the temperature of water was controlled within ±1 at 150deg-C. There were no significant circumferential difference in measured corrosion rate, and the maximum corrosion rate was observed at 1D or 2D downstream from the orifice. The ratios of the measured corrosion rate and the calculated wall shear stress at the 1D downstream from the orifice to the value at upstream under well developed flow agreed well. (author)

Standard practice for calculation of corrosion rates and related information from electrochemical measurements

CERN Document Server

American Society for Testing and Materials. Philadelphia

1989-01-01

1.1 This practice covers the providing of guidance in converting the results of electrochemical measurements to rates of uniform corrosion. Calculation methods for converting corrosion current density values to either mass loss rates or average penetration rates are given for most engineering alloys. In addition, some guidelines for converting polarization resistance values to corrosion rates are provided. 1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.

Lead-iron phosophate glass

International Nuclear Information System (INIS)

Sales, B.C.; Boatner, L.A.

1988-01-01

The lead-iron phosphate nuclear waste glasses (LIPNWG) are the subject of the present chapter. They were discovered in 1984 while the authors were attempting to find a sintering aid for certain types of crystalline monazite ceramic high-level nuclear waste forms. In the present chapter, the term waste glass is synonymous with nuclear waste glass (NWG), and the acronym LIP is often used for lead-iron phosphate. Lead-iron phosphate glasses, like many of the previously studied phosphate glasses, are corrosion resistant in aqueous solutions at temperatures below 100 degrees C, and they can be melted and poured at temperatures that are relatively low in comparison with the processing temperatures required for current silicate glass compositions. Unlike the phosphate glasses investigated previously, however, LIPNWGs do not suffer from alteration due to devitrification during realistic and readily, achievable cooling periods. Additionally, lead-iron phosphate glass melts are not nearly as corrosive as the sodium phosphate melts investigated during the 1960s; and, therefore, they can be melted and processed using crucibles made from a variety of materials

High-temperature oxidation of tungsten covered by layer of glass-enamel melt

International Nuclear Information System (INIS)

Vasnetsova, V.B.; Shardakov, N.T.; Kudyakov, V.Ya.; Deryabin, V.A.

1997-01-01

Corrosion losses of tungsten covered by the layer of glass-enamel melt were determined at 800, 850, 900, 950 deg C. It is shown that the rate of high-temperature oxidation of tungsten decreases after application of glass-enamel melt on its surface. This is probably conditioned by reduction of area of metal interaction with oxidizing atmosphere

Role of lead as modifier on the properties of lead iron phosphate nuclear waste glasses

International Nuclear Information System (INIS)

Hazra, G.; Mitra, P.; Das, T.

2011-01-01

Lead-iron phosphate glasses are a promising new waste form for the safe immobilization of both high level defence and high level commercial radioactive waste for long term disposal. Lead iron phosphate glasses have several advantages such as lower aqueous corrosion rate, lower processing temperature etc. (author)

Experimental investigation of aqueous corrosion of R7T7 nuclear glass at 90 degrees C in the presence of humic acids: A kinetic approach

International Nuclear Information System (INIS)

Gin, S.; Godon, N.; Mestre, J.P.; Vernaz, E.Y.; Beaufort, D.

1994-01-01

The dissolution kinetics of the French open-quotes R7T7close quotes nonradioactive LWR reference glass in solutions containing dissolved humic acids were investigated at 9O degrees C during static tests with imposed or free pH. Experiments conducted in highly dilute media, with a glass-surface-area-to-solution-volume (SA/V) ratio of 5 m -1 , showed that the glass dissolution surface reaction is catalyzed by humic acids. With higher degrees of reaction progress (SA/V = 100 m -1 and free pH) the humic acids impose pH modifications on the system compared with inorganic media; moreover, they directly or indirectly enhance the dissolution of certain alkali metals and transition elements, forming aqueous complexes with the latter. During experiments with an imposed pH of 8.5 (SA/V = 1300 and 5300 m -1 ), the humic acids appear to cause increased silica solubility that cannot be accounted for by the formation of silica complexes. A residual corrosion rate in the humic acid media exceeding the rate measured in inorganic media suggests that, in addition to silica, one or more element complexes formed by humic acids may be a kinetically limiting factor. This hypothesis must be confirmed, however, as the quantity of humic acids per unit glass surface area was too small in this experiment to allow unambiguous characterization of the phenomenon

Atomic size effect on critical cooling rate and glass formation

International Nuclear Information System (INIS)

Jalali, Payman; Li Mo

2005-01-01

Atomic size effect on critical cooling rate and glass formability in a model binary system is investigated using molecular dynamics simulation. To isolate atomic size effect from the rest of the factors that critically influence the glass formation, a hard sphere model is employed in conjunction with a newly developed densification method. The glass formability is defined as a set of optimal conditions that result in the slowest cooling rate of the glass-forming liquid. Critical cooling rates are identified from extensive molecular dynamics simulations. A kinetic glass-forming diagram is mapped out that marks the boundary between the glass-forming regions and competing crystalline phases in terms of the parameters of the atomic size ratio and alloy concentration. It is found that the potency of the atomic size difference on glass formation is influenced greatly by the competing metastable and equilibrium crystalline phases in the system, and the kinetic processes leading to the formation of these phases. The mechanisms of the atomic size effect on topological instability of crystal packing and glass formation are discussed

Laboratory testing of glasses for Lockheed Idaho Technology Co. - fiscal year 1994 report

International Nuclear Information System (INIS)

Ellison, A.J.G.; Wolf, S.F.; Bates, J.K.

1995-04-01

The purpose of this project is to measure the intermediate and long-term durability of vitrified waste forms developed by Lockheed Idaho Technology Co. (LITCO) for the immobilization of calcined radioactive wastes at Idaho National Engineering Laboratory. Two vitreous materials referred to as Formula 127 and Formula 532, have been subjected to accelerated durability tests to measure their long-term performance. Formula 127 consists of a glass matrix containing 5-10 vol % fluorite (CaF 2 ) as a primary crystalline phase. It shows low releases of glass components to solution in 7-, 28-, 70-, and 140-day Product Consistency Tests performed at 2000 m -1 at 90 degrees C. In these tests, release rates for glass-forming components were similar to those found for durable waste glasses. The Ca and F released by the glass as it corrodes appear to reprecipitate as fluorite. Formula 532 consists of a glass matrix containing 5-10 vol % of an Al-Si-rich primary crystalline phase. The release rates for components other than aluminum are relatively low, but aluminum is released at a much higher rate than is typical for durable waste glasses. Secondary crystalline phases form relatively early during the corrosion of Formula 532 and appear to consist almost entirely of the Al-Si-rich primary phase (or a crystal with the same Al:Si ratio) and a sodium-bearing zeolite. Future test results are expected to highlight the relative importance of primary and secondary crystalline phases to the rate of corrosion of Formula 127 and Formula 532

Disposition of actinides released from high-level waste glass

International Nuclear Information System (INIS)

Ebert, W.L.; Bates, J.K.; Buck, E.C.; Gong, M.; Wolf, S.F.

1994-01-01

A series of static leach tests was conducted using glasses developed for vitrifying tank wastes at the Savannah River Site to monitor the disposition of actinide elements upon corrosion of the glasses. In these tests, glasses produced from SRL 131 and SRL 202 frits were corroded at 90 degrees C in a tuff groundwater. Tests were conducted using crushed glass at different glass surface area-to-solution volume (S/V) ratios to assess the effect of the S/V on the solution chemistry, the corrosion of the glass, and the disposition of actinide elements. Observations regarding the effects of the S/V on the solution chemistry and the corrosion of the glass matrix have been reported previously. This paper highlights the solution analyses performed to assess how the S/V used in a static leach test affects the disposition of actinide elements between fractions that are suspended or dissolved in the solution, and retained by the altered glass or other materials

Glass and nuclear wastes

International Nuclear Information System (INIS)

Sombret, C.

1982-10-01

Glass shows interesting technical and economical properties for long term storage of solidified radioactive wastes by vitrification or embedding. Glass composition, vitrification processes, stability under irradiation, thermal stability and aqueous corrosion are studied [fr

Detrimental role of hydrogen on the corrosion rate of zirconium alloys

International Nuclear Information System (INIS)

Blat, M.; Noel, D.

1996-01-01

Recent studies have suggested that hydride precipitation at the metal/oxide interface could play a detrimental role on the waterside corrosion rate. Nevertheless, the mechanism of that detrimental role is not completely understood, and two hypotheses were investigated to understand the mechanism that controls the role of the hydrides. The first hypothesis is based on a mechanical effect: the hydrides precipitate at the metal/oxide interface and destroy the physical integrity of the barrier oxide layer. The second hypothesis is a modification of the transport properties of the oxide grown on the hydrided metal. The detrimental role of hydrides on the corrosion rate was studied by charging unirradiated Zircaloy-4 cladding material with hydrogen to a level higher than the limit of solubility at 400 C. Both gaseous and cathodic charging techniques were used. Static corrosion tests were carried out in autoclave with steam at 400 C on an as-received and hydrided sample. The detrimental role of hydrides is confirmed from the post-transition corrosion rate, and that effect is more significant for high cathodic charging. The results of the metallurgical examinations are discussed to provide an understanding of the mechanism. No relationship between hydrides, physical defects in the oxide, and local corrosion rate enhancement was found. Therefore, the results do not support the hypothesis of a mechanical effect at the scale of the performed examinations, but more detailed work is required to confirm this

Glass Formation, Chemical Properties and Surface Analysis of Cu-Based Bulk Metallic Glasses

Directory of Open Access Journals (Sweden)

Akihisa Inoue

2011-04-01

Full Text Available This paper reviews the influence of alloying elements Mo, Nb, Ta and Ni on glass formation and corrosion resistance of Cu-based bulk metallic glasses (BMGs. In order to obtain basic knowledge for application to the industry, corrosion resistance of the Cu–Hf–Ti–(Mo, Nb, Ta, Ni and Cu–Zr–Ag–Al–(Nb bulk glassy alloy systems in various solutions are reported in this work. Moreover, X-ray photoelectron spectroscopy (XPS analysis is performed to clarify the surface-related chemical characteristics of the alloy before and after immersion in the solutions; this has lead to a better understanding of the correlation between the surface composition and the corrosion resistance.

The influence of Zr substitution for Nb on the corrosion behaviors of the Ni-Nb-Zr bulk metallic glasses

Science.gov (United States)

Li, DengKe; Zhu, ZhengWang; Zhang, HaiFeng; Wang, AiMin; Hu, ZhuangQi

2012-12-01

The influence of Zr content on corrosion behaviors of the Ni61.5Nb38.5- x Zr x ( x=1, 3, 5, 7, 9 at.%) bulk metallic glasses (BMGs) in 1 M HCl aqueous solution was investigated by potentiodynamic polarization measurements and X-ray photo-electron spectroscopy (XPS). It was found that these BMG alloys possess superior corrosion resistance, that is, with large passive region of about 1.5 V and low passive current density (as low as 0.05 Am-2 for Ni61.5Nb31.5Zr7). XPS analysis indicates that the high corrosion resistance is attributed to the formation of Nb- and Zr-enriched surface films formed in the aggressive acid solution. The Zr substitution for Nb effectively reduces the Ni content, particularly the metallic state Ni content in the surface films, which depresses the electrical conduction of the surface films and reduces the passive current density, thus leading to the enhancement of the corrosion resistance of these Ni-Nb-Zr BMGs. These alloys may potentially be useful for engineering applications.

Recorded corrosion rates on copper electrodes in the Prototype Repository at the Aespoe HRL

Energy Technology Data Exchange (ETDEWEB)

Rosborg, Bo [Rosborg Consulting, Nykoeping (Sweden)

2013-04-15

Real-time corrosion monitoring by means of electrochemical methods has been applied in an effort to measure corrosion rates of pure copper in the Prototype Repository at the Aspo Hard Rock Laboratory. Copper electrodes were installed in bentonite blocks on top of the electrically heated copper canisters in two deposition holes (dh). Three nominally identical cylindrical copper electrodes were installed in dh 1 and another three in dh 5 a few days before the heat was turned on to the canisters in September 2001 and in May 2003 respectively. The temperature of the copper electrodes has been around 30 deg C in dh 1 and somewhat below 35 deg C in dh 5. Real-time corrosion monitoring for both electrode setups was first applied in January 2004, and then periodically in 2005, 2006, 2008, and most recently in the end of 2010 just before work to open the outer section of the Prototype Repository was started. The recorded corrosion rates fall below 1.3 {mu}m/year (using a default value of n=2 in the software to convert the corrosion current density to a penetration rate by means of Faraday's law, and with no correction applied for the used measuring frequency of 0.01 Hz; also disregarding highly scattered data obtained for the copper electrodes in dh 1 during 2010). While the recorded rates on the electrodes in dh 5 first increased from about 0.2 {mu}m/year in 2004 up to a maximum of 1.3 {mu}m/year a year later (the drainage of the inner and outer sections was temporary closed in the end of 2004), and then gradually decreased to 0.7 {mu}m/year in the end of 2010, the recorded rates on the electrodes in dh 1 show a quite different picture. The recorded rates fall in the range 0.4-0.7 {mu}m/year and do not reflect any obvious decrease. However, it is anticipated that a similar time dependence as observed for the electrodes in dh 5 could have been present early on in the exposure; the electrodes were installed in 2001 but the first measurements were performed in 2004. Also

Recorded corrosion rates on copper electrodes in the Prototype Repository at the Aespoe HRL

International Nuclear Information System (INIS)

Rosborg, Bo

2013-04-01

Real-time corrosion monitoring by means of electrochemical methods has been applied in an effort to measure corrosion rates of pure copper in the Prototype Repository at the Aspo Hard Rock Laboratory. Copper electrodes were installed in bentonite blocks on top of the electrically heated copper canisters in two deposition holes (dh). Three nominally identical cylindrical copper electrodes were installed in dh 1 and another three in dh 5 a few days before the heat was turned on to the canisters in September 2001 and in May 2003 respectively. The temperature of the copper electrodes has been around 30 deg C in dh 1 and somewhat below 35 deg C in dh 5. Real-time corrosion monitoring for both electrode setups was first applied in January 2004, and then periodically in 2005, 2006, 2008, and most recently in the end of 2010 just before work to open the outer section of the Prototype Repository was started. The recorded corrosion rates fall below 1.3 μm/year (using a default value of n=2 in the software to convert the corrosion current density to a penetration rate by means of Faraday's law, and with no correction applied for the used measuring frequency of 0.01 Hz; also disregarding highly scattered data obtained for the copper electrodes in dh 1 during 2010). While the recorded rates on the electrodes in dh 5 first increased from about 0.2 μm/year in 2004 up to a maximum of 1.3 μm/year a year later (the drainage of the inner and outer sections was temporary closed in the end of 2004), and then gradually decreased to 0.7 μm/year in the end of 2010, the recorded rates on the electrodes in dh 1 show a quite different picture. The recorded rates fall in the range 0.4-0.7 μm/year and do not reflect any obvious decrease. However, it is anticipated that a similar time dependence as observed for the electrodes in dh 5 could have been present early on in the exposure; the electrodes were installed in 2001 but the first measurements were performed in 2004. Also, saturation of

R7T7 glass alteration in the presence of mortar: effect of the cement grade

International Nuclear Information System (INIS)

Andriambololona, Z.; Godon, N.; Vernaz, E.

1991-01-01

R7T7 glass alteration was investigated in the presence of four mortars prepared from four different cement grades: 'CPA' Portland cement (mortar M1), CPA with pozzolana additive (M2), CPA with amorphous silica additive (M3) and 'CLK' blast furnace slag cement (M4). Glass specimens were also altered in Volvic mineral water and in a cement effluent. Glass corrosion in the cement media was greater than in Volvic water, but well below what could be expected from the high pH (approx 12.5). The relatively low alteration was probably related to the protective action of the calcium-enriched gel layer that formed at the glass surface. The glass corrosion rate was 2 to 3 times lower with cement containing pozzolana or silica gel additives or with CLK cement than with CPA cement alone. 8 refs., 8 figs

Physicochemical properties and long-term behavior of french R7T7 nuclear waste glass

International Nuclear Information System (INIS)

Vernaz, E.

1990-01-01

The French R7T7 nuclear glass composition was carefully selected to allow incorporation of some thirty different oxides found in fission product solutions. The resulting glass exhibits very low crystallization, and its physical and chemical properties are very similar to those of standard industrial glasses. Nuclear glasses have been shown to withstand α doses corresponding to several hundred thousand years under repository conditions. Predicting the long-term behavior of fission product glasses subjected to aqueous corrosion is no doubt the most difficult aspect of the problem. Predictions are necessarily based on mathematical models. A substantial research effort has been undertaken to identify all the basic corrosion mechanisms liable to control long-term alteration. These mechanisms are now relatively well understood, and provide the basis for developing the indispensable models. Realistic storage conditions exist under which glass alteration occurs at a very slow rate, and can fulfill its role as the first containment barrier for several tens of thousands of years

Volatile amines treatment: Corrosion rates and Atucha I nuclear power plant experience

International Nuclear Information System (INIS)

Iglesias, Alberto M.; Jimenez Rebagliati, Raul; Raffo Calderon, Maria C.; Manzi, Ricardo

2000-01-01

Steam generators water treatment with volatile amines in place of ammonia is usual today. This option seems an acceptable alternative to the generalize use of ammonia-sodium phosphate and has advantages when copper alloys are present. There are several amines that can work as corrosion inhibitor but the most useful for plant applications are: morpholine, ethanolamine and cyclohexylamine. In this work, are present the obtained results of corrosion rates measurements by electrochemical methods. The hydrothermal conditions of our experiences were similar to that of the Atucha I nuclear power plant (CNA I). pH, conductivity and dissolved oxygen measures were correlated with corrosion rates of the CNA I materials as carbon steel and admiralty brass. The faradaic impedance spectroscopy techniques allows a more detailed interpretation of corrosion rates process. Morpholine and ammonia behavior can be evaluated under power plant operations conditions with the accumulated experience of CNA I. Results are present throughout material release and his effects over heat transfer parameters. (author)

Water leaching of borosilicate glasses: experiments, modeling and Monte Carlo simulations; Alteration par l'eau des verres borosilicates: experiences, modelisation et simulations Monte Carlo

Energy Technology Data Exchange (ETDEWEB)

Ledieu, A

2004-10-15

This work is concerned with the corrosion of borosilicate glasses with variable oxide contents. The originality of this study is the complementary use of experiments and numerical simulations. This study is expected to contribute to a better understanding of the corrosion of nuclear waste confinement glasses. First, the corrosion of glasses containing only silicon, boron and sodium oxides has been studied. The kinetics of leaching show that the rate of leaching and the final degree of corrosion sharply depend on the boron content through a percolation mechanism. For some glass contents and some conditions of leaching, the layer which appears at the glass surface stops the release of soluble species (boron and sodium). This altered layer (also called the gel layer) has been characterized with nuclear magnetic resonance (NMR) and small angle X-ray scattering (SAXS) techniques. Second, additional elements have been included in the glass composition. It appears that calcium, zirconium or aluminum oxides strongly modify the final degree of corrosion so that the percolation properties of the boron sub-network is no more a sufficient explanation to account for the behavior of these glasses. Meanwhile, we have developed a theoretical model, based on the dissolution and the reprecipitation of the silicon. Kinetic Monte Carlo simulations have been used in order to test several concepts such as the boron percolation, the local reactivity of weakly soluble elements and the restructuring of the gel layer. This model has been fully validated by comparison with the results on the three oxide glasses. Then, it has been used as a comprehensive tool to investigate the paradoxical behavior of the aluminum and zirconium glasses: although these elements slow down the corrosion kinetics, they lead to a deeper final degree of corrosion. The main contribution of this work is that the final degree of corrosion of borosilicate glasses results from the competition of two opposite mechanisms

Glass compositions suitable for PFR wastes

International Nuclear Information System (INIS)

Boult, K.A.; Dalton, J.T.; Eccles, E.W.; Hough, A.; Marples, J.A.C.; Paige, E.L.; Sutcliffe, P.W.

1988-03-01

Previous work had identified glass compositions that were suitable for vitrifying current and future high level wastes from the Prototype Fast Reactor (PFR) fuel reprocessing plant. Further work on these glasses has shown that: a) Foaming and crystallisation can occur under certain conditions, both probably associated with the presence of iron in the waste. Either of these could lead to greater difficulties in processing. b) Inconel 690, the preferred JCM (Joule-heated Ceramic Melter) electrode material has an acceptable corrosion rate at 1200 0 C: ca 0.6mm.y -1 . c) The leach rates are unaffected by radiation damage. The density of the glass decreases slightly with α-dose, with a dependency that extrapolates, at infinite time, to an 0.13% linear expansion. d) The concentrations of the radiologically important elements Tc, Np, Pu and Am, observed in a 'repository simulation' leach test, were satisfactorily low. (author)

Determination of alpha dose rate profile at the HLW nuclear glass/water interface

Energy Technology Data Exchange (ETDEWEB)

Mougnaud, S., E-mail: sarah.mougnaud@cea.fr [CEA Marcoule, DEN/DTCD/SECM, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Tribet, M.; Rolland, S. [CEA Marcoule, DEN/DTCD/SECM, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Renault, J.-P. [CEA Saclay, NIMBE UMR 3685 CEA/CNRS, 91191 Gif-sur-Yvette cedex (France); Jégou, C. [CEA Marcoule, DEN/DTCD/SECM, BP 17171, 30207 Bagnols-sur-Cèze cedex (France)

2015-07-15

Highlights: • The nuclear glass/water interface is studied. • The way the energy of alpha particles is deposited is modeled using MCNPX code. • A model giving dose rate profiles at the interface using intrinsic data is proposed. • Bulk dose rate is a majoring estimation in alteration layer and in surrounding water. • Dose rate is high in small cracks; in larger ones irradiated volume is negligible. - Abstract: Alpha irradiation and radiolysis can affect the alteration behavior of High Level Waste (HLW) nuclear glasses. In this study, the way the energy of alpha particles, emitted by a typical HLW glass, is deposited in water at the glass/water interface is investigated, with the aim of better characterizing the dose deposition at the glass/water interface during water-induced leaching mechanisms. A simplified chemical composition was considered for the nuclear glass under study, wherein the dose rate is about 140 Gy/h. The MCNPX calculation code was used to calculate alpha dose rate and alpha particle flux profiles at the glass/water interface in different systems: a single glass grain in water, a glass powder in water and a water-filled ideal crack in a glass package. Dose rate decreases within glass and in water as distance to the center of the grain increases. A general model has been proposed to fit a dose rate profile in water and in glass from values for dose rate in glass bulk, alpha range in water and linear energy transfer considerations. The glass powder simulation showed that there was systematic overlapping of radiation fields for neighboring glass grains, but the water dose rate always remained lower than the bulk value. Finally, for typical ideal cracks in a glass matrix, an overlapping of irradiation fields was observed while the crack aperture was lower than twice the alpha range in water. This led to significant values for the alpha dose rate within the crack volume, as long as the aperture remained lower than 60 μm.

Long-term product consistency test of simulated 90-19/Nd HLW glass

International Nuclear Information System (INIS)

Gan, X.Y.; Zhang, Z.T.; Yuan, W.Y.; Wang, L.; Bai, Y.; Ma, H.

2011-01-01

Chemical durability of 90-19/Nd glass, a simulated high-level waste (HLW) glass in contact with the groundwater was investigated with a long-term product consistency test (PCT). Generally, it is difficult to observe the long term property of HLW glass due to the slow corrosion rate in a mild condition. In order to overcome this problem, increased contacting surface (S/V = 6000 m -1 ) and elevated temperature (150 o C) were employed to accelerate the glass corrosion evolution. The micro-morphological characteristics of the glass surface and the secondary minerals formed after the glass alteration were analyzed by SEM-EDS and XRD, and concentrations of elements in the leaching solution were determined by ICP-AES. In our experiments, two types of minerals, which have great impact on glass dissolution, were found to form on 90-19/Nd HLW glass surface when it was subjected to a long-term leaching in the groundwater. One is Mg-Fe-rich phyllosilicates with honeycomb structure; the other is aluminosilicates (zeolites). Mg and Fe in the leaching solution participated in the formation of phyllosilicates. The main components of phyllosilicates in alteration products of 90-19/Nd HLW glass are nontronite (Na 0.3 Fe 2 Si 4 O 10 (OH) 2 .4H 2 O) and montmorillonite (Ca 0.2 (Al,Mg) 2 Si 4 O 10 (OH) 2 .4H 2 O), and those of aluminosilicates are mordenite ((Na 2 ,K 2 ,Ca)Al 2 Si 10 O 24 .7H 2 O)) and clinoptilolite ((Na,K,Ca) 5 Al 6 Si 30 O 72 .18H 2 O). Minerals like Ca(Mg)SO 4 and CaCO 3 with low solubility limits are prone to form precipitant on the glass surface. Appearance of the phyllosilicates and aluminosilicates result in the dissolution rate of 90-19/Nd HLW glass resumed, which is increased by several times over the stable rate. As further dissolution of the glass, both B and Na in the glass were found to leach out in borax form.

