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Corrosion of copper by chlorine trifluoride; Corrosion du cuivre par le trifluorure de chlore

Abstract

The research described called for a considerable amount of preliminary development of the test methods and equipment in order that the various measurements and observations could be carried out without contaminating either the samples or this highly reactive gas. The chlorine trifluoride was highly purified before use, its purity being checked by gas-phase chromatography, micro-sublimation and infrared spectrography. The tests were carried out on copper samples of various purities, in particular a 99.999 per cent copper in the form of mono-crystals. They involved kinetic measurements and the characterization of corrosion products under different temperature and pressure conditions. The kinetics showed reactions of the same order of magnitude as those obtained with elementary fluorine. At atmospheric pressure there occurs formation of cupric fluoride and cuprous chloride. The presence of this latter product shows that it is not possible to consider ClF{sub 3} simply as a fluorinating agent. At low pressures an unknown product has been characterized. There are strong grounds for believing that it is the unstable cuprous fluoride which it has not yet been possible to isolate. A germination phenomenon has been shown to exist indicating an analogy between the initial phases of fluorination and those of oxidation. Important effects  More>>
Authors:
Vincent, L [1] 
  1. Commissariat a l'Energie Atomique, Saclay (France). Centre d'Etudes Nucleaires
Publication Date:
Jul 01, 1966
Product Type:
Thesis/Dissertation
Report Number:
CEA-R-2790
Resource Relation:
Other Information: TH: These sciences; 49 refs
Subject:
36 MATERIALS SCIENCE; CHEMICAL REACTION KINETICS; CHEMICAL REACTORS; CHLORINE FLUORIDES; COPPER CHLORIDES; COPPER FLUORIDES; CORROSION; GERMINATION; IMPURITIES; METALLOGRAPHY; MICROANALYSIS; MICROSTRUCTURE
OSTI ID:
20706588
Research Organizations:
CEA Saclay, 91 - Gif-sur-Yvette (France); Faculte des Sciences de l'Universite de Paris, 75 (France)
Country of Origin:
France
Language:
French
Other Identifying Numbers:
TRN: FR05R2790021793
Availability:
Available from INIS in electronic form
Submitting Site:
FRN
Size:
61 pages
Announcement Date:
May 01, 2006

Citation Formats

Vincent, L. Corrosion of copper by chlorine trifluoride; Corrosion du cuivre par le trifluorure de chlore. France: N. p., 1966. Web.
Vincent, L. Corrosion of copper by chlorine trifluoride; Corrosion du cuivre par le trifluorure de chlore. France.
Vincent, L. 1966. "Corrosion of copper by chlorine trifluoride; Corrosion du cuivre par le trifluorure de chlore." France.
@misc{etde_20706588,
title = {Corrosion of copper by chlorine trifluoride; Corrosion du cuivre par le trifluorure de chlore}
author = {Vincent, L}
abstractNote = {The research described called for a considerable amount of preliminary development of the test methods and equipment in order that the various measurements and observations could be carried out without contaminating either the samples or this highly reactive gas. The chlorine trifluoride was highly purified before use, its purity being checked by gas-phase chromatography, micro-sublimation and infrared spectrography. The tests were carried out on copper samples of various purities, in particular a 99.999 per cent copper in the form of mono-crystals. They involved kinetic measurements and the characterization of corrosion products under different temperature and pressure conditions. The kinetics showed reactions of the same order of magnitude as those obtained with elementary fluorine. At atmospheric pressure there occurs formation of cupric fluoride and cuprous chloride. The presence of this latter product shows that it is not possible to consider ClF{sub 3} simply as a fluorinating agent. At low pressures an unknown product has been characterized. There are strong grounds for believing that it is the unstable cuprous fluoride which it has not yet been possible to isolate. A germination phenomenon has been shown to exist indicating an analogy between the initial phases of fluorination and those of oxidation. Important effects resulting from the dissociation of the copper fluorides and the solubility of chlorine in this metal have been demonstrated. Finally, tests have shown the considerable influence of the purity of the gas phase and of the nature of the reaction vessel walls on the rates of corrosion which can in certain cases be increased by a factor of several powers of ten. (author) [French] Le travail a comporte une importante mise au point des appareillages et methodes d'essai, en vue de pouvoir effectuer differentes mesures et observations sans contaminer les echantillons, ni polluer ce gaz hautement reactif. Une purification poussee du trifluorure de chlore a ete effectuee, et controlee par chromatographie gazeuse, microsublimation et spectrographie infra-rouge. Les essais ont porte sur des cuivres de differentes puretes, principalement sur le cuivre a 99,999, sous forme de monocristaux. Ils ont comporte des cinetiques et la caracterisation des produits de corrosion dans differentes conditions de temperature et de pression. Les cinetiques ont montre des reactions du meme ordre de grandeur que celles obtenues avec le fluor-element. A pression atmospherique, il se forme du fluorure cuivrique et du chlorure cuivreux. La presence de ce compose permet d'ecarter definitivement l'assimilation du ClF{sub 3} a un simple agent fluorant. Aux basses pressions, un compose inconnu a ete caracterise. Il existe une tres forte presomption pour qu'il s'agisse du fluorure cuivreux instable, qui n'a pas pu etre encore isole. Un phenomene de germination a ete mis en evidence, montrant les analogies des phases initiales de fluoration avec celles de l'oxydation. Des effets importants resultant de la dissociation des fluorures de cuivre et de la solubilite du chlore dans ce metal ont ete mis en evidence. En dernier lieu, des essais ont montre l'influence considerable de la purete de la phase gazeuse et de la nature des parois sur les vitesses de corrosion qui peuvent dans certains cas etre multipliees par plusieurs puissances de dix. (auteur)}
place = {France}
year = {1966}
month = {Jul}
}