Corrosion Engineering Course Forms of Corrosion

KAFCO, Chittagong Bangladesh

Giel Notten gnotten@planet.nl

NTT Consultancy

Contents Forms of Corrosion

Introduction Electrochemical Uniform corrosion Galvanic corrosion or contact corrosion (two metal corrosion) Pitting Crevice corrosion; corrosion by differential aeration Intergranular corrosion Selective corrosion

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Contents Forms of Corrosion (continued)

Electrochemical mechanical Stress Corrosion Cracking (SCC) Corrosion fatigue Erosion corrosion Physical metallurgical mechanical Hydrogen (H) embrittlement Liquid Metal Embrittlement (LME)

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Contents Forms of Corrosion (continued)

High temperature - Chemical Oxidation / Sulphidation CO-attack Metal dusting Hydrogen (Nelson) attack Nitriding Creep
Atmospheric Corrosion Soil corrosion Microbiological Induced Corrosion (MIC)
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Classification of corrosion forms

Corrosion occurs in several, widely differing forms. Classification is usually based on factors like: Nature of the corrosive environment

Appearance of the corroded material of construction

Mechanism of corrosion

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Schematic illustration of different types of corrosion according to morphology

Oxide film or noble metal

General attack

Pitting

Crevice corrosion

Intercrystalline corrosion
Porous Cu

Exfoliation corrosion

Deposit corrosion

Brass (Cu+Zn) Load

Selective corrosion Stress

Graphitic corrosion

Cracks Stress corrosion cracking (SCC) Corrosion fatigue

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Survey of corrosion phenomena classified according mechanism

Electrochemical Electrochemical mechanical Physical metallurgical (mechanical) High temperature Chemical

Uniform corrosion
Galvanic corrosion

Stress Corrosion Cracking (S.C.C.)

Corrosion-fatigue

Hydrogen (H) damage

Liquid Metal Embrittlement (LME)

Oxidation sulphidation
CO attack Metal dusting Hydrogen (H2) attack

Pitting

Erosion - corrosion
Crevice corrosion Intergranular corrosion Selective attack

Nitriding Creep

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Forms of corrosion: frequency of occurrence (Basf)

3%

10%

33% uniform corrosion 11% corrosion fatigue

6% 4% 5% 1% 2% 6%

33%

19% transgranular S.C.C. 6% 2% 1% 5% 4% 6% intergranular S.C.C.

H-embrittlement H-Embrittlement
H2 - attack pitting intergranular corrosion mechanical (wear, erosion, cavitation) high temperature

11% 19%

3%

10% other corrosion forms

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Frequency of corrosion failure modes in several chemical industries

Basf
Uniform corrosion Local attack - pitting - crevice corrosion - galvanic corrosion - intergranular corrosion - selective leaching Electrochemical-mechanical - stress corrosion cracking - corrosion - fatigue - erosion - corrosion Physical - metallurgical - H - embrittlement - liquid metal embrittlement Other corrosion forms Period Total number of failures 33 5

Bayer
12 12

DuPont
28 14 2 1 10 6 24 3 7 2 3 4 year 685

1 7 1
37 22

25 11 6 2 14

8 4.5 year

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Forms of corrosion
Impact on integrity Uniform corrosion Local attack - pitting - crevice corrosion - galvanic corrosion - intergranular corrosion - selective leaching Mechenical-electromechanical - corrosion-erosion - stress corrosion - corrosion-fatigue Physical-metalurgical - H-embrittlement - liquid metal embrittlement Non-destructive testing-techniqe (V) UT X EC Reference: O + + V UT X (V) UT X V UT X (V UT X EC V EC ++ = very serious + = serious O = moderate - = miner V = visual UT = ultrasonic O ++ + V UT X EC M UT X EC M UT EC X = rontgen

