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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
2
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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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)
Metal sample mass increases (gold is the cathode, +) 0 + H+ Ag2+ H+ H+ eePlatinum H+ (1M H+)
Ag2+
H+
(1M H+)
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
Cd
25C
Ni
more anodic
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)
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.
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Aqueous Types
Galvanic Corrosion: Can be detrimental, or beneficial, the difference is up to the engineer!
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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O2 + 6e 4e- + 3H 2H2O
3+ + 4OH 2Fe2+ 6OH-
FeCl2(aq)
H+
H2
H2 H+ H+ H+ O2 OHFe2+ Fe eOHO2
H+ H+ H+
(partially passivates)
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14
15
O2 + 6e 4e- + 3H 2H2O
3+ + 4OH 2Fe2+ 6OH-
FeCl2(aq)
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
O2
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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
FeCl2(aq)
H2
H2 H+ H+ H+ Cr2+ Fe2+ e-
Fe-Cr(OH)2-3
Fe-Cr
O2 OHClM+ eH+
21
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.
22
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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Cr23C6
Air cool
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.
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
1Riley
25
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
1963
2Lula,
1954
3Shvartz, 1959
4Strauss
et al, 1930
5Bain,1933
6Hillert,
1969
7Tedmon,
1971 27
~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%
28
1Stickler
2Lula
et al, 1954.
3Strauss
et al, 1930
4Bain
et al,1933
5Hillert
et al, 1969
6Tedmon
29 et al, 1971
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
Ortner, Hall, 1984 1989 50nm 5nm probe probe size size
33
Hopkinson, B.E. and K.G. Carroll. Metallurgy: Chromium Distribution around Grain Boundary