#3SEPTEMBER 2012

The smallest component must be reliable

Offshore corrosivity

Surface treatment laboratory

SUCCESS STORIES

OPEN HOUSE

SEMINARS

editorial

Relocation to Kista

werea KIMAB is partner to industry, universities and public bodies in applied research and problem-solving. We focus on materials development, the manufacture and use of construction materials for demanding applications within fields such as energy, transport, infrastructure and process industries.
EXPeNDITURe ON MAINTeNANCe, repairs

and breakdowns caused by corrosion is a major cost for society today. With our three laboratories across Sweden and France, we are one of Europes leading corrosion institutes with cutting-edge competence in materials selection, design and protection methods for avoiding corrosion problems.
MAJOR INVESTMENTS WITHIN several research fields are a contributory factor behind our success. We have initiated a new membership programme within oil and gas in which, for example, we perform combined testing of corrosion and mechanical properties in a hydrogen sulphide environment a highly aggressive environment that is present during the extraction process for oil and gas.

UNIVERSITY COLLABORATION Is important to us and in particular our collaboration with KTH, Royal Institute of Technology in Sweden. With KTH, Mlardalen University and the Swerea Group, we are participating in XPRES, the national strategic investment, with the aim of creating an internationally recognised research and educational environment within the field of advanced production techniques. OUR eXPANDING OPeRATIONs, as

well as our French subsidiary (Institut de la Corrosion) and extensive participation in European RFCS projects - for which we act as coordinator for six of the projects - has enabled us to have access to an increasing network within the field of materials and corrosion research.
THE BUSINESS MODEL of developing cutting-edge skills to enable us to offer qualified support to customers and our 200 member companies has been successful. We can look back on growth of 50 per cent over the past four years. In order to manage continued expansion, the development of our laboratories in France is continuing and, during the spring of 2012, we moved to new and modern facilities in Kista, north of Stockholm, with larger capacity for experimental operations.

is the establishment of a virtual laboratory in which material and component manufacturing processes and systems can be described using 3D modelling and simulation techniques. Our in-house experimental resources enable us also to establish high quality input data and to verify experimentally the results that are obtained.
ANOTHeR MAjOR INvesTMeNT

Staffan Sderberg Managing Director

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A nuclear power station can contain some fairly aggressive environments for materials, and it is vital to avoid material failures.

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An automated corrosion monitoring system was applied for assessment of the corrosivity towards carbon steel and zinc in a accelerated corrosion test,

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Through a newly started joint industry project, Swerea KIMAB is aiming to help companies gain more knowledge about the corrosion rates on their offshore assets and the coatings systems in use.

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Swerea KIMAB, conduct a study of the properties and condition of PVDF piping systems that had been used to transport hydrouoric acid, hydrochloric acid and nitric acid for nearly 30 years in a steel pickling plant.

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Editors Tomas Hult, tomas.hult@swerea.se Margaretha Snnergaard, sonnergaard@swerea.se Advisory Board Eva Johansson, Sweden; Bertil Sandberg, Sweden; Johan Tidblad, Sweden; Dominique Thierry, France. Printing EO Graska Cover: Nuclear reactor Oskarshamn 3. (Photo: OKG). Corrosion News is published by Swerea KIMAB and Institut de la Corrosion Subscriptions Swerea KIMAB, Corrosion News PO-Box 7047 SE-164 07 Kista, Sweden corrosionnews@swerea.se www.swereakimab.se Corrosion News All rights reserved. No part of this publication may be reproduced in any form by any electronic or mechanical means without permission in writing from Swerea KIMAB.

Nearly 30 years in use and still going strong Why do reinforcement bars rust in concrete? New developments in the classication of corrosivity of atmospheres Meeting of ISO/TC 156 in Paris in June 2012 Offshore corrosivity The smallest component must be reliable... The right fuel and temperature keep the steam up Proper material choice for corrosive environments Institut de la Corrosion 10th anniversary Application of automated corrosion sensors BIOCOR: Oil & Gas Surface treatment laboratory Paints and linings for steel and related alloys structures in atmosphere and in immersion

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CORROSION NEWS #3 | 2012

Nearly 30 years in use and still going strong

PVDF plastic piping systems are free of corrosion, brittleness and cracking
Early 2008 the steel pickling plant Sandvik Materials Technology in Sweden closed down its operations. Swerea KIMAB, took advantage of the plant shut-down to conduct a study of the properties and condition of PVDF piping systems that had been used to transport hydrouoric acid, hydrochloric acid and nitric acid for nearly 30 years. The purpose of the tests was to gain knowledge of the actual corrosion condition as well as the probability of corrosion on joints in plastic piping systems after a lengthy period of use.
BY HANs-JRG SOMMeR

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n addition to corrosion resistance, the long-term behavior of the material was examined in an extensive series of tests. The testing included visual and microscopic studies, microtome cuts, thermal analyses, mechanical tests and an assessment of the residual stress. For evaluation purposes, the acquired data was compared with that of a factory-new PVDF pipe from GF Piping Systems. Furthermore, the condition of the socket welds was examined and the fusion work done on the

30-year-old pipes was also appraised. In steel pickling, piping systems are under extreme stress because of the aggressive media which need to be transported through them. That is why many metals are not even considered in the planning phase since they are not resistant to highly concentrated acids. In terms of metals, only a few precious metals (gold, platinum), high-alloy steels or special nonferrous alloys are suitable for this specific application area. In contrast, PVC-U-, PVC-C- or

PVDF pipes exhibit very good resistance to sulfuric acid, hydrofluoric acid or hydrochloric acid. From 1978, Sandvik Materials Technology utilized three parallel PVDF piping systems from GF Piping Systems to convey concentrated hydrofluoric acid (wt 7175%), nitric acid (wt 68%) and sulfuric acid (wt 96%). In December 2007 the nitric acid and hydrofluoric acid pipelines were taken out of service, but not disassembled. The sulfuric acid pipeline had already been shut down

CORROSION NEWS #3 | 2012

ten years earlier, but was only dismantled in 2008 along with the others. The PVDF pipes were installed outdoors and depending on the season were exposed to temperatures ranging from -20 C to +40 C. The pressure load reached 23 bar several times daily. The pipelines in the steel pickling plant were manufactured of Sygef PVDF material by GF Piping Systems and joined via socket fusion. Sygef is frequently used for chemicals distribution due to its excellent chemical resistance; Sygef is free of additives, dyes or stabilizing agents. The pressure rating of the PVDF pipes is 16 bar (PN16) for a diameter of 40 mm and a wall thickness of 2.5 mm. Before the pipes were removed, Swerea KIMAB took ten meters of pipe material including fusion joints and bends per pipeline for the test procedures.

by the contact with acid over a period of 2030 years, just as there were no differences detected between pipes installed indoors and outdoors.