Corrosion test plan to guide canister material selection and design for a tuff repository

International Nuclear Information System (INIS)

McCright, R.D.; van Konynenburg, R.A.; Ballou, L.B.

1983-11-01

Corrosion rates and the mode of corrosion attack form a most important basis for selection of canister materials and design of a nuclear waste package. Type 304L stainless steel was selected as the reference material for canister fabrication because of its generally excellent corrosion resistance in water, steam and air. However, 304L may be susceptible to localized and stress-assisted forms of corrosion under certain conditions. Alternative alloys are also investigated; these alloys were chosen because of their improved resistance to these forms of corrosion. The fabrication and welding processes, as well as the glass pouring operation for defense and commercial high-level wastes, may influence the susceptibility of the canister to localized and stress forms of corrosion. 12 references, 2 figures, 4 tables

Dynamic fatigue of a machinable glass-ceramic

Science.gov (United States)

Smyth, K. K.; Magida, M. B.

1983-01-01

To assess the stress-corrosion susceptibility of a machinable glass-ceramic, its dynamic fatigue behavior was investigated by measuring its strength as a function of stress rate. Fracture mechanics techniques were used to analyze the results for the purpose of making lifetime predictions for components of this material. This material was concluded to have only moderate resistance (N = 30) to stress corrosion in ambient conditions. The effects of specimen size on strength were assessed for the material used in this study; it was concluded that the Weibull edge-flaw scaling law adequately describes the observed strength-size relation.

Water leaching of borosilicate glasses: experiments, modeling and Monte Carlo simulations; Alteration par l'eau des verres borosilicates: experiences, modelisation et simulations Monte Carlo

Energy Technology Data Exchange (ETDEWEB)

Ledieu, A

2004-10-15

This work is concerned with the corrosion of borosilicate glasses with variable oxide contents. The originality of this study is the complementary use of experiments and numerical simulations. This study is expected to contribute to a better understanding of the corrosion of nuclear waste confinement glasses. First, the corrosion of glasses containing only silicon, boron and sodium oxides has been studied. The kinetics of leaching show that the rate of leaching and the final degree of corrosion sharply depend on the boron content through a percolation mechanism. For some glass contents and some conditions of leaching, the layer which appears at the glass surface stops the release of soluble species (boron and sodium). This altered layer (also called the gel layer) has been characterized with nuclear magnetic resonance (NMR) and small angle X-ray scattering (SAXS) techniques. Second, additional elements have been included in the glass composition. It appears that calcium, zirconium or aluminum oxides strongly modify the final degree of corrosion so that the percolation properties of the boron sub-network is no more a sufficient explanation to account for the behavior of these glasses. Meanwhile, we have developed a theoretical model, based on the dissolution and the reprecipitation of the silicon. Kinetic Monte Carlo simulations have been used in order to test several concepts such as the boron percolation, the local reactivity of weakly soluble elements and the restructuring of the gel layer. This model has been fully validated by comparison with the results on the three oxide glasses. Then, it has been used as a comprehensive tool to investigate the paradoxical behavior of the aluminum and zirconium glasses: although these elements slow down the corrosion kinetics, they lead to a deeper final degree of corrosion. The main contribution of this work is that the final degree of corrosion of borosilicate glasses results from the competition of two opposite mechanisms

Effect of Callovo-Oxfordian clay rock on the dissolution rate of the SON68 simulated nuclear waste glass

Energy Technology Data Exchange (ETDEWEB)

Neeway, James J., E-mail: James.Neeway@pnnl.gov [SUBATECH, Unité Mixte de Recherche 6457, École des Mines de Nantes, CNRS/IN2P3, Université de Nantes, BP 20722, 44307 Nantes cedex 3 (France); Abdelouas, Abdesselam; Ribet, Solange; El Mendili, Yassine [SUBATECH, Unité Mixte de Recherche 6457, École des Mines de Nantes, CNRS/IN2P3, Université de Nantes, BP 20722, 44307 Nantes cedex 3 (France); Schumacher, Stéphan [ANDRA, Parc de la Croix Blanche, 1/7 rue Jean Monnet, 92298 Châtenay-Malabry (France); Grambow, Bernd [SUBATECH, Unité Mixte de Recherche 6457, École des Mines de Nantes, CNRS/IN2P3, Université de Nantes, BP 20722, 44307 Nantes cedex 3 (France)

2015-04-15

Long-term storage of high-level nuclear waste glass in France is expected to occur in an engineered barrier system (EBS) located in a subsurface Callovo-Oxfordian (COx) clay rock formation in the Paris Basin in northeastern France. Understanding the behavior of glass dissolution in the complex system is critical to be able to reliably model the performance of the glass in this complex environment. To simulate this multi-barrier repository scenario in the laboratory, several tests have been performed to measure glass dissolution rates of the simulated high-level nuclear waste glass, SON68, in the presence of COx claystone at 90 °C. Experiments utilized a High-Performance Liquid Chromatography (HPLC) pump to pass simulated Bure site COx pore water through a reaction cell containing SON68 placed between two COx claystone cores for durations up to 200 days. Silicon concentrations at the outlet were similar in all experiments, even the blank experiment with only the COx claystone (∼4 mg/L at 25 °C and ∼15 mg/L at 90 °C). The steady-state pH of the effluent, measured at room temperature, was roughly 7.1 for the blank and 7.3–7.6 for the glass-containing experiments demonstrating the pH buffering capacity of the COx claystone. Dissolution rates for SON68 in the presence of the claystone were elevated compared to those obtained from flow-through experiments conducted with SON68 without claystone in silica-saturated solutions at the same temperature and similar pH values. Additionally, through surface examination of the monoliths, the side of the monolith in direct contact with the claystone was seen to have a corrosion thickness 2.5× greater than the side in contact with the bulk glass powder. Results from one experiment containing {sup 32}Si-doped SON68 also suggest that the movement of Si through the claystone is controlled by a chemically coupled transport with a Si retention factor, K{sub d}, of 900 mL/g.

Systems approach to nuclear waste glass development

International Nuclear Information System (INIS)

Jantzen, C.M.

1986-01-01

Development of a host solid for the immobilization of nuclear waste has focused on various vitreous wasteforms. The systems approach requires that parameters affecting product performance and processing be considered simultaneously. Application of the systems approach indicates that borosilicate glasses are, overall, the most suitable glasses for the immobilization of nuclear waste. Phosphate glasses are highly durable; but the glass melts are highly corrosive and the glasses have poor thermal stability and low solubility for many waste components. High-silica glasses have good chemical durability, thermal stability, and mechanical stability, but the associated high melting temperatures increase volatilization of hazardous species in the waste. Borosilicate glasses are chemically durable and are stable both thermally and mechanically. The borosilicate melts are generally less corrosive than commercial glasses, and the melt temperature miimizes excessive volatility of hazardous species. Optimization of borosilicate waste glass formulations has led to their acceptance as the reference nuclear wasteform in the United States, United Kingdom, Belgium, Germany, France, Sweden, Switzerland, and Japan

When can Electrochemical Techniques give Reliable Corrosion Rates on Carbon Steel in Sulfide Media?

DEFF Research Database (Denmark)

Hilbert, Lisbeth Rischel; Hemmingsen, Tor; Nielsen, Lars Vendelbo

2005-01-01

in combination with ferrous sulfide corrosion products cover the steel surface. Corrosion rates can be overestimated by a factor of 10 to 100 with electrochemical techniques - both by linear polarization resistance (LPR) and electrochemical impedance spectroscopy (EIS). Oxygen entering the system accelerates......Effects of film formation on carbon steel in hydrogen sulfide media may corrupt corrosion rate monitoring by electrochemical techniques. Electrochemical data from hydrogen sulfide solutions, biological sulfide media and natural sulfide containing geothermal water have been collected and the process...... of film formation in sulfide solutions was followed by video. It can be shown that capacitative and diffusional effects due to porous reactive deposits tend to dominate the data resulting in unreliable corrosion rates measured by electrochemical techniques. The effect is strongly increased if biofilm...

The long-term corrosion of glass by ground-water

International Nuclear Information System (INIS)

Cox, G.A.; Ford, B.A.

1993-01-01

Specimens of corroded soda and potash glasses, which had been exposed to groundwater for periods of up to about 1650 years, have been physically and chemically analysed. The morphology and compositional profiles of their finely laminated weathering crusts were determined by scanning electron microscopy and electron-probe microanalysis. It is shown that the surface layers on all specimens are depleted, to varying extents, of their principal constituents, with the exception of Si, Al and Fe. X-ray and electron diffraction studies have revealed the (tentative) identities of complex, poorly crystalline silicates and aluminosilicates within the largely amorphous crusts on potash glasses. The mean thickness of the crusts was found to correlate well with the free energy of hydration, ΔG o , of the pristine glasses. The rate of layer formation on the most durable specimens (ΔG o ∼ -15 kJ mol -1 ) was about 4 x 10 -3 μm year -1 . Deposits of calcite, calcium phosphate and manganese rich minerals occurred within the crusts; they were largely of external origin. Thus, in addition to the composition of the glass, the geochemistry of the local groundwater plays a decisive role in determining the identity of the compounds present within the weathering crusts. (author)

Corrosion resistance of metal materials for HLW canister

International Nuclear Information System (INIS)

Furuya, Takashi; Muraoka, Susumu; Tashiro, Shingo

1982-02-01

In order to verify the materials as an important artificial barrier for canister of vitrified high-level waste from spent fuel reprocessing, data and reports were researched on corrosion resistance of the materials under conditions from glass form production to final disposal. Then, in this report, investigated subjects, improvement methods and future subjects are reviewed. It has become clear that there would be no problem on the inside and outside corrosion of the canister during glass production, but long term corrosion and radiation effect tests and the vitrification methods would be subjects in future on interim storage and final disposal conditions. (author)

The corrosion rate of copper in a bentonite test package measured with electric resistance sensors

Energy Technology Data Exchange (ETDEWEB)

Rosborg, Bo [Division of Surface and Corrosion Science, KTH, Stockholm (Sweden); Kosec, Tadeja; Kranjc, Andrej; Kuhar, Viljem; Legat, Andraz [Slovenian National Building and Civil Engineering Institute, Ljubljana (Slovenia)

2012-12-15

LOT1 test parcel A2 was exposed for six years in the Aespoe Hard Rock Laboratory, which offers a realistic environment for the conditions that will prevail in a deep repository for high-level radioactive waste disposal in Sweden. The test parcel contained copper electrodes for real-time corrosion monitoring in bentonite ring 36, where the temperature was 24 deg C, and copper coupons in bentonite rings 22 and 30, where the temperature was higher. After retrieval of the test parcel in January 2006, a bentonite test package consisting of bentonite rings 35 - 37 was placed in a container and sealed with a thick layer of paraffin. Later the same year new copper electrodes were installed in the test package. In January 2007 electric resistance (ER) sensors of pure copper with a thickness of 35 {mu}m were also installed in the test package mainly to facilitate the interpretation of the results from the real-time corrosion monitoring with electrochemical techniques. The ER measurements have shown that the corrosion rate of pure copper exposed in an oxic bentonite/ saline groundwater environment at room temperate decreases slowly with time to low but measurable values. The corrosion rates estimated from the regularly performed EIS measurements replicate the ER data. Thus, for this oxic environment in which copper acquires corrosion potentials of the order of 200 mV (SHE) or higher, electrochemical measurements provide believable data. Comparing the recorded ER data with an estimate of the average corrosion rate based on comparing cross-sections from exposed and protected sensor elements, it is obvious that the former overestimates the actual corrosion rate, which is understandable. It seems as if electrochemical measurements can provide a better estimate of the corrosion rate; however, this is quite dependent on the use of proper measuring frequencies and evaluation methods. In this respect ER measurements are more reliable. It has been shown that real-time corrosion

The corrosion rate of copper in a bentonite test package measured with electric resistance sensors

International Nuclear Information System (INIS)

Rosborg, Bo; Kosec, Tadeja; Kranjc, Andrej; Kuhar, Viljem; Legat, Andraz

2012-12-01

LOT1 test parcel A2 was exposed for six years in the Aespoe Hard Rock Laboratory, which offers a realistic environment for the conditions that will prevail in a deep repository for high-level radioactive waste disposal in Sweden. The test parcel contained copper electrodes for real-time corrosion monitoring in bentonite ring 36, where the temperature was 24 deg C, and copper coupons in bentonite rings 22 and 30, where the temperature was higher. After retrieval of the test parcel in January 2006, a bentonite test package consisting of bentonite rings 35 - 37 was placed in a container and sealed with a thick layer of paraffin. Later the same year new copper electrodes were installed in the test package. In January 2007 electric resistance (ER) sensors of pure copper with a thickness of 35 μm were also installed in the test package mainly to facilitate the interpretation of the results from the real-time corrosion monitoring with electrochemical techniques. The ER measurements have shown that the corrosion rate of pure copper exposed in an oxic bentonite/ saline groundwater environment at room temperate decreases slowly with time to low but measurable values. The corrosion rates estimated from the regularly performed EIS measurements replicate the ER data. Thus, for this oxic environment in which copper acquires corrosion potentials of the order of 200 mV (SHE) or higher, electrochemical measurements provide believable data. Comparing the recorded ER data with an estimate of the average corrosion rate based on comparing cross-sections from exposed and protected sensor elements, it is obvious that the former overestimates the actual corrosion rate, which is understandable. It seems as if electrochemical measurements can provide a better estimate of the corrosion rate; however, this is quite dependent on the use of proper measuring frequencies and evaluation methods. In this respect ER measurements are more reliable. It has been shown that real-time corrosion

NDT method in determining the rate of corrosion applicable to risk based inspection

International Nuclear Information System (INIS)

Mohamed Hairul Hasmoni; Mohamad Pauzi Ismail; Ab Razak Hamzah

2004-01-01

Corrosion is a major problem in oil and gas industries, refineries and chemical process plants as the equipment is often exposed to corrosive environments or elevated temperature. Important equipment need to operate safely and reliably to avoid injuries to personnel and the public, and to prevent loss time and cost incurred due to loss of production and shutdown. The paper assess the approach in evaluating the technique of non-destructive testing (NDT) using Ultrasonic Testing (UT) in determining the rate of corrosion and remaining life of equipment applicable to Risk Based Inspection (RBI). Methods in determining the corrosion rate are presented using analytical method. Examples and data from MINT chiller water pipeline are presented to illustrate the application of these methods. (Author)

Integrated modelling of the glass-iron-clay system

International Nuclear Information System (INIS)

Bildstein, O.

2007-01-01

This report summarizes the results of integrated calculations on the near-field evolution in the VHLW/steel/bentonite/clay system. The calculations of the near-field evolution include different components: the vitrified waste packages, the steel container, the bentonite-based EBS (optional), the EDZ and the geological medium. Coupled reaction-transport (X-T) is used to simulate the corrosion of the steel canister and the glass alteration phase in presence of corrosion products (CPs), looking at mass transfer for chemical elements, especially iron and silica, pH, and porosity change. Calculations as performed give actual parameters for PA calculations: rate of glass alteration (through the calculated pH) as a function of time, extension of altered zone for iron-clay interactions with their own transport parameters, nature of CPs, effect on porosity distribution. According to the operational model currently used at the CEA and the calculations performed on the glass-iron-clay system, the alteration rate of glass and the evolution of the system strongly depend on the timing of CPs saturation with respect to silica sorption. The fate of silica which can be sorbed or precipitate is crucial to the lifetime of glass and to the overall evolution of the system. The other process that might influence the glass is the porosity decrease due to the precipitation of CPs and silica rich phases. However, it is difficult to assign a safety functions to clogging. It is scarcely observed in experiments, either because the conditions are not met for clogging or because the timescale of experiments does not allow for observable clogging. Moreover, the effect of mechanical stress in the NF has to be accounted for in the assessment of the effect of porosity changes. (author)

Integrated modelling of the glass-iron-clay system

Energy Technology Data Exchange (ETDEWEB)

Bildstein, O

2007-01-15

This report summarizes the results of integrated calculations on the near-field evolution in the VHLW/steel/bentonite/clay system. The calculations of the near-field evolution include different components: the vitrified waste packages, the steel container, the bentonite-based EBS (optional), the EDZ and the geological medium. Coupled reaction-transport (X-T) is used to simulate the corrosion of the steel canister and the glass alteration phase in presence of corrosion products (CPs), looking at mass transfer for chemical elements, especially iron and silica, pH, and porosity change. Calculations as performed give actual parameters for PA calculations: rate of glass alteration (through the calculated pH) as a function of time, extension of altered zone for iron-clay interactions with their own transport parameters, nature of CPs, effect on porosity distribution. According to the operational model currently used at the CEA and the calculations performed on the glass-iron-clay system, the alteration rate of glass and the evolution of the system strongly depend on the timing of CPs saturation with respect to silica sorption. The fate of silica which can be sorbed or precipitate is crucial to the lifetime of glass and to the overall evolution of the system. The other process that might influence the glass is the porosity decrease due to the precipitation of CPs and silica rich phases. However, it is difficult to assign a safety functions to clogging. It is scarcely observed in experiments, either because the conditions are not met for clogging or because the timescale of experiments does not allow for observable clogging. Moreover, the effect of mechanical stress in the NF has to be accounted for in the assessment of the effect of porosity changes. (author)

Reliability of Electrochemical Techniques for Determining Corrosion Rates on Carbon Steel in Sulfide Media

DEFF Research Database (Denmark)

Hilbert, Lisbeth Rischel; Hemmingsen, T.; Nielsen, Lars Vendelbo

2007-01-01

if the biofilm in combination with ferrous sulfide corrosion products cover the steel surface. Corrosion rates can be overestimated by a factor of 10 to 100 with electrochemical techniques - both by linear polarization resistance (LPR) and electrochemicel impedance spectroscopy (EIS). Oxygen entering the system......Effects of film formation on carbon steel in hydrogen sulfide (H2S) media may corrupt corrosion rate monitoring by electrochemical techniques. Electrochemical data from H2S solutions, biological sulfide media, and natural sulfide containing geothermal water have been collected, and the process...... of film formation in sulfide solutins was followed by video. It can be shown that capacitative and diffusional effects due to porous reactive deposits tend to dominate the data, resulting in unreliable corrosion rates measured using electrochemical techniques. The effect is strongly increased...

Elevated corrosion rates and hydrogen sulfide in homes with ‘Chinese Drywall’

International Nuclear Information System (INIS)

Allen, Joseph G.; MacIntosh, David L.; Saltzman, Lori E.; Baker, Brian J.; Matheson, Joanna M.; Recht, Joel R.; Minegishi, Taeko; Fragala, Matt A.; Myatt, Theodore A.; Spengler, John D.; Stewart, James H.; McCarthy, John F.

2012-01-01

In December 2008, the U.S. Consumer Product Safety Commission (CPSC) began receiving reports about odors, corrosion, and health concerns related to drywall originating from China. In response, a detailed environmental health and engineering evaluation was conducted of 41 complaint and 10 non-complaint homes in the Southeast U.S. Each home investigation included characterization of: 1) drywall composition; 2) indoor and outdoor air quality; 3) temperature, moisture, and building ventilation; and 4) copper and silver corrosion rates. Complaint homes had significantly higher hydrogen sulfide concentrations (mean 0.82 vs. 3 , p 2 S: 476 vs. 2 S: 1472 vs. 389 Å/30 d, p < 0.01). The abundance of carbonate and strontium in drywall was also elevated in complaint homes, and appears to be useful objective marker of problematic drywall in homes that meet other screening criteria (e.g., constructed or renovated in 2006–2007, reports of malodor and accelerated corrosion). This research provides empirical evidence of the direct association between homes constructed with ‘Chinese Drywall’ in 2006–2007 and elevated corrosion rates and hydrogen sulfide concentrations in indoor air. - Highlights: ► Environmental measurements in homes with and without “Chinese Drywall” ► Homes with “Chinese Drywall” had higher hydrogen sulfide concentrations ► Homes with “Chinese Drywall” had elevated corrosion rates ► Study provides empirical evidence of reported associations

The Secant Rate of Corrosion: Correlating Observations of the USS Arizona Submerged in Pearl Harbor

Science.gov (United States)

Johnson, Donald L.; DeAngelis, Robert J.; Medlin, Dana J.; Johnson, Jon E.; Carr, James D.; Conlin, David L.

2018-03-01

Contrary to previous linear projections of steel corrosion in seawater, analysis of an inert marker embedded in USS Arizona concretion since the 7 December 1941 attack on Pearl Harbor reveals evidence that the effective corrosion rate decreases with time. The secant rate of corrosion, or SRC correlation, derived from this discovery could have a significant impact on failure analysis investigations for concreted shipwrecks or underwater structures. The correlation yields a lower rate of metal thinning than predicted. Development of the correlation is described.

Relationship between the shear viscosity and heating rate in metallic glasses below the glass transition

International Nuclear Information System (INIS)

Khonik, Vitaly A.; Kobelev, N. P.

2008-01-01

It has been shown that first-order irreversible structural relaxation with distributed activation energies must lead to a linear decrease of the logarithm of Newtonian shear viscosity with the logarithm of heating rate upon linear heating of glass. Such a behavior is indeed observed in the experiments on metallic glasses. Structural relaxation-induced viscous flow leads to infra-low-frequency Maxwell viscoelastic internal friction, which is predicted to increase with the heating rate

Constraints on the affinity term for modeling long-term glass dissolution rates

International Nuclear Information System (INIS)

Bourcier, W.L.; Carroll, S.A.; Phillips, B.L.

1993-11-01

Predictions of long-term glass dissolution rates are highly dependent on the form of the affinity term in the rate expression. Analysis of the quantitative effect of saturation state on glass dissolution rate for CSG glass (a simple analog of SRL-165 glass), shows that a simple (1-Q/K) affinity term does not match experimental results. Our data at 100 degree C show that the data is better fit by an affinity term having the form (1 - (Q/K) 1 /σ) where σ = 10

Chemistry and kinetics of waste glass corrosion

International Nuclear Information System (INIS)

Bates, J.K.

1996-01-01

Under repository disposal conditions, the reaction of glass with water comprises the source term for release of radionuclides to the near-field environment. An understanding of glass reaction and the manner by which radionuclides are released is needed to design the waste package and to evaluate the total performance of the repository. The ASTM Standard C-1174-91 provides a general methodology for obtaining information related to the behavior of glass. This paper reviews the application of this standard to glass reaction. In the first step in the ASTM approach, the researcher identifies the materials and the conditions under which the long-term behavior is to be determined. Glass compositions have undergone a genesis over the past 15 years in response to concerns about feed streams, processing, and durability. A range of borosilicate compositions has been identified, but as new applications for vitrification occur, for example, immobilization of weapons plutonium and residue from plutonium processing, different compositions must be evaluated. The repository environment depends on the spatial emplacement of waste containers (glass and spent fuel), and both open-quotes hotclose quotes and open-quotes coldclose quotes scenarios have been proposed for the Yucca Mountain site. Regardless of the exact configuration, the near-field hydrology is expected to be unsaturated: that is, the waste packages are contacted initially by water vapor, and ultimately by small amounts of dripping or standing water. The behavior of glass can be studied as a function of composition within the constraints the environmental conditions place on the physical parameters that affect glass reaction (temperature, radiation field, groundwater composition, etc.). In the second step, the researcher reviews the literature and proposes a reaction pathway by which glass reacts in an unsaturated environment

Long-term leach rates of glasses containing actual waste

International Nuclear Information System (INIS)

Wiley, J.R.; LeRoy, J.H.

1979-01-01

Leach rates of borosilicate glasses that contained actual Savannah River Plant waste were measured. Leaching was done by water and by buffer solutions of pH 4, 7, and 9. Leach rates were then determined from the amount of 137 Cs, 90 Sr, and Pu released into the leach solutions. The cumulative fractions leached were fit to a mathematical model that included leaching by diffusion and glass dissolution

Long-term behavior of glass-ceramic zirconolite

International Nuclear Information System (INIS)

Martin, Ch.