EC = eddy-current M = magnetic

++ ++

M UT X M UT X EC NTT Consultancy

Uniform Corrosion

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Expressions of corrosion rates with conversion factors (Factors for conversion to:)
Given Unit g/m2 h g/m2 24 h g/dm2 24 h mg/dm2 24 h (mdd) mg/cm2 24 h lbs/ft2 24 h lbs/ft2 year mm/year mm/month m/48 h inches/year (ipy) inches/month (ipm) mils/year (mpy) mils/month (mpm) g/m2h 1,0 0.042 4,17 0,004 0,417 203 0,564 0,116d 1,39d 0,021d 2,95d 35,3d 0,003d 0,035d mm/year 8,64:d 0,360:d 36,0:d 0,036:d 3,60:d 1760:d 4,88:d 1,0 12 0,180 25,4 305 0,025 0,305 mils/year 340:d 14,2:d 1420:d 1,42:d 142:d 69200:d 192:d 39,4 473 7,18 1000 12 000 1,0 12

d = density (specific gravity) of the metal Examples: AISI 304(L) stainless steel = 7,9; titanium = 4,5; aluminium = 2,7
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Conversion factors for corrosion rates

mA.cm-2 mA.cm-2 cm.year ipy mdd g.m-2.day-1 cm.year-1 ipy mdd gm-2.day-1

1 3.06 nd/m 7.75 nd/m 0.0112 n/m 0.112 n/m

0.326 m/nd 1 2.54 0.00365/d 0.0365/d

o.129 m/nd 0.394 1 0.00144/d 0.0144/d

89.2 lm/dl 274 d 694 d 1 10

8.92 lm/nl 27.4 d 69.4 d 0.1 1

Reference: ipy

: inch per year

mdd : mg.dm-2.day n m d : valency of metal : atom weight : specific gravity (g.cm-3)

e.g. 1cm per year = 0.394 ipy NTT Consultancy

Uniform corrosion at 304L heat exchanger tube in acidic ammonium bisulphate environment

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Uniform corrosion at overflow plate out of the NOx absorption column of nitric acid plant

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Ruptured tube out of HP stripper Urea plant

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Top and bottom section out of carbon steel reboiler tube anone/anol recovery caprolactam plant

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Baffle plate (X6NiCrMoCu20-18-2-2) hydrolysis vessel caprolactam plant

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Suction line (304L) in the ammonia absorber of low pressure section of urea plant

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Suction line (304L) in the ammonia absorber of low pressure section of urea plant

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NH3- absorber (304L)

Desorption water (traces of NH3)

NH3-gas (traces of O2) HNO3

Corroded segment elbow 304L NTT Consultancy

Local overall corrosion in AISI 347 wall of precipitation reactor NP plant

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Preventive measures Uniform corrosion can be prevented or reduced by: - Application of proper material - Application of a corrosion allowance - Use of coating systems

- Addition of inhibitor systems

- Application of cathodic (or anodic) protection

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Hastelloy B-type welded with Hastelloy C-276 corroded in carbamate solution

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Increased corrosion at liquid level in 316L UG carbamate pipe line

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Galvanic corrosion

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Carbon-zinc battery (Leclanche cell)

+
MnO2 in moist ammonium chloride NH4+ CLH+ OHCLNH4+ CLNH4+ H+ OHCurrent Flow

Carbon center post (cathode)

Zinc Case (anode)

NH4+ CLOH- H+

Anode:

Zn Zn++ + 2e

Cathode: 2MnO2 + 2NH4+ + 2e Mn2O3 + 2H2O + NH3 NTT Consultancy

Explanation of the behaviour of the galvanic coupling of iron and zinc in acidic solution by means of schematic polarization curves

eq , H2/H+ corr , Fe eq , Fe/Fe2+

cathodic addition current densities anodic addition current densities
A+B B A

corr , Zn +Fe
corr , Zn eq , Zn/Zn2+
log icorr, Zn

log icorr , Fe

log icorr , Zn conn, met Fe

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Parameters influencing galvanic corrosion

- Environmental effects - Potential difference galvanic couple - Distance effect - Area effect

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Practical galvanic series for a number of metals and alloys in air saturated, neutral seawater
Metal
magnesium zinc alloy zamak Z400 zinc aluminium 99.5% mild steel cast iron GG-22 13% Cr-steel (active) 18% Cr-8% Ni-steel (active) lead 99.9% brass 60-40 copper monel K 70-30 cupronickel chromium and chromiumnickel steels (passive)

