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Lecture 7: Copper, Aluminium and General Corrosion Diagrams

NPTEL Web Course

Lecture 7 Copper, Aluminium and General Corrosion Diagrams


Keywords: Copper Diagram, Aluminium Diagram, Eh pH Diagram for Metals.

Similarly, Eh pH diagrams for other metal systems can be drawn. Various reactions pertaining to the Cu H2O O2 system along with the constructed Eh pH diagram are illustrated below (Fig.7.1).

Fig. 7.1 Eh pH diagram for copper

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 7: Copper, Aluminium and General Corrosion Diagrams

NPTEL Web Course

Construction of Al H2O O2 diagram

1. Al = Al+++ + 3e Eh = - 1.66 + log [Al+++]

2. 2Al + 3 H2O = Al2O3 + 6H+ + 6e Eh = -1.55 0.059 pH

3. 2Al+++ + 3H2O = Al2O3 + 6H+ Log K = 6 log [H+] 2 log Al+++ For [Al+++] = 10-6M, = - 6 pH 2 log Al+++ pH = - log = 3.9

4. Al + 2H2O = AlO2 - + 4H+ + 3e Eh = - 1.26 + 0.02 log AlO2 - 0.079 pH

5. Al2O3 + H2O = 2AlO2- + 2H+ pH = 14.6 + log [AlO2-] There are two solid species (Al and Al2O3 H2O) and two ionic species (Al+++ and AlO2-). Constructed Eh pH diagrams for the Al H2O O2 system are illustrated in Fig 7.2 and 7.3.

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 7: Copper, Aluminium and General Corrosion Diagrams

NPTEL Web Course

Fig. 7.2 Stability phases in the aluminium diagram

Immunity: Totally immune from corrosion attack and safe to use in the region. Cathodic protection may be used to bring the potential of a metal closer to that region by imposing cathodic shift. Passivation: Metal coated with an oxide or hydroxide film preventing all direct contact between the metal itself and the environment. Corrosion: Ionised form of aluminium is stable in this region and therefore susceptible to corrosion attack.

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 7: Copper, Aluminium and General Corrosion Diagrams

NPTEL Web Course

Fig. 7.3 Corrosion diagram for aluminium

3 regions: corrosion, passivation, immunity. Al+++ / AlO2 - is stable Aluminium oxide is stable Al is stable Passivity? Caused by thin oxide or hydroxide layer forming on metal surface, protecting the metal from anodic oxidation.
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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

- corrosion - passivity - thermodynamically immune to corrosion.

Lecture 7: Copper, Aluminium and General Corrosion Diagrams

NPTEL Web Course

However, oxide will itself corrode under certain conditions. Aluminium is an amphoteric metal (acid and alkali reactions) if pH < 4 if pH > 8.3 if 4 < pH < 8.3 - Al+++ stable - AlO2 - stable - Al2O3 stable and thus protects the metal

If the potential is sufficiently low aluminium itself is immune to corrosion. Eh pH diagrams as corrosion diagrams for several important metals such as aluminium, copper, magnesium, nickel, titanium and zinc are illustrated in Fig.7.4. A relative comparison of corrosion behaviour of the above metals in terms of Eh and pH brings about very useful comparisons: Nobler metals (copper, silver, gold and platinum) exhibit very large immunity regions. Active - passive metals such as titanium, and chromium exhibit a larger, stable passive region. Active metals such as magnesium exhibit a large corrosion region. Behaviour of copper, nickel, zinc and aluminium which are widely used in several environmental conditions with respect to corrosion and passivity as a function of pH and redox potentials is very important in the development of corrosion resistant alloys and application of protection techniques.

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 7: Copper, Aluminium and General Corrosion Diagrams

NPTEL Web Course

Fig. 7.4 Corrosion diagrams for various metals

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 7: Copper, Aluminium and General Corrosion Diagrams

NPTEL Web Course

Exercise 1. Through computer search and reference books construct and study Eh pH diagrams for various metallic systems such as: Noble metals (gold, silver, platinum and palladium). Active passive metals (chromium, titanium) High temperature metals (molybdenum, Tungsten) Active metals. 2. a) Comment on combination Eh pH diagrams to represent alloy behaviour in corrosion. b) Role of inhibitors in corrosion prevention through modified Eh pH diagrams. c) Modified Eh pH diagrams to predict passive behaviour, cathodic and anodic protection parameters. 3. Study computer generation and software programmes for Eh pH diagrams.

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 7: Copper, Aluminium and General Corrosion Diagrams

NPTEL Web Course

References 1. M. Pourbaix, Atlas of electrochemical equilibria in aqueous solutions, NACE, Houston (1974). 2. D.C. Silverman and A. L. Silverman, Potential-pH diagrams as aids for screening corrosion inhibitors and sequestering agents, corrosion, 66 No. 5, (2010). 3. P. B. Linkson, B.D.Philips, C. D. Rowles, The method of maximum constriction. An imporved algorithm for the computer generation of potential pH diagrams, Corrosion science, 19 (1979) p 613 -620. 4. Web information on software for corrosion prediction and generating of Eh pH diagrams.

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore