Preface FROSIO. The Norwegian Professional Council for Education and Certification of Inspectors for Surfice Treatment, sas founded in 1980 with the ain te educate and certify Surface Treatment Inspectors, For this purpose a Carriculuss: amd ain SO. hous ‘ourse Were established together with the Norwegian Standard NS 476, Paint and coatings Approval and certification af surtace treatment inspec tors, This handbook 3s an English translation of the Norwegian hautdbook SOverilatebehandtin years is att aid inthe trial mot Kortosjon”. which fers been used in Norway tor my ourse’ far candidates who avishes to become cert Tied by FROSIO as Inspector The handbook covers all tems given in the FROSTO Curriculum asd should therefore be good assistant te obtain the knowles and practical examination FROSIO therefore highly recommend this handbook for the training to obtain a PROSIO NS 476 certitiowe. needed t0 pass the theoretical FROSIO Bord KKK FROSIOContents 1 Corrosion Innvoduction ‘What ie corrasion? Corrosion theory Electrochemical series Corrosion environment and pH Corrosion types Uniform corrosion (general corrosion) Galvanic corrosion (bimetallic corrosion) Crevice corrosion on zs vi Pitting corrosion Erosion corrosion. Selective corrosion (deslicying corrosion). ‘Stress corrasion cracking Intergranuiar corrosion (intercrystaline corrosion) Conosion fatigue wv... it at Corrosion in different ervirionments Corrosion in air Corrosion in water Corrosion in soil Literature 2. Protection against corrosion Introduction Correct selection of materials Steel Weathering steels Stainless steels... Thanium anc nickel alloys Copper and copper allays Zine ‘Aluriniarn Constructional design to reduce corrosion C10VICES wesrneeen Geometrical effects Metallic joints Design to prevent unnecessary turbulence Using paints and coatings el Paints Pain: system selection and use of EN ISO 12944 [Linings (organic) Metal coatings Electroplating, Dipping in moiten metals. Thermal spraying (metalization} Cathodic protection... How does this type of cathodic protection work? Practical measurements Using sacrificial anodes Cathodic protection with Impressed current Combination of cathodic protection and paint coating systems Overprotection alia Corrosion inhibitors Corrosion monitoring... Literature ot3. Surface preparation and aplication equipment Introduction nnn Surface preparation equipment Wirebrushes SCIaPEFS wee Electric and pneumatic power tools... Mechanical grinding equipment . . ‘nding roundels, grinding wheels and grinding beds Chipping hammers and needle guns .. Flamecleaning equipment Equipment for dry opennozzie blasting Ejector equipment. oo Pressurized pot Application equipment Paint brushes Paint rollers Painting mits/gioves . Spray equipment Conventional spray equipment ‘Automatic gun Cleaning and maintenance HVLP spray equipment High pressure laivless) spray equipment ‘Compressed.air driven piston pumps Non-pneumatically drven piston pumps... Electromechanically driven piston pumps ... Electrohydrauiic driven piston pumps Diaphragm pumps Pulse chamber. Reduction valve Water separator Oikmist lubricator. Oil eup Coarse fiter Fine fiers... Paint hoses Swivel coupling Airless guns Paint supply in the spray head Paint inlet through the handle Extension pole guns... Nozzles Standard nozzles « Reversible tips. Adjustable nozzies Fine finish nozzles Selection and maintenance of nozzles. Airassisted airless. spraying «1. Cleaning and maintenance of spraying equipment Maintenance .. o Literature. 112 4. Pretreatment Introduction Cleaning and surface preparation 120 Degreasing, een £22 Degreasing in water soluble, alkaline chemicals, oe 323 Use of emulsifying solvents... 128Solvent based degreasing Dogreasing in trichloro ethylene vapours Mechanical and thermal surface preparation Abrasive blast cleaning .. Flame cleaning : Waterbased cleaning methods .- High pressure water cleaning and water jetting Pickling nese The pickling process Chemical conversion coatings. Phosphatizing .. Chromatizing . Chromatizing of zine Chromatizing of aluminium... fustromovrs or rust cleaning gens | based on Bhosphone ‘acid Wash priming. Literature Applicaton of coatings and nin. Introduction Rigging ... “ Containment of the area... Masking .. Ventilation Checklist for safety equipment. Preparation of the paint... Application. Application wih pant ler and paint gloves Conventional spraying .. The conventional spray gu. Pressure pot spray system Airless spraying... Safety precautions . Spraying technique Spray pattern defects Spray testing Faulty spray pattern in connection with conventional Spraying. Adjustments of faults . Other types of faults Defects in the paint or varnished surface . Defective spray patterns associated with high pressure spraying Corrective actions os Airassisted high pressure and HVLP high pressure Electrostatic spraying (Wet vamnsh/atr) Preheating .. Literature: int coating materials Introduction How does the paint coating system ‘wor Paint composition. Binder Pigments Extenders Solvents Additives Paint types Primers 424 126 127 128 431 132 133 135, 136, 138 138, 140 140 a4 441 142 144 145, 178, 179) 181, 181, 182Organic zincrieh paints. Inorganic zincrich paints, zine ati i silicate Zine alkali silicate Shopprimers Iron oxide shopprimer Zineich shopprimers Wash primers wa... Rust corwerters so nnn Physically drying paints. Chlorinated rubber pains Vinyl paints. Acrylic paints Waterborne paints. Bituminous paints Tar paints ‘Oxidatively curing paints Aliya paints Urethane alkyd paints Epoxy ester paints nce nnn Silicone paints, a Chemically curing paints .. Epoxy paints Goal tar epoxy paints Polyurethane paints. Solvent-ree epoxy / tar epoxy paints... Epoxy and polyurethane mastic paints Siloxane paints Polyester glassflake paints Cementitious paints.. Antifoulings.. Selection of paint coating system Literature Coating failures Introduction ... Loss of adhesion ... Peeling... ‘Saponification| Littings.. Defects in the surface vo -. Vacuoles/voids and biistering Craters oF poping Fisheyes Pinholes Cracking Checking Cracking Cosmetic defects Wenkling Bleeding Blushing... Water stains Chalking Application defects: Dry spray/overspray Orange peel... ‘Sags and curtains Coatings remaining soft 182 183, 184 185 485, 186 "186 187 187 188 189) 190 491, 193 194 "195 195, 196 197 “197, 198 198 200 201, 202 203 204 204 205 206 207 209 210 210 211 2a 242 213 214 215 217 219. 220 224, 1221 222 224 228 225 226 227 228 229 229 230 234, 232Rough sutace fens o° contamination inthe suf nnn 29 Degradation of coating 234 Idenitevion of coatings detects 235 Literature 235 8 Thermal spraying .. Introduction : Thermal spraying methods. Powder flame spraying Wire flame spraying. see Aro spraying Plasma spraying... . High velocity oxyfuel spraying Detonation spraying Restoration and enhancing Protective equipment for thermal spraying... 9. Passive fire protection Introduction oe co Demands to fire protection wnnnnne vo 246 ‘Main types of coatings . 2aT Organic coatings 2a7 Inorganic coatings... 248 Paint en . 249 Pretreatment and corrosion protection 249 Requirements to pretreatment. oe 249 Corrosion protection in case of epoxy coatings... 250 Gorrosion protection in case of inorganic coatings... " 250 Preparation of substrate, fiting of pins and wire mesh and application .....---. 250 Epoxy coatings 250 Inorganic coatings... . 252 Demands to passive fire protection... . 253 What are the types of fires? 25a What are the materials able to tolerate? 254 Fire classes sen . 255 Literature: fos "287 10 Concrete repair Introduction Concrete, composition and properties ‘Carbonation . Corrosion of the reinforcement steel Condition survey Carbonation depth Cover depth. Chioride contents Corrosion degree on reinforcement steel and stee! profiles Extent of cracks, crevices and corner damage Efflorescence : Strength and porosity of concrete Previous repairs . Surface preparation for concrete repairs Cleaning of concrete surfaces Removing deteriorated concrete Cleaning of the reinforcement steel... Aatiorosion reatment of te reinforcing ste. Bonding coat... Filing of repair areas275 276 217 279 Surface treatment Paint selection Electrochemical concrete rehabilitation Literature. 280 280 280 283 414 Other coatings and linings... Introduction Powder costings . Tar and asphalt costes Wax BBS. Tape ed Hotmeit coatings 284 Rubber linings 285 Metallic coatings... 286 Electrodeposited metal coatings nnnnnnnnnnn 286 Diosspin method CT 287 Hot dip galvanizing 288 Literature, 289 412 Quatty management systems, specifications, procedures and documentation ... 291, Introduction... sonnei oo 291, Quality management systems sn. O29 Quality management systems standard 292 180 9001:2000 . . 292 ‘Scope and application ... . 293 Quality management system son . 293 Management responsibility 293 Documentation requirements 234 Customer focus . 294 Management review .. 