CORROSION AND ITS PREVENTION

G. Chowdhury

Prof.(MET)

INTRODUCTION


Corrosion is an inevitable phenomenon. phenomenon. In fact our economy would be directly changed if there were no corrosion. corrosion. The approximate estimate of loss of metal due to corrosion, 2 to 2.5 billion dollars per annum all- over the world. allworld. In India it is Rs.600.00 crores. Rs.600. crores.

INTRODUCTION
    

Though corrosion is inevitable, its cost can be considerably reduced. reduced. An inexpensive Magnesium anode could double the life of a domestic hot water tank. tank. Washing a car to remove road-salt is roadhelpful. helpful. Proper selection of materials and good design reduces cost of corrosion. corrosion. A good maintenance-painting programme maintenancepays for itself many times

Corrosion Theory
All matters want to remain in the lowest energy state, where it is thermodynamically more stable  Barring a few exceptions, metallic oxides and salts are more stable than the metal itself  Hence, Natural Occurrence is in the form of Ores, which are nothing but oxides and salts  Metals are extracted from Ores through the application of considerable amount of energy  An energy hump prevents spontaneous reversal


Corrosion Theory


As a result they are forced to remain in High Energy State If some energy is provided to cross the hump, spontaneous reaction can occur Certain environments offer opportunities to these metals to combine chemically with other elements to form compounds and return to lower energy levels

Corrosion Theory


Contd

Corrosion is the primary means by which metals deteriorate. deteriorate. Most metals corrode in contact with water (and moisture in the air), acids, bases, salts, oils, aggressive metal polishes, and other solid and liquid chemicals. chemicals. Metals also corrode when exposed to gaseous materials like acid vapors, formaldehyde gas, ammonia gas, and sulfur containing gases. gases.

Corrosion Theory


Contd

 

Almost all metals exhibit a tendency to be oxidized, some more easily than oxidized, others. others. A tabulation of the relative affinity of this Series. tendency is called the Galvanic Series. Knowledge of a metal's location in the series is an important piece of information to have in making decisions about its potential usefulness for structural and other applications

FORMS OF CORROSION
CORROSION CAN BE OF TWO TYPES:


UNIFORM NONNON-UNIFORM OR SELECTIVE

UNIFORM CORROSION
IDEALLY, UNIFORM CORROSION TAKES PLACE BETWEEN A PURE UNSTRESSED METAL & AN UNIFORM ENVIRONMENT - DRY AIR OR CORROSIVE GAS - WET AIR OR CORROSIVE GAS - AERATED ACID OR CORROSIVE MEDIUM - NON-AERATED ACID OR CORROSIVE NONMEDIUM

SELECTIVE CORROSION


SELECTIVE OR NON UNIFORM CORROSION TAKES PLACE WHEN EITHER TWO DISSIMILAR METAL OR ENVIRONMENT IS PRESENT IT IS ESSENTIALLY AN ELECTROELECTROCHEMICAL REACTION LIKE A BATTERY OR GALVANIC CELL

SELECTIVE CORROSION


DISSIMILARITY CAN BE DUE TO

1. 2.

3. 4.

5.

DIFFERENT METALS OR PHASES DIFFERENT STRESS LEVEL DUE TO COLD WORKING OR GRAIN BOUNDARY DIFFERENT MICROSTRUCTURE DIFFERENT CONCENTRATION OF CONDUCTING MEDIUM DIFFERENT AVAILABILITY OF OXYGEN

SELECTIVE CORROSION


BASED ON THE FIELD CONDITION IT IS NAMED AS

1. 2. 3. 4. 5.

GALVANIC OR TWO-METAL CORROSION TWOCREVICE CORROSION PITTING CORROSION STRESS CORROSION INTERINTER-GRANULAR CORROSION ETC.

PRODUCTS OF CORROSION


ESSENTIALLY, THE CORROSION PRODUCTS ARE OXIDE, HYDRATED OXIDE OR SOME SALT WITH ACID RADICALS. WATER NORMALLY DOES NOT REACT WITH METAL DIRECTLY, BUT TAKES A LEADING ROLE IN PROPAGATING THE PROCESS.

