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INDUSTRIAL CORROSION AND CORROSION CONTROL TECHNOLOGY

H.M. Shalaby A. Al-Hashem M. Lowther J. Al-Besharah (Editors)

Published By Kuwait Institute for Scientific Research

INDUSTRIAL CORROSION AND CORROSION CONTROL TECHNOLOGY 1996

Sponsored by the Kuwait Institute for Scientific Research (KISR), the Kuwait Foundation for the Advancement of Science (KFAS), the Kuwait National Petroleum Company (KNPC), the Kuwait Oil Company (KOC), Ministry of Electricity and Water (MEW), Kuwait University (KU), Ministry of Oil (MO), the Gulf Cooperation Council-General Secretariat (GCC), Kuwait Chemical Society (KCS), Organization of Arab Petroleum Exporting Countries (OAPEC), and Petrochemical Industries Company (PIC).

INDUSTRIAL CORROSION AND CORROSION CONTROL TECHNOLOY


Proceedings of the 2nd Arabian Corrosion Conference Kuwait, October 12-15, 1996

Editors H.M. Shalaby, A. Al-Hashem, M. Lowther and J. Al-Besharah

PUBLISHED BY KUWAIT INSTITUTE FOR SCIENTIFIC RESEARCH P.O. BOX 24885, 13109 SAFAT, KUWAIT

Published by Kuwait Institute for Scientific Research P.O. Box 24885, 13109 Safat, Kuwait Publication Number: KISR 4890

Copyright 1996 by Kuwait Institute for Scientific Research The papers were reviewed for their technical contents. Editing was restricted to matters of format, general organization and retyping. The editors assume no responsibility for the accuracy, completeness or usefulness of the information disclosed in this book. Unauthorized use might infringe on privately owned patents of publication right. Please contact the individual authors for permission to reprint or otherwise use information from their papers This book was printed in Kuwait The 2nd Arabian Corrosion Conference

FOREWORD
The 2nd Arabian Corrosion Conference was held in the state of Kuwait during the period 1215 October, 1996 under the auspices of H.H. Sheikh Saad Al-Abdullah Al-Salem Al-Sabah, Kuwaits Crown Prince and Prime Minister. The present conference was scheduled to be held in Kuwait during 27-30 April, 1991, however, it was postponed due to the events that encompassed Kuwait and the Gulf region in 1990-1991. The 1st Arabian Corrosion Conference was held in Kuwait during 4-8 February, 1984. It was attended by over 300 scientists and engineers, representing 26 countries. The conference proceedings were published in two volumes by Pergamon Press under the title Corrosion: Industrial Problems, Treatment and Control Techniques. The conference provided a forum for the exchange of ideas between scientists and engineers from the region with their counterparts from the industrialized countries. The patronage of the present conference, the organizing bodies, and the emphasis on industrial corrosion and corrosion prevention reflect the keen interest of the countries in the region in actively combating corrosion problems. This also reflect the recognition of the economic impact resulting from the corrosion of materials. Kuwait and the other Arab countries rely heavily on the utilization of metallic materials in their oil-based industries. Seawater derived from the Arabian Gulf is used in water desalination and as an industrial cooling media. The salinity of the Arabian Gulf seawater is very high when compared to other seawater bodies. The Arabian Gulf countries are located in an arid environmental zone where the temperature during the summer months could reach 50oC and the humidity during the autumn season could become 80% in some of the Gulf states. All these factors contribute to the enhancement of the rate of corrosion of metals and/or cause unpredictable service failures. The program of the present conference includes a field visit to one of Kuwaits modern refineries and a trip to one of Kuwaits oil fields. The success of the conference is perhaps difficult to assess. However, the quality of the papers in this volume provides some indication.

The Editors

PREFACE
The technical program of the present conference includes five plenary lectures and fifty three scientific presentations from about twenty two countries. A number of honorary speakers, carefully selected from high ranking officials and policy makers, were also invited to address the conference. The honorary speakers are expected to provide an overview of the magnitude of corrosion related problems in the Middle East as well as the avenues of linkage between corrosion science and industrial applications. The conference papers were carefully selected to include a blend of fundamental and applied research, and industrial experience. Such a blend was thought to be essential for providing the participants from both industry and academia with a chance to become familiar with the challenges facing each group and the preventive actions to meet them. The papers were refereed in terms of scientific and technical content and format in accordance with internationally accepted standards. The papers in the proceedings are grouped in the following sections for quick reference:

Plenary Lectures Oil Field Corrosion Corrosion in Refinery and Petrochemical Industries Seawater Corrosion Corrosion in the Building Industry Fundamental Aspects Corrosion Protection and Monitoring Corrosion Management Novel Techniques

The plenary papers are mostly reviews covering important topic related to the objectives of the conference. The remaining papers cover various topics of major importance to corrosion in general and particularly to the oil-based and desalination industries. A good number of papers delt with corrosion protection and new techniques for corrosion monitoring. The task of editing this volume was facilitated by the efforts of the International Advisory Committee and the Scientific Committee for the conference who reviewed all the papers. The editorial board gratefully acknowledge these efforts; the cooperation, time and effort of all authors ; and the management of the Kuwait Institute for Scientific Research for allocating the required resources to prepare the manuscript of this volume.

The Editors

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TABLE OF CONTENTS
Foreword............................................................................................................................................v Preface...............................................................................................................................................vi Organizing Committees......................................................................................................................xi Acknowledgement.............................................................................................................................xii PLENARY LECTURES Corrosion Management V. Ashworth........................................................................................................................................1 The Deterministic Prediction of Damage D.D. Macdonald...............................................................................................................................17 Relevance of Laboratory Corrosion Tests in Corrosivity Assessment and Materials Selection: Case Studies R.D. Kane.........................................................................................................................................37 Corrosion of Condensers in Multi Stage Flash Evaporation Distillers A.M. Shams El Din...........................................................................................................................49 Correct Materials Selection for Desalination -The Key To Plant Reliability J.W. Oldfield....................................................................................................................................67 OIL FIELD CORROSION Corrosivity Prediction for Co2/H2s Production Environments S. Srinivasan and R.D. Kane.............................................................................................................89 Testing of Drilling Fluids Formulated From Tabuk Formation Clays M.N.J. Al-Awad, A.S. Dahab and M.E. El-Dahshan........................................................................111 Preventing Sulfate Scale Deposition in Oil Production Facilities C.J. Hinrichsen, M.J. McKinzie, S. He, J. Oddo, A.J. Gerbino, A.T. Kan, and M.B. Tomson...........127 Concerns Over the Selection of Biocides for Oil Fields and Power Plants: A Laboratory Corrosion Assessment J. Alhajji and M. Valliappan...........................................................................................................135 Evaluation of Microbially Influenced Corrosion Risks and Control Strategies in Seawater and Produced Water Injection Systems, Kuwait P.F. Sanders, M. Salman and K. Al-Muhanna.................................................................................149 Hydrogen Degradation of Steel - Diffusion and Deterioration M. Farzam...................................................................................................................................................165 Control Strategies for Thermophilic Sulphate-Reducing Bacteria P.F. Sanders, H.M. Lappin-Scott and C.J. Bass...............................................................................179 Corrosion Evaluation of Austenitic and Duplex Stainless Steels in Simulated Hydrogen Sulphide Containing Petrochemical Environments K. Saarinen and E. Hamalainen......................................................................................................191

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Damage of Pump Linkages and Tool Joints Caused by Crack Corrosion A. Kinzel.........................................................................................................................................201 Analysis of Soils Possibility to Give Rise to Pipe Metal Stress Corrosion Cracking V.G. Antonov and S.A. Loubenski....................................................................................................209 A Mysterious Downhole Corrosion Failure in an Oil Well A. Husain and A. Hasan..................................................................................................................215 CORROSION IN REFINERY AND PETROCHEMICAL INDUSTRIES Methodologies for Assessment of Crude Oil Corrosivity in Petroleum Refining S. Tebbal and R.D. Kane.................................................................................................................225 New Nickel Alloys Solve Corrosion Problems of Various Industries D.C. Agarwal and W.R. Herda....................................................................................................................233 Macro-Micro Segregation Bands (MMB) as a Main Factor Influencing Steel Applicability for the Petroleum Industry A. Mazur.........................................................................................................................................245 Fluid Catalytic Cracking Interstage and High-Pressure Cooler Corrosion S.M. Halawani................................................................................................................................255 Assessment of Cracks in a High Pressure Multilayered Reactor for its Fitness for Purpose A.M. Askari, M.I. AL-Kandari and P.K. Mukhopadhyay.................................................................263 Polythionic Acid Stress Corrosion Cracking of Incoloy 800: Case Study and Failure Analysis M.S. Mostafa and S.A. Hajaj...........................................................................................................273 Corrosion of Tube Heaters in Refineries: Symptoms and Cures A. Attou , A. Rais and H. Smamen...................................................................................................283 SEAWATER CORROSION Super Duplex Grade UNS S32750 for Seawater Cooled Heat Exchangers P.A. Olsson and M.B. Newman.......................................................................................................289 Evaluation of Aluminum Alloy 5083 Weldments to Stress Corrosion Cracking in Seawater A. Saatchi, M.A. Golozar and R. Mozafarinia.................................................................................301 Cavitation Corrosion Behavior of Some Cast Alloys in Seawater A. Al-Hashem, P.G. Caceres and H.M. Shalaby..............................................................................311 Microbiologically Induced Corrosion of a Stainless Steel Pipe H.H. Lee, M. Ali and K. Al-Omrani................................................................................................323 A Laboratory Study of Service Failure of Al-Brass Tubes in Arabian Gulf Seawater H.M. Shalaby, W.T. Riad and V.K. Gouda......................................................................................329 CORROSION IN THE BUILDING INDUSTRY Corrosion of Reinforced Concrete Structures and the Effects of the Service Environment S. Al-Bahar and E.K. Attiogbe........................................................................................................341

Corrosion of Concrete in Seawater viii

M. Pakshir and S. Esmaili...............................................................................................................353 Concrete Quality and its Effect on Corrosion of Steel Reinforcement E.K. Attiogbe and S. Al-Bahar........................................................................................................361 The Effect of the Type of Copper on its Corrosion Behavior in Kuwaits Soft Tap Water H.M. Shalaby and F.M. Al-Kharafi.................................................................................................371 FUNDAMENTAL ASPECTS Corrosion Behavior of Vanadium in Aqueous Solutions W.A. Badawy, F.M. AI-Kharafi and M.H. Fath-Allah......................................................................383 The Effect of UV Irradiation on Passive Films Formed on Type 304 and 316 Stainless Steels M.S. Al-Rifaie, C.B. Breslin, D.D. Macdonald and E. Sikora..........................................................395 Kinetics of High Temperature Corrosion of a Low Cr-Mo Steel in Aqueous NaCl Solution W.A. Ghanem, F.M. Bayyoum and B.G. Ateya................................................................................407 Corrosion and Passivation Behaviour of Aluminium and Aluminium Alloys: Mechanism of the Corrosion Process F.M. AI-Kharafi, W.A. Badawy and A.S. El-Azab............................................................................417 The Susceptibility of Molybednum and Vanadium-Bearing Austenitic Stainless Steel Weldments to Intergranular Corrosion M.K. Karfoul..................................................................................................................................431 Effect of Crystallization on the Corrosion Behavior of Amorphous FeCr9P6C3Si0.2 Alloy in 1 M H2SO4 F. Hajji, S. Kertit, J. Aride and M. Ferhat.......................................................................................441 CORROSION PROTECTION AND MONITORING Experience With VOC-Compliant Waterborne and High Solids Coatings in Corrosive Environments P Kronborg Nielsen........................................................................................................................449 Anticorrosive Film-Forming Nonpolluting Products Achieved in Romania R. Serban, N. Moga and E. Stockel.................................................................................................461 Cathodic Protection Under Disbonded Coatings of 56 Inch Gas Pipeline Along the Kangan-Shiraz M. Pakshir......................................................................................................................................471 Synergistic Effect Existing Between and Among a Phosphonate, Zn2+, and Molybdate on the Inhibition of Corrosion of Mild Steel in a Neutral Aqueous Environment S. Rajendran, B.V. Apparao and N. Palaniswamy...........................................................................483 Evaluation of Corrosion Inhibitors for Carbon Steel, Monel 400 and Stainless Steel 321 in a Monoethanolamine Environment Under Stagnant and Hydrodynamic Conditions J. Carew, H. Al-Sumait, A. Abdullah and A. Al-Hashem..................................................................493 Laboratory Evaluation of the Effects of Ozone on Corrosion Rates and Pitting of Engineering Alloys S. Nasrazadani...............................................................................................................................501 A Critical Comparison of Corrosion Monitoring Techniques Used in Industrial Applications M.S. Reading and A.F. Denzine......................................................................................................511

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Detection, Localization and Monitoring of Stress Corrosion Cracking, Hydrogen Embrittlement and Corrosion Fatigue Cracks During Service Conditions Using Acoustic Emission L. Giuliani......................................................................................................................................521 Electrochemical Monitoring of Aerobic Bacteria and Automation of Biocide Treatments L. Giuliani......................................................................................................................................533 Corrosion Monitoring for Integrity of Pipeline G.L. Rajani.....................................................................................................................................543 Power and Desalination Plants: Pumps, Corrosion and Maintenance H. Hosni, N.J. Paul and A. Masri...................................................................................................555 CORROSION MANAGEMENT Impact of Metallic Corrosion on the Kuwait Economy Before and After the Iraqi Invasion: A Case Study F. Al-Matrouk, A. Al-Hashem, F.M. AL-Kharafi and M. EL-Khafif.................................................567 Corrosion Problems in a Steam Condensate System and Treatment of Condensate for Recovery G.L. Rajani.....................................................................................................................................581 Improved Cathodic Protection of Above Ground Storage Tank Bottoms: MAA Refinery Experience A.K. Jain, L. Cheruvu and M.E. Al-Ramadhan................................................................................597 Impact on Ship Strength of Structural Degradation Due to Corrosion M.A. Shama....................................................................................................................................615 NOVEL TECHNIQUES Contact Electric Resistance (CER) Technique for Monitoring of Process Plants and for Solving Practical Corrosion Problems K. Saarinen and T. Saario..............................................................................................................627 Design of Radio Frequency Methods for Corrosion Processes Monitoring Yu.N. Pchelnikov, Z.T. Galiullin and A.S. Sovlukov.......................................................................637 A New, Rapid Corrosion Rate Measurement Technique for All Process Environments A.F. Denzine and M.S. Reading......................................................................................................647 Assessing Corrosion of Thick Marine Paints by Surface Corrosion Potential Mapping (SCM) and AC Impedance Spectroscopy (EIS) A. Husain........................................................................................................................................657 Optics and Lasers in Corrosion Laboratory K. Habib and F. Al-Sabti................................................................................................................669

Author Index...................................................................................................................................677 Subject Index..................................................................................................................................679

ORGANIZING COMMITTEE
Jasem Al-Besharah Khaled Al-Muhailan Abdulhameed Al Hashem Hamdy M. Shalaby Abbas Ali Khan Hussain Shareb Jamal Al-Hajji Khaled Shehab Khalifa Al-Feraij Abdel Monem Bedair Mohammad Ashkanani Mohammad Al-Rasheed Mohammed Al-Qalaf Abdul Khaliq Mustafa Khawla Al-Rifaee Chairman Rapporteur Coordinator Member Member Member Member Member Member Member Member Member Member Member Member KISR KFAS KISR KISR KFAS OAPEC KU KNPC MEW PIC KOC GCC KCS KISR MO

INTERNATIONAL ADVISORY COMMITTEE


Ahmed M. Shams El Din John Oldfield Russel D. Kane Digby D. MacDonald Member Member Member Member UAE UK USA USA

SCIENTIFIC COMMITTEE
Hamdy M. Shalaby Abdulhameed Al Hashem Khalid Habib Adel Hussein Waheed Badawi Afkar Hussain Emad Al Naser Eman A. Razzak Al-Shayji Lakshmipati Cheruvu Fahed Al-Otaibi Chairman Rapporteur Member Member Member Member Member Member Member Member KISR KISR KISR KISR KU KOC KOC KOC KNPC KNPC

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ACKNOWLEDGEMENT
The Organizing Committee was deeply honored by the patronage of H. H. The Crown Prince and Prime Minister Sheikh Saad Al-Abdullah Al-Salem Al-Sabah, which reflects his keen interest in science and technology. The Committee was also grateful for the financial support of the Kuwait Institute for Scientific Research, Kuwait Foundation for the Advancement of Science, Kuwait National Petroleum Company, Kuwait Oil Company, Ministry of Electricity and Water, Kuwait University, Ministry of Oil, the Gulf Cooperation Council, Kuwait Chemical Society, Organization of Arab Petroleum Exporting Countries, and Petrochemical Industries Company. The Committee would also like to extend its deep appreciation for the effort and time put forth by the distinguished honorary speakers, the members of the International Advisory Committee, and the Scientific Committee. We would like to thank our colleagues, the members of the working committees, at the Kuwait Institute for Scientific Research and the chairmen and cochairmen of the sessions, who provided unlimited assistance at times when it was really needed. Finally, we feel deeply indebted to the authors of papers and participants for their valuable contribution to the success of the conference

Jasem Al-Besharah Chairman, Organizing Committee

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CORROSION MANAGEMENT V. Ashworth Global Corrosion The White House, Victoria Road, Shifnal, England, TF11 8AF

ABSTRACT
The consequences of corrosion are often very costly. Little surprise, therefore, that a substantial engineering effort is directed towards its prevention and control. By contrast, little consideration seems to be directed towards making anti-corrosion effort cost-effective. This paper addresses the problem of ensuring value-for-money corrosion engineering and the possible limitation of unnecessary corrosion control activities. Corrosion in itself is not important, but the consequences of corrosion failure may well be. So the first step in corrosion management is a corrosion risk assessment to evaluate the risk associated with failure in any item. This is not an evaluation of the risk of failure alone, but of the consequences should that failure occur. Given an assessment of risk, a strategy of corrosion management can be constructed. This might involve lifetime corrosion control for items identified as producing a high risk. A less rigorous, but monitored, level of protection might be adopted for medium risk items, whilst no action at all may be considered necessary in the case of low risk items. Thus, resources are distributed according to the risk. Once a strategic approach has been defined, the tactics of corrosion management may be determined. These will include not only the specific corrosion control activity or activities that will be used in any given case, but also any monitoring and inspection requirements that are necessary. The object is to maintain corrosion within acceptable limits at minimum cost in all parts of the facility and throughout the facilitiys life. Key Words: Risk, probability, monitoring, inspection, corrosion management

INTRODUCTION The purpose of industry is to make a profit from the production of supplies and artefacts. In an increasingly competitive world, there is continuing pressure on prices. If the selling price is under pressure, profitability may only be maintained or increased by cutting costs. Any factor that serves to increase costs represents a tax on profits. Corrosion is one certain consequence of using engineering materials. Commonly, corrosion will be modest, but not always. In the hydrocarbon production and processing industries and the chemical industry, for example, the exception almost becomes the rule. Since corrosion brings a cost, it impacts profits.

Plenary Lectures

THE COST OF CORROSION The first formal attempt to assess the cost of corrosion to a nation was made in the UK in 1970 [1]. Since that time, similar studies have been published, in Australia [2], the US [3] and elsewhere. One surprising outcome is that the cost of corrosion to an industrialized nation is relatively constant at approximately 3.5% of the gross domestic product (GDP). To put the matter in context, this is substantially higher than the cost of fires which in the UK is put at ~0.5% GDP. Sedriks [4] reported the experience of the Dupont Company in the period 1968-71. After examining 685 plant failures, it was concluded that 55% were due to corrosion and 45% to mechanical failure. This may be regarded as a remarkable outcome given that, by the standards of the time, Dupont was corrosion aware and the greater proportion of the material that failed was stainless steel. The Dupont experience was mirrored by that of Britoil in the UK during the period 1978-88 [5]. As Table 1 shows, 33% of the failures that were analysed were attributed to corrosion. Table 1. Analysis of Oilfield Failures [5] Type Corrosion (all forms) Fatigue Mechanical damage/overload Brittle fracture Fabrication defects (not welding) Welding defects Other Frequency (%) 33 18 14 9 9 7 10

Not infrequently, corrosion hits the headlines because some particularly dramatic failure occurs resulting in the loss of life and property. At Flixborough Works in the UK, a chemical explosion related to a corrosion failure resulted in 28 fatalities, 36 serious injuries, virtual destruction of the plant and damage to some 2000 third party properties [6]. In Guadalajara, in the early 1990's, stray current corrosion of a water pipe produced a failure that caused erosion-corrosion of an adjacent gasoline line [7]. The leaking gasoline caught fire, producing an explosion in which tens of local inhabitants were killed. The accumulated corrosion failures at Dupont and Britoil were potentially costly and the two accidents were certainly so. That cost is ultimately borne by the community, but in the short term it falls on the industry concerned. There is a growing awareness in industry of the costs of corrosion. This engenders a desire for more effort and expenditure on corrosion prevention and control. Industry finds willing allies in meeting this goal from the companies that sell anticorrosion materials and systems. Their products and services are not free.

Ashworth

THE COST OF CORROSION PREVENTION AND CONTROL Expenditure on corrosion prevention and control is no less a tax on profits than the cost of corrosion itself. It is, therefore, entirely appropriate to ask if this expenditure is necessary. An accountant can usually produce figures to illustrate the impact of a corrosion failure on profit. Some tangible, and less tangible, inputs to the calculation are given in Table 2. Table 2. Cost of Corrosion Failure Safety hazards Loss of capital plant or equipment Fire/explosion Loss of production capacity Loss of product quality Maintenance/repair/replacement Loss of stored/entrained product Pollution clean-up costs Increased insurance premiums Loss of consumer confidence Alienation of workforce Increased scrutiny by statutory bodies Public image Accountants

By contrast, the accountant is rarely moved to make an assessment of the cost of not having a failure. If a plant and equipment operate without breaking down, everybody is usually well satisfied. It is rare to question whether the cost of achieving that performance has been excessive or even worthwhile. Table 3 lists some sources of possible over-spending in endeavouring to avoid corrosion failures. Table 3. Costs of Over-Protection Unnecessarily expensive materials Overdesign of metal sections Excessive weight Excessive inhibitor consumption Excessive monitoring Excessive inspection Excessive data handling Overdesigned CP systems Over-operated CP systems Excessive replacement stocks Premature retirement of equipment Over specified protective coatings

The items that relate to evident over-engineering in this list may be readily understood. However, two areas, monitoring and inspection, are worth singling out because they are so often regarded as a good thing, i.e., they have intrinsic merit. This is far from the case. Industrial corrosion monitoring is commonly excessive both in terms of the extent of monitoring and the sophistication of the equipment used. We need to remind ourselves that corrosion monitoring has never controlled any corrosion. This author believes that corrosion monitoring should be used almost exclusively in a process control function, the process, in this case, being corrosion. Thus, a monitoring device should only be used in circumstances where the output from it can validly be used to adjust some corrosion controlling function, e.g., inhibitor injection or cathodic protection (CP) output. It follows that probes should not be installed where such action cannot be taken, nor should they be installed where probes
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Plenary Lectures

installed elsewhere fulfil essentially the same function. In practice, these rules are observed more in their breach than in their application. Likewise, for reasons that are well understood, corrosion probes provide precise information on what is happening on the probe and, often, comparatively little about what is happening on the pipe or vessel wall. The value of the probe is that it detects change and prompts review and, possibly, action. Very often simpler means of detecting change than the use of corrosion-measuring devices will serve the same function at less cost, e.g., reference electrodes, pH probes, dissolved oxygen meters and moisture meters in the gas phase. They also have the merit, where relevant, of permitting continuous readout which allows the identification of the precise 'upset' that produces corrosion. Inspection is similarly open to over-engineering. How often is inspection carried out because we have the opportunity ? It is remarkable that upon shutdown, the internal inspection of tanks and vessels will often be considered mandatory. Yet pipelines or pipework that carry the same fluids are not inspected. It has been pointed out [8] that the cost of inspection is high, often equivalent to 2-6% of the invested capital. That is a significant tax on profits. What is often overlooked is that inspection can often be potentially dangerous and may even produce conditions conducive to corrosion, e.g., when sulphuric acid tanks are opened up for inspection. If corrosion costs money and corrosion control costs money, how do we target the optimum approach that strikes the correct balance between ignoring corrosion and seeking to control it ? The answer lies in

assessing the risk of corrosion failure on an item-by-item basis developing a lifetime corrosion management plan for each item to contain
corrosion at an acceptable level of risk This latter implies the need for risk modification, and sometimes, a defined degree of corrosion control activity. The goal is to maintain corrosion at an acceptable level. This begs the question: What is acceptable ? RISK It is a very dangerous game to talk about risk, largely because it is an ill-defined subject, and yet, everybody has a perception of what it is. What is clear is that risk is bad. We always associate risk with the likelihood of an undesirable or catastrophic event occurring. Thus, we talk of the risk of climbing, flying or crossing the road, but never of the risk of a traffic-free journey to work. Moreover, not everybody sees a particular risk in the same way. For example, we know that individuals are prepared to take a greater risk if they feel that they have some control over the process, or if the risk is associated with some activity considered to be beneficial [9]. That is why climbers do not appear to recognise the risk of climbing that is so self-evident to the rest of us. They feel a measure of personal control and perceive a personal benefit. In short, risk is subjective. This is a worrying matter if, before we can proceed to a corrosion management plan, we need to make a corrosion risk assessment. It is necessary to remove a little fuzziness. The most appropriate definition of risk is

Ashworth

Risk = Probability x Consequence (1) Despite its formality, this is not a very precise equation as we shall see. It does, however, indicate that risk is not simply a reflection of the probability of something bad happening. Probability Probability has the appearance of precision because it is a mathematical quantity. It derives from the stochastic nature of the frequency of the occurrence of events. Given sufficient failure data, a classic probability may be calculated to reflect the likelihood of a particular event occurring. In using the probability, it is important to be sure of its validity. Consider above-ground pipelines. The probability of failure, taking the overground pipeline population as a whole, is much less than the probability of failure of a small diameter (150250 mm) line. Considerable error can arise from using the former probability in the latter case. Nevertheless, given valid and relevant failure data, a useful quantitative probability can be assessed. Very commonly the failure data from which probability is calculated do not exist. The so-called Bayesian technique [10] can then be used to compute a probability. The technique uses prior knowledge (e.g., failure rates in similar, but not identical, circumstances elsewhere and the view of experts) and refines it steadily as specific information becomes available with plant operation. In the limit, of course, when the specific information database builds up sufficiently, the classic approach becomes more reliable. Probability has one other unfortunate characteristic: uncertainty. The probability of an occurrence may be low, but it can happen tomorrow. Consequences The consequences element in Eq. 1 relates to the perceived magnitude of the loss if the failure occurs. This is a very subjective matter since different people rate the various consequences of an individual event differently, and many even disagree about the consequences that derive from that event. Nevertheless, it is possible for these individuals to list the potential consequences and to rate each consequence on a scale of 1-10 to compute a consequence for Eq. 1. The number that emerges is entirely subjective. We see that the probability we use in Eq. 1 may hide a degree of uncertainty because of a lack of failure data, and it may include educated guesswork. Similarly, the consequence is a subjective valuation of the consequences of a failure. The outcome is a value for risk which, although numerical, is not exact. CORROSION RISK ASSESSMENT The foregoing does not seem to suggest that any form of risk assessment is likely to be productive. Yet the experience is that, in the case of corrosion, it can be helpful and rewarding. In carrying out a corrosion risk assessment it is axiomatic that corrosion does not matter, but its consequences do. The assessment then aims to combine objective estimates of the possibility of a corrosion failure with the operating company's view of the level of

Plenary Lectures

undesirability of the consequences of it occurring. It will be seen below that the probability component of the risk is rendered quantitative and that the consequence component remains subjective, but reflects accurately the perceptions and ambitions of the people that own and run the plant. Subjective it may be, arbitrary it is not. Methodology The methodology of conducting a corrosion risk assessment has been discussed in detail elsewhere [11]. Only a brief outline is presented here. If we take the example of a corrosion risk assessment in a refinery or chemical plant, it may be as coarse or as refined as the operator wishes. First, the plant is divided into systems, e.g., the gas sweetening unit. Second, each system is broken down into items. These usually comprise individual components, e.g., a vessel, a heat exchanger, a pump or a specifically identified length of pipework associated with the system. An item may be more widely defined in a coarse corrosion risk assessment or more closely defined in a fine analysis. In the latter case, for example, it may involve considering a vessel as a number of discrete items according to the known variation in fluid composition with height. Equally, it may be necessary to single out non-stressed relieved welds as separate items and, from an internal corrosion point of view, each dead leg. What follows is an outline approach to corrosion risk assessment which has proved to be successful. Other methods are available that operate somewhat differently [12,13], but aim to achieve the same objective. Life Factor The aim of the corrosion risk assessment is to assign a risk number to each item using a risk equation similar to equation (1). There are a variety of ways to deal with the probability element. The experience of the author's company is that it is best dealt with by assigning a life factor (L) that relates to the residual corrosion life of the item. The residual corrosion life is the anticipated time required for corrosion at the predicted rate, or rates, to lead to failure to perform the required mechanical duty. Given information on the materials of construction, the exposure environment, and the relevant circumstances (e.g., temperature, pressure, flow, heat transfer, and stress), the morphology of corrosion can be predicted with confidence. Where uniform attack is expected, maximum penetration rates can be calculated using conventional corrosion engineering practices, including public domain algorithms [14,15,16], in-house database information and, if necessary, modelling. If localized corrosion is expected (e.g., pitting attack or one of the cracking modes of failure), probabilistic analyses of failure [17 ] are more useful. For risk assessment purposes, the estimate of residual life in years is transposed to a dimensionless L. For example, an anticipated time to failure shorter than the time to the next shutdown would be assigned an L = 3. Anticipated lives beyond that point would attract L = 2, except where the residual life is put at >10 years in which case L = 1. Of course, this breakdown is arbitrary and the individual cut-offs, and the relative scoring, can be selected to match the requirements of the plant owners.

Ashworth

Consequence Factors The point has been made that the consequence of a corrosion failure are more important than the failure itself. Thus, the consequences that bear on plant operators' minds include:

Safety, Production, Emergency repair, Operability, Environment, Third party interests, Customer perception, and Public perception.

Adverse effects on any, or all, of these may often flow from an isolated failure. The consequence factor (C) is a numerical assessment of the perceived consequences of a corrosion failure. The number is arrived at using structured group discussions with plant management, operations personnel, maintenance engineers, loss prevention officers etc. It elicits a subjective assessment. However, because individuals work towards a consensus in a group, and the methodology of subsequent analysis is rigorous, the rankings produced accurately reflect, in a quantitative way, the operating aspirations of the company concerned. Thus, the C numbers provide the relative importance attached to any consequence. Since the risk numbers that finally emerge are not absolutes but reflect perceived risk in a relative manner, the subjectivity of the consequence analysis is not only permissible, but desirable. The risk assessment becomes plant specific. That is, identical plants operated by different companies or in different locations will produce different risk assessment results. There are two elements in establishing the value of C:

The individual consequence, and The events that can lead to that consequence.
Some consequences will always be regarded by company personnel as more undesirable than others; to that extent, the staff can develop a point loading to be applied to each. This gives a consequence rating (F); a typical set to emerge in one case is given in Table 4. Table 4. Typical Consequence Rating (f) Consequence risk of safety to personnel or public loss of production pollution loss of produce quality loss of consumer confidence Rating (F) 10 9 3 1 1

Plenary Lectures

It should be noted that the company in question is not concerned about contamination of the product by corrosion or any consequent alienation of the customer. This is a typical response from a primary producer; quite different numbers would have arisen in an assessment made in a food or pharmaceutical factory. The events that lead to a given consequence produce an event rating (P). It is clear that a number of events which might occur in a process plant, may lead to the same consequence. The company staff are able to identify and rank these events according to their perceived undesirability, as shown in Table 5. In this case, the table relates to two plants owned by the same company in which one uses the product of the other. Table 5. Typical Event Rating (P) Consequence Safety Event Crack in a toxic line or equipment Pinhole in a melt line Crack in a flammable line or equipment Crack in other HP line or equipment Pinhole in a flammable line or equipment Pinhole in other HP line or equipment Other cracks Pinhole in toxic line or equipment Other leaks Falling objects Plant no. 1 - no standby Plant no. 2 (HP) - no standby Plant no. 2 (LP) - no standby Plant no. 1 - standby Plant no. 1 - non-critical - no standby Plant no. 2 - standby Plant no. 2 - non-critical Plant no. 1 - non-critical - standby Marine Atmospheric Final product (colour only) Intermediate product Rating (P) 10 10 9 7 7 6 5 4 2 1 10 9 7 5 5 4 3 3 10 5 10 5

Outage

Pollution Quality

It is not uncommon when considering safety, for staff to take into account the inventory of a system. Thus, they will commonly regard a crack in a system or item with a high inventory and, therefore, a high potential for damage, as more significant than one where the inventory is small. Different values of P may then arise according to the volume of an unisolatable part of the system. Any item included in the unisolatable part attracts the P value for that part. The values of F and P are combined to yield C:
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Ashworth

C = Cx =

x = 1

x=n

fn (Fx, Px)

(2)

Where the subscript x refers to each of the consequences, e.g., safety, pollution etc. in turn. The Risk Equation The risk equation must reflect the operating company's perception of risk associated with various forms and rates of failure. The equation, which is derivative of Eq. 1, produces a numerical assessment of risk (R) and takes the form: R = fn (L, C) (3)

The shape of the function linking the life and consequence factors is determined by a formalized heuristic procedure. The function is modified through a series of computer iterations with the effect on the value of risk being assessed after each iteration. Allocation of Risk Classes The numerical value of risk can be calculated for each item in the plant. The higher the value of R for any item, the greater the risk and the more attention that must be focused on the local corrosion situation. In practice, the spread of numerical risk values amongst all the items within a plant usually proves to be a discontinuous spectrum. That is, the risk numbers tend to fall into clusters with distinctive breaks between. This is an inevitable consequence of data like those recorded in Tables 4 and 5. It permits a convenient reduction of the numeric data into risk classes (e.g., low, medium and high). Such a sub-division aids communication of the outcome of the corrosion risk assessment either on a narrative basis or as colour coded P and ID's. It also assists with establishing a corrosion management programme. Risk Modification The fact that, in assessing a new or existing plant, areas of high risk have been identified, does not mean that the risk must be tolerated. The aim should be to moderate the risk and to move to a more acceptable condition. Some methods of corrosion risk assessment [12] do not proceed as far as a risk equation or a risk number, but rather consider separately the perceived severity of the probability (L in this case) and the consequence (C). This produces a risk matrix as shown in Table 6. Table 6. Risk Matrix Consequence H M L H H HM M Probability M HM M ML

L M ML L

Plenary Lectures

Risk categories can then be devised as shown in Table 7: Intelligent risk modification aims to move towards Zone 3. This is not to aim at zero failure but to achieve, by good management, a tolerable level of risk. Table 7. Risk Categories High consequence High probability 1 Consequence Low consequence Low consequence High probability Low probability 2 3 Probability Using the risk equation approach, the aim is to concentrate resources on areas of high risk in order to reduce the risk number (i.e., modify the risk). Some care has to be taken here. It will often be the case that a high risk number will place the specific item in Zone 1 of Table 7. Clearly, for these items, it is important to move towards Zone 3 by means of corrosion control activities that reduce the risk number. Somewhat lower risk numbers may fall into either Zone 2 or Zone 4. Indeed, the same risk number may apply to either a low consequence/high probability situation or a high consequence/low probability. The former simply represent failures that will be an irritation; pinholing in a seawater cooling line. The latter are certainly more serious; pinholing in a dry flammable gas line, for example. In the case of Zone 2, the high probability means that sufficient data were available to assess the probability fairly accurately. By contrast, in the case of Zone 4, the reverse is true, and there may be considerable uncertainty. If the probability (in our case, L) has been calculated using tried and tested tools, then identical risk numbers that derive from high probability/low consequence and low probability/high consequence events are equally reliable. Where the L calculation has used limited data, an uncertain algorithm or stochastic techniques, that level of reliability is absent. Thus, in moving from Zone 1 towards Zone 3, it is often better to achieve Zone 2 rather than Zone 4. Equally, it may be more important to move from Zone 4 than to move from Zone 2. In general, the consequences of failure are usually not amenable to modification; thus, risk can only be modified by changing the probability. For that reason, and to introduce security, risk modification needs to pay attention to moving to situations where the probability is known or can be determined with some degree of confidence. High consequence Low probability 4

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CORROSION MANAGEMENT Corrosion risk assessment is not an end in itself. It identifies areas where corrosion may be safely ignored and where it must be attended to. It even provides the pointer to where resources will be spent with greatest reward. Thus, it provides the evidence that permits the construction of a cost-effective corrosion management programme. The objectives of a programme relate to the whole life of a facility and are to

Maintain corrosion within predetermined acceptable limits at minimum cost, Develop and facilitate rapid access to, records showing the corrosion status of
each item within the facility in order to form a basis for future corrosion management decisions, and to provide assurance for managers, owners and statutory bodies, and Ensure that corrosion upsets are quickly identified and appropriate remedial action is implemented, if necessary, to minimize the consequences of any failure. There is no universal corrosion management programme. Targeting these objectives is a unique exercise for every facility. However, the philosophy of corrosion management is common to them all. An overall strategy for corrosion management must first be agreed upon, and then the tactics become self-evident. Strategic Considerations The corrosion risk assessment will have produced a risk ranking for all items of a plant. This will enable a strategy for corrosion management to be set down. Table 8 illustrates a strategy that might be drawn up for an industrial facility. Table 8. A Corrosion Management Strategy Assessed Risk High Alternative Corrosion Management Options Corrosion prevention, or corrosion control for life, or corrosion control to meet planned maintenance or planned replacement Corrosion control for life, or planned maintenance No action, replace if required

Medium Low

It will be noted that corrosion prevention, or careful corrosion control, is dictated by a high risk classification. By contrast, a low risk classification justifies no corrosion controlling action. A medium risk requires some action. Thus, corrosion management involves a spectrum of activity from no action to considerable action according to the risk. However, taking no action, or taking action, is not corrosion management unless the decision to follow the particular course has been based on an assessment of risk. Action where it is not needed, like inaction where it is, represents a waste of resources and a tax on profits.

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Plenary Lectures

It will be recalled that corrosion risk assessment is carried out by dividing the plant into systems and items. Ultimately, the output relates to individual items. It is possible for an item within a system to have a high risk classification whilst other items in the same system belong to a lower risk class. The decision must then be made whether to apply corrosion control to the system in order to preserve the item, or to ensure corrosion prevention for the item (say, by the use of more corrosion-resistant material) and avoid dealing with the system. The application of the broad strategy does allow, and requires, some flexibility in the tactics adopted. Tactical Considerations The complete elimination of the chance of corrosion failure, i.e., corrosion prevention, in a high risk area is rarely possible in an existing plant. Invariably, it would require a significant engineering change, for example, replacement of existing materials by corrosionresistant alloys or modification of the process (e.g., addition of gas dehydration). Even with new plants, such proposals might raise major design and engineering problems, not to mention cost. It is much more likely that active corrosion control will be adopted with the objective of extending the time to failure of an item beyond the planned life of the plant, or up to some planned maintenance shutdown. The adoption of this tactic requires that:

the performance targets for the corrosion control are defined, and procedures are put in place to ensure the targets are met.
The performance target may be set in terms of an allowable rate of metal penetration. This approach will most commonly be adopted when uniform corrosion is anticipated. Alternatively, limits may be set on some parameter that is an indication of fluid corrosivity, e.g., electrode potential in anodic and cathodic protection systems, dissolved oxygen in oilfield water injection or boiler feedwater, pH, temperature, or dewpoint. Irrespective of which approach is adopted, it will be necessary to obtain on-line information to make adjustments as required. Thus, corrosion monitoring is necessary, and it then forms an essential segment of the corrosion management plan. Table 9 lists some monitoring techniques and indicates how they may be used in corrosion management. Table 9. Corrosion Monitoring in Corrosion Management Corrosion Control Strategy Examples of Adjustments and Activities Based on Data Monitoring Inhibition of crude oil On-line probes (e.g., Adjust inhibitor dosage, pipelines coupons, electrical resistance change inhibitor type, probes) discontinue inhibition De-oxygenation of boiler O2 probes Adjust oxygen scavenger, feed-water check pump seals, etc. Impressed current CP Potential Adjust system output Anodic protection of Potential Adjust system output sulphuric acid plant
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Monitoring Technique

Ashworth

Dehydration of process gas

On-line probes, moisture detection

Temporary inhibition, overhaul dehydrator

The key to effective corrosion management is information since it is on the basis of that information that on-going adjustments to corrosion control are made. Information is valid data. Thus, to make effective corrosion management decisions on a day-to-day basis, the monitoring data must be valid. This is not simply a requirement for the probes to be operating correctly. It requires that they be placed in the most appropriate places, i.e., at those points where the corrosion controlling activity might be expected to work, but where it might equally be expected to be least effective, e.g., remote from the inhibitor injection point. In many cases specially designed traps are introduced into a plant so that corrosion probes may be inserted. These often produce their own microenvironment, atypical of the plant itself, and with little hope of effective entry for an inhibitor. Data from a probe in such a location are unlikely to be relevant to corrosion management elsewhere in the system. Invalid data leads to ineffective corrosion management. Keeping Track In any facility the means of corrosion management will vary from place to place. In one location a corrosion resistant alloy may be used; in another, CP allied to coating may be employed, whilst elsewhere no action may be taken because the consequences of any failure are regarded as unimportant. In short, no corrosion management action is taken that does not contribute positively to meeting the objective of containing risk whilst maintaining the level of action at the minimum necessary. It is important to ensure that the targets are being met. Overshooting the target will involve excessive corrosion control costs, whilst undershooting the target may lead to a situation that cannot economically be recovered. Corrosion monitoring is not appropriate for the purpose since it rarely provides evidence of the metal loss from a pipe or vessel wall. That is, aggregating the output from probes over time does not give any indication of the loss of a section. The value of corrosion probes is that we rapidly develop experience so that we can be reasonably sure that when the probes read a given value, we are on target, and that a change in reading requires consideration of an adjustment to the corrosion controlling activity. Reference electrodes, pH probes, moisture meters etc. often fulfil the same function. Thus, corrosion probes and the like, do not provide quantitative performance assessment. That can only come from inspection and nondestructive testing (NDT). These activities are part of corrosion management since they provide reassurance, identify wasteful corrosion control activity, and permit reassessment of the corrosion management programme. The same critical approach that was adopted in setting up the corrosion control strategy must be applied to the inspection strategy. That is, the resources must be applied according to the risk. If we have attempted to modify the risk by instituting some corrosion control activity, we should be tracking the success, or excess, of the activity in our inspection programme. Thus, inspection is not based on convenience, inspecting because an item is accessible (at shutdowns, for example). It should be based on the premise that if the consequences of failure are to be avoided and the cost of control is to be minimized, inspection is necessary. There must, therefore, be a clear connection between the risk assessment output, the corrosion management strategy, the tactics of corrosion management and the inspection programme.
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Plenary Lectures

The key point approach to NDT is particularly effective. Here a limited number of points, in areas where validation is required, that are regarded as typical and extreme, are identified for NDT inspection at regular intervals. This provides, on a temporal basis, a readout of the progress of corrosion which will validate, or otherwise, the targeting achieved by, say, inhibitor injection. Similarly, during internal inspection, the risk assessment will have identified particular areas of concern, e.g., tube/tube sheet assemblies, tube baffles, and non-stress relieved welds, which must become the focus of activity. Again, this will confirm whether the corrosion control is adequate or perhaps is insufficient or excessive. The data that are produced from the inspection activities must be valid and limited in volume so as not to deter analysis or hide anomalies. Thus, it is important to restrict key points and inspections to critical positions and to limit the frequency of inspection and survey work. The time to the next inspection or survey should be indicated by the outcome of the current work. That is, a lifetime fixed interval programme will usually prove wasteful; inspection and survey should be carried out on an as-needed basis. A valuable template giving an approach to the re-classification of in-service inspection is to be published in 1996 [18] and has been reviewed in reference [12]. Review From time to time a corrosion management programme should be reviewed at both the strategic and tactical level. In human affairs, things change. The management of a facility will always be alive to current market trends, competitors activities, interest rate movements and so on. Inevitably, it may be necessary to revise the management objectives from time to time. Since the corrosion management programme was constructed to meet the objectives of an earlier plant management plan, it will be necessary to review the programme and possibly to alter it. Likewise, the pace of technological change is rapid compared to the anticipated lifetime of most facilities. Thus, newer, more effective, cheaper means of achieving the same ends may emerge, and indeed, it may be possible to adopt them in place of existing tactics within the corrosion management programme. Thus, the programme is not a fixed blueprint, but a means to an end that must be reviewed and revised to meet the current management objective. One objection that is raised to corrosion management planning comes from the corrosion engineers themselves. They draw attention to the fact that by fixing permissible rates of metal loss, the lifetime of the facility is effectively determined. Further, that management will often, at a later stage, decide to extend the required operating life. There is then a mismatch. The argument seems to be that corrosion management planning should ignore the present requirements and anticipate the future requirements of the management. This is an extremely wasteful approach. Certainly there is a possibility that a mismatch will occur and will need to be overcome. That will be achieved at some cost. That cost must be attributed to the decision to go for life extension and is, therefore, a natural consequence of that extension. It needs to be included in the cost benefit analysis of extension, not hidden in lifetime overspending in anticipation that life extension might be required. It may not be. ILLUSTRATIONS

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Ashworth

Two recent examples illustrate how corrosion risk assessment provided important results for the clients. In the first instance, the assessment of a petrochemical complex in the Middle East found the plant to be extremely well engineered from the corrosion standpoint. It was constructed predominantly in carbon steel, with excursions into more exotic metallurgy only where the process conditions demanded it. However, the assessment highlighted, somewhat to the client's surprise, the cooling water system as a high risk area. By using a closed system with secondary cooling by seawater and specifying high quality primary water with corrosion inhibitor injection, the designers had judged that it was possible to construct the majority of the cooling system in carbon steel. Certain that the primary heat exchangers were, however, constructed in a stainless steel due to the aggressivity of the process fluid, the corrosion risk assessment identified modes whereby the quality of the cooling water could be adversely affected (e.g., by leakage of seawater at secondary plate exchangers). Failure to maintain cooling water within specification would very rapidly lead to stress corrosion cracking of one of ten critical stainless steel process exchangers, failure of any one of which would halt production. In view of this, Global Corrosion put forward recommendations for modest on-line monitoring of cooling water quality. Tied to this was the setting up of a formal action plan to be followed in the event a sudden deterioration in water quality should be detected. The client accepted and implemented these recommendations but, unfortunately, not before one failure of the type predicted occurred. The second example derives from an installation, also in the Middle East. The corrosion risk assessment concluded that the absence of CP on water storage tanks, together with the prevailing soil conditions, would result in high tank bottom corrosion rates. Since an adequate supply of water was essential to maintain production, the assessment concluded that the prospective failure of the tanks constituted a high risk and it was strongly recommended that CP be installed. In the event the client was reluctant to accept and act upon the outcome of the report. Just under a year later the raw water tank perforated due to soil-side corrosion. The resulting loss of water caused a two week interruption in production, prompted a belated decision to install CP and engendered in the client a heightened appreciation of the benefits of corrosion risk assessment and the need for effective corrosion management. CONCLUSIONS Corrosion cannot be ignored for it will not go away. However, there is little merit in controlling corrosion simply because it occurs, and none in ignoring it completely. The consequences of corrosion must always be considered. If the consequence of corrosion can be lived with, it is entirely proper to take no action to control it. If the consequences are unacceptable, steps must be taken to manage it throughout the facilitys life at a level that is acceptable. To manage is not simply to control. Good corrosion management aims to maintain, at a minimum life cycle cost, the levels of corrosion within predetermined acceptable limits. This requires that, where appropriate, corrosion control measures be introduced and their effectiveness ensured by judicious, and not excessive, corrosion monitoring and inspection. Good corrosion management serves to support the general management plan for a facility. Since the latter changes as market
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Plenary Lectures

conditions, for example, change, the corrosion management plan must be responsive to that change. The perceptions of the consequences and risk of a given corrosion failure may change as the management plan changes. Equally, some aspects of the corrosion management strategy may become irrelevant. Changes in the corrosion management plan must, inevitably, follow. REFERENCES 1. T.P. Hoar (Chairman), Report of the Committee on Corrosion and Protection, HMSO, London, 1971 2. B.W. Cherry and B.S. Skerry, Corrosion in Australia - the Report of the Australian National Centre for Corrosion Prevention and Control Feasibility Study, Monash University, 1983. 3. L.H. Bennett, National Bureau of Standards Special Publication 511.1, NBS, Washington, 1978. 4. A.J. Sedriks, Corrosion of Stainless Steels, Wiley, 1979, p. 7. 5. Kermani, An Overview of Wet H2S Attack: Types, Causes and Problems, in Papers of the Conference on Wet H2S Attack on Steels, Institute of Mechanical Engineers, London, 1996. 6. F. Lees, Loss Prevention in the Process Industries, Vol 2, p863, Butterworth (1989) 7. J.M. Malo, V. Salinas and J. Uruchurtu, Materials Performance 33, 8, 1994, p. 63. 8. C. Edeleanu and J.G. Hines, Materials Performance 29, 12, 1990, p. 68. 9. P. Slovic, Science 236, 17 April 1987, p. 280. 10. M.E. Giuntini, Proceedings of Fourth Space Logistics Symposium, Florida, November 1992. 11. V. Ashworth and W.R. Jacob, Proc. Corrosion 32, Australasian Corrosion Association, 1992. 12. B. Spalford, Carbon steel equipment in wet H2S service, Papers of Conference on Wet H2S Attack on Steels, Institution of Mechanical Engineers, London, 1996. 13. Private communication, Shell-Expro, UK 14. C. de Waard, V. Lutz and D.E. Milliams, Corrosion 47, 1991, 976. 15. F.A. Posey and A.A. Palko, Corrosion 35, 38 (1979) 16. J.W. Oldfield, G.L. Swales and B. Todd, Proc. 2nd BSE/NACE Corrosion Conference, Bahrain, 1981. 17. M. Akashi, Proc. Conference of Life Prediction of Corrodable Structures, NACE, 1991. 18. EEMUA publication 179, A Working Guide for Carbon Steel Equipment in Wet H2S Service (to be published in 1996)

16

Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

THE DETERMINISTIC PREDICTION OF DAMAGE D.D. Macdonald Center for Advanced Materials The Pennsylvania State University 517 Deike Building, University Park, PA 16802, USA

ABSTRACT
As our industrial and infrastructural systems (refineries, power plants, pipelines, etc.) age, considerable economic incentive develops to avoid unscheduled outages and to extend operation beyond the design lifetime. The avoidance of unscheduled outages is of particular interest, because the failure of even a minor component can result in the complete shutdown of a facility. For example, the unscheduled shutdown of a 1000 Mwe nuclear power plant may cost the operator between US $1 million and US $3 million per day, depending upon the cost of replacement power and other factors. However, if component failures could be accurately predicted, maintenance could be performed during scheduled outages, the cost of which has already been built into the price of the product. With regard to life extension, the successful extension of operation beyond the design life translates into enhanced profits and the avoidance of costly licensing and environmental impact assessments associated with the development and construction of a new facility. In this case, as well, the key to successful operation is the ability to avoid downtime, and hence, to maintain production. Eventually, the frequency and severity of unscheduled outages will render operation uneconomic, and at that point, replacement of the facility is necessary. In order to develop effective inspection and maintenance scheduling and life extension technologies, it is first necessary to predict the evolution of damage into the future as a function of various system variables. The only effective prediction technologies are those based on determinism, in which the system behavior is described in terms of natural laws. In this paper, the deterministic prediction of damage, via damage function analysis (DFA), which provides a robust technology for estimating the damage function at future times, is described. The application of DFA to the prediction of pitting damage is illustrated by reference to pitting damage in condensing heat exchangers. Key Words: Corrosion damage, determinism, prediction, pitting corrosion.

INTRODUCTION Corrosion is a major cause of component failure, and hence, in the occurrence of unscheduled downtime, in complex industrial systems. In particular, the various forms of localized corrosion, including pitting corrosion, crevice corrosion, stress corrosion cracking (SCC), and corrosion fatigue (to name the common forms) are particularly deleterious because they frequently occur without any outward sign of damage, and because they often result in sudden and catastrophic failures. Thus, the development of effective corrosion damage prediction technologies is essential for the successful avoidance of unscheduled downtime and for the successful implementation of life extension strategies.

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Plenary Lectures

Corrosion damage is currently extrapolated to future times using damage tolerance analysis (DTA). In this strategy, known damage is surveyed during each subsequent inspection, and the damage is extrapolated to the next inspection period allowing for a suitable safety margin. We have argued [1] that this strategy is inaccurate and inefficient, and that in many instances it is too conservative. Instead, we argue that damage function analysis (DFA) is a more effective method for predicting the progression of damage, particularly when combined with periodic inspection. DFA is based upon the deterministic prediction of the rates of nucleation and growth of damage, with particular emphasis on the compliance of the embedded models with natural laws. Although corrosion is generally complicated mechanistically, a high level of determinism has been achieved in various treatments of both general and localized corrosion. The application of DFA is illustrated by reference to the development of damage due to pitting corrosion of stainless steels in condensing heat exchangers. Deterministic models have been developed for both the nucleation and the growth of damage, and these models have allowed us to calculate the damage function as a function of exposure time and system conditions. FUNDAMENTAL CONCEPTS In this paper, I outline a deterministic method for predicting the damage function for pitting corrosion in condensing heat exchangers [1,2]. This method is considered to be potentially superior to empirical (including stochastic and probabilistic) techniques, because it is mechanistically-based and hence provides analytical relationships between the damage function (i.e., number of pits versus pit depth presented in the form of a histogram [1]) and the damaging variables (e.g., chloride concentration and combustion parameters). Accordingly, deterministic methods are expected to be more efficient at using databases, because a lesser need exists to establish the damage function/damaging variable relationships empirically. Any deterministic model must account for the fact that localized corrosion involves nucleation and growth phenomena which occur sequentially for a single site but that tend to occur in parallel for an ensemble of pits. Furthermore, the model must account for the experimental observation that the parameters that characterize the breakdown event are distributed, due to the fact that the population of sites on any real surface is not homogeneous. Outlined below is one model that satisfies these (and many other) conditions related to the nucleation and growth of damage resulting from localized corrosion. While the model may not be complete (or even correct), it is deterministic in that the distribution function and the relationships between the model parameters and the damage function are analytic and follow from the natural laws. In illustrating this technology, I have chosen to discuss the prediction of the damage function for pitting corrosion, because this form of attack is almost ubiquitous in condensing heat exchangers. Furthermore, pitting corrosion displays most of the features of all forms of localized attack, including an induction time and the autocatalytic development of the damage. The algorithm developed in this study to estimate the damage functions for condensing heat exchangers contains five modules as outlined in Fig. 1. Also indicated are the parameters that propagate from one module to the next. The output of the algorithm can be specified in three forms:
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Macdonald

For a specified probability of failure, the algorithm estimates the damage


function as a function of exposure time and computes the number of pits with lengths exceeding the condenser wall thickness to predict the service life. For a specified probability of failure and design life, the algorithm calculates the wall thickness to ensure acceptable performance. For a specified wall thickness and design life, the algorithm calculates the failure probability.
MODEL INPUTS

Duty Cycle

Chloride Concentration

Condensate Temperature

Flue Gas Composition

Condensate Chemistry Model pH.[Cl-]* Mixed Potential Model Ecorr.pH. [Cl-] Pit Nucleation Model N(t).Ecorr.pH. [Cl-] Pit Growth Model N(tobs) vs. n(u) Damage Function Model

Service Life

Wall Thickness Specifier

Failure Probability

Figure 1.

Structure of the algorithm for the prediction of damage function (*parameters propagated from one model to the next)

Below I describe the various modules in this algorithm; however, due to the limited space available, I outline only the principles of these modules.
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The Condensed Chemistry Module (CCM) The composition of the flue gas will differ from burner to burner. With this in mind, we developed a generalized condensate model for the condensate environment. This model assumes the flue gas to be a mixture of CO, CO2, H2S, NO, NO2, SO2, SO3, and H2O. The relative proportions of these components may vary widely from furnace to furnace, depending on the nature of the ambient air, the air/gas ratio, and the impurities of the gas. The goal of the condensed chemistry module (CCM) is to calculate the pH and the composition of the condensate on the condenser surface. The pH is a key parameter in controlling the rates of pit nucleation and pit growth. The concentrations of species in the liquid layer determine the ionic conductivity of the solution, which has great impact on the pit growth rate. The module employs an equilibrium model along with mass balance and charge balance constraints, and computes ion activity coefficients using the extended Debye-Huckel theory. It is assumed that the condensed liquid film is in equilibrium with the ambient environment, so that equilibrium calculations are applicable. The details of this module are described in the literature [3]. A typical gas-fired heat exchanger is schematically shown in Fig. 2a [4]. The temperature ranges from approximately 308oK in the cold end to 353oK in the hot end, depending on the design of the heat exchanger. Typical values of the pH and chloride concentration in these different zones are given in Fig. 2b [4]. It is shown that the condensed liquid phase is enriched in chloride to the extent of approximately 150 ppm in the hot end. Acidification of the condensed thin liquid layer also occurs, in that pH values as low as 2.7 and 3.3 are found at the hot end and the cold end, respectively. In Fig. 2c, the computed pH for a typical composition of the flue gas and the chloride content of the condensate are presented. The calculation shows a variation in pH from 2.93 to 3.32 from the hot end down to the cold end. Recognizing the wide range of operating conditions and designs of condensing heat exchangers, it is concluded that good agreement is observed between the experimental data and theoretical prediction.

Cooling Air Exhaust

Heat Exchanger Simulator Flue Gas Flow Zone 1 Zone 2 T = 353-326oK Zone 3 Zone 4 Zone 5

T = 308-326oK

Cooling Air

Figure 2a. Schematic diagram of a typical heat exchanger in a gas-fired furnace [4]

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Macdonald

Figure 2b. Characteristics of flue-gas condensate from different zones [4]

Figure 2c. Calculated pH in the condensate as a function of temperature and chloride concentration (PCO = 2.60 x 10-5 atm, PCO2 = 6.80 x 10-2 atm, PSO2 = 9.37 x 10-9 atm, PSO3 = 2.00 x 10-9 atm, PH2S = 1.20 x 10-4 atm, PNO = 1.74 x 10-8 atm, PNO2 = 2.67 x 10-8 atm, PO2 = 1.00 x 10-4 atm)

The Mixed Potential Module (MPM) The mixed potential module (MPM), which is based on the Wagner-Traud hypothesis [5] for free corrosion processes, was developed to calculate the corrosion potentials of alloys in corrosive environments. The theory outlined here is essentially identical to that developed by Macdonald et al. for calculating corrosion potentials for stainless steel components in the heat transport circuits of boiling water reactors (BWRs) [6,7]. The theory is based on the physical condition that charge must be conserved in the system.

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Because electrochemical reactions transfer charge across a metal/solution interface at a rate measured by the partial currents, charge conservation demands that iR/O,j (E ) + icorr (E ) = 0
j=1

(1) where iR/O,j is the partial current density due to the j-th redox couple in the system, and icorr is the corrosion current density of the substrate. The currents are written as functions of the potential E to emphasize the fact that the partial currents depend on the potential drop across the metal/solution interface. Indeed, the solution to Eq. 1 provides the quantity that we seek (i.e., the corrosion potential). Note that in deriving Eq. 1, the surface of the alloy is assumed to be equally accessible to all reactions in the system.

Figure 3. Calculated and measured corrosion potentials as a function of temperature and oxygen partial pressure for alloy A129-4C (the solution composition for the experimental measurement: [HCl] = 200 ppm, [HF] = 40 ppm, [H2SO4] = 20 ppm, PCO = 2.60 x 10-5 atm, PCO2 = 6.80 x 10-2 atm, PSO2 = 9.37 x 10-9 atm, PSO3 = 2.00 x 10-9 atm, PH2S = 1.20 x 10-4 atm, PNO = 1.74 x 10-8 atm, PNO2 = 2.67 x 10-8 atm, PO2 = 1.00 x 10-4 atm) Experimental polarization curves and kinetic data for the reduction of oxygen on Alloy Al29-4C were used as input to the MPM. The module then calculates the corrosion potential of the alloy under the service condition, as shown in Fig. 3. The calculation indicates that if the solution is saturated with oxygen, the corrosion potential is only weakly dependent upon case of an operating condensing heat exchanger, the corrosion potential varies from -290 mV to -460 mV as the temperature increases from 300o to 370oK. The Pit Nucleation Module (PNM) As a result of an intensive effort over the past decade to develop an understanding of the breakdown of passive films, we have derived theoretical distribution functions for passivity
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breakdown that are in good agreement with experimental data [8-11]. We derived these distribution functions from our point defect model for the growth and breakdown of passive films, by assuming that breakdown occurs when a critical concentration of cation vacancies accumulates locally at the metal/passive film interface, such that decohesion occurs between the barrier layer and the metal substrate. Subsequently, localized dissolution and/or mechanical instability leads to rupture of the film [8]. We further assumed that the breakdown sites are normally distributed with respect to the diffusivity of cation vacancies within the film [9-11]. The full derivation of these distribution functions can be found in the literature [8-11]. From the point defect model [8], the breakdown voltage and the induction time for a single pit nucleation site on the surface are given by Vc = and 4.606RT J 2.303RT log o m / 2 log(a x ) J u F F FV tind = exp 1 + 2RT
1

(2)

(3)

respectively, where is the film stoichiometry ( MO / 2 ), is the dependence of the potential drop across the film/solution interface on applied voltage, ax is the activity of halide ion in the solution, is a relaxation time ( ~0), V = V-Vc, V is the applied voltage (or the corrosion potential under open circuit conditions),
o a J = D

(4)

and N = K v a
1+

exp Gs /RT
o

(5)

The parameters u and Jm are defined in the original derivation [8]. Assuming that the breakdown sites are normally distributed in terms of the cation vacancy diffusivity, dN = dD 1 2 D exp (D D) / 2 D
2 2

(6)

where D is the mean diffusivity and D is the standard deviation, the point defect model yields the following expressions for the distributions in the breakdown voltage and induction time [9-11]: 2 2 D dN = e(D D) / 2 D (7) 2 D dVc and
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Plenary Lectures

2 dN u / 2 (D D )2 / 2 D e V = /2 e 2 dt ind 2 D a a x (t ind )

(8)

where

= F/2RT

(9)

Eqs. 7 and 8 contain four important system parameters: D and D which describe the transport properties of cation vacancies in the passive film, and and which appear in the expression for the dependence of the potential drop across the film/solution interface on applied voltage and pH
o f/s = V + pH + f/s

(10)

All four parameters can be determined by independent experiments: D from electrochemical impedance spectroscopy, D from passivity breakdown induction time measurements [8], and and from film growth data, much of which exists in the literature. Accordingly, Eqs. 7 and 8 represent analytical distribution functions for the nucleation of pitting attack, provided that the assumptions in the model hold. Our previous work [9-11] has demonstrated the quantitative nature of these expressions for representing experimental distribution in Vc and tind, for those cases where sufficient experimental data are available for analysis. The Pit Growth Module (PGM) The pit growth module (PGM) computes the growth rate of an individual pit. Figure 4 shows schematically a typical pit that develops on the surface of a metal in contact with a thin liquid layer. The module developed in this study calculates the pit growth rate for a pit of cylindrical geometry. The details of the theoretical approach can be found in the literature [12,13], except that we developed a transmission line analog of the external environment from which the distributions in the electrostatic potential and the current in the external environment, as a function of distance away from the pit, can be estimated.
z Gas

h a0

Thin electrolyte film r

Metal

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Macdonald

Fe + n 4 H 2 O Fe

( OH ) ( 2 n n
4

) ) )

+ n4H + n5H + n6H

+ 2e + 3e + 2e

Cr + n 5 H 2 O Cr ( OH Ni + n 6 H 2 O Ni ( OH H2O H
+

)( n

3n
5

) ( 2 n n
6

+ OH

Figure 4. Schematic diagram of a pit on the surface of the condensing heat exchanger The principle of the transmission line approach is shown in Fig. 5, which yields the following equations for the distributions in the electrostatic potential (s ) and the current in the external environment
d 2s 1 d s =0 2 + dr r dr hZs s
d 2 I 1 dI I= 0 2 dr r dr hZs

(11)

(12)

where is the resistivity ( cm ) of the solution, Zs is the specific impedance ( cm 2 ) of the external surface, h is the electrolyte film thickness, and r is the radial distance from the C center of the cylindrical pit. Note that Zs is a function of distance [Zs(r) =- ( s m )/iN , where i C is the net cathodic current density]. The value of Zs(r) was determined iteratively when N solving Eq. 11 by substituting for the net current density the following expression
e( s s )/b a e( s s )/b c i = +i 1 1 -( s se )/b a 1 s se /b c p ( s ) + e e il,r i o il,f
e e

C N

(13)

where the first term on the right-hand side is the generalized Butler-Volmer equation for the oxygen electrode reduction
2H 2 O O 2 + 4H+ + 4e

(14)

and the second is the polarization current of the substrate, both of which are functions of the potential difference across the interface. The parameters se , io, il,f, il,r, ba, and bc in Eq. 13 are the negative of the equilibrium potential for Reaction 14, io is the exchange current density, il,f and il,r are the limiting current densities for Reaction 14 in the forward and reverse directions, respectively, and ba and bc are the corresponding Tafel constants. Note that the signs of the exponents in the first term in Eq. 13 are opposite to those normally defined because we have written the current in terms of the electrostatic potential in the solution with respect to the metal. We used the finite difference method to solve Eqs. 11 and 12 for s (r) and i c(r) , respectively.

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Plenary Lectures

The distribution of the electrostatic potential within the pit is obtained by solving Laplace's equation, assuming that the environment within the pit confine is electrically neutral,
= 0
2

(15)

The solution to Laplace's equation (Eq. 15) yields the following expression, assuming that the potential variation in the radial direction is negligible compared to that in the longitudinal direction:
Z Flue gas (O2) r r+dr Electrolyte film

Crevice

Metal Figure b (a) Element of electrolyte film on the metal surface. I Rdr S I-dI

Z(r)/dr m (b) Element of transmission line for calculating current and potential distributions radially from the crevice mouth.

Figure 5. Transmission line model for thin electrolyte film on the metal surface

s (z) = ( s0 sL ) + s0
z L

(16)

where sL is the electrochemical potential at the pit tip, L is the pit depth, and z is a negative quantity. We also apply the Butler-Volmer equation to the electrodissolution reaction occurring at the pit bottom to yield the electrochemical potential at the pit tip as [14]

sL = s00 + ba1n

i0 A 0 I0

(17)

where s00 is the (negative of the) standard electrochemical potential for the dissolution of the metal, i 0 is the standard exchange current density, ba is the anodic Tafel constant for metal 0 dissolution, and At is the effective active surface at the pit tip. The model outlined above is a variant of the Coupled Environment Fracture Model (CEFM) that we developed some time ago [15] for describing crack growth in stainless steel piping in nuclear power reactor heat

26

Macdonald

transport circuits. Thus, following our previous work [15], Eqs. 11, 12, 16, and 17 are solved for the unknowns s (r) , i c(r) , and Io, such that charge conservation, expressed as
I0 + i C dS= 0
N s

(18)

is obeyed, where I0 is the (positive) current exiting the pit mouth, and dS is an increment of the external surface (dS = 2 rdr ). Because the cathodic current due to oxygen reduction predominates on the external surface, the second term on the left side of Eq. 18 is negative. Once I0 is known, then the pit growth rate is calculated using Faraday's law: dL M I0 = dt 2 m Z FA (19)

where m is the density of the metal (g/cm3), M is the composition-averaged atomic weight of the alloy, and Z is the composition-weighted oxidation state of the metal dissolving at the pit tip. Finally, the pit length is calculated as a function of time using the recursive formula:

L(t) = L(t 1) +

dL t dt

(20)

where L(t-1) is the depth of the pit calculated from the previous time (t-1), and t is the increment in time. The Damage Function Module (DFM) By combining Eqs. 8 and 20 for a fixed density of potential breakdown sites (No, number/cm2), it is possible to estimate the pitting damage function. Thus, if one observes the system at time tobs, then the number of pits that nucleate over the time increment t at tind is N , as determined from Eq. 8. However, these pits will have grown to a depth L(t), as given by Eq. 20, at the time the system is examined. By moving the increment t from t = to t = t obs , the damage function is then generated in the form of the number of pits versus the depth of the pits. If this procedure is repeated for different observation times, a family of damage functions is generated that extends to greater depths with increasing tobs. By specifying the surface area of interest, it is possible to define the service life as the time taken for one or more pit to grow to the critical length, which in this case corresponds to the wall thickness of the condensing heat exchanger. The number of pits with lengths exceeding the critical dimension is simply calculated as
N L L crit = S N(L) L
L crit L max

(21)

where N(L) is the density of pits per unit surface area and per unit increment in pit length (number/cm3) in the damage function, S is the surface area of interest (cm2), L is the pit

27

Plenary Lectures

length, L is the increment of the pit length in the damage function, and Lcrit is the critical dimension. The service life is simply the time at which N L L crit = 1. DISCUSSION The procedure outlined above for estimating damage functions for localized corrosion is currently being developed to explore the impact of corrosion on condensing heat exchangers in domestic and industrial gas-fired furnaces. The practical problem lies in selecting the most cost-effective alloys for the condensing stages of heat exchangers, because of the highly competitive nature of the furnace manufacturing business. Consequently, little room exists for over-designing furnaces by employing highly-alloyed, costly materials to fabricate the condensing sections. Therefore, selection of materials with adequate pitting resistance, and of acceptable cost, is of prime concern to furnace manufacturers and users alike. It is evident, then, that the design and materials specifications for condensing heat exchangers would greatly benefit from the development of a deterministic method for predicting localized corrosion damage functions. This, in turn, could reduce the cost of the alloy by decreasing the required database, through the availability of deterministic relationships between the damage function and important environmental variables (including pH, [Cl-], and gas composition). In this study, I present predictions of the model in comparison with experimental damage functions measured on Type 304L stainless steel by G. Stickford, B. Hindin, and A.K. Agrawal of The Battelle Columbus Laboratories. For the experimental data, the damage functions are measured on condensing heat exchanger tubes after a given number of cycles, at the hot end (temperature ranging from 326o to 353oK) and at the cold end (temperature ranging from 308o to 326oK). Each cycle consists of 240 second with the burner on and 480 sesond with burner off, which represent the dry and wet conditions, respectively. It was shown in a previous study [4], that no significant difference exists in the damage functions between the hot end and the cold end; the damage functions are, therefore, plotted without distinction between the hot ends and cold ends. Based on this experimental finding, the model is constrained to the case where the surface is covered at all times by a condensing liquid phase (wet condition). However, I choose the appropriate temperature at the hot end to calculate the damage functions in order to avoid underestimating the damage. The experimental data reported by Battelle were measured at three levels of chloride concentration (3, 26, and 225 ppm) on a number of different candidate alloys. I present in this study only the damage functions for Type 304L stainless steel, as shown in Figs. 6, 7, and 8, as a function of chloride concentration. Not surprisingly, fewer pits were observed at the lower chloride concentration (3 ppm, Fig. 6). At higher chloride levels (26 and 225 ppm), the number of pits increased substantially (Figs. 7 and 8) and led to perforation of the wall in shorter time, thus reducing the service life. However, the experimental data show some inconsistencies, which are due to the fact that different tubes were used to determine the damage functions in each case. The chemical composition, the metallurgical history, and the surface state may vary from tube to tube. Because, the kinetics of the cathodic oxygen reaction on Alloy Al29-4C are considered to be essentially identical to those on Type 304L stainless steel, the parameters for Al29-4C were chosen for calculating the corrosion potential used in estimating the damage functions
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Macdonald

(Table 1). Calculated damage functions are presented in Figs. 9 through 12 for chloride levels of 3, 10, 26 and 225 ppm, respectively. The calculations clearly indicate the progressive nature of the nucleation and growth of pits on the alloy surface. It is predicted that at lower chloride concentrations (3 ppm), fewer pits exist on the surface of the steel, while at higher chloride concentrations (26 to 225 ppm), the number of pits increases substantially, leading to the majority of the pits perforating the wall thickness in a short period of time. The predicted service life is presented as a function of chloride concentration in Fig. 13, in comparison with the experimental data. The calculations indicate that the service life of a condensing heat exchanger is highly sensitive to the chloride level in the condensate, especially at the lower chloride concentration (3 ppm). The principal effect of increasing chloride is to accelerate pit nucleation, so that, in the limits of very high chloride concentration, (~>100 ppm) in the condensate, the failure time is dominated by pit growth. Because the pit growth rate is dominated by the conductivity of the external environment (i.e., the condensate film), for any given pH and oxygen concentration, and because the conductivity is dominated by non-chloride species, the failure time becomes constant at sufficiently high chloride levels. This corresponds to the situation where the entire service life is determined by the time required for the pits that nucleate on initial exposure of the alloy to condensate and grow through the condenser wall. Noting that the service life for the case shown in Fig. 13 is calculated to decrease from 1.55 x 108 s (4.92 years) for a chloride concentration of 3 ppm to 2.34 x 107 s (0.74 year) for a chloride concentration of 225 ppm, it is evident that the time required for an active pit to perforate the wall is about three-quarters of a year, corresponding to an average pit growth rate of 0.7 mm/year. Clearly, then, the increase in the service life on lowering the chloride concentration is due almost entirely to an increase in the initiation time, and it would seem that substantial service lives for this alloy can only be obtained if nucleation becomes the dominant phase in the development of damage. Finally, due to the fact that different tubes are used in determining the damage functions, the experimental data are rather scattered. In recognition of this observation, relatively good agreement is claimed between the experimental data and the theoretical prediction. Table 1. Values for Parameters Used in Calculating Damage Functions Parameter

O G A 1 O f/s O Gs

(Passive film stoichiometry) (Mole volume of passive film) (Gibbs energy of Cl- absorption) (Constant) (Gibbs energy of cation vacancy formation) (Relaxation time) (Electric field strength) (Constant) (Constant) (Critical areal concentration of vacancies)

Value 3 30 -60 -0.375 20 0 1 x 106 0.25 -0.001 1 x 1016

Units cm3/gm cation kJ/mol V kJ/mol s V/cm V No/cm2

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Plenary Lectures

Jm D

(Vacancy flux in metal phase) (Standard deviation in cation diffusivity) (Standard deviation in cation diffusivity)

0.12 x 107 vacancy 1.0 x 10-18 vacancy 0.5 D

Vacancies/cm2.s cm2/s cm2/s

The influence of the oxygen partial pressure on the development of damage functions has been calculated, and is shown in Fig. 14. The calculations indicate that oxygen has a great impact on the service life of heat exchangers. This is because oxygen, in the condensed liquid phase on the external surface, consumes the positive current associated with the pit tip dissolution process, thereby driving the growth of the pit. By decreasing the partial pressure of oxygen from 10-4 atm to 10-8 atm, the service life of a heat exchanger having the characteristics assumed in this work could be extended from 3.02 x 107 s (1 year) to 1.05 x 109 s (approximately 30 years).

Figure 6. Measured pitting damage functions for Type 304L stainless steel heat exchanger tubes under condensing conditions: [Cl-] = 3 ppm, temperature ranging from 308o to 353oK, pit counting interval = 2.54 x 10-3 cm. a) Tobs = 4.32 x 106 s; b) Tobs = 8.63 x 106 s; c) Tobs = 1.73 x 107 s; tube thickness = 5.34 x 10-2 cm, as indicated by the dashed line

Figure 7. Measured pitting damage functions for Type 304L stainless steel heat exchanger tubes under condensing conditions: [Cl-] = 26 ppm, temperature ranging from 308o to 353oK, pit counting interval = 2.54 x 10-3 cm. a) Tobs = 4.32 x 106 s; b) Tobs = 8.63 x 106 s; c) Tobs = 1.73 x 107 s; d) Tobs = 3.46 x 107 s; e) Tobs = 5.18 x 107 s; tube thickness = 5.34 x 102 cm, as indicated by the dashed line

Figure 8. Measured pitting damage functions for Type 304L stainless steel heat exchanger tubes under condensing conditions: [Cl-] = 225 ppm,
30

Macdonald

temperature ranging from 308o to 353oK, pit counting interval = 2.54 x 10-3 cm. a) Tobs = 4.32 x 106 s; b) Tobs = 8.63 x 106 s; c) Tobs = 1.73 x 107 s; tube thickness = 5.34 x 10-2 cm, as indicated by the dashed line

Figure 9. Calculated pitting damage functions for Type 304L stainless steel heat exchanger tubes under condensing conditions: [Cl-] = 3 ppm, temperature = 350oK, PCO = 2.60 x 10-5 atm, PCO2 = 6.80 x 10-2 atm, PSO2 = 9.37 x 10-9 atm, PSO3 = 2.00 x 10-9 atm, PH2S = 1.20 x 104 atm, PNO = 1.74 x 10-8 atm, PNO2 = 2.67 x 10-8 atm, PO2 = 1.00 x 10-4 atm, pit radius = 1.00 x 10-4 cm, initial pit depth = 1.00 x 10-3 cm, pit counting interval = 2.54 x 10-3 cm, a) Tobs = 6.30 x 107 s; b) Tobs = 1.58 x 108 s; tube thickness = 5.34 x 10-2 cm, as indicated by the dashed line

Figure 10. Calculated pitting damage functions for Type 304L stainless steel heat exchanger tubes under condensing conditions: [Cl-] = 10 ppm, temperature = 350oK, PCO = 2.60 x 10-5 atm, PCO2 = 6.80 x 10-2 atm, PSO2 = 9.37 x 10-9 atm, PSO3 = 2.00 x 10-9 atm, PH2S = 1.20 x 10-4 atm, PNO = 1.74 x 10-8 atm, PNO2 = 2.67 x 10-8 atm, PO2 = 1.00 x 10-4 atm, pit radius = 1.00 x 10-4 cm, initial pit depth = 1.00 x 10-3 cm, pit counting interval = 2.54 x 10-3 cm, a) Tobs = 3.15 x 107 s; b) Tobs = 4.10 x 107 s; c) Tobs = 4.41 x 107 s d) Tobs = 5.36 x 107 s e) Tobs = 6.30 x 107 s; tube thickness = 5.34 x 10-2 cm, as indicated by the dashed line
31

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Figure 11. Calculated pitting damage functions for Type 304L stainless steel heat exchanger tubes under condensing conditions: [Cl-] = 26 ppm, temperature = 350oK, PCO = 2.60 x 10-5 atm, PCO2 = 6.80 x 10-2 atm, PSO2 = 9.37 x 10-9 atm, PSO3 = 2.00 x 10-9 atm, PH2S = 1.20 x 10-4 atm, PNO = 1.74 x 10-8 atm, PNO2 = 2.67 x 10-8 atm, PO2 = 1.00 x 10-4 atm, pit radius = 1.00 x 10-4 cm, initial pit depth = 1.00 x 10-3 cm, pit counting interval = 2.54 x 10-3 cm, a) Tobs = 4.32 x 106 s; b) Tobs = 8.63 x 106 s; c) Tobs = 1.73 x 107 s d) Tobs = 2.52 x 107 s e) Tobs = 2.84 x 107 s; f) Tobs = 2.99 x 107 s; g) Tobs = 3.15 x 107 s; h) Tobs = 3.46 x 107 s; i) Tobs = 5.19 x 107 s; tube thickness = 5.34 x 10-2 cm, as indicated by the dashed line

Figure 12. Calculated pitting damage functions for Type 304L stainless steel heat exchanger tubes under condensing conditions: [Cl-] = 225 ppm, temperature = 350oK, PCO = 2.60 x 10-5 atm, PCO2 = 6.80 x 10-2 atm,
32

Macdonald

PSO2 = 9.37 x 10-9 atm, PSO3 = 2.00 x 10-9 atm, PH2S = 1.20 x 10-4 atm, PNO = 1.74 x 10-8 atm, PNO2 = 2.67 x 10-8 atm, PO2 = 1.00 x 10-4 atm, pit radius = 1.00 x 10-4 cm, initial pit depth = 1.00 x 10-3 cm, pit counting interval = 2.54 x 10-3 cm, a) Tobs = 1.58 x 107 s; b) Tobs = 2.21 x 107 s; c) Tobs = 2.52 x 107 s d) Tobs = 3.15 x 107 s; tube thickness = 5.34 x 10-2 cm, as indicated by the dashed line

Figure 13. The measured and calculated service life for Type 304L stainless steel heat exchanger tubes as a function of the chloride concentration (parameters are identical to that for Figs. 6-8 for experimental data and Figs. 9-12 for calculation)

33

Plenary Lectures

Figure 14.

The calculated service life for Type 304L stainless steel heat exchanger tubes as a function of the partial pressure of oxygen (temperature = 350oK, PCO = 2.60 x 10-5 atm, PCO2 = 6.80 x 10-2 atm, PSO2 = 9.37 x 10-9 atm, PSO3 = 2.00 x 10-9 atm, PH2S = 1.20 x 10-4 atm, PNO = 1.74 x 10-8 atm, PNO2 = 2.67 x 10-8 atm)

SUMMARY AND CONCLUSIONS A deterministic model has been developed to predict the damage functions for condensing heat exchangers in gas-fired furnaces. The model incorporates calculations for the condensed chemistry environment, the electrochemical corrosion potential of the alloy, and mechanistic treatments of the nucleation and growth of pits. The model predicts that the chloride concentration in the condensed liquid layer has great impact on the service life of the condensing heat exchanger, particularly at low chloride concentrations. At high chloride concentrations, the service life of the condensing heat exchanger is predicted to be relatively independent of the chloride concentration, corresponding to the dominance of pit growth in determining the failure time. The service life for the condensing heat exchanger with Type 304L stainless steel tubes is predicted to decrease from 1.55 x 108 s (4.92 years) for a chloride concentration of 3 ppm to 2.34 x 107 s (0.742 year) for a chloride concentration of 225 ppm. The model predicts that the service life of the condensing heat exchanger also depends strongly on the oxygen content in the flue gas; by decreasing the oxygen partial pressure from 10-4 atm to 10-8 atm, the service life of the condensed heat exchanger can be extended from 3.02 x 107 s (1 year) to 1.05 x 109 s (approximately 30 years). Recognizing the scattered nature of the experimental data, I conclude that the algorithm developed in this work provides estimates of the service life that are in good agreement with the available experimental data, even though no a priori fit of the experimental data to the model was made. ACKNOWLEDGEMENTS The author gratefully acknowledges the support of this work by the Gas Research Institute (GRI) through Contract No. 5090-260-1969, and G. Stickford, B. Hindin, and A.K. Agrawal at The Battelle Columbus Laboratories for supporting the experimental damage functions used in this study. REFERENCES 1. D.D. Macdonald and M. Urquidi-Macdonald, "The Corrosion Damage Functions: Interface between Science and Engineering," 1992 Whitney Award Address, NACE, Nashville, Tenessee, submitted to Corrosion, 1992. 2. R. Razgaitis, J.H. Payer, S.G. Talbet, B. Hindin, E.L. White, D.W. Locklin, R.A. Cudnik, and G.H. Stickford, Condensing Heat Exchanger Systems for Residential/Commercial Furnaces and Boilers, Phase II, Battelle Report to DOE/BNL, BNL Report No. 51943, October, 1985.

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3. D.D. Macdonald, M. Urquidi-Macdonald, S.D. Bhakta, N. Khalil, and H. Yashiro, Development of Analytical Methods for Predicting Damage Functions for Pitting Corrosion in Condensing Heat Exchangers, Final report to the Gas Research Institute, GRI No 5090-260-1969, January, 1992. 4. G.H. Stickford, B. Hindin, S.G. Talbert, A.K. Agrawal, M.J. Murphy, R. Razgaitis, J.H. Payer, R.A. Cudnik, and D.W. Locklin, Technology Development for CorrosionResistant Condensing Heat Exchanger, Final Report to the Gas Research Institute, GRI-85/0282NTIS PB86-172038, October, 1985. 5. C. Wagner and W. Traud, Z. Electrochem. 44, 1938, p. 391. 6. D.D. Macdonald, Corrosion 48, 1992, p. 194. 7. D.D. Macdonald, Proc. 5th Int. Symp. Environ. Degrad. Mat. Nucl. Power Systs: Water Reactors, Monterey, California, NACE, August, 1991. 8. L.F. Lin, C.Y. Chao, and D.D. Macdonald, J. Electrochem. Soc. 128, 1981, p. 1194. 9. D.D. Macdonald and M. Urquidi-Macdonald, Electrochim. Acta 31, 1986, p. 1079. 10. D.D. Macdonald and M. Urquidi-Macdonald, J. Electrochem. Soc. 134, 1987, p. 41. 11. D.D. Macdonald and M. Urquidi-Macdonald, J. Electrochem. Soc. 136, 1989, p. 961. 12. D.D. Macdonald, M. Urquidi-Macdonald, C. Liu, S. Bhakta, N. Khalil, and H. Yashiro, Proc. Int. Gas Res. Conf., Orlando, Florida, November, 1992. 13. D.D. Macdonald, M. Urquidi-Macdonald, and C. Liu, Paper No. 173, CORROSION 93, New Orleans, Louisiana, March, 1993. 14. D.D. Macdonald and M. Urquidi-Macdonald, Corros. Sci. 32, 1991, p. 51.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

RELEVANCE OF LABORATORY CORROSION TESTS IN CORROSIVITY ASSESSMENT AND MATERIALS SELECTION: CASE STUDIES R.D. Kane CLI International, Inc. 14503 Bammel-N. Houston, Suite 300, Houston, TX USA

ABSTRACT
Laboratory tests are a convenient means for simulating service environments for the purpose of evaluating both corrosiveness of the environment and material performance. Such tests can provide substantial information upon which engineering decisions can be made. These decisions generally will be made with greater confidence and a more efficient materials design. Measurements can be made under more controlled and reproducible conditions than are possible in field or plant situations. The consequences of process changes can be evaluated in advance of the actual situation. However, when conducting tests in simulated service environments, it is most important that the experimental methods be designed with the specific intent to provide meaningful, representative, correlative results. This presentation will review the various aspects that must be included when designing, conducting, and interpreting corrosion tests in simulated service environments. Several case studies will also be presented that involve petroleum applications, including the selection of corrosion-resistant alloys in sour petroleum production, inhibition of multiphase flow lines, assessment of crude oil corrosiveness, and corrosion under insulation. Key Words: Laboratory testing, correlation, oil and gas, multiphase production, corrosion under insulation, electrochemistry

INTRODUCTION There are many types of laboratory corrosion tests utilized for various purposes. These tests can range from simple glassware immersion tests involving freely corroding, nonstressed coupons to highly sophisticated exposure tests involving dynamic replenishment, heat and/or mass transfer and high pressures maintained only through autoclave, flow loop or pilot plant operations. Furthermore, they may also involve ancillary techniques which include a variety of DC or AC electrochemical methods and mechanical loading configurations. To extend the predictive capabilities of the tests results, modeling techniques and statistical experimental design programs can be employed that allow for identification or verification of mechanisms or for establishment of linkages between the results of the laboratory test and the intended service application while minimizing the number of tests required. LABORATORY TESTING: A BASIC AND IMPORTANT TOOL In many areas of technical activity, emphasis is now being placed on reducing the overall time, funding and effort allocated for testing, research, development and engineering. In
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Plenary Lectures

some cases, corrosion testing appears as only an afterthought. At the same time, there are pressures to provide systems with higher reliability and reduced operating costs. In simpler words, these engineering concepts can be referred to in four basic terms: Better, Cheaper, Faster, Safer [1]. One of the most important aspects that must be realized is that these are not necessarily mutually inclusive concepts. Usually, substantial scientific and technological developments are required before these terms can come together in a complex engineering system. Laboratory testing is one of the basic tools available to investigate complex interactions of variables that exist in real service applications. Data can be developed which both have applied engineering significance and provide insight into fundamental relationships in engineered systems that can in turn be used as stepping stones to achieve quantum leaps in efficiency, reliability and safety [2]. Furthermore, when compared to the costs generally associated with corrosion (which can be around 10% of revenues [3]), and those saved through application of corrosion testing, there can often be a cost reduction of between one and two orders of magnitude and, in some cases, more. NEED FOR SIMULATED-ENVIRONMENT TESTS The need for simulation varies greatly depending on the purpose of the test. For example, corrosion tests are usually conducted for three reasons [4]: screening-comparison of the response of two or more materials or material conditions relative to a particular form of corrosion (e.g., general corrosion, local pitting or crevice corrosion, and stress corrosion cracking); qualification-verification that the material has a required conformance to composition and that the metallurgical or fabrication processes have resulted in a microstructure that will provide adequate corrosion performance; evaluation-assessment of the influence of process changes (e.g., temperature, additives, inhibitors, and product purity). In many cases, relatively simple, standardized tests found in NACE, ASTM, and ISO documents can be conducted that are useful for these purposes. These are relatively simple environments often involving combinations of acids and salts that can be handled in standard glassware. [5-7]. However, a limitation common to many standardized tests is the difficulty in obtaining a direct correlation between the performance in such tests and actual in-service performance. To expand the applicability of standardized tests, substantial development work is often required which establishes such correlations. This work usually includes one or more of the following: review of service or failure records on a range of material conditions or over a range of process variables, analysis of field or in-plant tests in actual service environments, and use of laboratory exposure tests conducted under simulated service conditions. In many situations, the laboratory provides the most convenient avenue since it yields firsthand data that allows the engineers to make the fine distinctions in performance required to select the most cost-effective corrosion mitigation or control methods, and thereby gives the maximum cost benefit. THE REASONABLE WORST-CASE SCENARIO In the study of corrosion in simulated environments, the concept of a reasonable worstcase scenario has been a guiding light for those involved. Being reasonable includes two aspects: reasonable levels of corrosive severity and reasonable involvement of expense and time. It is often necessary to refine the set of exposure conditions by a process of
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prioritization so that only the most important variables related to the operable corrosion mechanisms are taken into account and thereby minimize testing costs. Keeping these two aspects in mind, one must first define and preserve the active in-service mechanism(s) of corrosion. Once this has been completed, one must identify the aggravating and mitigating factors that combine in the actual service condition to determine the severity of corrosion. SIMULATED ENVIRONMENT TEST PROCEDURES Several case studies are presented herein which highlight a few of the basic, yet important, concepts which provide the link between the laboratory and field conditions. Case Study No. 1: Simulation of Conditions of Deaeration or Aeration One of the most important and universally applicable situations that must be evaluated when conducting laboratory tests in simulated service environments is the need to produce a reasonable representation of the level of deaeration or aeration found in the actual environment. The main reason for the importance of this effect is that corrosivity, in many service applications, can change dramatically with changes in oxygen content. Aeration accelerates anodic corrosion processes with a concomitant increase in localized corrosion activity (i.e., pitting, crevice attack and stress corrosion cracking). Examples of oxygen effects can be seen in applications such as seawater injection, the use of heavy brine completion fluids in oilfield operations and desalination. As shown in Fig. 1, the corrosion rate of steel increases by an order of magnitude going from 10 ppb to just 100 ppb [8]. It only takes very low levels of oxygen contamination (about 1% of normal atmospheric saturation levels) to greatly accelerate corrosion. Furthermore, due to the sensitivity of corrosion reactions even in low levels of aeration, oxygen contamination can produce excursions to higher corrosion rates that have prolonged effects [9]. The increase in localized anodic attack produced by aeration can be illustrated by its interaction with other species such as chlorides and sulfides. An example, in terms of susceptibility to stress corrosion cracking (SCC), is the interaction between dissolved oxygen and chlorides in elevated temperature applications involving alkaline phosphate treated boiler water [10]. As the availability of oxygen increases above the 0.1 ppm (100 ppb) level, the tolerance for chloride is reduced resulting in a dramatic increase in susceptibility to SCC.

Figure 1. Corrosion rate vs temperature for various oxygen levels

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The situation in aqueous sulfide-containing environments is even more complicated since oxygen can result in the formation of elemental sulfur, acids, and in some cases, polysulfide species. These can synergistically interact with the oxygen effects mentioned previously to produce quite severe limitations on the corrosion and SCC performance of even very highly alloyed materials. Such conditions can be found in applications which involve pumping of sour oilfield brines, injection of wastewater and flue gas desulfurization. A comparison of the minimum required pitting resistance equivalent (PRE) for conditions involving a simulated sour oilfield service can be seen for identical situations (0.7 kPa H2S, 138kPa CO2, 2 meq/L HCO3, 30,000 ppm Cl-, 65oC) except one is aerated and one deaerated [11]. For the deaerated condition, the minimum pitting resistance equivalent [PRE = Cr + 3.3Mo + 11N + 1.5(W + Cb)] is only 12. This would indicate successful use of materials with > 12 Cr. However, this same environment under aerated conditions yields a minimum PRE value of 30. Under evaporative conditions, this can increase still further. Understanding the conditions of aeration in the service application is necessary to reproduce similar conditions in the laboratory corrosion test. For example, most geochemical systems naturally contain less than 10 ppb oxygen. By comparison, mechanical deaeration techniques usually will not go below 100 ppm. Multiple vacuum, ultra-low oxygen inert gas purge cycles and prolonged gas purges are usually required to get below 50 ppb oxygen. In some cases, oxygen scavengers must be used to obtain complete deaeration. However, these must be used carefully because they may, in some cases, add other chemical species into the environment that can complicate electrochemical measurements. Case Study No. 2: Simulation of Corrosion in Multiphase Environments There are many factors that need to be considered when conducting corrosion assessments in multiphase environments. These include important factors related to the dynamic or flowing nature of the fluids which determine the mode of flow [12] and the kinetic shear forces that are imparted by the flowing fluids on the pipe wall. There have been several major studies involving very sophisticated simulations of three-phase flow. These studies are particularly capital intensive and costly since major investments must be made in the handling, pumping and disposal facilities required for such tests. However, there are no real alternatives for investigating questions involving the direct effects of flow regime such as measuring the shear forces developed by particular flow regimes and operating conditions and the movement of inhibitors [13]. On a more practical basis, more simple yet reasonable approximations of multiphase flow conditions can be obtained using pseudo-three phase systems such as the flow loop shown in Fig. 2 [14]. These systems provide for the establishment of three phase conditions (gas/oil/water) in a reservoir autoclave. Under these conditions, the primary corrodents are dissolved gases (e.g., CO2, H2S and sometimes O2) and an aqueous brine or condensed water phase. Facilities for replenishment of both the gas and liquid phases must be considered depending on the exact nature of the environment. Simulation of the affects of a flowing environment is usually based on modeling the shear stress produced in service on the metal surface by the flowing liquid containing the dissolved gases using the equations given in Table 1 [15]. The main assumption utilized in this approximation is that the major contribution to the wall shear stress is usually made by the liquid phase. In most cases, this

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technique is valid since the contribution of liquid phase density and viscosity on the resultant shear stress predominates over that of the gas phase.

Figure 2. MAPS - Multiphase Autoclave Pipeline Simulator Of significance in most flowing multiphase systems is the handling of slug flow which is the predominate flow regime for horizontal and near horizontal flow applications. The main attribute of slug flow is the very high shear stresses and accompanying high turbulence in the region of the flow just ahead of the moving slug [16]. This effect results in levels of shear stress much greater than those produced by the bulk fluid. It has been proposed that this is the location where excessive corrosion is generated as a result of the effect of locally high shear stress and turbulence on both corrosion and inhibitor films. Investigations have recently focused on techniques such as flow loops and jet impingement to reproduce accurate simulations of such highly turbulent conditions for assessment of corrosion resistance and inhibitor performance [17]. Another major effect that must be addressed in multiphase systems is the potential role of the oil phase as a possible mitigation factor in terms of reducing the corrosion rate [18]. The properties of the hydrocarbon/liquid phase significantly influence the severity of the environment with respect to weight loss corrosion (see Fig. 3). In a typical case, oil/water mixtures remain relatively non-corrosive under flowing conditions of up to about 30% water cut resulting mostly from the preferential wetting and persistence of the oil phase on the metal surface. However, depending on the nature of the liquid hydrocarbon phase, some cases become corrosive with very low water cuts (<5%) while other cases do not become corrosive until more than 50% water is reached. The exact variables that relate to these mitigating
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effects have only been qualitatively investigated. Therefore, when simulating service applications, the exact nature of the oil phase should be considered since it may play a major role in the overall corrosivity of the system and in the efficacy of inhibitor treatments. Furthermore, the presence of the nonconductive oil phase in multiphase tests can also produce confusing results when electrochemical techniques are used as the sole basis for evaluation. Care must be utilized in the selection of corrosion monitoring techniques and the comparison of this data with the results of physical examination, mass loss and localized corrosion measurements. Table 1. Flow/Shear Stress Relationships Description Relationship VD Determine dimension-less Re = parameters to describe fluid flow characteristics (e.g., Reynolds number) to account for mass transfer effects f = z (Re, e/D) Determine friction factor, f, to account for pipe wall roughness (from Moody diagrams) fV 2 Determine wall shear stress, t, as = 2 a function of the friction factor and other flow properties. Vt Vs Determine flow regime (annular, fr = g . heff stratified, bubble, slug, etc.) to estimate correction factors (e.g., for slug flow, Jepson et al. use the Froude number as a basis to estimate turbulent intensity). r Laboratory simulation: Jet = 0.0112V R r impingement (Giralt and Trass) Laboratory simulation: Rotating = 0.0791Re0 . 3 r 2 2 cylinder electrode (D. C. Silverman) Summary: The corrosion rate in fully developed turbulent pipe flows computed from field parameters can be simulated in the laboratory produced. can be expressed in terms of wall shear stress. Wall shear stress through experimental methods, and hence similar corrosion rates.
2 . 0 2 0 .182 e 0

Case Study No. 3: Simulation of Geometry of Exposure One of the factors that can have a great impact on corrosion severity is the geometry of the service application. Obvious cases are those involving crevices, seams, laps and welds where the formation of an occluded cell can result in differences between local and bulk solutions. In some cases, the whole service condition may bring together somewhat unique combinations of solution and geometric variables which cannot be accurately simulated by
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simple immersion or atmospheric tests. One such case that illustrates this situation is exhibited by corrosion under insulation (CUI).

