Oxide Growth Mechanism on Zirconium Alloys PDF Download
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Author: F. Garzarolli
Publisher:
ISBN:
Category : Characterization of oxide layers
Languages : en
Pages : 21
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Book Description
In order to get a better understanding of the mechanisms governing corrosion of Zr-based alloys, several examinations have been performed on a variety of samples with uniform and nodular corrosion and different oxide layer thicknesses.
Author: F. Garzarolli
Publisher:
ISBN:
Category : Characterization of oxide layers
Languages : en
Pages : 21
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Book Description
In order to get a better understanding of the mechanisms governing corrosion of Zr-based alloys, several examinations have been performed on a variety of samples with uniform and nodular corrosion and different oxide layer thicknesses.
Author: Brendan Ensor
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Book Description
Zirconium alloys are commonly used as fuel claddings in nuclear reactors due in part to theirsuperior corrosion resistance. The addition of small concentrations of alloying elements prevents thecladding material from undergoing unstable oxide growth under the operating conditions of a nuclearreactor. Unstable oxide growth can also occur due to the presence of hydrides or exposure to neutron flux.The role of alloying elements in avoiding the transition from stable to unstable growth is examined in thisthesis. The goal is to determine the mechanism whereby oxide stabilization occurs.To accomplish this goal, a variety of experiments were performed, and the resulting oxide layerscharacterized with various techniques. Ten model Zr alloys were fabricated and tested in furnace at 600Cfor 40 hours in oxygen and in autoclave at 360C for up to 70 days to determine the causes of breakawayoxidation in pure Zr (and Zr alloys with small concentrations of alloying elements) and the role that alloyingelements play in causing this phenomenon. These alloys were carefully selected and included crystal barZr, sponge Zr, and alloys with small concentrations of Sn, Fe, and Cr. After testing, the alloys werecharacterized using scanning electron microscopy (SEM), Raman spectroscopy, and synchrotron -X-rayfluorescence (XRF) to determine how the structure of the oxide, tetragonal phase content, and alloyingelement distribution affected the formation of unstable oxide. Heterogeneous distribution of alloyingelements was linked to regions of unstable oxide (either nodule-like, grain boundary penetration, ordifferential grain-to-grain growth) and hypothesized to cause breakaway corrosion.The examination of stable oxide layers was then used as a baseline for comparison to cases ofunstable oxide growth in Zr and Zr alloys. One of the primary modes of examination of stable oxide layersformed on Zr alloys was microbeam synchrotron X-ray radiation diffraction and fluorescence, performedat the Advanced Photon Source (APS) at Argonne National Laboratory. This synchrotron X-ray source wasused to perform -X-ray diffraction (XRD), XRF, and 3D Laue spectroscopy. The XRD technique wasused to determine the oxide layer phase content, strain, and grain size as a function of corrosion temperatureand oxide thickness. The XRF technique was used to perform Fe X-ray absorption near-edge spectroscopyiv(XANES) to determine the oxidation state of Fe in the metal as a function of distance from the metal-oxideinterface for various corrosion temperatures. The 3D Laue spectroscopy technique was used to determineplastic deformation and elastic strain in the metal as a function of distance from the metal-oxide interface,corrosion temperature, and oxide thickness for crystal bar Zr and Zircaloy-4.Additionally, Zircaloy-4 samples were corroded in autoclave at 360C for up to 2804 days in andwere periodically weighed to determine oxide thickness. These samples had different coupon thicknessesthat altered the surface-to-volume ratio and led to a higher concentration of hydrogen for a given amountof oxide layer growth. The concentration of hydrogen was measured in archived samples to determine theeffect of hydrogen concentration on corrosion rate. It was observed that the corrosion rate of Zircaloy-4increased with increasing hydrogen concentration above the terminal solid solubility (TSS) of the material(and thus the precipitation of hydrides). More hydrogen caused earlier kinetic transition and areas ofadvanced oxide growth were associated with the locations of hydrides in the metal. It was hypothesizedthat the hydrides hardened the metal ahead of the interface and that the metal was then less able toaccommodate oxide growth stresses leading to earlier kinetic transition and mechanical cracking of theoxide.Finally, eleven Zircaloy-4 samples exposed to various temperatures (272-355C) and neutron fluxlevels (0-11.48 x 1013 n/cm2/s, E > 1 MeV) were examined using XRD and XRF to determine the effectof irradiation on oxide grain size, phase content, and the oxidation of Fe at the APS. With increasing neutronfluence, the grain size of the oxide increased, leading to less tetragonal phase in the oxide away from themetal-oxide interface. At the metal-oxide interface, higher amounts of tetragonal phase were observed withincreasing neutron fluence. This could be caused by the redistribution of Fe from second phase particles(SPPs) into the matrix or due to the hardening of the Zr matrix caused by the exposure to neutrons.The cases of unstable oxide growth examined here were linked to both the distribution and presenceof alloying elements in Zr and Zr alloys and to the level of stress in the oxide. These two phenomena appearto be the primary causes leading to regions of advanced oxide growth and careful consideration should begiven to them when designing and using future Zr alloys in advanced nuclear reactor concepts.
