The Treatment of Durability in CES Edupack a White Paper 1. Introduction

The Treatment of Durability in CES EduPack A white paper Mike Ashby, Cambridge UK March 2009 1. Introduction

Durability is a key material attribute, one central to the safety and economy of products. It is one of the more difficult attributes to characterize, quantify and use for selection because

• It is a function not just of the material but of the environment in which it operates • There are many mechanisms, some general, some peculiar to particular materials and environments • Material combinations (as in galvanic corrosion) and configuration (as in crevice corrosion) play a role.

Figure 1 shows some of the considerations involved. The central players are Materials and Environments. But the fact that a given material is resistant to a given environment is not enough – there are many other considerations, some of them listed on the Figure. First there is the Industrial sector in which the material is to be used: some are limited to material lightweight materials, some to non-flammable materials, some to bio- compatible materials. Second, there are many Mechanisms of attack, some general, some appearing only under special conditions. Third, there are Protection methods, some generally applicable (like painting), some specific to particular combinations of material and environment (such as inhibitors). And finally there are issues of Design , often specific to a given industry. Thus there are preferred material choices for use in a given environment – those that, through experience, best meet both the primary constraint of resisting attack and the secondary constraints of stiffness, strength, cost, and the like.

Figure 1. CES EduPack records deal explicitly with materials and environments. The other information is captured, as far as possible, in Notes attached to the each environment field, in the way shown in Figure 3.

1 This White Paper describes the way in which Durability is treated in CES EduPack. Section 2 lists the environments. Section 3 describes the data organisation and information provision in CES EduPack. Section 4 illustrates how the database is used. Appendix A reviews currently available software for durability selection. Appendix B gives examples of the data.

2. The materials and the environments

The material set is that of the CES EduPack Level 2 database. It contains records for 97 materials, organized under the headings shown in Table 1. The records contain a description and image of the material, data for general, mechanical, thermal and electrical properties, properties relating to the impact of their use on the natural environment, design guide-lines, technical notes, typical uses and trade names.

Table 1. The material families and classes.

Family Class

Metals and alloys Ferrous Non ferrous Polymers and elastomers Elastomers Thermoplastics Thermosets Ceramics and glasses Cement and concrete Fired clay Glasses Minerals and stone Technical ceramics Hybrids Composites Foams Natural materials

Table 2 lists the 53 environments – it is a subset of a longer list of the kind found in the Chemical Resistance tables of CES EduPack or the compilation by Schweitzer (1995) or that used by NACE, expanded by the addition of Built Environments (to include use in Architecture) and Thermal Environments (giving a way to select materials for use at high temperatures).

Table 2. The 53 environments

Chemical environments

Water & Aqueous Solutions Water (fresh) Water (salt) Soils, acidic (peat) Soils, alkaline (clay) Alcohols, aldehydes, keytones Wine Acetaldehyde Acetone Acids Ethyl alcohol (ethanol) Acetic acid (10%) Ethylene glycol Acetic acid (glacial) Formaldehyde (40%) Citric acid (10%) Glycerol Hydrochloric acid (10%) Methyl alcohol (methanol) Hydrochloric acid (36%) Hydrofluoric acid (40%) Halogens and gases Nitric acid (10%) Chlorine gas (dry) Nitric acid (70%) Fluorine (gas) Phosphoric acid (10%) Oxygen (gas) Phosphoric acid (85%) Sulfur dioxide, SO 2 Sulfuric acid (10%) Sulfuric acid (70%) Built environments Industrial atmosphere Alkalis Marine atmosphere Sodium hydroxide (10%) Rural atmosphere Sodium hydroxide (60%) UV radiation (sunlight) Flammability Fuels, oils and solvents Amyl acetate Thermal environments Carbon tetrachloride Cryogenic (down to -273 C) Chloroform Tolerance to 150 C Crude oil Tolerance to 250 C Diesel oil Tolerance to 450 C Lubricating oil Tolerance to 850 C Paraffin oil (kerosene) Tolerance above 850 C Petroleum (gasoline) Silicone fluids Toluene Turpentine Vegetable oils White spirit

3 3 The way Durability is treated in CES EduPack

When CES EduPack is opened in Browse or Select mode, the user has the ability to choose a selection template . One of the options under EduPack Level 2 is Materials with Durability, as shown in Figure 2. This presents, under the heading Durability , the 53 environments, grouped under eight headings: Water & Aqueous solutions, Acids, Alkalis etc. as listed in Table 2 Each material is given a ranking in each environment, using a 4 point scale: Excellent (A), Satisfactory (B), Doubtful (C), Unsatisfactory (D). Table B3 of Appendix B lists a subset (about one third of the total) of the materials and environments with their ranking on this scale.

File Edit View Select Tools…

Browse Search Select

Table: MaterialUniverseMaterialUniverse

Subset: EduEdu Level Level 2 2

Edu Level 1

Edu Level 2 Edu Level 2 with durability Edu Level 2 with eco props Edu Level 2……..

Figure 2. Opening the CES EduPack data base with durability attributes.

Materials to resist a given environment are best selected using a Limit stage . Figure 3 shows part the display for environments under the heading of Acids . Ticking the box for Excellent , or those for Excellent and for Satisfactory , for a chosen environment, limits the selection to materials that carry these rankings.

This, however, may not always be the best way to select materials for durability because there are other issues involved. Durability can be achieved by choosing a material that does not corrode or react in a given environment. But it can also be achieved by protection with corrosion inhibitors, by coatings, or – when corrosion is uniform rather than localised – simply by providing sufficient section that the loss over the design life does not compromise the integrity of the component. The preferred choice of material or coating may, for economic reasons, not be the one most resistant to attack, but a cheaper one that is still satisfactory in its performance. This information, and more, is contained in sets of Notes , accessed by double clicking on the group name (e.g. on “Acids”) or on the name of the environment (e.g. “Hydrochloric acid”). Figure 3 illustrates the two sorts of notes that are accessed by double clicking on the headings and environment names. These are described next.

