1988 CAE 0-018 To my wife Erna, for her love, patience and support.FOREWORD Corrosion is a phenomenon that causes important losses of materials, energy and money because it leads to demand for increased maintenance. loss of product and production due to unplanned outages, and sometimes even to serious accidents. It is well known that there are many forms of corro- sion and also many remedies to combat them. Unfor- tunately, these remedies are not always applied, if only because those engaged in design, fabrication, mainte- hance or use of apparatus, machines and other equipment are not aware of these possibilities. In other eases, insuf- ficient knowledge may lead to application of methods of corrosion control in the wrong way or in the wrong situation, Also, obtaining advice from specialists is often difficult as they talk a different language and because the details of the operational conditions, which may be very important, are not known to the specialist. This highlights the need for further education and instruction of these engaged in the above-mentioned fields. Unfortunately, however, much of the educational ‘material available is rather specialized and sometimes t00 theoretical and of too high a scientific level to be of direct use for the people concerned with the solution of corrosion problems in practice. In other cases, it is dif- ficult to use these educational aids for self-study or as a 100] in the solution of practical problems. Having been concerned with corrasion education and instruction for many years, I therefore greatly welcome the publication of this “Corrosion Atlas”, which certainly fills a gap in the progression from theory to practice. It is. 1088 CAE 0.00 of great importance that these who are responsible for the design, operation and maintenance of the varied and often very complicated systems and machinery employed Jn today’s technology should apply this work extensively in their daily work ‘This atlas is not only an important educational aid for self-study and special courses, but it can also be used as part of existing general courses in technical schools and colleges and in universities. Its unique illustrative material presents an opportunity to make these courses less ab- stract and theoretical and to give a much closer link with the practice of corrosion and corrasion control than usual, ‘The author of this Ailas is to be congratulated on the excellent result of his activities. Praise is also due to the organization of which the author is a manager for its support of this work, which is of great value for modern technology. I sincerely hope that many persons will take advantage of this publication: in teaching, in sel/instevetion or in trying to solve the practical corrosion problems with which they are confronted in their day-to-day work, Enschede, The Netherlands January 1988 P.J. Gellings Professor of Inorganic Chemistry and Materials Science, University of Twenievil PREFACE Krachtwerktuigen is a Dutch, independent, non-profit association of indusirial companies and institutions and Jt represents the collective and individual interests of its 3000 members in the field of energy and environment. ‘The Corrosion Department gives advice abcut corzo- sion prevention in the design state and about corrosion ‘control in the operational stage. By means of lectures and Publications and by providing corrosion courses for siu= denis, the department makes a contributien towards the further dissemination of know-how on corrosion and corrosion prevention. For instance, since 1983 Kracht- werktuigen has organized a fully practice-oriented corro- sion course for industrial engineers, in which a large number of corrosion case histories are dealt with. It was this course that originally led to the compilation of this atlas, which has meanwhile developed into an essential part of the course. ‘The case histories, which relate not oaly to corrosion but also to such phenomens as cavitation, erosion, fa- tigue, superheating and plastic attack, are collected in two volumes, classified by material. Volume 1 contains the case histories relating to carbon steels. Volume 2 contains those relating to stainless steels and non-ferro ‘materials. For ease of accessibility to the engineer, the ‘case histories are subdivided according wo system and phenomenon. In addition, a separate phenomena index hnas been added. With reference to the classification, the case history coding is as follows, The first two digits of the code refer to the material of the object attacked. the second two digits to the system from which the corroded part originates, the third two digits refer to the phenomencn, and the last two digits to the numerical sequence in those instances in which several sheets deal with the same subject. In this photographic atlas, theory has been reduced to 2 minimum. A brief introduction to the subject and 4 comprehensive list of references at the end of Volume 2 will serve as a guide for those wishing to undertake further exploration of corrosion and corrosion control. In addition, an explanatory list of definitions of technical and corrosion terms used is included. ‘The atlas has deliberately been produced in loose-leaf form because this allows supplements and possible re- placements to be made in future. Also, users of this atlas are requested to send new casc histories, if possible accompanied by samples of the corroded material, to the compiler; this would provide a valuable source of further information, and as such would be most appreciated. In Particular, attack of surface coatings and high aickel alloys remains rather under-represented. A blank form is included on page A1S which may be used for sending the relevant information. 