U.

Kamachi Mudali
Corrosion Science and Technology Division Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102
Email: kamachi@igcar.gov.in

Cost of Corrosion

Corrosion Uniform, Localised Wear Adhesive Wear, Abrasive Wear, Corrosive Wear, Fretting Wear Fracture Ductile, Brittle Fatigue Low Cycle, High Cycle, Fretting Surface Scale Oxidatation, Carburisation, Sulphidation

(Anodic)

Corrosion is the destructive interaction between a material and its environment Rusting is the most common type of corrosion attack observed on iron base materials in all types of environments

H2 (Cathodic) 2H+ + 2eO2 + 4H+ + 4e2H2O (Acidic) O2 + 2H2O + 4e 4H+ (Basic)

Mn

ne

Fe Al

Fe 2 Al 3

2e 3e

Corrosion occurs by metal dissolution (oxidation) at anode; electron released thereby is consumed by reduction of ions at ca thode; During corrosion anodic current cathodic current

Uniform corrosion can be described as corrosion reaction that takes place uniformly over the surface of the material, thereby causing a general thinning of the component and an eventual failure of the material. Corrosion rate measured in mils per year or mm per year. Factors affecting general corrosion - Moisture - Temperature - Contaminants - Corrosion Control
Uniform Corrosion on Carbon Steel Manhole

State of metal surface characterized by low corrosion rate in a potential region that is strongly oxidizing for the metal
Type 1: low corrosion rate on anodic polarisation Cr, Ti, Stainless steels, nickel Type 2: low corrosion rates in active potentials Lead in sulfuric Acid

Breakdown of passivity
Aggressive ions, chemical and mechanical break down of passive film, presence of susceptible sites at metal surface

Uniform corrosion Localized corrosion

Naturally formed surface films protect the surface until an aggressive ion penetrate and damage the protective nature

OHFe3+ O= OHFe3+ O= OHFe3+ O=

O= Fe3+ O= O= 2OHH2 O Fe3+ 2OHH2 O

O= Fe3+ ClO= Fe3+ ClO=

H2 O 2OHFe3+ H2 O 2OHFe3+ H2 O 2OHFe Fe2+

Iron Electrolyte Passive film FeOOH

O= O=

(a)

(b)

(c)

Salt island FeOCl

a) Slow dissolution of passive film forming Fe 3+ b) accelerated dissolution at a soluble salt island forming Fe 2+ c) direct anodic dissolution at a pit initiation site forming Fe 2+

Corrosion resistant surfaces were produced over iron and bronzes for retaining the beauty and structural integrity over many centuries

Body, Chassis, Engine assembly, Brake controls, Coolant pumps, Crank case emissions, Cylinder block, Carburetor, Exhaust system and Cooling systems Pitting corrosion, galvanic corrosion and crevice corrosion occurred in the motor vehicle on both external and internal parts Most of the corrosion problems are due to wrong materials, poor design, improper maintenance and abuse of vehicle

Corrosion - integral and unavoidable part of petroleum refining operation. Refinery operations involve inflammable hydrocarbons, highly tox ic or explosive gases, strong acids, caustic operating at high tempera tures. Low temperature refinery corrosion : < 260 C, water High temperature refinery corrosion : > 260 C, No water Corrosive Agents in Refineries Inorganic compounds salts MgCl2, CaCl 2, Hydrogen sulphide, HCl, H2SO4, NaOH, crude oil contaminants, process chemicals
Fish-mouth opening in Feed Super heater Tube in Hydrogen Unit

Corrosion failure of boiler tube

Fouling on

Manmade Substrates

Failed location

Uniform Corrosion Pitting Corrosion Crevice Corrosion Intergranular Corrosion Stress Corrosion Cracking Fretting Corrosion Hydrogen Embrittlement Corrosion Fatigue Erosion Corrosion Galvanic Corrosion High Temperature Corrosion Microbially Influenced Corrosion

Failure occurred within six months of service as compared to the guaranteed life of 5 to 10 years. Coil is filled with 70% methanol brine with 30% water, and the outside of the coil was exposed to acetone vapour containing nitrogen.

Crevice corrosion is localized corrosion which might occur in small areas of stagnant solution in crevices, joints and under corrosion deposits .
(b)

(a)

(a) Crevice corrosion of type 316 stainless steel in acid conden sate under a PTFE spacer; (b) typical schematic morphology with att ack greatest at the mouth of the crevice.