Figure 3. The way information on Durability information is stored and accessed in CES EduPack. Opening a LIMIT stage reveals a list of the environments, each with a 4-point check box

for material selection. Each heading is linked to pages of Science notes , and each environment name is linked to Environmental notes pages like those shown here, listing information relating to the other factors shown in Figure 1.

Science notes. The headings (Water and Aqueous solutions, Acids, Alkalis etc) are linked to Science notes that outline the underlying science – the chemical reactions, the rate of attack etc. – associated with the subject of the heading. Thus “Acids” in Figure 3 is linked to pages of Science notes about the nature of acid attack. They parallel the Science notes attached to the mechanical, thermal, electrical and optical properties in the database.

Environment notes. The environments (Acetic acid, Citric acid, Hydrochloric acid etc) are linked to Notes of a different kind. Their purpose is to capture some of the peripheral information suggested by Figure 1. Each Environmental note is headed by the environment name and chemical formula. The first item in the Note (“ where found ”) lists the circumstances under which this environment in encountered. Table B1 of Appendix B lists some of these. The second lists the industrial sectors in which it is commonly encountered, drawn from the list in Table 3. The third describes the problems caused by a given environment, particularly the classes of material that are most vulnerable to it.

This introductory information is followed by a list of the preferred materials and coatings used when the design requires resistance to that environment (Table B4 of Appendix B lists a subset). The purpose is to direct the user to the Metals, Polymers and Ceramics and Glasses most commonly used to contain, transport or process the environment. The choice is influenced both by resistance to attack and by the economics of its use, and for that reason is not always the most obvious one. Materials for which records can be found in CES EduPack

5 Level 2 are shown without brackets. Those that are not in Level 2, but for which properties can be found in Level 3 are shown in brackets.

Below this are two further notes. The first lists inhibitors that slow the rate of attack by the environment, though they seldom prevent it entirely (Table B2 of Appendix B gives examples). Inhibitors are material- specific – thus the inhibitors for HCl attack of iron differ from those for HCl attack of aluminium or titanium. The metal to which a given inhibitor applies is shown in brackets after the inhibitor name. The second note simply indicates the underlying mechanism, more fully described in the Science notes attached to the headings.

Table 3. Industrial sectors

Industry Particular environments Petroleum Petroleum, oils, solvents, sulphuric acid, sulphur, salt and fresh water, soil Food processing Acetic acid, citric acid, sulphur dioxide, vegetable oils, fresh and salt water, wine Chemical engineering Acids, alkalis, halogen gases, oils Engineering manufacture Industrial fluids, Fuels and oil Construction (housing, industrial building Soils, Built environments (Industrial, marine, rural) Radiation, Energy conversion (ic engines, steam and gas turbines) Thermal environments: Hot liquids and gasses Marine engineering (shipping, off-shore engineering) Salt water, industrial solvents Aerospace (airframes) Fresh and salt water, radiation Bio-engineering Fresh and salt water, body fluids

Domestic (cooking, cleaning) Fresh and salt water, dilute acids and alkali, vegetable and animal fats

4. Using the Durability data in CES EduPack

The use of the database is best illustrated by examples. In each example the CES system has been opened in Level 2 Materials with Durability.

Example 1. The waste stream of a fertilizer plant includes dilute sulfuric acid. The dilute acid is stored in surface tanks some distance from the plant. It is suggested that the ducting to carry the acid to the tanks could, most economically, be made of wood. Is this a totally crazy suggestion?

• Browse: opening the records for Hardwood:oak or for Softwood: pine we find:

Softwood: pine

Durability: acids Sulfuric acid (10%) Acceptable Sulfuric acid (70%) Unacceptable

The suggestion should be taken seriously, provided the strength of the acid is below 10%.

6 Example 2. A polymer coating is sought to protect components of a microchip processing unit from attack by hydrogen fluoride (HF). Results of Limit stage • Tree stage: limit the selection to Polymers. Ionomer (I) • Limit stage: require Excellent in Hydroflouric acid (40%). Polychloroprene (Neoprene, CR) The results are shown in the box. Polyethylene (PE) • Opening the Environmental notes for Hydrofluoric acid Polypropylene (PP) (40%) confirms that fluorocarbon polymers give good Polytetrafluoroethylene (PTFE) protection, and provides information about inhibitors, suggesting that steel components can be protected by doping the HF solution with one of these.

Hydrofluoric acid (40%), HF. Preferred materials and coatings.

Metals Polymers and composites Ceramics and glasses Lead PTFE Graphite Copper Fluorocarbon polymers Stainless Steel Rubber Carbon Steels (Monel) (Hastelloy C) (Platinum, Gold, Silver)

Inhibitors. Thiourea, arsenic oxide, sodium arsenate (all for Fe).

Example 3 . A food processing plant uses dilute acetic acid for pickling onions. The acid is piped to and from holding tanks. Select Results of Limit stage a suitable material for the pipes and tanks, given that, to have sufficient strength and toughness to tolerate external abuse they Commercially pure lead must be made of a metal. Commercially pure titanium Titanium alloys • Tree stage: limit the selection to metals. Nickel-based superalloys Nickel-chromium alloys • Limit stage: require Excellent in Acetic acid (10%). Stainless steel The results are shown in the box. Tin • Opening the Notes for Acetic acid (10%) gives the following information about preferred materials and coating.

Acetic acid (10%), CH 3COOH: Preferred materials and coatings.