1988 CAB (-0vii The author expresses the hope that the Corrosion Atlas may become a tool for the engineer, which, by making visual comparisons possible, will provide him with indications as to the causes and possible control of the corrosion confronting him in practice, but above all that it will serve as a work of reference from which he can derive the necessary information to prevent corrosion altogether. However, in view of the fact that corrosion is often a complex process, it should be stressed that usc of this atlas should not be allowed to lead to unjustified simplification of the problem, For many corrosicn prob- Jems, the assistance of a corrosion specialist will of course remain incispensable. Acknowledgements Compilation of this Corrosion Atlas was made possi- ble above all by enthusiastic contribution and discussion of corrosion material by many attendees at the sbove- mentioned course, and the cooperation of a number of industries and organizations which made corroded material from their own collections freely available: in alphabetical sequence, these are: AKZO Zout Chemie Nederland BV. Hengelo DSM BY. Geleen and Lmuiden 1Cl Holland BV. Rozenburg, NY. KEMA, Armhem Shell Nederland Raffinaderij BV. Pernis Stichting Doelmatig Verzinkea ‘The Hague VEG-Gasinstituat NV. Apeldoorn I take this opportunity to offer my sincere thanks to all of the above for this cooperation. A word of gratitude is also due to Miss Angela Put for her valuable manage- ‘ment assistance. The Dutch-English translation was done with great care by Mr. ALN.R. Wright. The excellent colour photographs are the work of Huub de Jonge (the ‘macroprints), while Paul W. van Maaren produced the mictoprints. Useful advice was received from two re- ‘viewers and is gratefully acknowledged, Case histories 02.05.1401, 02.05.1402 and 06.05.14.02 are taken from “Das Gesicht der Korrosion”, by Dipl. Ing. A.F. Bertling and Dr. Ing. EA. Ulrich, 1971, with kind permission of the publishers, TUV Bavaria, West Germany, Amersfoort, The Netherlands January 1988 Evert DD. During Manager, Corrosion Department, KrachwerkiuigenCONTENTS Volume 1 Foreword, Preface, Classification of the case histories, Phenomena Index, Section A: General information Introduction, Glossary of terms used in this work, Background information on the Interphako® technique, Information about the microprints, Information about magnifications of some macroprints, Steel qualifications used, Blank form, Section B: Case histories (Gor classification, see pp. xi and xii) ‘Carbon steels Volume 2 Section B: Case histories (continued) Stainless steels and non-ferro materials Section C: Supplementary information List of national corrosion associations, Bibliography for corrosion study, Information on supplements, 1988 CAE 0-0ix. Page ix Al Al All ALS AL Als Als a 3 aCLASSIFICATION OF THE CASE HISTORIES * ‘MAIN CLASSIFICATION BY MATERIALS ‘Volume 1: Carbon steels OL. Unprotected carbon steels (non- and low.alloyed steels, cast irons, cast steels) 02, Galvanized stecls (hotdip galvanized, electroplated and continuous zinc plated) 03, Carbon steels provided with a coating other than zine (see 02.) and plastic linings (sce 10.) ‘Volume 2: Stainless steels and non-ferro materials 04, Siainless steels (martensitic, ferrtic, austenitic, pre- cipitation-hardening, special grades) 05, Nickel base alloys 06. Copper and its alloys 07. Aluminium, magnesium and their alloys 08. Lead, tin and zine 09. Noble and reactive metals (silver, gold, titanium, Zirconium ete.) 10. Plastics and plastic linings 11. Concrete 12. Other materials (glass, wood) FIRST SUB-CLASSIFICATION, BY SYSTEMS (1, steam systems (boiler feed systems, steam boilers, refuse incineraiors, waste heat boilers, steam pipes and steam using equipment) (2, steam condensate systems (steam using equipment, condensate pipes and pumps) 03, gas turbines 04, heating systems (central heating systems, hot water heating systems, thermal oil systems) 05. cold and hot tapwater systems (drinking water sys- tems, storage boilers, transport pipes) 06. cooling water systems (once through and circulating systems) 07. cooling systems (with freon, ammonia or brine) * The cae history coding sas follows. The fst swo digits ofthe code refer the material ofthe objet attached, the second two digits tthe sisiem from which the corroded part originate, the third two digits refer to the phosomenen, end the lart two digits wo the numerical Sequence in those instances in which several shee del withthe same abject. 1988 CAE 0-0ni os. 09. 10, 1. 12, 13, 4 15. 16, water treatment and sewage treatment plants (for well water, boiler feed water and waste water) air ueatment and gas purification systems (air condi tioning units, gas scrubbers, absorption filters) extinguishing systems (tanks, sprinkler pipes, pumps) process installations (equipment for the production, storage and transport of products and chemicals; chemical cleaning systems) ‘marine installations (other than cooling systems) vacuum and compressed air systems gas supply systems electric installations (including cables) civil constructions SECOND SUB-CLASSIFICATION, BY PHENOM- 01 02 03, 4, 05. 06 on, os, ©, 10. u. 2. 2B 4 15, 16, WV. ENA ‘oxygen attack carbonic acid corrosion (by dissolved carbon dioxide, including aggressive water) alkalinity corrosion (corrosion by Iyes and alkaline waters) acid corrosion sulphide corrosion (e.g. due to sulphate-reducing bacteria) sulphidation (high temperature corrosion by sulphate) sulphur corrosion chlorine corrosion attack by salt deposition ammonia corrosion corrosion by solder chloride attack galvanic corrosion (due to couple action, to cementa- tion of more noble metal particles or to reversal of potential) deposit attack dealloying aitack (or selective leaching, eg. dezincifi- cation) graphitization stress corrosion cracking (trans- and intergranular, including caustic embrittlement)OL. Oxygen attack of carbon steel of carbon steel of carbon stee! of carbon stee! of carbon steel ‘of carbon steel of carbon steel of carbon steel of carbon steel of carbon stee! of carbon stee! of carbon steel of carbon steel of east steel consequence of 02. Carbonic acid corresion of carbon steel of carbon steel of carbon steel of carbon steel of carbon