Visual and microscopic testing In the visual inspection, PVDF pipes through which hydrofluoric or sulfuric acid was conducted showed no signs of corrosion, i.e. no visible surface damage, no blistering or debonding, no swelling. The only noticeable effect was a light brown discoloration of the hydrofluoric and sulfuric acid pipes. The discoloration was spread consistently over the length of the pipeline, whereas the acid permeation of sulfuric acid reached a depth of 0.2 mm. The discoloration was caused by a chemical reaction of the acids with the polymers. On the other hand, pipelines that were exposed to nitric acid did not exhibit any discoloration. The microscopic tests did not show any signs of corrosion either. Thermal analysis The melting point and crystallization test conducted on the basis of dynamic differential calorimetry (DSC) showed that there was no significant difference between spot samples taken from the interior of the pipe and the main body of the test pipe. The crystallinity also revealed no degeneration of the polymer chains. This indicates that the PVDF material had not been weakened
CORROSION NEWS #3 | 2012

Mechanical testing The tensile stress tests done at room temperature on all three PVDF pipes and the new pipe uncovered no major differences in the mechanical properties. These results coincide with the results from the thermal analysis and the microtome examination, according to which there was no or merely a minimal degeneration of the PVDF pipes used in this application. Impact resistance was tested in a room of which the temperature corresponded to the guidelines of ISO norm 179. Six test specimens were taken from each of the three pipes. None of the specimens showed any brittleness behavior in the impact resistance test. Inspection of fusion joints When inspecting the old fusion joints, the question also arose as to the quality of fusion welds with old pipe material. In other words, how safely can material which has been penetrated with acid be

fused in case of maintenance and repair work? Respective sections from the three PVDF pipes were sent to a company which specializes in acid technology. Their findings turned out to be similarly positive for all three pipe sections with IR butt fusion joints: the fusion quality was consistently good with slight pressure. Only on the hydrofluoric sample was there a bit of blistering in the fusion area. In the socket fusion joints used on the hydrofluoric and nitric acid pipes, no fissuring was detected. Fissures were, however, found in all the examined socket fusion joints which had been exposed to sulfuric acid. It is a known fact that socket fusion causes such effects. The examined fissures were up to two millimeters deep and although they weakened the components to a certain extent, they never represented a safety risk even at an operating pressure of 23 bar over a period of 20 years. An additional method which contributes to the safety of pipe systems used to convey aggressive media is BCF (bead and crevice-free) fusion, developed by GF Piping Systems. This low-stress

After more than thirty years of use, the PVDF plastic pipes are still intact. They are only slightly discolored by the corrosive acids that under high pressure pass through them.

jointing technique is highly appreciated by professionals and has stood the test of time in a multitude of applications. Additionally, a front discoloration, 6.5 mm deep, was noted on the socket joints in the hydrofluoric acid application. Assuming that this is a sign of permeation, it is possible to calculate an average permeation of 1.2 mm a year (according to Ficks law of diffusion). Generally, however, the socket fusion method has proven reliable in manufacturing piping systems that are, for example, used to convey hydrofluoric or nitric acid.

Conclusion The extensive testing performed by Swerea KIMAB showed that PVDF pipes from GF Piping Systems still have excellent resistance to corrosion even under the harshest conditions and after more than 20 years of use. Other than a slight discoloration of the pipe material, no other signs of corrosion, fissuring or brittleness were determined on the pipes examined. Moreover, the microtome cuts of the pipe walls revealed no indication of local material brittleness. Since chemicals at certain temperatures or pressures can cause macromolecular chains to split off or separate, it was necessary to test the molecular structure of the pipes, even if there was no significant degeneration of the material during the utilization period. The mechanical properties of the pipes were not altered during the course of use. This result coincides with the results of the thermal analysis, according to which there was no significant or substantial degeneration. On the basis of the test results, Swerea KIMAB generally recommends socket fusion as the preferred fusion process for PVDF pipes. Assuming that the operating conditions would have remained consistent with those during the previous 2030 years, the creep behavior data lead us to conclude that the examined pipes would have been suitable for a much longer period of use with a safety factor of 2.8 or higher.

FACTS
The investigated pipes was taken from Sandvik Materials Technology's steel pickling plant.
THe AUTHOR HANs-JRG SOMMeR is head of Chemical/Mechanical Support and Claims at Georg Fischer GF Piping Systems, Schaffhausen, Switzerland.

CORROSION NEWS #3 | 2012

in short

NeW MeMbeR CONsORTIA

Surface Technology
we are now initiating the much-requested membership programme, MRC Surface Technology. In its rst stage, the programme will focus on surface treatment systems, increased understanding concerning corrosion protection and other functional properties of surfaces. Joint projects are going to be run within surface properties, surface analysis and different types of surface treatment. As well as the properties of surfaces in nished products, understanding processcritical parameters will also be included to ensure that selected applications obtain the very best surface treatments. Swerea KIMAB has many years of experience concerning surfaces and now, in collaboration with interested companies, we will be concentrating on developing current and future requirements within the eld. Do not hesitate to contact us for further information about the programme or about surface technology ideas in general.
AT SWeReA KIMAB

Contact: Johan Nordstrm johan.nordstrom@swerea.se

NURIA FUERTES began her PhD thesis in April 2012 on Use of localised electrochemical techniques for studying stress corrosion cracking of stainless steels. Swerea KIMAB recently purchased a Scanning Vibrating Electrode Technique (SVET) which will be used in the project to perform in-situ observations of crack nucleation and growth during stress corrosion. Other applications of this technique include investigation of pitting corrosion, galvanic corrosion and corrosion resistance of coatings. Nuria has worked at Swerea KIMAB since June 2010 in the research group Metallic Materials in Corrosive Environments.

The Benedicks collection

IN A leTTeR

Contact: Nria Fuertes nuria.fuertes@swerea.se was a qualied mining engineer. In addition to the translation of the book, the Hoover couple have added valuable comments.s The Benedicks collection contains many of the more important publications on Swedish mining. All books by the father of the Swedish mining industry, Sven Rinman, are included in the collection, for example. Most of the Benedicks collection of books are now stored in the Hagstrmer Library, a medico-historical research library and museum of books in Stockholm, Sweden. Contact: Louise Parnefjord louise.parnefjord@swerea.se

to the board of the Swedish Metallographic Institute on 20 December 1945, Carl Benedicks assigned ownership of his books, off-prints and journals to the Institute. Benedicks was the founder of the Metallographic Institute (Swerea KIMAB). From 1921, when the Metallographic Institute was founded, and for fteen years after that, he was its director. The collection ranges over six centuries and comprises metallurgy, mineralogy, and mining, but also general chemistry, physics and reference works of a historical nature. The majority of the collection consists of prints from the period of hand printing up to the end of the 19th century. These books

are the most valuable in terms of cultural history and science, as well as in nancial terms. An example of an interesting book is Vanoccio Biringuccios De la Pirotechnia (1540) which is one of the classic books within the science of mining. Another classic is Georg Agricolas De Re Metallica. Most editions of this title are included, but two are of particular interest. The Italian work Larte de Metalli (1563) which is probably not held by any other library in Sweden. The second edition, which is also in the collection, was translated by Herbert Clark Hoover and his wife. Hoover later became President of the United States, but

CORROSION NEWS #3 | 2012

Why do reinforcement bars rust in concrete?

BY JOHAN AHlsTRM

Reinforcement bars cast in concrete normally have a very low rate of corrosion. The low corrosion rate is due to the concretes high alkalinity; the pH value in concrete is about 1213. Corrosion can occur in environments where chlorides are present, which are transported through the concrete to the reinforcement bar surface and break down the steels passivity. Many tests have been made to determine the chloride concentration threshold value on the reinforcement bar surface that is required to initiate corrosion. The distribution in the results from these tests is quite wide, and can probably be explained by different experimental methods having been used as well as different external environmental factors.