Figure 3. Effect of hydrocarbon/liquid phase on weight loss corrosion CUI can result from a build-up of water and contaminants in the annular space between the metal surface and the thermal insulation. It is compounded by situations such as hot wall effects and alternate wetting and drying. The problem typical of CUI is that corrosion rates are typically greater than predicted based on aqueous corrosion data produced from either open or closed system measurements [19]. In an open system, corrosion rates are generally low due to the decreasing solubility of oxygen with increasing temperature. The CUI situation more closely represents a closed system; however, prior studies attempting to simulate CUI by these methods have generally been unsuccessful. Recently, experiments were conducted with a special test cell designed to model CUI (see Fig. 4) [20]. This novel approach included the use of an internally heated metal tube and isolated ring specimens surrounded by insulating material. The annular space was filled with a simulated atmospheric condensate. Corrosion was assessed using ring specimens that could be monitored using linear polarization resistance (LPR) techniques per ASTM G59, mass loss per ASTM G1 and localized corrosion rate per ASTM G46 [21-23]. Tests incorporated isothermal conditions, thermal cycling and alternate wet dry conditions. Figure 5 shows the comparison of isothermal and cyclic tests. The mass-loss corrosion rates show values comparable to those associated with CUI in field and plant operations. Of particular interest is the variation in corrosion rate with time for the cyclic tests. The trend indicates that periods of maximum corrosivity involve the periods during re-wetting of the metal surface following the dry cycle. The peaks in corrosion rate are 2 to 3 times the steady state corrosion rates. Furthermore, for cyclic wet-dry conditions, the steady state corrosion rate also increases with time. The benefit of protective surface treatments which results in much lower rates of corrosion versus time can also be seen.

Case Study No. 4: Need for Environment Replenishment


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Two major concerns when simulating service conditions in the laboratory are the changes in severity that may be caused by depletion of reactive constituents in the corrosive environments and build-up of corrosion products or by-products. Both can modify the corrosivity of the environment to produce a variation in the severity of corrosion from that in the service application. Therefore, periodic monitoring of the laboratory environment may be required to determine the rate of consumption or build-up of various species. Additionally, replenishment may be necessary to eliminate the undesirable effects that they can produce.

Figure 4. Corrosion under insulation (CUI) cell designed by CLI International, Inc.

Figure 5. Instantaneous and mass-loss corrosion rates for a corrosion under insulation (CUI) system An example illustrating these situations is industrial applications having high partial pressures of carbon dioxide (100-600 psia) in combination with low to moderate hydrogen
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sulfide partial pressures (0.01 to 1.0 psia). These conditions illustrate the importance of both liquid and gas phase replenishment in these high CO2/low H2S systems. In such systems, the steel corrosion product (Fe+2) is soluble in the aqueous phase at low to intermediate temperature (< 60 oC). Additionally, this reaction is accompanied by an increase in the HCO3 concentration, which has a buffering effect resulting in increased pH. These factors can result in the premature formation of a protective FeCO3 scale. Furthermore, corrosion will also tend to consume the initial low-level supply of hydrogen sulfide. These three effects, if not controlled, will generally result in an artificially low corrosion rate for steel when compared to the service application. An autoclave procedure is needed for replenishment of the gaseous and/or liquid phases so that the test duration can be prolonged and accurate corrosion assessment can be achieved [24]. Additionally, in most cases, replenishment procedures should be combined with the careful use of a large solution volume to specimen surface area ratio to achieve optimum results. In cases where a low hydrogen sulfide partial pressure is being utilized, special care must be taken to maintain the intended amount of this reactive constituent. The difficulty in this process increases directly with the corrosion rate of the materials being tested, the total specimen surface area and decreasing hydrogen sulfide partial pressure. The case shown in Fig. 6 is for replenishment involving tests of corrosion resistant alloys [25]. It can be seen that following the first gassing, the desired hydrogen sulfide partial pressure was achieved, but it decreased to a very low level after a short exposure period. At least two more replenishments were required to achieve acceptably constant levels of hydrogen sulfide in the test environment.

Figure 6. H2S partial pressure vs time Case Study No. 5: Acceleration of Corrosion Processes One of the greatest needs in laboratory corrosion testing is the ability to attain accurate simulation of the test conditions while simultaneously achieving acceleration. The test conditions must produce a reasonable mechanistic simulation yet achieve a degree of acceleration which allows the laboratory test to predict future in-service events in a reasonably short period of exposure time. This is perhaps the most difficult combination of requirements. Oftentimes, tests that are accelerated produce artifacts in the data related to the influence of corrosion mechanisms which are not present in the actual service. Such tests
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must be approached and conducted with caution. Examples of beneficial acceleration techniques are electrochemical techniques such as controlled polarization, mechanical techniques such as slow strain rate and fracture mechanics testing, and elevated temperature short duration tests on polymeric materials using Arrhenius. modeling techniques. An example of electrochemical acceleration in a simulated environment was used to produce corrosion films on wear test specimens in a short period of exposure (< 10 days) that were comparable to those produced on actual components over a long period of service (1.5 years). The first step was to achieve accurate simulation of the service environment which, in this case, was high purity cooling water for a boiling water reactor (BWR). Since the intended fluid flow rate was low (2.2-2.8 ft/sec), a rotating cage setup located inside of the autoclave reservoir was utilized [26] (see Fig. 7). The cage employed a special contactor system to allow for application of a controlled anodic current while monitoring electrochemical current. To minimize corrosion of the internal fixtures and application of the anodic current to only the specimens, the fixture was constructed from pre-oxidized Zr-alloy parts.

Figure 7. Rotating cage setup An extensive literature/experience survey was conducted to determine the rate of steel corrosion with time in the BWR environment and the chemical structure of oxide that would be expected [27]. Based on this information, it was estimated that the corrosion film would be composed of a-Fe2O3 near the surface and Fe3O4 near the metal/oxide interface and, after 18 months of exposure, it would be about 24,000 thick. Using the simulated environment, a test was developed that utilized a slight anodic current to accelerate corrosion. Following a series of qualification tests, corrosion films were produced which were a the mixed iron oxide composition very close to the requirements. After an exposure period of ten days, the films were found to be between 15,3000 and 30,600 in thickness. These test specimens were subsequently utilized to conduct frictional wear tests so that the actuating force required to manipulate control valves could be estimated.
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ACKNOWLEDGMENTS I wish to thank the staff of CLI International, Inc. for their hard work and dedication and also the CLI clients which have provided financial support for many technical investigations. Both have been essential, and have contributed greatly to the development and use of the techniques highlighted in this paper. I also give my appreciation to Ms Delia Cuellar, who has worked and collaborated with me for many years. Thanks are also given to those key people who have helped to provide a guiding light into the practical applications of laboratory testing: Dr. J Brison Greer, Mr. Walter K. Boyd, Professor Joe Payer, Dr. Peter Rhodes and Mr. Bill Ashbaugh. REFERENCES 1. K. Lewis, Corrosion and Failure Prevention Using Appropriate Materials Selection during Design: Better, Cheaper, Faster, Safer, Presentation at the Golden Gate Materials Technology Conference, San Francisco, California, February 1-3, 1995. 2. J.H. Payer, Increased Reliability and Useful Life through Better Understanding of Corrosion Processes, Plenary Lecture, Seventh Middle Eastern Corrosion Conference, Bahrain Society of Engineering/NACE International, Manama, Bahrain, February 2628, 1996, pp. 50-53. 3. B.C. Syrett, Cost Effective Corrosion Control in Electric Power Plants, Plenary Lecture, Seventh Middle Eastern Corrosion Conference, Bahrain Society of Engineering/NACE International, Manama, Bahrain, February 26-28, 1996, pp. 1-18. 4. J.W. Spence, et.al., Planning and Design of Tests, Corrosion Tests and Standards, R. Baboian, ed., MNL 20, ASTM, West Conshohocken, Pennsylvania, 1995, pp. 33-39. 5. ASTM G31, Standard practice for laboratory immersion corrosion testing of metals, ASTM Annual Book of Standards, Section 3.02, West Conshohocken, Pennsylvania. 6. ASTM A262, Standard practices for detecting susceptibility to intergranular attack in austenitic stainless steels, ASTM Annual Book of Standards, Section 3.02, West Conshohocken, Pennsylvania. 7. ASTM G48, Standard test methods for pitting and crevice corrosion resistance of stainless steels and related alloys by the use of ferric chloride solution, ASTM Annual Book of Standards, Section 3.02, West Conshohocken, Pennsylvania. 8. J.W. Oldfield and B. Todd, Corrosion considerations in selecting metals for flash chambers, Desalination 31, 1979, pp. 365-383. 9. A. Ikeda et.al., Corrosion Behavior of Low and High Alloy Tubular Products in Completion Fluids for High Temperature Deep Wells, Paper No. 46, NACE Corrosion/92, March 1992, NACE, Houston, Texas. 10. M. Fontana, Corrosion Engineering, 3rd edition, McGraw-Hill, Inc., New York, 1986. 11. R.D. Kane and S. Srinivasan, Socratestm: Selection of Corrosion Resistant Alloys through Environmental Specification, CLI International, Inc., Houston, Texas, 1996. 12. C.A. Palacios and J.R. Shadley, CO2 Corrosion of API N-80 Steel at 71oC (160oF), Paper No. 476, NACE Corrosion/91, March 1991, NACE, Houston, Texas. 13. X. Zhou and W.P. Jepson, Corrosion in Three Phase Oil/Water/Gas Slug Flow in Horizontal Pipes, Paper No. 26, NACE Corrosion/94, March 1994, NACE, Houston, Texas.

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14. Course Materials, MAPStm - Multiphase Autoclave Pipeline Simulator, Short Course on Corrosion Test Methodologies for Inhibitor Evaluation, CLI International, Inc., Houston, Texas, 1995. 15. S. Srinivasan, Internal report on flow modeling for laboratory simulation of field effects, CLI International, Inc., Houston, Texas, 1995. 16. W.P. Jepson, The Effect of Multiphase Flow on the Performance of Corrosion Inhibitors in Oil and Gas Pipelines, Seventh Middle Eastern Corrosion Conference, Bahrain Society of Engineering/NACE International, Manama, Bahrain, February 2628, 1996, p. 80. 17. K.D. Efird et al., Experimental Correlation of Steel Corrosion in Pipe Flow with Jet Impingement and RCE Laboratory Tests, Paper No. 81, NACE Corrosion/93, March 1993, NACE, Houston, Texas. 18. K.D. Efird, Petroleum Testing, Corrosion Tests and Standards, R. Baboian, ed., MNL 20, ASTM, West Conshohocken, Pennsylvania, 1995, p. 354. 19. W.G. Ashbaugh, Corrosion under thermal insulation, Metals Handbook Volume 13: Corrosion, 9th edition, ASM International, Materials Park, Ohio, 1987, p. 1145. 20. Private Communication, W.G. Ashbaugh, D. Abayarathna, R. Kane (CLI International, Inc., Houston, Texas) N. McGowen (Elisha Technologies - Moberly, MO), March 1996. 21. ASTM G59, Standard practice for conducting potentiodynamic polarization resistance measurements, ASTM Annual Book of Standards, Section 3.02, West Conshohocken, Pennsylvania. 22. ASTM G1, Standard practice for preparing, cleaning and evaluating corrosion test specimens, ASTM Annual Book of Standards, Section 3.02, West Conshohocken, Pennsylvania. 23. ASTM G46, Standard practice for examination and evaluation of pitting corrosion, ASTM Annual Book of Standards, Section 3.02, West Conshohocken, Pennsylvania. 24. Course Materials, MARStm - Multiphase Autoclave Replenishment System: Short Course on Corrosion Test Methodologies for Inhibitor Evaluation, CLI International, Inc., Houston, Texas, 1995. 25. Private Communication, M.S. Cayard to R.D. Kane (CLI International, Inc., Houston, Texas, March 1996. 26. R.D. Kane, High Temperature and High Pressure Testing, Corrosion Tests and Standards, R. Baboian ed., MNL 20, ASTM, West Conshohocken, Pennsylvania, 1995, p. 108. 27. T. Honda, et al., Corrosion of ferrous materials and deposition of trace metal ions in high purity water at high temperature, Corrosion Engineering 36, 1987, pp. 257-266.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CORROSION OF CONDENSERS IN MULTI STAGE FLASH EVAPORATION DISTILLERS A.M. Shams El Din Material Testing Laboratory, Water and Electricity Department, Abu Dhabi, UAE

ABSTRACT
All Arab Gulf States suffer from shortages in freshwater resources. The deficiency is made up for by desalinating seawater, mainly by the multi stage flash (MSF) evaporation technique. Depending on its design, an MSF distiller has between 16 and 39 cells, arranged in one or two decks. The basic element of a cell is the condenser which converts the vapor into the distillate. The condenser is a structure incorporating many components, each susceptible to a variety of corrosion forms. The lecturer will describe the fine features allowing the characterization of the types of attack affecting the water boxes, tube-plates, tube supports and the tubes themselves. Counter measures necessary to remedy the defects and/or eliminate their causes will be mentioned. Vapor side corrosion of condenser tubes made of copper-base alloys will be high lighted. Attack causes the thinning of the tube walls and the contamination of the distillate by copper above permissible limits. A number of operational processes affect the corrosion of MSF condensers. The roles of seawater chlorination, ferrous sulphate dosing, scaling and ball cleaning, acid cleaning and distiller outage will be treated in some detail. Key Words: Water boxes, tubes, tube supports and plates, vapour side corrosion, chlorination, ferrous sulphate dosing, scaling, ball cleaning, acid cleaning, shut-down

INTRODUCTION All Arabian Gulf States suffer from a scarcity of freshwater resources. The available underground water is either nonrenewable, or gradually builds up salinity as a result of exhaustive pumping. On the other hand, rainfall over the area is scant and unpredictable, and extends over a fairly long period of time. Potable water deficiency is remedied by desalinating seawater. Two techniques, viz. distillation and reverse osmosis, are commonly employed. Distillation, which represents the largest share, is generally carried out by multi stage flash (MSF) evaporation. An MSF distiller is a mammoth metallic structure operating on seawater at temperatures between ambient and 100-115C. It incorporates a variety of components, each designed to perform a definite task in the overall process of distillation. The number of stages of an MSF unit is a design parameter and may vary between 16 and 39. A schematic presentation of an
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18 stage (cell) MSF distiller is given in Fig. 1. Fresh, chlorinated, settled seawater is passed through the condensers of cells 18, 17 and 16 (heat rejection section) to raise its temperature to 42C. Part of this water, to be used as makeup water, is deaerated and mixed with return brine in the flash side of cell 18. Between 15 and 30% of this mixed water is rejected as blowdown, and the rest is pumped into the condenser tubes of cell 15, which represents the start of the heat-gain section. As water passes through cells 14, 13, 12, etc., its temperature rises gradually. Following cell 1, the water passes through the brine heater to bring its temperature up to the top value for distillation. Coming out of the brine heater, the water goes through the flash chambers of the various cells in the reverse direction of flow in the condensers, i.e., cells 1, 2, 3, and so forth. The water distills under vacuum, and its temperature progressively decreases. The basic element of a cell in an MSF evaporation unit is the condenser which converts the vapor into distillate. The condenser is a multicomponent structure comprising the water boxes, the tube plates, the tube supports and the tubes themselves. A typical condenser is represented diagrammatically in Fig. 2. During operation, all parts of the condenser suffer corrosion in a variety of ways, depending on the material they are manufactured of. It is estimated that between 80 and 85% of distillers outages are the result of defects occurring in the condenser system, in particular the tubes. The shape of failure can in many instances be the same, but its causes may differ widely. The choice of the necessary countermeasures depends, therefore, on the successful deciphering of the fine features of attack. The present paper describes the different forms of corrosion which affect the four basic components of condensers in MSF distillers. The material included is largely based on observations made by the author in the Umm Al Nar Power and Desalination Plant (Abu Dhabi, UAE) during the past 14 years. The presentation is of an orientative nature and is intended to serve a wide spectrum of people. For the normal operator, with little or no experience in corrosion, it is an introduction to the subject. For the operation engineer it evokes awareness and interest in material performance. For the corrosion specialist, it lists alternative countermeasures. No attempt is made to deal with the theory of metal corrosion. For the first two categories of persons this is not necessary, while for the specialist the information is assumed to be well known. The reader must, however, be well aware of the terms associated with the common forms of corrosion, viz. general- (uniform-), galvanic(bimetallic-), crevice-, pitting-, intergranular-, dealloying- and erosion-corrosion, as well as corrosion cracking. Further, it is beyond the scope of the present paper to enlist all materials suitable for constructing part or all of the condenser system of MSF plants. Broadly speaking, these fall into four classes: mild- and carbon steels, stainless steels, copper-base alloys and titanium alloys. Details of the composition of these materials, their physical properties and their corrosion characteristics are well documented [1-15].

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Figure 1. Schematic presentation of an 18-stage MSF distiller

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Figure 2. Schematic presentation of an MSF condenser. CORROSION OF WATER BOXES A variety of materials is used to manufacture water boxes. In some old, small units cast iron was used. Cast iron undergoes severe general attack in flowing seawater, which is intensified by contact to copper alloys used as tubes and tube plates. For this reason, unprotected iron water boxes were designed with above-normal thicknesses to ensure longer service life. Corrosion of iron protects the copper-base components of the distiller and raises the resistance of copper tubes against erosion-corrosion [16-18]. Excessive attack on the iron water boxes leads to graphitization and the loss of mechanical strength. Graphitization also promotes the galvanic corrosion of copper alloys. Means of preventing attack on iron water boxes involve their isolation from seawater with appropriate paints or rubber-lining. This approach is ideal so long as the cover remains intact. Once it has failed, though, excessive corrosion takes place as a result of the area ratio. Parts of the failed linings might adhere to tube plate and/or block tube entrances, causing crevice and pitting attack. Corrosion of iron water boxes by seawater can be harnessed through cathodic protection. Sacrificial zinc anodes are commonly employed. These must be monitored to ensure their presence and active functioning. Nowadays, MSF water boxes are manufactured of copper-base alloys; e.g., aluminium bronze and gunmetal. Solid or claded cupro-nickels are more customary. There is no difference between the corrosion resistance of these materials in the massive and the cladded states, so long as seawater does not creep behind the clading. When this happens, severe galvanic corrosion of the base plate takes place. Aluminium bronze, and the cupro-nickels are relatively immune to general attack by seawater. They suffer, however, erosion-corrosion when the water flow exceeds a certain, material-dependent velocity. Attack is more severe if the water carries sand, shell fragments, entrapped air or vertices. This type of attack is recognized by the marks developed on the metal surface which depict the water flow pattern. Erosion-corrosion is reduced, or even eliminated, by improving the intake filtration systems and/or by reducing the flow velocity. Eroded areas are cleaned and filled with fiberglass or similar coatings, resistant to impingement. The water boxes undergo corrosion when parts of the surface are shielded by nonconducting materials (e.g., plastic sheets and pieces of failed coatings) brought in with the water. In the heat-rejection cells, where temperature still allows them to flourish, barnacles and shells escaping the band screen can attach themselves to the surface of the water box. There they not only promote crevice attack, but they also secrete harmful sulphur- and nitrogen-containing chemicals. Failure of water boxes might also result from material defects. These include alloy inhomogeniety, defect welds, phase changes resulting from preferential cooling, foreign inclusions, stresses and cracking. There is no general remedy for all types of faults. Frequent inspection of the metal surface for microcracks and pits is recommended, especially following commissioning. Attacked areas may be ground and filled with a neutral filling. Excessive
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corrosion will require removal of the defective area and careful repair welding. Most cases of water box failure can be eliminated through cathodic protection using sacrificial iron anodes. The released ferrous ions also improve the corrosion resistance of the copper condenser tubes and tube plates. CORROSION OF TUBE PLATES Tube plates are commonly manufactured from stainless steel or copper-base alloys (i.e., brasses, bronzes, and cupro-nickels). These materials are used as such or are clad over Csteel. The choice of plate material is made on the basis of mechanical characteristics, cost considerations and compatibility to condenser tubes. Depending on their composition, and the operational and environmental conditions, tube plates undergo different forms of corrosion: Erosion-Corrosion This results from the impact of seawater at velocities higher than design the values, from impingement attack by entrained gas bubbles or from abrasion with sand loaded water. The metal surface assumes a rough touch and acquires a shiny silver or golden luster due to the loss of the natural protective film. Attack need not cover the whole plate since turbulence and vortices are not equally distributed on the surface. Countermeasures against erosion-corrosion involve the reduction of flow velocity, the removal of suspended material from the circulating water and the release of entrapped gases. Severely attacked plate areas are ground and filled with a neutral coating. Ferrous sulphate dosing improves surface film resistance to erosioncorrosion. Crevice Corrosion Tube plates may undergo crevice attack when covered by nonconducting material (e.g., polythene sheet, paint flakes etc.). In heat-rejection cells, barnacles and shell animals continue to strive and stick to the surface of tube plates. During their life the organisms produce organic nitrogen and sulphur compounds which intensify the attack on copper alloys. The released copper ions eventually kill the animal, and crevice attack continues thereafter by way of an oxygen concentration cell mechanism. As a result of the large thickness of the tube plate, it is improbable that crevice attack will continue undetected till it cuts through the metal. The water box is likely to be opened, for one reason or the other, at which time preventive and corrective measures are undertaken. These involve screening water properly at the intake, raising the chlorination level to discourage the entry of marine organisms, and cleaning and filling present crevices with neutral filling followed by a coat of hard epoxy resin. Crevice/Galvanic Corrosion Another type of tube-plate failure develops on claded plates with imperfect tube holes. Expansion of the tubes leaves behind narrow spaces which are filled with seawater. Corrosion starts as crevice corrosion until the water reaches the base metal under-covered where the attack is accelerated as galvanic corrosion. Left for a long time, attack might eat through the thickness of the plate. During its early stages, when the crevice corrosion is only operative, corrosion might escape the attention of the inexperienced or hasty eye. Careful

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examination will reveal, however, tiny recessions between the tubes and plate. A steel needle tip will measure the depth of attack. During the galvanic phases however, corrosion is recognized by the brown stains of iron oxides oozing from between the tubes and the plate. Counter-measures against crevice/galvanic attack involve the rerolling (re-expansion) of the tubes. In most cases, this proves to be adequate for eliminating the clearance between the tubes and the plate. If this fails, more stringent measures are undertaken. These involve the thorough cleaning of the inside of the dried crevice with the help of steel needles until it is free of corrosion products. An air compressor producing a micro-jet might prove useful. This is followed by the intrusion of a natural fill and a cover with a hard epoxy resin. When the claded tube plate and the tubes are of the same material, welding after cleaning presents another practical alternative. Corrosion by Dealloying Tube plates made out of uninhibited brasses (i.e., copper-zinc alloys) undergo rapid and severe dezincification by seawater, especially at high temperatures. Dealloying occurs in patches in what is commonly referred to as plug-type attack. Naval brass (i.e., brass with 0.5-1.0% tin) undergoes differential attack in which the defected areas are covered with easily detachable scales of the corrosion products. This type of attack is designated as exfoliation or layer-type corrosion. Uninhibited brasses should not be used as tube plates in condensers operating on seawater. Their use in small units is not due to good performance but to over-dimensions which prolong their life span. Dezincification is remedied by grinding the dealloyed areas and filling the depressions with an appropriate neutral material. The whole plate surface, and preferably, the tube ends as well, are coated with an approved epoxy resin. Cathodic protection with sacrificial mild steel anodes will ensure stiffing of corrosion should the coat fail. CORROSION OF CONDENSER TUBES Failure of condenser tubes constitutes the largest cause of distiller outages, so the choice of tube material is accordingly crucial. Tubes have to have reasonably high thermal conductivity, sufficient ductility to expanded into the tube plate, and their corrosion performance should be well understood. Last but not least is the question of cost. Three types of materials present themselves. These are copper-base alloys, stainless steels, and titanium. Each possesses its own merits and limitations, and will be treated separately. Corrosion of Copper-Base Condenser Tubes [19-29] Copper-base alloys suitable for manufacturing condenser tubes encompass the brasses, the bronzes and the cupro-nickels. Simple brasses are 70/30 copper-zinc alloys, occasionally with 0.5-1.2% tin or lead [12]. These must be inhibited by minute amounts of arsenic, antimony or phosphorus to prevent dezincification. Aluminium brasses are a family of copper-zinc alloys containing between 1.8 and 2.5% aluminium, with minor quantities of iron, nickel, manganese and lead. Tubes of these brasses exhibit excellent resistance to brines at high temperature. They do, however, suffer erosion-corrosion at flow rates above about 2 ms-1, and are not immune to polluted (i.e., H2S and NH3) seawater. Their relatively low price is, however, an appreciated asset.
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Bronzes, on the other hand, are copper-tin alloys. As a rule, simple bronzes are superior in property to simple brasses. The reader must be aware of the confusion associated with the nomination of bronzes [12]. Materials like aluminium bronzes (i.e., C 63700 and C 65200) and manganese bronzes (i.e., C 67500 and C 67800) are in fact high-tensile brasses, designated as bronzes just to praise their properties. True bronzes contain up to 13% tin. Gun metals contain both tin and zinc; types A and LG 3 are resistant to erosion-corrosion. The resistance is further improved through additions of 1.0-2.0% nickel as in Admiralty gun metal G1. An important material for condenser tubes running on seawater is the so called AP bronze, which contains 8% tin, 1% aluminium and 0.1% silicon. In contrast to aluminium brass, AP bronze withstands corrosion by H2S-polluted seawater. Its life expectancy is estimated to be 2-4 times that of aluminium brass [30,31]. In nonpolluted seawater, aluminium brass is preferred to aluminium bronze on the basis of cost [32]. Copper and nickel are freely soluble in one another and form an extended solid solution. A large number of alloy compositions were prepared and their resistance to corrosion by seawater was evaluated [33]. Two alloys, viz. the 90/10 and the 70/30 were specially attractive, particularly after the discovery of the beneficial effect of small additions (up to 2%) of iron and manganese. As tube materials, the cupro-nickels withstand flow velocities up to 6.0 ms-1 [34] and are fairly resistant to fouling in seawater. They are, however, easily affected by polluted water. Nowadays condensers with tubes made of 90/10 and 70/30 cupronickels represent some 85% of all copper-base condensers. Copper-nickel alloys containing 0.5% chromium were recently reported [35,36]. These are described as exhibiting high tolerance to erosion and impingement attack. Similar effects are achieved through additions of solutionized iron [37]. Copper-base condenser tubes fail much in the same way; the only difference being the extent and rate of attack. Failure is commonly manifested as a pore leading to the admixing of the brine with the distillate. Many reasons are responsible, however, for pore production. A clear understanding of pore morphology is, therefore, essential in establishing the cause of corrosion and in ensuring the choice of appropriate measures to prevent the further escalation of the problem. From the water side, condenser tubes may fail by: Crevice Corrosion Crevice corrosion in condenser tubes results wherever parts thereof get covered by nonconducting materials such as seashells, barnacles, sand, clay, and damaged sponge balls. Damage from barnacles attaching themselves to tube walls is limited to the cells of the heat rejection section where environmental conditions (i.e., temperature, oxygen content, and nutrients) still allow their growth. Barnacles can anchor anywhere along the tubes length and induce corrosion by way of depleting oxygen and secreting harmful chemicals. Due to gravity, under-deposit attack develops at the bottom of the tubes. Very seldom, do they cross the five and seven oclock limits. Another feature characterizing crevice attack is that the pore lies in the centre of a clear imprint of the cover that initiated the attack. Elongated pores follow, in most cases, the flow direction although oval cuts with their major axes perpendicular to the flow have been recorded. A linear succession of pores along the tubes length indicates a thick sand or clay deposit. Contrary to some claims [38], crevice attack

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does not develop under alkaline scales. The main constituents of the scales, CaCO3 and Mg(OH)2, act as anodic inhibitors. Crevice corrosion of condenser tubes can be stopped or greatly reduced by controlling the entry of undesirable material. This requires the proper functioning of the band screen and the appropriate chlorination of the feedwater to discourage marine life inside the lowtemperature cells. Dead shells and barnacles do not adhere to tube walls. Prolongation of the time of stagnation in the settling basins helps prevent the accumulation of sand and silt inside the tubes. The use of Tapproge ball cleaning, brush cleaning and back-flushing of the tubes during shutdown, and the eventual acid-washing of the distiller remove tenaciously held deposits and bodies. Stress-Corrosion Cracking (SCC) The expansion of tubes in the tube plate results in the accumulation of stresses along the diameter-change zone. Although these stresses are within the range of the design values, they induce, on the long run, the cracking of the tubes. Cracking takes the form of a circumferential cut, perpendicular to the direction of flow. The cut is located only a few centimeters from the tube edge and can readily to be ascertained with an inspecting finger. Metallographic examination reveals that cracking is mainly intergranular [28] but transgranular attack is not uncommon. The frequency of failure at tube inlets exceeds by far that at outlets, suggesting that turbulance assists cracking. Stress corrosion cracking (SCC) of aluminium-brass tubes has been recorded in the first cells of the heat-gain section of the distiller [39]. In the high temperature cells, tubes of 70/30 cupro-nickel sometimes exhibit failure features very similar to those of aluminium-brass. Corrosion of 70/30 cupro-nickel by SCC has not been reported before, and the matter requires further investigation [40]. SCC requires special agents for initiation. Three materials for copper-base alloys are recognized, viz., ammonia, hydrogen sulphide and mercury. The first two result from decomposition of marine organisms and/or sewage discharged into the sea. Pollution by mercury comes mainly from industrial activities in the vicinity of the desalination plant. Chlorination of seawater at the intake removes ammonia and hydrogen sulphide. Sewage treatment on land before discharge into the sea removes or reduces the amounts of the two pollutants. Application of special paints to tubes ends isolates the areas susceptible to attack. In Abu Dhabi the problem of SCC of aluminium-brass tubes was controlled through cathodic protection of the water boxes, tube plates and tube terminals by sacrificial iron anodes [39]. Already perforated tubes are recovered through tube inserts. These are either metallic, in which case they must be galvanically compatible to the tubes and tube plate, or of man-made materials. In this last case they should not be made of nylon or amide-based polymers. These substances readily hydrolyze in seawater to yield ammonia which promotes cracking. Erosion-Corrosion Erosion-corrosion of copper-base condenser tubes, occurs whenever the naturallydeveloped- or artificially induced film on their surface is destroyed [41-43]. This happens when the water flow rate exceeds the upper limits of tolerance of the material. Erosion is manifested in the form of grooves, gullies, waves, rounded holes or horse-shoes, lined up in the direction of the flow. Erosion is more prominent at tube inlets due to turbulence. It produces a rough surface which ends where the flow turns laminar. Erosion-corrosion can proceed till complete failure occurs, producing pores elongated along the direction of flow.
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The rate and extent of attack increases when the water carries suspended sand or entrained gases. Counter-measures against flow-induced attack involve reduction of the water flow rate, extension of the time of stagnation in sedimentation basins, and controlled use of ball cleaning. Excessive ball cleaning, especially when of the hard type, removes the inhibiting film from inside the tubes. Filming by ferrous sulphate or through sacrificial iron anodes will restore the film. Too much chlorination of seawater at the intake is also detrimental to the passivating film. Eroded tube inlets are repaired with appropriate tube inserts. Corrosion by Polluted Waters Polluted seawater contain ammonia and/or hydrogen sulphide. Both materials are products of the decay of dead animals and organisms. The two pollutants attack copper condenser tubes. Hydrogen sulphide reacts spontaneously with copper tubes to produce a black, porous copper sulphide film. Being nonprotective, the film allows further attack until the metal is eaten through [44-49]. Attack is more rapid if the polluted water is loaded with slime and silt. Under the slime, attack by sulphide is considered a special type of deposit corrosion in which metal deterioration is initiated by the presence of hydrogen sulphide rather than by a deficiency in oxygen. Attack by sulphide-polluted water is identified by the black coloration of the tube inside. Treatment of the black film with dilute acid sets free the hydrogen sulphide, known by its characteristic bad odor. On the micro-scale range, the presence of sulphide is ascertained through its catalyzing the evolution of nitrogen gas bubbles from a drop of iodine-sodium azide solution. The test is carried out under a magnifying lens or microscope. Sulphide corrosion can be dealt with in a variety of ways. Suitable tube material can be chosen if it is known from the start that only polluted water is available. Extension of the intake facilities away from the source of polluted water is a second alternative. When present in small amounts, hydrogen sulphide is oxidized by chlorination. This must, however, be carefully controlled. The same also applies to rubber ball cleaning if sulphide-polluted sludge is in abundance. Seawater polluted with ammonia affects the corrosion of copper base condenser tubes in two distinct ways: it induces SCC and the rate of crack propagation increases with pollutant content; and ammonia and ammonium salts enhance the general attack by dissolving and complexing with the copper ions. The tubes lose their protective film and acquire a shiny appearance. Eventually the tubes fail when they become perforated at weak points. Failure can occur anywhere along the tube length and the resulting pore takes any form. Ammonia attack is suspected when daily analysis of the brine shows a constant, high level of copper. There is no direct solution to the problem of corrosion by ammonia-polluted seawater. If the source of pollution is permanent, relocation of the seawater intake might prove practical. If pollution is widespread, a change to ammonia-resistant tubes, e.g., titanium or stainless steels, might be considered. Chlorination of ammoniated seawater is effective in removing low levels of pollution. The two agents react to produce chloramines which are weaker disinfectants than chlorine itself. The formation of chloramines reduces, but does not completely eliminate the problem of ammonia-corrosion since chloramines readily hydrolyze
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to the original harmful material. Ferrous sulphate dosing retards the aggressive action of small amounts of ammonia by forming an inhibiting ferric oxide film. Corrosion of Stainless Steel Condenser Tubes There is a wide variety of stainless steels that can be used as condenser tubes in MSF distillers [7,50-52]. In flowing seawater, the performance of stainless steel tubes is quite satisfactory. They withstand general corrosion and are not affected by the flow velocities operating in a distiller. Normal steels are susceptible to SCC in solutions of high chloride content at high temperatures. As the tubes are not subject to any noticeable stresses, this type of attack is unlikely to develop. In stagnant solutions, on the other hand, normal stainless steels are liable to undergo pitting corrosion [53-56]. During a long outage, the distiller must be carefully drained and flushed with ample quantities of potable water to prevent chloride attack. Stainless steel tubes are also prone to crevice corrosion, which develops under barnacles, stuck rubber balls and the like. The same procedures described in case of copperbase tubes apply in such cases. Weld areas and the heat affected zones are weak points where intergranular and pitting attack readily propagate on stainless steel in a desalination unit [57,58]. Spot and arc welding is to be applied, and annealing should be carried out whenever feasible. Finally, stainless steel tubes mounted on copper-base tube plates will lead to their rapid deterioration by galvanic action [59-62]. Cathodic protection using sacrificial mild steel anodes overcomes this problem. Corrosion of Titanium Condenser Tubes Titanium tubes exhibit excellent resistance to general-, pitting- and crevice corrosion. They withstand erosion-corrosion and impingement attack at flow velocities as high as 20 ms-1. They are also immune to SCC and are unaffected by polluted seawater. Titanium has, however, a low thermal conductivity, and this is resolved by reducing the tube wall thickness. To compensate for the loss in rigidity, a larger number of tube supports are installed. Titanium tube plates are expensive, and the expansion of titanium tubes, therein, can lead to crevice corrosion [65,66] at temperatures at and above 80C. Organic sealants (e.g., dimethacrylate) used to fill the tube/ tube plate interface worsen rather than improve the situation, as crevice corrosion starts at about 80C [66]. Two alternatives can be applied to prevent titanium/titanium crevicing. The first involves seal welding and this has the advantage of preventing crevice attack completely. It has, however, the drawbacks of being expensive and requiring skilled personnel. The second procedure is the coating of the titanium tubes/tube plates with a palladium oxide (PdO)/titanium oxide (TiO2) mixture. The coating is prepared in situ from a mix solution of palladium chloride (PdCl2) and titanium chloride (TiCl3) followed by thermal oxidation in air [67]. This type of sealant prevents crevice attack in 15% NaCl of pH 3 at 120C [67]. The mounting of titanium tubes on copper-base tube plates prevents the crevice corrosion of the tubes. However, because of the large difference in their free corrosion potentials, titanium induces the galvanic corrosion of the tube plate [62,66,68]. To stop attack, cathodic protection of the plate and tube ends by impressed currents [69,70] or sacrificial anodes [71,72] has been suggested. Unless very carefully controlled, protection can do more harm than good. Protection should not reduce the potential of titanium to lower

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than -0.50 V versus the saturated calomel electrode (SCE) [66] or -0.65 V versus SCE [71]. Polarization to more negative potentials will cause the absorption of hydrogen in titanium and the formation of titanium hydride. This causes a loss of ductility and cracking of the tubes. Normal mild steel is not recommended as anode material as it shifts the potential of titanium to values more negative than those recommended for safe protection. An iron/9% nickel alloy is recommended to keep the potential at the desired value [66]. A recent study from this Laboratory [73] revealed that hydrogen uptake by titanium can take more than one form, depending on the type of anode used. Titanium tubes are not recommended for use in the high temperature cells and in the brine heater, where they are likely to pick up hydrogen from the hot brine. In their place, tubes of 70/30 cupro-nickels can be installed. CORROSION OF TUBE SUPPORTS Tube supports are elements of MSF distillers not readily accessible for inspection and repair. The functions of tube supports are to keep the tube bundle in position, to act as guide for long tubes and to prevent the tubes from sagging and vibrating. Because tube supports are exposed to deaerated steam, they were assumed to suffer no corrosion. Accordingly, they have been made of the cheapest material, viz. mild steel. In fact, however, mild steel tube supports are heavily corroded by reaction with steam as well as by galvanic contact with the nobler material of the tubes. By the time the supports change into iron oxide lumps which make it extremely difficult, if not completely impossible, to extract failed tubes or retube the condenser. There is nothing that can be done to save C-steel supports in contact with stainless steel, copper alloys or titanium tubes, from completely failing. Nowadays tube supports are specified to be of the same material as the tubes themselves. VAPOR-SIDE CORROSION Until now, we have considered the forms of corrosion affecting components of MSF condensers in contact with seawater. Cases have also been recorded, where corrosion occurs on the vapor side. One such case has already been mentioned, namely, the corrosion of Csteel tube supports bearing condenser tubes. Occasionally reference is made to the vapor side corrosion of copper-base condenser tubes [74,75]. Such attack is recognized through shining tube surfaces, an outside reduction in wall thickness and an above-normal (>0.1 ppm) increase in the Cu2+ content of the distillate. This occurs mainly in the high temperature cells of the distiller. The general belief [76] is that the vapor is largely contaminated with CO2 resulting from the high temperature decomposition of the HCO -3 ion of the brine [95]. The formed carbonic acid, H2CO3, is assumed to be sufficiently strong at high temperatures to attack the copper tubes. Apparently this explanation is an over simplification of a more complex process. At the temperatures of the first heat gain cells, the solubility of CO2 in the vapor is both limited and transient. However, neither copper nor its alloys displace hydrogen from acid solutions. If H2CO3 is to exert a corroding action it must do so by dissolving the cuprous and cupric oxides formed on the metal surface. Practical experience confirms this conclusion. Condenser tubes undergoing overhaul acquire black coloration as a result of air oxidation. When returning to service, the distillate exhibits above-normal copper-content and has to be dumped back into

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the sea. Considerable time (up to 60 hours [75]) elapses before the copper concentration in the distillate returns to permissable limits. For copper tubes to continue corroding, their surface has to reoxidize. This occurs through the oxygen (air) dissolved in the flashing brine. As this is limited, the rate of corrosion falls to low values. Higher corrosion rates point to the presence of tiny leaks in cell gaskets. A vacuum leak test (or pressure leak test) on the distiller will confirm this assumption. Vapor-side corrosion of copper condenser tubes can be serious if seawater is polluted by ammonia or hydrogen sulphide. What has been said regarding water-side corrosion applies to vapor-side corrosion too. OPERATION PROCESSES AFFECTING CORROSION IN MULTI STAGE FLASH (MSF) DISTILLERS In running an MSF plant, certain processes are carried out the aim of which is to overcome an operational difficulty and/or to improve production efficiency. These processes affect the corrosion of distiller components in variety of ways. In some instances, the role of a certain parameter can be beneficial at one level and detrimental at another. The successful operation of the distiller depends, therefore, on a proper understanding and careful execution of the process. The following operations deserve special mention: Chlorination of Seawater Chlorination of seawater at the intake is carried out to discourage marine organisms from entering the distiller and to prevent bifouling. There is no single chlorination procedure that applies to all units. The adoption of a certain course of action evolves from trial and error and depends on factors such as geographic location, bioactivity, temperature, and water purity. For example, in Umm Al Nar (Abu Dhabi) chlorination is carried out continuously to a level of 0.4 ppm. This ensures a residual chlorine content of about 0.25 ppm in the condenser tubes. To prevent organisms from building up resistance, shock dosing at 1 ppm is achieved for 1 hour. once a week [78]. Chlorine reacts with water to produce hydrochloric and hypochlorous acids : Cl2 + H2O = HCl + HClO. Both acids are directly neutralized by seawater alkalinity. The hypochlorous ion, ClO-, is a strong oxidizing agent which raises the free corrosion potentials of alloys to higher values. This raises the susceptibility of normal stainless steels to pittings- and crevice corrosion, particularly in regions of stagnation [79]. Similarly, chlorination of seawater interferes with the process of ferrous sulphate dosing. Chlorination is stopped before, during and for some time after dosing to allow the iron-oxide film the chance to build up properly. On the other hand, chlorine injection destroys pollution by hydrogen sulphide, and neutralizes, to some extent, ammonia polluted seawater. Ferrous Sulphate Dosing Copper-base condenser tubes have little resistance to erosion-corrosion and to corrosion by hydrogen sulphide-polluted seawater. Both types of attack are greatly inhibited by ferrous sulphate dosing [80]. The ferrous ion readily hydrolyzes and oxidizes to colloidal FeOOH, which adheres strongly to tube surface. The iron oxide film improves the naturally formed copper oxide and offers better protection. Two to three hours before sulphate dosing, chlorination of the seawater is stopped. The sulphate is injected at a rate of 3 ppm for one hour per day for one month at tube inlets. Chlorination can be resumed after two hours. During the second and third months, ferrous sulphate dosing is reduced to 2 and 1 ppm for
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one hour per day, successively. During the whole period of treatment, sponge ball treatment is reduced to one or two times per week for one hour. The success of sulphate dosing is recognized through the uniform coloration of the tube plates and tubes with a light- to deepbrown film, which does not peel off when scratched with a nail. A number of factors interfere with film formation. These involve waters flowing at high rates or carrying large amounts of sand, slime or deposits; excessive or continuous ball cleaning; chlorination directly before, during or after sulphate dosing and/or the presence of entrapped, polluted dead waters. Scaling in Condenser Tubes Scale formation in the condenser tubes is one of the major problems encountered during the operation of MSF distillers. Scaling impairs heat transfer, causes tube blockage and can induce corrosion. Scale formation is an inherent product of the composition of seawater, which contains HCO -3 , Ca2+ and Mg2+ ions. The thermal decomposition of the HCO -3 leads to the deposition of calcium carbonate and magnesium hydroxide. Two alternative techniques are employed to prevent (retard) scale formation. The first involves the controlled acidification of the makeup water to convert the HCO -3 ion into CO2. Either sulphuric or hydrochloric acids is used; the first is preferred on the basis of cost considerations. An addition of 100-200 ppm sulphuric acid is normally used, and the evolved CO2 is stripped off either in a separate degassing tower or in the MSF vacuum deaerator. Unless very carefully carried out, acidification can lead to serious corrosion of the condenser tubes and the deaerator system. To overcome this problem under-acidification has been proposed [81]. Laboratory experiments have shown that 80% of the acid required to completely neutralize the bicarbonate ions is sufficient to prevent scale formation for a long time [82]. Another technique to prevent corrosion involves the neutralization of excess acid. Following degassing, the brine pH is brought back to ~7.5 through the controlled addition of caustic soda. This technique is elaborate and expensive [83]. The second approach for scale prevention is the use of antiscaling agents. These are polymeric, surface-active substances which adsorb on active centers of CaCO3 and Mg(OH)2 crystallites. This inhibits them from forming a continuous layer. A small amount of the inhibitor (2-5 ppm) is needed to retard scale formation, and the method is known as a threshold treatment [84]. A large variety of antiscalants is available on the market, and the nature of the scale depends on the compound used. Polyphosphates, for example, give rise to dense, fluffy, grayish-brown deposits [85]. Maleic anhydride polymers, on the other hand, yield thin, hard scales [86]. A hybrid technique for scale control has been suggested [87]. It involves the use of lessthan-stiochiometric quantities of a mineral acid together with small quantities of a threshold antiscalant. Under-acidification eliminates the problem of acid corrosion of tubes, while the removal of the largest part of the waters alkalinity allows lower concentrations of the antiscalant to be used. This represents a sizable reduction in cost. Sponge Ball Cleaning The retardation of scale formation in the condenser tubes through dosing of antiscaling agents is usually coupled with the technique of sponge ball cycling (Tapproge ball cleaning). The rubber balls are slightly larger than the interior diameter of the tubes and are forced
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through by the pressure of circulating water. As they travel through the tubes, the balls wipe out the tubes insides and prevent scale crystallites from building a solid layer. As the balls pass randomly through the tubes, they are cycled for enough time to ensure the cleaning of the maximum number of tubes. There is no standard procedure for ball cycling. This varies between one or more cycles per day and continuous cycling. The duration of a cycle also differs from one plant to another. On the market are sponge balls with different surface hardness. The choice of the appropriate type depends on the seawater purity, type and concentration of the additive used, nature of the deposit and distiller top temperature. A trial to optimize sponge ball cleaning was recently published [88]. Sponge balls can affect tube corrosion in many ways. Soft balls and/or short treatment times might be ineffective and allow sand, silt and scale deposition which lead to crevice attack. The same result might be noted when the number of balls is insufficient. On the other hand, balls that are too hard can induce erosion-corrosion by stripping the protective film from the metal surface. Also, it is not uncommon for balls to get stuck inside the tubes, promoting crevice attack. Finally, as mentioned above, ball cleaning damages the fresh iron hydroxide film resulting from ferrous sulphate dosing.

Acid Cleaning Antiscaling agents do not inhibit completely the formation of alkaline scales; they only retard their growth. Even when their use is coupled with sponge ball cleaning, a scale film continues to grow inside the condenser tubes. Due to their bad thermal conductivity, a situation is eventually reached when the gained output ratio of the distiller drops below a preset value. The operation of the distiller becomes impractical (noneconomical) and an acidwash of the distiller is necessary. The washing process is carried out by circulating warm (~65C) fresh seawater through the water boxes and condenser tubes of the cells and the brine heater. Enough inhibited acid is added to the water to bring its pH value to 1.8-2.0. For copper-base condensers either hydrochloric or sulphuric acids can be used. The pH of the water is monitored, and its value rises as result of reaction with the scale. Extra acid is added to bring the pH to its lower value and the process is repeated until no further increase in pH is recorded for a long time (usually two hours). The acid water with the accumulated sludge is discharged, and the distiller is flushed clean with fresh seawater. The use of an improper corrosion inhibitor [89] or insufficient quantities of a suitable one leads to general attack on the tube material. The same washing procedure described above applies to condensers with titanium tubes as well. However, because of the high tendency of titanium to absorb hydrogen, weak organic acids, e.g., citric [90] or sulfamic [91] acids are used instead. A few organic compounds marketed under trade names, e.g., Galvane (ICI) and IBIT [91], are said to retard acid attack on titanium. Distiller Outage As is clear by now, seawater is an extremely aggressive medium which attacks all of the metallic components of an MSF unit. The fact that distillers operate for long times with little damage is due to two main reasons:
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the exploitation of certain material properties manifested during operation; the application of protective and preventive measures during operation.
To the first reason belongs:

The ability of stainless steels to withstand the corrosive action of flowing seawater,
while being quickly and severely attacked by the same water under stagnation, and The readiness by which copper-base alloys develop protective surface films which offer some resistance to the action of flowing water. Preventive and protective measures that can taken during operation are mentioned in detail in previous sections. These involve degassing to remove oxygen (depolarizer) and carbon dioxide (acidity) from the brine, ferrous sulphate dosing to increase the protection of copper tubes, chlorination to discourage marine organisms from gaining access to the inside of the distiller, use of antiscalants and ball cleaning to minimize scale formation and the application of cathodic protection to prevent tube failure. Accordingly, as long as these measures are observed and the distiller is operating, the corrosion of its components is largely under control. This well balanced system of protection is lost once the distiller is shut down. Upon opening the water boxes and the flash chambers, air (oxygen) fills the entire unit, and accelerates ongoing corrosion. On the other hand, brine stagnation inside condenser tubes causes the settling of sand and silt, and occasionally a few sponge balls. This initiates crevice corrosion. Stagnation also promotes the pitting corrosion of stainless steel components. Unless the shutdown is for a short time (i.e., a maximum of two days) precautions against attack should be applied. These involve the draining of the stagnant brine from the distiller, followed by a thorough flushing with potable or distilled water. The washings should likewise be drained out. During long outages, all inlets and outlets should be left open to remove humidity and speed up the drying of the distillers inside. The various components of the unit should be examined and the necessary corrective measures taken. REFERENCES 1. T.H. Rogers, Marine Corrosion, New York: John Wiley, 1968. 2. F.L. LaQue, Marine Corrosion, New York: John Wiley, 1975. 3. D. Pecker and I.M. Bernstein, Handbook of Stainless Steels, New York: McGrawHill, chapter 14, 1977. 4. Inco, Copper-Nickel and Other Alloys for Desalination Plant, London: INCO Europe Ltd., 1981. 5. European Federation of Corrosion Publications, No. 3, General Guidelines for Corrosion Testing of Materials for Marine Applications, London: The Institute of Metals, 1989. 6. European Federation of Corrosion Publications, No. 10, Marine Corrosion of Stainless Steels, London: The Institute of Materials, 1993. 7. Nickel Development Institute, Guidelines for Selection of Nickel Stainless Steels for Marine Environments, Natural Waters and Brines, Toronto: NIDI, vol. 2, 1987. 8. Nickel Development Institute, Materials for Saline Water, Desalination and Oilfield Brine Pumps, NIDI, 1988.

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9. B. Todd, Proceedings 25th Annual Conference of Metallurgists, Toronto, 1986. 10. J.V. Dawson and B. Todd, BCIRA J., 1987, p. 1. 11. A.M. Shams El Din, Corrosion Resistant Materials for Desalination Plants, Abu Dhabi, Internal Report to WED, 1991. 12. A.M. Shams El Din, Desalination 93, 1993, p. 499. 13. T. Hodgkiess, Desalination 93, 1993, p. 445. 14. J.A. Carew, M. Abdel-Jawad and Y. Al-Wazzah, Desalination 95, 1994, p. 53. 15. Titanium Engineering Alloys, Product Promotion Brochure, 1988. 16. F.L. LaQue and W.C. Stewart, Corrosion 8, 1952, p. 259. 17. J.M. Popplewell, R.J. Hart and J.A. Ford, Corrosion science 13, 1973, p. 295. 18. R.F. North and M.J. Pryor, Corrosion science 8, 1968, p. 149; 1969, 9, p. 509. 19. S. Kido and T. Shinohara, Desalination 22, 1977, p. 369. 20. T.G. Temperley, Desalination 31, 1979, p. 353. 21. K. Hill, Desalination 34, 1980, p. 325. 22. K.R. Frhner, Desalination 21, 1977, p. 147. 23. B. Wallen and T. Andersson, ACOM 2, 1987. 24. P.T. Gilbert, Materials performance 21, 2, 1982, p. 47. 25. G. Odone, A. DeMaio and F. Fioravanti, J. IDA 1, 2, 1985. 26. C. Lakshmipati, Corrosion Maintenance, 1984, p. 305. 27. M.W. Joseph, F.W. Hammond and T.S. Lee, Corrosion 86, Houston, 1986, Paper No. 226. 28. R. Cigna, A. DeMaio, L. Giuliani and G. Gusmano, Desalination 38, 1981, p. 269. 29. G.A. Gehring, C.K. Kuester and J.R. Maurer, Corrosion 80, Houston, 1980, Paper No. 32. 30. T. Atsumi, A. Ogiso, K. Nagata and S. Sato, 10th Intern. Cong. Met. Corros., Madras, India, 1987. 31. T. Atsumi, A. Ogiso, K. Nagata and S. Sato, Sumito Light Metal Technical Reports 29, 4,1988, p. 257. 32. S. Sato, K. Nagata and S. Yamauchi, Corrosion 81, Ontario, Canada, 1981, Paper No. 195. 33. G.L. Bailey, Journal Institute of Metals 79, 5, 1951p. 243. 34. K.D. Efird, Corrosion 33, 1, 1977, p. 3. 35. D.B. Anderson and F.A. Badia, ASME J. Engineering for Power, 1973. 36. D.B. Anderson, Corrosion 81, NACE, Toronto, 1981, Paper No. 197. 37. S. Sato and K. Nagata, Somitomo Light Metal Technical Reports 19, 1978, p. 83. 38. V.K. Gouda and W.T. Riad, 9th Europ. Cong. Corrosion, Utrecht, Holland, 1989, p. P1-197. 39. A.M. Shams El Din, Wsia J. 11, 2, 1984, p. 1. 40. A.M. Shams El Din, WED, Abu Dhabi, unpublished results. 41. W.E. Heaton, Br. Corros. J. 13, 1978, p. 57. 42. T. Sydberger and U. Lotz, J. Electrochem. Soc. 129, 1982, p. 276. 43. J.M. Popplewell and E.A. Thiele, Corrosion 80, Houston, 1980, Paper No. 30. 44. J.A. Ellor and G.A. Gehring, Corrosion 86, Houston, 1986, Paper No. 225. 45. J.N. Al-hajji and M.R. Reda, Corrosion science 34, 1993, p. 163. 46. A.M. Beccaria, G. Poggi, P. Traverso and M. Ghiazza, Corrosion science 32, 1991, p. 1263.
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47. K. Habib, Desalination 89, 1992, p. 41. 48. B.C. Syrett, Corrosion 80, Houston, 1980, Paper No. 33. 49. G.A. Gehring, R.L. Foster and B.C. Syrett, Corrosion 83, Anaheim, 1983, Paper No. 76. 50. Trent Tube, Stainless Steel Pipe and Tube Alloy Handbook, Product Promotion Brochure, 1992. 51. K.R. Frhner, Desalination 21, 1977, p. 147. 52. A.J. Sedriks, Corrosion 45, NACE, 1989, p. 510. 53. T. Hodgkiess and A. Asimakopoulos, Desalination 38, 1981, p. 247. 54. T. Hodgkiess, W.T. Hanbury and M.N. Hejazian, Desalination 44, 1983, p. 223. 55. H.P. Hack, Materials performance 22, 1983, p. 24. 56. T.S. Lee, R.M. Kain and J.W. Oldfield, Materials performance 23, 1984, p. 9. 57. T. Rogne and J.M. Drugli, Corrosion 86, NACE, 1986, Paper No. 230. 58. H. Al Zahrani, S. Somuah and N.M.A. Eid, 12th Inter. Symp. Desalination and Water Reuse, Malta, 1991, vol. 4, p. 349. 59. B. Wallen and T. Andersson, ACOM 2, 1987, p. 1. 60. G.A. Gehring, C.K. Kuester and J.R. Maurer, Corrosion 80, NACE, 1980, Paper No. 32. 61. G.A. Gehring and J.R. Maurer, Corrosion 81, NACE, 1981. 62. G.A. Gehring and R.J. Kyle, Corrosion 82, NACE, 1982, Paper No. 60. 63. J.A.S. Green, B.W. Gamson and W.F. Westerbaan, Desalination 22, 1977, p. 359. 64. A.R. Morris, Desalination 31, 1979, p. 387. 65. S. Kido and T. Shinohara, Desalination 22, 1977, p. 369. 66. T. Fukuzuka, K. Shimogori, H. Satoh and F. Kamikubo, Desalination 31, 1979, p. 389. 67. K. Shimogori, H. Satoh, F. Kamikubo and T. Fukuzuka, Desalination 22, 1977, p. 403. 68. P.D. Simon, Corrosion 83, NACE, 1983, p. 60. 69. J.P. Fulford, R.W. Schutz and R.C. Lisenbey, Joint ASME/IEEE Power Generation Conference, Miami Beach, Florida, 1987, Paper No. 78 - JPGC-Pwr-F. 70. J.I. Lee, P. Chung and C.H. Tsai, Corrosion 86, NACE, 1986, p. 259. 71. T. Moroishi and H. Miyuki, Titanium 80, vol. 4, 4th Intern. Conf. on Titanium, Kyoto, 1980, p. 2713. 72. K. Kohsaka, K. Kitaoka, Y. Masuyama, M. Oshiyama, M. Yamamoto and K. Kashida, Seawater Desalination Group, Development Committee of Japan Titanium Group, Product Promotion Brochure, May 1984, and April, 1986. 73. A.M. Shams El Din, T.M.H. Saber and A.M. Taj El Din, Paper presented before the IDA Congress on Desalination and Water Sciences, Abu Dhabi, 1995. 74. R. Heaton and T.A. Douglas, Desalination 41, 1982, p. 71. 75. E.A. Al-Sum, Sh. A. Aziz, A. Al-Radif, M.S. Said and O. Heikal, Proc. IDA and WRPC World Conf. Desal. and Water Reuse, Yokohama, 1993, vol. I, p. 501. 76. A.H. Khan, Desalination Processes and Multi-Stage Flash Distillation Practice, Elsevier, 1986, p. 441. 77. A.M. Shams El Din nd R.A. Mohammed, Desalination 99, 1994, p. 73. 78. A.M. Shams El Din, B. Makkawi and Sh.A. Aziz, Desalination 97, 1994, p. 373. 79. B. Wallen, ACOM 4, 1989, 1990.
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80. T.W. Bostwick, Corrosion 17, 1961, p. 12. 81. Office of Saline Water, Res. Develop. Report, 1968, Vol. 559. 82. J.W. McCutchan, UCLA, Dept. Eng. Rept., 1967, No. 67-1. 83. M.N. Elliot, Desalination 6, 1969, p. 87. 84. K.S. Spiegler and A.D.K Laird, Principles of Desalination, 2nd ed., Part B., New York: Academic Press, 1980, p. 672. 85. A.M. Shams El Din, Desalination 61, 1987, p. 89. 86. A.M. Shams El Din, Desalination 69, 1988, p. 147. 87. F. Butt, F. Rahman, A. Al-Abdallah, H. Al-Zahrani, A. Maadhah and M. Amin, Desalination 54, 1985, p. 307. 88. F. Al-Bakeri, F. and H. El Hares, Desalination 94, 1993, p. 133. 89. T.M.H. Saber, A.M. Tag El Din and A.M. Shams El Din, Br. Corros. J. 27, 1992, p. 139. 90. A.M. Shams El Din, H.A. El Shayeb and F.M. Abd El Wahab, J. Electroanalyt. Chem. 214, 1986, p. 567. 91. Japan Titanium Society, Product Promotion Brochure, September 1991.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CORRECT MATERIALS SELECTION FOR DESALINATION: THE KEY TO PLANT RELIABILITY J.W. Oldfield Cortest International 23 Shepherd Street Sheffield, S3 7BA, UK

ABSTRACT
Large scale desalination really began with the multi-stage flash (MSF) plant built by Weir Westgarth in Kuwait in 1960. This and similar plants elsewhere used mainly carbon steel and brass alloys in their construction. Corrosion problems with these early plants led to costly shutdowns and maintenance. As knowledge of the requirements of materials has grown there has been a steady upgrading of materials and this, together with improved control of operation has resulted in much better reliability and performance. This paper presents a state of the art review of factors which are important in the selection and use of materials in MSF and reverse osmosis (RO) desalination plants. Economics play an important part in materials selection and are given consideration in general terms. Key Words: Desalination, MSF, RO, corrosion, materials.

INTRODUCTION Large scale desalination really began with the multi-stage flash (MSF) plant built by Weir Westgarth in Kuwait in 1960. This and similar plants built elsewhere used mainly carbon steel and brass alloys for their construction. Experience in these early plants, particularly when acid-dosing was used as an antiscalant, was that corrosion problems were often extremely severe leading to costly shutdowns and maintenance. As knowledge of the requirements of materials to meet the conditions in MSF plants has grown, there has been a steady upgrading of materials, and this, together with improved control of operation, has resulted in much better reliability and performance. This paper presents a state of the art review of the factors which are important for selection and use of materials in MSF and reverse osmosis (RO) desalination processes. As the risk of corrosion is always present in desalination, corrosion plays a major part in determining material selection. Corrosion is a process involving the reaction of a material with its environment, and this paper reviews materials for usiing incomponents in the environments encountered in MSF and RO processes. In MSF plants these environments are sea water, deaerated sea water and brine, distillate and incondensible gases; in RO plants they are sea water, brackish waters and brines. Economics play an important part in materials selection and are given consideration in general terms. For general reference an appendix is included giving typical compositions of materials used in desalination plants.
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BEHAVIOUR OF MATERIALS IN SEA WATER AND BRINE ENVIRONMENTS General Considerations Sea water is the most corrosive of the natural environments that materials have to withstand, but it is much less corrosive than many environments encountered in industry, such as mineral acids. This situation has important implications for desalination materials in that there is a wide range of corrosion resistant alloys readily available, which have been developed for the chemical and process industries, and which are resistant to sea water. However, many of these materials are much more expensive than those used in industries which have traditionally handled sea water, such as shipping and power plant. In these industries, carbon steel, cast iron, copper base alloys and standard grades of stainless steel have been the usual choice for sea water applications. The desalination industry followed traditional practice and whilst in many cases this proved satisfactory, in others it did not. Upgrading, therefore, largely involved economic decisions-as the better materials were always available, the main problem was to decide what level of cost and performance was acceptable. Corrosion of Carbon Steel in Sea Water Sea water is a complex environment consisting of a mixture of inorganic salts, dissolved gases and organic compounds [1]. However, it also supports living matter in the form of both macro-organism (e.g., fish, shellfish, seaweed etc) and micro-organisms. All of these can have an influence on corrosion processes. Sea water is a well buffered solution, so the pH remains fairly constant at about 8. This means that most corrosion processes are dependent on the presence of oxygen. For carbon steels immersed in sea water, the rate of corrosion is mainly dependent on the oxygen content and the temperature of the sea water, the composition of the steel has relatively minor influence even when small amounts of alloying elements are added. Table 1 gives data on several steels exposed in the Pacific Ocean near Panama. Table 1. Corrosion of Steel in Sea Water [2] Steel Nominal Composition 0.2 5% C 0.22% C 0.31% Cu 2% Ni 0.6% Cu Corrosion Rate (mm/yr) 1 year 16 years 0.15 0.075 0.15 0.077

Carbon Copper-Bearing

Low Alloy Cu0.15 0.076 Ni Chromium Steel 0.08% C 3% Cr 0.05 0.110 Nickel Steel 5% Ni 0.16 0.080 Grey Cast Iron 0.24 0.147 Samples immersed below minimum low tide. Tidal flow 0.3 m/sec. Water temperature 15.5-32.2C. Surfaces pickled before exposure.

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In most engineering applications sea water flows over the metal surfaces so, it is important to have corrosion data under these conditions. Figure 1 [3] shows how flow rapidly increases corrosion of carbon steel in sea water. This is mainly due to the increase in the mass flow of oxygen to the corroding surface. In applications where continuous flow is required, a corrosion rate of about 1 mm/yr can be assumed for carbon steel and cast iron.

Figure 1. Effect of velocity on corrosion of carbon steel in sea water

Figure 2. Estimates of corrosion of carbon steel in deaerated sea water Deaeration, by reducing the oxygen content, would be expected to reduce corrosion, and
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in general, this is found to be the case (Fig. 2). However, in MSF plants, where deaeration occurs as part of the process, two other factors have an important effect. These are temperature and flow rate. Few test data have been measured under controlled oxygen, flow and temperature conditions, but Oldfield and Todd [4] have modelled the process and compared calculated and actual test data. Comparison with measured data [5] show that even with good deaeration, high corrosion rates can be experienced at high flow rates and high temperatures. At low corrosion rates, the measured and calculated corrosion rates are in good agreement, but at higher rates the calculated values are significantly above the measured values. This was attributed to the buildup of rust scales on the steel. Although these are not protective, they do provide a barrier to oxygen access to the surface and reduce the rate of attack. Corrosion of Copper Base Alloys in Sea Water Copper alloys have been used traditionally in marine engineering for heat exchanger tubing and for cast and wrought components in pumps and valves. These alloys form good protective films in sea water, and provided these films are undamaged, corrosion is slight. However, the protective films are susceptible to damage by fast flowing sea water, and this is an important factor in selecting these alloys for applications involving flow-for example, heat exchanger tubing. Table 2 gives data on some commonly used heat exchanger alloys. Table 2. Jet Impingement Tests on Copper Base Alloys Alloy Admiralty Brass Aluminium Brass 90/10 Cupronickel 7 0/30 Cupronickel 66/30/2/2 CuNiFeMn Depth of Attack (mm). (jet velocity = 5.5 m/s) 0.60 0.13 0.06 0.03 0.025 (jet velocity: 12 m/sec)

In deaerated sea water copper alloys can still form protective films and show higher resistance to corrosion than in natural water. This is because the potential of copper alloys in sea water is much higher than the potential at which hydrogen can evolve; thus, in the absence of oxygen, corrosion is negligible. However, as in the case of carbon steel, low oxygen levels with high flow rates can cause impingement attack as shown by Anderson [6], but the rate of attack was much lower than in aerated sea water. Further data on corrosion of heat exchanger tubing alloys in deaerated sea water is given in Fig. 3 [7]. These data indicate that at low temperatures and oxygen levels, corrosion of the three alloys tested is acceptably low. However, at high temperatures with high oxygen levels, although the cupronickels continue to show low corrosion rates, aluminium brass is attacked. Thus, in MSF plants, where aluminium brass tubing is used, it is confined to the lower temperature recovery stages with the cupronickels being used in the higher temperatures areas.

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Figure 3. Effect of oxygen content on corrosion of Cu base alloys in deaerated sea water Corrosion of Stainless Steels in Sea Water When chromium is added to steel, there is a marked increase in corrosion resistance, and at about 12% chromium, the alloys form a protective passive film and are referred to as stainless steels. Although the iron-chromium ferritic stainless steels are used commercially, the greatest tonnage of stainless steels are the austenitic iron-nickel-chromium alloys. These have better ductility and weldability than the ferritic alloys, and as they usually contain about 18% chromium, they have better corrosion resistance. In sea water, general attack on these alloys is negligible; however, they are prone to localised attack due to their high chloride content. This attack is particularly severe in crevices such as occur with overlapping surfaces, under seals and gaskets, and in similar areas. Resistance to this type of attack is improved by adding molybdenum to the alloys. The most commonly used grade of stainless steel in marine environments contains about 17% chromium, 12% nickel and 2.5% molybdenum and is commonly referred to by its US AISI designation, Type 316. Localised attack is stimulated by the difference in oxygen level within the pit or crevice and that in the surrounding area. In deaerated sea water, where the oxygen level is low, the risk of localised pitting and crevice corrosion of stainless steels is greatly reduced. Table 3 gives data on some stainless steels in aerated and deaerated sea water. These show that pitting in deaerated sea water and high chloride-containing brines is much less severe than in aerated sea water. Another characteristic of stainless steels is their ability to remain passive even in very fast flowing sea water. Table 4 gives data on some materials in fast flowing sea water. Carbon steel and cast iron are rapidly attacked. The copper base alloys suffer erosioncorrosion, but the stainless steel and nickel-base alloys are virtually unattacked. Table 3. Stainless Steels in Aerated and Deaerated Sea Water and Brine Alloy Environment Velocity (m/s) 0 0 0 40 40 Max Depth of Attack (mm) 2.400 P (486 days) 0.170 P (547 days) 0.600 P (547 days) 0.027 G (/year) [8] 0.180 G (/year) [8]

Type 316 North Atlantic Ocean Type 316 Sea water (100C, 25 ppb 02) Type 304 Sea water (100C, 25 ppb 02) Type 316 130 g/l Cl- (pH 7, 8.25 ppb 02) 13-4 CrNi 130 g/l Cl- (pH 7, 8.25 ppb 02) P = Pitting G = General corrosion

Table 4. Corrosion in Fast Flowing (35-42 m/s) Natural Sea Water Alloy Carbon Steel Cast Iron Corrosion Rate (mm/yr) 4.50 13.20
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Gunmetal (85/5/5/5 CuSnZnPb) Ni Aluminium Bronze Type 316SS Ni Cu Alloy 400

1.32 0.97 <0.01 0.01

Where the alloys are to be welded, the low carbon or stabilised grades (L grades) should be used as the heat of welding can cause carbide precipitation in the heat affected zone, in conventional grades. Although Type 316 stainless steel and its variants, such as Type 316L, represent the greatest tonnage of stainless steel used in desalination, higher grades, with improved resistance to pitting and crevice corrosion are available and are used particularly in RO systems. These alloys have higher molybdenum contents than Type 316, and nitrogen is also added as this improves resistance to localised attack and is inexpensive. In assessing resistance to pitting and crevice corrosion, a simple formula relating the chromium, molybdenum and nitrogen contents is often used: Pitting resistance equivalent number (PREN) = Cr% + 3.3Mo% + 16N% (1)

The PREN is useful for ranking the resistance of different stainless steels, and it is generally accepted that if it exceeds 40 the alloy can be considered resistant to pitting and crevice corrosion in sea water. Austenitic stainless steels with approximately 20% chromium, 20-25% nickel, 6% molybdenum and 0.2% N (PREN = 43) are now widely used in critical applications in aerated sea water. Another important group of stainless steels finding increasing application, are the duplex alloys. These have a mixed ferrite/austenite structure which provides increased strength. They normally have higher chromium and lower nickel contents than the austenitics, and when alloyed with molybdenum and nitrogen, they have similar resistance to pitting and crevice corrosion. Alloys with about 25% chromium, 7% nickel, 3.5% molybdenum and 0.2% nitrogen (PREN = 40) have similar resistance to the 6% molybdenum austenitics. Nickel-base alloys, based on nickel-copper (often referred to as MonelTm alloys) and nickel chromium, have characteristics similar to the stainless steels in sea water. They are prone to pitting under static and low flow conditions and become passive in fast flowing sea water. The nickel copper alloys are used in pumps, particularly for shafts, where their high corrosion-fatigue strength and good corrosion resistance are advantageous. Titanium Titanium has excellent resistance to sea water under static, low and high flow conditions and does not suffer crevice attack. There are many titanium alloys, but the type used in desalination is pure titanium containing low levels of iron, oxygen and nitrogen. It is generally referred to as Grade 2 (ASTM B338 Grade 2). It has good resistance to deaerated sea water and brine but can suffer crevice corrosion in hot deaerated brine [9]. As a result, laboratory investigations were carried out to define safe limits for the use of titanium (Fig. 4) [10].

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Figure 4. Crevice corrosion of titanium - safe use limits Titanium is cathodic to most other metals, and care is needed in multi-metal systems. As titanium is expensive, it is often used for only part of a system, e.g., for tubing with copper alloy tube plates and water boxes. In such cases, the copper alloy may suffer severe galvanic attack. Gehring [11] measured attack on aluminium bronze Type C61400 of 7.4 mm/year when coupled to titanium in a simulated condenser tube/tube plate test. Simon [12] reported severe corrosion on tube plates in the same alloy in a steam condenser with titanium tubes. Galvanic corrosion can be controlled by fitting cathodic protection in the water boxes. Iron anodes are normally used as these avoid any problem of hydriding of titanium which has been experienced with impressed current systems [13]. Iron anodes can be used at up to 70C in deaerated sea water, but above this temperature hydriding can occur. Anodes of 9% nickel steel can then be used above 70C to avoid hydriding [14].

BEHAVIOUR OF MATERIALS IN VAPOUR SIDE ENVIRONMENTS General Considerations Sea water contains dissolved gases notably oxygen and carbon dioxide and these are evolved during thermal processes both to reduce corrosion and to improve heat transfer. At high temperatures the bicarbonate ions present in sea water decompose releasing large quantities of carbon dioxide in the first few stages. Where acid dosing is used for antiscaling, carbon dioxide is released externally in a decarbonator, and less carbon dioxide is generated during the process. Oxygen is sometimes removed in a separate deaerator, and levels of 10-20 ppb in the sea water feed can be achieved reliably. In some cases, the final reject stage is used as a deaerator, and although this reduces the oxygen level, it is difficult to achieve constantly the low levels obtained with a separate deaerator. In addition to the normal gases dissolved in sea water other gases such as ammonia and hydrogen sulphide are sometimes present and may be evolved during the process. Also, most sea water is treated with chlorine to control marine growth leaving a low residual amount in the plant feed. In most cases, this does not cause any problems, but in acid dosed plants, it can give rise to bromine emission, and in additive plants, where ammonia is present in the sea water, bromamine and chloramine can be evolved. Carbon Dioxide Corrosion Carbon dioxide dissolves in water forming a weak acid, and when sufficient is present to lower the pH to less than 5, rapid attack on steel can occur [15]. In the case of copper base alloys, the acidity caused by carbon dioxide in condensates can remove protective films but as the potential of these alloys is higher than that required for hydrogen release, oxygen must be present to cause corrosion. However, there is usually sufficient oxygen available to cause corrosion if the pH falls to a level which damages the film. In this context the problems occur only where incondensable gases are allowed to accumulate in areas of the vapour space where venting is poor. It can also occur in vent condensers where the gases removed from the plant are concentrated prior to exhausting to the atmosphere. Stainless steels and titanium are
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resistant to corrosion by carbon dioxide and are often used in venting systems for this reason. The solubility of carbon dioxide decreases with increases in temperature, so that for a given carbon dioxide concentration, the lowest pH levels occur at low temperatures. Figure 5 [16] illustrates this effect for various carbon dioxide partial pressures and temperatures. Corrosion data on the alloy materials used in desalination are very sparse as vapour space corrosion has not been studied extensively. Vapour Side Corrosion due to Halogen Emission Most desalination plants using sea water are treated with chlorine to control marine growth in the intake systems. Ideally the chlorination is controlled so that only a low residual, i.e., 0.1-0.2 ppm, is left at the evaporator, but use of shock dosing and higher than required injection levels often produce higher levels. When added to sea water, chlorine reacts with bromides, which are always present, and within a few seconds the chlorine has been converted to bromine species. As these have a similar antifouling effect to chlorine, in most cases, this reaction is of no significance. However, the compounds actually present at a given sea water pH differ. This is illustrated for bromine in Fig. 6 [17] where it can be seen that bromine gas in solution is present even at pH 7, whereas, as shown in [17], chlorine in solution is not present above about pH 5. This has important consequences for acid-dosed plants as the pH is lowered to 4-5 by this treatment and even after decarbonation is still usually about pH 6. Under these conditions, when deaerated, the bromine gas in solution is stripped out with other gases and enters the venting system where it can cause severe corrosion.

Figure 5. Effect of partial pressure of carbon dioxide on pH

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Figure 6. Distribution of bromine in sea water In additive-dosed plants, where there is no reduction in pH, stripping out of bromine gas does not occur. However, there have been corrosion problems in the venting systems of these plants due to halogen compounds evolving by a different mechanism [18]. In this case the presence of ammonia in the sea water led to the formation of chloramines and bromamines. As these compounds are volatile, they were stripped out into the venting system where they decomposed forming acidic halogen compounds. As chlorine and bromine compounds are highly corrosive, the best method of corrosion control is to limit their presence by maintaining as low a residual chlorine level in the sea water feed as is compatible with controlling fouling. This residual can, if necessary, be removed by adding bisulphite to the feed. CORROSION IN PRODUCT WATER Untreated product water from distillation processes is slightly acidic due to dissolved carbon dioxide. Also, it contains very little dissolved solids, which in natural waters often provide a scaling and buffering effect, stabilising the pH. As long as it remains deaerated, its corrosive effects on construction materials such as carbon steel are slight. However, within the plant, it is usual to handle product water in stainless steel in order to maintain its purity. Stainless steels are resistant to corrosion in fresh water, and normally no corrosion occurs; however corrosion problems have been experienced as a result of both hydrotesting and disinfectant procedures. When aerated, product water is corrosive to the construction materials commonly used in distribution systems. It will dissolve lime in concrete and asbestos cement piping, and attack carbon steel and cast iron resulting in 'red water' when the dissolved iron precipitates. In order to avoid these problems, the water is hardened by adding calcium carbonate and bicarbonate. Product water from RO processes may contain up to 500 ppm dissolved, solids and as this process does not normally involve deaeration, this water can be corrosive. As RO membranes remove larger ions such as calcium and magnesium more effectively than those of sodium and chlorine, the product water may be relatively higher in these aggressive nonscaling ions. In the case of carbon steel and concrete piping, the scaling tendency of the water should be checked, and if necessary, the water hardened as for distillate. For stainless steels general corrosion is not a problem but some grades may suffer pitting and crevice corrosion. Selection of the appropriate grade can be made by means of a computerised expert system [19]. SELECTION OF MATERIALS FOR MULTI-STAGE FLASH (MSF) DESALINATION PLANTS General Considerations The MSF process is a materials-intensive process, approximately 25 Kg of heat exchanger tubing is required for each cubic meter of output per day. Evaporator bodies, tube plates, tube support plates, waterboxes, piping and pumps all require considerable amounts of materials. In order to optimise materials selection in terms of cost and performance, it is
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necessary to use a variety of materials, restricting the more expensive alloys to those areas of the plant where they are needed. As the cost of alloy materials, such as stainless steels, have decreased in cost relative to carbon steel and maintenance costs, there has been a tendency for the industry to make greater use of alloy materials to achieve higher reliability and lower overall water costs. Thus, factors influencing materials selection are considered for the main components of MSF units in the following sections. Heat Exchanger Tubing A typical MSF unit can be considered in three sections as regards technical requirements for tubing. These are the reject section, brine heater and recovery section. Table 5 [20] shows that the failure rates for tubing in these three sections of the plant vary significantly. Table 5. Failure Rates (Including Tube Replacements) for All Alloys in Distillation Plants Tubing Component Brine Heater Heat Recovery Head Reject Failure Rate (%) 4.90 0.81 2.46

Heat Rejection Section. This section handles natural sea water, and copper-base alloys have often been selected for tubing. The most common cause of failure in these alloys is impingement attack, which can be caused by partial blockage due to debris passing the screens, unsatisfactory flow conditions in the water boxes and unsatisfactory entry conditions to the tube, i.e., any condition that can lead to local turbulence and high velocities (i.e., the normal design velocity is about 2 m/sec.) Table 2 gives data on the resistance of copper base alloys to this type of attack, and it is useful to note that the cost of these alloys is on the same order as their resistance to impingement corrosion. In unpolluted sea water with good intake screening and flow conditions, the copper base alloys perform well. However, modifications to the sea water composition by pollutants or by over-chlorination can give rise to corrosion problems. These are considered below. Effect of Sulphides. Sulphides may be present in sea water from the decomposition of organic matter, effluents from nearby sewage works or action of sulphate reducing bacteria (SRB). Normally when sulphides form in the sea water, there is a reduction in oxygen content, and in some cases the oxygen is completely removed. In this case, corrosion is not severe. However, in most cases the sulphides exist in aerated sea water, and this mixture of sulphides and oxygen, or preexposure to sulphides followed by exposure to aerated sea water, is very damaging to most copper base alloys. The sulphides enter the protective films and reduce their resistance so that they are easily damaged by flowing sea water at velocities which they would normally withstand. Table 6 [21] illustrates this effect on four widely used heat exchanger alloys. Sulphide levels as low as 20 ppb can be damaging to copper base alloys. Although copper base alloys such as cupronickels are not prone to severe pitting or crevice corrosion in static natural sea water, they can suffer this type of attack if sulphides are

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present. Where the heat exchanger has operated in clean sea water and has formed good protective films, these alloys can endure occasional exposure to sulphides. Ferrous sulphate dosing can also reduce the effects of sulphides [22]. However where sulphides occur regularly, the use of titanium can often be justified.

Table 6. Effects of Sulphides and Chlorine on Impingement Attack in Sea Water Depth of Attack (mm) Sea Water 0.1 ppm 0.25 ppm Sulphides Chlorine Aluminium Brass 0.26-0.28 0.56-0.90 0.07-0.20 90/10 Cupronickel 0.04-0.06 0.24-0.44 0.09-0.10 70 /30 Cupronickel 0.07-0.12 0.62-1.03 0.12-0.15 66/30 /2/2 CuNiFeMn 0.01-0.02 0.98 0.05 Velocity in test zone 7.5 m/sec. Effect of Ammonia. When organic matter decomposes in sea water, ammonia forms as well as sulphides. It may be present from other sources such as effluent from ammonia plants, of which there are several in the Arabian Gulf, and sewage plants. The main effect of ammonia is to cause severe pitting under crevice conditions with heat transfer [23]. Table 7 gives data on the effect of ammonia under crevice conditions. The pitting is often accompanied by deposition of copper, sometimes outside the pit. Addition of iron markedly reduces this type of attack, as shown by data in the table. Table 7. Crevice Corrosion in Sea Water Containing Ammonia Depth of Attack (mm) No Iron Plus Iron Ammonia 0 ppm 2 Ammonia 0 ppm 2 Aluminium brass 0.010 0.090 0.010 0.000 90/10 Cupronickel 0.015 0.100 0.015 0.000* 70/30 Cupronickel 0.015 0.075 0.000 0.015 66/30/ 2/2 CuNiFeMn 0.000 0.065 0.005 0.000* *Incipient pits-too small to measure; average of two tests in each case. Two month test in Campbell test rig. 0.042 ppm iron added continuously. Effect of Chlorine. Chlorine, added to control marine growth, can influence corrosion of copper base alloys. As can be seen in Table 8, low levels of residual chlorine are not damaging, indeed in some cases, they reduce corrosion. However, at higher levels, chlorine increases the effect of flow, and impingement attack becomes more likely [24, 25]. Effects of sand. Suspended matter, such as sand, can cause corrosion effects on copper base alloys in sea water. If it forms deposits in tubes, then some deposit attack, which is a
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Alloy

Alloy

Plenary Lectures

form of crevice corrosion, can occur beneath the deposit. Under flowing conditions, sand can cause damage to the protective films on copper alloys giving rise to impingement attack. In this context, two factors are important, namely, the sand content and the size of the sand particles [26]. The cupronickels have better resistance to sand than aluminium brass. The 70/30 cupronickel with 2% iron and 2% manganese was developed specifically for use in waters with high sand content, e.g., 4000 ppm, and is often specified for reject section tubing. Titanium has excellent resistance to sand erosion and is used where very high sand content occurs. Table 8. Effect of Carbon Steel and Ni Resist Type II on Crevice Corrosion of Type 316 Stainless Steel in Sea Water Crevice Attack No of Sites Maximum Depth Initiated of Attack mm 1:0 (Control) 42 3.18 10:1 (Steel) 0 0.00 50:1 (Steel) 0 0.02 50:1 (Ni-Resist) 0 0.00 30-day test; multicrevice assembly with 120 crevice sites; flow velocity 0.5 m/sec Heat recovery Section. The data from Table 5 indicate that this section of the plant presents fewer corrosion problems than others. This is to be expected as in the recovery section, the sea water and brine are usually deaerated so that there is little oxygen to support a corrosion reaction. The main corrosion risk is from vapour side corrosion, and as this is more likely in the first few stages, where carbon dioxide is evolved by the decomposition of bicarbonates in the sea water, these are normally vented directly to the vacuum system. Also, the tubing is made from materials with higher resistance to vapour side corrosion, that is to say, 70/30 cupronickel rather than the 90/10 CuNi alloy or aluminium brass. When vapour side corrosion occurs, it takes the form of fairly uniform thinning of the tube wall which eventually perforates. The attack is often concentrated at the tube plates or tube support junction with the tube and with acidic condensates. This is sometimes reported as a galvanic effect, for example, when the tube support plates are stainless steel, but it can occur when these are of the same material as the tubing or are even of carbon steel. Brine Heater. The data in Table 5 indicate that corrosion conditions in the brine heater are the most severe in the plant. However, if the causes of these failures are examined [20], it can be seen that most failures are due to mechanical damage during descaling rather than to corrosion. The need, therefore, for tubing in this section is for mechanical strength and for this reason, 70/30 cupronickel is the usual choice, and it is normally used at at 1.2 mm thickness. Tube Plates The main requirements of tube plates are mechanical strength and corrosion resistance. They should be galvanically compatible with the tube material and preferably slightly anodic to it so as to give some cathodic protection. As they are much thicker than the tube, some corrosion can be tolerated provided it does not disturb the tube/tube plate joint which is
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Area Ratio (SS:C. Steel or Ni Resist)

Oldfield

usually made by roller expansion. Water Boxes The most popular type of MSF design is the cross-tube type, and this requires a large number of water boxes with interconnecting piping. For large units, the most economic material for water boxes is carbon steel, but this needs protection if severe corrosion is to be avoided. Paint coatings have not proven to be reliable means of protection as they are easily damaged and require increased maintenance and inspection. Thick (3-5 mm) rubber linings can be used for the reject section but are not reliable for the hot recovery sections where they can become detached under vacuum. The most common solution for large water boxes is the use of 90/10 cupronickel clad steel with a 2-3 mm thickness of the alloy material. This has been used in many plants and is an economic and reliable form of construction. Evaporator Bodies The most common material of construction for evaporator bodies is carbon steel. In early plants, this was the only material used, but experience has shown that it could suffer severe corrosion, even in deaerated sea water and brine and alloy materials were introduced. The use of stainless steels such as Type 316 (low carbon or stabilised grades) began with attempts to repair areas of severe attack and proved very successful. In the absence of oxygen, the well-known tendency of these alloys to pit in sea water was inhibited, and provided care was exercised at shutdowns, when oxygen had access to the plant, stainless steel proved reliable. An alternative to stainless steels for chamber lining is 90/10 cupronickel. This has been used successfully for many years for evaporator shells for small plants [27] and in clad steel plate form can be used to construct large evaporator shells. Components in the brine spaces such as brine gates, weirs and nozzles, are normally made from stainless steel even in unlined spaces. The galvanic effect is slight and does not usually give rise to any problems. However, where only part lining with stainless steel is used, there is a risk of galvanic attack where the large area of stainless steel meets the carbon steel. This can be controlled by coating the stainless steel in the final lined stage. Vapour Spaces The mixture of water vapour, carbon dioxide and air entering the vapour spaces causes condensation on the walls and roof of the vapour spaces. These may cause corrosion as they are slightly acidic (due to the dissolved carbon dioxide), and if sufficient oxygen is present, it may add to the corrosion rate. Corrosion of steel in these spaces has been studied [16], and it was concluded that the main cause was oxygen in-leakage to the vacuum stages. Corrosion in these spaces is normally found in the mid-plant areas, and the highest rates of attack are in those stages immediately before the stage where cascaded gases are vented. Attack is also greatest above the distillate transfer trough where gases from the higher temperature stages are released as the distillate flashes on passing down the plant. Serious cases have been seen in acid dosed plants with excellent deaeration. These findings, together with the absence of carbonates in the corrosion product, which is mostly magnetic iron oxide Fe304 led to the conclusion that carbon dioxide played only a small part in the attack and that air in-leakage
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Plenary Lectures

was the basic cause. Careful attention to air tightness in one affected plant led to a 60% reduction in the corrosion rate. As stainless steels have very high corrosion resistance to carbonic acid and low-chloride distillate, even when oxygen is present, the use of this material for interstage walls and roof lining can control this type of attack. Stainless steels are often used in these spaces for parts such as tube support plates, distillate troughs, tube bundle stay bars and vent piping. However attention to air in-leakage is advised where carbon steel is used. Demisters Wire mesh demisters are normally fitted to prevent carryover of droplets of brine. Because the wire is very thin, usually 0.1-0.2 mm diameter, it is necessary to use materials with high resistance to general corrosion. Originally the nickel-copper Alloy 400 was widely used and gave good performance except where sulphides were evolved from the brine. This alloy is still used but most plants now use Type 316 stainless steel which performs well even when sulphides are present. Venting System Piping and Ejectors. Vacuum on the evaporator is normally produced by steam ejectors drawing gases from different sections of the plant. The first three stages are normally vented directly to the system, and gases evolved in lower temperature stages are cascaded to two or three points before being drawn off into intermediate ejectors and condensers. Where the last stage is used for deaeration or if a separate deaerator is fitted, the gases are drawn off into the deaerator condenser. Stainless steels Types 304 or 316 are normally used for the vent piping, headers within the piping system and baffles within the tube bundles. At lower temperatures some use has been made of glass-reinforced plastic piping (GRP), but stainless steels are needed for the higher temperatures, and most plants use them throughout. The ejectors are also made from stainless steel with nozzles in grades such as Alloy 20. Provided the chloride content of the gases remains low, the stainless steels work well, the only risk being from external stress corrosion cracking at temperatures above about 60C. To minimise this risk, painting of the stainless steel is advised, particularly under insulation where chlorides can accumulate. Condensers. Two types of condenser are used in venting systems, namely, shell and tube type, and barometric. As they have different materials requirements, they are considered separately. The shells of shell and tube type condensers are normally made in Type 316L stainless steel to resist the incondensible gases. In some cases, copper alloys such as aluminium bronze are used, but this is not common. For tubing, copper base alloys have a limited life due to vapour side attack in the high concentration of gases drawn from the plant which are mixed with ammonia from the ejector steam when hydrazine is used in the boilers. As the attack is usually fairly uniform, several years of life are possible, and some plants use copper base alloys with regular renewal. However in most cases it is more economic to use a resistant material and thin wall welded titanium tubing 0.7 mm thick is the usual choice. High alloy stainless steel such as UNS S31254 has been used successfully for tubing in ejector condensers in the Middle East. These were roller expanded into an existing naval
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Oldfield

brass tube plate and were in perfect condition after one year of service [28]. The advantage of using this alloy is the ease of descaling compared to titanium. For shell and tube units, tube plates and water boxes require similar considerations as for the reject section stages. In general copper base alloys are used with anodes in the water boxes to control galvanic effects when titanium or stainless steel tubes are fitted. Barometric condensers are essentially vessels into which sea water is sprayed. The large deaerator condenser can be made from GRP as temperatures are low; however, at higher temperatures, metals are necessary. Standard stainless steels such as Type 316L are prone to pitting in the sea water spray. Anodes are sometimes fitted to prevent this, but in a spray situation, they are not reliable. As the higher temperature units are relatively small, it is economic to make them from sea water resistant alloys such as the 6% molybdenum stainless steels. Sea Water Pumps Wet pit vertical lift pumps are normally chosen for large MSF units. Pump parts must withstand fast flowing sea water, and the normal choice for those parts exposed to the most severe conditions, such as impellers, is stainless steel. The reason for this is evident from the data in Table 4 where stainless steel Type 316 is seen to passivate in very high velocity sea water. The nickel copper Alloy 400 behaves similarly. Although stainless steels are excellent for flow conditions it is also necessary to consider static conditions, and as can be seen from Table 6, they are then subject to severe pitting. Thus, an all stainless steel pump would have problems at shutdown. Such problems have been reported [29]. One method of overcoming this is to make the static parts of the pumps of a material which gives cathodic protection to stainless steels at shutdowns. The material normally chosen is Ni-Resist, a high alloy cast iron. Table 8 [30] gives data on Ni-Resist and stainless steel galvanic couples showing that this combination can control pitting and crevice corrosion under static conditions. The usual grade of Ni-Resist used is Type D-2W. This has good sea water corrosion resistance but is subject to stress corrosion cracking in warm sea water and brine. Failures have occurred in service on castings which have not been stress relieved. However, when stress relief heat treated for a few hours at 650-675C and furnace cooled the alloy has proven resistant to cracking. It is essential, therefore, to apply this treatment before service and after any weld repairs. In recent years, there has been a trend towards the use of duplex stainless steels in sea water pumps. These are stronger than the standard austenitic alloys such as Type 316 and the grades used have higher resistance to pitting and crevice corrosion. In this case, to protect against pitting at shutdowns, it is advisable to operate the pumps for a short period every few days. Brine Recycle and Blowdown Pumps These are in many ways similar to the sea water pumps described above, but are barreltype or canned pumps. The impeller, shaft and other internals are often made from Type 316 stainless steel or its cast equivalent. The casings are often made of Ni Resist Type D-2W, and these again need to be stress relieved as cracking, particularly of diffusers, has been
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Plenary Lectures

experienced in service. The barrels or cans are usually fabricated from clad steels. The cladding is normally Type 316L stainless steel, but 90/10 cupronickel is also used. In some cases, thick, 3-5 mm, vulcanised rubber is used. Distillate Pumps The distillate leaving the plant is slightly acidic but not strongly corrosive until it becomes aerated. However, to maintain its purity, it is usual to use stainless steels for the pumps. Type 316 stainless steel is often used. Although this is not really necessary to handle low chloride distillate, there is always a risk during hydrotesting that it will be exposed to high chlorides. If this risk can be eliminated, then stainless steels such as Type 304 or 420 could be used. SELECTION OF MATERIALS FOR REVERSE OSMOSIS (RO) SYSTEMS General RO is a membrane process, and it is important to ensure freedom from corrosion products and similar material in the feed which might block the membranes. The use of stainless steels for piping and other components in the plant is, thus, advantageous as these alloys suffer virtually no general corrosion in waters. The problem is to ensure freedom from pitting, as most waters contain chlorides, are aerated and depending on their concentration and the other salts in the water, can cause pitting and crevice corrosion. In the case of sea water, selection is fairly straightforward and is often based on the PREN as described earlier. In the case of brackish waters, which can vary greatly as regards the concentration of salts present and their relative amounts, selection of the optimum grade of stainless steel is more difficult. Some of the factors involved in the selection of alloys for important components in RO systems are considered in the following sections. High Pressure Piping: Sea Water Systems The high pressure piping consists of large-bore pipes which convey high pressure feed from the pumps to the membrane banks. The feed is then distributed to rows of membrane cells by headers with connections to individual cells. A similar arrangement handles the effluent brine and permeate. Compression fittings, sometimes incorporating rubber O-rings, are used to connect various sections of the piping, and these provide sites very favourable to crevice corrosion. It is necessary, therefore, to use stainless steels with high resistance to crevice corrosion in sea water. Many plants have used a 6% molybdenum austenitic stainless steel. Nordstrom and Olsson [31] list 13 plants using this type of alloy. High Pressure Sea Water Pumps These pumps operate at about 70 bar pressure, and like the piping, should not add corrosion products to the feed. The problem is to avoid pitting and crevice corrosion and, as Ni-Resist is not suitable for these pumps (as its strength is too low), this means that alloys such as 6% molybdenum austenitics or duplex stainless steels with high PRENs should be used. However, the main risk of pitting occurs at shutdown, and by ensuring that the pumps do not stand idle for more than a few days, lower grades can be used. Draining and flushing with low chloride permeate is needed for longer periods of shutdown.

