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Improved Oxidation Resistance of Zirconium Resulting from Addition of Small Amounts of Copper; Amelioration de la Resistance a l'Oxydation du Zirconium par de Faibles Additions de Cuivre; Povyshenie soprotivlyaemosti k okisleniyu tsirkoniya posle dobavlenij nebol'shikh kolichestv medi; Aumento de la Resistencia del Circonio a la Oxidacion por Agregado de Pequenas Cantidades de Cobre

Abstract

The authors have tried to explain the process by which the addition of small amounts of copper improves the resistance of zirconium to oxidation by pressurized carbon dioxide between 600 and 700 Degree-Sign C. The resulting alloys, particularly that with 2.5% copper, seem to offer interesting possibilities as cladding or structural materials for the fuel elements of reactors of the heavy water-carbon dioxide type. The corrosion of zirconium by carbon dioxide amounts essentially to oxidation, in which two processes are involved: (1) the building up of a layer of monoclinic zirconia, through which oxygen diffuses by migration of the anionic vacancies: (2) the dissolution and diffusion of oxygen, which penetrates into the metal. The combination of gravimetric data and measurements of the thickness of the oxide layers permits evaluation of the two corresponding diffusion coefficients. This calculation has been extended, by analogy, to the case of binary zirconium-copper alloys with a concentration of copper less than or equal to 4% by weight. Comparison of the results obtained shows that the apparent diffusion coefficient of oxygen in the oxide layer that is formed decreases as the copper content of the alloy in question increases; as regards the apparent diffusion coefficient of  More>>
Authors:
Loriers, H.; Darras, R.; Baque, P. [1] 
  1. Centre d'Etudes Nucleaires de Saclay (France)
Publication Date:
Feb 15, 1966
Product Type:
Conference
Report Number:
IAEA-SM-66/49
Resource Relation:
Conference: Symposium on Thermodynamics with Emphasis on Nuclear Materials and Atomic Transport in Solids, Vienna (Austria), 22-27 Jul 1965; Other Information: 25 refs., 9 figs., 2 tabs.; Related Information: In: Thermodynamics. Vol. II. Proceedings of the Symposium on Thermodynamics with Emphasis on Nuclear Materials and Atomic Transport in Solids| 673 p.
Subject:
36 MATERIALS SCIENCE; CARBON DIOXIDE; CLADDING; CONCENTRATION RATIO; COPPER; COPPER ALLOYS; CORROSION RESISTANCE; CRACKING; DIFFUSION; DISSOLUTION; FUEL ELEMENTS; HEAVY WATER; MONOCLINIC LATTICES; OXYGEN; REACTION KINETICS; VACANCIES; ZIRCONIUM; ZIRCONIUM OXIDES
OSTI ID:
22121919
Research Organizations:
International Atomic Energy Agency, Vienna (Austria); International Union of Pure and Applied Chemistry, Commission on Thermodynamics and Thermochemistry, Research Triangle Park, NC (United States)
Country of Origin:
IAEA
Language:
French
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA13M2415078030
Submitting Site:
INIS
Size:
page(s) 391-405
Announcement Date:
Aug 27, 2013

Citation Formats

Loriers, H., Darras, R., and Baque, P. Improved Oxidation Resistance of Zirconium Resulting from Addition of Small Amounts of Copper; Amelioration de la Resistance a l'Oxydation du Zirconium par de Faibles Additions de Cuivre; Povyshenie soprotivlyaemosti k okisleniyu tsirkoniya posle dobavlenij nebol'shikh kolichestv medi; Aumento de la Resistencia del Circonio a la Oxidacion por Agregado de Pequenas Cantidades de Cobre. IAEA: N. p., 1966. Web.
Loriers, H., Darras, R., & Baque, P. Improved Oxidation Resistance of Zirconium Resulting from Addition of Small Amounts of Copper; Amelioration de la Resistance a l'Oxydation du Zirconium par de Faibles Additions de Cuivre; Povyshenie soprotivlyaemosti k okisleniyu tsirkoniya posle dobavlenij nebol'shikh kolichestv medi; Aumento de la Resistencia del Circonio a la Oxidacion por Agregado de Pequenas Cantidades de Cobre. IAEA.
