European Federation of Corrosion Publications NUMBER 31 Corrosion of Reinforcement in Concrete Corrosion Mechanisms and Corrosion Protection Papersfrom EUROCORR '99 Edited by J. MIETZR, . POLDER B. ELSENER AND Published for the European Federation of Corrosion by IOM Communications Book Number 746 Published in 2000 by IOM Communications Ltd 1 Carlton House Terrace, London SWlY 5DB IOM Communications Ltd is a wholly-owned subsidiary of The Institute of Materials 02 000 IOM Communications Ltd All rights reserved ISBN 1-86125-133-5 Neither the EFC nor The Institute of Materials is responsible for any views expressed in this publication Typesetting by spiresdesign Made and printed in Great Britain Reinforced concrete is such a widely used construction material that in most of the world the cost of damage and repair is an important issue despite the fact that the majority of structures are undamaged and have a long service life. In fact, only a small fraction of the total stock is responsible for most of the problems with reinforcement corrosion as the main cause. Owners, engineers and researchers are trying to find solutions to the problems that are involved. Although the most important factors in the corrosion of reinforcing steel are well known necessary work continues in the understanding of rate controlling mechanisms, in developing test methods to assess the severity of existing corrosion and in producing computer based diagnostic systems. Various methods to protect structures have been applied for many years and new ideas have been introduced in recent decades. Cathodic protection of reinforcement is a successful method to stop ongoing corrosion and this application is being extended to new types of structures, to the use of new materials and to links with conventional repairs. Other new technologies in the field are the use of stainless steel, inhibitors and water repellent treatments for improved service life. This volume in the EFC series brings together the full papers presented in the successful session ”Corrosion of Steel in Concrete’’ at E UROCORR ’99 held at Aachen, Germany. Thirteen papers were accepted after peer review, and included contributions from The Czech Republic, Denmark, Germany, Italy, The Netherlands, Norway, Poland and Switzerland. The papers are grouped under two headings: Corrosion Mechanisms and Corrosion Measurements Corrosion Protection of Reinforced Concrete Structures We thank all authors who were willing to share their valuable ,.nowlecge with others and who participated in discussions. The editors hope these papers will encourage readers to apply the ideas and results that were presented to their own problems. The work reported in this volume can be read in conjunction with other EFC publications from this Working Party, for example: EFC 18 Stainless Steels in Concrete: State of the Art Report EFC 24 Electrochemical Rehabilitation Methods for Reinforced Concrete Structures: State of the Art Report EFC 25 Corrosion of Reinforcement in Concrete: Monitoring, Prevention and Rehabilitation and in conjunction with further volumes in preparation on the subjects of inhibitors for use in concrete, and embeddable reference electrodes for concrete. J. MIETZ Chairman of the EFC Working Party on Corrosion in Concrete R. POLDER B. ELSENER European Federation of Corrosion Publications Series Introduction The EFC, incorporated in Belgium, was founded in 1955 with the purpose of promoting European co-operation in the fields of research into corrosion and corrosion prevention. Membership is based upon participation by corrosion societies and committees in technical Working Parties. Member societies appoint delegates to Working Parties, whose membership is expanded by personal corresponding membership. The activities of the Working Parties cover corrosion topics associated with inhibition, education, reinforcement in concrete, microbial effects, hot gases and combustion products, environment sensitive fracture, marine environments, surface science, physico-chemical methods of measurement, the nuclear industry, computer based information systems, the oil and gas industry, the petrochemical industry, coatings, automotive engineering and cathodic protection. Working Parties on other topics are established as required. The Working Parties function invarious ways, e.g.b y preparing reports, organising symposia, conducting intensive courses and producing instructional material, including films. The activities of the Working Parties are co-ordinated, through a Science and Technology Advisory Committee, by the Scientific Secretary. The administration of the EFC is handled by three Secretariats: DECHEMA e. V. in Germany, the Sociktk de Chimie Industrielle in France, and The Institute of Materials in the United Kingdom. These three Secretariats meet at the Board of Administrators of the EFC. There is an annual General Assembly at which delegates from all member societies meet to determine and approve EFC policy. News of EFC activities, forthcoming conferences, courses etc. is published in a range of accredited corrosion and certain other journals throughout Europe. More detailed descriptions of activities are given in a Newsletter prepared by the Scientific Secretary. The output of the EFC takes various forms. Papers on particular topics, for example, reviews or results of experimental work, may be published in scientific and technical journals in one or more countries in Europe. Conference proceedings are often published by the organisation responsible for the conference. In 1987 the, then, Institute of Metals was appointed as the official EFC publisher. Although the arrangement is non-exclusive and other routes for publication are still available, it is expected that the Working Parties of the EFC will use The Institute of Materials for publication of reports, proceedings etc. wherever possible. The name of The Institute of Metals was changed to The Institute of Materials with effect from 1 January 1992. The EFC Series is now published by the wholly-owned subsidiary of The Institute of Materials, IOM Communications Ltd. A. D. Mercer EFC Series