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Recovery Turbines: Sea Water Systems The effluent brine from these plants is at high pressure and can be used to recover energy. The machines used for this purpose are impulse turbines, i.e., Pelton Wheels, or reaction turbines which are centrifugal pumps running in reverse. Materials selection for the reaction-turbine type is based on the same criteria as for the high pressure feed pumps. For Pelton Wheels, duplex stainless steels are favoured. In this case resistance to cavitation corrosion is important as sheets of cavitation can form at the discharge nozzles, and if these impinge on the buckets of the wheel, they can cause severe damage. High Pressure Piping: Brackish Water Systems Selecting the optimum grade of stainless steel is more difficult in this case as the compositions of these waters can vary greatly. This problem has been addressed by Oldfield and Todd [32] using a corrosion engineering guide (CEG) based on a mathematical model which has been verified by exposure testing. In the mathematical model of crevice corrosion, the main corrosion problem in these systems has been converted into a user friendly computer program, which, once given the necessary input data makes predictions of performance. The CEG also enables the user to see how minor variations in their conditions might influence the prediction, thus it enables them to see if the material selected is near its limit of usage or whether there is a margin of safety to allow for variations in conditions. Although the CEG takes into account many more factors than alternative methods of prediction, there are factors which it does not consider, e.g., the presence of sulphides, unusual anions. When such conditions are encountered, additional advice should be sought. However, in most circumstances the CEG will select an appropriate grade of stainless steel. High Pressure Pumps: Brackish Water Systems The selection of suitable grades of stainless steel is based on the same criteria as selection for piping in the previous section. SUMMARY AND CONCLUSIONS When selection of materials is based on their known behaviour in relevant corrosion environments such as natural sea water, and when this is coupled with service experience, reliable performance can be obtained in desalination processes. This treatise has documented relevant data and experience, and has indicated how materials can be selected for the main components of MSF and RO process plants. Selection of materials is a continually changing process as new materials are developed, experience is gained and relative costs of materials and labour change. However, the need to make the optimal selection of materials will always remain, and if based on sound technical data and experience, can be achieved. REFERENCES 1. J. Lyman and R. Babel, Chemical aspects of physical oceanography, J. Chemical Education 35, 3, 1938, pp. 113-115. 2. C.R. Southwell, J.D. Bultmann and A.L. Alexander, Corrosion of metals in tropical
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environments: Final report of 16-year exposures, Materials Perform., July 1976, pp. 9-26. 3. H.R. Copson, Effects of velocity on corrosion, Corrosion 16, 1960, pp. 86-92. 4. J.W. Oldfield and B. Todd, Corrosion considerations in selecting metals for flash chambers, Desalination, 1979, 3, pp. 365-383. 5. F.W. Fink E.L. White and W.K. Boyd, U.S. Department of Interior R&D Progress Report No. 255, December 1966. 6. D.B. Anderson, Copper-nickel and other alloys for desalination, Inco Publication No. 4319, pp. 39-47. 7. Desalination Materials Manual, Dow Chem for the U.S. Office of Water Research and Technology, May 1975. 8. G. Pini and J. Weber, Materials for pumping sea water and media with chloride content, Sultzer Technical Review, 1975, p. 158. 9. S. Kido and T. Shinohara, Corrosion under heat flux encountered in desalination plant, Desalination, 1977, 22, pp. 369-378. 10. K. Shimogori, H. Sato, F. Kamikubo and T. Fukuzuka, Corrosion resistance of titanium in MSF desalination plant, Desalination, 1977, 22, pp. 403-413. 11. G.A. Gehring and R.J. Kyle, Galvanic corrosion in steam surface condensers tubed with either stainless steel or titanium, NACE Corrosion '82, Paper No. 60, 1982. 12. P.D. Simon, Tube sheet corrosion and mitigation techniques in a sea water cooled titanium-aluminium bronze condenser, NACE Corrosion '83. Paper No. 77, 1983. 13. J.P. Fulford and R.W. Shutz, Characteristics of titanium condenser tube hydriding at two Florida Power and Light Company plants, ASME/IEEE Power Generating Conference, Miami Beach, Oct. 1987. 14. T. Fukuzuka, K. Shimogori, H. Sato and F. Kamikubo, Corrosion problems and their prevention in desalination plant with titanium tube, Proc. of Intl. Congress in Desalination and Water Re-use, Nice, October 1979, pp. 389-397. 15. P.F. George, J.A. Manning and C.D. Schrieber, Desalination Materials Manual, May 1975. 16. J.W. Oldfield and B. Todd, Vapour side corrosion in MSF plants, Desalination, 1978, 66, pp. 171-184. 17. J.W. Oldfield and B. Todd, Corrosion problems caused by bromine formation in MSF desalination plants, Desalination 1981, 38, pp. 233-245. 18. W.S.W Lee, J.W. Oldfield and B. Todd, Corrosion problems caused by bromine formation in additive dosed MSF plants. Desalination 1983, 44. pp. 209-221. 19. Crevice Corrosion Engineering Guide, Nickel Development Institute, Publication and Computer Disk D-0003. 20. E.H. Newton, J.D. Birkett and J.M. Ketteringham, Survey of materials in large desalting plants around the world, A.D. Little & Co., March 1972. 21. R. Francis, The effect of sulphide and chlorine on the corrosion of copper alloy heat exchanger tubing. BNF Paper R421/5, September 1984. 22. H.P. Hack and T.S. Lee, David Taylor Naval Ship and Research Development Centre Report DTN SRDC/SME - 81/91, January 1982. 23. R. Francis, The effect of ammonia and chlorine on the corrosion of copper alloy heat exchanger tubes. BNF paper R241/4, June 1984. 24. S. Sato, Sumitomo Light Metal Industries Review, July 1962. 25. R. Francis, The effect of chlorine additions to cooling water on corrosion of copper alloy
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condenser tubes, Materials Performance, August 1982, p. 44. 26. S. Sato, Recent aspects of corrosion protection in condenser tubes. Boshoku Gijutsu (Corrosion Engineering), 24, 6, 1975. pp. 313-331. 27. D.A. Rayney, Choose CuNi tubes, Ni steel for ascension desalination, Nickel 6, 3, 1991. 28. J. Olsson and B. Wallen, Experience with a 6% Mo stainless steel in saline water, BSE/NACE Conference, Bahrain 1984. 29. S. Zaharani, B. Todd and J.W. Oldfield, Bimetallic corrosion in MSF desalination plants. Galvanic Corrosion, ASTM STP978 HP Hack Ed, ASTM, 1988, pp. 323-335. 30. T.S. Lee and A.H. Tuthill, Guidelines for the use of carbon steel to mitigate crevice corrosion of stainless steel in sea water, NACE Corrosion '82. Paper No. 63, 1982. 31. A.J. Sedriks and K.L. Money, Corrosion fatigue properties of nickel-containing materials in sea water, International Nickel Publication A1258, 1978. 32. J. Nordstrom and J. Olsson, Which stainless steel to use for SWRO plants, Symposium Internacional De Desalacion y Reuso Del Aqua, Canagua 1992. 33. J.W. Oldfield and B. Todd, Economic selection of stainless steels for desalination and industrial water applications using a computerised corrosion engineering guide (CEG), 6th Middle East Corrosion Conf. Vol. 2, January 1994, p. 771.

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APPENDIX Nominal Composition of Alloys Copper Base Alloys Alloy UNS No Cu (%) 90\10 Cupronickel 70\30 Cupronickel 66\30\2\2 CuNiFeMn Aluminium Brass Admiralty Brass Naval Brass Aluminium Bronze NiAl Bronze (W) Admiralty Gunmetal Leaded Gunmetal NiAl Bronze (C) Rem = Remainder W = Wrought C = Cast Titanium UNS No Ti (%) Grade 2 Fe (%) R50400 Rem 0.3 Maximum % in all cases O( %) N( %) H (%) C (%) 0.25 0.03 0.015 0.1 C70600 C71500 C71640 C68700 C44300 C46400 C61400 C63000 C90300 C83600 C95800 Rem Rem Rem Rem Rem Rem Rem Rem Rem Rem Rem 10 30 30 5 5 1.5 1 2 2 4 4 1 1 2 1 1.5 1 22 29 37 2 5 2 7 10 9 1 1 10 5 5 0.04A s 0.04A s Ni Fe Mn Zn Al Sn Pb Other (%) (%) (%) (%) (%) (%) (%)

Stainless Steels a) Austenitic Alloy 304 304L 316 316L 317 317L 317LMN
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UNS No S30400 S30403 S31600 S31603 S31700 S31703 S31726

C (%) 0.08 0.03 0.08 0.03 0.08 0.03 0.03

Cr (%) Ni (%) Mo (%) 18 10 18 10 17 12 2.5 17 12 2.5 19 13 3.5 19 13 3.5 18 13 4.5

Other

0.18N

Oldfield

904L b) Superaustenitics Alloy 254SM O 1925 hMO AL-6XN HR25 4 c)

N08904

0.03

20

25

4.5

1.5Cu

UNS No S31254 N08926 N08367 S31254

C% 0.03 0.03 0.03 0.02

Cr (%) Ni (%) Mo (%) N (%) Other 20 18 6 0.2 0.7Cu 21 25 6 0.19 21 25 6.5 0.2 20 18 6 0.2 0.7Cu

Duplex and Superduplex Alloys Alloy 2205 3RE6O Ferralium Zeron 100 SAF 2507 DP3W UNS No S31803 S31500 S32550 S32760 S32750 S32974 C (%) Cr (%) Ni (%) Mo (%) N (%) Other 0.02 22 5.5 3 0.17 0.03 18.5 5 2.5 0.1 0.04 25 6 3 0.18 2Cu 0.03 25 7 3.5 0.25 0.8W + 0.8Cu 0.03 25 7 4 0.3 0.02 25 7 3.2 0.3 2W + 0.5Cu

Nickel Base Alloys Alloy Alloy 400 Alloy 500 A lloy 825 Alloy 625 UNS No C (% max) Cr (%) Ni (%) Mo (%) Cu (%) Other N04400 63 min 31 2Fe N05500 63 min 31 2.7Al + 0.6Ti N08825 0.05 21 42 3 2.5 30Fe N06625 0.1 21 Rem 9 3.5Nb Rem = Remainder

Ni Resist Alloy Cast Irons Alloy UNS No C (% max) Cr (%) Ni (%) Other Type 2 F41002 3.0 2 20 Type D-2 F43000 3.0 2 20 Type D-2W 3.0 2 20 0.15Nb Graphite Form Flake Spheroidal Spheroidal

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Industrial Corrosion and Corrosion control Technology sbalaby, H.M et aI. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CORROSIVITY PREDICTION FOR CO2/H2S PRODUCTION ENVIRONMENTS

CLl International, Inc. 14503 Bammel N. Houston # 300 Houston, TX 77014, USA

One of the most fundamental issues in current day corrosion research is assessment of corrosion rates in steels and determination of corrosivity of typical operating environments in oil and gas production. Such assessment requires an understanding of the role of primary environmental and metallurgical variables and underlying mechanisms of corrosion. This paper presents a novel hierarchical approach to assess system corrosivity and predict corrosion rates in carbon steels in production environments containing CO2 and/or H2S. Critical environmental parameters that influence system corrosivity are identified and the effects of these parameters on corrosion are examined. Modeling for synergistic assessment of system corrosivity as a function of relevant operating parameters is presented and is accompanied by a description of a computer program to capture the model described. Key Words: CO2 H2S, Corrosivity, Prediction, Corrosion rates, Computer Model INTRODUCTION CO2/H2S corrosion in oil and gas production environments represents one of the most important areas of corrosion research. It is so because of the criticality of the need to assess corrosive severity as a means to ensure safe utilization of steels, which have wide application in just about every sphere of oil and gas production and refining. Even though CO2/H2S corrosion and concomitant mechanisms have been areas of significant work over the last thirty years, there still exists a need to accurately predict corrosivity of CO2/H2S environments from a standpoint of defining limits of use for carbon steels. Even though numerous predictive models have been developed and are being developed [1,2]; most of the available predictive models tend to be either very conservative [3] in their interpretation of results or focus on a narrow range of parametric effects, thereby limiting the scope of the model's application in realistic assessment of corrosivity and corrosion rates. Often times, data required by the models are not easily accessible or available to the operators who need to employ the model, thereby limiting the applicability of the models to situations of reduced practical importance [4,5]. In this context, the issue of corrosivity assessment for carbon steels can be restated in terms of the following critical requirements:

- Development of a predictive model that utilizes commonly available operational parameters, - Utilization of existing laboratory/field data and theoretical models to obtain realistic assessments of corrosivity and corrosion rates, and - Development of a computational approach that integrates both numerical (read "laboratory trends") and heuristic (i.e., field data and experience) information and knowledge about corrosivity prediction. In this paper, a methodology to determine system corrosivity and to predict corrosion rates in steels is described, consistent with the objectives stated above. The method adopted here attempts to capture both the effect of critical parameters on corrosion rates as well as that of parameter interactions. The model described in this paper has been encoded into a Widows-based computer program, Predict, that would allow the end user to predict corrosion rates. The primary variables in corrosivity prediction in the model are the acid gases CO2 and H2S that contribute to the typically acidic pH found in production environments. The model uses the widely accepted de WaardMilliams [3] relationship for CO2 corrosion for an initial determination of CO2-based corrosion rates. However, the effective CO2 partial pressure in the system is not based on the operating partial pressure but on one obtained from the system pH. This rate is further refined to account for the presence of H2S, corrosion products, temperature effects etc. A technical description of different corrosivity modeling parameters and their effects is given in ensuing sections of this paper. The underlying idea here has been to develop a prediction model that accurately represents the state-of-the-art in theoretical analyses as well as parametric correlations based on laboratory and field data. The model has also been compared with actual field conditions in an effort to compare system predictions [6] with field observations. In developing any corrosivity model, it is important to recognize the role of superposition of different parameters. Such recognition requires a clear understanding of independent parameter effects and how corrosion rate progresses when subjected to the effects of two or more variables. While the current prediction model is primarily concerned with environmental constituents and their corrosive effects, it is also important to recognize the significant role of metallurgy in fashioning appropriate corrosion behavior. The influence of compositional and alloying elements has been chronicled but has hitherto not been rigorously studied in assessing resistance to system corrosivity. A brief discussion of metallurgical factors in corrosivity determination is provided elsewhere in this paper. CO2/H2S-BASED CORROSION: TECHNICAL BACKGROUND AND LITERATURE REVIEW CO2-based corrosion has been one of the most active areas of research, with several predictive models for carbon steel corrosion assessment. These efforts range from a predictive model that begins with CO2 corrosion [2,3] to models that focus on specific aspects of the corrosion phenomena (such as flow-induced corrosion or erosion corrosion) [4,5] and models that empirically relate corrosion rates to gas production and water production rates [7]. Crolet and Bonis [8] use the. physical chemistry of the corrosive medium as the key notion and take

into account ionic strength, pH and specific ionic species as relevant factors. Other relevant efforts include those by Ikeda et al. [9] that look at the influence ofH2S and O2 on CO2-based corrosion as well as those by Adams et al. [10]. Many of these efforts suffer from significant drawbacks in that - They focus on a narrow range of parametric effects, for example, there is relatively little published information on the effects of H2S in production systems and how sulfide scaling can affect the CO2 corrosion process, - Some models focus on just one component of corrosivity, such as erosional effects, wall shear stress effects or flow effects, and have opted to ignore effects of chemical species (i.e., factors such as pH, H2S, CO2 etc.), and - Other models totally rely on laboratory data for predictive modeling, with the consequence that the simplifying assumptions made in developing laboratory models often lead to results that can be far removed from what is observed in the field. The current model attempts to integrate laboratory data and field experience within the framework of the relevant controlling parameters that are most prominent in oil and gas production. It is important to realize that while arcane theoretical models are interesting from an academic standpoint, the controlling parameters in a model must also represent data easily available to oil and gas production personnel. The current model attempts to integrate principles hitherto delineated in developing the predictive model. While there have been several studies focusing on the exact mechanism of metal dissolution in CO2-containing waters, the efforts of de Waard and Milliams, and others [2,3,9] present a commonly accepted representation wherein anodic dissolution of iron is a pH dependent mechanism as given by Bockris [2], and the cathodic process is driven by the direct reduction of undissociated carbonic acid. These reactions can be represented as [3]

The buildup of the bicarbonate ion can lead to an increase in the pH of the solution until. Conditions promoting precipitation of iron carbonate are reached, leading to the reaction given below

Iron carbonate solubility, which decreases with increasing temperature, and the consequent precipitation of iron carbonate are significant factors in assessing corrosivity. The charge transfer controlled reaction involving carbonic acid and carbon steel (or Fe) can be represented in terms of the concentration or partial pressure of dissolved CO2 in the medium to

arrive at a corrosion rate equation that incorporates the order of the reaction and an exponential function that approximates for Henry's reaction constant's temperature dependence. This corrosion rate equation is given as [2]

The corrosion rate obtained by Eq. 4 has typically been seen as the maximum possible corrosion rate without accounting for iron carbonate scaling. A nomogram representing Eq. 4 is given in Fig. 1 [2], which also includes a scale factor to account for the formation of protective carbonate films that lead to a reduced corrosion rate at higher temperatures.

The above correlation describes CO2-based corrosion. There have been other significant efforts to demonstrate the effects of other environmental variables such as pH, H2S, chlorides, bicarbonates, water/gas/oil ratios, velocity etc. Effects of H2S on corrosion rates in the laboratory have been studied and presented by Videm and Kvarekval [11], and Ikeda et al. [9]. Ikeda et al.' s work indicates that the preferential formation of an iron sulfide film can decelerate the corrosion rate, especially at temperatures above 20C and extending up to 60C. Above I50C, the corrosion reaction falls back to the standard CO2-based corrosion with an FeC03 film that is more stable than the FeO2 film. Videm and Kvarekval's work supports the theory that even small amounts of H2S can provide instantaneous protection at temperatures in the range of 70-80C.

Lotz et al. [12] have chronicled the role of the hydrocarbon condensate in providing corrosion mitigation in specific production systems. The role of the type of oil or gas condensate is important from the standpoint of accurate assessment as reported by Choi et al. and Efird [13,14]. Other studies evaluating effects of critical parameters such as pH and velocity on CO2 corrosion include those by Dugstad and Lunde [15] as well as Lotz [16]. Other predictive models also include those by Gunatlun [17] and Bonis and Crolet [18] wherein a combination of the parameters discussed herein along with electrochemical considerations have been utilized to arrive at a determination of the corrosion rate. The primary objective of the corrosivity prediction model described in this paper is to address the need of developing a predictive method that would synthesize different parametric relationships based on information from literature, laboratory research/data and practical experience/expertise. It has often been observed that laboratory data and the ensuing models represent poor and often inadequate simulation of field conditions [19]. It is also necessary to understand that field data is typically sparse and can be negated by other production data. The need to integrate field data/experience and laboratory models stems from the fact that the laboratory data can provide significant pointers and trends that can be used in conjunction with field data and experience. The idea is to develop a methodology that can integrate analytical and heuristic models. To this end, this predictive system mirrors other successful development efforts undertaken by the authors in the areas of evaluation of CRAs and cracking in steels [20,21]. The central theme is to develop a computer program that can bring together different types of modeling knowledge to provide a realistic solution to the significant question of predicting corrosion rates in typical production environments. CORROSIVITY PREDICTION MODEL DESCRIPTION A flowchart delineating the hierarchical reasoning structure of the predictive model is given in Fig. 2. The first step in corrosivity determination is computation of the system pH, since it is the hydrogen ion concentration that drives the anodic dissolution. Further, the role of pH in promoting or mitigating CO2-based corrosion has been extensively chronicled [19,22]. For production environments, where it is the dissolved CO2 or H2S that contributes significantly to a suppressed pH, the pH can be determined as a function of acid gas partial pressures, bicarbonates and

temperature, as shown in Fig. 3 [23]. From a practical standpoint, the contribution of H2S or HC03, or temperature to pH determination is another way of representing effective levels of CO2 that would have produced a given level of pH. This type of pH determination has been found to be quite accurately applicable in other modeling efforts involving verification of the relationship given by Bonis and Crolet [23]. While it has been documented that the CO2 corrosion mechanism is dissimilar to that of strong acids like HCI (as CO2 corrosion is now understood to progress through direct reduction of H2C03 to HC03 - rather than reduction of II' ions), and that carbonic acid corrosion is much more corrosive than that obtained from a strong acid such as HCI at the same pH [19], there is also significant agreement that lower pH levels obtained from higher acid gas presence leads to higher corrosion rates. Conversely, higher levels of pH obtained through buffering in simulated production formation water solutions have been shown to produce significantly lower corrosion rates even at higher levels of CO2 and/or H2S [24]. Data about the effects of pH from another study are shown in Fig. 4 [15]. Hence, it is more meaningful to determine the

Where Cl and C2 are constants, pH2S and pCO2 are partial pressures in bar and the HCO3 concentration is represented in meq/l (61 mg/l). The system pH is given by the larger number between PHI and pH2. Correspondingly, if the temperature is higher than 100C, there is a slight reduction in the hydrogen ion concentration as shown in Fig. 3, but the change in pH can be accounted for by a change in the value of the constants in Eq. 5 and 6 above. Once the system pH is determined, the effective CO2 partial pressure can be determined from Eq. 5 as,

where pCO2. is the effective partial pressure of CO2 in a production system that can produce the prevalent level of hydrogen ion concentration. The effective CO2 partial pressure from Eq. 7 can be used in Eq. 4 to determine an initial corrosion rate for C02-based corrosion. The corrosion rate so obtained is modified to account for the formation of a FeCO3 film (Fe304 at higher temperatures), the stability of which varies as a function of the operating temperature. The scale correction factor shown in Fig. 1 is used to determine the initial corrosion rate from the nomogram in Fig. 1 [2]. It is generally estimated that this corrosion rate presents a maximum corrosion rate even though it has been reported that the rates computed by the nomogram are reached or exceeded in systems with high flow rates. It is important to recognize that this corrosion rate has to be modified to account

for the effect of other critical variables in the system. Further, this rate does not indicate modality (general or localized), but rather, represents the maximum rate of attack. As mentioned earlier, it is necessary to superposition the effects of other critical system parameters. The flowchart in Fig. 2 provides a list of the sequential effects that are important from a standpoint of corrosivity determination. In addition to the system pH, these include: H2S partial pressure, maximum operating temperature, dissolved chlorides, gas-to-oil ratio, water-to-gas ratio/water cut, oil type and its persistence, elemental sulfur/aeration, fluid velocity, type of flow, and inhibition type and efficiency. H2S Oilfield production environments, in recent years, have been characterized by an increasing presence ofH2S and related corrosion considerations. Even though H2S is probably the most significant concern in current-day corrosion and cracking evaluation, the role ofH2S in corrosion in steels has received much less attention when compared to the widely studied CO2 corrosion. [26]. However, H2S-related corrosion and cracking has remained one of the biggest concerns for operators involved in production because of the significance of H2Srelated damage [27]. In the current modeling effort, in addition to the contribution in pH reduction, H2S has a threefold role: - At very low levels of H2S 0.01 psia), CO2 is the dominant corrosive species, and at temperatures above 60C, corrosion and any passivity is a function of F eC03 formation-related phenomenon, and the presence of H2S has no realistic significance. - In CO2 dominated systems [26,28], the presence of even small amounts of H2S (ratio of pC02/pH2S > 200), can lead to the formation of an iron sulfide scale called mackinawite at temperatures below 120C. However, this particular form of scaling, which is produced on the metal surface directly as a function of a reaction between Fe++ and S ., is influenced by pH and temperature [27]. This surface reaction can lead to the formation of a thin surface film that can mitigate corrosion. The authors are currently pursuing laboratory studies to characterize the stability and formation of mackinawite in sour systems.

- In H2S dominated systems (ratio of pCO~pH2S < 200), there is a preferential formation of a metastable sulfide film in preference to the FeC03 scale; hence, there is protection available due to the presence of the sulfide film in the range of temperature of 60-240C. Here, initially it is the mackinawite form of H2S that is formed as a surface adsorption phenomenon. At higher concentrations and temperatures, mackinawite becomes the more stable pyrhotite. However, at temperatures below 60C or above 240C, the presence of H2S exacerbates corrosion in steels since the presence of H2S prevents the formation of a stable FeC03 scale [9,29]. Further, it has been observed that FeS film itself becomes unstable and porous and does not provide protection. Also, the scale factor applicable for CO2 corrosion with no H2S (shown in Fig. 1) becomes inapplicable. Even though there is agreement amongst different workers that there is a beneficial effect of adding small amounts of H2S at about 60C, Ikeda et al. [9] and Videm and Kvarekval [11] present divergent results at higher concentrations and higher temperatures. The effect ofH2S adopted in the predictive model reflects work published by Murata et al. [29] for CO2dominated systems. Figure 5 [29] shows the combined effects of temperature and gas composition on the corrosion rate of carbon steels. Figure 6 [9] shows the effect of varying degrees ofH2S contamination on C02 corrosion. It is to be noted that the role ofH2S in C02 corrosion is a complex issue governed by the film stability of FeS and FeC03 at varying temperatures and is an area of further active research by the authors.

Temperature Temperature has a significant impact on corrosivity in CO~2S systems. Corrosion rate as a function of different levels of CO2 and temperature is given in Fig. 7 [2]. It has to be noted that once the corrosion products are formed, there is a significant mitigation in corrosivity. It is also apparent that the carbonate film is more stable at higher temperatures and affords greater protection at higher temperatures. Figure 7 also shows that at temperatures beyond 120C, the corrosion rate is almost independent of the CO2 partial pressure of the system. The carbonate film may, however, be weakened by high chloride concentrations, or it can be broken by high velocity. In H2Sdominated systems, because no carbonate scale may be formed and the FeS film becomes porous and unstable at temperatures beyond 120C, significant localized corrosion may be observed.

Chlorides Produced water from hydrocarbon formations typically contains varying amounts of chloride salts dissolved in solution. The chloride concentration in this water can vary considerably, from zero or a few parts per million in condensed water to saturation in formation waters having high total dissolved salts/solids (TDS). In naturally deaerated production environments, the corrosion rate increases with increasing chloride ion content over the range 10,000 ppm to 100,000 ppm [30]. The magnitude of this effect increases with increasing temperature over 60C (1 50F). This combined effect results from the fact that chloride ions in solution can be incorporated into and penetrate surface corrosion films, which can lead to

destabilization of the corrosion film and increased corrosion. This phenomenon of penetration of surface corrosion films increases in occurrence with increases both in chloride ion concentration and in temperature. Bicarbonates Bicarbonates in the operating environment have a significant impact on corrosion rates. On one hand, high levels of bicarbonates can provide higher pH numbers leading to corrosion mitigation even when the partial pressures of CO2 and HzS are fairly high. Bicarbonates, which can be present in substantial quantities in formation waters (up to 20 meq/l) [31], have a natural inhibitive effect when present. Condensed water in production streams typically contains no bicarbonates. Velocity Next to the corrosive species that instigate corrosion, velocity is probably the most significant parameter in determining the corrosivity of production systems. Fluid flow velocities affect both the composition and extent of corrosion product films. Typically, high velocities (> 4 m/s for uninhibited systems) in the production stream lead to the mechanical removal of corrosion films, and the ensuing exposure of the fresh metal surface to the corrosive medium leads to significantly higher corrosion rates. Corrosion rate as a function of flow velocity and temperature is shown in Fig. 8 [15].

In multiphase (i.e., gas, water, and/or liquid hydrocarbon) production, the flow rate influences the corrosion rate of steel in two ways. First, it

determines the flow behavior and flow regime. In general terms, this is manifested as static conditions (i.e., little or no flow) at low velocities, stratified flow at intermediate conditions, and turbulent flow at higher flow rates. One measure which can be used to define the flow conditions is the superficial gas velocity. In liquid (i.e., oil / water) systems, this is replaced with the liquid velocity. Velocities less than 1 m/s are considered static. Under these conditions corrosion rates can be higher than those observed under moderate flow conditions. This occurs because under static conditions, there is no natural turbulence to assist the mixing and dispersion of protective liquid hydrocarbons or inhibitor species in the aqueous phase. Additionally, corrosion products and other deposits can settle out of the liquid phase to promote crevice attack and underdeposit corrosion. At velocities between 1 and 3 m/sec, stratified conditions generally still exist. However, the increased flow promotes a sweeping away of some deposits, and increasing agitation and mixing. At 5 m/sec flow velocity, corrosion rates in uninhibited applications start to increase rapidly with increasing velocity [31]. The data shown in Fig. 9 [31] demonstrate the effects of velocity on corrosion rate for both inhibited and non-inhibited systems. For inhibited applications, corrosion rates of steel increase only slightly at velocities between 3 and 10 m/sec, as a result of mixing of the hydrocarbon and aqueous phases. At velocities above about 10 m/sec, corrosion rates in inhibited systems start to increase due to the removal of protective surface films by the high-velocity flow.

Flow-related effects on corrosivity have been linked to the wall shear stress developed and is an area of intense research in the community [32]. Flowinduced corrosion is a direct consequence of mass and momentum transfer effects in a dynamic flow system where the interplay of inertial and viscous forces is responsible for accelerating or decelerating metal loss at the fluid/metal interface. While flow-induced corrosion is a significant component of predictive modeling discussed herein, the topic of flow-related effects is being actively researched by the authors and forms the focus of another publication. Another relevant aspect of flow- or velocity-induced corrosion is erosion-corrosion [33] and refers to the mechanical removal of corrosion product films through momentum effects or through impingement and abrasion. Guidelines for velocity limits with respect to erosional considerations are given in API-14E in terms of the density of the fluid medium [34]. Water/Gas/Oil Ratios The predictive model classifies systems as oil dominated or gas dominated on the basis of the gas/oil ratio (GOR) of the production environment. If the environment has a GOR < 890 m3/m3 (5000 scf/bbl in English units) [35], the tendency for corrosion and environmental cracking is often substantially reduced. This is caused by the possibly inhibiting effect of the oil film on the metal surface, which effectively reduces the corrosivity of the environment. However, the inhibiting effect is dependent on the oil phase being persistent and acting as a barrier between the metal and the corrosive environment. The persistence of the oil phase is a strong factor in providing protection, even in systems with high water cuts. In oil systems with a persistent oil phase and up to 45% water cut, corrosion is fully suppressed, irrespective of the type of hydrocarbon [12]. Relative wet ability of the oil phase versus the water phase has a significant effect on corrosion [36]. Metal surfaces that are oil wet show significantly lower corrosion rates [37]. The predictive model described in this paper provides for a significant reduction in the corrosion rate (up to a factor of 4) based on the type of oil phase, i.e., persistent, mildly persistent and not persistent. However, the degree of protection can be quantified only as a function of water cut and velocity. The persistence determination is a more complex task and requires knowledge of the kerogen type and hydrocarbon density. It is important to

understand the type of crude oil in terms of the organic compounds that make up the crude to determine wettability effects. Figure 10 shows data that relate the acid number of the crude to oil wettability, and Fig. 11 shows corrosion rate as a function of produced water content for different crude oil/produced water mixtures [36]. While the effect of persistence of the oil medium is significant on corrosion rates, it is even more difficult to quantify precise compositional elements of oil medium that contribute to wettability and persistent oil film formation. Such quantification is possible by rigorous laboratory testing of different actual, uncontaminated (read "deaerated") production water samples, so as to determine the extent of protection.

In oil systems, the water cut acts in synergy with the oil phase to determine the level of protection from the hydrocarbon phase. However, at very low water cuts 5%), the corrosive severity of the environment is lessened due to the absence of adequate aqueous medium to promote the corrosion reaction. In gas-dominated systems, there are two measures to evaluate the availability of the aqueous medium. If the operating temperature is higher than the dew point of the environment, no condensation is going to be possible, leading to highly reduced corrosion rates. Corrosion under condensing conditions (i.e., operating temperature less than the dew point) is a function of the rate of condensation and transport of corrosion products from the metal surface [38]. If the total water in a condensing system as measured by the water-to-gas ratio is < 11.3 m3/Mm3 (2 bbl water/MSCF gas), corrosivity is substantially reduced.

Aeration/Sulfur The presence of oxygen significantly alters the corrosivity of the environment in production systems. Old field and Todd [39] chronicled how the presence of oxygen could significantly increase corrosion rates due to acceleration of anodic oxidation. While the corrosion rate increases with oxygen, the rate of oxygen reduction as a catholic reaction is further exacerbated by - Increased operating temperature, - Increased fluid flow leading to increased mass flow of oxygen to the metal surface, and - Increased oxygen concentration Data showing increases in corrosion rate as a function of oxygen concentration for differing temperatures are shown in Fig. 12 [39]. The presence of elemental sulfur is similar to that of free oxygen since elemental sulfur also acts as a strong oxidizing agent. Inhibition/Inhibition Effectiveness Appropriate inhibition is a critical criterion for effective use of carbon steels in corrosive production systems. Inhibition has been typically found to be viable in flows with velocity in the range of 0.3-10 mfs. Requirements for the type of inhibitor and the method of delivery depend on the type of system (Le., production tubing or horizontal flow lines) to be inhibited. Inhibition efficiency (IE) describes the efficacy of an inhibitor treatment in

mitigating weight loss corrosion and is an important factor in assessing corroslV1ty. It is based on either laboratory or field data where inhibited and uninhibited corrosion rates are compared using the following equation:

Values of IE near 1.0 represent conditions with maximum efficacy of the inhibitor treatment. Conditions which affect IE include: Inhibitor concentration, Severity of the corrosive environment, Service temperature, Solubility of the inhibitor in the aqueous phase, Phase behavior of the inhibitor and carrier fluid in the service environment, and Persistence of the inhibitor on the metal surface.

The predictive model evaluates inhibition efficacy on the basis of velocity, hydrocarbons to-water ratio and dissolved chloride levels. The method of delivery (e.g., batch, continuous, pigging, etc.) is also an important factor in determining the appropriateness of inhibition for a given set of operating conditions. The corrosion rate predicted in the current model can be represented in terms of three broad rules that guide the computer model's decision making: - Effect of fundamental system variables such as CO2, H2S, pH, temperature, and velocity on corrosion rate; - Effect of parameter interactions on corrosivity, such as, the influence of temperature on the carbonate or sulfide film stability, or flow

effects on corrosion products and the ensuing loss of protective films as a function of velocity, temperature, acid gases and pH; and - Effects of system modifiers such as oil film persistence (or lack of it) or the crude type, water cut, dew point, aeration and inhibition. Corrosion rate, thus predicted, incorporates the synergy of the effects of all the critical system variables and provides a more realistic estimation of corrosivity than would be available with conservative theoretical models that focus on a limited number of parameters. The significance of the reasoning in the predictive model stems from the fact that the decisions made synthesize different types of corrosion knowledge: - Theoretical models that provide the effects of different parameters, - Data from laboratory tests that provide insight on parametric correlations and trends of parametric effects, and - Experience-based heuristics that facilitate proper interpretation of data from both the laboratory and field. The predictive model in this paper has been implemented as a Windowsbased computer program with an interface as shown in Fig. 13. Based on data specified for different parameters, the system will instantaneously display the following results: - System pH, - Predicted corrosion rate called corrosion index (in mpy or mmpy), - A textual recommendation in the results box indicating whether the predicted corrosion rate is within the specified allowance for the particular system, and - A corrosion index bar that graphically represents the corrosion rate. The user can specify data for any of the parameters and watch the effect of that parameter on the corrosion rate in the system instantaneously. The system starts with a set of default values and calculates a corrosion rate based on any changes to the displayed values. A typical consultation will involve the following five steps: - Specification of pH-Related Data: At the outset, the system determines a corrosion rate only if the operating environment is acidic or has

aeration. If the specified environment has no acid gases or there is sufficient buffering to produce a pH higher than 7.0, the system will predict zero or very low corrosion rates, except under conditions of aeration. So, the first step in consulting the system involves the specification of the acid gas (H2S and CO2) partial pressures as well as the bicarbonate content of the environment. - Temperature/Gas-Water Ratios: Temperature has a significant impact on corrosion rates as described in the previous section. Corrosion rates typically increase with increasing temperature. If the gas-to-oil ratio indicates gas-dominated conditions (as opposed to an oil-dominated system), the system uses the water-to-gas ratio and the dew point as the means to determine the availability of an aqueous medium to measure corrosion. So, depending on the value entered for the gas-to-oil ratio, the system will let the user specify the relevant water-related parameters. If the gas-to-oil ratio is < 5000 scribble (which denotes an oil well), the system uses the water cut and oil persistency to determine the wetness effect.

- Chlorides/Sulfur: Chloride and sulfur typically make corrosion worse if the process has been initiated by the presence of acid gases. Their role, while not as critical as that ofH2S or CO2, is significant because these parameters can significantly increase corrosion rates in mildly corrosive systems. - Velocity/type of Flow: Flow parameters are very critical in both determining and controlling corrosion effects. Erosion corrosion as well as the protection (or the lack of it) from corrosion films is very much a function of fluid velocity. - Inhibition/Corrosion Allowance: Inhibition choices in the system allow the user to select applicable methods of inhibition for vertical or horizontal flow and determine the extent of corrosion mitigation. In some cases, the system might provide no protection due to inhibition because of high velocities or chloride concentrations. The system's rules assess the appropriateness of the method of inhibition delivery for a given set of conditions. FUTURE WORK Predicting the corrosivity of production environments is a complex and challenging task from several standpoints. While the system described in this paper captures the effects and interaction of several critical parameters, significant opportunity exists for enhancing the system's analytical and modeling capabilities. Further work in refining the predictive model described herein is governed by the following factors: Many of the fundamental mechanisms driving corrosion are well understood; however, there is still a large body of ongoing research grappling with providing accurate phenomenological models. Formation of sulfide films and their stability as a function of temperature and pH are areas that require quantification and better modeling. A large number of parameters influence the corrosion process, and a complex set of parameter interactions exacerbate or mitigate corrosion. New data generated in the laboratory or field is critical to refining the existing model. The current work does not include mass transfer and momentum transfer effects on surface corrosion. However, further work is aimed at including

flow models that capture the effects of inertial and viscous forces in single phase and multi-phase flows. Wall shear stress developed as a function of prevalent flow regimes has a direct influence on corrosion rate and is the focus of considerable research in both industry and academia [32,40]. The metallurgy of steels used -m CO:z/H2S production environments is critical to determining environmental corrosivity.Metallurgical factors include microstructure, material processing (e.g., annealed, quenched and tempered, normalized etc.) and other morphology-related factors like hardness of welds and residual stresses. The addition of residual and alloying elements (e.g., Cr, Cu, Ni, etc.) has been shown to have a significant impact on corrosion performance [41,42]. While there is some data available for understanding the effects of metallurgy on corrosivity in CO2 environments, very little information is available on metallurgical effects versus corrosivity in H2S environments, and this represents an area of active research. The authors have currently initiated a research program on testing to quantify metallurgical effects as they relate to corrosion in typical production environments [43]. CONCLUSIONS Predicting the corroslV1ty of CO:z/H2S production environments is a complex and challenging task requiring a clear understanding of the role of several critical parameters from theoretical and practical standpoints. While theoretical models are valuable from a perspective of mechanistic comprehension, it is necessary to integrate different kinds of data knowledge and experience-based expertise to provide a realistic basis for corrosion prediction. A hierarchical predictive model has been developed to integrate the effects and interactions of several critical parameters enrooted to determining system corrosivity. The model has been implemented as a Widows-based computer program and incorporates a framework that facilitates further refinement. The authors would like to recognize and thank the contributions of researchers and pioneers in corrosion modeling, whose efforts, available in the public domain, provided the firmament on which the model presented in this paper has been built. The authors also acknowledge the contributions of numerous workers within the authors' organization whose untiring efforts have contributed significantly to the development of the corrosivity model.

REFERENCES - C.S. Fang et al., Computer model of a gas condensate well containing carbon dioxide, Corrosion/89, Paper No. 465, New Orleans, Louisiana, USA, 1989. - C. de Waard and U. Lotz, Prediction of CO2 corrosion of carbon steel, Corrosion/93, Paper No. 69, New Orleans, Louisiana, USA, 1993. - C. de Waard and D.E. Milliams, Carbonic acid corrosion of steel, Corrosion 31,5, 1975, p.I77. - E. Dayalan et al., Modeling CO2 corrosion of carbon steels in pipe flow, Corrosion/95, Paper No. 118, Orlando, Florida, USA, 1995. - lD. Garber et al., Down hole parameters to predict mist flow and tubing life in gas condensate wells, Corrosion/94, Paper No. 25, Baltimore, Maryland, USA, 1994. - RD. Kane and S. Srinivasan, Proceedings of CLI Workshop on Oil and Gas Corrosivity, Abu Dhabi United Arab Emirates, April 1995. - L.H. Gatzky and RH. Hausler, A novel correlation of tubing corrosion rates and gas production rates, Advances in CO2 Corrosion, Vol. 1, NACE, 1984, p. 87. - lL Crolet and M Bonis, A tentative method for predicting the corrosivity of wells in new CO2 fields, Advances in CO2 Corrosion, Vol. 2, NACE, 1985, p. 23. - A Ikeda et al., Influence of environmental factors on corrosion in CO2 wells, Advances in CO2 Corrosion, Vol. 2, NACE 1985, pp. 1-22. - C.D. Adams et al., Methods of prediction of tubing life for gas condensate wells containing CO2, 23rd OTC, Houston, Texas, USA, 1991. - K. Videm and l Kvarekval, Corrosion of carbon steel in C02 saturated aqueous solutions containing small amounts ofH2S, Corrosion/94, Paper No. 12, 1994. - U. Lotz. et al., The effect of oil or gas condensate on carbonic acid corrosion, Corrosion/90, Paper No. 41,1990. - H. l Choi et al., Corrosion rate measurements of L-80 grade down hole tubular in flowing brines, Corrosion/88, Paper No. 213, St. Louis, MissoUSA, 1988. - KD. Efird, Predicting corrosion of steel in crude oil production, Materials Performance 30, 3, March 1991, pp. 63-66. - A Dugstad and L. Lunde, Parametric study of CO2 corrosion of carbon steel, Corrosion/94, Paper No. 14, 1994.

- U. Lotz, Velocity effects in flow-induced corrosion, Corrosion/90, Paper No. 27, Houston, Texas, USA, 1990. - Y. Gunatlun, Carbon dioxide corrosion in oil wells, Paper SPE 21330, SPE Middle East Oil Show, Bahrain, 1991. - M.R. Bonis and IL. Crolet, Basics of prediction of risks of CO2 corrosion in oil and gas wells, Corrosion/89, Paper No. 466, New Orleans, Louisiana, USA, 1989. - RH. Hausler and D.W. Stegmann, CO2 corrosion and its prevention by chemical inhibition in oil and gas production, Corrosion/88, Paper No. 363, S10 Louis, Missouri, USA, 1988. - RD. Kane and S. Srinivasan, Reliability assessment of Wet H2S refinery and pipeline equipments: A knowledge-based systems approach, Serviceability of Petroleum, Process and Power Equipment, D. Bagnoli, M. Prager and D.M. ScWader (Eds.), PVP Vol. 239, ASME, New York, 1992. - S. Srinivasan and RD. Kane, Expert systems for selection of materials in sour service, Proceedings of the 72nd Annual GPA Convention, GPA, 1993, pp. 88-92. - G.S. Linda et al., Effect of pH and temperature on the mechanism of carbon steel corrosion by aqueous carbon dioxide, Corrosion/90, Paper No. 40, Las Vegas, Nevada, USA, 1990. - M. Bonis and IL. Crolet, Practical aspects of the influence of in-situ pH on H2S induced cracking, Corrosion Science 27, 10/11, 1987, pp. 10591070. - RD. Kane et al., Internal reports on multi-client program on safe use limits for steels, CLI International, Inc., Houston, Texas, 1992-1994. - S. Srinivasan and RD. Kane, Methodologies for reliability assessment of sour gas pipelines, Proceedings of the Fifth International Conference on Pipeline Reliability, Gulf Publishing Co., Houston, Texas, USA, 1995. - S.N. Smith and E.I Wright, Prediction of minimum H2S levels required for slightly sour corrosion, Corrosion/94, Paper No. 11, Baltimore, Marland, 1994. - RD. Kane, Roles ofH2S in behavior of engineering alloys, International Metal Reviews 30,6, 1985, pp. 291-302. - M.II Simon Thomas and Ie. Loyless, CO2 corrosion in gas lifted oil production: - Correlations of predictions and field experience, Corrosion/93, Paper No. 79, 1993.

- T. Murata et al., Evaluation of H2S containing environments from the view point of OCTG and line pipe for sour gas applications, Paper No. OTC 3507, 11th Annual OTC, Houston, Texas, USA, 1979. - B. Lefebvre et al., Behavior of carbon steel and chromium steels in CO2 environments, Advances in CO2 Corrosion, Vol. 2, NACE 1985, pp. 5571. - L.K Sood et al., Design of surface facilities for Khuff gas, SPE Production Engineering, July 1986, pp. 303-309. - K D.Efird et aI., Experimental correlation of steel corrosion in pipe flow with jet impingement and rotating cylinder laboratory tests, Corrosion/93, Paper No. 81, New Orleans, Louisiana, USA, 1993. - J.S. Smart Ill, A review of erosion corrosion in oil and gas production, Corrosion/90, Paper No. 10, 1990. - API 14-E, Recommended practice for design and installation of offshore production platform piping system, ill Edition, API, Dallas, 1981. - NACE Material RecommendationMR-01-75-94, NACE International, 1994. - K.D. Efird, Petroleum testing. in: Corrosion Tests and Standards: Application and Interpretation, R. Baboian (Eds.), ASTM, 1995, pp. 350358. - John S. Smart ill, Wet ability: A major factor in oil and gas system corrosion, Corrosion/93, Paper No. 70, New Orleans, Louisiana, 1993. - S. Olsen, Corrosion under dewing conditions, Corrosion/91, Paper No. 472, Cincinnati DOhio, USA, 1991. - J. Old-field and B. Todd, Corrosion considerations in selecting metals for flash chambers, Desalination 31, 1979, pp. 365-383. - E. Dayalan et al., Influences of flow parameters on CO2 corrosion behavior of carbon steels, Corrosion/93, Paper No. 72, New Orleans, Louisiana, USA, 1993. - Dugstad et al., Influence of alloying elements upon the CO2 corrosion rate of low alloy carbon steels, Corrosion/91, Paper No. 473, Cincinnati, Ohio, USA, 1991. - M. Kimura et al., Effects of alloying elements on corrosion resistance of high strength line pipe steel in wet CO2 environment, Corrosion/94, Paper No. 18, 1994 - R.D. Kane et al., Prediction and assessment of corrosivity for use of steels in multi-phase CO2/H2S environments, Multi-Client Proposal, CLI International, Inc., Oct. 1995.

Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

TESTING OF DRILLING FLUIDS FORMULATED FROM TABUK FORMATION CLAYS M.N.J. Al-Awad1, A.S. Dahab2 and M.E. El-Dahshan3
1

Petroleum Engineering Department, College of Engineering, King Saud University P.O. Box 800, Riyadh 11421, Saudi Arabia
2

Petroleum Engineering Department, College of Engineering, Cairo University, Giza, Egypt

Chemical Engineering Department, College of Engineering, King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia

ABSTRACT
There are huge drilling operations in most areas of the Kingdom of Saudi Arabia nowadays searching for potential hydrocarbon reservoirs. The increasing expense of importing drilling fluid components for oil and gas wells, drilling, especially clays, necessitates the testing of some local clays which are less expensive and are abundantly available. Therefore, representative Tabuk formation clay samples from the northern and central provinces of Saudi Arabia have been studied. The clays were mineralogically investigated using x-ray diffraction and scanning electron microscopy. The physicochemical properties of clay suspensions with and without common drilling fluid additives were measured. These properties include rheology, filtration loss, density and pH. The thermal stability of clay minerals and suspensions was studied. Since sample 2 of the Tabuk clay produced better results, its thermal stability was further studied by autoclaving its suspensions at temperatures between 25 and 121oC after the addition of high-viscosity carboxy methyl cellulose (HV-CMC) and XC-polymer. A concentration of 10% by weight of sample 2 of the Tabuk formation clay plus 1% NaOH and 0.5 XCpolymer produced the best rheological, filtration and thermal stability. Corrosion in drilling operations is strongly related to the composition of drilling fluids. A concentration of 10% by weight of sample 2 of the Tabuk formation clay plus 0.5% NaOH and 0.5 XC-polymer developed minimum corrosion rates as revealed by corrosivity tests (static and dynamic) and surface morphology investigations Key Words: Corrosivity, drilling fluids, thermal stability, rheology, Tabuk formation, clays

INTRODUCTION Clays in Saudi Arabia are represented by numerous commercial stocks [1-2]. The mineralogical, chemical and mechanical analysis of these clays led to their use in different industrial applications. The use of these national clays in the drilling of oil, gas or water wells in the Kingdom as well in other Arabian Gulf countries will save millions of dollars that otherwise would be spent on purchasing these materials. In the Khurays and Qasim regions, many kinds of clays are found and can be studied [3]. Other unexplored areas for commercial utilization of clay and shale are abundant in the northern region of the Kingdom, especially in

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the Tabuk formation. The clay deposits of AsSarat in the southern region of the Kingdom represent another possible source of clay minerals [4]. The geological studies of the Ummer Radhuma and Dammam formations have indicated the presence of numerous types of clay minerals, especially palygorskite, in these formations [5,6,7]. In Saudi Arabia, the utilization of clays, especially in the drilling of oil and water wells, has been very limited. The intense exploration for oil and water in the Kingdom as well as other Gulf countries, necessitates the use of local raw materials in this important industry [8]. EXPERIMENTAL PROCEDURE This study specifically aims to achieve the following objectives:

Geological sampling of good clay occurrence in the northern province of Saudi


Arabia, (Characterization of clay and non-clay minerals by mineralogical and mechanical analysis of clay samples, and Testing of the application of Tabuk formation clays in drilling fluids by: a) Measuring the rheological behavior of clay suspensions, and correlating the mineralogical analysis and rheological properties, b) Studying the stability of formulated drilling fluids at high temperatures and in chemically complex environments, c) Activating those clays shown to be of lower filtration, yield or rheological properties, and d) Study of the corrosivity of the formulated drilling fluids. Figure 1 represents a flow diagram of tests and analysis conducted in this study. METHODS OF CHARACTERIZATION Oriented clay films were prepared on glass slides after having been dried at 40-50oC in an oven. The slides then were analyzed with a Philips x-ray diffractometer with a graphite monochromator and a Cu-target x-ray tube operated at 35 kV and 15 mA. The precise determination of the shape of the clay particles was made by the electron microscope. The samples were mounted on stubs to be coated with gold for 3 minutes at 15 on an EMSCOPE SC-500 sputter coater, and then examined with a JEOL-35 FC scanning electron microscope. All rheological properties, both at room and high temperatures, were investigated using the standard devices offered by courtesy of Baroid Petroleum Services. The corrosivity of the formulated drilling fluids was investigated using various laboratory test equipment including a dynamic flow loop (Fig. 2), a static test reservoir, a pH meter and a low power microscope with a camera.

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Figure 1. Schematic diagram of tests and analysis

Figure 2. Schematic diagram of the closed dynamic loop RESULTS AND DISCUSSION Characterization The importance of the granulometric analysis goes back to the fact that the clays which contain more than very small amounts of non-clay minerals, especially in the size of sand and silt, will not be suitable for drilling fluid applications. Sand can import undesirable properties to drilling fluids and have an erosive action on pumps and drill strings. The granulometric analysis of Tabuk formation clays showed that more than 95% of the samples had fineness fractions of < 37 mm as shown in Table 1. The good rheology of the suspensions prepared from Tabuk formation clays is caused in part by the fineness of the Tabuk formation clays. The results obtained from x-ray diffractograms (Fig. 3) showed that the samples consisted exclusively of illite and kaolinite, interpreted by the presence of the principal peaks characterizing both clays. The non-clay minerals characterized by the diffractograms were mainly quartz. For further investigation, the samples were examined by the scanning electron microscope to study the texture of the clay minerals present. The electron micrographs of the Tabuk formation clays indicated the presence of disordered illite between kaolinite particles, as shown in Fig. 4. Dehydration curves of the Tabuk formation clays are shown in Fig. 5. These clays lost their absorbed water at 100oC, whereas the interlayer water was lost between 100 and 400oC. The hydroxyle water was lost in the range of 400-600oC. It was very difficult to distinguish the clay minerals from such curves because mixtures of different minerals occur in the samples. Table 1. Granulometric Analysis of Tabuk Formation Clays

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Sieve Size (mm) 500 300 150 100 63 40 Fines

Weight (%) Sample 1 0 0.2 0.3 0.3 1.6 2.6 95

Weight (%) Sample 2 0 0 0 0 0.3 0.5 99.2

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Figure 3. X-ray diffractogram of Tabuk formation clays, raw samples 1 and 2, at 25oC

(a) Sample 1

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(b) Sample 2 Figure 4. Scanning electron micrographs of Tabuk formation clays

Figure 5. Dehydration curves of Tabuk formation clays Rheology The rheological properties of drilling fluids play a very important role in determining the overall success of drilling operations. In order to obtain properly functioning drilling fluids, the rheological properties should be carefully investigated. Thus, the ability to use material in a drilling fluid depends on the materials flow, filtration and electrochemical characteristics. The testing of other properties can be achieved in many ways, the most important of which is the measurement of rheological behavior. In the case of mineral suspensions,this type of measurement is influenced among other things by the temperature, weight percent of solids, quantity and sign of superficial charges, clay mineralogy, and type of mixing water [9,10]. It is practically impossible to study individually the effect of each of the previous parameters on the rheological behavior of clay suspensions. However, the establishment of rheograms and viscosity measurements can indicate modifications in suspensions behavior. Figures 6 and 7 give typical examples of shear stress-shear rate relationships obtained when formulating Tabuk formation clays in freshwater. These figures indicate the presence of relations which accurately describe the flow characteristics of a drilling fluid over the shear rate ranges normally encountered in the wellbore. The suspensions possessed a pesudo-plastic behavior
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even with concentrations of clay solids below 10%. Table 2 gives the typical relationships of plastic and the apparent viscosities, yield point and density of Tabuk formation clays suspensions in freshwater. Such rheological behavior is typical for clay-water systems formed using illite and kaolinite clays. The filtration loss was too high for it to be used as a drilling fluid without using fluid loss control additives. In order to obtain a drilling fluid exhibiting minimum corrosion rates, NaOH was added, and concentrations of 0.5 to 1.0% by weight, were found adequate to develop the desired properties. 0.5 percent XC-Polymer by weight was added to improve the fluid rheology and filtration loss. Figure 8 shows the reheograms of the drilling fluids prepared from 10% by weight Tabuk formation clay (sample 2) plus 1.0% NaOH with the addition of various additives; the filtration behavior of the best additives are shown in Fig. 9. Figure 10 shows a comparison between the drilling fluid formulated from Tabuk formation clay suspension (10% Tabuk formation clay sample 2, 0.5% XC-polymer, and 1% NaOH) with common drilling clays.

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Figure 6. Shear stress-shear rate relationships for Tabuk formation clay (sample 1) suspension using freshwater

Figure 7.

Shear stress-shear rate relationships for Tabuk formation clay (sample 2) suspension using freshwater

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Figure 8. Shear stress-shear rate relationships for 15% Tabuk clay (sample 2) suspension with various additives

Figure 9. API and HT-HP filteration loss of 10% by weight of Tabuk formation clay (sample 2) suspension in freshwater

Figure 10. Natural and conditioned (10% Tabuk clay + 0.5% XC-polymer + 1% NaOH) clay
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suspensions formulated from Tabuk formation clay (sample 2) compared to common clays Table 2. Rheological Properties of Tabuk Formation Clays Clay weight (%) Density (ppg) Sample Sample 1 2 8.9 8.9 9.3 9.1 9.7 9.4 Yield Point (lb/100 ft2) Sample Sample 1 2 4.5 3.0 5.0 4.0 7.5 6.3 Apparent Viscosity (cp) Sample Sample 1 2 2.94 2.94 3.74 3.74 5.27 5.27 Plastic Viscosity (cp) Sample Sample 1 2 1.1 1.1 2.14 2.14 2.15 2.15

10 15 20

Corrosivity Corrosion is noted for its destructive effect on materials, and its consequences on the economy. Corrosion has been a problem in the petroleum industry throughout its history. Drilling fluid components play major roles in corrosion processes. To understand the influence of drilling fluids on the rate of corrosion, certain factors should be studied, such as their physical and chemical properties. Corrosion within a drilling well was simulated by immersing test specimens in the drilling fluid at a fixed exposure time and temperature in both static and dynamic conditions. The loss in weight of the test specimen served to measure the rate of corrosion. Drilling fluids formulated from Tabuk formation clays (sample 2) were investigated for their corrosivity on three different types of casing alloys, namely: mild steel, J-55 casing grade and K-55 casing grade. 10% by weight suspension of Tabuk formation clay (sample 2) was chosen to study the corrosivity of Tabuk formation clays with and without the addition of NaOH. Coupons made from the chosen alloys were made and appropriately placed inside either the static cell or the dynamic loop, depending on the type of test to be performed. Then the formulated drilling fluid was added to the test apparatus. Both tests were run for two week periods at 58oC. After termination of the test, the samples were cleaned with inert fluid, and their weights were recorded and their surfaces were carefully examined using a low-power microscope. The following formula was used to calculate the corrosion rate [11].
WL mpy = 22273 DAT

(1)

where mpy W D A T = penetration rate in mm-inch/year, = weight loss in grams, = density in gm/cm3, = area in contact with the test fluid in in2, and = exposure time in hours.

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where mpy is the penetration (corrosion) rate in mm/year. As shown in Table 3, mild steel had corrosion rates under dynamic conditions that were two-fold greater than in static conditions. This can be attributed to the effect of shear forces on the surface of the metal caused by the

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Figure 11. Surface morphology of steel coupons tested under static conditions for 2 weeks using a drilling fluid formulated from 10% Tabuk formation clay (sample 2) + 0.5% XC-polymer with and without the addition of NaOH
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Figure 12. Surface morphology of steel coupons tested under dynamic conditions for 2 weeks using a drilling fluid formulated from 10% Tabuk formation clay (sample 2) + 0.5% XC-polymer with and without the addition of NaOH
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flow of the test fluid. Mild steel was found to have the lowest resistance to corrosion by activated Tabuk formation clays, while K-55 had the highest resistance to corrosion under the same test conditions. In the static tests, all three samples corroded at the same rate. The corrosion rates were significantly reduced when NaOH was added to the test fluids. This was due to the ability of NaOH to change the test fluids environment from being acidic (pH = 5) to being alkaline (pH = 11), as shown in Table 3. The surface morphology of the tested steels before and after the addition of NaOH for both static and dynamic tests is shown in Figs. 11 and 12. It is clear from the figures that the metal surfaces were more severely corroded before the addition of NaOH. Table 3. Corrosion Tests Results of Tabuk Formation Clays Test Coupon Static Test (mpy) Dynamic Test (mpy)

A B C D Mild Steel 0.26 0.10 1.7 0.255 K-55 0.25 0.10 1.0 0.212 J-55 0.23 0.10 0.8 0.189 A: Static test (10% sample 2 without additives, pH = 5) B: Static test (10% sample 2 + 0.5% XC-polymer + 0.5% NaOH, pH = 11) C: Dynamic test (10% sample 2 without additives, pH = 5) D: Dynamic (10% Sample 2 + 0.5% XC-polymer + 0.5% NaOH, pH = 11) CONCLUSIONS 1. The tested clays made from Tabuk formation clays contain more than 95% fines by weight (< 40 mm). They are exclusively composed of the clay minerals illite and kaolinite together with small amounts of interstratified minerals and quartz. 2. The rheological properties of the Tabuk formation clay suspensions indicate that they lie in the range of typical native clays. After the addition of common drilling fluid additives, the suspensions had more or less the same flow behavior as commercial clays. Therefore, it is recommended that this clay be used in formulating low-weight drilling fluids. 3. The formulated drilling fluids made from Tabuk formation clay (sample 2) are thermally stable up to the tested temperatures of 25-121oC. 4. Corrosion tests on the drilling fluids formulated from Tabuk formation clays (sample 2) indicated that the fluids possessed minimal corrosivity. 5. The application of Tabuk formation clays in oil well drilling is recommended especially after performing economical feasibility studies. REFERENCES 1. A.S. Dahab, Evaluation of some Saudi shales for use in drilling fluids, First Conference on Indigenous Raw Materials and Their Industrial Utilization in the Gulf Region, Kuwait, November 1-4, 1986. 2. M.M. Aba-Husayn and A.H. Sayegh, Mineralogy of Al-Hasa desert soils, Saudi Arabia,
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Clay and Clay Minerals, 1977, pp. 138-147. 3. A.S. Mashhady, M. Reda, M.J. Wilson and R.C. MacKenzie, Clay and silt mineralogy of Saudi soils from Qasim, Saudi Arabia, International Soil Soc. 31, 1980, pp. 101-115. 4. W.C. Overstreet, D.B. Stoeser, E.F. Overstreet and G.H. Goundarzi, Tertiary Laterite of the As Sarat Mountain, Asir Province, Saudi Arabia., Bulletin No. 21, DGMR, Geddah, 1977, p. 30. 5. N. Guven and L.L. Carney, The hydrothermal transformation of Sepiolite to stevensite and the effect of added chlorides and hydroxides, Clay and Clay Minerals 27, 1979, pp. 253-260. 6. S.S. Sayari and J.G. Zotl, Quaternary Period in Saudi Arabia, Vo.1, Springervertag, New York, 1978. 7. S.Y. Lee, J.B. Dixon and M.M. Aba Husayen, Mineralogy of Saudi Arabia Soil, Eastern Region, Soil. Society of America Journal 47, 1983, pp. 321-326. 8. M.N.J. Al-Awad, Rheology, thermal Stability and Corrosivity of Saudi Clays from the Central province, M.Sc. thesis, Department of Petroleum Engineering, College of Engineering, King Saud University, Riyadh, Saudi Arabia, 1990. 9. A.S. Dahab, Y. Champetier and J.F. Delon, Quelques Argiles Egyptiennes dans Le Domaine des Boues de Forage Petrolieurs, Min. Ind. J., France, April 1985, pp. 183-187. 10. M.G. Fontana and D.G. Norbert, Corrosion Engineering, Updated Textbook Edition, McGraw Hill, 1978.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

PREVENTING SULFATE SCALE DEPOSITION IN OIL PRODUCTION FACILITIES C.J. Hinrichsen1, M.J. McKinzie2 S. He3, J. Oddo4, A.J. Gerbino5, A.T. Kan3 and M.B. Tomson3 Texaco E&P Technology Department P.O. Box 770070, Houston, TX 77215-0070, USA Texaco E & P P.O. Box 8992, Corpus Christi, TX 78468, USA
3 2 1

Rice University, Department of Environmental Science and Engineering P.O. Box 1892, Houston, TX 77251, USA Water Research Institute, Inc. P.O. Box 980636, Houston, TX 77098, USA OLI Systems, Inc. American Enterprise Park 108 American Rd., Morris Plains, NJ 07950, USA
5 4

ABSTRACT
Scale deposits are a concern for oil producers not only throughout the United States and United Kingdom (North Sea) but also within parts of the Middle East, primarily in Egypt and the Arabian Gulf region. In addition to plugging perforations and reducing production volumes, certain types of sulfate scale deposits are becoming an environmental issue. Considering the varied problems often associated with the chemical and mechanical removal and disposal of sulfate scale deposits, the best, most cost-effective method for dealing with sulfate scale is simply to try to find a way to prevent the scale deposits from occurring in the first place. In order to achieve this goal, an effective sulfate scale inhibition program must be developed. As part of its efforts in this area, Texaco has actively participated in a research consortium which is developing new technology specifically aimed at preventing the deposition of barium sulfate scales in oil field production facilities. Barium sulfate is a particularly troublesome form of scale due, in part, to its extreme insolubility. Removing barium sulfate with chemical scale dissolvers is often a very difficult process. This paper will present the results of a recent case history in which Texaco is currently applying scale control technology with notable success. Specifically, the process of screening and selecting a scale inhibitor suited to the temperature, mineralogy, and brine chemistry of the producing formation will be described. The design and implementation of the scale squeeze treatment will then be discussed. This technology can also be applied in preventing other sulfate-type scales and for inhibiting calcium carbonate scale as well. Key Words: Scale inhibition, barium sulfate, scale inhibitors, squeeze treatment, scaling tendency, scale prediction, laboratory testing, NORM

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INTRODUCTION The A.E. Guerra No. 43 well, located in South Texas, produces 8.5 MMSCFPD, 50 BOPD, and 120 BWPD. The reservoir is relatively deep (approximately 14,000 ft). The bottom hole temperature is typically about 340F, and the reservoir pressure is approximately 6997 psi. The reservoir formation is composed of calcite (20 - 40%), quartz (25 - 30%), feldspar (20%), and clay minerals (10 - 35%). Among the clay minerals, illite is typically 80% and chlorite is around 20%. The porosity is about 18%. The permeability varies from 0.01 to 0.05 mDarcy, and it is a fracture-stimulated reservoir. The content of carbon dioxide in the gas phase is about 0.5%. Two months after production commenced, scale buildup was discovered when a tubing caliper survey was run. Shortly thereafter, gas production dropped from 10 MMSCFPD to 5 MMSCFPD. Two types of water-formed scale deposits, barium sulfate and calcium carbonate, were encountered in the production system (mainly in the downhole tubing). Hard deposits of barium sulfate scale pose a severe operational problem to production operations since they cannot be easily removed once deposited and have occasionally been associated with naturally occurring radioactive materials (NORM) [1]. In this case, fortunately, the barium sulfate scale was not contaminated with NORM. Before the squeeze treatment, discussed in this paper, barium sulfate and calcium carbonate scales had to be periodically removed by chipping or broaching with wire-line tools. This operation is expensive, time-consuming, and risky considering the possibility of losing the tools in the well. The annual cost for the frequent mechanical removal of the scale deposits was estimated to have been US $87,000. Under the sponsorship of the Gas Research Institute (GRI), the Brine Chemistry Consortium at Rice University and Water Research Institute conducted an integrated study of the scaling condition in the subject well and designed a treatment plan to control barium sulfate scaling. This paper summarizes the laboratory design and field implementation of a scale inhibitor squeeze treatment. First, a brine analysis and scaling tendency are described. Next, laboratory tests of scale inhibitors are presented. Finally, the field squeeze treatment is detailed and the results are shown. BRINE CHEMISTRY AND SCALING TENDENCY Brine samples were taken at the wellhead and analyzed in the laboratory. The chemical composition of the brine and other information concerning the well are listed in Table 1. The chemical analysis was performed at room temperature and pressure. The concentration of each cation was analyzed using inductively coupled plasma spectrometry.The chloride concentration and bicarbonate alkalinity were determined by titration. The concentration of sulfate was determined by a turbidimetric method and found to be very small (< 5 mg/1). The scaling tendency of the brine, expressed as a saturation index (SI), was calculated under various production conditions using the EQPITZER program [2]. EQPITZER is a computer program for calculating the SI of brines with respect to common water-formed scale deposits such as calcite, gypsum, anhydrite, celestite, and barite. The SI for a sparingly soluble salt, M+A-, is defined as the logarithm of the ratio of the ionic activity product divided by the thermodynamic solubility product: SI = log[(aM+ aA-)/Ksp] (1)
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An SI > 0 indicates a supersaturated solution and, hence, a probability for scale deposition. No scale is anticipated, however, when the calculated SI < 0 (i.e., the brine is undersaturated). Table 1. Chemical Composition of the A.E. Guerra Brine Species Na Mg2+ Ca 2+ Sr2+ Ba2+ Fe (total) ClSO42Alkalinity (HCO3-) Ionic Strength (M) pH (meas.) at surface CO2(g) in the gas phase
+

Concentration (mg/1) 19871.8 54.0 6500.0 700.0 550.0 12.0 43000.0 <5.0 281.0

(mmol/l) 864.4 2.2 162.2 8.0 4.0 0.2 1228.6 <0.052 4.6 1.42 7.10 0.5%

The calculated saturation indices are presented in Table 2. It can be concluded that a serious calcium carbonate scaling potential will develop (the SI is greater than 1.0) as the reservoir pressure drops. This is verified by the occurrence of calcium carbonate scale in the tubing near the perforations where there is a significant pressure reduction. Table 2. Calculated Saturation Index (SI) for the A.E. Guerra Brine with Respect to Common Water-Formed Scale Deposits Parameters Temperature (F) Pressure (psi) pH (calc) SI (calcite) SI (barite) SI (celestite) SI (anhydrite) Downhole 236 6997 5.34 -0.27 -0.23 -1.60 -2.05 Wellhead 236 397 6.71 1.21 0.01 -1.37 -1.75 Surface 236 14.7 7.94 2.24 0.03 -1.35 -1.72 77 14.7 7.91 1.94 1.17 -1.70 -2.70

In the case of barium sulfate, however, a decrease in pressure to atmospheric conditions is expected to only shift the SI up to 0.03 (near equilibrium). In fact, barium sulfate scale was noted within downhole sections of the tubing string despite the fact that the calculated SI suggested near equilibrium (SI = 0.01) conditions would prevail either downhole or at the wellhead. The calculated SI for barium sulfate predicts that a potential for barite scale will
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only occur when the temperature is reduced to 77F (SI = 1.17). The discrepancy between the calculated SI and field observations could be due to the fact that the original brine analysis may have incorrectly reflected the true downhole concentrations of barium and sulfate. INHIBITOR EVALUATION AND SQUEEZE SIMULATION In view of the declining gas production rate and the potential for further scale deposition, it was decided to treat the subject gas well by a scale squeeze treatment. Given the US $4 MM cost to drill and complete the well and the additional US $1.5 MM cost for the fracture operation, a carefully planned series of laboratory tests was conducted to ensure not only that the scale squeeze treatment would be effective but also that the chemical treatment would not contribute to any formation damage. Several commercially available scale inhibitors were tested in the laboratory for their efficiency at preventing barium sulfate scale deposition. Both static and dynamic tests were conducted. The static testing of inhibitor efficiency was based on the measurement of the nucleation induction period for barium sulfate in the presence of inhibitors [3], specifically, the relative prolongation of the nucleation induction period in the presence of various scale inhibitors, each at the same concentration. The static test results were then used to rank the scale inhibitors according to their efficiency in delaying the nucleation process. The dynamic testing of scale-inhibitor effectiveness was performed in the laboratory using a high-temperature and high-pressure flow-through apparatus which is designed to simulate a production system [4]. The dynamic test results are useful in ranking the scale inhibitors based upon the minimum effective dose for each inhibitor (The minimum effective dose is the minimum concentration required to prevent any scale deposition). Several common commercial scale inhibitors were tested. These inhibitors include 1hydroxyethylidene-1,1-diphosphonic acid (HEDP), nitrilotrimethylene phosphonic acid (NTMP), hexamethylene diamine tetramethylene phosphonic acid (HDTMP), diethylene triamine pentamethylene phosphonic acid (DTPMP), bis-hexamethylene triamine tetramethylene phosphonic acid (BHTMP), polyacrylates (PAA, molecular weight from 1000 to 7000), phosphinopolycarboxylates (PPPC, molecular weight from 1900 to 3800), and sulfonated polyacrylic acid (SPA, molecular weight of 3500). Based on the static and dynamic test data, BHTMP was found to be effective and superior to other scale inhibitors, and was recommended for squeeze-treatment use. Once the scale inhibitor testing was complete, a simulation of the squeeze process was conducted in the laboratory in order to obtain information concerning the retention and release of the BHTMP inhibitor onto and off of the A.E. Guerra core material. First, the BHTMP inhibitor solution was pumped into a column packed with synthetic materials having a mineralogical composition similar to the formation rock. The column was then shut in for two days. Next, the column was turned around and a synthetic brine was pumped through the packed column from the opposite direction. These two steps are designed to simulate the inhibitor injection and subsequent return flow. The concentration of BHTMP in the return flow was continuously monitored for over 60 pore volumes. The flow rate was 10 ml/min. The inhibitor return data is presented in Fig. 1.
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a
100000 0.5% 10000 5%

BHTMP (Acid Active, mg/l)


1000

100

10

1 0 20 40 60 80 100

Pore Volumes

The return concentration of the inhibitor b


30

20

Inhibitor Return (%)

10 0.5 % 5% 0 0 20 40 60 80 100

Pore Volumes

The inhibitor return percentage Figure 1. The squeeze simulation result of BHTMP in synthetic core materials. The open circles represents data from squeezing 0.5% inhibitor acid, while the solid diamonds represent data from squeezing 5.0% inhibitor acid

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Two sets of simulations were performed using two different injection concentrations (5% and 0.5% BHTMP). The inhibitor concentration remained over 1 mg/l for over 100 pore volumes (Fig. 1a) and the percentage of inhibitor returned was less than 30% (Fig. 1b). INHIBITOR SQUEEZE DESIGN Based on the information derived from both the laboratory evaluation of commercially available scale inhibitors and from the column simulation of an inhibitor squeeze under simulated field conditions, a scale inhibitor squeeze treatment was designed for the A.E. Guerra No. 43 gas well. The squeeze process included five phases, which are listed in Table 3. Table 3. Design of a Scale Inhibitor Squeeze Treatment Phase Volume Additive (bbl) Composition Concentration 1 (Preflush)* 25 HCl 0.5% 2 Pill 270 BHTMP (110 gals) 3537 mg/l 3 Overflush 250 Filtered field brine 4 Shut-in (48 hours) 5 Production Since an acid treatment had been used two days prior to the actual squeeze treatment, in order to remove any existing scale, no acid preflush was used for this squeeze. Normally, however, an acid preflush would be recommended. The preflush solution (i.e., 0.5% hydrochloric acid with a corrosion inhibitor) was used to clean the production tubing by removing calcium carbonate scale deposits. The squeeze pill consists of the scale inhibitor (i.e., bis-hexamethylene triamine tetramethylene phosphonic acid, BHTMP in acid form) dissolved in filtered produced water. An overflush was used to push the inhibitor pill farther into the reservoir formation. A shut-in period of two days was necessary to allow adsorption of the inhibitor onto the formation rock through a reaction of the inhibitor acid with the formation material. INHIBITOR SQUEEZE LIFETIME AND ECONOMIC IMPACT The inhibitor squeeze was performed on December 21, 1993. After the two-day shut-in, the well was returned to production. Long-term monitoring of the inhibitor return has been performed since the squeeze. The concentration of the inhibitor returned as a function of the cumulative volume of brine produced since the squeeze is presented in Fig. 2. The inhibitor concentration remained above 1 mg/l for the initial 20,000 bbl of brine produced (approximately 167 days) and maintained around 0.5 mg/l for over 50,000 bbl of brine produced (about 417 days) (Fig. 2a). After 18 months, the amount of inhibitor returned was less than 20% of the total amount of the inhibitor squeezed (Fig. 2b). Process

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a
1000

100

10

BHTMP (Acid Active, mg/l)


.1 0 10000 20000 30000 40000 50000

Cumulative Volume of Brine (bbl)

The concentration of BHTMP in produced brines. b


20

15

10

Inhibitor Return (%)


0 0 10000 20000 30000 40000 50000

Cumulative Volume of Brine (bbl)

The percentage of BHTMP in produced brines. Figure 2. The return of inhibitor BHTMP as a function of brine flow back in the A.E. Guerra well after the squeeze

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After the squeeze, the Guerra well produced gas and oil with few problems due to scale formation for about 18 months. During this period, the well was periodically tested for downhole scale. Recently, the gas production fell off due to a blockage caused by scale formation. Scale samples were recovered and found to be mostly barium sulfate. A new squeeze treatment is planned. Since a light deposit of calcium carbonate was found in the end of the production tubing, the next squeeze treatment will include a mixed inhibitor treatment for preventing both calcium carbonate and barium sulfate scale deposition. The cost savings for the chemical squeeze are estimated to be over US $80,000/year for this well alone. Furthermore, 24 days of added production per year has been realized by not having to shut in the well for scale removal. This has produced an additional US $150,000/year in cash flow. CONCLUSIONS The problem of barium sulfate scaling in downhole tubing in the subject gas well was eliminated by a scale inhibitor squeeze using BHTMP. The squeeze has lasted for 18 months. Cost savings are estimated to be more than US $80,000/year. The following conclusions can be drawn from this case study: 1. BHTMP is an efficient inhibitor of barium sulfate scaling, especially in high calcium brines. 2. Inhibitor squeeze treatment is an effective and economic method for controlling scale deposition in downhole conditions in an oil and gas production system. 3. In the inhibitor squeeze treatment, blends of inhibitors may be needed instead of a single inhibitor to control the formation of mixed mineral scales, such as barium sulfate and calcium carbonate. Such combinations are presently being tested. ACKNOWLEDGMENTS This work was supported, in part, by the Gas Research Institute and by a consortium of companies including Texaco, Inc.; Conoco, Inc.; Champion Technologies, Inc.; FMC Corporation; Product Additives Division; and Zapata, Inc. The authors would like to thank Texaco, Inc. for permission to publish this paper. The authors would also like to express their deep appreciation to Saudi Arabian Texaco for supporting this presentation at the Second Arabian Corrosion Conference. REFERENCES 1. J.E. Oddo and M.B. Tomson, Algorithms can predict; inhibitors can control NORM scale. Oil and Gas Journal, 1994, pp. 33-37. 2. S.L. He and J.W. Morse, Prediction of halite, gypsum and anhydrite solubility in natural brines under subsurface conditions, Computers and Geosciences 19, l, 1993, pp. 1-22. 3. S.L. He, J.E. Oddo and M.B. Tomson, The inhibition of gypsum and barite nucleation in NaCl brines at temperatures from 25 to 90C, Appl. Geochemistry 9, 1994, pp. 561567.

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4. J.E. Oddo and M.B. Tomson, Elevated temperature-pressure flow simulator, U.S. Patent No. 5,370,799.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CONCERNS OVER THE SELECTION OF BIOCIDES FOR OIL FIELDS AND POWER PLANTS: A LABORATORY CORROSION ASSESSMENT J. Alhajji and M. Valliappan Kuwait University P.O. Box 5969, Safat 13060, Kuwait

ABSTRACT
Control of microbially induced corrosion (MIC) involves the application of biocides that eliminate the deleterious microorganisms, resulting in a reduced corrosion rate of the material of interest. However, the electrochemical properties of such chemicals in promoting or inhibiting corrosion processes are not well understood. The present investigation is focused on the evaluation of biocides commonly used in the oil fields and power sectors, from an electrochemical point of view. This study examines the use of oxidizing and nonoxidizing biocides in sulfide contaminated saline solutions. Gluteraldehyde (1,5-pentanedial) was chosen as a nonoxidizing biocide and ammonium chloride, which is the principal chemical used in the in-situ generation of chloramine, as the oxidizing biocide. A chemical environment of sulfide in seawater in a deaerated state was set up to simulate the conditions occurring during biological processes. The biocides investigated were found to alter the corrosion tendencies of mild steel and pitting tendency of 316L stainless steel in this environment. Key Words: Mild steel, stainless steel, glutaraldehyde (1,5-pentanedial), ammonium chloride, sulfide, biocides, corrosion, microbially induced corrosion, MIC

INTRODUCTION Extensive available literature [1-4] relating to microbially induced corrosion (MIC) has indicated that MIC certainly remains as an incessant problem for the corrosion world. Moreover, MIC is regarded as an intolerable corrosion problem, and multi-disciplinary effort have been expended to undermine its detrimental effects and to understand the phenomenon and its mechanisms [5-9]. All the engineering materials in general use, notably carbon steel and stainless steels in oil fields and the power sectors are susceptible to some form of microbial corrosion which usually arises from the activities of a wide range of microorganisms and their usually oxidizing metabolic products. The biological influences can be divided into three general categories [10]: production of differential aeration or chemical concentration cells, production of organic and inorganic acids as metabolic by products, and production of sulfides under oxygen-free (i.e., anaerobic) conditions. Several studies have focused on MIC of carbon steels [3] and steel alloys containing 2-3% Mo [6-8]. Control of MIC usually involves the utilization of chemical biocides. These chemicals are sometimes misunderstood and misused in processes involving aqueous environments due to a lack of understanding of the nature of the problem. Very little effort [11] has been made to investigate the effects of biocides that are used in oil fields and
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power generation systems on the electrochemical behavior of metallic materials. Most of the research [12-13] has been concerned with the biocidal properties of the chemicals that are used to combat biologically induced corrosion problems and not the electrochemical properties of those chemicals. Biocides are categorized as either oxidizing or nonoxidizing toxicants. The selection and application of suitable biocide treatment depends on the broad spectrum activity, pH, economics, compatibility with the other chemicals used for treatment, and most importantly, suitability with the materials of construction from a corrosion point of view. Glutaraldehyde (1,5-pentanedial), a nonoxidizing biocide, is extensively used in oil fields. Chlorination is commonly employed in the treatment of freshwater systems. Chlorine is the most widely used industrial oxidizing biocide. Ammonium chloride, an oxidizing chemical, is commonly used in the in-situ generation of chloramine as an oxidizing biocide. The present investigation is focused on investigating the electrochemical nature of glutaraldehyde, as a nonoxidizing chemical, on the corrosion effects of mild steel and 316L stainless steel in deaerated synthetic seawater media containing sulfide to simulate the effects of biogenic sulfides generated by sulfate reducing bacteria (SRB) the most documented deleterious organism in MIC, under anaerobic conditions. Also, ammonium chloride, an oxidizing chemical, is investigated under similar conditions simulating biogenic sulfides generated by SRB. EXPERIMENTAL PROCEDURE Carbon steel (UNS G10200) and 316L stainless steel (UNS 316003) of exposed areas of 1 cm2 were used for this study. The working electrodes were polished with emery papers to a 600 grit finish. The polished specimens were successively rinsed with analar grade acetone and double distilled water, and then air dried. Experiments for corrosion measurements were conducted utilizing standard seawater. This was prepared with distilled water and standard seawater salt. Standard seawater salt (Marinemix + Bio-Elements from Wiegandt GMBH & Co., F.R. Germany) was used to reduce the variability of effects resulting from conducting measurements using natural seawater. Experiments were also conducted in sulfide polluted seawater. The sulfide was introduced using research-grade sodium sulfide (Na2S). The level of sulfide in the seawater was checked by the iodimetric method of analysis. The synthetic seawater solutions were deaerated using purified nitrogen gas. Sulfide was introduced to these solutions as sodium sulfide in the concentrations of 1 and 10 ppm. Glutaraldehyde (1,5pentanedial) was selected as the nonoxidizing-type of biocide in concentrations of 10, 50 and 100 ppm and, ammonium chloride was selected as the oxidizing agent in the concentration range of 1, 5 and 10 ppm. Electrochemical measurements employing linear polarization, Tafel extrapolation, potentiodynamic polarization and AC impedance techniques were carried out in the three-electrode cell assembly (EG&G). The reference electrode used was a saturated calomel electrode (SCE), located in a glass tube fitted with vycor frit and the electrochemical circuit was completed with an encapsulating cylindrical platinum counter electrode. Polarization resistance (Rp) values were obtained by using linear polarization applying Ecorr + 0 mV across the working electrodes surface. Tafel polarization studies were performed by imposing Ecorr + 250 mV with respect to the open circuit potential (OCP). The
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anodic polarization experiments were run at a scan rate of 0.5 mV/sec using a potentiostat 5 (EG&G model 273A). AC impedance data were generated as a function of frequency (10 Hz-10 mHz) by imposing a sinusoidal voltage signal of 5 mV across the interface. The complex impedance data were acquired using a frequency response analyzer (Schlumberger model SI1255) controlled by a computer. All the electrochemical measurements were made o under stagnant conditions at room temperature (i.e., 19 + 1 C). RESULTS AND DISCUSSION The Tafel polarization curves for mild steel in seawater and a sulfide-polluted system under deaerated conditions are presented in Fig. 1a. Increasing the sulfide concentration resulted in a shift in potential in the active direction. Also, increasing the sulfide level resulted in a significant change in the values of ba and bc. At the same time, this resulted in an increase in the corrosion rate for a higher concentration of sulfide, i.e., 10 ppm. Clearly the presence of sulfide has a significant influence on the rate of the cathodic and anodic reactions. From a comparison of the values of ba and bc at the two sulfide concentrations of interest, it can be seen that increasing the sulfide concentration resulted in bc tending towards increasing values which indicates a diffusion-limiting reaction occurring at the surface. This is clearly a result of exposure to higher concentrations of sulfide ions which resulted in the development of an oxidized layer acting as a diffusion barrier. Thus, it is possible that the corrosion reaction was under mixed control. The limiting diffusion current was observed on the cathodic branch of the polarization curve, as can be seen in Fig. 1a. This is consistent with the conclusions of Iofa [14] that sulfide participates directly in the cathodic reactions and is simply a catalyst which speeds up the discharge of hydrogen ions. Various mechanisms have been proposed for the intensification of the corrosion rate due to the presence of hydrogen sulfide [14-18]. An example of one such mechanism is that proposed by Panasenko [16], i.e., Fe + HS
-

Fe(HS-)ads Fe(HS) + 2e Fe
2+ +

(1) (2) (3)

Fe(HS-)ads Fe(HS)
+

+ HS-

It is clear that sulfide acts as a catalyst promoting ferrous ion generation. This will lead to an increase in the concentrations of ferrous ions near the interface. The adsorption of HSions will produce a negative charge on the surface which will accelerate the hydrogen discharge reaction through another simultaneous cathodic reaction [15]: HS + e Hads + Hads
-

Hads + S H2

2-

(4) (5)

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-500
Seawater

-500
1 ppm Sulfide
SCE

-600
SCE

-600 -700 -800 -900 -1000 -1100

10 ppm Sulfide

0 ppm Glutaraldehyde 10 ppm Glutaraldehyde 50 ppm Glutaraldehyde 100 ppm Glutaraldehyde

Potential, mV

-700 -800 -900

-1000 -1100 -9 -8 -7 -6 -5
2

-4

-3

-2

Potential, mV

-10

-9

-8

-7

-6

-5
2

-4

-3

-2

log (i[A/cm ])

log (i[A/cm ])

(a)
-500
-500 -600
SCE 0 ppm Glutaraldehyde 10 ppm Glutaraldehyde 50 ppm Glutaraldehyde 100 ppm Glutaraldehyde

(b)

-600
SCE

Potential, mV

-700 -800 -900

Potential, mV

-700 -800 -900

0 ppm NH 4Cl 1 ppm NH 4Cl 5 ppm NH 4Cl 10 ppm NH 4Cl

-1000 -1100 -10 -9 -8 -7 -6 -5


2

-1000 -1100
-4 -3 -2

-10

-9

-8

-7

-6

-5
2

-4

-3

-2

log (i[A/cm ])

log (i[A/cm ])

(c)
-500 -600
SCE 0 ppm NH 4Cl 1ppm NH Cl 4 5 ppm NH Cl 4 10 ppm NH Cl
4

(d)

Potential, mV

-700 -800 -900

-1000 -1100 -10 -9 -8 -7 -6 -5


2

-4

-3

-2

log (i[A/cm ])

(e) Figure 1. Polarization diagrams for mild steel in seawater: (a) without biocides; (b) with glutaraldehyde and 1 ppm sulfide; (c) with glutaraldehyde and 10 ppm sulfide; (d) with ammonium chloride and 1 ppm sulfide; and (e) with ammonium chloride and 10 ppm sulfide
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At the pH of the present solution (9.7 9.75) S is not stable and thus the reaction S
2-

2-

+ H2O

HS- + OH

(6)

takes place, by which hydroxide ions are produced, increasing the pH of the solution. However due to the high concentration of ferrous ions near the interface, another partial reaction will compete with the reaction in Eq. 4, that is the precipitation of the solid sulfide according to the following reaction: Fe
2+

+ HS

Various Iron Sulfides (Insoluble)

(7)

Thus in this case, the corrosion current measurements for steel have indicated significant increases in the presence of low concentrations of sulfide which is due to the formation of a corrosion product which acts as a physical barrier to the corrosion reaction. However, the anodic polarization curves from Fig. 1a show an increase in the anodic dissolution for a sulfide-added system. To investigate the effect of oxidizing biocide on the mild steel-sulfide-polluted seawater system, glutaraldehyde and ammonium chloride were introduced. The Tafel polarization curves for mild steel in deaerated sulfide-polluted seawater with various concentrations of either glutaraldehyde or ammonium chloride are presented in Figs. 1b-e. The parameters obtained from the linear polarization and Tafel extrapolation methods are given in Tables 1 and 2. It can be seen from these tables that the addition of sulfide increases the corrosion rate of mild steel, especially in higher concentrations of sulfide as reflected both in the measurement of Rp and corrosion current, icorr. Table 1. The Electrochemical Parameters of Mild Steel and Stainless Steel in Unpolluted Seawater Alloy Mild Steel Parameter OCP (mV vs SCE) Rp, LP (K cm2) icorr, (A/cm2) Rp,Imp (K cm2) Epit, (mV vs SCE) Ipit (A/cm2) Rp, LP (Kcm2) Measured Value 776 12.38 0.508 6.87 64 2.69 236.3

Stainless Steel

As the conditions in the present investigation involve is a simulated chemical environment undergoing biological processes, the behavior of mild steel in the sulfidepolluted, oxygen-free system is similar to its behavior in an anaerobic sulphate reducing bacteria (SRB) environment. Sulfide ions present in the oxygen-free chloride system are aggressive to mild steel, and the resultant product is iron sulfide which has no inhibiting or intact properties on the metal surface to prevent further dissolution. However, the addition of
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glutaraldehyde and ammonium chloride alterred the corrosion tendencies, as depicted in Tables 1 and 2. In the lower concentration of sulfide, the addition of glutaraldehyde in the concentrations of 10 and 100 ppm had no profound effect on the dissolution, but in the intermediate concentration of 50 ppm, it increased the corrosion rate of mild steel. It is interesting to note that the accelerating mode of corrosion in the presence of a low sulfide concentration, i.e., 1 ppm and a glutaraldehyde concentration of 50 ppm, is completely reversed in the high sulfide concentration, i.e., 10 ppm, where the minimum corrosion current was measured, when compared with the other concentrations of glutaraldehyde. Table 2. The Effects of the Investigated Biocides on the Electrochemical Parameters of Mild Steel in Sulfide Polluted Seawater Sulfide Concentration 1 ppm
Biocides Investigated None Glutaraldehye Conc. ppm OCP, mV vs SCE -784 -810 -780 -799 -809 -806 -818 Rp (LP) K cm2 10.670 10.46 3.447 10.03 8.577 2.047 2.815 icorr, A/cm2 0.49 0.535 2.12 0.617 0.579 4.44 0.70 Rp (Imp) K cm2 6.333 9.931 1.734 6.685 5.370 1.223 7.236

10 ppm
OCP, mV Rp (LP), icorr, vs SCE K cm2 A/cm2 -794 3.012 1.29 -816 -738 -816 -815 -782 -732 7.880 16.62 4.310 13.31 4.14 18.8 0.93 0.4 1.09 0.524 1.40 0.372 Rp (Imp) K cm2 2.2610 5.133 --4.383 -------

10 50 100 1 5 10

Ammonium Chloride

The addition of ammonium chloride to the sulfide polluted system increased the corrosion current and reduced the Rp values in the lower concentration of 1 ppm sulfide. However, this scenario was not observed in the higher concentration of 10 ppm sulfide level where decreases in the corrosion current values were noted for an increase in the ammonium chloride concentration, except at 5 ppm. The Nyquist plots and Bode magnitude diagrams obtained form the AC impedance measurements are presented in Figs. 2 and 3, respectively. Because of the distinct advantage of the Bode magnitude plots over the Nyquist plots in the low frequency range, the Rp values obtained from the Bode plots were taken into account for the analysis and are presented in Tables 1 and 2. These measurements also indicated the similar trends observed in the DC polarization measurements. Some investigators [11] have shown that the analyses of results from the AC impedance method are more appropriate than the DC polarization for the biocide added system where potentiodynamic measurements yielded higher corrosion rates because of the change in the surface of the system exposed to the biological environment during the polarization. It is a general belief that the addition of biocide to the MIC system results in the elimination or the control of the deleterious microorganisms, thereby reducing the corrosion rate of the material of interest. The results from the previous investigations [19,28] on the glutaraldehyde-added system were of a conflicting nature, because of the effect attributed to the release of metabolic products during glutaraldehyde treatment which might change local pH and/or inorganic species adjacent to the metal/solution interface, thereby interfering with the corrosion of steel.
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5 0 ppm Sulfide 1 ppm Sulfide 10 ppm Sulfide

6 0 ppm Glutaraldehyde 10 ppm Glutaraldehyde 50 ppm Glutaraldehyde 100 ppm Glutaraldehyde

(KOhm.cm )

(KOhm.cm )
imaginary

2
3 2 1 0 0 1 2 3 4 5 2 6 7

4 3

imaginary

0 0 2 4 6 8 2 10 12

real

(KOhm.cm )

real

(KOhm.cm )

(a)
6
12 0 ppm Glutaraldehyde 10 ppm Glutaraldehyde 50 ppm Glutaraldehyde 100 ppm Glutaraldehyde

(b)

(KOhm.cm )

10 8 6 4 2 0 0

(KOhm.cm )

0 ppm NH 4Cl 1 ppm NH Cl 4 5 ppm NH 4Cl 10 ppm NH Cl


4

4 3

imaginary

imaginary

Z
1 0
2 4 6 real 8 2 10 12

10

(KOhm.cm )

real

(KOhm.cm )

12 2

14

16

(c)
14 12 10 8 6 4 2 0 0 2 4 6 real 8 2 10 12 0 ppm NH Cl 4 1 ppm NH Cl 4 5 ppm NH Cl 4 10 ppm NH 4Cl

(d)

imaginary

(KOhm.cm )

(KOhm.cm )

(e) Figure 2. Nyquist plots for mild steel in seawater: (a) without biocides; (b) with glutaraldehyde and 1 ppm sulfide; (c) with glutaraldehyde and 10 ppm sulfide; (d) with ammonium chloride and 1 ppm sulfide; and (e) with ammonium chloride and 10 ppm sulfide
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4 0 ppm Sulfide 3.5 2 1 ppm Sulfide 10 ppm Sulfide


4 0 ppm Glutaraldehyde 10 ppm Glutaraldehyde 50 ppm Glutaraldehyde 100 ppm Glutaraldehyde 3 2.5

3.5

Log |z|, Ohms-Cm

2.5

Log |z|, Ohms-Cm


-4 -2 0 2 4 6

2 2 1.5 1 -4 -2 0

1.5

Log [frequency], Hz

Log [frequency], Hz

(a)

(b)

4.5 4

Log |z|, Ohms-Cm

Log |z|, Ohms-Cm

3.5 3 2.5 2 1.5 1 -4 -2 0

0 ppm Glutaraldehyde 10 ppm Glutaraldehyde 50 ppm Glutaraldehyde 100 ppm Glutaraldehyde

4.5 0 ppm NH 4Cl 4 3.5 3 2.5 2 1.5 1 1 ppm NH Cl


4

5 ppm NH 4Cl 10 ppm NH 4Cl

-4

-2

Log [frequency], Hz

Log [frequency], Hz

(c)

(d)

4.5 0 ppm NH Cl
4

1 ppm NH 4Cl 5 ppm NH 4Cl 10 ppm NH Cl


4

Log |z|, Ohms-Cm

2 3.5 3 2.5 2 1.5 1 -4 -2 0 2

Log [frequency], Hz

(e) Figure 3. Bode plots for mild steel in seawater: (a) without biocides; (b) with glutaraldehyde and 1 ppm sulfide; (c) with glutaraldehyde and 10 ppm

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sulfide; (d) with ammonium chloride and 1 ppm sulfide; and (e) with ammonium chloride and 10 ppm sulfide It is believed that glutaraldehyde enters into interaction with sulfide and forms thioglutaraldehyde that polymerizes on the metal surface. It is possible that organic compounds are capable of entering into chemical interaction with the sulfide present, forming on the metal surface insoluble compounds (i.e., Eq. 6) that constitute a peculiar kind of phase barrier. It is possible that localized alteration of pH at the electrode surface (Eq. 4,) makes this mechanism possible. However, the addition of ammonium chloride can certainly decreases the resistance of mild steel in any sulfide system because of its oxidizing nature. In the 1 ppm sulfide system, the co-presence of ammonium chloride and oxidized forms of sulfide promotes the corrosion process. Increasing the concentration of sulfide in a system containing NH4Cl, resulted a the decrease in the corrosion current. This can be attributed to the formation of species such as sulfate as the oxidized product of sulfide in the presence of NH4Cl. Also the increased dissolution rate observed in the intermediate concentration of 5 ppm of ammonium chloride compared with other concentrations call attention to the existence of a critical concentration of oxidizing-types of chemicals, like passivators added to a neutral medium. Stainless Steel The anodic polarization curves for stainless steel in deaerated sulfide added to a biocide system are presented in Figs. 4a-e. These curves yielded important parameters which are presented in Tables 1 and 3, and are relevant to the assessment of 316L stainless steel in a biocide added system. The pitting potential values shown in Tables 1 and 3 clearly indicate the influence of sulfide on the passivity of stainless steel in a deaerated, biocide-free system. It is well known that sulfide anions present in polluted seawater lead to the formation of an oxide layer of poor protective characteristics, which facilitates the initiation of corrosion attack [21]. Moreover, the presence of sulfide in a stainless steel-seawater system is generally detrimental to the pitting resistance of all stainless steel grades. The biologically generated sulfide can also modify the local chemistry of the marine environment and prevent the repair of the passive film of the stainless steel [22]. Table 3. The Effects of the Investigated Biocides on the Electrochemical Parameters of 316L Stainless Steel in Sulfide Polluted Seawater Sulfide Concentration 1 ppm
Biocides Investigated None Glutaraldehye Conc. (ppm) Rp, cm 275.7 10 50 100 1 5 10 278.6 180.6 219.7 144.4 392.7 164.4
2

10 ppm
2

Ip, A/cm 2.55 2.44 2.70 2.55 3.2 2.17 3.45

Epit mV vs SCE 251 159 95 198 104 172 158

Rp, cm 148.6 206.7 238.9 169.3 226.9 172 152.1

Ip, A/cm2 3.04 3.4 2.52 3.08 3.02 5.06 3.13

Epit mV vs SCEE 142 223 125 193 264 196 169

Ammonium Chloride

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600
400 300
SCE Seawater 1 ppm Sulfide 10 ppm Sulfide

400

200 100 0 -100 -200 -300 -400 -10 -9

Potential, mV

SCE

0 ppm Glutaraldehyde 10 ppm Glutaraldehyde 50 ppm Glutaraldehyde 100 ppm Glutaraldehyde

Potential, mV

200

-200

-400
-8 -7 -6
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(e) Figure 4. Polarization diagrams for 316L stainless steel in seawater: (a) without biocides; (b) with glutaraldehyde and 1 ppm sulfide; (c) with

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glutaraldehyde and 10 ppm sulfide; (d) with ammonium chloride and 1 ppm sulfide; and (e) with ammonium chloride and 10 ppm sulfide

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250
200 0 ppm sulfide

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(e) Figure 5. Nyquist plot for 316L stainless steel in seawater: (a) without biocides; (b) with glutaraldehyde and 1 ppm sulfide; (c) with glutaraldehyde and 10 ppm sulfide; (d) with ammonium chloride and 1 ppm sulfide; and (e) with ammonium chloride and 10 ppm sulfide in seawater

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6 0 ppm Sulfide 1 ppm Sulfide 5 10 ppm Sulfide

6 0 ppm glutaraldehyde 10 ppm glutaraldehyde 50 ppm glutaraldehyde 100 ppm glutaraldehyde

Log |z|, Ohms-Cm

Log |z|, Ohms-Cm


-4 -2 0 2 4 6

2 4

1 -4 -2 0 2 4 6

Log [frequency], Hz

Log [frequency], Hz

(a)

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6 0 ppm glutaraldehyde 10 ppm glutaraldehyde 50 ppm glutaraldehyde 100 ppm glutaraldehyde


6 0 ppm NH Cl 4 1 ppm NH 4 Cl 5 ppm NH Cl 4 10 ppm NH 4Cl

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-4 -2 0 2 4 6

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(d)

6 0 ppm NH 4Cl 1 ppm NH 4Cl 5 ppm NH 4Cl 10 ppm NH 4Cl

Log |z|, Ohms-Cm

2 4 3 2 1 -4 -2 0 2

Log [frequency], Hz

(e) Figure 6. Bode plot for 316L stainless steel in seawater: (a) without biocides; (b) with glutaraldehyde and 1 ppm sulfide; (c) with glutaraldehyde and 10 ppm sulfide; (d) with ammonium chloride and 1 ppm sulfide; and (e) with ammonium chloride and 10 ppm sulfide
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In the present investigation, the effect of sulfide on the passivity breakdown, thereby increasing the pitting tendency, for the increase in sulfide concentration is clearly revealed. The addition of glutaraldehyde, a nonoxidizing biocide, also resulted in a lower pitting potential than the blank system. The least was observed for the intermediate concentration of 50 ppm. The analysis based on the anodic current density corresponds to the passive region indicating that the susceptibility mode is more pronounced than in the biocide-free system. The addition of ammonium chloride as an oxidizing chemical changed the entire scenario and involved an increased susceptibility of stainless steels to pitting. The pitting potential values from Tables 1 and 3 indicate this effect. This is not the case all the time or for all concentrations investigated. Increases in the concentration of sulfide to 10 ppm with the addition of NH4Cl resulted in improved pitting resistance based on the pitting potential values compared to the blank one. The anodic current density values corresponding to the passive region showed a high value for the concentration of 5 ppm of ammonium chloride. The same concentration for mild steel in a sulfide-polluted system increased the dissolution rate. Under inorganic, near neutral conditions, sulfide and other sulfur species are known to decrease both the pitting potential and the repassivation potential of stainless steels [23]. Particularly, chloride ions are aggressive to stainless steels. The pitting potential is reduced as the concentration of chloride increases [24]. However, the effects of the aggressive anions are reduced by the presence of inhibiting anions. Notably sulfate [24], hydroxide [25] and acetate [25] inhibit the pitting corrosion of stainless steel to varying extents, and this was the case observed in the present investigation for higher concentrations of sulfide where the presence of an oxidizing agent led to the formation of sulfate as the resultant oxidizing product. Figures 5a-e and 6a-e-show the complex plane impedance diagrams (Nyquist plots) and the Bode plots for 316L stainless steel in seawater with and without a sulfide polluted system (i.e., addition of glutaraldehyde and ammonium chloride. These plots do not allow a reasonable estimate for Rp because the valid Rp values can only be obtained using the AC impedance technique if the low frequency locus in the complex plane impedance diagram is essentially complete. The behavior, however, is of the Warburg type for diffusion controlled reactions. CONCLUSIONS 1. The oxidizing and nonoxidizing biocides generally alter the corrosion tendency of mild steel and the pitting tendency of 316L stainless steel in sulfide polluted environments. 2. The increase in corrosion rate of mild steel was observed for the glutaraldehyde concentration of 50 ppm added to the lower concentration of sulfide i.e., 1 ppm. This trend completely reversed for a higher concentration of sulfide i.e., 10 ppm. 3. The increase in the concentration of sulfide, i.e., 10 ppm, for the oxidizing type of chemical added to the synthetic seawater resulted in a decrease of the corrosion rate of mild steel as well as a lower pitting susceptibility for stainless steel. ACKNOWLEDGMENT This work was supported financially by the Kuwait Foundation for the Advancement of Science (KFAS) and Kuwait University. This support is gratefully acknowledged.

