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The choice of materials is numerous for many applications, although as the working environment becomes more aggressive, i.e. at extreme temperatures, the choice of suitable materials becomes more limited. Materials selection for process plant is important due to the variety of environments found. This document contains information about materials suitable for the various environments encountered in the process industry, highlighting some of the environments where these materials can be used, and those where they should not be used. A short list of relevant standards is also included with some of the sections. There are few generalisations to be made about the resistance of materials to chemicals, such as are found in processing plants. The number of chemicals that may be found are very large and the conditions of use, temperature, concentration, fluid velocity, degree of aeration, purity, stress state, etc. can differ from one application of the same material to another. Unfortunately, the science of corrosion is not yet able to predict the behaviour of a system solely on the basis of fundamental relationships, and although a vast amount of empirical data is available, it is not complete and may not be readily accessible [1].

Generally material properties are split into the mechanical properties and other properties. The mechanical properties are related to the behaviour of the material under all loading conditions. These include tensile strength, yield strength, stress-rupture strength, creep strength and toughness. These properties are important when designing pressure retaining vessels. Other properties include the corrosion resistance, thermal, electrical and magnetic properties. The resistance to atomic radiation can also be important in some cases. A list of the expected ranges of some of properties for materials used for process equipment is shown in Table 1 [2]. Stress rupture properties are important as rupture strengths for steels can fall significantly, e.g. from 450 MPa to 60 MPa over a temperature increase of less than 200C, as the operating temperature is increased above 400C.

Tables 2-5 contain information regarding the selection of materials for different corrosive environments and components. Further information on the use of different materials can be found later in this document. Table 2 shows the best combination of metal and corrosive that usually represent the best corrosion resistance for the least amount of money [3]. Table 3. lists some of the environments that may cause stress corrosion of metals that are used in the process industry [3]. Further information on environments that can cause unwanted forms of

corrosion in these materials are shown in Table 4 [3]. Advice should be sought for resistance specific alloys as this table represents a summary of all data and takes no account of the different heat treatments or impurity levels of the metals. Table 5 shows the materials that are generally recommended for pump components [4]. This table lists the low cost, preferred and maximum life options.

One other important factor to consider is the cost of the material and its processing into the finished item. Some of the more corrosion resistant materials such as stainless steels and titanium can be expensive to produce, due to the chemical content, or difficult to fabricate, i.e. weld, cut, form and grind. In these cases an alternative is to use a less resistant material with allowance for the greater corrosion, or one that has been lined or coated with other materials which will improve its resistance while maintaining structural strength.

Fabrication of materials can lead to significant differences during in-service performance. The chemical composition of wrought and cast alloys can be different, leading to a reduction in the corrosion resistance. Cast alloys generally have lower material properties than their wrought counterparts and can be more brittle. Welding of materials, e.g. stainless steels, can lead to changes in material properties and chemical compositions in the heat affected zone (HAZ), if the right procedures are not followed. This can lead severe corrosion around the HAZ.

Other effects which can affect the performance of a structure are the impurities in materials, contamination (from fabrication or working environment), velocity of fluids in working environment, bimetallic corrosion, high temperature (creep and loss of strength), low temperature (brittleness), improper use of inhibitors,

7.1 Cast Irons Useful standards: BS 1591. Many types of cast iron exist, they can be brittle or ductile, with high or low strength due to the amount of alloying. The basic cast irons are white cast iron which are extremely hard and brittle. Malleable iron which shows good ductility and ductile irons which can be altered by heat treatment to have similar mechanical properties to ordinary steel [1].