Metals Polymers and composites Ceramics and glasses Aluminum HDPE Glass Stainless steel PTFE (Porcelain) Nickel (Graphite) Nickel alloys Titanium (Monel)

The metals are essentially the same as those found by the limit search – the only difference is the inclusion of aluminum. But the other two columns suggest an alternative approach: that of making the pipe work out of a cheap steel and either lining it with HDPE or PTFE, or enameling it to give a glass surface. These are attractive alternatives since, in food processing, any leaching of metal ions into the product is unacceptable.

7 Example 4. Metal pipe work on an oil rig must carry hydrochloric acid solution to acidify the well. Use the database to explore ways of providing and protecting the pipe. Results of Limit stage

• Tree stage: limit the selection to metals. • Limit stage: require Excellent in Hydrochloric acid (10%). Commercially pure lead Stainless steel The results are shown in the box. HCl is a particularly aggressive Titanium alloys acid. Only three alloys survive.

• Opening the Notes for Acetic acid (10%) we learn that HCl is a particularly aggressive acid, difficult to contain and transport. The preferred material and coating, and the inhibitors are listed.

Hydrochloric acid (10%), HCl . Preferred materials and coatings.

Metals Polymers and composites Ceramics and glasses Copper HDPE Glass Nickel and nickel alloys PP Titanium GFRP (Monel) Rubber (Molybdenum) (Tantalum) (Zirconium) (Platinum, Gold, Silver)

Inhibitors. Ethylaniline, mercaptobenzotriazole, pyridine and phenylhydrazine, ethylene oxide (all used for Fe), phenylacridine (Al), napthoquinone (Al), thiourea (Al), chromic acid (Ti), copper sulphate (Ti).

Titanium would appear to be the best, though expensive, choice: its inherent resistance to attack by HCl is high, and inhibitors exist that give added protection. The alternative, suggested by the table, is that the pipe work is lined with HDPE or enameled.

Example 5. An auto maker is concerned about the consequences of the introduction of bio-methanol, CH 3OH or bio-ethanol C 2H5OH into auto fuels. The particular concerns are

(a) Corrosion of aluminum components, particularly the engine block, by methanol or ethanol.

(b) Possible damage to GFRP or CFRP body panels of some models by spillage of methanol or ethanol- containing bio-fuels.

Are the concerns justified? What can be done if they are?

• Browse: opening the records for Cast aluminum alloys Cast Al-alloys and for Sheet molding compound (SMC) yields the information shown in the boxes. Clicking on the Durability: alcohols, aldehydes, ketones environment name brings up the Notes pages, also Ethyl alcohol (ethanol) Acceptable useful. Methyl alcohol (methanol) Acceptable Cast aluminum alloys are “Acceptable” in both alcohols – not the highest rating, so some corrosion is possible. The problem, as the Note explains, is the take up of water, Inhibitors for aluminum. Potassium dichromate, which, if allowed, brings the risk of electro-chemical alkali carbonates or lactates (Al), corrosion. Lobbying for the inclusion of inhibitors in the fuel might be justified.

SMC (and also CFRP) gets a more severe rating of “Limited use”. This is a cause for concern – prolonged Sheet molding compound, SMC exposure to either of the two alcohols, if present in large concentration in the fuel, could result in degradation of the Durability: alcohols, aldehydes, ketones body panels. It will be necessary to explore alcohol- Ethyl alcohol (ethanol) Limited use resistant surface coatings if the use of bio-fuels becomes Methyl alcohol (methanol) Limited use widespread.

Example 6. As a materials consultant you are asked to prepare a survey of the strength and resistance of materials to strong sodium hydroxide, NaOH. The client, the manager of a paper-making plant that uses NaOH in one step of the paper-making process, is interested in metals, polymers and polymer based composites as alternatives for parts of the pipe work, valves and pumps.

• Select: Custom – define you own subset. Create a database that contains only the materials of interest to the client: metals, polymers and polymer-matrix composites. • Graph stage : make a Graph with Yield strength on the y-axis and Sodium hydroxide (60%) on the x- axis. • Label the materials by clicking on the bars. Where the name is too long or for some other reason you want to edit it, click twice, slowly , on the label. When it turns blue you can edit it. To reformat the color, type face or size, right-click on the label and select Format at the bottom of the menu that appears. It lets you change the font and its size and color. • Add a title by clicking on the A in the tool bar above the chart. • Open the Environmental Notes for Sodium Hydroxide (60%) The resulting chart, shown below, provide an overview at the CES Level 2 of strength of materials and their durability in strong NaOH of materials. The Notes, also shown, give further information about where the environment is encountered and the materials that are most resistant to it.

Figure 4. A chart made with the CES EduPack Level 2 with durability properties, surveying the durability of chosen material classes in NaOH.

Sodium hydroxide (60%) (caustic soda), NaOH

Where found. Sodium hydroxide of this concentration is found in drain cleaners as a 50% solution, is used to produce alumina, paper and bio diesel, and is used to clean and etch aluminum.

Industrial sectors. Chemical engineering, domestic, petroleum, engineering manufacture.

The problem. The strong alkalis NaOH, KOH (potassium hydroxide), and NH 4OH (ammonium hydroxide) are all corrosive and toxic. Vapors are dangerous.

Preferred materials and coatings.

Metals Polymers and composites Ceramics and glasses

Nickel and its alloys PVC Glass Stainless steels LDPE Graphite HDPE PTFE (PE-CTFE)

Underlying mechanisms. Basic attack ; stress corrosion cracking .