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REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. H.A. Videla, M.F.L. Demele and G.J. Brankevich, Corrosion 44, 1988, pp. 423-426. S.C. Dexter, K.E. Lucas and Y. Gao, in Biologically Induced Corrosion, S.C. Dexter, ed., NACE, Houston, Texas, 1986, pp. 144-153. R.C. Salvarezza and H.A. Videla, Corrosion 36, 1980, pp. 550-553. R. Johnson and E. Bardal, Corrosion/86, Paper No. 227, NACE, Houston, Texas, 1986. R.G.J. Edyvean, Proceedings 6th International Congress on Marine Corrosion and Fouling, 1984, Athens, pp. 469-483. R.G.J. Edyvean and L.A. Terry, UK Corrosion84, Institute of Corrosion84, Institute of Corrosion Science and Technology, UK, 1984, pp. 195-198. G. Kobrin, in Biologically Induced Corrosion, S.C. Dexter, ed., NACE, Texas, USA, 1986, p. 33. R.E. Tantnall, Materials Performance 19, 8, 1980, p. 88. R.J. Soracco, D.H. Pope, J.M. Eggars and T.N. Effinger, Corrosion/88, Paper No.83, NACE, Houston, Texas, 1988. C.A.C. Sequeira, Proceedings 2nd EFC Workshop on Microbial Corrosion, The Institute of Materials, UK, 1992, p. 9. M. Elbonjdaini and V.S. Sastri, Corrosion/95, Paper No. 213, NACE, Texas, USA, 1995. J.E. Lamot, Proceedings First European Federation of Corrosion Workshop on Microbial Corrosion, The European Federation of Corrosion, 1988, pp. 224-234. W.I.J. Poulton and R.W. Lutey, Proceedings International Congress on Microbially Induced Corrosion, Tennessee, USA, 1990. Z.A. Iofa, Zashchite Metallov 6, 5, 1970, p. 491. I.L. Rozenfeld, Corrosion Inhibitors, McGraw-Hill, New York, 1981. V.F. Panasenko, Candidates Dissertation, Poly-Tech. Institute, Kiev, 1972. H. Kaesche, Werkstoffe und Korrosion 21, 3, 1970, p. 185. P. Bolmer, Corrosion 21, 3, 1965, p. 69. R.G. Eager, J. Leder, J.P. Stanley and A.B. Theis, Corrosion/88, Paper No. 84, NACE, Houston, Texas, USA, 1988. J.S. Luo, P. Angell and D.C. White, Proceedings 9th Asian-Pacific Corrosion Control Conference, Taiwan, China, 1995, p. 592. R.G.J. Edyvean and H.A. Videla, Proceeding 2nd EFC Workshop on Microbial Corrosion, the Institute of Materials, UK, 1992, p. 18. Z. Szklarska-Smialowska and E. Lunarska, Werkstoffe und Korrosion 32, 1981, p. 478. R.C. Newman, H.S. Isaacs and B. Alman, Corrosion 38, 1982, p. 261. H.P. Leckie and H.H. Uhlig, J. Electrochem. Soc. 113, 12, 1966, p. 1262. Z. Szklarska-Smialowska, Pitting Corrosion of Metals, NACE, Houston, Texas, USA, 1986, p. 285.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

EVALUATION OF MICROBIALLY INFLUENCED CORROSION RISKS AND CONTROL STRATEGIES IN SEAWATER AND PRODUCED WATER INJECTION SYSTEMS, KUWAIT P.F. Sanders1, M. Salman2 and K. Al-Muhanna2
1

Oil Plus Limited, Hambridge Road, Newbury, Berkshire, RG14 5TR, England Kuwait Institute of Scientific Research, P.O. Box 24885, 13109 Safat, Kuwait

ABSTRACT
Injection of seawater and produced (effluent) water for secondary oil recovery can encourage the growth of bacteria, particularly in biofilms on pipewall surfaces. One particular problem in water injection systems is the uncontrolled growth of sulphate-reducing bacteria (SRB) which leads to increased corrosion of the process plant. Injection water sources in Kuwait range from brackish water (total dissolved solids, i.e., TDS = 4,000 mg/l) through seawater (TDS = 30,000 mg/l) to highly saline brines (TDS = 200,000 mg/l). In addition, some of these water sources are highly sulphide sour and may require treatment to prevent scaling, corrosion or iron sulphide precipitation. Studies were undertaken to evaluate the relative risks of microbially influenced corrosion in a range of Kuwaits water sources, using a combination of field sampling and laboratory biofouling trials. Bacteria isolated from the field surveys were used to evaluate remedial treatments such as chlorine, chemical biocides and mechanical removal. Recirculating biofouling loops were set up with the appropriate site water, and inoculated with the bacteria from the system so that an active biofilm was set up on small steel studs. These biofouled studs were treated with proprietary antibacterial products under various dose regimes in order to select the most appropriate control regime for particular water chemistries and process options. Key Words: Microbially influenced corrosion, seawater, water injection systems, secondary oil recovery, remedial treatments

INTRODUCTION Pitting corrosion is characteristic of sulphate reducing bacteria (SRB) attack of steels, with the pits being open and filled with soft black corrosion products in the form of iron sulphides [1,2]. When the corrosion products are removed, the metal underneath is bright but rapidly rusts on exposure to air. With buried pipelines in anaerobic environments, such as waterlogged clay soils, the corroded area as a whole, will be covered with a film of iron sulphides. In aerobic environments, SRB corrosion invariably occurs beneath deposits of inorganic or organic detritus, microbial slimes, or tubercules caused by the action of the ironoxidising bacteria [3,4]. Unique features of corrosion caused by SRB are that it occurs at neutral pH and in anaerobic environments. Oxygen is not involved, and the corrosion products include iron

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sulphides. The exact mechanisms of the corrosion reactions are still under debate, and a range of possible mechanisms has been proposed [1,2]. Normal electrochemical corrosion would not be expected to occur under anaerobic conditions, because the cathode becomes polarized by the build-up of a layer of atomic hydrogen. SRB are potentially able to stimulate the normal electrochemical corrosion mechanism by a number of possible means, the most widely accepted being

The enzymic removal of polarizing cathodic hydrogen, The formation of iron sulphides which are themselves cathodic to steel, The formation of elemental sulphur upon re-oxidation of the sulphides, The formation of aggressive iron phosphides by SRB.

It is now generally accepted that, although all of these mechanisms may operate in nature, the production of iron sulphides and cathodic depolarisation are the two most important corrosion mechanisms. Control of microbes can be effected by chlorination, ozonization, by means of ultraviolet (UV) light and/or organic biocides. A combination of these methods is commonly used to minimise microbially influenced corrosion and reservoir souring in oilfield water injection and reservoir systems. For seawater injection dosing systems, chlorine injection at the seawater lift pumps is the most common primary method of control [5]. However, chlorine is generally lost at the deaeration stage by reaction with oxygen scavenger, and biological control is therefore maintained in the remainder of the system by the use of organic chemical biocides. The most common strategy is a regular (frequently weekly) batch treatment for 3-6 hours. The dose rate and contact time are both critical in order to optimise the killing effect of the biocide;: in most cases laboratory trials are used to determine the best treatment. Most water injection systems, therefore, employ chemical biocide treatments [6,7] with varying degrees of success [8,9]. Great care must be taken in selecting and applying biocides to ensure that they are compatible with the system, can be handled safety, and have no environmental impact. Additionally, both batch and low-level continuous treatments of organic biocides will ultimately lead to the build-up of resistant and tolerant strains of the bacteria. Biocide effectiveness will, therefore, decline with time, and monitoring must take place to identify when a change in biocide type is required. In most cases, a proprietary organic biocide is used as a batch dose to replace the continuous microbiological control exerted by chlorine. There are many biocides offered by chemical supply companies, which may carry out field tests to determine which of their range is best suited to a particular problem. An unbiased view can, however, only be given by the operator or an independent laboratory carrying out a testing program for products from a range of supply companies. Despite the apparent large range of biocides, there are, in fact, a relatively limited number of molecules that are regularly used. The most widely used biocides are listed below. Many products are mixtures of one or more biocides with surfactant that aids penetration of deposits and provides cleansing action.

Chlorine and chlorine-releasing compounds, Aldehydes, e.g., glutaraldehyde, formaldehyde, that combine with genetic
material to prevent cell replication and protein formation,
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Quaternary ammonium compounds and quaternary phosphonium compounds


which are good penetrating agents and attack the outer membrane of cells causing rupture and leakage of their contents, and Amines, e.g. guanide compounds, that attack genetic material and prevent cell growth and replication. Miscellaneous compounds such as acrolein (substituted alkene) and isothiazalones have been successfully tested against SRB. They are beginning to be used in water injection systems for specific applications. Biocide test methods for water injection systems fall into two main categories: planktonic and sessile methods. The following outlines illustrate the basics of the methods. In many cases, a combination of the two methods must be used in order to arrive at the most effective and appropriate microbiological control regime for a specific system. Traditional methodology has concentrated on determining the numbers of SRB and other bacteria suspended in fluids, typically in water from injection, oil production and oil storage facilities [10]. Recent work has shown clearly that these planktonic bacteria are a very small fraction (typically less than 1%) of the total population [11]. Novel, rapid methods can sometimes be used to assess the numbers or activity of bacteria [12], but they must be used with care to ensure that results are reliable [9]. Planktonic Biocide Tests These typically follow the methods of CCEJV [13] and have the basic weakness that they do not measure the ability of the treatment to penetrate biofilms. Planktonic bacteria are more susceptible to biocides than are sessile ones, and a lower effective concentration is indicated from these tests than from sessile tests. Bacteriostatic Test This is a simple screening test to rank a large number of potential treatments. Biocide is added to SRB growth media at a range of concentrations, followed by an inoculum of SRB from the system, freshly grown in SRB media. The bottles are incubated and checked for SRB growth by blackening. A minimum inhibitory concentration (MIC) can be determined for each biocide. This test does not measure bacterial kill but merely the biocides ability to prevent growth. Time-Kill Test) The time-kill (TK) test provides a more realistic test: system water samples are used, and killing ability is determined. It is more time-consuming, however, and is typically used to select the most suitable from a small number of biocides. Biocide is added in the desired concentration to water samples from the system, followed by an inoculum of SRB from the system, freshly grown in SRB media. Sub-samples are taken at intervals and tested by MPN for surviving SRB. After incubation, time-kill curves are plotted and a suitable concentration/contact time combination can then be selected. Sessile Biocide Tests

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Simple recirculating biofilm generators are set up in the laboratory to mimic system conditions, allowing biofouling to occur with bacteria freshly isolated from the system. After a period of biofouling, the biostuds are removed and placed in stirred test biocide solutions in anaerobic seawater. After the desired contact time, these are removed and the surviving bacteria are enumerated, thus enabling TK curves to be determined for each biocide. Special Tests Appropriate test methods should be devised for other systems; for example, biocides for reservoir application should be tested at high temperature and pressure and with the presence of sand. Sand-packed columns are also useful for selecting biocides for hydrocarbon reservoir production system applications. Field Test Methods Both planktonic and sessile biocide trials can be carried out in the field on samples of water, solids or biostuds, derived from the system. A side stream is ideal for this purpose as biostuds can be used. Whilst laboratory derived results may relate to the system under study, it is generally better to carry out such tests in the field, under system conditions, so that the results can be directly related to the system [9,14,15]. In order to confirm the performance of a selected biocide regime, close monitoring of the system should be carried out before and after any change is made, by analysing the biostuds before and after biocide dosing. Once effectiveness is confirmed, monitoring can revert to a normal schedule until biocide-resistant and tolerant strains build up in the system. METHODS Three different systems in Kuwait were studied for their biocide treatment requirements. These were

A seawater injection system, A complex produced water/effluent, and A highly sour aquifer water injection project.
The biocide test methods were selected to be as relevant as possible for each individual system, ranging from MIC tests, through time-kill tests on biofouled studs to complex dynamic tests in a recirculating loop system. Bacteria were isolated from each site and grown in nutrient-enriched media. The media were based on standard formulations, but the brine composition was, in each case, matched to that of the system under investigation. Minimum Inhibitory Concentration (MIC) Test In order to obtain very basic information on the biocide, MIC tests were carried out [13]. A stock culture of mixed general aerobic bacteria (GAB), general anaerobic bacteria (GAnB) and SRB was used. Each vial was inoculated with the active stock culture (0.1 ml). The vials were then immediately injected with small volumes (ca 0.1 ml) of the biocide, diluted in anaerobic, sterile, effluent water. In this way, a wide range of biocide concentrations was set up to obtain general data on the various biocides.

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Planktonic Time-Kill (TK) Tests As with the MIC tests, these methods followed the CCEJV methods [13], using a bacterial suspension in 125 ml Wheaton bottles. Water was filtered (Whatman No. 1), dispensed in 100 ml volumes into 125 ml Wheaton bottles and autoclaved (121C/15 minutes) before cooling under nitrogen and capping. Stock biocide solutions were made up (10,000 ppm) and relevant volumes accurately dispensed into the Wheaton bottles using a variable automatic pipettor. Each Wheaton bottle was then immediately inoculated with 1 ml of the stock culture and stirred on a multipoint magnetic stirrer at 850 rpm. Samples were withdrawn from the Wheaton bottles at 0, 1, 3 and 6 hour contact times, and MPN analyses were conducted. Chlorine was dosed (as a solution of sodium hypochlorite) into aerobic, unfiltered water. Because the free chlorine concentrations were low and the chlorine demand was high, hypochlorite was redosed midway through the contact period in an attempt to retain a residual chlorine concentration. Sessile Time-Kill (TK) Tests Biofilm Generation Biofilms were generated using the Biocide Evaluation Test Rig (BETR) system (Figs. 1 and 2). This had six sessile bacterial monitoring tubes (SBMTs), each with 24 carbon steel studs. The BETR was run on a daily feed and bleed system.

Figure 1. Schematic diagram of 6 SBMT mounted in the recirculating BETR

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Figure 2. Detailed schematic diagram of 1 SBMT Water was treated with a minimal concentration of nutrients to encourage bacterial growth. It was then autoclaved to remove oxygen and cooled under nitrogen to maintain anaerobic conditions. The reservoir was filled with 20 litres of appropriate water and dosed with nutrients. The pH of the water was adjusted using dilute HCl and/or NaOH. Anaerobic conditions were maintained throughout by purging with nitrogen during all manipulations. After pH adjustment, the water was added to the main reservoir of the BETR under a nitrogen blanket. Upon initial start-up, 20 litres of the relevant water plus nutrients was inoculated with 100 ml of SRB, 100 ml of GAB and 100 ml of GAnB stock cultures for enrichment. Each SBMT was run in parallel with the others. Six SBMTs were set up at the same time and treated identically. Flow was maintained continuously at 8 litres per minute, equating to 1.0 metre per second, this being a typical velocity for water injection systems. Throughout the period of the test, the water flowing through the BETR was typically of the following characteristics: dissolved oxygen was <10 ppb, temperature was 30-34C, free chlorine was 0, and residual bisulphite was 0. The SBMT were run without any additional sulphide in an attempt to encourage bacteria to colonise the rig. The effect of sulphide, if required, was accounted for during the biocide dosing phase. Some tests studs were tested with sulphide at 75 mg/l, whilst parallel tests were undertaken without any additional sulphide.

Biocide Dosing Biocides were supplied in labelled bottles by the chemical vendors. Samples were withdrawn from the bottles and used in the laboratory tests. Table 1 gives the details of the products supplied for testing. For stirred biocide tests, products were made up to the desired concentration in site water in 125 ml Wheaton bottles; dispensing was carried out using adjustable automatic micro pipettors and suitable dilution. For the sulphide-free tests, the studs were added directly to the biocide solution; for the tests containing sulphide, a stock sulphide solution was made up and the appropriate volume added to the Wheaton bottle to give the desired concentration, prior to adding the stud to the biocide. Studs were removed from the SBMTs and suspended in the biocide/sulphide solution before assessing surviving bacterial numbers. For dynamic tests, biocides were injected directly into the SBMTs at the desired concentration, and the studs were removed before and after dosing. Subsequently, biocide doses were repeated at increasing concentrations to identify the most effective regime. Bacterial Evaluation The exposed surface of the stud was scraped carefully and all deposits were transferred to 10 cm3 of sterile seawater diluent. The diluent tube was then treated for 30 seconds in an ultrasonic bath followed by 60 seconds in a vortex mixer and a further 30 seconds in the ultrasonic bath. This treatment disrupts biofilm/deposits but does not kill bacteria. The treated diluent tube was used to inoculate triplicate series (to 10-7) of the following media,
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specially formulated for the bacteria grown from each site: SRB - Postgates B; GAB glucose-based aerobic broth; Gan - glucose based anaerobic broth. One cubic centimetre of the diluent was injected into each broth series and 1 in 10 dilutions were made. The procedure followed industry standard practice for MPN (most probable number) tests [13]. GAB and GAnB results were taken after 5 days of incubation at 30C. SRB results were taken after 28 days of incubation at 30C. CASE HISTORY 1: PRODUCED EFFLUENT WATER REINJECTION SYSTEM, WEST KUWAIT A complex system with various water sources for potential reinjection into the oil reservoir was tested. A 50:50 mixture of produced water and aquifer water was selected to be A full range of tests was carried out on 9 biocide products (see Table 1). MIC, planktonic time-kill, sessile time-kill, chlorination and mechanical removal were all tested, with and without 75 mg/l of sulphide. Due to the high salinity and high H2S content of the water, bacterial fouling was low in both the system and the laboratory BETR. In fact, it proved difficult to isolate bacteria from the system. The simple MIC tests yielded a generalized ranking of the products, but little information could be gained about the realistic dose rates required. More information was obtained from the planktonic time-kill tests, particularly with respect to speed of kill. The most realistic testing (against sessile bacteria) in the sulphide-free scenario gave a very similar ranking to the planktonic tests. Very importantly, however, the resulting recommended dose rates are much higher against sessile bacteria because of the high bactericide demand caused by the presence of inactivating organic materials in the biofilm. Table 1. Results of Testing of Nine Biocide Products on a Complex Produced Effluent Water
Biocid e Formulation Ranking (MIC) Planktonic Time-Kill (Sweet) Ranking Dose (ppm/hrs) 6 100/6 5 100/6 5 2= 100/6 4 1 1 100/1 25/3 25/6 100/6 3 500/6 3 5 1 Planktonic Time-Kill (Sour) Ran Dose king (ppm/hrs) 3 100/3 Sessile Time-Kill (Sweet) Ranki Dose ng (ppm/hrs) 5 >>500/6 6 >>500/6 4

1A 1B 1C 1D 1E 1F 1G 1H

1I

Mixed Aldehydes + QAC + QPC Mixed Aldehydes + QAC Glutaraldehyde + QPC Aldehydes + QAC Fatty Amines Aldehydes + QAC + Surfactant Glutaraldehyde Mixed Aldehydes + QAC + Surfactant Formaldehyde +

4 2= 8 2= 1 5= 5= 7

Sessile ( Rankin g 2

2= 2= 1

100/6 100/6 25/6

2 4 1

500/6 >500/6 500/3

5=

100/3

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QPC

representative of the system. This mixture had a TDS of 130,000 mg/l. One stream had a TDS of 259,000 mg/l, whilst another was of brackish water composition. One of the waters contained a sulphide level of 75 mg/l, and therefore, sour conditions were also tested. A similar picture emerged from the sour testing. As with the sulphide-free tests, the sessile ranking was similar to the planktonic ranking for the sulphide-containing tests. The only difference in the rankings was that Biocide 1A (effective in planktonic tests) was not very effective in the sessile tests, probably due to a lack of penetration into the biofilm. Again, a much higher demand for biocide is indicated when the sessile and planktonic tests are compared. The comparison of the planktonic and sessile rankings (Table 2) indicates the comparability between the two types of tests. Chlorination at conventional levels will not, in fact, be effective in controlling planktonic bacteria, even under the most favourable conditions. GAB numbers were initially 1.4 x 105/ml, and no measurable reduction was detected at 0.2 mg/l over 2 hours. Even at 2 mg/l for 2 hours, GAB were only reduced to 4.5 x 104/ml (i.e., less than one order of magnitude). GAnB showed slightly better kill rates, but 2 mg/l free chlorine only reduced numbers by one order of magnitude (from 4.5 x 104/ml to 3.0 x 103/ml). SRB behaved similarly (1.5 x 104/ml was reduced to 1.4 x 103/ml by 2 mg/l chlorine over 2 hours). Chlorination was, therefore, not considered as a feasible treatment regime for this system. Physical removal of corrosion deposits, biofouling, scale, settled solids, etc., in pipelines and vessels is a common cleanup method. A wide range of cleaning tools and devices are available to mechanically clean pipelines. These include foam spheres, nylon brush pigs, wire brush pigs, flexible plastic pigs and (the most aggressive) milling pigs. Normal oilfield operations combine chemical treatment programs (including biocides) with regular pigging operations of pipelines. Different types of physical removal of biofilms were tested, using the biofouled studs from the SBMTs. Initial bacterial populations consisted of 2.5 x 104 GAB, 2.0 x 104 GAnB and 4.5 x 104 SRB per stud. The biofilm was very thin and corrosion products were not in evidence. This meant that even a small physical perturbation was sufficient to dramatically reduce the numbers of sessile bacteria. Table 2. A Comparison of Planktonic and Sessile Rankings Bactericide 1H 1F 1D 1G 1A 1B Planktonic Ranking 1 2= 2= 4 6 5 Sessile Ranking 1 2 3 4 5 5 Sessile Ranking (a) Sweet (sulphide stripped) Recommended Dose (Sessile) 500 ppm/3 hours 500 ppm/6 hours 500 ppm/6 hours > 500 ppm/6 hours >> 500 ppm/6 hours >> 500 ppm/6 hours Recommended Dose

(b) Sour (sulphide at 75 mg/l) Bactericide Planktonic Ranking


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1G 1A 1E 1C 1F 1I

2 3 4 5 1 6

1 2 3 4 5 6

(Sessile) 500 ppm/3 hours 500 ppm/6 hours 500 ppm/6 hours > 500 ppm/6 hours >> 500 ppm/6 hours >> 500 ppm/6 hours

A single pass of a stiff nylon brush was the most gentle of the treatments, probably relating to use of a foam pig in a real system. Even this minimal treatment reduced the biofilm population to 4.5 x 102 GAB, 1.5 x 103 GAnB and 1.5 x 102 SRB per stud, a reduction of 1 or 2 orders of magnitude. A more aggressive treatment with a wire brush produced even better results, with residual populations of 1.5 x 102, 9.5 x 101 and 9.5 x 101 GAB, GAnB and SRB respectively. This treatment would reflect the use of a wire brush pig in a pipeline, and the results demonstrate the dramatic cleanup effects of such a treatment. Reductions were in the region of 3 orders of magnitude for all 3 microbial groups tested, and very low residual microbial populations were left on the surface of the cleaned steel. Finally, vigorous use of a sterile stiff plastic scraper resulted in the most effective removal of biofilm. Only 7 GAB, 7 GAnB and 75 SRB per stud remained after this treatment. These numbers can be considered to be insignificant and the conclusion must be that this treatment effectively removed all the biofilm, leaving only a few bacteria in inaccessible micro-environments. Such treatment probably equates to the use of a combined brush/scraper pig in the field. Although the trial could not be carried out on long-term corroded surfaces (which would be more difficult to clean by mechanical means), the results demonstrate that mechanical removal, if practised regularly and frequently, would be an effective biofouling/microbially induced corrosion preventative measure. This would be particularly true if pigging was combined with chemical biocide treatment. Under normal circumstances, a biocide treatment would be used to kill those bacteria easily accessible on surfaces and to loosen biofouling deposits. The mechanical scraper (pig) would then be used a few hours later to complete the removal process, perhaps followed immediately by a second biocide slug. CASE HISTORY 2: AQUIFER/EFFLUENT WATER INJECTION SYSTEM, SOUTH KUWAIT This was another mixed water injection system, this time with sulphide in all of the streams. A more limited test program was deemed adequate given the low biofouling measured in the field and the laboratory. Three separate waters were tested:

Aquifer A - low sulphate, 186,000 TDS, 140 mg/l sulphide Effluent B - moderate sulphate, 76,000 TDS, 250 mg/l sulphide Mixed waters - moderate sulphate, 108,000 TDS, 220 mg/l sulphide
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Eight biocides were submitted for testing; the products were pre-screened in the vendors laboratories for tolerance to sulphide and salinity (see Table 3). The testing in this case was undertaken at the suppliers dosages, on fouled studs from SBMTs. Bacteria from the system were used to inoculate the SBMTs, one SBMT being set up for each water chemistry. Aquifer A The aquifer water was very highly saline and contained very low bacterial numbers during the site analysis. Bacteria were only detected when 100 ml of water was filtered; the low numbers are due to

The high temperature of the water, The high salinity of the water, and The high sulphide concentration of the water.
The bacteria were likely to be present in a dormant, inactive, state and bacterial growth was evidently minimal under the aquifer conditions. This low growth was confirmed by the minimal growth seen in the SBMTs. Even after 48 days of biofouling under ideal conditions (35C, nutrients added, steady flow), bacterial colonisation of the studs was miniscule. Under normal conditions, such rigs (with seawater for example) would have a population of 106 GAB and 105 SRB after 14 days, and 107 GAB and 106 SRB after 28 days. It is likely that the aquifer water is sulphate-limited which would be an additional factor predisposing the water to low bacterial growth, particularly that of SRB. Table 3 Composition of Biocides Submitted for Testing (a) Case History 1 Biocide Formulation 1A Mixed aldehydes + QAC + QPC 1B Mixed aldehydes + QAC 1C Glutaraldehyde + QPC 1D Aldehydes + QAC 1E Fatty amines 1F Aldehydes + QAC + surfactant 1G Glutaraldehyde 1H Mixed aldehydes + QAC + surfactant 1I Formaldehyde + QPC QAC = Quaternary Ammonium Compound QPC = Quaternary Phosphonium Compound (b) Case History 2 Biocide

Formulation

2A 2B
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Suppliers Recommended Dose/contact time 500 ppm/3 hours 500 ppm/3 hours

Sanders et al.

2C 2D 2E 2F 2G 2H (c) Case History 3 Biocide 3A.1 3A.2 3B.1 3B.2 3C.1 3C.2 3D.1 3E.1 3E.2

Fatty amine arylquaternary + fatty amine salt Aldehydes + QAC Aldehydes QAC Aldehydes + QAC Glutaraldehyde + QPC

400 ppm/4 hours 400 ppm/4 hours 500 ppm/3 hours 400 ppm/3 hours 300 ppm/4 hours 1000 ppm/4 hours

Formulation

Aldehydes Aldehydes + amines Aldehydes + amines Glutaraldehyde + QPC Fatty amines Aldehydes + QAC Formaldehyde + QAC + QPC Aldehydes Aldehydes + QAC

Suppliers Recommended Dose/contact time 700 ppm 3 hours/week 700 ppm 3 hours/week 1000 ppm 4 hours/2 weeks 1000 ppm 4 hours/2 weeks 250 ppm 4 hours/week 250 ppm 4 hours/week 600 ppm 4 hours/week 200 ppm 4 hours/week 200 ppm 4 hours/week

Given the low biofouling population, it is not surprising that most biocides worked well, reducing numbers to zero. For the sweet system, the ranking for the aquifer water (Aquifer A) was 2H = 2G = 2E > 2C = 2B, and for the sour system, (140 ppm sulphide), the ranking for the aquifer water was 2G = 2A = 2F > 2D > 2H These rankings are based upon very small differences in performance. Effluent B The effluent SBMTs blackened due to the production of sulphide by SRB, but SRB growth and biofouling was slow. Bacteria were present in the system in moderate numbers. However, the salinity of the water was high (76,000 TDS), which would have reduced the growth rate of any bacteria. GAB were easier to kill then were SRB in this system. This is unusual (GAB are usually more resistant to biocides in biofilms than are SRB) and suggests that an active biofilm was not present on the studs. This was probably due to the combined effects of high salinity and residual corrosion inhibitor from the site water. Given the very low initial biofouling population, the rankings of the biocides were as follows. For the sweet (no sulphide) situation in the effluent water (effluent B): 2H > 2G = 2E > 2C = 2B,
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and for the sour water (250 ppm sulphide) situation in the effluent water (Effluent B): 2H > 2G > 2F > 2A > 2D As for aquifer A, the bacterial numbers were very low, and the differences between the biocides were minor. Mixed Water This water appeared to be the worst case from a biofouling point of view. This was likely to be due to the addition of sulphate to the aquifer water from the effluent water, the dilution of the aquifer's high salinity, and the dilution of possibly biostatic corrosion inhibitors from the effluent water. Control numbers of 300-650 GAB and 115-450 SRB per stud were recorded on this SBMT, and most biocides reduced numbers substantially. As with other SBMTs, GAB were reduced more than SRB, suggesting that a coherent biofilm did not form on the studs. Most biocides performed better in the sweet tests than in the sour tests, suggesting that many biocides initially acted as sulphide scavengers, thus reducing the effective biocide concentration. For the non-sour tests (no added sulphide), with mixed water C (mixed effluent and aquifer) the biocide ranking was 2H > 2C > 2G > 2E > 2B and for the sour tests (sulphide added at 220 ppm), with water C (mixed 2H/effluent/aquifer), the biocide ranking was 2H > 2G > 2D > 2F > 2A CASE HISTORY 3: SEAWATER INJECTION SYSTEM, NORTH KUWAIT This is a conventional seawater injection system and, in this case, dynamic trials were undertaken by injecting alternate biocides directly into the pre-fouled, recirculating SBMTs. One SBMT was used for each combination biocide treatment. Formulations of the biocides are shown in Table 3. Biocides were dosed to the other 5 SBMTs over a 4 week period, steadily increasing the dose from 50% to 100% of the manufacturers recommended dose concentration, retaining the recommended frequency and dosage time. In all cases, a pronounced saw-tooth effect was evident, with bacterial numbers recovering rapidly once the biocide was removed from the system. This saw-tooth effect is regularly seen in such trials and in field monitoring of water injection systems. Biocides tend to kill only a proportion of the bacteria present in biofilms, and the survivors rapidly grow to re-form the active biofilm. This confirms the need to dose biocide frequently in order to keep sessile bacterial populations at a low level. Biocide Regime A Both biocides were each dosed up to 700 ppm of the product for 3 hours once per week (i.e., two biocide treatments each week). Biocide 3A.1 was an aldehyde mixture that did not foam, whilst 3A.2 was a mixture of aldehydes and amines that did form foam when agitated.

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At half the recommended dose (350 ppm), biocide 3A.1 did not perform well, but biocide 3A.2 reduced bacterial numbers to ca 103 per stud. At three-quarters of the recommended dose (525 ppm), biocide 3A.1 was more effective, particularly against SRB, but biocide 3A.2 was only marginally more effective. At 90% of the recommended dose (630 ppm), biocide 3A.1 reduced numbers to 104 per stud while biocide 3A.2 reduced numbers to 102-103 per stud. At 700 ppm, biocide 3A.1 reduced bacterial numbers to 103 per stud, and biocide 3A.2 reduced them to 101 to 102 per stud. Bacterial numbers appear to recover rapidly (within a few days) after all the biocide doses. After the 75% dose of biocide 3A.2, however, numbers did not recover to their original level: 104-105 cells of each bacterial type were present compared to 106 per stud in the early stages of the trial. The data indicate that 3A.2 (containing an amine) was particularly effective at 630 ppm and above, and that 3A.1 above 525 ppm was able to support the effects of 3A.2. Continued treatment at 630-700 ppm with this biocide regime would be likely to maintain (and probably substantially reduce) sessile bacterial populations under these conditions. Biocide Regime B These biocides were dosed only once per week with the recommended concentration being 1000 ppm; 3B.1 was an aldehyde and amine blend dosed for 4 hours, 3B.1 was a mixed glutaraldehyde and THPS blend, again dosed for 4 hours. Biocide 3B.1 was strongly foaming whilst biocide 3B.2 did not foam when agitated. This once-per-week treatment gave good kill of all 3 bacterial types at 750 ppm (106/stud was reduced to 102-103 per stud), but within a few days the initial bacterial population levels were reestablished. There appears to be no significant difference in the data from the 1000 ppm dosing regime as compared to the 750 ppm dosing regime for GAB and GAnB (numbers were reduced to 101-103 per stud). Data from the Regime B trial indicated that one biocide dose per week is insufficient, and that 750 ppm for 4 hours is as effective as 1000 ppm for 4 hours. Biocide Regime C The biocides were dosed twice per week. Biocide 3C.1 was a fatty amine (250 ppm, 4 hours) and biocide 3C.2 was an aldehyde/QAC mixture (250 ppm, 4 hours). Both biocides formed foam when agitated, so they would not be suitable for dosing upstream of a deaerator tower. Biocide 3C.1 was very effective against GAB, GAnB and SRB;: even at 125 ppm, bacterial numbers were reduced from 106 to 102-103. Above 187 ppm, 3C.1 reduced numbers even further, in some cases to below 10 cells per stud. Biocide 3C.2 was, however, less effective. Even at 250 ppm, numbers were reduced by only 1 or 2 orders of magnitude. Despite the relatively poor performance of biocide 3C.2, however, there was a general downwards trend in bacterial numbers over the course of the trial and continuation with such a regime would probably lead to effective microbiological control. The most effective biocide in this case appeared to be 3C.1. Biocide 3C.2 could be improved by increasing the dosing concentration or changing to an alternative type. Biocide Regime D This vendor chose to submit only one chemical for testing, at a recommended dosing rate of 600 ppm for 4 hours once per week. The biocide was a complex blend of formaldehyde,
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QAC and THPS. It formed foam when agitated, and thus, might only be dosed downstream of a deaerator tower. At 300 ppm, bacterial numbers were reduced to 103 per stud, but at 450 ppm they were reduced to only 104. At 540 - 600 ppm, bacterial numbers were reduced to between 102 and 103 per stud, but only transiently. There was no apparent downwards trend in the data, and effective microbiological control did not seem to have been imposed by this regime, probably due to the infrequency of dosing. Biocide Regime E Regime E biocides were dosed twice per week. Biocide 3E.1 was a mixture of aldehydes, dosed at 200 ppm for 4 hours, while biocide 3E.2 was an aldehyde/QAC blend, again dosed at the recommended 200 ppm for 4 hours once per week. Biocide 3E.1 did not foam and thus could be dosed upstream of deaerator towers, whilst biocide 3E.2 did form foam and so would only be suitable for dosing downstream of such a tower. This biocide regime was particularly ineffective (apart from some transient reduction in SRB numbers early on). No consistent reduction in bacterial numbers was observed over the course of the treatment. Even if the concentration of the products were increased, effective control could not be guaranteed. The ranking derived from these trials is given in Table 4.

Table 4. Ranking of the Different Biocide Regimes Most Effective Regime C Regime A Regime B Regime D Regime E Biocide 3C-1 effective at 50% dose; biocide 3C.2 less effective even at 100% dose Effective at 90% dose Effective at 50% dose but needs twice per week Effective at 90% dose but needs twice per week Ineffective at 100% dose

Least Effective CONCLUSIONS

It is clear from this trial that one biocide treatment per week is insufficient to achieve good kill of biofilm bacteria. The data clearly show that two doses per week of an effective chemical can give good control of a well established biofilm. Such dosing would also minimize the buildup of biofilm in the first place if implemented from the startup of the system. In order to assess the suitability of any biocides for the system, other factors must be taken into account: 1. System demand. Sufficient residual biocide must be present at the end of the water distribution system to exert control there. A higher dose may be required at the main treatment plant to ensure that the minimum effective concentration is maintained at the system extremities, if there is a significant

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biocide demand. System biocide demand must be determined as soon as the plant is in operation. 2. Environmental impact. Certain of the biocide components may have an adverse environment impact, and this must be assessed. 3. Safety considerations. All biocides are harmful but some may contain, for example, carcinogens, and these may be banned from use in Kuwait. 4. Physical properties. Foaming tendency, for example, is critical in deciding where in the system particular biocides can be dosed. Other factors such as precipitation in the formation should also be considered. 5. Consistency of supply. Selected products must be continuously available so that there are no periods when biocide cannot be supplied. 6. Chemical reliability. All products supplied in bulk should conform to the samples tested without any changes in composition. Random testing of supply for fingerprinting should be implemented to ensure consistency. 7. Local service base. Biocide vendors should ideally have a permanent base in Kuwait to deal with technical questions and to provide a local testing and advisory service. REFERENCES 1. 2. 3. 4. 5. A.K. Tiller, Aspects of microbial corrosion, In Corrosion Process, R.N. Parkins Ed., Applied Science, 1982, pp. 115-160. W.A. Hamilton, Sulphate-reducing bacteria and anaerobic corrosion, Annual Reviews of Microbiology 39, 1985, pp. 195-217. G. Kobrin (Ed), A Practical Manual on Microbiologically Induced Corrosion, NACE, 1993. G.H. Booth, Microbial Corrosion, M & B Monograph CE/1, Mills & Boon, 1971. P.F. Sanders and D.L. Robinson, Corrosion control using continuous residual chlorine, In Microbial Corrosion (Proceedings of the 2nd European Federation of Corrosion Workshop on Microbially Induced Corrosion), European Federation of Corrosion, Publication No. 8, Institute of Materials. C.A.C. Sequeira and A.K. Tiller Eds., 1992, pp. 198-209. P.F. Sanders, Monitoring and control of sessile microbes: Cost effective ways to reduce microbial corrosion, In Microbial Corrosion 1, Elsevier Applied Science, C.A.C. Sequeira and A.K. Tiller Eds., 1988, pp. 191-223. W.J. Georgie, P.I. Nice and S. Maxwell, Selection, optimisation and monitoring of biocide efficiency in the Statfjord water injection systems, In UK Corrosion 91, 1991. I. Ruseska et al., Biocide testing against corrosion causing oilfield bacteria helps control plugging, Oil and Gas Journal 80, 1982, pp. 253-264. P.F. Sanders and L. Latifi, On-site evaluation of organic biocides for cost-effective control of sessile bacteria, In Proceedings of the Second International Conference on Chemistry in Industry, American Chemical Society, Vol. I, Paper O-30, 1994, pp 242-257.

6.

7.

8. 9.

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10. Review of current practices for monitoring bacterial growth in oilfield systems. CCEJV 1987. Document number 001/87. Corrosion Control Engineering Joint Venture, CCEJV, UK. 11. J.W. Costerton and G.G. Geesey, Microbial contamination of surfaces, In Surface Contamination (1),. K.L. Mittal Ed., Plenum Pub., 1979, pp. 211-222. 12. P.F. Sanders, Rapid methods for detecting microbial corrosion, In Proceedings of UK Corrosion 92, Volume 3, Session D. Institute of Corrosion, 1992. 13. Review of current practices for monitoring bacterial growth in oilfield systems, 1987, Document No. 001/87, Corrosion Control Engineering Joint Venture CCEJV/NACE. 14. P.F. Sanders, Control of microbiologically induced corrosion using field and laboratory methods. International Biodeterioration 24, 1988, pp. 239-246. 15. P.F. Sanders and J.F.D. Stott, Assessment, monitoring and control of microbiological corrosion hazards in offshore oil production systems. NACE Corrosion 87. Paper No. 367, 1987.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

HYDROGEN DEGRADATION OF STEEL - DIFFUSION AND DETERIORATION M. Farzam Faculty of Petroleum Eng. University of Petroleum Industry, Ahwaz, Iran

ABSTRACT
Following aqueous surface electrochemical reactions and hydrogen reduction, atomic hydrogen will diffuse through steel, to reside at the microstructural defects with possible catastrophic failures to follow. Carbon steel, low alloy steel or high strength low alloy steel under no-load, static or cyclic loading will be affected by the presence of hydrogen. Such an effect is mainly influnced by temperature, alloying, residual and applied stress, and partial pressure of hydrogen. Permeation tests were conducted by Devanathan's electrochemical method and a newly invented electro-vacuum method. Experiments illustrated that as the microstructure changed the diffusion constant, D, changed. Ingress of hydrogen increased with the reduction of voltage and pH. Thickness would not have a realistic effect, but cold work reduced D. The difference in D measured by the two methods of permeation was due to the variation in material, apparatus design and operation. Hydrogen degradation during stress corrosion and corrosion fatigue tests is one of the two processes of crack propogation. Immersion, dynamic polarization, stress corrosion (dynamic and static), corrosion fatigue tests, cathodic protection and fractographic studies were conducted in seawater and sour (hydrogen sulfide generated by sulfate reducing bacteria) environments. In all, it was concluded that with regards to Nernest's equation, as the partial pressure of hydrogen increased, the hydrogen concentration gradient (Fick's first law) increased and D increased. Furthermore, the speed of hydrogen diffusion increased. In the sour environment, the overtaking mechanism of failure was found to be hydrogen embrittlement rather than anodic dissolution. Key Words: Hydrogen degradation, hydrogen diffusion, diffusion constant, corrosion fatigue, stress corrosion cracking

INTRODUCTION The sources of hydrogen production in the industry are many: water dissociation Fe-H2O reaction effect of pH and bacteria
+ H 2 O H + OH

(1) (2) (3)

2Fe+ 3 H 2 O
+ H +e H

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After atomic hydrogen production at the cathodic side of a corrosion cell, hydrogen will diffuse into steel residing at the lattice interstitial sites, grain boundaries, vacancies, impurities and alloying elements. The bonding energy of such interactions is different (see Fig. 1 and Table 1). Trap sites are either low energy reversible (e.g., interstitial solutes 3-15 KJ/mol [1]) or high energy irreversible (e.g., TiC particles 96 KJ/mol [1]) It is believed that steels with high energy traps will release hydrogen at about 2500C and at higher temperatures. Generally, hydrogen will not saturate and therefore is less likely to damage the austenitic stainless steels, but carbon steel, and ferritic or martensitic steels will be degraded, and finally cracked. Table 1. Trap Energy [1] Trap Interstitial Solutes (C, N) Si Atom Ti Atom Vacancy Y Vacancy Dislocation Elastic Stress Field Dislocation Core (Screw) Dislocation Core (Mixed) 1/2 H2 (Vapour /Liquid) Grain Boundary Free Surface AlN Interface Fe3C Interface TiC Interface EB (KJ/mol)
B

NT (m-3) 1025 1027 1027 <1023 1023 19 10 - 1026 1019 - 1026 1019 - 1026 --19 10 - 1023 1021 24 10 - 1025 1024 - 1025 1024 - 1025

~3-15 >20 26 46 126 20 20 - 30 59 29 ~59 70 - 95 65 84 96

Figure 1. Lattice trapping [1]


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Hydrogen degradation will appear in one of the following forms: (1) (2) (3) Hydrogen embrittlement, Hydrogen blistering, Hydrogen induced cracking.

As little as H<1 ppm is enough to damage steel. Figure 2 shows a 20"-oil line pipe (Cheshmeh Khosh) damaged by hydrogen blistering.

Figure 2. Hydrogen blistering (Cheshmeh Khosh) Taking into account the tensile strength of steel, the H2 gas pressure in the blister must have been about 104 atm. There are number of theories describing the mechanisms of H degradation: (1) (2) (3) (4) (5) (6) Pressure theory, Surface energy, Enhanced plastic flow, Transport model, Hydride formation, Decohesion theory.

Since the diffusion of hydrogen into austenitic stainless steel will not increase the internal gas pressure, the pressure theory cannot be generally applicable. As far as the surface energy theory is concerned, as the oxygen absorption at the surface will not reduce the surface energy (with higher adsorption energy than H), this theory may not always be applicable. The third theory, which discusses the enhancement of plastic deformation in the presence of H, has rarely been approved and reported. The fourth theory describes hydrogen transportation by dislocations, but in the absence of dislocations, hydrogen will also diffuse and be transported. There is an interaction of hydrogen with alloys such as Nb, e.g., Nb-H which is a brittle compound (the fifth theory). Such an effect cannot also be a prime factor of degradation.

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It is generally believed that the last theory; decohesion theory, is the major responsible factor weakening the Fe-Fe bonds, and that a hydrogen failure is a result of the participation of all six theories. The temperature at which hydrogen will inflict its severest damage is at about 25oC [2]. Figure 3 shows that the crack advance at this temperature is maximum. The figure also shows that the higher the steels strength, the faster the crack propagation rate. The effect of hydrogen when coupled with static and cyclic stresses will be reflected as stress corrosion, corrosion fatigue or a combination of the two, i.e., stress corrosion fatigue [4]. The hydrogen diffusion characteristics previously reported by Devanathan and Stachurski [5] (Fig.4) showed that it takes an incubation period tb before hydrogen reaches the exit surface. The amount of hydrogen reaching the exit side increases and reaches a steady-state with time. Time tb and the area under the curve are representative of the metals characteristics.

Figure 3. Crack advance vs temperature in AISI 4130 [2]

Figure 4. Hydrogen diffusion curve [5]


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Hydrogen diffusion obeys Fick's first law:


J = -D dc dx

(4)

where J is the flux in mol/cm2S, D is the diffusion constant in cm2/S, C is the concentration in mol/cm3 and X is the distance hydrogen travels in cm.
D = D0 exp Q RT

(5)

where D is a constant, Q is the activation energy in J/mol, R is the gas constant in J/mol K and T is the temperature in K. It has been shown experimentally that:

D=

L 6t lag

(6)

where L is the thickness in cm and tlag = 0.63 J steady-state. From Fig. 4, tlag is measured at the intersection of the vertical line with the tangent of the slope at 0.63PS.S.. Some researchers [6] have used the 0.83PS.S.. Devanathan and colleagues [5] showed that as the voltage decreased, the amount of hydrogen diffused increased and D was not a function of thickness. Detailed research has been conducted on the effect of microstructure on hydrogen diffusion [7]. The concluding remarks on such an effect are that the structural inhomogeneities; line defects, impurities (TiC) or martensitic laths, will trap hydrogen and degrade the microstructure. The lower the hydrogen-defect bonding energy and the less such microstructural inhomogeneities, the less the amount of trapped hydrogen and the less the likelihood of hydrogen degradation. Table 1 shows the variation of such energies with defects. Other researchers have reported their findings on the increase of the number of dislocations and therefore the amount of trapped hydrogen and trapping energies [8,9]. Having a homogeneous structure reduces the risk of hydrogen damage. Variation of D with microstructure and alloying is definite, and it may be stated that the lower the D, the lower the amount of diffused hydrogen [10]. Therefore, if the amount of trapped hydrogen is lowered, the possibility of hydrogen damage is decreased. It may be suggested that by controlling the microstructure, hydrogen degradation is controlled. Considerable research has been previously conducted on the fractography of fractured surfaces. In a stress corrosion cracking study in H2S, Huang and Shaw [11] showed that the crack morphology was quasi-brittle and the observed white markings were considered as a sign of the presence of hydrogen. EXPERIMENTAL PROCEDURE Diffusion measurements have been either conducted by electrochemical charging [5] or a dry gas technique [8]. In the electrochemical method, a steel sample is situated between an anodic cell and a cathodic charging cell. When a potential difference between the two sides is
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established due to the presence of hydrogen on the cathodic side, H diffusion takes place and after awhile is detected at the anodic side. Hydrogen diffusion increases with time reaching a maximum of a steady-state amount. As the negative charging potential is increased, the PS.S. is increased (Nernest equ.). This article represents more than ten years of reseach, beginning at Sheffield University (U.K.) then at Heriot-Watt University (U.K.), and then in Iran. The electrochemical technique was used at Sheffield, while a newly invented method which is a cross technique between the electrochemical and vacuum (gaseous) techniques was employed in Scotland. The results were then correlated with stress corrosion, corrosion fatigue, and case studies. Figures 5 and 6 show the apparatus used in the present investigation.

Figure 5. Devanathan cell construction used for elecrochemical testing

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Figure 6. Apparatus used for electro-vacuum testing The electro-vacuum testing used a cathodic electrochemical cell to charge the hydrogen into steel, and a vacuum (10-7 torr) side leading to a mass-spectrometer to detect the amount of hydrogen diffused through, using a computer. Table 2 gives details of the alloying elements of the steels tested by the electrochemical method. The API 5LX-65 was used to transport liquid gas. Hydrogen-induced cracking was observed in this steel during service, and cracking occured at positions where the microstructure due to the segregation of Mn (= 2%), was martensitic. The steels structure was similar to BS4360 (Table 2). Table 2. Analysis of Steels Used for Hydrogen Permeation Test (Devanathan) Material API X-65 (Low S) API X-65 (High S) BS 4360 BS 4360 (Quenched) C 0.079 0.089 0.13 0.13 Mn 1.33 1.38 1.57 2.23 Si 0.29 0.31 0.32 0.31 S 0.004 0.031 0.007 0.01 P 0.006 0.005 0.008 0.008 Cr 0.11 Ni 0.15 -

The steel samples were Pd-plated and tested in caustic soda (0.1N NaOH) at potentials lower than -1300 mV. During these tests, the effects of thickness, voltage and plastic deformation (after 72% R.A) on variation in D were recorded. Table 3 shows some of the results obtained. Table 3. Results of Devanathan Test (0.1 N NaOH, 2 mm thick) Material API X-65 (Low S) API X-65 (High S) BS 4360 BS 4360 (Quenched) tlag (min) 68.75 77.5 69 253 D (cm2/S X 10-6 ) 1.61 1.43 1.61 0.44

Table 4 gives details of the alloys tested by the electro-vacuum method. Table 4. Steel Analysis Used for Hydrogen Permeation Test (Electro-Vacuum) Material API X-52 AISI 4340 C 0.14 0.38 Mn 1.33 0.73 Si 0.33 0.2 S 0.003 0.016 P 0.008 0.13 Cr 0.05 1.08 Ni 0.03 1.38

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API 5LX - 52 steel may also be used to carry liquid gas or other petroleum products, and AISI 4340 is used as a well casing material. Table 5 shows the results obtained in 0.1N NaOH for these latter two steels. Table 5. Results of Electro-Vacuum Test (0.1N NaOH, 2 mm Thick) Material API X-52 AISI 4340 tlag (min) 242 541 D (cm2/S X 10-7) 4.58 2.05

For the reason of an actual simulation, the steel samples were not plated in the latter tests. During these tests, the effects of environmental change, thickness and voltage were examined (see Table 6). Two cases of fractured surfaces were compared with one another to find footprints of hydrogen. 1. A case of stress corrosion fatigue of high strength steel cables that failed in H2S environment, 2. Another case of stress corrosion fatigue of N.I.O.C drill pipes. It is worth mentioning that other stress corrosion and corrosion fatigue tests were conducted that are not all stated here. The stress corrosion tests were conducted either statically (80%Syield) or dynamically (slow strain rate = 10-5 S-1). The corrosion fatigue tests were conducted at 0.167 Hz frequency and constant stress range. These latter tests were conducted on AISI l055, 1075, and 50B60 in putrid seawater (H2S = 200 ppm) [14]. As the emphasis here is on the kinetics of hydrogen diffusion rather than on fracture morphology, only a few fractographs are presented in this paper. Some of the linear polarization, potential and pH measurements conducted on the cables show the rate and possible change in the types of reactions. Immersion tests were also conducted in the sour environment. Table 6. Results of Electro-Vacuum Test (0.5mm) Material AISI 4340 AISI 4340 AISI 4340 API X-52 API X-52 API X-52 API X-52 Inh. : Inhibitor H2S : Seawater + H2S Environment 0.1 N NaOH Seawater Seawater + Inh. 0.1 N NaOH Seawater H2S H2S + Inh. tlag (min) 82 62 56 90 62 28 42.5 D (cm2/S X 10-7) 0.84 1.12 1.24 0.77 1.12 2.48 1.63

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RESULTS AND DISCUSSION Diffusion tests conducted by the Devanthan's electrochemical method (Table 3) showed that with the increase in sulphur in X-65, D, the diffusion coefficient decreased from 1.61 X 10-6 to 1.43 X 10-6 cm2/S. This was due to the increase in MnS surface area. MnS would act as a trap impeding hydrogen transport. The measured D for BS 4360 was similar in value to that for X-65 and was equal to 1.61 X 10-6 cm2/S. Alloy BS 4360 with higher Mn when quenched showed an increased tlag and a decreased D of 0.44 X 10-6 cm2/S (Table 3). This result was attributed to the presence of fine laths of martensite which is saturated in carbon and is an internaly stressed structure (shear-induced transformation). Figure 7 compares the behaviors of X-65 and the quenched 4360. The figure shows 4360 to have the longer tb. Recharging the test sample (second transient) after the first transient produced a shorter tb and increased D. This was ascribed to the saturation of the traps during the first transient. Lowering the steady-state flux was a sign of reduction in dc/dx according to Fick's first law. However, this may change (i.e., increase the steady-state) for a different alloying element. When BS 4360 was cold worked (72% reduction in area, 0.5 mm thickness), tb increased from 6 to 112 min, and D decreased from 4.62 x 10-6 to 5.34 x 10-7 cm2/S. This was due to increased dislocation density (106 to 1012 cm/cm3) acting as strong traps. Vicker's hardness showed an increase from 183 to 272 HV. When the charging voltage was decreased from -1300 to -1700 mV; D increased from 4.3 x 10 to 6.9 x 10-6 cm2/S. This may be explained according to the Nernest's equation (increase in hydrogen partial pressure):
6

Figure 7. Hydrogen diffusion measurements conducted by Devanathans method (2mm thick) (i) X-65 (low S); (ii) X-65 (high S); (iii) BS 4360; and (iv) BS 4360 (Quenched)
-E = - E 0 + RT ln P H 2 - constant PH ZF

(7)

As the thickness was decreased from 2 to 0.5 mm, D increased from 1.6 x 10-6 to 4.3 x 10-6 cm2/S. This change was only due to the kinetics of the electrodes surface. The electro-vacuum

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tests conducted on API X-52 and AISI 4340 (Fig. 8) were made without Pd coating of the test samples. Published research has shown that the volume of hydrogen diffusing through would increase with the increase in surface scratches as a result of the increase in surface area [12]. Thus, during the present series of tests, all the samples were polished with 600 grade SiC paper and used uncoated. Other investigators reported unsuccesful test results if the samples were not Pd-coated [13]. In the present work, the measured D for X-52 was twice that of 4340. A comparison of the alloying elements of the two metals indicates that AISI 4340 has a higher amount of C, Cr, Ni and S. It is generally believed that elements on the right-hand side of Fe in the periodic table (C, Ni, etc.) repel hydrogen while elements on the left-hand side of Fe (Cr, Nb, etc.) attract hydrogen. A comparison of D values for the electro-vacuum tests with those of the electrochemical experiments reveals that D was 10 times larger (faster) for the electrochemical tests. This is most likely due to the surface impedance of the scales (absence of Pd) in addition to variations resulting from the electro-vacuum test method. Table 6 shows that D changed with the changes in the test environment. Testing AISI 4340 in 0.1N NaOH provided D = 0.84 x 10-7 cm2/s, which is similar to that for API X-52. But when X-52 was tested in H2S, X-52, D increased from 0.77 to 2.48 x 10-7 cm3/S. Linear polarization tests conducted in H2S on AISI 1074 showed that FeS resulted in cathodic depolarization (see Fig. 9). Thus, with the increase in cathodic reaction, the amount of hydrogen reduction and diffusion would increase. This matches the results obtained during diffusion (Table 6).

Figure 8. Hydrogen diffusion measurements by the electro-vacuum testing technique


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Figure 9. Linear polarization (cathodic side) in: (1) seawater + H2S = 300 ppm; and (b) 3.5% NaCl solution The free corrosion potential of a steel in the presence of H2S will change with time. Figure 10 shows that with time (after 219 h) the potential of AISI 1055 increased from -720 to -560 mV. This may be due to the change in FeS stoichiometry, perhaps to FeS2. When the corroded surface was cleaned, it was noted that pits had formed under the black FeS layer (see Fig. 11).

Figure 10. Changes in Ecorr in different H2S concentrations for AISI 1055
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Figure 11. Pitting corrosion of AISI 1055 in H2S Corrosion fatigue and stress corrosion tests were conducted on wires and wire-ropes (AISI 1055, 1074, and 50B60) in an H2S environment. In the fatigue tests, the number of cycles to failure decreased as the maximum stress increased. This was considered as a sign of stress corrosion fatigue failure. Cracks were noted to originate from the corrosion-pits formed under the perforated FeS layer (Fig. 12). Thus, one can say that the crack initiation mechanism is anodic dissolution.

Figure 12. Initiation of microcracks from surface pits (anodic dissolution)


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White markings as a result of hydrogen embrittlement were observed on the fractured surface (Fig. 13). Thus, hydrogen embrittlement could be the mechanism of crack propagation.

Figure 13. Signs of hydrogen embrittlement (white markings) Drill pipe failure (N.I.O.C) showed that in the alkaline environment of the drill mud (pH = 10), fracture was due to a combination of tensile and torsional cyclic stresses. The fractured surface showed a thumbnail fatigue fracture with surface scratches and microcracks acting as the initiating sites. Thus, the initiation and propagation mechanisms seem to be via anodic dissolution. However, the presence of cyclic loading may imply stress corrosion fatigue failure. CONCLUSIONS 1. 2. 3. 4. 5. 6. With an increase in sulphur content, tLag increased. Quenched BS 4360 had a D four times slower than pearlitic structure. D measured by the electro-vacuum method was ten times that by Devanathan. In the presence of H2S, D increased. In the presence of inhibitors, D did not decrease. Reduction in voltage increased D.

REFERENCES 1. R. Gibala and A.J. Kumnick, Hydrogen trapping in iron and steels, in: Hydrogen Embrittlement and Stress Corrosion Cracking, Ed., R. Gibala and R.F. Hehemann, ASM, 1984, p. 61. 2. H.H. Johnson, Overview on hydrogen degradation phenomena, in: Hydrogen Embrittlement and Stress Corrosion Cracking, Ed., R. Gibala and R.F. Hehemann, ASM, 1984, p. 3 3. F.P. Ford, Stress Corrosion Cracking, in Corrosion Processes, Ed., R.N. Parkins, Applied Science Publishers, 1982, p. 271. 4. J. Congleton and I.H. Craig, Corrosion Fatigue, Applied Science Publishers, 1982, p. 209.

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5. M.A.V. Devanathan and Z. Stachurski, Mechanism of hydrogen evolution on iron in acid solutions by determination of permeation rates, Journal of the Electrochemical Society, 1964, p. 619. 6. J. McBreen, L. Naris and W. Beck, A method for determination of the permeation rate of hydrogen through metal membranes", Journal of the Electrochemical Society, Nov. 1966, p. 1220. 7. I.M. Bernstein and A.W. Thompson, The role of microstructure in hydrogen embrittlement, in: Hydrogen Embrittlement and Stress Corrosion Cracking, Ed., R. Gibala and R.F. Hehemann, ASM, 1984, p. 135. 8. H.H. Johnson and R. Way Lin, Hydrogen and deutrium in iron, in: Hydrogen Effects in Metals, Ed., I.M. Bernstein and A.W. Thompson, 1984, ASM, p. 3. 9. K.K. Kim and S. Pyon, Hydrogen permeation through 3.3% Ni-1.6% Cr steel during plastic deformation, Scripta Metallurgica 22, 1988, p. 1719. 10. C.H. Tseng, W.Y. Wei and J.K. Wu, Electrochemical methods for studying hydrogen diffusivity, permeability in AISI 420 and AISI 430 stainless steels, Materials Science and Technology 5, Dec.1989, p. 1236. 11. H. Huang and W.J.D. Shaw, Cold work effects on sulphide stress cracking of pipeline steel exposed to sour environment, Corrosion Science 34, 1, 1993. p. 61. 12. R.L. Reuben, Ph. D. Thesis, Hydrogen Permeation, Open University, U.K. 1980. 13. I.M. Bernstein and A.W. Thompson, Proc. Mechanisms of Environmental Embrittlement in Materials Metal Society, 1978, p. 403. 14. M. Farzam, R. Brook and R.G.J. Edyvean, The fracture of steel wire, strand and rope in marine environments, 31st Corrosison Science Symposium, 11-14 Sept. 1990, Newcastle, England.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CONTROL STRATEGIES FOR THERMOPHILIC SULPHATE-REDUCING BACTERIA P.F. Sanders1, H.M. Lappin-Scott2 and C.J. Bass2
1 2

Oil Plus Limited, Hambridge Road, Newbury, Berkshire, RG14 5TR, England

University of Exeter, Hatherly Building, Department of Biological Sciences, Prince of Wales Road, Exeter, EX4 4PS, England

ABSTRACT
Thermophilic (high-temperature requiring) sulphate-reducing bacteria (tSRB) are responsible for both corrosion of oil production facilities and souring of produced oil. During oil recovery, a range of chemicals is injected into oil reservoirs for various operational reasons. Such chemicals may be designed to inhibit microbial growth, or to specifically inhibit general corrosion. Other chemicals, such as scale inhibitors, oxygen scavengers, H2S scavengers and surfactants, may be also injected. To date, there is little published data on the effect of any of these chemicals on the micro-flora that is known to exist in the oil formation. The effect on sulphide production using a tSRB isolated from an oil bearing chalk formation was monitored in the presence of rock surfaces and individual chemicals. The presence of a surface increased sulphide production, whilst oilfield chemicals produced a variety of responses, from complete inhibition to significant enhancement of sulphide production. Differences were observed within the various classes of treatment chemicals. Some molecules appeared to break down more easily than others under reservoir conditions and thus served to stimulate sulphide production. The data obtained will help to manage oil reservoirs in a more cost-effective and environmentally friendly manner, minimizing both sulphide production and microbial corrosion by determining appropriate chemical selection and dosing regimes. Key Words: Thermophilic sulphate-reducing bacteria, corrosion of oil production facilities, oilfield chemicals, management of oil reservoirs

INTRODUCTION The production of oil worldwide is adversely affected by the growth of bacteria, particularly the sulphate-reducing bacteria (SRB). These may be mesophilic (mSRB), growing optimally at 30C, or thermophilic (tSRB), growing optimally at 60C. Although SRB are encountered in many anaerobic environments, their principal habitat is marine situations, either in sediments or suspended in seawater, where sulphate concentrations are high. SRB activity enhances corrosion of iron and steel in storage tanks, pipelines and equipment as well as creating problems of toxicity and spoilage of the gas and oil. In the reservoir itself, permeability reductions may be caused by growth of bacteria in the pore spaces of the rock leading to reduced recovery efficiency [1-4]. Most attention has been paid to mSRB growing in seawater treatment facilities, where biofilms containing mSRB are responsible for enhancing the corrosion of steel [5]. Recently tSRB have been isolated from
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oilfield reservoirs and production systems [6-8], with significant implications for maintenance and integrity of hot oil production pipework and associated plants [9]. tSRB have also been detected in injection water and open seawater [7,10], together with other thermophilic heterotrophic bacteria, indicating the presence of widespread consortia of thermophilic bacteria in these environments. Temperatures may reach 120C in some oil-bearing formations [11], but are typically 80-100C. tSRB have been shown to grow or survive in this range of temperature [4,7]. Actively growing tSRB readily attach to surfaces, assisted by the production of large amounts of exopolysaccharide [12] and survive adverse conditions by the formation of dormant cells which have been shown to retain viability for long periods of time [8]. These dormant cells may pass through the reservoir rock since they are small and produce less exopolysaccharide. They thus contaminate both the deep reservoir and the production system. In some situations, even starved cells may attach to surfaces and form part of a developing biofilm [13]. Biofilms containing tSRB and other thermophilic bacteria can thus develop on rock surfaces as well as on metal surfaces. When such a biofilm develops on exposed steel, corrosion can be initiated by the production of sulphide or organic acids [14]; when it forms within rocks, permeability reduction can occur. Many microorganisms are able to survive wide and rapid variations in environmental conditions. Renewed interest in the ability of microorganisms to survive low nutrient status has prompted research into bacterial starvation responses [15]. Oil/water mixes produced from reservoirs frequently contain tSRB as they enter topside facilities. Nutrient availability in such situations will vary with the origin of the produced water; therefore, any tSRB in these locations will be responding directly to nutrient stress as well as temperature shifts. Some cells will adopt a starvation/survival mode which may take the form of reduction in cell size with reduced levels of metabolic activity [7]. Additionally, cells adhere to available surfaces [10] and subsequently form biofilms in topside production systems. The ability of tSRB to switch between different growth states, depending upon the environmental conditions, allowing the bacteria to survive extreme or adverse conditions has been described [11]. This, in turn, means that reservoir sulphide souring and corrosion in high temperature systems will be encouraged if a change to more favourable conditions occurs. Biofilms (consisting of vegetative, active, tSRB and other thermophilic anaerobic bacteria) developing in hot oil production systems will give rise to increased sulphide production, which may eventually lead to significant souring of the produced fluids [17]. In addition, the activity of thermophilic bacteria on hot metal surfaces will lead to an increase in microbially influenced corrosion (MIC) due to the local production of corrosive metabolites such as sulphide and organic acids [9,18,19]. The studies described in this paper are part of an ongoing investigation into the survival and activity of tSRB in oilfield reservoirs. A wide range of tSRB was enriched and isolated from a series of surveys on and around North Sea installations. Samples included raw seawater, injection water, well-head samples, production separators and overboard discharge lines at three major oil field production/injection facilities. These isolates were used to conduct a series of laboratory trials related to the control of reservoir souring and associated corrosion implications. Particular emphasis was placed upon the relative importance of starved, dormant (non-sulphide-producing) growth states, the active (sulphide producing)
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vegetative state, and the availability of surfaces and chemical treatments on sulphide generation rates. METHODS Thermophilic Sulphate-Reducing Bacteria Cultures Two oilfields were selected for the isolation of high-temperature, hydrogen sulphideproducing bacterial enrichments. Both fields had fractured chalk reservoir rock, and were experiencing seawater breakthrough and increasing hydrogen sulphide concentrations in the produced fluids. Two consortia (EX251 and EX258) from hot oil producing systems were studied for their tolerances to chemicals and reactions to surfaces. Growth Media Three anaerobic media selective for SRB were prepared: MCP, EX2 and SWM. MCP is a modification of Postgate's E. It contained Na lactate (70% w/w solution 12.5 ml 11 ), Na acetate (50 g l-1), Na propionate (1.0 g l-1), and Na butyrate (0.4 g l-1) with NaCl (25 gl1 ). EX2 contained KH2PO4 (0.4 g l-1), NH4Cl (1.0 g l-1), CaCl2 (0.1 g l-1) MgSO4.7H2O (2.0 g l-1) FeSO4.7H2O (0.5 g l-1), yeast extract (1.0 g l-1), Na2SO4.2H2O (1.0 g l-1), NaHCO3 (2.4 g l1 ), Na pyruvate (6.0 g l-1) and NaCl (25.0 g l-1). SWM was used when a clear medium was required. Na pyruvate (6.0 g l-1) and yeast extract (oxoid, 1.0 g l-1) was added to one liter of artificial seawater solution (ASW). After these additions, the prepared medium was sterilized by filtration (with Whatman's presterilized cellulose acetate filter, 0.45 mm pore size) and dispensed in presterilized bottles in an anaerobic cabinet. Spectrophotometric Sulphide Assay The micro method described here is a modification of those described by Truper and Schlegel [20] and relies on the liberation of sulphide by acidification and subsequent development of methylene blue from n,n-dimethyl-p-phenylene diamine sulphate. Influence of Surface Area on Sulphide Production This experiment was designed to determine whether the area of available surface in a culture vessel exerted an influence on the amount and rate of sulphide production of a culture of tSRB cells. Culture EX251 was selected for this experiment. Several sets of four injection vials were set up containing 0 (control), 0.01, 0.1 and 1 g of washed Bunter sand with 9 ml of SWM. Each vial was inoculated with one milliliter of a three day old culture of EX251 and incubated at 60C. At predetermined sample times, three vials were removed from each treatment set and sampled for sulphide production and metabolic activity. Sulphide Production from EX251 in Long Term Contact with Oil Formation Rock Chalk core chips were distributed in 15 g quantities in a series of presterilized, loosely stoppered injection bottles and placed in an oven at 110C for 36 hours. The bottles were placed in an anaerobic cabinet overnight to deoxygenate the rock pore spaces. EX251 was inoculated as follows: sterile, full strength SWM, 1/10 strength SWM (diluted with ASW) and ASW. 1/10 strength SWM was added to the uninoculated control. Each bottle was crimp sealed to maintain the anaerobic status of the contents and then incubated at 60C. Samples were withdrawn at intervals over several months for sulphide assay.

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Treatment Chemicals and Sulphide Production To determine whether the tSRB utilize a chemical additive, FWM was used. The low nutrient level medium, FWM/8, was prepared by making up 125 ml of FWM to one litre with ASW. Enhanced sulphide production, as compared with an untreated control, indicates the utilization of the chemical by tSRB. Vials containing a two milliliter standard scoop of silica sand (BDH, 100 mesh) were filled with either high or low nutrient medium (FWM or FWM/8) in the anaerobic cabinet. Vials were stoppered, capped and autoclaved at 115C for 10 minutes prior to use. Also, 90 ml of fresh C2 medium was inoculated with five milliliter of a one-week old culture of EX258 grown in C2 medium and incubated at 60C for three days. Chemicals were suitably diluted in either high or low nutrient medium to enable a one milliliter addition to the appropriate individual test vials at the start of the test. On the first day of the test, one milliliter of a three day old EX258 culture was injected into each vial. This was followed by a one milliliter addition of each test chemical to the appropriate set of vials. Each set was sampled for sulphide as soon as the chemical inoculations were complete. The remaining vials were placed in the 60C incubator for the remainder of the test. At predetermined time intervals three vials were randomly selected from each chemical treatment set for sulphide analysis as described above. RESULTS AND DISCUSSION Sulphide Production by Thermophilic Sulphate-Reducing Bacteria with Varying Amounts of Available Surface Figure 1 shows the rate and extent of sulphide production from one consortium inoculated into vials containing defined amounts of crushed Bunter sandstone as a surface for attachment and growth. During the first 24 hours, sulphide concentrations in all four treatments (0, 0.01, 0.1 and 1 g sand) increased to between 30 and 40 ppm, with the least sulphide assayed from the vials containing the most sand (i.e., one gram). However, after a further 24 hours of incubation, the situation was reversed, with those vials containing the most additional surface area yielding the most sulphide (35 ppm). The rest of the range of experimental vials showed a range of sulphide concentrations in accordance with the available surface area. This range was further emphasized at 72 and 96 hours. Sulphide concentration appeared to be directly linked to the available surface area incorporated in the experimental vials. Up to 30 hours of incubation, there was no significant difference between the means. At 54 hours, the mean of data from the vials incorporating one gram of sand was found to be significantly different from the other treatments and the control. By 102 hours of incubation, there was a more significant difference, with the means of each of the sand treatments being significantly different from the control. Thus, increasing the amount of available surface significantly increased the amount of sulphide generated. Sulphide Production by Thermophilic Sulphate-Reducing Bacteria in Long Term Contact with Oil Formation Rock The previously white chips of oil-bearing chalk which were inoculated with ten milliliter of SWM grown culture of EX251 (containing little precipitated material) blackened overnight in an anaerobic cabinet before the experimental nutrient additions were made. The colour change was retained throughout the nine month course of this experiment and was not
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observed in the control bottles containing only chalk chips and SWM/10 medium. The sulphide production is plotted against time in Fig. 2 for each of the nutrient treatments given to the EX251 cells in contact with the chalk. In the bottles with SWM at full strength, there was a rapid increase in sulphide concentrations in the first two days, similar to the previous experiment. This was followed by further increases over the ensuring four weeks until the maximum assayed sulphide was 100 ppm. The concentration of sulphide then steadily diminished to 55 ppm over a period of six months. Extra nutrient was added at the start of week 34, and sulphide measurements continued. Due to dilution caused by the added nutrient, the sulphide concentrations were reduced immediately after the fresh nutrient was added; however, within two days, the SWM cultures showed renewed sulphide production which peaked at 60 ppm within ten days of the extra nutrient being supplied.

Figure 1. Sulphide produced from EX251, grown in the presence of 0.01, 0.1 or 1 g sand compared with a control containing no additional surface. n = 3; all error bars displayed (+/- SE of mean). At 54 h, p < 0.05 for 1 g sand treatment and by 102 hours all sand treatments were significantly different from the control (p < 0.01) When SWM/10 was added to the bottles, there was a discernible increase in sulphide output in the first three to four weeks; the maximum sulphide concentration achieved was 20 ppm and thereafter remained at about 15 ppm until the nutrient addition at week 38. After an initial drop in assayed sulphide to 10 ppm, the sulphide concentration again rose in the following ten days to 15 ppm, and as in the first part of the experiment, gradually declined.

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In the experiments where cultures were offered ASW only, low levels of sulphide (c. 10 ppm) were observed when in contact with the chalk chips until the 36th week. The final two readings, taken at 37 and 38 weeks, showed a reduction in assayed sulphide to 6 and 3 ppm respectively. No sulphide was detected in the control series without added bacterial culture.

Figure 2. Long term survival and sulphide generation from cells of EX251 on oil-bearing chalk chips. Sulphide produced consistently available nutrient at start of experiment. After further addition of nutrient at 34 weeks, renewed sulphide generation occurred. Results plotted are the average of duplicate readings from two separate experimental vessels in each case Both cultures EX251 and EX258 secreted extracellular polysaccharide which aids attachment to surfaces [12,21]. The presence of exopolysaccharide in corrosive biofilms on metal surfaces containing SRB from Brazilian oilfield waters has been demonstrated by ruthenium red staining techniques followed by electron microscopy [22]. Similar procedures used in the authors laboratory have demonstrated the presence exopolysaccharide secretion by tSRB. The implication of the results is that thermophilic reservoir SRB reduce sulphate more efficiently when attached to a surface such as sandstone, chalk or metals. Work by Laanbrook and Geerlings [23] demonstrated an increase in sulphide production by SRB cultures when clay particles were incorporated in the growth media. Other studies, on nonsubterranean mSRB taken from paddy fields and lake sediments, have suggested a physiological advantage for bacteria attached to particulate material in sulphate deficient situations [24]. It is also possible that attached cells were disadvantaged due to a reduction of cell surface area available for solute transport at the physical points of contact in non-sulphide limited conditions. This conclusion does not agree with other researchers [14, 25] who have consistently reported the advantageous properties of commensal biofilm habitats. However, it is clear from the work described here that there are factors affecting the metabolism of sulphide-generating organisms in biofilms which have yet to be fully examined.

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Effects of Treatment Chemicals on Thermophilic Sulphate-Reducing Bacteria A wide range of treatment chemicals is employed in the oil production process. These chemicals are designed to prevent scale formation (scale inhibitors), prevent corrosion (corrosion inhibitors), and remove trace amounts of oxygen from the water (oxygen scavengers), as well as the biocides which are designed to kill bacteria in the injection water and the near wellbore area. The use of organic and inorganic chemicals could have a significant impact upon the growth of bacteria in the system. A test method was devised which assesses the impact of the chemicals on tSRB in different growth states. A wide range of treatment chemicals was tested, as shown in Table 1. Future testing will make use of sandpod and cross-flow rock core flood equipment. Typical sulphide production curves from some of the chemicals are shown in Figs. 3-18. Sulphide production by EX258 was affected in a variety of ways by treatment with the chemicals tested. In some instances there was a clear indication of a detrimental effect (i.e., enhanced sulphide production in comparison with the control). In others, the effect was to reduce the amount of sulphide produced (i.e., an effective control of sulphide). In some cases there was a switch in the effect noted, most frequently from an initially beneficial response to a detrimental response. This may be due to degradation of the applied chemical or adaptation of the tSRB to its presence.

Figure 3. Sulphide production by EX258, treated with THPS at 100 ppm, under high nutrient conditions

Figure 4. Sulphide production by EX258, treated with THPS at 25 ppm, under high nutrient conditions

Figure 5. Sulphide production by EX258, treated with THPS at 100 ppm, under low nutrient conditions

Figure 6. Sulphide production by EX258, treated with THPS at 25 ppm, under low nutrient conditions

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Table 1. Generic Types of Oilfield Treatment Chemicals Tested, Together with Concentrations Typically in-Use and Tested
Injection Water Type Chemical Function Scale Inhibitor Sea or Aquifer Water Produced Water 20 20 20 20 20 20 10

Corrosion Inhibitor

Filter Aid

Chemical Type and Dose Rate (ppm) Polyacrylate 5 Polyacrylate Phosphinocarboxylic acid 20 Polycarboxylate Polyvinyl sulphonate 20 Phosphonate Copolymers 20 Ethylene diamine tetra MPA Organic phosphonate 5 Diethylene-triamine-penta MPA Amines Imidazoline (oil sol) Substitued alcohols Amine salts (water sol) Quaternary amines 5 Carboxylic acids Polyamine 1 Ferric sulphate Ferric chloride Ammonium bisulphite Sodium bisulphite 7 14 Polyacrylamide Polyglycol Phenol formaldehyde alkoxylate Polyol Polyamine Oxyalk phenolic + PAG Oxyalk phenolic Anthroquinone QAC Isothiazolone THPS Glutaraldehyde

Oxygen Scavenger

Deoiler Demulsifier

2-10 10 30

20 2-4

Biocide

Continuous 100-400 100-400 Penta methylene phosphate PCA Hexaphosphonate Sulphonated polymer

Scale Inhibitor Squeeze

Drag Reducer Dispersant Antifoam

Polymer in mineral oil

70 Fatty acids & esters (intermittent) Silicones in HC 20 20

Under high nutrient conditions, EX258 consistently produced a maximum of 100-120 ppm sulphide after three days. Under low nutrient conditions, this sulphide production was limited to 40-50 ppm. THPS-biocide (a quaternary phosphonium compound) fully inhibited sulphide production at a 100 ppm dose rate under low nutrient conditions (Fig. 5); when high nutrient conditions prevailed, there was an initial inhibition of sulphide production for four days (Fig. 3). However, the biocide evidently acted as a biostat since sulphide generation occurred at day 7. At 25 ppm, this effect was more pronounced, with sulphide production occurring in both high and low nutrient conditions (Figs. 4 and 6).

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Figure 7. Sulphide production by EX258, treated with glutaraldehyde at 100 ppm, under high nutrient conditions

Figure 8. Sulphide production by EX258, treated with glutaraldehyde at 25 ppm, under high nutrient conditions

Figure 9. Sulphide production by EX258, treated with glutaraldehyde at 100 ppm, under low nutrient conditions conditions

Figure 10. Sulphide production by EX258, treated with glutaraldehyde at 25 ppm, under low nutrient conditions

Figure 11. Sulphide production by EX258, Figure 12. Sulphide production by treated with ammonium bisulphite EX258, treated with ammonium (oxygen scavenger) at 7 ppm continuous, bisulphite (oxygen scavenger) at 7 ppm under high nutrient conditions continuous, under low nutrient conditions

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Figure 13. Sulphide production by EX258, treated with proprietary surfactant, at 30 ppm slug, under high nutrient conditions

Figure 14. Sulphide production by EX258, treated with proprietary surfactant, at 30 ppm slug, under low nutrient conditions

Figure 15. Sulphide production by EX258, treated with phosphonate corrosion inhibitor, at 20 ppm continuous, under high nutrient conditions

Figure 16. Sulphide production by EX258, treated with phosphonate corrosion inhibitor, at 20 ppm continuous, under low nutrient conditions

Figure 17. Sulphide production by EX258, treated with QAC corrosion inhibitor, at 20 ppm continous, under high nutrient conditions

Figure 18. Sulphide production by EX258, treated with QAC corrosion inhibitor, at 25 ppm continuous, under low nutrient conditions

Glutaraldehyde showed a similar pattern of sulphide generation, but in this case, control appeared to be less effective, and sulphide concentrations were higher than in the control after two to three day period (Figs. 7-10). These results emphasize that under-dosing biocides can lead to stimulation rather than reduction in the souring problem. No effect on sulphide generation rates was seen when oxygen scavenger was used (Figs. 11-12). Although widely used in seawater injection systems for oxygen control, such chemicals are thought to be unlikely to stimulate additional sulphide from SRB activity in the formation. Some surfactants (used in production systems) were effective as biocides against tSRB (Figs. 13-14), and the use of produced water containing such compounds would exhibit a good degree of microbiological control near the wellbore. Corrosion inhibitors (added in seawater and produced water injection systems) showed a wide range of effects on sulphide production by tSRB (Figs. 15-18). This is due to the variety
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of active agents used in this class of chemical: phosphonate types appear to enhance sulphide production, having no biocidal properties, whilst QAC formulations can act as very good biocides. The combined effects of chemical dosing can now be assessed with respect to the potential for enhancing or depressing sulphide production by SRB. ACKNOWLEDGEMENTS We wish to thank Agip SpA, Chevron U.K. Ltd, Maersk Olie og Gas A.S., Nalco/Exxon Energy Chemicals Ltd., the Saudi Arabian Oil Company and the UK Department of Trade and Industry for their valuable support and help during this study. REFERENCES 1. B.N. Herbert and P.D. Gilbert, Isolation and growth of sulphate-reducing bacteria, in: Microbiological Methods for Environmental Biotechnology, 1984, pp. 235-257. 2. W.P. Iverson and G.J. Olson, Problems related to sulfate-reducing bacteria in the petroleum industry, in: Atlas R.M. (ed) Petroleum Microbiology, MacMillan Publishing Company, New York, 1984, pp. 619-641. 3. B.N. Herbert, Reservoir souring. in: Hill Shennan, Watkinson (eds) Microbial Problems in the Offshore Oil Industry, J Wiley and Sons Ltd, London, 1987, pp. 6372. 4. C.J. Bass, P.F. Sanders and H.M. Lappin-Scott, Starvation and survival of thermophilic sulphate-reducing bacteria from North Sea oil reservoirs. in: Proc 6th Int Symp Microbial Ecology, International Committee on Microbial Ecology (ICOME), 1992, Paper C4-3-3. 5. W. Lee, Z. Lewandowski, P.H. Nielsen and W.A. Hamilton, Role of sulfate-reducing bacteria in corrosion of mild steel: A review, Biofouling 8, 1995, pp. 165-194. 6. J.T. Rosnes, T. Torsvik and T. Lien, Spore forming thermophilic sulfate-reducing bacteria isolated from North Sea oilfield waters, Appl Environ Microbiol 57, 1991, pp. 2302-2307. 7. C.J. Bass, H.M. Lappin-Scott and P.F. Sanders, Bacteria that sour reservoirs: New concepts for the mechanism of reservoir souring by sulfide generating bacteria, J. Offshore Technol 1, 1993, pp. 31-37. 8. K.O. Stetter, R. Huber, E. Blochl, M. Kurr, R.E. Eden, M. Fielder, H. Cash and I Vance, Hyperthermophilic archaea are thriving in deep North Sea and Alaskan oil reservoirs, Nature 365, 1994, pp. 743-745. 9. P.F. Sanders, H.M. Lappin-Scott and C.J. Bass, Corrosion implications of thermophilic sulphate-reducing bacteria in oil reservoirs, Proceedings UK Corrosion 94, Vol. 4, Bournemouth, 1994, pp. 116-127. 10. S. Walsh, H.M. Lappin-Scott, H. Stockdale and B.N Herbert, An assessment of the metabolic activity of starved and vegetative bacteria using two redox dyes, J Microbiol Methods 24, 1995, pp. 1-9. 11. M. Magot, C. Hurtevent and J.L. Crolet, Reservoir souring and well souring. in: Progress in the Understanding and Prevention of Corrosion, 1993, pp. 573-575. 12. C.M.L. Cutinho, F.C. Magalhaes and T.C. Araujo-Jorge, Morphology of the surface coat and extracellular matrix of sulphidogenic biofilms enriched in sulphate-reducing
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13.

14. 15.

16. 17. 18.

19.

20.

21. 22.

23. 24. 25.

bacteria involved in biocorrosion processes in the offshore oil extraction industry off Brazil's coast, J. Gen Appl Microbiol 40, 1994, pp. 271-276. H.M. Lappin-Scott, C.J. Bass, K. McAlpine and P.F. Sanders, Survival mechanisms of hydrogen sulphide producing bacteria isolated from extreme environments and their role in corrosion, Int Biodegrad Biodeterior 34, 1994, pp. 305-319. W.A. Hamilton, Sulphate-reducing bacteria and anaerobic corrosion, Ann Rev Microbiol 39, 1985, pp. 195-217. H.M. Lappin-Scott, C.J. Bass and P.F. Sanders, Monitoring and detection of different growth states of thermophilic SRB, In: Proceedings UK Corrosion 1992, Volume 3, Session D, 1992. A.S. Kaprelyants, J.C. Gottschal and D.B Kell, Dormancy in non-sporulating bacteria, FEMS Microbiology Reviews 104, 1993, pp. 271-286. R.Y. Morita, Review: The starvation-survival state of microorganisms in nature and its relationship to the bioavailable energy, Experientia 46, 1990, pp. 813-817. W.J. Cochrane, P.S. Jones, P.F. Sanders, D.M. Holt and M.J. Mosley, Studies on the Thermophilic Sulfate-reducing Bacteria from a Souring North Sea Oil Field, Society of Petroleum Engineers (SPE), European Petroleum Conference Paper SPE 18368, 1988. M.J. Mosley, D.M. Holt, W.J. Cochrane and P.S. Jones, Laboratory studies on the growth and activity of thermophilic sulphate-reducing bacteria in relating to the colonisation and corrosion of steel surfaces at high temperatures, Proceedings UK Corrosion 89, Blackpool, 1989. H.G. Truper and H.G. Schlegel, Sulfur metabolism in Thiorhodaceae 1. Quantitative measurements on growing cells of Chromatium okenii, Antonie van Leeuwenhoek J Microbiol 30, 1964, pp. 225-238. H.M. Lappin-Scott and J.W. Costerton, Bacterial Biofilms and Surface Fouling, Biofouling 1, 1989, pp. 323-342. C.M.L. Cutinho, F.C. Magalhaes and T.C. Araujo-Jorge, Ultrastructure of sulphidogenic biofilms rich in sulphate-reducing bacteria causing corrosion in the offshore oil extraction platforms off Brazil's Atlantic coast, J. Gen Appl Microbiol 40, 1994, pp. 227-241. H.J. Laanbrook and H.J. Geerlings, Influence of clay particles (Illite) on substrate utilisation by sulfate-reducing bacteria, Arch Microbiol 134, 1983, pp. 161-163. M.S. Fukui and S. Takii, Survival of sulfate-reducing bacteria in oxic surface sediment of a seawater lake, FEMS Microbiol Eco 73, 1990, pp. 317-322. H.M. Lappin-Scott, J. Jass and J.W. Costerton, Microbial Biofilm Formation and Characterization, SAB Technical Series, Vol. 30, Denyer, Gorman and Sussman (eds), Blackwell Scientific Publications, 1993, pp. 1-12.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CORROSION EVALUATION OF AUSTENITIC AND DUPLEX STAINLESS STEELS IN SIMULATED HYDROGEN SULPHIDE CONTAINING PETROCHEMICAL ENVIRONMENTS K. Saarinen1 and E. Hamalainen2
1

VTT MANUFACTURING TECHNOLOGY P.O. Box 1704, FIN-02044 VTT, Finland

Helsinki University of Technology, Laboratory of Engineering Materials Puumiehenkuja 3, FIN-02150 Espoo, Finland

ABSTRACT
The combined effect of hydrogen sulphide, carbon dioxide and chlorides on the sulphide stress cracking (SSC) behavior of several austenitic and duplex stainless steels was studied in high temperature environments by using slow strain rate (SSR) tests and immersion tests of stressed specimens. The initiation of SSC is considered to require the breakdown of the passive film whereby the localized corrosion resistance can be related to the SSC resistance and to the pitting resistance equivalent number (PREN) of an alloy. The evaluation of the usefulness of different PREN values showed that the SSC resistance of a certain alloy can be evaluated by using the PREN values including the nickel content of an alloy. According to the results, as the PREN values increase, the SSC resistance increases. In the environments studied, the critical temperature for cracking of austenitic alloys having a PREN value under 45 was below 150C, and as the PREN value was over 70 the critical temperature for cracking was higher than 150C. The nickel-based alloy having a PREN value of 140 was not susceptible to SSC even at a temperature of 230C with high partial pressures for H2S and CO2. When the SSR test was used, brittle behavior was observed in the duplex alloy having a PREN value of 56, even with small amounts of H2S in the chloride environment. Key Words: Alloy steels, stainless steel, corrosion, stress corrosion, cracking (fracturing), petrochemical environments, oil fields, hydrogen sulphide

INTRODUCTION Corrosion of steels in sour gas environments is a complex process involving many reactions between the environment and construction materials producing different kinds of corrosion products [1]. For passivating alloys, the reduction of sulphur is the most feasible cathodic reaction that accelerates localized corrosion in cathodically reducible corrosion systems [2]. The anodic dissolution has been observed to increase and the passivation of corrosion-resistant alloys has been observed to retard significantly as the hydrogen sulphide content of the environment increases [3]. Besides hydrogen sulphide, other chemicals appearing in the solution have to be considered [4]. In sour wells, the oil and natural gas are often contaminated by hydrogen sulphide, the content of which may vary from a few parts per million up to 30% [5]. In the presence of
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hydrogen sulphide, the atomic hydrogen that is produced on the surface of the steel by the corrosion reactions tends to enter the steel and cause embrittlement. This phenomenon is called sulphide stress corrosion cracking (SSC). SSC susceptibility is enhanced by chlorides, and the results obtained by Fliethmann et al. indicate that the cracking mechanism is a mixed mechanism of hydrogen- and chloride-induced SSC [6]. Besides cracking, considerable general corrosion can be observed due to presence of carbon dioxide that acidifies the mixture of brine and oil [5]. In order to optimize the SSC behavior of the austenitic and duplex stainless steels, the chemical composition and the ferrite/austenite ratio have to be considered [7]. Also the microstructure, hydrogen diffusion coefficients [8] mechanical properties, heat treatment conditions, grain size and form of nonmetallic inclusions play an important role in the SSC resistance of construction materials [9,10]. Thus, for reasonable assessment of the applicability of a duplex stainless steel in a specific sour environment, it is important to consider practical experience and to use suitable SSC test methods, both regarding the loading procedure and the environment [11,12]. Localized corrosion resistance is related to the chemical composition, and thereby, to the pitting resistance number (PREN) of an alloy. The initial process of SSC can be the breakdown of passive film [7,13] whereby the increase in the chromium and molybdenum content of the alloys increases the passivity of the surface layer. However, it has been pointed out that the ferrite phase of duplex stainless steels is richer in chromium and molybdenum than the austenitic phase, and hence, the PREN of the austenitic phase seems to play a more important role in pitting resistance, and hence, in SSC resistance of duplex stainless steels than the PREN of the ferrite phase [7]. The SSC susceptibility of duplex stainless steels is also greatly affected by the ferrite/austenite ratio, distribution and grain size. The threshold stress for SSC in simulated sour environments has been observed to be highest at the -content of 40 to 45%, and an alloy with a -content exceeding 80% is reported to have a high susceptibility to pitting and intergranular corrosion [14]. To evaluate the SSC behavior of selected austenitic and duplex stainless steels in high temperature H2S solutions, slow strain rate (SSR) tests and immersion tests of stressed specimens were used. EXPERIMENTAL PROCEDURE Test Materials The austenitic stainless steels investigated in this study were delivered by Outokumpu Polarit Oy, and the duplex stainless steels and the two experimental powder metallurgically produced alloys were delivered by Rauma Materials Technology Oy. The reference materials selected were Nicrofer 6020, Nicrofer 5716 and Nicrofer 5923; they were and manufactured by VDM Nickel-Technologies AG and delivered by Cronimo Co. The chemical compositions of the test materials and their PRENs are presented in Table 1. PREN1, PREN2 and PREN3 reflect the effect of alloying elements, and PREN number 4 correlates with the ferrite content in a duplex alloy so that the higher the PREN4 value, the lower the ferrite content. Test Equipment and Test Environments The high temperature sulphide stress cracking studies were carried out by using the SSR method with round tensile test specimens (Fig. 1) and U-bend specimens. To insure the stability of the test environment during testing, the Materials Research Shuttle Laboratory facility was used. The facility consists of a high temperature and high pressure autoclave with a room
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temperature storage tank and a recirculation loop. The facility is also equipped with an environment monitoring system to control the water chemistry of the autoclave. The facility is assembled into a freight container (Fig. 2) that was transferred outside the laboratory facilities in order to avoid any indoor leakages of hydrogen sulphide. The corrosion potential measurements were carried out using an Ni/NiSO4 reference electrode, and the results are presented in the scale of a standard hydrogen electrode. Table 1. Nominal Composition of the Materials Used in the Study as Provided by the Manufacturers Material POLARIT 725 POLARIT 757 POLARIT 774 POLARIT 778 DUPLOK 21 DUPLOK 22 DUPLOK 25 DUPLOK 26 DUPLOK 27 DUPLOK 27 PM Inconel 625 PM Nicrofer 6020 Nicrofer 57161 Nicrofer 5923 C 0.027 0.049 0.02 0.024 0.012 0.013 0.015 0.023 0.01 0.04 0.02 0.01 0.01 0.01 Si 0.41 0.49 0.55 0.4 0.6 0.53 0.43 0.2 0.28 0.38 0.51 0.13 0.05 0.12 Mn 1.45 1.51 1.46 0.46 0.58 0.52 0.62 0.72 0.52 1.16 0.32 0.17 0.37 0.15 S 0,001 0.007 0.001 0.001 0.008 0.01 0.008 0.01 0.008 0.005 0 P 0.034 0.029 0.015 0.019 0.032 0.033 0.03 0.03 0.032 0.022 0 0.005 0.005 0.005 Cr 18 17.1 20 19.8 20.7 23 24.5 26.2 27.1 25.9 21.6 21.8 19 22.5 Ni 8.6 10.6 24.7 21.5 8.3 6.1 6.4 7.6 7.9 6.6 Bal. Bal. Bal. Bal. Mo 0.019 2.51 4.48 6.15 2.8 3 3 2.95 3 3.3 8.2 8.5 15 14 Cu 0.18 0.16 1.67 0.79 1.25 0.19 1.45 0.68 2.5 2.1 0.06 0.06 0.08 0.01

Material Al Co Nb Fe N PREN1 PREN2 PREN3 PREN4 POLARIT 725 0.001 0.17 0 Bal. 0.0565 20 35 30 POLARIT 757 0 0.21 0 Bal. 0.046 27 42 45 POLARIT 774 0.022 0.22 0 Bal. 0.0765 37 76 73 POLARIT 778 0.024 0.37 0 Bal. 0.21 47 72 79 DUPLOK 21 0.03 0.05 0.06 Bal. 0.05 32 42 49 -8 DUPLOK 22 0.02 0.1 0.02 Bal. 0.15 38 40 50 -10 DUPLOK 25 0.03 0.07 0.04 Bal. 0.14 39 42 52 -11 DUPLOK 26 0.02 0.07 0.02 Bal. 0.22 43 46 55 -9 DUPLOK 27 0.01 0.05 0.03 Bal. 0.24 45 47 57 -10 DUPLOK 27 PM 0.02 0.05 0.01 Bal. 0.25 45 44 56 -9 Inconel 625 PM 0.02 0.06 3.7 4 0 49 172 140 Nicrofer 6020 0.16 0.05 3.4 3 0 50 173 142 1 Nicrofer 5716 0.09 0.1 0.04 6.5 0 69 172 171 Nicrofer 5923 0.2 0 0.03 0.5 0 69 170 167 1 The tungsten (W) content of the alloy Nicrofer 5716 is 4% PREN1 = Cr + 3.3 Mo + 32 N. PREN2 = Cr + 2 Ni + 1.5 Mo [15]. PREN3 = Ni + 1.2 Cr + 5.5 Mo [16]. PREN4 = Ni + 0.5 Mn + 30*(C + N) - 1.1*(Cr + Mo + 1.5 Si) + 8.2 [14]

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The test environments were water-based deaerated solutions containing different amounts of NaCl, H2S and CO2. The materials tested in each experiment and the test type are presented in Table 2. Also given in Table 2, are the contents of the different species in each experiment and the pH value of the test solutions. The exposing time of the U-bend specimens in test 1 was 100 hours and in test 2 it was 400 hours. After testing, the specimens were examined using an optical microscope; the failures were reported. For failure cases, a fractographical inspection was performed.
0.05 A-B 3.810.05

0.03 A-B
Rmin6.4

A
M8

Rmin6.4

0.4

B
M8

12.5

25.40.05
70

12.5

Figure 1. Dimensions of round tensile test specimens machined for the SSR tests. Before testing the specimens were polished electrolytically

Figure 2. Schematic representation of the Materials Research Shuttle Laboratory used in the SSR tests. During testing, the test
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environment was kept constant with a water recirculation system Table 2. Test Matrix of the Studies Test 1 NaCl Temperature [wt-%] [C] 5 200 H2S [bar] 8 CO2 [bar] pH 3 Materials Tested POLARIT 725 POLARIT 757 DUPLOK 22 All in Table 1 except Inconel 625 PM Inconel 625 PM DUPLOK 27 PM DUPLOK 27 PM DUPLOK 27 PM Test Type U-bend

2 3 4 5 6

20 25 20 20 20

150 230 93 93 93

5 70 20 0.5 0.1

50 35 40 85

3 2.5 2.7 2.6 4.2

U-bend SSRT SSRT SSRT SSRT

RESULTS In test 1, failures were observed in all of the alloys tested. In the austenitic alloys, the fracture was brittle and intergranular. In the duplex alloy, the fracture partly followed the phase boundaries between the ferrite and austenite faces, but mainly the fracture was transgranular and brittle. The corrosion potential of all the alloys during the experiment was near -100 mV (SHE). In test 2, failures were observed in the alloys POLARIT 725 and POLARIT 757. The failure mode in these austenitic alloys was mainly intergranular, as observed in test 1. No failures in the duplex alloys were observed despite clear general and pitting corrosion. Pitting corrosion was observed in the duplex alloys having a PREN1 value smaller than 40. In the austenitic alloys, no similar pitting corrosion was observed. The corrosion potential of all the alloys during experiment was near -100 mV (SHE). In test 3, no evidence of brittle behavior was found for Inconel 625 PM. The fracture was ductile, and the elongation to fracture was 40% which corresponds to the elongation observed in the SSR test conducted in a nitrogen gas reference environment. In test 4, the fracture of the DUPLOK 27 PM specimen was brittle and transgranular. The elongation to fracture was only 8%, and the reduction in area was 18%. In the reference test in nitrogen gas, the elongation to fracture was 32% and the reduction in area 60%. In test 5, the hydrogen sulphide partial pressure was much lower than in test 4. The fracture was still brittle and transgranular. Also secondary cracking was observed (Fig. 3). The elongation to fracture was 26%, and the reduction in area was 25%. In test 6, the hydrogen sulphide partial pressure was still lower than in test 5. The fracture was mainly brittle (Fig. 4), but ductile areas were also observed in the fracture surface (Fig. 5). The initiation and the outermost circle of the fracture surface were brittle, whereas the center of the fracture surface was ductile.