2003-01-01

This work is a part of the investigation of new containment matrices considered for specific conditioning of radionuclides after separation. The aim was to demonstrate the long-term aqueous corrosion resistance of the glass-ceramic zirconolite considered for the conditioning of plutonium and the minor actinides. This material is composed of crystals of zirconolite (CaZrTi 2 O 7 ) dispersed in a residual vitreous phase. It appears that glass-ceramic zirconolite presents a better kinetic behavior than the nuclear glass R 7T7. This is mainly due to a more important rate decrease that occurs more rapidly, that induces a quantity of glass altered at least 10 times as small as for R 7T7 glass. This high slowdown of the alteration rate is attributed to the formation of an alteration film that has been the subject of a specific study. We have demonstrated that the rate decrease was controlled as for the R7T7 glass by the amorphous phase of the alteration film forming a diffusion barrier for reactive species. It seems that the porosity is not the single parameter that explains the protective effect of the gel. The main differences compared with R7T7 glass are that silicon does not control the alteration of the material and that the gel is composed of two distinct phases. We have in particular identified a dense phase enriched in titanium and neodymium that probably influences deeply the kinetics. (author)

In-situ monitoring of undercoating corrosion damage by Direct Optical Interrogation (DOI)

Science.gov (United States)

Lopez-Garrity, Meng

An approach referred to as "Direct Optical Interrogation" (DOI) has been developed as an extension of the thin film pitting approach developed and used by Frankel and others. Samples were prepared by depositing Al and Al-Cu alloy metallizations about 800 nm thick on glass substrates. These metallizations were then coated with various coatings and coating systems. Samples were introduced to aggressive environments and the progression of corrosion of the metallization under the coating was monitored in situ using low power videography. Because metallizations were thin, corrosion quickly penetrated through the metal layer to the glass substrate and then spread laterally. Measurement of the lateral spread of corrosion enabled non-electrochemical assessment of the corrosion kinetics. In Al-Cu thin films, both aged and as-deposited, corrosion sites are irregularly shaped because there is not enough cathodic current to propagate the entire corrosion site margin at equal rates. In a number of cases, corrosion propagates with a filamentary morphology resembling filiform corrosion. Cu played a strong role in determining under coating corrosion morphology and growth kinetics in experiments with Al-Cu thin films substrates. As-deposited Al-Cu metallizations were more corrosion resistant than aged metallization and both were more corrosion resistant than pure Al. Cu-rich dendrites were formed on the corrosion front. Corrosion rate (current density) was calculated using Faraday's law by collecting corrosion site perimeter and bottom area. Systematic exploration of the effects of a chromate and chromate-free conversion coatings, chromate and chromate-free primer coatings and the presence or absence of a polyurethane topcoat confirmed the extraordinary corrosion protection by chromates. A commercial praseodymium-pigmented primer coating was not particularly effective in retarding undercoating corrosion site growth unless paired with a chromate conversion coating. The presence of a

Glass microspheres for brachytherapy

International Nuclear Information System (INIS)

Prado, Miguel O.; Prastalo, Simon; Blaumann, Herman; Longhino, Juan M.; Repetto Llamazares, A.H.V.

2007-01-01

We developed the capacity to produce glass microspheres containing in their structure one or more radioactive isotopes useful for brachytherapy. We studied the various facts related with their production: (Rare earth) alumino silicate glass making, glass characterization, microspheres production, nuclear activation through (n,γ) nuclear reactions, mechanical characterization before and after irradiation. Corrosion tests in simulated human plasma and mechanical properties characterization were done before and after irradiation. (author) [es

A general model for the dissolution of nuclear waste glasses in salt brine

International Nuclear Information System (INIS)

McGrail, B.P.; Strachan, D.M.

1988-07-01

A mechanistic model describing a dynamic mass balance between the production and consumption of dissolved silica was found to describe the dissolution of SRL-165 defense waste glass in a high-magnesium (PBB3) brine at a temperature of 90/degree/C. The synergetic effect of the waste package container on the glass dissolution rate was found to depend on a precipitation reaction for a ferrous silicate mineral. The model predicted that the ferrous silicate precipitate should be variable in composition where the iron-silica ratio depended on the metal-to-glass surface area ratio used in the experiment. This prediction was confirmed experimentally by the variable iron-silica ratios observed in filtered leachates. However, the interaction between dissolved silica and iron corrosion products needs to be much better understood before the model could be used with confidence in predicting radionuclide release rates for a salt repository. If the deleterious effects of the iron corrosion products can be shown to be transient, and the fracturing of the glass can be minimized, it appears that the performance of SRL-165 defense waste glass will be near the NRC regulatory criterion for fraction release of one part in 100,000 in PBB3 brine at 90/degree/C under silica-saturated conditions. 47 refs., 6 figs., 1 tab

DETERMINATION OF HLW GLASS MELT RATE USING X-RAY COMPUTED TOMOGRAPHY

Energy Technology Data Exchange (ETDEWEB)

Choi, A.; Miller, D.; Immel, D.

2011-10-06

The purpose of the high-level waste (HLW) glass melt rate study is two-fold: (1) to gain a better understanding of the impact of feed chemistry on melt rate through bench-scale testing, and (2) to develop a predictive tool for melt rate in support of the on-going frit development efforts for the Defense Waste Processing Facility (DWPF). In particular, the focus is on predicting relative melt rates, not the absolute melt rates, of various HLW glass formulations solely based on feed chemistry, i.e., the chemistry of both waste and glass-forming frit for DWPF. Critical to the successful melt rate modeling is the accurate determination of the melting rates of various HLW glass formulations. The baseline procedure being used at the Savannah River National Laboratory (SRNL) is to; (1) heat a 4 inch-diameter stainless steel beaker containing a mixture of dried sludge and frit in a furnace for a preset period of time, (2) section the cooled beaker along its diameter, and (3) measure the average glass height across the sectioned face using a ruler. As illustrated in Figure 1-1, the glass height is measured for each of the 16 horizontal segments up to the red lines where relatively large-sized bubbles begin to appear. The linear melt rate (LMR) is determined as the average of all 16 glass height readings divided by the time during which the sample was kept in the furnace. This 'visual' method has proved useful in identifying melting accelerants such as alkalis and sulfate and further ranking the relative melt rates of candidate frits for a given sludge batch. However, one of the inherent technical difficulties of this method is to determine the glass height in the presence of numerous gas bubbles of varying sizes, which is prevalent especially for the higher-waste-loading glasses. That is, how the red lines are drawn in Figure 1-1 can be subjective and, therefore, may influence the resulting melt rates significantly. For example, if the red lines are drawn too low

Properties and performance of spin-on-glass coatings for the corrosion protection of stainless steels in chloride media

DEFF Research Database (Denmark)

Lampert, Felix; Jensen, Annemette H.; Din, Rameez U.

2018-01-01

Spin-on-glass deposition was investigated as viable alternative to increase the durability and performance of 316L steel in chloride environment. The buildup of a detrimental interface oxide was prevented by non-oxidative thermal curing of the coatings, which leads to a transformation...... silica. Electrochemical analysis by cyclic polarization indicated that the coatings behave as imperfect barrier coatings, which may enhance the passive properties of the substrates; however, there is still some statistical scatter in the quality of the coatings. While there is a tendency for an increase...... of the upper limit of the breakdown potential, there is also a decrease of the lower limit. It was found that such lower quality coatings showed, in association with substrate defects, unevenly distributed coating flaws, which may act as initiation points of pitting corrosion and decrease the corrosion...

Insights on the Role of Copper Addition in the Corrosion and Mechanical Properties of Binary Zr-Cu Metallic Glass Coatings

Directory of Open Access Journals (Sweden)

Junlei Tang

2017-12-01

Full Text Available The effect of copper addition on the corrosion resistance and mechanical properties of binary Zr100–xCux (x = 30, 50, 80, 90 at.% glassy coatings was investigated by means of electrochemical measurements, scanning electron microscopy (SEM, energy dispersive analysis spectroscopy (EDS, X-ray photoelectron spectroscopy (XPS and nano-indentation techniques. The corrosion resistance in 0.01 M deaerated H2SO4 solution and the mechanical properties of the Zr-Cu glassy coatings depend considerably upon the copper content in the glassy matrix. The top surfaces of the Zr-Cu coatings with lower Cu content were covered by a compact protective ZrO2 passive film. The competition between the oxidation of Zr atoms (ZrO2 film formation and the oxidation–dissolution of Cu atoms assumed the most important role in the electrochemical behavior of the Zr-Cu glassy coatings. The generation of ZrO2 on the surface benefited the formation of passive film; and the corrosion resistance of the metallic glass coatings depended on the coverage degree of ZrO2 passive film. The evolution of free volume affected both the mechanical and corrosion behaviors of the Zr-Cu glassy coatings.

Elevated corrosion rates and hydrogen sulfide in homes with 'Chinese Drywall'

Energy Technology Data Exchange (ETDEWEB)

Allen, Joseph G.; MacIntosh, David L. [Environmental Health and Engineering, Inc., 117 Fourth Avenue, Needham, MA (United States); Harvard School of Public Health, 677 Huntington Avenue, Boston, MA (United States); Saltzman, Lori E. [U.S. Consumer Product Safety Commission, Bethesda, MD (United States); Baker, Brian J. [Environmental Health and Engineering, Inc., 117 Fourth Avenue, Needham, MA (United States); Matheson, Joanna M.; Recht, Joel R. [U.S. Consumer Product Safety Commission, Bethesda, MD (United States); Minegishi, Taeko; Fragala, Matt A.; Myatt, Theodore A. [Environmental Health and Engineering, Inc., 117 Fourth Avenue, Needham, MA (United States); Spengler, John D.; Stewart, James H. [Environmental Health and Engineering, Inc., 117 Fourth Avenue, Needham, MA (United States); Harvard School of Public Health, 677 Huntington Avenue, Boston, MA (United States); McCarthy, John F., E-mail: jmcccarthy@eheinc.com [Environmental Health and Engineering, Inc., 117 Fourth Avenue, Needham, MA (United States)

2012-06-01

In December 2008, the U.S. Consumer Product Safety Commission (CPSC) began receiving reports about odors, corrosion, and health concerns related to drywall originating from China. In response, a detailed environmental health and engineering evaluation was conducted of 41 complaint and 10 non-complaint homes in the Southeast U.S. Each home investigation included characterization of: 1) drywall composition; 2) indoor and outdoor air quality; 3) temperature, moisture, and building ventilation; and 4) copper and silver corrosion rates. Complaint homes had significantly higher hydrogen sulfide concentrations (mean 0.82 vs. < LOD {mu}g/m{sup 3}, p < 0.05), and significantly greater rates of copper sulfide and silver sulfide corrosion compared to non-complaint homes (Cu{sub 2}S: 476 vs. < 32 A/30 d, p < 0.01; Ag{sub 2}S: 1472 vs. 389 A/30 d, p < 0.01). The abundance of carbonate and strontium in drywall was also elevated in complaint homes, and appears to be useful objective marker of problematic drywall in homes that meet other screening criteria (e.g., constructed or renovated in 2006-2007, reports of malodor and accelerated corrosion). This research provides empirical evidence of the direct association between homes constructed with 'Chinese Drywall' in 2006-2007 and elevated corrosion rates and hydrogen sulfide concentrations in indoor air. - Highlights: Black-Right-Pointing-Pointer Environmental measurements in homes with and without 'Chinese Drywall' Black-Right-Pointing-Pointer Homes with 'Chinese Drywall' had higher hydrogen sulfide concentrations Black-Right-Pointing-Pointer Homes with 'Chinese Drywall' had elevated corrosion rates Black-Right-Pointing-Pointer Study provides empirical evidence of reported associations.

Long-term leach rates of glasses containing actual waste

International Nuclear Information System (INIS)

Wiley, J.R.; LeRoy, J.H.

1979-01-01

Leach rates of borosilicate glasses that contained actual Savannah River Plant waste were measured. Leaching was done by water and by buffer solutions of pH 4, 7, and 9. Leach rates were then determined from the amount of 137 Cs, 90 Sr, and plutonium released into the leach solutions. The cumulative fractions leached were fit to a mathematical model that included leaching by diffusion and glass dissolution. 5 figures, 3 tables

Monitoring of corrosion rates of Fe-Cu alloys under wet/dry condition in weakly alkaline environments

International Nuclear Information System (INIS)

Kim, Je Kyoung; Nishikata, Atsushi; Tsuru, Tooru

2002-01-01

When the steel, containing scrap elements like copper, is used as reinforcing steel bars for concrete, the steel is exposed to alkaline environments. in this study, AC impedance technique has been applied to the monitoring of corrosion rates of iron and several Fe-Cu (0.4, 10wt%) alloys in a wet-dry cycle condition. The wet-dry cycle was conducted by exposure to alternate conditions of 1 hour-immersion in a simulated pH10 concrete solution (Ca(OH) 2 ) containing 0.01M NaCl and 3 hour-drying at 298K and 50%RH. The corrosion rate of the iron is greatly accelerated by the wet-dry cycles. Because the active FeOOH species, which are produced by the oxidation of Fe(II, III)oxide in air during drying, act as very strong oxidants to the corrosion in the wet condition. As the drying progresses, iron shows a large increase in the corrosion rate and a small shift of the corrosion potential to the positive values. This can be explained by acceleration of oxygen transport through the thin electrolyte layer In contrast to iron, the Fe-Cu alloys show low corrosion rates and the high corrosion potentials in whole cycles

Crystallization of Yttrium and Samarium Aluminosilicate Glasses

OpenAIRE

Lago, Diana Carolina; Prado, Miguel Oscar

2016-01-01

Aluminosilicate glasses containing samarium and yttrium (SmAS and YAS glasses) exhibit high glass transition temperatures, corrosion resistance, and glass stability on heating which make them useful for technological applications. Yttrium aluminosilicate glass microspheres are currently being used for internal selective radiotherapy of liver cancer. During the preparation process, crystallization needs to be totally or partially avoided depending on the final application. Thus knowing the cry...

Prediction of pipeline corrosion rate based on grey Markov models

International Nuclear Information System (INIS)

Chen Yonghong; Zhang Dafa; Peng Guichu; Wang Yuemin

2009-01-01

Based on the model that combined by grey model and Markov model, the prediction of corrosion rate of nuclear power pipeline was studied. Works were done to improve the grey model, and the optimization unbiased grey model was obtained. This new model was used to predict the tendency of corrosion rate, and the Markov model was used to predict the residual errors. In order to improve the prediction precision, rolling operation method was used in these prediction processes. The results indicate that the improvement to the grey model is effective and the prediction precision of the new model combined by the optimization unbiased grey model and Markov model is better, and the use of rolling operation method may improve the prediction precision further. (authors)

Electrochemical characterization of Zr-based thin film metallic glass in hydrochloric aqueous solution

International Nuclear Information System (INIS)

Chuang, Ching-Yen; Liao, Yi-Chia; Lee, Jyh-Wei; Li, Chia-Lin; Chu, Jinn P.; Duh, Jenq-Gong

2013-01-01

Recently thin film metallic glass represents a class of promising engineering materials for structural applications. In this work, the Zr-based thin film metallic glass (TFMG) was fabricated on the Si and AISI 420 substrates using a Zr–Cu–Ni–Al alloy and pure Zr metal targets by a pulsed DC magnetron sputtering system. The chemical compositions, crystalline structures, microstructures and corrosion behavior in hydrochloric (HCl) aqueous solutions of Zr-based TFMGs were investigated. The results showed that the surface morphologies of Zr-based TFMG were very smooth. A compact and dense structure without columnar structure was observed. The amorphous structure of Zr-based TFMG was characterized by the X-ray diffractometer and transmission electron microscopy analyses. After the potentiodynamic polarization test, the better corrosion resistance was achieved for the Zr-based TFMG coated AISI 420 in 1 mM HCl aqueous solution. Based on the surface morphologies and chemical analysis results of the corroded surfaces, the pitting, crevice corrosion and filiform corrosion were found. The corrosion mechanisms of the Zr-based TFMG were discussed in this work. - Highlights: ► Zr-based thin film metallic glass with amorphous structure. ► Better corrosion resistance of Zr-based thin film metallic glass observed. ► Pitting, crevice and filiform corrosion reactions revealed. ► The Cu-rich corrosion products found in the pit. ► Nanowire and flaky corrosion products formed adjacent to the filiform corrosion path

Effect of glass composition on waste form durability: A critical review

International Nuclear Information System (INIS)

Ellison, A.J.G.; Mazer, J.J.; Ebert, W.L.

1994-11-01

This report reviews literature concerning the relationship between the composition and durability of silicate glasses, particularly glasses proposed for immobilization of radioactive waste. Standard procedures used to perform durability tests are reviewed. It is shown that tests in which a low-surface area sample is brought into contact with a very large volume of solution provide the most accurate measure of the intrinsic durability of a glass composition, whereas high-surface area/low-solution volume tests are a better measure of the response of a glass to changes in solution chemistry induced by a buildup of glass corrosion products. The structural chemistry of silicate and borosilicate glasses is reviewed to identify those components with the strongest cation-anion bonds. A number of examples are discussed in which two or more cations engage in mutual bonding interactions that result in minima or maxima in the rheologic and thermodynamic properties of the glasses at or near particular optimal compositions. It is shown that in simple glass-forming systems such interactions generally enhance the durability of glasses. Moreover, it is shown that experimental results obtained for simple systems can be used to account for durability rankings of much more complex waste glass compositions. Models that purport to predict the rate of corrosion of glasses in short-term durability tests are evaluated using a database of short-term durability test results for a large set of glass compositions. The predictions of these models correlate with the measured durabilities of the glasses when considered in large groupings, but no model evaluated in this review provides accurate estimates of durability for individual glass compositions. Use of these models in long-term durability models is discussed. 230 refs

DEFENSE HIGH LEVEL WASTE GLASS DEGRADATION

International Nuclear Information System (INIS)

Ebert, W.

2001-01-01

provide models and parameter values that can be used to calculate the dissolution rates for the different modes of water contact. The analyses were conducted to identify key aspects of the mechanistic model for glass dissolution to be included in the abstracted models used for PA calculations, evaluate how the models can be used to calculate bounding values of the glass dissolution rates under anticipated water contact modes in the disposal. system, and determine model parameter values for the range of potential waste glass compositions and anticipated environmental conditions. The analysis of a bounding rate also considered the effects of the buildup of glass corrosion products in the solution contacting the glass and potential effects of alteration phase formation. Note that application of the models and model parameter values is constrained to the anticipated range of HLW glass compositions and environmental conditions. The effects of processes inherent to exposure to humid air and dripping water were not modeled explicitly. Instead, the impacts of these processes on the degradation rate were taken into account by using empirically measured parameter values. These include the rates at which water sorbs onto the glass, drips onto the glass, and drips off of the glass. The dissolution rates of glasses that were exposed to humid air and dripping water measured in laboratory tests are used to estimate model parameter values for contact by humid air and dripping water in the disposal system

The Corrosion Rate Measurement of Inconel 690 on High Temperature andPressure by Using CMS100

International Nuclear Information System (INIS)

Sriyono; Febrianto

2000-01-01

The corrosion rate measurement of Inconel 690 on high temperature andpressure had been done. By using an Autoclave, pressure and temperature canbe simulated. The environment of this experiment is 0.1 ppm of chloridesolution, which permit to dissolved in secondary cooling of steam generator.The corrosion rate measurement was done on temperature between 150 o C and230 o C with step 10 o C. Pressure experiment is the pressure, which occurredin Autoclave. Corrosion rate is measured by CMS100. From the Tafel analysis,corrosion rate of Inconel 690 linearity increased from 6.548 x 10 -5 mpy to4.331 x 10 -4 mpy. It concludes that Inconel 690 is resist on corrosionenvironment, so it's most using on the fabrication of steam generator tubeson the advanced power plant. (author)

Y-Si-Al-O-N Glass Fibers.

Science.gov (United States)

The excellent mechanical properties and outstanding water corrosion resistance of Y -Si-Al-O- N glasses indicate that they are attractive candidate...materials for forming into high performance glass fibers. Fibers of glasses containing, respectively,3.2 and 6.6 wt% N were drawn freehand in air, and

Ultrasonic Measurement of Erosion/corrosion Rates in Industrial Piping Systems

Science.gov (United States)

Sinclair, A. N.; Safavi, V.; Honarvar, F.

2011-06-01

Industrial piping systems that carry aggressive corrosion or erosion agents may suffer from a gradual wall thickness reduction that eventually threatens pipe integrity. Thinning rates could be estimated from the very small change in wall thickness values measured by conventional ultrasound over a time span of at least a few months. However, measurements performed over shorter time spans would yield no useful information—minor signal distortions originating from grain noise and ultrasonic equipment imperfections prevent a meaningful estimate of the minuscule reduction in echo travel time. Using a Model-Based Estimation (MBE) technique, a signal processing scheme has been developed that enables the echo signals from the pipe wall to be separated from the noise. This was implemented in a laboratory experimental program, featuring accelerated erosion/corrosion on the inner wall of a test pipe. The result was a reduction in the uncertainty in the wall thinning rate by a factor of four. This improvement enables a more rapid response by system operators to a change in plant conditions that could pose a pipe integrity problem. It also enables a rapid evaluation of the effectiveness of new corrosion inhibiting agents under plant operating conditions.

Leach rate studies on glass containing actual radioactive waste

International Nuclear Information System (INIS)

Walker, D.D.; Wiley, J.R.; Dukes, M.D.; LeRoy, J.H.

1980-01-01

Borosilicate glass containing radioactive wastes from the Savannah River Plant have been leached for 900 days. The International Standards Organization's (ISO) static leach test procedure was used on glass buttons in various leachants. Leach rates based on 90 Sr and 137 Cs analyses were similar: 2 x 10 -8 to 3 x 10 -8 g/(cm 2 )(d) in distilled water, 1 x 10 -8 to 3 x 10 -7 g/(cm 2 )(d) in pH 7 buffer, 3 x 10 -7 to 7 x 10 -7 g/(cm 2 )(d) in pH 9 buffer, and 7 x 10 -6 to 8 x 10 -5 g/(cm 2 )(d) in pH 4 buffer. Rates based on Pu analyses were the same as above in distilled water and pH 9 buffer, but were lower by an order of magnitude in pH 4 and pH 7 buffers. Almost all leach rates remained constant between 200 and 900 days of leaching. Increasing the concentration of the buffering agents had no effect on the leach rates at pH 7 (phosphate) and pH 9 (carbonate), but dramatically increased the rates at pH 4 (acetate). Leach rates did not differ significantly between high aluminum and high iron waste glasses

Behaviour of rare earth elements, as natural analogues of transuranium elements, during weathering of basaltic glasses

International Nuclear Information System (INIS)

Daux, V.; Crovisier, J.L.; Petit, J.C.

1991-01-01

Subglacial basaltic glasses from Iceland have been studied in order to investigate REE behaviour low-temperature weathering. Just as actinides accumulate in the hydrated superficial corrosion layer of borosilicate glasses, REEs are found to be enriched in the natural corrosion layer of basaltic glasses (palagonite). However, this enrichment is only relative for basaltic glasses [fr

Corrosion product identification and relative rates of corrosion of candidate metals in an irradiated air-steam environment

International Nuclear Information System (INIS)

Reed, D.T.; Swayambunathan, V.; Tani, B.S.; Van Konynenburg, R.A.

1989-01-01

Previously reported work by others indicates that dicopper trihydroxide nitrate, Cu 2 NO 3 (OH) 3 , forms on copper and copper alloys subjected to irradiated moist air near room temperature. We have performed experiments over a range of temperature and humidity, and have found that this species is formed at temperatures up to at least 150 degree C if low to intermediate relative humidities are present. At 150 degree C and 100% relative humidity, only Cu 2 O and CuO were observed. The relative general corrosion rates of the copper materials tested in 1-month experiments at dose rates of 0.7 and 2.0 kGy/h were Cu > 70/30 Cu--Ni > Al-bronze. High-nickel alloy 825 showed no observable corrosion. 29 refs., 4 tabs

Modeling relations between the composition and properties of French light water reactor waste containment glass

International Nuclear Information System (INIS)

Ghaleb, D.; Dussossoy, J.L.; Fillet, C.; Pacaud, F.; Jacquet-Francillon, N.