Figure 5. The Environmental notes for Sodium hydroxide (60%)

10 5. References

ASM (2008) “Handbooks on line”, Vol 13a, b, c, ASM International, Metal s Park, Ohio, USA. Bradford, S.A. (1993) “Corrosion control”, Van Nostrand Reinhold, New York, NY, USA. ISBN 0-442-01088- 5. (Excellent introduction to the practical side of corrosion control with tables of materials to withstand a range of environments.) CORROSION DATA for Brass, Carbon Steel, 316 Stainless Steel and coatings. www.lancevalves.com/pdfs/corrosiondata.pdf Copper Development Association (2008) Corrosion data for bronze, copper, brass, copper-nickel and gun metals http://www.hghouston.com/coppers/corrosion_cu.html DECHEMA Corrosion Handbook (2004) Corrosive Agents and their Interaction with Materials : Methanol. alkanols. acetic acid, acetates, sodium hydroxide, formic acid, alkaline earth chlorides, aliphatic amines. Elsevier, Oxford, UK. ISBN: 0-444-50833-3. ( The DECHEMA Corrosion Handbook is an English- language compendium of corrosion data based on the DECHEMA-WERKSTOFF-TABELLE) DeRenzo, D.J. (1985) “Corrosion resistant materials handbook”, 4 th edition, William Andrew Publishing/Noyes. ISBN 978-0-8155-1023-9 ( A handbook of commercially available corrosion resistant materials for a specific environments). Fontana, M.G. (1986) “Corrosion engineering” McGraw Hill, St. Louis, USA. ISBN 0-07-021463-8. Fluoropolymer Chemical Resistant Charts (2008) http://www.texloc.com/closet/cl_chemical_resistance_chart.html Fontana, M.G. and Greene, N.D. (1967) “Corrosion engineering” McGraw Hill, St. Louis, USA. Library of Congress Number 67-19901. NACE (1983) “Corrosion Guide”, 2nd Edition edited by K. M. Pruett, Compass Publications. (An e xtensive tables and guidelines for the oxidation and corrosion characteristics of metals and polymers.) Nibco (2008) “Chemical resistance guide for plastic and metal valves and fittings”, www.nibco.com ProFlow Dynamics chemical resistance selector (2008) http://www.proflowdynamics.com/viewcorrosion.aspx Rabold, E. (1968) “Corrosion guide”, 2 nd edition, Elsevier, Amsterdam, Holland. Library of Congress No. 67- 19853. Schweitzer, P.A. (1983), editor, Corrosion and corrosion protection handbook”, Marcel Dekker, NY, USA. ISBN 0-8247-1705-8. Schweitzer, P.A. (1998) “Encyclopaedia of corrosion technology”, Marcel Dekker, New York, USA. ISBN 0- 8247-0137-2. (A curious compilation, organized alphabetically, that mixes definitions and terminology with tables of data.) Schweitzer, P.A.(2004) “Corrosion resistance tables”, 5 th edition, Marcel Dekker, NY, USA. ISBN 0-8247- 5673-8, 5674-6, 5675-4 and 5676-2. (A four-volume compilation of tables of of the corrosion resistance of a limited set of polymers, metals and non-metals in some 800 different industrial fluids and chemicals.) Speller, F.N. (1951) “Corrosion causes and prevention”, 3 rd edition, MeGraw Hill, New York, NY, USA. (p157 et seq). Tretheway, K.R. and Chamberlain, J. (1995) “Corrosion for science and engineering” 2 nd edition, Longman Scientific and Technical, Harlow, UK. ISBN 0-582-238692 . (An unusually readable introduction to Corrosion Science, filled with little bench-top experiments to illustrate principles.) Uhlig, H.H. (1948) “The corrosion handbook”, Wiley and Sons, New York, NY, USA. (A vast compendium of corrosion information, ordered by material, the life’s work of one of the fathers of the field, but now, inevitably, rather dated.) Waterman, N.A. and Ashby, M.F. (1991) “Elsevier Materials Selector”, Elsevier, Oxford, UK. ISBN 1-85-166- 605-2 and, in the CRC edition, ISBN 0-8493-7790-0. (A 3-volume compilation of materials data for design,

11 Appendix A. Software for durability selection.

Most texts and existing software systems focus on the materials and environments that are associated with a particular industrial sector (the oil industry, food processing, aerospace...). Few attempt a broader sweep, as we do here, seeking to cover a many materials and sectors. Existing software for corrosion selection is listed in Table 1. The first two come closest to the methods we develop here. Those that were accessible are reviewed on the next page..

Table A1. Software for corrosion information and selection.

Company Software Web address DeZurik Materials Selection Guide http://www.dezurik.com/ ProFlow Dynamics Corrosion Database http://www.proflowdynamics.com/ViewCorrosion.aspx Corrosion Source Predict http://www.corrosionsource.com/software/predict.htm Corrosion Source Online Corrosion Problem http://www.corrosionsource.com/handbook/CPS/#type Solver enpICDA Internal Pipeline http://www.enpicda.com/demo/index.php?page=main Corrosion Predictor IMOA - http://www.imoa3.webinfoserver.com/flash.html NORSOK Standard http://www.standard.no/pronorm-3/data/f/0/10/40/5_10704_0/M-506.pdf The Nickel Institute Crevice corrosion guide http://www.nickelinstitute.org/index.cfm/ci_id/10646.htm for stainless steels Argentum Solutions ThermExpert http://www.argentumsolutions.com/thermexpert_intro.html MESA Products CP Design Centre http://www.cpdesigncenter.com/private/private_index.html Inc. - Stainless Steels - Material http://www.sci.fi/~benefon/Metallurgy.php Properties Online Ashcroft Corrosion Guide - InterCorr Socrates http://intercorr.com/software/socrates/soc.html Honeywell Strategy http://hpsweb.honeywell.com/Cultures/en- US/Products/AssetApplications/corrosion/StrategySoftware/default.htm CC Technologies CorLAS http://www.cctechnologies.com/products/software/corlas/index.htm Acet Asset Condition http://www.acet.co.uk/ Evaluation Tool Elsyca Cat Pro http://www.elsyca.com/CorrosionProtectionACMitigation/Technology/Ca tPro/tabid/3763/Default.aspx Technical RSTRENG http://www.ttoolboxes.com/products/rstreng.htm Toolboxes NACE Online NACE corrosion http://www.knovel.com/web/portal/basic_search/display?_EXT_KNOVE database L_DISPLAY_bookid=532