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Figure 3. SEM micrograph of the DUPLOK 27 PM specimen after test 5 secondary cracks are visible (35x)

Figure 4. SEM micrograph of the brittle fracture surface


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of the DUPLOK 27 PM specimen after test 6 (2000x)

Figure 5. SEM micrograph of the ductile fracture surface of the Duplok 27 PM specimen after test 6 (2000x) DISCUSSION The corrosion resistance of passivating alloys is mainly determined by the stability of the protective layer on the alloy surface. According to the high temperature pH-potential diagrams for Fe-S-H2O, Cr-S-H2O and Ni-S-H2O systems [17], at pH 3, the surface layers in deaerated systems consist mainly of nickel and iron sulphides. As the content of the alloying elements of the alloys increases, the volume of the sulphides in the surface layer increases. In the high temperature water containing sulphur, the breakdown of molybdenum sulphide greatly influences the corrosion behavior of highly alloyed alloys containing molybdenum [17]. Despite the fact that the SSC susceptibility of a certain alloy is the sum of several factors like chemical composition, microstructure, mechanical properties and heat treatment conditions, in this study the main considerations were the chemical compositions of the alloys studied. It is known that the corrosion cracking susceptibility of austenitic alloys increases as the temperature increases. The more alloying elements the material has, the higher the critical cracking temperature is. In this study, a temperature of 150C in test 2 was high enough to cause intergranular cracking in the austenitic alloys having a PREN1 value under about 30, a PREN2 value under about 40 and a PREN3 value under about 45. Therefore, the critical temperature for cracking of austenitic alloys having the PREN values mentioned is below 150C. On the other hand, no failures were observed in the austenitic alloys having a PREN1 value over 37, a PREN2 value over 72 and a PREN3 value over 73. Therefore, the critical temperature for cracking of austenitic alloys having the PREN values mentioned is over 150C. Since only iron and nickel
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sulphides are stable in the environments studied, the failure cases of the austenitic alloys were apparently related to the various nickel contents of the different alloys. The nickel contents of the unfailed specimens were clearly higher than those of the failed specimens. Therefore, for materials selection purposes, the PREN equations including the nickel content of alloys are recommended for use in H2S-containing environments. It is also known that the cracking resistance of duplex alloys is enhanced compared to austenitic alloys having the same level of alloying elements and mechanical properties. Normally the initiation and the growth of cracks in duplex stainless steels take place in the ferrite phase of an alloy. In this case, however, the cracking was observed to grow not only in the ferrite phase, but also in the austenite phase. This was probably due to the high contents of hydrogen sulphide, and therefore high contents of hydrogen, in the test environments. In test 1, the duplex alloy failed although the PREN1 value of the duplex alloys was much higher than that of the failed austenitic alloys. The PREN2 and PREN3 values including the nickel content of the alloys were, however, at the same level in all of the failed specimens. Therefore, the correlation between the content of alloying elements and the SSC resistance was better with the PREN values including the nickel content of an alloy. In test 2, the difference between the PREN2 and PREN3 values was noted. The PREN2 value showed no difference between the failed austenitic alloys and the unfailed duplex alloy. The PREN3 values of the failed austenitic alloys were lower than the PREN3 value of the unfailed duplex alloy. Therefore, the PREN3 value is recommended for evaluating the SSC resistance of austenitic and duplex alloys. The usefulness of the PREN4 value correlating with the ferrite content of a duplex alloy could not be evaluated in this study due to the small number of experiments with different duplex alloys. The SSR tests showed that the SSR method is aggressive since brittle behavior was observed in the DUPLOK 27 PM alloy having a PREN3 value of 56 even with small amounts of H2S in the environment. The fracture surface of DUPLOK 27 PM was mainly transgranular and mainly in the ferrite phase. The nickel-based alloy Inconel 625 PM was on the contrary resistant towards SSC even at very high temperature with high contents of hydrogen sulphide, carbon dioxide and chlorides in the environment. CONCLUSIONS In this work the evaluation of the corrosion and SSC behavior of several austenitic and duplex stainless steels in hydrogen sulphide containing environments was made using the SSR test method and U-bend specimens. According to the results: 1. When evaluating the SSC resistance of a specific alloy, the PREN values including the nickel content should be used, 2. The PREN3 value, which did not over emphasize the effect of nickel, gave the best correlation between the content of alloying elements and SSC, 3. The critical temperature for cracking of austenitic alloys having a PREN3 value under 45 was below 150C in aggressive H2S-containing environments, 4. The critical temperature for cracking of austenitic alloys having a PREN3 value over 70 was higher than 150C in aggressive H2S-containing environments,

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5. A small decrease in H2S partial pressure had a greater effect on the SSC resistance of DUPLOK 22 than bigger changes in the temperature and in the NaCl content of the environment, 6. In the austenitic alloys, the fracture mode was mainly intergranular, 7. In the duplex alloys, the fracture occurred partly on the phase boundaries of the ferrite and austenitic faces, but the fracture was mainly transgranular, 8. The nickel-based alloy Inconel 625 PM was not susceptible to SSC, even in extremely aggressive H2S-containing environments, 9. SSR is an aggressive test method, and brittle behavior was observed in the DUPLOK 27 PM alloy having a PREN3 value of 56 even with small amounts of H2S in the environment, and 10. As the hydrogen sulphide partial pressure was lowered to 0.1 bar, partly ductile fracture was observed in the DUPLOK 27 PM alloy. ACKNOWLEDGEMENTS This study was financed by the Technology Development Centre of Finland, Outokumpu Polarit Oy, Rauma Materials Technology Oy and VTT Manufacturing Technology. The authors acknowledge these organizations for their financial support and for providing the test materials. Also Cronimo Co. is acknowledged for providing the reference test materials. REFERENCES 1. G.I. Ogundele and W.E. White, Some observations on the corrosion of carbon steel in sour gas environments, Corrosion 42, 7, 1986, pp. 398-408. 2. A. Miyasaka, et al., Environmental aspects of SCC of high alloys in sour environments, Corrosion 45, 9, 1989, pp. 771-780. 3. A. Miyasaka, et al., Prediction of critical environments for active-passive transition of corrosion resistant alloys in sour environments, ISIJ International 31, 2, 1991, pp. 194200. 4. Z.A. Foroulis, Role of solution pH on wet H2S cracking in hydrocarbon production, Corrosion Prevention & Control, August 1993, pp. 84-89. 5. R. Garber, et al., Sulfide stress cracking resistant steels for heavy section wellhead components, Journal of Materials for Energy Systems, 1985, pp. 91-103. 6. J. Fliethmann, et al., Autoklaven-Untersuchungen der Spannungsribkorrosion von Fe-CrNi-Legierungen in NaCl/CO2/H2S-Medien, Werkstoffe und Korrosion 43, 1992, pp. 467474. 7. M.F. Brunella, et al., Stress corrosion cracking in sour environments of martensitic and duplex stainless steels, Proceedings of International Conference on Stainless Steels, Chiba, June 10-13, 1991. Tokyo 1991, ISIJ, Vol. 1. pp. 264-271. 8. Th. Bollinghaus, H. Hoffmeister and C. Middel, Scatterbands for hydrogen diffusion coefficients in steels having a ferritic or martensitic microstructure and steels having an austenitic microstructure at room temperature, Welding in the World 37, 1, 1996, pp. 16-23.

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9. S.V. Artamoshkin, Effect of the microstructure and nonmentallic inclusions on the susceptibility of low-alloy steels to sulfide stress corrosion cracking. Translated from Fiziko-Khimicheskaya Mekhanika Materilov 27, 6, 1991, pp. 60-66. 10. A.A. Omar, et al., Factors affecting the sulfide stress cracking resistance of steel weldments, CORROSION/81, April 6-10, 1981, Toronto. Canada. Paper No. 186. 11. H. Eriksson and S. Bernhardsson, The applicability of duplex stainless steels in sour environments, Corrosion 47, 8, 1991, pp. 719-727. 12. M.C. Place, et al., Qualification of corrosion resistant alloys for sour service, CORROSION/91, March 11-15.1991, Cincinnati, Ohio, USA, Paper No. 1. 13. A. Miyasaka and H. Ogawa, Corrosion performance and applications limits of corrosionresistant alloys in oilfield service, Corrosion 51, 3, 1995, pp. 239-247. 14. T. Kudo, et al., Stress corrosion cracking resistance of 22 % Cr duplex stainless steel in simulated sour environments, Corrosion 45, 10, 1989, pp. 831-838. 15. K. Denpo, et al., A selection method for high alloy materials for sour service, Proceedings of Engineering Solutions for Corrosion in Oil and Gas Applications, Milan, Italy, November 14-17, 1989. pp. 2-1 - 2-14. 16. S. Azuma and T. Kudo, Crevice corrosion of corrosion-resistant alloys in simulated sour gas environments, Corrosion 47, 6, 1991, pp. 458-463. 17. C.M. Chen, et al., Computer-calculated potential pH diagrams to 300C, Electric Power Research Institute, California, USA, Palo Alto 1983, EPRI NP-3137, Vols. 1-2.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

DAMAGE OF PUMP LINKAGES AND TOOL JOINTS CAUSED BY CRACK CORROSION A. Kinzel Amtliche Materialprfanstalt fr Werkstoffe des Maschinenwesens und Kunststoffe Appelstr. 11 A, D-30167 Hannover, Germany

ABSTRACT
The Amtliche Materialprfanstalt (AMPA) is an official materials testing institute and a subordinate board of the Ministry for Economy, Technology and Traffic of Lower Saxony, which is a federal state of the Federal Republic of Germany. The AMPA works in a lot of fields of materials testing, quality testing, quality assurance and damage investigation. The special fields of the AMPA include acceptance testing, supervision and inspection in the field of plant and pipeline construction for natural gas and oil. Because of this, the AMPA is often used by operators of pipelines or plants to give their expert opinions in cases of damage. Two damage investigations will be given in this article. They are damage to several pump linkages and damage to a tool-joint. Key Words: Pump linkage, tool joints, damage investigation, acceptance tests, inspection

INTRODUCTION Pump linkages and tool joints are used for pumping oil and gas from a depth of about 1,500 m in northern Germany. The pump linkages have lengths of about 6-10 m and diameters of 7/8 in up to a depth of 400 m and 3/4 in beyond that depth. The pump linkages reported here are directly connected. Because of tapping of different caverns from one starting point, the drilling hole is often curved in to a horizontal drilling situation. The pump linkages can follow these curves, because of their oscillating movement within the hole, the linkages have proctection devices against mechanical damage made of plastic which are placed at several defined areas along every linkage. The puming frequency is low-cycle and depends on the length and weight of the equipment. The pumped medium is a mixture of about 2% crude oil and 98% salty water. These pump linkages are connected directly, whereas other pumping equipment uses tool joints to connect their linkages. The tool joint has a length of about 0.5 m and a diameter of about 0.2 m. The pumping rate is about 2,000 l/minute. PUMP LINKAGE The damaged pump linkages were made of 20 NiMo 8. These linkages can normally be used for an operating time of about 18 months. For the case of damage in question, the pump linkages broke after an operating time of 3-6 months. Operation was between 4,000 and 13,000 hours for at least 1.1-3.5 million oscillating units. All of them were broken at depths
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of 500-1,000 m, so the broken linkages were 3/4 in diameter. These pump linkages were broken directly beneath the connecting areas of the linkages. Besides this, the mode of operation of pumping was changed. The frequency of pumping was halved, which led to increased vibration in the pump linkages. The mechanical stress on pump linkages is oscillating stress because of its own weight, and therefore, mass inertia, as well as bending stress especially in the transition sections to more bend-stiff areas. Further on, corrosion is caused by aggressive components within the pumped oil (salty water) especially if the corrosion protective layer is damaged. Visual inspection showed that there was no visible coarse surface damage. All breaks were in transition sections to more bend-stiff areas of the pump linkage (Fig. 1) and looked very similar to fatigue fracture or crack corrosion (Fig. 2). The corrosion protective layer was not regular in terms of thickness of layers and showed small blisters on the surface (Fig. 3). Within a metallographic inspection, a faultless purity and texture was noticed. The pump linkages had no faults in the material and its texture. Near the surface, a slight reduction of carbon content was visible (Fig. 4) as well as a rough surface in the base material with detached corrosion protective layer (Fig. 5). Testing of the mechanical and technological properties of the puming linkages disclosed no faults. The required tensile strength and extension could be reached by all test samples. Also the materials composition met the demands.

Figure 1. Breaking of a pump linkage (K 2149/6)

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Figure 2. Breaking area (K2149/11)

Figure 3. Blisters on the protective surface (K2165/20)

Figure 4. Reduction of carbon content near the surface (M 23370)

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Figure 5. Rough surface of base material with a detached corrosion protective layer (M 233415) TOOL JOINT The object of this investigation was a broken tool joint (7 3/8 in OD x 4 9/16 in ID, 5 1/2 in IF connector with 5 in drill pipe, grade G 105, Fig. 6). The built-in rope length was 3,600 m, the pumping rate was 2,000 l/min at a pressure of 180 bar, the coupled load was 160 tons, and the torque at top-drive about 41,500 N/m. The breaki was at a depth of 2,173 m and occurred while clearing the hole. The linkage had been stored in open air from 1986 to joining in 1995.

Figure 6. Broken tool joint (K 2182/27A) The break was vertical to the tool joint axis and looked like a fatigue fracture (Fig. 7). The starting point of the break was near the transition area to the pivot (Fig. 8), and the fatigue fracture area was only a small part of the whole break area. Near the starting point, a corrosion area with cracks was detected. A metallographic inspection revealed faultless purity and texture. The materials analysis met the demand as did the mechanical properties of the material.

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Figure 7. Break area of the tool joint (K 2182/25A)

Figure 8. Starting point of the break (K 2185/1) DAMAGE ANALYSIS Pump Linkage Within the transition sections to more bend-stiff areas, there is a combination of normal oscillating stress and bending stress. Further on, and combined with an aggressive pumped medium and a damaged corrosion protective layer, tension-induced corrosion had started. After initiating a first crack, this had lead to crack corrosion. A second crack about 24 mm below the first one was detected at one of the pumps linkages, which is another indication of crack corrosion (Fig. 9). Increased cracking is mostly determined by oscillating frequency, tension amplitude and corrosion effects. The low-cycle operation of the pump linkages may have had a negative effect. The area near the cracks starting point had a low crackincreasing velocity and a lot of corrosion effects, whereas the break area showed a higher crack-increasing velocity combined with reduced corrosion effects. The damage was caused by an insufficient corrosion protective layer covering the rough materials surface with an irregular thickness. The small blisters may have been caused by fouling or corrosion before being coated by the protective layer or by a lack of resistance to the aggressive medium. Therefore, it can be concluded that the damage-causing event was a coating process which did not meet the demand. Tool Joint Because the tool joint was stored in the open air for a long time, corrosion was initiated within the damaged area. Besides this, the damaged area is a transition area to a zone with increased tension. The combination of both, corrosion and the tension during operation lead to the first cracks. Further operation and the tension peak lead to crack growth, crack
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corrosion and fatigue fracture. Because of the low percentage of fatigue fracture area, it can be concluded that the operation tension must have been high to break the tool joint.

Figure 9. Corrosion crack about 24 mm below the break (M 23414) CONCLUSIONS Corrosion caused by inadequate protective layers or by incorrect storing leads to initiation of cracks during operation. The oscillating of the parts increases the cracking. This is very dangerous for operation because the failure could not be detected in most cases by visual inspection before use. The failure seemed very surprising for the operation team, and a cost-intensive repair must be done, while the pumping system is not in operation. Therefore, attention has to be paid to effective quality management and quality inspection before using such parts to avoid these failures.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

ANALYSIS OF SOILS POSSIBILITY TO GIVE RISE TO PIPE METAL STRESS CORROSION CRACKING V.G. Antonov and S.A. Loubenski All-Russian Scientific Research Institute of Natural Gases and Gas Technology (VNIIGAS), p. Rasvilka, Leninsky rajon, Moscow region, 142717, Russia

ABSTRACT
The target of the present study is to analyse the possibility of soils, sampled along the routes of gas mains laid without cathodic protection, to give rise to pipe metal stress corrosion cracking (SCC). The tests included soils taken both on gas pipelines operated for 30 years without failure and on pipelines that had failed due to SCC. The pipe steel specimens were tested by the constant rate slow deformation method in soil suspensions taken on gas pipelines that had failed due to SCC. A change of the main parameters which characterise steel resistance to cracking was observed. This change included a decrease in the plastic properties of the metal, namely, a decrease in the relative elongation and reduction of area, and the formation of surface corrosion cracks near the place of failure. The results of the experiments show that the soils taken on gas pipelines which had failed due to SCC may promote the formation of surface corrosion cracks. Key Words: Stress corrosion cracking, gas pipeline, soil, constant rate slow deformation method.

INTRODUCTION Today, SCC is one of the serious problems in the gas industry. Last year, SCC was the cause of some failures in gas pipelines in Western Siberia and Central and Northern Russia. The attempts to explain SCC on gas mains only by hydrogen embrittlement or carbonate cracking are not correct since many years of experience in the operation of offshore cathodic protected gas pipelines and laboratory tests of the resistance of pipe steels to hydrogen embrittlement show that the content of hydrogen absorbed by the metal under cathodic polarization is less than the critical content which leads to embrittlement. The Laboratory of Corrosion-Resistance Materials and Corrosion (VNIIGAS) has conducted investigations which showed that SCC of pipe steels at potentials from 1.0-1.2 V (SHE) in carbonate media with hydrogen numbers between 7.0 and 11.0 had not occurred. THE TARGET OF THE INVESTIGATION The target of the present study was to analyse the potential of soils sampled along the routes of gas mains to give rise to pipe metal stress corrosion at corrosion potentials, i.e., without a cathodic protection system.

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EXPERIMENTAL PROCEDURE The investigations were carried out on soils taken on gas mains which had not been subjected to failure due to SCC (soils A and B), on soils taken on failed gas pipelines having been under operation from 6 to 18 years that failed due to SCC (C (Western Siberia), D (Northern Russia), and E (Central Russia)), on aqueous solutions of carbonates and chlorides, on a medium specially designed in VNIIGAS for conducting corrosion tests, and a selection of pipe steels. The pipe steel samples were made according to NACE Standard TM 0177 (Testing of Metals for Resistance to Sulphide Stress Cracking at Ambient Temperatures). The soil samples were dried and crushed in a mortar. A weighted sample was placed in a flask followed by the addition of distilled water in the ratio of 1000 g water to 1000 g soil. The suspension was placed in a cell and was given some time to settle. The corrosion tests were conducted on round specimens 6.0 mm in diameter, using a special test unit (MP- 5-8B type) with a travel rate of active entertainment of 1.8 x 10-6 m/sec. The specimens were measured and marked before the test in order to determine their relation elongation and reduction of area after the test. The specimens were degreased with organic solvent using a common method and placed in a 250-cm3 cell. Then the cell was filled with the test solution. The specimens were held for 72 hours followed by setting the required deformation rate. All tests were carried out at natural aeration and ambient temperature. The tests on SCC resistance were conducted on not fewer than 4 specimens in each medium. The tests ended when the specimen failed. Failed specimens were washed, dried and measured. The test results were omitted when failure took place in the units holder, or due to metallurgical defects or along the marks. The SCC resistance was estimated by the relative change in the properties of the metal tested in air and in corrosive media, and by the formation of secondary corrosion cracks on the specimens surface. The elongation and reduction of area were calculated on the basis of GOST 1497-84 (Metals: Methods of Tensile Tests): = (l - l0) x 100 / l0 (1)

where : = the elongation (%) l0 = the initial design length of a specimen (mm) l = the length of a specimen after its failure (mm) = (S0 - S) x 100 / S0 (2)

where: = the reduction (%) S0 = the initial cross-section area of a specimen (mm2) S = the minimal cross-section area of a specimen after its failure (mm2)

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RESULTS AND DISCUSSION The test results are given in Tables 1, 2, 3 and 4. The electrochemical measurements made on pipe steels in aqueous suspensions of soils showed the following:

The pH values of the aqueous extracts of soils sampled on failed gas pipelines were
between 5.6 and 6.0 (C, D, and E), and the pH of soil suspensions (A and B) are between 7.6 and 10.6. Failures of pipe steels due to SCC were not observed in soils A and B.

The corrosion potentials of pipe steels in the soils sampled on gas pipelines which
failed due to SCC are between -0.56 and -0.58 V (SHE) (C, D, and E), the corrosion potential in soil with a pH of 7.6 (A) was -0.48 V (SHE), and the corrosion potential in soil with a pH of 10.6 (B) was -0.20 V (SHE).

The general corrosion rate for pipe steels in all types of soil did not exceed 0.01
mm/year. Aqueous suspensions of soils C, D, and E contained hydrogen sulphide, acetic acid, formic acid and compounds of lead, selenium and arsenic. The SCC resistance tests showed that in such systems as aqueous solutions of chlorides and carbonates and the soil suspensions A and B, the main parameters characterising steel resistance under this test method are close to the parameters of the steel set tested in air. Table 1. Resistance of Steel X-65 Specimens to SCC Determined by the Constant Rate Slow Deformation Method in Media of Different Compositions Medium pH Corrosion Potential, V (SHE) - 0.43 -0.44 -0.06 -0.44 -0.20 -0.52 -0.56 (%) 20.4 10.8 23.6 21.7 18.8 23.0 15.3 17.2 (%) 65.0 25.8 59.9 66.9 57.6 60.0 42.2 45.6 No Yes No No No No Yes Yes Presence of Corrosion Cracks

Air (Control) Solution Developed by VNIIGAS 3% NaCl NaHCO3 - NaCO3 Soil of Pipeline A Soil of Pipeline B Soil of Failed Pipeline C Soil of Failed Pipeline D

5.1 6.8 9.6 7.6 10.4 5.8 5.8

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Soil of Failed Pipeline E

5.6

-0.56

21.3

56.1

Yes

When pipe steel specimens were tested in the soil suspensions sampled on the pipelines which failed due to SCC, there was a change in the main parameters characterising steel resistance to cracking, namely, a decrease in the metal ductility (decrease in elongation and reduction of area) and the formation of surface corrosion cracks near the point of failure. Table 2. Resistance of Steel X-70 Specimens to SCC Determined by the Constant Rate Slow Deformation Method in Media of Different Compositions Medium pH Corrosion Potential, V (SHE) - 0.43 -0.44 -0.52 (%) 25.2 7.4 21.0 14.3 , (%) 46.1 11.0 43.1 21.2 No Yes No Yes Presence of Corrosion Cracks

Air (Control) Solution Developed by VNIIGAS 3% NaCl Soil of Failed Pipeline C

5.1 6.8 5.8

Table 3. Resistance of Steel X-56 Specimens to SCC Determined by the Constant Rate Slow Deformation Method in Media of Different Compositions Medium pH Corrosion Potential, V (SHE) - 0.43 -0.44 -0.52 -0.56 , (%) 28.1 21.0 21.2 14.2 16.1 , (%) 59.4 38.1 50.1 48.3 38.1 No Yes No Yes Yes Presence of Corrosion Cracks

Air (Control) Solution Developed by VNIIGAS 3% NaCl Soil of Failed Pipeline C Soil of Failed Pipeline D

5.1 6.8 5.8 5.8

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Table 4. Resistance of Iron (99.9%) Specimens to SCC Determined by the Constant Rate Slow Deformation Method in Media of Different Compositions

Medium

pH

Corrosion Potential, V (SHE) - 0.43 -0.44 -0.52

, (%) 24.2 19.3 23.9 23.2

, (%) 77.5 53.5 72.8 75.0

Presence of Corrosion Cracks

Air (Control) Solution Developed by VNIIGAS 3% NaCl Soil of Failed Pipeline C CONCLUSIONS

5.1 6.8 5.8

No Yes No Yes

The laboratory test results show that the soils sampled on gas pipelines which failed due to SCC favour the formation of surface corrosion cracks, i.e., the main cause of SCC was the physical-chemical interaction between the metal and the components of the soils (hydrogen sulphide, acetic acid, formic acid and compounds of lead, selenium and arsenic).

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

A MYSTERIOUS DOWNHOLE CORROSION FAILURE IN AN OIL WELL A. Husain and A. Hasan Materials Application Department Kuwait Institute for Scientific Research P.O. Box 24885-Safat 13109, Kuwait

ABSTRACT
Recently, the failed downhole tubing from one of the oil wells in a Kuwaiti oil field was examined at the Materials Application Department of the Kuwait Institute for Scientific Research. This paper presents the results of a failure investigation carried out on the J55 steel tubing materials used in many downhole oil wells in that particular oil field area. The results showed that the failure of the tube was due to localized attack in the form of pitting and crevice corrosion that initiated on the internal surface of the tubes. In contrast, no downhole tubing failures were reported for any of the other oil wells located in the same field and exposed to the same aquifer environment and operation conditions. The internal side of the failed tube plate was exposed to the oil/water stream with a 73% water cut and high salinity content in addition to CO2 and H2S corrosive gases. The preliminary results of the investigation indicate that the likely causes of this type of tubing corrosion failure may be related to corrosive environmental effects combined with metallurgical or mechanical properties of the steel tubing material. Moreover, the combined effects of both chloride and CO2 and H2S species under certain condition are widely known to cause accelerated, premature corrosion failure in oil well tubing. In this study, a material failure case in the oil field will be discussed. Several attempts were made to determine the exact cause of the failure found in this oil well. However, no convincing evidence as to the specific cause of the failure was found, due to the additional detrimental effects of many other factors. Key Words: Oil field corrosion, oil well tubings, downhole equipment corrosion, CO2 corrosion, H2S corrosion.

INTRODUCTION Recently, two steel joints in a section of downhole tubing failed due to severe perforations. Visual inspection revealed that the downhole tubing experienced severe corrosion damage and complete perforations of the tubes walls. To elucidate the causes of the tubing failure, the company requested the Kuwait Institute for Scientific Research (KISR) to carry out specific tensile, hardness, and scanning electron microscopy (SEM) examinations. The problem was first thought to be an isolated example of a manufacturing defect; however, the present study indicates that the cause of failure merits further investigation. Information gathered on the oil well and failed parts indicates that only one well, No. W41, experienced accelerated corrosion failure. It was indicated that the downhole tubing was exposed to the oil/water stream for 0 days prior to failure. Two perforated tube joints were
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supplied by the company for an investigation into the causes of the perforations. The first tube sample, designated as Joint No. 33, had one perforated hole (Fig. 1a). The second tube sample, designated as Joint No. 60, had four perforated holes (Fig. 1b). An additional nonperforated tube was also examined to compare its quality with that of the failed tubes. Each tube measured 35 cm in length, 60.75 mm in outside diameter and 4.49 mm in wall thickness.(Appendix A contains full details of the operations condition and production data). This report presents the results of the investigation as well as a discussion of the likely causes of failure and a possible solution to the problem. LABORATORY EXAMINATIONS Chemical Analysis and Metallographic Examinations of the Material The material of the tube was chemically analyzed to confirm its composition and to ensure that it complied with the requirements of the API J55 specifications. The analysis was carried out on a cleaned section cut from the tubes. A metallographic examination was carried out to identify the microstructures of the asreceived, perforated tubing samples. The examination was conducted on metallographically prepared specimens cut from one of the failed tube joints. The metallographic preparation included grinding the specimens with silicon carbide papers of the grade sequence: 320, 600, 1000 and 1200 grit. This was followed by polishing with 3 and 6 m diamond abrasive pastes, and rinsing with distilled water and acetone. Finally, the specimens were etched in 2% nital etchant solution to reveal the microstructure and the second phase precipitates or inclusions. Microscopic Examinations of Perforations and Energy Dispersive Spectroscopic (EDS) Analysis Optical microscopy and SEM were used to observe the perforations and the dark hydrocarbon deposits, or scale, found along the internal surfaces of the tubes. The failed tubes were initially sectioned into two halves in a longitudinal direction away from the defective areas before the microscopic examinations. The examinations were conducted before and after the removal of the deposits as well as on the etched surfaces. The purpose of etching was to identify the microstructure at the initiation sites of the perforations. Qualitative EDS analysis was carried out to determine the composition of the deposits both inside and outside the perforations. X-ray diffraction (XRD) analysis was carried out to determine the composition of the deposits scrubbed from the internal surfaces of the perforated tubes. Mechanical Properties of the Tubing Materials Mechanical tensile and hardness tests were conducted to investigate the quality of the failed as-received tubing material sample. These tests were carried out to confirm the tubings mechanical properties as well as to ensure that they complied with the requirements of the API J55 specifications for downhole tubing material.

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(a)

(b)

(c)

Figure 1. Perforation resulting from localized corrosion attack of internal tubing surface:
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(a) Joint No. 33; (b) Joint No. 60; and (c) condition of interior of tubing surface RESULTS Chemical Composition and Microstructure of the Material Table 1 presents the results of the chemical analysis of the material of the perforated tubes and the as-received un-used tubes. The alloy of both tube samples was carbon steel with minor elemental constituents of Cu, Si and Cr. The carbon and sulfur contents of the alloy were not properly determined due to analytical limitations. Table 1. Chemical Composition of the As-Received and Perforated Tubes Element AsReceived Tube (wt% 0.45-0.6 0.3 0.015 0.03 0.32 1.45 0.06 Balance Perforated Tube (wt% 0.45-0.6 0.33 0.05 0.03 0.33 1.56 0.06 Balance Error

C Si S P Cu Mn Cr Fe

0.05 0.05 0.005 0.005 0.005 0.005 0.01 0.01

Structurally, as indicated by the equilibrium diagram of iron and iron carbide, the alloy for both tubes was composed of ferrite and pearlite. The structure of the iron-carbon alloy is shown in the photomicrographs of Fig. 2a and b. It can be seen that the microstructure is typical of carbon steel material in terms of the presence of equal proportions of ferrite and pearlite phases. Microscopic Examinations of Perforations and EDS Analysis of Deposits in the Failed Tubes Visual and optical microscopic examinations of the failed tubes revealed several perforations that appeared to originate from inside the tubes. Examinations of the internal surfaces, after splitting the tubes into halves, showed numerous crevices and pit-like shapes in a somewhat straight line along the longitudinal axis. The internal surfaces also exhibited many rounded, mutually intersecting pits lying partially beneath a mixture of dark scale of hydrocarbon deposits with iron oxide and dry oil residue. The scales were observed inside and around penetrated areas. Cleaning the metals surface revealed the presence of crevice corrosion in addition to the observed pits. The crevice attack appeared the same beneath all kinds of deposits, with an approximate depth of 1.21 mm. Some of these crevices or pit-like shapes penetrated the full thickness of the tubing (Fig. 1c). Visual examinations of the asreceived tubing indicated the presence of mill scale that covered the internal surface of the tube.
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EDS analysis of the deposits inside the pit-like shapes showed that they were enriched mostly with sulfur, chloride, calcium and iron and, to a much lesser extent, with manganese and silicon (Fig. 2c). Sulfides were present in the deposits and corrosion products. Aggressive sulfur-and chloride-containing species were also concentrated beneath the iron oxide layer (Fig. 2d).

(a) as-received tube

(b) perforated tube

(c) EDS analysis inside of pits

(d) EDS analysis beneath deposit layer

Figure 2: (a and b) SEM micrographs of etched specimens both showing ferrite and pearlite phases distributed in equal proportion; and (c and d) EDS analysis of compounds in the perforated side
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XRD analysis of the scrubbed scale obtained after cleaning the internal surfaces of the perforated tubes indicated the presence of magnetite (Fe3O4), iron oxide hydroxide [FeO(OH)], iron carbonate (FeCO3) and iron. This suggests that the layers of deposit present on the internal surfaces of the tube are possibly from mill scale (as Fe3O4) and also from corrosion by-products of carbonic acid combined with iron in the form of FeCO3. Mechanical Properties of the Tubing Material Table 2 presents the mechanical properties of the tubing material in terms of tensile strength, yield strength, and hardness. The results of the mechanical testing showed that the tubing materials fall within the same range of API J55 specifications. Table 2. Mechanical Properties of the Tubing Material Tubing Material As-received Tube Perforated Tube Tensile Stress* (MPa) 675 675 Tensile ** Stress (MPa) 695 + Yield ** Stress (MPa) 480 + Rockwell Hardness (HRB) 94 94

*Approximate tensile stress based on hardness measurements. + Standard tensile test samples were not prepared due to severe perforations of the tube wall (data obtained with tensile test machine).

DISCUSSION Both the optical microscopy and the SEM examinations indicate that the failure of the tube was caused by a typical case of localized corrosion caused by differential acid concentration cell. The fact that localized attack occurred on the internal surfaces of the tubing at accelerated rates during 10 days of exposure indicates that the cause of this corrosion phenomenon is related to the aggressive nature of the environment. Under normal conditions in deaerated oil field environments of CO2 and H2S, one would not expect corrosion perforation to occur at such a fast rate. Generally, the corrosion rates of steel are not as high in sour water systems (i.e., those usually observed in oil field systems with a high water cut) as they are in CO2 systems due to the somewhat protective nature of sulfide scale (FeS mackinawite) relative to iron carbonate (FeCO3) unless oxygen contamination has occurred [1]. Typically, deaerated systems with less than 0.02 bar CO2 partial pressure are not considered excessively corrosive to steel, but they can exhibit corrosion rates of up to 0.20 mm/year (10 mpy). As the partial pressure increases, the corrosion rate increases. At 0.5 bar CO2 partial pressure, the corrosion rate of steel (i.e., 1 mm/year (40 mpy)) is high enough to require inhibition if the bicarbonate is low as in condensed water systems. At 2.0 bar CO2 partial pressure, the system would be at a pH in the range of 3.5-4.5, and can be considered
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severe from the standpoint of weight loss corrosion (i.e., a corrosion rate of > 2.5 mm/year (100 mpy)). The combination of hydrogen sulfide and carbon dioxide is more aggressive than hydrogen sulfide alone and is frequently found in oil field environments. Once again, the presence of even minute quantities of oxygen can be disastrous. In all cases, increased velocity would be expected to increase the corrosion rate of steel [2]. The following ferrous corrosion products would form with H2S and CO2 in the presence of oxygen and low solid water. For corrosion, they are the only products of concern: Fe + H2S FeS + H2 (Sour corrosion) Fe + H2O + CO2 FeCO3 + H2 (Sweet corrosion) 4Fe + 3O2 2Fe2O3 (Oxygen corrosion) (1)

(2)

(3)

The iron sulfide produced by reaction (Eq. 1) generally adheres to the steel surfaces as a black powder or scale. The scale tends to cause local acceleration of corrosion because the iron sulfide is cathodic to the steel; this usually results in deep pitting during O2 reduction reactions along this FeS layer. Oxygen will provide a high electrochemical potential because it is a strong, rapid oxidizing agent. This means that it will easily combine with electrons at the cathode, and allow the corrosion to proceed at a rate limited primarily by the rate at which oxygen can diffuse to the cathode. The primary concern in this case would be when the H2S partial pressure is 0.05 psi. As a first approximation, calculations of the partial pressure of both carbon dioxide and hydrogen sulfide are useful for the present case study in predicting the degree of corrosivity of the oil well (i.e., No. W-41): Partial pressure of CO2 = 1500 x 0.07 = 105 psi Partial pressure of H2S = 1500 x 0.001 = 1.65 psi Using the CO2 partial pressure as a yardstick to predict corrosion, it was found that the CO2 partial pressure was above 30 psi, which usually indicates the onset of corrosion, however, in this study, the volume fraction of CO2 over that of H2S was < 200. This indicates that the presence of small concentrations of H2S play a prominent role in the corrosion mechanism involved in the reactions (Eqs. 1-3). If the given volume fraction is > 200, then carbon dioxide will be the controlling factor for the reactions; this does not apply to the present case and its oil field environment. According to a computer modeling program [3] used in this study to estimate the corrosion rate on the pitted tubing, and based on the analysis of the production data in addition to the operation conditions given in Appendix A, the following two cases were predicted:

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1. The production of oil and formation water with H2S and CO2 under deaerated conditions (i.e., oxygen is excluded) would result in a corrosion rate resulting in tubing perforation after more than two years of exposure, and 2. Changing the production conditions to include oxygen in addition to H2S and CO2 would result in a worst-case corrosion rate leading to tubing failure in about eight days (10 days in service to actual failure). Based on the examination and this preliminary computer analysis from CLI International, Inc., it was assumed that case 2 is likely to model the situation involved in the tubing failure. However, according to on-site field inspection of the oil well and observation of the huge amount of gas pressure released from the wellhead, when the pressure valve was opened, the theoretical assumption based on the combined effects of oxygen and corrosive gases could not be accurate because oxygen had no chance to diffuse into the well tubing under such a high-pressure release of gas at the outlet. Moreover, there was no chance for oxygen to be drawn into the well through leaky valves or the expansion of joints in this solidly designed oil well tubing part. Therefore, the only solution was to look for other causes of damage that would have enhanced the corrosivity of the gases (i.e., CO2 and H2S) and could have contributed to the acceleration of the rate of corrosion attack. On observing the case history of the oil well (see Appendixes A and B) and by comparing the performance of this oil well with respect to the nearest oil wells located within one kilometer in the same oil field, the following suspected factors can be assumed: The failure of the tubing was initiated due to differential acid concentration cell (case 1) that had been established beneath crevices that were hydrocarbon in nature, and being strengthened with a very high propagation rate of corrosion attack caused by one or more of the following suspected factors:

Failure in the electrical submersible pump materials (ESP) as indicated in


Appendix B, Electrical power problems (i.e., a rectifier power supply problem), Galvanic coupling effects between the materials of the ESP and the internal surface of the tube, Failure including doglegs, splits, and leakage of the well casing materials at a certain depth adjacent to the well tubing promoted after the burning of the well during the Iraqi invasion, and Faulty electrical ground connection (ground electrical contact was made to the well tubings), and Stray current effect from either the ESP or other exterior effects.

CONCLUSIONS 1. Metallographic examination, SEM and mechanical testing of the tubing did not show any major differences between the as-received and the failed tubing in terms of mechanical properties or the presence of second phase particles and inclusions. The minor additions of Cu, Cr and Si did not contribute much to the poor corrosion properties of the steel tubing; however, the presence of higher contents of nonhomogenous MnS in both tubing specimens may also indicate the possibility of

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MnS inclusion caused by variable degrees of extrusion during pipe manufacturing. Manganese sulfide inclusions are known to be detrimental to corrosion resistance. 2. Oxygen was not the most likely cause of the perforation. 3. A solution to combat the tubing corrosion problem is to use a more expensive approach by carefully evaluating and selecting corrosion-resistant alloys or to inhibit corrosion with chemicals to minimize corrosive attack on the steel tubing. 4. Internal coating of tubing using powder coating systems (e.g., Tuboscope Vetco International) or fiberglass reinforcements have proven to be successful in many oil industry and downhole applications. REFERENCES 1. F.W. Smith, Structure and Properties of Engineering Alloys, New York, MacGrawHill, 1993. 2. NACE. Corrosion control in petroleum production. National Association of Corrosion Engineers, Publication No. TPC 5, Houston, Texas, 1979. 3. Private communication with Dr. R.D. Kane during his visit to Kuwait, 1995.

APPENDIX A Case History for Well No. W-41 Industry: A Kuwaiti oil production Specimen location: Downhole tube from Well No. W-41 Specimen orientation: Vertical Years/days in service: 10 days Salinity: 80,000 to 90,000 ppm Average water cut: 73%-Temperature: 116oF (47oC). Total pressure: 1250-1500 downhole CO2 Concentration: 7 vol% H2S Concentration: 0.11 vol% Failed samples given: Two failed tubing samples with tube specifications J55-2 3/8 in. O.D. Sample designation: Sample No. 3 from Joint No. 33. Downhole tubing depth: 1008 ft Failure condition: One perforated hole Sample designation: Sample No. 4 from Joint No. 60. Downhole tubing depth: 1832 ft Condition: 4 perforated holes Engineering component connection: Electrical submersible pump (ESP) at 2,258 ft Oil well fluid level: static 527 ft. Dynamic 558 ft

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APPENDIX B .History of the Premature Failure of Downhole Equipment and Tubings in Well No. W-41.
Visual Inspection Findings of Pulled Equipment Failure Failure Run Life No. Date (months) 1 Jan. 2.5 90 2 May 3.5 90 3 Oct. 5 92 Pump ___ ___ corroded Motor burnt shorted burnt Protector leaking leaking ___ Separator ___ damaged ___ PSI Cable Failed Tubing Joint Joint No. of No. Holes ___ ___ ___ pump Joint. #29 #30 #59 ___ one hole one hole Remarks

not R.C. work damage ___ ___ ___ ___

Iraqi Invasion DDI while RIH DDI while RIH

Jan. 90 Jul. 93 Jan. 94 Nov. 94

good

5 6

6 6

___ good

burnt with 2 holes burnt Ext. corr. erosion corrosion. shorted (red alloy)

___

good

___

good

External corrosion Erosion corrosion

___ good

Ext. Corr. left in hole F.C. burned & parted good pump Joint one hole

DDI while RIH

10

good (red alloy)

Nov. 94

0.5

good (red alloy)

Jan. 95 Feb. 95 Mar. 95

1.5

10

10 days

11

40 days

good (carbon steel) good (carbon steel) good (carbon steel)

12

Jul. 95 Sept. 95

42 days

13

Failed tubing Jts (Times Failed) Depth of tubing Section Failed Frequently

29 (1)

good (carbon steel) good (carbon steel) 30 (1)

hole & good Ext. Corr. (Red Alloy) (carbon steel) reused shorted good +big hole stuck (Red Alloy) (carbon (carbon steel) steel) good good good (carbon (carbon (Red Alloy) steel) steel) good good good (carbon (Carbon (red alloy) steel) steel) wire bolts<------corroded---connection --------->red alloy loose (carbon steel) good good 1/16 inch hole (carbon (red (red alloy) steel) alloy) good red red alloy (carbon alloy steel) 33 37 39 (1) (1) (1)

___

hi Volt hi Amp

___

good

___

good

#59 3 holes DDI while &#63 &1 RIH hole (KSRC) #33 1 hole KISR &#60 &4 hole #37, #39, #50 5 holes 3 holes 7 holes

___

___

___

___

#50, #58, #59

red alloy 50 (2) 58 (1) 59 (3) 60 (1)

N-80 grade tubing N-80 grade tubing 63 pup (1) joint (2)

900 ft- 1000 ft

1800 ft- 1925 ft

Production data for Well No. W-41: Operating Conditions: -Average production rate = 2,750 BFPD At subsurface (downhole) -Average water cut = 73% Temp.:116C -Salinity = 80,000- 90,000 ppm Pressure:1250-1500 psi -Setting depth of: CO2 Conc.:7 Vol.% Electrical Submersible Pump (ESP) = 2,258 ft. H2S Conc.:0.11 Vol% Dynamic fluid level = 558 ft. Static fluid level = 527 ft. -GOR = 635

At Surface 85C 110 psi 15 Vol.% 1.1 Vol.%

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

METHODOLOGIES FOR ASSESSMENT OF CRUDE OIL CORROSIVITY IN PETROLEUM REFINING S. Tebbal and R.D. Kane CLI International, Inc. 14503 Bammel N. Houston, Suite 300 Houston, Texas 77014-1149, USA

ABSTRACT
Lower quality opportunity crudes are now processed in most refineries, and the source of the crudes may vary daily. These feedstocks, if not properly handled, can result in reduction in service life of equipment as well as costly failure and downtime. Analytical tools are needed to predict their high-temperature corrosivity toward distillation units. Threshold levels of total sulfur and total acid number (TAN) have been used for many years as rules of thumb for predicting crude corrosivity. However, it is now realized that they are not accurate in their predictive ability. Crudes with similar compositions and comparable with respect to process considerations have been found to be entirely different in their impact on corrosion. Naphthenic acid content, sulfur content, velocity, temperature, and materials of construction are the main factors affecting the corrosion process. Despite progress made in elucidating the role of the different parameters on the crude corrosivity process, the main problem is in calculating their combined effect, especially when the corroding stream is such a complex mixture. The TAN is usually related directly to naphthenic acid content. However, discrepancies between analytical methods and interference of numerous components of the crude itself lead to unreliable reported content of naphthenic acid. The sulfur compounds, with respect to corrosivity, appear to be related more to their decomposition at elevated temperature to form hydrogen sulfide than to their total content in the crude. This paper reviews the present situation regarding crude corrosivity in distillation units, with the aim of indicating the extent of available information, and areas where further research is necessary. Key Words: Naphthenic acid corrosion, crude oil corrosion, high temperature corrosion

INTRODUCTION The quality of crude oils processed around the world is worsening. The higher densities of crudes and higher contents of sulfur, acids and other impurities found in crude oils have increased the likelihood of corrosion failures in the processing plants. Moreover, it is now realized that many of the old rules of thumb, namely threshold levels of sulfur and total acid number (TAN) or neutralization number, do not appear to be accurate in their predictive ability. Analytical tools are needed to predict their high-temperature corrosivity toward distillation units. Sulfur at a level of 0.2% and above is known to be corrosive to carbon and low alloy steels at temperatures from 230C (450F) to 455C (850F). When sulfur is the only contaminant, McConomy curves [1], with the help of correction factors, are used to predict the relative corrosivity of crude oils and their various fractions as well as the effect of

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operational changes on corrosion rates already experienced in the field. However, when naphthenic acids are present, crude corrosivity prediction becomes more complex. Crudes with similar compositions and comparable with respect to process considerations have been found to be entirely different in their impact on corrosion. MANIFESTATION OF NAPHTHENIC ACID CORROSION Naphthenic acids are organic acids present in many crude oils from around the world, especially those from California, Venezuela, the North Sea, Western Africa, India, China, and Russia. They have the following generic chemical formula: R(CH2)nCOOH, where R is a cyclopentane ring and n is typically greater than 12. Naphthenic acid corrosion is differentiated from sulfidic corrosion by the nature of the corrosion (i.e., pitting and impingement) and by its severe attack at high velocities in crude distillation units. Crude feedstock heaters, furnaces, transfer lines, feed and reflux sections of columns, atmospheric and vacuum columns, heat exchangers, and condensers are among the type of equipment subject to this type of corrosion [2]. Damage is in the form of unexpected high corrosion rates on alloys that would normally be expected to resist sulfidic corrosion. Isolated, deep pits in partially filmed areas and/or impingement attack in essentially film-free areas is typical of naphthenic acid corrosion [3,4]. In many cases, even very highly alloyed materials (i.e., 12 Cr, AISI 316 and 317, and in some severe cases even 6% Mo stainless alloys) have been found to exhibit sensitivity to corrosion under these conditions. PARAMETERS AFFECTING NAPHTHENIC ACID CORROSION TAN (or neutralization number), sulfur content, velocity, degree of vaporization, temperatures, and alloy composition (i.e., Cr and Mo) were found to be the main factors affecting the corrosion process. Total Acid Number The TAN was related in early studies to the naphthenic acid corrosion rate, and its threshold was believed to be around 0.5 mg KOH/g [3]. Analysis of crudes TAN distribution as a function of the true boiling point showed where the acids concentrated in the refinery and resulted in better correlation of TAN with corrosion experienced in the field [5]. However, correlating the TAN of specific cut to their corrosivity was still far from being reached. Even naphthenic acid weight percent did not correlate to experienced corrosion [6]. A standard laboratory test was developed and showed promising crude corrosivity prediction. An index called the naphthenic acid corrosion index (NACI) was calculated from the exposure of a carbon steel coupon at 500F (260oC) for 48 hours in the fraction to be tested [7]. The index was the ratio of the corrosion rate of the coupon in mills per year (mpy) to the weight of its corrosion film in milligrams per square centimeter. It was postulated that a calculated ratio under 10 indicated sulfidic corrosion while a higher index indicated naphthenic acid attack. However, this index was developed from static test results, and correlations to high velocity might not be that simple and need to be verified. Moreover, carbon steel was the material used in these tests while most of the refineries process naphthenic crudes with a minimum alloy of 5 Cr.

Sulfur Content
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Most crude oil feedstocks vary greatly in both the amount of sulfur and the type of sulfide species present. It is believed that the sulfur content does not reflect the true effect of sulfur. A more important factor may be the capability of these sulfur compounds to form H2S during heating in the refining process [8]. At low temperatures, certain sulfur compounds in the crude may reduce the severity of naphthenic acid corrosion [9]. In this case, the sulfide film may offer some degree of protection from the acidic corrosion. At higher temperature conditions, the presence of naphthenic acids was found to increase the severity of sulfidic corrosion. Presumably, the presence of these organic acids disrupted the sulfide film, thereby promoting sulfidic corrosion on alloys that would normally be expected to resist this form of attack (i.e., 12 Cr and higher alloys). Figures 1 and 2 show the effect of chromium and molybdenum content as well as TAN and sulfur on the corrosion rate of crude fractions tested in the laboratory at a velocity of about 3 m/s (10 ft/s) and temperature of 370C (700F) for three days. In the vacuum heater feeder line (VHFL) cut the 1.5 Cr and 5 Cr showed the same corrosion rate, but in the long resid (LR) fraction the 5 Cr and 9 Cr behaved similarly. In general, the corrosion rate decreased steadily with increase in Cr and Mo. However, both TAN and sulfur content do not correlate in any way to corrosion rate. In the VHFL, the fraction with medium TAN and sulfur was the most corrosive to low alloy steels. In the LR, the fraction with the lowest TAN and sulfur was the most corrosive. In this case, blending a high TAN crude to lower the acid content did not provide the expected results and aggravated corrosion. These cases are common and refinery experience shows that prediction of corrosion is more complex than it is believed to be. Temperature Naphthenic acid corrosion occurs primarily in high velocity areas of crude distillation units in the 220 to 400C (430 to 750F) temperature range. No corrosion damage is found at temperatures above 400C (750F) probably, because of the formation of coke at the metal surface. The corrosion rate of all alloys of importance to the distillation units increases with increases in temperature. Velocity The flow regime and the degree of vaporization have a significant effect on both sulfidic corrosion and naphthenic acid corrosion. The higher the acid content generally, the greater the sensitivity to velocity. In fact, in some cases, it appears possible to obtain very high corrosion rates even at very low levels of naphthenic acid content (i.e., TAN 0.3) and low sulfur content when combined with high-temperature and high velocity. Materials of Construction The normal materials of construction used in crude distillation units are carbon steel , 5 Cr, 9 Cr, 410SS, and 316SS [10]. If only sulfur is present and the temperature is above 288C (550F), 5 Cr or 12 Cr cladding is recommended for crudes over 1% sulfur when no operating experience is available [2]. If hydrogen sulfide is evolved, 9 Cr minimum is preferred. In contrast to high-temperature sulfidic corrosion, low-alloy steels containing up to 12% Cr provide no benefits over carbon steel in naphthenic acid service [1]. With 316 SS (with 2.5% Mo minimum) or better, with 317 SS with a higher Mo content (3.5% minimum), cladding of the vacuum column is recommended when TAN is above 0.5 mg KOH/g and in an atmospheric column when the TAN is above 2.0 mg KOH/g [2].
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120

VHFL I (TAN = 0.35, S = 4.17%) Corrosion Rate (mpy) VHFL II (TAN = 1.64, S = 1.06%)
80

VHFL III (TAN = 0.54, S = 2.09%)

40

0 0 5 10 15 20 25

Cr + Mo (%)

Figure 1. Effect of Cr and Mo content on the general corrosion rate of alloys in three vacuum heater feeder line oil cuts

50

LR I (TAN = 0.35, S = 0.6%, H2S = 2.0%) Corrosion Rate (mpy)


40

LR II (TAN = 2.35, S = 0.9%, H2S = 2.0%)

30

20

10

0 0 5 10 15 20 25

Cr + Mo (%)

Figure 2. Effect of Cr and Mo content on the general corrosion rate of alloys in two long resid oil cuts MITIGATION METHODS Mitigation of naphthenic acid corrosion includes blending, inhibition, and materials upgrading [11]. Blending is the most preferred method and is accomplished by diluting a high TAN crude with a low TAN one, thus reducing the acid content to a level which corresponds to an acceptable corrosion attack. Injection of corrosion inhibitors may provide
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adequate and economic protection if it is closely monitored and used for specific fractions that are known to be particularly severe, or if it fluctuates with feedstock quality. When possible, upgrading the construction materials to a higher chrome and/or molybdenum alloy is the best solution for long term reliability. CRUDE CHEMISTRY AND CORROSIVITY CORRELATION Most of the laboratory studies and refinery experience so far have shown that crude corrosivity prediction is very complex and that further studies are needed to correlate the chemistry of crudes to refinery corrosion. Unfortunately, crude chemistry (sulfur and TAN), process variables (temperature and velocity), and failure analysis (sulfidic and/or naphthenic acid corrosion) are far from being assessed uniformly throughout the industry. To be able to achieve correlations among refineries and between laboratories and plants, the measurement method for each parameter needs to be defined precisely. Naphthenic Acid Distribution Naphthenic acid content is generally expressed in terms of TAN. ASTM D974 is a colorimetric method., with reproducibility of 15% and interference from inorganic acids, esters, phenolic compounds, sulfur compounds, lactones, resins, salts, and additives such as inhibitors and detergents. ASTM D664 is a potentiometric method with reproducibility of 20 to 44% depending on the end point (i.e., buffer or inflection), type of oil (i.e., used or fresh), and titration mode (i.e., automatic or manual), and the same interfering impurities as ASTM D974. Both ASTM methods do not differentiate between naphthenic acids, phenols, carbon dioxide, hydrogen sulfide, mercaptans, and other acidic compounds present in the oil. In addition, the two methods were compared [5], and D664 yielded numbers that were 30 to 80% higher than D974. Thus, prediction of crude corrosivity based on TAN alone could be misleading. Additionally, for assessment of plant corrosion effects, the naphthenic acid content needs to be determined for each cut in order to predict exactly where the acids will concentrate during the distillation of the crude. The isolation and analysis of naphthenic acids from crude oil may be performed adequately with methods such as UOP 565 (potentiometric) and UOP 587 (colorimetric), chromatographic separations, or other available analytical techniques [12,13]. The relative abundance of naphthenic acid and its average molecular weight (i.e., boiling point) may be determined. In addition, the assays of crude must be current [2]. Once steam flooding or other recovery method is begun in an oil field, the specific gravity and the organic and sulfur content of the crude can change. Fire flooding, when used in some fields, tends also to increase the naphthenic acid content. Hydrogen Sulfide Evolution with Temperature Sulfur is the most abundant element in petroleum other than carbon and hydrogen. It may be present as elemental sulfur, hydrogen sulfide, mercaptans, sulfides, or polysulfides. The total sulfur content is generally analyzed with the ASTM D4294 method using x-ray fluorescence. Halides and heavy metals interfere with this method. The capability of these sulfur compounds to form H2S during heating in the refining process, rather than their total content, is believed to correlate to corrosion in the plants [8]. However, a standard procedure for determining hydrogen sulfide evolution with temperature is not currently available.

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Figure 3. Schematic diagram of a rotating autoclave

Figure 4. Schematic diagram of a jet impingement apparatus Wall Shear Stress Fluid flow velocity has long been used as the parameter for comparing flow among refineries and between laboratory and field. However, this concept was found to lack predictive capabilities and was replaced by data related to fluid flow parameters such as wall shear stress and Reynolds number [14]. Wall shear stress, rather than velocity, is the parameter directly proportional to corrosion through the removal of normally protective films. The wall shear stress in the field is proportional to (1) the density and viscosity of the liquid and vapor in the pipe at temperature, (2) the degree of vaporization in the pipe, and (3) the pipes diameter. Wall shear stress in the laboratory depends on the geometry and dimensions
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of the laboratory apparatus. Figure 3 shows a schematic diagram of a rotating autoclave with a condenser for the return of light components, and Fig. 4 is a schematic diagram of a jetimpingement laboratory setup. Both of these apparatus are used in the laboratory to simulate corrosion in the field at high velocities. Table 1 compares the shear stress level between the field and the laboratory. The results show that the wall shear stress changes drastically with the degree of vaporization, and that identical fluid flow in the laboratory and the field do not correspond to the same level of shear stress. Table 1. Wall Shear Stress (in Pascals) Calculated at Different Velocities (VGO cut of 0.7 Specific Gravity and 0.55 Centistokes Viscosity at 700oF) Velocity 3 m/s (10 ft/s) 18 4 6 m/s 16 m/s (20 ft/s) (50 ft/s) Laboratory Setup 58 N/A 13 80 Plant 158 691 111 514 47 286 33 m/s (100 ft/s) N/A 298 2830 2080 862 66 m/s (200 ft/s) N/A 1049 10291 5148 2210

Rotoclave Jet Impingement

DV = 0% 46 DV = 30% 32 DV = 70% 14 DV = Degree of vaporization

Table 2. Effect of Velocity on General and Pitting Corrosion Rates Alloy General Corrosion Rate (mpy) Pitting Corrosion Rate (mpy) at 10 ft/s at 200 ft/s at 10 ft/s at 200 ft/s 5 Cr 21.8 25.5 0.0 201.1 9 Cr 20.3 24.2 0.0 191.8 317 SS 3.29 6.09 0.0 28.7 Laboratory Testing Laboratory studies are directed at the simulation of field conditions under controlled and reproducible conditions. CLI International, Inc. is currently involved in a major multiclient effort to provide more systematic understanding and a methodology for handling crude corrosivity and naphthenic acid corrosion issues. The interpretation of laboratory results and their correlation to the plant need to be analyzed carefully. The temperature of fluid and specimens in laboratory studies most likely are equal. However, in furnaces and heat exchangers of crude distillation units, temperature differences between the stream and the metal skin may be as high as 85 to 100C (150 to 200F) [1]. Rates of corrosion found in laboratory testing may correspond to the maximum corrosion rates found in the field. This usually results from the short test duration in the laboratory. The corrosion rate is usually high initially and then decreases with time because of the formation of protective films. The laboratory corrosion rates may also be much lower than those experienced in the field if the composition of the test solution changes with time as a result of degradation of its corrosive components. The type and rate of corrosion may be easily calculated in the laboratory. Table 2 shows the effect of velocity on the general and localized corrosion rates of three alloys after
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Corrosion in Refinery and Petrochemical Industries

three days of exposure. Differences in flow velocity on the general corrosion of the three alloys was minimal. However, a significant increase in the pitting corrosion rate with increases in flow from 10 ft/s to 200 ft/s was found especially for the 5 Cr and 9 Cr alloys. Corrosion rates in the field are evaluated by on-line monitoring tools which indicate only general corrosion rates unless the equipment is inspected for pitting and/or impingement. CONCLUSIONS It has clearly been proven through extensive laboratory and plant studies that predicting crude corrosivity by using the general rules of total acid and sulfur content is not reliable especially with the wide range of crude oil feedstocks being processed today. Naphthenic acid content and distribution in side cuts, hydrogen sulfide evolution with temperature, wall shear stress, temperature at the metal surface, and materials of construction are the main factors affecting the crude corrosivity process. The exact mechanisms which are operating are not precisely known at this point, and much research and testing is necessary to build a more comprehensive understanding. Based on the complexity of the situation and the current level of understanding, each case must be dealt with on an individual basis until a more comprehensive methodology for assessment can be developed. It is possible, however, to provide a practical assessment of the plant corrosion process by establishing a more comprehensive database from both laboratory and field experience where the various parameters affecting naphthenic acid corrosion can be more extensively and unambiguously defined and quantified. This information will serve as a firm basis for materials selection decisions, feedstock blending requirements and plant operating conditions. REFERENCES 1. L. Garverick, Ed., Corrosion in the Petrochemical Industry, ASM International, 1994. 2. R.A. White and E.F. Ehmke, Materials Selection for Refineries and Associated Facilities, NACE, Houston, Texas, 1991. 3. W.A. Derungs, Corrosion 12, 12, 1956, p. 617t. 4. J. Gutzeit, Materials Performance 16, 10, 1977, p. 24. 5. R.L. Piehl, Materials Performance, January 1988, and Paper No. 196, Corrosion/87, NACE. 6. E. Babian-Kibala, et al., Naphthenic acid corrosion in a refinery setting, NACE Conference, Corrosion/93, Paper No. 631, 1993. 7. H.L. Craig, Naphthenic Acid corrosion in the refinery, Paper No. 333, Corrosion/95, NACE. 8. R.L. Piehl., Corrosion, June 1960, p. 305t. 9. Heller, Materials Protection, September 1963. 10. F. Blanco and B. Hopkinson, Experience with naphthenic acid corrosion in refinery distillation process units, NACE Conference, Corrosion/83, Paper No. 99, 1983. 11. G.L. Scattergood and R.C. Strong, Naphthenic acid corrosion: An update of control methods, NACE Conference, Corrosion/87, Paper No. 197, 1987. 12. Tseng-Pu Fau, Energy and Fuels 5, 3, 1991, p. 371. 13. I. Dzidic, et al., Analytical Chemistry 60, 13, July 1, 1988, p. 1318. 14. K.D. Effird, et al., Experimental correlation of steel corrosion in pipe flow jet impingement and rotating cylinder laboratory tests, Corrosion/93, Paper No. 81, NACE.
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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

NEW NICKEL ALLOYS SOLVE CORROSION PROBLEMS OF VARIOUS INDUSTRIES D.C. Agarwal1 and W.R. Herda2 VDM Technologies 11210 Steeplecrest, # 120, Houston, Texas 77065, USA Krupp-VDM GmbH P.O. Box 1820, 58778 Werdohl, Germany
2 1

ABSTRACT
The materials of construction for the modern chemical process and petrochemical industries not only have to resist uniform corrosion caused by various corrodents, but must have sufficient localized corrosion and stress corrosion cracking resistance as well. These industries have to cope with both the technical and commercial challenges of rigid environmental regulations, the need to increase production efficiency by utilizing higher temperatures and pressures, using more corrosive catalysts, and at the same time possess the necessary versatility to handle varied feed stock and upset conditions. Over the past 30 years improvements in alloy metallurgy and a fundamental understanding of the role of various alloying elements has led to newly developed Ni-Cr-Mo and Ni-Mo alloys, which not only extend the range of usefulness of existing alloys by overcoming their limitations, but are also cost-effective and open new avenues of applications. This paper presents the various metallurgical, thermal stability and corrosion resistance characteristics of some newer alloys along with actual case histories, where these alloys have solved specific problems. Key Words: Nickel alloys, chemical process industries, petrochemical applications, localized corrosion, uniform corrosion, acid corrosion, Alloy 59, Alloy 31, Alloy 33, Alloy B-2, Alloy B-4

INTRODUCTION At one time one, of the major factors in any material selection was initial cost with little thought given to maintenance and the cost associated with lost production due to unscheduled equipment downtime. In today's economic environment, increased maintenance costs and downtime have placed a greater emphasis on the need for reliable, safe and versatile performance of process equipment. Prior to the 1950's, the alloy choices to combat corrosion were very limited. The latter half of the 20th century saw a phenomenal growth in the development of new nickel-based alloys due to improved melting and thermo-mechanical processing innovations, a better fundamental understanding of the role of various alloying elements and their effect on both corrosion and physical metallurgy behavior. Even though the standard austenitic stainless steels (Alloy 304L and 316L) have been and continue to be the workhorse of many industries, their vulnerability to localized corrosion and chloride stress corrosion cracking (SCC) has been a major problem in
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Corrosion in Refinery and Petrochemical Industries

many chemical processes. The knowledge that chromium and molybdenum improved the localized corrosion resistance and increased nickel enhanced the chloride SCC resistance led to different alloys with varying nickel, chromium, molybdenum and iron contents. The knowledge that in certain low nickel containing alloys nitrogen could be added to impart certain unique mechanical, metallurgical and corrosion characteristics was used to come up with a completely new 6% Mo alloy class which was very cost-effective and in certain cases approached or equaled the corrosion resistance of the more expensive high nickel containing alloys. Two alloys of this 6% Mo stainless steel class, with varying chromium and nickel contents, were developed to bridge the performance gap between the standard austenitic stainless steel and the very high performance nickel-based alloy of the Ni-Cr-Mo family such as Alloy C-276, Alloy C-22 and the most recent and advanced development, Alloy 59. Table 1 gives some of the alloy groupings of the materials of construction used today, whereas Table 2 lists the effects of the various alloying elements in the Ni-Cr-Mo-containing alloys. As one moves upward from Type 304 stainless steel metallurgy (Group I of Table 1) to higher alloys groupings such as Groups II, IV and VI, corrosion resistance improves, as evidenced by their chemical composition and the higher calculated pitting resistance equivalent (PRE) shown in Table 3. This higher PRE accounts for the improved corrosion resistance of the various alloys in a variety of environments. For interested readers, a list of references is provided for further in depth reading to gain a better understanding of these newer developments [1-16]. Table 1. Some Austenitic Corrosion Resistant Alloys for Combating Aqueous Corrosion Alloy Group I II III IV V VI VII Generic Description Iron-based 18-8 austenitic SS alloys High performance austenitic SS alloys Ni-based general purpose alloys 6% Mo superaustenitic SS alloys Ni-based special alloys Nickel based high performance alloys Typical Alloys 304, 316, 317 904L, 20, 28, 825 200, 400, 600, 800 1925hMo, 31*, 254SMo, B-2, B-3*, B-4* G-3, G-30, 625, C-276, C-4, C-22, 59*, 686* 33*

Chromium based high performance wrought super austenitic SS * Newer developments in the last 6 years. C-FAMILY Ni-Cr-Mo ALLOYS

Alloy C, the oldest alloy of this family (now obsolete), was superseded by Alloy C-276 in the early 1960's, due to improvements in melting technology. Between 1983 and 1994, three new alloys of this family were introduced to the market place: Alloy C-22 in the mid 1980's, Nicrofer 5923hMo-Alloy 59-in the late 1980's, and Alloy 686 in the early 1990's. Alloy 59 has the highest pitting resistance equivalent and the lowest iron content (Table 3), which provides for improved corrosion resistance over other alloys in a variety of standard laboratory environments, as shown in Table 4. Eliminating tungsten and reducing the iron content to very low levels, formulated an alloy with superior thermal stability characteristics, as shown in Table 5. This data clearly shows the detrimental effects of tungsten on the thermal stability of the various alloys, all of which
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contain tungsten, except Alloy 59. Not only is the uniform corrosion behavior and the thermal stability improved, its localized corrosion resistance as measured by the standard ASTM G48 test method in 10% FeCl3 is also enhanced. Table 6 clearly shows the beneficial effects of higher PRE due to the highest Cr plus Mo content in Alloy 59. Further details on Ni-Cr-Mo alloys are provided elsewhere [1-3,10,11,14,15,16]. Applications of Alloy 59 Due to its highest PRE and these unique corrosion-resistant properties, Alloy 59 has found a number of successful applications, where other nickel-based alloys have been either inadequate or marginal in performance. Some of these applications are described below. Pollution Control Combustion gases from burning fossil fuels or from waste incineration of municipal or hazardous waste contain acidic pollutants such as SO2, SO3, HCl and Nox, which must be scrubbed before the gases are released into the atmosphere. The equipment most frequently employed to achieve this is a wet scrubber. Operating conditions in critical sections of wet scrubbing systems can be extremely severe: for example, in condensates chloride levels may approach 100,000 ppm at pH values below 1 and temperatures of 80C. Laboratory and field testing has shown Alloy 59 to be one of the very few metallic materials able to withstand such aggressive corrosive conditions. In one lignite fired power station in Germany, 40 month field test rack data showed Alloy 59 to be the only alloy free of any localized attack. Table 2. Alloying Elements and Their Major Effects Alloying Element Ni

Cr Mo

W N

Cu Ti, Cb, Ta Fe

Main Features and Benefits Provides metallurgical compatibility to various alloying elements. Improves thermal stability and fabricability. Enhances corrosion in mildly reducing and alkali media, and improves chloride SCC. Provides resistance to oxidizing corrosive media. Enhances localized corrosion resistance. Provides resistance to reducing (nonoxidizing) corrosive media. Enhances localized corrosion resistance and chloride SCC. Provides solid solution strengthening. Behaves similar to Mo, but is less effective. Is detrimental to thermal stability. Provides solid solution strengthening. Austenitic stabilizer-economical substitute for nickel. Enhances localized corrosion resistance, thermal stability and mechanical properties. Improves resistance to seawater. Enhances resistance to H2SO4 and HF containing acid environments. Carbon stabilizers. Improves HAZ corrosion resistance. Provides matrix for metallurgical compatibility to various alloying elements. Enhances resistance to oxidizing corrosive

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media. Reduces cost by replacing nickel, and enhances scrap utilization.

Table 3. Typical Chemical Composition of Some Ni-Cr-Mo Type Alloys UNS # Alloy Ni Cr Mo Fe Others S30400 304 8 18 72 18 S31603 316L 12 17 2.3 66 24 N08904 904L 25 21 4.8 48 Cu N08020 20 38 20 2.4 34 Cu, Cb N08825 825 40 22 3.2 31 Cu N08028 28 31 27 3.5 36 Cu, Cb N08926 1925hMo 25 21 6.5 46 Cu, N-0.2 N08031 31** 31 27 6.5 32 Cu, N-0.2 N06985 G-3 48 23 7 20 Cu, Cb R20033 33** 31 33 1.6 32 Cu, N-0.4 N06625 625 62 23 9 3 Cb N10276 C-276 57 16 16 5 W N06022 C-22 57 22 13 3 W N06686 686** 56 21 16 2 W N06059 59** 59 23 16 1 * PRE = Pitting Resistance Equivalent = % Cr + 3.3 (% Mo) + 30 N ** Recent Alloy Developments PRE*

37 29 32 38 48 54 45 50 52 69 65 74 76

Table 4. Comparison of Some Ni-Cr-Mo Alloys in Various Boiling Corrosive Environments Uniform Corrosion Rate (mpy)* Alloy Alloy C-22 686 36 60 7 12 4 8 2 52 231 18 <5 308 34 392 354 92 -

Alloy Media C-276 ASTM 28A 168 ASTM 28B 55 Green Death 26 10% HNO3 19 65% HNO3 750 10% H2SO4 23 50% H2SO4 240 1.5% HCl 27 10% HCl 239 10% H2SO + 1% HCl 87 10% H2SO4 + 1% HCl (90C) 41 * To convert to mm/y, multiply by 0.0254.
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Alloy 59 24 4 5 2 40 8 176 15 179 70 3

Agarwal and Herda

Table 5. Thermal Stability Per ASTM G28B After Sensitization Treatment at 1600F Corrosion Rate (mpy)* Alloy 22** Alloy 686** 339 17 313 85 1000 Not tested

Sensitization (hr) Alloy C-276 Alloy 59*** 1 >1000 4 3 >1000 4 5 >1000 17 * To convert to mm/y, multiply by 0.0254 ** Alloys C-276, 22 and 686 - Heavy pitting attack with grains falling due to deep intergranular attack. *** Alloy 59 - No pitting attack. Table 6. Critical Pitting and Crevice Corrosion Temperature Per ASTM G-48 Alloy Critical Pitting Corrosion Critical Crevice Corrosion Temperature (oC) Temperature (oC) 316 15 <0 904L 45 25 u20 15 <10 825 30 <5 G-3 70 40 1925hMo 70 40 625 77.5 57.5 33 85 40 31 >85* 65 22 >85* 58 C-276 >85* >85* 686 >85* >85* 59 >85* >85* * At temperatures exceeding 85C, 10% FeCl3 chemically breaks down. PRE 24 32 29 32 45 38 52 50 54 65 69 74 76

**

The municipal incinerator of Essen-Karnap in Germany originally had a scrubber with a rubber lining, installed in 1987. After some 20,000 hours of service, the rubber lining failed, when liquid permeated it and attacked the underlying carbon steel substrate. A decision to install a metal lining was taken end of 1991. Following extensive laboratory and field tests in other plants belonging to the same owners, Alloy 59 was selected for this lining. In 1992, 55 tons of alloy 59 were used for this project. Examination after two years of operation revealed no detectable loss of thickness or any localized attack of Alloy 59. A further advantage is that the quantity of deposits retained on the lining of the absorber was reduced by a factor of one
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thousand, which significantly reduced periodic cleaning costs. Many hundreds of tons of Alloy 59 have been ordered in recent years for flue gas desulphurization systems of both power stations and incinerators throughout the world [14]. Synthesis of Acrylates and Methacrylates One process for the synthesis of acrylic or methacrylic esters involves reacting the corresponding acids with fatty alcohols, in the presence of para-toluene sulphonic acid as a catalyst. The reaction temperature is 130C, and the reaction is carried out under oxidizing conditions. Heating is by an internal steam coil. Following rapid failure of the material previously used for the steam heating coil, a series of plant tests was made with alloys including 904L, 28, G-3, 625, C-276, 31, and 59. The only alloy, which showed no pitting or crevice corrosion, and a corrosion rate of less than 0.01 mm/yr, was Alloy 59. A steam heating coil made of Alloy 59 was installed in 1993 and has operated without any problems ever since. Aluminum Refining When aluminum scrap is remelted, the molten metal is protected from oxidation by a layer of sodium and potassium chlorides. During the refining process this salt layer becomes contaminated with ammonium chloride. These chloride salts then have to be purified and recovered. This is done by dissolving them in water, and then recrystallizing the solution. In one European plant, the solution thus obtained contains 20-25% NaCl, 6-8% KCl and 5-8% NH4Cl. The pH is in the range 4.5 to 6. The evaporator operates at a temperature of 107C. The initial plant was built in rubber-lined steel, and failed rapidly due to cracking of the rubber lining and subsequent corrosion of the underlying carbon steel. A plant test in 1994 with Alloy 59 showed that after some 3800 hours of operating time, no corrosion could be detected. The recystallization plant has since been rebuilt in Alloy 59. Metals Processing In a copper plant, the SO2-rich gas from the flash furnace is scrubbed with a solution of 5% H2SO4 at a temperature of 45-60C. The acid produced has a concentration of typically around 50-55% H2SO4 and a temperature of about 75C. The chloride and fluoride contents of this acid are both high, at about 7000 ppm. Tests were carried out using both Alloy 59 and Alloy 31. Corrosion rates for both alloys were below 0.013 mm/yr with no localized corrosion. Following these tests, Alloy 31 was purchased for the scrubber internals handling the produced acid, and Alloy 59 for the induced draft fans. These have been in successful operation for the last two years with no detectable corrosion. Since then another order has been placed. Citric Acid Production Citric acid is produced in one plant by reacting calcium citrate with 95%-98.5% sulphuric acid at 95C-97C. A pilot installation of Alloy 254SMo failed rapidly. A three month test with Alloy 59 gave a corrosion rate of 0.05 mm/yr. The first of four reactors made of Alloy 59 was installed in 1990, and continues to operate well with no problems. Effluent Treatment Effluent from an acetic acid derivatives plant is cooled in Alloy C-276 plate heat exchangers. These require frequent replacement. Initial tests suggested that Alloy 59 might be a better alternative, so more extensive testing was carried out. The test conditions, and the

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corrosion rates observed during testing led to the selection of Alloy 59 to replace Alloy C-276 for the new effluent treatment plant. Fine Chemicals Production At one major chemical company, the production of fluorinated organic chemicals requires a halogen exchange reaction in which one fluorine atom is substituted for chlorine in the molecule. This reaction is carried out at about 100C in the presence of ammonium fluoride and a proprietary catalyst. Because of the severely corrosive conditions, extensive tests were made with Alloy 59 and with other alloys of the Ni-Cr-Mo and Ni-Mo family. The lowest corrosion rate was exhibited by Alloy 59. A 2600 US-gallon reactor (9.8m3) (Fig. 1) was built to ASME code requirements and has been giving excellent performance over the past 24 months. It is expected that a life cycle cost analysis will show Alloy 59 to be at least 50% cheaper than the next best candidate alloy belonging to the Ni-Mo family, Alloy B-2. Due to the excellent performance of Alloy 59, another bigger ASME vessel has now been ordered by the same chemical company (4,000 gallons capacity).

Figure 1. ASME code vessel made of Alloy 59 producing chlorinated and fluorinated chemicals Alloy 625 was giving only three years life in a column in a fine chemicals plant. The operating conditions were a temperature of 140C and a medium consisting of 83.1% water, 14.3% sodium bisulphate, 0.34% sodium sulphate, 0.02% acetone, 0.46% isopropanol, 0.06% copper sulphate, 0.04% DCNB, and 1.5% various organics. Tests were carried out both at the inlet to the column, and at the foot of the column. Based on the results of these tests, an inquiry was issued for a new column to be built in Alloy 59.
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There are many other applications of Alloy 59 which continue to find increasing usage and specification in the various industries throughout the world. This alloy is covered under appropriate ASTM, AWS and ASME specifications. 6% Mo ALLOYS These alloys, such as Alloy 1925hMo, were derived from alloy 904L metallurgy by increasing the molybdenum content from 4.5% to 6.5% and fortification with 0.2% nitrogen. This addition of nitrogen provided added benefits of improved localized corrosion resistance, thermal stability and mechanical properties. These alloys are readily weldable with over-alloyed filler metals, such as Alloy 625, Alloy C-276 or Alloy 59 to compensate for segregation of molybdenum occurring in the interdentritic regions of weldments. A higher chromium-nickel version of these alloys known as Alloy 31 further improves the corrosion resistance characteristics in a variety of media. Its corrosion resistance in sulfuric acid in medium concentration range is superior to even that of Alloy C-276 and Alloy 20 (Table 7). However, one must be careful, when specifying this alloy for higher concentrations and temperatures. At 80% concentration and temperatures above 80C, Alloy 31 exhibits active behavior. The 6Mo alloys have found extensive usage in pulp and paper, phosphoric acid, copper smelters, sulfuric acid production, pollution control, rayon production, specialty chemicals production, marine and offshore applications, heat exchangers using seawater and brackish water as coolant, pickling baths and many other applications. These alloys are covered under appropriate ASTM and ASME specifications. More details on these 6Mo alloys are presented elsewhere [4-8]. Some applications of 6Mo alloys are presented in Tables 8 and 9. Table 7. Corrosion Resistance in Sulfuric Acid Corrosion Rate (mpy) 80C Alloy Alloy Alloy 20 10 10 11 18 C-276 4 3 4 15 31 <0.1 <0.2 0.4 0.8

60C H2SO4 Alloy Alloy Alloy Alloy (%) 20 C-276 31 20 <5 <1 <0.1 40 <5 <2 <0.1 60 >5 <2 <0.1 80 5 <1 0.2 To convert to mm/y multiply by 0.0254

100C Alloy Alloy 20 >25 >25 >50 >50 C-276 >1 10 11 240 31 0.3 0.6 1 249

Table 8. Some Typical Industrial Applications for Alloy 1925hMo Offshore/Marine Seawater lines Product coolers Reverse osmosis Desalination plants Chemical Process Industry - Organics
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Ethyl acetate production Thermoplastic rubber (catalyst strippers) TDI and MDI production Organic intermediates (chloride catalysts) Fine chemicals (pharmaceuticals, agrochemicals)

H2SO4 distribution systems Metasilicate production Sodium perchlorate crystallizers Hydrofluoric acid producton scrubbers Ammonium chloride evaporators Catalyst strippers Wet exhaust fans Phosphoric acid digestion systems

Table 9. Some Industrial Applications of Alloy 31 Chlorine dioxide bleach washers Acid pickling industries acid plants Waste water reclamation from uranium ore leaching process Phosphoric acid production Heat exchangers in chloride media/seawater/brackish water ALLOY 33 Alloy 33 the most recent innovation [12,13], is a chromium-based, fully austenitic wrought super stainless steel (33 Cr, 32 Fe, 31 Ni, 1.6 Mo, 0.6 Cu, 0.4 N). This alloy has excellent resistance to both acidic and alkaline corrosive media, mixed HNO3/HF acids, localized corrosion and stress corrosion cracking. Due to its high nitrogen content, this alloy has excellent mechanical properties. Its high PRE (Table 3) makes it a very cost-effective alloy in comparison to the Ni-Cr-Mo alloys such as G-3, G-30 and 625. Its localized corrosion resistance is equal to or better than some of the Ni-Cr-Mo alloys (Table 6). Table 10 shows some of the corrosion resistance data of Alloy 33 in various corrosive environments. In comparison to other high chromium alloys such as Alloys G-30, 690 and 28, Alloy 33 shows excellent corrosion resistance behavior. This alloy on a cost/performance basis has the potential of being an excellent alternative to many alloys currently in use such as the 825, 904L, 20, 28, 6Mo alloys, G-3, G-30 and in some cases even Alloy 625. Some of the testing done with Alloy 33 in sulfuric acid environments, nitration involving nitric acid, phosphoric acid, acid pickling, nuclear waste reprocessing, and the pulp and paper industry, has shown it to give excellent results. The alloy has performed exceptionally in concentrated sulfuric acid at high temperatures as shown by the data in Table 10. Many companies are seriously considering using this alloy in their various processes. Table 10. Corrosion Resistance of Alloy 33 and Others in Various Media Media Sulfuric Acid 98% H2SO4 Temperature 100C 150C 200C Corrosion Rate (MPY) Alloy Alloy Alloy 33 A611 28-4-2 1.6 0.8 1.2 3.2 32 21 1.6 24 2.8
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Alloy Alloy Alloy Alloy Phosphoric Acid Temperature 33 G-30 28 690 85% H3PO4 100C 8 12 8 50 154C 43 53 56 Alloy Alloy Alloy Alloy Mixed Acid Temperature 33 G-30 28 690 12% HNO3 + 0.9% HF 90C 10 11 230 24 12% HNO3 + 3.5% HF 90C 48 48 >500 252 32% HNO3 + 0.4% HF 90C 11 20 38 58 56% HNO3 + 0.4% HF 90C 66 96 135 187 Table 11. Chemical Composition of Ni-Mo Alloys Alloy (UNS No.) B (N10001) B-2 (N10665) B-3 (N10675) B-4 (N10629) B-4(C) (A) Maximum Decade Introduced Ni 1920s Bal. 1970s Bal. 1990s 65(B) 1990s Bal. 1990s Bal. (B) Minimum Composition (wt. %) Mo Fe Cr 26-30 4-6 1(A) (A) 26-30 2 1(A) 27-32 1-3 1-3 27-30 2-5 0.5-1.5 28 3 1.3 (C) Typical composition

C 0.05(A) 0.01(A) 0.01(A) 0.01(A) 0.006

Table 12. Laboratory Test Results and Potential Hazards Test Results Tensile El (%) ASTM G 30 at 700C after U-Bend 1 h, 700C 1 h (700C) 10% H2SO4 for 100 h 5 Failure Potential Hazards Cracking SCC during during fabrication service High risk High risk

Ni-Mo Grade Standard Alloy B-2 UNS N10665 Fe (2% Maximum) Cr (1% Maximum) Controlled-Chemistry Alloy B-2 UNS N10665 Fe (1.6-2.0%) Cr (0.5-1.0%) Alloy B-4 UNS N10629 Fe (2-5%) Cr (0.5-1.5%)

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None

Reduced risk

48

Significantly reduced risk

None Significantly reduced risk

B-FAMILY Ni-Mo ALLOYS


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Alloy B, the original alloy in the Ni-Mo family, developed in the 1920's, suffered from HAZ corrosion in nonoxidizing acids (i.e., acetic, formic and hydrochloric) due to its higher carbon content. In the decade of the 1960's, improved AOD melting technology led to development of Alloy B-2. This alloy solved the HAZ problem, but suffered from poor fabricability. Recent developments of controlled chemistry Alloy B-2 (Table 12) and, Nimofer(R) 6629 - Alloy B-4 UNS N10629 - (Table 11 and Table 12) solved both these problems by eliminating/reducing formation of detrimental intermetallic phases, with further improvement in corrosion resistance behavior. Table 11 gives the basic developments of the alloys in the Ni-Mo family, and Table 12 shows the improvements in fabricability and corrosion resistance. Greater details on fundamental behavior and understanding of Ni-Mo alloy systems are presented elsewhere [1,9,10]. Alloy B-2 has been successfully used in production of acetic acid, pharmaceuticals, alkylation of ethyl benzene, styrene, cumene, organic sulfonation reactions, melamine, herbicides, and many other products. Alloy B-4, the improved version of alloy B-2, is being tested and considered for various applications in many other industries. CONCLUSIONS The understanding of the role of alloying elements in nickel-based alloys has led to the recent innovations in both high and low nickel-containing Ni-Cr-Mo alloys. Higher molybdenum and chromium contents, together with nitrogen fortification, have opened up an entirely new class of 6Mo alloys with unique properties, and has provided some specific benefits to industry. A better understanding of the physical metallurgy of Ni-Cr-Mo and Ni-Mo alloy systems has further contributed to the development of the newer improved alloys, which has helped to expand the range of usefulness of existing alloys for the modern chemical process and other industries requiring higher performance levels in the present day aggressive environments. Alloy 59 many successful applications and its ever increasing specifications in various industries clearly proves the above facts. A new chromium-based fully wrought super stainless steel (Alloy 33) and the two alloys of the 6Mo family (Alloy 1925hMo and Alloy 31) show excellent promise of solving many corrosion problems of today's chemical process and other industries in a costeffective manner. The newest alloy of the Ni-Mo family, Alloy B-4 and the controlled chemistry Alloy B-2 have not only solved the fabricability problems associated with the old Alloy B-2, but have also improved upon its corrosion resistance behavior. REFERENCES 1. W.Z. Friend, Corrosion of Nickel and Nickel Base Alloys, John Wiley & Sons, Inc., New York, 1980, pp. 248-367. 2. R. Kirchheiner, M. Kohler and U. Heubner, A new highly corrosion resistant material for the chemical process industry, flue gas desulfurization and related applications, Corrosion/90, Paper No. 90, NACE International, Houston, Texas, USA, 1990. 3. D.C. Agarwal, et al., Cost effective solution to CPI corrosion problems with a new Ni-CrMo alloy, Corrosion/91, Paper No. 179, NACE International, Houston, Texas, USA, 1991. 4. D.C. Agarwal, M.R. Jasner and M.B. Rockel, 6% Mo austenitic stainless steel selection for offshore applications, Offshore Technology Conference 1991, Paper No. 6598, Houston, Texas, USA, 1991.

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5. D.C. Agarwal, et al., The 6% Mo superaustenitics: The cost effective alternative to nickel alloys, Proceedings first Pan American Corrosion and Protection Congress, Mar del Plata, Argentina, November 25-30, 1992, Vol. 1, pp. 103-114. 6. M. Rockel and M. Renner, Pitting, crevice and stress corrosion resistance of high chromium and molybdenum alloy stainless steels, Werkstoffe und Korrosion 35, 1984, p. 537. 7. CroniferR 1925hMo, An advanced high alloy austenitic stainless steel for offshore hydrocarbon and seawater applications, VDM Report No. 10/2, July 1992, Krupp-VDM, Werdohl, Germany. 8. U. Heubner, R. Kirchheiner and M. Rockel, Alloy 31-A new high alloyed Ni-Cr-Mo steel for the refinery industry and related applications, Corrosion/91, Paper No. 321, NACE International, Houston, Texas, USA, 1991. 9. D.C. Agarwal, U. Heubner, M. Khler and W. Herda, UNS N10629: A new Ni-28% Mo alloy, Materials Performance 33, 10, 1994, pp. 64-68. 10. D.C. Agarwal, U. Heubner and W.R. Herda, Fundamental considerations during fabrication and construction of nickel alloy components for CPI, Conference Proceedings, First International Symposium on Process Industry Piping, December 1417, 1993, Orlando, Florida, USA. 11. Corrosion characteristics and applications of newer high and low nickel containing NiCr-Mo alloys, Conference Proceedings, 12th International Corrosion Congress, September 19-24, 1993, Houston, Texas, USA. 12. M. Kohler, U. Heubner, K.W. Eichenhofer and M. Renner, Alloy 33, A new corrosion resistant austenitic material for the refinery industry and related applications, Corrosion/95, Paper No. 338, NACE International, Houston, Texas, USA, 1995. 13. M. Kohler, et al., Progress with Alloy 33, A new corrosion resistant chromium-based austenitic material, Corrosion/96, Paper No. 428, NACE International, Houston, Texas, USA, 1996. 14. D.C. Agarwal, Alloy selection methodology and experiences of the FGD industry in solving complex corrosion problems: The last 25 years, Corrosion/96, Paper No. 447, NACE International, Houston, Texas, USA, 1996. 15. D.C. Agarwal and W.R. Herda, Alloying effects and innovation in nickel base alloys for combating Aqueous corrosion, VDM Report No. 23, February 1996, Krupp-VDM, Werdohl, Germany. 16. F.E. White, G.K. Grossmann, H. Decking and D.C. Agarwal, Experience with the Use of Alloy 59 in Industrial Applications, Corrosion/96, Paper No. 433, NACE International, Houston, Texas, USA, 1996.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

MACRO-MICRO SEGREGATION BANDS (MMB) AS A MAIN FACTOR INFLUENCING STEEL APPLICABILITY FOR THE PETROLEUM INDUSTRY A. Mazur The Academy of Mining and Metallurgy Al. Mickiewicza 30, Krakow, Poland

ABSTRACT
From a corrosion engineering point of view, in spite of common opinion, correctly welded steel joints are not the weakest points of reliable constructions. The results of long-term tests have shown the leading role of MMB structure in corrosion crack initiation and propagation. Such a band structure often exists in weldable steel sheets selected for pressurized systems in the petroleum industry. A practical aspect of the results reported is connected with steel quality recommendations for reliable construction. The lack of an MMB structure or an MMB width limited to below 0.01 mm [1] should guarantee the steels resistance to hydrogen-induced cracking. Key Words: Segregation band, corrosion cracking, line-pipe steels, branching effects, hydrogen sulfide

INTRODUCTION The pressurized installations of the petrochemical industry belong to those most reliable constructions that minimize the danger of catastrophic failure, sometimes of large-scale losses. The probability of material failures is (in a simple way of thinking) proportional to the total length of the pressurized system, e.g., piping-net, pressure vessels, etc. Of course, it also depends on inspection systems efficiency. Therefore, many petrochemical plants have been compactly built to minimize the length of piping and energy losses. However, the history of failure analysis shows that an ideal inspection system does not exist in spite of serious improvement in testing equipment and maintenance. Thus, the probability of catastrophic failures increases with plant operation time, as is shown in Fig. 1. In the past, petrochemical plants were constructed based on the burst-before-leak (BBL) concept. This concept is no longer acceptable because any of the pressurized installations can produce a chain-like reaction damaging sometimes costly and vital parts of a compactly built plant. Many such-constructed plants are still in operation. The accumulation of information on the environment-material - stress relationships shows that the BBL concept is no more in use. Since about 1970, a new concept of leak-before-burst (LBB) has been widely applied in the designing and engineering calculations for reliable construction. This concept takes into consideration the role of material flaws in the brittle fracture phenomenon and the influence of corrosive environments on catastrophic failures. Thus, the materials susceptibility to
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corrosion fracture as a time-dependent parameter in terms of a critical stress intensity factor for stress and environment action (KISCC) values should be taken into account.

Figure 1. Probability of catastrophic failures versus plant operation time The results presented in this paper consist of three main parts: 1) failure analysis of a gas-plants serious accident due to corrosion crack initiation and propagation, 2) persistent macro-micro segregation bands (MMB) role in the delayed corrosion fracture of pressurized installations, and 3) the concept of weldable steels susceptibility to corrosion crack initiation in parent metal and welding joints. FAILURE ANALYSIS A line-pipe 30 (762 mm) in diameter transporting hydrocarbon condensate at about 430 psi (3 MPa) pressure exploded after about 17 years of gas-plant operation. The lengthwise split shown in Fig. 2a produced a gigantic torch that heated up the other installations nearby until a few blasts happened. The resulting damage destroyed nearly the whole main parts of this plant (Fig. 2b).

Figure 2a. Lengthwise split of 30 line-pipe surrounding plant

Figure

2b.

Damage

to

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installations During the gas-plants operation, the hydrocarbon condensate from time to time also contained some (about 500 ppm) H2S which was dependent on the actual natural gas sources. That detrimental compound reacted with the steel, producing internal cracks and delaminations in the pipe-wall (Fig. 3). The corrosion cracks penetrated into the inner surface of the pipe-wall, as shown in Fig. 4.

Figure 3. Internal delaminations in a 30 line-pipe wall.

Figure 4. Corrosion crack traces on the inner surface of the line-pipe wall

The active hydrogen atoms produced by the reaction of: Fe + H2S FeS + 2H (1)

diffused through the iron crystal lattice decreasing the steels ductility. A bend test specimen taken from the burst 30 diameter pipe exhibited almost no ductility (Fig. 5). The fracture surface showed fully brittle features (Fig. 6).

Figure 5. Lack of ductility of bend-test specimen

Figure 6. Fracture surface of test


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specimen after bend-test. The very low energy values of the Charpy impact test confirmed the bend and tensile test results. The fracture surface after the impact test also showed a brittle character and a number of internal fissures (cracks along laminations) which are clearly visible in Fig. 7. Such fissures, spreading along the steels rolling direction, were the narrow cracks produced by hydrogen-induced high molecular pressure [2]. The evidences of the detrimental reaction of H2S with the steels surface were obtained by using the sulfur prints method. Such a print after optical magnification (shown in Fig. 8) illustrates the heavy FeS deposit (black spotted layer) on the inner pipe-wall surface. The outer surface is free of such a layer (Fig. 9). The black spots are randomly distributed in the steel-walls cross section. They are the traces of non-metallic inclusions of (Fe, Mn)S-type left after the metallurgical processes typical for weldable steel production. The internal fissure completely filled by FeS deposit is shown in Fig. 10.

Figure 7. Fracture surface of Charpy-V specimen with internal fissures

Figure 8. Sulfur print tracing heavy FeS deposit as black spots on the the inner pipe-wall surface

Figure 9. Outer surface of the pipe free of FeS deposit

Figure 10. Internal corrosion crack (fissure) completely filled by FeS deposit

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All mechanical and metallurgical tests clearly showed that hydrogen atoms diffused into the steel-wall dramatically decreased the steels ductility and produced a great number of cracks (fissures). During the long period of gas-plant operation, these cracks penetrated through the pipe-wall cross section until the last steel fiber was broken. At that moment, the pipe catastrophically burst producing the long opening crack visible in Fig. 2a. A very detailed material testing of the other pipes operating under the same conditions during the same period of time (as the burst pipe) also showed the hydrogens action, but it was limited to a relatively thin layer on the inner surface of the pipe. FeS deposit was found there, but the steels ductility was still high, according to the standards. The question is, why one pipe was so greatly affected by hydrogen sulfide (and stresses) but another one operating in the same environment was not susceptible to corrosion cracking. The most probable answer was suggested already by Mazur [1], but the next experiments gave more information about the influence of structural constituents (especially segregation bands) on the susceptibility to hydrogen crack initiation and propagation in weldable pipeline steels. SEGREGATION BANDS IN STEELS During laboratory investigations, two types of segregation bands were found. The first one was connected with persistent chemical segregations inherited by hot-worked steel after crystallization. It is well known that the most detrimental elements in steel are sulfur and phosphorus. Sulfur is present as non-metallic inclusions (sulfides) elongated along the rolling direction. They act as the traps for diffusing hydrogen atoms through the crystal lattice. Phosphorus is present in steel as dissolved atoms in solid solution and can be traced metallographically by the use of special etchants. The Oberhoffer reagent [3] does not react with steel if the phosphorus content is high (white band) but strongly etches the surface of low-phosphorus steel. Such a wide macro-micro segregation band (MMB) in pipe-steel with localized corrosion cracking is shown in Fig. 11.