steel of galvanized steel of galvanized steel cof copper (with oxygen) of copper (with oxygen) of copper (aggressive water) of glass 03. Alkalinity corrosion of carbon steel of carbon steel of galvanized steel of aluminium of aluminium of glass-fibre reinforced vinyl ester of glass-fibre reinforced polyester of glass 04. Acid corrosion of carbon steel 35.8, of carbon steel 35.8 of carbon steel of carbon steel of carbon steel of galvanized steel of sainless steel of stainless steel of stainless steel of stainless steel 1988 CAE 0-Oxiii PHENOMENA INDEX ao.o1.o ao1.91.02 1.01.01.03 01.01.01.04 01.01.91.05 01.01.01.06 01.01.01.08 01.02.01.01 01.02.01.02 01.04.91.01 01.04.01.02 01.05.01.01 01.05.91.01 01.01.01.07 10.0401.01 01.02.02.01 01.02.02.02 01.02.02.03 01.05.02.01 01,09.02.01 0202.02.01 20792.01 06.02.02.01 06.02.02.02 06.05.02.01 1202.02.01 01.01.03.01 01.11.93.01 0211.03.01 07.04.03.01 07.09.03.01 30.11.03.01 10.11.03.02 1201.03.01 01.01.04.01 1.01.04.02 (1.01.04.03 1.11.04.01 1.11.04.02 (2.01.04.01 04.08.0401 0411.04.01 04.11.04.02 04.11.04.03 10. Te 2 of stainless steel of stainless steel of stainless steel of bronze of glass-fibre reinforced epoxy Sulphide corrosion of carbon steel of carbon steel of carbon steel of carbon steel of catbon steel of carbon steel of nickel alloy of copper of aluminium Sulphidation of low-alloyed steel of nickel alloy Sulphur corrosion of low-alloyed steel Chiorine corrosion of silver of zirconium ). Corrosion by salt deposition of aluminium of aluminium Ammonia corrosion of galvanized steel of copper of copper of copper of bronze of bronze Corrosion by solder of copper Chloride attack of galvanized steel of stainless steel of stainless steel of stainless steel of stainless steel xi 04.11.04.04 04.11.0405 04.11.04.06 0611.04.01 10.11.04.01 01.0505. 01,06.05.01 01.10.05.01 01.11.05.01 01.11.05.02 01.14.05.01 105.03.05.01 06.05.05.01 07.06.05.01 01.01.05.01 05.01.06.01 01.11.07.01 0911.08.01 09.11.08.02 0709.09.01 07.09.09.02 0216.10.01 06.04.10.01 06.05.10.01 0613.10.01 0601.10.01 06.07.10.01 (06,06.11.01 0216.12.01 04.06.12.01 04,08.12.01 04.08.12.02 (04,08.12.03of aluminium of aluminium 25, Corrosion underneath insulation, of carbon sieel of carbon steel of carbon steel of carbon sieel of stainless steel of stainless steel of copper of copper 26, Stray current corrosion of carbon steel of carbon sieel of stainless stecl of lead 27. Fatigue of carbon steel 28. Fatigue corrosion of carbon steel 29. Age embrittlement cof Bessemer stee] 30. Superheating attack Creep of carbon steel 35.8 of carbon steel 35.8 of lead of high density polyethylene Oxidation of nickel alloy Cracking cof carbon steel 35.8 31. Thermal shock, of polytetrafluaroethylene 32, Erosion and deformation of carbon steel 35.8 of carbon steel 37 of stainless steel of stainless steel of copper (deformation) of copper (deformation) of copper of bronze B. Cavitation of carbon steel of carbon steel of carbon steel of east ion 1988 CAE 0-Dav 07.07.2401 07.16.2401 01.02.2501 01.07.2501 01.11.2501 01.11.2502 04.01.2501 04.11.2501 06.05.2501 06.11.2501 01.05.2601 01.14.2601 04.11.2601 08.15.2601 111.2701 01.04.2801 01.11.29.01 01.01.3001 91.01.30.02 08.11.30.01 10.11.3001 05.03 30.01 01.01.30.03, 10.11.31.01 1.01 32.01 0111.32.01 04.01.32.01 04.11.32.01 06.01.32.01 06.02.32.01 (06.05 32.01 06.06.32.01 0101.33.02 01.02.33.01 01.02.33.02 01.01,33.01 38, 238, 4. a2. of cast iron of cast steel of stainless steel Erosion corrosion of carbon steel 35.8 of carbon steel 35.8 of carbon steel 35.8, of carbon steel of carbon steel of carbon steel of carbon steel of carhon steel of cast iron of low alloyed steel of stainless steel of copper of copper of copper ‘of copper of bronze of bronze of naval brass of aluminium brass of titanium Fretting and false brinelling of chromium steel Stress cracking in plastics of polypropylene of polypeopylene of polyvinylidene fluoride of polyvinylidene ftuoride Diffusion in plasties of polytetialuoroethylene of polytetrafluorcethylene Of glass-fibre reinforced epoxy Manufacturing errors in plastic linings of perfiuoroatkoxy of uorided ethylene~propene Degradation of plasties of ethyiene-propylene dimer rubber Coating failures of baked coating of phenol formaldehyde resin of baked coating of phenol formadelhyde resin Carbonation of concrete of reinforced concrete Frost damage to conerete of reinforced concrete ww 01.02.3303 01.04.3301 0411.33.01 01.01.3401 o1.01.3402 01.01.3403 01.02.2401 01.02.3402 01.06.3401 01.11.2401 01.11.3403 01.06.3402 01.11.3402 04.09.34.01 06.02.34 01 06.05.3401 06.05.3402 06.05.34.03 06.01.3401 06.10.3401 06.06.3401 06.11.3401 09.11.3401 04.11.3501 10.09.3601 10.11.36.03 10.11.3601 10.11.3602 10.0237.01 10.11.3701 10.02.37.02 10.11.3801 10.11.38.02 10.11.39.01 0301.40.01 0305.40.01 11.16.41.01 11.16.42.01a INTRODUCTION GENERAL ASPECTS OF CORROSION, CORRO- SION CONTROL AND CORROSION PREVENTION 1. Definition of corrosion ‘The generally accepted definition of corrosion reads as follows: Corrosion is the undesired attack of a material as a result of Chemica! or electrochemical reactions with components from the environment Attack, decay or becoming unserviceable hy physical, mechanical or biological causes are therefore excluded. Examples of such phenomena are supecheating, wear, erosion, cavitation, swelling of plastics. decay of wood, cete. On the other hand, corrosion is considered as includ- ing combined forms of attack in which the simultaneous ‘occurrence of corresion by chemical or electrochemical attack and the effect of the other above-mentioned causes, leads to an item becoming uaserviceable at an above-nor- ‘mal rate. Examples of these phenomena are stress corro- sion, erosion corrosion and fatigue corresion. The definition distinguishes between chemical and electrochemical reactions, for corrosion can be subdi- vided into electrochemical corresion and chemical corro- sion. Electrochemical corrosion is the more common. By electrochemical corrosion is meant corrosion