Author:
Publisher:
ISBN:
Category : Oxidation
Languages : en
Pages : 48
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Book Description
The oxidation rate was found to be relatively insensitive to various types of surface preparations in the temperature range 400 to 700 deg C. No dependence of reaction rate on oxygen pressure was observed. The cubic rate law also was obeyed by foil specimens at 700 deg C; however, the rate constants were slightly larger than values obtained from parallelepiped samples.
Author: Craig M. Eucken
Publisher: ASTM International
ISBN: 080311463X
Category : Nuclear fuel claddings
Languages : en
Pages : 794
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Book Description
The proceedings of the Ninth International Symposium on [title], held in Kobe, Japan, November 1990, address current trends in the development, performance, and fabrication of zirconium alloys for nuclear power reactors. the bulk of the most recent work on zirconium alloy behavior has concerned corr
Author: George P. Sabol
Publisher: ASTM International
ISBN: 0803124066
Category : Nuclear fuel claddings
Languages : en
Pages : 907
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Author: Gerry D. Moan
Publisher: ASTM International
ISBN: 0803128959
Category : Nuclear fuel claddings
Languages : en
Pages : 891
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Book Description
Annotation The 41 papers of this proceedings volume were first presented at the 13th symposium on Zirconium in the Nuclear Industry held in Annecy, France in June of 2001. Many of the papers are devoted to material related issues, corrosion and hydriding behavior, in-reactor studies, and the behavior and properties of Zr alloys used in storing spent fuel. Some papers report on studies of second phase particles, irradiation creep and growth, and material performance during loss of coolant and reactivity initiated accidents. Annotation copyrighted by Book News, Inc., Portland, OR.
Author: T. L. Mackay
Publisher:
ISBN:
Category : Zirconium
Languages : en
Pages : 26
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Author: B. Cox
Publisher:
ISBN:
Category : Irradiation effects
Languages : en
Pages : 21
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Book Description
The linear growth of relatively thick (>300 nm) interference-colored oxide films on zirconium alloy specimens exposed in the Advanced Test Reactor (ATR) coolant at ?55°C was unexpected. Initial ideas were that this was a photoconduction effect. Experiments to study photoconduction in thin anodic zirconium oxide (ZrO2) films in the laboratory were initiated to provide background data. It was found that, in the laboratory, provided a high electric field was maintained across the oxide during ultraviolet (UV) irradiation, enhanced growth of oxide occurred in the irradiated area. Similarly enhanced growth could be obtained on thin thermally formed oxide films that were immersed in an electrolyte with a high electric field superimposed. This enhanced growth was found to be caused by the development of porosity in the barrier oxide layer by an enhanced local dissolution and reprecipitation process during UV irradiation. Similar porosity was observed in the oxide films on the ATR specimens. Since it is not thought that a high electric field could have been present in this instance, localized dissolution of fast-neutron primary recoil tracks may be the operative mechanism. In all instances, the specimens attempt to maintain the normal barrier-layer oxide thickness, which causes the additional oxide growth. Similar mechanisms may have operated during the formation of thick loosely adherent, porous oxides in homogeneous reactor solutions under irradiation, and may be the cause of enhanced oxidation of zirconium alloys in high-temperature water-cooled reactors in some water chemistries.
Author: E. Ahlberg
Publisher:
ISBN:
Category : Congress
Languages : en
Pages : 19
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Book Description
The oxide growth rate of zirconium alloys, e.g., Zircaloy-2 and Zircaloy-4, has been proposed to be controlled mainly by the transformation of the zirconium oxide from tetragonal to monoclinic structure at some distance from the metal-oxide interface, leading to cracking. This oxide growth rate model is inconsistent with our results. Zirconium alloys of varying chemical composition but with identical manufacturing process had markedly different oxide growth and hydriding properties in autoclave testing (400°C steam). The materials were characterized by several methods, e.g., electron microscopy (SEM), X-ray diffraction (XRD), and electrochemical impedance (EIS). The SEM and some of the XRD investigations of the oxide were performed on the metal-oxide interface after dissolution of the metal. The oxide growth developed through three different stages with an altered oxide morphology at the metaloxide interface at each stage. The developments of the stages were correlated with the oxide growth rate. Impedance measurements suggested that the oxide film had three layers, the outermost being extensively porous. Relaxation of the oxide film stress showed that the compressive stress in the oxide was not essential for retention of a significant amount of the tetragonal phase.
Author: B. Cox
Publisher:
ISBN:
Category :
Languages : en
Pages : 10
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