Editor, The Institute of Materials, London, UK Vl.lIl. Series Introduction EFC Secretariats are located at: Dr B A Rickinson European Federation of Corrosion, The Institute of Materials, 1 Carlton House Terrace, London, SWlY 5DB, UK Mr P Berge Federation Europeene de la Corrosion, Societe de Chimie Industrielle, 28 rue Saint- Dominique, F-75007 Paris, FRANCE Professor Dr G Kreysa Europaische Foderation Korrosion, DECHEMA e. V., Theodor-Heuss-Allee 25, D-60486, Frankfurt, GERMANY Contents Series Introduction uii Preface ix Foreword X Part I - Corrosion Mechanisms and Corrosion Measurements 1 1. Oxygen Reduction on Mild Steel and Stainless Steel in Alkaline Solutions 3 S. JAGGI, B. ELSENERA ND H. BOHNI 2. Investigations on Cathodic Control of Chloride-Induced Reinforcement 13 Corrosion M. RAUPACAHN D J. GULIKERS 3. Critical Factors for the Initiation of Rebar Corrosion 25 L. ZIMMERMANB.N E,L SENERAN D H.B OHNI 4. Field Tests of Chloride Penetration into Concrete with Microsilica 35 0. VENNESLAANNDD J. HAVDAHL 5. Comparison of Electrochemical Data and Mass Loss Corrosion Rate 41 Measurements for Steel Reinforcement in Concrete P. NOVAKA ND R. MALA Part 2 - Corrosion Protection of Reinforced Concrete Structures 49 6. Corrosion and Protection in Reinforced Concrete: A Computerised 51 System for Studying its Phenomenology, Causes, Diagnosis and Remedies P.P EDEFERRI vi Contents 7. Organic Corrosion Inhibitors for Steel in Concrete 61 B. ELSENERM, . BUCHLERA ND H.B OHNI 8. Corrosion Protection of Reinforcement by Hydrophobic Treatment 73 of Concrete R. B. POLDERH, . BORS~AEN D J, DE VRIES 9. Cathodic Protection of Concrete Ground Floor Elements with 85 Mixed-in Chloride G. SCHUTENJ., LEGGEDOOARN D R. B. POLDER 10. Sacrificial Anodes for Cathodic Prevention of Reinforcing Steel 93 Around Patch Repairs Applied to Chloride-Contaminated Concrete G. SERGAI ND C. L. PAGE 11. Layer Zinc Anodes in Cathodic Protection of Steel Reinforcement 101 W. BOHDANOWICZ 12. Lifetime Extension of Thermally Sprayed Zinc Anodes for 109 Corrosion Protection of Reinforced Concrete Structures by Using Organic Top-coatings I. SPRIESTERSBACAH. M, ELZER1., W ISNIEWSKI, A. WINKEALNDS M .K NEPPER 13. Practical and Economical Aspects of Application of Austenitic 121 Stainless Steel, AIS1 316, as Reinforcement in Concrete 0.K LINGHOFFETR., F RaLUND, B. KOFOEDA, . KNUDSENF, .M .J ENSEN AND T. SKOVSGAARD List of Abbreviations 135 Index 137 Part 1 Corrosion Mechanisms and Lorrosion Measurements 1 Oxygen Reduction on Mild Steel and Stainless Steel in Alkaline Solutions S. JAGGI, B. ELSENER and H. BOHNI Institute of Materials Chemistry and Corrosion, Department of Civil Engineering Swiss Federal Institute of Technology, ETH Honggerberg, CH-8093 Zurich, Switzerland ABSTRACT The cathodic polarisation curve of steel in alkaline solutions always shows three regions: (1)o xygen reduction with a Tafel behaviour at potentials cathodic to the open circuit potential followed by (2) a diffusion limited current of oxygen reduction at more negative potentials and (3) hydrogen evolution at very negative potentials. The diffusion limited region of the cathodic current density is controlled both by the oxygen concentration in solution and the flow rate whereas in the Tafel region (charge transfer) the temperature and the pretreatment of the sample determine the intensity of the current density and the slope of the Tafel line. On stainless steels the cathodic reduction currents are lower then on mild steel. It can be concluded that under usual corrosion conditions for steel in concrete the cathodic oxygen reduction is not diffusion limited but charge transfer controlled. 1. Introduction The corrosion reaction, i.e. the anodic dissolution of steel in concrete, has to be sustained by a corresponding cathodic reaction: in general, this is the reaction of oxygen with water producing hydroxyl ions: 0, + 2H,O + 4e- -+ 40H- (1) The availability of oxygen at the steel surface and the reaction kinetics of oxygen reduction are thus key factors in the corrosion of steel in concrete. Quite often the reduction of oxygen at the steel surface in alkaline environments is called diffusion limited although only a few papers report results on kinetics and mechanism of oxygen reduction on passive iron or steel in alkaline solutions [1,2]. The influence of oxygen on corrosion of steel in concrete has been studied [3-51. In this work, the influence of oxygen content, temperature and ageing of the passive film on the oxygen reduction reaction on normal and stainless steel in alkaline solutions has been studied. The results are discussed with respect to the mechanism of oxygen reduction and the importance for corrosion of steel in concrete. 4 Corrosion of Reinforcement in Concrete: Corrosion Mechanisms and Corrosion Protection 2. Experimental Potentiodynamic polarisation curves (scan rate 1 mVs-l) were recorded in an electrochemical flow cell (Fig.1) at defined temperatures and hydrodynamic conditions. The flow velocity was regulated by the flux of solution, 1 mLs' corresponds to a flow velocity of ca. 1.4 mms-I. The counter electrode was a platinum wire spiral and the reference electrode was a saturated calomel electrode. The materials tested (working electrode) were mild steel and DIN 1.4301 stainless steel cylinders with a diameter of 8 mm, embedded in resin and mounted in the flow cell. For each experiment the samples were freshly ground with 180 grit emery paper in water, cleaned with ethanol in an ultrasonic bath, rinsed with deionised water and immersed for 24 h in the alkaline test solution open to air to form the passive film. As electrolytes 0 . 1N~a OH and synthetic pore solution (Table 1) were used. The temperature (5-47OC), oxygen concentration (open to air or saturated) and flow velocity (stagnant or 1 mLs-l) were varied; in addition, experiments with prolonged immersion times (ageing of the passive film up to 4 months) of the samples were performed. Fig. 2 Schematic representation of the electrochemical pow-cell that allows the registration of cathodic polarisation curves under controlled temperature, potential and oxygen content.