CORROSION NEWS #3 | 2012

There is a critical chloride threshold which dictates steel corrosion rate for each quality of concrete. The corrosion rate is largely determined by the concretes moisture content. The moisture content affects the concretes resistivity and transport of both oxygen and chlorides. The time it takes for chlorides to be transported to the reinforcement bar surface where corrosion begins is called the initialisation period. A propagation stage begins thereafter; see figure . Concrete with high moisture content has relatively low resistivity and slow transport of oxygen. The propagation rate is consequently low even if the chloride concentration is significantly higher than the chloride threshold value. Concrete with low moisture content exhibits rapid transport of oxygen and high resistivity, which produces a low rate of corrosion as well. At a specific moisture interval however, the transport of oxygen can be high at the same time as resistivity is low, which produces a high corrosion rate. It is at this specific moisture interval that the chloride threshold values should be determined. The corrosion rate for steel in watersaturated concrete constructions is usually low due to slow transport of oxygen to the reinforcement bar surface. However, if the reinforcement bars are in contact with a more noble material, the corrosion rate can show a marked increase. The magnitude of the galvanic effects for steel in concrete are determined by among other things, chloride and the oxygen concentration. If the chloride concentration is low, the reinforcement bar can maintain passivity despite electrical contact with a more noble material, and the rate of corrosion will thus be low. In one case, sacrificial anodes of aluminum were installed to protect the reinforcement bars in a concrete construction for transporting seawater. The reinforcement bars were unintentionally in electrical contact with pumps made of stainless steel and the sacrificial anodes rapidly deteriorated. The stainless steel pumps probably took up a large portion of the protective current compared with the reinforcement bars. There is therefore a risk that
CORROSION NEWS #3 | 2012

Schematic diagram of corrosion process for steel in concrete.

the reinforcement bars were not being sufficiently protected by the sacrificial anodes. On this basis, a PhD project has been initiated to investigate how the moisture content in concrete affects the chloride threshold values, as well as to investigate the risk for galvanic corrosion of steel in concrete. The PhD project encompasses experimental methods for determining the chloride threshold values, modeling of corrosion processes and field studies of concrete constructions situated in seawater.

at Lund University (LTH). The project is co-financed by the Elforsk Krnkraft concrete programme, SBUFs development fund and Swerea KIMAB.

Contact:
Johan Ahlstrm johan.ahlstrm@swerea.se

Application of the results The purpose of the project is to survey in detail which factors interact in chloride-initialized reinforcement bar corrosion and to establish relevant threshold values for these. Increased understanding and clearer limit values for chloride-initialized reinforcement bar corrosion enable more reliable assessments of condition. Project information The PhD project will be conducted through collaboration between Swerea KIMAB and the Faculty of Engineering
Test conguration for determining moisturecontents effects on the corrosion chloride value.

New developments in the classication of corrosivity of atmospheres

BY: JOHAN TIDBLAD AND KATERINA KREISLOVA

The international standards ISO 9223-9226 are the original source for the corrosivity categories C1C5 used for the classication of the corrosivity of atmospheric environments, thus serving as a basis for the choice of corrosion protection systems for many different industrial applications. Revised versions of these standards were issued in the beginning of 2012 including the addition of a new corrosivity category CX and improved procedures for estimating corrosivity categories.

of atmospheric corrosivity is helpful for the selection of materials and protection against corrosion, for estimating the lifetime of coatings and materials and can also serve as a guide when choosing appropriate corrosion tests. The corrosivity categories C1C5 are well accepted and used when selecting structural metals, protective coatings and have been incorporated in other normative and guidance documents throughout the world. The system was originally developed in the 1980s and the previous version of ISO 9223 was dated 1992. This article gives an overview of the new versions issued in the beginning of 2012 starting with a description of the scientific field work underpinning the standards.
A sysTeM fOR ClAssIfICATION

Field exposure programs Even though the standards ISO 92239226 are well accepted they have also been the subject of some criticism. This
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was mainly related to the part of the standard that describes procedures for estimating corrosivity categories based on environmental data, as opposed to the more reliable way to determine the corrosivity category by exposure of standard specimens. This was realized early and due to the fact that the first versions of the standards were based to a great extent on data from the temperate region. Therefore, the ISOCORRAG exposure program was initiated. It was carried out by nations involved in the standardization work and included 53 test sites in 13 countries on four continents. It was conducted during an eight-year period 19841995 and included six subsequent one-year exposures and long-term exposures for 2, 4 and 8 years. The data from this exposure program form the core of the data used in the revision of ISO 9223 (one-year data) and ISO 9224 (long term data) and has been summarized in ISOCORRAG International

Exposure Program. ISOCORRAG International Atmospheric Exposure Program: Summary of Results. Editors: Sheldon W Dean, Dagmar Knotkova, Katerina Kreislova, ASTM The MICAT exposure program was organized and carried out in 19881992 by 14 Iberoamerican countries and covered 72 test sites. Since the MICAT program more or less fully adopted the methodology for the ISOCORRAG program and in addition covered additional climatic conditions it was natural to create a common database used for deriving improved ways of estimating corrosivity categories based on environmental data.

Classication, determination and estimation (ISO 9223) Corrosion rates exceeding the upper limit of category C5, i.a. 200 m a-1 for carbon steel, were previously considered out of the scope of the standard.
CORROSION NEWS #3 | 2012

During the analysis of the data from the ISOCORRAG and MICAT programs it was realized that several marine sites in subtropical/tropical regions had values above the upper limit of C5. Since these are natural environments that should be covered by the standard, a new category CX have been added, with upper limit 700 m a-1 for carbon steel, referring to specific marine and marine/industrial environments, typically in a warm climate. Dose-response functions, i.e. functions giving an estimate of the corrosion rate based on environmental parameters, have been developed for the ISO 9223 metals carbon steel, zinc, copper and aluminum based on measured annual values of temperature, relative humidity, SO2 concentration/deposition and chloride deposition. This is a significant improvement compared to the previous standard in terms of reliability of predicted corrosivity categories. Even so, the standard gives an important distinction between the determination (typical error 5%) of the corrosivity category by exposure of

standard specimens and the estimation (typical error 50%) of the corrosivity category based on environmental parameters. Furthermore, the effect of clean and acid rain was considered at an early stage but could not be included in the dose-response functions despite their importance for atmospheric corrosion. These new functions are an integral part of the KorrField database and prediction program developed by Swerea KIMAB.

Guiding values for the corrosivity categories (ISO 9224) The newly issued ISO 9224 provides instructions for predicting corrosion attack after extended and long-term exposures. Detailed formulas are provided for carbon steel, zinc, copper and aluminium and in addition specific criteria to be taken into account for alloying elements in weathering steels and alloys of zinc, copper and aluminium. Measurement of environmental parameters (ISO 9225) Description of measurements of

environmental parameters focus on temperature, relative humidity SO2 and salinity since these are given in the dose-response functions. New methods are considered including for example passive samplers for pollutants and conversion factors are given between selected pollution measurement methods. The methodologies to measure environmental parameters are now similar to those described in ISO 11844, which deals with classification of low corrosivity of indoor atmospheres.