204 Internal audits cnn Sooccceee 295 Human resources, 295, Design and development... 295, Identification and traceability 295, Product realization aoe 295, onto of nonconterning Produc Sonn 295 Corrective actions ener concn nen sees 298 Quality control . 296 Specifications and procedures 297 What is @ specification and what does it consist of? 237 Extracts trom a specification concerning surface preparation of steel... 298 Procedures .. Svnnnnnn 299 Communication 299 Reports a. 300 Daily log . . 301 Progress reports IIE 203 Nonconformity reports 303 Techical reports 303 13 upacton mato and equtpment nnn sons 310 Iniraduction nn — 310 rspection routines. 310 Inspection of the substrate 341 Assessment of rust grades of steel ae 312 Assessment of visual cleanliness 313, Chemical cleanliness: conn 318 ‘Suisteate fOUBHMESS wns nes 324Comparators ... Determination of roughness . Determination of the climatic conditions... Sling psychrometer How to measure tho relative humidity of the ar andthe dew pont temperature? . . Control of the liquid paint Condition in the can Viscosity Density Volume Solids Control of the paint film ‘Measuring the wet paint flim .. Calculation of paint fim thickness Calculation of paint consumption. Measuring dry film thickness... Cutting instruments Adhesion Cross Cut test, 1S0 2409 Xeut Test . se Pulkoff test 150 4624 Pulloff testers... Pinholes, voids and other ccsting detects Curing .. Identification of unknown pai Coating concition survey prior t0 maintenance painting, Evaluation of degradation of painted sutaoes Testing at the paint manufacturer... Mechanieal properties. Elasticity an Gloss, Colour Opacity Accelerated testing Sutcoor exposure test Literature Appendix to Chapter 13... ‘Appendix 1 150 8501.1 Preparation af steel substrates before application of paints and related products ~ Visual assessment of surface cleaniiness ... Appendix 2 1S0 8504/ Suppl:1994 Visual assessment of surface cleanliness ~ Informative Supplement to part 1: Representative photographic examples. of the change of appearance imparted to steel when biast cleaned with different abrasives, Appendix 3 150 8501.2 Preparation grades of previously coated stes! surfaces ater localized removal of previous coatings Appenaix 4 130 8501-3 Preparation grades of welds, cut edges and other areas with surface imperfections... Appendix 5 ISO 8501-4 Preparation grades of coated and uncoated steel Substrates after removal of rust and previous coatings by high pressure waterfetting wn Appendix 6 180 TR 8602-1 Field test for solubie ion corrosion products. Appendix 7 ISO 85022 Laboratory determination of chloride on cleaned surfaces ..... Appendix 8 ISO 85023 Assessment of dust on stesl surfaces prepared Tor painting (pressure-sensitive tape method) Appendix 9 Determination of relative humidity and dew point on steel 324 325 330 3a 0 383 334, “336 336 337 340 342 347 348, 349 349, 350 351, 354 "357 358 359, 360 363 364 365 365, 366 366 366 367 368, 370 370 art 372 373 374 "375 376 377,surfaces prepared for painting 378 ‘Appendix 10 1S0 8502:6 Extraction of Soluble contaminants for naive «The Bresle method . 379 Appendix 14 1S0 85029 Field ni {or the conductomeiric determination of water-soluble salts . . 380 ‘Appendix 12 Use of [SO 8503-4 to determine the roughness on blast cleaned steel surfaces. 381 Appendix 13 Use of wet film gauges in accordance with ISO 2808 to determine the wet flim thickness of coatings... “ se 382 Appendix 14 Adjustment of dry fim thickness gauges based on magnetic pulloff principle «0. 383 Appendix 15 Adjustment of dy fim thickness gauges based on ‘magnetic induction principe . 384 Appendix 16 Measurement of, and acceptance criteria for, the dry fim ‘thickness on rough surfaces (ISO 19840 (in progress) 385 ‘Appendix 17 Measuring dry film thickness by destructive means (ASTM D 4138) 386 Appendix 48 Measuring adhesion using the Gross Gut Test (180 2409)... 387 Appendix 49 Measuring adhesion using the tape test (ASTM D 3359) 3E8, Appendix 20 Adhesion testing using pulLoff test equipment (1S0 4624) nuns. 389 Appendix 21 Holiday detection of coatings using the low voltage wet sponge method (ASTM D 5162) 390 Appendix 22 Holiday detection of coatings using the high voltage spark test method (ASTM D 5162)... 301, Appendix 23 Measuring MEK resistance of ethyl silicate (inorganic) Zinexich primers by solvent rub (ASTM D 4752) 392 14 Health, safety and environment. vn 394 Introduction... 394 Health and safety laws and regulations . 395, Gompary procedures for compliance wth ews end requatens 396 Safety from accidents and injuries 396 ‘Scatfold work.. 398, Working with biast cleaning and grinding equipment. 800 Working with airless equipment 404 Electric equipment Working in confined areas and tanks Physical working environment factors... Noise Lighten so Gimatic conditions swan nnnnnnnnnnn nnn, 408 Strain a 409 Chemical hazards in the working environment COUSIN aa Solvent on on matt How do solvents atfect the body? 412 Dust foe ALB Occupational exposure limits for substances in the wots air 414 Skincorrosive and sensitizing substances ee AIS, Labelling of chemical products .. 419 ecupational a requtements wo a2t Safety Data Sheets (SDS) . 422 Fire nazard .. 423 Flammable and explosive substances 423 Technical fre prevention measures .. 426 Fire extinguishing... 428 Measures for improving the working ‘environment... 429 Assessment 429 etion plans nner nn oo 484Changing working procedures... Substitution of nazardous products: Persanal protection equipment... Respiratory protection Environmental problems Environmentally hazardous waste ... Actions in case of spillage and leaks 45 Economy and cost calculations, Introduction .. Cost factors ‘Area calculations: Plates .. sn ‘Area of a tank surface Surface preparation costs, Paint costs .. Cost estimates . vo Comparison of various siternatives Literature. - Index aa “un fas, ans at a aa9 aai 4ai 4a 4431 Corrosion Introduction Annually corrosion costs society vast sums. In the Western World the costs have been estimated to constitute approximately 3-4% of the gross national product. ‘A major part of the damage is due to too little knowledge about corrosion and the conditions which cause corrosion. Ifthe selection of materials is not considered carefully enough, the result can be extensive corrosion damage. It has been esti- inated that improved knowledge about corrosion and corrosion protection can re- sluce costs by approximately 15%. In case of corrosion protection by means of paint coatings the applicator and the inspector are important. In order to ensure that the job is carried out correctly they inust have a good understanding of subjects like corrosion, surface preparation ul protection against corrosion. Later in the book these subjects will be discussed tn rater detail. What is corrosion? 11s common opinion that corrosion is the same as rust, which is not entirely true. Rust is the corrosion product formed when iron and steel corrode. But many other ‘materials are also attacked. The patina on copper and white rust on zinc are well- known examples. These are also corrosion products. Consequently, corrosion is the deterioration or breakdown of materials due to a reaction with the environ- ent esiles destroying metals, corrosion also contributes towards breaking down ‘cancrete and plastic materials. Why. hen, are a number of construction materials around us broken down, and how cloes this happen? If we look at the metals, most of them are produced by A.Cornosion 15,applying large amounts of energy to the raw material, the ore. The state in which, the metal is found in nature is generally said to be its most stable state or form. As ore, the metal is usually combined with oxygen, carbon, sulphur, and other ele. ‘ments sheets Pipes Energy Water Manufacture Oxygen aw materi ae igure 1.1 Production and deterioration by corrosion of iron/stee! In the manufacturing of metals energy is applied to the raw material, ore. During the process the ore melts and the metal is separated from the slag products. Milling takes place while the metal is in a red-hot state. During milling the red-hot steel gets into contact with air and a thin layer is formed on the surface. This layer is usually called mill scale. Mill scale is brittle and only protects the metal as long as itis intact. If the stee] is left outdoors, the mill scale will eventually crack and the steel begin to rust. By this breakdown, the corrosion, steel is transformed into rust. Chemically speaking, rust has almost the same composition as ore. The process has now come toa close. It started with ore and has now ended up with rust. The iron is again at a lower and more “natural and stable” state of energy. Metal production can be compared to a ball placed at the foot of a hill. By applying energy we move the ball uphill. When the ball is placed on the ground at the higher level, it wil start rolling until it reaches the lowest level and stops. Innature al ore O siavie condition Figure 1.2 ‘This is what happens: The ball, which was at a stable level, was transferred to a non-stable level. Due to physical reasons the ball rolls down the hill and finally comes to a halt at the foot of the hill. The ball will again be at its most stable level. 