1994-01-01

Models have been developed to calculate the density, molten-state viscosity and initial corrosion rate according to the chemical composition of glass formulations used to vitrify high-level fission product solutions from reprocessed light water reactor fuel. Developed from other published work, these models have been adapted to allow for the effects of platinoid (Ru, Pd, Rh) inclusions on the molten glass rheology. (authors). 15 refs., 10 figs., 1 tab

Simulation of corrosion product activity in pressurized water reactors under flow rate transients

International Nuclear Information System (INIS)

Mirza, Anwar M.; Mirza, Nasir M.; Mir, Imran

1998-01-01

Simulation of coolant activation due to corrosion products and impurities in a typical pressurized water reactor has been done under flow rate transients. Employing time dependent production and losses of corrosion products in the primary coolant path an approach has been developed to calculate the coolant specific activity. Results for 24 Na, 56 Mn, 59 Fe, 60 Co and 99Mo show that the specific activity in primary loop approaches equilibrium value under normal operating conditions fairly rapidly. Predominant corrosion product activity is due to Mn-56. Parametric studies at full power for various ramp decreases in flow rate show initial decline in the activity and then a gradual rise to relatively higher saturation values. The minimum value and the time taken to reach the minima are strong functions of the slope of linear decrease in flow rate. In the second part flow rate coastdown was allowed to occur at different flow half-times. The reactor scram was initiated at 90% of the normal flow rate. The results show that the specific activity decreases and the rate of decrease depends on pump half time and the reactor scram conditions

Influence of cooling rate on the microstructure and corrosion behavior of Al–Fe alloys

International Nuclear Information System (INIS)

Dorin, T.; Stanford, N.; Birbilis, N.; Gupta, R.K.

2015-01-01

Highlights: • Increasing the cooling rate from 0.1 to 500 °C/s, mass loss rate decreased by 6 times. • Increase in corrosion resistance was attributed to the refined Fe-intermetallics. • Increased cooling rate resulted in increased Fe content in solid solution. • Direct strip casting can produce alloys with higher acceptable content of impurities. • Direct Strip Casting is a potential candidate to improve recyclability of Al alloys - Abstract: The effect of Fe in Al is technologically important for commercial Al-alloys, and in recycled Al. This work explores the use of the novel rapid solidification technology, known as direct strip casting, to improve the recyclability of Al-alloys. We provide a comparison between the corrosion and microstructure of Al–Fe alloys prepared with wide-ranging cooling rates (0.1 °C/s to 500 °C/s). Rapid cooling was achieved via direct strip casting, while slow cooling was achieved using sand casting. Corrosion was studied via polarisation and immersion tests, followed by surface analysis using scanning electron microscopy and optical profilometry. It was shown that the corrosion resistance of Al–Fe alloys is improved with increased cooling rates, attributed to the reduced size and number of Fe-containing intermetallics.

The Dissolution Behavior of Borosilicate Glasses in Far-From Equilibrium Conditions

Energy Technology Data Exchange (ETDEWEB)

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin PG; Ryan, Joseph V.; Asmussen, Robert M.

2018-02-10

In far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this paper is to study effects of these variables on three model waste glasses (SON68, ISG, AFCI). To do this, experiments were conducted at temperatures of 23, 40, 70, and 90 °C and pH(RT) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. The results from these tests were then used to parameterize a kinetic rate model based on transition state theory. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Discrepancies in the absolute dissolution rates as compared to those obtained using other test methods are discussed. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies. The results were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), which is capable of providing a robust uncertainty analysis. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, the effect of glass composition on the rate parameter values could possibly be obtained. This would allow for the possibility of predicting the forward dissolution rate of glass based solely on composition

Results of testing the Grambow rate law for use in HWVP glass durability correlations

International Nuclear Information System (INIS)

Kuhn, W.L.; Bunnell, L.R.

1996-03-01

A theory based on Grambow's work on hydration of glass as linear function of solution composition was evaluated. Use of Grambow's linear rate law for correlation of durability with glass composition is not recommended. Dissolution rate of the glass was determined using the rate of release of sodium with an ion selective electrode. This method was tested first applying it to initial dissolution rate of several glasses at several temperatures with zero initial concentration of silicic acid. HW39-2, HW39-4, and SRL-202 from Savannah River were tested; there was significant scatter in the data, with the dissolution rates of HW39 glasses and the SRL glass being comparable within this scatter. The dissolution rate of SRL-202 at 80 C and pH 7 for silicic acid concentrations 0, 25, 50, and 100% saturation, was found to decrease dramatically at only 25% of the saturated silicic acid concentration, which does not conform to the linear theory

Controlling corrosion rate of Magnesium alloy using powder mixed electrical discharge machining

Science.gov (United States)

Razak, M. A.; Rani, A. M. A.; Saad, N. M.; Littlefair, G.; Aliyu, A. A.

2018-04-01

Biomedical implant can be divided into permanent and temporary employment. The duration of a temporary implant applied to children and adult is different due to different bone healing rate among the children and adult. Magnesium and its alloys are compatible for the biodegradable implanting application. Nevertheless, it is difficult to control the degradation rate of magnesium alloy to suit the application on both the children and adult. Powder mixed electrical discharge machining (PM-EDM) method, a modified EDM process, has high capability to improve the EDM process efficiency and machined surface quality. The objective of this paper is to establish a formula to control the degradation rate of magnesium alloy using the PM-EDM method. The different corrosion rate of machined surface is hypothesized to be obtained by having different combinations of PM-EDM operation inputs. PM-EDM experiments are conducted using an opened-loop PM-EDM system and the in-vitro corrosion tests are carried out on the machined surface of each specimen. There are four operation inputs investigated in this study which are zinc powder concentration, peak current, pulse on-time and pulse off-time. The results indicate that zinc powder concentration is significantly affecting the response with 2 g/l of zinc powder concentration obtaining the lowest corrosion rate. The high localized temperature at the cutting zone in spark erosion process causes some of the zinc particles get deposited on the machined surface, hence improving the surface characteristics. The suspended zinc particles in the dielectric fluid have also improve the sparking efficiency and the uniformity of sparks distribution. From the statistical analysis, a formula was developed to control the corrosion rate of magnesium alloy within the range from 0.000183 mm/year to 0.001528 mm/year.

Conditions for testing the corrosion rates of ceramics in coal gasification systems

Energy Technology Data Exchange (ETDEWEB)

Hurley, J.P.; Nowok, J.W. [Univ. of North Dakota, Grand Forks, ND (United States)

1996-08-01

Coal gasifier operating conditions and gas and ash compositions affect the corrosion rates of ceramics used for construction in three ways: (1) through direct corrosion of the materials, (2) by affecting the concentration and chemical form of the primary corrodents, and (3) by affecting the mass transport rate of the primary corrodents. To perform an accurate corrosion test on a system material, the researcher must include all relevant corrodents and simulate conditions in the gasifier as closely as possible. In this paper, the authors present suggestions for conditions to be used in such corrosion tests. Two main types of corrosion conditions are discussed: those existing in hot-gas cleanup systems where vapor and dry ash may contribute to corrosion and those experienced by high-temperature heat exchangers and refractories where the main corrodent will be coal ash slag. Only the fluidized-bed gasification systems such as the Sierra Pacific Power Company Pinon Pine Power Project system are proposing the use of ceramic filters for particulate cleanup. The gasifier is an air-blown 102-MWe unit employing a Westinghouse{trademark} ceramic particle filter system operating at as high as 1100{degrees}F at 300 psia. Expected gas compositions in the filter will be approximately 25% CO, 15% H{sub 2}, 5% CO{sub 2}, 5% H{sub 2}O, and 50% N{sub 2}. Vapor-phase sodium chloride concentrations are expected to be 10 to 100 times the levels in combustion systems at similar temperatures, but in general the concentrations of the minor primary and secondary corrodents are not well understood. Slag corrosiveness will depend on its composition as well as viscosity. For a laboratory test, the slag must be in a thermodynamically stable form before the beginning of the corrosion test to assure that no inappropriate reactions are allowed to occur. Ideally, the slag would be flowing, and the appropriate atmosphere must be used to assure realistic slag viscosity.

Formation of secondary phases during the corrosion of vitrified nuclear waste

International Nuclear Information System (INIS)

Zimmer, P.

2003-11-01

The first aim of this work was the examination of the formation and long-term stability of secondary phases that form during an aquatic attack on simulated, vitrified nuclear waste. In the glasses used for the investigations actinides had been replaced by rare earth elements (chemical analogues), other radionuclides by inactive isotopes. For predictions about the long-term safety of nuclear waste disposals it is important to identify secondary phases that have formed during the glass corrosion process and to determine their stability. Two different saline solutions (rich in MgCl 2 and in NaCl, respectively) are relevant as a corrosion medium for waste disposals. It showed that in such an environment sulfates, silicates and molybdates represent the main new formations of minerals after 7.5 years of corrosion. However, the formation, long-term stability and sorption characteristics of those minerals regarding rare earth elements depend to a high degree on the corrosion medium as well as on changes in the geochemical environment in the course of the experiment. By means of SEM/EDX barytes of different morphology with up to 15% w/w Sr ((Ba,Sr)SO 4 ) were identified in both corrosion media; they were capable of binding long-term stable radionuclides like Sr. Furthermore, pure rare earth (RE) sulfates were observed in the saline solution rich in MgCl 2 . This formation of RE-sulfates has not been described in the literature so far. Depending on the saline solution, the secondary silicate and molybdate minerals that formed on the glass surfaces differed noticeably in their sorption characteristics and their stability. Another focus of the work was a more profound understanding of the glass corrosion mechanism in the presence of metallic iron since steel jackets are used as technical barriers for the vitrified nuclear waste in nuclear waste disposals. Another important point in connection with the mobilization and immobilization of radionuclides released during glass

Energy absorption at high strain rate of glass fiber reinforced mortars

Directory of Open Access Journals (Sweden)

Fenu Luigi

2015-01-01

Full Text Available In this paper, the dynamic behaviour of cement mortars reinforced with glass fibers was studied. The influence of the addition of glass fibers on energy absorption and tensile strength at high strain-rate was investigated. Static tests in compression, in tension and in bending were first performed. Dynamic tests by means of a Modified Hopkinson Bar were then carried out in order to investigate how glass fibers affected energy absorption and tensile strength at high strain-rate of the fiber reinforced mortar. The Dynamic Increase Factor (DIF was finally evaluated.

Influence of LMFBR fuel pin temperature profiles on corrosion rate

International Nuclear Information System (INIS)

Shiels, S.A.; Bagnall, C.; Schrock, S.L.; Orbon, S.J.

1976-01-01

The paper describes the sodium corrosion behavior of 20 percent cold worked Type 316 stainless steel fuel pin cladding under a simulated reactor thermal environment. A temperature gradient, typical of a fuel pin, was generated in a 0.9 m long heater section by direct resistance heating. Specimens were located in an isothermal test section immediately downstream of the heater. A comparison of the measured corrosion rates with available data showed an enhancement factor of between 1.5 and 2 which was attributed to the severe axial temperature gradient through the heater. Differences in structure and surface chemistry were also noted

Electrochemical Corrosion Studies for Modeling Metallic Waste Form Release Rates

International Nuclear Information System (INIS)

Poineau, Frederic; Tamalis, Dimitri

2016-01-01

The isotope 99 Tc is an important fission product generated from nuclear power production. Because of its long half-life (t 1/2 = 2.13 ∙ 105 years) and beta-radiotoxicity (β - = 292 keV), it is a major concern in the long-term management of spent nuclear fuel. In the spent nuclear fuel, Tc is present as an alloy with Mo, Ru, Rh, and Pd called the epsilon-phase, the relative amount of which increases with fuel burn-up. In some separation schemes for spent nuclear fuel, Tc would be separated from the spent fuel and disposed of in a durable waste form. Technetium waste forms under consideration include metallic alloys, oxide ceramics and borosilicate glass. In the development of a metallic waste form, after separation from the spent fuel, Tc would be converted to the metal, incorporated into an alloy and the resulting waste form stored in a repository. Metallic alloys under consideration include Tc–Zr alloys, Tc–stainless steel alloys and Tc–Inconel alloys (Inconel is an alloy of Ni, Cr and iron which is resistant to corrosion). To predict the long-term behavior of the metallic Tc waste form, understanding the corrosion properties of Tc metal and Tc alloys in various chemical environments is needed, but efforts to model the behavior of Tc metallic alloys are limited. One parameter that should also be considered in predicting the long-term behavior of the Tc waste form is the ingrowth of stable Ru that occurs from the radioactive decay of 99 Tc ( 99 Tc → 99 Ru + β - ). After a geological period of time, significant amounts of Ru will be present in the Tc and may affect its corrosion properties. Studying the effect of Ru on the corrosion behavior of Tc is also of importance. In this context, we studied the electrochemical behavior of Tc metal, Tc-Ni alloys (to model Tc-Inconel alloy) and Tc-Ru alloys in acidic media. The study of Tc-U alloys has also been performed in order to better understand the nature of Tc in metallic spent fuel. Computational modeling

Corrosion study for a radioactive waste vitrification facility

International Nuclear Information System (INIS)

Imrich, K.J.; Jenkins, C.F.

1993-01-01

A corrosion monitoring program was setup in a scale demonstration melter system to evaluate the performance of materials selected for use in the Defense Waste Processing Facility (DWPF) at the DOE's Savannah River Site. The system is a 1/10 scale prototypic version of the DWPF. In DWPF, high activity radioactive waste will be vitrified and encapsulated for long term storage. During this study twenty-six different alloys, including DWPF reference materials of construction and alternate higher alloy materials, were subjected to process conditions and environments characteristic of the DWPF except for radioactivity. The materials were exposed to low pH, elevated temperature (to 1200 degree C) environments containing abrasive slurries, molten glass, mercury, halides and sulfides. General corrosion rates, pitting susceptibility and stress corrosion cracking of the materials were investigated. Extensive data were obtained for many of the reference materials. Performance in the Feed Preparation System was very good, whereas coupons from the Quencher Inlet region of the Melter Off-Gas System experienced localized attack

Edge-Strengthening of Structural Glass with Protective Coatings

OpenAIRE

Lindqvist Maria; Louter Christian; Lebet Jean-Paul

2012-01-01

In modern buildings, glass is increasingly used as a load-carrying material in structural components, such as glass beams. For glass beams especially the edge strength of glass is important. However, the strength of glass is not a material constant but depends on various parameters, which makes glass, amongst other things, a challenging building material. One of the parameters influencing glass strength is the combination of humidity and stress, which may cause stress corrosion. The aim of th...

Nano-Continuum Modeling of a Nuclear Glass Specimen Altered for 25 Years

Energy Technology Data Exchange (ETDEWEB)

Steefel, Carl

2014-01-06

The purpose of this contribution is to report on preliminary nano-continuum scale modeling of nuclear waste glass corrosion. The focus of the modeling is an experiment involving a French glass SON68 specimen leached for 25 years in a granitic environment. In this report, we focus on capturing the nano-scale concentration profiles. We use a high resolution continuum model with a constant grid spacing of 1 nanometer to investigate the glass corrosion mechanisms.

A method for measuring the corrosion rate of materials in spallation neutron source target/blanket cooling loops

International Nuclear Information System (INIS)

Lillard, R.S.; Butt, D.P.

1999-01-01

This paper summarizes the ongoing evaluation of the susceptibility of materials in accelerator target/blanket cooling loops to corrosion. To simulate the exposure environment in a target/blanket cooling loop, samples were irradiated by an 800 MeV proton beam at the A6 Target Station of the Los Alamos Neutron Science Center (LANSCE). To accomplish this, a cooling water loop capable of exposing corrosion samples to an 800 MeV proton beam at currents upwards of 1 mA was constructed. This loop allowed control and evaluation hydrogen water chemistry, water conductivity, and solution pH. Specially designed ceramic sealed samples were used to measure the real-time corrosion rates of materials placed directly in the proton beam using electrochemical impedance spectroscopy (EIS). EIS was also used to measure real-time corrosion rates of samples that were out of the proton beam and downstream from the in-beam samples. These out-of-beam probes primarily examined the effects of long lived water radiolysis products from proton irradiation on corrosion rates. An overview of the LANSCE corrosion loop, the corrosion probes, and data from an in-beam alloy 718 probe are presented

Promising Ta-Ti-Zr-Si metallic glass coating without cytotoxic elements for bio-implant applications

Science.gov (United States)

Lai, J. J.; Lin, Y. S.; Chang, C. H.; Wei, T. Y.; Huang, J. C.; Liao, Z. X.; Lin, C. H.; Chen, C. H.

2018-01-01

Tantalum (Ta) is considered as one of the most promising metal due to its high corrosion resistance, excellent biocompatibility and cell adhesion/in-growth capabilities. Although there are some researches exploring the biomedical aspects of Ta and Ta based alloys, systematic characterizations of newly developed Ta-based metallic glasses in bio-implant applications is still lacking. This study employs sputtering approach to produced thin-film Ti-based metallic glasses due to the high melting temperature of Ta (3020 °C). Two fully amorphous Ta-based metallic glasses composed of Ta57Ti17Zr15Si11 and Ta75Ti10Zr8Si7 are produced and experimentally characterized in terms of their mechanical properties, bio-corrosion properties, surface hydrophilic characteristics, and in-vitro cell viability and cells attachment tests. Compare to conventional pure Ti and Ta metals, the developed Ta-based metallic glasses exhibit higher hardness and lower modulus which are better match to the mechanical properties of bone. MTS assay results show that Ta-based metallic glasses show comparable cell viability and cell attachment rate compared to that of pure Ti and Ta surface in a 72 h in-vitro test.

Hydrothermal alteration of the glass R7T7. Glass dissolution kinetics at 150 and 2500, role of neo-formed phases

International Nuclear Information System (INIS)

Caurel, J.

1990-01-01

The glass R7T7 is chosen in France for vitrification of solution from reprocessing. Safety requires the knowledge of R7T7 long term behavior in deep geologic formations. Temperature dependence of leaching between 50 and 300 0 C is studied by static tests for 7 days. An activation energy of 30kJ/Mole is calculated between 50; 75 or 100 0 C and 250 0 C. Results suggest similar corrosion mechanisms between 90-100 and 250 0 C by a complete change between 250 and 275 0 C. Glass corrosion kinetics at 150 0 C and 250 0 C between 1 day and 1 year evidence the precipitation of aluminosilicates and formation of thick amorphous gels progressively enriched with silica. Glass dissolution at 150 0 C and 250 0 C is simulated with the geochemical DISSOL code. Results suggest that dissolution kinetics are controlled by activity of H 4 SiO 4 in solution only. Silica contained into the gel controls corrosion kinetics different from 0. Even if the nature of dissolution mechanisms does not seem modified between 150 and 250 0 C, sample cracking at 250 0 C induces an increase of dissolved glass that does not allow a direct comparison of corrosion kinetics between 150 and 250 0 C [fr

Glass-ceramic coated Mg-Ca alloys for biomedical implant applications.

Science.gov (United States)

Rau, J V; Antoniac, I; Fosca, M; De Bonis, A; Blajan, A I; Cotrut, C; Graziani, V; Curcio, M; Cricenti, A; Niculescu, M; Ortenzi, M; Teghil, R

2016-07-01

Biodegradable metals and alloys are promising candidates for biomedical bone implant applications. However, due to the high rate of their biodegradation in human body environment, they should be coated with less reactive materials, such, for example, as bioactive glasses or glass-ceramics. Fort this scope, RKKP composition glass-ceramic coatings have been deposited on Mg-Ca(1.4wt%) alloy substrates by Pulsed Laser Deposition method, and their properties have been characterized by a number of techniques. The prepared coatings consist of hydroxyapatite and wollastonite phases, having composition close to that of the bulk target material used for depositions. The 100μm thick films are characterized by dense, compact and rough morphology. They are composed of a glassy matrix with various size (from micro- to nano-) granular inclusions. The average surface roughness is about 295±30nm due to the contribution of micrometric aggregates, while the roughness of the fine-texture particulates is approximately 47±4nm. The results of the electrochemical corrosion evaluation tests evidence that the RKKP coating improves the corrosion resistance of the Mg-Ca (1.4wt%) alloy in Simulated Body Fluid. Copyright © 2016 Elsevier B.V. All rights reserved.

Simulation of corrosion product activity in ion- exchanger of PWR under acceleration of corrosion and flow rate perturbations

International Nuclear Information System (INIS)

Mirza, N.M.; Mirza, S.M.; Rafique, M.

2005-01-01

In this paper computer code developed earlier by the authors (CPAIR-P) has been employed to compute corrosion product activity in PWRs for flow rate perturbations. The values of radioactivity in ion exchanger of Pressurized Water Reactor (PWR) under normal and flow rate perturbation conditions have been calculated. For linearly accelerating corrosion rates, activity saturates for removal rate of 600 cm/sup 3// s in primary coolant of PWR. A higher removal rate of 750 cm/sup 3// s was selected for which the saturation value is sufficiently low (0. 28 micro Ci/cm/sup 3/). Simulation results shows that the Fe/sup 59/ Na/sup 24/, Mo/sup 99/, Mn/sup 56/ reaches saturation values with in about 700 hours of reactor operation. However, Co/sup 58/ and Co/sup 60/ keep on accumulating and do not saturate with in 2000 hours of these simulation time. When flow rate is decreased by 10% of rated flow rate after 500 hours of reactor operation, a dip in activity is seen, which reaches to the value of 0.00138 micro Ci cm/sup -3/ then again it begins to rise and reaches saturation value of 0.00147 cm/sup 3//s. (author)

Simulation of natural corrosion by vapor hydration test: seven-year results

International Nuclear Information System (INIS)

Luo, J.S.; Ebert, W.L.; Mazer, J.J.; Bates, J.K.

1996-01-01

We have investigated the alteration behavior of synthetic basalt and SRL 165 borosilicate waste glasses that had been reacted in water vapor at 70 degrees C for time periods up to seven years. The nature and extent of corrosion of glasses have been determined by characterizing the reacted glass surface with optical microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive x-ray spectroscopy (EDS). Alteration in 70 degrees C laboratory tests was compared to that which occurs at 150-200 degrees C and also with Hawaiian basaltic glasses of 480 to 750 year old subaerially altered in nature. Synthetic basalt and waste glasses, both containing about 50 percent wt SiO 2 were found to react with water vapor to form an amorphous hydrated gel that contained small amounts of clay, nearly identical to palagonite layers formed on naturally altered basaltic glass. This result implies that the corrosion reaction in nature can be simulated with a vapor hydration test. These tests also provide a means for measuring the corrosion kinetics, which are difficult to determine by studying natural samples because alteration layers have often spelled off the samples and we have only limited knowledge of the conditions under which alteration occurred

Chromium steel corrosion rates and mechanisms in aqueous nickel chloride at 300C

International Nuclear Information System (INIS)

Forrest, J.E.; Broomfield, J.P.; Mitra, P.K.

1985-01-01

Rapid corrosion of PWR steam generator carbon steel support structures and consequential denting of steam generator tubes led to investigation of alternative support designs and materials. In recent designs of steam generators the carbon steel drilled hole tube support plate has been replaced by one of quatrefoil or trefoil shape to minimize the contact area. These plates are now made of more corrosion resistant chromium steel (approx. 12%Cr) to ensure that they are less vulnerable to attack in the event of adverse boiler water chemistry. This study was initiated to examine the corrosion behavior of a range of chromium steels in the acid chloride environments characteristic of tube/support plate crevices under adverse boiler water conditions. Objectives of the study were to: 1) determine the relative susceptibility of candidate tube support plate steels to acid chloride corrosion; 2) investigate the corrosion product morphology and its relationship to the corrosion mechanism; 3) determine the effect of environment aggressiveness on 12%Cr (A405) steel corrosion rates and mechanisms; and 4) investigate the effect of restraint stress/environment on denting potential of A405. Experimental method and results are discussed

Tests on dynamic corrosion by water. Influence of the passage of a heat flux on the corrosion kinetics. pH measurement in water at high temperature; Essais de corrosion dynamique par l'eau. Influence du passage d'un flux thermique sur la cinetique de corrosion. Mesure du pH dans l'eau a haute temperature

Energy Technology Data Exchange (ETDEWEB)

Coriou, H; Grall, L; Hure, J; Saint-James, R [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Berthod, [Societe Grenobloise d' Etudes et d' Applications Hydrauliques, 38 (France); peintre, Le [Centre National de la Recherche Scientifique (CNRS), 38 - Grenoble (France)

1958-07-01

The passage of a heat flux through the surface of a metal placed in a corrosive medium influences the rate of corrosion, these being higher than under adiabatic conditions. The apparatus developed for corrosion tests is described, it is possible to obtain with this equipment: 1) Heat fluxes greater than 200 W/cm{sup 2}, across aluminium canning, which is cooled by water (temperature 50 deg. C), circulating with flow rates of the order of 5 to 6 m/s. 2) Heat fluxes which can go up to 150 W/cm{sup 2}, across canning of zircaloy or stainless steel. The cooling fluid is pressurized water at a temperature around 280 deg. C, the flow-rate of circulation reaching 6 m/s. The results obtained on aluminium canning are studied from the viewpoint of corrosion, paying particular attention to cavitation phenomena which can cause serious damage in certain special circumstances. After developing a glass electrode system capable of supporting high pressures, the authors have investigated materials capable of functioning as a hydrogen electrode and of resisting satisfactorily corrosion by water at 200 deg. C. Various possibilities have been examined: electrodes of special glasses, quartz, metals, with a membrane etc... The results of the various tests and the practical limits of utilisation are given. (author)Fren. [French] Le passage d'un flux thermique a travers la surface d'un metal place dans un milieu corrosif influence les vitesses de corrosion, celles-ci etant plus elevees que dans des conditions adiabatiques. On decrit les appareils mis au point, pour essais de corrosion. Ils permettent d'obtenir: 1) A travers des gaine aluminium des flux thermiques depassant 200 W /cm{sup 2}. Les gaines sont refroidies par l'eau (temperature 50 deg. C), circulant a des vitesses de l'ordre de 5 a 6 m/s. 2) A travers des gaines en zircaloy ou acier inoxydable des flux thermiques pouvant s'elever a 150 W/cm{sup 2}. Le fluide de refroidissement est de l'eau sous pression a une temperature

Chloride-induced corrosion mechanism and rate of enamel- and epoxy-coated deformed steel bars embedded in mortar

International Nuclear Information System (INIS)

Tang, Fujian; Chen, Genda; Brow, Richard K.

