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CORROSION 1.Introduction:- Millions of rupees are spent on losses incurred due to corrosion or for prevention of corrosion. Proper selection of material and good design reduces costs of corrosion. In addition good maintenance programme reduces costs of corrosion. 2. Definition. Corrosion is the deterioration of a material due interaction with its environment. OR Loss of useful properties of a material as a result of chemical or electrochemical reaction with its environment. OR Corrosion is a extraction metallurgy in reverse.

EXTRACTION METALLURGY

ORE

METAL

CORROSION

3. The term 'material' used in a definition of corrosion includes both metals and non metals. Non-metals like plastics, ceramics, rubber also corrodes. A few examples of non metallic corrosion are -deterioration of paint and rubber by sunlight or chemicals, fluxing of the lining of a steel making and attack of a solid metal by another molten metal (liquid metal corrosion). Rusting is a form reserved for steel and iron corrosion. 4. Corrosion Principle. Most of the engineering metals exist in nature as ores in form of metallic oxides, sulfides, chloride etc. These forms of metals have low free energy content and therefore they are more stable. When metals are extracted from the ores, they have more free energy, become unstable and tend to regain stability by reverting back to their original state. Engineering metals, therefore, react with the aggressive surrounding environment forming

compounds like metallic oxides, sulphides etc. The process is known as oxidation. 5. Corrosive Environment. Air, moisture, FW, distilled, salt and mine waters. Rural, urban & industrial atmospheres. Steam, Gases such as chlorine, ammonia, hydrogen sulphide, sulpher-di-oxide and fuel gases. Mineral acids such as HCl, H2SO4 and nitric. Organic acids such as nephthenic, acetic and formic are some of the corrosive environments. In general inorganic materials are more corrosive than the organic and marine environments are more aggressive than most inland environment. Marine environments can be described as follows:(a) (b) (c) (d) (e) (f) (g) 6. Marine atmosphere Splash zone Areas immersed during high tide Areas between high tide and low tide. Sea water Mud Coastal Areas

Harmful Effects. The harmful effects of corrosion are:(a) (b) (c) (d) (e) (f) Bad appearance Maintenance and operating costs Plant shutdowns Contamination of product Loss of valuable product Effects on safety and reliability

7.

Corrosion Resistance. Factors affecting corrosion resistance of a metal are:Electrochemical

Physical/chemical

Corrosion Resistance

Metallurgical

Thermodynamic

8.

Corrosion Rate Expression (Mills per Year). Mpy = 534W DAT

W D A T 9.

= Weight loss mg = Density of specimen g/cm3 = Area of specimen = Exposure time in hrs

Electrochemical Reactions. (a) Ion An electrically charged atom that has lost or gained an electron. When zinc is placed in dilute HCl a vigorous reaction occurs. H2 gas is evolved and the zinc dissolves forming a solution of zinc chloride. Zn + HCl = ZnCl2 +H2

Noting that the chlorine ion is not involved in the reaction, this equation can be written as Zn + 2H+ = Zn2 + H2 In the above reaction Zn is oxidised to zinc ions and hydrogen ions are reduced to hydrogen. (b) Oxidation - Anodic reaction- increase in valence or production of electrons. i.e. Zn = Zn2++2e (c) Reduction Cathodic reaction Decrease in valence or consumption of electrons) i.e. 2H+ + 2e=H2 During Metallic corrosion the rate of oxidation equals the rate of reduction. Fe + 2HCl = Fecl2 + H2 2Al + 6HCl = 2AlCl2 + 3H2

(d) Anodic Reactions. Zn = Zn2+ + 2e Fe = Fe2+ + 2e Al = Al 3+ + 3e No. of electrons produced equals the valence of the ion. (e) Cathodic Reactions. (i) Hydrogen Evolution. 2H+ +2e = H2 (ii) Oxygen Reduction (acid solutions) 02 + 4H+ + 4e = 2H2O (iii) Oxygen Reduction (Neutral or basic solutions) O2 + 2H2O + 4e = 4OH (f) Ferrous in Sea water. Fe = Fe2+ + 2e (anodic reactions) 02 + 2H2O + 4e = 4OH- (Cathodic Reaction) 2Fe + 2H2O + O2 = 2Fe2+ + 4OH- = 2Fe(OH)2 (Ferrous Hydroxide) Ferrous hydroxide is unstable in oxygenated solution and is oxidised to the ferric salt. 2Fe(OH)2 + H2O + O2 = 2Fe(OH)3 (Rust) Note: Anodic and cathodic reactions occurring during corrosion are mutually dependent. It is possible to reduce corrosion by reducing the rates of either reaction i.e. coating the surface of metal with paint or other non-conducting film. Pure water is much less corrosive than impure or natural water because of its high electrical resistance. 10. Polarisation. Retardation of Electro-chemical reaction. It depends on various physical & chemical factors. Passivity refers to the loss of chemical reactivity experienced by certain metals and alloys under particular environmental conditions. 11. Forms of Corrosion. The various forms of corrosion are:(a) Uniform or general corrosion