Potential
-1.32 -0.94 -0.78 -0.67 -0.40 -0.35 appr. -0.30 appr. -0.30 -0.26 -0.07 +0.10 +0.12 +0.34

appr. +0.40

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Measures to prevent galvanic corrosion A number of preventive measures, procedures or practices can be used to combat or minimize galvanic corrosion: - Select combinations as close together as possible in the galvanic series - Avoid unfavourable area effect - Insulate dissimilar metals wherever possible - Apply coatings with caution - Add inhibitors if possible - Design for replacement of anodic parts - Install a third metal which is anodic to both metals in galvanic contact
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Galvanic corrosion in carbon steel T-joint next to brass fitting

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Galvanic corrosion at stainless steel blind plate due to carbon depostis

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Galvanic corrosion of aluminium instrument air line at locations of coupling with carbon steel pipeline

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Galvanic corrosion in carbon steel pipeline welded to stainless steel pipeline in sulphuric acid environment

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Pitting Corrosion

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Mechanism of pitting

H2O

O2

Cl-

Cl-

H2O

O2

2H2O + O2 + 4e-

4(OH)-

2H2O + O2 + 4eo o o o o o o o - +2 H+ H + 2e 2 H2 2H + 2e e-

4(OH)-

Passive oxyde layer

eeMeCl2 + H2O e-

Me(OH)2 + HCl Me2+ Me2+

Me2+

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Anodic polarisation curves of material with active/passive behaviour in a halide free and halide containing environment

2 H2O O2 + 4 H+ + 4e Anodic polarization curve In halide free solution

Me + H2O + X- MeOHX+ + H+ + 3e
Epitt

Anodic polarization curve In halide containing solution 2 Me + 3 H2O Me2O3 + 6 H+ + 6e (passivation) Me Men+ + n e (active dissolution) ipass log i
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Epass

Parameters influencing pitting

- Environmental influences: presence of halides redox potential pH temperature

- Velocity effects

- Alloy composition: PREN = %Cr + 3.3.%Mo + 16.%N

- Metallurgical aspects

- Presence of high temperature oxides

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Effect of pH on the pitting potential of several stainless steels in 3% NaCI solution (temp. 25C)
+ 0,8
Pitting Potential (V) + 0,6 + 0,4 316 + 0,2 0 -0,2 -- 0,4 1 3 5 7 pH 9 11 304 430

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Effect of temperature on the pitting potential of several stainless steels in a 3% NaCI-solution

+ 0,4

Pitting Potential (V)

+ 0,2

AISI 316
AISI 304

AISI 430

-0,2

- 0,4 20 40 60 Temperature 80

100 C

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Effect of Cr-content on the pitting potential of Fe/Cr-alloys in an aerated 0.1 N NaCI solution (temp. 25C)
+ 0,7 +0,6 Pitting Potential (V) + 0,5 + 0,4 + 0,3

+ 0,2
+ 0,1 0 - 0,1 10 20 30 40 Cr - content 50 60 weight %

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Effect of Mo-content on the pitting potential of Fe-15% Cr13% Ni-alloys in an aerated 0.1 N NaCI solution (temp. 25C).
0,6 Pitting Potential (V) 0,5 0,4 0,3 0,2

0,1
0 0 1 2 Mo-content 3 weight %

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Effect of Ni-content on the pitting potential of Fe-15% Cralloys in an aerated 0.1 N NaCI solution (temp. 25C).

+ 0,15 Pitting Potential (V) + 0,10 + 0,05 0

0,05
- 0,10
10 20 30 Ni content 40 50 60 weight %

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Causes of pitting attack

- Local defects in protective layer - Adsorption and penetration of specific ions in the oxide layer; e.g. chloride and bromide ions (stagnant conditions)

- Presence of ferric and cupric ions or other species which increase the redox potential (e.g. H2O2) in a chloride containing environment (electron acceptors)
- Foreign metal particles in oxide layer; e.g. iron particles of steel brush in stainless steel - Stray currents

- Microbiological influences (presence of microbiological slime film)

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Measures to prevent pitting attack