2016-01-01

The chloride-induced corrosion mechanisms of uncoated, pure enamel (PE)-coated, mixed enamel (ME)-coated, double enamel (DE)-coated, and fusion bonded epoxy (FBE)-coated deformed steel bars embedded in mortar cylinders are investigated in 3.5 wt.% NaCl solution and compared through electrochemical tests and visual inspection. Corrosion initiated after 29 or 61 days of tests in all uncoated and enamel-coated steel bars, and after 244 days of tests in some FBE-coated steel bars. In active stage, DE- and FBE-coated steel bars are subjected to the highest and lowest corrosion rates, respectively. The uncoated and ME-coated steel bars revealed relatively uniform corrosion while the PE-, DE-, and FBE-coated steel bars experienced pitting corrosion around damaged coating areas. Due to the combined effect of ion diffusion and capillary suction, wet–dry cyclic immersion caused more severe corrosion than continuous immersion. Both exposure conditions affected the corrosion rate more significantly than the water–cement ratio in mortar design.

Development and evaluation of an instantaneous atmospheric corrosion rate monitor

Science.gov (United States)

Mansfeld, F.; Jeanjaquet, S. L.; Kendig, M. W.; Roe, D. K.

1985-06-01

A research program was carried out in which a new instantaneous atmospheric corrosion rate monitor (ACRM) was developed and evaluated, and equipment was constructed which will allow the use of many sensors in an economical way in outdoor exposures. In the first task, the ACRM was developed and tested in flow chambers in which relative humidity and gaseous and particulate pollutant levels can be controlled. Diurnal cycles and periods of rain were simulated. The effects of aerosols were studied. A computerized system was used for collection, storage, and analysis of the electrochemical data. In the second task, a relatively inexpensive electronics system for control of the ACRM and measurement of atmospheric corrosion rates was designed and built. In the third task, calibration of deterioration rates of various metallic and nonmetallic materials with the response of the ACRMs attached to these materials was carried out under controlled environmental conditions using the system developed in the second task. A Quality Assurance project plan was prepared with inputs from the Rockwell International Environmental Monitoring and Service Center and Quality Assurance System audits were performed.

The importance of the strain rate and creep on the stress corrosion cracking mechanisms and models

International Nuclear Information System (INIS)

Aly, Omar F.; Mattar Neto, Miguel; Schvartzman, Monica M.A.M.

2011-01-01

Stress corrosion cracking is a nuclear, power, petrochemical, and other industries equipment and components (like pressure vessels, nozzles, tubes, accessories) life degradation mode, involving fragile fracture. The stress corrosion cracking failures can produce serious accidents, and incidents which can put on risk the safety, reliability, and efficiency of many plants. These failures are of very complex prediction. The stress corrosion cracking mechanisms are based on three kinds of factors: microstructural, mechanical and environmental. Concerning the mechanical factors, various authors prefer to consider the crack tip strain rate rather than stress, as a decisive factor which contributes to the process: this parameter is directly influenced by the creep strain rate of the material. Based on two KAPL-Knolls Atomic Power Laboratory experimental studies in SSRT (slow strain rate test) and CL (constant load) test, for prediction of primary water stress corrosion cracking in nickel based alloys, it has done a data compilation of the film rupture mechanism parameters, for modeling PWSCC of Alloy 600 and discussed the importance of the strain rate and the creep on the stress corrosion cracking mechanisms and models. As derived from this study, a simple theoretical model is proposed, and it is showed that the crack growth rate estimated with Brazilian tests results with Alloy 600 in SSRT, are according with the KAPL ones and other published literature. (author)

The effect of texture, heat treatment and elongation rate on stress corrosion cracking in irradiated zircaloy

International Nuclear Information System (INIS)

Pettersson, K.; Stany, W.; Hellstrand, E.

1979-03-01

Irradiated zircaloy samples with different textures and heat treatments have been tested concerning stress corrosion. Irradiated samples of Zr-1Nb, pure Zr and beta quenched zircaloy have also been investigated. Stress-relieve annealled zircaloy is even after irradiation more sensitive to stress corrosion than recrystallized zircaloy. Zr-1Nb and beta quenched zircaloy are much more sinsitive to stress corrosion than the samples with different textures. As a rule irradiated zircaloy is sensitive to stress corrosion at stresses far below the yield point. The breaking stress decreases with the elongation rate. The extension of cracks is much faster in irradiated zircaloy than in unirradiated zircaloy. There is no simple failure criterium for irradiated zircaloy. However for a certain stress and a certain elongation rate the probability for a failure before this stress is reached with a constant elongation rate can be given. (E.R.)

Corrosion potential detection method, potential characteristic simulation method for reaction rate and plant monitoring system using the same

International Nuclear Information System (INIS)

Sakai, Masanori; Onaka, Noriyuki; Takahashi, Tatsuya; Yamanaka, Hiroshi.

1995-01-01

In a calculation controlling device for a plant monitoring system, concentrations of materials concerning reaction materials in a certain state of a reaction process, and an actually measured value for the potential of a material in this state are substituted into a reaction rate equation obtained in accordance with a reaction process model. With such procedures, a relation between the reaction rate (current value) and the potential of the material can be obtained. A potential at which the reaction rates of an anode reaction and a cathode reaction contained in a corrosion reaction are made equal is determined by a numerical value calculation, based on an electrochemical hybrid potential logic by using the reaction rate equation, the reaction rate information relative to the corrosion reaction of the material and the concentration of the material concerning the corrosion reaction is obtained by a numerical value calculation. Then, simulation for the corrosion potential is enabled based on the handling corresponding to the actual reaction. Further, even for a portion which can not be measured actually, the corrosion potential can be recognized by simulation. (N.H.)

Low leach rate glasses for immobilization of nuclear wastes

International Nuclear Information System (INIS)

Chick, L.A.; Buckwalter, C.Q.

1980-10-01

Improved defense and commercial waste glass have about one order of magnitude lower leach rates at 90 0 C in static deionized water than reference glasses. This durability difference diminishes as the leaching temperature is raised, but at repository temperature less than 150 0 C, the improved compositions would have considerable advantages over reference glases. At the melting temperatures necessary for most of the high-durability glasses, volatility was found to be higher than that experienced in processing current reference glases. Higher volatilities might be compensated for by specific design of the off-gas system for improved off-gas treatment and volatile materials recovery. 6 figures, 2 tables

Fouling of heat exchanger surfaces by dust particles from flue gases of glass furnaces

Energy Technology Data Exchange (ETDEWEB)

Mutsaers, P.L.M.; Beerkens, R.G.C.; Waal, H. de (Nederlandse Centrale Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek, Delft. Inst. of Applied Physics)

1989-08-01

Fouling by dust particles generally leads to a reduction of the heat transfer and causes corrosion of secondary heat exchangers. A deposition model, including thermodynamic equilibrium calculations, has been derived and applied to describe the deposition (i.e. fouling) process and the nature of the deposition products in a secondary heat exchanger. The deposition model has been verified by means of laboratory experiments, for the case of flue gases from soda-lime glass furnaces. Corrosion of iron-containing metallic materials, caused by the deposition products, has been briefly investigated with the same equipment. There is a close similarity between the experimental results and model calculations. The largest deposition rates from flue gases on cylindrical tubes in cross-flow configuration, are predicted and measured at the upstream stagnation point. The lowest deposition rates are determined at downstream stagnation point locations. At tube surface temperatures of approximately 520 to 550 K, the fouling rate on the tube reaches a maximum. In this temperature region NaHSO{sub 4} is the most important deposition product. This component is mainly formed at temperatures from 470 up to 540 K. The compound Na{sub 3}H(SO{sub 4}){sub 2} seems to be stable up to 570 K, for even higher temperatures Na{sub 2}SO{sub 4} has been found. These deposition products react with iron, SO{sub 3}, oxygen and water vapour forming the complex corrosion product Na{sub 3}Fe(SO{sub 4}){sub 3}. NaHSO{sub 4}, which is formed at tube surface temperatures below 540 K, causes more severe corrosion of iron-containing materials than Na{sub 2}SO{sub 4}. Maintaining temperatures of the heat exchanger surfaces above 550 to 600 K reduces the fouling tendency and corrosion in case of flue gases from oil-fired soda-lime glass furnaces. (orig.).

Corrosion and runoff rates of Cu and three Cu-alloys in marine environments with increasing chloride deposition rate.

Science.gov (United States)

Odnevall Wallinder, Inger; Zhang, Xian; Goidanich, Sara; Le Bozec, Nathalie; Herting, Gunilla; Leygraf, Christofer

2014-02-15

Bare copper sheet and three commercial Cu-based alloys, Cu15Zn, Cu4Sn and Cu5Al5Zn, have been exposed to four test sites in Brest, France, with strongly varying chloride deposition rates. The corrosion rates of all four materials decrease continuously with distance from the coast, i.e. with decreasing chloride load, and in the following order: Cu4Sn>Cu sheet>Cu15Zn>Cu5Al5Zn. The patina on all materials was composed of two main layers, Cu2O as the inner layer and Cu2(OH)3Cl as the outer layer, and with a discontinuous presence of CuCl in between. Additional minor patina constituents are SnO2 (Cu4Sn), Zn5(OH)6(CO3)2 (Cu15Zn and Cu5Al5Zn) and Zn6Al2(OH)16CO3·4H2O/Zn2Al(OH)6Cl·2H2O/Zn5Cl2(OH)8·H2O and Al2O3 (Cu5Al5Zn). The observed Zn- and Zn/Al-containing corrosion products might be important factors for the lower sensitivity of Cu15Zn and Cu5Al5Zn against chloride-induced atmospheric corrosion compared with Cu sheet and Cu4Sn. Decreasing corrosion rates with exposure time were observed for all materials and chloride loads and attributed to an improved adherence with time of the outer patina to the underlying inner oxide. Flaking of the outer patina layer was mainly observed on Cu4Sn and Cu sheet and associated with the gradual transformation of CuCl to Cu2(OH)3Cl of larger volume. After three years only Cu5Al5Zn remains lustrous because of a patina compared with the other materials that appeared brownish-reddish. Significantly lower release rates of metals compared with corresponding corrosion rates were observed for all materials. Very similar release rates of copper from all four materials were observed during the fifth year of marine exposure due to an outer surface patina that with time revealed similar constituents and solubility properties. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Glass packages in interim storage

International Nuclear Information System (INIS)

Jacquet-Francillon, N.

1994-10-01

This report summarize the current state of knowledge concerning the behavior of type C waste packages consisting of vitrified high-level solutions produced by reprocessing spent fuel. The composition and the physical and chemical properties of the feed solutions are reviewed, and the vitrification process is described. Sodium alumino-borosilicate glass compositions are generally employed - the glass used at la Hague for LWR fuel solutions, for example, contains 45 % SiO 2 . The major physical, chemical, mechanical and thermal properties of the glass are reviewed. In order to allow their thermal power to diminish, the 3630 glass packages produced (as of January 1993) in the vitrification facilities at Marcoule and La Hague are placed in interim storage for several decades. The actual interim storage period has not been defined, as it is closely related to the concept and organization selected for the final destination of the packages: a geological repository. The glass behavior under irradiation is described. Considerable basic and applied research has been conducted to assess the aqueous leaching behavior of nuclear containment glass. The effects of various repository parameters (temperature, flow rate, nature of the environmental materials) have been investigated. The experimental findings have been used to specify a model describing the kinetics of aqueous corrosion of the glass. More generally all the ''source term'' models developed in France by the CEA or by ANDRA are summarized. (author). 152 refs., 33 figs

Applicability test of glass lining material for high-temperature acidic solutions of sulfuric acid in thermochemical water-splitting IS process

International Nuclear Information System (INIS)

Iwatsuki, Jin; Tanaka, Nobuyuki; Terada, Atsuhiko; Onuki, Kaoru; Watanabe, Yutaka

2010-01-01

A key issue for realizing the thermochemical IS process for hydrogen production is the selection of materials for working with high-temperature acidic solutions of sulfuric acid and hydriodic acid. Glass lining material is a promising candidate, which is composed of steel having good strength and glass having good corrosion resistance. Since the applicability of glass lining material depends strongly on the service condition, corrosion tests using glass used in glass lining material and heat cycle tests using glass lining piping were carried out to examine the possibility of using the glass lining material with high-temperature acidic solutions of sulfuric acid. It was confirmed that the glass lining materials exhibited sufficient corrosion resistance and heat resistance in high-temperature sulfuric acid of the IS process. (author)

Use of glass-reinforced plastic vessels in petrochemical production plants

International Nuclear Information System (INIS)

Makarov, V.G.; Baikin, V.G.; Perlin, S.M.

1984-01-01

At present, petrochemical plant production equipment is made of scarce high-alloy steels and alloys or carbon steel with subsequent chemical protection. Traditional methods of protection frequently do not provide reliable and safe service of equipment for the length of the normal operating life. One of the effective methods of combatting corrosion is the use of glass-reinforced plastic equipment. Glass-reinforced equipment is not subject to electrochemical corrosion and has a high chemical resistance. Weight is approximately a third of similar vessels. The paper provides recommendations and precautions for the production, installation, use and maintenance of glass-reinforced plastic vessels

Relationship between reaction layer thickness and leach rate for nuclear waste glasses

International Nuclear Information System (INIS)

Chick, L.A.; Pederson, L.R.

1984-02-01

Three leaching tests, devised to distinguish among several proposed nuclear waste glass leaching mechanisms, were carried out for four different waste glasses. In the first test, the influence of a pre-formed reaction layer on elemental release was evaluated. In the second test, glass specimens were replaced with fresh samples halfway through the leaching experiment, to evaluate the influence of the concentration of glass components in leaching. Finally, regular replacement of the leachant at fixed time intervals essentially removed the variable changing solution concentration, and allowed an assessment of the influence of reaction layer thickness on the leaching rate. Results for all glasses tested indicated that the reaction layer presented little or no barrier to leaching, and that most of the retardation on leaching rates generally observed are attributable to saturation effects. 20 references, 6 figures, 1 table

Effect of diamond-like carbon coating on corrosion rate of machinery steel HQ 805

Science.gov (United States)

Slat, Winda Sanni; Malau, Viktor; Iswanto, Priyo Tri; Sujitno, Tjipto; Suprapto

2018-04-01

HQ 805 is known as a super strength alloys steel and widely applied in military equipment and, aircraft components, drilling device and so on. It is due to its excellent behavior in wear, fatigue, high temperature and high speed operating conditions. The weakness of this material is the vulnerablality to corrosion when employed in sour environments where hydrogen sulfide and chlorides are present. To overcome the problems, an effort should be made to improve or enhance the surface properties for a longer service life. There are varieties of coatings developed and used to improve surface material properties. There are several kinds of coating methods; chemical vapour deposition (CVD), physical vapour deposition (PVD), thermochemical treatment, oxidation, or plasma spraying. This paper presents the research result of the influence of Diamond-Like Carbon (DLC) coating deposited using DC plasma enhanced chemical vapor deposition (DC-PECVD) on corrosion rate (by potentiodynamic polarization method) of HQ 805 machinery steel. As a carbon sources, a mixture of argon (Ar) and methane (CH4) with ratio 76% : 24% was used in this experiment. The conditions of experiment were 400 °C of temperature, 1.2 mbar, 1.4 mbar, 1.6 mbar and 1.8 mbar of pressure of process. Investigated surface properties were hardness (microhardness tester), roughness (roughness test), chemical composition (Spectrometer), microstructure (SEM) and corrosion rate (potentiodynamic polarization). It has been found that the optimum condition with the lowest corrosion rate is at a pressure of 1.4 mbar with a deposition duration of 4 hours at a constant temperature of 400 °C. In this condition, the corrosion rate decreases from 12.326 mpy to 4.487 mpy.

An expert system for corrosion rate monitoring and diagnosis in the heating circuits of nuclear power plants

International Nuclear Information System (INIS)

Balducelli, C.; Conte, E.; Federico, A.G.; Tripi, A.; Ronchetti, C.

1988-01-01

The radiation field of out of core components of a water reactor primary plant depends on corrosion product equilibria. The computer programs that try to simulate the behaviour of the corrosion products and the radiation build up didn't provide good results, especially in describing several different plants with the same program. In order to obtain better results the authors decided to use a different approach, building an expert system, which performs on-line corrosion rate monitoring by means of a number of probes connected to an automatic corrosimeter, evaluates expected corrosion rate values and behaviours, and, if there are discrepancies, performs a diagnosis, providing suggestions to overcome the difficulty. (author)

Lead-iron phosphate glass: a stable storage medium for high-level nuclear waste

International Nuclear Information System (INIS)

Sales, B.C.; Boatner, L.A.

1984-01-01

Results are presented which show that lead-iron phosphate glasses are a promising new waste form for the safe immobilization of both high-level defense and high-level commercial radioactive waste. Relative to the borosilicate nuclear waste glasses that are currently the ''reference'' waste form for the long-term disposal of nuclear waste, lead-iron phosphate glasses have several distinct advantages: (1) an aqueous corrosion rate that is about 1000 times lower, (2) a processing temperature that is 100 0 to 250 0 C lower and, (3) a much lower melt viscosity in the temperature range from 800 0 to 1000 0 C. Most significantly, the lead-iron phosphate waste form can be processed using a technology similar to that developed for borosilicate nuclear waste glasses

Estimation of flow rates through intergranular stress corrosion cracks

International Nuclear Information System (INIS)

Collier, R.P.; Norris, D.M.

1984-01-01

Experimental studies of critical two-phase water flow, through simulated and actual intergranular stress corrosion cracks, were performed to obtain data to evaluate a leak flow rate model and investigate acoustic transducer effectiveness in detecting and sizing leaks. The experimental program included a parametric study of the effects of crack geometry, fluid stagnation pressure and temperature, and crack surface roughness on leak flow rate. In addition, leak detection, location, and leak size estimation capabilities of several different acoustic transducers were evaluated as functions of leak rate and transducer position. This paper presents flow rate data for several different cracks and fluid conditions. It also presents the minimum flow rate detected with the acoustic sensors and a relationship between acoustic signal strength and leak flow rate

Long-term release from high level waste glass. Part IV. The effect of leaching mechanism

International Nuclear Information System (INIS)

Freude, E.; Grambow, B.; Lutze, W.; Rabe, H.; Ewing, R.C.

1984-01-01

A linear time dependence for the corrosion under near saturation conditions is considered, and a rate equation in the QTERM code is used to model the long-term behavior of the German glass, C-31-3EC, JSS A, and SRL TDS 131. 22 refs., 4 figs., 1 tab

Alteration of rhyolitic (volcanic) glasses in natural Bolivian salt lakes. - Natural analogue for the behavior of radioactive waste glasses in rock salt repositories

International Nuclear Information System (INIS)

Abdelouas, A.

1996-06-01

Alteration experiments with the R7T7 glass in three salt brines, saturated respectively in MgCl 2 , MgCl 2 -CaCl 2 and NaCl, showed that the solubilities of most radionuclides are controlled by the secondary phases. Nd, La, and Pr are trapped in powellite, Ce in cerianite, U in coffinite, and Sr is partially immobilized in barite. There is a good similarity between the secondary phases formed experimentally on volcanic glasses and the R7T7 glass altered in MgCl 2 CaCl 2 -saturated brine (formation of hydrotalcite and chlorite-serpentine at short-term and saponite at long-term). These results support the use of volcanic glasses alteration patterns in Mg-rich solutions (seawater, brines) to understand the long-term behavior of nuclear waste glasses and to evaluate the stability of the secondary phases. The study of the sediments of Uyuni (Bolivia) showed that the corrosion rate of the rhyolitic glass in brines at 10 C is 12 to 30 time lower than those of rhyolitic glasses altered in high dilute conditions. The neoformed phases in the sediments are: Smectite, alunite, pyrite, barite, celestite and cerianite. The low alteration rate of rhyolitic glasses in brines and the formation of secondary phases such as smectite, barite and cerianite (also formed during the experimental alteration of the R7T7 glass), permit us to expect the low alteration of nuclear waste glasses at long-term in brines and the trapping of certain radionuclides in secondary phases. (orig.) [de

Influence of irradiation and radiolysis on the corrosion rates and mechanisms of zirconium alloys

International Nuclear Information System (INIS)

Verlet, Romain

2015-01-01

The nuclear fuel of pressurized water reactors (PWR) in the form of uranium oxide UO 2 pellets (or MOX) is confined in a zirconium alloy cladding. This cladding is very important because it represents the first containment barrier against the release of fission products generated by the nuclear reaction to the external environment. Corrosion by the primary medium of zirconium alloys, particularly the Zircaloy-4, is one of the factors limiting the reactor residence time of the fuel rods (UO 2 pellets + cladding). To optimize core management and to extend the lifetime of the fuel rods in reactor, new alloys based on zirconium-niobium (M5) have been developed. However, the corrosion mechanisms of these are not completely understood because of the complexity of these materials, corrosion environment and the presence of radiation from the nuclear fuel. Therefore, this thesis specifically addresses the effects of radiolysis and defects induced by irradiation with ions in the matrix metal and the oxide layer on the corrosion rate of Zircaloy-4 and M5. The goal is to separate the influence of radiation damage to the metal, that relating to defects created in the oxide and that linked to radiolysis of the primary medium on the oxidation rate of zirconium alloys in reactor. 1) Regarding effect of irradiation of the metal on the oxidation rate: type dislocation loops appear and increase the oxidation rate of the two alloys. For M5, in addition to the first effect, a precipitation of fines needles of niobium reduced the solid solution of niobium concentration in the metal and ultimately in the oxide, which strongly reduces the oxidation rate of the alloy. 2) Regarding the effect of irradiation of the oxide layer on the oxidation rate: defects generated by the nuclear cascades in the oxide increase the oxidation rate of the two materials. For M5, germination of niobium enriched zones in irradiated oxide also causes a decrease of the niobium concentration in solid solution

Electrochemical Corrosion Studies for Modeling Metallic Waste Form Release Rates

Energy Technology Data Exchange (ETDEWEB)

Poineau, Frederic [Univ. of Nevada, Las Vegas, NV (United States); Tamalis, Dimitri [Florida Memorial Univ., Miami Gardens, FL (United States)

2016-08-01

The isotope ⁹⁹Tc is an important fission product generated from nuclear power production. Because of its long half-life (t_1/2 = 2.13 ∙ 10⁵ years) and beta-radiotoxicity (β⁻ = 292 keV), it is a major concern in the long-term management of spent nuclear fuel. In the spent nuclear fuel, Tc is present as an alloy with Mo, Ru, Rh, and Pd called the epsilon-phase, the relative amount of which increases with fuel burn-up. In some separation schemes for spent nuclear fuel, Tc would be separated from the spent fuel and disposed of in a durable waste form. Technetium waste forms under consideration include metallic alloys, oxide ceramics and borosilicate glass. In the development of a metallic waste form, after separation from the spent fuel, Tc would be converted to the metal, incorporated into an alloy and the resulting waste form stored in a repository. Metallic alloys under consideration include Tc–Zr alloys, Tc–stainless steel alloys and Tc–Inconel alloys (Inconel is an alloy of Ni, Cr and iron which is resistant to corrosion). To predict the long-term behavior of the metallic Tc waste form, understanding the corrosion properties of Tc metal and Tc alloys in various chemical environments is needed, but efforts to model the behavior of Tc metallic alloys are limited. One parameter that should also be considered in predicting the long-term behavior of the Tc waste form is the ingrowth of stable Ru that occurs from the radioactive decay of ⁹⁹Tc (⁹⁹Tc → ⁹⁹Ru + β⁻). After a geological period of time, significant amounts of Ru will be present in the Tc and may affect its corrosion properties. Studying the effect of Ru on the corrosion behavior of Tc is also of importance. In this context, we studied the electrochemical behavior of Tc metal, Tc-Ni alloys (to model Tc-Inconel alloy) and Tc-Ru alloys in acidic media. The study of Tc-U alloys has also been performed in order to better understand the

Biocorrosion Evaluation on a Zr-Cu-Ag-Ti Metallic Glass

Science.gov (United States)

Kumar, Shresh; Anwar, Rebin; Ryu, Wookha; Park, E. S.; Vincent, S.