Evaluation of standard specimens (ISO 9226) In the previous version of the standard it was possible to evaluate corrosion either by exposing flat standard specimens or by exposing special wire helix specimens. Since the analysis showed that they are not equivalent it is now only possible to determine the corrosivity category by flat standard specimens. Contact:
Johan Tidblad Johan.tidblad@swerea.se

Meeting of ISO/TC 156 in Paris in June 2012

bout 50 experts from nine countries (Australia, China, Czech Republic, France, Germany, Japan, Korea, Sweden and UK) participated the week of 1115 June 2012 at the meeting of ISO/TC 156, Corrosion of metals and alloys, and its 13 working groups. The meeting was held at Espace la Rochefoucauld in Paris, France, and was hosted by AFNOR, the French standardization body. The chairman of the committee is Gran Engstrm, Swerea KIMAB, and the secretariat is at CMISI in China. Read more about the results from the working groups at: http://www. swerea.se/en/Start22/WorkingAreas/ovrigt/Standardisation/
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Offshore corrosivity
BY ANDReW GORDON & MARTIN jNssON

CORROsION ON OffsHORe INsTAllATIONs requires almost constant maintenance in order to keep structural members and safety critical elements fit for purpose. On board an offshore installation the corrosivity varies depending on the height from sea level and wind direction, as well as other environmental effects such as temperature. Many companies choose to repair degraded coatings on the bases of prequalification tests carried out onshore or in the laboratory, and also plan maintenance using corrosion rate data from estimations or again from onshore or lab tests. Swerea KIMAB is aiming to help companies gain more knowledge about the corrosion rates on their offshore assets and the coatings systems in use. Through a newly started joint industry project (JIP) Swerea KIMAB is looking at these aspects, in which samples of various materials and coating systems will be placed offshore and subsequently analysed in order to build up a picture of corrosivity and coating system effectiveness. It is envisioned that the JIP will be made up of oil and gas operators, their

service companies, coating manufacturers as well as materials and equipment manufacturers. The data obtained from the experiments will be used by specialists (designers and maintenance teams) and this will allow them to better understand the conditions in which their equipment and materials are designed to be used. Materials and paint companies could also have access to unique testing environments that would allow them to prove existing products or trial development products. There is a particular requirement to improve the maintenance of coatings on offshore installations in the North Sea currently. The Health and Safety Executive (HSE) in the UK are in the midst of their KP4 (Key Programme 4) project, which looks at the procedures used by asset owners in regards to safety and operability. In the previous project, KP3, coating maintenance (or fabric maintenance as it is known in the industry) was found to be an area that required significant improvement. The problem with this type of maintenance is
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that it requires favourable weather conditions, and with restrictions on bed space for example, the logistics of such work becomes very difficult to manage.

Prequalication tests in the environment With an accurate picture of which areas of an installation corrode faster or slower operators can plan their maintenance more effectively, ensuring resources are allocated where they are most needed as well as allowing them to defer maintenance activities if required. The selection and use of coating systems can be tailored more effectively by carrying out the prequalification tests in the environment in which they will be used rather than just in accelerated laboratory tests or onshore exposures. Swerea KIMAB has a long history of conducting research into materials and corrosion having successfully completed similar studies for infrastructure and automotive companies. The data obtained has helped populate the Korrfield database and enabled companies to select materials more effectively for the environments in which they operate. The previous studies involved placing samples in very hostile environments such as on the underside of heavy good vehicles, and so provides Swerea KIMAB with the expertise for ensuring samples are safely exposed and easy to evaluate. Focussed on oil and gas operators The first round of meetings with companies has been completed and has been focussed on oil and gas operators based in Aberdeen, UK. However, the aim is to encompass as many participants as possible in order to generate a data set that will be useful not only to current installations in the North Sea but also to new projects and other regions of the world. If you are a paint company, materials manufacturer, equipment manufacturer or have an influence on the use and/or maintenance of materials used in the offshore environment this project could be of benefit to you. Please feel free to get in contact if you wish to learn more. Contact: andrew.gordon@Swerea.se martin.jonsson@swerea.se
CORROSION NEWS #3 | 2012 Maintenance scheduling should take into account known degradation rates of materials and coating systems in operating environments.

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The smallest component must be reliable

A nuclear power station can contain some fairly aggressive environments for materials, and it is vital in these environments to try and avoid material failures. Thomas Blomfeldt of Swerea KIMAB keeps a check on the condition of the polymer materials at nuclear sites.
BY MARIA slUND

stations are often associated with meltdowns, like at Chernobyl or, last year, at Fukushima a nightmare scenario that is thankfully a rare occurrence. However, even small equipment failures can result in big problems for the operators, such as production losses or injury to personnel. For that reason safety and reliability are paramount, and this philosophy filters down to every component in the system including nuts, bolts and gaskets. The safety margins specified by the
RIsks IN NUCleAR POWeR

nuclear power station owners have been set for very good reasons. At the same time, for financial reasons, they do not want to replace materials unnecessarily, says Thomas Blomfeldt, who has the task of determining the remaining service life of a rubber joint, for example. Swerea KIMAB has several teams working on inspecting different types of material, Thomas specialises in polymers, both as an expert at Swerea KIMAB and as a research scientist. 80 per cent of his working hours involve

inspecting and evaluating samples from nuclear power stations. Thomas is a frequent visitor at Swedens three nuclear power stations, this year he has inspected seven out of the total of ten reactors. Plastic and rubber may not be what you first think of when you see a nuclear power station. However, there are large quantities of polymers there. In a reactor building the cables alone correspond to the street lighting system of a medium-sized Swedish town. In adCORROSION NEWS #3 | 2012

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manufacturers. Another problem is that over time, some additives have had approval removed and are off the market. Plasticisers are a well-known example, explains Thomas. The additives in polymers that existed when the nuclear power stations were initially brought into operation are not always available today. Testing and research are required to determine whether new additives are working. The fact that the grades can differ is easily understood when you know that the additives can sometimes constitute more than half of the material involving plasticisers, pigment and bulking agents. In addition, our nuclear power stations are undergoing upgrades currently, which makes further demands on the materials. New materials and those that have been in service are both analysed at the laboratory. The tests cover relevant material properties, what happens in different load cases, what happens to the additives and whether the material can influence the nuclear power stations
Oskarshamn nuclear power plant, Photo: OKG.

operating environment. By comparing materials that have undergone accelerated testing with materials that have been aged in the actual environment, service life can be estimated with the greatest possible accuracy. Because of that, we are in the process of building up a bank of materials data, based on the test results, says Thomas. On the basis of these tests, Swerea KIMAB provides recommendations as to whether a material ought to be replaced or if, by a good margin, it can be expected to last for a further number of years. We also help the materials suppliers with input data when they are developing new products, says Thomas. Today, Swerea KIMAB only has a presence on the Swedish market, but there are ambitions to become established in the rest of Europe, including France. Contact: thomas.blomfeldt@swerea.se

dition, there are joints, gaskets, surface coatings, and so on, he explains. The nuclear power stations are shut down every year for planned maintenance, that is when the audits are done. The owners of the nuclear power stations determine what is to be audited. This year I have been working within the research project of Swedish research foundation, Elforsk, studying polymers in concrete structures. That may involve anything from coatings to rubber gaskets and ordinary sealants, says Thomas. Heat, oxygen and radiation are harsh on all polymer materials in a nuclear power station. Thomas and his colleagues at Swerea KIMAB do on-site inspections and also take samples back to the laboratory in Kista. One of the greatest problems with polymers is that they are less standardized, compared with steel for example. The grades vary between various
CORROSION NEWS #3 | 2012

The reactor hall at the Swedish nuclear reactor Oskarshamn 3. (Photo: OKG).