16 Conrosion ProtectionIn principle, this is also what happens during the production of metal. To extract the metal, found only in limited quantities inthe ore, energy is required. Due to the energy expended, the metal in the ore is transferred from its stable level to a non- stable level. The metal has now been extracted from the ore, but extemal conditions like moisture and oxygen cause the corrosion process to start. The corrosion proc- ess is a natural process which under the right circumstances (i.e. oxygen supply and high humidity) tries to convert the metal back to its most stable state, which is ‘ore. The chemical compositions of ore and the corrosion product are very much alike, If we want to preserve the metal, something must be done. In order to prevent the corrosion process from starting, we use paints, coatings and linings, or other barriers to stop any direct contact between the metal and the environment Onygen Water ae ities: Figure 1.3 Eventually mill scale will crack and the steel begin to corrode Corrosion theory In order for a metal to corrode the surface of the metal must be covered by an electrically conductive liquid or substance (electrolyte) and oxygen. Water, either fresh water or sea water, and soil are examples of electrolytes. Pollution in the ait may dissolve in water and make it conductive. Metals have a tendency to release electrically charged atoms (ions) when in contact with water, For some metals this tendency is weak, for example in the case of platinum and gold. Such metals are called noble metals. ‘Other metals release a large number of ions in contact with water, for example aluminium and zinc. Such metals are called ignoble ot base metals. If we immerse two different metals in a conductive liquid (an electrolyte) with- out any electrical connection between them, both metals corrode at a certain rate. Butif the metals are joined together electrically, the rate of corrosion increases on the less noble metal. How fast the corrosion takes place depends on a number of factors, including the metal types, for how long humidity is present, pollution on the surface, ete Table 1.1 gives the corrosion rate in ym/year (thousandth millimetre per year) for the metals steel, aluminium, copper and zinc after two, five and ten years’ exposure at a testing station on the west coast of Sweden. The corrosion of the metals takes place at very different rates, which is mainly due to the formation of oxide films and corrosion products on the metal surfaces. It can also be noted that porous corrosion product like rust to some extent results in a reduced corrosion rate over time (given in pm/yeat), A. Commosion 47Table 1.1 Rate of corrosion in pon/year for different metals after 2, Sand 10 veuy of exposure in a marine environment [1] [ 2 years 5 years 10 years ser S11 «32.8 ——~«20.7 Aluminium 0.48 0.76 0.35 Copper | 18 14 0.74 __ Zine [36 26 “ar In order to explain this in more detail, think of an example where iron is in contact with copper in an electrolyte. When an iron atom leaves the metal surface, it 1 leases two electrons and becomes an iron ion, The sites where this takes place a called anodes. The anode is consumed by corrosion. The electrons pass through the iron to the copper — the cathode. At the cathode hydroxyl ions are formed, which ‘combine with the iron ions. After this, a reaction takes place with oxygen in the air to produce rust, which may be called water-containing iron oxide. 2 Volunter copper (cathode) {anode} Figure 1.4 Corrosion of the less noble of two metals increases if the metals are connected in an electrolyte Zine case | — Paper Manganese oxide Figure 1.5 A dry cell battery illustrates the corrosion process 18 Conrasiov protectionA simple illustration of the corrosion process is provided by the activity within a dry cell battery. The dry cell battery consists of a carbon or graphite rod in a substance able to conduct electricity (an electrolyte). This substance is enclosed by a zine case. The carbon or graphite rod is more noble than the zine case. If a small light bulb is inserted between the poles of the battery, it will ight up. ‘The battery supplies the power. When in use, the battery is being discharged. This, is because the zinc case (the anode) corrodes. If the process is allowed to continue Jong enough, the battery will eventually stop working and could start to leak. The corrosion process has corroded the zinc case surrounding the electrolyte. Conse- ‘quently, the less noble of the two metals in contact has broken down and, being the anode, zinc has delivered the energy to the cathode, However, in order for corrosion to take place, itis not necessary that dissimilar metals are joined, as in this example. It is a well-known fact that steel rusts if exposed outdoors in wind and weather. The reason is that steel is not microscopi cally uniform. contains a number of small areas with noble and base particles, On unpainted stec! mill scale, graphite grains, or other noble particles tend to be- come small cathodes, while the bulk material (the steel) becomes the anode, These areas form among themselves small corroding “batteries”. The corrosion attacks ignoble areas on the steel (anodes). At the cathode there is no breakdown of the metal, but the solution around the cathode becomes alkaline. +iCatnoses) (Anodes) Figure 1.6 A steel surface consists of numerous areas with noble and base parti- cles. Among themselves these areas form small “batteries” In simple terms, the corrosion process can be described as follows: iron + oxygen + water — iron ions + hydroxy! ions —> iron hydroxide (rust) The iron ions and the hydroxyl ions react with one another and form rust. At the cathode there may also be other reactions than the formation of hydroxyl ions. In acidic solutions (acids) hydrogen gas is formed. Deposit of noble particles from a solution at the surface of the metal may also be a cathode reaction. Itis important to note that if we can prevent the metal surface from getting into contact with air (oxygen) and an electrolyte (water), we are actually able to prevent corrosion This is to a great extent utilized in practice. Just think of closed water-filled systems where there is little exchange of the water, for example in central heating systems (radiators) in blocks of houses and office buildings. The limited quantity of 1.Cornosion 19‘oxygen present in the water when the system is taken into use is quickly consumed due to corrosion, When the oxygen has been consumed, the corrosion attack within the system ceases There are many ways in which we can prevent metal surfaces from getting into contact with moisture. For example, surfaces can be painted or applied with other types of coatings. But it is also practically possible to remove or reduce humidity in closed-in constructions to such an extent that the formation of a conductive water film is not possible. This principle is used world-wide on bridges made as steel box girder constructions. Outside, the steel construction can be applied with a duplex system in the form of thermally sprayed zinc coating and paint, but inside the steel isonly primed. A dehumidifying system ensures that the relative humidity inside the structure is constantly approximately 40%. ‘The idea is that at such low relative humidity the formation of an electrolyte inside is not possible, This prevents any internal corrosion, Electrochemical series The corrosion resistance of a metal indicates the ability of the metal to resist cor: rosion in a defined environment. How resistant metals or alloys are, depends on factors such as the type of metal and the environment to which it is exposed. Inall metals or alloys (mixtures of metals) a certain amount of energy is stored, ‘This amount of energy can be measured in volt. These measurements are usually called potential or voltage measurements ‘The difference in potential between two metals can be measured by a voltmeter However. in order to measure the potential of the metals, either alone or together, a reference electrode must be used. A reference electrode serves as a kind of zero point. Such a reference electrode is called the standard hydrogen electrode, often abbreviated SHE. It has a potential of 0 V in a defined solution at 25°C. -O> Voltmeter Reference electode Figure 1.7 Potential measurement with reference electrode For potential measurements in sea water the reference electrodes listed below are used. When a certain reference electrode is referred to, the chemical names or the abbreviations in the parentheses are occasionally used. 20 Corrosion protectionTable 