CORROSION MECHANISM


UNIFORM CORROSION (DRY) 1. SOME METALS LIKE Ag, Tin etc. etc. DIRECTLY REACTS WITH ATOMOSPHERIC OXYGEN OR SO2 TO FORM COMPOUND 2. THE FILM OF CORROSION PRODUCT FORMED PREVENTS/SLOWS DOWN FURTHER REACTION 3. NOT PREVELANT IN STEEL EXCEPT SS

CORROSION MECHANISM


OXIDATION CORROSION: 4Mp4Mn+ + 4ne-

(Loss of electron)

Metal ion nO2 + 4ne- p 2nO2(Gain of electron) Oxide ion Overall 4M + nO2 p 4Mn+ + 2nO2Metal ion Oxide ion
Metal oxide

CORROSION MECHANISM


UNIFORM CORROSION (WET): 4Mp4Mn+ + 4ne(loss of electron) 2nH2O + nO2 + 4ne- = 4n(OH)- (gain of electron) Mn+ + n(OH)- = M(OH)n

IF ENOUGH OXYGEN IS PRESENT, IT CAN FORM HIGHER OXIDES. WHEN OXYGEN SUPPLY IS POOR, A MIXURE OF HIGHER AND LOWER OXIDES MAY BE FORMED.

CORROSION MECHANISM


UNIFORM CORROSION IN ACID OR ELECTROLYTE MEDIUM (NON(NONAERATED)  Fe + HCl = FeCl2 + H2  Fe + CuSO4 = FeSO4 + Cu HYDROGEN OR COPPER TENDS TO FORM A PROTECTIVE FILM SLOWING DOWN FURTHER REACTION

ELECRTOCHEMICAL REACTIONS OF ZINC IN AIR FREE HCI

CORROSION MECHANISM


UNIFORM CORROSION IN ACID OR ELECTROLYTE MEDIUM (AERATED)



AS ENOUGH OXYGEN IS PRESENT HYDROGEN IS CONSUMED AS H2O AND THE PROTECTIVE FILM DISSAPEARS. DISSAPEARS. THAT IS WHY IN PLAIN WATER CONTAINING OXYGEN, THE RATE OF CORROSION IS QUITE FAST AS COMPARED TO DISTILLED WATER. WATER.

Electro-chemical reactions of Zn in aerated HCl acid

CORROSION MECHANISM
SELECTIVE CORROSION (GALVANIC)  TWO METALLIC PARTS, ANODE & CATHODE  THEY MAY OR MAY NOT BE PHYSICALLY DISTINCT AND SEPARATE  CONDUCTING ELECTROLYTE  ANODE DISSOLVES SELECTIVELY IN PREFERENCE TO CATHODE

CORROSION MECHANISM


AT ANODE:M Mn+ + ne- M n+ p Dissolved in solution. AT CATHODE:2nH2O + nO2 + 4ne- = 4n(OH)(dissolved constituents in the conducting medium accepts the electron to form some ions, (OH)-, O2- etc.) The metallic & non-metallic ions reacts to form corrosion products

MECHANISM OF WET CORROSION BY HYDROGEN EVOLUTION

CORROSION MECHANISM
RUST FORMATION:
 

 

At Anode, Fe2+ or Fe3+ ions are formed At Cathode, (OH)- ions are formed in presence of water and oxygen Both combine to form Fe(OH)2 or Fe(OH)3 This product, called Yellow Rust, corresponds to Fe2O3 3H2O If the supply of oxygen and water is limited, the corrosion product may even be black anhydrous oxide, Fe3O4, known as Magnetite

MECHANISM OF WET CORROSION BY OXYGEN ABSORPTION.