12 Brief reviews of readily accessible software tools for Durability.

DeZurik Materials Selection Guide Purpose: Dezurik MSG is used in a range of industries to select materials appropriate for a given environment. Ease of use Quite easy, although the layout is not perfect, and a large proportion of data is missing. Industry coverage: All Environment coverage A wide range of environments. Materials: Cast Iron, Ni-Resist, Carbon Steel, 304 SS, 316 SS, 317 SS, Duplex, Alloy 20, Monel, Nickel, Hastelloy B, Hastelloy C, Titanium, Bronze, Acid-Bronze, Aluminium.

ProFlow Dynamic Corrosion Database Purpose: A free online database for finding a material suitable for use in specified environments. Ease of use Excellent. Select environment and performance needed, and click submit. Very fast. Industry coverage: All. Environment coverage: Very wide range. Materials: Alloy 20, Aluminium, Brass, Buna N, Carbon Steel, Carpenter Custom, Delrin, Ductile Iron, EPDM, Grafoil, Hastelloy C, Hypalon, Monel, Neoprene, Nylon, PTFE, SS316, Viton.

IMOA Stainless Steel Selector Purpose: Flash program using a scoring system to select stainless steels for use in an open air environment Ease of use: Very easy to use, simply select the conditions relevant to the purpose. Industry coverage: Building. Environment coverage: Very limited, open air environments only. Materials: Stainless Steels

Predict 2.0 Purpose: Predict is used to find the corrosion rate of a material in a given environment. Ease of use Confusing at first, can be made to work quite well with experience. Industry coverage: Intended for any industry using stainless steels. Environment coverage: User defined concentrations of common corrosive agents. Materials: Unclear, though it seems to be some form of steel (composition not given).

Knovel Online Corrosion Database Purpose: Online database containing corrosion compatibility data for a wide range of materials and environments. Ease of use Unknown. Industry coverage: All. Environment coverage: Very wide range. Materials: Very wide range.

Socrates 8.0 Purpose: Socrates screen a material database using the environment, the application and certain required mechanical characteristics. Ease of use Simple, but need a good estimation of environment composition. Industry coverage: The oil industry, specifically tubing, liners, wellheads, subsurface equipment, flow lines and specialty equipment. Environment coverage: User defined partial pressures of common corrosive agents. Materials: Wide range of stainless steels and Ni-based alloys; Alpha, Beta and Alpha-Beta Titanium; Cobalt- based alloys; Zirconium.

13 Appendix B. Examples of the content of CES EduPack dealing with Durability

Table B1. Commonly encountered liquid environments*

Environment Where encountered Water and aqueous solutions

Water (fresh) Fresh water is ubiquitous: any object: exposure to high humidity, rain or washing acquires a film of water containing (unless distilled) dissolved oxygen and, usually, other impurities. Water (salt) Materials in marine environments are exposed to salt water and wind-carried spray. Seawater varies in composition depending on the location It is typically 3.5%. Soils Soils differ greatly in composition, moisture content and pH. The single most important property of a soil that determines its corrosive behaviour is its electrical resistivity – a low resistivity means that the water in the soil has high concentration of dissolved ions. A resistivity below 10 9 µohm.cm is very corrosive; one with a resistivity above 2 x 10 10 µohm.cm is only slightly corrosive. The choice of material for use in soil depends on this and on the pH. Acidic (peaty) soils have a low pH, alkali soils (those containing clay or chalk) have a high one. Body fluids Body fluids include blood, urine, saliva sweat and gastric fluids. All are water-based with high ion-content, some acidic, stimulating electro-chemical and acid attack. Acids and alkalis

Acetic acid, CH 3COOH Acetic acid is an organic acid made by the oxidation of ethanol. It is used in the production of plastics, dyes, insecticides and other chemicals. Dilute acetic acid (vinegar) is used in cooking. Hydrochloric acid, HCl Hydrochloric acid is used as a chemical intermediate, for ore reduction, for pickling steel, in acidizing oil wells and in other industrial processes. In dilute form it is a component of household cleaners. Hydrofluoric acid, HF Hydrofluoric acid is used for the etching of glass, synthesis of fluorocarbon polymers, aluminum refining, as an etchant for silicon-based semi-conductors and to make UF 6 for uranium isotope separation.

Nitric acid HNO 3 Nitric acid is used in the production of fertilizers, dyes, drugs and explosives.

Sulphuric acid, H 2SO 4 Sulfuric acid, of central importance in chemical engineering, is used in making fertilizers, chemicals, paints and in petrol refining. It is a component of acid rain. Sodium hydroxide, NaOH Sodium hydroxide of this concentration is found in some household cleaners, the making of soap and in the cleaning in food processing. Fuels, oils and solvents

Benzene, C 6H6 Benzene is used as an industrial solvent, as well as in the synthesis of plastics, rubbers, dyes and certain drugs. It is also found in tobacco smoke.