When service conditions are not especially aggressive, cast iron is widely used, as in mixers, digesters, pump bodies, etc., and it has some advantage over stainless steel for salt or caustic soda evaporating pans as it is not subject to stress corrosion cracking. The corrosion rate of cast iron in dilute caustic solutions, below 30% concentration, is negligible. Above this level, the addition of 1-3% nickel is said to be beneficial in controlling the rate of attack. Nevertheless, cast iron is used for caustic fusion pots where the thick walls compensate for the initial high corrosion rate which falls to acceptable levels after a few days [1, 3]. Grey cast irons, typically 2-4% C and 1-3% Si, cheap easily cast into intricate shapes, can be alloyed to improve corrosion resistance and strength [1]. The high nickel austenitic cast irons containing up to 35% Ni (BS 3468 : 1962) are substantially more resistant to attack by both dilute sulphuric acid and caustic soda than standard ferritic irons, and this is typical of a wide range of aggressive situations [1]. The high chromium cast irons (and similarly the high chromium steels) are more useful in environments containing plenty of oxygen or oxidising agents. They are not so good in solutions containing those anions which can penetrate the protective film, such as halides, and do not offer resistance to hydrochloric or sulphuric acids under most conditions. They have some advantage with dilute nitric acid. Their main attraction, however, lies in the resistance to high temperature corrosion, which enables use for furnace parts, heat exchangers, etc. [1]. High silicon cast irons, > 14% Si have better corrosion resistance than most cast irons, although they are susceptible to hydrofluoric acid, hydrochloric, hydrobromic, sulphurous acids and halogen acids. Other conditions which produce halogenic anions may also be corrosive. Good service is given in nitric and sulphuric acids and in mixtures of the two. The silicon irons are not recommended for alkalis. Addition of 3% Mo to these cast irons leads to increased resistance to hydrochloric acid, chlorides and pitting. Welding of these cast irons can be difficult and is not practical with complex shapes [1]. Ni-Resist are the toughest of the cast irons, with high nickel (14-32%) and chromium (1.75-5.5%) contents, also with and without copper (up to 7%). Tensile strengths typically 170-310 MPa [1]. Ni-Hard is a white cast iron (~4% Ni and 2% Cr) is a very hard cast iron which has found wide application where erosion-corrosion resistance is needed in near-neutral and alkaline solutions or slurries [1]. 7.2 Low-Carbon Steels Useful standards: BS 1501, BS 1503, BS 3603, BS 10213, BS EN 10028, BS PD 6525. Despite its relatively poor resistance to corrosion, low-carbon steel is the most widely used material for chemical plant operating up to temperatures of

400C. Where corrosive attack is unacceptably severe, either in terms of the life of the plant or because of adulteration of the product by iron salts produced, then the move will be made to more highly alloyed systems as described, or to low carbon structures with specifically selected linings, particularly when strength dictates a heavy section [1]. 7.3 Low Alloy Steels Useful standards: BS 1501, BS 1503, BS 3146, BS EN 10028, BS PD 6525 Carbon steel is alloyed, singly or in combination, with chromium, nickel, copper, molybdenum, phosphorus, and vanadium in the range of a few percent or less to produce low-alloy steels. The higher alloy additions are usually for better mechanical properties and hardenability. The lower range of about 2% total maximum is of greater interest from the corrosion standpoint. Strengths are appreciably higher than plain carbon steel [1]. 7.4 Stainless Steels Useful standards: BS 1501, BS 1503, BS 3604, BS 3605, BS PD 6525 Stainless steels may be defined as alloy steels containing at least 10% Cr with or without other elements. It has been customary in the USA to include with stainless steels those alloys that contain as little as 4% Cr. Together, these steels are form a family known as stainless and heat resisting steels. Few of these alloys contain more than 30% Cr or less than 50% iron (Fe) [5]. Stainless steels are categorised by many different methods, the main groups are, ferritic, martensitic, austenitic, duplex and precipitation hardening stainless steels. These groups may be split into subdivisions and also can be listed as standard and non-standard steel grades, Table 6. The five main groups are generally defined by the parameters shown in Table 6. In general performance is improved with higher chromium and nickel contents, lower carbon content and by the presence of molybdenum. Useful service can be obtained in sulphuric acid, particularly under conditions of plentiful oxygen supply or small additions of an oxidant, e.g. CuSO 4 or HNO3. Hydrochloric acid is more aggressive to stainless steels and use is restricted to dilute systems and austenitic stainless steels are used extensively in nitric acid plant [1]. Type 430 ferritic stainless steel is used in ammonia oxidation plants for making and storing nitric acid. Types 442 and 446 find application where heat resistance is required such as furnace parts and heat-treating equipment. They possess good resistance to high-temperature oxidation and sulphur gas attack because of their high chromium content. These materials do not possess good structural stability or high-temperature strength and should be selected with care. Ferritic stainless steels have good resistance to stress corrosion, particularly in chloride containing waters [1]. Austenitic stainless steels generally have better corrosion resistance than