FOUR TYPES OF ELECTROCHEMICAL CELL

* GALVANIC CELL OR DISSIMILAR METAL CELL

* CONCENTRATION CELL

* DIFFERENTIAL STRESS CELL

* DIFFERENTIAL TEMPERATURE CELL

GALVANIC CELL
Galvanic cells (also known as composition cells) cells) arise when two metals with dissimilar compositions or microstructures come into contact in presence of an electrolyte. electrolyte.
THE TWO MOST COMMON EXAMPLES :
 

DISSIMILAR METALS MULTIMULTI-PHASE ALLOY

Dissimilar metals:


Formed by two single-phase metals in singlecontact, such as iron and zinc, or nickel and gold. gold. The metal that is higher on the Electrochemical Series will be the cathode. cathode. The other metal will suffer anodic reactions and will corrode. corrode.

MultiMulti-phase alloy:


Formed by a metal alloy composed of multiple phases, such as a stainless steel, a cast iron, or an aluminum alloy. alloy. The individual phases possess different electrode potentials, resulting in one phase acting as an anode and subject to corrosion. corrosion.

Stress Cell


Stress cells can exist in a single piece of metal where a portion of the metal possesses more stored strain energy than the rest of the metal. metal. The three most common examples: examples:  Grain boundaries  High localized stress  Cold worked

Grain boundaries:


By definition, metal atoms situated along grain boundaries are not located in a regular crystal array (i.e. a grain). (i. grain). Their increased strain energy translates into an electrode potential that is anodic to the metal in the grains proper. proper. Thus, corrosion can selectively occur along grain boundaries

High localized stress:



Localised high-stress regions will be highanodic to low-stress regions and can lowcorrode selectively. selectively. For example, bolts under load are subject to more corrosion than similar bolts that are unloaded. unloaded. A good rule of thumb is to select fasteners that are cathodic to the metal being fastened in order to prevent fastener corrosion. corrosion.

Cold worked:


Regions within a metal subjected to coldcoldwork contain a higher concentration of dislocations, and as a result will be anodic to non-cold-worked regions. non-coldregions. Thus, cold-worked sections of a metal will coldcorrode faster. faster. For example, nails that are bent will often corrode at the bend, or at their head where they were worked by the hammer

Concentration Cell
Concentration cells can arise when the concentration of one of the species participating in a corrosion reaction varies within the electrolyte. electrolyte.

The two most common examples

 

Electrolyte concentration Oxygen concentration

Electrolyte concentration: concentration:



If a region of the electrolyte (adjacent to the metal) exhibits a decreased concentration of metal ions, this region would become anodic to the other portions of the metal surface. surface. As a result, in this portion, the metal would corrode faster in order to increase the local ion concentration to homogenize. homogenize. The situation may occur in an anchored ship where the immersion line gets washed by waves. waves.

Oxygen concentration


Perhaps the most common concentration cell affecting engineered structures is that formed due to dissolved oxygen. oxygen. When oxygen has access to a moist metal surface, corrosion is promoted and oxygen get depleted. depleted. If the depletion is not replenished, it forms an anodic cell in comparison to high oxygen area. area.

Oxygen concentration


As a result, sections covered by dirt or scale will often corrode faster, since the flow of oxygen to these sections is restricted. restricted. An increased corrosion rate will lead to increased residue, further restricting the oxygen flow to worsen the situation. Pitting situation. often results from this Runaway" reaction

FACTS ABOUT CREVICE CORROSION:

Corrosion is accelerated inaccessible areas.

in

apparently

Corrosion is accelerated under accumulation of dirt, sand, or other contaminants. Contacts between metals & non metallic surfaces (Rubber gaskets, woods, plastics, glass, asbestos etc.) are prone to Crevice Corrosion

MECHANISM OF DIFFERENTIAL ATTACK CAUSED BY THE PRESENCE OF DROP OF SALT SOLUTION ON THE IRON SURFACE.

ANODE IS FORMED AT INACCESSIBLE LOCATION,WHERE OXYGEN IS LESS AVAILABLE.

EMF SERIES
Potential difference between metals exposed to solution containing unit activity are measured at constant temperature. It is presented in tabular form known as EMF series. All potentials are referred against Hydrogen electrode. Potential between metals are determined by taking the absolute differences between their standard EMF potentials.