2018-04-01

Metallic glasses are in high demand for fabrication of variety of innovative products, in particular surgical and biomedical tools and devices owing to its excellent biocompatible properties. In the present investigation, a novel Zr39.5Cu50.5Ag4Ti6 metallic glass composition was synthesized using melt spinning technique. Potentiodynamic polarization studies were conducted to investigate bio-corrosion behaviour of Zr39.5Cu50.5Ag4Ti6 metallic glass. The test were conducted in various simulated artificial body conditions such as artificial saliva solution, phosphate-buffered saline solution, artificial blood plasma solution, and Hank’s balanced saline solution. The bio-corrosion results of metallic glass were compared with traditional biomaterials. The study aims to provide bio-compatible properties of Zr39.5Cu50.5Ag4Ti6 metallic glass.

Corrosion assessment of refractory materials for high temperature waste vitrification

International Nuclear Information System (INIS)

Marra, J.C.; Congdon, J.W.; Kielpinski, A.L.

1995-01-01

A variety of vitrification technologies are being evaluated to immobilize radioactive and hazardous wastes following years of nuclear materials production throughout the Department of Energy (DOE) complex. The compositions and physical forms of these wastes are diverse ranging from inorganic sludges to organic liquids to heterogeneous debris. Melt and off-gas products can be very corrosive at the high temperatures required to melt many of these waste streams. Ensuring material durability is required to develop viable treatment processes. Corrosion testing of materials in some of the anticipated severe environments is an important aspect of the materials identification and selection process. Corrosion coupon tests on typical materials used in Joule heated melters were completed using glass compositions with high salt contents. The presence of chloride in the melts caused the most severe attack. In the metal alloys, oxidation was the predominant corrosion mechanism, while in the tested refractory material enhanced dissolution of the refractory into the glass was observed. Corrosion testing of numerous different refractory materials was performed in a plasma vitrification system using a surrogate heterogeneous debris waste. Extensive corrosion was observed in all tested materials

Effects of glass composition on the residual rate of alteration and modelling parameters

International Nuclear Information System (INIS)

Fleury, Benjamin

2013-01-01

This PhD thesis deals with the long-term behavior of the French nuclear glasses R7T7. An experiment plan (based on 27 glass compositions) is developed for studying the effect of glass composition on the residual rate of alteration. The impact of Mg-phase precipitation on glass alteration is also studied and several modelling exercises are performed. There is one order of magnitude between the different measurements (rate or pH...) associated with the different glass compositions. The statistical treatment of these measurements results in predictive equations and several observable trends are valid for all materials with a composition complying with the experiment plan conditions. The effect of Si, Na, B and Al on alteration (.i.e, gel and secondary phase's formation, pH) is confirmed, the influence of Zn, Zr and Ni-Co is evidenced. The role of Cr has to be clarified. Experiments show that glass alteration rate in underground water, which contains high level of Ca and Mg, is one order of magnitude higher than in the case of pure water. The glass composition plays the same role for the alteration in the two types of solution. During alteration, the late addition of Mg introduces a time lag in the resumption response because silicon is first provided from partial dissolution of the previously-formed alteration gel. The nucleation process does not limit Mg-silicate precipitation whereas a pH above 8-8.5 is necessary for Mg-silicate precipitation. The glass alteration rate can be a limiting factor if the quantity of Mg supplied to the reaction is enough. The Mg silicate phase seems to have systematically a molar ratio Mg/Si between 0.2 and 0.4. It is also shown that the air tightness of the reactor influences the rate of dissolution of CO 2 in the solution leading to a decrease of pH. Finally, modelling exercises with GRAAL show promising results. Such modelling is required in order to extend the prediction of the long-term alteration behavior to different glass

Fundamental problems on immiscibility, crystallization, and chemical interaction between stainless steel 304 and glasses for radioactivewaste glasses

International Nuclear Information System (INIS)

Inoue, Tadashi; Yokoyama, Hayaichi

1982-01-01

Immiscibility and crystallization, and chemical interaction with stainless steel, SUS 304, which is designed as a canister material, were investigated on non-radioactive glasses with simulated waste of 26.4 wt%. Although glasses whose initial color was black changed to yellow or yellow-brown by heat-treatment at 600 0 C, the change of color was hardly observed by the treatment at 850 0 C. Molybdenum oxide and molybdate were detected in all heat-treated glasses. It was deduced that the compounds were existing as meta-stable particle corresponding to immiscibility particle at 600 0 C and as stable crystallized particle at 850 0 C. The chemical interaction occurred at the interface between glasses and SUS 304, whose surface was attacked by boundary corrosion proceeding to uniform corrosion with increasing temperature and time. Chromium oxide layer was mainly formed in the region suffered chemical interaction. It was deduced that the chemical interaction was moderated due to the formation of protective layer, which mainly consisted of nickel oxide, at the same time as the formation of Cr 2 O 3 layer. (author)

Corrosion behavior and pitting susceptibility of in-situ Ti-based metallic glass matrix composites in 3.5 wt.% NaCl solutions

Science.gov (United States)

Xu, K. K.; Lan, A. D.; Yang, H. J.; Han, P. D.; Qiao, J. W.

2017-11-01

The Ti62Zr12V13Cu4Be9, Ti58Zr16V10Cu4Be12, Ti46Zr20V12Cu5Be17, and Ti40Zr24V12Cu5Be19 metallic glass matrix composites (MGMCs) were prepared by copper mould casting. The corrosion resistance and the pitting susceptibility of Ti-based MGMCs were tested on their cross-sectional areas in 3.5 wt.% NaCl solutions by potentiodynamic polarization measurements. The composites with lower Ti contents (Ti40Zr24V12Cu5Be19 and Ti46Zr20V12Cu5Be17) exhibit a low resistance to the chloride induced pitting and local corrosion. The preferential dissolution of amorphous matrix is explained by the high chemical reactivity of beryllium element compared to that of stable dendrites and by the detected lower Ti and V contents. However, fairly good passivity was found in the composite with higher Ti contents (Ti62Zr12V13Cu4Be9). XPS measurements revealed that protective Ti-enriched oxide film was formed on the composite surface, additionally, lower content of beryllium element in amorphous matrix hinder the selective corrosion of amorphous matrix. The assessment of experimental observation leads to a proposed corrosion mechanism involving selective dissolution of amorphous matrix and chloride induced pitting process.

Evaluation of models of waste glass durability

International Nuclear Information System (INIS)

Ellison, A.

1995-01-01

The main variable under the control of the waste glass producer is the composition of the glass; thus a need exists to establish functional relationships between the composition of a waste glass and measures of processability, product consistency, and durability. Many years of research show that the structure and properties of a glass depend on its composition, so it seems reasonable to assume that there also is relationship between the composition of a waste glass and its resistance to attack by an aqueous solution. Several models have been developed to describe this dependence, and an evaluation their predictive capabilities is the subject of this paper. The objective is to determine whether any of these models describe the ''correct'' functional relationship between composition and corrosion rate. A more thorough treatment of the relationships between glass composition and durability has been presented elsewhere, and the reader is encouraged to consult it for a more detailed discussion. The models examined in this study are the free energy of hydration model, developed at the Savannah River Laboratory, the structural bond strength model, developed at the Vitreous State Laboratory at the Catholic University of America, and the Composition Variation Study, developed at Pacific Northwest Laboratory

Effectiveness of Ti-micro alloying in relation to cooling rate on corrosion of AZ91 Mg alloy

International Nuclear Information System (INIS)

Candan, S.; Celik, M.; Candan, E.

2016-01-01

In this study, micro Ti-alloyed AZ91 Mg alloys (AZ91 + 0.5wt.%Ti) have been investigated in order to clarify effectiveness of micro alloying and/or cooling rate on their corrosion properties. Molten alloys were solidified under various cooling rates by using four stage step mold. The microstructural investigations were carried out by using scanning electron microscopy (SEM). Corrosion behaviors of the alloys were evaluated by means of immersion and electrochemical polarization tests in 3.5% NaCl solution. Results showed that the Mg 17 Al 12 (β) intermetallic phase in the microstructure of AZ91 Mg alloy formed as a net-like structure. The Ti addition has reduced the distribution and continuity of β intermetallic phase and its morphology has emerged as fully divorced eutectic. Compared to AZ91 alloy, the effect of the cooling rate in Ti-added alloy on the grain size was less pronounced. When AZ91 and its Ti-added alloys were compared under the same cooling conditions, the Ti addition showed notably high corrosion resistance. Electrochemical test results showed that while I corr values of AZ91 decrease with the increase in the cooling rate, the effect of the cooling rate on I corr values was much lower in the Ti-added alloy. The corrosion resistance of AZ91 Mg alloy was sensitive towards the cooling rates while Ti-added alloy was not affected much from the cooling conditions. - Highlights: • Effect the cooling rate on grain size was less pronounced in the Ti-added alloy. • The morphology of the β phase transformed into fully divorced eutectics. • Ti addition exhibited significantly higher corrosion resistance. • Ti micro alloying is more effective than faster cooling of the alloy on corrosion.

Effects of annealing on the microstructure, corrosion resistance, and mechanical properties of RE{sub 65}Co{sub 25}Al{sub 10} (RE=Ce, La, Pr, Sm, and Gd) bulk metallic glasses

Energy Technology Data Exchange (ETDEWEB)

Zheng, Zhou [School of Materials Science and Engineering, University of Jinan, No. 336, West Road of Nan Xinzhuang, Jinan 250022 (China); Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, No. 336, West Road of Nan Xinzhuang, Jinan 250022 (China); Xing, Qi; Sun, Zhenxi; Xu, Jing; Zhao, Zhengfeng [School of Materials Science and Engineering, University of Jinan, No. 336, West Road of Nan Xinzhuang, Jinan 250022 (China); Chen, Shuying; Liaw, Peter K. [Department of Materials Science and Engineering, University of Tennessee, Knoxville, TN (United States); Wang, Yan, E-mail: mse_wangy@ujn.edu.cn [School of Materials Science and Engineering, University of Jinan, No. 336, West Road of Nan Xinzhuang, Jinan 250022 (China); Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, No. 336, West Road of Nan Xinzhuang, Jinan 250022 (China)

2015-02-25

The effects of annealing on the microstructure, corrosion resistance and mechanical properties of the RE{sub 65}Co{sub 25}Al{sub 10} (RE=Ce, La, Pr, Sm, and Gd) bulk metallic glasses (BMGs) were studied. Microstructural changes are induced after annealing below the onset crystallization temperature of 484 K, resulting in the variation of thermal stability and crystallization behavior. A proper annealing enhances the corrosion resistance in 3.5 wt% NaCl solution, which can be attributed to reduction of the electrochemical activity and galvanic coupling effects in the chloride solution. Moreover, the RE-based BMG annealed at 484 K possesses the higher corrosion potential and lower corrosion current density, combined with the corrosion morphologies, which suggests the best corrosion resistance. Annealing can also obviously change the mechanical properties and fracture morphologies. It presents that free volume annihilation can cause more difficulty in the elastic atom rearrangement for the as-annealed RE-based BMGs.

Effect of caffeine inhibitor in corrosion rate and microstructure of KS01 carbon steel and AISI 1045 at media sea water

International Nuclear Information System (INIS)

Sulistioso Giat S; Setyo Purwanto; Deswita; Ari Handayani; Berta Vidyananda

2013-01-01

Many synthetic materials are good inhibitors for the prevention of corrosion . Many inhibitors are toxic, because of the influence of these toxic properties, recently use organic materials as corrosion inhibitors, that are not hazardous and environmentally friendly. In this study caffeine compounds used as corrosion inhibitors. This compound could be used as corrosion inhibitor because of the existence of their chemical groups that containing free electron pair, that is nitrogen. Corrosion rate testing conducted in sea water medium taken from the Northern region of Indramayu with variations of the concentration of caffeine 0, 50, 100, 150, and 200 ppm to determine the optimum concentration of caffeine in corrosion rate of carbon steel AISI 1045 and KS01 that a widely used on the cooling system in the industry. Corrosion rate of KS-01 steel before used in inhibitor media is 25,07 mpy that less than corrosion rate of carbon steel AISI 1045, is 45,82 mpy . The results of this study indicate that caffeine is able to inhibit the corrosion rate of both of samples with optimum efficiency KS01 for 64.38%, and AISI 1045 of 66.63%. The optimum concentration of caffeine to inhibited AISI 1045 is 150 ppm and for KS01 is 100 ppm,. Beside that analysis of microstructure for both samples have done, for media before and after inhibitor addition. (author)

Corrosion rate of construction materials in hot phosphoric acid with the contribution of anodic polarization

Energy Technology Data Exchange (ETDEWEB)

Kouril, M. [Institute of Chemical Technology, Technicka 5, 166 28 Prague (Czech Republic); Christensen, E. [Technical University of Denmark, Kemitorvet, 2800 Kgs. Lyngby (Denmark); Eriksen, S.; Gillesberg, B. [Tantaline A/S, Nordborgvej 81, 6430 Nordborg (Denmark)

2012-04-15

The paper is focused on selection of a proper material for construction elements of water electrolysers, which make use of a 85% phosphoric acid as an electrolyte at temperature of 150 C and which might be loaded with anodic polarization up to 2.5 V versus a saturated Ag/AgCl electrode (SSCE). Several grades of stainless steels were tested as well as tantalum, niobium, titanium, nickel alloys and silicon carbide. The corrosion rate was evaluated by means of mass loss at free corrosion potential as well as under various levels of polarization. The only corrosion resistant material in 85% phosphoric acid at 150 C and at polarization of 2.5 V/SSCE is tantalum. In that case, even a gentle cathodic polarization is harmful in such an acidic environment. Hydrogen reduction leads to tantalum hydride formation, to loss of mechanical properties and to complete disintegration of the metal. Contrary to tantalum, titanium is free of any corrosion resistance in hot phosphoric acid. Its corrosion rate ranges from tens of millimetres to metres per year depending on temperature of the acid. Alloy bonded tantalum coating was recognized as an effective corrosion protection for both titanium and stainless steel. Its serviceability might be limited by slow dissolution of tantalum that is in order of units of mm/year. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Glasses for the solidification of high-level radioactive waste: their behavior in the presence of water

International Nuclear Information System (INIS)

Grauer, R.

1983-02-01

Because of their amorphous structure, glasses are particularly suitable for the solidification of the mixture of high-level radioactive wastes resulting from reactor fuel reprocessing: they are not sensitive to variations in the compositions of waste oxides and are resistant to the damaging effects of radiation. The borosilicate glasses used for this purpose have been investigated for about 25 years, and waste vitrification techniques have been tested on a commercial scale. In view of possible accidents in a final waste repository, the chemical resistance of this type of glasses to attack by groundwaters is of special interest. The present report deals with the corrosion behaviour of glasses and discusses the most significant controlling parameters. The dissolution rates needed for safety analysis must be determined in relatively short-term experiments. Since the results can depend strongly on the type of test procedures used, a critical assessment of these techniques is necessary. Experimental results are illustrated by means of selected examples. Particular emphasis is placed upon the effects of increased temperatures and of nuclear radiation. The models which have been proposed for the estimation of the long-term behavior of vitrified waste are not yet fully complete and require improvement. Furthermore, the actual dissolution rates which are used in such models should be revised: to be desired are values which take into account the actual environmental conditions at the storage site. It should be noted, however, that even with current conservative input data on corrosion rates, a lifetime on the order of 10 5 years can be expected for the glass blocks to be deposited. The report concludes with recommendations fo further investigations

Tests on dynamic corrosion by water. Influence of the passage of a heat flux on the corrosion kinetics. pH measurement in water at high temperature; Essais de corrosion dynamique par l'eau. Influence du passage d'un flux thermique sur la cinetique de corrosion. Mesure du pH dans l'eau a haute temperature

Energy Technology Data Exchange (ETDEWEB)

Coriou, H.; Grall, L.; Hure, J.; Saint-James, R. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Berthod [Societe Grenobloise d' Etudes et d' Applications Hydrauliques, 38 (France); Le peintre [Centre National de la Recherche Scientifique (CNRS), 38 - Grenoble (France)

1958-07-01

The passage of a heat flux through the surface of a metal placed in a corrosive medium influences the rate of corrosion, these being higher than under adiabatic conditions. The apparatus developed for corrosion tests is described, it is possible to obtain with this equipment: 1) Heat fluxes greater than 200 W/cm{sup 2}, across aluminium canning, which is cooled by water (temperature 50 deg. C), circulating with flow rates of the order of 5 to 6 m/s. 2) Heat fluxes which can go up to 150 W/cm{sup 2}, across canning of zircaloy or stainless steel. The cooling fluid is pressurized water at a temperature around 280 deg. C, the flow-rate of circulation reaching 6 m/s. The results obtained on aluminium canning are studied from the viewpoint of corrosion, paying particular attention to cavitation phenomena which can cause serious damage in certain special circumstances. After developing a glass electrode system capable of supporting high pressures, the authors have investigated materials capable of functioning as a hydrogen electrode and of resisting satisfactorily corrosion by water at 200 deg. C. Various possibilities have been examined: electrodes of special glasses, quartz, metals, with a membrane etc... The results of the various tests and the practical limits of utilisation are given. (author)Fren. [French] Le passage d'un flux thermique a travers la surface d'un metal place dans un milieu corrosif influence les vitesses de corrosion, celles-ci etant plus elevees que dans des conditions adiabatiques. On decrit les appareils mis au point, pour essais de corrosion. Ils permettent d'obtenir: 1) A travers des gaine aluminium des flux thermiques depassant 200 W /cm{sup 2}. Les gaines sont refroidies par l'eau (temperature 50 deg. C), circulant a des vitesses de l'ordre de 5 a 6 m/s. 2) A travers des gaines en zircaloy ou acier inoxydable des flux thermiques pouvant s'elever a 150 W/cm{sup 2}. Le fluide de refroidissement est de l

Elemental redistribution behavior in tellurite glass induced by high repetition rate femtosecond laser irradiation

International Nuclear Information System (INIS)

Teng, Yu; Zhou, Jiajia; Khisro, Said Nasir; Zhou, Shifeng; Qiu, Jianrong

2014-01-01

Highlights: • Abnormal elements redistribution behavior was observed in tellurite glass. • The refractive index and Raman intensity distribution changed significantly. • The relative glass composition remained unchanged while the glass density changed. • First time report on the abnormal element redistribution behavior in glass. • The glass network structure determines the elemental redistribution behavior. - Abstract: The success in the fabrication of micro-structures in glassy materials using femtosecond laser irradiation has proved its potential applications in the construction of three-dimensional micro-optical components or devices. In this paper, we report the elemental redistribution behavior in tellurite glass after the irradiation of high repetition rate femtosecond laser pulses. The relative glass composition remained unchanged while the glass density changed significantly, which is quite different from previously reported results about the high repetition rate femtosecond laser induced elemental redistribution in silicate glasses. The involved mechanism is discussed with the conclusion that the glass network structure plays the key role to determine the elemental redistribution. This observation not only helps to understand the interaction process of femtosecond laser with glassy materials, but also has potential applications in the fabrication of micro-optical devices

Effect of various lead species on the leaching behavior of borosilicate waste glass

International Nuclear Information System (INIS)

Lehman, R.L.; Kuchinski, F.A.

1984-01-01

A borosilicate nuclear waste glass was static leached in pure water, silicate water, and brine solution. Three different forms of lead were included in specified corrosion cells to assess the extent to which various lead species alter the leaching behavior of the glass. Weight loss data indicated that Pb/sub m/ amd PbO greatly reduce the weight loss of glass when leached in pure water, and similar effects were noted in silicate and brine. Si concentrations, which were substantial in the glass-alone leachate, were reduced to below detection limits in all pure water cells containing a lead form. Lead concentration levels in the leachate were controlled by lead form solubility and appeared to be a significant factor in influencing apparent leaching behavior. Surface analysis revealed surface crystals, which probably formed when soluble lead in the leachate reacted with dissolved or activated silica at the glass surface. The net effect was to reduce the lease of some glass constituents to the leachate, although it was not clear whether the actual corrosion of the glass surface was reduced. Significantly different corrosion inhibiting effects were noted among lead metal and two forms of lead oxide. 9 refs., 7 figs., 3 tabs

Review of corrosion causes and corrosion control in a technical facility

International Nuclear Information System (INIS)

Charng, T.; Lansing, F.

1982-06-01

Causes of corrosion of metals and their alloys are reviewed. The corrosion mechanism is explained by electrochemical reaction theory. The causes and methods of controlling of both physiochemical corrosion and biological corrosion are presented. Factors which influence the rate of corrosion are also discussed

Evaluation of flow accelerated corrosion by coupled analysis of corrosion and flow dynamics. Relationship of oxide film thickness, hematite/magnetite ratio, ECP and wall thinning rate

International Nuclear Information System (INIS)

Uchida, Shunsuke; Naitoh, Masanori; Okada, Hidetoshi; Uehara, Yasushi; Koshizuka, Seiichi

2011-01-01

Systematic approaches to evaluate flow accelerated corrosion (FAC) are desired before discussing application of countermeasures for FAC. First, future FAC occurrence should be evaluated to identify locations where a higher possibility of FAC occurrence exists, and then, wall thinning rate at the identified FAC occurrence zone is evaluated to obtain the preparation time for applying countermeasures. Wall thinning rates were calculated with two coupled models: 1.static electrochemical analysis and 2.dynamic oxide layer growth analysis. The anodic current density and the electrochemical corrosion potential (ECP) were calculated with the static electrochemistry model based on an Evans diagram. The ferrous ion release rate, determined by the anodic current density, was applied as input for the dynamic double oxide layer model. Some of the dissolved ferrous ion was removed to the bulk water and others precipitated on the surface as magnetite particles. The thickness of oxide layer was calculated with the dynamic oxide layer growth model and then its value was used as input in the electrochemistry model. It was confirmed that the calculated results (corrosion rate and ECP) based on the coupled models were in good agreement with the measured ones. Higher ECP was essential for preventing FAC rate. Moderated conditions due to lower mass transfer coefficients resulted in thicker oxide layer thickness and then higher ECP, while moderated corrosion conditions due to higher oxidant concentrations resulted in larger hematite/magnetite rate and then higher ECP.

Designing biocompatible Ti-based metallic glasses for implant applications

International Nuclear Information System (INIS)

Calin, Mariana; Gebert, Annett; Ghinea, Andreea Cosmina; Gostin, Petre Flaviu; Abdi, Somayeh; Mickel, Christine; Eckert, Jürgen

2013-01-01

Ti-based metallic glasses show high potential for implant applications; they overcome in several crucial respects their well-established biocompatible crystalline counterparts, e.g. improved corrosion properties, higher fracture strength and wear resistance, increased elastic strain range and lower Young's modulus. However, some of the elements required for glass formation (e.g. Cu, Ni) are harmful for the human body. We critically reviewed the biological safety and glass forming tendency in Ti of 27 elements. This can be used as a basis for the future designing of novel amorphous Ti-based implant alloys entirely free of harmful additions. In this paper, two first alloys were developed: Ti 75 Zr 10 Si 15 and Ti 60 Nb 15 Zr 10 Si 15 . The overheating temperature of the melt before casting can be used as the controlling parameter to produce fully amorphous materials or bcc-Ti-phase reinforced metallic glass nano-composites. The beneficial effect of Nb addition on the glass-formation and amorphous phase stability was assessed by X-ray diffraction, transmission electron microscopy and differential scanning calorimetry. Crystallization and mechanical behavior of ribbons are influenced by the amount and distribution of the nano-scaled bcc phase existing in the as-cast state. Their electrochemical stability in Ringer's solution at 310 K was found to be significantly better than that of commercial Ti-based biomaterials; no indication for pitting corrosion was recorded. Highlights: ► Link between biocompatibility and glass-forming ability of alloying additions in Ti ► Selection of Ti–Zr–Si and Ti–Zr–Nb–Si glass-forming alloys ► Two novel glassy alloys were developed: Ti 75 Zr 10 Si 15 and Ti 60 Nb 15 Zr 10 Si 15. ► Glass-formation, thermal stability, corrosion and mechanical behavior were studied. ► Assessing the suitability for orthopedic applications.