resulting from reaction between a metal surfecs and an ion-con- ducting environment. Such corrosion can occur if the metal comes into contact with a liquid in which an electrolyte (a substance which, when dissolved in water oF another solvent, is separated into ions) is dissolved oF with a melted electrolyte (for example, salts or oxides). Most cases of electrochemical corrosion occur in aqueous environments such as mains water, boiler water, cooling, water, sea water, ele, solutions of salts, acids and bases, a humid atmosphere and a wet scil. Melted salts and onganic solutions of electrolytes are used to a far lesser extent, and therefore occur far less frequently as environ- ment in which electrochemical corrosion can occur, By chemical corrosion is meant corrosion resulting from reactions between @ metal surface and gases (gese- ous elements or gaseous compounds). Because this form of corrosion usually occurs at temperatures substantially, higher than ambient temperature it is also referred 10 as high-temperature corrosion. An example of this is sulphidation, 2. The consequences of corrosion ‘The consequences of corrosion are both technical and economic in nature. Corrosion shortens the life of pro- duction facilities and transport systems by causing their premature collapse, sometimes accompanied by acci- 1988 CAE 0-A001 dents. Repairs required to remedy leakages and blockages push up the cost of maintenance. Malfunctions in pro- duction facilities resulting from corrosion give rise to loss of output. Contamination of products by metal oxides and contamination of the environment can also occur as 4 result of corrosion, Of the world’s iron production, 10%, 4s lost annually by rust formation alone. The total direct, and indirect costs associated with corrosion amount to some 4% of gross national product, which means about 3500 per year per head of the population in the industrialized countries, Of this loss, approximately one quarter can potentially be saved by taking appropriate corrosion prevention measures in good time. 3. The theory of electrochemical corrosion In the electrochemical corrosion process, there are always at least two reactions invelved, namely an anodic or oxidation reaction, during which a metal dissolves while releasing electrons, for example: Fes Fe" +2e and a cathodic or reduction reaction, in which the elec trons formed are removed, for example: in acidic solution: 2H’ +2e> Hy in neutral aerated solution: 0, +2H,0 + 4e > 40H- Whether 2 metal will corrode, however, depends on ‘two factors, namely: (9 the level of the equilibrium potential of the cathodic and anodic reactions in relation to one another, in which case that of the anodic reaction should always be lower than that of the cathodic reaction; ithe speed of the corrosion reaction (that is, the summed reactions at the anode and cathode), which in turn depends on various factors, such as nature of| the reactions taking place, the concentration and supply of the reacting substances, and the form of the corresioa products, In addition to the occurrence of oxidation and reduction reactions, other factors also play a role, such as tempera- ture, the velocity of cletrolyte movement and the resis~ tance of the electrolyte. In the laboratory, the corrosion potential and the speed of the corrosion reaction can be accurately de- termined for any metal in any environment, by measur- ing polarisation curves with a potentiostat.sSkiomal_analysi for idenieaton‘Sysiematies for diagnosing the causes of corrasion (A) Gather data on the corroded part (the system) (@) type of construction (description, drawing, sketch) and purpose; (©) composition of material (type code of metal or alloy), (©) any pretreatment and/or surface treatment (coatings); (@) contact with other metals, (B) Gather data on the corroded surface by means of inspection (@) appearance (pitting, uniform, cracking, flow pat- tem, depth, ete) to be recorded by visual report, photographs, drawings, etc; (©) corrosion produets present on the surface (chem- ical analysis) (©) other deposits present on the surface, originating {rom elsewhere or from the environment (chem ical analysis) (@) appearance of coating (intact, pitting. blistering, exfoliation, under-rusting, et.) (©) Recording the operating conditions (@) nature of the environment (gas, liquid, solid or mixture), (b) composition of environment (chemical analysis, agaressiveness in relation to the present material, contaminations), constant or variable (average, ‘minimum /maximum); (©) physical data (temperature, pressure, flow veloc- iy), (@) mechanical aspects: load (static/dynamie, mag- nitude, tensile/pressure, frequency of load fluctuations); (©) operation (continuous, intermittent, standard/ nonstandard conditions, repairs, maintenance, inspections) (D) Supplementary data (@) age, time 10 failure of the corroded part; (b) damage occurred before, measures taken (which checks (© is the corrosion specific or more general in the plant or the system: (@) what checks on surface treatment (coatings)? (E) Additional examination (a) material: identification by chemical analysis and ‘mechanical testing, non-destructive testi (b) corrosion appearance: simple microscopic exam- ination, with application of replica technique if necessary; (©) cause of corrosion: metallographic examination, scanning electron microscopy, X-ray diffraction, etc. (@) corrosion measurements on-site and/or long- term tests and electrochemical analysis in the laboratory; (©) literature research, (F) Reporting (@) analysis of the results and statement of the diag- 1988 CAE 0-A005 (b) conclusions and recommendations for short-term and long-term measures (10 be drawn up in consultation with the user, and taking into account the scale of the damage), 6 Corrosion control For control of the corrosion, a selection may be made from among the following measures: (@ Choice of a different material. Application of another more corrosion-resistant material. However, the