Chapter 7 Electrochemistry §7.13 Corrosion and protection of metals

1) Corrosion: Destruction of materials due to the chemical, electrochemical and physical attack of the media. Railway bridge in Boston White marble of Jinshui Bridge, Beijing Stone Sculpture before the Capitol, Washington D.C. 1. General introduction

One-fifth of the iron and steel produced annually in the world is used to replace rusted metal. Since corroded metal often loses its structural integrity and attractiveness, corrosion of metal probably results in disaster and has great impact on national economics and safety. Brass sculpture before the Capitol, Washington D.C. Brooklyn Bridge, New York Warship of Pacific Fleet, Russia

2) Why does metal undergo corrosion? Only few elements exist in free element state in natural circumstance. Corrosion of metal, i.e. conversion of element to stable compound, is thermodynamically favored. Naturally occurring copper single crystals, Museum of Natural Sci., Washington, D.C. USA Naturally occurring copper sheet Naturally occurring gold

2. Classification of corrosion 1) Based on materials: Corrosion of metals; Corrosion of non-metals (wood, plastic, concrete, stone, etc.) 2) Based on Media: natural corrosion; industrial corrosion (with surface solution containing acid, base, H 2 S, etc.) 3) Based on mechanism: chemical corrosion (2Fe + O 2 = 2FeO); electrochemical corrosion; biochemical corrosion

4) Based on uniformity: general corrosion; local corrosion 5) Other kinds: tension corrosion; contact corrosion; friction corrosion; external current corrosion; Concussion corrosion

3. local corrosion Local corrosion is initiated due to the ununiformity of metal and / or solution. 1) The ununiformity of metal: 2) The ununiformity of metal surface 3) The ununiformity of solution

(1) multiphase texture; (2) crystal boundary; (3) crystal facet; (4) impurities; (5) enrichment; (6) tension and deformity 1) The ununiformity of metal:

Corrosion of crystal boundary intergranular corrosion Trans-crystal corrosion transgranular corrosion (1) multiphase texture (2) crystal boundary;

Crystal plane (111)(100)(110)(120) Relative corrosion rate (3) crystal facet; (4) impurities; (5) enrichment; Fe Fe = Fe e  Fe 2+ OH  Cl  Fe 2+ Impurity O2O2 O 2 + 2H 2 O + 4e   4OH  Mechanism of Pitting corrosion pH can attain 3.5 ~ 4

Tension corrosion Anodic region Cathodic region Reactions: Anodic reaction: Fe  Fe 2+ +2e ¯ Cathodic reaction: 2H 2 O + 2e¯  H 2 +2OH ¯ Nails in a solution with phenolphthalein and K 3 [Fe(CN) 6 ]

(6) tension and deformity Where is anodic region and cathodic region?

These two beakers contain 1.0 mol·dm -3 Cu(NO 3 ) 2 solutions, a copper electrode, and a salt bridge. If the two copper electrodes were connected together, would a current flow between them?

3) The ununiformity of solution (1) Concentration difference of metal ions; (2) Concentration difference of media ions; (3) Accumulation of H + in pit or cracks; (4) Concentration difference of dissolved oxygen 2) The ununiformity of metal surface (1) Smoothness of the surface; (2) Micropore in protective layer; (3) Corrosion products

Different aeration corrosion Waterline corrosion Crack corrosion (4) Concentration difference of dissolved oxygen O2O2 O2O2 O2O2 O2O2 O2O2 Where does corrosion take place and where does rust form?

4 Theoretical consideration of electrochemical corrosion Zn + 2 HCl  ZnCl 2 + H 2 Why does Zn of 99.5 % purity dissolve in dilute HCl in 1 min, while that of % purity does not dissolve even after 8 h? anode reaction: Zn  Zn e  Cathode reaction: 2H + + 2e   H 2 Conjugation reaction

2H + + 2e   H 2 H 2  2H + + 2e  Zn  Zn e  Zn e   Zn  re Zn 2+ /Zn  re H + /H 2 lg j corr  / V lg j  corr Conjugation reaction Corrosion current Corrosion / stable / mixed potential

 re Zn 2+ /Zn  re H + /H 2 2H + + 2e   H 2 H 2  2H + + 2e  Zn  Zn e  Zn e   Zn lg j corr  / V lg j  corr Positive shift of the  metal or increase of the hydrogen evo- lution overpotential can both hinder the corrosion of the metal.

Copper wire Why does copper wire accelerate corrosion of iron nail? metala Fe0.7 Cu0.87 value of a in Tafel equation

5. Corrosion protection 1) Application of coatings: (1) metal coating: electroplating, chemical plating Zn (anodic protective layer) Sn (cathodic protective layer) (2) non-metal coating: paint (polymer coating); anticorrosion oil; porcelain enamel; plastic; glass (packaging of IC); inherent oxide layer, etc. Coating forms a barrier layer to inhibit corrosive species from reaching metal surface. coating Corrosive species metal

Both thick inorganic coating and organic coating were applied to protect the cable and steel structure of Brooklyn Bridge, New York, USA.

When Al contacting with the air, a thin inherent layer of aluminum oxide forms on its surface. Being stable in the air, water and even some dilute acidic solution, this thin oxide layer inhibits further corrosion of the metal. With potential of naked aluminum of – 0.6 V, the oxide-coated aluminum becomes more stable even than the common metals, such as iron, zinc, etc.

2) Alloying Stainless steel: containing chromium and nickel, both of which form inherent oxide film that change steel’s reduction potential. To be stainless steel, the chromium content needs to be at least 10.5%. The corrosion rate of stainless steel at general corrosion may be as low as 1 cm for 10 6 years.

3) Electrochemical protection Let the potential of iron kept at the stable zone of iron. Cathodic protection: with sacrificial anode with auxiliary anode Anodic protection: set the metal at stale zone of Fe 3 O 4. passivation potential Fe 2+ Fe 2 O 3 Fe pH  / V Fe 3 O 4 Fe 3+ FeO 2 2 

Cathodic protection: with sacrificial anode magnesium / aluminum / zinc alloys Cathodic protection: with auxiliary anode: Pipeline

4) Inhibitor (1) Inorganic inhibitor: Anodic inhibitor cathodic inhibitor C / mol·dm -3 Corrosion rate mm / h NO 2  CrO 4 2  SiO 3 2  HPO 4 2  CO 3 2  react with corrosion product or ions in solution to form inorganic deposition coating. silicate, phosphate, chromate, nitrite, etc.

Self-assembled monolayer of alkanethiols (2) Organic inhibitor: small molecules, usually containing N, S, O, P atoms, can readily adsorb onto metal surface. metal

1) Cu does not react with dilute sulfuric acid, but why does the solution gradually turn blue upon exposure of the system to the air? 2) Why can Au dissolve in NaCN solution when the air was purged. 3) Annihilation can reduce corrosion rate of metal, why? Discussion: