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Corrosion

Corrosion
Corrosion: a chemical or electrochemical reaction between a material and its environment that produces a deterioration of the material and its properties Electrochemical reaction: chemical reactions in which elements are added or removed from a chemical species and at least one of the species undergoes a change in the number of valance electrons Electrochemical Corrosion: Wet (aqueous) - systems that corrode at low T with a liquid electrolyte Dry (oxidation) - corrosion that occurs at high T (generally over 500C) Aqueous: Uniform or General Galvanic or Two-metal Crevice Pitting Intergranular Velocity-assisted Environment-assisted cracking Oxidation: High Temperature No moisture nor dissolved electrolytes Low Temperature surfaces where T< 135C condensation of the acidic sulphur and chlorine-containing gases
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Chemical Corrosion
Liquid Metal Embrittlement: - The dissolution-diffusion model adsorption of the liquid metal on the solid metal induces dissolution and inward diffusion under stress these processes lead to crack nucleation and propagation - brittle fracture theory adsorption of the liquid metal atoms at the crack tip weakens inter-atomic bonds and propagates the crack - diffusion penetration penetration of liquid metal atoms to nucleate cracks which under stress - ductile failure model adsorption of the liquid metal leads to weakening of atomic bonds and nucleation of dislocations which move under stress, pile-up and work harden the solid. dissolution helps in the nucleation of voids which grow under stress and cause ductile failure Examples: Hg and aluminum alloys, Bi and copper alloys
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Electrochemical Corrosion - Oxidation


Low Temperature surfaces where T< 135C condensation acidic sulfur chlorine-containing gases High Temperature: no moisture nor dissolved electrolytes e.g. direct reaction with oxygen Y2O3 Y2O3-X Fe Fe2O3

Oxidation Ellingham Diagram


Low Temperature surfaces where T< 135C condensation acidic sulfur chlorine-containing gases High Temperature: no moisture nor dissolved electrolytes e.g. direct reaction with oxygen Y2O3 Y2O3-X Fe Fe2O3 4Fe + 3O2 2Fe2O3

G = G0 + RT ln k K = [C]c [D]d [A]a [B]b K= Po


2 5

Used for oxidation and reduction of ore

Galvanic Corrosion
Galvanic Cell Two half cells Half cell charge balance metal solution of metal salt One cell oxidizes the other direction depends on driving force General Reaction An+ + neBm+ + memA + nBm+ A B nB + mAn+ Daniell Cell Zn(s) Cu2+ + 2eZn (s) + Cu2+ Zn2+ + 2e- Anodic Cu(s) Cathodic Zn2+ + Cu (s)

Standard Hydrogen EMF Test 25C


Used to develop EMF Series Two outcomes: Metal sample mass decreases (iron is the anode, -) 0 eFe2+ eIron Fe2+ H+ H+ H+ H2 + eePlatinum Gold e- e
-

Metal sample mass increases (gold is the cathode, +) 0 + H+ Ag2+ H+ H+ eePlatinum H+ (1M H+)

Ag2+

Fe2+ (1M Fe2+)

H+

Ag2+ (1M Ag2+)

(1M H+)

Vmetal < 0 (relative to Pt)

Vmetal > 0 (relative to Pt)


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Standard EMF Series

EMF series o Vmetal metal Au +1.420 V Cu +0.340 Pb - 0.126 Sn - 0.136 Ni - 0.250 o V = Co - 0.277 0.153V Cd - 0.403 Fe - 0.440 Cr - 0.744 Zn - 0.763 Al - 1.662 Mg - 2.262 Na - 2.714 K - 2.924
Data based on Table 17.1, Callister 6e.

more cathodic

Ex: Cd-Ni cell

Metal with smaller o Vmetal corrodes.

Cd

25C

Ni

more anodic

1.0 M 1.0 M Cd2+ solution Ni2+ solution

Aqueous Types
Standard Calomel Electrode (SCE): antiquated contains mercury! reaction between: Hg Hg2Cl2 (calomel) aqueous phase: saturated KCl in H2O referenced as 0V redox potential is +0.2444 V vs. SHE at 25 C Standard Hydrogen Electrode (SHE): modern method

Aqueous Types
Galvanic Corrosion: Two metals in contact act similar to a model corrosion cell electrically conduction path driving force (EMF) electrolyte (aqueous solution, air)

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Aqueous Types
Galvanic Corrosion: Can be detrimental, or beneficial, the difference is up to the engineer!

Stainless steel bolts in zinc plated steel.

Zinc anodes on painted LAS.

in both cases, the zinc is less noble. Its use determines the success of the system

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Aqueous Types
Uniform Corrosion: most common corrosion type corrosion rate is often expressed as a distance per year usually mils (1 mil = .001 inches = .0254 mm) Mils penetration per year (MPY) = 534 x W / (At) W = weight loss in milligrams = density (g/cm3) A = area (in2) t = time (hrs) < 1 MPY is outstanding, 5-20 good, 50-200 poor

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Simple Aqueous Corrosion (uniform)


Require four components: anode, cathode, conduction path (contact), and electrolyte Anaerobic Fe Fe2+ + 2eH2 Anodic Cathodic Fe Aerobic (Dissolved Oxygen)
3+ + 3e 2eFe2+

Anodic 6OH 4OH2Fe(OH)3 2 Cathodic

2H+ + 2eFe2+ + 2Cl-

O2 + 6e 4e- + 3H 2H2O
3+ + 4OH 2Fe2+ 6OH-

FeCl2(aq)

2Fe(OH)3 H+ ClFe2+ Fe e(active corrosion) eeCl-

Fe2O3 + 3H2O Rust

H+

H2

H2 H+ H+ H+ O2 OHFe2+ Fe eOHO2

H+ H+ H+

(partially passivates)
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Controlling Uniform Corrosion


Uniform Corrosion: The earliest attempts at slowing corrosion involved additions of copper to steel Still used today High Strength Low Alloy Steel not made to specific chemical composition specific mechanical properties. carbon content between 0.050.25% retain formability and weldability <2.0% Mn Cu, Ni, Nb, N, V, Cr, Mo, Ti, Ca, Zr, or rare earth elements (Y, Hf) Cu, Ti, V, and Nb are added for strengthening purposes Cu, Si, Ni, Cr, P increase corrosion resistance Zr, Ca, and REs control inclusion shape Control-rolled, pearlite-reduced, microalloyed, acicular ferrite, dual-phase, and Weathering

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Controlling Uniform Corrosion


Weathering Steel: HSLA steel with ~0.3 wt. % Cu additions forms adherent, solid oxide layer dont need to be painted use of uncoated weathering steel initial cost savings of >10% (dont need to be painted) life cycle cost savings >30% (durability) The first bridge using this material was built over the New Jersey Turnpike in 1964.

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Simple Aqueous Corrosion (uniform)


Require four components: anode, cathode, conduction path (contact), and electrolyte Anaerobic Fe Fe2+ + 2eH2 Anodic Cathodic Fe Aerobic (Dissolved Oxygen)
3+ + 3e 2eFe2+

Anodic 6OH 4OH2Fe(OH)3 2 Cathodic

2H+ + 2eFe2+ + 2Cl-

O2 + 6e 4e- + 3H 2H2O
3+ + 4OH 2Fe2+ 6OH-

FeCl2(aq)

2Fe(OH)3 H+ ClFe2+ Fe e(active corrosion) eeCl-

Fe2O3 + 3H2O Rust

H+

H2

H2 H+ H+ H+ O2 OHFe2+ Fe eOHO2

H+ H+ H+

(partially passivates)
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Stainless Steels
What is stainless steel? - an iron alloy containing >12% chromium Applications - endless applications chemical handling, marine applications, aesthetics - one purpose: corrosion resistance

Petrochemical

nuclear

architecture

consumer
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Introduction
Stainless Steel - rustless, stainless, inox (inoxydable) - originally a miracle material Stain-less Steel - each SS type has its weakness Austenitics - pH value < 1.0 - chlorides acidic chlorides (MgCl2 and BaCl2) seawater - galvanic self, more noble alloys Sensitization - improper heat treatment intergranular corrosion New York Times: Jan 31, 1915

New York Times: Jan 22, 1922


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How do Stainless Steels Work? Passivation