choice of material is determined not only by the corro- sion resistance but also by the mechanical properties and, ‘economic considerations. (i) Design modifications. By adapting the design, treatment and construction, the part of the system can be rendered less vulnerable to corrosion. (ii) Application of coatings. In this way material can be separated from the environment (metallic, inorganic non-metallic or organic coatings to be applied after proper pre-treatment). iv) Change of environment, for example ‘© removal of oxygen and/or raising the pH © dosing of inhibitors in combination with proper checks: change /control of temperature, flow velocity, stray currents. (¥) Intervention in the reactions, in particular with electrochemical methods such as cathodic protection (with sacrificial anodes or with inert anodes with impressed current) and anodic protection (for example to stainless steel). (vi) Changing the procedures. Introduction or modifi- cation of procedures for start-up, shut-down, operation and stoppage; recommendations concerning inspection. corrosion monitoring, maintenance. 7. Corrosion prevention ‘The analysis and diagnosis of damage as discussed in Section 5 is required in the case of corrosion occurring in.ar GLOSSARY OF TERMS USED IN THIS WORK | Alkalinity reduction Anaerabie Anode Anodic protection Autemperator Boiler feed water Carbonation of concrete Carbonic acid Carburization Cathode Cathodie protection 1988 CAE 0-A007 (part) removal of the carbo- ate and bicarbonate alkslinity from water, mosily by ion ex- changers. free of air or uncombined oxy: zen, an electrode at which oxidation of the anode surface (metal ions centering the solution) er some component of the solution is occurring, a technique to reduce corrosion of metal surface under some conditions by passing sufficient anodic current to it 10 cause its electrode potential to enter and remain in the passive region (this technique needs very little current flow but it leads to in- tensified corrosion in case of power breakdown), a heat exchanger in which the superheated steam is cooled by boiler water at the outside. mixture of steam condensate and make-up water. the attack of concrete by carbon dioxide. The calcium hydroxide is transformed to calcium bi- carbonate that is flushed by water, corrosion by water that has be- come aggressive by dissolved carbon dioxide (CO, + HO +2H*). It the absorption of carbon into a metal surface. the electrode of an electrolytic cell at which reduction occurs (eg. cations taking up electrons and being discharged, oxygen being reduced). a technique to reduce corrosion of a metal surface by passing sufficient (impzessed) cathodic current 10 it, of by attachment to a sacrificial anode (usually Caustic embrittlement Cavitation Cementation Creep Crevice corrosion Deaerator Dealkalization Dealloying Decarburization Mg, Al or Zn), to cause its anodic dissolution rate to be: come negligible. that form of stress corrosion | cracking occurring in steel ex posed t0 alkaline solitons damage of a material associated | with collapse of cavities (or vapour bubbles) in the liquid at 2 solid-liguid interface, in the high pressure regions of an unit. Dinegebangwonea eon | let side of pumps or across con- trol values of orifice plates. Minimum intemal pressure hin the unit must lays be | ‘greater than the “bubble point” Of the liguid to avoid this type of attack the continuous plastic eloaga- tion of a metal under an ap- plied stress. localized corrosion resulting from the formation of a dif- ferential acration cell in a ere vice, formed between 2 metal and a non-metal, or between ‘oxo metal surfaces, | a mosily horizontal tank in Which the boiler feed water is liberated from dissolved oxygen | (and other gases) by intensive | contact with fresh steam, ac- cording the laws of Henry and Raoult. see Allalnity reduction | the selective corrosion (e- moval) of a moalis constituent from an alloy, usually in the | form of ions (3. dezincific | tion; also known a8 parting or selective leaching the withdrawal of carbon from sul oatiiea (ommucs ot | methane by hot hydrogen at- tack).planation in Background Infor. pH and pH, (see Langelerin- mation on the Interphako” dex): Ri pH,-pH, and is Technique, pp. All-A12). interpreted as follows: Kafe ine ack a form of weld decay some: Bee alte (KLA) times observed on stabilized 50 ne r stainless steel the zone attack St ee Sayer marony em very sng 50-60 slight scaling ten- dency Langelier_ index the Langelier index (Li) or 60-65. in balance, pitting saturation inden is a theoretical posible derived quantity for the judge 65-75 slightly corrosive ment. of corrorive or sling 73-910. strongly corrosive aualiies of water. The index is 90 very strony or deduced from the real pH, and ronive tho calculated saturation pH, PH, of the water: Licph” Season cracking aterm usually applied to stress ae a Rear ee Ta, Sorrsion cracking of brass, lows Stainless steel all stets with a chromium con- Li Tendency of the tent of at least 12%. seater Strey current corrosion that is caused by stray 0 song sang eo A corrosion currents from some external souree. The metal is attacked at +05 ling tend- ° ssigpe seallagiien the spot where the current ‘ency, not corrosive 0.0 in balance, pitting eaves: possible Stress corrosion premature cracking of metals - 0S slightly corrosive, cracking (SCC) produced by the combined ac- not scaling, tion of corrosion and surface <—20 strongly corrosive tensive stress (residual or ap- Liquid metal embrittlement of metal epee (ettess acon cuon ste embrittlement caused by penetration of other specific 10 particular metals in particular solutions. Carboa molten metals. steels in hot alkali solutions, Magnetite Fe,O,, black iron oxide which austenitic steels in hot chloride is formed in water or steam in solutions and copper based al- tho case of deficiency of oxygen, Joys in solutions containing I is magnetically attractable ammonia can be suscepiible Nividing the absorption