1.2 Potentials for different reference electrodes in relation to the standard hydrogen electrode (SHE) [Reference electrode Electrolyte Potential versus SHE (V)_ Zine ‘Sea water approximately -0.78 V | Silver/silver chloride (SSC) Sea water approximately +0.25 V Copper/copper sulphate (CSE) Sea water approximately +0.32 V Calomel (SCE) Kel approximately 40.245 V_| Itcan be seen that a reference electrode of zinc is negative compared to the standard hydrogen electrode, and that the other three are more positive. Metals and alloys can be ranked in electrochemical series according to their corrosion resistance. Such electrochemical series are established by measuring the potential of a metal or an alloy in a defined environment. The most widely known and used series is the galvanic series in sea water. A closer look at the galvanic series quickly reveals which of two joined metals will corrode. Table 1.3 shows that both zinc and aluminium and their alloys are less noble than steel. If two metals are placed in electrochemical contact, the less noble metal will suffer increased corrosion. This circumstance is of great practical importance, for example in connection with corrosion protection. For this reason, alloys of zine, aluminium and magnesium, which are all less noble than steel, are used for ca- thodic protection of steel structures. The lowest possible rate of corrosion is desired when two metals are joined. In order to achieve this, the metals must be insulated from each other in stich a Way that they are not in direct electrical contact. If this is not possible, it must be en sured that their relative positions are not too far apart in the electrochemical series. ‘The driving force behind corrosion processes has been mentioned, ie. the differ- ences in potential between the metals. The greater the difference in potential, the fiercer the attack will be on the less noble of the two metals, Toa very large extent the corrosion attack on a metal also depends on the me- dium or environment to which it is exposed. Aluminium alloys and stainless steel alloys do not corrode to any great extent when exposed in urban or industrial at- mospheres. However, the attack may be important ifthe same alloys are exposed to for example sea water. In the galvanic series a few metals or alloys are listed twice. This is due to the fact that some metals are covered by a thin and protective oxide film. As long as this oxide film is intact, it helps the metal to remain passive. If the film has been removed or damaged, for example through abrasion, the position in the galvanic series changes. The metal now has a higher tendency to corrode. Metals with such an oxide film include stainless steel, nickel alloys and alu- minium alloys. If there is plentiful supply of water and oxygen, these oxide films are self-repairing. Under layers of dirt and pollutants the supply of oxygen may become too low. In such sites the oxide film is not repaired and corrosion may occur, Under such conditions, some process industries have experienced problems with crevice and pitting corrosion of “ordinary” stainless steel. This has resulted in a change to higher grade stainless steel types. for example ASTM $31254 A.Comosion 24.Table 1.3 Galvanic series in flowing sea water (2.5-4 m/s), temperature range I1- 30°C. Potentials are measured versus saturated calomel reference electrode (SCE) (2) ao chan ot Crevice and pitting corrosion are types of corrosion which cause localized corro- sion attacks on metals. The attack often starts where there is a poor exchange of electrolyte in narrow crevices or in pits. This type of attack often takes place very quickly and may result in the metal corroding completely through, Galvanic corrosion is also found if the external conditions between two equally noble metals result in a difference in potential, Such a difference may occur due to a difference in oxygen concentration, for example on piles submerged in sea water. 22 Connosion prGalvanic corrosion isa type of corrosion which occurs when there is metallic con- tact between two metals in a corrosive environment. The selection of appropriate materials requires thorough knowledge of metals and alloys and their behaviour in different environments. Corrosion environment and pH Indoors, in dry rooms, there is little danger of corrosion because the tinuous electrolyte being formed on the surface. In the case of outdoor exposure, the corrosion attack depends on the environment. The more polluted the environ- ‘ment, the faster the corrosion attack will be, Many of the industrial gases emitted into the atmosphere are transformed into acids or alkalis. Such solutions attack metals as well as other construction materials. In order to indicate whether a solution is acidic or alkaline, the pH value of the solution is measured. The pH value is usually measured within a range from 0 to 14, Pure water has the pH value of 7, which is a neutral solution. If pH value of less than 7 is measured, itis an acidic solution. The closer to 0, the more acidic the solution, Rain water often has a pH value around 5 because it has taken up acidic pollution ‘The pH scale is logarithmic. This means that for every single point above or below a pH value of 7, the solution will be ten times more concentrated, A solution with a pH value of 5 is consequently 10x 10 = 100 times more concentrated than a neutral solution with pH value 7. ete |= hale Neutral oo, 23 4 5 6 7 8 9 0 1 2 13 14 Figure 1.8 The pH scale Alkaline substances have pH values from 7 to 14. Examples of such substances are sodium hydroxide (caustic soda, lye), ammonia and cement. Acidic substances have pH values from 0 to 7. Examples of such substances are hydrochloric acid and sulphuric acid. Their area of use includes pretreatment (pick- ling) of steel before hot dip galvanizing, “The corrosion attack on metals is often intensified in acidic and alkaline solu tions. Both aluminium and zine sustain very severe attacks in contact with alkalis. However, if steel is immersed in an alkaline solution, the steel is passivated. A thin iron oxide film is formed on the surface which offers good protection against corro- sion, and the rate of corrosion is reduced considerably. Reinforcing steel bars are well protected and kept passivated by the alkaline environment in concrete ‘The decisive factor for the corrosion process is whether water from rain, dew or condensation due 1 a high relative humidity of the air is present on the metal surface. However. the consequences may vary considerably, When it rains, contaminants like salts and dirt collected on the surf -e will be 1Conrasion 23,washed away. But in case of high humidity or condensation on the steel, such con- taminants are not washed off. Contaminants in the form of dust and salt attract moisture (they are hygroscopic), and this prolongs the time of wetness, For this reason, structures in an environment of high humidity, but little precipi- tation, may sustain severe corrosion attacks. Auminium Zine Stee! =f sikaine solution Figure 1.9 Contact with strong alkalis will cause attack on both zinc and alu- ‘minim, but not on steel Corrosion types So far the deterioration of materials by the process of corrosion has been described in very general terms. In the case of corrosion on metals, the attacks are usually given a more detailed characterization, primarily based on the appearance charac- teristics of the attack. A more detailed description will now be given of some of the most common types of corrosion found on metals. Uniform corrosion (general corrosion) When corrosion develops at approximately the same rate over the entire metal sur- face, itis called uniform corrosion. ‘This type of corrosion results in a fairly even breakdown of the metal. An attack like this causes both anode and cathode reactions to occur on the same metal. Areas of different nobleness can be found due to particles of foreign metals being present in the metal surface or inthe electrolyte. thnically speaking, this type of corrosion is not very problematic. The life- time of various alloys in various environments can be calculated, If the attack takes place at arate of approximately 0.1 mm/year, it will take 20 years before a metal thickness of 2 mm has corroded away completely. Normally requirements to both strength and lifetime are taken into consideration and the metal thickness increased by a corrosion allowance. Figure 1.10. Uniform corrosion 24 Conmasion PROTECTONAnoold galvanized roof where the zinc has corroded away is an example of uniform corrosion. Attacks on low alloy and weathering steels are often of this type. This corrosion type can be seen on most metallic materials. Uniform corrosion can be reduced by selecting the right material adding inhibitor (to systems carrying liquid) using cathodic protection using coatings/linings Galvanic corrosion (bimetallic corrosion) One of the most widely