- Avoid presence of chlorides, especially in presence of ferric and cupric ions and other species which increase the redox potential - Application of inhibitors like silicates, chromates, phosphates
- Increase of pH

- Remove porous oxide layers due to welding

- Avoid stagnant conditions - Change alloy compositions (PREN = %Cr + 3.3%Mo + 16%N)
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Materials with increased pitting resistance X8Cr17 (AISI 430) X2CrNi19-11 (AISI 304L) X2CrNiMo17-12-2 (AISI 316L) X2CrNiMoN25-22-2 X2CrNiMoN22-5-3 X2CrNiMoN17-13-5 (ASN5W) X2NiCrMoCu25-20-4-2 (2RK65) X2NiCrMoCu31-27-4-1 (Sanicro 28) Hastelloy B2 Hastelloy C-276 Hastelloy C-4 Hastelloy C-22 Titanium, Zirconium, Tantalum
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Extensive growth of pit diameter below surface

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Pitting of 17% Cr steel tube in cooling water with chlorides

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Pitting occurrence depending on Mo content in AISI 304, benzene storage tank with water phase, containing ammonium sulphate and SO2

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Pitting in C-steel recirculation line of condensate tank

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Pitting in X3CrNiMoN17-13-5 (ASN5W) heating coil of separator in MVC recovery of a PVC plant

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Pitting in X3CrNiMoN17-13-5 (ASN5W) heating coil of separator in MVC recovery of a PVC plant

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Pitting in AISI 316 pipeline

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Pitting in AISI 304 (0.0% Mo) in SO2 containing benzene

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Pitting in lower section of horizontal pipeline

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Pitting in 316L heat exchanger tube due to stagnant cooling water

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AISI 316L thermosyphon pipeline of benzoic acid column phenol plant

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AISI 316L thermosyphon pipeline of benzoic acid column phenol plant

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Leakage in nozzle cyclohexanone reactor due to pitting in 316L cladding

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Pitting in 316L cladding of nozzle for agitator in cyclohexanone reactor

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Local overall corrosion in AISI 347 wall of precipitation reactor NP plant

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Pitting in 304L test coupon in FeCl3 environment

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Crevice Corrosion

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Crevice corrosion - initial stage

O2 CIO2 Na+ C1O2 M+ OHOH+ O2 M+ O2 Na+

OH-

e e

C1Na+ M+ M+ OHO2 Na+

M+

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Crevice corrosion - later stage

Na+ O2 C1O2 OH-

O2

OH-

O2

OH-

e
M+ C1M+ M+ M+ C1C1-

O2 O2
OH-

C1O2 OHC1C1C1C1M+ M+

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Differential aeration cell (U.R. Evans)

Air or oxygen Three-way tap Electron flow

Anode:

Fe Fe++ + 2e

Cathode: O2 + 2H2O + 4e 4OH+

Miliammeter Porous partition Potassium chloride solution Steel (Fe) cathode NTT Consultancy Steel (Fe) anode

Water line attack, caused by a differential aeration cell

AIR
O2 Fe CATHODE O2 + 2H2O + 4e 4OHNaOH FORMED HERE O2

ANODE Fe Fe++ + 2e

O 2

FeCl2 FORMED HERE

SEA WATER

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Parameters influencing crevice corrosion

- Design - Environment risk of deposit presence of halides; oxygen - Alloy composition

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Causes of crevice corrosion

Crevice corrosion is usually attributed to one or more of the following parameters:

- Lack of oxygen in the crevice - Build-up of detrimental ion species in the crevice - Changes in acidity (decrease of pH) in the crevice

- Depletion of an inhibitor in the crevice

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Preventive measures - Application of more resistant construction material like high Ni / Mo alloys - Make full penetration welds to avoid crevices - Design vessels for complete drainage

- Weld (internal bore weld) instead of rolling in tubes in

tubesheets - Inspect vessels and remove deposits frequently

- Remove wet packing materials during long shut

downs - Use solid non absorbent gaskets, such as PTFE
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Crevice corrosion at a stainless steel orifice

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Crevice corrosion in carbon steel bottom plate condensate tank due to presence of stainless steel disc.