of nitrogen Sulphate-reducing these. bacteria, of which the atoms by a metal; it may re bacteria genus Desulphovibrio is the main dissolved, oF form metal most commonly occurring, re- nitrides duce sulphates to sulphides in Oxygen scavenger a. chemical substance which numb comdilous (€5-ln not aerated well water or under de- posits in aerated water). The sulphide attacks stee] and other metals. The presence of hydro- ‘gen or organic matter stimu lates this corrosion. liberates the boiler feed water from oxygen by means of a chemical reaction. An oxygen scavenger is used instead of or in addition to a deacrator, p-alkaliity the acid consumption in meq/I on tivation of alkaline (boiler) Transeramular cracking transverse the grains water up to pH 8.2 cracking Ryzner index The Ryznar index (Ri) or sta. Weld decay @ term applied to areas adjac: ent to welds of certain alloys which have been subjected to intergranular corrosion because ‘of metallurgical changes in the alloy (commonly applied to certain grades of stainless steel) bility index is an empirically derived quantity for the judge- ‘ment of corrosive or scaling qu- alitics of the water. This index an also be caleulated from the 1988 CAE 0-A008an BACKGROUND INFORMATION ON THE INTERPHAKO® TECHNIQUE When metal surfaces are examined with a light micro- seope, both amplitude and phase objects are observed. In the former case, the wave amplitude of the reflected light hhay changed. We observe differences 0f intensity, In the latter ease, & phase shift occurs between the light waves themselves. This phase shift cannot be observed with an ordinary light microscope. Phase objects can be differen- tiated into two groups, namely geometrical and physical phase objects. Figure 1 shows the optical principle of an amplitude and the éwo types of phase objects. Geometri- cal phase objects cause phase shifis because of height dilferences, but their optical behaviour is identical to that of their environment. Physical phase objects exhibit a deviant behaviour in relation to their environment; there sre no light path differences caused by height differences. ‘When light is reflected from an optically denser medium, that is to say # medium which has a higher refraction index and dielectric constant, this light undergoes a phase rotation. For non-conductors, such as glass, this rotation is 180°. For conductors, such as metals and their inter- metallic compounds, the zotatin is always smaller than 180°. Figure 2 shows a table illustrating in graph form the “calculated” phase rotation for a number of metals and non-metals under incident light at a wavelength of 589 nm. In order to be able to see phase objects on microscopic slides using the light microscope, for metallographical purposes use is made of a phase contrast attachment on an interference microscope. Phase contrast is employed relatively seldom as coatrasting method. However, for the study of very small phase objects (<8 um) this technique is more suitable than the more commoa inter- ference-contrast technique. The halo effect which occurs MOIRA WooO© i» Fig 1. Schematic reprecentation of the epical principe of amplitude and phase objects in nsigent light. Key: IW=incdent wave, RW= reflesive wave, M-mmatis, A—amplitde object, Ph, ~ ssomstic pase object, Ph}, = physical pane odjec. 1988 CAE 0-A011 in phase contrast tends to enhance the contrast. Interference contrast, usually known as differential interference contrast (DIC), is normally achieved by means of light-polarizing elemenis — for example, Wollaston prisms. Accordingly, in this Atlas we have invariably worked with polarized light, which is not al- ways desirable for the investigation of corresion prod- ucts. This technigue is at the expense of the aperture of the objective. In goneral, a light microscope is suitable for either phase contrast or interference contrast. Ia phase contrast, the constraint will generally lie in the character of the ring-shaped obstruction (positive or negative con- trasi). In order to obtain both quantitative polarization microscopy together with phase contrast, dark ground climination and interference microscopy, a number of tmicroprints for this Atlas were made with the sid of a sivall Mach-Zehnder interferometer according to Beyer and Schéppe of Carl Zeiss Jena/Jenoptik, Jena. This system makes it possible to work with transmitted and reflecied light and with positive and negative phase con- trast, “central” dark ground elimination, the interference shearing method with DIC, total image splitting with interference fringe and also with Interphako". For the latter, 2 phase contrast attachment is used together with the interferometer. In most cases this allows unetched objects nevertheless t9 obtain a good contrast. Geometti- cal phase objects with a height difference of approx. 2 nm ‘and phase shifts of approx. \/400 are still visually ob- servable. With this microscope, phase objects are con- verted into amplitude objects" which can be seen and Ineasured because of theit intensity differences and col- cour differences. ee eh 2 Saifisziisi 3 wl fEs23882528 me wo i ve") +r [ ‘nor i } |] Fig 2, Caoulaton of phase rotation under reflection by various metas ‘and ror-metals under perpendicalar incident light and 2 wavelength of 589 am, calculated according 19 the optical constants for compact material given in feference tbs.Case History 01.01.1701 01.01.1802 01.04.22.01 01.04.2801 ouinaso1 01.11.2004 oan14o1 401.1901 401.2501 04.11.1203 Magni- fication 100 x10 100 500 x50 x50 100 x25 x25 x25 ORMATION ABOUT THE MICROPRINTS Etching Agent 35 see. nital 5% Colour etching according 10 Beraha Colour etching according to Beraha 2% nital None None None None None None Contrasting Technique Interphako® Interphako" Tnterphako® Interphako* Interphako* Interphako" Interphako" Interphako" Case History 0411.18.05 0411.19.01 0411.21.01 0511.18.01 06,03.16.01 06,05.16.02 06.06.16.02 06,06.18.01 07.09.19.01 Megni Jication x25 x50) xs0 25 x25 x50 x25 100 x25 