observed corrosion types, and often the most dangerous type, is galvanic corrosion. This type of corrosion occurs when there is metallic contact between two metals in a corrosive environment. The corrosion is acceler- ated on the base metal and is reduced on the noble metal. Cathooe ‘node Figure 1.11 Galvanic corrosion The attack on the base metal, the anode, is most severe close to the point of contact and decreases with increased distance from i ‘The driving force behind galvanic corrosion is the difference in potential be- tween the two metals. The attack is severe if metals located far apart in the electrochemical series are joined together. ‘The appearance characteristics of the attack depend on several factors, The relative area sizes of the anode and cathode and the conductivity of the electrolyte are among the most important factors. A large cathode coupled to a small anode often leads to a faster and more severe corrosion attack than in the case of a small difference in area. The offshore oil industry has experienced problems with some types of welding electrodes used for welding of carbon steel. By accident insufficiently alloyed elec- trodes compared to the pipes were used. This resulted in complete corrosion of the ‘welded joints in record time and extensive damage to the materials, The reason is galvanic corrosion caused by a large cathode area (the pipes) and a small anode area (the welds). ‘The galvanic series in sea water (see Table 1.3) was mentioned above. To a certain extent this series provides a possibility for predicting the risk of galvanic corrosion. Below some examples of various types of attack caused by galvanic contact between dissimilar metals will be discussed. The Statue of Liberty in New York City was completed in 1886. The copper statue was supported internally by a framework of iron and steel. The copper skin and the steel were originally insulated from each other by means of asbestos fabric impregnated with shellac. Over the years the asbestos fabric had deteriorated and started to work as a wick between the metals, In the early 80°s the steel framework 1 Conosion 25had become extensively damaged due to galvanic corrosion, The corrosion attack on the steel and cracking of the rust had caused deformation of the copper skin in a number of places. During the restoration an effort was made to prevent galvanic corrosion. Most of the steel was replaced by stainless steel alloys and the metals were insulated from each other by means of Teflon gaskets/inserts. [3] ‘A number of wheel houses on ships are made of aluminium. This has resulted in galvanic corrosion in the interface between steel and aluminium, but the prob- ems have now been reduced by changing the joining techniques and by using anticorrosion paints Galvanic corrosion can be reduced by using filler metals for welding which are nobler than the parent material changing the materials used in order to avoid harmful contacts between noble and base material insulating materials from each other using metal coatings or paint coatings avoiding the deposit of nobler metal ions on the surface. Crevice corrosion Narrow crevices exposed to a liquid, typically water-containing solutions, may be open enough to allow the liquid to penetrate, but still so narrow that the liquid becomes stagnant within them. If this is the case, crevice corrosion may occur, The driving force for this type of corrosion is a difference in oxygen content inside and outside the crevice. The most pronounced crevice corrosion occurs on metals which are passive or easily passivated, such as stainless steel, aluminium and steel in predominantly alkaline environments. For example in sea water the passive oxide layer on some ‘metals may be broken down by aggressive chloride ions, Crevice corrosion occurs in flanged joints, under rivet heads and screw heads, in overlaps and when the metal is covered by for example dirt, sand, corrosion products or marine growth. water more re in — ‘ovygen becomes the ‘cathode region | the crevice becomes the oxygen depiotod ara, Le. Cathodic reaction: ~ %40,+H,0428=20 Figure 1.12 Crevice corrosion 26 —Conrosion prorecToNIn some cases crevice corrosion in flanged joints or beneath rubber hoses mounted by clamps onto stainless steel piping in sea water has had an extent of several millimetres per year. The reason is that sea water has penetrated but the exchange hhas not been frequent enough, which again leads to too low oxygen content to ‘maintain the oxide film. Stainless steel pipe with soa water Ne ee ‘ond LOLOL: send Sik Crevice cortosion Figure 1.13 Crevice corrosion on stainless steel Crevice corrosion can be reduced by a number of practical precautions: Use welding instead of flanged joints and bolted joints whenever possible. Minimize the number of sharp edges, comers and possibilities for liquid pock- ets Drain areas which are not continuously filled with liquid. Do not use packings that absorb water. ‘Take solid particles and suspensions which may adhere to the walls into consid- eration. Pitting corrosion Pitting corrosion is a type of corrosion which involves localized attacks on metals. ‘The attack is in the form of localized pits. This corrosion type may arise on a number of metals, but itis often found on metals with a passivating oxide film. like aluminium and stainless steel. Such attacks may result in extensive damage. Often 1Comwasion 27the diameter of the corrosion pits is relatively small, but they grow in depth. The pittings may also be covered by corrosion products, which makes them difficult to spot Figure 1.14 Pitting corrosion ‘The relative sizes of the cathode and anode areas also determine the corrosion rate. ‘The larger the cathode area relative to the anode area, the more severe the attack. The problem is also related to defects either in the oxide film or otherwise in the material. Attacks on stainless steel are often more severe than on ordinary steel. If the oxide film is attacked by chloride ions, it will be on weak spots in the film. The difference in area between the cathode and the anode is consequently very big. ‘Ordinary steel has considerably more defects and the cathode and anode areas will be more equal in size. The oxide film on the stainless stec! has few defects and acts as cathode to the metal. ‘The corrosion rate inside each pitting can be considerable and may cause the material to corrode through relatively quickly. Pitting corrosion is often seen in conditions where the metal is passive. Pitting corrosion may also act like bimetallic corrosion. This happens when the water contains traces of more noble metal ions which are deposited on the metal surface. Major corrosion attacks may take place when copper ions are deposited as metallic copper on aluminium and steel Also a fairly noble material like copper may experience pitting corrosion. In copper pipes this may be due to the water quality or deposits from the water, Also residues in the pipes of carbon-containing drawing agent from the manufacturing process may be the reason. Heating of the pipes during their fabrication causes it to ‘carbonize and a thin layer of carbon or graphite may be left on the Walls of the pipe. Graphite is more noble than copper. The difference in area size between cathode and anode is big, and often major corrosion attacks are seen. Some materials are highly resistant to pitting corrosion. They are usually char- acterized by a high content of chromium, nickel and molybdenum. Other metals are susceptible to this type of corrosion in chloride-containing environments and are. for example, not used in sea water nor in the chemical process industry. In chloride-containing environments ordinary stainless stec! usually has too lit- tle resistance against corrosion, On the other hand, special high alloy, stainless and acid-resistant steels, copper-nickel alloys and nickel and titanium alloys can be used with excellent results. Pitting corrosion can be reduced or prevented by selecting more suitable materials ‘changing the corrosion environment 28 Consosion ProrectIon‘rode ‘Cathode Anode ‘node Cathode Anode ‘cathose node Cathode Figure 1.15. The corrosion attack is determined by the relative area sizes of the cathode and the anode, and by the conductivity of the electrolyte Erosion corrosion Erosion corrosion is a type of corrosion which occurs when a metal is exposed to ‘mechanical abrasion and a corrosive environment at the same time. Liquid or gas flowing at high velocity in pipes may cause erosion corrosion. ‘Turbulence is formed in the pipes. The mechanical impact causes the protective surface layers to be wor off or damaged at the surface. Erosion corrosion may occur on most metals, but copper alloys are especially ‘susceptible to this type of corrosion attack. Depending on the temperature of the fresh water, the maximum water velocity in non-replaceable distributing pipes is 1- ‘2 m/s, perhaps slightly