Figure 11. Wide MMB with localized corrosion cracking (MMB)

Figure 12. Schematic concentration of phosphorus in narrow and wide segregation bands

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As the MMB becomes wider, the phosphorus concentration should be relatively higher. Assuming sinusoidal change of the phosphorus concentration in steel, the schematic situation in two steels of similar average phosphorus content, but different MMB width, is shown in Fig. 12. The phosphorus concentration in the wide MMB is higher than in the narrow one. Therefore, the susceptibility of wide MMB to corrosion crack initiation and propagation is higher because of the embrittling influence of phosphorus. Usually in wide MMB, nonmetallic inclusions are present and act as internal stress-risers, accelerating corrosion crack initiation and propagation. The second type of structural band is often observed in ferrite-pearlite hot-worked weldable steels. An example of such a band structure is shown in Fig. 13 after etching in a typical solution of 4% HNO3 in alcohol (nital); the dark constituent is pearlite, and the white is ferrite.

Figure 13. Structural bands in hot worked pipe steel. nonmetallic

Figure 14. Wide MMB with short corrosion cracks

and

inclusions (Oberhoffer etchant) That type of band structure is common for carbon segregation during austenite to ferrite and pearlite phase transformation. Usually the band structure is more developed as the steel contains cosegregants like manganese, chromium, and silicon. These elements effectively change the carbon atoms activity during their diffusion in the solid solution.

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Figure 15. Structural constituents present in the specimen shown in Fig. 14 across after nital etching

Figure 16. Linear microprobe analysis of phosphorus content a wideMMB

Both types of segregation bands are often present in weldable steels. But from a safety point of view, the persistent MMB-type should be treated as the weakest area for corrosion crack initiation and propagation. When the MMB, are wide, the susceptibility of the steel to corrosion fracture is high. Such a wide MMB with a number of non-metallic inclusions is shown in Fig. 14. Corrosion cracks are shown by arrows. A different area of the same specimen, but nital-etched, is shown in Fig. 15. There is visible band structure, but in marked areas there are also elongated nonmetallic inclusions and microcracks which most probably belong to the wide MMB. These features are not clearly visible in the micrograph because of the type of etchant (nital) used. A microprobe linear analysis made across the wide MMB confirmed an increase in the phosphorus content at these sites (Fig. 16). CORROSION CRACKS IN WELDED JOINTS The influence of MMB directionality on corrosion crack propagation was tested on the arc-welded specimens. For the laboratory tests, an A-52 grade weldable steel was selected. The calculated carbon equivalent, CE , was 0.38; thus, the ordinary arc-welding procedure was used. From the welded K-joints (Fig. 17), the crack-opening-displacement (COD)-type specimens were taken. The MMB structure, with an average width of 57 microns, was distributed along the rolling direction in the parent steel sheets. The constant load cantilever bend test [4] for stress corrosion susceptibility measurement of the welded joints was used. NACE water solution (5% NaCl, 0.5% CH3COOH) saturated by H2S up to pH 3.5-3.8 acted on a short fatigue precrack made at the mechanically cut Vnotchs front. The COD specimens were taken in such a manner (Fig. 18) that precracks were likely to initiate corrosion cracks in different zones of the welded joint, i.e., fusion zone (FZ), heat affected zone (HAZ) and parent metal (PM). At the beginning, the lowest stresses acted on the precracked notch. As the test time was increased, the real cross section decreased due to corrosion crack propagation. Thus, the stresses that acted at the crack front steadily increased. Therefore, at the beginning of testing and because of low stresses, corrosion crack propagation was controlled by a dissolution mechanism. At some crack distance, when the crack length was long enough, its propagation became controlled by a mechanical factor (stress).

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Figure 18. Mechanical notch placed in parent metal (PM) heat affected zone (HAZ) and fusion zone (FZ) The above analysis explains why the corrosion crack at the beginning of testing (low value of the initial stress-intensity factor KIi) propagated perpendicularly to the surface in the form of a wide fissure. Over distance, KIi increased significantly to such a value that the corrosion crack split into two branches propagating more or less parallel to the specimens surface. This change in the direction of the corrosion crack coincided with the rolling and MMB directions. At this stage, the stress-structure factor (mechanical) began controlling the further process of corrosion crack development. Such untypical branching effect for weldable carbon steels was first promoted by the presence of MMB in the tested specimens.

Figure 17. Arc-welded steel sheets.

Figure 19. Branching process starting at point A in the parent metal (unetched) Figure 19 shows the branching effect in parent metal. From point A, the primary corrosion crack split into two branches parallel to the rolling direction. The most interesting observations were found for the specimens with a V-notch placed in a heat-affected zone (HAZ). The micrograph shown in Fig. 20 was taken for a specimen not fully broken during corrosion crack propagation After using Anczyc etchant [5], revealing MMB as black bands, it is quite clear that up to area A the corrosion crack propagated as a wide fissure perpendicular to the specimens surface; similar to the primary crack shown in Fig. 19. From point A (Fig. 20), the primary corrosion crack split into two cracks parallel to the rolling direction. One very short branch was arrested by the fusion zone where no band structure exists, but the longer crack propagated towards the parent metal along the MMB. As the time of the corrosion test was increased, these long cracks, parallel to the rolling direction cracks and propagated in the wide bands, joined the deeper placed MMB by short step-wise cracks visible in area B (Fig. 20).
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At some distance of the corrosion cracks in the cross section, the critical stress-intensity factor (KIC) was reached and the specimen had to break by fast fracture mechanism. After branching, the corrosion crack rate became constant due to stress reduction at the multiplied crack fronts in spite of the increasing values of the stress-intensity factor (KIi). The da and KIi is shown in Fig. 21. relationship between the corrosion crack rate dt

Figure 20. Primary corrosion crack perpendicular to the specimens surface; the crack initiated in the HAZ and split into two longitudinal branches with the longer branch propagating towards the PM and the shorter one towards the FZ (Anczyc etchant)

Figure 21. Corrosion-crack rate versus stress-intensity factor (KIi).

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In all tested specimens, a dominant role of the MMB structure in branching was found. The corrosion cracks always propagated towards the parent metal where MMB existed, but the branches propagated towards the weld-bead were arrested due to the lack of MMB structure there. Therefore, the corrosion cracking of the weldable steels depends on more or less developed MMB structure. With greater MMB width, is greater the steel is more susceptible to corrosion crack initiation and propagation. The results of KISCC measurements for specimens with precracks (notches) placed in the three different zones of welded joints have shown that parent metal (steel sheet) exhibited the highest susceptibility to corrosion cracking in terms of a KISCC to KIC ratio that was 0.72 only. For HAZ and FZ this ratio was close to 1.0, i.e., both zones are nearly immune to applied environment and stresses. Most of the published results did not analyze the role of structural bands in branching effects. Published micrographs of branching cracks [6] most probably have propagated along the rolling directions of austenitic steels and high strength aluminium alloys. ACKNOWLEDGMENT This research was partially sponsored by The University Status Research Fund of The Academy of Mining and Metallurgy, Krakow, Poland. REFERENCES 1. 2. A. Mazur, Materials Performance 34, 1995, pp. 52-54. A. Ikada, Y. Morita, F. Terasaki, and M. Takeyama, On the hydrogen induced cracking of line pipe steel under wet hydrogen sulphide enviroment, Proc. 2nd International Congress, Pergamon Press, Paris, 6-10 June 1977. L. Habraken, J.L. de Brouver, De Ferri Metallographia, CNRM, Vol. 1, Bruxelles, Press Acadmiques Europennes, 1977, p. 41. B.F. Brown, The application of fracture mechanics to stress-corrosion cracking, Metallurgical Reviews 13, 1968, p. 21. K. Przybylowicz, Metaloznawstwo, Part I, Struktura metali i stopow, metody badania, Krakow, AGH Publ., 1989, p. 179. M.O. Speidel, Branching of Stress Corrosion Cracks in Aluminium Alloys, in: The Theory of Stress Corrosion Cracking in Alloys, Ed., J.C. Scully, Brussels, NATO Publ., 1971, pp. 345-354.

3. 4. 5. 6.

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FLUID CATALYTIC CRACKING INTERSTAGE AND HIGH-PRESSURE COOLER CORROSION S.M. Halawani Saudi Aramco - Jeddah Refinery Department Engineering Division - Operations Engineering Unit Admin. Bldg. Room # 218, P.O. Box 5250, Jeddah 21441, Saudi Arabia

ABSTRACT
The fluid catalytic cracking unit (FCCU) is one of the most profitable process units in the petroleum refining industry. The FCCU converts less valuable heavy hydrocarbons into lighter, more valuable components by cracking the larger molecules in the presence of a catalyst. During the conversion process, many highly corrosive chemical species are evolved from the catalytic reactions. One of the principal areas of the FCCU that comes into contact with such corrosive chemicals is the unsaturated gas concentration section. This section receives corrosive hydrocarbon gases from the FCCU Fractionation section, which come into contact with various pieces of equipment. This paper describes the economic penalty of frequent shutdowns or reduced throughput that have been caused by this type of corrosion at the Jeddah Refinery. The specific example addressed in this paper is corrosion of the wet gas compressor interstage and high-pressure coolers. This costly problem was resolved by a simple and easy solution over several other more costly alternatives. The solution that was selected involved proper distribution and adjustment of water wash to the shell side of the interstage and high-pressure coolers. This water also serve to prevent the disposition of ammonium chloride salts on the external surfaces of the cooler tubes. Key Words: Fluid catalytic cracking unit, molecules, catalyst, conversion process, unsaturated gas concentration section, shutdowns, ammonium chloride

INTRODUCTION Equipment deterioration is one of the major expenses in the petroleum refining industry. This problem can have several different causes, but is generally mechanical (erosion) or chemical (corrosion) in nature. This paper describes one of the corrosion problems that occurred in the fluid catalytic cracking unit (FCCU) at the Jeddah Refinery. This corrosion problem caused throughput reductions, safety hazards, equipment deterioration and high maintenance costs. The resolution of the problem took several years to identify the causes, and to develop and implement corrective action. In the end, the solution was very simple and easy to implement.

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DISCUSSION The Jeddah Refinery is located in the city of Jeddah, Kingdom of Saudi Arabia. The majority owner and operator of the refinery is Saudi Aramco, which is the worlds largest company in the petroleum industry. The Jeddah Refinery processes light and heavy Arabian crude oil, and has a capacity of 90,000 bbls/day. The major process units consist of Atmospheric and Vacuum Distillation, Hydrodesulfurization, Catalytic Reforming, and Catalytic Cracking units. The unit under discussion in this paper is the Fluid Catalytic Cracking Unit or FCCU. Feed The FCCU processes a variety of different feedstocks, basically from Vacuum Distillation units at the Refinery, and from the Lube Oil Refinery located adjacent to the refinery. The feedstocks include heavy vacuum gas oils, slack waxes, and 100 SUS distillate. Types of Corrosion in FCCUs Several types of corrosion can take place in FCCUs. The types can be grouped into two major categories [1]: Hydrogen charging; and Carbonate cracking Hydrogen charging includes sulfide cracking, blistering, hydrogen induced cracking, and stress-oriented hydrogen-induced cracking. Carbonate cracking is also known as intergranular stress corrosion cracking. Table 1. Materials of Construction of Coolers Cooler Part Shell & Heads Tube Sheet Stationary & Floating Tubes ( Straight Type) Material A-515 Gr.60 (CS for high temp service) A-181 Gr. I (Rolled Steel) ASTM B-111, No. 687 (Cu-Ni Alloy)

Interstage and High Pressure Cooler System Serious corrosion problems were experienced in the exchangers that cool the FCCU wet gas compressors first and second stage discharge streams. This system can be described as follows (Fig. 1):

The first stage compressor discharge is cooled by two parallel banks of exchangers,
each consisting of two exchangers operating in series, labeled G-E1 A/B/C/D. The second stage compressor discharge is also cooled by two parallel banks of exchangers, each consisting of two exchangers operating in series, labeled G-E2 A/B/C/D. Seawater passes through the tube side at lower pressure than the hydrocarbon gases that pass through the shell side. All coolers are TEMA type AES, which consist of four tube passes per cooler.
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Figure 1. Schematic of water wash line of fractionation system FCCU


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GE-1 A/B/C/D tube number = 164 (each) GE-2 A/B/C/D tube number = 452 (each) The coolers are constructed from the materials shown in Table 1.
Water Wash Role One of the factors that plays a major role in the system is the wash water to the hydrocarbon inlets of G-E1 A, G-E1 C, G-E2 A, and G-E2 C (Fig. 1). The vapor stream from the main column overhead receiver at the FCCU (compressor suction) contains various contaminants which may cause corrosion, plugging, or fouling. These contaminants include ammonia, sulfides, cyanides, chlorides and phenols. Since most of these contaminants are ionic or polar species and are readily soluble in water, a wash-water stream is used to concentrate them in the aqueous phase. The contaminated water stream is subsequently removed from the system. A wash-water rate of about 7 vol. % of the fresh feed is recommended for washing these exchangers. The water should be clean, preferably steam condensate, to prevent adding more problems, such as salts or dissolved oxygen, to the system. The water is injected after the compressor first stage (i.e., to GE-1 A/B/C/D ) and is pumped out of the interstage suction drum to the second stage outlet (i.e., to GE-2 A/B/C/D ). The water is finally collected at the high-pressure receiver boot and transferred to the main column overhead coolers for further washing. There is always water present in the main column and the gas concentration section from stripping steam. If the wash water is not used to flush out the corrodants, the water present can become highly corrosive from absorption of these corrodants. Sulfides levels in excess of 20,000 ppm have been reported in the overhead receiver water. Hydrogen blistering and general corrosion attack may become quite severe, especially if feed sulfur is greater than 1% wt., or nitrogen is greater than 1000 ppm. While the main column overhead receiver water may be basic (i.e., pH greater than 7.0), most of the ammonia that is responsible for this high pH drops out in the main column receiver. The water in the gas concentration section may become acidic from hydrogen sulfide and cyanides. If there is any oxygen present, elemental sulfur may be formed from oxidation of the sulfides. This elemental sulfur will cause problems in meeting gasoline product specifications. Wash water will solve many of these problems by diluting the corrosives, and keeping the waters pH in the range of 8.0-9.0, where sulfide oxidation is greatly reduced. TROUBLESHOOTING The corrosion problem that took place in the subject coolers caused the following drawbacks: - Hydrocarbons leakage into the seawater, which caused safety and environmental hazards; - Decreased FCCU throughput to repair these leaks; - Erosion and corrosion of tubes ends; - Broken bolts on the floating heads at the coolers;

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- Shortened service life for tubes (i.e., 4 months period); - Bulging of cladding. The specific corrosion for each group of coolers was as follows: Corrosion of GE-1 A/B/C/D

Bulging of cladding at the floating head; Leakage of the brass tube caused by corrosion.
Corrosion of GE-2 A/B/C/D

Bulging of cladding at the floating head; Erosion in the tube ends in the floating tube sheet with marine life deposit; Erosion in top pass of floating tube sheet. Fracture of bolts in floating head.

Several potential causes of the corrosion problems were discussed with a reputable consultant. The areas considered included:

Foreign materials in seawater causing corrosion; Contamination of seawater by hydrogen sulfide (H2S); H2S leakage from shell side; H2S stress corrosion cracking of bolts; H2S blistering of cladding; Wrong design of floating head; Bacteria causing iron sulfide (FeS) deposits in the seawater supply.

RECOMMENDATIONS The following recommendations were considered for this corrosion problem:

Seawater velocity in the tube side to be maintained between 0.9-1.8


meters/Second; Installation of sacrificial iron anodes on the channel and floating heads; Injection of a filming inhibitor, i.e., iron sulfate (FeS04), into the wash water; Removal of foreign materials from the seawater by filtering; Installation of plastic inserts at tube inlets to prevent erosion; Eddy current examination during the inspection of the unit, Review of the design of the floating head; Checking of the hardness of the bolts which should be less than 235 BHN (Brinnel Hardness Number); Changing of tube material to a corrosion-resistant type. (i.e., titanium).

Many recommendations were made, but one very important process related point was not taken into consideration. This point concerned the water wash to the compressor coolers to wash off ammonium chloride salts and other corrosion species.

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Figure 2. Schematic of proposed water wash line of fractionation system FCCU after introducing modifications

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Originally, the total volume of wash water was routed to the first stage intercooler. In checking the existing system, it was determined that one-half of the total wash water quantity was sent to another user (M/C overhead cooling system). This caused the amount of wash water sent to the interstage coolers to be half of the recommended quantity (20 gpm). This deviation was corrected by injecting the recommended wash water quantity to the first stage intercooler and by installing restriction orifices on each of the parallel cooler trains (Fig. 2). CONCLUSIONS After careful consideration, the following steps were taken to correct the corrosion problems in the FCCU wet gas compressor interstage and high-pressure coolers: 1. The wash water rate was adjusted to 20 gpm as provided for in the original design. 2. Restriction orifices were installed on each branch to ensure equal distribution of wash water to each branch. After completing these actions, only very rare leaks have been observed in the compressor interstage and high-pressure coolers. In summary, when troubleshooting problems, all related items must be taken into consideration, even if they appear to be very minor at the time. Obviously, it was much less expensive to adjust the wash water rates and distribution than to install titanium bundles, which was one of the recommendations considered. REFERENCES 1. R.C. Strong, V.K. Majestic and S.M. Wilhelm, Basic steps lead to successful FCC corrosion control, NALCO Reprint SL-47 (reprinted from Oil and Gas Journal), Sept. 30 and Oct. 7, 1991.

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ASSESSMENT OF CRACKS IN A HIGH PRESSURE MULTILAYERED REACTOR FOR ITS FITNESS FOR PURPOSE A.M. Askari, M.I. Al-Kandari and P.K. Mukhopadhyay Industrial Safety Division, Shuaiba Refinery, Kuwait National Petroleum Company

ABSTRACT
The high-pressure Kero hydrodesulfurizer reactor in the Shuaiba Refinery of the Kuwait National Petroleum Company was commissioned in 1968. By 1973, routine inspection revealed small cracks up to 3/16 in. (4.8 mm) deep which gradually increased in size necessitating weld repair in 1981. However, subsequent inspection in 1985 revealed reappearce of the cracks, and by 1990, the cracks were about 1 in. (25.4 mm) deep and 13 in. (330.2 mm) long. This reactor was built in the 1960s without adequate control of the chemistry (J-factor) and impact properties to reduce temper embrittlement. In view of the this and possible damage due to hydrogen embrittlement after 20 years of service, further in-situ repair by welding was ruled out. Instead, a fitness-for-purpose study was made utilizing recent developments in fracture mechanics techniques and available software to ensure safe and reliable operation by pressure down rating the reactor. Key Words: Kero hydrodesulfurizer reactor, J-factor, temper embrittlement, hydrogen embrittlement, fitness-for-purpose, fracture mechanics

INTRODUCTION Chromium-molybdenum steels used for the construction of hydro-processing reactors are known to undergo material degradation in service. The most important material degradations are temper embrittlement and hydrogen embrittlement. The first generation of reactors, built in the 1960s when the current controls on chemistry and impact properties were not exercised, are prone to temper embrittlement. Therefore, when cracks are found in a reactor during routine inspection, an assessment to predict the continued safe and reliable operation of the reactor requires serious consideration. In the past, in the absence of adequate tools to quantify the impact of such defects, plant engineers faced difficult decisions in such circumstances. The decision, in some cases, may be very conservative requiring long-term plant shutdown for costly repair/replacement. The availability of computer softwares and standards providing guidance on methods for assessing the acceptability of flaws, e.g., British Standard BSI PD6493 and other such standards, have provided engineers with much needed tools upon which a more careful recommendation can be based for continued safe operation of such equipment. This paper describes the assessment and current status of the cracks found in a Kero hydrodesulfurizer reactor at the Shuaiba Refinery, Kuwait National Petroleum Company, and highlights the importance of such assessment techniques. CONSTRUCTION AND HISTORY OF THE REACTOR
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The Kero hydro-unifiner reactor is a multilayered reactor consisting of 14 layers each in. (12.7 mm) thick made of a high strength material (JSW 2HS) and a core plate of SA 387 Gr D i.e., 2 1/4 Cr 1 Mo steel. At either end of the multilayered shell is a forged ring to which hemispherical heads (SA 387 Gr D) are welded. The reactor has 347 stainless steel type cladding on the inside surfaces The construction details are shown in Fig. 1. The plant was commissioned in 1968, and the design pressure and temperature of the reactor are 2800 o psig. (19.3 Mpa) at 750F (399 C). The cracks were first detected in this reactor by ultrasonic flaw detection (UFD) during routine inspection in 1972. The cracks were up to 3/16 in. (4.8 mm) deep on the inner side of the welds between the bottom forged ring and the heads. The configuration of the welds and approximate locations of the cracks can be seen in Fig. 2. These cracks were monitored on a run-to-run basis till 1978 when UFD indicated flaws up to 1.5 in. (38.1 mm) deep at some locations. These cracks were successfully repaired and after repair no significant defect was detected by UFD. Subsequent inspection in 1986 revealed the reappearance of the cracks. During a 1990 inspection, cracks were detected up to 1 in. (25.4) deep at places and 13 in. (330.2 mm) long in the circumference in the weld between the forged ring and the bottom head. Alarmed by the dimensions of the cracks and realizing the little chance for further weld repair, a fitness-for-purpose study was conducted to determine the reactors continued safe and reliable operation with the existing cracks. ASSESSMENT FOR BRITTLE FRACTURE To assess failure due to the existing cracks by brittle fracture due to embrittlement of the material, the stress-intensity approach was used. This approach is based on the assumption that crack propagation will occur when the stress intensity (K) at the crack tip reaches a critical value Kc. Under plane-strain condition, this critical stress intensity for tensile loading is termed as KIC. A general expression for K [1] can be written as K=M

(1)

where M = a constant specific to a given flaw size and geometry, = stress in the system, remote from the crack, and a = dimension of the crack. As the cracks at the weld joint between the bottom forged ring and head were the worst, the assessment of the cracks was done for these cracks, although cracks were present in other joints. The structural integrity assessment was carried out by the use of the licensed software, Crackwise, from the Welding Institute (TWI), UK [2]. Several of the inputs required were arrived at as follows:

Flaw dimensions, as found by UFD, were grouped as per the guidelines provided
in BSI Standard PD 6493 [3].

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Figure 1. Sketch of the kero hydrodesulfurizer reactor

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Figure 2. Weld configuration and approximate cracks location

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Figure 3. FAD for the existing crack under 2800 psig for A387-D (level 1)

Geofac software licensed by the Fracture Search Inc. [4] was utilized for
calculation of the M factor for the existing crack. Fracture toughness data was obtained from the co-relation given in PD 6493 [3] between fracture toughness and charpy V-notch values, where the charpy V-notch values were measured by removing boat samples from a similar reactor. The analysis was carried out for both high-pressure operation at 2800 psi (19.3 Mpa) and medium-pressure operation at 1300 psi (8.96 Mpa) at level 1, which is a somewhat conservative assessment. The analysis was done for both materials, i.e., 2HS and SA 387 Gr D as the cracks were present at the weld between these two materials. The fracture analysis diagrams (FADs) for the 387Gr D material are presented in Figs. 3 and 4. As can be seen from the FAD, the cracks are considered to be safe from failure by brittle fracture at 1300 psig (8.96 Mpa) operation, but not safe when the pressure is raised to 2800 psig (19.3 Mpa).

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Figure 4. FAD for the existing crack under 1300 psig for A387-D (level 1) ASSESSMENT FOR HYDROGEN EMBRITTLEMENT The second assessment was done for the combined effect of hydrogen embrittlement and temper embrittlement, as several studies have shown that the threshold stress intensity for cracking in hydrogen (i.e., KIH) can be appreciably reduced in steel that has been subjected to prior temper embrittlement. Wadate et al. [5] have provided a correlation between KIH and embrittlement properties measured by fracture appearance transition temperature (FATT) as follows: KIH = .0014 FATT 2 - 0.421 FATT + 57.0 where KIH is expressed in Mpa (2)

m and FATT in degrees celsius.

In the absence of actual data on FATT, the correlation between the J-factor i.e., (Si + Mn) x (P + Sn) x 10-4 and FATT has also been provided [6]. Table 1. Data Analysis for the Existing Crack Under 2800 psig for A387-D (level 1)

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Table 2. Data Analysis for the Existing Crack Under 1300 psig for A387-D (level 1)

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In the present study, a detailed chemical analysis was done for boat samples removed from a similar reactor which has a similar manufacturing and operating history. This resulted in a J-factor of 350, and a corresponding KIH of 30 MPa m0.5 after 100,000 hours of operation. The stress intensity factor (KIc) for 1300 psi (8.96 Mpa) operation was calculated to be 35.6 Mpa m0.5 for the worst crack present. Since KIc > KIH the cracks are of the propagating type. However, the rate of crack growth, i.e., da/dt = 2.4 x 10 x K to be considered very insignificant. DISCUSSION From the above analysis, it was concluded that the reactor was not safe for operation at its originally designed pressure of 2800 psi (19.3 Mpa) (Fig. 3 and Table 1). However, it was considered safe to operate at 1300 psi (8.96 Mpa) (Fig. 4 and Table 2) at which the plant was found to be still capable of producing products to standard specifications. At 1300 psi (8.96 Mpa) operating condition, from a hydrogen embrittlement point of view, the chances of crack growth is a possibility, but as the rate of crack growth is found to be quite low, it was considered safe to operate the reactor by down grating the pressure to 1300 psig (8.96 Mpa). No significant crack growth could be detected after operating at the lower pressure of 1300 psig (8.96 Mpa) between last two UFD inspections made in 1992 and 1995. It is, however, fully recognized that in the event of further crack growth, in-situ welding repair will not be possible due to the metallurgical degradation of the reactors materials. Also, due to the more stringent specifications required for kerosene in respect to smoke point (i.e., 28 mm minimum), the reactor needs to be operated at high-pressure at around 2300 psi. Our analysis shows that with the existing crack, operation of the reactor will not be safe at 2300 psi. Accordingly, it has been decided to procure a new reactor for operation at 2300 psi. Till such time, the reactor will continue to operate at 1300 psi with run-to-run monitoring by UFD. CONCLUSIONS The above discussion highlights the advantages offered by fracture mechanics techniques for finding acceptable solutions at the plant level. Such solutions can be achieved by analyzing the fitness-for-purpose of the equipment to continue operation without compromising the safety and integrity of such important equipment. ACKNOWLEDGMENT The authors wish to thank the management of KNPC for permission to publish this paper. Encouragement and support provided by Refinery Manager Mr. A.L. Al-Houti is sincerely acknowledged. REFERENCES 1. Viswanathan, Damage Mechanisms and Life Assessment of High Temperature Components, ASME International, Ohio, 1989, pp. 21-57. 2. Crackwise Software, The Welding Institute (TWI), UK.
-24 11.7

[7], works out to be 3.39 x 10 mm/year which was

-6

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3. PD 6493, Guidance on Methods for Assessing the Acceptability of Flaws in Fusion Welded Structures, BSI, 1991. 4. Geofac Software, The Fracture Search Inc., Ohio. 5. Wadate, J. Wantanable and Y. Tanka, Prediction of the remaining life of high temperature pressure reactors made of Cr-Mo steels, Trans. ASME, J. Pressure Vessel Tech. 107, Aug. 1985, pp. 230-238. 6. Wadate, T. Nomura and J. Watanabe, Hydrogen effect on remaining life of hydroprocessor reactors, Corrosion 44, 2, 1998, p. 106. 7. Viswanathan, Damage Mechanisms and Life Assessment of High Temperature Components, ASME International, Ohio, Ohio, 1989, pp. 329-382.

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POLYTHIONIC ACID STRESS CORROSION CRACKING OF INCOLOY 800: CASE STUDY AND FAILURE ANALYSIS M.S. Mostafa and S.A. Hajaj Industrial Safety Division, Mina Abdulla Refinery Kuwait National Petroleum Company, Kuwait

ABSTRACT
A high-pressure warm-separator (HPWS) off gas air cooler made of Incoloy 800 failed at one of its inlet nozzles. Inspection and nondestructive testing (NDT) showed cracks in the shape of sun rays surrounding the weld of the chemical cleaning nozzle connected to the inlet nozzle. Chemical analysis, metallographic examinations, and microhardness measurements indicated that the cracks were due to polythionic acid stress corrosion cracking. Cracking was promoted by the presence of carbide precipitation and residual stresses resulting from the manufacturing and welding practices. Key Words: Polythionic acid, stress corrosion cracking, Incoloy 800, case study, failure analysis

INTRODUCTION An atmospheric residue desulphurization unit (ARDS) was commissioned in the early 1988 as a part of the modernization project of Mina Abdulla Refinery. The unit is designed to process 65,900 BPSD of atmospheric residue. At the heart of the unit is a pair of parallel fixed-bed reactor trains containing desulphurization catalyst. The chemical basis for the process is the catalytic reaction of hydrogen with sulfur-containing hydrocarbons to produce sulfur-free hydrocarbon and hydrogen sulfide. The incoming residue feed is preheated by exchange with the reactor effluent and a fired heater. The feed is mixed with hot-recycled gas, and is sent to the reactor where it is desulphurized. Finally, the reactor effluent goes to a series of separators to release the dissolved light ends (Figs. 1 and 2). The high-pressure warm-separator (HPWS) off gas air cooler consists of a series of eight banks air cooler, operating at 180C under a gas pressure of 21 bar, and handling a mixture of H2, NH3, H2S and hydrocarbon. Each bank has two inlet and two outlet nozzles, 4 in. diameter. There are two chemical cleaning nozzles, 1.5 in. diameter, per bank, one of each in the inlet and outlet nozzles. The air cooler headers, nozzles and tubes are all made of Incoloy 800 in accordance with ASTM B 407-UNS-N08800 (see Tables 1 and 2). Wash water is injected into the air cooler effluent to prevent the deposition of solid ammonium salts (i.e., NH4Cl and NH4OH). The ammonium salts are readily removed by the wash water (see Table 3).

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Figure 1. A schematic flow diagram of the atmospheric residue desulphurization unit (ARDS)
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Figure 2. A schematic diagram of high pressure warm separator off gas air cooler (HPWS)
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Table 1. Specified Mechanical Properties of Incoloy 800 (ASTM B407, UNS No. 8800) Tensile Strength (ksi) 65 Yield Strength (ksi) 25 Elongation (%) 30

Table 2. Specified Chemical Composition of Incoloy 800 (ASTM B407, UNS No. 8800) Element Nickel Chromium Iron (min.) Manganese Copper Silicon Sulfur Aluminium Titanium Amount (%) 30-35 19-23 39.5 1.5 0.75 1.0 0.015 0.15-0.60 0.15-0.60

Table 3. Specifications of Wash Water Component Total dissolved solids (max. ppm) Dissolved oxygen (max. Ppm) Sodium (max. Ppm) Potassium (max. Ppm) Total hardness (max. Ppm) Organic material (max. Ppm) pH Conductivity ((mattscm-1) Amount 3.0 0.05 0.10 0.10 0.10 1.0 7.0-8.0 5.0

HISTORICAL DATA AND BACKGROUND OF THE UNIT Two successive incidents of hazardous on-stream leakage developed from the HPWS off gas air cooler, one during the commissioning period and the other 11 days after the introduction of fuel oil feed. The tubes and headers are made of duplex stainless steel conforming to SA-669 and UNS S31500, respectively. Inspection revealed extensive cracking of many of the headers partition plate/tube sheet welds and also of the headers corner welds. In all cases, cracking included tube end welds that failed and caused leaks to occur. Metallurgical examination revealed almost 100% ferrite coarse-grained heat affected zone (HAZ) near the welds due to improper design, fabrication
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and welding technique. Hydrogen embrittlement of the HAZ developed under normal operating conditions leading to weld cracking and subsequent leakage. Repair of the cracked headers of the eight banks is impractical, costly and not guaranteed to lead to solving the problem. Furthermore, the use of the remaining uncracked banks is not advisable given the potential for similar problems. They are also not recommended for reconditioning for the same reasons. It was recommended to use a completely new air cooler with improved design. The new air cooler was fabricated from Incoloy 800, in a similar manner to those used in other neighboring refineries. CRACKING IN INCOLOY 800 OFF GAS AIR COOLER NOZZLE The new air cooler made of Incoloy 800 conformed to ASTM B 407-UNS 08800. It was delivered in 1992 and was installed to replace the then existing carbon steel air coolers. In early January 1995, one four inch diameter inlet nozzle of one of the air cooler banks leaked during start-up of the unit after a maintenance shutdown. The leak was located around the weld of the 1.5 in. diameter chemical cleaning nozzle connected to the 4 in. diameter inlet nozzle. All 32 inlet and outlet nozzles, 16 of which had chemical cleaning nozzles, were checked with fluorescent dye, and 8 more 4 in nozzles were found to have cracks. Nine nozzles (inlet and outlet) were totally replaced with 321 stainless steel. The new nozzles were not provided with chemical cleaning nozzles. Metallography and microhardness tests were carried out to determine the reason for failure. Some sections were given to an outside consultant and to the manufacturer. Initial Observations and Nondestructive Testing (NDT) The leaky 4 in. diameter nozzle was removed from the header and the internal surface was checked with fluorescent dye. Cracks were observed on the internal surface of the 1.5 in. diameter nozzle weld. The cracks were seen to initiate from the weld toe and were perpendicular to the weld (Fig. 3). Cracks were also observed in the 4 in. diameter nozzle at the wall deposit to the weld. Small indications of cracks were also noted at the nozzle-to-flange weld. The leaky 4 in. diameter nozzle was first cut longitudinally into two halves. The half containing the 1.5 in. nozzle was further cut and one quadrant was given to the representative of the designer, while another identical quadrant was used for the in-house investigation. The other half was preserved for further analysis by an outside party. Metallography The in-house sample containing cracks was first cut longitudinally. It was then cut into two transverse cross sections. The first sample revealed intergranular corrosion of the base metal (i.e., in the 4 in. diameter nozzle). Severe carbide precipitation was noticed at the grain boundaries (Fig. 4). The examined section was away from the weld. Severe disintegration and also loss of grains was also noticed (see Fig. 5), rendering the structure very weak. The ASTM grain size was found to be 4.5-5. Also, the microhardness of the base metal was 169 BHN, which is considered normal.

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Figure 3. A photograph showing internal view of nozzle section following the application of dye penetrant. Cracks are seen to initiate from the weld toe and are perpendicular to the weld

Figure 4. A stereo micrograph showing intergranular corrosion and grain boundary precipitation (400x). Etchant: HNO3-HCl-Acetic
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Figure 5. Severe intergranular corrosion with disintegration and loss of grains in the base metal (50x). Etchant: HNO3 - HCl - Acetic.

Figure 6. Intergranular cracking in the longitudinal section, showing crack initiation from weld toe and loss of grains
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The second sample revealed intergranular cracking in the longitudinal cross section. The cracks were in the base metal (i.e., in the 4 in. diameter nozzle). The cracks were noticed to initiate from the weld toe and to travel to the other edge through the base metal (Fig. 6). Carbide precipitation, disintegration and loss of grains were observed once again . The ASTM grain size of the second sample was 4.5-5 and the mircrohardness of the base metal was 165 BHN, which is considered normal. The second sample also revealed intergranular corrosion and cracking on the transverse cross section. The cracks appeared to propagate along the grain boundaries. Carbide precipitation, disintegration and loss of grains were also noticed within the examined cross section. Fractography The fractured surfaces were examined using scanning electron microscopy (SEM). Crystalline facets were noticed (Fig. 7), especially in the region of crack initiation.

Figure 7. SEM fractograph showing separated grain facets and secondary cracking Chemical Analysis The chemical composition analysis confirmed that the material was identical in composition to Incoloy 800. Energy dispersive spectroscopic analysis revealed the presence of sulfur. Reasons for Failure: Analysis and Ven Diagram for Stress Corrosion Cracking Intergranular corrosion (IGC) of the base metal (i.e., 4 in. diameter nozzle) indicated that carbides had precipitated on the grain boundaries during the manufacturing process, because
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the operating temperature of 340F is too low for such precipitation to occur during service. Precipitation of carbides also occurred in the HAZ during welding, as was observed during the examination. All 1.5 in. diameter chemical injection nozzles were replaced at the time of installation due to the leakage of the original nozzles during hydrotesting. This resulted in the HAZ being affected twice. However, IGC was noticed on the base metal far away from the weld which confirms the existence of microstructural deficiencies during manufacturing. Precipitation of carbides makes the grain boundaries prone to corrosion and cracking. The presence of a corrosive medium such as polythionic acid would promote corrosion of the grain boundaries under such conditions. The presence of IGC suggested the formation of such acid during shutdown, which is very likely in the absence of neutralization before shutdown. Although Incoloy 800 is considered superior to austenitic stainless steels, it is still susceptible to polythionic acid corrosion attack and the system should be neutralized before opening, as recommended in NACE RPO1-70-93. Understandably, the presence tensile stresses is required to initiate and propagate cracks along the corroded grain boundaries. In the present case, stresses can be present in the form of residual stresses as a result of the manufacturing practices and welding. Furthermore, the 1.5 in. diameter nozzle welds appeared under bending stress. CONCLUSIONS The material (Incoloy 800) was received in a sensitized condition which is considered to be inferior and unacceptable. Welding of the chemical cleaning nozzles considerably affected the HAZ. Formation of polythionic acid during shutdown promoted the IGC process. Indeed, energy dispersive analysis confirmed that sulfide was present. The pattern of cracking was consistent with the radial stress around the weld. Based on the investigation, a recommendation was made to recheck all the 4 in. inlet and outlet nozzles for cracking with fluorescent dye penetrant as well as the 321 stainless steel. Considering the hazards involved, it was preferable to replace all of the original Incoloy nozzles, even if they were not cracked. Because there was a strong possibility that all nozzles from the same manufacturing batch would contain harmful precipitations, in-situ metallography (replica) was highly recommended for all the nozzles and headers to determine the presence of carbide precipitation. Thus, a firm specialized in the field of in-situ metallography was hired to test all of the inlet and outlet nozzles, headers, drains, vents and tubes.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CORROSION OF TUBE HEATERS IN REFINERIES: SYMPTOMS AND CURES A. Attou, A. Rais and H. Smamen Entreprise Nationale de Raffinage de Petrole Raffinerie dArzew BP 37 Arzew, Algerie.

ABSTRACT
Tube heaters (THs) in oil refineries play a strategic role in heating hydrocarbons. However, they may suffer from corrosion damage if service conditions differ from those they are designed to operate under and/or if not enough attention is given to the composition/heat treatment of the tube materials and the composition of the combustible products. We experienced this problem with a cylindrical vertical heater made from convection tubes made of material ASTM A106, and radiation tubes made of ASTM 335 Gr P11. After seven years in service, the heaters tube surfaces showed severe crevice corrosion damage. A number of analyses and tests were carried out to study the materials characteristics and to compare them with those of a sound heater. Tests included metallurgical analysis, microhardness, grain compactness, carbon concentration and chemical analyses of the combustible products. This paper describes the results of each testing technique and identifies the origin of the corrosion damage as grain compactness/heat treatment and the presence of corrosive agents in the combustible products and in the air mixed with vapours coming from a nearby cooling tower. Key Words: Tube heaters, hydrocarbons, corrosion, grain compactness, combustibles.

INTRODUCTION Tube heaters (THs) are widely used in the process of refining crude oils. Different products are extracted at different temperatures: Naphtha up to 200C, Kerosene between 200C and 300C, and Diesel between 20C and 380C. Other extracted products are usually referred to as fuel. To reach these temperatures, a number of heating methods are used.

Steam heating, Electrical heating, Heat exchangers, and By direct firing (THs). THs are chosen when other methods fail to give the desired elevated temperature or for economical reasons. They were first invented in the USA at the beginning of the 20th century and are classified either by their heat transfer method, i.e., radiation or radiation/convection, or by their external appearance, i.e., box heaters, cell heaters, cylindrical heaters, etc. The tube materials used in these heaters are usually: A 335 Gr P11 (1 Cr Mo), ASTM A 200 Gr P 22 (2 Cr Mo), A335 Gr P5 (5% Cr, Mo), or A106 Gr B. The combustibles used
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are fuel gas, fuel oil or natural gas. In the literature, corrosion damage of THs is well documented [1,2]. Most authors agree on the following causes:

Type of tube material, Hydrogen [H2] damage, H2-induced cracking, Hydrogen sulphide [H2 S] damage, and Oxidation/decarburization. This study is part of a plant life-expectancy study and concerns two heaters after seven years of service. CORROSION INVESTIGATION OF TWO FURNACES: TH1 AND TH2 Operation Conditions The operating conditions are summarized in Table 1. Table 1. Operating Conditions of TH1 and TH2 Characteristic Design Temperature (oC) Operation Temperature (oC) Design Pressure (kg/cm2 G) Operating Pressure Fluid Material Dimensions (mm) Operating Time Skin Temperature (C) Combustible H2 Partial Pressure (kg/cm G)
2

Steady State TH1 TH2 452 400 225/355 280 27.0 39 21.16-23.7 29 HC + H2 Oil + H2 + light HC A335 Gr P11 A335 Gr P11 141.3 x 6.6 88.9 x 7.62 1972 - to date 1983 - to date 315/504 507 90% H2+10% CxHy 0.8 max 0.8 max Natural gas + Hydrogen

Start-Up State TH1 TH2 200 200

H2

H2

Although the two furnaces appear to be identical, the corrosion damage in TH2 is very pronounced compared to that in TH1.

Visual Examination

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After 60,000 hours of service, the outer surface of the tubes of TH1 showed a layer of black scale 0.4 mm thick (Fig. 1). The corrosion rate was estimated to be 0.06 mm per year. This is the usual oxidation/decarburization mechanism.

Black Scale

Oxide Layer

Base Metal

Figure 1. A photograph showing oxidation of the outer surface of tubes (100x) The TH2 tubes showed a similar pattern. However, in TH2, certain regions of the outer surface showed traces of yellow deposit on the oxide layer, just like a drip of a runny paint on a wall. The yellow deposit was found to contain 0.2 1% sulphur. Under the oxide layer, a significant number of voids and blisters were detected (Fig. 2). These voids tended to concentrate near the weld, the heat affected zone and bends.

Base metal 2. H2-filled voids 3. Sulphur deposits

1. Oxide layer

After 60,000 hours service

Figure 2. Schematic diagram showing the degradation mechanism of the TH2 tubes Metallographic Examination The examination results for TH1 and TH2 (Figs. 3 and 4, respectively) are given in Table 2.

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Figure 3. A photograph showing the outer surface structure of TH1 (50x)

Figure 4. A photograph showing the TH2 structure (50x)

Table 2. Characteristics of the Outer Surface Structure of TH1 and TH2 Characteristics Skin Grain Structure Base Average Grain Diameter (mm) Grain Density (grains/mm2) Hardness tests TH1 : 155 HV5 mid - thickness 130 -160 HV5 skin TH2 : 140 HV5 skin Chemical Analysis of the Combustible Products The chemical analysis of the combustible products is given in Table 3. TH 1 Black scale 4 mm thick Decarburization up to 0.25 mm Ferrite-Pearlite fully annealed 0.041 512 TH 2 Idem Ferrite-Pearlite normalised 0.088 128

Table 3. Chemical Composition of Furnace Fuels COMPOSITION TH1 (Reforming Gas) <150 <10 86.95 6.28 3.88 2.27 0.33 0.05 TH2 (Natural Gas)* >150 83.54 7.656 1.951 0.544 0.199 5.621 0.19

H2S (ppm) HCl (ppm) H2 (% vol) C1 (% vol) C2 (%vol) C3 (% vol) C4 (% vol) C5 (% vol) N2 He * The TH2 fuel is a mixture of 95% vol. natural gas + 5% vol. hydrogen fuel-gas

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DISCUSSION The Nelson curves, Fig. 5, as compiled in API 941[2] indicate the safe area of operation for carbon steel and low alloy steel, as related to hydrogen partial pressure and temperature. Referring to these curves and the operating conditions in Table 1, it can be stated that both THs operate safely as regard to hydrogen damage. However, the presence of H2S in the combustible product of TH2, acts as a catalyst in maintaining H2 in the atomic state, which diffuses easily in the relatively coarse grain structure [3]. The accumulation of H2 in voids, many of which form at grain boundaries, results in the development of high stresses that ultimately blister the metal (Fig. 6).

1.Oxide 2.Blistered surface 3.Moisture + sulphates = H2SO4

Figure 5. Operating limits for steel in hydrogen Figure 6. Blistered outer surface of service TH1 tubes During shutdown, the moisture and condensing vapor coming from a nearby cooling tower react with the sulphur deposited on tubesouter surfaces to form H2SO4 [4]. The difference in conditions between the newly blistered surface and the scaled surface gives rise to a galvanic cell [5], and hence to electrochemical corrosion. The frequency of start-stop cycle for TH2 is much higher than that for TH1, by a ratio of 5 to 1 per year. CONCLUSIONS In refineries and chemical plants, furnace availability has become a major business problem. This paper describes corrosion damage on two tube furnaces when service conditions differ from those of the design and/or when not enough attention is given to the: 1. Chemical composition of structure of tube material, 2. Composition of the combustibles, and 3. Site position of the furnace. The two furnaces discussed are made from the same material, A335 Gr P11, and apparently operate under similar conditions. After 60,000 hours of service, both furnaces showed corrosion damage with oxidation up to 0.4 mm thick and decarburization up to 0.25
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mm deep. However, one of the furnaces revealed additional corrosion damage in the form of surface blistering. A number of tests were carried out and indicated the following causes: 1. Presence of H2 and H2S in the combustible product, 2. Low grain density, i.e., coarse grain structure of tube materials, 3. Position of the heater near a cooling tower which favors vapors condensation during shutdown periods, and 4. Number of stop-start cycles. REFERENCES 1. J. Baas and R. Warner, How much life is left in your olefin unit ?, Hydrocarbon Processing, December 1992, pp. 81-87. 2. API Publication 941, Steel for Hydrogen Service at Elevated Temperatures and Pressures in Petroleum Refineries and Petrochemical Plants, 4th edition, April 1990. 3. A.C. Million, L'Hydrogene dans les aciers et dans les joints souds, DUNOD, Paris 1971. 4. Fired heaters and stacks, Guide for Inspection of Refinery Equipment, 2nd edition, 1976, Chapter 1X, API, 1976. 5. J.A. Dean, Langes Handbook of Chemistry, 13th edition, McGraw-Hill Company, 1972, pp. 6-33.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

SUPER DUPLEX GRADE UNS S32750 FOR SEAWATER COOLED HEAT EXCHANGERS P.A. Olsson and M.B. Newman R&D Centre, AB Sandvik Steel, S-811 81 Sandviken, Sweden

ABSTRACT
The super duplex stainless steel grade UNS S32750 is presented as a candidate material for seawater-cooled heat exchangers. Due to its duplex structure, with roughly equal amounts of ferrite and austenite, the material possesses high strength and superior resistance to erosion-corrosion. In addition, the high alloying content of the material gives rise to excellent resistance to pitting and crevice corrosion as well as to stress corrosion cracking (SCC). The benefits of a super duplex stainless grade for this type of application are reviewed, mainly as a comparison with other materials such as different copper-based alloys, low alloyed stainless steels and titanium. The better resistance to erosion-corrosion is emphasized as well as a close description of why stainless steels, despite the fact that their thermal conductivity is much lower than that of copperbased alloys, still can compete as heat exchanger material in systems operating with seawater as a cooling medium. Key Words: Seawater, heat exchangers, super duplex stainless steel, erosion, heat transfer, corrosion resistance

INTRODUCTION Selecting a proper tube material for heat exchangers working with seawater as a cooling medium is a difficult task. Traditionally different copper-based alloys such as brasses, bronzes and copper-nickel alloys as well as carbon steels have been used most extensively. For severe steam-side environments high alloyed nickel-based alloys or titanium have been chosen. In applications where copper-based tubulars have failed, the stainless steel grade UNS S32750 (SAF 2507) is an alternative to the more expensive titanium and nickel based alloys for retubing. UNS S32750 is a high alloyed super duplex stainless steel, with excellent material properties. Together with high strength, hardness and resistance to erosion-corrosion, UNS S32750 possesses excellent resistance to localized corrosion such as pitting and crevice corrosion as well as stress corrosion cracking (SCC), in a seawater environment. The chemical composition and mechanical properties of UNS S32750 are given in Tables 1 and 2 below.

Table 1. Chemical Composition of UNS S32750 (Weight-Percent)

Seawater Corrosion

C (max.) Si (max.) Mn (max.) P (max.) S (max.) 0.030 0.8 1.2 0.035 0.02

Cr 25

Ni 7

Mo 4

N 0.3

Table 2. Mechanical Properties of UNS S32750 Rp0.2 (min) 550Mpa SEAWATER It is often stated that the composition of seawater is more or less the same world-wide. The variation is, however significant. The total dissolved solids, mainly sodium chloride, vary from approximately 8000 ppm in the Baltic Sea to 60,000 ppm in bay areas of the Arabian Gulf. The composition on which artificial seawater is based is about 35,000 ppm total salt which is a typical value for most seawater. The pH value in the water is approximately 8. Seawater temperature varies between only a few degrees Celsius at great depths and in the polar regions, and 30-35C in areas close to the equator and in the Arabian Gulf. When studying the corrosiveness of seawater, the main environmental factors are chloride content, pH, temperature, residual chlorine and oxygen contents, fouling, and galvanic and biological action as well as flow rate. In addition, the presence of impurities, mainly sulphides, must be considered for copper-based materials used in heat exchangers with seawater as cooling medium. The situation regarding polluted seawater will be dealt with below. The nominal saturation for dissolved oxygen in seawater is about 6-8 ppm at 25-30C. At higher temperatures the oxygen content decreases, and at lower temperatures it increases. The dissolved oxygen may also decrease to essentially zero due to bacterial action or biological or chemical oxygen demand. Copper-based alloys as well as stainless steels perform best in water having enough oxygen to keep fish alive (3-4 ppm) [1]. However, copper-based alloys do not stand up well in polluted seawater, in which dissolved oxygen has been consumed in the decay process and sulphides are present. However, tubes of UNS S32750 or titanium can serve successfully in such water. Polluted Seawater The deleterious effect of sulphides on the corrosion resistance of copper-nickel alloys in seawater has been reported by many investigators [2]. The most important parameters, excluding the dissolved sulphide content, affecting this behavior include the hydrodynamic conditions, oxidation products of dissolved sulphide, pH value, degree of turbulence, exposure time and effects of chlorine and other pollutants such as ammonia. The oxidation of dissolved sulphide by molecular oxygen not only results in a decrease of the oxygen concentration available for corrosion but also may cause considerable change in the pH of the environment [3]. The corrosion rates of both copper-based alloys and stainless steel grades are dependent on pH, making pH control of the water a major concern for operating units. Rp1.0 (min) 640Mpa Rm 800-1000 MPa A (min) 25% Hardness (Vickers) Average 290

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Dissolved sulphide ions greatly reduce the corrosion resistance of Cu-Ni alloys in aqueous systems. This effect, in flowing deoxygenated seawater, was shown by MacDonald et al. [3]. Only a low concentration of dissolved sulphides (<0.85 ppm) is necessary to cause a dramatic decrease of the polarization resistance. In the case of a 90Cu-10Ni alloy, this sulphide concentration was sufficient to lower the polarization resistance by a factor of 8, whereas for a 70Cu-30Ni alloy it was lowered by a factor of 70. Higher sulphide levels have little further impact. The upper sulphide concentration limit for copper-based alloys is controversial. Lee et al. [4] found that 0.1 ppm and even lower levels of sulphide are detrimental to copper-nickel alloys, and Carew and Islam [5] showed that small additions of sulphides dramatically affect the resistance to erosion-corrosion of copper-nickel alloys. In contrast to this, Woods et al. [6] concluded that 90Cu-10Ni alloys exposed in partially aerated and deaerated seawater containing up to 8 ppm sulphides did not suffer from corrosion attacks but instead built up a protective layer of Cu2S. Brasses have better resistance to sulphide-induced corrosion than Cu-Ni alloys have, but not as good as stainless steel in general and UNS S32750 in particular. UNS S32750 may also suffer from sulphide-induced corrosion attacks under certain circumstances but not at the levels expected in even highly polluted seawater. Tests performed in NACE solution (5% NaCl and 0.5% CH3COOH and saturated with H2S) at room temperature, an environment much more aggressive than polluted seawater, have shown that UNS S32750 is very resistant to sulphide-induced cracking. No cracking occurred on the UNS S32750 samples irrespective of the applied stress. Depending on the sulphide and oxygen levels in the water, at pH levels far below 4, sulphides may initiate corrosion of UNS S32750. This situation is, however, most unlikely to occur in seawater-cooled heat exchanger systems, and no such case has so far been reported. Microbially Induced Corrosion (MIC) Microbiological biofilms develop on all surfaces in contact with aqueous environments [7]. Water temperature, pH, content of organic and inorganic ions affect the microbiological settlement. MIC is used to designate corrosion caused by the presence and activities within biofilms. The reactions are usually localized and can include sulphide, acid or ammonia production as well as metal deposition, oxidation or reduction. Copper-based alloys are vulnerable to biocorrosion. Differential aeration, under deposit corrosion and cathodic depolarization are some of the reported corrosion mechanisms for MIC on copper-based alloys [7]. CO2, H2S and NH3 accelerate localized attack. It has also been shown [8] that Alloy 400 (UNS N04400) is highly susceptible to MIC in Arabian Gulf seawater. Stainless steels, mainly the low alloyed 304 and 316 austenitic grades but also the more highly alloyed grade 904L, suffer from MIC. Favorable conditions, in general, for it to occur are stagnant conditions, organic nutrients in the water, sediment, absence or neglect of chlorination practices as well as the presence of chlorides and sulphates. Most troublesome for both copper-based alloys and stainless steel materials are sulphatereducing bacteria (SRB). The SRB are notorious for interfering with the formation of and actually removing the protective surface oxide film. Severe localized pitting can occur on iron-bearing 90Cu-10Ni if exposed even briefly to anaerobic seawater [9]. Some SRB use hydrogen, depolarizing the cathodic surface and accelerating attack on a crevice site. SRB-

Seawater Corrosion

induced corrosion is often characterized by an encrusted deposit over a deep pit with a black powdery sulphide corrosion product underneath. At temperatures below approximately 35C, a biofilm present on a stainless steel surface will raise the open circuit potential to +300-400 mV (SCE). At this temperature, the potential increases the risk for localized attack on standard austenitic grades but not for a high alloyed material such as UNS S32750. At temperatures above 40C, the micro-organisms in the biofilm are no longer active resulting in a potential drop to essentially 0 mV (SCE) for the stainless steel material. Since localized attacks such as pitting are dependent mainly (excluding solution content) on potential and temperature the potential drop at higher temperatures is advantageous. Thus at low temperatures, the open circuit potential is elevated but not so much that it will initiate localized attack on UNS S32750, and at high temperatures the potential is kept low so corrosion attack will for that reason not initiate. Tests carried out at the Sandvik Steel R&D Centre have shown that UNS S32750 does not suffer from corrosion attacks at 95C in natural seawater. There have not been any reports of MIC attacks on UNS S32750 in operation. Chlorination In order to prevent the buildup of biofilm and to remove already attached biological species, it is common practice to chlorinate the seawater by the addition of a hypochlorite solution to the system. The usual objective is to keep residual chlorine levels below 0.5 ppm at the inlet tube sheet, but this level sometimes is exceeded and the residue is normally higher at the point of injection [1]. There is a marked difference in behavior between copperbased alloys and high alloyed stainless steel. Zanoni et al. [10] investigated the iron and manganese alloyed copper-nickel alloy C71640 and its behavior in flowing natural seawater with different chlorination levels. It was shown that 0.5 ppm free chlorine is the upper limit for the material to maintain good resistance to localized corrosion. With intermittent chlorination, which is used for economic and environmental reasons, higher doses of chlorine are used but during limited time periods. A common time period for chlorination is 2 x 15 minutes each day. The amount of chlorine added to the system varies, but levels up to several parts per million are not uncommon for heat exchanger cooling systems. This can make low alloyed stainless steels and copper-based alloys unsuitable for these systems. Grade UNS S32750 can, however, maintain its resistance to corrosion even at these high levels of chlorination. When added continuously, the chlorination of seawater increases the corrosion potential for the material to approximately +600 mV (SCE). At this high potential level, localized corrosion attacks will initiate on UNS S32750 surfaces at 75-80C in stagnant conditions and at approximately 10C above this at flow rates typical for seawater cooled heat exchanger units. When adding chlorine intermittently, the open circuit potential will be lower than with continuous chlorination but will vary with sharp potential peaks at the time of chlorine addition.

EROSION-CORROSION

Olsson and Newman

Erosion-corrosion can be defined as the acceleration of attack caused by a rapidly flowing corrodent sometimes containing solid particles capable of causing erosion or wear. Soft metallic materials such as copper, brass, aluminium and lead are prone to this form of attack, but most metals are susceptible to erosion-corrosion to some extent in particular flow situations. This form of attack is the main problem that besets copper alloys in seawater cooling systems. As the flow rate increases, brasses and bronzes become more prone to impingement attack. Aluminium brass and copper-nickel alloys offer greater resistance to higher flow rates, but both have maximum limits which must not be exceeded or the surface film will be destroyed. The resistance of some copper-based alloys can be improved with small quantities of iron present in the alloy or the water. The iron apparently produces a tougher film. This has led to the use of iron sacrificial pieces in the water boxes of heat exchangers using copper-based tubes and tube plates [11]. Normal flow velocities within heat exchangers are in the range between 1.5 and 3.0 m/s, but in extreme cases, the velocity of the seawater can rise to 4.5 m/s [1]. Most of the copperbased alloys cannot resist the erosion-corrosion of seawater at flow velocities above 3 m/s, a fact that excludes most brasses and bronzes, which perform best at water velocities below 2.2-2.5 m/s, from proper seawater cooling service for heat exchangers. Copper-nickel alloys have better erosion-corrosion resistance than brasses and bronzes but are limited in their applications. In polluted seawater, the situation is worse. Carew and Islam [5] performed erosioncorrosion tests in seawater with varying sulphide additions (0, 1, 3, 5 ppm). In the test rig, the seawater had velocities in the range between 0.2 and 8 m/s and except for 90-10 and 7030 Cu-Ni alloys also a duplex grade (UNS S32550) and a few nickel-based alloys were tested. It was concluded that the 90-10 Cu-Ni alloy suffered from severe erosion damage with no sulphides added. With a 1 ppm sulphide concentration, erosion damage was also seen on the 70-30 Cu-Ni alloy. Neither on the duplex grade nor on the nickel-based alloys could erosion damage be seen. At the higher sulphide levels, the erosion-corrosion seemed to decrease. Seawater used in cooling systems for heat exchangers and condensers often contains small amounts of sand particles. This severely increases the risk of erosion damage to copper-based alloys. Most pronounced is the effect on units equipped with brass tubing material, and attacks are frequently found at the inlet ends of condenser tubes and heat exchangers. Stainless steels, in general, and duplex grades, in particular, have much better erosion-corrosion resistance than all copper-based alloys. There is no risk of erosioncorrosion damage of UNS S32750 at the velocities occurring in seawater-cooled heat exchangers. Erosion-corrosion testing performed at SINTEF [12] showed that UNS S32750 had low erosion-corrosion rates in seawater containing 0.25% of silica sand particles at a flow rate as high as 18.3 m/s. HEAT TRANSFER The thermal conductivity of stainless steel is much lower than that of copper-based alloys. If this were the only criterion for selecting a proper alloy for the heat exchanger application, stainless steel would never have been selected. In Table 3, the thermal conductivities of some different materials are given [13].

Seawater Corrosion

Table 3. Thermal Conductivities (W/mK) of Some Materials (the values are all approximate) Carbon and Low Alloyed Steel 40-55 Stainless Steel Including UNS S32750 15 Brasses Bronzes Cu-Ni Alloys 30-50 Glass

120

70

0.9

As can be seen from Table 3, UNS S32750 has a thermal conductivity 2-10 times lower than all copper-based alloys. However, the heat transfer properties of tubular products cannot be based exclusively on the thermal conductivity of the material itself. Other factors such as the steam film, corrosion products, deposits and cooling water film must be considered. Actually, the thermal conductivity of the tubular material in a heat exchanger has so little influence on the overall heat transfer performance of the system that this term can be neglected when calculating heat transfer rates. Table 4 illustrates the various factors affecting resistance to heat transfer in actual service. It is obvious that surface films affect overall performance to a far greater degree than the metal wall, which accounts for no more than 2% of the total resistance to heat flow. Table 4. Influence of Various Factors on the Heat Resistance of a Water-Cooled Heat Exchanger [14] Steam Side Water Film 18% Steam Side Fouling 8% Tube Wall 2% Water Side Fouling 33% Water Side Film 39%

Despite poorer thermal conductivity properties, UNS S32750 offers as good heat flow properties as copper-based alloys do for seawater-cooled heat exchanger and condenser units. GALVANIC CORROSION Galvanic processes occur between different metals when they are coupled to each other via a conductive media such as seawater. Current will flow with oxidation taking place at the anode, and reduction (normally oxygen reduction) occurring at the cathode. If the two metals' free corrosion potentials, Ecorr, differ by hundreds of millivolts from one another, the metal with the more noble Ecorr value will become predominantly cathodic and the metal with the more active Ecorr value will be the predominantly anodic one and will corrode. If the difference is of the order of tens of millivolts, galvanic corrosion is less likely. In Table 5, the corrosion potentials in natural seawater for some metals and alloys are given. The values shall all be seen as approximate values, since the corrosion potentials differ with both flow rate and temperature of the seawater.

Olsson and Newman

Table 5. Galvanic Series in Seawater (the values are all approximate) Metal/ Alloy Voltage (mV/SCE) Zn -1050 Steel -600 Brasses -300 Cu-Ni Alloys -200 Ti 0 UNS S32750 +50 Pt +250

According to the text above and Table 5, galvanic corrosion is likely to occur copperbased tubulars are replaced with stainless steel or titanium tubing if the tube sheets are not replaced at the same time. Investigations made on severely corroded, copper-based, alloy tube sheets in connection with stainless steels and titanium have shown that the whole inside of the noble alloy tubes becomes effective as a cathode in copper-based alloy coupled to stainless or titanium [15]. Stainless steel or titanium tubing increases copper-based alloy tube sheet attack to a point where impressed current cathodic protection normally is required to control tube sheet corrosion. If titanium is to be used as replacement tubes, the cathodic protection unit must be controlled to avoid hydriding of the tubes. The oxide film that normally covers the surface of titanium has been shown to be an effective barrier to hydrogen penetration. In environments where this film is unstable or where the oxide film has been damaged by abrasion, hydrogen absorption can occur [16]. At potentials below approximately -700 mV (SCE), production of hydrogen will occur and the risk for hydriding of titanium increases. If zinc is used as a cathodic protection material, the potential will be significantly lower than this in seawater, 1000 mV (SCE), and hydrogen absorption is most likely to take place in the titanium tubulars. The R&D Centre at AB Sandvik Steel has performed tests on UNS S32750 in connection with zinc in solutions comparable to seawater at a potential of -1000 mV (SCE). The tests were conducted at a temperature of 80C, and the results show that hydrogen embrittlement will not harm the material in normal service situations. If pure iron is used instead of zinc as a cathodic protection material the risk for hydrogen embrittlement will totally disappear for UNS S32750. In contrast, it has been observed [16] that hydriding of titanium occurs most frequently in solutions containing H2S where galvanic couples with iron exist. Thus, when choosing UNS S32750 instead of titanium when replacing copper-based alloy tubulars in heat exchangers, the problem with hydrogen absorption and embrittlement is reduced to a minimum if the tube sheets are correctly cathodically protected. STRESS CORROSION CRACKING Low alloyed stainless steel grades, such as types 304 and 316, are prone to chlorideinduced SCC at temperatures above 50C which is one of the reasons why these materials cannot be used in many of the seawater-cooled heat exchanger systems operating today. Duplex grades do, however, possess very good resistance to stress corrosion due to their dual microstructure and alloying contents. In seawater cooling systems for condensers and heat exchangers, UNS S32750 can be considered as being immune to SCC, and no such case has been reported. Neither has titanium suffered from SCC in seawater-cooled heat exchangers. Copper-based alloys do not normally suffer from SCC in these applications, but brasses have a clear tendency towards SCC in the presence of ammonia or ammonium salts [17].

Seawater Corrosion

LOCALIZED CORROSION Stainless steels suffer from localized attacks, i.e., pitting and crevice corrosion, in chloride-containing solutions such as seawater. Crevice sites are unlikely to occur if the chlorination procedures are carried out correctly and a continuous flow is maintained inside the tubes. Much of the sediment entrained in cooling water deposits out in the bottom of condenser and heat exchanger tubing at velocities below about 1-1.5 m/s and during shutdowns. Any unit designed or operated at lower velocities is a prime candidate for under sediment crevice attack, MIC or both [15]. Therefore, it is of great importance to rinse the inside of the tubes during shutdowns with freshwater, independent of material used for the tubulars. As for crevice attacks, the primary cause of pitting is the presence of chloride ions. Often pitting attacks are initiated at defects at the surface like slag inclusions or chromiumrich precipitates around which a chromium depleted zone is present. Welds are very likely the initiation sites for localized attacks because of their sometimes inhomogenous structure and the presence of intermetallic precipitates in the melted or heat-affected zones adjacent to the welds. Therefore, seamless tubes are preferred to welded ones. Pitting is temperature-dependent, but will not occur in UNS S32750 in seawater at normal potentials. However, chlorination of the seawater increases the open circuit potential to approximately +600mV (SCE). At this high potential, pitting occurs very rapidly in low alloyed stainless steels. For UNS S32750, the risk of pitting in seawater systems is very low, provided the temperature is kept below 75-90C, depending on the flow rate of the cooling water. Tests performed at the R&D Centre at AB Sandvik Steel have shown that the critical pitting temperature (CPT), i.e., the lowest temperature at which pitting initiates in a given environment, increases with flow rate. The tests were performed in synthetic seawater with the material being put to a potential of +600 mV (SCE). For stagnant conditions at this potential, the CPT is 75-80C. For flow rates above 1.6 m/s, the lower flow rate limit for most heat exchangers, it was shown in the tests performed at Sandvik that pitting would not initiate at temperatures below 85C; CPTs at 90C and above were measured for flow rates at 2.2 m/s. According to Quik and Gedeuke [18], super duplex grades of the UNS S32750 type can be used in unchlorinated seawater cooling systems up to 100C provided a constant flow can be assured. CASE HISTORY 1: SEAWATER CONTAINING H2S In a condenser equipped with copper-nickel material (90Cu-10Ni tubes and 70Cu-30Ni tube sheet), the tubes started leaking after less than four weeks in service. The seawater contained H2S in an amount such that the environment became very corrosive to copper-based alloys. As replacement tubing, the main candidate materials were UNS S32750 and titanium. Due to the risk of hydriding of the titanium tubes because of hydrogen generation when cathodically protected (to suppress the galvanic action between the titanium and the Cu-Ni tube sheet) and vibration effects due to the lower rigidity of the thin-walled titanium tubes, thereby causing risk of fatigue failure, UNS S32750 was chosen as the replacement material, and the tubes were installed in October 1995.

Olsson and Newman

CASE HISTORY 2: SEAWATER CONTAINING SAND Seawater containing sand can be a very severe environment for copper-based alloys, particularly for brasses. An example of this is a vacuum overhead condenser operated by a refinery in Singapore which failed in such an environment. At flow rates as low as 1.5 m/s the admiralty brass system started to leak because of erosion-corrosion effects. The maximum seawater temperature when the failure occurred was 60C. Flow rates between 1.0 and 1.5 m/s are seen by most operators as the minimum rate to prevent sediment build-up in seawater cooling systems. These two facts, that flow rate should be kept above 1.0-1.5 m/s and that admiralty brass failed at a fluid velocity of 1.5 m/s, imply that admiralty brass must be seen as an unsuitable material for cooling systems working with seawater containing sand particles. In 1993, UNS S32750 tubes were installed, and they have performed perfectly since. CASE HISTORY 3: SAF 2507 LIMITING PARAMETERS In a heating medium dump cooler operating on an oil platform UNS S32750 tubes suffered from localized attack and started leaking after having been exposed to seawater at too high a temperature. Initially the cooler was equipped with UNS S31254 tubes which failed after 18 months in service. UNS S32750 tubes were used as replacement material. The service conditions inside the tubes, when working properly, i.e., with a continuous flow, were aerated, chlorinated (0.8 ppm) seawater at a temperature of T=27-33C. However, stagnant conditions or very low flow rates occurred every now and then in the cooler which made the seawater increase its temperature because of a warmer (100-240C) mineral oil on the shell side. Temperatures above 80C at certain "hot spots" adjacent to the baffles, combined with chlorides from the seawater, made pitting of the tubes possible. After 30 months of service, the UNS S32750 material started leaking. DISCUSSION By emphasizing different aspects of seawater, and its influence on the heat exchanger material, it has been shown that within certain limits UNS S32750 is a better choice than mainly copper-based alloys, and also, due to the duplex grade's lower price, a better choice than titanium and nickel-based alloys for seawater-cooled heat exchanger applications. UNS S32750 possesses extremely good erosion-corrosion properties compared to copper-based alloys, which have been shown to suffer from this form of attack even at very low flow rates of the fluid. Not only the fluid velocity of the water, but also the sand, H2S, CO2 and NH3 contents play an active role in the erosion and corrosion behavior of the copper-based alloys. To prevent biofilm formation of the metal surface exposed to seawater, chlorination of the water is widely used. With constant chlorination the levels of residual chlorine in the system most often are in the range between 0.1 and 0.4 ppm. The upper limit for copperbased alloys is approximately 0.5 ppm chlorine, whereas UNS S32750 can tolerate as much as several parts per million [19]. The trend today is toward the use of intermittent chlorination, which will lead to high chlorine levels (several parts per million) for shorter periods each day. With the use of UNS S32750, there should be no corrosion problem due to these higher levels.

Seawater Corrosion

If exclusively taking thermal conductivity levels of different materials into account, one can conclude that UNS S32750 has approximately 2-10 times worse properties than copperbased alloys. As shown in this paper, however, the thermal conductivity of the tube material contributes only 2% of the overall heat transfer of the system and can thus be neglected. Seawater can, depending on its content and temperature, be corrosive to copper-based alloys as well as to high alloyed stainless steels such as UNS S32750. In natural seawater with no chlorine added, temperatures as high as 95C have been shown to not be high enough to initiate corrosion attacks alone. When normal continuous chlorination procedures are used, however, the open circuit potential rises to approximately +600 mV (SCE) for UNS S32750. At this potential, the CPT for UNS S32750 is 75-80C for stagnant conditions and 10C higher if a continuous flow above 1.5 m/s is maintained. CONCLUSIONS 1. Copper-based alloys suffer from erosion-corrosion damage at flow rates occurring in seawater-cooled heat exchangers. UNS S32750 does not suffer from erosion at fluid velocities far above those likely to be maximum for heat exchanger applications. 2. Normal chlorination procedures, continuous or intermittent, will not initiate corrosion of UNS S32750 as long as temperature and flow rate are kept within specified ranges. 3. Despite the lower thermal conductivity of UNS S32750 compared to copper-based alloys, the overall heat transfer capacities of the different material systems are equal. 4. UNS S32750 does not suffer from pitting corrosion attacks at 95C in unchlorinated seawater or at 75-80C in stagnant chlorinated solutions. With flow rates above 1.5 m/s, typical for heat exchanger systems, tests have shown the critical temperature limit to be above 85C. These test results are good indications of the temperature intervals within which UNS S32750 can be used. 5. With much better erosion and corrosion properties than copper-based alloys and with properties at least as satisfactory as those of titanium and nickel-based alloys, UNS S32750 must be considered to be one of the very best alternatives for seawater-cooled heat exchangers in need of tube replacement. REFERENCES 1. 2. 3. 4. Tuthill, Chemical Engineering 97, 1, 1990, pp. 120-124. Reda and Alhajji, British Corrosion Journal 30, 1, 1995, pp. 56-62. MacDonald, Syrett and Wing, Corrosion 35, 8, 1979, pp. 367-378. Lee, Hack and Tipton, Proceedings 5th International Congress on Marine Corrosion and Fouling, May 1980, Barcelona, Spain, Comit International Permanent pour la Recherche sur la Preservation des Materiaux en Mileau Marin. Carew and Islam, Materials Performance 34, 4, 1995, pp. 54-57. Woods, Amos and McNeil, Corrosion/92, April 1992, Nashville, Tennesse, USA, Paper No.180. Wagner and Little, Materials Performance 32, 9, 1993, pp. 65-68. Gouda, Banat, Riad and Mansour, Corrosion 49, 1, 1993, pp. 63-73.

5. 6. 7. 8.

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9. MTI, Performance of tubular alloy heat exchangers in seawater service in the chemical process industries, Publication No.26, St. Louis, Missouri, USA, Materials Technology Institute of the Chemical Process Industries, Inc. & NiDi, August 1987, pp. 8-9. 10. Zanoni, Gusmano, Montesperelli and Traversa, Corrosion 48, 5, 1992, pp. 404-410. 11. Tretheway and Chamberlain, Corrosion for Students of Science and Engineering, 2nd ed., Hong Kong, Longman Group Limited, 1990, pp. 285-288. 12. Rogne and Solem, Erosion-corrosion testing of stainless steels, SINTEF Corrosion Center, Publication No. STF34 F93017, February 1993. 13. Hedner (ed.), Formelsamling i Hallfasthetslara, The Department of Mechanics of Materials, The Royal Institute of Technology, Stockholm, Sweden, 1990, pp. 205-213. 14. Davison and Miska, Chemical Engineering 86, 2, 1979, pp. 129-133. 15. NiDi, Guidelines for selection of nickel stainless steels for marine environments, natural waters and brines, Publication No.11003, NiDi reference book series, 1987, pp. 3-6 16. Covington, Corrosion 35, 8, 1979, pp. 378-382. 17. Rckert, Werkstoffe und Korrosion 47, No.2, 1996, pp. 71-77. 18. Quik and Gedeuke, Stainless Steel Europe 6, No.10, 1994, pp. 46-51. 19. Gartland and Drugli, Crevice corrosion of high alloyed stainless steels in chlorinated seawater, Part I: Practical aspects, Corrosion /91, March 11-15, 1991, Cincinnati, Ohio, USA, Paper No.510.

Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

EVALUATION OF ALUMINUM ALLOY 5083 WELDMENTS TO STRESS CORROSION CRACKING IN SEAWATER A. Saatchi1, M.A. Golozar1 and R. Mozafarinia2
1

Materials Engineering Department, Isfahan University of Technology, Isfahan, Iran


2

Defense University, Shahin-Shahr, Iran

ABSTRACT
The susceptibility of aluminum-alloy 5083 and its weldments to stress corrosion cracking (SCC) was investigated using constant strain and slow strain rate (SSR) tests in actual seawater, in the Bandar Bushehr region, and in 3.5% NaCl solution, respectively. Also, electrochemical polarization and immersion tests were performed to study the corrosion rate of the aluminum alloy and its weldments. In addition, long-term tests, on actual sections of a marine vessel for a period of one year, were used to investigate the corrosion behavior of alloy 5083 and its weldments in Bushehr seawater. Scanning electron microscopy (SEM) was employed to characterize the nature of corrosion and SCC in the specimens tested under various conditions. The results indicated higher corrosion rates in 3.5% NaCl solution than in seawater. Also, the corrosion rates of welded specimens were higher than those of unwelded specimens. In addition, the results revealed no susceptibility to SCC of the alloy and its weldments in Bushehr seawater. Key Words: Aluminum alloy 5083, stress corrosion cracking, weldments, Persian Gulf

INTRODUCTION Aluminum alloy 5xxx series are non-heat-treatable alloys containing Mg and are widely used for the construction of marine structures and vessels. On the other hand, during the welding of these alloys, Mg2Al3 precipitates along the grain boundaries. Mg2Al3 is anodic with respect to the base metal, and thus may render the alloy susceptible to stress corrosion cracking (SCC). SCC often causes unexpected costly failures. This is due to a lack of visual evidence of corrosion as compared with uniform and localized corrosion. SCC is a cracking phenomenon under the conjoined action of tensile stress and corrosion, which happens for some metals in specific environments. In other words, there are three main factors acting together in SCC: tensile stress, which can be working or designed stress, or residual and thermal stresses due to welding and other operations; the corrosion environment which is affected by major and minor chemical composition, temperature, velocity or turbulence, and even biological activities of the environment; and the susceptibility of the metal to SCC, which can be affected by the chemical composition, microstructure, and thermal and mechanical operations.

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Seawater is a complex biochemical broth. Its nominal chemical composition is 2.9% NaCl plus 0.4% MgSO4, but in reality it contains traces of just about everything one can imagine [l]. Its high chlorinity makes it corrosive to most metals and alloys. Chloride also causes localized corrosion and SCC in many metals. The action of biological organisms also create a complex situation for predicting the performance of alloys in seawater. So whereas there are cases in which the results of SCC of steel in nominal seawater are identical to the results in 3.5 NaCl solution [2,3], there are other cases where different behavior has been reported [4]. The purpose of this study was to evaluate the SCC susceptibility of aluminum alloy 5083 and its weldments in Persian Gulf water. The test station was located in Bandar Bushehr, toward the north of the Persian Gulf. Table 1 shows the chemical composition of the Bushehr seawater. The salinity of the water is high, which is manifested by its 2.34% chloride content. In the laboratory, slow strain rate (SSR) tests were performed in natural seawater and in 3.5% NaCl solution. In the field, constant strain rate tests were performed in Bandar Bushehr seawater for 12 months at various depths below the waters surface. Also, two specimens simulating the most critical sections of a marine vessel with regard to welding, manufacturing and internal operational stresses were immersed at a depth of 5 m below the waters surface for 1 year. In addition, the corrosion rates of the base metal and the weld metal were measured using weight loss and electrochemical polarization tests. Optical and scanning electron microscopy (SEM) were also employed to investigate the microstructure of the weld metal, heat affected zone (HAZ) and fracture surfaces of the specimens. Table 1. Chemical Composition of Bandar Bushehr Seawater
Dissolved solids (%) Total Hardness (ppm) Ca (ppm)
2+

Mg (ppm)

2+

pH

Dissolved O2 (mg/l)

Salinity (gm/l)

Cl (%)

6052

1335

7387

4.09

7.8

5.98

42.48

2.34

EXPERIMENTAL PROCEDURE Specimens Preparation The specimens for the various tests were cut from a 5 mm plate of the Al alloy 5083-O. The chemical composition and mechanical properties of the alloy are shown in Tables 2 and 3, respectively. For weldments, the one-sided V-notch was used. Tungsten metal arc with inert gas (TIG) and filler material 5183 were used for welding. Table 2. Chemical Composition of Aluminium Alloy 5083-O (in wt.%) Si 0.4 Fe 0.4 Cu 0.1 Mn 0.4-1.0 Mg 4.0-4.9 Cr 0.05-0.025 Zn 0.25 Ti 0.15 Al balance

Table 3. Mechanical Properties of Aluminum Alloy 5083-O


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Temper O Immersion Tests

Tensile Stress (MPa) 290

Yield Stress (MPa) 145

Elongation (%) 22

Immersion tests were used to measure the corrosion rate of the base metal, with and without welding, using the ASTM Gl standard. The specimens dimensions were 20 x 50 x 5 mm. Polarization Tests The cathodic and anodic polarization of the alloy and weld metals in actual seawater and 3.5% NaCl solution were determined by a potentiodynamic technique based on ASTM G587. The corrosion rates of the specimens were also calculated using the linear polarization technique. The electrochemical measurements were performed using a standard potentiostat, Wenking model ST72, with a Ag/AgCl reference electrode.

Figure 1. The details of specimens used for constant strain stress corrosion tests (a) unwelded; (b) cross weld; and (c) longitudinal weld

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Constant Strain SCC Tests Figure 1 shows the details and types of specimens which were used for these experiments. The test plates on these fixtures were either plain, i.e., without welding (Test Piece a) or welded (Test Pieces b and c). The welding direction was either parallel to the rolling direction of the plate or perpendicular to it. Constant strain SCC tests were performed according to ASTM G39. The specimens were exposed to Persian Gulf seawater off the Bandar Bushehr coast at depths of 5, 7, and 9 m for 12 months. The applied stress on all the specimens was the yield stress of the alloy. In order to avoid galvanic and crevice corrosion, the H-beam, nuts and bolts at both ends of the specimens were made from the same alloy. Also, two specimens (Part Nos. l and 2) simulating the most critical condition of a marine vessel (shown in Fig. 2) were immersed at a depth of 5 m below waters surface in Bandar Bushehr for one year. Part No. 1 had severe forming stresses along with welding residual stresses. Part No. 2 was a hollow vessel with extensive welds containing air at a pressure of 3.5 atm.

Figure 2. Part Nos. l and 2 simulating the most critical condition of a marine vessel Slow Strain Rate (SSR) Tests Figure 3 shows the details of the specimens which were used in SSR tests. For these tests an SSR testing machine, based on the recommendations of Parkins [5], was designed and -6 -1 constructed. The strain rate used was 3 x l0 s . This was based on the previous results obtained [6,7]. Stress-strain curves for specimens without welding and welded in the gauge
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length area were obtained. These curves were plotted in various conditions including: air, seawater and 3.5% NaCl solution. The fracture surfaces of the SSR specimens were studied using SEM (JEOL model S6400).

Figure 3. Details of the specimens used in the SSR tests: (a) unwelded; and (b) welded Intergranular Corrosion Tests In order to determine the extent of precipitation of Mg2A13 and its effect on intergranular corrosion, intergranular corrosion tests were performed on specimens with the dimensions 50 x 6 x 5 mm in concentrated nitric acid based on ASTM G67-80. The weight loss was measured. RESULTS AND DISCUSSION Figures 4 and 5 show the potentiodynamic polarization curves of the base metal and weld metals in Bandar Bushehr seawater and in a 3.5% NaCl solution. All the data in these curves are summarized in Table 4. The corrosion rates obtained for the base metal and weld metal using the linear polarization technique and immersion tests are also summarized in Table 4. In laboratory tests, specimens show a lower corrosion rate in seawater than in 3.5% NaCl solution. This could be due to the lower salinity of the seawater compared to the 3.5% NaCl solution. In all the test methods, welded specimens showed higher corrosion rates than unwelded ones. This is due to the precipitation of anodic Mg2Al3 in grain boundaries in the HAZ during welding. Table 3 shows that the corrosion rates obtained by electrochemical methods were an order of magnitude higher than those obtained in either immersion tests in the laboratory or in actual field conditions. This is obviously due to the fact that the duration of the immersion tests in actual field conditions was long enough for hard marine fouling to develop on the surface of the metal and thus protect it from further corrosion. Table 4 also
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shows that the corrosion rates in actual field conditions were higher than the corrosion rates in the laboratory immersion tests. This clearly indicates that the corrosion conditions in the sea were more intense than in the laboratory situations.

Figure 4. Potentiodynamic polarization curves for aluminium alloy 5083 in seawater and 3.5% NaCl solution

Figure 5. Potntiodynamic polarization curves for welded alumimium alloy 5083 in seawater and 3.5% NaCl solution

Table 4. Polarization and Immersion Test Results


Polarization Test Results Corrosion Corrosion Corrosion Potential Rate Current Density (mpy) Unwelded Unwelded Seawater 3.5% NaCl Solution seawater 3.5% NaCl Solution 2.4 x 10 4.6 x 10
-2 -2

Specimen type

Environment

(mA/cm2) 0.054 0.105

(mV) -859 -765

Immersion Tests in Laboratory Corrosion Rate (mpy) 8.4 x 10 1.2 x 10


-4 -3

Immersion Tests in Bandar Bushehr corrosion Rate (mpy) 1 x 10 --3 -3

Welded Welded

2.9 x 10 4.4 x 10

-2 -2

0.066 0.095

-848 -800

1.1 x 10 9.2 x 10

-3 -4

1.54 x 10 --

Figure 6 shows typical constant strain rate specimens and Part Nos. l and 2 that were immersed at various depths below the waters surface in Bandar Bushehr region for 12 months before cleaning. Severe hard fouling can be seen. After cleaning the specimens, they were inspected for cracks. No cracking was observed in either of the specimens. These results, summarized in Table 5, indicate that neither the base metal, nor the welded specimens show any cracking under stress after 12 months of exposure to Bandar Bushehr seawater.
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Figure 6. Constant strain test specimen and Part Nos. 1 and 2 before cleaning exposed in Bandar Bushehr seawater for 12 months Table 5. Results of Constant Strain Tests and Simulated Service Condition Tests in Bandar Bushehr Seawater for 12 months
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Specimen Type Unwelded Transverse weld Longitudinal weld Unwelded Transverse weld Longitudinal weld Part No. 1 Part No. 2

Depth (m) Splash zone Splash zone 5 5 5 5 5 5

Results No cracks No cracks No cracks No cracks No cracks No cracks No cracks No cracks

Figures 7 and 8 show the typical stress strain curves for the aluminum alloy 5083 with and without welding obtained by the SSR testing machine. The specimens were tested in air, as well as in seawater and 3.5% NaCl solution. The results obtained from these tests are summarized in Table 6. There is no indication of SCC susceptibility from these test results.

Figure 7. Load versus strain for aluminum alloy 5083 in air, seawater, and 3.5% NaCl solution

Figure 8. Load versus strain for welded aluminum alloy 5083 in air, sea water, and 3.5% solution

Figure 9 shows a typical SEM fractograph of the fractured surface of the SSR test specimens. All the fractured surfaces showed dimple fracture and no indication of susceptibility to SCC in the environments tested. Table 7 summarizes the intergranular test results in nitric acid, according to ASTM G6780. The data shows that the average weight loss of the unwelded specimens was 2.46 mg/cm2, and that of the welded specimens was 3.54 mg/cm2. These rates are below the range of integranular susceptibility according to the ASTM standard.

Table 6. SSR Test Results on Aluminum Alloy 5083

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Specimen Unwelded Welded Unwelded Welded Unwelded Welded

Environment Air Air Seawater Seawater 3.5% NaCl solution 3.5% NaCl solution

Failure Time (h) 24.40 17 24.30 21.16 26 20.43

Max Load (N) 1900 1100 1600 1802 1540 1610

Failure Load (N) 1490 1050 1380 1690 1320 1600

Failure Stress 2 (N/mm ) 99.3 70 92 113 88 106.6

Figure 9. Typical SEM fractograph of the fractured surface of an SSR test specimen in seawater: (a) unwelded; and (b) welded Table 7. Intergranular Test Results on Welded and Unwelded Aluminum Alloy 5083 Specimen Area (mm ) 1333 1227 1552 1025
2

Unwelde d Unwelde d Welded Welded

Initial Weight (gr) 4.0915 3.8998 6.2633 2.8906

Final Weight (gr) 4.0515 3.8765 6.2028 2.8581

Weight Loss (gr) 0.04 0.0233 0.0605 0.0325

Weight Loss 2 (gr/cm ) 3 1.91 3.9 3.17

Average (mg/cm )
2

Rating

acceptable 2.46 acceptable 3.54

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CONCLUSIONS 1. Constant strain specimens and also simulated marine vessel parts made from aluminum alloy 5083 with and without welding, immersed in Persian Gulf seawater at various depths for 12 months did not show any cracking tendency. 2. SSR test results and SEM fractographs of the fractured surfaces did not show any indication of SCC susceptibility of this alloy with or without welding. 3. Welding aluminum alloy 5083 with TIG, increased the corrosion rate, due to grain boundary precipitation, but the intergranular corrosion rate remained in the acceptable range. REFERENCES 1. G.A. Gehring, Materials Performance 9, 1987, p. 9. 2. G. Sandoz, Stress Corrosion Cracking in High Strength Steels and in Titanium and Aluminum alloys, B.F. Brown, ed., Naval Research Laboratory, 1972. 3. G. Sandoz, Metallurgical Transactions 2, 1971, p. 1055. 4. H.P.Lockie and A.W. Loginow, Corrosion 14, 1968, p. 291. 5. R.N. Parkins, ASTM STP 665, 1987, pp. 2-25. 6. M. Sobhani, M.Sc. Theses, Materials Engineering Department, Isfahan University of Technology, 1990. 7. R. Mozafarinia, M.Sc. Theses, Materials Engineering Department, Isfahan University of Technology, Iran, 1994.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CAVITATION CORROSION BEHAVIOR OF SOME CAST ALLOYS IN SEAWATER A. Al-Hashem, P.G. Caceres and H.M. Shalaby Materials Application Department Kuwait Institute for Scientific Research, P.O. Box 24885, 13109 Safat, Kuwait

ABSTRACT
This paper summarizes the results of extensive laboratory research carried out on the cavitation corrosion behavior of three cast alloys in seawater. The alloys studied were nodular cast iron (NCI), nickel-aluminum bronze (NAB) and duplex stainless steel (DSS). The work included measurements of free corrosion potential, potentiodynamic polarization and mass loss in presence and absence of cavitation. The cavitation tests were made using an ultrasonically induced cavitation facility at a frequency of 20 kHz. Cavitation caused an active shift in the free corrosion potential and increased the anodic polarization current for the three cast alloys. In quiescent seawater, the rates of mass loss were very low for all of the alloys studied. Cavitation increased the rates of NCI, NAB and DSS by 930, 186 and 20 times, respectively. However, the application of cathodic protection decreased the rates of NCI, NAB and DSS by about 50%, 47% and 19%, respectively. Morphological examinations revealed that thin scales were formed on NCI in quiescent seawater, while NAB suffered from selective corrosion of the copper-rich phase. On the other hand, DSS was almost free of corrosion in quiescent seawater. Cavitation made the surfaces of the alloys very rough, exhibiting large size cavities and ductile tearing. The cavitation damage started at the graphite nodules and ferrite matrix in NCI, the boundaries of columnar grains in NAB, and the ferrite/austenite boundaries and the austenite islands in DSS. Cross-sectional examinations revealed microcracks in the bulk of the alloys. The formation of microcracks was attributed to cavitation stresses and preferential phase corrosion. Key Words: Nodular cast iron, nickel-aluminum bronze, duplex stainless steel, cavitation corrosion, microstructure, corrosion morphology, seawater corrosion

INTRODUCTION During the last few years, extensive research was made in our laboratory in the investigation of the flow-dependent corrosion behavior of cast alloys used in the manufacturing of seawater valves and pumps. This research was due to the repeated failures of such components in the seawater systems of the petroleum refineries in Kuwait. Failure analysis [1-3] revealed that the damage was due to a combination of several factors that included cavitation corrosion, erosion-corrosion and preferential phase corrosion. This paper summarizes the results of laboratory cavitation studies made on nodular cast iron (NCI), nickel-aluminum bronze (NAB) and duplex stainless steel (DSS). The work was aimed at (1) determining the relative susceptibility of the three cast alloys to cavitation damage; (2)

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determining the effect of the application of cathodic protection in minimizing the degree of damage; and (3) characterizing the role played by the different phases of the alloys during cavitation. Cavitation may be defined as the growth and collapse of vapor bubbles due to localized pressure changes in a liquid. The collapse process takes place extremely rapidly, producing strong shock waves that damage the material. Because a few million bubbles may collapse in a second, damage quickly occurs. Published work [4,5] has shown that both mechanical and electrochemical factors are involved in cavitation. Many investigators [4-7] have indicated that cavitation can be reduced by applying cathodic protection to the cavitating body. EXPERIMENTAL PROCEDURE A study was made on specimens machined from the base of a failed NCI valve, the upper casing of a failed NAB pump, and commercially cast DSS. Table 1 shows the chemical composition of the alloys studied. Table 1. Chemical Composition of Cast Alloys Used in the Cavitation Studies Element (%)
Cast Alloy NCI NAB DSS C 3.54 0.04 Si 2.26 0.57 Mn 0.40 1.20 0.54 P 0.05 Cr 24.40 Ni 4.90 5.60 Mo 2.50 Cu 80.00 Al 9.00 N2 0.12 Fe Bal 4.90 Bal

NCI: Nodular cast iron NAB: Nickel-aluminum bronze DSS: Duplex stainless steel The microstructure of NCI after polishing and etching in 4% nital solution consists of spheriodal graphite in a ferrite matrix. The microstructure of NAB after etching in a 10% solution of ferric nitrate consists of columnar grains of phase, which is a face-centered cubic (fcc) copper-rich solid solution; a small volume fraction of lamellar eutectoidal phases of phase or retained , which is martensitic; and intermetallic phases of basically four morphologies (designated as I, II, III, and IV). The I, II, and IV phases are all ironrich precipitates with a body-centered cubic (bcc) structure based on aluminum-ironintermetallic (Fe3Al), while the III phase is a nickel-rich precipitate based on the structure of aluminum-nickel intermetallic (NiAl) [8]. The microstructure of DSS after etching in 15% ethanolic solution consists of a ferrite matrix in which austenite grains were present as islands. All the specimens used in the present work were in the form of discs, measuring 1.6 cm in diameter and 0.27 cm in thickness. However, in the case of the cavitation testing, the specimens had threads, as they were machined in accordance with the requirements of ASTM G32-92 [9]. Before testing, all the specimens were mechanically ground with silicon carbide paper, cleaned, degreased, and then weighed. For the morphological studies, some specimens were etched before testing.

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The study was made in untreated seawater collected from the Arabian Gulf. This seawater is very saline (46,000 TDS), and it has a pH of about 8.0. The composition of this seawater has been previously reported [10]. The cavitation tests were carried out at a frequency of 20 kHz and an amplitude of 25 m using an ultrasonically induced cavitation facility. The facility consists of a generator, a converter, and a disrupter horn. The test specimens were mounted on a special holder which was placed at a distance of 0.125 cm from the apparatus horn. The specimens area facing the horn, and thus exposed to cavitation, was 1 cm2. The seawater was contained in an open 600-ml Pyrex beaker surrounded by a copper cooling coil in a water bath. The seawater electrolyte was maintained at 25 + 1oC by controlling the flow rate and the temperature of the circulating chilled water. The cavitation tests were made under free corrosion and cathodic protection (CP) conditions. In the later tests, the specimens were kept at a single potential value more negative than the free corrosion potential by 50 mV for NCI and NAB and 100 mV for DSS. The specimens were weighed after different time intervals in order to determine the rate of mass loss as a function of cavitation time. In order to compare the rate of mass loss in the presence of cavitation with that obtained in its absence, the rate of mass loss was also determined for specimens immersed in quiescent seawater under free corrosion conditions. In order to evaluate the role of cavitation on the electrochemical behavior of the materials, open-circuit potential and potentiodynamic polarization measurements were made under quiescent and cavitation conditions. The polarization tests were carried out using standard equipment at a scan rate of 0.5 mVs-1 starting from a potential value more negative than the open-circuit potential. A saturated calomel reference electrode (SCE) and a graphite counter electrode were used in these experiments. To follow up on the development of cavitation damage and to identify the susceptibility of the constituent phases to cavitation, detailed morphological examinations were made on all tested specimens using scanning electron microscopy (SEM). RESULTS AND DISCUSSION Effect of Cavitation on Rates of Mass Loss The rates of mass loss under quiescent conditions were very small for all alloys. In the presence of cavitation, the mass loss behavior was quite similar for the three cast alloys. In all cases, the rate of mass loss initially increased till it reached a maximum. Then, it sharply decreased with the increase of cavitation time, followed by a slow decrease till a steady-state was reached. This behavior remained unchanged in the presence of CP. However, the rates of mass loss of specimens cavitated under free corrosion conditions were substantially higher than those obtained in presence of CP. Figure 1 is given as an example to show the rates of mass loss obtained for NAB and DSS, while Table 2 gives a summary of the rates of mass loss at the steady-state for the three cast alloys after various test conditions.

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Figure 1. Rates of mass loss of: (a) NAB; and (b) DSS specimens, exposed to seawater under various conditions. Table 2. Rates of Mass Loss (in mg.hr-1.cm-2) for Cast Alloys Exposed to Seawater Under Various Test Conditions Test Condition Cavitation under free corrosion Cavitation under CP Quiescent NCI: Nodular cast iron NAB: Nickel-aluminum bronze DSS: Duplex stainless steel NCI 3.12 1.56 3.36 x 10-3 NAB 1.50 0.80 8 x 10-3 DSS 0.64 0.52 2.5 x 10-4

It is clear from Table 2 that the rates of mass loss of the cavitated specimens under CP were lower than those under free corrosion conditions by about 50% for NCI, 47% for NAB and 19% for DSS. This difference should be equivalent to the electrochemical corrosion rates of the alloys. A comparison of the mass loss rates obtained under quiescent conditions with those obtained under cavitation conditions indicates that the kinetics of electrode process are
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enhanced by cavitation. In other words, the greatest portion of damage during cavitation is due to mechanical breakdown of the material surface and subsequent particle separation and ejection from the metal. However, the results clearly show that DSS is quite resistant to electrochemical corrosion in seawater. Thus, although cavitation has exposed fresh metal surfaces to the aggressive environment, the enhancement of electrochemical corrosion in DSS was not as significant as in NCI or NAB. In the present study, CP was applied to the cavitated specimens in order to separate the electrochemical corrosion component from the mechanical one. The present results indicate that the application of CP during cavitation reduces the rates of mass loss for all the investigated alloys. Since the rates of mass loss in quiescent seawater were very low, this decrease cannot be solely attributed to the elimination of electrochemical dissolution. Thus, the reduction in the rate of mass loss during cavitation under CP could be due to a combination of two factors, namely: bubble collapse cushioning due to the development of cathodic gas and diminished electrochemical dissolution [6]. Effect of Cavitation on the Electrochemical Behavior of Cast Alloys The potentials of NCI and NAB specimens exposed to seawater under cavitation and quiescent conditions were measured as a function of time. Table 3 shows the initial potential values obtained upon immersion and the final potentials at steady-state. Table 3. Corrosion Potentials (in mV vs. SCE) of Cast Alloys Exposed to Seawater under Quiescent and Cavitation Conditions Quiescent Initial Values At Steady-state NCI -560 -740 NAB -260 -245 NCI: Nodular cast iron NAB: Nickel-aluminum bronze Alloy Cavitation Initial Values At Steady-state -560 -650 -325 -300

It is clear from Table 3 that cavitation causes an active shift in the corrosion potential of NCI and a noble shift in the case of NAB. However, it is worth noting that the application of cavitation causes an immediate active shift in the initial corrosion potential of NAB. In order to validate this effect, the measurements were repeated on NAB and DSS under a pulsating cavitation condition. In these experiments, the materials were alternatively exposed to periods of cavitation and quiescence for one hour each. Figure 2 is given as an example to show that the application of cavitation immediately shifted the potential to a more active value. When cavitation was stopped, the potential rapidly shifted back to that of the quiescent condition. The rapid activation of the corrosion potential can be explained in terms of the destruction of the passive film and the creation of fresh metal surfaces. On the other hand, the rapid reversal of the free corrosion potential when cavitation was stopped suggests that the repassivation kinetics is quite fast. A similar potential shift was previously reported for copper-manganese-aluminum alloys cavitated in seawater [11].