Exching Agent None None Colour etching according to Beraha Unknown None Colour etching, according to Beraha None None Noae Contrasting Technique Interphako®™ Interphako® Interphako” Interphako* nterphako” Interphako™ INFORMATION ABOUT MAGNIFICATIONS OF SOME MACROPRINTS Case History 01.05.01.01 06.02,34.01 1988 CAE 0-A013 Magnification x25 x25 Case History (06.06.11.01 06.06.18.02 Magnification x25 x25 a3CASE HISTORY CORROSION ATLAS 01.01.1802 MATERIAL Carbon steel (35.8). SYSTEM, Steam system (low pressure). PART Steam pipe section, PHENOMENON Intergranular stress corrosion (caustic embrittlement). APPEARANCE Crack at weld, TIMETO FAILURE Unknown, ENVIRONMENT Low-pressure steam (3.5 bar). CAUSE Because of a leak in the production process, SO% caustic soda entered the low-pressure steam system via the injection condensate for desuperheating. Under these circumstances, normally harmless tensile stresses neat welds led to caustic embrittlement. REMEDY + Improvement of the quality control of the condensate by means of conductivity monitoring; or + Injection of demineralized water. 1988 CAE 0-BO16CORROSION ATLAS CASE HISTORY 01.11.18.01 MATERIAL, Carbon steel, Caustic soda transport system, Pipe section, PHENOMENON Stress corrosion (caustic embrittlement). APPEARANCE Cracking at suspension point. TIME TO FAILURE 304 years ENVIRONMENT 31% NaOH: temperauure 50°C. CAUSE Combination of stresses at the suspension point coupled with the high alkalinity REMEDY Replacement of the pipe by a new pipe with support at several points in order to reduce the stresses. 1988 CAE 0-BO71CASE HISTORY CORROSION ATLAS 01.01.01.01 MATERIAL Carbon steel, SYSTEM Boiler feed system. PART Feed line from deaerator to boiler, PHENOMENON Oxygen attack, APPEARANCE Pituing with brown nodules. TIME TO FAILURE About 2 years. ENVIRONMENT Deacrated feedwater is @ mixture of steam condensate and dealkalized and softened make-up water; pH 5, chloride (CI”) 10 p.p.m; temperature 105°C. CAUSE Excessive oxygen in the feedwater owing to malfunctioning deaerator. REMEDY Improve deaerator operation: identify the cause of the malfunctioning by internal inspection to examine atomizers and stcam injection nozzles, and by meesurement of the residual oxygen content under various loads. Improve the boiler feedwater ‘composition. keeping it alkaline. 1988 CAE 0-B001 CASE HISTORY CORROSION ATLAS 01.01.01.02 MATERIAL Carbon steel (35.8).CASE HISTORY CORROSION ATLAS 01.01.01.03 MATERIAL Carbon stool. SYSTEM High pressure boiler. PART Economizer pipe. PHENOMENON Oxygen attack, APPEARANCE Longitudinal crack TIMETOFAILURE Unknown, ; ENVIRONMENT Beier feadwater in the pipe; flue gases around the pipe. | z= CAUSE The application of periodical shot-peeing, o clean the fue gas side of the economizer, led 10 regular disturbance of the magnetite layer. The damaged spot is sensitive to further attack by traces of oxygen in the boiler feedwater, REMEDY + Regular inspection of the setting of the distributor pivot in the shot-peening unit + Alternative: change to ultrasonic cleaning. 1988 CAE 0-B003CASE HISTORY CORROSION ATLAS 01.01.01.04 MATERIAL Carbon steel (35.8). SYSTEM Boller (12 bar. shell type boilen. PART ‘Smoke tube (before and after cleaning), PHENOMENON Oxygen attack. APPEARANCE Pitting covered with blisters; pits about 2 mm in depth. TIME TO FAILURE 13 years, j ENVIRONMENT Poorly conditioned boiler water. CAUSE Failure to use oxygen scavengers during the first § years’ operation (no deacrator present). REMEDY Desing of an oxygen scavenger (tubes replaced). 1988 CAE 0-B004CORROSION ATLAS CASE HISTORY 01.01.01.05 MATERIAL, Carbon steel (35.8). SYSTEM Boiler (shell type boiler, 19 bar). PART ‘Smoke tubes. PHENOMENON ‘Oxygen aitack, APPEARANCE Pitting attack underneath corrosion nodules at the bottom of the smoke tubes. TIME TO FAILURE Approx. 10 years, ENVIRONMENT Boller water; p alkalinity 12-20 meg/\ (600-1000 ppm. CaCO,); chloride (CI”) 130-220 p.p.m phosphate (PO}- ) 50-70 p.p.m iton (Fe**) 15-50 p.p.m.!! CAUSE Malfunctioning deaerator: as the deserator was being charged, the pressure fell below 1.25 bar and the temperature below 103°C because of excessive over-capacity of the ‘make-up water pump. As a result of the leak, blockage with boiler water salts had ‘occurred elsewhere in the smoke tubes. REMEDY ‘The make-up water pump should be throttled in such a way that the volume of feed water is in accordance with the capacity of the steam pressure regulator in the steam supply line. 1988 CAF 0-B005CASE HISTORY CORROSION ATLAS 01.01.01.06 MATERIAL Carbon steel (358). SYSTEM Boiler (water tube boiler; 85 bar, 515°C). PART Downcomer tube from drum, PHENOMENON Oxygen attack, APPEARANCE ‘Small pits in the upper part of the downcomer tubes below the drum. TIMETOFAILURE 11 years ENVIRONMENT Conditioned boiler water. CAUSE Poor conditioning owing to insufficient excess of hydrazine during shutdown periods, REMEDY + Maintaining a higher excess of hydrazine (at least 100 p.p.m.) in the boiler water during the shutdown periods. with periodical checks on the excess + Alternative to hydrazine: a modem non-toxic organic oxygen scavenger, for example erythorbiec acid (D-isoascorbic acid) or hydroquinone. 1988 CAE 0-BC06CASE HISTORY CORROSION ATLAS ae MATERIAL cance ig a ae SYSTEM. ‘Steam system (7 bar). 