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Crevice corrosion in 304L test coupon

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Filiform corrosion at a bonnet of a car

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Filiform corrosion at varnished steel light reflector n

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Principle of filiform corrosion

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Intergranular Corrosion

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Grain boundary in a polycrystalline metal (two-dimensional representation)

Grain boundery

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Precipitations affecting intergranular corrosion

Precipitates with cathodic behaviour versus grains; e.g. CuAl2 in Al-base alloys;Fe3C in iron base alloys. Anodic grain or grain boundary.

Precipitations on grain boundaries; precipitates are inert e.g. Cr23 C6 Mo6C; W6C. Depleted zone of components necessary for corrosion resistance.

Precipitates with anodic behaviour versus grains; e.g. Mg5Al8 and MgZn2 in Al-base alloys; Fe4N in iron base materials.

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Chromium carbides on grain boundaries of austenitic stainless steel

20 m

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Chromium carbide precipitations on grain bounderies of austenitic stainless steel

50 m

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Concentration of Cr as function of distance from the grain boundery

% Cr 18 1.6% 16.4 12 10 critical value

Precipitate of (Cr.Fe)23C6 t=0 t = t1 t

grain boundery

distance from grain boundery

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Weld decay zones

1300 Temperature C

850

450

weld decay zones

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Weld decay zones

A

1250 Temperature C 1050

B
HAZ

850

C
450

weld A B HAZ C D

10

20

30

40

50

60

time, sec.
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Intergranular attack in austenitic microstructure

125 m

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Intergranular attack in austenitic microstructure

100 m

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Aspects influencing intergranular corrosion

- Sensitizing temperature - Chemical analysis of stainless steel - Carbon content - Titanium or niobium content - Chromium content - Nickel content - Molybdenum content - Silicon content - Nitrogen content - Microstructure - Ferrite or austenite - Grain size - Environment to which the sensitised steel is exposed

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TTC diagram according to Rocha; Influence of carbon content on susceptibility to intergranular corrosion of CrNi18-9
900 Sensitisation temperature in C

800 0.09 700 0.06

600

0.04 0.03

0.02
500 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5

Annealing time t in hrs

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Schematic chart showing solution and precipitation reactions in types 304, 321 and 347
Melting point C 1250 Titanium / Niobium carbides precipitate Chromium carbides dissolve 850 Chromium carbides precipitate 450 No reactions Titanium / Niobium carbides dissolve Chromium carbides dissolve

50

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Tests to determine susceptibility to intergranular corrosion of stainless steels

Test Environment Standard Test duration In hours 5 x 48h Criterion Affects carbide weight loss microsc. exam. weight loss -phase

Huey test

65% HNO3 boiling 10% HNO3 3% HF 70C 6% CuSO4 16% H2SO4 boiling Cuchips 19% g/l Fe2(SO4)3 50% H2SO4 boiling 10% oxalic acid room temp.

ASTM A262 practice C Stac spec 53961 ASTM A262 practice D ASTM A262 practice E

HNO3/HF test Strauss test

2 x 2h

+
24h 1 electric resistance 2 bending 3 noise weight loss microsc. exam anodic etching pattern

+ + +

Streicher test Oxalic acid test

ASTM A262 practice B ASTM A262 practice A

120h

1.50 min 1 A/cm3

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Polarization diagrams for austenitic Cr Ni-steel in sulphuric acid

Huey Streicher

potential

Strauss

a. b.

Quench-annealed Sensitized Current Density logi

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Measures to prevent intergranular attack of stainless steels

- Decrease the carbon content to <0.03 or even <0.02% - Annealing at 1050C and quenching - Alloying with strong carbide formers; stabilizing with Ti (5 x C-content) or Nb (10 x C-content) - Homogeneous annealing at 900C

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Weld decay in AISI 304 pipe material welded to a flange

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Weld decay in a 316 pipeline

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Intergranular corrosion in fork flange of level switch

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Intergranular corrosion in 316 fork flange of level switch

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Intergranular corrosion in fork flange of Mobrey level switch