Table 10-1 Standard EMF Series for Metals 10MetalMetal-metal ion equilibrium Electrode potential vs. normal hydrogren electrode at 250C (volts)

Noble or cathodic

Au-Au+3 AuPt-Pt+2 PtPdPd-Pd+2 AgAg-Ag+1 HgHg-Hg3+2 CuCu-Cu+2 H2-H+ PbPb-Pb+2 SnSn-Sn+2 Ni-Ni+2 NiCoCo-Co+2 CdCd-Cd +2 Fe-Fe+2 FeCr-Cr+2 CrZnZn-Zn+2 Al-Al+3 AlMgMg-Mg+2 NaNa-Na+1 K-K+1

+1.498 +1.2 +0.987 +0.799 +0.788 +0.337 0.000 -0.126 -0.136 -0.250 -0.277 -0.403 -0.440 -0.744 -0.763 -1.662 -2.363 -2.714 -2.925

Active or anodic

GALVANIC SERIES
Covers most engineering metals and alloys.

Gives more practical prediction of galvanic relationship than the EMF series. The series is based on potential measurements & galvanic corrosion tests in un-polluted sea water. The relative nobility of a material can be predicted by measuring its corrosion potential.

GALVANIC SERIES Contd Contd



Galvanic series relationships are useful as a guide for selecting metals to be joined Helps in the selection of metals having minimum tendency to interact galvanically Indicates the need of protection to be applied to lessen interactions. interactions.

GALVANIC SERIES Contd Contd



In general, the further apart the materials are in the galvanic series, the higher the risk of galvanic corrosion, which should be prevented by design. design. However, it does not provide any information on the rate of galvanic corrosion and thus serves as a basic qualitative guide only.

Table 10-2 Galvanic Series of Some Commercial Metals and Alloys in Seawater Noble or cathodic Platinum Gold Graphite Titanium Silver 18-8 stainless steel (passive) Nickel (passive) Silver solder Cupronickels (60-90Cu, 40-10Ni) Bronzes (Cu-Sn) Copper Brasses (Cu-Zn) Nickel (active) Tin Lead Lead-Tin solders 18-8 stainless stel (active) Steel or iron 2024 Aluminum (4.5Cu 1.5Mg 0.6Mn) Cadmium Commercially pure aluminum Zinc Active or anodic Magnesium and magnesium alloys

GALVANIC SERIES


A small anode/cathode area ratio is highly undesirable. In this case, the galvanic current is concentrated onto a small anodic area. Rapid thickness loss of the dissolving anode tends to occur under these conditions. That is why a tin plating gets perforated much faster than Zn plating.

FACTORS INFLUENCING CORROSION:NATURE OF METALS ( POSITION IN GALVANIC SERIES)

RELATIVE AREAS OF ANODIC & CATHODIC PARTS.

PURITY OF METALS.

PHYSICAL STATE OF METALS.

SOLUBILITY OF CORROSION PRODUCTS.

VOLATILITY OF CORROSION PRODUCTS.

NATURE OF THE CORRODING ENVIRONMENT.

 TEMPARATURE.

 HUMIDITY OF THE AIR.

 PRESENCE OF IMPURITES IN ATMOSPHERE.

 PRESENCE OF SUSPENDED PARTICLES IN AIR. FORMATION OF OXYGEN CONCENTRATION CELL.

PREVENTION OF CORROSION:-

- MATERIAL SELECTION.

- DESIGN & FABRICATION PROCEDURE.

- ALTERATON OF ENVIRONMENT.

- CATHODIC PROTECTION. * SACRIFICIAL ANODE METHOD. * EXTERNAL POWER SUPPLY.

-APPLICATION OF PROTECTIVE COATING:* ELECTRO PLATING. * FLAME SPRAYING. * CLADDING. * HOT DIPPING. * VAPOUR DEPOSITION. * DIFFUSION. *CHEMICAL CONVERSION.(ANODISING. PHOSPHATING, CHROMATIZING.) *ORGANIC COATING. (PAINTS, VARNISHES, ENAMELS, LACQUERS, etc.)