Oxidation Begins with Cr and Fe oxidation forms passivating layer very rapid (ms) HCP Cr2O3 layer kinetic inhibitor tenacious allows cold work, welding, etc Aerobic (Dissolved Oxygen) Fe Fe2+ + 2e4OH2Fe(OH)2 Anodic Cathodic

O2 + 4e- + 2H2O 2Fe2+ + 4OH-

O2

Fe-Cr(OH)2-3 OHO2 OHCr2O3 Cr-rich base metal e-

Fe2+ Fe-Cr e(fully passivates)

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Transpassive Corrosion
Breakdown increased potential (e.g. very low pH) attacks passivating layer accelerated in pitted area pitting Low pH Corrosion Fe Fe2+ + 2eH2 Anodic Cathodic

2H+ + 2eFe2+ + 2Cl-

FeCl2(aq)

H2

H2 H+ H+ H+ Cr2+ Fe2+ e-

Fe-Cr(OH)2-3

Cr2O3 Cr-rich base metal

Fe-Cr

Fe2+ e(partially passivates)


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Breakdown of the Passivating Layer


Crevice Corrosion 1) Oxygen is consumed in crevice by slow passive corrosion 2) Passive corrosion continues, and pH falls by Cr3+ hydrolysis O2 + 4e- + 2H2O 4OH- (Cathodic) Cr Cr3+ + 3e- (Anodic) Cr3+ + 3H2O Cr(OH)3 + H+ H+ + ClHCl(aq) localized decrease in pH (<2) 3) Passive film breaks down in acid and rapid active corrosion starts 4) Active corrosion causes even stronger acidification and stabilizes the crevice corrosion

O2 OHClM+ eH+

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Breakdown of the Passivating Layer


Breakdown Surface Roughness Flow Local environment pH Film disruption chloride ions Underlying microstructure inclusions slip bands surface roughness phase interfaces grain boundaries Stress gradients Steel Cl- ClClH+ H+ H+ Electrolyte

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Carbide Formation
Chromium Additions to Steel - Beginning in 18201 - added to medium steel (0.10-0.30% C) improved hardenability - 1913, stainless steel invented Harry Brearley Brown Firth Laboratories Fe-12.8% Cr-0.24% C (martensitic) Carbide Formation - too brittle for practical use 1000C - solubility limit (<0.02%C) - Cr23C6 precipitates 800C 600C 400C 0.1 hr 1 hr 10 hr 100 hr 1000hr
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Fe-Cr Fe-Cr-0.1C Phase Diagram Phase Diagram (Calphad) Air cool

Cr23C6

Chromium Additions - Carbide


Temper-Brittleness brittle carbide on grain boundary limitation with early Fe-Cr alloys Carbon Content Lower C, less propensity to carbide formation move the nose stainless iron c. 1920

1000C 800C 600C 400C

Air cool

Cr23C6 0.05% 0.15% 0.30% 1 hr 10 hr 100 hr 1000hr


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Quench 0.1 hr

Sourmail, Aitchison, T.L. Stainless Engineering Steel. Steels: University An exposition of Cambridge. of the 2010. properties. D. Van Nostrand Company. New York. 1921.

Nickel and Chromium Additions


Fe-Ni Austenite stabilizer demotes martensite formation tough, solid solution 1889 first nickel additions (for strength)1

Austenitic Stainless Steel 1914 austenitic stainless steel invented <1% C, <20% Ni and 15-40% Cr Friedrich Krupp AG Eduard Maurer and Benno Strauss Provide ductility, toughness, workability

Fe-Ni Phase diagram (Calphad)

1Riley

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Not so Fast
Austenitic Stainless Steel - invented in 1914 Friedrich Krupp AG Eduard Maurer and Benno Strauss - limited use throughout the war effort high temperature applications (e.g. valves) Krupp Krankheit (Krupps Disease) that peculiar property of nickel chromium steels known as temper-brittleness - intergranular disintegration without apparent external cause - decay is always observed from the surface corrosion process - only in isolated cases traced to faulty heat treatment
Aitchison, L. Engineering Steels: An exposition of the properties. D. Van Nostrand Company. New York. 1921. 26

Sensitization Corrosion Theories


Microcell Theory1 local galvanic couple (Cr-Fe)23C6 cathode (noble) matrix anode weakness: self healing, >12% Cr Stress Theory2 local stresses around carbide imperfect passivation weakness: magnitude Carbide Corrosion Theory3 carbides preferentially corrode 18% weakness: noble Cr 4,5,6,7 Chromium Depletion Theory 12% Cr below passivating generally applicable 8%
1Stickler,