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The right fuel and temperature keep the steam up

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CORROSION NEWS #3 | 2012

All waste-to-energy plants are affected by corrosion, to a greater or lesser extent. This is because they are exposed to extreme conditions in the form of high temperatures and corrosive fuels. Above all, the problems are due to the fact that the substances in the ue gases precipitate and attack parts of the system. It is the salts (chlorides) that are the greatest villains of the piece.
BY jOHAN HRD Af seGeRsTAD

IT MIGHT be COMPAReD a little with what happens to cars that are exposed to salt on the roads, says Rikard Norling, Research Leader for Corrosion in Hot Environments at Swerea KIMAB. When cars are exposed to salt-laden coatings, we gradually get rust attacking. What can occur is in a worst-case scenario that holes and other damage form in parts of the system. The corrosion can also mean that pipes, and components, thin out and have to be replaced after a period of time. That type of disruption involves operating stoppages and repair costs, says Rikard. Salts and ash from the combustion process also mean that insulating deposits are formed within the system and output must then be reduced, in order to avoid overheating. In turn that leads to a lower degree of efficiency to put it quite simply, lower energy or heat output. Combustion plants are usually subdivided into combined heat and power stations, condensing power stations and heat-only boiler stations. The systems are used for the production of electricity and/or heating (district heating). Within industry there are also a number of different systems that are used in the industrial processes, such as the soda recovery boilers at paper mills. There are no collective statistics on the number of combustion plants in Sweden, but an estimate made by the Swedish Environmental Protection Agency a few years ago indicates that there are approximately 3500 plants within the district heating sector alone. The energy authority calculates that the production of electricity from biomass combustion amounts to around

100TWh per year. A combined heat and power station is able to produce both electricity and heating at the same time. A system that only produces electricity and where the excession heat is cooled is called a condensing power station. In these plants more electricity is produced than in combined heat and power stations, but since the heat is cooled away the fuel consumption is viewed as being lower. Systems that only produce district heating are called heat-only boiler stations. Combustion plants are subject to various types of attack. High temperature corrosion arises on metallic surfaces with temperatures of around 500 degrees Celsius or over. In that case, it is primarily a matter of sodium and potassium chlorides being precipitated out. The risk of high temperature corrosion is highest in plants in which energy is produced from waste. One normal way of reducing this risk is to keep the vapour temperature at lower levels, around 400 degrees C, when waste is used as the fuel. However it also means that energy production in the plant reduces quite a lot. In addition, problems may then arise as a consequence of the precipitation of zinc and lead which form corrosive dsposits. Corrosion also occurs in cooler parts of the system as a consequence of the condensation of water which can contain sulphuric acid and hydrochloric acid from the flue gases. The fuel used for the waste-to-energy is therefore really crucial, maintains Rikard Norling. In simplified terms, the types of fuel can be subdivided into coal, biomass and waste. In this context, coal is the kindest whereas different types of waste, may contain many

substances that give rise to corrosion, including potassium, sodium, PVC, and metals such as zinc and lead. Biofuel is positioned somewhere between these, depending on how clean it is. The fuel that causes most problems is therefore waste. Here people usually differentiate between household waste and commercial/industrial waste. The latter are often better separated, and therefore cleaner. Whereas virtually everything may be found in household waste. In reality, however, many systems that combust waste run on a mixture of both household and commercial waste and it is an advantage to stick to similar fuel over a period of time, to avoid unexpected problems occurring, explains Rikard. Recycled wood is also problematic. Waste may comprise demolition waste, recycled loading pallets and similar items and it therefore does not count as biomass since it could contain metals, impregnation chemicals, remnants of paint, plastic etc. If you investigate carefully it would probably be possible to find a sample card of the whole periodic table in this type of waste The materials in the actual plants can also have an impact and can be very varied. There can be low-alloy parts, or stainless steel materials depending on the age and design of the plant. As experts in corrosion, Swerea KIMAB is commissioned by the heating and energy industry for projects such as taking measurements and samples at the plants. Yes, apart from working on research within the field, for example, we take measurements that can be used to determine the useful life of various materials, says Rikard. We also investigate the causes of component failures.
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CORROSION NEWS #3 | 2012

Steam outlet

Steam turbine

Generator

Inlet steam Steam drum Superheater Waterwall boiler tubes Economizer Feedwater inlet Air preheater Electrostatic precipitator Flue gas condenser

Steam turbine condenser

Downcomer Fuel

Stack

District heating out to customer Combustion chamber Primary air fan Secondary air fan District heating in from customer

Schematic diagram of a combustion plant.

In Sweden, and the other Nordic countries, it is most common today to fire combustion plants with biomass and waste, while in other parts of Europe coal is used as a fuel. Traditionally, more coal has been used there for a long time, and it will certainly continue to do so for some time. However, we are noticing an increase in interest in other fuels. It is

probably a sign of the times, and because of the EUs endeavours to reduce carbon dioxide emissions, we will probably be seeing an increase in the use of both biomass and waste as fuels. It is difficult to foretell whether that might give rise to potential new commissions for Swerea KIMAB. we have a tradition of participating in EU projects within the field, and the difficulties

that can be expected with new fuels could definitely lead to an even greater amount of research collaboration with European players, concludes Rikard Norling.

Contact: Rikard Norling rikard.norling@swerea.se

Investigation of cracks
Fortum discovered cracks in the downcomer (a type of pipeline) at the Hsselbyverket plant, a combined heating and power station outside Stockholm. Crack formation had previously also been established at other plants, which is why an investigation was also required at the Hsselbyverket station. Swerea KIMAB was engaged to investigate the tubes. The fears were that the cracks would be critically deep, thereby posing a huge risk of a failure, especially bearing in mind the fact that the plant and the tubes had been in operation since 1958, with no extensive replacements of any parts having been undertaken since then. According to Fortums operations and maintenance personnel the indications
IN 2011, eNeRGy COMPANy

case

safeguarded operations at Hsselbyverket CHP station

were that the cracks could be as deep as 6 millimetres, with the total thickness of the tube material being 12 millimetres. However, the investigations results were reassuring. The cracks were relatively shallow at around 0.2 millimetres and, in addition, they had not started to spread to any great extent. The length of the cracks varied from a few millimetres to around 300 millimetres, and they ran lengthwise along the pipe. It was a fair assumption that the cracks arose as a consequence of fatigue, although it has not been possible to establish this unequivocally. Certain details also made it evident that the crack formation could be connected with the manufacture of the tubes, but that could not be ascertained denitely either. Nor were there any signs that corrosion could have caused the cracks. Swerea KIMAB therefore believed that there was no immediate danger to operations, but recommended that careful and more frequent checks should be made as to whether the crack formation was increasing. Swerea KIMAB also suggested that the crack formation could be ground away in order to be able to see more easily whether new cracks arise. That was done at the plant and certain parts of the tube were also replaced. Because of this, operations were able to continue without any major, expensive repairs or interventions on this occasion.
CORROSION NEWS #3 | 2012

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NeW PROjeCT:

Proper material choice for harsh and corrosive environments in the pulp and paper industry
THe CHeMICAls UseD IN pulp and paper industry are often very corrosive, such as chlorine dioxide and spent acid in the bleaching step and in the recovery cycle with green, black and white liquor. There is also a constant development of the processes in the pulp and paper industry which often leads to increased pressures and temperatures, which often increase the corrosion rates. In addition, improved chemical recycling can lead to enrichment of corrosive species in the system due to closed loops. The use of eucalyptus, which is common in mills outside of Scandinavia, is for example causing a more corrosive environment than traditionally used raw materials. Since the service reliability is of very high concern, for both health and economic reasons, this calls for proper material choice. Swerea KIMAB has over the years worked extensively with material and corrosion issues for the pulp and paper industry, including both metallic and polymeric

materials. Two member research consortia are handling with these issues; MRC Corrosion in pulp and paper industry as well as the MRC Corrosion Properties of Polymeric Materials. The best choice of material often vary depending on the concentration and temperature of the chemical but can also vary depending on the time it is intended to be in service. At some occasions it might be necessary to replace a pipe-line or a vessel or similar just for a month or two before it can be replaced properly. This kind of temporary solution could call for a much less expensive material solution than what would normally be recommended for that service. This makes it very hard to nd any information on what material that can be just good enough for these types of applications. A new project Proper material choice for harsh and corrosive environments in the pulp and paper industry starts during the fall 2012. The project is nanced by grant from forsk on a two year basis and by the two member research consortia. The project aims at producing a guideline with information for selecting the most suitable material, plastic and/ or metallic, for the pulp and paper industry in some selected and prioritized chemical environments.