1988 CAE 0-B007CASE HISTORY CORROSION ATLAS 01.01.01.08 MATERIAL Carbon steel. SYSTEM Boiler (gas turbine waste heat boiler, 41 ban). PART. Pipe from condensate preheater installed in stack to recover heat from the flue gases. PHENOMENON Oxygen attack. APPEARANCE Pitting, TIMETOFAILURE About 3 years. ENVIRONMENT. Steam condensate low in oxygen and carbonic acid (boiler feed with complerely desalted and deaerated water); temperature from 60°C rising to 141°C. CAUSE Incorrect positioning of the control valve, aamely in the condensate feed line, allowed vacuum 10 form in the preheater when the valve was closed. The resultant inhaled air caused oxygen pitting. REMEDY Relocation of the control valve in the discharge line prevented the formation of 1988 CAE 0-B008CASE HISTORY CORROSION ATLAS 01.01.03.01 MATERIAL, Carbon steel SYSTEM ‘Vertical waste heat boiler of a catalytie cracker. PART Quench cooker pipe section, PHENOMENON Attack due to high alkalinity quan i me ey 48-47 48 49 50 51 32 33 Bh ‘ss 30 7 APPEARANCE Uniform attack with cracking TIME TO FAILURE ENVIRONMENT Alkaline boiler water around the pipes. Cracked gases, 400-900°C, through the pipes. CAUSE As a result of defects in the water treatment, deposits had formed on the pipe plate, under which the boiler water concentrated strongly, leading to high lecal caustic concentrations REMEDY Impcovement of the boiler water treatment and its testing, 1988 CAE 0-R009CASE HISTORY CORROSION ATLAS 01.01.04.01 MATERIAL Carbon steel (35.8). SYSTEM Boiler (12 bar, shell type boiler) PART ‘Smoke tube PHENOMENON Acid corrosion, APPEARANCE Grooved attack over the entire surface. TIMETO FAILURE —_Cortosion took place in 3 hours. ENVIRONMENT Cleaning acid (inhibited hydrochlonc acid 9.5%, 95°C), Chemical cleaning was nevessary following deposition of iron oxide and hardness sediments. CAUSE ‘The uncontrolled performance of a chemical cleaning weatment to the boiler, with failure to notice inhibitor breakdowa. Combined with an excessive pipe wall temperature, this resulted in 400 kg of steel being dissolved on a heated surface of 100 REMEDY ‘The smoke tubes were replaced at the cleaning firm's expense. L 1988 CAE 0-B010CASE HISTORY CORROSION ATLAS 01.01.04.02 MATERIAL Carbon steel (35.8). SYSTEM, High pressure boiler, fired with heavy oil PART Fumace evaporator tube. PHENOMENON Acid corrosion. APPEARANCE TIMETOFAILURE Unknown, ENVIRONMENT Deposits with acidic sulphur components at the flue gas side, CAUSE During shutdown, the sulphur compounds reacted with water to form sulphuric acid, which attacked the steel REMEDY + After taking the boiler out of service, clean it on the flue gas side with, for example, limed water or ammonia to neutralize the sulphur oxide. + Alternative: change to firing with low sulphur oil or natural gas. BIBLIOTECA ‘COOPERATIVE DE PRODWTOSES DE CARA AGUCAR E_ALCOOL DO 1988 CAE 0-B011 COPERSUPARCASE HISTORY CORROSION ATLAS 01.01.04.03 MATERIAL Unalloyed steel. SYSTEM Refuse incinerator. PART ERW (clectric resistance welded) furnace tube. ‘Acid corrosion PHENOMENON APPEARANCE Severe attack to the longitudinal seam weld, TIME TO FAILURE Unknown, ENVIRONMENT Flue gases contaminated with HCI originating from the combustion of plastics (PVC ee), CAUSE As a result of a difference in structure between the weld and the hase material, partly caused by welding at low frequency, the weld seam is selectively attacked by the HCI (at temperatures below the dew point) REMEDY Use a seamless tube. Higher frequency welding. + Application of post weld heat treatment (PWHT) for normalizing the welds. 1988 CAE 0-BO12CASE HISTORY, CORROSION ATLAS 01.01.0601 MATERIAL Steel (13 CrMo 9 10). SYSTEM Boiler (water tube boiler, 61 bar, 430°C. oil-fired), PART Superheating tube, PHENOMENON Sulphidation APPEARANCE Extemal uniform attack leading to cracking by superheating. TIME TO FAILURE, 5 years ENVIRONMENT. Deposit containing over 70% sodium sulphate and 4% vanadium oxide. The presence of oxides of heavy metals (V, W, Nb) catalyses the oxidation at high temperature. Heavy oil contains sulphur, vanadium and sodium. At wall temperatures above 600°C vanadium oxide and sodium sulphate melts occur on the supetheater tubes, leading to corrosion of the steel REMEDY Initially, dosing of various oi! additives proved ineffective; subsequently, for other reasons @s well, switched to firing sulphur-free natural gas; the entire superheater was replaced 1988 CAE 0-BOL3CASE HISTORY CORROSION ATLAS 01.01.17.01 MATERIAL, CANi cast iron, | SYSTEM. Boiler feedwater system, PART Boiler feed pump impeller. PHENOMENON Graphitization, APPEARANCE Soft granular surface which gives off black powder; material receded about 1 nim. TIMETOFAILURE 14 years (6000 operating hours) ENVIRONMENT Deaerated boiler feedwater consisting of demineralized water and condensate, which | | 2 mixture of di- and tri-sodium phosphate was added to alkalize the boiler water. pH 76-85; 0, 835, since no patina layer is formed. Moreover, the galvanization method applied yielded a zinc coating of only 20-25 pm, without formation of iron—zine alloy. This coating is therefore extremely sensitive to attack. Softened water in itcelf is also aggressive to zine. REMEDY + Construction of the system in stainless steel or hot-dip galvanized steel (zine coating approx. 100 um), + In the latier case use of less aggressive cleaning chemicals and of non-softencd cleaning water, + Or de-rusting and re-painting the system periodically 1988 CAE 048099CASE HISTORY, CORROSION ATLAS 02.16.10.01 MATERIAL Hot-dip galvanized steel. SYSTEM Cattle shed. PART Rear support of partition wall between the cows. PHENOMENON Ammonia corrosion. i APPEARANCE Irregular pitting. TIMETOFAILURE 1} years. | ENVIRONMENT Cow manure, | CAUSE ‘The defective construction (plastic sleeve was applied too low) and failure to remove the manure regularly, allowed the zinc coating 10 be dissolved by ammonia and corrosive substances from the manure, after which the steel was attacked and rusted through, REMEDY Installation of new partitions, making sure that the protective plastic sleeve reaches the proper height (approx. 10 em above the beam). 1988 CAE 0-B100CASE HISTORY CORROSION ATLAS 02.16.1201 MATERIAL Hot-dip galvanized stee! SYSTEM Gate on rollers. PART ‘Tubular railings. PHENOMENON Chloride attack. APPEARANCE, Pitting (typical of chloride corrosion). TIMETOFAILURE 2! years. ENVIRONMENT Atmosphere. CAUSE During the galvanizing process, flux (zinc ammonium chloride) and tine oxide remained on certain railings, substances which when wet are corrosive to stec. REMEDY Replacement of the corroded sailings and re-galvanization of the entire gate. 1988 CAE O-BIOL