Carbon tetrachloride, CCl 4 Carbon tetrachloride is used principally to manufacture refrigerants, as a dry- cleaning solvent and as a pesticide (now banned in the US). Crude oil Refined petroleum is not corrosive to metals, but crude oil usually contains saline water, sulfur compounds and other impurities, some acidic. Diesel oil Diesel oil is a specific fractional distillate of crude oil. It is the primary fuel for truck, shipping and non-electric and diesel-electric rail transport. Its use for car propulsion is increasing. Diesel oil acts both as fuel and as lubricant in the engine. Kerosene (paraffin oil) Paraffin is used as aviation fuel, as well as being commonly used for heating and lighting on a domestic level. It is used to store highly reactive metals to isolate them from oxygen. Lubricating oil Oil is used as a lubricant in most metal systems with moving parts. Typically, these are mineral oils, and frequently contain sulfur. Low sulfur synthetic oils can also be produced. Lubricating oil is less corrosive than petroleum and diesel oil because it is base on hydrocarbons with higher molecular weight. Petroleum (gasoline) Petroleum is a volatile distillate of crude oil. It is used mainly to power engines, for cars, light aircraft and agricultural equipment. It often contains additives such as lead, ethanol or dyes.

Silicone fluid, ((CH 3)2SiO) n Silicone oils are synthetic silicon-based polymers. They are exceptionally stable and inert. They are used as brake and hydraulic fluids, vacuum pump oils, and as lubricants for metals and for textile threads during sewing and weaving of fabrics.

14 Vegetable oil Vegetable oils are derived from olive, peanut, maize, sunflower, rape and other seed and nut crops. They are widely used in the preparation of foods. They are the basis of bio-fuels. Alcohols, aldehydes, ketones Acetone is the simplest of keytones. It is widely used as a degreasing agent and a

Acetone, CH 3COCH 3 solvent, and as a thinning agent for polyester resins and other synthetic paints (commonly nail varnish), a cleaning agent and as an additive in automobile fuels. It is used in the manufacture of plastics, drugs, fibers and other chemicals.

Ethyl alcohol, C 2H5OH Ethanol is made by fermentation, and thus in alcoholic beverages. It is used medically as a solvent for disinfectants and for cleaning wounds before dressing them. It is used industrially as a solvent, a dehydrating agent and as a “green” fuel for cars.

Methyl alcohol, CH 3OH Methanol is used in glass cleaners, stains, dyes, inks, antifreeze, solvents, fuel additives and as an extractant for oil. It is also used as a high-energy fuel for cars, aircraft and rockets, and is a possible fuel for fuel cells.

Formaldehyde, CH 2O Formaldehyde is used as a disinfectant in medical applications. It is used industrially to make many resins (including melamine resin and phenol formaldehyde resin) and glues, including those used in plywood. It is found in car exhausts and tobacco smoke. It is the basis of embalming fluids.

15 Table B2. Corrosion inhibitors and the materials for which they work

Environment Inhibitors (materials) Water and aqueous solutions

Water (fresh) Calcium bicarbonate (Steel, Cast Iron), polyphosphate (Cu, Zn, Al, Fe), calcium hydroxide (Cu, Zn, Fe), sodium silicate (Cu, Zn, Fe), sodium chromate (Cu, Zn, Pb, Fe), potassium dichromate (Mg), sodium nitrite (Monel), benzoic acid (Fe), calcium and zinc metaphosphates (Zn). Water (salt) Sodium nitrite (Fe), sodium silicate (Zn), calcium bicarbonate (all metals), amyl stearate (Al), methyl-substituted dithiocarbamates (Fe) Soils Calcium nitrate is added to concrete to inhibit corrosion of steel reinforcement in soils. Acids and alkalis

Acetic acid, CH 3COOH (10%) Thiourea, arsenic oxide, sodium arsenate (all for Fe). Hydrochloric acid, HCl (10%) Ethylaniline, mercaptobenzotriazole, pyridine and phenylhydrazine, ethylene oxide (all used for Fe), phenylacridine (Al), napthoquinone (Al), thiourea (Al), chromic acid (Ti), copper sulphate (Ti). Hydrofluoric acid, HF (40%) Thiourea, arsenic oxide, sodium arsenate (all for Fe)

Nitric acid HNO 3 (10%) Thiourea, arsenic oxide, sodium arsenate (all for Fe), hexamethylene tetramine (Al), alkali chromate (Al)

Sulphuric acid, H 2SO 4 (10%) Phenylacridine (Fe), sodium chromate (Al), benzyl thiocyanate (Cu and Brass), hydrated calcium sulphate (Fe), aromatic amines (Fe), chromic acid (Ti), copper sulphate (Ti) Sodium hydroxide, NaOH (10%) Alkali silicates, potassium permanganate, glucose (all for Al) Fuels, oils and solvents

Benzene, C 6H6 Anthraquinone (Cu and Brass)

Carbon tetrachloride, CCl 4 Formamide (Al), aniline (Fe, Sn, Brass, Monel and Pb), mesityl oxide (Sn) Diesel oil PTFE suspension (all metals), chlorinated hydrocarbons (all metals), poly- hydroxybenzophenone (Cu) Kerosene (paraffin oil) PTFE suspension (all metals), chlorinated hydrocarbons (all metals), poly- hydroxybenzophenone (Cu) Lubricating oil PTFE suspension (all metals), chlorinated hydrocarbons organozinc compound selected such as zinc dithiophosphate and zinc dithiocarbamate.(all metals), poly-hydroxybenzophenone (Cu) Petroleum (gasoline) PTFE suspension (all metals), chlorinated hydrocarbons (all metals) Vegetable oil Anthraquinone (Cu and Brass) Alcohols, aldehydes, ketones

Ethyl alcohol, C 2H5OH Potassium dichromate, alkali carbonates or lactates (Al), benzoic acid (Cu and Brass), alkaline metal sulphides (Mg), ethylamine (Fe), ammonium carbonate with ammonium hydroxide (Fe)

Methyl alcohol, CH 3OH Sodium chlorate with sodium nitrate (Al), alkaline metal sulphides (Mg), neutralised stearic acid (Mg), Polyvinylimidazole (Cu).