(b) (c) (d) (e) (f) (g) (h)

Galvanic or two metal corrosion Crevice Corrosion Pitting Inter granular corrosion Selective leaching or parting Erosion Corrosion and Stress corrosion.

12. Uniform Surface Corrosion or General Attach. This form of corrosion is the most common and is typified by steel rusting in air. It is something called uniform attack. It is uniform in the sense that all exposed areas are attacked at more or less the same rate. Normally characterised by chemical or Electrochemical reaction that proceeds uniformly over entire exposed surface. Metal become thinner and eventually fails. i.e. Piece of zinc or steel immersed in dilute H2SO4. It causes greatest distruction of metal on tonnage basis. Life of equipment can be accurately estimated with simple tests. It can be controlled/prevented by:(a) (b) (c) Selection of proper materials Inhibitors Cathodic protection.

13. Galvanic or two-metal Corrosion. A potential difference usually exists between two dis-similar metals when they are immersed in a corrosive or conducting solution (electrolyte). If these dis-similar metals are placed in contact (electrically connected), this potential difference produces electron flow between them. The less resistant metal becomes anode & more resistant becomes cathode. i.e. Dry cell battery. The driving force for current & corrosion is the potential developed between the two metals. Potentials between metals are determined by taking the absolute differences between their standard emf potentials. 14. The basic requirements necessary for bimetallic corrosion to take place are:(a) Presence of an electrolyte. (b) Electrical connections between the metals. (c) Difference in potential between the two metals. (a) Presence of Electrolyte. Electrolyte does not necessarily mean a bulk solution. Atmosphere where condensed film arising from rainwater, dew etc., is present is also conducive to bimetallic corrosion. Salt deposit on the surface in marine environment act as an effective electrolyte. In fact any damp material in contact with metallic components can provide suitable conditions for bimetallic corrosion e.g., damp cloth, lagging etc. Electrical conductivity of an electrolyte plays an important role

in bimetallic corrosion. Conductivity of seawater is 50 times that of fresh water. Hence bimetallic corrosion is far more severe in marine environment. It is therefore necessary that bimetallic joints must be kept clean, dry and free from salt deposition. (b) Electrical Connection between the Metals/ Alloys. For bimetallic corrosion to take place, the two alloys concerned in bimetallic corrosion must be electrically connected. If two different alloys are immersed in a solution and joined together or are in electrical contact, bimetallic corrosion can occur. (c) Difference in Potential between two Metals/ Alloys. For any corrosion cell to operate there must be potential difference between the electrodes. The intensity of corrosion is directly proportional to their distance between the alloys in the galvanic series. For example, the intensity of corrosion will be very high if Titanium is connected with Magnesium, whereas it will be much lesser if Titanium is connected with Austenitic stainless steel. Temperature can influence the relative position of alloys in the galvanic series. Velocity and aeration can also affect the potential difference between two alloys which are generally known as a couple. 15. It should, therefore, be the endeavour of the designer and the maintainer to obviate occurrence of above-mentioned conditions in order to prevent onset of bimetallic corrosion. 16. Galvanic Series. Galvanic series of alloys and metals commonly used in sea water is as follows:CATHODIC Titanium Austenitic Stainless Steels (passive) Chromium Steels High Nickel Alloys (passive) Silver Solders Bronze, Gunmetal, Cupro Nickels Copper, Admiralty Brass Nickel (active) Naval Brass Lead, Tin Austenitic Stainless Steel (active) High Nickel Cast Iron . Chromium Stainless Steel (active) Carbon Steel, Cast Iron Aluminum Alloys Cadmium Aluminum Zinc Magnesium