Loriers, H., Darras, R., and Baque, P. 1966. "Improved Oxidation Resistance of Zirconium Resulting from Addition of Small Amounts of Copper; Amelioration de la Resistance a l'Oxydation du Zirconium par de Faibles Additions de Cuivre; Povyshenie soprotivlyaemosti k okisleniyu tsirkoniya posle dobavlenij nebol'shikh kolichestv medi; Aumento de la Resistencia del Circonio a la Oxidacion por Agregado de Pequenas Cantidades de Cobre." IAEA.
@misc{etde_22121919,
title = {Improved Oxidation Resistance of Zirconium Resulting from Addition of Small Amounts of Copper; Amelioration de la Resistance a l'Oxydation du Zirconium par de Faibles Additions de Cuivre; Povyshenie soprotivlyaemosti k okisleniyu tsirkoniya posle dobavlenij nebol'shikh kolichestv medi; Aumento de la Resistencia del Circonio a la Oxidacion por Agregado de Pequenas Cantidades de Cobre}
author = {Loriers, H., Darras, R., and Baque, P.}
abstractNote = {The authors have tried to explain the process by which the addition of small amounts of copper improves the resistance of zirconium to oxidation by pressurized carbon dioxide between 600 and 700 Degree-Sign C. The resulting alloys, particularly that with 2.5% copper, seem to offer interesting possibilities as cladding or structural materials for the fuel elements of reactors of the heavy water-carbon dioxide type. The corrosion of zirconium by carbon dioxide amounts essentially to oxidation, in which two processes are involved: (1) the building up of a layer of monoclinic zirconia, through which oxygen diffuses by migration of the anionic vacancies: (2) the dissolution and diffusion of oxygen, which penetrates into the metal. The combination of gravimetric data and measurements of the thickness of the oxide layers permits evaluation of the two corresponding diffusion coefficients. This calculation has been extended, by analogy, to the case of binary zirconium-copper alloys with a concentration of copper less than or equal to 4% by weight. Comparison of the results obtained shows that the apparent diffusion coefficient of oxygen in the oxide layer that is formed decreases as the copper content of the alloy in question increases; as regards the apparent diffusion coefficient of the oxygen in the alloy, though this is only slightly modified at 600 Degree-Sign C, at 700 Degree-Sign C it too decreases when the copper content is increased to 2.5%. The improved oxidation resistance associated with slowing down of the diffusion processes results, in particular, in prolongation of parabolic-type kinetics whereas, in the case of non-alloyed zirconium or other alloys, cracking in the oxide layer rapidly leads to linear oxidation kinetics as a result of the phenomenon of peeling. (author) [French] Les auteurs ont cherche a interpreter l'amelioration apportee par de faibles additions de cuivre a la resistance a l'oxydation du zirconium par le gaz carbonique sous pression entre 600 et 700 Degree-Sign C. En effet, les alliages correspondants, notamment celui a 2,5% de cuivre, semblent offrir des possibilites interessantes comme materiaux de gainage ou de structure pour les elements combustibles des reacteurs de la filiere eau lourde-gaz carbonique. La corrosion du zirconium par le gaz carbonique se ramene essentiellement a une oxydation, au cours de laquelle deux processus interferent: 1. l'edification d'une couche de zircone monoclinique, a travers laquelle l'oxygene diffuse par migration des lacunes anioniques, 2. la dissolution et la diffusion de l'oxygene, qui passe en insertion dans le metal. La combinaison des donnees gravimetriques et des mesures d'epaisseur des couches d'oxyde permet d'evaluer les deux coefficients de diffusiqn correspondants. Ce calcul a ete etendu par analogie au cas des alliages binaires zirconium-cuivre, de concentration en cuivre inferieure ou egale a 4% en poids. La comparaison des resultats obtenus montre que le coefficient de diffusion apparent de l'oxygene dans la couche d'oxyde formee decroit lorsque la teneur en cuivre de l'alliage envisage augmente; d'autre part, le coefficient de diffusion apparent de l'oxygene dans l'alliage, s'il est peu modifie a 600 Degree-Sign C, decroit a 700 Degree-Sign C lorsque la teneur en cuivre augmente jusqu'a 2,5%. L'amelioration de la resistance a