Contact: Tobias Olli, MRC Corrosion in pulp&paper industry tobias.olli@swerea.se Karin Jacobson, MRC Corrosion Properties of Polymeric Materials karin.jacobson@swerea.se

Institut de la Corrosion has celebrated its 10th anniversary

INsTITUT De lA CORROsION, the

French subsidiary of Swerea KIMAB established in Brest (France) since 2002 has celebrated its 10th anniversary on May 23rd together with customers and employees. After a day rich in meetings, a relaxing dinner was organized in the splendid location of Saint Mathew tip close to Brest. Dominique Thierry (MD) expressed his gratitude to the customers for their support but also to all the employees of Institut de la Corrosion who contributed to the success of the company. Special congratulations were addressed by Danile Quantin (Arcelormittal), Per-Erik Augustsson (SSAB) and Staffan Sderberg (MD, Swerea KIMAB).

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CORROSION NEWS #3 | 2012

19

Application of automated corrosion sensors

for monitoring the rate of corrosion during accelerated corrosion tests

Figure 1: Photograph of watertight AirCorr O logger with mounted Fe-250m sensor for heavy corrosive environments.

BY TOMAs PROsek AND NATHAlIe Le BOZeC

AN AUTOMATeD CORROsION MONITORING sysTeM

Figure 2: Schematic drawing of corrosion sensor (left) and photograph of Fe-250m sensor (right).

using the electrical resistance technique namely AirCorrTM (see Figure 1 and 2) developed in a European Project (MUSECORR*) was applied for assessment of the corrosivity towards carbon steel and zinc in different phases of a complex accelerated corrosion test, namely New VDA This test was selected for this study because it includes a variety of technical phases such as a salt spray phase (NaCl 1 wt.%, pH neutral), wet and dry cycles at several temperatures up to 50C and a freezing phase at 15 C, see Figure 3. A watertight AirCorr O logger of 1006537 mm with a tightness of IP 65 designed for highly corrosive environments was used, see Figure 1 and 2. The attached sensor is protected with a robust polyurethane casting and can be replaced when reaching the end of the life. AirCorr corrosion logger registers the changes in real time and
CORROSION NEWS #3 | 2012

20

the data can be read via a wireless interface. From the measurements, the developed small and battery-driven atmospheric corrosion loggers provided high sensitivity allowing for sub-angstrom (<1010 m) measurements of corrosion depth and good accuracy. The actual corrosion rate was affected by the exposure history due to a limited rate of wetting/drying and oxygen and ion transport to the reaction interface under a layer of corrosion products. The hysteresis was particularly strong for carbon steel. Except the freezing phase, the steel corrosion rate varied in a narrow range from 0.2 to 0.6 m/hour. For zinc, the corrosion rate varied from 0.001 to 0.1 m/hour in particular phases of the cycle with the maximum in the salt spray phase. 75% of the metal corroded in the salt spray phase and in the following drying period representing only 13% of the total test time. During drying phases, the corrosion rate usually dropped when the relative humidity decreased below about 75 %, i.e. close to the deliquescence point of sodium chloride Examples of records of corrosion depth registered by two loggers with fresh zinc sensors, L1 and L2, during three consecutive week cycles, C1, C2 and C3, are plotted in Figure 4. The obtained data suggest that the proposed test cycle allowed for rather efficient drying of the zinc surface, which is believed to be crucial for the formation of corrosion products with certain protective ability observed also in field conditions. AirCorr loggers may also be used on operating vehicles in order to assess the corrosion aggressiveness towards steel and zinc as a function of locations on operating vehicle. The corrosion loggers were successfully applied also in extreme corrosive environments represented by outdoor locations on operating ships navigating in worldwide ocean.

60
50

100
80
salt spray (NaCl 1wt%)

40 30 20

60
40 20 0

Cycle A
T RH

10
0

12

16

20

24

Time, h
60
50

100

40 30

60
40

20
10 0

Cycle B
T
RH
0 4 8 12 16 20 24

20
0

Time, h
60 50 100
80

Temperature, C

40 30 20 10 0

60
40

Cycle C
T RH
20 0

-10 -20 0 4 8 12 16 20

24

Time, h

Figure 3: Sub-cycles of N-VDA test (VDA 233-102).

4.0

B1

A1

C
Salt spray

A2

B2
L1/C1

B3

A3

Corrosion depth [ m]

Contact: Tomas Prosek tomas.prosek@institut-corrosion.fr Nathalie LeBozec Nathalie.lebozec@institut-corrosion.fr

3.0
Salt spray

2.0

L2/C1 L1/C2 L1/C3

1.0

L2/C2

L1: logger 1 Zn 25m L2: logger 2 C1, C2, C3: 1st, 2nd & 3rd cycle
72 96 120 144 168

0.0

24

48

* MUSECORR project funded by European Commission FP 7 (contract number 226539).

Exposure time [hours]

Figure 4: Record of corrosion depth measurements with Zn-25m sensors in N-VDA test.

Relative Humidity, %

Freezing phase (-15 C)

Relative Humidity, %

80

Temperature, C

Relatie humidity, %

Temperature, C

CORROSION NEWS #3 | 2012

21

ACTIvITIes WITHIN THe MARIe CURIe NeTWORk, BIOCOR

Oil & Gas

BY EvA JOHANssON, IUlIAN COMANesCU & ClAes TAXN

WATeR INjeCTION or water flooding is widely used as a secondary recovery method to increase the production of oil, usually from mature, oil fields. The figure shows a schematic drawing of the injection water process. The water injection pipeline, WIP, is usually several kilometers in length and is typically made of carbon steel. Due to availability and economy, the water used comes from different sources as; sea water, aquifer water, produced water (recovered from the oil-water mix extracted from oil fields) or fresh water. Even though the water is degassed and often corrosion inhibitors, oxygen scavenger, and scale inhibitors are added, failures

due to corrosion occur. Referring to data from 2008 (1) approximately 40 % of the world oil and gas pipe lines (3 x 106 km) is approaching nominal design life and corrosion represents 20-40% of recorded failures. Most of the industries are carrying out regularly inspections of the interior walls in order to obtain corrosion status of the pipelines. These can either be performed by so called intelligent pigging tools and/or by exposure of corrosion coupons. Typical data received are corrosion rate, corrosion pit depth, presence of biological consortia and corrosion products. Recent assessment and monitoring

has shown that MIC (microbiologically influenced corrosion) plays an important role in the internal corrosion of the pipelines. Other corrosion phenomena to consider are CO2 corrosion and under-deposit corrosion. Swerea KIMAB is taking part in the Marie Curie Network Project BIOCOR (see further information beside). At Swerea KIMAB, we focus on collecting and assessing data from corrosion failures on WIP of carbon steel in order to improve the understanding of the influence of bacterial activity on corrosion and develop a basis for better management of pipeline systems. Observation data taken to consideration
CORROSION NEWS #3 | 2012

22

are water quality, process parameters, and composition of corrosion products, biological consortia, pipeline geometry and pigging operation information, biocide treatment. The work is done in close collaboration with the industrial partners. Parallel to the activities of collecting data, attempts towards predictive models of bio corrosion are made. Models for prediction of life time or to locate areas of extend corrosion damage can be divided in two general categories: Models based on data and Models based on first electrochemical and hydrodynamic principles. By application of reasonable simplifications of the biological processes and application of basic corrosion principles, much of the observed corrosion can be understood and possibly also predicted. Field data will then be used to calibrate and validate candidate predictive model formulations. So far, the work has been published at three conferences and two papers will be presented at Eurocorr 2012 in September 2012 (26). Supports to the project work are two Biocor visiting scientists Prof. Robert E. Melchers, Newcastle University, Australia and Prof. Mirna UrquidiMacdonald, Penn State University, USA. They have stayed at Swerea KIMAB during some months in object to assist the project with their experience in corrosion modeling.