higher on coupling pipes, before erosion corrosion arises. Copper alloys are also widely used for transport of sea water. These velocities for sea water should not be exceeded: copper alloys mis aluminium brass 1.8 avs copper-nickel alloys 2.5-3.5 m/s Erosion corrosion is often due to the fact that the construction has an unsuitable design. Inside the pipe the corrosion can be caused by uneven weldings ot pipes, inserted by welding, which jut in too far and thereby cause the flow of the water to change. Over time this results in a sort of undermining of the material. The attack is often shaped like a horse shoe. 1.Conposion 29Figure 1.16 Erosion corrosion on copper Selective corrosion (dealloying corrosion) Selective corrosion can appear on brass and cast iron if they are exposed in sea water. This type of corrosion causes one of the alloying elements to be preferen- tially attacked. The attack may be local or uniform over the entire surface. As a result, the geometry of the object may remain unchanged, but since one of the elements has been removed, it eaves a porous material with little or no mechanical strength. Well-known examples of selective corrosion are the dezineification of brass and the graphitization of cast iron Brass is an alloy of zinc and copper. Certain brass alloys with a high content of zinc are susceptible to selective corrosion. If such an alloy is used in sea water, the zinc will corrode and leave a porous matrix of copper. Consequently, the brass has lost its strength, Once the attack has reached this stage, only smail impact is re quired to cause for example a pipe to break, When brass is dezincified, the attack can be seen as small reddish-brown areas on the brass. Here the zinc has corroded and the visible spots are the porous matrix of the copper. No corrosion LLL LLL LLL LLL LLL Selective corrosion (tng corrosion) Selective corrosion (of the surface} WLLL Soloctve corrosion fot al the material) Figure 1.17 Selective corrosion 30 Corosiow pnorecrionCast iron has a high content of carbon. Graphitization results in corrosion of the iron, leaving a porous matrix of carbon in the material. As a result of the attack the iron in the cast iron will disappear and leave a dark area consisting of graphite (carbon). This may happen if cast iron is immersed in sea water. Stress corrosion cracking Stress corrosion cracking (SCC) isa term given to inter- or transgranular cracking of metals by joint action of static tensile stress and a specific environment. This type of corrosion is very common in many industries. Great concern has been given to SCC both on onshore and offshore locations. Different types of metals or alloys will be more or less sensitive than others to a given solution or environment. Metal Solutions causing SCC Carbon steel Nitrate solutions (NO, ) Copper alloys Ammonia solutions (NH) Stainlesssteels Chloride solutions (CI) Insulated stainless steel pipes for the transport of fresh water or sea water at tem peratures of approximately 60°C are particularly susceptible to stress corrosion cracking. Such pipes are ofien insulated with cellular glass insulation. Before ap- plying the insulation, the stainless steel is often sweep-blasted with a fine mineral abrasive and then painted with epoxy or similar coatings. Itis common practice to specify paints without zinc metal or chlorine-containing constituents. ‘The risk of stress corrosion cracking on stainless steel can be reduced by stress~ relief annealing to remove residual stresses from welding or cold-work. Figure 1.18. Stress corrosion cracking on stainless steel in chloride-containing environment at 60°C 1 Conmosion 34Intergranular corrosion (intercrystalline corrosion) Intergranular corrosion is localized attacks on of around the grain boundaries of a metal with little impact on the rest of the surface. All metals are composed of microscopic metal grains. Intergranular attack occurs along the grain boundaries of the metal This type of corrosion especially affects austenitic stainless steel with a carbon content of approximately 0.05-0.08%, for example of the ASTM 304 and ASTM, 316 types. These types of steel may be susceptible to corrosion attacks if they have been subject to heat treatment within the temperature range of 400-800°C. The heating causes a deposit of chromium carbide on the grain boundaries. This deposit takes place at the expense of a small zone on the grain boundary where chromium contents are reduced. In this little zone the material loses its “stainless-ness”, 50 t0 speak. Intergranular corrosion of austenitic stee! often takes place in connection with welding. The areas around the welds are often subjected to the relevant temperature range for a short period of time. This results in a localized attack around the weld, oon both sides of it Intergranular corrosion usually occurs in very specific environments, for exam~ ple chloride-containing environments. In order to avoid this type of corrosion itis common practice to select a material quality like ASTM 304L or 316L with a low content of carbon (lower than 0.03% C), or other alloys stabilized with titanium or niobium which bind carbon and form titanium or niobium carbide instead of chro- mium carbide. Figure 1.19 Intergranular corrosion Corrosion fatigue When a metal is subjected to either temporary or continuous stresses, cracking may suddenly occur above a certain stress level. This may take place in spite of the stresses being considerably smaller than what is otherwise known to be the tensile stress of the material. This is usually called fatigue. When this fatigue takes place in a corrosive environment, itis called corrosion fatigue. In the case of corrosion fatigue the material may be broken down earlier than in the case of ordinary fa- tigue. Corrosion fatigue causes cracking of the material and total destruction may be the result. Microscopes are often used for the evaluation of the surface of the fra, ture. In this case lines can be observed on the smooth part of the surface, so-called striations. The striations have the same curvature towards the starting point. 32 Coanasion PROTECTION“<= Dynamic stress pe Figure 1.20 Fatigue corrosion Corrosion in different environments Corrosion in air Corrosion of unpainted steel or other metals takes place at a relative humidity higher than approximately 60-70%. Because the air contains oxygen, the decisive factor for the corrosion is how long the metal surface is wet. The length of time when the surface is wet is usually called the time of wetness. The time of wetness is defined as the period of time when the relative humidity of the air is above 80% and the air temperature above 0°C. In urban and industrial atmospheres there is a particularly high amount of solid particles in the air, including soot, sand and chloride and sulphate salts. Such salts are hygroscopic (attract water) and water soluble. Thereby they increase the corro- sion in air, In some cases itis also a determining factor for the corrosion attack whether the water on the metal surface is due to condensation or rain. In very polluted environ- ments rain will wash away contaminants. Condensation rarely creates so much water that the contamination is actually washed off the surface. Corrosion attacks caused by condensation may be more severe than those caused by rain water. ‘The corrosion rates of for example aluminium alloys, stainless steel, copper alloys and zinc are generally lower than of stec] exposed to the air. Corrosion in water Structures to be immersed in water are often built of metallic materials. There are ‘wo main types of water: fresh water and sea water. Corrosion attack in water depends on the temperature, pH value and oxygen and salt contents of the water. Fresh water In areas of the world where the drinking water is soft, with a low calcium content the water is corrosive. Ata number of waterworks attempts have been made to reduce the internal corrosion of the water piping system. Such attempts include increasing the calcium contents and the pH value of the water. Hard water is less 1.Conrosion 33corrosive than soft water. This is due to the content of calcium and magnesium salts in the water. Ifthe content of such salts is sufficiently high, there will be a deposit of for example calcium carbonate, which reduces the rate of corrosion. Sea water As opposed to this, pure sea water in the oceans of the world has a constant compo- sition and corrosivity. The salt content is approximately 3.5% and pH 8.1. [4] From the chloride contents of the sea water a relatively high corrosion rate for ste] should be expected. But to some extent the contents of calcium and magnesium salts reduce the attacks. Such salt layers have a protective effect. This is especially the case in connection with cathodic protection where the formation of hydroxide results in increased pH value and deposit of calcium and magnesium salts on the