Predictive Surface Roughness Model for End Milling of Machinable Glass Ceramic

Energy Technology Data Exchange (ETDEWEB)

Reddy, M Mohan; Gorin, Alexander [School of Engineering and Science, Curtin University of Technology, Sarawak (Malaysia); Abou-El-Hossein, K A, E-mail: mohan.m@curtin.edu.my [Mechanical and Aeronautical Department, Nelson Mandela Metropolitan University, Port Elegebeth, 6031 (South Africa)

2011-02-15

Advanced ceramics of Machinable glass ceramic is attractive material to produce high accuracy miniaturized components for many applications in various industries such as aerospace, electronics, biomedical, automotive and environmental communications due to their wear resistance, high hardness, high compressive strength, good corrosion resistance and excellent high temperature properties. Many research works have been conducted in the last few years to investigate the performance of different machining operations when processing various advanced ceramics. Micro end-milling is one of the machining methods to meet the demand of micro parts. Selecting proper machining parameters are important to obtain good surface finish during machining of Machinable glass ceramic. Therefore, this paper describes the development of predictive model for the surface roughness of Machinable glass ceramic in terms of speed, feed rate by using micro end-milling operation.

Predictive Surface Roughness Model for End Milling of Machinable Glass Ceramic

International Nuclear Information System (INIS)

Reddy, M Mohan; Gorin, Alexander; Abou-El-Hossein, K A

2011-01-01

Advanced ceramics of Machinable glass ceramic is attractive material to produce high accuracy miniaturized components for many applications in various industries such as aerospace, electronics, biomedical, automotive and environmental communications due to their wear resistance, high hardness, high compressive strength, good corrosion resistance and excellent high temperature properties. Many research works have been conducted in the last few years to investigate the performance of different machining operations when processing various advanced ceramics. Micro end-milling is one of the machining methods to meet the demand of micro parts. Selecting proper machining parameters are important to obtain good surface finish during machining of Machinable glass ceramic. Therefore, this paper describes the development of predictive model for the surface roughness of Machinable glass ceramic in terms of speed, feed rate by using micro end-milling operation.

Copper corrosion in pure oxygen-free water

International Nuclear Information System (INIS)

Moeller, K.

1995-12-01

The study was initiated following reports on corrosion of Copper in water in absence of Oxygen. Quartz glass tubes containing pure water and Copper plates were sealed in two different ways, using Palladium or Platinum foils, respectively. Tests were also performed with Copper wires. The insulated systems contained Oxygen initially. The Oxygen was dissolved in the water, and in the air column between the water surface and the Palladium/Platinum foils. The tubes were kept in a hot cabinet at 50 C for a total of two years. The exposed plates were analyzed in different ways, e g using reflectance FTIR. The amounts of oxide formed were also weighed. The following conclusions could be drawn: No difference in color was observed for the Pd and Pt seals except in one case for the Copper wire, where only a slight difference was noticed. No significant difference in oxidation between the plates with Pd or Pt seals in quartz glass tubes. No oxide growth was observed during the last year. The corrosion rate at 50 C is below 2.3 micrograms Copper/cm 2 /year. A certain imbalance was noted between the amounts of oxides formed, and expected amount estimated from the original amount of oxygen in the system. A significant amount of water has 'disappeared' from the tubes. 17 refs, 10 figs, 3 tabs

An experimental comparison of three wire beam electrode based methods for determining corrosion rates and patterns

International Nuclear Information System (INIS)

Tan, Y.-J.

2005-01-01

Laboratory experiments have been carried out to examine the advantages and limitations of three wire beam electrode (WBE) based techniques, including the noise resistance R n -WBE method, the overpotential-galvanic current method, and the galvanic current method, in determining corrosion rates and patterns. These techniques have been applied simultaneously to several selected corrosion systems of different characteristics. It has been found that the R n -WBE method has advantages over other WBE based methods when applying to WBE surfaces under uniform corrosion. However, the R n -WBE method has been found to be unsuitable for low noise level corrosion systems. It has also been found that both R n -WBE and overpotential-galvanic current methods are similarly applicable to WBE surfaces under nonuniform corrosion. However, the galvanic current method has been found to be suitable only for WBE surfaces under highly localised corrosion. Some related issues regarding R n calculation such as trend removal and its effects on corrosion mapping have also been discussed

Radiation effects in glass and glass-ceramic waste forms for the immobilization of CANDU UO2 fuel reprocessing waste

International Nuclear Information System (INIS)

Tait, J.C.

1993-05-01

AECL has investigated three waste forms for the immobilization of high-level liquid wastes that would arise if used CANDU fuels were reprocessed at some time in the future to remove fissile materials for the fabrication of new power reactor fuel. These waste forms are borosilicate glasses, aluminosilicate glasses and titanosilicate glass-ceramics. This report discusses the potential effects of alpha, beta and gamma radiation on the releases of radionuclides from these waste forms as a result of aqueous corrosion by groundwaters that would be present in an underground waste disposal vault. The report discusses solid-state damage caused by radiation-induced atomic displacements in the waste forms as well as irradiation of groundwater solutions (radiolysis), and their potential effects on waste-form corrosion and radionuclide release. The current literature on radiation effects on borosilicate glasses and in ceramics is briefly reviewed, as are potential radiation effects on specialized waste forms for the immobilization of 129 I, 85 Kr and 14 C. (author). 104 refs., 9 tabs., 5 figs

Prediction on corrosion rate of pipe in nuclear power system based on optimized grey theory

International Nuclear Information System (INIS)

Chen Yonghong; Zhang Dafa; Chen Dengke; Jiang Wei

2007-01-01

For the prediction of corrosion rate of pipe in nuclear power system, the pre- diction error from the grey theory is greater, so a new method, optimized grey theory was presented in the paper. A comparison among predicted results from present and other methods was carried out, and it is seem that optimized grey theory is correct and effective for the prediction of corrosion rate of pipe in nuclear power system, and it provides a fundamental basis for the maintenance of pipe in nuclear power system. (authors)

The effect of quench rate on the microstructure, mechanical properties, and corrosion behavior of U-6 Wt Pct Nb

International Nuclear Information System (INIS)

Eckelmeyer, K.H.; Romiy, A.D.; Weirick, L.J.

1984-01-01

The effect of cooling rate on microstructure, mechanical behavior, corrosion resistance, and subsequent age hardenability is discussed. Cooling rates in excess of 20 Ks -1 cause the parent γ-phase to transform martensitically to a niobium supersaturated variant of the α-phase. This phase exhibits low hardness and strength, high ductility, good corrosion resistance, and age hardenability. As cooling rate decreases from 10 Ks -1 to 0.2 Ks -1 , microstructural changes (consistent with spinodal decomposition) occur to an increasing extent. These changes produce increases in hardness and strength and decreases in ductility, corrosion resistance, and age hardenability. At cooling rates less than 0.2 Ks -1 the parent phase undergoes cellular decomposition to a coarse two-phase lamellar microstructure which exhibits intermediate strength and ductility, reduced corrosion resistance, and no age hardenability. An analysis of the cooling rates indicates that fully martensitic microstructures can be obtained in plates as thick as 50 mm

Hot corrosion of the steel SA213-T22 and SA213-TP347H in 80% V2O5-20%Na2SO4 mixture

International Nuclear Information System (INIS)

Almeraya, F.; Martinez-Villafane, A.; Gaona, C.; Romero, M.A.; Malo, J.M.

1998-01-01

Many hot corrosion problems in industrial and utility boilers are caused by molten salts. The corrosion processes which occur in salts are of an electrochemical nature, and so they can be studied using electrochemical test methods. In this research, electrochemical techniques in molten salt systems have been used for the measurements of molten corrosion processes. Electrochemical test methods are described here for a salt mixture of 80%V 2 O 5 -20%NaSO 4 at 540-680 degree centigrade. To establish better the electrochemical corrosion rate measurements for molten salt systems, information from electrochemical potentiodynamic polarization curves, such as polarization resistance and Tafeol slopes were used in this study to generate corrosion rate data. The salt was contained in a quartz crucible inside a stainless retort. The atmosphere used was air. A thermocouple sheathed with quartz glass was introduced into the molten salt for temperature monitoring and control. Two materials were tested in the molten mixture: SA213-T22 and SA213-TP347H steels. The corrosion rates values obtained using electrochemical methods were around 0.58-7.14 mm/yr (22.9-281 mpy). The corrosion rate increase with time. (Author) 7 refs

Alteration of nuclear glass in contact with iron and claystone at 90 °C under anoxic conditions: Characterization of the alteration products after two years of interaction

International Nuclear Information System (INIS)

Schlegel, Michel L.; Martin, Christelle; Brucker, Florence; Bataillon, Christian; Blanc, Cécile; Chorro, Matthieu; Jollivet, Patrick

2016-01-01

The present study investigates the alteration of a fractured glass block in contact with iron and Callovo-Oxfordian claystone at 90 °C under anoxic and water-saturated conditions. The alteration rates and the nature of glass alteration products at the different compact interfaces (glass-clay, glass-iron) and in cracks were assessed by solution chemistry and microscopic-scale techniques (scanning electron microscopy coupled with energy-dispersive X-ray microscopy, microRaman spectroscopy, and X-ray absorption fine structure spectroscopy). A significant but modest (two-fold) increase in glass alteration in contact with steel was observed, leading to an average alteration rate over the experiment of about 0.007–0.014 g/m"2/d. This rate is significantly lower than forward rate r_0 in clay-equilibrated groundwater (1.7 g/m"2/d), indicating that a decrease of the alteration rate was not hindered by the steel presence. The corrosion–alteration interface was made up of successive layers of corrosion products in contact with iron, a layer of Fe silicates, and an altered glass layer enriched in Fe. Characterization of the glass block in direct contact with claystone revealed that the thickness of altered glass was much more important than at the glass-iron interface. The altered glass layer in contact with clay was slightly enriched in Fe and Mg, and depleted in alkali cations. Altered glass layers in cracks were usually limited to fringes thinner than 2 μm, with a thickness decreasing from the crack mouth, indicating that alteration is controlled by transport in the cracks. The fractures were partially filled with calcite and lanthanide hydroxocarbonate precipitates. These results contribute to the understanding of nuclear vitrified waste-iron-corrosion products interactions in a deep geological repository. - Highlights: • Anoxic alteration of glass in contact with iron and clay at 90 °C for two-years. • Alteration rates of 0.015 and 0.5 g/m"2/d at glass

Measuring the corrosion rate of steel in concrete – effect of measurement technique, polarisation time and current

DEFF Research Database (Denmark)

Nygaard, Peter Vagn; Geiker, Mette Rica

2012-01-01

, are in some studies considered the main reasons for the variations. This paper presents an experimental study on the quantitative effect of polarisation time and current on the measured polarisation resistance – and thus the corrosion current density – of passively and actively corroding steel. Two...... electrochemical techniques often used in instruments for on-site corrosion rate measurements are investigated. On passively corroding reinforcement the measured polarisation resistance was for both techniques found to be highly affected by the polarisation time and current and no plateaus at either short or long...... rate for actively corroding steel. For both techniques guidelines for polarisation times and currents are given for (on-site) non-destructive corrosion rate measurements on reinforcement steel in concrete....

Effects of grain size on the corrosion resistance of pure magnesium by cooling rate-controlled solidification

Science.gov (United States)

Liu, Yichi; Liu, Debao; You, Chen; Chen, Minfang

2015-09-01

The aim of this study was to investigate the effect of grain size on the corrosion resistance of pure magnesium developed for biomedical applications. High-purity magnesium samples with different grain size were prepared by the cooling rate-controlled solidification. Electrochemical and immersion tests were employed to measure the corrosion resistance of pure magnesium with different grain size. The electrochemical polarization curves indicated that the corrosion susceptibility increased as the grain size decrease. However, the electrochemical impedance spectroscopy (EIS) and immersion tests indicated that the corrosion resistance of pure magnesium is improved as the grain size decreases. The improvement in the corrosion resistance is attributed to refine grain can produce more uniform and density film on the surface of sample.

Material Removal Rate for Magnetorheological Finishing (MRF) of Optical Glasses with Nanodiamond MR Fluid

Energy Technology Data Exchange (ETDEWEB)

DeGroote, J.E.; Marino, A.E.; Wilson, J.P.; Bishop, A.L.; Jacobs, S.D.

2007-07-13

We present a material removal rate model for MRF of optical glasses using nanodiamond MR fluid. The new model incorporates terms for drag force, polishing particle properties, chemical durability and glass composition into an existing model that contains only terms for the glass mechanical properties. Experimental results for six optical glasses are given that support this model.

Material Removal Rate for Magnetorheological Finishing (MRF) of Optical Glasses with Nanodiamond MR Fluid

International Nuclear Information System (INIS)

DeGroote, J.E.; Marino, A.E.; Wilson, J.P.; Bishop, A.L.; Jacobs, S.D.

2007-01-01

We present a material removal rate model for MRF of optical glasses using nanodiamond MR fluid. The new model incorporates terms for drag force, polishing particle properties, chemical durability and glass composition into an existing model that contains only terms for the glass mechanical properties. Experimental results for six optical glasses are given that support this model

Understanding the structural drivers governing glass-water interactions in borosilicate based model bioactive glasses.

Science.gov (United States)

Stone-Weiss, Nicholas; Pierce, Eric M; Youngman, Randall E; Gulbiten, Ozgur; Smith, Nicholas J; Du, Jincheng; Goel, Ashutosh

2018-01-01

The past decade has witnessed a significant upsurge in the development of borate and borosilicate based resorbable bioactive glasses owing to their faster degradation rate in comparison to their silicate counterparts. However, due to our lack of understanding about the fundamental science governing the aqueous corrosion of these glasses, most of the borate/borosilicate based bioactive glasses reported in the literature have been designed by "trial-and-error" approach. With an ever-increasing demand for their application in treating a broad spectrum of non-skeletal health problems, it is becoming increasingly difficult to design advanced glass formulations using the same conventional approach. Therefore, a paradigm shift from the "trial-and-error" approach to "materials-by-design" approach is required to develop new-generations of bioactive glasses with controlled release of functional ions tailored for specific patients and disease states, whereby material functions and properties can be predicted from first principles. Realizing this goal, however, requires a thorough understanding of the complex sequence of reactions that control the dissolution kinetics of bioactive glasses and the structural drivers that govern them. While there is a considerable amount of literature published on chemical dissolution behavior and apatite-forming ability of potentially bioactive glasses, the majority of this literature has been produced on silicate glass chemistries using different experimental and measurement protocols. It follows that inter-comparison of different datasets reveals inconsistencies between experimental groups. There are also some major experimental challenges or choices that need to be carefully navigated to unearth the mechanisms governing the chemical degradation behavior and kinetics of boron-containing bioactive glasses, and to accurately determine the composition-structure-property relationships. In order to address these challenges, a simplified

Effect of temperature, of oxygen content and the downstream effect on corrosion rate of structural materials in liquid sodium

International Nuclear Information System (INIS)

Ilincev, G.

1988-01-01

The effects were experimentally tested of temperature and of oxygen content on the corrosion rate of structural materials in liquid sodium and on reducing the corrosion rate down the sodium stream. The results of the experiments are shown in graphs and tables and are discussed in detail. The duration of all tests was standard 1,000 hours. The test parameters were set such as to determine the effect of temperature on corrosion of a quantity of various materials in sodium with a low oxygen content (1.2 to 2 ppm) at temperatures of 500 to 800 degC and in sodium with a high oxygen content (345 ppm) at temperatures of 500 to 700 degC. More experiments served the determination of the effect of a different oxygen content varying between 1.2 and 2 ppm at a constant temperature of 600 degC. The materials being tested included main structural materials used for fast reactor construction and materials allowing to establish the effect of main alloying elements on their corrosion in liquid sodium of different temperatures and purity grades. The relationships showing the effects of temperature and oxygen content in sodium on the rate of corrosion of various structural materials in hot parts of the installation and on the reduction in the rate of corrosion downstream due to sodium saturation with corrosion products were constructed using the experimental results. (Z.M.). 15 figs., 2 tabs., 7 refs

High rate operation of micro-strip gas chambers on diamond-coated glass

CERN Document Server

Bouclier, Roger; Million, Gilbert; Ropelewski, Leszek; Sauli, Fabio; Temmel, T; Cooke, R A; Donnel, S; Sastri, S A; Sonderer, N

1996-01-01

Very high rate operation of micro­strip gas chambers can be achieved using slightly conducting substrates. We describe preliminary measurements realized with detectors manufactured on boro-silicate glass coated, before the photo-lithographic processing, with a diamond layer having a surface resistivity of around 1014 ‡/o. Stable medium-term operation, and a rate capability largely exceeding the one obtained with identical plates manufactured on uncoated glass are demonstrated. If these results are confirmed by long-term measurements the diamond coating technology appears very attractive since it allows, with a moderate cost overhead, to use thin, commercially available glass with the required surface quality for the large-scale production of gas micro-strip detectors.

Alteration of R7T7-type nuclear glass in deep geological storage conditions

International Nuclear Information System (INIS)

Combarieu, G. de

2007-02-01

This PhD thesis is aimed to study the alteration of SON68 glass, French inactive glass of R7T7-type, in contact with near field materials of a deep geological storage (French concept from ANDRA) which are mainly metallic iron and Callovo-Oxfordian clay. Therefore, experiments involving a 'glass-iron-clay' system at lab-scale have been carried out. Interactions between glass, iron and clay have been characterised from submicron to millimeter scale by means of SEM, TEM, XRD and XAS and Raman spectroscopies in terms of chemistry and crystal-chemistry. In the mean time, a conceptual model of glass alteration has been developed to account for most of the experimental observations and known mechanisms of alteration. The model has been then transposed within the transport-chemistry code HYTEC, together with developed models of clay and iron corrosion, to simulate the experiments described above. This work is thus a contribution to the understanding of iron corrosion in Callovo-Oxfordian clay and subsequent glass alteration in the newly formed corrosion products, the whole process being considered as a lab-scale model of a deep geological storage of radioactive wastes. (author)

Coupling of Nuclear Waste Form Corrosion and Radionuclide Transports in Presence of Relevant Repository Sediments

International Nuclear Information System (INIS)

Wall, Nathalie A.; Neeway, James J.; Qafoku, Nikolla P.; Ryan, Joseph V.

2015-01-01

Assessments of waste form and disposal options start with the degradation of the waste forms and consequent mobilization of radionuclides. Long-term static tests, single-pass flow-through tests, and the pressurized unsaturated flow test are often employed to study the durability of potential waste forms and to help create models that predict their durability throughout the lifespan of the disposal site. These tests involve the corrosion of the material in the presence of various leachants, with different experimental designs yielding desired information about the behavior of the material. Though these tests have proved instrumental in elucidating various mechanisms responsible for material corrosion, the chemical environment to which the material is subject is often not representative of a potential radioactive waste repository where factors such as pH and leachant composition will be controlled by the near-field environment. Near-field materials include, but are not limited to, the original engineered barriers, their resulting corrosion products, backfill materials, and the natural host rock. For an accurate performance assessment of a nuclear waste repository, realistic waste corrosion experimental data ought to be modeled to allow for a better understanding of waste form corrosion mechanisms and the effect of immediate geochemical environment on these mechanisms. Additionally, the migration of radionuclides in the resulting chemical environment during and after waste form corrosion must be quantified and mechanisms responsible for migrations understood. The goal of this research was to understand the mechanisms responsible for waste form corrosion in the presence of relevant repository sediments to allow for accurate radionuclide migration quantifications. The rationale for this work is that a better understanding of waste form corrosion in relevant systems will enable increased reliance on waste form performance in repository environments and potentially

Coupling of Nuclear Waste Form Corrosion and Radionuclide Transports in Presence of Relevant Repository Sediments

Energy Technology Data Exchange (ETDEWEB)

Wall, Nathalie A. [Washington State Univ., Pullman, WA (United States); Neeway, James J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Qafoku, Nikolla P. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Ryan, Joseph V. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2015-09-30

Assessments of waste form and disposal options start with the degradation of the waste forms and consequent mobilization of radionuclides. Long-term static tests, single-pass flow-through tests, and the pressurized unsaturated flow test are often employed to study the durability of potential waste forms and to help create models that predict their durability throughout the lifespan of the disposal site. These tests involve the corrosion of the material in the presence of various leachants, with different experimental designs yielding desired information about the behavior of the material. Though these tests have proved instrumental in elucidating various mechanisms responsible for material corrosion, the chemical environment to which the material is subject is often not representative of a potential radioactive waste repository where factors such as pH and leachant composition will be controlled by the near-field environment. Near-field materials include, but are not limited to, the original engineered barriers, their resulting corrosion products, backfill materials, and the natural host rock. For an accurate performance assessment of a nuclear waste repository, realistic waste corrosion experimental data ought to be modeled to allow for a better understanding of waste form corrosion mechanisms and the effect of immediate geochemical environment on these mechanisms. Additionally, the migration of radionuclides in the resulting chemical environment during and after waste form corrosion must be quantified and mechanisms responsible for migrations understood. The goal of this research was to understand the mechanisms responsible for waste form corrosion in the presence of relevant repository sediments to allow for accurate radionuclide migration quantifications. The rationale for this work is that a better understanding of waste form corrosion in relevant systems will enable increased reliance on waste form performance in repository environments and potentially

The corrosion rate measurement of Inconel 690 on high temperature and pressure by using CMS100

International Nuclear Information System (INIS)

Sriyono; Satmoko, Ari; Febrianto; Hidayati, N R; Arifal; Sumarno, Ady; Handoyo, Ismu; Prasetjo, Joko

1999-01-01

The corrosion rate measurement of Inconel 690 on high temperature and pressure had been done. By using an Autoclave, and temperature can be simulated. For reducing the pressure on Autoclave so its can be measure by Corrosion Measurement System 100(CMS100), the electrodes placement had designed and fabrication on the cover of Autoclave. The electrodes of CMS100 are reference electrode, working electrodes and counter electrodes. The electrodes placement are made and and designed on two packages, these are Salt bridge and Counter-specimen placement. From the result of testing these both of placement are able to 90 bar (pressure) and 280 C (temperature) operation rate measurement was done on temperature variation from 150 0C, 190 0C, 200 0C, 210 0C, 220 0C and 230 0C, and the solution is 0.1 ppm chloride. The pressure experiment is the pressure, which occurred in Autoclave. From the Tafel analysis, even through very little The corrosion current increased from 150 C to 230 C it is 2,54x10-10 a/cm2 to 1,62x10-9 A/cm2, but the the corrosion rate is still zero

Experimental alteration of R7T7 glass in salt brines at 90 deg C and 150 deg C

International Nuclear Information System (INIS)

Godon, N.; Vernaz, E.; Gin, S.; Beaufort, D.; Thomassin, J.H.

1991-01-01

Static experiments have been developed to investigate the R7T7 glass corrosion in four natural salt brines (brines 1 and 3: pure halite, brines 2 and 4: high Mg, K fluid inclusions rich halite), at 90 deg C and 150 deg C with 0.7 cm -1 S/V ratio and at 11 different running times. Analysis of brines after alteration (pHmeter and ICP) added to a detailed study of the crystalline phases developed at the interface glass-brine (XRD,SEM and Microprobe), showed that the influence of the compositional difference is more important on the nature of the secondary phases formed than on the corrosion rate of the glass. After 91 days of alteration at 150 deg C stady states to be reached (after 40 days at 90 deg C). A long term experiment (1 year) is necessary to confirm this hypothesis. 7 refs., 7 figs., 2 tabs

Corrosion-fatigue studies of the Zr-based Vitreloy 105 bulk metallic glass

International Nuclear Information System (INIS)

Horton Jr, Joe A.; Morrison, M.L.; Buchanan, R.A.; Liaw, Peter K.; Green, B.A.; Wang, G.Y.