ANODIC

17. Distance effect. Accelerated corrosion due to galvanic effect is usually greater near the junction and decreases with increasing distance from that point. 18. Area Effect. Ratio of cathodic to anodic area has an important effect on galvanic corrosion. Large cathode and small anode accelerates the rate of corrosion and large anode and small cathode decreases the corrosion rate. This leads to axiom If one of two dis-similar metals in contact is to be coated the more noble or more corrosion resistant should be coated. 19. Design engineers should be particularly aware of the possibilities of galvanic corrosion. Exa. Domestic hot water tanks made of steel fail where copper tubing is connected to the tank. Pump shafts and valve stems made of steel or more corrosion resistant materials fail because of contact with graphite packing. 20. The potential generated by galvanic cell consisting of dissimilar metals can change with time. As corrosion progresses, reaction products or corrosion products may accumulate at either the anode or cathode or both. This reduces the speed at which corrosion proceeds. 21. Minimising Bimetallic Corrosion. There are a number of ways in which bimetallic corrosion can be minimised or even prevented. Wherever the following practicable guidelines should be followed:(a) Construct equipment and structures for marine service from one material. (b) Where above is not possible, select combination of alloys which are closely placed together in the galvanic series. (c) Avoid small anode area and large cathode area situations and ensure that critical components are nobler. (d) If necessary add extra thickness to the less noble component and increase the anodic area. (e) Insulate dissimilar alloys when insulating bolted joints ensure that a non-conductive sleeve insulates the shank of the bolt. Check that the components are effectively insulated. (f) Protect the bimetallic couple with suitable resistant coatings. (g) Design should be such that anodic components could be replaced easily. (h) Monitor structure during their service life to ensure that preventive measures to combat bimetallic corrosion remains effective. Any modifications during service life should be checked for possible bimetallic effects. (j) Where appropriate cathodic protection can be used.

(k) Ensure that absorbent materials like lagging are prevented from coming in contact with the alloys in the structure. 22. Beneficial Applications of Galvanic Corrosion. (a) Dry cells (b) Cathodic Protection : Galvanised (zinc-coated) steel is the classical example of cathodic protection of steel. The zinc coating is put on the steel not because it is corrosion resistant but because it is not. The zinc corrodes preferentially and protects the steel. Magnesium is often connected to under ground steel pipes to suppress their corrosion. Cathodic protection is also obtained by suppressing current. (c) Cleaning Silver :- Most house hold silver/silver sulphide is cleaned by rubbing with an abrasive. This removes silver and is particularly bad for silver plate because costly material is being removed. Simple method is placing the silver in an aluminium pan containing water and baking soda (do not use sodium chloride). Current generated by the contact between silver and aluminium causes the silver sulphide to be reduced back to silver. No silver is actually removed. The silver is then rinsed with warm soapy water. 23. Localised Corrosion. Metals corrode because of their thermodynamic instability in a particular environment and the mechanisms involve the existence of anodic and cathodic sites on the metal surface. In general corrosion, sites change from being predominantly anodic to cathodic and vice versa. In some situations, however, this happens to a much smaller extent, or not at all, so the corrosion becomes localised at a number of anodic areas, the general surface being predominantly cathodic. This type of corrosion is usually complex and unpredictable in the sense that it is not usually possible to predict/ predetermine exactly where the attack will occur or even its extent. The factors that are likely to cause localised attack and must be taken into account in the design of the structure or component are as follows:(a) Heterogeneity of Metal & Metal Surface. Difference in Metallurgical structures, difference metallurgical conditions due to thermal or mechanical treatment, discontinuity in protective coating. Crevices and dissimilar metals in contact fall in this category. (b) Heterogeneity of Environment. Difference in aeration, difference in temperature, velocity, salinity etc. 24. Crevice Corrosion. This type of attack is usually associated with small volumes of stagnant solution caused by holes, gasket surfaces, lap joints, surface deposits and crevices under bolt and rivet heads. As a result this form of corrosion is called crevice corrosion or sometimes deposit or gasket corrosion. Corrosion takes place when crevice is formed between two surfaces with the inside of the crevice being anodic to the external surface. The large cathodic

current acting on the small anodic area is the crevice results in an intensive local attack, which leads to excessive corrosion inside the crevice. Stainless steel and other corrosion resistant alloys are particularly susceptible to crevice attack under certain conditions. The width of the crevices can be from very small upto 3mm to allow crevice corrosion. Deposits that may produce crevice corrosion are sand, dirt, corrosion products and other solids. Contact between metal and nonmetallic surfaces can cause crevice corrosion as in the case of a gasket, wood, plastics, rubber, glass, concrete, asbestos, wax and fabrics are examples of materials that can cause this type of corrosion. The rust itself may lead to a situation where crevice can form. This type of corrosion can lead to shearing of bolt as the corrosion product formed in the crevice can exert pressure on the joint. 25. Corrosion reaction involves dissolution of metal M (iron or steel) and reduction of oxygen to hydroxide ions. Oxidation Reduction M = M+ + e O2 + 2H2O + 4e = 4OH-