surface. Corrosion is oxygen dependant and will be severe in the splash zone since the water is continuously enriched with oxygen. At the same time the salt deposits are washed away, and the effect from the deposited salt layer is reduced. ‘Also the velocity of flow may be of importance for the attack on some alloys. A high flow velocity causes the protective layer of corrosion products to be worn away. In extreme cases also parts of the actual material may be torn away. Espe- cially copper alloys are susceptible to this type of corrosion, which is called ero- sion corrosion. On stainless steel the risk of such attacks is very small. At too low velocity of flow or in stagnant liquids crevice corrosion may occur. Corrosion in soil Structures which are fully or partly buried in soil will be exposed to corrosion. The attacks in soil will 0 a very large extent depend on the type of soil and humidity, salt and oxygen contents, pH value, etc.,.and may be quite extensive. In order to reduce the extent of the corrosion itis important that the soil around buried structures is well drained. This is the case of gravel, sand and moraine. In such types of soil the oxygen contents are consequently high. ‘Ground leve! LT ‘cable or pipe Soil, sand, gavel Clay Sond, gravel Oxygen contents: High Low High Electrode reaction: 0,42H,0s4e-s40H Fo-sFe®+20" 0,+2H,0+d0-»40H PPD 2 ate. Figure 1.21 Corrosion attack in soil 34 Corrosion prorecrionIn mixed clay-containing soils variations in the oxygen contents may occur. Clay lumps near the surface result in low supply of oxygen. In such places there isa risk of localized corrosion attacks. Structures to be placed fully or partly in contact with soil over a prolonged period of time, should if necessary be protected. This especially applies to steel, which is often protected by thick organic coatings of coal tar or rubber. Alloys of lead and copper have better resistance to corrosion in soil. Literature 1 Torsten Johnsen and Cecilia Aronsson: Korrosionshastigheten hos fistelement. Slutraport. K-report 1995-7, Korrosionsinstitutet, Stockholm, 2 LaQue, F.L., Marine Corrosion - Causes and Prevention, John Wiley & Sons Inc., New York, 1975 3 R, Baboian, E. Blaine Cliver, B. Lawrence Bellante: The Statue of Liberty Res- oration, Proceedings of the Statue of Liberty ~ Today for Tomorrow Confer- ence. National Association of Corrosion Engineers, Houston, Texas, 1990 4 Einar Mattson: Electrokemi och korrosionslara. Bulletin no. 100, Korrosionsinstitutet, Stockholm, 1987. He 1900's cone2 Protection against corrosion Introduction In the previous chapter various types of corrosion and influence from the environ- ‘ment have been discussed. We will now have a closer look at other methods of corrosion prevention: + correct selection of materials appropriate construction design use of paints and coatings cathodic and anodic protection conditioning of the environment Correct selection of materials A number of handbooks contain tables showing whether a metal/alloy is suitable fora given corrosive environment. Information on the corrosion rates of a number of metallic materials in connection with various concentrations of chemicals and temperatures may be listed. Based on information in the handbooks, experiences from projects etc., suitable metals/alloys are selected. Conditions such as lifetime requirements and accessibility for replacement are also of great importance. Many factors play a part in the selection of materials. The final selection is often made on the basis of considerations related to corrosion engineering and the ‘economy. Farther considerations may concern various combinations of materials and the risk of special types of corrosion under the given environmental conditions. ‘Various metals and their areas of use will be given a short description below. Steel Pure iron finds insignificant technical use. On the other hand, iron alloyed with, carbon and smaller amounts of the elements manganese and silicon constitutes the 36 Conrossow ProrecTOnmost widely used metallic construction material. ‘Types of steel where the tensile strength properties are mainly determined by the carbon contents are called carbon steel or unalloyed steel. Steel (carbon steel) has a carbon content of up to 1.3%, while in the case of east iron it is even higher, be- tween 2-4%. Apart from carbon, such steels also contain minor quantities of sul- pphur, phosphonus, silicon and manganese from the manufacturing process, Other elements can also influence the properties of the steel. For example, the silicon content is very important for the thickness of the zine coating produced by means of hot dip galvanizing. By alloying steel (carbon steel) with small quantities of the alloying elements chromium, nickel, molybdenum, phosphorus and vanadium a large variety of steel qualities is obtained. Such steel qualities are usually called low alloy steels. The total contents of the alloying elements rarely exceed a few per cent. The corrosion resistance of unalloyed steel and low alloy steel is more or less the same. Steel used for building constructions have excellent mechanical properties, but will corrode in the atmosphere at humidities above 60-70%. The rate of corrosion is influenced by factors such as time of wetness, pH value and air pollution. During milling (rolling) of the steel mull scale is created. Mill scale will act as a cathode on the steel, if not completely removed. At first mill scale acts asa barrier nd reduces the corrosion of the steel, but when the mill scale cracks and flakes off, the corrosion rate of such exposed localized areas will increase due to unfavourable cathode-anode ratios. The rust formed provides only slight protection of the stee). Structural steel and plates of large thicknesses are usually supplied hot rolled, ‘whereas thinner sheets (below 4 mm) are cold rolled. The thin sheets do not have nil sale, Due to corrosion, but also for cosmetic reasons, it is common practice to pro- vide the steel with some sort of protective treatment. In most cases this is accom- plished by painting the steel. ‘Mil scale Outdoor exposure An Figure 2.1 At outdoor exposure mill scale cracks and steel corrodes Weathering steels Weathering steel is a special type of low alloy steels which, when exposed out- dloors, has better resistance against corrosion than ordinary structural steels, The improved resistance is a result of the weathering steels having been alloyed with slightly higher amounts of chromium, phosphorus and copper. 2 Provecrion acawst cornosion 37‘The weathering steels rust during an initial period of 1.5-4 years in roughly the same way as carbon steels, During this period a uniformly dense and dark rust, layer called patina develops on the surface. The dense rust layer now causes corro- sion to take place at a slower rate. [1] ust (porous) ust (dense) Figure 2.2 After a few years a dense rust layer (patina) is formed on weathering steels Due to the decorative rust layer and lower rate of corrosion it is not common prac~ tice to paint weathering steel. The construction design is of the utmost importance. Discoloration of light-coloured materials such as concrete is a problem if rain wa- {er is not drained effectively from the weathering stecl. Corrosion ym) 44 umyyear Reterence steet : 3 5 Years Figure 2.3 Corrosion of Atmofix 52A and an unalloyed reference steel exposed ‘outdoors in highly polluted atmosphere [1] 38 Connosion protecTonOn surfaces which are constantly damp or exposed to a marine environment no patina will be formed. Weathering steels are consequently more suitable for struc~ lures which are exposed to alternate periods of wetness and dryness. ‘Weathering steels are probably more widely known by their trade names, such as Cor-Ten A and B, Patinax 37, Atmofix 52, etc. Inthe USA approximately 2000 bridges built from weathering steel during the period around 1960 to 1980 have not been painted. After some time extensive cor- rosion problems have been observed which will result in a considerable reduction of the calculated lifetime of the structure if nothing is done about it. Blast cleaning to Sa 2% and subsequent application of epoxy mastic systems is now being consid- 2) ‘The term Sa is one of four degrees of cleanliness defined in connection with blast cleaning. A degree of cleanliness of Sa 2¥4 corresponds to very careful blast cleaning of the steel to the extent that almost all rust is removed. Stainless steels As opposed to low alloy steels, stainless stecls contain substantial amounts of al- laying elements in the range of 15-30%. Generally, the various types of stainless steels are grouped after their crystalline structure, such as ferritic, austenitic, and ferritic-austenitic. Differences in the struc~ lure result in differences in their corrosion properties. In chloride-containing envi- ronment with a risk of pitting and crevice corrosion, steels of an austenitic structure ue