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Figure 2. Effect of cavitation on the free corrosion potential of DSS in seawater The potentiodynamic polarization curves of NCI and NAB were similar in terms of a gradual increase in the anodic current with the increase in potential in the absence of an active-passive transition for the cavitated and non-cavitated specimens (see Fig. 3a). The presence of cavitation, however, increased both the cathodic and anodic currents. Moreover, it caused a small active shift in the corrosion potential. In the case of DSS, the alloy underwent a direct transition from active dissolution to passivity without exhibiting an active/passive transition (Fig. 3b). Cavitation was seen to have a small effect on the polarization behavior of DSS. The gradual increase in the anodic current of NCI and NAB with the increase in potential in the absence of cavitation can be ascribed to a mass transfer phenomenon controlled by two processes, namely: formation of soluble corrosion products during anodic polarization and diffusion processes through adherent corrosion products or film. In the case of NAB, film formation is mostly controlled by Al ion diffusion in the Alox phase [12]. In the presence of cavitation, the corrosion product layer is destroyed by the collapse of bubbles. Under these conditions, the anodic current increases as a result of activated electrochemical dissolution and the cathodic current increases as a result of increased charge transfer for oxygen reduction. It was rather surprising to find that cavitation had a small effect on the polarization behavior of DSS in seawater. The direct transition from active dissolution to passivity indicates that the alloy spontaneously passivated in seawater. Within the anodic region, there were two competing processes of passive film destruction and repassivation. However, the presence of cavitation possibly led to a slow-down in the repassivation process. Thus, the polarization behavior was not significantly affected, except for the small increase in current.

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Figure 3. Potentiodynamic polarization curves for: (a) NAB; and (b) and DSS, immersed in seawater under quiescent and cavitation conditions Effect of Cavitation on Surface Damage In stagnant seawater, a loosely adherent, corrosion product layer was formed on NCI. After cavitation for 2-10 minutes, erosion markings were visually observed. When SEM examinations were made, the NCI surface was found to have suffered from localized surface damage, as early as after 1 minute of cavitation. The damage was in the form of fragmentation and removal of graphite nodules. This led to the formation of circular craters of cavities; while the surrounding matrix remained smooth and unattacked (Fig. 4a). After 5 min., microcavities (erosion pits) developed in the ferrite matrix along with other cavities caused by the loss of graphite. After 10 to 30 minutes, the attacked areas became larger and engulfed the microcavities. Longer cavitation testing (5.5 hours) showed ductile removal of material from the matrix (Fig. 4b). These characteristics did not change in the presence of CP. However, the time needed to reach a specific stage of damage was longer under CP. Examinations of cross-sections revealed cracks, 3-21m long, that propagated into the matrix. These cracks originated at the bottom of deep craters. In general, cavitation corrosion increases in corrosive liquids such as seawater due to the combined action of electrochemical corrosion and the fluid mechanical component. Arabian Gulf seawater seems to be more aggressive than other water bodies, as it contains higher salt and different pollutants [10]. In the present work, erosion pits appeared randomly in the ferrite matrix of NCI due to ductile tearing caused by the sudden collapse of liquid bubbles. This indicates that cavitation damage in cast iron is not only initiated at graphite nodules as mentioned by Okada et al. [13], but also in the ferrite matrix.

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Figure 4. SEM micrographs of NCI after cavitation testing in seawater. (a) after 1 minute, fragmented graphite nodules and formation of cavities; and (b) after 5.5 hours, ductile removal of material from ferrite matrix The surface of NAB specimens exposed to stagnant seawater appeared visually darker than the unexposed specimens. SEM examinations indicated that the phase was preferentially attacked at the /IV interfaces and the precipitate-free zone did not suffer from any attack (Fig. 5a). Dissolution of the phase was also noted around the dendritic (rosette-like) II precipitates and at the globular and lamellar III precipitates. The fact that the precipitates were not attacked, indicates that the precipitates are cathodic with respect to the copper-rich phase. Thus, corrosion of NAB alloy in quiescent seawater is galvanic in nature. SEM examinations revealed that the surface of the NAB specimen became slightly rough after 3 hours of cavitation. After 13 hours of cavitation, the surface roughness increased and several microcavities appeared in the attacked area (Fig. 5b). As the cavitation time increased to 25 and 40 hours, the surface became very rough and contained large size cavities. Cleaning the specimen that had been cavitated for 40 hours in acetone revealed ductile tearing and grain boundary attack. In the presence of CP, the number of microcavities increased, but grain boundary attack was absent. Examination of a cross-section of a specimen cavitated for 58 hours revealed microcracks, 5-10 m in length, emanating from the bottoms of cavities (Fig. 5c). The microcracks appeared to initiate and propagate in the phase, favoring sites adjacent to phases.

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(c) Figure 5. SEM micrographs of NAB after: (a) exposure to quiescent seawater for 48 hours, showing preferential attack of the phase; (b) cavitation testing for 13 hr, showing increased surface roughness; and (c) cavitation testing for 58 hr, showing cavities and microcracks in crosssection The presence of cavities and ductile tearing in cavitated NAB specimens is readily explainable in terms of the known devastating effects of cavitation. On the other hand, the presence of grain boundary attack indicates that electrochemical dissolution due to structural heterogeneity indeed contributes to the surface damage. The presence of microcracks in the bulk of the material is similar to that reported for the NAB vertical-type pumps and sleeve valves that prematurely failed in Arabian Gulf seawater [1,2]. Although selective phase corrosion may have played a role in causing the microcracks, the contribution of cavitation stresses should not be discounted. The DSS specimens exposed to quiescent seawater under free corrosion conditions were found to be free of any corrosion attack. When SEM examinations were made on the DSS cavitated in seawater under free corrosion conditions, damage was seen after 30 minutes of cavitation. At this stage, a few small, shallow voids were seen inside the austenite islands and at the phase boundaries. Slip lines were also observed in the ferrite matrix with microvoids developing at emerging slip steps. Furthermore, some austenite islands partially extruded and experienced metal loss (Fig. 6a).

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Figure 6. SEM micrographs of DSS after cavitation testing in seawater. (a) after 30 minutes, void formation at emerging slip steps and partially extruded austenite; and (b) after 90 minutes, total removal of an extruded austenite and extension of damage to ferrite
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After 70 minutes of cavitation, the formation of voids along the slip steps and the material removal from the extruded austenite became more extensive. Slip lines were also seen within the ferrite matrix and cleavage-like facets within the damaged austenite. After 90 minutes of cavitation, the extruded austenite was totally removed and the loss in material extended to the ferrite matrix (Fig. 6b). As the cavitation time was increased to 4 hours, the whole metal surface suffered from extensive damage and the formation of cavities. At this stage, ductile tearing, cleavage-like facets, river patterns and crystallographic steps were seen on the damaged surface. When the examinations were repeated on a specimen cavitated for 40 hours under CP, the surface roughness appeared to be somewhat less than under free corrosion conditions. Laboratory-etched cross-sections of specimens cavitated for 40 hours revealed microcracks in the bulk of the alloy. The cracks appeared to initiate in the ferrite matrix. The propagation of the cracks appeared to be impeded by the austenite islands and to branch along parallel slip systems. In some cases, however, cracks were seen extending into the austenite grains. The high ductility of the austenite could explain the extrusion of surface austenite. The presence of cleavage facets within the damaged austenite suggests the occurrence of a brittle mode of failure in addition to the ductile mode. This was rather surprising. The brittle mode of failure in the austenite may be due to a strain-induced martensitic transformation [14]. The localized nature of cavitation seems to have led to an increase in work hardening of the ferrite matrix, activation of slip systems and initiation of surface cracks. Thus, the earliest deformation caused by the slip is expected to occur on the {110} plane and in the [111] direction. The localization of plastic strain would also facilitate material removal by ductile shearing of surface asperities. The repetitive stress mode of cavitation causes the cracks to propagate laterally, giving rise to the observed cleavage-like facets. The cracks in the bulk of the material express the fact that the plastic shock waves produced by cavitation can travel deep into the material. The role of the austenite islands in impeding crack propagation has been previously reported in stress corrosion cracking [6] and hydrogen embrittlement studies [15]. It is feasible that passage of the propagating crack through an austenite obstacle is facilitated by the formation of -martensite. CONCLUSIONS 1. Cavitation caused an active shift in the free corrosion potential and increased the anodic polarization current of NCI, NAB and DSS. 2. The rates of mass loss of the three cast alloys were very low in quiescent seawater. When compared with quiescent conditions, cavitation increased the rates of mass loss at the steady state by 930, 186 and 20 times for NCI, NAB and DSS, respectively. The application of CP decreased the rates of mass loss by about 50%, 47% and 19%, respectively. This reduction was attributed to bubble collapse cushioning due to cathodic gas and diminished electrochemical dissolution. 3. In quiescent seawater, thin scales were formed on NCI, while NAB suffered from selective corrosion of the copper-rich phase at the interfaces with the intermetallic precipitates. DSS was almost free of corrosion.

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4. Cavitation made the surfaces of the alloys very rough, with large size cavities and ductile tearing. The damage started at the graphite nodules and ferrite matrix in NCI. In NAB, the damage started at the boundaries of columnar grains. In the case of DSS, slip lines formed in the ferrite matrix, austenite islands extruded, and voids developed at emerging slip steps. Cleavage facets were evident within the damaged austenite. The extrusion of the austenite was attributed to its high ductility, while the presence of cleavage facets was explained in terms of strain-induced martensite. Cross-sectional examinations revealed microcracks in the bulk of the cast alloys. The formation of microcracks was attributed to cavitation stresses and preferential phase corrosion.

ACKNOWLEDGMENT The authors of this paper would like to acknowledge the support given by the Kuwait Foundation for the Advancement of Science, the Kuwait National Petroleum Company, the Petrochemical Industries Company, and the Abu Dhabi National Oil Company (Project No. 86-08-02). REFERENCES 1. 2. 3. 4. H.M. Shalaby and J.K. Cheriyan, KISR Report No. 2799, September 1988. M. Islam, R. Abdul Wahab and S. Al-Kharraz, KISR Report No. 2913, January 1989. V.K. Gouda, H.M. Shalaby and W.T. Riad, Materials Performance 28, 8, 1989, p. 53. H.M. Shalaby, A. Al-Hashem, H. Al-Mazeedi and A. Abdullah, British Corrosion Journal 30, 1, 1995, p. 63. 5. J.G. Auret, O.F.R.A. Damm, G.J. Wright and F.P.A. Robinson, Corrosion 49, 11, 1993, p. 910. 6. C.M. Preece, Cavitation erosion, in Treatise on Material Science and Technology, Vol. 16, C. C.M. Preece, ed. (New York, NY: Academic Press, 1979), p. 249. 7. A. Al-Hashem, P.G. Caceres, W.T. Riad and H.M. Shalaby, Corrosion 51, 5, 1995, p. 331. 8. F. Hasan, J. Iqbal and N Ridley, Materials Science Technology 1, 1985, p. 312. 9. ASTM G32-92, Standard Test Method for Cavitation Erosion Using Vibratory Apparatus (Philadelphia, Pennsylvania: ASTM, 1992). 10. H.M. Shalaby, S. Attari, W.T. Riad and V.K. Gouda, Corrosion 48, 3, 1992, p. 206. 11. K.R. Trethewey, T.J. Haley and C.C. Clark, British Corrosion Journal 23, 1, 1988, p. 55. 12. A. Schussler and H.E. Exner, Corrosion Science 34, 11, 1993, p. 1803. 13. T. Okada, Y. Iwai and A. Yamamoto, Wear 84, 1983, p. 297. 14. J.A. Venables, Philosophical Magazine 7 1962, p. 35. 15. W. Zheng and D. Hardie, Corrosion 47, 10, 1991, p. 792.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

MICROBIOLOGICALLY INDUCED CORROSION OF A STAINLESS STEEL PIPE H.H. Lee, M. Ali and K. Al-Omrani Sabic Industrial Complex for Research & Development PO Box 42503, Riyadh 11551, Saudi Arabia

ABSTRACT
Microbiologically induced corrosion (MIC) is recognized as a major cause of metallic component failure in many natural waters and soils. Most recently, a MIC failure occurred in the stainless steel piping system in a chemical plant in Saudi Arabia. This failure case was discussed and compared with the documented case histories in the published literature involving MIC of stainless steels. Key Words: Microbiologically induced corrosion (MIC), stainless steel, localized corrosion

INTRODUCTION In late July of 1995, leakage was detected in the newly installed stainless steel (Grade 321 stainless) pipe in a chemical plant in Saudi Arabia. The leakage was observed in the stainless steel core pipe which was enveloped by an outer jacket pipe for heat transfer medium oil. Evidence of pinholes was found in the lowest sloping, horizontal section of the core pipe, always around the 7 o'clock to 5 o'clock positions and about 0-8 mm from the weld. The remainder of the pipes at a higher elevation have been found to be acceptable with no leakage. The original hydrotest using untreated fresh water was conducted for the newly constructed pipe line in January of 1995, followed by air blowing to remove excess water. This line was turned to the operating personnel of the chemical plant in March of 1995. System hydrostatic leak testing was conducted by the plant personnel in April of 1995. Pinhole leakage was observed in late July of 1995. Between April of 1995 and the leakage was detection, the pipeline was never in use. In August of 1995, an investigation was initiated on the cause of this failure. The investigation and analysis results are reported in this paper. VISUAL AND MICRO EXAMINATION One small pipe sample about 4 cm in length was cut from the failed stainless steel pipeline for examination and evaluation. The sample included the weldment and pinholes. This sample was cut along the longitudinal direction to expose the inner pipe surface for examination. The measured outside diameter (OD) of the stainless steel pipe sample in asreceived condition was 88 mm with 3 mm in wall thickness. There was no observed corrosion on the outer surface, as shown in the photograph in Fig. 1a. However, there were reddish-brown corrosion products mixed with some light black oxides at and near the welded
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zone of the inner surface, especially at the 5 to 7 o'clock position. One pit is clearly visible at approximately the 6 o'clock position adjacent to the weldment, as shown in the photograph in Fig. 1b. The area including the pit was cut for further examination under scanning electron microscope (SEM). Figure 2a is a SEM photograph of the pit clearly indicating that the pit was initiated from the inner surface at area near the weldment. Figure 2b is a SEM photograph of the front view of

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Figure 1. Photographs of: (a) outer surface; (b) inner surface of the failed pipe sample, indicating a pit growing nd propagating sideways from the inner surface adjacent to the weldment the pit indicating that the pit was turning sideways under the inner pipe surface. Figure 3 is a SEM photograph of the side view of the pit looking from the cross-sectional direction of the pipe showing a large under-surface cavity. This pit under examination did not penetrate the whole pipe wall thickness. It clearly indicates that the pit was generated due to corrosion and not from material defect. ANALYSIS OF THE FAILURE MECHANISM Based on the laboratory examination result, there are two possible environments which could produce the type of pitting corrosion of stainless steel pipe as observed in the present case. These include environment containing appreciable concentrations of chloride (Cl-), and environment containing bacteria which could microbiologically induce corrosion of stainless steels. These possibilities are further discussed in reference to the present failure case: Pitting Corrosion of Stainless Steel in Environment Containing Chloride It is known that stainless steel will develop pitting corrosion in environments containing chloride ions because of the breakdown of surface passivity [1]. Generally, this requires an appreciable concentration of chloride ions. For examples, stainless steels exposed to seawater will develop surface pits in a matter of months to several years depending on the steels composition. The tendency is greater in the martensitic and ferritic stainless steels than in the austenitic steels. Austenitic stainless steels containing molybdenum (such as types 316 and 317) are more resistant to pitting corrosion in seawater. Pitting of these alloys will develop in seawater within a period of 1-2.5 years [1]. The present failed stainless steel pipe was never exposed to an aqueous environment containing appreciable amount of chloride ions prior to the detection of the leakage. The type of pitting corrosion observed at this chemical plant is not caused by chloride ions from the environment. Localized Biological Corrosion of Stainless Steels Biological corrosion is defined as the deterioration of metals as a result of the metabolic activities of microorganisms [2]. Many case histories involving MIC of stainless steels are well documented in the published literature [2]. Most of them involved sulfate-reducing bacteria which accelerate the localized corrosion of stainless steels especially at welded areas. One case history, as cited by Kobrin [3], is considered most relevant. It occurred in the early 1980s in a new chemical plant in Texas, USA. Type 304 stainless was used for resistance to corrosion by wet carbon dioxide. Included were underground sump tanks and drainage piping. Untreated well water was used for hydrostatic testing after installation. No special effort was made to remove the water or dry the systems after testing was complete. Initial indication of a problem occurred several months after the hydrotest, following removal of a tank to a fabrication shop for minor modifications. Leaks developed during a routine shop hydrostatic test. Internal visual and liquid dye penetrant inspection showed pits and cracks under rusting colored nodular deposits primarily along welds. Pits had small 'mouth' at the surface, opening to large, bottle-shaped cavities below. As plant personnel opened the stainless vessels and the pipes for inspection, they found many
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pits, primarily at welds, and noted rust-colored deposits in mixture with brownishwhite slime deposits. Limited analyses showed the presence of sulfate reducing and iron bacteria in the various deposits [4].

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Figure 2. SEM photographs of: (a) the pit adjacent to the weldment (7X); and (b) the pit as seen from the inner pipes surface (25X)

Figure 3. SEM photograph of the pit hole from the cross-sectional direction indicating the pit growing sideways under the surface (25X) The above reported case history is very similar to what has been observed at the chemical plant in Saudi Arabia for the present pipeline pitting failure. It appears that some water still remained in the lowest sloping horizontal section of the core pipe at the chemical plant after the initial hydrotest conducted in January of 1995. Obviously the untreated water used for the initial hydrotesting contained some sulfate reducing bacteria which caused the subsequent biologically induced corrosion. As showed in the SEM photograph in Fig. 3, some rod-shaped material is visible inside the pit. It is possible that the rod-shaped material could be a colony of the corroding bacterial consortium. According to the literature, there are many bacteria found in the corroded metals in the form of filaments. One example is the filament-form thermophillic bacterium found in the failed brazed fillet reported by Walch and Mitchell [5]. This filament form of organism has variable lengths from 20 to over 200 m. Although Sabic R&D does not have the facilities to positively identify the type of organism observed, it is fairly clear that the present pipeline failure observed at the chemical plant was caused by biologically induced corrosion. Furthermore, the shape of the pit, i.e., with a small mouth on the surface and a large bottle-shaped cavity below, is a positive indication of bacterial corrosion. CONCLUSIONS

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Based on the examination results and the evidence obtained, the cause of the pitting corrosion in the stainless steel piping system observed was caused by biologically induced corrosion. After the piping system was repaired or replaced as required, it was recommended that hydrotesting be conducted using demineralized water to eliminate the possibility of microbiologically induced corrosion. The piping system was thoroughly drained and dried immediately after testing. There was no reoccurrence of MIC since. REFERENCES 1. H.H. Uhlig and R.W. Revie, Corrosion and Corrosion Control, John Wiley & Sons, 1985. 2. Metals Handbook, Ninth Edition, Vol. 13, Corrosion, p. 2, ASM International, 1987. 3. G. Kobrin, Reflections on microbiologically induced corrosion of stainless steels, in: Biologically Induced Corrosion, Conference Proceedings, National Association of Corrosion Engineers, 1986, pp. 33-46. 4. ibid., p. 37. 5. M. Walch and R. Mitchell, Microbial influence on hydrogen uptake by metals, in: Biologically Induced Corrosion, Conference Proceedings, National Association of Corrosion Engineers, 1986, pp. 201-214.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

A LABORATORY STUDY OF SERVICE FAILURE OF AL-BRASS TUBES IN ARABIAN GULF SEAWATER H.M. Shalaby1, W.T. Riad1 and V.K. Gouda2
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Kuwait Institute for Scientific Research P.O. Box 24885, 13109 Safat, Kuwait

National Research Center, Dokki, Giza, Egypt

ABSTRACT
Failure analysis and a laboratory study were made on Al-brass tubes. The failure investigation was conducted on tubes that had failed during service in Arabian Gulf seawater. The investigation revealed that the tubes failed due to perforations after suffering from various forms of corrosion. Crevice attack and erosion-corrosion of the horseshoe grooving type were the most serious corrosion forms. Other corrosion forms were also observed such as inlet edge cutting, inlet edge beveling, pitting, dezincification and intergranular attack. Lodgments, local high velocities and turbulence were considered the most important factors causing the perforations. In order to understand the role played by the presence of seawater pollutants, a systematic laboratory study was conducted to evaluate the effects of manganese (5 ppm) and chlorine (4 ppm) on the corrosion behavior of Al-brass in stagnant and flowing (0.1 and 2.2 m/s) seawater. Under stagnant conditions, both pollutants had little effect on the free corrosion potential. In flowing seawater, manganese caused a noble shift in the corrosion potential at 0.1 m/s and an active shift at 2.2 m/s. Chlorine addition caused an electropositive shift at both flow velocities. During polarization, the presence of either pollutant caused cathodic depolarization and elimination of the active/passive transition. Microscopic examination revealed that the film formed in the presence of manganese was thicker and more porous than that formed in clean seawater. Scattered nodules of basic copper chlorides formed on the tubes surface in the presence of chlorine. As in the field failed tubes, crevice corrosion, intergranular attack and dealloying were found beneath the basic chloride nodules. Key Words: Aluminum brass, corrosion failure, manganese, chlorine, pollutants

INTRODUCTION In Kuwait, refineries and desalination plants utilize Arabian Gulf seawater in heat exchangers, evaporators and condensers fitted with Al-brass tubes. Although the alloy is recommended for the heat recovery stages in multistage flash distillation (MSF) plants [1], a high incidence of tube failures have been reported [2-6]. The diagnosis of failure of Al-brass tubes in surface condensers, conducted by Gouda et al. [4], indicated that the tubes failed due to severe erosion-corrosion in the form of horseshoe-shaped grooves. On the other hand, Khatak and Gnanamoorthy [5] attributed leaks developed at random locations in Al-brass condenser tubes after one year of operation to crevice corrosion under seawater deposits. Furthermore, Chandrasekhariah and Mukherjee [6]
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attributed the failure of Al-brass condenser tubes after six months of service to crevice corrosion resulting from lodgments of organic deposits. The aim of this paper is to establish a link between a failure investigation of Al-brass tubes and a laboratory study on the effect of seawater pollutants. It was hopped that establishing such a link would throw more light on the mechanism of failure. EXPERIMENTAL PROCEDURE Failure analysis was undertaken on ten failed Al-brass tubes made according to ASTM C68700. The tubes were removed from the heat recovery stage of a desalination plant that used treated seawater. The design flow velocities were 1.5-2.14 m/s, and the temperatures were 42C at the inlet stage and 82.6C at the outlet stage. Visual, macroscopic, metallographic and scanning electron microscopic (SEM) examinations were conducted on the tubes before and after the removal of corrosion products. X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS) were used for the analysis of the corrosion products and deposits. Also, chemical analyses were made to verify the materials conformity. The laboratory corrosion tests were conducted under stagnant and flow conditions (0.1 and 2.2 m/s) using Arabian Gulf seawater at room temperature. The tests were made on fresh (unused) Al-brass using clean seawater and seawater containing 5 ppm manganese or 4 ppm chlorine. Chlorine was added in the form of sodium hypochlorite solution, and the concentration of free chlorine was monitored using an ion selective analyzer and was replenished daily. Manganese was added in the form of manganese chloride. The work under stagnant conditions involved measurements of the open-circuit corrosion potential and potentiodynamic polarization tests. The tests were made in duplicate using specimens in the form of discs measuring 2 cm in diameter and 1 mm in thickness. Before the test, specimens were mechanically ground using 800 grit silicon carbide paper, polished with 3 m diamond paste, and ultrasonically cleaned with detergent and acetone. Teflon holders was designed to expose a specimen area of 1.6 cm2. The potentiodynamic polarization tests were carried out at a scan rate of 30 mV/min starting from a cathodic potential value of -700 mV relative to the open-circuit potential and scanning was stopped at a potential of + 700 mV. A potentioscan with IR compensation controls, saturated calomel reference electrodes (SCE) and cylindrical graphite counter electrodes were used in these experiments. A circulating test rig in the form of a flow loop made of PVC pipes was used to carry out the work under flow conditions. The rig was designed in such a manner that the Al-brass tubes (10 cm in length, 1 mm in thickness and 1.6 cm in outer diameter) were exposed to laminar flow at the same flow velocity. The tubes were internally ground with 600 grit silicon carbide paper and soldered on the outside to copper wires to record the corrosion potential. In this paper, average values of the open-circuit potential are reported. At the end of the stagnant and flowing laboratory tests, the specimens were examined for corrosion morphology and the composition of corrosion products. Again, SEM, EDS and XRD techniques were used. The corrosion morphology was examined before and after removing the corrosion products. The corrosion products were removed by immersion in 5% citric acid for 24 hours, followed by ultrasonic cleaning in acetone. RESULTS Failure Investigation
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Visual observation showed that the internal surfaces of the failed tubes were covered by pale green and orange, nonhomogeneous deposits mainly located at the mouth of the tubes and occasionally in the middle of the tubes. The orange product was generally more adherent than the green deposits. XRD and EDS analysis of the corrosion products indicated the presence of a nonhomogeneous mixture of cuprous oxide and copper hydroxychloride (paratachamite), in addition to sea salts such as calcium carbonate and magnesium hydroxide. Inspection of the tubes after removal of the scales and corrosion products revealed various localized forms of attack at the tubes mouth, in addition to metal thinning downstream. In most of the tubes, the inlet edges suffered from inlet-beveling attack and inlet edge cutting (Fig. 1), while at a distance of 3 cm from the inlet edges, localized craters of various depths, shapes, sizes and angles (45-90 to the water flow direction) were located. Perforations were found in some craters. Also, in some tubes containing horseshoe-shaped grooves, perforations were apparent on the metal surface underneath the orange colored product. Another form of localized corrosion (minute pits) was identified in many of the tubes under scattered, localized black deposits. Inspection was also conducted on unused Albrass tubes which showed the initiation of minute pits covered by a black corrosion product. Metallographic cross-sections were prepared for areas that suffered from localized corrosion and craters. Examinations of the cross sections revealed the occurrence of dezincified and nonuniform porous surfaces as well as shallow pits in the -brass structure. Examinations of polished longitudinal sections at the craters revealed the presence of intergranular attack at the craters borders. Transverse sections at the same location did not reveal the penetration of intergranular cracking. Laboratory Corrosion Tests in Stagnant and Flowing Seawater As can be seen from Figs. 2 and 3, the potential-time behavior of Al-brass exposed to pollutant-free seawater under stagnant and 0.1 m/s flow conditions was about the same. The initial average potentials showed slight ennoblement during the first few days of testing, followed by a small active shift until a steady-state was reached. When the flow velocity was increased to 2.2 m/s, the corrosion potential in clean seawater gradually shifted to more noble values (Fig. 4). Visual examination of the Al-brass tested in stagnant clean seawater revealed a surface that was mostly yellow-brown in color and contained a few small green precipitates which increased in number and became darker in color on tubes exposed to seawater flowing at 0.1 m/s. On these latter tubes, beige and white precipitates were also observed. SEM examination showed that the green precipitates were granular in nature, well compacted and had formed on top of a thin, smooth, and adherent oxide film. EDS analysis indicated that the green precipitates were rich in chloride and sulphur. After film removal with 5% citric acid, the surface was free of any significant corrosion damage. The tubes tested in clean seawater flowing at 2.2 m/s appeared to be similar to those tested at 0.1 m/s. However, SEM examination showed that the surface film on the tubes tested at 2.2 m/s had been stripped off from several areas, exposing the underlying bare metal. Higher SEM magnification revealed that the bare surfaces had suffered from metal dissolution that increased in intensity along the grain boundaries. A few scattered, small shallow cavities were seen on the intergranularly attacked surface.

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The potentiodynamic polarization of Al-brass in stagnant clean seawater is given in Fig. 5. A small active/passive transition peak is apparent ,and the active peak is followed by a very small passive region and a small transpassive peak. The current slowly increased with further increase in potential. Microscopic examination of the specimen showed general metal dissolution associated with severe intergranular attack.

(a)

(b)

(c)

(d)

Figure 1. Photographs of forms of corrosion attack observed on the failed tube inlets: (a) holes, craters and depression (1.1x); (b) horseshoe grooving and hole (1.8x); (c) edge cutting and bevelling (8x); and (d) crater with elongated hole (10x) The addition of 5 ppm manganese to stagnant seawater did not change the potential-time behavior of Al-brass with respect to that in clean seawater (Fig. 2). On the other hand, the presence of manganese increased the corrosion potential by 100 mV during potentiodynamic
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polarization in stagnant seawater (Fig. 5). It also shifted the cathodic branch of the polarization curve towards higher current densities, eliminated the active/passive peak and made the anodic peak to take place at slightly less positive potentials, suggesting selective dissolution from the alloy. Optical microscopic examination of the sample used in the polarization test revealed once again that general metal dissolution and intergranular attack had occurred.

Figure 2. Potential-time behavior of Al-brass in stagnant seawater: (a) seawater; (b) seawater containing 5 ppm manganese; and (c) seawater containing 4 ppm chlorine

Figure 3. Potential-time behavior of Al-Brass in seawater flowing at 0.1 m/s: (a) seawater; (b) seawater containing 5 ppm manganese; and (c) seawater containing 4 ppm chlorine

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Figure 4. Potential-time behavior of Al-Brass in seawater flowing at 2.2 m/s: (a) seawater; (b) seawater containing 5 ppm manganese; and (c) seawater containing 4 ppm chlorine

Figure 5. Potentiodynamic polarization behavior of Al-brass in stagnant seawater: (a) clean seawater; (b) seawater containing 5 ppm manganese; and (c) seawater containing 4 ppm chlorine In seawater flowing at 0.1 m/s, the presence of manganese shifted the corrosion potential to a peak value of about -110 mV during the first two days of testing. Then, the potential gradually shifted towards a more active value, reaching a more or less steady state of about 210 mV after eight days of testing (Fig. 3). At 2.2 m/s, a different potential-time behaviour was attained in the presence of manganese. In this latter case, the corrosion potential remained much more active, being on the same order as that obtained within the steady-state region under stagnant conditions. The surface film formed in manganese-containing seawater flowing at 0.1 m/s was morphologically similar to that formed in clean seawater under stagnant and flow conditions. However, in the presence of manganese, the film was thicker and covered most of the extrusion marks. At 2.2 m/s, the film formed in the presence of manganese became much thicker and more porous when compared with the film formed in clean seawater at the same flow velocity. Furthermore, the film stripped off the surface in many areas. Within the stripped-off areas, the surface was intergranularly attacked and contained a few small, shallow cavities (Fig. 6a).
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The effect of the addition of 4 ppm chlorine on the potential-time behavior of Al-brass is shown in Figs. 2-4. In stagnant seawater, the potential underwent an initial ennoblement during the first few days of testing which was followed by a shift towards active values till a steady state was attained after about ten days of testing (Fig. 2). At the steady state, the corrosion potential in the presence of chlorine was close to that in clean stagnant seawater, indicating a negligible effect of chlorine. Statistical hypothesis testing also confirmed that there was no significant differences at the l and 5% levels of significance. In seawater flowing at 0.1 m/s, the addition of chlorine shifted the corrosion potential to a noble value of about -100 mV after two days of exposure, and the potential remained close to that value for the remaining period of testing (Fig. 3). At a 2.2 m/s flow velocity, the potential-time behavior in the presence of chlorine was to a good extent similar to that obtained in clean seawater at the same flow velocity (Fig. 4). Although potential fluctuations occurred in both cases, the potential values were close to each other and remained relatively stable after about ten days of testing. SEM examination of the Al-brass tested under open-circuit conditions in chlorinecontaining stagnant seawater revealed features similar to those noted in clean seawater. On the other hand, the surface of tubes tested in chlorine-containing seawater flowing at 0.1 m/s was slightly greenish in color and contained a few green nodules. EDS of the nodules revealed that they were enriched with chloride and sulphur. The surface appeared (under SEM) to be covered by an adherent film, however, a few areas seemed to be covered by a smooth, wavy scale layer. After removing the surface film, the bare surface was found to have suffered from minor general corrosion associated with increased surface roughness in the form of micro pits. When the seawater flow velocity was increased to 2.2 m/s, the film formed in chlorinecontaining seawater became a thick, scale layer containing scattered mounds or nodules (Fig. 6b). In some areas, the scale looked like a layer of dried, broken mud, and in others it was multilayered. The scale was not stripped off as in the case of clean seawater and seawatercontaining manganese flowing at the same velocity (i.e., 2.2 m/s), which suggests that the scale was adherent to the surface. XRD analysis of the corrosion products scrubbed off the surfaces of tubes after testing showed major peaks of copper hydroxychloride in addition to cuprous chloride. After removing the scale, SEM examination showed that the bare surface contained a significant number of relatively large isolated and interconnected cavities in pitlike shapes (Fig. 6c). Inside and around the cavities, the bare surface was porous (spongy) in nature. However, away from the cavities, the surface appeared to be quite similar to that observed after testing in clean seawater or in the presence of manganese.

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(a)

(b)

(c) Figure 6. SEM micrographs of Al-brass tested in seawater at 2.2 m/s, showing: (a) the surface after testing in the presence of manganese; (b) nodules on top of the scale formed in the presence of chlorine; and c) cavities observed after removing the scale The addition of chlorine to stagnant seawater shifted the cathodic branch of the polarization diagram towards higher current densities (Fig. 5). It also caused the formation of a small reduction peak. The addition of chlorine appears to diminish the passive region and make the anodic peak take place at a slightly less positive potential than in clean seawater. After the termination of the polarization test, microscopic examination revealed the same featues as those observed in clean seawater. DISCUSSION Service Failure of Al-brass It has been reported that the good performance of copper alloy tubing in desalination plants is due to the formation of a protective film composed of cuprous oxide [1]. Other deposits on top of the film, such as cupric oxychloride, cupric hydroxide, copper carbonates and iron oxides, may also contribute to the corrosion protection. In fact, the corrosion products on the surface of the field-failed tubes were a nonhomogeneous mixture of cuprous oxide, copper hydroxychloride and paratachamite, in addition to sea salts such as calcium carbonate and magnesium hydroxide. The nature of these scales appeared to be inadequate to protect Al-brass in Arabian Gulf seawater. Visual inspection of the failed tubes showed that inlet edge cutting and bevelling had occurred in most of the tubes, while typical horseshoe grooving was evident in some tubes. All these forms of attack were indicative of flow velocity related problems at the tube inlets

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only, although the flow velocity inside the tubes was within the safe range specified for Albrass (2.4 m/second) [1]. The design of the water-box inlet and baffles may create local turbulent flow patterns that exceed the maximum allowable flow velocity to avoid erosion-corrosion. Sato and Nagata [7] reported that the water velocity passing a partial obstruction in the bore of a condenser tube can reach 8 m/second even though the overall velocity is in the range of 2 m/second. The existence of lodgments such as shells, biofouling deposits or corrosion scales may also create areas of localized high velocity and turbulence leading to localized corrosion and under-deposit attack. In the present failure case, crevice corrosion was observed under lodgments, and the surfaces of the creviced areas were porous in nature, suggesting the occurrence of dealloying. Similar results were noted by Efird and Verink [8], and Schleithoff and Schmitz [9] where the type of attack in the crevices was dealloying. Schleithoff and Schmitz [9] indicated that the presence of magnesium in the alloy was responsible for the lose of arsenic which was added to prevent dezincification. On the other hand, it has been reported [10] that in the crevice attack of copper alloys exposed to flowing seawater, cuprous ions are produced within the crevice and react with chloride ions to form ionic copper chloride complexes, leading to local acidification and enhancement of corrosion. Examinations of metallographically polished sections from areas that had suffered from crevice attack revealed the presence of intergranular corrosion and cracking. Todd [11] reported failure of Al-brass tubes exposed to polluted seawater in a desalination plant. The failure of the tubes was due to severe intergranular corrosion. In the present failure case, minute pits were also observed under scattered and localized black sulphide deposits. Similar attack was reported for Al-brass tubes in another application utilizing Arabian Gulf seawater [4]. It has been reported that a copper sulphide deposit formed in polluted seawater is more cathodic than cuprous oxide formed in clean seawater. Therefore, galvanic corrosion between the base metal at breaks in the large areas of cathodic sulphide film can result in rapid failure by pitting attack [12,13]. Effect of Seawater Pollutants It is well established that Al-brass tubes perform satisfactorily if the seawater is clean, i.e., not contaminated with any pollutants. Previous work [14] has shown that the major constituent of the film formed in clean seawater is of the hydrotalcite family of basic mixed hydroxy-carbonates [Mg6Al2(OH)16CO3.4H2O]. In the presence of an intermediate chlorine level, the composition of the normal surface film changes. Francis [14] suggested that this change is achieved by substituting increasing amounts of copper for magnesium and chloride ion for the hydroxyl ion, resulting in a film with low resistance to mechanical damage. However, there are confliting results on the effect of chlorine. Studies under stagnant or low flow velocities have often resulted in reduced corrosion rates in the presence of chlorine [15,16], while other work at higher velocities [17,7], has shown dramatically increased corrosion. Sato et al. [18] reported catastrophic damage to Al-brass tubes in chlorinated seawater, caused by malignant impingement attack. They explained this phenomenon on the basis that manganese ions present in seawater react with the residual chlorine from chlorination, and thus MnO2 is formed as colloidal particles depositing on the corrosion product film and forming an active cathode in areas of turbulence around lodgments. Consequently, galvanic
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action is enhanced, leading to intensified erosion-corrosion damage. Gouda et al. [19] also considered that the presence of significant amounts of manganese on the surface of failed Albrass condenser tubes used in a refinery in Kuwait as one of the factors contributing to accelerated erosion-corrosion of the tubes. In all these failure investigations, the exact role of manganese was not studied or clearly defined. The above discussion suggests that the present failure case cannot be attributed to the wrong choice of material. However, when using Al-brass, several precautions have to be taken to ensure the long life of the tubes. Pollutant-free water should be used for hydrotesting tubing followed by thorough drying prior to boxing for shipping. The circumstances of the present failure case and the confleting results with regard to the effect of pollutants made it necessary to carry out a systematic laboratory study on the effects of manganese and chlorine on the corrosion of Al-brass. It was hoped that such a study might throw more light on the exact role of seawater pollutants in the failure of the Al-brass tubes. The effect of sulfide pollution was not studied, as it is well covered in the literature [12,13]. In the present laboratory work, the addition of 5 ppm manganese caused an electropositive shift in the free corrosion potential reached during testing in seawater flowing at 0.1 m/s. It also caused a similar shift under potentiodynamic polarization in stagnant seawater. These results can be explained on the basis of the mixed potential theory and morphological examination. According to Pourbaix [20], a slightly oxidizing agent such as that of oxygen, can oxidize manganous solutions with the formation of solid oxides: brownblack Mn3O4, black Mn2O3 or various varieties of anhydrous or hydrated MnO2 which are brown or black. These oxides are more noble than Al-brass, and their presence on the surface of the metal is similar to that of a galvanic couple or the addition of an oxidizer to the system. Under such conditions, the corrosion potential of the system is shifted to more noble values, the corrosion rate is increased, and the hydrogen evolution rate is decreased. The fact that the free corrosion potential was of the same order in stagnant clean seawater and in seawater containing manganese could possibly be due to the lack of sufficient diffusion of manganese (or manganese oxides) to the Al-brass surface. On the other hand, the activation of the corrosion potential noted at a 2.2 m/s flow velocity could be due to the stripping of the protective film, exposing fresh metal to the corrosive environment. The increase in thickness of the surface film as a result of the addition of manganese would increase the corrosion rate of the metal. The increase in film thickness might help the stripping action which might result from the shear stress between the surface and the layer of seawater closest to it. The increase in film thickness and its associated increase in corrosion rate could be a factor in the development of the observed intergranular attack. Thus, the present results suggest that the presence of manganese in seawater affects the growth and stability of the protective layer. The present laboratory work revealed the strong oxidizing effect of chlorine. This was apparent from the electropositive shift in the corrosion potentials (Figs. 3 and 4) and the cathodic depolarization relative to that in clean seawater (Fig. 5). Furthermore, the morphological examination showed that the surface film formed in Al-brass in the presence of chlorine was different than that formed in clean seawater or in the presence of manganese. However, another scale layer which was different than the primary film was observed in some areas (Fig. 6b). XRD showed that the corrosion products scrubbed off the surface of Al-brass
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were basically copper oxychlorides and copper chlorides. It appears that the film formed on Al-brass changes in the presence of free chlorine. The presence of a totally different scale layer of basic copper compounds in the form of multiple layers or nodules in localized areas could significantly change the corrosion rate. The basic chloride nodules could act as sites for further precipitation of other compounds, such as calcium carbonate, leading to nonhomogeneous mixtures of several compounds, as was observed in the present failure case. The presence of these nodules increases the local acidity underneath the scale, leading to crevice corrosion, intergranular attack and dealloying, as was observed in both the laboratory work and the field-failed tubes. Furthermore, the presence of these nodules could induce localized increases in velocity and turbulence, resulting in erosion-corrosion at high flow velocities. CONCLUSIONS 1. The failure investigation revealed that the Al-brass tubes failed due to various forms of corrosion. Crevice attack and erosion-corrosion of the horseshoe grooving type were the most serious forms. Inlet edge cutting, inlet edge beveling, pitting, dezincification and intergranular attack were also observed. The failure of the tubes was ascribed to lodgments, increased local high velocities and turbulence. 2. The laboratory study indicated that the addition of 5 ppm manganese or 4 ppm chlorine had little effect on the free corrosion potential of Al-brass in stagnant seawater. In flowing seawater, manganese shifted the corrosion potential to more noble values at 0.1 m/s and to more active values at 2.2 m/s. Chlorine addition caused electropositive shift at both flow velocities. 3. During potentiodynamic polarization, the presence of either pollutant caused cathodic depolarization, electropositive shift of the corrosion potential and elimination of the active/passive transition. 4. SEM examination of the laboratory tested specimens revealed that the film formed in the presence of manganese was relatively thick and porous. The addition of chlorine caused the localized precipitation of a scattered scale layer in the form of nodules of basic copper chlorides. Similar to the field-failed tubes, crevice corrosion, intergranular attack and dealloying were found beneath the nodules. REFERENCES 1. H. Tuthill, Materials Performance 26, 9, 1987, pp. 12-22. 2. A.D. Little, Survey of Service Behaviour of Large Evaporative Desalting Plants, US Department of Commerce, Office of Water Research and Technology, 1981. 3. V.K. Gouda and W.T. Riad, Kuwait Institute for Scientific Research, Report No. 2767, 1988. 4. V.K. Gouda, J.A. Carew and J.K. Cheriyan, Kuwait Institute for Scientific Research, Report No. 2605, 1988. 5. S. Khatak and J.B. Gnanamoorthy, Failure of an Aluminium Brass Condenser Tube: Handbook of Case Histories in Failure Analysis, Vol. 2, ASM International, Materials Park, Ohio, USA, 1993, pp. 192-193.

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6. M.N. Chandrasekhariah and T.K. Mukherjee, Transactions of the Indian Institute of Metals 31, 1978, p. 459. 7. S. Sato, and K. Nagata, Sumitomo Light Metal Technical Report No. 19, Japan, 1983, p. 296. 8. K.D. Efird, and E.D. Verink, Jr., Corrosion 33, 9, 1977, pp. 328-331. 9. K. Schliethoff and F. Schmitz, Practical Metallography 20, 2, 1983, pp. 88-91. 10. M. Schumacher, ed., Sea Water Corrosion Handbook,.Park Ridge, New Jersey, Noyes Data Corporation, 1979. 11. B. Todd, Desalination 3, 106, 1967. 12. H.P. Hack and J.P. Gudes, Inhibition of sulfide-induced corrosion with a stimulated iron anode, Corrosion/79, NACE, Atlanta, Georgia, USA, March 12-16, 1977, p. 10. 13. D.D. Macdonald, B.C. Syrett and S.S. Wing, Corrosion 35, 1979, p. 367. 14. R. Francis, Corrosion Science 26, 3, 1986, p. 205. 15. D.B. Anderson and B.R. Richards, Journal of Engineering for Power, July 1966. 16. I. Campbell and N.K. Searle, Conference on Fouling and Corrosion of Metals in Sea Water, SMBA Dunstaffnage, April 1982. 17. R. Francis, Materials Performance 44, 2, 1982. 18. S. Sato, K. Nagata and S. Yamauchi, Evaluation of various preventive measures against corrosion of copper alloy condenser tubes by seawater, Presented at Corrosion/81, NACE, Toronto, Canada, April 6-10, 1981. 19. V.K. Gouda, S. Abo-Namous, W.T. Riad and A.M. Abdullah, Kuwait Institute for Scientific Research, Report No. 3266, 1989. 20. M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, 2nd ed., National Association of Corrosion Engineers, 1974.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CORROSION OF REINFORCED CONCRETE STRUCTURES AND THE EFFECTS OF THE SERVICE ENVIRONMENT S. Al-Bahar and E.K. Attiogbe Civil Engineering &Building Department Kuwait Institute for Scientific Research P.O. Box 24885, 13109 Safat, Kuwait

ABSTRACT
Corrosion of steel reinforcement is a major cause of concrete deterioration in Kuwait and other Arabian Gulf countries. The selection of effective repair schemes for corroding structures requires that the corrosion damage be assessed and quantified. The symptoms of corrosion-induced deterioration in two reinforced concrete structures in Kuwait are documented and discussed. The investigative techniques employed identified the nature of the service environment and its role in promoting corrosion of steel reinforcement in the concrete structures. The failure to account for the service environment of the structures through implementation of corrosion preventive measures contributed to the deterioration of the structures. Both ingress of chloride ions and carbonation of the concrete were the causes of the corrosion-induced deterioration. Key Words: Carbonation, chlorides, concrete structures, reinforced concrete, reinforcement corrosion, service environment

INTRODUCTION The service environment plays an important role in the durability and serviceability of reinforced concrete structures. The Arabian Gulf region provides one of the most aggressive environmental conditions for concrete structures. This environment is characterized by high temperature and humidity cycles, and severe ground and ambient salinity with high levels of chlorides and sulfates in the soil and groundwater. Such environmental conditions have promoted an extensive degree of deterioration in concrete structures within 10-15 years of construction [1]. Structures exposed to the marine environment, groundwater conditions and industrial pollution have suffered the most. In Kuwait, as in other Arabian Gulf countries, the symptoms of deterioration in reinforced concrete structures have shown that corrosion of steel reinforcement is the major form of deterioration [2]. Studies conducted on the conditions of marine and non-marine structures in Kuwait have shown corrosion to be caused primarily by ingress of chloride ions aided by carbonation and sulfate attack, while carbonation of concrete is a major cause of corrosion in some non-marine structures. Cracking of concrete caused by sulfate attack can facilitate the ingress of chloride ions. A visual inspection of selected structures showed evidence of corrosion to be extensive (Fig. 1) and widely spread [3]. The observations made
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during the visual inspection of these structures point to the vital role the service environment played in the extent of corrosion-induced deterioration of the structural elements. The discussions in this paper include information obtained from relevant data on the corrosioninduced deterioration of two reinforced concrete structures in Kuwait.

Figure 1. Spalled concrete and corroded steel reinforcement MECHANISMS OF CORROSION IN REINFORCED CONCRETE Chloride-Induced Corrosion The alkaline environment in concrete (pH of approximately 13) protects reinforcing steel from corroding through the formation of a passivating iron-oxide layer on the steels surface. However, when concrete is exposed to chloride solutions, the steels passivating layer is destroyed, and in the presence of an adequate supply of oxygen, the steel corrodes. The destruction of the passivating layer depends on the molar ratio of chloride ions to hydroxide ions (Cl-/OH-). When Cl-/OH- molar ratios are higher than 0.6, steel seems to be no longer protected against corrosion, probably because the iron-oxide layer becomes either permeable or unstable under these conditions [4]. It is generally accepted that chloride ions react with ferrous ions to form a soluble complex which upon reaction with hydroxide ions leads to the formation of rust, Fe(OH)2. The chloride ions are then released back into solution for further reaction with ferrous ions. A typical reaction between ferrous and chloride ions is as follows Fe + 4Cl
2

2+

FeCl4

(1)

FeCl4 + 2OH

Fe( OH )2 + 4Cl

(2)

In Kuwait, the groundwater in the coastal zone generally contains high levels of chlorides and sulfates. Typical values for five residential areas within the coastal zone are
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presented in Table 1. Both the chloride and sulfate values for each area are either within or above the ranges for onset of concrete deterioration in accordance with the Uniform Building Code [5]. Whereas concrete distress caused by expansive sulfate attack is known to be suppressed in the presence of chloride ions, the chlorides promote corrosion of steel reinforcement [6,7]. As such, the groundwater in the coastal zone of Kuwait would be expected to induce corrosion when in contact with unprotected reinforced concrete elements. Table 1. Chloride and Sulfate Levels in Groundwater in Different Coastal Areas in Kuwait Coastal Area Sulaibikhat Shuwaikh Shaab Salwa Fahaheel Ranges for onset of concrete deterioration Carbonation-Induced Corrosion A second cause of corrosion in reinforced concrete is carbonation of the concrete cover on the steel reinforcement. Atmospheric carbon dioxide (CO2) combines with moisture in the concrete to form carbonic acid. This acid then reacts with the cement hydration products, particularly calcium hydroxide (Ca(OH)2), to form calcium carbonate (CaCO3) and lower the pH of the concrete. CO2 + H2O + Ca(OH)2 CaCO3 + 2H2O (3) Chloride (ppm) 10,423 642 41,126 752 3,092 500 - 1,500 Sulfate as SO4 (ppm) 6,004 2,134 1,685 1,677 6,647 150 - 1,500

When the pH is lowered below 11.5 at the level of the steel reinforcement, the passivating layer is destroyed causing corrosion to occur [4]. The rate of carbonation of the concrete is influenced by the concentration of CO2 in the atmosphere, and by the diffusion rate of CO2 which is dependent on the permeability and moisture content of the concrete. If the moisture content of the concrete is very low, carbonation does not occur because of the lack of water. If the moisture content is very high (i.e., saturated concrete pores), there is again very little carbonation because of the very low rate of CO2 diffusion in water. Carbonation is greatest where the pores of the concrete are partially filled with water. Carbonation-induced corrosion in the Arabian Gulf region is usually due to insufficient concrete cover on the steel reinforcement [6]. The low cover thicknesses seem to be the result of a lack of an adequate specified minimum cover and poor control during construction. In the United Arab Emirates (U.A.E.) and Bahrain [6,8], carbonation-induced corrosion has been documented in interior concrete elements which received little or no curing. Studies in Kuwait have shown that carbonation due to poor construction practices was the cause of corrosion of non-marine concrete structures [2].

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CORROSION PROTECTION MEASURES FOR NEW STRUCTURES The measures implemented during the construction of reinforced concrete structures to provide protection from corrosion-induced damage caused by the effects of the service environment usually involve the following approaches: sealing the concrete surface to prevent ingress of chlorides, modifying the concrete to reduce its permeability, and protecting the reinforcing steel to reduce the effects of chlorides when they do reach the steel. Multiple levels of protection may be applied consisting of two or more of these approaches. In the Arabian Gulf region, the protection systems frequently used are silica-fume concrete, epoxycoated reinforcing bars, and calcium nitrite chemical admixture [9]. The full effectiveness of these protection systems can only be achieved if good concrete construction practices are adopted. In Kuwait, corrosion protection systems are not used as normal concrete construction practice, enhancing the vulnerability of reinforced concrete structures to corrosion-induced deterioration. Good concrete construction practices, such as those specified by the American Concrete Institute (ACI) [10] and the Construction Industry Research and Information Association (CIRIA) [11], include limiting chlorides in the concrete ingredients, providing adequate concrete cover on reinforcing steel, and allowing adequate curing to enhance hydration and reduce the permeability of the concrete. The implementation of these practices is a first step in the construction of corrosion-resistant concrete structures and in the effective use of corrosion protection systems. INVESTIGATION AND REPAIR OF CORROSION DAMAGE The assessment of the effects of a given service environment on the extent of corrosion damage requires a thorough investigation to be undertaken on the structure. This investigation is a necessary first step for a successful repair of the damage. A typical investigation includes the following: visual inspection of the structure to assess the condition of the structural members and to select locations for obtaining concrete samples, nondestructive testing to identify locations of extensive degradation in concrete properties, and laboratory testing of material samples removed from the structure. These investigative procedures were recently applied to two reinforced concrete structures in Kuwait, one a commercial building and the other an oil refinery structure. Visual Inspection The visual inspection identified the nature of the service environment and its role in promoting corrosion in the structure. The visual inspection of the 25-year old commercial building revealed that the humidity level in the inspected area was high and was enhanced by a lack of ventilation. Heavy deposits of salt were formed on the structural members due to leakage from a brine tank in an upper floor laundry room. These are ideal conditions for corrosion to occur, as evidenced by the severely corroded reinforcement in a portion of the structure shown in Fig. 2. In the oil refinery structure, chloride-laden steam from a hot seawater collector escaped freely into the environment around the structure. Figure 3 shows that extensive cracking and brown rust stains were observed on the concrete surface.

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Figure 2. Deteriorated concrete with heavily corroded steel reinforcement

Figure 3. Extensive cracking and rust stains on concrete surface Nondestructive Testing Rebound hammer and ultrasonic pulse velocity tests were performed to evaluate the quality of the concrete in different parts of the structures. The ultrasonic pulse velocity or rebound hammer data were compared for specific parts of the structures to determine the relative levels of degradation in concrete quality. A lower value for the ultrasonic pulse velocity or the rebound hammer number indicates a lower concrete quality. The data showed that, for the commercial building, the level of degradation in concrete properties was extensive in structural elements adjacent to expansion joints when compared to elements further from the expansion joints, as is illustrated in Fig. 4 by the ultrasonic pulse velocity data for different structural members. This extensive degradation was due to exposure of the concrete in the vicinity of the expansion joints to moisture from leakage through the joints.

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For the oil refinery structure, lower values for ultrasonic pulse velocity and rebound number were obtained for structural elements with extensive cracking.
5000
Adjacent to Expansion Joint Further from Expansion Joint

4000

3000

2000

1000

0000

Slab

Beam

Column

Structural Member
Figure 4. Ultrasonic pulse velocity data for concrete in different structural members Concrete Cover and Carbonation Depth A covermeter was used to determine the thickness of concrete cover provided on the reinforcement to protect against corrosion. Core samples were removed from the structure to determine the extent of carbonation of the concrete cover utilizing phenolphthalein solution. Data obtained for the commercial building showed that carbonation depth exceeded the cover thickness in some structural members, as illustrated in Fig. 5 for beams. In these members, carbonation would be expected to contribute to corrosion of the reinforcement. Concrete Quality Cores were removed from selected structural members to assess water absorption and voids content characteristics of the concrete in order to determine the ability of the concrete to resist ingress of moisture and salts. The water absorption and voids content data indicated that, overall, the concrete in the structures was highly porous. The water absorption values for the concrete samples ranged from 6 to 8% and the voids content values ranged from 15 to 18%. These values are quite high and indicate that the concrete in the structures has a low resistance to the ingress of moisture and chlorides. Chloride Content of Concrete Concrete powder samples within three depth ranges from the surface of the concrete (010 mm, 10-25 mm, and 25-50 mm) were obtained from selected structural members. These samples were used to determine the acid-soluble chloride contents of the concrete to assess the potential for reinforcement corrosion and concrete deterioration. The concentrations of chloride in the structures were found to exceed the threshold values for initiation of corrosion.
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Figure 6 shows a typical chloride concentration profile in the structural elements of the commercial building. For the concrete in the commercial building, the threshold chloride value is estimated to be 0.025% by mass of concrete based on the ACI Committee 222recommended acid-soluble chloride limit of 0.20% by mass of cement [12].
5
Concrete Cover Carbonation Depth

Beam 1

Beam 2

Beam 3

Structural Member
Figure 5. Concrete cover compared with carbonation depths in beams

0.10

0.08

0.06

0.04 Estimated limit for corrosion initiation = 0.025% mass of concrete 0.02

0.00

0.5

1.75

3.75

Chloride Penetration Depth (cm)


Figure 6. A typical chloride concentration profile in beams

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Chloride Diffusion: The chloride diffusion model based on Ficks second law [13-15] was used to determine the characteristics of chloride penetration into the concrete. The model is expressed as C = C o erfc where C Co D t erfc = = = = = x (4) 2 Dt

chloride concentration at a distance x from the concrete surface surface chloride concentration effective diffusion coefficient time a mathematical function (Gaussian error function complement)

The chloride data was used with Eq. 4 to calculate values for D and Co by performing a nonlinear regression analysis. These values were used with Eq. (4) in conjunction with the threshold chloride value and the thickness of concrete cover to estimate the time to initiation of corrosion in the structural elements of the commercial building to be in the range of 2-6 years. This indicates that corrosion started early in the life of the 25-year old building and, therefore, measures could have been taken earlier to control its progress. Table 2. Steel Section Loss Due to Corrosion Structural Member Original Diameter of Bar, d (cm) 1.0 1.6 1.4 1.6 1.0 2.0 2.0 1.4 1.0 1.0 1.8 1.8 1.0 1.0 1.0 Mass of Corroded Bar/Unit Length, ms (g/cm) 5.73 15.76 10.08 15.48 5.92 22.64 22.39 10.56 3.17 2.35 13.80 13.05 5.92 5.88 5.87 Average Reduction in Bar Diameter, d (m) 366 22 1222 164 208 850 956 920 2834 3830 3048 3460 208 240 248 CrossSectional Area Loss (%) 7.2 0.3 16.7 2.0 4.1 8.3 9.3 12.7 48.6 61.9 31.0 34.7 4.1 4.7 4.9

Slab

Beam

Column

Loss of Steel Section: Some cores removed from the structural members contained pieces of steel bars. These steel bars were cleaned using Clarke's solution [16] and weighed to determine their mass loss per unit length. The relation between mass, volume and density was used to calculate the average reduction in bar diameter based on the original diameter of
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the steel bars and a density of 7.86 g/cm3 for the steel. The values of average reduction in bar diameter were used to calculate the cross-sectional area loss of the steel reinforcement at different locations in the structural elements, as presented in Table 2 for the commercial building. The estimates for steel section loss were as high as 62% in parts of the commercial building and 88% in parts of the oil refinery structure. At these levels of steel section loss, extensive cracking of the concrete would be expected, as was observed in the structures. Eq. 4 was used with the estimated values of D and Co to calculate the maximum chloride concentrations at the level of the steel reinforcement. The values for the commercial building are summarized in Table 3, in addition to values of average thickness of concrete cover, average depth of carbonation and maximum section loss of steel reinforcement. These results show that both chlorides and carbonation were responsible for corrosion of the steel reinforcement. Chloride-induced corrosion is indicated where the maximum chloride concentration at the level of the steel reinforcement exceeds the threshold value of 0.025% by mass of concrete and the carbonation depth is less than the thickness of the concrete cover. Carbonation-induced corrosion is indicated where the carbonation depth exceeds the cover thickness and the chloride concentration is less than the threshold value. Table 3. Extent and Cause of Corrosion of Reinforcing Steel Structural Member Slab Adjacent to Expansion Joint Max. Chloride Concentration at 0.001 Steel Level (% Mass of Concrete) Average Concrete 4.0 Cover (cm) Average 4.5 Carbonation Depth (cm) Max. Steel 16.7 Section Loss (%) Type of Carbonation Corrosion* -induced corrosion 1.540 Beam Further from Expansion Joint 0.003 0.058 Column

3.0 0.0

3.0 4.0

4.0 4.2

61.9 Chlorideinduced corrosion

12.7 Carbonationinduced corrosion

4.9 Chloride-induced corrosion with carbonation contributing

* Based on chloride threshold value of 0.025% by mass of concrete.

Guidelines for Repair of Corrosion Damage

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The information gained from the corrosion damage investigation provides the basis for a successful repair of the structure. In general, the arrest of chloride-induced corrosion requires the removal of chloride contaminated concrete around the steel reinforcement. This would require the mechanical removal of the contaminated concrete or the application of an electrochemical method for chloride removal. Carbonation-induced corrosion can be arrested by installing surface barriers. Surface applied barriers which have low vapor transmission allow the uncarbonated concrete to re-alkalize or increase the pH of the carbonated concrete, pushing the carbonation front back toward the surface. The carbonation process in cracked concrete can be arrested by using elastomeric membranes for crack bridging or by using crack sealants. Electrochemical technology can also be used to transport alkalies into carbonated concrete [17]. The following general guidelines are appropriate when repairing corrosion-induced damage in reinforced concrete structures.

Cracked concrete should be repaired after an adequate preparation of the concrete


surface to ensure a good bond between the repair and the base concrete, Whenever possible, cracked concrete cover should be removed to at least 2 cm beyond corroded steel bars, During repair of cracked concrete cover, all exposed, severely corroded reinforcement (i.e., > 25% section loss) should be repaired by providing new reinforcement, After concrete repair, protective coating may be applied on the surfaces of the structure to protect against the ingress of moisture, chlorides and gases, and Periodic monitoring of the structure may be undertaken, following completion of the repair work, to assess the extent of any further corrosion activity.

CONCLUSIONS 1. The following conclusions are drawn based on the discussions in this paper: 2. The investigative techniques employed provided information on the nature of the service environment and its role in promoting corrosion of steel reinforcement in the concrete structures. 3. Lack of adequate measures to mitigate the effects of the service environment contributes significantly to corrosion-induced deterioration of reinforced concrete structures in Kuwait. 4. Both chloride-induced corrosion and carbonation-induced corrosion are found to occur in the structures. REFERENCES 1. Rasheeduzzafar; F.H. Dakhil and A.S. Al-Gahtani, Deterioration of concrete structures in the environment of the Middle East, ACI Journal 81, 1, 1984, pp. 13-20. 2. H.M. Shalaby, Case studies of corrosion and deterioration of reinforced concrete structures in the State of Kuwait, First International Conference on Deterioration and Repair of Reinforced Concrete in the Arabian Gulf, Bahrain, 1985, pp. 309-320.

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3. S. Al-Bahar and E. Attiogbe, Corrosion-induced deterioration of reinforced concrete structures in Kuwait, Concrete Under Severe Conditions, Environment and Loading., Proceedings CONSEC 95, International Conference, K. Sakai, N. Banthia and O.E. Gjorv Eds, Sapporo, Japan, Vol.1, August 1995, pp. 564-573. 4. P.K. Mehta, Concrete: Structure, Properties, and Materials, Prentice-Hall, Inc., Englewood Cliffs, New Jersey, 1986. 5. Uniform Building Code, International Conference of Building Officials (ICBO), California, 1991. 6. Z.G. Matta, Deterioration of concrete structures in the Arabian Gulf, Concrete International 15, 7, 1993, pp 33-36. 7. B.C. Gerwick, International experience in the performance of marine concrete, Concrete International 12, 5, 1990, pp 47-53. 8. C. Le Sage de Fontenay, A study of the effect of concrete admixtures, concrete composition and exposure conditions on carbonation in Bahrain, First International Conference on Deterioration and Repair of Reinforced Concrete in the Arabian Gulf, Bahrain, 1985, pp. 467-483. 9. Z.G. Matta, Protecting steel in concrete in the Persian Gulf, Materials Performance, 1994, pp. 52-55. 10. ACI 318, Building Code Requirements for Reinforced Concrete, American Concrete Institute, Detroit, 1989. 11. CIRIA, Guide to Concrete Construction in the Gulf Region, CIRIA Special Publication 31, 1984. 12. ACI Committee 222, Corrosion of Metals in Concrete, American Concrete Institute, Detroit, 1989. 13. J. Crank, Mathematics of Diffusion, 2nd Edition, Oxford University Press, 1975. 14. N.S. Berke, D.W. Pfeifer and T.G. Weil, Protection against chloride-induced corrosion, Concrete International 10, 12, 1988, pp. 45-55. 15. O.E. Gjorv, K. Tan and M. Zhang, Diffusivity of chlorides from seawater into highstrength lightweight concrete, ACI Materials Journal 91, 5, 1994, pp. 447-452. 16. ASTM G 1, Standard practice for preparing, cleaning, and evaluating corrosion test specimens, Annual Book of ASTM Standards, Vol. 03.02, Philadelphia, Pennsylvania, USA, 1990. 17. P.H. Emmons, Concrete repair and maintenance illustrated, R.S. Means Company, Inc., Massachusetts, USA, 1993.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CORROSION OF CONCRETE IN SEAWATER M. Pakshir and S. Esmaili Department of Materials Science and Engineering Shiraz University, Shiraz, Iran

ABSTRACT
Attack and disintegration of concrete structures under the influence of aggressive fluids, wet gases, etc., are understood as corrosion of concrete. The corrosion of concrete is a chemical, colloidchemical process, yet often a physicochemical one, while that of concrete reinforcement is mainly electrochemical. Many sea harbor jetties, docking facilities and concrete-supported oil platforms are subjected to the marine environment in the Persian Gulf, and therefore become corroded. In the present paper, using an aerated synthetic seawater representative of Persian Gulf environment, we have tried to investigate the time required for corrosive agents such as chloride and oxygen to penetrate through the concrete. The influence of the concrete's cover depth and corrosion rate of the rebar has also been studied. Key Words: Concrete, reinforcement, concrete cover, seawater, corrosion

INTRODUCTION In recent years, the performance of concrete in marine environments has assumed considerable importance because of the offshore activity of gas and oil exploration in various countries. Thus, concrete performance in marine environments has been investigated by several researchers [1,2,31. The interaction between the concretes service environment and the concrete itself can lead to deterioration of reinforced concrete structures, and in some cases, render the structures unsuitable for their designed purposes. The interaction is often with the chemical species in the environment [4]. For concrete in a marine environment, there appears to be a direct correlation between low permeability (i.e., high strength) and good durability. Therefore, concrete sea structures, such as harbor structures and offshore platforms, are built using high quality concrete [5]. In general, concrete is a fine, porous material. Pore sizes vary from a few angstroms to several millimeters. This pore system is more or less filled with a solution which contains varying quantities of salts. The problems associated with the application of reinforced concrete in marine environments are well known. These problems have led to extensive research on the corrosion of metal in concrete structures. Concrete reinforcement is usually protected from corrosion by the highly alkaline environment (pH about 11.5) of the concrete surrounding it.
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As a result, the steel surface frequently develops a protective oxide layer which is difficult to dissolve, and hence limits its disintegration [1,6,7]. Corrosion of the steel normally happens either by the carbonation of the concrete around it which reduces the alkalinity, or through the presence of even small quantities of chlorides in the concrete cover. The depth of penetration of chloride is a function of time and the permeability of the concrete [8]. Once the steel has become depassivated, the rate of corrosion will depend, among other factors, upon the availability of moisture and oxygen near the steel surface [9,10]. In the absence of either moisture or oxygen, corrosion will not occur. The corrosion of steel causes the metal to be converted in different stages into various ferric oxides and ferric hydroxide [11]. This change leads to an increase in volume. Damage resulting from corrosion can also be seen in the form of cracks parallel to the embedded steel, and finally cracking and spalling of the concrete which accelerates the rate of corrosion. The corrosion of reinforcing steel in concrete results from an electrochemical process [12] accompanied by anodic and cathodic reactions. Iron is transferred in the solution as hydrated ions with two electrons left in the reinforcing steel. These two electrons are transferred to the cathodic area to assimilate in the cathodic reaction. EXPERIMENTAL PROCEDURE The experiments performed were designed with two purposes: the first was to study the time that a corrosive agent takes to penetrate through the concrete cover to the reinforcing steel, and the second was to investigate the influence of the depth of cover for a fixed watercement (w/c) ratio. Tests were performed on mortar specimens partially submerged in an aerated seawater (Table 1). The mortar specimens were made with ordinary Portland cement and had w/c ratios of 0.4, 0.5, 0.6, and 0.7, with a cement-sand ratio of 1:3. Table 1 Chemical Composition of Artificial Seawater NaCl (g/l) 32 MgCl2.6H2 O (g/l) 6 MgSO4.7H2O (g/l) 5 CaSO4.2H2O (g/l) 1.5 KHCO3 (g/l) 0.2

The aggregate used was crushed stone, and it was used in a dry condition when the concrete was mixed. The sand was ordinary local river sand. The specimens made were 20 x 55 x 80 mm with two round carbon steel bars 7 mm in diameter embedded symmetrically. The steel bar was embedded 50 mm into the mortar, and to avoid the formation of a differential aeration cell, the ends of the embedded bars were insulated with adhesive tape. The Portland cement was cured at 20C for 28 days. Since the procedure required a constant 2 current density (mA/mm ) over the reinforcement surface, the specimens were exposed to seawater in the tank for several days to obtain a uniformity of moisture in the concrete before the impressed current was applied. Direct current (DC) was impressed on the specimen from a DC rectifier, and a potentiometer was used to control the current applied to each specimen.

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Current direction was so arranged that the reinforcing steel bars served as anodes and a stainless steel rod was employed as a counter electrode to serve as a cathode (Fig. 1). The potential of each specimen was measured daily using a saturated calomel electrode with a voltmeter twice a day, and any drift was corrected by adjusing the potentiometer. Potential readings were taken with the power on. The readings represented the polarization potential of the reinforcement plus the voltage drop across any corrosion product film at the reinforcement /cement interface. In order to study the effect of different cover depths on the corrosion rate of reinforcing steel, 200 x 300 x 125 mm slab specimens with a 25 mm pond cast on top were made from Portland cement at a w/c ratio of 0.5. Each specimen contained two carbon steel electrode rods of 3 mm diameters embedded at four depths of cover, i.e., 10 , 20 , 30 and 40 mm. The electrochemical corrosion measurements of the embedded steel reinforcement were carried out by means of polarization resistance measurements and rest potentials. The corrosion rates were calculated from the polarization resistance value using the Stern-Geary equation, i.e.: Icorr = Iappl / 2.3 E (ca / (c + a)) (1)

Icorr was calculated on the assumption that both the anodic and cathodic Tafel constants, a and c, had values of 120 mV/decade.

Figure 1. Schematic illustration of polarization measurements

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RESULTS AND DISCUSSION The corrosion of concrete reinforcement in aerated seawater is expressed in terms of potential and current in the embedded rebar as a function of exposure time. The temperature and oxygen content of the seawater were checked regularly. The temperature varied from 20C to 25C, depending on the time of year, while the oxygen content was kept about 7 ppm at all times. The electrochemical potential was measured via a high-impedance millivoltmeter against a calomel electrode. Figure 2 shows the typical half-cell potential versus time behavior of embedded steel reinforcement in aerated seawater. It shows that the time required for the reinforcing steel to be in an active potential is about 3.5 weeks for a w/c ratio of 0.7 and increases to about 13 weeks for a w/c ratio of 0.4. In other words, the time for the corrosive agent to reach the embedded steel is the time it takes the steel reinforcement to change from a passive potential to an active potential, which occurs when sufficient chloride ions and oxygen are present to cause corrosion of the steel bar. Therefore, one can assume that a high w/c ratio makes the concrete permeable enough for the corrosive agent to penetrate to the reinforcing steel and then depassivate it. Thus, as the w/c ratio increased, the potential of the reinforcing steel bar became less noble. A general decrease in the observed corrosion current was found to occur with decreases in the w/c ratio (Fig. 3). In order to accelerate the corrosion process, a constant electrical potential of 3.5 V was impressed into the embedded steel bar.

Figure 2. Corrosion potential vs. exposure time

Figure 3. Corrosion current density (Icorr) vs. exposure time

Concrete cracking due to corrosion of the reinforcement was observed after 14 weeks for a w/c ratio of 0.4, after 10.5 weeks for a w/c ratio of 0.5, after 4.5 weeks for a w/c ratio of 0.6 and after 4 weeks for a w/c ratio 0.7. Therefore, the sharp rise in current in Fig. 3 is related to the time the appearance of the cracks was observed. However, the failure of the concrete
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specimen due to the corrosion of the steel reinforcement is related to the initial current of the steel bar, and as can be seen, the initial current of the steel bar depends upon the w/c ratio of the covered concrete. Therefore, for the reinforced steel embedded in the concrete with a lower w/c ratio, the initial current was lower and it took a longer time for the corrosive agent to reach the steel reinforcement and cause corrosion failure. The results of measurement of the distribution of the corrosion potential and corrosion current density of the reinforcing steel after 70 days of exposure for different cover thicknesses are shown in Figs. 4 and 5.

Figure 4. Corrosion current density vs. exposure time

Figure 5. Corrosion potential vs. exposure time

In the case of a cover thickness of 10 mm, the degree of corrosion was large, and the specimen had a crack of about 0.2 mm due to the corrosion of the reinforcing steel. The corrosion of the steel rebar at the location of the crack was particularly remarkable. On the other hand, with an increased cover thickness of 40 mm, very little corrosion of the reinforcing steel bar was observed. Visual examination of the reinforcement bar after 70 days revealed a white deposit on the surface. The amount of the deposit varied with the depth of the cover thickness. On microscopic examination, the deposit appeared to be crystalline in structure and was very dense in nature (Fig. 6). Chemical analysis of the deposit showed that it consisted of a mixture of calcium carbonate and magnesium hydroxide. Since seawater contains a lot of magnesium sulfate, which is the most harmful salt as far as cement attack is concerned, it reacts with calcium hydroxide and by substitution of the magnesium for calcium, secondary gypsum in flat prisms and brucite Mg(OH)2 in superimposed platelets are formed (Fig. 7).

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(a) Crystallization of the brucite layer aragonite layer

(b) Crystallization of the

(c) Aragonite deposit on the brucite layer Figure 6. Morphology of calcareous deposits after seventy days of exposure to seawater

Figure 7. The dissolution of calcium hydroxide and the formation of secondary gypsum CONCLUSIONS Since seawater contains a lot of chloride in various forms as well as sulfate salts, the initial period of attack is the time taken for the chloride and sulfate ions to penetrate from the surface through the concrete cover and reach the steel reinforcement bar. During this period, the steel is in the passive state until the threshold value of these aggressive ions is reached for corrosion to initiate in the presence of oxygen. A possible form of corrosion attack on the reinforcement in the initial stage was pitting corrosion. There is good reason to assume that the number of pits was fairly high, as was true in the case of a 10 mm cover thickness. Also, since the amount of available cathodic current was constant, regardless of the number of pits, the average anodic current was small. Therefore, the most important consequence of pitting is that oxygen is consumed in the process, i.e., as oxygen is consumed, the steel potential drifts to a negative value and corrosion takes place. Hence, the availability of oxygen is one of the main controlling factors

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of the corrosion of steel rebar in concrete. The amount of corrosion discovered when the reinforcement was removed was insignificant as the depth of cement cover increased, small spots of corrosion products were in a few instances visible at the surface. A high water-cement ratio makes concrete permeable enough for the aggressive ions to penetrate to the reinforcing steel easily and then depassivate the reinforcement. Thus, as the water-cement ratio of the concrete increases, the potential of the reinforcing steel becomes less noble and the electric resistance of wet concrete drops due to yje low permeability which accelerates the corrosion of reinforcing steel. REFERENCES 1. P.K. Mehta and P.J. Monteiro, Concrete: Structure, Properties and Materials, 2nd ed., Prentice Hall, Englewood Cliffis, 1993. 2. P. Rodriguez, E. Ramirez and A. Gonzalez, Magazine Concrete Research 46, 167, June 1994, pp. 81-91. 3. O.A. Kayyali and M.N. Haque, Magazine Concrete Research 47, 172, Sept. 1995, pp. 235-242. 4. D. Bawega, H. Roper and V. Sirivivatnanon, Cement and Concrete Research Journal 23, 1993, pp. 1418 -1430. 5. H.H. Haynes, American Concrete Institute, Detroit, Michigan, USA, SP-65, 1982, pp. 2138. 6. C. Androde, Corrosion of Steel in Concrete: Monitoring Techniques, Report of the Technical Committee 60-csc Rilem, Champman and Hall , New York, USA, 1988. 7. P. Lambert, C.L. Page and P.R.W. Vassie, Materials and Structures 24, 1991, pp. 351358. 8. C. Liam, S.K. Roy and D.O. Northwood, Magazine Concrete Research 42, 160, Sept. 1992, pp.205-215. 9. A. Gonzalez, A. Molina, E. Otero and W. Lopez, Magazine Conerete Research 42, 150, March 1990, pp. 23-27. 10. C.L. Page and P. Lambert, Journal of Materials Science 22, 1987, pp. 942-946. 11. C.A. Lawrence, British Ceramic Proceedings, Cement and Concrete Association, Wexham, UK, No.35, 1984, pp.277-293. 12. K. Okado and T. Miyagawa, American Concrete Institute, Detroit, Michigan, USA, SP65, 1982, pp.237-254.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CONCRETE QUALITY AND ITS EFFECT ON CORROSION OF STEEL REINFORCEMENT E.K. Attiogbe and S. Al-Bahar Civil Engineering & Building Department Kuwait Institute for Scientific Research P.O. Box 24885, 13109 Safat, Kuwait

ABSTRACT
To minimize the incidence of premature deterioration of concrete, issues that need to be carefully attended to include the establishment of material specifications that match the severity of the service exposure conditions, and the implementation of construction practices that enable the desired level of durability to be obtained. The paper discusses the characteristics of concrete ingredients that relate to corrosion-induced deterioration of reinforced concrete structures. The role of supplementary cementing materials in enhancing the resistance of concrete to reinforcement corrosion and the effects of high ambient temperatures on the corrosion-related behavior of the concrete microstructure are discussed. Selecting appropriate concrete materials that compensate for the aggressiveness of the exposure condition is a critical factor in ensuring the durability of reinforced concrete. Key Words: Concrete durability, concrete materials, concrete quality, reinforced concrete, reinforcement corrosion

INTRODUCTION The performance of concrete under harsh service conditions, such as those prevalent in the Arabian Gulf region, is controlled by the interaction between the concrete and the environment. Corrosion of steel reinforcement has been established as the major cause of premature deterioration of concrete structures in the Arabian Gulf states [1-5]. Reinforced concrete structures constructed with a design life of 50 years or more have become structurally unsound within 10 to 20 years. The factors that promote this premature deterioration of concrete structures include the use of unsuitable concrete mix ingredients, poorly designed concrete mixes, and improper concrete placement and curing. Chlorides are the primary cause of corrosion in reinforced concrete structures in Kuwait and other Arabian Gulf states, with carbonation as a secondary cause [1-3]. A number of studies have evaluated the role of different concrete ingredients in enhancing the corrosion resistance of reinforced concrete, as well as the corrosion performance characteristics of concrete materials used in the Arabian Gulf region [6-10]. In this paper, the characteristics of concrete ingredients with respect to corrosion of reinforcement are discussed. In addition, the paper presents the basis for producing durable concrete that is resistant to reinforcement corrosion in the hot and arid environment of the Arabian Peninsula.

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CONCRETE MATERIALS Aggregates Aggregates used for concrete mixes in Kuwait and other Arabian Gulf states are typically contaminated with dust and salts. To enhance the durability of concrete made with these aggregates, it is prudent to wash the aggregates to remove or minimize the chloride and sulfate salts. However, due to the scarcity of water in the region, the aggregates may not be washed prior to use in the concrete mix [1,3,9], enabling the corrosive action of the chlorides to commence at a very early stage when the concrete is still very weak and porous. In Kuwait, the sand is usually washed, whereas the coarse aggregate is sieved to remove dust prior to use in concrete mix. Table 1 shows the chloride and sulfate levels in washed sand and sieved coarse aggregate used for a residential building project. While the chloride levels are lower than the limits for concrete deterioration as specified by the CIRIA Guide [11], the level of sulfate in the sieved coarse aggregate is greater than the CIRIA Guides limit. Where cracking of concrete takes place due to high levels of sulfate contamination, chloride ingress from the salt-laden atmosphere in the coastal zone can occur leading to reinforcement corrosion. Therefore, adequate steps must be taken to minimize both chlorides and sulfates in concrete aggregates. Table 1. Chloride and Sulfate Concentrations in Aggregates Material Sand (Washed) Coarse Aggregate (Sieved) Limits for Concrete Deterioration Mix Water Potable or desalinated water is scarce in the Arabian Gulf region. As such, brackish service water (nondesalinated tap water) is sometimes used in mixing concrete [1,9]. This practice introduces quantities of chloride and sulfate into the concrete at the time of mixing. In a study undertaken by Rasheeduzzafar et al. [7], the chloride and sulfate concentrations in brackish water used to evaluate the influence of construction practices on concrete durability were 1294 ppm and 375 ppm, respectively, compared with corresponding concentrations of 32 ppm and 32.5 ppm in potable water. The salt concentrations in the brackish water are within the ranges specified by the Uniform Building Code [12] for onset of concrete deterioration. These ranges are 500-1500 ppm for chlorides and 150-1500 ppm for sulfates. The chloride concentration of 1294 ppm exceeds the maximum concentration of 500 ppm recommended by the CIRIA Guide for water used in mixing or curing reinforced concrete. Use of mix water of drinking quality would reduce the risk of corrosion in reinforced concrete structures. Portland Cement Chloride (% mass of agg.) <0.001 <0.001 0.06 (sand) 0.03 (coarse) Sulfate (% mass of agg.) 0.092 0.596 0.4

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The major compounds in portland cement are tricalcium silicate (C3S), dicalcium silicate (C2S), tricalcium aluminate (C3A) and tetracalcium aluminoferrite (C4AF). The C3A phase has the ability to bind chlorides, resulting in the formation of insoluble calcium chloroaluminate compound (3CaO.Al2O3.CaCl2.10H2O) or Friedel's salt. This reduces the amount of free chloride ions in the concrete pores and, hence, lowers the corrosion risk. Figure 1 shows that the concentration of free or unbound chlorides decreases with an increase in the C3A content of cement [8]. The unbound chlorides were found to be 86, 58, 51 and 33% of the total chlorides in concrete made with cements having C3A contents of 2.04, 9.10, 11.02 and 14.00%, respectively. Studies have shown that the time to initiation of corrosion increases with increasing C3A content of cement [6,8]. However, the chloride-binding capacity of C3A decreases with an increase in the chloride concentration, becoming almost ineffective when concrete is exposed to high chloride concentrations [8]. In addition, the long-term effectiveness of chloride binding by C3A in reducing corrosion risk is not yet clear, as the chlorides may be released later in the life of the concrete structure due to carbonation or sulfate attack of the concrete [13,14]. Thus, it appears that cements high in C3A should not be depended upon solely for the purpose of reducing the risk of corrosion in reinforced concrete structures.
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Figure 1. Effect of the C3A content of cement on chloride binding The composition of modern portland cements, particularly that of cements used in the Arabian Gulf region, usually is characterized by markedly higher C3S-to-C2S ratios than those in older cements [8]. Therefore, the modern cements have a higher rate of hydration and strength gain than the older cements. When concretes made with the modern cements are specified in terms of 28-day strength only, they usually satisfy the specification at higher water-cement ratios than concretes made with the older cements. In general, this would lead to a more permeable concrete with a low resistance to reinforcement corrosion due to the ingress of chloride solutions. Specifying concrete merely on strength considerations while ignoring factors relevant to its durability would result in durability problems of varying severity. Reducing the risk of reinforcement corrosion requires laying down specific
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provisions for using concrete permeability characteristics, along with strength, to match concrete quality to environmental exposure conditions. CONCRETE MIX CHARACTERISTICS Water-Cement Ratio Lowering the water-cement ratio (w/c) of concrete reduces its permeability to ingress of chloride solutions. Lower w/c concretes have a higher electrical resistivity which impedes the flow of corrosion current. The rate of oxygen diffusion is also substantially reduced the lower the w/c, contributing to significant enhancements in polarization resistance and, thereby, to reductions in the magnitude of corrosion current. Low w/c concretes are, however, limited in their effectiveness in delaying the onset of chloride-induced corrosion. A reduction in w/c from 0.50 to 0.35 improved the time to initiation of corrosion by only 20% [10]. This marginal increase in the time to corrosion initiation is attributed to the fact that the reduction in the permeability of the concrete due to a lowering of the w/c is less effective in the case of diffusivity of chloride solutions than in the case of diffusivity of plain water [15]. That is, chloride ions in solutions, particularly in high concentrations, are able to diffuse through concrete made with plain portland cement at much faster rates than with diffusion of water. Enhanced resistance to chloride ion ingress is obtained when supplementary cementing materials, such as silica fume, are used in the concrete mix in addition to lowering the water-cementitious materials ratio. Supplementary Cementing Materials The permeability of concrete is significantly reduced when supplementary cementing materials such as condensed silica fume, fly ash or blast furnace slag are used with portland cement. The decreased permeability substantially increases resistance to chloride penetration and reduces the rate of carbonation. The supplementary cementing materials produce concretes with low chloride diffusivity and high electrical resistivity. A 9% replacement of cement by silica fume reduced the chloride diffusivity by a factor of about 5 [16]. Figure 2 shows the increase in electrical resistivity of concrete with increasing content of silica fume [17]. The effect is more pronounced the higher the cement content. For a 400 kg/m3 cement content, the increase in resistivity was 550 and 1600% for silica fume additions of 10 and 20%, respectively. The times to initiation of corrosion for silica fume concretes compared with plain cement concretes are presented in Fig. 3 [6], showing that silica fume significantly delays the onset of corrosion. Figure 3 indicates that there may not be any significant advantage in increasing the cement replacement by silica fume in Type I portland cement concrete (C3A content of 9 to 14%) to more than 10%. This is of considerable practical significance in the Arabian Gulf region, where the cost of silica fume is reported to be over ten times the cost of ordinary portland cement [6]. A fly ash replacement level of 30% by mass of cement increased corrosion initiation time by a factor of about 2 [9]. For blast furnace slag, effective replacement levels to reduce the risk of corrosion are 50 to 70% by mass of cement [18]. The benefits of using supplementary cementing materials can only be fully realized if the concrete is treated properly during construction. With regard to silica-fume concrete, for example, the typical low water content and lack of bleeding may give rise to plastic shrinkage cracking, particularly in the hot and arid environment of the Arabian Gulf region. Techniques
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for dealing with this problem include starting the curing process early and using evaporationretarding materials. The implementation of good concrete construction practices that account for the characteristics of the particular supplementary cementing material used are essential to enhancing the resistance of concrete to reinforcement corrosion.
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Figure 2. Effect of silica fume on electrical resistivity of concrete

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Figure 3. Time to initiation of corrosion for replacement of cement by silica fume Corrosion-Inhibiting Chemical Admixture Calcium nitrite admixture is a commonly used chemical corrosion inhibitor for reinforced concrete structures. It is added to the concrete mix during batching and enhances the stability of the passivating layer on the surface of the reinforcing steel. Nitrite ions react

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with ferrous ions according to Eq. 1 [19] to produce a stable passive layer of ferric oxide (Fe2O3):
2 Fe2 + + 2OH + 2 NO2 2 NO + Fe2O3 + H2O

(1)

The chloride and nitrite ions compete for ferrous ions. If the chloride ion concentration is greater, the corrosion process will start. If, on the other hand, the nitrite ion concentration is greater, passive layer will form to close off the iron surface. Equation 1 shows that during the reaction between the nitrite and ferrous ions, the supply of nitrite is depleted. The effectiveness of the calcium nitrite admixture, therefore, is dependent on an accurate prediction of the chloride loading of the structure over its expected design life and, hence, on the selection of an appropriate dosage of the admixture. In the hot and chloride-laden environment of the Arabian Gulf region, selection of an appropriate amount of calcium nitrite should be carefully considered for cost-effective use of the admixture. CONCRETE PLACEMENT AND CURING Concrete placement, such as placement with bucket or by pumping, should be carried out in such a manner as to ensure that the concrete remains cohesive. Inadequate consolidation of the in-place concrete contributes significantly to the corrosion-induced deterioration of concrete structures. Poor placement and consolidation is manifested in the form of large voids, extensive honeycombing, rock pockets and bugholes, resulting in concrete of high permeability. The effect of consolidation on corrosion initiation was evaluated by Rasheeduzzafar et al. [7]. The results showed that the time to initiation of corrosion increases with the consolidation effort, which was taken as the length of time for consolidating concrete specimens on a vibrating table. Full or 100% consolidation was reached when the emission of air bubbles ceased and the concrete surface was covered with a thin layer of cement paste. With 40, 60 and 70% of full consolidation effort, the time to initiation of corrosion is, respectively, 60, 76 and 95% of the corrosion initiation time in specimens where full consolidation is achieved. Curing is essential to producing high-quality concrete, and even more so in the hot-arid climatic conditions of the Arabian Gulf region where extremely rapid, excessive evaporation of moisture occurs from concrete surfaces. Water lost by evaporative drying can seriously hamper the cement hydration reactions and the filling of capillary pores by the hydration products. Hydration can take place only when the vapor pressure in the capillaries is sufficiently high (i.e., about 80% of the saturation pressure). Below 30% saturation pressure, there is only negligible hydration [20]. As such, the initiation stage and duration of curing are crucial to producing durable, corrosion-resistant concrete under the climatic conditions in the Gulf region. The beneficial effect of moist curing on the time to initiation of corrosion was demonstrated by Rasheeduzzafar et al. [7]. Figure 4 shows that the time to initiation of corrosion increases with the length of the curing period. Placement and curing of concrete under the high ambient temperature conditions in the Gulf region can cause visible thermal cracking of the newly placed concrete. Also, concrete exposed to such high ambient temperatures at early ages develops cracks within its microstructure, as shown in Fig. 5. This early-age cracking can lead to ingress of chlorides
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either from the salty groundwater or from the salt-laden atmosphere in the coastal zones of the region. In addition, studies have shown that the higher the curing temperature, the higher the porosity of concrete [21-23]. In a study of the microstructure of concrete cured to the same degree of hydration at temperatures of 5, 20 and 50oC [21], the volume of hydration products was found to decrease and the porosity was found to increase with an increase in curing temperature (Table 2). This effect of the curing temperature on the microstructure leads to increased chloride penetration of concrete cured at higher ambient temperatures. For concretes of different compositions, the rate of chloride diffusion increased by a factor of at least 3 when the curing temperature was increased from 23 to 70oC [22]. Hot weather concreting measures as outlined by ACI [24] and CIRIA [11] need to be carefully followed to minimize the detrimental effects of high ambient temperatures. In addition, supplementary cementing materials may be used to mitigate the effects of elevated temperature curing.
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Figure 4. Effect of curing period on time to initiation of corrosion

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Figure 5. Cracking within concrete microstructure Table 2. Effect of Curing Temperature on Concrete Microstructure Curing Temperature (oC) 5 20 50 CONCLUDING REMARKS Based on the discussions in this paper, the following comments are offered as recommendations to reduce the risk of corrosion in reinforced concrete structures: 1. Adequate steps must be taken to minimize both chlorides and sulfates in concrete aggregates, 2. Concrete mix water should be of drinking quality, 3. Concrete permeability characteristics should be considered along with strength requirements when specifying concrete quality to match specific environmental conditions, 4. Low w/c ratio concrete used in conjunction with supplementary cementing materials is effective in enhancing resistance to reinforcement corrosion, 5. Adequate placement and consolidation is necessary to produce concrete with low permeability to the ingress of chloride solutions, 6. Moist curing of sufficient duration is highly beneficial in delaying the onset of corrosion, and 7. Measures necessary for hot weather concreting should be carefully implemented to minimize the detrimental effects of high ambient temperatures on concrete durability. REFERENCES 1. Rasheeduzzafar; F.H. Dakhil and A.S. Al-Gahtani, Deterioration of concrete structures in the environment of the Middle East," ACI Journal 81, 1, 1984, pp. 13-20. 2. H.M. Shalaby, Case studies of corrosion and deterioration of reinforced concrete structures in the State of Kuwait, First International Conference on Deterioration and Repair of Reinforced Concrete in the Arabian Gulf, Bahrain, 1985, pp. 309-320. 3. Z.G. Matta, Chlorides and corrosion in the Arabian Gulf environment, Concrete International 14, 5, 1992, pp. 47-48. 4. A.A. Hamid, Improving structural concrete durability in the Arabian Gulf, Concrete International 17, 7, 1995, pp. 32-35. 5. S. Al-Bahar and E. Attiogbe, Corrosion-induced deterioration of reinforced concrete structures in Kuwait, Proceedings CONSEC 95, International Conference, K. Sakai, N. Banthia and O. E. Gjorv, Eds, Sapporo, Japan, Vol.1, August 1995, pp. 564-573. Hydration Product (% vol.) 84.6 78.4 74.7 Porosity (% vol.) 4.3 10.9 15.1

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6. Rasheeduzzafar, S.S. Al-Saadoun and A.S. Al-Gahtani, Reinforcement corrosionresisting characteristics of silica-fume blended-cement concrete, ACI Materials Journal 89, 4, 1992, pp. 337-344. 7. Rasheeduzzafar, A.S. Al-Gahtani and S.S. Al-Saadoun, Influence of construction practices on concrete durability, ACI Materials Journal 86, 6, 1989, pp. 566-575. 8. Rasheeduzzafar, Influence of cement composition on concrete durability, ACI Materials Journal, 89, 6, 1992, pp. 574-586. 9. S.E. Hussain and Rasheeduzzafar, Corrosion resistance performance of fly ash blended cement concrete, ACI Materials Journal 91, 3, 1994, pp. 264-272. 10. O.S.B. Al-Amoudi, Durability of reinforced concrete in aggressive sabkha environments, ACI Materials Journal 92, 3, 1995, pp. 236-245. 11. CIRIA, Guide to Concrete Construction in the Gulf Region, CIRIA Special Publication 31, 1984. 12. Uniform Building Code, International Conference of Building Officials (ICBO), California, 1991. 13. K. Treadway, Corrosion period, in: Corrosion of Steel in Concrete, RILEM Report of Technical Committee 60 CSC, P. Schiessl Ed., Chapman & Hall, London, 1988. 14. W.G. Hime, The corrosion of steel: random thoughts and wishful thinking, Concrete International 15, 10, 1993, pp. 54-57. 15. O.E. Gjorv and O. Vennesland, Diffusion of chloride ions from seawater into concrete, Cement and Concrete Research 9, 1979, pp. 229-238. 16. O.E. Gjorv, K. Tan and M. Zhang, Diffusivity of chlorides from seawater into highstrength lightweight concrete, ACI Materials Journal 91, 5, 1994, pp. 447-452. 17. O.E. Gjorv, Effect of condensed silica fume on steel corrosion in concrete, ACI Materials Journal 92, 6, 1995, pp. 591-598. 18. J. Geiseler, H. Kollo and E. Lang, Influence of blast furnace cements on durability of concrete structures, ACI Materials Journal 92, 3, 1995, pp. 252-257. 19. J.M. Gaidis and A.M. Rosenberg, The inhibition of chloride-induced corrosion in reinforced concrete by calcium nitrite, Cement, Concrete and Aggregates 9, 1, pp. 3033. 20. T.C. Powers, A discussion of cement hydration in relation to the curing of concrete, Proceedings, Highway Research Board, Vol. 27, 1947, pp. 178-188. 21. K.O. Kjellsen, R.J. Detwiler and O.E. Gjorv, Development of microstructure in plain cement pastes hydrated at different temperatures, Cement and Concrete Research 21, 1991, pp. 179-189. 22. R.J. Detwiler, C.A. Fapohunda and J. Natale, Use of supplementary cementing materials to increase the resistance to chloride ion penetration of concretes cured at elevated temperatures, ACI Materials Journal 91, 1, 1994, pp. 63-66. 23. H.H. Patel, C.H. Bland and A.B. Poole, The microstructure of concrete cured at elevated temperatures, Cement and Concrete Research 25, 1995, pp. 485-490. 24. ACI Committee 305, Hot Weather Concreting, American Concrete Institute, Detroit, 1991.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

THE EFFECT OF THE TYPE OF COPPER ON ITS CORROSION BEHAVIOR IN KUWAITS SOFT TAP WATER H.M. Shalaby1 and F.M. Al-Kharafi2
1

Kuwait Institute for Scientific Research, P.O. Box 24885, 13109-Safat, Kuwait.
2

Kuwait University, Faculty of Science, P.O. Box 5969, 13060-Safat, Kuwait.

ABSTRACT
This paper presents the results obtained from a study of the corrosion behavior of annealed, halfhard and hard-drawn copper pipes in Kuwaits soft tap water at room temperature. Accelerated electrochemical experiments and long-term immersion tests were used to evaluate the performance of the copper pipes under stagnant and flow conditions. The free corrosion potentials reached during the long-term immersion tests were close to each other regardless of the tempering state of the copper. The copper pipes, however, suffered from mild general corrosion which was more apparent in the hard-drawn material. This result was further confirmed using inductively-coupled plasma spectrometry (ICPS). Potential-step polarization experiments indicated that the hard-drawn copper exhibited the highest anodic current densities and the least noble breakdown potential among the investigated tempering states. At low frequency, the impedance of the as-received half-hard copper was lower than that of the annealed and hard-drawn copper. However, the impedance measurements showed deviations from capacitive behavior when pitting occurred on polished copper. The half-hard copper exhibited the largest pits in terms of depth and diameter, followed by the annealed and harddrawn copper. The differences observed were explained in terms of the nature of the oxide film, the tempering state of the copper and its purity. Key Words: Copper pipes, tap water, general corrosion, pitting corrosion, polarization behavior, impedance.