Initially these reactions occur uniformly over the entire surface, including the interior of the crevice. Charge conservation is maintained in both the metal and solution. Every electron produced during the formation of a metal ion is immediately consumed by the oxygen reduction reaction. Also, one hydroxyl ion is produced for every metal ion in the solution. After a short interval the oxygen within the crevice is depleted because of the restricted convection, so oxygen reduction ceases in this area. Oxygen depletion has an important indirect influence, which becomes more pronounced with increasing exposure. After oxygen is depleted, no further oxygen reduction occurs, although the dissolution of metal M continues. This tends to produce an excess of positive charge in the solution (M+), which is necessarily balanced by the migration of chloride ions into the crevice. This results in an increased concentration of metal chloride within the crevice. Except for the alkali metals (e.g. sodium and potassium), metal salts, including chlorides and sulphates, hydrolyse in water. M+ Cl- + H2O = MOH + H+ ClAs the corrosion within the crevice increases the rate of oxygen reduction on adjacent surfaces, this cathodically protects the external surfaces. Thus during crevice corrosion the attach is localised within shielded areas, while the remaining surfaces little or no damage takes place. All materials are susceptible to crevice corrosion provided the crevice width is sufficiently narrow.

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26.

Combating Crevice Corrosion. (a) Use welded butt joints instead of reveted or bolted joints in new equipment. Sound welds and complete penetration is necessary to avoid porosity and crevices on the inside (if welded only from one side). (b) Close crevices in existing lap joints by continuos welding, caulking or soldering. (c) Design vessels for complete drainage, avoid sharp corners and stagnant areas. Complete draining facilities, washing and cleaning tends to prevent solids from settling on the bottom of the vessel. Inspect equipment and remove deposits frequently. Remove wet packing materials during long shutdowns. Use solid, non-absorbent gaskets such as Teflon, wherever possible. Weld instead of rolling in tubes in tube sheets.

27. Pitting. Pitting is a form of extremely localised attack that results in holes in the metal. Generally a pit may be described as a cavity or hole with the surface diameter about the same or less than the depth. Pitting is one of the most destructive and insidious form of corrosion, leading to perforation and equipment failure. Usually the depth of penetration in the pitted areas is greater than that of surface corrosion in the surrounding area. Depending upon the extent of pitting, the loss of metal may be slight or may also lead to penetration of the metal resulting in leak in ships hull, tanks containing fluids and system pipes. In most cases presence of chloride is necessary for pitting. It is found to be greater in static conditions. 28. Rapid dissolution occurs within the pit, while oxygen reduction takes place on adjacent surfaces. This process is self-stimulating and self-propagating. The rapid dissolution of metal within the pit tends to produce an excess positive charge in this area, resulting in the migration of chloride ions to maintain electroneutrality, thus, in the pit there is a high concentration of MCl and as a result of hydrolysis, a high concentration of hydrogen ions. Both hydrogen and chloride ions stimulate the dissolution of most metals and alloys, and the entire process accelerates with time. Since the solubility of oxygen is virtually zero in concentrated solutions, no oxygen reduction occurs within the pit. The cathodic oxygen reduction on the surfaces adjacent to the pits tends to suppress corrosion. In a sense, pits cathodically protect the rest of the metal surface. It appears that pitting, though quite similar to crevice corrosion, desires special consideration since it is a self-initiating form of crevice corrosion. Simply, it does not require a crevice, it creates its own. Pitting is usually associated with stagnant conditions such as a liquid in a tank or liquid trapped in a low part of an inactive pipe system. Velocity or increasing velocity often decrease pitting attack. 29. Prevention of Pitting. In general methods suggested for combating crevice corrosion apply also for pitting.

