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Some impedance measurements of anodic films formed on tantalum and niobium in sulphuric acid

✍ Scribed by P.H.G. Draper


Publisher
Elsevier Science
Year
1963
Tongue
English
Weight
405 KB
Volume
8
Category
Article
ISSN
0013-4686

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✦ Synopsis


The variations of the equivalent parallel resistance and capacitance of anodic films formed on Ta and Nb in varying concentrations of H2SO4 suggest that the volume of film formed per coulomb is much greater in 100)~, acid, although the dielectric constant is substantially unchanged. The field required for growth on Ta in 100 ~ acid is about 85 )~o of that in aqueous solutions, where it is constant up to about 60K H2SO4. Slow conversion of films formed in 100K acid occurs when they are immersed in dilute H~SO4; this change is very rapid when charge is passed. Virtually no change occurs in the converse case, indicating that the change in fihn properties found during growth in 100K acid is a characteristic of the growth process.

Marked corrosion or dissolution of the film material in 100K H2SO4 is apparent with Ta at temperatures much above 50Β°C, and above 25Β°C for Nb.

The similarity of the behaviour of the loss factor, tan 6, with both metals, as the film thickness is increased, suggests that areas of high loss, but not of low dielectric constant, arise by the trapping of solution, and that these exert a predominating influence.

R6sumg--Les variations de r~sistance et de capacitance de fihns anodiques sur Ta et Nb, form6s dans H2SO4 de diverses concentrations, indiquent que le volume de film engendr6 par coulomb s'accroit nettement pour l'acide /t 100K, bien que la constante di61ectrique demeure pratiquement inchang6e. Le champ ngcessaire avec Ta dans H2SO~ pur vaut environ 85~ de celui propre fi des solutions aqueuses, qui se maintient constant jusqu'/160 ~ d'H2SO~. Les films engendr6s dans H2SO4 purse transforment lentement par immersion dans H2SO~ dilu~, mais trSs rapidement si l'on charge conjointement. II apparalt que l'6volution des propri6t6s du film pendant sa croissance clans H2SO4 pur caract6rise le processus-m&me de cette croissance. Une corrosion (ou une dissolution) marqu6e du film, dans H2SO4 pur, se manifeste avec Ta ou Nb, ~ des tempgratures nettement sup6rieures /~ 50'PC ou 25Β°C. Le comportement similaire du facteur de pertetger, propre aux deux m~taux pendant la croissance du film, d6note l'influence pr6dominante des portions occluses de la solution.

Zusammenfassung--Bei den in Schwefels~iure verschiedener Konzentration gebildeten anodischen Filmen auf Ta und Nb kann eine Ver~inderung des fiquivalenten Parallelwiderstandes und der Parallelkapazit~it festgestellt werden, welche darauf schliessen l~,sst, dass alas in 100 Prozent iger Schwefelsfiure pro Coulomb gebildete Schichtvolumen bedeutend gr6sser ist, obschon die Dielektriziffitskonstante substantiell unver~ndert bleibt. Die zum Schichtwachstum bei Tantal in 100 Prozent Schwefels~ure erforderte Feldstfirke ist nur ca. 75 Prozent derjenigen, welche in w~isseriger L6sung notwendig ist, und die bis zu einer Konzentration von ca. 60~o H2SO4 konstant bleibt. Schichten gebildet in 100K iger H~SO~ erleiden beim Eintauchen in verdiJnnte Schwefelsfiure eine langsame Verfinderung, welche sehr rasch vor sich geht, falls ein Ladungsaustausch stattfindet. Virtuell finder im umgekehrten Falle keine Ver~inderung statt; ein Anzeichen dafiir, dass die bei Filmen gebildet in 100K H2SO4 gefundenen ver~inderten Eigenschaften auf einen spezifischen Wachstumsprozess zur~ickzuftihren sind.

Deutliche Korrosion oder AuflBsung der Schicht in 100~ H2SO4 wird bei Ta im Temperaturbereich tiber 50Β°C merkbar; bei Nb tiber 25Β°C.

Die ,g, hnlichkeit des Verhaltens des Verlustfaktors tg 6 mit wachsender Schichtstfi.rke bei beiden Metallen macht es wahrscheinlich, dass Zonen mit hohem Verlust, aber nicht mit kleiner Dielektrizitfitskonstanten, durch Einschluss von L6sungsanteilen entstehen, welche einen sehr starken Einfluss ausiiben.


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