INTRODUCTION Generally, copper plumbing tubes have a service life of several decades. In some waters, however, pitting can occur. Pitting of copper was first recognized in the UK in the late 1940s when annealed and half-hard tubes were reported to be perforated in cold, fresh, hard water within one or two years of service [1]. The pits were hemispherical in shape and contained cuprous chloride and oxide. They were covered with copper carbonate corrosion product. This type of pitting has been termed type 1 in the literature. Susceptibility to this type of pitting has been attributed to the formation of a carbonaceous film during annealing. In the late 1960s, pitting of another type (termed type 2) was identified in Sweden [2] on hard-drawn tubes exposed to hot, soft water with pH values of 5-7. The pits were deep and narrow in shape. They were covered with basic copper sulfate corrosion product. According to case studies performed in Japan [3], the susceptibility to type 2 pitting is highly dependent on water quality, but is seemingly independent of the presence of carbon films.

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A case study of the failure of copper tubes in the soft tap water of Kuwait revealed characteristics which were different from those of types 1 and 2 [4]. The morphological features of the pits were similar to those of type 1, while the water composition and the corrosion products were those of type 2. Moreover, pitting occurred in cold and hot water irrespective of the tempering state of the copper. These discrepancies promoted the present authors to evaluate the corrosion behavior of annealed, half-hard, and hard-drawn copper pipes in Kuwait's soft tap water. EXPERIMENTAL PROCEDURE The study was conducted on seamless copper water pipes made to ASTM B88-83a, type L (annealed and hard-drawn) and to BS 2871 Part 1, type Y (half-hard). The pipes made to ASTM B88-83a measured 28.57 mm in outer diameter and 1.27 mm in wall thickness, while the pipes made to BS 2871 measured 28 mm in outer diameter and 1.2 mm in thickness. Microscopic examinations of the as-received copper pipes revealed attack of grain boundaries in the annealed copper; presence of a thick and porous film on the half-hard copper; and a rough surface with longitudinal grooves on the hard-drawn copper (Fig. 1). The amount of carbon present on the internal surfaces of the as-manufactured pipes was found to be 15.5, 6.75 and 3.15 mg/dm2 for the annealed, half-hard and hard-drawn pipes, respectively. The pipes were tested under stagnant and flow conditions in laboratory tap water at room temperature. Table 1 shows the chemical composition of the water used. Pipe sections, measuring 10 cm each, were used in their as-received condition to study the corrosion behavior of copper in stagnant tap water. The pipes were tested in horizontal position and were connected with PVC pipes to form a U shape. The pipes were welded on the outside to copper wires for measurement of the open-circuit potential and for conducting direct current (DC) potential-step polarization experiments. At the end of the immersion period, the tap water was chemically analyzed for its copper content using inductively-coupled plasma spectrometry (ICPS). A test rig was used to measure the open-circuit potentials of the as-received copper pipes in flowing tap water. The rig was in the form of flow loops made of PVC pipes. The rig was composed of a fiber glass tank (160 l capacity), a circulation pump, and six horizontal copper pipes measuring 30 cm in length each. The pipes were connected in parallel with common water inlet and outlet. The water tank contained a ball valve for maintaining the water level. The time of water flow in the rig was automatically controlled using a timer switch. The timer switch was adjusted to allow water to flow for 0.5 hours followed by a period of 5.5 hours of stagnation. The water flowed to waste after passing through the tubes. The flow velocity in the rig was adjusted to 0.4 and 1.0 m/s using valves connected to the inlet and outlet of the rig. The details of the test rig have been described elsewhere [5] The potential measurements were performed against a saturated calomel electrode (SCE) for a period of about 180 days. In the potential-step polarization tests, the pipes were left in the stagnant water until their potential reached a quasi steady state before the application of potential. This usually took a period of about 2 months. Polarization started from the corrosion potential in the anodic direction in steps of 20 mV. The current was recorded after 10 minutes at each step of polarization. A scanning potentiostat and a strip-chart potentiometric recorder were used, whereas graphite rods served as counter electrodes.

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(a)

(b)

(c) Figure 1. SEM micrographs showing the surface appearance the as-received copper before testing: (a) annealed copper; (b) half-hard copper; and (c) hard-drawn copper

DC potentiostatic polarization and alternating current (AC) electrochemical impedance measurements were also made on copper specimens in the form of discs, measuring 2.4 cm in diameter. These tests were carried out on as-received and polished copper in 1-l glass cells containing stagnant water. Polishing was achieved with diamond paste of grades 15 and 6 m. The specimens were mounted in holders made of Teflon so that only one side (1.5 cm2 in area) was exposed to the water. Again, a SCE served as the reference, whereas platinum sheet was used as the counter electrode. The potentiostatic polarization tests were made at a single potential value of 200 mV for 4 and 6 days. The impedance measurements were taken after separate potential measurements and DC potentiostatic polarization experiments. In both cases, the potential of the specimens was left to reach a quasi steady state before the measurements were taken at an amplitude of 10 mV. Table 1. Chemical Composition of Kuwait's Soft Tap Water pH Conductivity (Scm-1) M alkalinity (CaCO3, mgl-1) HCO3- (mgl-1) Total hardness (MgCO3, mgl-1) Ca hardness (CaCO3, mgl-1) Mg hardness (MgCO3, mgl-1) Cl- (mgl-1) 7.6 540.0 30.0 37.0 135.3 86.3 49.0 80.2
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SO42- (mgl-1) SiO2 (mgl-1) HCO3-/SO42-

118.0 2.1 0.31

After the termination of the tests, the specimens were left to dry in a desiccator. Optical and scanning electron microscopy (SEM) were used to examine the surface. The depth and diameter of the pits were measured using a micrometer attached to the optical microscope. RESULTS AND DISCUSSION Potential and Polarization Behaviors Figure 2 shows the potential-time behavior of as-received copper pipes of different tempering states during testing in stagnant tap water. It can be seen from the figure that the potential was initially negative, but rapidly shifted to the positive direction within the first few days of testing. It is apparent from the figure that the potentials became more or less steady (with occasional fluctuations) after about 100 days of testing. The potentials reached were close to each other regardless of the tempering state, being on the order of 5-15 mV. The copper concentrations in the stagnant water were 0.7, 0.8 and 1.5 mg/l for the as-received annealed, half-hard and hard-drawn copper, respectively. It is worth noting that the concentration of copper in the water was higher for the hard-drawn material. The same potential-time behavior as above was obtained during testing under a flow/stagnation sequence at 0.4 and 1.0 m/s. Again, the tempering state of the metal did not significantly affect the potential values at the steady state. However, the increase in flow velocity appeared to slightly shift the steady state potentials to more positive values. Optical microscopic examinations of the copper pipes used in the above measurements revealed that the flow/stagnation sequence caused more precipitation of corrosion products than full stagnation. The copper pipes tested in stagnant water experienced very little corrosion, mostly in the form of bluish-green stains. On the other hand, a significant amount of bluish-green corrosion products were observed on the internal surfaces of the copper pipes tested under flow/stagnation sequence of tap water. The precipitated corrosion products were more pronounced on the lower halves of the pipes. They covered a large area of the surface and were not in the form of mounds as is usually observed during pitting of copper. The amount of precipitated corrosion products was observed to be more in the hard-drawn pipes than in the half-hard and annealed ones.

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Figure 2. Potential-vs-time curves for as-received copper pipes tested in stagnant tap water Figure 3 shows potential-vs-current curves obtained during potential-step polarization tests carried out on as-received copper pipes in stagnant tap water. The hard-drawn copper exhibited the highest anodic current densities and the least noble breakdown potential among the investigated tempering states. The hard-drawn copper was followed by the annealed and half-hard copper in terms of the noble shift in the breakdown potential. Optical examinations showed the presence of scattered and agglomerated small cubic crystals on the surfaces of the annealed and hard-drawn materials. The oxide layer that was observed on the as-received half-hard material before the start of the test became less porous and more diffuse after the test, suggesting that the generated current was consumed in repairing the highly defective oxide layer. No pitting corrosion was found in the as-received materials. The present results suggest that hard-drawn copper is somewhat more prone to corrosion than half-hard or annealed copper in Kuwait's tap water. Since general corrosion was only observed during the testing period, the attained results do not necessarily imply that harddrawn tubes are more susceptible to pitting than the other tubes in the soft tap water of Kuwait. In the case of copper pipes tested in hard waters, Devroey and Depommier presented evidence to show that hard-drawn tubes were more resistant to pitting than half-hard tubes, which were in turn more resistant than annealed tubes (unpublished data). Cornwell et al. [6] attributed these differences to carbon deposits on the surface of the annealed tubes which were formed during bright annealing operations. The superior performance of the hard-drawn tubes, on the other hand, was attributed to a protective effect exerted by the drawing lubricant in the pores of the hard-drawn tubes. In the case of soft water, such as in Kuwait, Sato et al. [3] indicated that the susceptibility to pitting is highly independent of the presence of carbon film. In such cases, it is possible that the stored energy within the metal due to the manufacturing process of the hard-drawn tubes, becomes an activating factor for corrosion.

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Figure 3. Potential-step anodic polarization curves for as-received copper pipes tested in stagnant tap water Lucey [7] and Rossum [8] stated that failures of copper pipes usually occur at the bottom of horizontal copper pipes because only rarely should debris cling to vertical or steep surfaces. The presence of a large amount of corrosion products on the bottom surfaces of the copper pipes may pose a danger by creating differential aeration or concentration cells at longer exposure duration, leading to the pitting type of corrosion attack. An interesting finding in this work is that a relatively well defined breakdown potential is exhibited in the potential-step polarization diagrams of as-received copper (Fig. 3). This breakdown potential is usually termed critical pitting potential to signify the onset of pitting. Critical pitting potentials have been reported for copper in different waters [6,9,10]. In our study, the as-received copper suffered from general corrosion. Thus, the breakdown potential of copper cannot always be considered to be a critical pitting potential as in the case of a stainless steel immersed in a chloride-containing environment. Impedance Response The impedance response of as-received annealed, half-hard, and hard-drawn copper is given in Fig. 4. At low frequencies, the impedance of the annealed material is higher than that of the hard-drawn, and in order, of the half-hard copper. This result clearly expresses the nature of the oxide films formed on these materials. The low impedance of the half-hard copper is, therefore, possibly due to the presence of a thick, porous crystalline scale.

Figure 4. Bode-plots for as-received copper of different tempering states in stagnant tap water.

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An attempt was made to study the kinetic behavior of the pitting of copper using impedance spectroscopy. Figure 5 shows the impedance spectra in Bode format obtained for polished annealed copper after free corrosion and potentiostatic polarization in stagnant tap water at 200 mV for 4 and 6 days. The overall behavior of the impedance-vs-frequency curves was similar in all cases with the exception of a slight change for the specimen tested under free corrosion condition in the frequency range of 1 < f < 1000 Hz. On the other hand, a significant change is noted in the phase angle-vs-frequency curves. Potentistatic polarization appeared to cause a decrease in the phase angle peak which is associated with a shift towards higher frequencies. Furthermore, the low frequency part of the spectra changed in a manner which suggested that pitting had occurred. A comparison of Figs. 4 and 5 indicates that when the air-formed oxide film was removed by polishing, the impedance of the material decreased significantly. The AC impedance technique has been found to be successful in investigating the kinetics of general corrosion [11]. Recently, however, some investigators [12,13] have shown that the technique can be used to detect the initiation and growth of pitting. The present results also indicate that the impedance technique can be a useful tool for the study of pitting of copper in tap water. The results showed that a dominant capacitive behavior existed in the case of polished copper immersed in tap water under free corrosion conditions. This suggests that the surface of copper is to some extent blocked by the surface film under these conditions. On the other hand, deviations from the capacitive behavior are noted in the case of polarized copper specimens (Fig. 5). These deviations can signify the presence of pitting. They are possibly caused by a diffusion process through the porous oxide scale which was elevated from the metal surface.

Figure 5. Bode-plots for polished annealed copper tested in stagnant tap water after different testing conditions.
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Pit Depth and Diameter SEM examination of polished copper specimens which underwent potentiostatic polarization in tap water at 200 mV for 4 days showed a reddish-brown scale covering the surface regardless of the tempering condition of the tested specimens. The scale was totally disbonded from the metal surface by an average distance of about 8.5 m. When the corrosion products were removed with a soft tissue, numerous pits were found in the metal underneath the scale. Figure 6 shows the percentage of pits against the pit depth or diameter for the different copper after potentiostatic polarization in tap water at 200 mV for 4 days. It can be clearly seen from Fig. 6 that the half-hard copper exhibited the largest depth and diameter of pits when compared with the annealed and hard-drawn copper. The majority of the pits in the hard-drawn copper had about the same depth as in the annealed. On the other hand, the pit diameter was clearly smaller in the hard-drawn copper than in the annealed, as can be seen in Fig. 6b. In fact, the average pit depths were 0.022, 0.059 and 0.021 mm, while the corresponding average pit diameters was 0.092, 0.126 and 0.05 mm for the annealed, halfhard and hard-drawn copper, respectively. The number of pits after 4 days of polarization was almost the same (7-10 pits/cm2) for all tempering states. This number remained almost unchanged when the potentiostatic polarization time was increased from 4 to 6 days. The average pit depth for the annealed and half-hard copper after 6 days of polarization was 0.035 and 0.065 mm, respectively. These results indicate an increase in average depth for the annealed copper of about 60% and for the half-hard copper of 10%. However, increasing the polarization time increased the maximum pit depth of about 20% of the pits in the annealed copper to 0.05 mm (a 25% increase in the maximum depth) and of 17% of the pits in the half-hard to 0.17 mm (a 90% increase in the maximum depth).

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Figure 6. Percentages of pits of: (a) different depths, and (b) diameters, grown on polished annealed, half-hard and hard-drawn copper during potentiostatic polarization in tap water at 200 mV for 4 days. The fact that the hard-drawn material exhibited smaller diameter pits is readily explainable in terms of the large deformation of the grains. On the other hand, it is rather difficult to explain the behavior of the half-hard copper. The differences in behavior could possibly be due to differences in the alloying elements and not the carbon content. The purity of the phosphorus de-oxidized annealed and hard-drawn copper (high residual phosphorus) was 99.9%, whereas the purity of the half-hard copper was 99.85. Pipes made of the former only contain phosphorus and silver as residual elements, whereas pipes made of the latter contain phosphorus, arsenic, antimony, bismuth, iron, lead, etc. The present work also showed that the number of pits did not increase with increases in the polarization time, suggesting that the number of pitting sites is more or less the same regardless of the differences in manufacturing procedure and carbon content. These results lend support to the observation made by Sato et al. [3] that pitting corrosion of copper in soft tap water appears to be independent of the presence of a carbon film on the metal surface. In a previous work [9], the present authors showed that pitting corrosion of copper starts at the grain boundaries. Since there are no data available in the scientific literature with regard to the diameter or depth of pits developed in copper in tap water, the authors assumed that the cross-section of a pit grown along the grain boundaries of hard-drawn copper would appear deep and narrow. Thus, the authors postulated that the shape of the pits depends on the deformation of the grains. The present results provided the needed experimental proof that the shape of the pits depends on the tempering state of the copper and not on the type of water as was assumed previously [14]. For copper, which is rarely passivated, the mechanisms for pitting and general corrosion seem to be different than those of passivable metals, such as stainless steels. In the presence of the oxide film formed during manufacturing, as-received copper was found to experience corrosion of a general nature while under anodic polarization. Thus, the protective oxide film on copper functions not by making the corrosion rate minimal as in the case of passivable metals, but by scattering the dissolution process to become through large amount of pores. In the case of the polished material, a reddish-brown scale was formed. This scale separated from the metal surface, creating the occluded cell required for pitting initiation. Thus, the disbondment of the oxide film creates the requirements necessary for pitting corrosion to occur. CONCLUSIONS 1. During long-term immersion tests, the free corrosion potentials of the as-received annealed, half-hard and hard-drawn copper were close to each other regardless of the tempering state of copper. The copper pipes, however, suffered from mild general corrosion which was more apparent in the hard-drawn material. This result was further confirmed using ICPS. 2. At low frequencies, the impedance of the as-received half-hard copper was lower than that of the annealed and hard-drawn copper. When pitting occurred on polished
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copper, the impedance measurements showed deviations from the capacitive behavior. These deviations were attributed to a mass transport phenomenon through the porous oxide scale. The AC impedance technique was found to be useful in studying the pitting of copper. 3. The half-hard copper exhibited the largest depth and diameter of pits followed by the annealed and hard-drawn copper. The number of pits was about the same (7-10 pits/cm2) for all types of copper and remained unchanged with increases in polarization time. The difference in the size of pits was ascribed to the degree of purity of the copper. ACKNOWLEDGMENT The authors of this paper would like to acknowledge the Kuwait Foundation for the Advancement of Science for its financial support of this work through contract project No. 87-08-06. REFERENCES 1. H.S. Campbell, Journal Institute of Metals 77, 1950, p. 345. 2. E. Mattsson and A.M. Fredriksson, British Corrosion Journal 3, 1968, p. 246. 3. S. Sato, T. Minamoto, K. Seki, H. Yamamoto, Y. Takizawa, S. Okada, S. Yamauchi, Y. Hisamatsu, I. Suzuki, T. Fujii, T. Kodama, H. Baba and K. Nawara, Proceedings International Symposium on Corrosion of Copper and Copper Alloys in Building, Tokyo, Japan, 1982, p. 17. 4. F. Al-Kharafi, H.M. Shalaby and V.K. Gouda; Proceedings 10th International Congress on Metallic Corrosion, Madras, India, November 1987, p. 767. 5. F.M. Al-Kharafi and H.M. Shalaby, Corrosion 51, 1995, p. 469. 6. F.G. Cornwell, G. Wildsmith and P.T. Gilbert, British Corrosion Journal 8, 1973, p. 202. 7. V.F. Lucey, British Corrosion Journal 2, 1967, p. 175. 8. J.R. Rossum, Journal American Water Association 77, 1985, p. 70. 9. H.M. Shalaby, F.M. Al-Kharafi and V.K. Gouda, Corrosion 45, 1989, p. 536. 10. M. Pourbaix, Corrosion 25, 1969, p. 267. 11. D.C. Silverman and J.E. Carrico, Corrosion 44, 1988, p. 280. 12. M. Keddam and R. Oltra, Materials Science Forum 8, 1986, p. 167. 13. F. Mansfeld and H. Shih, Journal Electrochemical Society 135, 1988, p. 1,171. 14. E. Mattsson, Corrosion Australasia 6, 1981, p. 4.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CORROSION BEHAVIOR OF VANADIUM IN AQUEOUS SOLUTIONS W.A. Badawy, F.M. AI-Kharafi and M.H. Fath-Allah Department of Chemistry, Faculty of Science Kuwait University, P.O. Box 5969 Safat, 13060 Kuwait

ABSTRACT
Vanadium is an important transition metal used in various industrial applications; especially as a structural material in metallurgical applications. The electrochemical behavior of vanadium is an important subject due to its application in redox flow batteries. The behavior of the metal in aqueous solutions of different pH in oxygen-saturated and oxygen-free electrolytes was investigated. The behavior of vanadium electrodes in alkaline solutions (pH > 8) differed from its behavior in acidic or neutral solutions (pH 1-8). Open-circuit potential measurements revealed that the steady-state potential was a linear function of the solutions pH. The slope of the linear relation changed from 0.039 V/decade for solutions of pH < 8 to -0.058 V/decade for solutions of pH > 8. Electrechemical impedance spectroscopy, which represent an effective method for studying corrosion phenomena, has shown that the metal undergoes active dissolution in aqueous media. In solutions of pH > 8, the corrosion behavior of the metal can be simulated to a Randles equivalent circuit model. In oxygen-saturated solutions, the electrodes surface is covered with a thin oxide film. The interaction of this film with the ambient electrolyte depends on the solutions pH. Polarization measurements have shown that the rate of corrosion in acidic solutions is not affected by the prevailing gas. In alkaline solutions, the removal of air or oxygen from the ambient electrolyte leads to a decrease in the corrosion rate. Key Words: Corrosion, electrochemistry, impedance, passivity, polarization, vanadium

INTRODUCTION Vanadium is an important transition metal due to its use and the use of its alloys as structural materials not only in metallurgical applications but also in nuclear reactors [l]. The metal ions are used extensively in redox flow batteries [2-5]. Unlike many transition metals, vanadium shows active behavior [6-10]. The electrode potential of vanadium and the effect of oxygen on this potential were the subjects of the very early studies concerning this metal [11,12]. The active behavior of vanadium and its anodic dissolution in aqueous solutions was investigated [13,14]. It was found that the rate of metal dissolution is independent of the hydrogen ion concentration or the nature of the anions present. The rate determining step was + a monovalent adsorbed intermediate (V ads) [14]. Investigations of the anodic behavior in acidic solutions containing different anions and cations have shown that the metal undergoes 2+ active dissolution in all acidic solutions except those containing Ba at a pH > 4, and that the active dissolution of the metal occurs through a monovalent intermediate [15]. The behavior of the metal in both acidic and basic media was found to obey the Tafel approximation of the Butler-Volmer equation over a wide range of potentials [16]. Extensive studies have been
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carried out in glacial acetic acid and have shown oxide film formation in the presence of sodium borate and water [17,18,19]. The present investigation was aimed at throwing more light on the electrochemical behavior of vanadium in aqueous solutions and on the effect of solution pH and oxygen on the corrosion and passivation processes occurring at the electrode/electrolyte interface. EXPERIMENTAL PROCEDURE Massive, cylindrical, spectroscopically pure, vanadium rods (Alderich-Chemie) were used as working electrodes; they were mounted in glass tubes of appropriate internal diameter 2 with an epoxy resin leaving a front surface area of 0.302 cm to contact the electrolyte. An all glass three electrode cell with a large surface area, Pt, counter electrode and a Ag/AgCl/Cl (3 M KCl) reference electrode was used. The solutions were prepared from analytical grade reagents and triple distilled water. The buffer solutions covering a pH range of 1-13 were prepared according to Clark and Lub's series [20]. The pH of each solution was controlled before each experiment, and the electrodes were mechanically polished with successive grades of emery papers down to 1200 grit, then wiped with a smooth cloth and washed with triple distilled water. In this way, the electrodes acquired reproducible, bright silvery surfaces. After polishing and rinsing, the electrodes were immersed directly in the test solutions. Electrochemical impedance spectroscopy (EIS) investigations were carried out using the IM5d-AMOS system (Zahner Elektrik GmbH & Co., Kronach, Germany). The 5 input signal was usually 10 mV peak to peak in the frequency domain of 0.1-10 Hz. Frequencies down to 0.1 MHz were also investigated. Polarization measurements were performed using an EG&G (Princeton Applied Research) model 273A Potentiostat/Galvanostat interfaced to an IBM PS3 computer. The potentiostatic measurements were traced using programs that enable ohmic drop compensation. The steady-state potential, ESS, measurements were controlled separately using a high impedance value voltmeter (Keithley type 197A Autoranging Multiplier, England). All measurements were carried out at constant room temperature of 22oC. The potentials were measured against the Ag/AgCl/Cl- reference, and then refered to the normal hydrogen electrode (nhe). The gases used for deaeration or solution saturation were purified and dried before being bubbled in the electrolytic cell. The gas was bubbled for at least 20 min. in the test solution prior to each experiment. The details of the experimental procedures were as described elsewhere [10,21]. RESULTS AND DISCUSSION Steady-State Potential Measurements The potential of the vanadium electrode was traced over a period of 180 min. in naturally aerated aqueous solutions covering a pH range from 1 to 13. In all solutions, the electrode potential became more positive with time. A typical example of the variation of the electrode potential with immersion time in the buffer solutions is presented in Fig. 1A. In this figure, the results in solutions of pHs 2, 7 and 12 are presented. The steady-state potential, Ess , measured after 180 min. of electrode immersion in each solution is plotted against the pH of the solution, and is presented in Fig. 1B. The results reveal that ESS is pH-dependent over the

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whole pH range. The Ess versus pH relation is linear and can be presented by an empirical equation of the form: Ess = a - b pH (1)

where a is a constant representing the value of ESS extrapolated from the linear relation at pH = 0. As can be seen from Fig. 1B, the ESS versus pH relation has an inflection between pH = 8 and pH = 9 which means that the slope, b, changes. In the basic medium, i.e., pH > 8, the slope of the linear relation is very close to the value of 0.059 V/pH, which was calculated from the Nernst equation for a pH indicator electrode with one electron electrode process at o 25 C according to: E = E - 0.059 pH n
o o

(2)

E is the standard pH-independent electrode potential and n is the number of electrons involved in the electrochemical process. Therefore, the value of n for basic solutions (pH > 8) is equal to 1. In acidic and neutral solutions (pH < 8), on the other hand, the slope of the Ess versus pH relation is < 0.059 V/pH. A value of 0.039 V/pH was calculated. This can be + explained by the interaction of both H and OH ions with the electrodes surface which is essentially covered with a passive film or an adsorbed O2 film as will be discussed later. In regions where the OH ions are inaccessible to the electrode surface, solvation of the electrode occurs, and deviation from the n = 1 process is observed [22]. The vanadium electrode can be considered to be a pH indicator electrode taking into account the inflection in the ESS versus pH relation and the values of a and b in each pH in the range 1-8 Ess = 0.180 - 0.039 pH and in solutions of pHs > 8 Ess = 0.380 - 0.058 pH (4) (3)

The steady-state potential values obtained according to Eqs. 3 and 4 are quite different 2+ from the standard electrode potentials assigned for the systems V/V (Eo = -1.19 V) and 2+ 3+ o V /V (E = - 0.26 V) [22]. This supports the notion that the electrode process cannot be represented by a simple equilibrium relationship such as that given for the simple redox 2+ 2+ 3+ equilibria of the metal and its ions, e.g., the V/V or V /V Systems. This can be understood on the basis that the solution does not contain significant concentrations of those ionic species, and that the electrodes surface is covered by a thin oxide film in aqueous solutions. Consistent with this is the dependence of the steady-state potential on the prevailing gas and the stirring conditions of the solution.

Effect of Oxygen on the Steady-State Potential


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The electrodes potential was traced in naturally aerated, oxygen-saturated and oxygenfree solutions of different pHs. Oxygen was removed from the solution by bubbling N2 or H2 at least 20 min. before electrode immersion. A typical example of the results in solutions of pH = 12 is presented in Fig. 2. The results reveal that the electrodes potential is sensitive to the oxygen concentration in the solution. Under all conditions, the potential became more positive with immersion time until it reached a steady-state value. The use of either N2 or H2 to remove oxygen from the solution did not produce any remarkable difference; the steadystate potential lay, in both cases, in approximately the same range ( -385 mV (nhe) in pH = 12). In oxygen-saturated solutions, the Ess shifted in the positive direction by 100 mV. This shift can be attributed to the presence of a thin oxide film on the electrodes surface. The same trend was observed over the whole pH range from 1 to 13.

Figure 1. (A) Variation of the electrode potential Figure 2. with time of the vanadium electrodes in naturally aerated solutions of different pHs (o) pH = 2 () pH = 7 () pH = 12 (B) Steady-state potential (Ess) vs. pH for the vanadium electrode in naturally aerated buffer solutions

Effect of the prevailing gas on the electrode potential of vanadium in solutions of pH 12 (o) naturally aerated () O2-saturated () N2-saturated () H2-saturated

The sensitivity of metals with active/passive transitions towards oxygen is well known, especially for those which do not show active dissolution like niobium, tantalum and titanium [10,21,24]. The passivation of vanadium in aqueous solutions was discussed very early by
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Muthman and Frauenberger [11]. Later, it was suggested that the passivity is due to the presence of a gaseous film [12]. Unlike many transition metals, vanadium has an active corrosion behavior with a limited tendency for passivation. The passivation behavior of the metal was explained earlier by the presence of a chemisorbed oxygen film [25]. Dry or moist o oxygen did not tarnish the polished metals surface, and even hot water (60-85 C) had no effect on the surfaces brightness. The decrease of the steady-state potential on oxygen removal by bubbling of N2 or H2 in the test solution can be considered as an indication of the presence of a thin oxide film on the electrodes surface. The oxide film formed represents a non-stoichiometric oxidation state of the metal which is responsible for the observed behavior of the metal in each solution. Removal of oxygen by bubbling of N2 or H2 in the solution leads to dissolution of the formed oxide, and hence, a decrease of its thickness leading to a shift of the steady-state potential in the negative direction (Fig. 2), and the following equilibrium state is shifted to the left: 2V + xO2 2VOx The value of x determines the stoichiometric factor n of Eq. 2. In acidic solutions, where an excess of hydrogen ions are present, the interaction between the non-stoichiometric oxide film and the hydrogen ion takes place and the electrodes potential is determined by the hydrogen ion concentration according to: V-Ox + 2x H + 2xe V + x H2O
+ -

(5)

(6)

The value of x in this case, and hence, the value of n of Eq. 2, can be calculated from the slope of the first segment of the steady-state potential/pH relation (Fig. 1B), i.e., in the pH range of 1-8. slope = -0.039 V = - 0.059 n where n = 2x i.e., n = 1.5

In basic solutions, the interaction between the electrodes surface and the solution occurs through OH ions according to: V- Ox + 2OH VO1+X + H2O + 2 e
-

(7)

The lower oxides of vanadium are basic and very unstable [25]; therefore, they cannot protect the metal from corrosion as in the case of the valve metals with active/passive transitions.

Open-Circuit Impedance Measurements EIS is a powerful tool for investigating electrochemical and corrosion systems, since it is essentially a steady-state technique that is capable of accessing relaxation phenomena with
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relaxation times that vary over several orders of magnitude and permits single averaging, within a single experiment to obtain highly precise levels. The open-circuit impedance of vanadium electrodes was traced for 180 min. after electrode immersion in the test solutions. Typical data for pHs of 2, 7 and 12 are presented as Bode plots in Fig. 3.

(A) in solution of pH 2

(B) in solution of pH 7

(C) in solution of pH 12 Figure 3. Bode plots of the vanadium electrodes in naturally aerated solutions at different time intervals from electrode immersion () 15 min. () 60 min. (----) 130 min. Bode plots are recommended as standard impedance plots since the phase angle, , is a sensitive parameter for indicating the presence of additional time constants in the impedance spectra [10,26-28]. It employs frequency as an independent variable, so that a more precise comparison between experimental and calculated impedance spectra can be made [29-31]. The use of the log versus log format enables equal representation of all experimental data over the whole frequency domain.
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The EIS spectra in Fig. 3 contain only one capacitive contribution represented by the linear variation of the electrodes impedance, Z, with the frequency, f, [26-28]. In acidic and neutral solutions (pH = 1-8), there is a part of the spectrum where the phase angle is independent of frequency (Fig. 3a and b at f < 1 Hz). Such behavior is explained by the assumption of frequency dispersion and surface inhomogeneity [29]. For such systems, the electrode impedance is given by: Rp Z = I + (sCRP)

(8)

where RP is the polarization resistance which is considered to be a pure charge transfer resistance, C is the electrode capacitance and is a fit parameter ( 0 < < 1 ) that is correlated to the angle of rotation of the center of the capacitive semicircle, , below the real axis: = (1- ) /2 s = j where j = (9)

1 and = 2 f.

The value of the fit exponent corresponds to the extent of dispersion and is attributed to surface inhomogeneity [29,30]. A nonlinear concentration of metal ions will occur, since preferential charge transfer takes place at active sites. The impedance spectra of Fig. 3 show that there is an active dissolution of the metal, as can be identified by the decrease of the polarization resistance with immersion time in each solution. The rate of dissolution is limited and is dependent of the solutions pH. The impedance spectra of the electrodes in solutions of pHs of 2, 7 and 12 after 180 rnin. of electrode immersion are collectively presented in Fig. 4. The results show clearly that the behavior of vanadium in basic solutions is different from its behavior in acidic or neutral solutions. In solutions of pH 12, a phase maximum at a frequency of 1 Hz was observed. To be sure that there was no second time constant at lower frequencies, impedance measurements down to frequencies of 1 MHz were taken. A typical example of these measurements for solutions of pH 12 is presented in Fig. 5. The behavior of the electrode in basic solutions is very similar to an ideally corroding system with a single time constant corresponding to the corrosion reaction rate determining step. This behavior can be simulated by a simple equivalent circuit model of the Randles type which consists of a parallel combination of a resistor, RP , representing the polarization or charge transfer resistance and a capacitor, C , representing the capacitance of the electrode/electrolyte interface. This parallel combination is in series to a small resistor, Rs , equivalent to the electrolyte resistance. The data in Fig. 5 were subjected to a procedure of data fitting [31] to fit the experimental data in this figure to the electronic model described. Good agreement was obtained between the experimental and theoretical data for values of RP = 10.22 k, C = -2 170.4 F cm , and Rs = 42 . The fitting procedure for the results of solutions of pH of 12

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Fundamental Aspects

had around 2% mean error in the absolute impedance and 1.2 mean error in the phase angle. Deviations of the phase angle from ideal behavior were found to be related to the polishing of the electrodes surface. The impedance data presented show that the vanadium electrode, although it showed active dissolution, it had a great tendency towards oxygen and the surface was covered with a thin film of non-stoichiometric oxide or a mixture of oxides of varying valences. The instability of such oxides explain the corrodibility of vanadiums surface. The increased rate of corrosion with increases in the pH of the solution was varied by measuring the corrosion currents and polarization resistance in each solution. The values of these parameters in pHs 2, 7 and 12, are presented in Table 1.

Figure 4. Bode plots of vanadium electrode after Figure 5. 130 min. immersion in naturally aerated solutions of pH 2 (), pH 7 (----) and pH 12 ()

Bode plot of the vanadium electrode in naturally aerated solution of pH = 12 in the -3 5 frequency range 10 to 10 Hz

Table 1. Values of the Polarization Resistance, RP , Corrosion Current, icorr, and Corrosion Potential Ecorr, of the Vanadium Electrode in Naturally Areated Solutions of Different pHs pH 2 7 12 RP 2 (kcm ) 5.012 2.880 1.652 icorr -2 (Acm ) 0.407 1.239 3.930 Ecorr (mV) -215 -407 -597

The effect of the prevailing gas on the impedance behavior of the vanadium electrode was also investigated. An example of these measurements in solutions of pH 12 is presented in Fig. 6. After 3 hrs of electrode immersion, the impedance behavior in H2 or N2 saturated solutions is quite similar. In air or oxygen-saturated solutions, the measured polarization resistance is lower. Polarization measurements have shown that the corrosion current
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decreases in the presence of an inert gas in basic solutions. In acidic solutions, on the other hand, the corrosion rate is not much affected by the inert gases. These results are summarized in Table 2. The results of polarization experiments are in good agreement with the + explanation based on Eqs. 6 and 7. In acidic solutions, the interaction of the excess H ions with the surface film leads to the removal of this film without any appreciable change in the rate of corrosion of the metal by changing the gas. In basic solutions, the formation of the non-stoichiometric, unstable, basic oxides is responsible for the increased rate of corrosion of the metal. The formation of the oxide film and its stoichiometry is dependent of the presence of air or O2 in the solution. Removal of air or oxygen from a basic solution shifts the equilibrium of Eq. 5 to the left, and hence, decreases the rate of corrosion as can be seen from the values of the corrosion currents presented in Table 2. The presence of the surface film is confirmed by capacitance measurements. In all solutions, the electrode capacitance showed an approximately constant value within a wide potential range (-100 - +100 mV from the -2 steady-state potential). In acidic solutions, an average capacitance value of 25 Fcm was measured. This value is higher than the reported value of the Helmholtz capacitance (17 -2 Fcm ) [32]. The higher capacitance value can be attributed to the presence of adsorbed electroactive species on the surface film. The concentration of these electroactive species at the electrodes surface is constant in the potential range where the electrode capacitance is potential-independent.

Figure 6. Effect of the prevailing gas on the impedance characteristics of the vanadium electrode in solutions of pH 12 (- -) oxygen, () nitrogen, (----) naturally aerated, (....) hydrogen Table 2. Corrosion Currents of Vanadium in Solutions of pHs 2, 7 and 12 Saturated with Different Gases Gas icorr (A-cm )
-2

Rp (kcm )
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Fundamental Aspects

Air Oxygen Nitrogen Hydrogen

pH 2 0.407 1.057 1.578 1.046

pH 7 1.239 2.939 1.967 1.082

pH 12 3.930 17.50 1.710 0.928

pH 12 1.652 1.596 2.352 2.072

Effect of Temperature on the Corrosion Behavior of Vanadium To study the effect of temperature on the corrosion behavior of vanadium, an all glass, double walled cell was used with the same arrangement of counter, reference and working electrodes. The measurements were made in naturally aerated solutions of pHs 2, 7 and 12. In all solutions, the general trend was an increase in the rate of corrosion with increasing temperature. Polarization measurements were taken at each temperature, and the corresponding corrosion current, iCorr , which represents the rate of corrosion, was obtained. A plot of log icorr versus 1/T obeys the familiar Arrhenius equation [33]. d logicorr = Ea 2 dT RT where Ea is the activation energy which is given by Ea = NA a (11) (10)

a is the energy relative to the ground state energy which an atom or molecule must have in order to react, i.e., the activation energy per molecule, whereas Ea is the molar activation energy. Figure 7 presents the Arrhenius plots obtained in solutions of pH 2, 7 and 12. In the solutions investigated, almost parallel Arrhenius plots were obtained, which means that the activation energy of the corrosion process lies in the same range without regard to the solutions pH. Calculation of the activation energy of the corrosion process in each solution gave the values presented in Table 3. The values given in Table 3 show that the activation -1 energy of the corrosion process is less than 40 kJmol , which supports the view that the dissolution of the metal is a one-electron charge transfer process [34]. This supports the mechanism suggested by Armstrong and Henderson [14], and the corrosion reaction may be presented by V(s)

V(I) + e
2+

+ -

(12)

H2O + V(I)ads. fast VO +2H +3e (13) This reaction is enhanced in basic media, and hence, the rate of corrosion increases. In accordance with this, the calculated activation energy in solutions of pH 12 is slightly lower.

Table 3. Activation Energy of the


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Corrosion of Vanadium in Naturally Aerated Solutions of pHs 2, 7, and 12 pH 2 7 12 Ea, (kJ mol ) 34.8 36.4 30.6
-1

Figure 7. Log icorr vs 1/T relations for the corrosion behavior of vanadium in naturally aerated solutions of pH 2 (o), pH 7 () and pH 12 () CONCLUSIONS The steady-state potential of vanadium is sensitive to the solutions pH and can be used for pH calculations. The rate of corrosion of the metal in basic media decreases with the removal of air or oxygen. In acidic or neutral solutions, the prevailing gas has no significant effect on the rate of the corrosion process. Activation energy calculations support a oneelectron transfer step as the rate-determining corrosion process. ACKNOWLEDGMENT This work has been supported by Kuwait University, Research Grant No. SCO59. The financial support of the research administration is gratefully acknowledged. REFERENCES 1. W.J. Tomlinson, R. Rushton, R. Cindery and S. Palmer; J. Less Common Met. 132, 1987, p. 1. 2. E. Sum and M. Skyllas-Kazacos, J. Power Sources 15, 1985, p. 179. 3. E. Sum, M. Rychcik and M. Skyllas-Kazacos, J. Power Sources 16, 1985, p. 35. 4. M. Rychcik and M. Skyllas-Kazacos, J. Power Sources 19, 45, 1987, p. 45. 5. M. Kazacas and M. Skyllas-Kazacos, J. Electrochem. Soc. 136, 1989, p. 2759 6. T. Hurlen and W. Wilhelmsen, Electrochim. Acta 31, 1986, p. 1139. 7. W.Wilhelmsen and T. Hurlen, Electrochim. Acta 32, 1987, p. 85. 8. S. Hornkjol, Electrochim. Acta 33, 1988, p. 337. 9. W.A. Badawy, J. Appl. Electrochem. 20, 139, 1990, p. 139. 10. W.A. Badawy and K.M. Ismail; Electrochim. Acta 38, 1993, p. 2231. 11. W. Muthman and F. Fraunberger, Sitzbl. Bayr. Akad. Wiss., 1904, p. 201. 12. G.C. Schmidt, Z. Phys. Chem. 106, 1923, p. 105.
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13. R. Kammel, T.Kishi, T.Takei and H. Winterhager, Metalloberflaesche 24, 1970, p. 335. 14. R.D. Armstrong and M. Henderson, J. Electroanal. Chem. 26, 1980, 381. 15. S. Homkjol and I.M. Homkjol, Electrochim. Acta 36, 1991, p. 571. 16. A. Deschanvers and G. Nouet, Bull. Soc. Chim. Fr. 718, 1975, p. 1589. 17. A.G. Keil and R.E. Salomon, J. Electrochem. Soc. 112, 643, 1965, p. 643 and 115, 1968, p. 628. 18. A.G. Keil and R.E. Salomon, J. Electrochem. Soc. 115, 1968, p. 628. 19. R.G. Keil and K. Ludwig, J. Electrochem. Soc. 118, 864, 1971, p. 864. 20. G.D. Fasman, Practical Handbook of Biochemistry and Molecular Biology, CRC Press Inc., Boca Raton, Florida, 1989. 21. F.M. AI-Kharafi and W.A. Badawy, Electrochim. Acta 40, 1995, p. 2623. 22. A. Belanger and K. Vijh Ashok, J. Electrochem. Soc. 121, 225,1974, p. 225. 23. P.W. Atkins, Physical Chemistry, 5th Ed., Oxford University Press, Oxford, 1994. 24. W.A. Badawy, A. Felske and W.J. Plieth, Electrochim. Acta 34, 1989, p. 1771. 25. M. Pourbaix Atlas of Electrochemical Equilibria in Aqueous Solutions, Pergamon Press, London, UK, 1966, pp. 234-245. 26. A.J. Brock and G.C.Wood, Electrochim. Acta 12, 395, 1967, p. 395. 27. D.D. Macdonald, S. Real, S.I. Smedley and M. Uraquidi-Macdonald; J. Electrochem. Soc. 135, 2410, 1988, p. 2410. 28. C.M.A. Brett, Corros. Sci. 33, 1992, p. 203. 29. K. Juttner, W.J. Lorenz, M.W. Kendig and F. Mansfeld, J. Electrochem. Soc. 135, 1988, p. 322. 30. K. Juttner, Electrochim. Acta 35, 1990, p. 1501. 31. W.A. Badawy, S.S. El-Egamy and K.M. Ismail, British Corros. J 28, 1993, p. 133. 32. J.O.M. Bockris and A.K.N. Reddy, Modern Electrochemistry, 2nd ed., Chap. 7, Plenum Press, New York, USA, 1977. 33. R.G. Martimer, Physical Chemistry, The Benjamin/Cummings Publishing Company Inc., Redwood City, California, USA, 1993. 34. G.A. Wright, J. Electrochem. Soc. 114, 1967, p. 1263.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

THE EFFECT OF UV-IRRADIATION ON PASSIVE FILMS FORMED ON TYPE 304 AND 316 STAINLESS STEELS M.S. Al-Rifaie, C.B. Breslin, D.D. Macdonald and E. Sikora Center for Advanced Materials, The Pennsylvania State University, 517 Deike Building, University Park, Pennsylvania, 16802, USA

ABSTRACT
The effect of monochromatic ultraviolet (UV) light on the passive films formed on Types 304 and 316 stainless steels (SS) is described. Under UV irradiation 304SS and 316SS specimens, in neutral and acidic solutions, exhibited an increased resistance to localized corrosion (pitting). This resistance to localized corrosion was gauged by an increase in induction time, an increase in breakdown potential, and some significant changes in the current noise at constant potentials. All these changes indicate that shining UV light on a metal specimen can sometimes decrease its susceptibility to pitting. It was observed that the extent of photoinhibition of localized attack (PILA) depends on the nature of the passive film, the period of illumination, and the incident photon energy. It was also observed that the PILA effect can, in some cases, last for over 200 hours after the illumination has been removed. Increased pitting resistance was observed with higher energy incident photons. The minimum apparent incident photon energy corresponds to the band gap of the metal specimen (375 nm for SS). The optimum illumination period observed in these experiments was approximately 5 hours. In alkaline solutions a much decreased PILA effect was observed, this decrease in PILA was attributed to the formation of a precipitate layer. This precipitate layer in turn interfered with the incident photon interaction with the barrier layer. Finally, a possible explanation of PILA is given within the framework of the Point Defect Model (PDM). Key Words: Photoinhibition, stainless steel, localized corrosion, pitting, UV, PDM, passive films

INTRODUCTION The initiation and propagation of pits and the corresponding breakdown of the passive film that forms on metals and alloys is of great fundamental interest in electrochemistry and corrosion science. Numerous efforts, ranging from the addition of inhibitors [1] to the alloying of base metals [2-5], have been made in an attempt to prolong the effective life of the passive film. Recently, it has been shown that irradiating immersed electrodes with ultraviolet (UV) light can inhibit localized corrosion. The first observation of this kind was made when polycrystalline nickel, in chloride-containing solution, was irradiated with white light [6]. Other observations supporting photoinhibition of localized attack (PILA) include similar effects on 304 stainless steel (SS) [7] and even pure iron under UV irradiation [8-9]. The purpose of this study is to examine the effects of UV irradiation on the photoinhibition of 304SS and 316SS in chloride-containing solutions. These results could help shed light on

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how PILA affects SSs and lay the groundwork for photoinhibition as a new form of corrosion control. EXPERIMENTAL PROCEDURE Test specimens were prepared from Types 304 and 316 SS rods, which were covered with lacquer, mounted in a PVC holder and then embedded in a two-component epoxy resin. The exposed surface, approximately 0.8 cm2 in area, was polished mechanically with successively finer grades of SiC paper and 0.05 alumina powder to a mirror finish. The chemical composition of the SS samples used is shown clearly in Table 1. Table 1. Chemical Composition of 304 SS and 316 SS (in Wt %) SS Type C 304 0.08 316 0.08 Mn 2 2 Cr 18 16 Ni 8 12 P S 0.04 0.003 0.04 0.003 Si 1 1 Mo Trace 2 Fe Bal. Bal.

The electrochemical cell consisted of a three-electrode PTFE cell equipped with a quartz window to allow irradiation of test electrodes. A saturated calomel electrode (SCE) was used as the reference electrode, and a platinum wire, coiled inside the cell, was used as the auxilliary electrode. All test solutions were prepared from Analar-grade reagents and deionized water, and were deoxygenated with nitrogen. The pH of the solution was adjusted to 7.5 with NaOH, or alternatively, buffered to pH 7.5 with a 0.15 mol dm-3 H3BO3/0.007 mol dm-3 Na2B4O7 solution.
B

The working electrodes were irradiated at wavelengths between 300 and 425 nm using a 150 W UV-enhanced Xe lamp (Oriel Model 6254) and a 1/8 monochromator (Oriel Model 77250). The incident power density at 300 nm was 0.4 mW cm-2, giving a photon flux of 6.04 x 1014 cm-2. The photon flux was maintained at approximately this value at each wavelength by adjusting the light intensity at the surface. Electrochemical tests were carried out using a Solartron/Schlumberger Electrochemical Interface (Model 1286). In potentiodynamic polarization tests, the working electrodes were polarized at a rate of 0.1 mV s-1 in the anodic direction up to the breakdown potential. In illumination experiments, the electrodes were illuminated continuously throughout the potential scan. The breakdown potential was recorded as the potential at which the current exceeded 80 A cm-2. In current-time measurements, the electrodes were initially polarized at a potential in the passive region for a 30-minute period, and then the potential was stepped to an appropriate point where metastable pitting could be observed for the non-illuminated specimens. The current transients were then recorded as a function of time, using a Keithley Model 576 data acquisition unit at a sampling rate of 90 mS. Additional experiments involved polarizing the working electrodes, under illumination for periods of up to 15 hours, and then determining the breakdown potential using the potentiodynamic polarization method. The exact same polarization periods were used for the illuminated and non-illuminated electrodes.

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RESULTS AND DISCUSSION Figure 1 shows typical anodic polarization curves for type 304 SS in a neutral 0.5 mol dm-3 NaCl solution (unbuffered) under conditions of illumination and non-illumination. Figure 1 clearly shows that when the sample was illuminated, an increase in pitting resistance resulted. This increase in pitting resistance was indicated by a shift of both the breakdown potential and the initial metastable pitting potential towards the more noble direction.

Figure 1. Potentiodynamic polarization curves for type 304 SS in neutral 0.5 mol dm-3 NaCl under: (a) non-illumination; and (b) illumination at 300 nm The effect of illumination on the breakdown potentials of 304 SS and 316 SS can perhaps be seen more clearly from the data shown in Table 2, which shows averages of the breakdown potentials for 304 SS and 316 SS as a function of chloride concentration. In each case, an average increase of about 60 40 mV in the breakdown potential can be observed upon illumination. Another observation that can be made from the data is that the breakdown potentials of the illuminated 304 SS specimens approach those of the 316 SS specimens in the dark. This observation could suggest a comparable degree of passivity enhancement between alloying and illumination under these conditions. An even greater increase in the breakdown potential, approximately 150 50 mV, was observed on prior illumination of the specimens at 300 nm for periods exceeding 5 hours. In these experiments, the electrodes were polarized in a 0.1 mol dm-3, NaCl buffered solution at +250 mV (SCE) for various periods of time under illumination and non-illumination. The specimens were then polarized from +250 mV (SCE) in the anodic direction at a rate of 0.1
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mV s-1 up to the breakdown potential. The displacement in the breakdown potential was calculated by subtracting the average breakdown potential for the specimens polarized in the dark from the average breakdown potential for the specimens polarized in the light. Each experiment was repeated three times. This data are shown graphically in Fig. 2, where the average displacement in the breakdown potential, Eb is shown as a function of the prior illumination period. Table 2. Breakdown Potential Values for 304 SS and 316 SS Under Light and Dark Conditions [Cl-] mol dm-3 304 SS Eb (dark) 304 SS Eb (light) 316 SS Eb (dark) 316 SS Eb (light) 0.025 355 7 mV (3) 420 10 mV (3) 430 10 mV (3) 490 11 mV (4) 0.5 275 18 mV (20) 350 20 mV (22) 330 20 mV (17) 395 20 mV (17) 2.0 160 8 mV (4) 210 15 mV (5) 230 12 mV (5) 290 10 mV (4) Eb in mV vs. SCE Light = 300 nm The numbers in parentheses indicate the number of times the experiment was repeated

Figure 2. Displacement in the breakdown potential, Eb, as a function of the illumination period for 316 SS at +250 mV (SCE) in a buffered 0.1 mol dm-3 NaCl solution

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Further evidence for photoinhibition of pitting attack was obtained from current-time measurements where the current decay transients were monitored as a function of time for illuminated (300 nm) and non-illuminated 316 SS. These data are shown in Fig. 3. It is evident from Fig. 3 that illumination causes a delay in the onset of metastable pitting, even after approximately 110 minutes, the illuminated film was still able to repassivate while the dark film had started breaking up after only 25 minutes. Therefore, illumination seemed to postpone metastable pitting by at least a factor of 3, which in itself is quite astounding. One of the questions that this study aims to answer is how prior illumination affects the passive film on 304 SS and 316SS. In order to quantify the permanent nature of the photoinhibition effect, the pitting susceptibility of 316SS was studied at various periods of time with prior illumination. The specimens were illuminated at 300 nm for 80 minutes under polarizing conditions in a neutral 0.5 mol dm-3 NaCl solution. The specimens were then immersed under open-circuit conditions (dark) in a borate buffer solution (pH of 7.5), and removed at selected intervals. The breakdown potential was determined in a neutral 0.5 mol dm-3 NaCl solution using the potential scan method. Identical experiments were carried out in the dark; the specimens were polarized in the chloride solution (dark) for 80 minutes, removed and immersed in the borate solution. The breakdown potential was determined at selected intervals. Data collected in this manner for periods up to 350 hours are shown in Fig. 4, where the breakdown potential is plotted against the immersion period following illumination or polarization.

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Figure 3. Current-time decay profiles for 316 SS polarized at 285 mV (SCE) in a neutral 0.025 mol dm-3 NaCl solution under: (a) dark, and (b) light (300 nm) conditions

Figure 4. Breakdown potential of illuminated and non-illuminated 316SS in 0.5 mol dm-3 NaCl as a function of the immersion period in a borate buffer solution (dark) following polarization or polarization and illumination at 300 nm. (a) on a linear scale; and (b) on a semi-log scale A clear difference between the breakdown potentials measured for the illuminated and non-illuminated specimens can be seen for immersion periods up to about 220 hours, indicating that the photoinhibition effect persists over this period of time. The gradual increase in breakdown potential (i.e., a shift towards the more noble direction) may be attributed to a crystallization process or chromium-enrichment in the passive film. A similar trend was observed for 304SS. The influence of solution pH, and thus the nature of the passive film, on the extent of photoinhibition was studied by polarizing and illuminating the electrodes in solutions of varying acidity. A 0.5 mol dm-3 NaCl solution was used as the test solution; the pH was adjusted to the desired value by the addition of NaOH or HCl. All irradiation experiments were carried out at 300 nm. The breakdown potentials were determined from polarization measurements for specimens polarized in the dark and under conditions of continuous
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illumination. Each experiment was carried out at least three times. The displacement in the breakdown potential, Eb, was calculated as the difference between the light and dark breakdown potentials. The average displacements in the breakdown potentials for 304SS and 316SS are shown as a function of pH in Fig. 5; the degree of scatter in the average displacements was 30 mV. An essentially constant increase in the breakdown potentials, of approximately 60 mV, was observed on illumination, except for those specimens polarized in the alkaline solutions, where no apparent photoinhibition effect was detected. However, it was found that the photoinhibition effect was partially restored under these alkaline conditions (pH of 10) by the addition of a 0.01 mol dm-3 EDTA solution to the test solution. The pH in this region was adjusted with NaOH and maintained at 10 on addition of the complexing EDTA agent. The average displacements in the breakdown potentials for both 304SS and 316SS at a pH of 10 on addition of the EDTA were 45 and 50 mV, respectively. The presence of EDTA at other pH values did not enhance the photoinhibition effect. This seems to suggest that the precipitated layers formed in alkaline environments are photoelectrochemically inactive, but that the addition of a chelating agent hinders the formation of this layer, allowing the photons to reach the barrier layer.

Figure 5. Displacement in the breakdown potential, Eb, as a function of the pH of a 0.5 mol dm3 NaCl solution, on illumination of: (a) 304SS; and (b) 316SS at 300 nm
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The effects of variations in the photon energy on the breakdown potential displacement (a measure of photoinhibition) are shown graphically in Fig. 6. A constant photon flux was maintained at each wavelength. A neutral 0.5 mol dm-3 NaCl solution was used as the test solution. A total of twenty experiments were carried out for each of the SSs under conditions of non-illumination in order to obtain adequate reference breakdown potentials. The amount of scatter in the breakdown potentials, under these conditions, was on the order of 20 mV. The mean value of the breakdown potential calculated for 304SS in the dark was 272 mV (SCE), while that for 316SS in the dark was 327 mV (SCE). Displacements in the breakdown potential, Eb, on illumination were calculated as the difference between the breakdown potentials in the light and the dark. It can be seen from Fig. 6 that the degree of photoinhibition depended on the photon energy, with the photoinhibition effect decreasing with wavelengths exceeding 375nm.

Figure 6. Displacement in the breakdown potential, Eb, measured in a 0.5 mol dm-3 NaCl solution, as a function of the incident light wavelength on illumination of: (a) 304SS; and (b) 316SS The induction periods for 316SS specimens polarized at +285 mV (SCE) in a 0.025 mol dm NaCl solution can be plotted as a function of varying photon energy as shown in Fig. 7. Figure 7 also shows the induction periods measured for identical experiments carried out in the dark. These data points are plotted at each wavelength so that the increase in the induction period on illumination is evident. The induction periods were measured as the time
-3

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between the application of the polarizing potential and the first metastable pitting events in which the current exceeded 500 nA. It is clear from this figure that the induction time was reduced slightly with decreasing photon energy.

Figure 7. Measured induction periods as a function of the incident light wavelength for 316SS polarized at +285 mV (SCE) in 0.025 mol dm-3 NaCl. Induction periods for non-illuminated specimens are also shown for reference (i.e., dark triangles at each wavelength) In previous papers [6,7], PILA has been interpreted using the PDM for the growth and breakdown of passive films [10] as the photo-quenching of the electric field within the barrier layer. The PDM has already been developed to give theoretical expressions for the breakdown potential, Eb, and the induction time, tind. It is proposed that on illumination, incident photons (with energies in excess of the band gap of the metal) generate electron-hole pairs that are separated by a steep potential gradient in a manner which quenches the electric field. Once the electric field is decreased, the theoretical expressions predict a higher breakdown potential and a larger induction time. Therefore, Figs. 1-7 are indeed consistent with a PDM interpretation of the photoinhibition effect since they predict that incident photon energy increases pitting resistance. It is not clear, at least from the experimental evidence shown here, how the electric field itself is quenched. The data presented in Fig. 5 suggests that the formation of a precipitate layer on the metal specimens polarized in the alkaline solutions screens the barrier layer from the incident
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photons, and thus inhibits the generation of electron-hole pairs (and subsequent quenching of the electric field). This is supported by the experiments in which the PILA effect was partially restored on addition of the complexing agent, EDTA. This complexing agent may hinder the formation of the precipitate layer, and hence, facilitate the photon-barrier layer interaction. Also, the fact that the PILA effect remains unaffected (in neutral and acidic solutions), or increases (in alkaline solutions), in the presence of EDTA suggests that it is unlikely that photo-induced reactions, involving oxidized iron, at the film/solution interface account for the photoinhibition effect. The semipermanent nature of PILA is evident in this study (as shown in Figs. 4 and 7) and other studies [8,9]. The PILA effect remaining after the irradiation has been removed seems to indicate that the photoinhibition effect cannot be explained solely by the changing of the electronic structure of the film. Consequently, it is postulated that the suppression of the electric field strength also modifies the vacancy distribution. If we assume that the thickness of the barrier layer (L) is 3 nm, and the cation vacancy diffusivity is on the order of 10-19 cm2s-1 [12], we can calculate an approximate relaxation time (t=L2/D). The relaxation time of the vacancy structure is thus estimated to be around 9 x 105 s. If we then compare this value with the period of 220 hours (7.92 x 105 s, from Fig. 4), there is good agreement between the two values, suggesting that the photoinhibition effect persists until the vacancy structure relaxes. Figure 2 also supports this idea in the sense that longer illumination periods lead to an increased PILA effect by altering the vacancy structure more dramatically, and therefore, requiring a larger relaxation time with increasing illumination time. Another possible explanation of PILA is that the UV irradiation leads to a chromium enrichment of the passive film. Since the PILA effect on pure iron [8,9] and nickel [6] cannot be explained by chromium enrichment of the passive film; a more likely possibility is one in which both the electric field is quenched and the passive film is enriched in chromium simultaneously. CONCLUSIONS The results of this work show that photoinhibition of pitting corrosion can be achieved for SSs on illumination with UV light. Increases in both the breakdown potential and induction period, and a decrease in the frequency of metastable pitting events were observed upon irradiation. It was also found that this PILA effect depended on the photon energy (with photons having energies above the band gap of the specimen being more effective), the illumination period, the pH of the test solution, and the nature of the resulting passive film. It appeared that the precipitate layer formed on passivation of 304SS and 316SS in alkaline solutions (pH > 10) adversely affected the interaction of the incident photons with the barrier layer. The addition of EDTA, a complexing agent, partially restored the PILA effect, which seems to support the hypothesis that the precipitate layer is indeed hindering the photon-barrier layer interaction. These observations can be explained within the framework of the PDM in terms of the generation of electron-hole pairs and consequent photo-quenching of the electric field. This in turn modifies the vacancy structure, leading to an enhancement in the pitting resistance of the specimens, that remains effective for some 220 hours. ACKNOWLEDGEMENT

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The authors gratefully acknowledge the support of this work by the Electric Power Research Institute under Contract No. RP8041-07, and by the US Department of Energy/Basic Sciences Division through Grant No. DE-FG02-91ER45461. REFERENCES 1. M. Ohi, H. Nishihara and K. Aramaki, Corrosion 50, 1994, p. 226. 2. R.G. Wendt, W.C. Moshier, B. Shaw, P. Miller and D.L. Olson, Corrosion 50, 1994, p. 819. 3. B.A. Shaw, G.D. Davis, T.L. Fritz, B.J. Rees and W.C. Moshier, Journal of the Electrochemical Society 138, 1991, p. 3288. 4. A.J. Sedriks, Corrosion of Stainless Steels, The Electrochemical Society, Princeton, New Jersey, 1979. 5. P.M. Natishan, E. McCafferty and G.K. Hubler, Journal of the Electrochemical Society 135, 1988, p. 321. 6. S.J. Lenhart, M. Urquidi-Macdonald and D.D. Macdonald, Electrochimical Acta 32, 1987, p. 1739. 7. E. Sikora, M.W. Balmas, D.D. Macdonald and R.C. Alkira, Corrosion Science, in press. 8. P. Schmuki and H. Bohni, Journal of the Electrochemical Society 139, 1992, p. 1908. 9. P. Schmuki and H. Bohni, Electrochimical Acta 40, 1995, p. 775. 10. D.D. Macdonald, Journal of the Electrochemical Society 139, 1992, p. 3434.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

KINETICS OF HIGH TEMPERATURE CORROSION OF A LOW Cr-Mo STEEL IN AQUEOUS NaCl SOLUTION W.A. Ghanem1, F.M. Bayyoumi1 and B.G. Ateya2
1 2

Central Metallurgical Research and Development Institute, Helwan, Egypt.

Corresponding Author Department of Chemistry, Faculty of Science, Cairo University, Cairo, Egypt.

ABSTRACT
The kinetics of corrosion of a low Cr-Mo steel alloy were studied over a temperature range of 75250 C in 1 m NaCl in the absence and in presence of various levels of contamination with CuCl2. We measured corrosion rates, weights of corrosion product (magnetite) film and total (integral) weight loss of the alloy over exposure times of 1-480 hours. The corrosion rate decreased rapidly with time, before it leveled off at longer time periods, indicating the formation of a protective corrosion product film. The ability of the alloy to retain an adherent corrosion product (magnetite) film was expressed in terms of a retention coefficient. This increased with temperature and exposure time, and decreased with the level of contamination with CuCl2. The effect of temperature was attributed to the improvement of the crystallinity of the corrosion product. On the other hand, the effect of the CuCl2 was attributed to the electro-deposition of Cu and its impregnation within the corrosion product, which became less adherent. The free corrosion potential was affected by the presence of the CuCl2 in a fashion compatible with the Wagner-Traud theory of mixed potential.
0

Key Words: Kinetics, corrosion, steel, high temperature, sodium chloride solution, copper chloride.

INTRODUCTION The corrosion of steel in high temperature aqueous environments is encountered in many industrial applications, e.g., boiling water reactors [1], desalination plants [2], high temperature aqueous fuel cells [3], and steam generators [4]. In such environments, contaminants, which are present in the aqueous media at trace levels, are concentrated by several orders of magnitude to form highly corrosive solutions [5]. Due to the active nature of iron, it corrodes in high temperature deaerated water and steam giving rise to the formation of ferrous (Fe2+) species which change to ferrous hydroxide, Fe(OH)2, and magnetite, Fe3O4 [6-10]: i.e., 3 Fe + 6 H2O = 3Fe(OH)2 + 3 H2 3 Fe(OH)2 = Fe3O4 + H2O + H2 The overall reaction is represented by: 3 Fe + 4 H2O = Fe3O4 + 4 H2 (3)
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Some of the resulting magnetite adheres to the surface in the form of a film which affects the kinetics of any subsequent corrosion of the steel. The rest of the resulting magnetite spalls off the surface into the electrolyte. The qualities of the adherent magnetite film depend on the temperature, composition of the environment and exposure time. The objectives of this paper are to study the kinetics of corrosion of a low Cr-Mo steel in high temperature NaCl solution, and the mechanism of protective film formation during this process. Particular attention is given to the effect of contamination of the electrolyte with CuCl2 on the integrity of the protective film, and hence, on the subsequent corrosion. The effects of CuCl2 concentration, temperature and exposure time on the adherence of the magnetite film were also determined. EXPERIMENTAL PROCEDURE All measurements were performed in an autoclave fabricated from 316 type stainless steel. The autoclave consisted of two parts. A (Teflon) PTFE cell was machined to fit tightly into the autoclave, to accommodate the electrolyte. Further details are given elsewhere [11]. The cell was preheated for about 5 hours to obtain thermal stability [12,13]. The autoclave was placed in a furnace connected with the temperature regulator to the heating source. A NiCr thermocouple was used to regulate the temperature. It was inserted into a stainless steel tube coated with a layer of PTFE. The corrosion rate measurements were taken on coupons (2 x 5 x 0.2 cm) made of a low Cr-Mo steel of the following composition (wt%): 2.3 Cr; 1.0 Mo, 0.46 Mn, 0.2 Si, 0.13 C, 0.015 P, 0.007 S and Fe balance. They were annealed at 900oC for 1 hour in an argon atmosphere and furnace-cooled. Their microstructure revealed fine dispersed carbide in a matrix of ferrite. Before use, they were polished successively down to 600 grit using silicon carbide paper, rinsed with ethyl alcohol and distilled water, and then dried in the air. Three electrolytes were used: (I) 1 molal (m) NaCl, (II) 0.999 m NaCl + 5 x 10-4 m CuCl2 and (III) 0.9 m NaCl + 5 x 10-2 m CuCl2. They were deaerated by boiling the electrolyte under reflux for 15 miutes to give an oxygen content of < 0.1 ppm (as estimated polarographically). The volume of the electrolyte in each test was 200 ml. The tests lasted for various durations, i.e., 1, 3, 6, 12, 24, 48, 96 and 480 hours and were performed in triplicate. Two of the three specimens were subjected to successive descaling by immersing for 20 minutes in a 20% ammonium citrate solution at 80oC [14] to dissolve the corrosion products. They were then rinsed with distilled water, dried and weighed until a constant weight was obtained. We calculated the integral weight (Wi ) i.e., the weight of the alloy which dissolved up to a particular time, and the weight of the corrosion product film (Wf ) which remained adherent per square centimeter of the area after a particular time. After each test, the solution was found to contain some solid (spalled) corrosion products. The working electrode consisted of a rectangular sheet about 9 cm long, 0.5 cm wide and 0.2 cm thick. It was insulated with PTFE in such a way that an area of 1 cm2 was exposed at its end. The other end was threaded and connected to a stainless steel rod of 0.3 cm diameter through a stainless steel connector. A graphite rod of 0.5 cm diameter and about 10 cm length was used as a counter electrode, and an Ag/AgCl was used as a reference electrode [12,15]. RESULTS AND DISCUSSION
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Corrosion Rate Figure 1 (a-c) illustrates the variation of the corrosion rate with time of immersion at various temperatures in electrolyte I, electrolyte II and electrolyte III. Figure 1d compares the behavior in the three electrolytes at 2500C. They clearly reveal same significant features. During short time periods, the corrosion rate decreased rapidly with the time of immersion before it tended to level off after longer time periods. This behavior is characteristic of protective film formation [16]. There was a strong detrimental effect of CuCl2 on the ability of the magnetite film to protect the substrate alloy. As the temperature and/or exposure time increased, the corrosion rate decreased. The present work reveals that the mechanism of corrosion changes after a transition time, , the magnitude of which, generally, decreases as the temperature of the test increases. At and beyond this transition time, an adherent layer of the corrosion product was shown to protect the substrate alloy by acting as a diffusion barrier [11,17], thus reducing the rate of corrosion. Before this transition time, the alloy corrodes more freely with a higher rate of corrosion. It was found that, at a given temperature, increasing the concentration of CuCl2 increased the transition time, [17]. Retention Coefficient The retention coefficient is introduced here to give a quantitative expression of the ability of the alloy to retain an adherent corrosion product film on its surface under a corrosive environment. It is defined as the ratio of the weight of the adherent (magnetite) film, Wf (adh.), at a particular time of immersion to the total weight of the (magnetite) film which would form if the integral weight loss of the alloy were to be totally consumed in forming the film material (magnetite), i.e., Wf (total). The later value is related to the integral weight loss Wi by a chemical factor (CF), which in the present case is given by the ratio of the molecular weights of Fe3O4 and 3 Fe i.e., CF = 232/168 = 1.38. Thus, the retention coefficient is given by Retention coefficient = Wf (adh.) /Wf
(total)

(4)

The retention coefficient was determined at various temperatures, CuCl2 concentrations and time intervals. Figure 2 (a-d) illustrates the variation of the retention coefficient, , with the time of immersion for the three electrolytes at various temperatures. The curves clearly reveal that increased as the temperature increased, and decreased as the concentration of CuCl2 increased. Reaction 2, which is called the Schikorr reaction [18], has been extensively studied [19,20]. Ferrous hydroxide, Fe(OH)2, decomposes rapidly above 1000C [21] , but relatively slowly at lower temperatures. Robertson [22] stated that the corrosion of steel in hot water is controlled by the dehydration of the hydroxide phase (Eq. 2), which proceeds when the metal/solution interface becomes saturated with Fe(OH)2. Consequently, two factors affecting reaction 2,

The saturation of Fe(OH)2 at the metal/solution interface which is time


dependent, and

The temperature, which enhances the reaction in the forward direction and
affects the solubility [23] and crystallinity of the magnetite film [17].
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This explains the higher values obtained at higher temperatures, that longer exposure times, and hence, the increased efficiency of the film in retarding corrosion. On the other hand, the presence of CuCl2 in the electrolyte decreased . This has previously been shown [17] by xray diffraction and scanning electron microscopy to be due to the electro-deposition of Cu and its impregnation within the magnetite film, which then becomes less adherent.

Figure 1. Variation of the corrosion rate with the time of immersion at different temperatures in: (a) sol. I, 1 m NaCl; (b) sol. II, 0.999 m NaCl + 0.0005 m CuCl2; (c) sol. III, 0.9 m NaCl + 0.05 m CuCl2.; and (d) at 250oC in different solutions

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Figure 2. Variation of the retention coefficient, , with the time of immersion at different temperatures in: (a) sol. I, 1 m NaCl; (b) sol. II, 0.999 m NaCl + 0.0005 m CuCl2; (c) sol. III, 0.9 m NaCl + 0.05 m CuCl2; and (d) at 250oC in different solutions Comparing the results in Figs. 1 and 2, it can be concluded that, in most cases, as the retention coefficient decreases, the corrosion rate increases. In other cases, both the retention coefficient and the corrosion rate increase in the same direction. This result indicates that the film formed, though retained on the alloy surface, is unable to protect it from subsequent corrosion. Potential-Time Curves Figure 3 illustrates the time variation of the free corrosion potential, Ecor , of the alloy at different temperatures in electrolytes I, II and III. It is seen that Ecor shifts toward the noble direction as the concentration of CuCl2 increases. This is in agreement with the results of Lin et al [23]. The increase in temperature above 750C shifted the values of Ecor in electrolytes I and II closer to each other than they were at 750C. In electrolyte III, increasing the temperature shifted the free corrosion potential to more noble values. A comparison of these free corrosion potential values with the equilibrium potentials of the hydrogen evolution (H2O/H2) and copper reduction (Cu/Cu++) reactions is in order to identify the cathodic half reactions. Table 1 lists the values of the equilibrium potentials of both systems at various temperatures in electrolytes I, II and III. Note that these Ecor values are considerably negative (cathodic) with respect to the reversible equilibrium potentials of the Cu/Cu++ or the H2O/H2 electrode systems [6]. The approximate values for Cu/Cu++ system in electrolytes II and III are calculated at various temperatures using the Nernst equation, i.e., Cu2+ + 2e Cu (5) (6)

E = E0 Cu/CuCl2 + 2.303 RT/2F log [Cu2+]

The values of E0 were obtained from Latimer [24]; the activity of the Cu2+ species was taken equal to its concentration. The values of E (H2O/H2) at different temperatures were taken from Pourbaix diagrams [6, 25,26]. Consequently, under the potentials shown in Fig. 4, the cathodic half cell reaction involves both the reduction of water i.e., reaction 7 2 H2O + 2 e H2 + 2 OH(7)

and the electro-deposition of Cu according to reaction 5, while the anodic reaction involves the dissolution of the iron, i.e., reaction 8 Fe + H2O Fe(OH)+ + H+ + 2e (8)

Since the concentration of Cu2+ is rather small in electrolyte II, the time behavior of Ecor is not significantly different from that in electrolyte I at the higher temperatures i.e., 125, 175 and

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2500C. Alternatively, in presence of higher concentration of CuCl2, the rate of reaction 5 is greatly enhanced leading to an increase in the corrosion rate. The results of Figure 3 can be explained within the domain of the Wagner-Traud theory of mixed potential [27,28], shown schematically in Fig. 4, which illustrates the effect of a significant increase in the rate of the cathodic reaction on the corrosion rate (Icor) and the corrosion potential (Ecor). For the sake of simplicity, we neglect the changes in the anodic polarization curves of reaction 5 brought about by adding CuCl2. Upon changing the cathodic half cell reaction from reaction 7 to reaction 5, Fig. 4 shows a significant increase in the corrosion current, Icor , and a significant shift in the mixed (free corrosion) potential towards more noble values. Both phenomena were confirmed by the experimental measurements shown in Figs. 1 and 3.

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Figure 3. Time variation of the free corrosion potential for the alloy at different temperatures in: electrolyte I (1 m NaCl); II (0.999 m NaCl + 0.0005 m CuCl2), and III (0.9 m NaCl + 0.05 m CuCl2) Table 1. Approximate Values of the Electrode Potential, V (NHE) of the Cu/Cu2+ Calculated at Various Temperatures Using the Nernst Equation in Electrolytes II and III and of the H2O/H2 Systems in Electrolytes I, II and III [6, 25,26] Electrolyte I H2O/H+ - 0.442 - 0.551 Electrolyte II Cu/Cu2+ H2O/H+ + 0.312 - 0.405 + 0.309 + 0.305 + 0.299 - 0.484 Electrolyte III Cu/Cu2+ H2O/H+ + 0.329 - 0.361 + 0.327 + 0.326 + 0.325 - 0.415

Temperature 750C 1250C 1750C 2500C

Figure 4. Schematic representation of the effect of CuCl2 on the mixed potential of iron in the corrosive medium CONCLUSIONS Inspection of the results presented reveals the following conclusions:

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1.

At short times, the corrosion rate decreases rapidly with the time of immersion before it tends to level off at longer times. This behavior is characteristic of protective film formation The retention coefficient is introduced to give a quantitative expression for the ability of the alloy to produce an adherent corrosion product film under the corrosive environment. Increasing the temperature enhances the ability of the alloys surface to retain the film. The concentration of CuCl2 has an opposite effect. The results of potential-time curves measured in different electrolytes reveal that Ecor shifts in the noble direction to an extent that increases with the concentration of CuCl2. This is compatible with the Wagner-Traud theory of mixed potential. The increase in temperature above 750C shifts the values of Ecor in electrolyte I and II closer to each other than they are at 750C.

2.

3.

ACKNOWLEDGMENT The authors express their warm gratitude to Prof. A.A. Abdul Azim, the former chairman of CMRDI, for valuable discussions. REFERENCES 1. B.C. Syrett, Materials Performance 30, 8, 1992, p. 52. 2. O. Osborn and F.H. Coley, in High Temperature High Pressure Electrochemistry in Aqueous Solutions, Houston, NACE 4, 1976, p. 7. 3. F.T. Bacon, in High Temperature High Pressure Electrochemistry in Aqueous Solutions, Houston, NACE 4, 1976, p. 24 4. M.J. Wootten, G. Economy, A.R. Pebler and W.T. Linsay. Jr., Materials Performance 17, 2, 1978, p.30. 5. C.B. Ashmore, M.H. Hurdus, A.P. Mead, P.J B. Silver, L.Tomlinson and D.J. Finnigan, Corrosion 44, 1988, p. 334. 6. M. Pourbaix, in Atlas of Electrochemical Equilibria in Aqueous Solutions, London, Pergamon Press, 1974, p. 305. 7. J.E. Castle and G.M.W. Mann, Corrosion Science 6, 1966, p. 253. 8. J. Robertson, Corrosion Science 29, 1989, p. 1275. 9. J. Jelinek, P. Neufield, Corrosion 38, 1982, p. 98. 10. G. Butler, H.C.K. Ison and A.D. Mercer, British Corrosion Journal 6, 1971, p. 23. 11. F.M. Bayyoumi, M.Sc. Thesis, Cairo University, 1995. 12. M.H. Lietzke, R.S. Greeley, W.T. Smith and R.W. Stoughton, Journal of Physical Chemistry 64, 1960, p. 652. 13. D.D.G. Jones and H.G. Masterson, in Advances in Corrosion Science and Technology, Vol. 1, New York, Plenum Press, 1970, p. 1. 14. F.A. Champion, in Corrosion Testing Procedures, London, Chapman and Hall, 1964, p. 192. 15. D.D. Macdonald, A.C. Scott and P. Wentrcek, Journal of the Electrochemical Society 126, 1979, p. 908 16. U.R. Evans, in The Corrosion and Oxidation of Metals: Scientific Principles and Practical Applications, New York, St. Martins Press , 1960, p. 819. 17. W.A. Ghanem, F.M. Bayyoumi and B.G. Ateya, Corrosion Science, in press, 1996.
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18. G. Schikorr, Z. Anorg. Allg. Chem. 212, 1933, p. 533. 19. U. R. Evans and J.N. Wanklyn, Nature 162, 1948, p. 27. 20. B. McEnaney and D.C. Smith., Corrosion Science 18, 1978, p. 591. 21. F.J. Shipko and D.L. Douglas, Journal of Physical Chemistry 60, 1956, p. 1519. 22. J. Robertson, Corrosion Science 32, 1991, p. 443. 23. C.C. Lin, F.R. Smith, N. Ichikawa and M. Itow, Corrosion 48, 1992, p. 16. 24. W.M. Latimer, in The Oxidation States of the Elements and Their Potentials in Aqueous Solutions, 2nd ed., New York, Prentice Hall, 1961. 25. H.E. Townsend, Jr., Corrosion Science 10, 1970, p. 343. 26. V. Ashworth and P.J. Boden, Corrosion Science, 10, 1970, p. 709. 27. C. Wagner and W. Traud, Z. Elektrochem. 44, 1938, p. 391. 28. D.D. Macdonald, Corrosion 48, 1992, p. 194.

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Industrial Corrosion and Corrosion Control Technology Shalaby, H.M. et al. (Editors) 1996 Kuwait Institute for Scientific Research. Printed in Kuwait

CORROSION AND PASSIVATION BEHAVIOUR OF ALUMINIUM AND ALUMINIUM ALLOYS MECHANISM OF THE CORROSION PROCESS F.M. Al-Kharafi, W.A. Badawy and A.S. El-Azab Department of Chemistry, Faculty of Science Kuwait University, P.O. Box 5969 Safat, 13060 Kuwait

ABSTRACT
Aluminum and Al-alloys represent technologically and industrially important materials. The electrochemical behavior of these materials in different solutions represents a major subject of investigation. The corrosion characteristics of naturally passivated Al, Al-Cu, Al-6061 and Al-7075 were studied in nitric acid and nitric acid containing chloride solutions. The effect of the concentration of anions on the corrosion behavior of these materials was traced. Electrochemical impedance spectroscopy (EIS) is a powerful tool in studying corrosion and passivation problems. Besides polarization techniques, the method has been applied successfully to investigate the corrosion behavior of Al and Al-alloys. The Al-6061 alloy was found to be the most corrosion resistant. In all cases, the naturally occurring passive film was too thin to impart complete passivity. Equilibrium occurred between barrier film dissolution and surface passivation especially in dilute solutions (< 0.1 M HNO3). The electrode/electrolyte interface was fitted to a parallel resistor/capacitor combination. The barrier film formed on Al or Al-6061 behaved like a perfect dielectric whereas that formed on Al-Cu or Al-7075 alloys deviated from the ideal capacitor behavior. X-ray photoelectron spectroscopy (XPS) experiments have shown that Al-Cu alloys contain remarkable amounts of Cu on the material surface. Scanning electron microscopy (SEM) investigations have shown that the presence of Cu on the alloy surface initiates flawed regions which are responsible for the increased corrosion rate of the Cu-containing alloys. Key Words: Aluminium, aIuminium alloys, corrosion, electrochemistry, impedance, passivation

INTRODUCTION Due to the technological importance of Al and Al-Alloys and their increased industrial applications, the electrochemical behavior of these materials represents an important subject for many investigators [1-10]. Investigations have been conducted to optimize the anodic polarization and passive film growth [11-15]. The effect of anions like Cl and the mechanism of their attack on the metallic surface has been a major research subject [5,10,16,17]. The corrosion and passivation behavior of aluminum and its alloys has been subjected to intensive investigation [18-21]. The use of nitric acid and nitric acid/phosphoric acid mixtures in the surface finishing of aluminum and aluminum alloys, especially in the household industry, required detailed information about the electrochemical behavior of these materials in this medium [17,22-25].

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Several techniques have been used to study the corrosion and passivation behavior of metals and alloys. Electrochemical impedance spectroscopy (EIS) is becoming a well established method for investigating electrochemical systems in which the solid/electrolyte interface plays the main role [26]. One of its important aspects is the direct matching that often exists between experimental impedance data and data obtained from discrete electrical components which represent physical processes taking place in the system under investigation [27]. Such electronic components are usually termed electronic models or equivalent circuits. EIS and other polarization techniques are very useful in studying the corrosion and passivation behavior of Al and its alloys. The polarization resistance, RP , which represents the major indication of kinetic facility [28], and electrode capacitance, C , which represents the main source for calculating the barrier layer thickness and its dielectric properties [29] are the main factors used to describe and control the corrosion and passivation of these materials [22-25]. In the present investigation, the electrochemical behavior of mechanically polished, naturally passivated Al, Al-Cu, Al-6061 and Al-7075 was investigated in nitric acid and nitric acid containing chloride solutions. An electronic model for the barrier layer/electrolyte interface was described. The effect of chloride ion concentration on the corrosion and passivation behavior of the metal and its alloys in nitric acid solutions was studied. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to investigate the materials surface. EXPERIMENTAL PROCEDURE Commercial-grade aluminum and aluminum alloys (Al-Cu, 6061 and 7075) were used as electrodes. The mass spectroscopic analysis of these materials is presented in Table 1. Electrodes in the form of cylindrical rods were mounted into glass tubes of appropriate internal diameter with an epoxy resin leaving an exposed surface area of 0.50 , 0.21 , 0.20 and 0.21 cm2 for Al, Al-Cu, Al-6061 and Al-7075, respectively, to contact the test solution. The electrolytic cell was an all glass, three electrode cell with a large surface area Pt counter electrode and Ag/AgCl/Cl- (3 M KCl) reference electrode. The electrolytic solutions were prepared using analytical grade reagents and triply distilled water. All measurements were carried out at a constant room temperature of 25oC. The potentials were measured against the Ag/AgCl/Cl- (3M KCI) reference {Eo = 0.1970 V(nhe)}. Before each experiment, the electrode was mechanically polished with successive grades of emery paper down to 3/0, and then with a smooth cloth and washed with triply distilled water. In this way, the electrodes surface acquired a reproducibly bright appearance. For comparison, some experiments were carried out after chemical etching of the electrodes surface to be sure that the mechanical polishing had no effect on the alloys structure. The electrodes were chemically etched in a 80oC heated mixture of phosphoric, acetic and nitric acids for 5 minutes [22,23]. The impedance data obtained for both mechanically polished and chemically etched electrodes showed almost the same trend with slightly higher impedance values (5-10% higher) for the chemically etched surface at different time intervals of electrode immersion in the test solution. EIS measurements were performed using the IM5d-AMOS system (Zahner Elektric GmbH & Co., Kronach, Germany). All experiments involved single frequency measurements in the frequency domain of 0.1-105 Hz. To check the presence of another time
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constant at lower frequencies, some experiments were conducted over a bandwidth of 1 mHz - 105 Hz. The input signals amplitude was usually 10 mV peak to peak. Polarization measurements were carried out using an EG&G (Princeton Applied Research) Model 273A potentiostat/galvanostat interfaced to an IBM PS/3 computer. The XPS experiments were carried out using an ESCA-Lab 200 (VG instruments). The surface was etched as required by argon ion bombardment. In each spectrum, the XPS peaks of C 1S, O 1S, Al 2P and Cu 2P1 and 2P3 were traced. The electrodes surface was examined by SEM before and after immersion in the test solution. The details of experimental procedures were as described elsewhere [22-25]. Table1. Mass Spectrometric Analysis of the Different Electrode Materials in Mass % Alloy
Al Al6061 Al-Cu Al7075

Al
99.23 97.09 93.43 90.93

Cu
0.043 0.201 4.80 1.17

Mg
0.217 1.40 0.229 2.21

Si
0.038 0.601 0.047 0.272

Fe
0.164 0.193 0.499 0.124

Mn
0.001 0.012 0.024 0.067

Ni
0.010 0.010 0.012 0.007

Zn
0.027 0.029 0.025 4.95

pb
0.001 0.000 0.721 0.000

Sn
0.003 0.000 0.006 0.000

Ti
0.006 0.016 0.015 0.024

Cr
0.001 0.248 0.001 0.046

RESULTS AND DISCUSSION Corrosion Behaviour in Nitric Acid Solution, Equivalent Circuit for the Electrode/Electrolyte Interface The impedance behavior of the different electrodes was investigated in 0.1 M HNO3. The mechanically polished electrodes were left in 0.1 M HNO3 until a steady state was reached, and then the impedance data were recorded. Although Bode plots for impedance data presentation are always recommended as standard impedance plots [26], they sometimes lead to no indication of features hidden at high frequency [10]. In such cases, the Nyquist plot format is more favorable. For data fitting procedures, Bode plots are always used since all experimental data are equally represented, and the phase angle is very sensitive for indicating the presence of additional time constants in the impedance spectra. In our experiments, both formats were used. Typical Nyquist plots of Al-7075 alloy electrodes taken at different time intervals from the steady state are presented in Fig. 1. Bode plots as a function of immersion time in the test electrolyte of Al-6061 are presented in Fig. 2. For all electrodes, the impedance Nyquist plot at any time interval consists of two semicircles (two phase maxima in the Bode plot). A high frequency semicircle, which is due to the interaction between the electrode surface and the electrolyte, is associated with a high field conduction mechanism through the oxide film and its thickness, and a low frequency loop which is concerned with the relaxation processes occurring in the barrier layer either in the bulk or at the surface, which is typical of passivated surfaces. Below the assigned low frequency of the experiment (i.e., 0.1 Hz), no reproducible data could be obtained. In the very low frequency range (0.1-100 mHz), the structural changes of the interfacial region were faster than the measurements and no reliable data could be obtained [30-33]. The diameter of the high frequency semicircle changed with the time of immersion in the electrolyte. For all alloy electrodes, the diameter decreased with immersion time which reflects a decrease in the polarization resistance of the barrier layer, Rp, and its

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thickness, . Pure Al electrodes showed continuous increases of diameter with immersion time in nitric acid solutions (Fig. 3). The increase in the diameter with time indicates oxide film thickening which means continuous passivation of Al in nitric acid solutions as was observed before [22]. The barrier layer thickness was calculated from the impedance data according to C = I/ 2 f Zim C = A 0 / (1) (2)

where C is the electrodes capacitance, f is the frequency, Zim is the electrodes impedance, A is the electrodes area, 0 is the permittivity of free space (8.85 x 10-14 Fcm-l), is the barrier layer thickness and is the oxide film dielectric constant taken as 8.4 [33] considering that the barrier layer consists mainly of A1-203. The calculated barrier layer thickness after a long period of electrode immersion ( 4 hours) in the test solution ranges between 0.2 and 0.6 nm for all electrodes irrespective the barrier layer thickening or thinning that occurred at the electrode/electrolyte interface. This thickness is about one-tenth of the thickness of the barrier layer occurring on Al or Al alloys in neutral solutions (pH = 7) [6,34]. The presence of such a barrier layer on Al or its alloys after long immersion times in nitric acid solution ( 4 hours in 0.1 M solution) indicates the remarkable passive behavior of these materials in these electrolytes.

Nyquist plots of Al-7075 electrode at different time intervals of immersion in 0.1 M HNO3 (steady state potential = -258 mV vs. Ag/AgCl/Cl- [3 M KCl]) () 45 min (steady state), () 75 min, (---) 135 min, (- - -) 250 min.
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Bode plots of Al-6061 electrode at different time intervals of immersion in 0.1 M HNO3 (steady state potential = -532 mV vs. Ag/AgCl/Cl- [3 M KCl]) () 45 min (steady state), () 75 min, (---) 135 min, (- - -) 250 min.

Al-Kharafi et al.

The polarization and impedance data are in good agreement. Figure 4 presents the Tafel polarization curves of the four materials investigated after reaching the steady state in 0.1 M HNO3. The values of the polarization resistance, Rp , corrosion current, icorr , and steady state potential, Ecorr , for the different electrodes as obtained from these measurements are presented in Table 2. Figure 5 presents the impedance data of the electrodes after 250 minutes of electrode immersion under the same conditions. Taking into consideration the polarization resistance and corrosion current data given in Table 2, the stability order of the investigated materials after reaching the steady state in 0.1 M HNO3 (i.e., 45 minutes of electrode immersion) follows the sequence: Al-6061 > Al > Al-7075 > Al-Cu After a long immersion time in the test solution (i.e., 4 hours), Al attained of comparable stability or became even more passive than the Al-6061 alloy and the order changed to: Al > Al-6061 > Al-7075 > Al-Cu

Nyquist plots of aluminium electrodes at different time intervals of immersion in 0.1 M HNO3 (steady state potential = 650 mV vs. Ag/AgCl/Cl- [3 M KCl]) () 45 min (steady state), () 75 min, (---) 135 min, (- - -) 250 min.

Tafel polarization curves of Al-Cu (1), Al-7075 (2), Al-6061 (3) and Al (4) after 45 min of electrode immersion in 0.1 M HNO3

This is clearly reflected in the Nyquist plots of Fig. 5. The change in the order of stability of Al and Al-6061 after long immersion times in the nitric acid solution is due to the
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observed passivation of aluminum from the moment of immersion in nitric acid (Fig. 3). The polarization resistance of the Al-electrode increased from 230 cm2 after 45 minutes of electrode immersion in 0.1 M HNO3 solution at 25oC, to 372 cm2 after 250 minutes of electrode immersion in the same solution under the same conditions. Table 2. Values of RP , icorr and Ecorr (vs. Ag/AgCl/3M Cl-) for the Different Electrodes Measured in 0.1 M HNO3 at the Steady State ( 45 min from electrode immersion) Electrode Al-6061 Al Al-7075 Al-Cu Rp, ( cm ) 502 374 276 269
2

icorr, (A cm2) 113.5 121.2 169.6 196.1

Ecorr, (mV) -500 -778 -271 -111

The data presented in this section show that Al-6061, either from the moment of immersion in nitric acid or after a long period of immersion, represents the most stable alloy in this solution of the alloys investigated. The results reveal that the presence of the small amount of Mg (1.4%) improves the passivation behavior of the aluminum alloy. The mass spectrometric investigation of the alloy showed that it contains 1.40% Mg and 0.60% Si. Such a combination in a heat-treatable wrought alloy leads to the formation of a Mg2Si phase, which is the basis for precipitation hardening. Either in solid solution or as submicroscopic precipitate, Mg2Si has a negligible effect on electrode potential. The alloy is normally used in a heat-treated form; therefore, no detrimental effects derive from the major alloying element or from the minor components like Cr and/or Zn which are usually added to control the grain structure. Copper additions which increase strength in the alloy are limited to very small amounts 0.2% in this alloy (Al-6061), to minimize its effects on corrosion resistance [35]. Increasing the copper content decreases the corrosion resistance of the alloy, as can be seen for Al-7075 (1.17% Cu) and Al-Cu (4.80% Cu) in Table 2. The electrochemical system can be represented by a theoretical model consisting of a parallel combination of resistor, Rp , and capacitor, C , in series with the electrolyte resistance, RS, [22,23]. Other equivalent circuit models including capacitive features and inductive features are successful in describing the electrochemical behavior of Al or its alloys in the very low frequency regions, (i.e., f < 0.1 Hz) [10,19,36]. Since it is necessary to compare the electrochemical behavior of Al and the investigated alloys, it is useful to reduce the theoretical model to the least number of components which can describe the dielectric properties of the oxide film. The capacitor/parallel resistor model, investigated in the high frequency region (f > 0.1 Hz) is suitable for such investigation. At high frequencies the resistance of the inductive features becomes included in the polarization resistance, RP , which is equivalent to the corrosion resistance, Rcorr , of the material. The capacitive features of the high frequency semicircle are related to the barrier layer itself [30,33]. The impedance data of the different electrodes were correlated to the model described above. A procedure of data fitting with minimum error was used in which a fitting program was applied to fit the experimental data to the computer-generated data. The program used
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enables data fitting in the required range of frequency. For the measurements presented, it was necessary to fit experimental data of the high frequency semicircle to the computergenerated data of the proposed model. For data fitting procedures, Bode plots are always recommended as standard impedance plots [26,37]. Figure 6 presents the experimental Bode plots for Al-6061 after 4 hours of electrode immersion in 0.1 M HNO3 (dotted line) correlated to the computer-generated data of RS = 25.2 , Rp = 1.39 k and C = 2.36 F according to the data fitting program. The data fitting of Al-6061 gives a mean error in the absolute impedance of 1.4% and a mean deviation in the phase angle, , of 1.00. The procedure of data fitting was applied to other electrode materials and also to impedance spectra taken at different time intervals of electrode immersion in the test solution. The Al and Al-6061 impedance data represent the best fitt to the theoretical model after reaching the steady state, whereas Al-Cu showed the largest deviation. The absolute impedance and phase angle deviation for Al-Cu electrodes after 4 hours of electrode immersion in 0.1 M HNO3 solution are 3.1% and 1.6o, respectively. The small deviation of the absolute impedance values obtained with Al-6061 and pure Al indicate that the barrier layer on these materials approaches ideal capacitor behavior.

Nyquist plots of Al-Cu (), Al7075 (), Al (----) and Al-6061 (- -) after 250 min of electrode immersion in 0.1 M HNO3. The values of Rp for each electrode in 2 cm are 122, 142, 372 and 234, respectively Effect of Chloride Ion Concentration

Computer fitted data of RS = 25.2 , Rp = 1.39 k and C = 2.3 F () to experimental Bode plot of Al-6061 after 250 min of electrode immersion in 0.1 M HNO3 ()

In this series of experiments the effect of chloride ion concentration on the corrosion and passivation behavior of Al, Al-Cu, Al-6061 and Al-7075 was investigated. The electrodes
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were mechanically polished and investigated in 0.1 M HNO3 solutions containing different concentrations of Cl- ions ranging between 3.5 mM and 0.35 M. A typical example of the data from these investigations is presented as Nyquist plots for the Al-Cu alloy in Fig. 7. For all investigated materials in all measurements, two semicircles were recorded. A high frequency semicircle and a low frequency inductive loop. The diameter of the high frequency semicircle depended on the concentration of Cl- (Fig. 7). It decreased as the concentration of Cl- ions increased. This means that the natural passivity of Al or Al alloys decreases in the presence of chloride ions, as was reported for aluminum. Chloride ions attack the base metal by dissolving the passive film at defective areas [16,37,38]. The decrease of polarization resistance and passive layer thickness with increasing Cl- ion concentrations means that the native barrier layer is too thin to impart complete passivity. As the concentration of Clincreases, the extent of surface attack increases and Cl- spreads laterally beneath the original native film leading to the loss of its passive characteristics with the formation of a nonprotective, oxyhalide layer on the metallic surface [16,24,25]. At very low concentrations of Cl- (i.e., 3.5 mM), the rate of barrier layer removal is very low and is exceeded by the rate of passive film repair that occurs in nitric acid solutions; hence, no remarkable attack can be observed. In this case, oxide film thickening occurs as was indicated by the increase of 1/C versus t relations [17,24,25]. At higher concentrations of Cl- (i.e., > 35 mM), the rate of barrier film removal is compensated for by the rate of passive film formation, and equilibrium is attained in which an approximate constant value of can be calculated. The remaining barrier layer thickness and its polarization resistance depends on the electrode material. Figure 8 presents the effect of Cl- ions with the same concentration (i.e., 35 mM) on the different electrode materials. As can be seen from the Nyquist plots of Fig. 8, Al-6061 has better corrosion resistance against Cl- than the other alloys investigated and even better resistance than aluminum itself. The Al-Cu and Al-7075 alloys are much affected by the presence of chloride ions. A remarkable decrease in the corrosion resistance of both alloys with the increase of the concentration of Cl- was recorded. This behavior can be attributed to the alloys constituents. The presence of Mg in the Al-6061 alloy improved the corrosion characteristics of the alloy in chloride media, whereas the presence of Cu increased the corrosion rate of the alloy. The values of corrosion resistance of the different materials after reaching the steady state in 0.1M HNO3 containing 35 mM Cl- took the order, Rp Al-6061 > Rp Al > Rp Al-7075 > Rp Al-Cu. The values in k-cm2 for the sequence are 0.754, 0.382, 0.157 and 0.097 for Al-6061, Al, Al-7075 and Al-Cu, respectively. The presence of Cu on the alloys surface was confirmed by XPS measurements. Figure 9 presents the XPS spectra for Al, Al-Cu and Al-6061. In all spectra, the characteristic peaks of aluminum (Al 2P at 75.5 eV and Al 2S at 120.0 eV), oxygen (O 1S at 532.5 eV) and carbon (C 1S at 285.5 eV) were recorded. The XPS of Al-Cu (Fig. 9b) contains additional copper peaks (Cu 2P3 at 932.5 eV and Cu 2Pl at 952.5 eV) which indicate the presence of Cu on the electrodes surface even after 3 hours of electrode immersion in the test solution. The XPS of Al-6061 did not show a pronounced Mg peak, i.e., the characteristic sharp Mg XPS peak (Mg 1S at 1305 eV) is not present [39]. This means that Mg is present more likely in the form of Mg2Si in the Al-6061 bulk and not on the alloys surface. The similarity between the XPS spectra for Al and Al-6061 (compare Fig. 9a and b) explains the close corrosion behavior of both materials and supports the conclusion that the barrier layer on both materials consists of a stable Al2O3 film. The presence of Cu on the Al-Cu surface is responsible for
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the higher rates of corrosion recorded for this alloy. It initiates cathodic areas or flawed regions which leads to the observed decrease in the corrosion resistance after long immersion times in the test electrolyte. The presence of flaw