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30. Inter- granular Corrosion. Inter-granular corrosion can be caused by impurities at the grain boundaries, enrichment of one of the alloying elements or depletion of one of these elements in the grain boundary areas. Small amount of iron in aluminium, wherein the solubility of iron is low, have been shown to Seagate in the grain boundaries and cause inter-granular corrosion. It has been shown based on surface tension considerations, the zinc content of a brass is higher at the grain boundaries. Depletion of chromium in the grain boundary region results in inter-granular corrosion. In some alloys under certain environmental conditions grain boundaries are much more active than the rest of the areas. In such cases corrosion may occur at the grain boundaries. When these alloys are heated within a certain range of temperature they become susceptible to inter granular corrosion. Failures associated with welded structure and the material attacked inter-granularly is called weld decay. A particular type of this attack occurs near welds and is called weld decay. A zone in the heat affects area of the weld reaches the sensitising temperature or the temperature when the alloy becomes susceptible to inter granular corrosion under some service conditions. 31.Control for Austenitic Stainless Steels. Commonly used methods for control or minimising inter-granular corrosion are:(a) (b) (c) High temp solution heat treatment commonly termed quench annealing or solution quenching. Adding elements that are strong carbide formers (called stabilisers) and Lowering the carbon content to below 0.03%.

32. Selective Leaching. This form of attack is sometimes called dealloying which explains its nature. Removal of one element from a solid alloy by corrosion process e.g. removal of zinc from brass alloy (de-zincification). Selective leaching may occur uniformly or locally (plug type). Alloys are composed of different metals and under certain conditions selective leaching of one metal can occur. Most common example of this type of corrosion are selective removal of zinc from brasses and the de-alloying of aluminium bronze in sea water/ Condenser tubes are prone to this type of attack leading to perforation. Commonly accepted mechanism of selective leaching is (a) The brass dissolves (b) The zinc ions stay in solution and (c) The copper plates back on. Zinc is quite reactive while copper is more noble. Zinc can corrode slowly in pure water by cathodic ion reduction of H2O into H2 gas and OH ions. Dezincification can proceed in absence of O2. Presence of O2 increases rate of dezincification. 33. Prevention of Selective Leaching. (a) Reducing the aggressiveness of the environment (i.e. O2 removal) (b) Cathodic Protection (c) Alloying with inhibitors.

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34. Graphitization. Gray cast iron sometimes shows the effects of selective leaching. The C.I. appears to become graphitised in that the surface layer has the appearance of graphite and can be easily cut with a pen knife. 35. Velocity Effect on Corrosion. The rate of corrosion generally increases with velocity. At higher velocities a number of specific forms of corrosion can be manifested which are as follows:(a) Erosion Corrosion. Acceleration or increase in rate of deterioration or attack on a metal because of relative movement between corrosive fluid and the metal surface. Generally this movement is quite rapid and mechanical wear effects or abrasion are involved. Metal is removed from the surface is dissolved ions or it forms solid corrosion products that are mechanically swept from the metal surface. Erosion corrosion is characterised in appearance by grooves, gullies, waves, rounded holes and valleys and usually exhibits directional pattern. Exa. SS alloy pump impeller, condenser tubes, piping bends, elbows and tees, valves pumps, blowers, centrifugal, propellers, impellers, agitators, agitated vessel, heat exchanger tubing such as heaters & condensers, measuring devices such as an orifice, turbine blades, nozzles, ducts & vapour lines, scuppers, cutters, grinders, mills, baffles and equipment subjected to spray. SS corrosion depends on passivity. Subsequently SS is vulnerable to erosion corrosion. Galvanic effect accelerates erosion corrosion. Heat treatment/hardening helps in reducing erosion corrosion attack. Combating Erosion Corrosion. (i) Materials with better resistance to erosion corrosion. (ii) Design- shape/geometry- Increasing diameter, streamlining bends, increasing thickness of materials, ferules, easily replaceable parts. (iii) Alteration of the environment- De-aeration, addition of inhibitors. Reducing temp. (iv) Coatings:- Hard facing, welded overlays. (v) Cathodic protection. (b) Impingement Attack. This form of attack occurs when fluids impinge at a fairly high velocity on the metal surfaces. This typically happens in pipe systems where an abrupt change in the direction of flow at a bend can lead to localised failure. (c) Cavitation Damage. This is the form of attack caused by the formation and collapse of bubbles in sea water at the metal surface. Conditions of high velocity flow and pressure changes lead to Cavitation attack. This type of attack is usually localised and severe. 36. Stress Corrosion Cracking. The general corrosion of the structural metals leads to the loss of cross section so eventually they may fail under a load that they could originally sustain. Protective coatings are applied to steel to control the loss of metal and hence prevent mechanical failures. There are