2007-01-01

The purpose of this study was to characterize the stress-life behavior of the Vitreloy 105 BMG alloy in the four-point bending configuration in a 0.6 M. NaCl electrolyte. At high stress amplitudes, the corrosion-fatigue life was similar to the fatigue lives observed in air. The environment became increasingly detrimental with decreases in stress, and the corrosion-fatigue endurance limit decreased to about 50 MPa, an 88% decrease relative to testing in air. Similar to the tests conducted in air, oxide particles were found on the fracture surfaces but did not appear to significantly affect the corrosion-fatigue lives. However, wear and the resultant corrosion at the outer loading pins resulted in crack initiation in most of the samples. Thus, these results are considered conservative estimates of the corrosion-fatigue behavior of this BMG alloy. Monitoring of the samples and the open-circuit potentials revealed that the onset of significant crack growth occurred at an average of 92% of the total fatigue life. The mechanism of corrosion-fatigue degradation was found to be anodic dissolution

Synergy effect of naphthenic acid corrosion and sulfur corrosion in crude oil distillation unit

Energy Technology Data Exchange (ETDEWEB)

Huang, B.S., E-mail: yinwenfeng2010@163.com [College of Materials Science and Engineering, Southwest Petroleum University, Sichuan, Chengdu, 610500 (China); Yin, W.F. [College of Mechatronic Engineering, Southwest Petroleum University, Sichuan, Chengdu, 610500 (China); Sang, D.H. [Sheng Li Construction Group International Engineering Department, Shandong, Dongying, 257000 (China); Jiang, Z.Y. [College of Materials Science and Engineering, Southwest Petroleum University, Sichuan, Chengdu, 610500 (China)

2012-10-15

Highlights: Black-Right-Pointing-Pointer The corrosion of a carbon-manganese steel and a stainless steel in sulfur and/or naphthenic acid media was investigated. Black-Right-Pointing-Pointer The corrosion rate of the carbon-manganese steel increased with the increase of the acid value and sulfur content. Black-Right-Pointing-Pointer The critical values of the concentration of sulfur and acid for corrosion rate of the stainless steel were ascertained respectively. Black-Right-Pointing-Pointer The stainless steel is superior to the carbon-manganese steel in corrosion resistance because of the presence of stable Cr{sub 5}S{sub 8} phases. - Abstract: The synergy effect of naphthenic acid corrosion and sulfur corrosion at high temperature in crude oil distillation unit was studied using Q235 carbon-manganese steel and 316 stainless steel. The corrosion of Q235 and 316 in corrosion media containing sulfur and/or naphthenic acid at 280 Degree-Sign C was investigated by weight loss, scanning electron microscope (SEM), EDS and X-ray diffractometer (XRD) analysis. The results showed that in corrosion media containing only sulfur, the corrosion rate of Q235 and 316 first increased and then decreased with the increase of sulfur content. In corrosion media containing naphthenic acid and sulfur, with the variations of acid value or sulfur content, the synergy effect of naphthenic acid corrosion and sulfur corrosion has a great influence on the corrosion rate of Q235 and 316. It was indicated that the sulfur accelerated naphthenic acid corrosion below a certain sulfur content but prevented naphthenic acid corrosion above that. The corrosion products on two steels after exposure to corrosion media were investigated. The stable Cr{sub 5}S{sub 8} phases detected in the corrosion products film of 316 were considered as the reason why 316 has greater corrosion resistance to that of Q235.

Radiation effects in glass and glass-ceramic waste forms for the immobilization of CANDU UO{sub 2} fuel reprocessing waste

Energy Technology Data Exchange (ETDEWEB)

Tait, J C

1993-05-01

AECL has investigated three waste forms for the immobilization of high-level liquid wastes that would arise if used CANDU fuels were reprocessed at some time in the future to remove fissile materials for the fabrication of new power reactor fuel. These waste forms are borosilicate glasses, aluminosilicate glasses and titanosilicate glass-ceramics. This report discusses the potential effects of alpha, beta and gamma radiation on the releases of radionuclides from these waste forms as a result of aqueous corrosion by groundwaters that would be present in an underground waste disposal vault. The report discusses solid-state damage caused by radiation-induced atomic displacements in the waste forms as well as irradiation of groundwater solutions (radiolysis), and their potential effects on waste-form corrosion and radionuclide release. The current literature on radiation effects on borosilicate glasses and in ceramics is briefly reviewed, as are potential radiation effects on specialized waste forms for the immobilization of {sup 129}I, {sup 85}Kr and {sup 14}C. (author). 104 refs., 9 tabs., 5 figs.

Erosion and erosion-corrosion

International Nuclear Information System (INIS)

Isomoto, Yoshinori

2008-01-01

It is very difficult to interpret the technical term of erosion-corrosion' which is sometimes encountered in piping systems of power plants, because of complicated mechanisms and several confusing definitions of erosion-corrosion phenomena. 'FAC (flow accelerated corrosion)' is recently introduced as wall thinning of materials in power plant systems, as a representative of 'erosion-corrosion'. FAC is, however, not necessarily well understood and compared with erosion-corrosion. This paper describes firstly the origin, definition and fundamental understandings of erosion and erosion-corrosion, in order to reconsider and reconfirm the phenomena of erosion, erosion-corrosion and FAC. Next, typical mapping of erosion, corrosion, erosion-corrosion and FAC are introduced in flow velocity and environmental corrosiveness axes. The concept of damage rate in erosion-corrosion is finally discussed, connecting dissolution rate, mass transfer of metal ions in a metal oxide film and film growth. (author)

Corrosion of metallic materials. Dry corrosion, aqueous corrosion and corrosion by liquid metal, methods of protection

International Nuclear Information System (INIS)

Helie, Max

2015-01-01

This book is based on a course on materials given in an engineering school. The author first gives an overview of metallurgy issues: metallic materials (pure metals, metallic alloys), defects of crystal lattices (point defects, linear defects or dislocations), equilibrium diagrams, steels and cast, thermal processing of steels, stainless steels, aluminium and its alloys, copper and its alloys. The second part addresses the properties and characterization of surfaces and interfaces: singularity of a metal surface, surface energy of a metal, energy of grain boundaries, adsorption at a material surface, metal-electrolyte interface, surface oxide-electrolyte interface, techniques of surface analysis. The third chapter addresses the electrochemical aspects of corrosion: description of the corrosion phenomenon, free enthalpy of a compound and free enthalpy of a reaction, case of dry corrosion (thermodynamic aspect, Ellingham diagram, oxidation mechanisms, experimental study, macroscopic modelling), case of aqueous corrosion (electrochemical thermodynamics and kinetics, experimental determination of corrosion rate). The fourth part addresses the different forms of aqueous corrosion: generalized corrosion (atmospheric corrosion, mechanisms and tests), localized corrosion (galvanic, pitting, cracking, intergranular, erosion and cavitation), particular cases of stress cracking (stress corrosion, fatigue-corrosion, embrittlement by hydrogen), and bi-corrosion (of non alloyed steels, of stainless steels, and of aluminium and copper alloys). The sixth chapter addresses the struggle and the protection against aqueous corrosion: methods of prevention, scope of use of main alloys, geometry-based protection of pieces, use of corrosion inhibitors, use of organic or metallic coatings, electrochemical protection. The last chapter proposes an overview of corrosion types in industrial practices: in the automotive industry, in the oil industry, in the aircraft industry, and in the

A comparison of the performance of nuclear waste glasses by modeling

International Nuclear Information System (INIS)

Grambow, B.; Strachan, D.M.

1988-01-01

A model selected for the licensing process must be based on a physical and chemical understanding of the glass corrosion mechanism. The purpose of this paper is to show that a dissolution/precipitation model can be used to better understand the effects of various system variables on glass dissolution. The application and validation of this model are also discussed. A dissolution/precipitation model developed appears applicable to experiments with a wide range of solution compositions as well as to more complex systems, such as the bentonite/glass/water system the steel corrosion product/glass/water system, or the dissolution of natural basalt glass in a geologic environment. This model is based on solution chemistry and transition state theory. The theoretical background of this model is discussed elsewhere and is used to describe the dissolution behavior of three nuclear waste glasses. These glasses were selected because they represent a wide range of behavior and, therefore, could be used to illustrate the capabilities of the dissolution/precipitation model. The effects of parameters, such as temperature and starting solution composition, on the dissolution behavior of glass are also discussed. 27 refs., 10 figs., 1 tab

Thin Glass Coatings for the Corrosion Protection of Metals

DEFF Research Database (Denmark)

Lampert, Felix

in corrosion sensitive applications. Since the deposition of SiOx thin films is a well-established technology, the SOG technology was directly benchmarked to PVD-based SiO2 coatings. The coating adhesion was assessed by cross cut testing and increasing load scratch testing and the efficiency of the sub...... with localized corrosion and do not impact the heat transfer or the component performance. The herein presented approach focuses primarily on the formation of SiOx-like thin films from Hydrogen Silsesquioxane (HSQ) –based “spin-on-glass” (SOG) precursor. The technology is well known for the deposition...

Corrosion and alteration of materials from the nuclear industry; La Corrosion et l'alteration des materiaux du nucleaire

Energy Technology Data Exchange (ETDEWEB)

Beauvy, M.; Berthoud, G.; Defranceschi, M.; Ducros, G.; Feron, D.; Guerin, Y.; Latge, C.; Limoge, Y.; Madic, C.; Santarini, G.; Seiler, J.M.; Vernaz, E.; Richet, C.

2010-07-01

The control of the corrosion phenomenon is of prime importance for the nuclear industry. The efficiency and the safety of facilities can be affected by this phenomenon. The nuclear industry has to face corrosion for a large variety of materials submitted to various environments. Metallic corrosion operates in the hot and aqueous environment of water reactors which represent the most common reactor type in the world. Progresses made in the control of the corrosion of the different components of these reactors allow to improve their safety. Corrosion is present in the facilities of the back-end of the fuel cycle as well (corrosion in acid environment in fuel reprocessing plants, corrosion of waste containers in disposal and storage facilities, etc). The future nuclear systems will widen even more the range of materials to be studied and the situations in which they will be placed (corrosion by liquid metals or by helium impurities). Very often, corrosion looks like a patchwork of particular cases in its description. The encountered corrosion problems and their study are presented in this book according to chapters representing the main sectors of the nuclear industry and classified with respect to their phenomenology. This monograph illustrates the researches in progress and presents some results of particular importance obtained recently. Content: 1 - Introduction: context, stakes and goals; definition of corrosion; a complex science; corrosion in the nuclear industry; 2 - corrosion in water reactors - phenomenology, mechanisms, remedies: A - uniform corrosion: mechanisms, uniform corrosion of fuel cladding, in-situ measurement of generalized corrosion rate by electrochemical methods, uniform corrosion of nickel alloys, characterization of the passive layer and growth mechanisms, the PACTOLE code - an integrating tool, influence of water chemistry on corrosion and contamination, radiolysis impact on uniform corrosion; B - stress corrosion: stress corrosion cracking

A combined neural network and mechanistic approach for the prediction of corrosion rate and yield strength of magnesium-rare earth alloys

Energy Technology Data Exchange (ETDEWEB)

Birbilis, N., E-mail: nick.birbilis@monash.ed [ARC Centre of Excellence for Design in Light Metals, Monash University (Australia); CAST Co-operative Research Centre, Monash University (Australia); Cavanaugh, M.K. [Department of Materials Science and Engineering, The Ohio State University (United States); Sudholz, A.D. [ARC Centre of Excellence for Design in Light Metals, Monash University (Australia); Zhu, S.M.; Easton, M.A. [CAST Co-operative Research Centre, Monash University (Australia); Gibson, M.A. [CSIRO Division of Process Science and Engineering (Australia)

2011-01-15

Research highlights: This study presents a body of corrosion data for a set of custom alloys and displays this in multivariable space. These alloys represent the next generation of Mg alloys for auto applications. The data is processed using an ANN model, which makes it possible to yield a single expression for prediction of corrosion rate (and strength) as a function of any input composition (of Ce, La or Nd between 0 and 6 wt.%). The relative influence of the various RE elements on corrosion is assessed, with the outcome that Nd additions can offer comparable strength with minimal rise in corrosion rate. The morphology and solute present in the eutectic region itself (as opposed to just the intermetallic presence) was shown - for the first time - to also be a key contributor to corrosion. The above approach sets the foundation for rational alloy design of alloys with corrosion performance in mind. - Abstract: Additions of Ce, La and Nd to Mg were made in binary, ternary and quaternary combinations up to {approx}6 wt.%. This provided a dataset that was used in developing a neural network model for predicting corrosion rate and yield strength. Whilst yield strength increased with RE additions, corrosion rates also systematically increased, however, this depended on the type of RE element added and the combination of elements added (along with differences in intermetallic morphology). This work is permits an understanding of Mg-RE alloy performance, and can be exploited in Mg alloy design for predictable combinations of strength and corrosion resistance.

A combined neural network and mechanistic approach for the prediction of corrosion rate and yield strength of magnesium-rare earth alloys

International Nuclear Information System (INIS)

Birbilis, N.; Cavanaugh, M.K.; Sudholz, A.D.; Zhu, S.M.; Easton, M.A.; Gibson, M.A.

2011-01-01

Research highlights: → This study presents a body of corrosion data for a set of custom alloys and displays this in multivariable space. These alloys represent the next generation of Mg alloys for auto applications. → The data is processed using an ANN model, which makes it possible to yield a single expression for prediction of corrosion rate (and strength) as a function of any input composition (of Ce, La or Nd between 0 and 6 wt.%). → The relative influence of the various RE elements on corrosion is assessed, with the outcome that Nd additions can offer comparable strength with minimal rise in corrosion rate. → The morphology and solute present in the eutectic region itself (as opposed to just the intermetallic presence) was shown - for the first time - to also be a key contributor to corrosion. → The above approach sets the foundation for rational alloy design of alloys with corrosion performance in mind. - Abstract: Additions of Ce, La and Nd to Mg were made in binary, ternary and quaternary combinations up to ∼6 wt.%. This provided a dataset that was used in developing a neural network model for predicting corrosion rate and yield strength. Whilst yield strength increased with RE additions, corrosion rates also systematically increased, however, this depended on the type of RE element added and the combination of elements added (along with differences in intermetallic morphology). This work is permits an understanding of Mg-RE alloy performance, and can be exploited in Mg alloy design for predictable combinations of strength and corrosion resistance.

Laboratory investigations on the corrosion rate of A42 carbon steel in various secondary circuit chemistries representative of hydraulic tests conditions

International Nuclear Information System (INIS)

Brussieux, C.; Clinard, M.H.; Guillodo, M.; Alos-Ramos, O.

2014-01-01

Ammonia and hydrazine are currently used in the chemical conditioning of steam generators hydraulic test medium to minimize the corrosion rate of carbon steels. However, hydrazine is classified carcinogenic by the European Commission. Significant effort is therefore ongoing to limit its use or even replace it. The results presented in this paper were obtained in the frame of an EDF and AREVA research program on the subject. The corrosion rate of carbon steel in alkaline media with hydrazine was thoroughly studied. However, most studies concern polished coupons and very few data are available for carbon steel covered with oxides layer(s) representative of the layer(s) which can be found in a SG after operation. In this context, the corrosion rate at 25°C of carbon steel pre-oxidized by an autoclave treatment was studied. The tests coupons were submitted to a secondary circuit chemical conditioning treatment in an autoclave at 280°C during 30 days prior to the corrosion rate measurement. The corrosion rates were measured during two months by an electrochemical method (polarization resistance) in test media composed with deionized water, ammonia and hydrazine under an air blanket at 25°C. Similitudes with steam generators' volume/surface ratios were respected during these tests. The coupons submitted to an autoclave treatment were covered by a duplex magnetite layer. After exposure to hydrazine and ageing, the structure of the magnetite layer contains bigger crystallites than after ageing without exposure to hydrazine. The corrosion rate of passive A42 steel exposed to hydrazine was stable and low even after the complete consumption of hydrazine during at least 50 days. The corrosion rate of passive A42 steel not exposed to hydrazine grew steadily to reach the same corrosion rates as polished carbon steels within 50 days. The hydrazine consumption rate observed in the presence of magnetite covered A42 carbon steel was found higher than 1mg/kg/hour. To explain

Modeling the dissolution behavior of defense waste glass in a salt repository environment

International Nuclear Information System (INIS)

McGrain, B.P.

1988-02-01

A mechanistic model describing a dynamic mass balance between the production and consumption of dissolved silica was found to describe the dissolution behavior of SRL-165 defense waste glass in a high-magnesium brine (PBB3) at a temperature of 90 0 C. The synergistic effect of the waste package container on the glass dissolution rate was found to depend on a precipitation reaction for a ferrous silicate mineral. The model predicted that the ferrous silicate precipitate should be variable in composition where the iron/silica stoichiometry depended on the metal/glass surface area ratio used in the experiment. This prediction was confirmed experimentally by the variable iron/silica ratios observed in filtered leachates. However, the interaction between dissolved silica and iron corrosion products needs to be much better understood before the model can be used with confidence in predicting radionuclide release rates for a salt repository. 25 refs., 4 figs., 1 tab

The Effect of superficial cracks of the concrete on the behavior and corrosion rate of steel rebars in Persian Golf (Booshehr)

International Nuclear Information System (INIS)

Afshar, A.; Rajabi, A.

2001-01-01

The presence of superficial cracks in concrete increases the diffusion of destructive agents into concrete and the corrosion of rebars will take place. In the present work, the effects of cracks width on the behavior and corrosion rate of steel rebars in the concrete containing cements type I and II at Persian Gulf water have been studied. The results show that the corrosion rate of steel rebars in the concrete with cracks width less than 0.4 mm is negligible, but with increasing the cracks width to 0.7 mm, the corrosion rate increase rapidly. Also, the corrosion gate of gebars in the concrete containing cement type I is more than that of cement type II. The visual inspection of the surface area of gebars shows that the corroded area is 6-7 times of the crack width and length

Leaching and mechanical properties of cabal glasses developed as matrices for immobilization high-level wastes

International Nuclear Information System (INIS)

Ezz-Eldin, F.M.

2001-01-01

This paper discusses the leaching behavior of simulated high-level-waste cabal glass (CaO-B 2 O 3 -Al 2 O 3 ) as a bulk specimen. During leach tests, the glass is immersed in either deionized water or in groundwater for up to 57 days at 70 deg. C. Based on the results, mechanisms observed with the leaching of the glass in deionized water or groundwater are discussed. Three factors, i.e., time of immersion, type of leaching solution and irradiation effect, are extensively studied. The corrosion was found to be linear with time in the limit of investigation (1-57 days) but with different rates depending on the type of solution and glass composition. Effects of γ-irradiation on the glass together with groundwater were found to decrease the glass durability. The evolution of the damage on mechanical and physical properties of the glass before and after leaching or irradiation was also discussed. The addition of waste oxide changes the properties of the glass matrix, so the influence of the guest oxides on the properties of host materials is also discussed

In situ one-year burial experiments with simulated nuclear waste glasses

International Nuclear Information System (INIS)

Hench, L.L.; Spilman, D.; Buonaquisti, T.; Werme, L.

1985-01-01

Two simulated nuclear waste glasses were corroded in an in-situ experiment in the Stripa mine up to one year at 90 degree C and ambient temperature. Changes in compositional in-depth profiles were measured using Fourier transform infrared reflection spectroscopy, SIMS and Rutherford back-scattering. For glass/glass interfaces, both glasses showed depletion of Na, Cs and B, but for the more corrosion resistant glass, the lower depletion is ascribed to the formation of a thin (0.2 nm) coherent and dense outer layer enriched in Mg, Ca, Sr, Ba, Zn-Al and Si, which impedes both ion exchange and network attack of the bulk underneath. For the bentonite interfaces, cation exchange of Ca, Mg, Al and Fe from the bentonite for primarily Na and B is found to produce a glass surface that has three silicate-rich layers. The larger concentrations of M/super2+/ and M/super3+/ cation and the high silica content of the reaction layers result in a considerably retarded rate of ion exchange after the formation of these layers during the first three months of burial. The granite interfaces showed the lowest rate of attack. This appears to be due to a large increase of Fe and Al within the glass surfaces exposed to granite. The results obtained using Rutheford back-scattering confirm the results obtained using the other techniques for surface analysis. Analysis of burial samples cast in steel mini-canisters show no significant effects associated with the steel canister-glass interface. (author)

The effect of clay on the dissolution of nuclear waste glass

Science.gov (United States)

Lemmens, K.

2001-09-01

In a nuclear waste repository, the waste glass can interact with metals, backfill materials (if present) and natural host rock. Of the various host rocks considered, clays are often reported to delay the onset of the apparent glass saturation, where the glass dissolution rate becomes very small. This effect is ascribed to the sorption of silica or other glass components on the clay. This can have two consequences: (1) the decrease of the silica concentration in solution increases the driving force for further dissolution of glass silica, and (2) the transfer of relatively insoluble glass components (mainly silica) from the glass surface to the clay makes the alteration layer less protective. In recent literature, the latter explanation has gained credibility. The impact of the environmental materials on the glass surface layers is however not well understood. Although the glass dissolution can initially be enhanced by clay, there are arguments to assume that it will decrease to very low values after a long time. Whether this will indeed be the case, depends on the fate of the released glass components in the clay. If they are sorbed on specific sites, it is likely that saturation of the clay will occur. If however the released glass components are removed by precipitation (growth of pre-existing or new secondary phases), saturation of the clay is less likely, and the process can continue until exhaustion of one of the system components. There are indications that the latter mechanism can occur for varying glass compositions in Boom Clay and FoCa clay. If sorption or precipitation prevents the formation of protective surface layers, the glass dissolution can in principle proceed at a high rate. High silica concentrations are assumed to decrease the dissolution rate (by a solution saturation effect or by the impact on the properties of the glass alteration layer). In glass corrosion tests at high clay concentrations, silica concentrations are, however, often higher

The effect of clay on the dissolution of nuclear waste glass

International Nuclear Information System (INIS)

Lemmens, K.

2001-01-01

In a nuclear waste repository, the waste glass can interact with metals, backfill materials (if present) and natural host rock. Of the various host rocks considered, clays are often reported to delay the onset of the apparent glass saturation, where the glass dissolution rate becomes very small. This effect is ascribed to the sorption of silica or other glass components on the clay. This can have two consequences: (1) the decrease of the silica concentration in solution increases the driving force for further dissolution of glass silica, and (2) the transfer of relatively insoluble glass components (mainly silica) from the glass surface to the clay makes the alteration layer less protective. In recent literature, the latter explanation has gained credibility. The impact of the environmental materials on the glass surface layers is however not well understood. Although the glass dissolution can initially be enhanced by clay, there are arguments to assume that it will decrease to very low values after a long time. Whether this will indeed be the case, depends on the fate of the released glass components in the clay. If they are sorbed on specific sites, it is likely that saturation of the clay will occur. If however the released glass components are removed by precipitation (growth of pre-existing or new secondary phases), saturation of the clay is less likely, and the process can continue until exhaustion of one of the system components. There are indications that the latter mechanism can occur for varying glass compositions in Boom Clay and FoCa clay. If sorption or precipitation prevents the formation of protective surface layers, the glass dissolution can in principle proceed at a high rate. High silica concentrations are assumed to decrease the dissolution rate (by a solution saturation effect or by the impact on the properties of the glass alteration layer). In glass corrosion tests at high clay concentrations, silica concentrations are, however, often higher

GLASS-FIBRE REINFORCED COMPOSITES: THE EFFECT OF ...

African Journals Online (AJOL)

HOD

mechanical and corrosion wear behaviour of any reinforced composites. In other ..... physical properties of glass fibre reinforced epoxy resin and the following .... waste in concrete and cement composites," Journal of Cleaner Production, vol.

Humid-air and aqueous corrosion models for corrosion-allowance barrier material

International Nuclear Information System (INIS)

Lee, J.H.; Atkins, J.E.; Andrews, R.W.

1995-01-01

Humid-air and aqueous general and pitting corrosion models (including their uncertainties) for the carbon steel outer containment barrier were developed using the corrosion data from literature for a suite of cast irons and carbon steels which have similar corrosion behaviors to the outer barrier material. The corrosion data include the potential effects of various chemical species present in the testing environments. The atmospheric corrosion data also embed any effects of cyclic wetting and drying and salts that may form on the corroding specimen surface. The humid-air and aqueous general corrosion models are consistent in that the predicted humid-air general corrosion rates at relative humidities between 85 and 100% RH are close to the predicted aqueous general corrosion rates. Using the expected values of the model parameters, the model predicts that aqueous pitting corrosion is the most likely failure mode for the carbon steel outer barrier, and an earliest failure (or initial pit penetration) of the 100-mm thick barrier may occur as early as about 500 years if it is exposed continuously to an aqueous condition at between 60 and 70 degrees C