(Cr-Fe)23C6 <12Cr 18Cr-8Ni

1963

2Lula,

1954

3Shvartz, 1959

4Strauss

et al, 1930

5Bain,1933

6Hillert,

1969

7Tedmon,

1971 27

Chromium Depletion Theory

~70% Cr

18% Cr 12% Cr 18% 5.68% C 0.3% C 0.1% C 0.08% C 20nm 0nm 20nm Cr 12% 8%
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Chromium Depletion Theory II


Microcell Theory1 local galvanic couple (Cr-Fe)23C6 cathode (noble) matrix anode weakness self healing resistance above 12% Cr Stress Theory2 local stresses around carbide imperfect passivation weakness magnitude 18% Chromium Depletion Theory3,4,5,6 Cr below passivating Cr 12% generally applicable 8% Vacancy Theory3,4,5,6 sintering preferential diffusion weaknesses rate <12Cr (Cr-Fe)23C6 18Cr-8Ni

1Stickler

and Vinckier, 1963

2Lula

et al, 1954.

3Strauss

et al, 1930

4Bain

et al,1933

5Hillert

et al, 1969

6Tedmon

29 et al, 1971

1930 Strauss, Schottky, and Hinnber


Goal/Hypothesis Provide explanation for Krupp Krankheit Method Relate problem to heat treatment carbide formation Increasing Carbon Content 0.04% C, 9.30% Ni, 18.3% Cr 0.06% C, 9.22% Ni, 18.0% Cr 0.12% C, 8.40% Ni, 18.6% Cr strain

UTS

Summary 1) > potential w/> C = carbides 2) > carbide precip at > T, but < corrosion 3) depletion in immediate region, at higher t the C had more time to diffuse 4) > hardness - martensite being formed? (magnetism detected) 5) corrosion still seen in austenitic nickel-containing alloys (no magnetism) 7) 25%Cr, 20% Ni, 0.15% C has only weak tendency to intergranular corrosion
Strauss, B., H. Schottky, and J. Hinnber. Zeitschrift fr anorganische und allgemeine Chemie. Vol 188. No. 1. pp 309-324. 1930. 30

Modeling efforts
Shvartz and Kristal C control for sensitization Cr control for self-healing Baumel GB diffusion for sensitization volume diffusion for self-healing Strawstrm and Hillert sensitization and self-healing uniform grain boundary film alloy-carbon-M23C6 local equilibrium Tedmon, Vermilyea, and Rosolowski sensitization only non uniform carbide film free energy of carbide formation 20nm 0nm 20nm

Strawstrom, C., and M. Hillert. An Improved Depleted-Zone Theory of Intergranular Corrosion of 18-8 Stainless Steel. Journal of the Iron and Steel Institute. Vol 207. pp 77-85. 1969. 31

Analytical Techniques
Early Studies Corrosion Testing (Moneypenny-)Strauss Test: H2SO4-CuSO41 Huey Test: boiling HNO3 optical microscopy showed pits/trenches low resolution no chemical information Models all proposed before proof of depletion Strauss, Schottky, and Hinnber, 1930 Bain , Aborn and Rutherford,1933 Strawstrm and Hillert, 1969 Tedmon, Vermilyea, and Rosolowski, 1971 Bain, 1933
1Strauss et

Aitchinson, 1921

al, 1930

2Mahl,

1940

2Schaefer

and Harker, 1942 32

Proof of Chromium Depletion


First Confirmation Joshi and Stein, 1972 Auger electron spectroscopy fracture surfaces sulfur, silicon, nitrogen, and phosphorus at GB confirmed Cr-depletion Subsequent Study AES1,2 Atom Probe13 STEM/EDS3,4,5,6,7,8,9,10,11,12 increasing resolution 1977 >50nm 1983-1984 50nm 1983-1986 25nm 1989 5nm Model Validation main chromium depletion effect

Ortner, Hall, 1984 1989 50nm 5nm probe probe size size
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Hopkinson, B.E. and K.G. Carroll. Metallurgy: Chromium Distribution around Grain Boundary

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