Material-Environment for SCC

Material Austenitic SS (annealed) Environment Cl-, OH-, HTHP Water HTHP Water, dilute Cl-, OH-, F-, polythionic acid OH-, NO3-, CO3- & HCO 3solutions, anhydrous NH3 moist air, Cl- & Water, Cl- - H2S Red fuming HNO 3, hot molten salts, methanol, salt water

Unfortunate Facts of SCC Cracking takes place in otherwise best alloys Passive alloys resistant to general corrosion High strength steels prone to cracking Cracking at RT in pure water

Austenitic SS (sensitised) Carbon & Low Alloy Steel High Strength Low Alloy Steel Ti alloys

Kmax
Both crack initiation propagation are influenced and

Synergistic interaction of cyclic plastic deformation and environment

mean

Unlike SCC no specific corrosive environment / materials combination is necessary

K min K min Kmax frequence wave shape R-ratio mean stress

R=

Fatigue life data, S -N curves, for a high strength steel under different environmental conditions

Sulphur

Halogen

Su
Ash/Salt Deposits

tion hida lp

Haloge nation
Carbon

Flue Ash/Hot Corrosion

Eutectics

g Low Meltin n o Liquificati Molten M Corros etal ion

O2, H2, H2O CO, CO 2, H2S, SO2 NH3, N2, NO2 Cl

Carburization

Nitridation Nitrogen

lt ten San Mol sio Corro

Molten Metal

Molten Salts

Applications above 600 C - More than one mechanism acts to degrade the material Principal modes of high temperature corrosion in industrial envi ronments, as well as the interaction between oxygen activity and principal corrodent activity

High temperature corrosion "dry corrosion" or "scaling is a form of corrosion that happens at temperatures well above room temperature and does not require a liquid electrolyte. Oxidation Sulphidation Carburisation Metal Dusting Chloridation Hot Corrosion". High temperature corrosion occurs in various industries such as: power generation (nuclear and fossil fuel), aerospace and gas turbine, heat treating mineral and metallurgical processing, chemical processing, refining and petrochemical, automotive, pulp and paper, waste incineration

Serious problem Temperature and pressure, Hydrocarbon danger of fire if rupture occurs. Sulfidic corrosion >2600C 5400C - no liquid water - common problem in refineries Sulphur compounds from crude oil, polysulfide, H 2S, mercaptans, aliphatic sulfides, disulfides Sulfur compounds react with metal surface and form sulphide products

Corrosion of Economizer Coil in Catalytic Reforming Unit

Hydrogen can degrade materials by: hydrogen blistering hydrogen embrittlement decarburization hydrogen attack Blistering Hydrogen enters the lattice of a metal, diffuses to voids, creates high internal stresses blisters are created Blistering may occur during exposure to: hydrocarbons; electroplating and pickling of metals; chemical process streams; H-containing atm. during welding; general corrosive environments.
Cross section of a carbon steel plate removed from a petroleum process stream showing a large hydrogen blister. Exposure time: 2 years.

Prevention of Blistering
use steels with few or no voids; use coatings; remove impurities that can promote hydrogen evolution . . . S 2- (particularly bad), As, CN-, etc.; use different materials (Ni-base alloys have low diffusion rates for hydrogen).

Crevice attack
Biofilm on 304SS

MOB

MIC refers to corrosion and ensuing loss of metal caused by biological organisms. MIC is a common problem in industrial processes due to the presence of microbes, adequate nutrients and corrosive byproducts.

Good Engineering Practice

Select material/environmental combination based on literature & experience Reduce service and residual Stress Follow procedure/code/practice in Design/Fabrication/Operation

Improve Environment
Control of Impurities

Improve Material
Alloying element to reduce scaling Forming protective layers on surface

Adopt Protective Measures

Painting Coating Plating New materials

MECHANICAL
Shot Peening Laser Peening Roll bonding

PHYSICAL
Sputtering Laser Treatment Physical vapor deposition (PVD) Evaporation Ion implantation Spraying (cold)

THERMAL
Flame Hardening Laser Treatment Induction Hardening Electron Beam Heating Diffusion (Hot Dip) Cladding Spraying (hot)

Surface Modification / Coatings

CHEMICAL Electroplating Anodising Electroless plating Self Assembly Electrophoritic deposition Chemical vapor deposition (CVD)

THERMOCHEMICAL Boriding Nitriding Carburizing Metallizing Plasma, Ion Treatment Laser Alloying

Conservation of materials; desired surface morphology/finish; Fu nctional; Treatment efficiency; Thickness; Integrity; Simplicity; Cost & E conomics 100 m 10 m

Process

1 m 1000 m 0.1 m

Thickness

Dependence of thermal processes taking during heating of metals by CO2 laser radiation on density of absorbed power and on time -ofexposure (duration of action beam on material)

Advantages
- can be used for all metals - installation cost is low - corrosion rate can be reduced to zero

Limitations
- can only be used in weak to moderate environments - operating conditions must be determined by empirical testing.

Impressed Current Sacrificial Anode

A corrosion inhibitor is a chemical compound that, when added in small concentration, stops or slows down corrosion of metals and alloys. Inhibitors slow corrosion processes by either: Increasing the anodic or cathodic polarization behavior ( Tafel slopes) Reducing the movement or diffusion of ions to the metallic surfa ce Increasing the electrical resistance of the metallic surface. Classification of inhibitors - passivating inhibitors - cathodic inhibitors - organic inhibitors - precipitation inhibitors - volatile corrosion Inhibitors Examples of Corrosion inhibitors Hexamine, phenylenediamine, dimethylethanolamine , sodium nitrite, cinnamaldehyde, condensation products of aldehydes and amines (imines), chromates, nitrites, phosphates, hydrazine, ascorbic acid, and others.

Corrosion of Soul