Gas

Separator Production pipeline

Oil

Hydrocyclon

Produced water re-injection Sea water Aquifer water Oil Reservoir

Schematic diagram of the injection water process.

Degasser

Injection Pipeline

Publications:
A. C. Palmer, R. A. King, Subsea Pipeline Engineering 2nd Edition 2008. I. Comanescu, C. Taxn, E. Johansson; Data Base and Corrosion Model for MIC in Oil & Gas- An Industry Relevant Approach for Management of Bio-corrosion in Oil & Gas Transport Systems, Poster Eurocorr 2011, Stockholm. I. Comanescu, R.E. Melchers, C. Taxn; Assessment of MIC in Carbon Steel Water Injection Pipelines, SPE155199, SPE International Conference and Exhibition on Oileld Corrosion, Aberdeen, UK, May 28-29, 2012. I. Comanescu, R.E. Melchers, C. Taxn; Life Time Assessment of Offshore Water Injection Pipelines as a Function of Microbiologically Inuenced Corrosion, Proceedings of the Twenty-second (2012) International Offshore and Polar Engineering Conference, Rhodes, Greece, June 1722, 2012. C.Taxn, I.Comanescu, R. E. Melchers, Framework model for under deposit corrosion in water injection pipelines, The European Corrosion Congress 2012, Istanbul, Paper No.: 1527 (in press). I. Comanescu, R.E. Melchers, C. Taxen, Correlation between MIC and water quality, pigging frequency and biocide dosing in oil eld water injection pipelines. The European Corrosion Congress 2012, Istanbul, Paper No.: 1527 (in press).
CORROSION NEWS #3 | 2012

BIOCOR partners.

BIOCOR
FACTS

ITN

BIOCOR is a Marie Curie Initial Training Network (ITN) funded by the EU 7th Framework People Programme. www. biocor.eu The overall goal is to provide the European Community with new multidisciplinary expertise in the area of bio-corrosion in order to develop more efcient knowledge-based solutions for the industry. The project is designed to the benet of the industry and as such a problem-oriented approach is chosen to tackle microbial inuenced corrosion (MIC) in two large industrial sectors: the oil and gas industry and the power supply facilities. The project is accomplished by 12 European research teams and 5 associated partners. The project started in September 2009 and ends in August 2013.

23

Surface treatment laboratory

Chromate-based conversion coatings have excellent adhesion and corrosion properties. Unfortunately, they are toxic and carcinogenic, and consequently there are needs to replace these coatings with safer products. More globally, many coating products have to be modified or replaced which require numerous tests and the optimization of the whole process from A, the metal cleaning, to Z, the curing of the topcoat. In this context, the French corrosion institute has installed a new surface treatment laboratory in Brest. This laboratory has been designed to reproduce the whole painting process as used in the coil industry from surface cleaning to paint curing, not to mention analytical techniques needed to control the process and products.

Figure 1: Paint laboratory with, from left to right, roll coater, washing machine and oven.

Figure 2: Fourier Transform InfraRed (FTIR) spectrometer.

FOR MANy INDUsTRIAl seCTORs such as building, automotive or aerospace, metallic materials are frequently used under the form of painted parts. The application of organic coatings could have an aesthetic function but it also often provides a corrosion protection for these metallic structures. Then, it appears logical to investigate the painting process to improve and optimize the

service life of painted materials. Moreover, in the last decades, environmental regulations have driven to prohibit or, at least to limit, the use of some hazardous substances widely used in the painting products, such as chromates. Thus, most painting processes include a pretreatment step, or conversion coating, that provides adhesion and corrosion resistance of polymer/metal interfaces.

Coating process and characterization tehcniques The first step in all surfaces coating process is the cleaning of metallic materials. The importance of this step is often underestimated which lead to many failures of coated parted in service. The laboratory is equipped with a washing machine that sprays the cleaning solution on the metallic parts (Figure 1). This method, frequently used in the industry, is much more efficient that the traditional dipping process usually experimented for laboratory studies. For steel and zinc-based materials, the cleaning solutions consist in alkaline cleaners. The temperature, time of cleaning or pH of cleaners can be modulated to investigate and optimize this step. The control of cleaned surfaces could be the simple water break test which involves the examination of cleaned parts to check the presence of a continuous water film. However, for a precise assessment of cleaning process, the water-contact angle measurement can be performed. Thus, the angle of a
CORROSION NEWS #3 | 2012

24

drop of water on a metallic surface is linked to its surface energy and so to its cleanliness. A clean metallic surface is usually more hydrophilic, i.e. a lower contact angle, than the oiled and oxidized substrates. Thanks to specific equipment that measures and records the spreading of water droplet on surfaces, the cleanliness of metallic material can be precisely evaluated. Additional measurement with the Fourier Transform InfraRed (FTIR) at grazing angle can also give information on oil or oxides presence on surface (Figure 2). The main step following the cleaning is the application of a conversion coating, or pre-treatment. Conversion coatings are applied in continuous steel or aluminium sheet production lines and within the paint shop of the automotive industry. In a similar way, the pretreatment is applied using a roll coater (Figure 1). This machine reproduces, at a smaller scale, the application method used by the coil industry. The rolling speed, roll pressure can be adjusted to find optimum parameters. It has been shown that structure and thickness of conversion coatings formed with this method can be dramatically different from the dipping method, used in most laboratory studies. After a drying step in the oven, pre-treated surface can be coated with organic coatings.

baths. A complementary technique, Fourier Transform InfraRed spectroscopy (FTIR) at grazing angle is also very useful to analyse thin coatings such as conversion coatings. It provides information on the chemical compounds forming this thin layer. Thanks to cooperation with the local university (Universit de Bretagne Occidental), additional analytical techniques such as X-Ray photon spectroscopy (XPS) or Scanning Kelvin Probe Force Microscopy (SKPFM) are also used to investigate new conversion coatings and to improve our understanding on the formation mechanisms of these nanometer-thick layers.

Handheld analyser A handheld X-ray Fluorescence, XRF, spectrometer, as shown in Figure 3, is useful for the control and analysis of conversion coatings. XRF technique basically consists in exciting the matter to analyse with X-Rays. The matter generates a fluorescence radiation, specific to the analysed element. The handheld analyser can detect and quantify elements heavier than the magnesium. By using a specific calibration, XRF can be used to determine the quantity of titanium/zirconium or silicon applied on metallic surfaces. This technique is frequently used in production for the control or products on the line. The analyser can also be used to the control of pre-treatment
CORROSION NEWS #3 | 2012

R&D project in progress Finally, primer and topcoat could be applied on the pre-treated surfaces and the thermal curing of paint can be carried out in an oven at a specific temperature called Paint Metal Temperature. This curing step must be performed in a specific oven that guarantee a very precise and stable temperature (Figure 4) One R&D project, sponsored by 8 industrial companies, is in progress to investigate the structure and to understand the formation mechanisms of some chrome-free pre-treatment on Zn-Al and Zn-Al-Mg coated steel. This project is focused on pretreatments based on Titanium/Zirconium (Ti/ Zr) chemistry, silanes or a combination of both. Commercial as well as model treatment products are tested and the role of different steps in the pretreatment are analyzed in the light of the structure and properties of these conversion layers. This newly installed laboratory, associated with other equipment of the Institut de la Corrosion, offers many opportunities to apply and investigate green pre-treatments and organic coatings in development for many industrial fields, form building to aeronautics. Contact:
Gilles Rannou Gilles.rannou@institut-corrosion.fr

Figure 3: X-ray Flurorescence (XRF) analyser installed on the measurement stand.