Corrosion Performance of Metals

The following numbers refer to the corrosion rates, expressed in terms of depth of metal removed in unit time, for mild steel and various stainless steels in different acids. (reference) (reference) Penetration rates (mm/year) for various steels in different acids

Steel Mild Steel 13% Chromium 12% Chromium 12% Nickel 17% Chromium 18% Chromium 8% Nickel

70% HNO3 (60 oC) Very high 0.15 0.05 0.1 Nil

20% HCl (20 oC) 38 120 5 35 25

80% H2SO4 (20 oC) 0.4 4.5 0.5 0.7 1.5

Corrosion Performance of Metals contd..



Stainless steels would provide better life than mild steel in hot concentrated nitric acid In hydrochloric acid only the 12 per cent Chromium & 8 per cent Nickel steel is significantly better than the mild steel Mild Steel in the sulfuric acid is better than any of the stainless steels, costing about an order of magnitude less per unit weight. weight.

Corrosion Performance of Metals contd..

These differences are largely related to  Differing oxidizing characteristics of the acids. acids.  The corrosion resistance of stainless steels mainly depends upon the formation of a protective chromium oxide film upon their surfaces. surfaces.  So, in the absence of an adequate supply of oxygen, as with the hydrochloric acids, the chromium addition is of little benefit. benefit.

Corrosion Performance of Metals contd..

 

The same point can be made in relation to other forms of corrosion Molybdenum additions to ferritic steels are beneficial with respect to stress corrosion cracking resistance in carbonate environments, but are detrimental in hydroxide solutions. solutions. Stainless steels represents a class of highly corrosion resistance steel.

BUT REMEMBER

Corrosion Performance of Metals contd..



Stainless steel is not stainless IN ALL ENVIRONMENT. It is not most corrosion- resistant. It is not a specific alloy. A group of nearly 30 different alloys ( 11.5-30%Cr, 0-22% Ni).

Corrosion Performance of Metals contd..



Stainless steels are less resistant alloys in chloride-containing mediums & stressed structures than ordinary structural steel. Stainless steel are most susceptible to localised corrosion- inter-granular corrosion, stress corrosion & pitting than ordinary steels. A large number of corrosion failure can be directly attributed to the indiscriminate selection of stainless steel.

Corrosion Performance of Metals contd..



The important point to be grasped is that in specifying the operating conditions for a component or structure it is vital that the environmental conditions be defined with as much precision as any other parameters, such as stress, temperature etc. etc. Only by so doing can the selection of a material from the corrosion resistance viewpoint be made satisfactorily

COMBINATIONS OF METAL & CORROSIVE ENVIRONMENT THE MAXMIMUM AMOUNT OF CORROSION RESISTANCE FOR THE LEAST AMOUNT OF MONEY.
1. NITRIC ACID - STAINLESS STEEL 2. CAUSTIC - NICKEL & ICKEL ALLOYS 3. HYDROFLUORIC ACID - MONEL 4. HOT HYDROCHLORIC ACID - HASTELLOYS ( CHORIMETS) 5. DILUTE SULFURIC ACID - LEAD 6. NONSTAINING ATOMSPHERIC EXPOSURE - ALUMINUM 7. DISTILLED WATER - TIN 8. HOT STRONG OXIDIZING SOLUTIONS - TITANIUM. 9. CONCENTRATED SULFURIC ACID MILD STEEL

GUIDELINE FOR DESIGN & FABRICATION PROCESS: Weld

rather containers.

than

rivet

tanks

&

other

Bottom of tank & containers should be sloped towards drain holes for easy cleaning. Easy replacement systems of corrosion prone components. Avoid excessive mechanical stresses in components exposed to corrosive medium. Avoid electrical contact between dissimilar materials to prevent galvanic corrosion.

Avoid sharp bend in piping system.

Avoid hot spot during heat transfer system.

Design to exclude air.

Avoid heterogeneity, dissimilar metals, vapour spaces, uneven heat, & stress distribution.

CATHODIC PROTECTION OF AN UNDERGROUND TANK USING IMPRESED CURRENT.

PROTECTION OF AN UNDERGROUND PIPELINE WITH A MAGNESIUM ANODE.

CATHODIC PROTECTION OF A DOMESTIC HOT-WATER TANK USING A SACRIFICIAL ANODE.

THANK U