16 Table B3 Corrosion-resistance ranking of materials in common environments

Environmen t Aqueous Acids and alkalis Fuels, oils and solvents Alcohols and environments aldehydes

Methyl Alcohol(methanol) Sodium HydroxideSodium (10%) HydroxideSodium (60%) Hydrochloric (10%)Acid

HydrofluoricAcid (40%) ParaffinOil (Kerosene) Ethyl Alcohol(ethanol) CarbonTetrachloride

Formaldehyde(40%) Petroleum(gasoline) Soils, alkaline Soils, (clay)

Sulfuric (10%)Acid

acidic Soils, (peat) AceticAcid (10%) Nitric(10%)Acid VegetableOils SiliconeFluids LubricatingOil Water(fresh) Water(salt) Diesel OilDiesel Benzene

Acetone

Material

Metals Ferrous Cast iron B C B B C D D D B A B A A A A A A A A A B A B High carbon steel B C B B C D D D D B B A A A A A A A A A B A B Medium carbon steel B C B B C D D D D B B A A A A A A A A A B A B Low carbon steel B C B B C D D D D B B A A A A A A A A A B A B Low alloy steel B C B B C D D D D B B A A A A A A A A A B A B Stainless Steel A A A A A A C A B A A B A A A A A B A A A A A Non-ferrous Aluminum alloys A B D A C C D C D D D A A A A A A A A A A A C Copper alloys A A A A C C D B C A A A A A A A A A A A A A A Lead alloys A A A A B C D B B B D A A A A A A A A A A A A Magnesium alloys A C C C C D D D D B B A A A A A A A A A A A A Nickel alloys A A A A A B D B B B B A A A A A A A A A A A A Titanium alloys A A A A A A A A B A A A A A A A A A A A A A A Zinc alloys A B B A C D D D C C C A A A A A A A A A A A A Ceramics Glasses Borosilicate glass A A A A A A D A A A B A A A A A A A A A A A A and glasses Glass ceramic A A A A A A D A A A A A A A A A A A A A A A A Silica glass A A A A A A D A A A A A A A A A A A A A A A A Porous Soda-lime glass A A A A A A D A A A B A A A A A A A A A A A A Brick A A A A A A D A A A A A A A A A A A A A A A A Concrete A A A A B B D B B A A A A A A A A A A A A A A Stone A A A A C C D C C A A A A A A A A A A A A A A Technical Alumina A A A A A A D A A A A A A A A A A A A A A A A Aluminum nitride A A A A A A D A A A A A A A A A A A A A A A A Boron carbide A A A A A A D A A A A A A A A A A A A A A A A Silicon A A A A A A D A A A A A A A A A A A A A A A A Silicon carbide A A A A A A D A A A A A A A A A A A A A A A A Silicon nitride A A A A A A D A A A A A A A A A A A A A A A A Tungsten carbides A A A A A A D A A A A A A A A A A A A A A A A Zirconia A A A A A A D A A A A A A A A A A A A A A A A Composites Al / SiC composite A B D A C B D C D D D A A A A A A A A A A A A CFRP A A C C C A D C A C A B A A A A A A A D C A D GFRP A A C C C A D C A C A B A A A A A A A D C A D

17 Table B3 (continued). Corrosion-resistance ranking of materials in common environments

Environment Aqueous Acids and alkalis Fuels, oils and solvents Alcohols and environments aldehydes

Methyl Alcohol(methanol) Sodium HydroxideSodium (10%) HydroxideSodium (60%) Hydrochloric (10%)Acid

HydrofluoricAcid (40%) ParaffinOil (Kerosene) Ethyl Alcohol(ethanol) CarbonTetrachloride

Formaldehyde(40%) Petroleum(gasoline) Soils, alkaline Soils, (clay) Sulfuric (10%)Acid

acidic Soils, (peat) AceticAcid (10%) Nitric(10%)Acid VegetableOils SiliconeFluids LubricatingOil Water(fresh)

Water(salt) Diesel OilDiesel Benzene

Acetone

Material

Natural Woods and Bamboo B B B C B B D B B D D B B B B B B B B B B B B materials paper Cork A B C C B B D B B D D B B B B B B B B B B B B Leather B C D D C C D C C D D C C C C C B B B C B B B Paper and cardboard D D D D D D D D D D D B B B B B B B B B B B B Wood B B B C B B D B B D D B B B B B B B B B B B B Polymers Elastomers Butyl Rubber B B B C B C C C B C C D D D D D C B D B B C B EVA B B D A D D D D D A C D D B A B C A D D D B D Isoprene Rubber (IR) A A A A A A A A A A A D D D D D D A C A A A A Natural Rubber (NR) A A A A A C C C A A C D D D D D D A D A A A A Neoprene, CR A A A A A A A C A A A D D C A B D A A A A C A Polyurethane (elPU) A A D C D C D C C C D D D C C A B A A D D D D Silicone elastomers (SI) A A A A A C D C C A A D D D D D D C C C A C A Thermo- ABS A A A A A A C A A A A D D A A A A A A D D A D plastics Cellulose polymers (CA) A A D D D A D D D D D A A A A A A A B D C D D Ionomer (I) A A A A A A A A A A A C D A C B B B B A C C C Nylons (PA) B B B C B D D D D C C A A B B A A B B A A A A Polycarbonate (PC) A A A A A A A A A A C D A C A A A A A D A A A Polyetheretherketone (PEEK) A A A A A A D A A A A A A A A A A A A A A A A Polyethylene (PE) A A A A A A A A A A A B B A A A A B A B A A A PET A A B C B A C A A C D A A A A A A B A C A A A Acrylic (PMMA) A A A A A A D A D A A D C A A B A C A D C A D Acetal (POM) A A A A A C D C D A A A A A A A A C A C A A A Polypropylene (PP) A A A A A A A A A A A C C A A A A A B A A A A Polystyrene (PS) A A A A A A D B A A A D A C C A C A C D A C B Teflon ( PTFE) A A A A A A A A A A A A A A A A A A A A A A A Polyurethane (tpPUR) A B C A C C D D B A D D D C C B B C A D D D D Polyvinylchloride (tpPVC) A A A A A A B D A A A C A B A A A B B C A A A Thermo- Epoxies A A C C C A D C A C A B A A A A A A A D C A D sets Phenolics A A A D A A D A A D D A A A A A A B A A A A A Polyester A A C D C A D A A D D D A A A A A A B D D A A