Figure 4: Paint oven.

25

Member Research Consortia (MRC): Paints and linings for steel and related alloys structures in atmosphere and in immersion
THe MRC which was created in May 2010 is devoted to the protection of steel structures by paints and linings in atmosphere and immersion for application in shipbuilding industry, offshore and infrastructure. R&D projects focus essentially on topics regarding surface preparation, durability of paint systems in accelerated corrosion tests or eld exposure 6 companies are members of this MRC. They include for examples ship building company, Oil and Gas Company or paint suppliers. Several projects are currently on-going, such projects related to assessment of paint systems in accelerated corrosion tests and eld exposures.

R&D Activity Testing the corrosion resistance of marine and offshore paint systems for C5M environment is crucial in order to make an appropriate and durable selection of the coatings as well as

to validate surface preparations. The selection of the coatings is often based on results from accelerated corrosion tests performed in laboratory, such as the conventional salt spray test (ISO 9227, ASTM B-117) or using cyclic corrosion tests. Among cyclic corrosion tests that are used for the qualication of offshore coatings, two major test methods may be conducted upon which specications ISO or NACE are selected. Indeed, these refer to ISO 20340 Annex A and ASTM D5894 as cited in NACE TM 0304 (Offshore plateform atmospheric and splash zone maintenance coating system evaluation) and TM0404 (Offshore plateform atmospheric and splash zone new construction coating system evaluation) and more generally in NACE SP0108 (Standard Practice Corrosion Control of Offshore Structures by Protective Coatings). These testing methods differ a lot regarding the test duration (3 months for

ASTM versus 6 months in ISO), the salt solution (Synthetic seawater in ASTM versus NaCl in ISO), the cycles as well as the sample preparation (scribe). However, there are no data in the open literature comparing both testing methods in ranking offshore and marine coatings for C5M environments. Two interconnected projects were thus initiated. Project 1: Field performance of marine/offshore coating systems (CoatField-C5M) The aims of the project are : To assess the performance of about 10 different paint systems applied on steel in stationary marine atmospheres of C5M class on long term duration To assess the performance of about 10 different paint systems applied on steel on real structure such as on operating ship on long term duration To compare the performance

of the coating systems as a function of exposure conditions To compare eld data with data from accelerated corrosion tests Project 2: Comparison of NACE and ISO standards for C5M atmosphere (CoatTestC5M) The aims of the project are: To assess the performance of different paint systems applied on steel in ISO 20340 (Annex A) To assess the performance of different paint systems applied on steel in ASTM D5894 (as cited in TM0304 and TM0404) To compare the results obtained in both testing conditions

Contact: Nathalie Le Bozec nathalie.lebozec@ institut-corrosion.fr

26

CORROSION NEWS #3 | 2012

3rd International Symposium

COIl COATeD sTeel:

DURAbIlITy AND TesTING Of ADvANCeD MATeRIAls

ment of new test methods and Alloy coatings for construction and automotive industry. The attendance is limited to 65 participants to ensure high interactivity and facilitate discussions after each session moderated by Dominique Thierry.
THe PRINCIPAl THeMe of the symposium is the relevance of accelerated testing methods and their further improvement. Rapid material assessment in accelerated and laboratory tests is crucial for product development and quality control. However, we have to keep asking ourselves how relevant the techniques we use are for life time prediction as many of them showed poor correlation to material performance in service conditions. AlTHOUGH THe MAIN focus of the symposium is the development, corrosion performance and testing of coil coated materials for building applications, there are presentations relevant also for the automotive industry. The last session is fully devoted to new zinc coatings alloyed with magnesium and aluminium intended not only for roong and siding but also for car bodies and home appliances. Presentations will include recent studies aiming at understanding the inhibition effect of magnesium, results of series of accelerated tests and data from eld. A leAfleT WITH a list of presentations, details about the venue and a registration form is available on www.institut-corrosion.fr. The registration is open until September 30, 2012.

28 November 2012 Paris, C2RMF, Palais du Louvre

MOsT Of Us would agree that exchange of ideas is often easier and more efcient at smaller and highly focused conferences gathering people with the same professional interest. This may explain the success of Coil Coating Symposium organized by Institut de la Corrosion and Member Research Consortium Corrosion properties of coil-coated products in 2005 and 2008. The third edition of the symposium is scheduled for November 28, 2012. Thirteen papers were invited by organizers and split into three sessions: New pretreatment and paint technologies, Reliability of accelerated tests and develop-

Contact: Tomas Prosek, tomas.prosek@institut-corrosion.fr.

Work Shop SeaTechWeek 2012 Institut de la Corrosion

OCTObeR 23, 2012

MATeRIAls AND CORROsION IN MARINe AND OffsHORe WIND ENeRGy INDUsTRy

Tuesday, 9th of October 2012 Le Quartz, Brest, France Marine and offshore wind energies are rapidly developing in Europe. Consequently, large efforts and investments are performed in this eld (a recent study showed that the 10 years investment demand was estimated at about 130 billon in Northern Europe). Seawater and offshore environments are known to be very corrosive media for most materials. In addition systems may be exposed to high mechanical stresses. To comply with these demanding operating conditions, the material selection for marine energy systems (e. g. offshore wind energy or marine energy) must be perform with very special care. Corrosion and anti-corrosion systems must be considered from the beginning of any marine energy project, together with a well dened corrosion management policy. In this workshop, engineering, producers and end users are invited to expose and discuss corrosion and material issues related to marine and offshore wind energy systems. Presentations about material selection, corrosion, anti-corrosion systems and corrosion monitoring systems will be given by European technical experts. Forum discussions will be held at the end of the presentations. Contact: Nicolas Larch. nicolas.larche@institut-corrosion.fr

Open house
Ne W RA TO R
sTe

lA

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I ON
DI NN

bO

WelCOMe TO SWeDeN and

Kista in October. 23. We will be inviting customers and member companies to an inauguration featuring open house, lectures, a question and answer session, and a demonstration of the new laboratories. We hope that many of you will be able to participate during the day and evening. We look forward to meeting you all in Kista.

PO

I es

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R es

eR

CORROSION NEWS #3 | 2012

27

Calendar
October 9, 2012
Work Shop at SeaTechWeek 2012 Materials and Corrosion in Marine and Offshore Wind Energy Industry Location: Le Quartz, Brest, France nicolas.larche@institut-corrosion.fr

October 23, 2012

Swerea KIMAB Open House We will be inviting customers and member companies to an open house, at our new location in Kista. Location: Swerea KIMAB, Stockholm, Sweden More information at www.swereakimab.se

November 28, 2012

Coil coated steel: Durability and testing of advanced materials Location: Paris, C2RMF, Palais du Louvre, France More information: www.institut-corrosion.fr or mail, tomas.prosek@institut-corrosion.fr.

Courses
FRANCe sWeDeN

Certication in cathodic protection for the seawater application sector: Level 1

October 817, 2012

Korrosionslra
Del 1 September 2528, 2012 Del 2 October 16-18, 2012

Inspektr av rostskyddsmlning
December 3-7 This courses are in Swedish.

Level 1S
January 28February 1, 2013 This courses are in French (English on demand)

More information at www.institut-corrosion.fr

More information at www.swereakimab.se