150 m

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Pump impeller 304 cast, completely corroded intergranularly (environment HNO3)

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Knife-line attack in 347 plate material

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Influence of cold-deformation on intergranular corrosion in outer filament of AISI 304 plate material

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Test coupons with intergranular attack after Strauss test

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Strain induced intergranular cracking in AISI 316L urea grade liner material in top head reactor

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Strain induced intergranular cracking in 316L urea grade liner material in in top HP scrubber

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Microphoto of strain induced intergranular cracking

250 m

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Microphoto of strain induced intergranular cracking

100 m

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Microphoto of strain induced intergranular cracking

20 m

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Strain induced intergranular cracking in liner top urea reactor

10 mm

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Preferential locations of stress induced intergranular cracking

cracks

strip

liner

vessel wall

cracks vessel wall

liner ground weld area

cracks

cracks

strip cracks

liner
vessel wall
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Strain induced intergranular cracking in 304L material in top head of AN neutra reactor R6501 urea plant

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Intergranular corrosion in a Hasstelloy C spray nozzle in a saturator cooler

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Weld decay and knife-line attack in Hastelloy B plate material out of a SO2 separator

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Exfoliation corrosion in a bottom plate of an AIMg3 storage tank. The attack started from outside

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Microscopic view of exfoliation corrosion in AIMg3

150 m

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Exfoliation corrosion in AlMg3

100 m

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Exfoliation corrosion in AlMg3

200 m

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Exfoliation corrosion in AlMg3

50 m

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Selective corrosion / selective leaching

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Examples of selective attack

- Selective attack of specific phase in microstructure

- Selective attack of weld deposit material

- Dezincification of brass - layer type dezincification - plug type dezincification - Graphitization of cast iron

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Selective attack of the pearlite phase in the ferritepearlite microstructure of carbon steel (HII)

100 m

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Selective attack of ferrite in a weld in austenitic 316L stainless

50 m

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Selective attack of weld deposit material in carbon steel petrol pipeline

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Potential curves at connection welds

different materials

Weld decay zone

High temperature zone

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SMAW covered steel electrodes

Fe3O4 TiO2 CaF2

acid SiO2 CaCO3 SiO2 MgCO3

rutile CaCO3 SiO2 MgCO3

basic CaCO3 MgCO3

- increase in sensitivity for moisture - higher purity - increase in mechanical properties - increase in corrosion resistance

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SMAW covered steel electrodes

Fe3O4 TiO2 CaF2

acid SiO2 CaCO3 MgCO3 SiO2

rutile CaCO3 MgCO3 SiO2

basic CaCO3 MgCO3

concave

flush normal penetration

convex less penetration, increased risk for fatigue

deep penetration

- increase in contamination - improved executive weldability (appearance)

Compromise: root run + filler layers: basic; cap layer: rutile

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Selective attack of weld deposit material in 304L material

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Selective attack of ferrite in ledeburitic cast chromium steel (CrMo30-2) pump material

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Layer type dezincification of a brass heat exchanger tube

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Layer type dezincification

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Plug type dezincification in a brass heat exchanger tube

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Plug type dezincification

350 m

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Dezincification in brass water tap

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Dezincification and SCC in brass

20 m

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Dezincification in brass

20 m

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Measures to prevent dezincification

- Reducing aggressiveness of environment by means of changing the pH, chloride and oxygen removal

- Increasing velocity to avoid formation of deposits

- Softening the water can have favourable influence by preventing scale formation - Cathodic protection - Changing alloy composition

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Measures to prevent dezincification (continued) Changing the alloy: - Decrease of Zn content: red brass (15% Zn) is almost immune to dezincification

- Addition of 1% tin (Sn) to a 70 30 brass (Admiralty Brass)

- Further improvement by addition of As, Sb or P as inhibitors. E.g.: Arsenic Admiralty Metal contains about 70% Cu, 29% Zn, 1% Sn and 0.04% As. As is also added to aluminium (2% Al) brasses.

- For severe corrosive environments: cupro-nickels (70-90% Cu; 10-30%Ni)

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Graphitization in cast iron spray nozzle

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Graphitization in cast iron partition plate of waste water pump

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