18 Table B4. Preferred materials and coatings for given environments

Environment Metals Polymers and composites Ceramics and glasses Water and aqueous solutions

Water (fresh) Aluminum alloys, Stainless steels, Galvanized PET, HDPE, GFRP. All polymers are Glass, Concrete, Brick, Porcelain steel, Copper alloys. corrosion free in fresh water, though some absorb up to 5%, causing swelling. Water (salt) Copper, Bronze, Stainless steels, Galvanised PET, HDPE, GFRP. All polymers are corrosion Glass, Concrete, Brick steels, Lead, (Platinum, Gold, Silver) free in salt water, though some absorb up to 5%, causing swelling. Soils Steel, bare in high-resistivity soil, coated or HDPE, PP, PVC, Most polymers (except PHB, Brick, Pottery, Glass, Concrete with galvanic protection in those with low PLA and those that are bio-degradable) resistivity. corrode only slowly in soil. Body fluids Cobalt-chromium alloys, Nickel-titanium Acrylic, Silicone, Ultra high mol. wt. Hydroxyapatite, Alumina bio-ceramic, alloys (Nitinols), Nickel-chromium alloys, polyethylene (UHMWPE) Bioglass ceramic, Calcium phosphate bio- ceramic, Glass-ionomer, Vitreous carbon, Precious metals implants, Silver amalgam, Zirconia bio-ceramic Stainless steel, Titanium, Gold, Platinum Acids and alkalis

Acetic acid, CH 3COOH (10%) Aluminum, Stainless steel, Nickel and nickel HDPE, PTFE Glass, Porcelain, Graphite alloys, Titanium, Monel Hydrochloric acid, HCl (10%) Copper, Nickel and nickel alloys, Titanium, HDPE, PP, GFRP, Rubber Glass Monel, Molybdenum, Tantalum, Zirconium, (Platinum, Gold, Silver) Hydrofluoric acid, HF (40%) Lead, Copper, Stainless Steel PTFE, Fluorocarbon polymers, Rubber Graphite Carbon Steels, Monel, Hastelloy C, (Platinum, Gold, Silver)

Nitric acid HNO 3 (10%) Stainless steel, Titanium, 14.5% Silicon cast PTFE, PVC, Phenolics, PE-CTFE Glass, Graphite iron, Alloy 20 (40Fe, 35Ni, 20Cr, 4Cu))

Sulphuric acid, H 2SO 4 (10%) Stainless steel, Copper, Nickel based alloys, PET, PTFE, PE-CTFE, Phenolics Glass, Graphite Lead, Tungsten, 14.5% Silicon cast iron, Zirconium, Tantalum, Alloy 20 (40Fe, 35Ni, 20Cr, 4Cu), (Platinum, Gold, Silver) Sodium hydroxide, NaOH (10%) Nickel and its alloys, Stainless steels, PVC, LDPE, HDPE, PTFE, PE-CTFE Glass, Graphite Magnesium

19 Table B4. (continued) Preferred materials and coatings for given environments

Environment Metals Polymers and composites Ceramics and glasses Fuels, oils and solvents

Benzene, C 6H6 Carbon steel, Stainless steel, Aluminum, Brass PTFE Glass, Graphite

Carbon tetrachloride, CCl 4 Carbon steel, Stainless steel, Aluminum, POM, PTFE, Rubber Glass, Graphite Hastelloy C, Monel, (Platinum, Gold, Silver) Crude oil Carbon steel, Aluminum, Stainless steels HDPE, PTFE, Epoxies, Polyimides Glass, Porcelain, Enamelled metal

Diesel oil Carbon steel, Stainless steel, Brass, Copper, HDPE, PP, PTFE, Buna (nitrile) rubber, Viton, Glass Aluminum, Monel GFRP Kerosene (paraffin oil) Carbon steel, Stainless steel, Aluminum, HDPE, PP, PTFE, GFRP Glass Monel Lubricating oil Stainless steel, Carbon steel, Aluminum HDPE, PP, PTFE, Rubber Glass Petroleum (gasoline) Carbon steel, Stainless steel, Brass, PTFE, HDPE, PP, Buna (nitrile) rubber, Glass Aluminum, Hastelloy C, Alloy 20 (40Fe, Viton,GFRP 35Ni, 20Cr, 4Cu))

Silicone fluid, ((CH 3)2SiO) n Carbon steel, Aluminum HDPE, PP, PET Glass

Vegetable oil Aluminum, Carbon steel, Stainless steel HDPE, PP, PET Glass Alcohols, aldehydes, ketones

Acetone, CH 3COCH 3 Aluminum, Carbon steel, Stainless steel PTFE, HDPE, PP copolymer (PPCO) Glass, Graphite

Ethyl alcohol, C 2H5OH Steel, Stainless steel, Copper PTFE, HDPE, PP, GFRP Glass

Methyl alcohol, CH 3OH Steel, Stainless steel, Lead, Monel PTFE , HDPE, PP Glass

Formaldehyde, CH 2O Stainless steel, Monel, Hastelloy C PTFE, HDPE, PET, POM, Nitrile or butyl Glass, GFRP rubber