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however situations where the simultaneous effects of tensile stress and corrosion cracking and can lead to rapid failure of an alloy, unlike a structural failure arising from ordinary corrosion over a long period. Following are the silent features of stress corrosion cracking:(a) Stress corrosion cracking may occur at a stress well below the yield point of an alloy. (b) All structural alloys are susceptible in specific environments and conditions. (c) This form of attack occurs only under tensile stress. (d) The stress may be externally applied or induced in the alloy i.e. by cold working. (e) Generally stress corrosion tends not to occur under conditions of general corrosion but is situations of local attack e.g. pitting. 37. Corrosion Fatigue. Fatigue is the tendency for a metal or alloy to fracture under conditions of repeated cyclic stresses at loads below the ultimate tensile strength of the material. Corrosion fatigue is the term used to describe the failures of alloys by cracking under the influence of both fatigue and corrosion acting together. The effect of conjoint action of corrosion and fatigue is much more severe than the sum total of their individual actions. Thus metal/ alloy subjected to fatigue must be prevented from corrosion to avoid pre-mature failure. PREVENTION OF CORROSION 38. The commonly used methods for prevention of corrosion are as follows:(a) (b) (c) (d) (e) (f) Protection by design and fabrication methods. Modifying corrosive environment Application of protective coatings Use of alloying elements Application of inhibitors Cathodic protection

39. Protection by Design and Fabrication Methods. The design of any plant/ equipment or structure is done so as to achieve optimum performance. Generally performance, economy and life cycle costs are predominant factors in any design. Due care is taken to avoid features that may lead to corrosion in order to achieve optimum life cycle cost of the plant/ equipment or structure. However due to various conflicting requirements and limitations it may not always be possible to use the best available corrosion resistant materials and to eliminate all the features that may lead to corrosion. For example steel is well known to get corroded in sea water, yet it is used for ship construction due to numerous other advantageous features.

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40. Design/ Maintenance Considerations. Inability to use the best available material for corrosion resistance and elimination of all features conducive to corrosion does not mean total surrender of protective measures and effective maintenance. The basic requirements of a good design in this context can be considered under the following headings: (a) Features that promote corrosion. (b) Access for Maintenance. (c) Bimetallic Connections. (d) Selection of Materials. (e) Special situations. (a) Features that Promotes Corrosion. A number of design features, which may be necessary for other requirements, can promote corrosion. It is, therefore, necessary to look for these and similar features closely and take extra care for their maintenance. While carrying out modifications, additions and alterations avoidance of these must be borne in mind. Some typical features which can be seen in structures and tanks are as follows: (i) Entrapment of Moisture and Salt. Moisture, salts and dirt can collect in many parts of a structure. Open channels and angles can collect water, which as it evaporates, may leave concentrated salt solutions in contract with the protective coating on the structure. This can lead to premature failure of the protective coating. This situation can be avoided at design stage by inverting the sections. Another solution could be by welding plates over the sections. However due to some constraints if none of the above mentioned solutions is possible, maintenance of such areas must be done effectively to ensure quick removal of the accumulated water. Moisture can be a problem where absorbent materials such as wood or lagging material is in contact with metals, particularly steel or aluminium alloys. This can lead to serious localised corrosion in marine situations unless suitable attention is paid. (ii) Deck Level Connection. Problems frequently occur at deck level where steel columns/ structural members rest or pass through the deck. Around these members some dirt/ dust/ derbies gets collected at the deck level. This dust absorbs moisture and leads to corrosion of the deck as well as the structural member passing through the deck. Similar situations occur where service pipes/ cable glands pass through the deck. This is the reason why corrosion takes place in these areas more than the surrounding plain surfaces. Bulkheads are often found corroded in locations where they meet the decks. Specific care is needed to maintain these areas clean and coated with approved painted to avoid corrosion.