l'oxydation, liee au ralentissement des processus de diffusion, se traduit en particulier par le maintien prolonge d'une cinetique du type parabolique, alors que, dans le cas du zirconium non allie ou d'autres alliages, la fissuration de la couche d'oxyde conduit rapidement a une cinetique d'oxydation lineaire, a la suite du phenomene de desquamation. (author) [Spanish] Los autores procuraron interpretar el efecto favorable que pequenas cantidades de cobre ejercen sobre la resistencia del circonio a la oxidacion por accion del anhidrido carbonico a presion, entre 600 y 700 Degree-Sign C. Las aleaciones correspondientes y, en particular las que contienen 2,5% de cobre, parecen ofrecer interesantes posibilidades como materiales en vainas o para estructuras de elementos combustibles destinados a reactores del tipo agua pesada-anhidrido carbonico. La corrosion del circonio por efectos del anhfdrido carbonico se reduce esencialmente a una oxidacion, en el curso de la cual interfieren dos procesos: 1. La formacion de una capa de oxido de circonio monoclfnico, a traves de la cual se difunde el oxigeno por migracion de huecos anionicos; 2. la disolucion y difusion del oxigeno en el seno del metal. La combinacion de datos gravimetricos con medidas del espesor de las capas de oxido, permite evaluar los dos coeficientes de difusion correspondientes. Por analogia, este calculo se ha extendido al caso de las aleaciones binarias circonio-cobre con un contenido de cobre inferior o igual a 4% en peso. La comparacion de los resultados obtenidos pone de manifiesto que el coeficiente de difusion aparente del oxigeno en la capa de oxido formada, disminuye cuando aumenta el contenido de cobre de la aleacion; por otra parte, si bien el coeficiente de difusion aparente del oxigeno en la aleacion sufre una pequeBa modificacion a 600 Degree-Sign C, disminuye a 700 Degree-Sign C cuando el contenido de cobre aumenta hasta 2,5%, El mejoramiento de la resistencia a la oxidacion, unido a la mayor lentitud de los procesos de difusion, se traduce en particular por la persistencia de una cinetica de tipo parabolico, mientras en el caso del circonio no aleado o aleado con otros metales, la formacion de fisuras en la capa de oxido conduce rapidamente a una cinetica de oxidacion de caracter lineal, como resultado del fenomeno de descamacion. (author) [Russian] Izlagaetsja vopros o tom, chto dobavlenie nebol'shih kolichestv medi povyshaet soprotivljaemost' k okisleniju cirkonija, vyzyvaemomu uglekislym gazom pod davleniem pri temperature mezhdu 600 Degree-Sign i 700 Degree-Sign S. Dejstvitel'no, sootvetstvujushhie splavy, v chastnosti splav s 2,5% medi, vidimo, predstavljajut interes v kachestve materialov dlja pokrytija ili konstrukcionnyh materialov dlja toplivnyh jelementov reaktorov tipa tjazhe- laja voda - uglekislyj gaz. Korrozija cirkonija, vyzyvaemaja uglekislym gazom, svoditsja po sushhestvu k okisleniju, v techenie kotorogo voznikajut dva processa: 1) sozdanie monoklinicheskogo cirkonievogo sloja, cherez kotoryj kislorod rasseivaetsja putem migracii anionnyh ''dyrok''; 2) rastvorenie i diffuzija kisloroda, kotoryj protekaet putem ego vvedenija v metall. Sochetanie gravimetricheskih dannyh i izmerenij plotnostej sloev okisi pozvoljaet opredelit' dva sootvetstvujushhih kojefficienta diffuzii. Jetot raschet po analogii raspro- stranjaetsja na sluchaj s dvojnymi, medno-cirkonievymi splavami pri koncentracii medi nizhe ili ravnoj 4 ves%. Sravnenie poluchennyh rezul'tatov pokazyvaet, chto kojefficient diffu- zii kisloroda v obrazovavshemsja sloe okisi umen'shaetsja s uvelicheniem kolichestva medi v rassmatrivaemom splave; s drugoj storony, sootvetstvujushhij kojefficient diffuzii kislo- roda v splave, esli on neskol'ko izmenen pri 600 Degree-Sign S, umen'shaetsja pri 700 Degree-Sign S s uvelicheniem kolichestva medi do 2,5%. Povyshenie soprotivljaemosti k okisleniju, svjazannoe s zamedle- niem processov diffuzii, dostigaetsja, v chastnosti, v rezul'tate prodolzhitel'nogo sohrane- nija kinetiki parabolicheskogo tipa, v to vremja kak v sluchae s nesoedinennym cirkoniem ili s drugimi splavami rastreskivanie sloja okisi v rezul'tate otslaivanija bystro privodit k linejnoj kinetike okislenija. (author)}
place = {IAEA}
year = {1966}
month = {Feb}
}