often preferred over ferritic or ferritic-austenitic structures. The table below gives a summary of some of the most common stainless alloys, their crystalline structures and grades according to various standards. Vuble 2.1. Common terms for various high alloy steels in accordance with EN, ASTM and UNS UNS | Structure % Mo | EN ASTM 43000 | Fenitio > 0.04/165) | 30400 an | 0.04 | 18.1 4016 | 430— 4301 | 304 4307 | 304L 83 002/181 8.3 0.04) 16.9 /10.7) 26 1 1 | 1 | s30403 | Austenitic 1.4436 | 316 $31600 | Austenitic 1.4432 | 316L | $31603 | Austenitic | 0.02/16.9 10.7| 26 1.4539 | 904. | NoB904 | Austenitic | 0.01 20 | 25 | 4.3 1.4547 | $31254 | $31254 | Austenitic | 0.01] 20 | 18 | 64 | 1.4652 | $32654 | $32654 | Austenitic | 0.01) 24 | 22 | 7.3 1.4462 | $32205 | s31803 | Duplex | 0.02) 22 | 5.7 | 3.4 1.4410 | $32750 | $32750_| Duplex | 0.02) 25 {he main alloying element in stainless alloys is chromium. When chromium is used foralloys, a thin and protective chromium-oxide film is formed on the surface of 2 Prorection xcansr cornosion 39.the metal. The alloy must as a minimum have a chromium content of approximately 119 to prevent rust from appearing on the steel. Stainless steel must have access to oxygen in order to maintain the oxide film, Besides alloying stainless steel with chromium, also nickel and molybdenum are added. An example of a stainless steel of this type is steel with approximately 17% chromium, 11% nickel and 2.6% molybdenum, see Table 2.1 Many countries have standards for stainless steels. The terms ASTM 304 and ASTM 316 from American Society for Testing and Materials (ASTM) designate examples of stainless steels. It is quite common to describe stainless steel as 18/8 steel. The figures indicate the contents of chromium and nickel, respectively, in the steel. Molybdenum can also be added. An alloy with 17% chromium, 11% nickel and 2.6% molybdenum corresponds to ASTM 316. Other steel qualities have better corrosion resistance to sea water compared to the types mentioned above. The material ASTM $31254, often referred to as 254 SMO or 6 Mo, is a high quality steel alloy containing 20% chromium, 18% nickel and 6.1% molybdenum. When this material was first introduced on the market, tests showed good corrosion resistance against crevice corrosion at temperatures up to approximately 40°C. However, subsequent practical experience has shown that the material has been subject to pitting/crevice corrosion even at lower tem- peratures. ‘The corrosion resistance of ASTM 31254 in for example sea water is much better than that of an “ordinary” stainless steel, for example ASTM 304. This is due to the high alloy contents. Under particularly corrosive conditions also ASTM '$31254 may have too little corrosion resistance, and other materials must be cho- sen. Formability and weldability are greatly improved when nickel and molybdenum are added. It is a general misconception that stainless steels do not corrode. In sea water a number of these alloys will suffer extensive corrosion, Despite the fact that alloys with a chromium content of minimum 12% result in steel qualities which do not rst, these types will nevertheless be subject to corrosion, Defects in te oxide ‘tm may result in| Passive condition piting corgsion| ative condition Figure 2.4 Active and passive condition 40 Conrasion pRorEcTIONIn chloride-containing environments localized corrosion attacks will occur. Pitting and crevice corrosion may result in complete perforation of pipe walls or severe attacks on seal faces on flanges. Intercrystalline corrosion isa type of corrosion which may appear on stainless steels with a high carbon content (0.05-0.08% C). Welding of stainless steels with high carbon content may cause precipitation of chromium carbides, leading to depletion of chromium to below 12% in the metal adjacent to the precipitates, which is thus no longer “stainless”. If the steel is exposed to an aggressive environment, such sites may become anodic to the rest of the metal, and may corrode. This type of corrosion attack can be reduced by selecting stainless alloys with low carbon contents (< 0.03%) or possibly adding small quantities of titanium or niobium in order to prevent the formation of chromium carbide. Alternatively, the steel can be heat treated at high temperature and cooled very rapidly so that no chromium carbides can be formed ‘There are many areas of use for stainless steels, from household articles (cut- lery, saucepans, etc.) to use for the transportation and storage of aggressive liquids, including chloride-containing substances. Water salts Piting corrosion ‘Oxide fm Figure 2.5 Pitting corrosion on stainless steel Titanium and nickel alloys Titanium alloys have excellent corrosion resistance when exposed in both marine and industrial atmospheres. They are also suitable for use in fresh water and in sea water. Due to high initial costs the use of titanium alloys has been limited. But under demanding conditions the selection of titanium alloys may be advantageous be- cause they have a number of excellent properties. This has been the case in the process industry which has had good experience with the use of titanium for pumps, valves, etc. Also the oil industry has started to use titanium, for example for heat exchangers, ‘Nickel alloys are considered among the most corrosion-resistant alloys in exist- ence. Such alloys are used in particularly aggressive media, and when long life~ times are required. They are extremely resistant towards sea water with high veloc- ity of flow. In stagnant and slow sea water they may be subject to pitting and crevice corrosion. (3 "You may have heard mention of materials such as Monel, Chlorimet, Hastelloy B and C, and Inconel, which are all examples of nickel alloys. CHON AGANIST CORROSION — 44.Copper and copper alloys Copper is a relatively noble, but soft metal, By alloying copper a large number of alloys with many different areas of use are produced. Well-known alloys are brass (copper and zinc) and bronze (copper and tin), just to mention a few. The rate of corrosion of copper in air is low, approximately 0.5-2.5 pm/year This is due to the fact that the corrosion product formed on copper is very dense and durable. Most people have probably at some point in time seen the green patina, verdigris, on objects made of copper. ‘The use of copper for construction has a long tradition. Copper alloys are often used for roofs, mountings, statues, ete. Copper and copper alloys ate also widely used for water-bearing pipes, con- densers and heat exchangers as well as for components like valves, pumps, etc. ‘When selecting materials, attention must be paid to the medium which the alloy will get into contact with. This is perhaps especially important in connection with the transport of fresh water and sea water in the pipes. Copper pipes used for hot and cold water piping and hot water appliances are well-known, For transport of sea water more resistant copper alloys should be chosen. Alloys of copper-nicke! or aluminium-brass are often used for this purpose. Copper alloys are generally sensitive tothe velocity of flow in the pipes. Ata too high velocity, erosion corrosion may arise. In order to avoid such damage on “ordi- nary” copper pipes, the flow velocity of the sea water should not exceed approxi- mately 1 m/s. In the case of copper-nickel the upper limit is considered to be ap- proximately 3.5 m/s. Besides erosion corrosion, copper alloys are also attacked by pitting corrosion, Selective corrosion may occur on various brass alloys. ‘The tendency of fouling is smaller on copper than on other metals, Consequently, copper alloys are extensively used in water-bearing pipes, and for the same reason copper-containing antifouling paints are used on ships’ hulls, Zine When we consider the areas of use of hop dip galvanized steel, this is utilized for a number of purposes where long lifetime without extensive maintenance is required, Apart from the advantage of a low corrosion rate of hot dip galvanized steel in a ‘number of atmosphere types, the zine coating also provides corrosion protection of the steel in case of damage. A major part of the steel used for power masts, railings, lamp posts, crash barriers, etc. is hot dip galvanized. It has been estimated that approximately 40% of all zinc produced on a world-wide basis is used for corro- sion protection of steel. [4] Zinc coatings can be applied to stee! by various methods that will be discussed later. Depending on the method of application and the thickne: i provide excellent protection to steel for many years, depending on the exposure environment, Corrosion on zinc in air is generally slow. In urban and industrial atmospheres ittakes place at 1-10 pm/year. In rural and marine atmospheres itis even lower and only approximately 0.5-2 m/year. Sacrificial anodes made of zinc are used for cathodic protection of steel. 42 Cornosiox pRoTecnon