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(iii) Crevices. These are formed at joints where small gap remain between the components of the joints. Due to this reason properly designed welded joints are preferred to bolted joints. Correct design of joints can avoid occurrence of crevices. Area where crevices do exist due to design constraints should be kept clean and protected with approved paint. (iv) Shapes. The shape of structural members has a bearing on performance of protective paints. Rounded shapes are easier to coat and are less prone to damage than edges on rectangular sections. As far as possible, rounded sections should be used for structures. However, this may not always be practical therefore extra attention should be paid to maintenance of edges where paints wear off faster. (b) Access for Maintenance. One of the important factors to be considered while designing a structure or system is provision of access for maintenance. However, in a warship both weight and space are at a premium. Any additional weight or extra space to be provided can have a telling effect on performance of the ship. Therefore some areas are inevitably difficult to reach and maintain, fortunately effective tools are now available to assist the maintainer in looking after such areas. However, by virtue of their inaccessibility such areas tend to get neglected and the defects arising due to corrosion also remain hidden until a breakdown occurs. This can be avoided through vigilant and innovative maintenance. (c) Special Situations. During the design/ maintenance of certain specific structures/ systems care should be exercised to obviate the features that may lead to corrosion. Some of the commonly used structures/ systems are enumerated below:(i) Tanks. Design of tanks plays an important role in ensuring that they provide long-term service. The main points to be considered while constructing these tanks a new or as a retrofit during As and As are as follows:(aa) The drainage should be at lowest point. (ab) Stagnant areas at outlets should be avoided. (ac) There should be adequate access for protecting the exterior of the tanks and there should be free flow of air around them. (ad) Top should be designed to ensure that no water stagnates there, but runs off material. (ae) Pipes and outlet materials should be compatible with those of the tanks material. (af) On steel tanks the interior coatings must be capable of with standing the liquids stored in the tanks and must be

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pore free. In sizable tanks sufficient access must be provided for maintenance of internal coatings. (ag) Internal struts or other components such as heaters, inside the tanks should be insulated from non compatible material and preferably should not be nobler material than tanks. (ii) Welds and Fasteners. Welds by their nature tends to produce discontinuities in the surface of the alloys and these can lead to metallurgical variation and potential sites for coating break down. Use of correct electrode and correct welding technique can by and large solve the metallurgical problems. However the maintenance needs to take care of the coating applied. Bolted components can also lead to many problems due to the difficulty in coating them effectively, bimetallic corrosion and presence of crevices. Therefore, a careful design, judicious selections of material and effective maintenance are necessary to ensure longevity of bolted joints. (iii) Flowing Water System. In structural components, only external surfaces are required to be protected from corrosion however in flowing water systems internal surfaces for the pipes can be attacked by corrosion if adequate care is not taken at design stage. Some of the important considerations are as follows:(aa) Alloys chosen for the pipes should be such that they resist impingement. (ab) Features that affect smooth flow should be avoided. 41. Modifying Corrosive Environment. Environments can be made less corrosive either of removal of harmful constituents or by addition of constituents that will reduce the corrosion effect. 42. Application of Protective Coatings. Various types of protective coatings (organic or inorganic) could be used to chemically seal the material substrate from aggressive corrosion environment. Coatings may be metallic or non-metallic coatings. They are applied by electroplating, hot dipping, spraying, vaporising or any other suitable methods. 43. Use of Alloying Elements. The addition of small or large amount of alloying element may prevent or reduce corrosion i.e. aluminium bronze, copper or chromium (less than 1%) increase the corrosion resistance of steel. 44. Application of Inhibitors. An inhibitor may be defined as a chemical substance, which added in small quantities to the environment, may decrease

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the rate of corrosion. Various types of inhibitors such as acid, anodic and cathodic are available for protection. CATHODIC PROTECTION 45. Principle. During corrosion process the direction of corrosion current within the electrolyte is form local cell anode to the local cell cathode. If an adequate opposing current is supplied to the corroding metal, via different anodes, more and more electrons would be received by the corroding metal. The local cathodic reaction rate under these situations would be suppressed. Corrosion current therefore gets suppressed and corrosion also gets suppressed, The externally applied current thus makes the entire hull as cathode. This technique of corrosion prevention is known as cathodic protection. 46. Method. The commonly used methods of cathodic protection are:(a) Sacrificial Anodes (b) Impressed Current Cathodic Protection (ICCP) 47. Sacrificial Anodes. In this method a more anodic material is electrically connected to the metal to be protected. The electrical shorting of the dissimilar metal in a conducting electrolytic solution produces galvanic current. The metal which is low in hierarchy of galvanic series of metals (anode) gets consumed and the one which is nobler gets protected. The disposition, number and type of sacrificial anodes to be used depend on the protective potential required, underwater areas of the hull, period of protection and properties of anode material. Sacrificial anodes are generally made of Aluminium alloy, magnesium alloy or zinc. 48. Impressed Current Cathodic Protection (ICCP). It involves the supply of electrons from an external source to the metal to be protected. In this system inert anode (Non-Consumable) are used which are capable of carrying large current for impressing direct current (DC) from a rectifier unit on board on ships under water hull. The direct current source reverses the natural polarity and allows the materials to act like anodes. This system consists of following components:(a) Inert Anode. These are fabricated out of lead alloys or titanium coated with platinum or niobium, Reference Electrode. Reference electrodes measure and (b) monitor the hull potential i.e. the amount of current flowing on ship surface. It is mounted in the structure to measure the potential value in auto control unit to permit proper regulation of anode current.

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(c) Auto Control Unit:- It continuously regulates the anode current to keep the structural potential at present constant value. (d) Dielectric Shield. To avoid the risk of over protection the area around the anodes about 150 cm2 should have a dielectric shield, comprising of GRP mat and epoxy for spreading current evenly on the surface. 49. Ship staff is to measure the hull potential regularly and record the same as follows:(a) Once in fortnight using an external Zn or Ag/ AgCl reference electrode in case of sacrificial anode. (b) Daily hull potential readings are to be noted. A log book is to be maintained to record the hull potential as per the format given in Navy Order 16/2000. 50. Comparison of ICCP and Sacrificial Anode method. Both these methods have its own advantages and dis-advantages. Many ships use both these methods simultaneously to get maximum benefits of both the methods. Advantages of Sacrificial Anodes (a) Low maintenance Disadvantages of Sacrificial Anodes

(a) More replacement schedule and high requiring cost (b) Protects as soon as underwater (b) Structure Loading (c) Uniform current distribution (c) Higher friction drag (d) High reliability under uniform (d) Low performance at lower temperature consumption and in polluted sea water. (e) No requirement of power (e) More number of anodes required (f) Less supervision required (g) Less installation cost Advantages of ICCP (a) No anode replacement schedule (b) Auto current regulation (c) Less No. of anodes or flush fitted anodes reduces friction drag Disadvantages of ICCP (a) High initial cost (b) Trained people required (c) Continuous current feeding is must (d) Over protection may result.

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51. Interpretation of Hull Potential Readings. HULL POTENTIAL IN mv With Respect To Zn With Respect To Ag/ Ref Electrode Agcl Ref Electrode Less than 170 Less than 880 Between 170 - 270 Between 880 to -780 More than 270 More than 780 STATE OF HULL

Over protected Fully protected Nearly protected

SELECTION OF MATERIAL FOR MARINE ENVIRONMENTS 52. The basic aim when selecting material is to achieve an economic solution for the particular situation, but this is not an easy task. Although comparative costs of various materials can be obtained, it is far more difficult to predict their performance in intended field conditions. Therefore selection of material for any application has to be done after careful consideration of a number of factors. 53. General Considerations. The factors which should be considered in general before a material is selected are:(a) (b) (c) (d) (e) (f) (g) (h) (j) (k) (l) (m) Cost in relation to life and maintenance of replacement. Mechanical and physical properties. Availability in the required form. Ease of forming and fabrication. Weld ability/ or ease of soldering or brazing. Ease of installation, repair and replacement. Heat transfer characteristics. Vibration effects. Thermal Expansion. Bio- fouling characteristics. Strength/ weight ratio. Corrosion Resistance

53. Service Environment. It is important to consider the environment in which a material is required to perform the intended function. Some of the aspects to be considered are as follows:(a) (b) (c) (d) (e) (f) Velocity of the fluids coming in contact with the material. Will the material be used immersed, or in splash zone. Environmental temperature. Whether high pressures are involved. Fouling, general contamination or pollution. Vibration Problems.

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54. Design and Operating Considerations. The following aspects are to be considered: (a) Is the design such that a range of alloys will be used in contact with each other. In such cases, bimetallic corrosion problems are to be taken into consideration? Will the plant or equipment be operating continuously? Will welding be required? Are suitable fasteners available? Will the design or operating lead to specific types of corrosion e.g Impingement, Cavitation, pitting, crevices etc.?

(b) (c) (d) (e)