ferritic and martensitic stainless steels. These steels are susceptible to stress corrosion cracking particularly in chloride environments. A more detailed list of these environments is shown in Table 7[3]. 7.5 Aluminium and its Alloys Aluminium is a reactive metal, but develops an aluminium oxide coating or film that protects it from corrosion in many environments. This film is quite stable in neutral and many acid solutions but is attacked by alkalis. This oxide film forms in many environments, but can artificially produced by passage of electric current, anodising. The high copper alloys are utilised mainly for structural purposes. The copper free or low copper alloys are used mainly in the process industries where better corrosion resistance is required. Aluminium alloys lose strength rapidly when exposed to temperatures of 175C and higher. Aluminium shows excellent mechanical properties at cryogenic temperatures [3]. The wrought Al-Mg alloys (5xxx series) are used for pressure vessels for cryogenic temperatures, as well as having high corrosion resistance to chloride solutions. The miscellaneous Al alloys (8xxx series) have good resistance to water at high temperature and pressure [6]. 7.6 Magnesium Alloys Magnesium alloys are susceptible to stress corrosion, erosion corrosion and attacked by most acids except chromic and hydrofluoric. Greater resistance than aluminium alloys to alkalis. 7.7 Lead and its Alloys Useful standards: BS 334, BS 6582. Lead alloys are susceptible to erosion corrosion and are generally used for lining steel in process equipment. Chemical lead (containing 0.06% copper) is used and is resistant to sulphuric, chromic, hydrofluoric, and phosphoric acids; neutral solutions and seawater. Rapidly attacked by acetic acid and generally not used in nitric, hydrochloric, and organic acids. Tensile strength 16 MPa at room temperature, rapidly drops at increasing temperature. 7.8 Titanium Titanium is a reactive metal and depends on a protective film (TiO2) for corrosion resistance. Titanium has resistance to seawater and other chloride salt solutions, hypochlorites and wet chlorine, nitric acid including fuming acids. Salts such as FeCl3 and CuCl2 that tend to pit other metals actually inhibit corrosion of titanium. It is not resistant to relatively pure sulphuric and hydrochloric acids but does a good job when they are heavily contaminated with heavy metal ions such as ferric and cupric. Alloying with 30% Mo greatly increases resistance to hydrochloric acid. Titanium should not be used in relatively pure hydrofluoric acids or dry chlorine [3]. Titanium-lined equipment, being explosively bonded to thick steel sheet, is very resistant to corrosion in nitric acid, even at boiling point. Its performance in sulphuric and hydrochloric acids which produce hydrogen on the metal is

considerably enhanced by small amounts of oxidising agents. Titanium in contact with corroding metal, i.e. steel, absorbs hydrogen and becomes brittle. Catastrophic failures of heat exchangers were reported due to contact with teflon and a plastic containing lead [3]. Titanium alloys can be susceptible to crevice corrosion, mainly at joints, seams, welds etc. The alloys also show a marked loss of strength at temperatures above 400C. Titanium alloys have higher corrosion and erosion resistance than copper [6]. 7.9 Copper and Copper Alloys Useful standards: BS 1306, BS 5624. Copper combines corrosion resistance with high electrical and heat conductivity, formability, machinability, and strength when alloyed. Not corroded by acids unless oxygen or other oxidising agents (e.g. HNO 3) are present. Copper-based alloys are resistant to neutral and slightly alkaline solutions with the exception of those containing ammonia, which cause stress corrosion and sometimes rapid general attack. In strongly reducing conditions at high temperatures (300-400C), copper alloys are often superior to stainless steels [3]. Copper and brasses (Cu Zn alloys) are subject to erosion corrosion and dezincification. The bronzes (Sn, Al, or Si additions to Cu) and aluminium brass are much better in this respect. The bronzes are stronger and harder. The cupronickels with small iron additions are also superior in erosioncorrosion resistance [3]. Copper is extensively used in water piping, valves, heat-exchanger tubes and tube sheets, stills, tanks and other vessels [1]. 7.10 Nickel and its Alloys Useful standards: BS 3146. Nickel is resistant to many corrosives and is a natural for alkaline solutions. Most tough corrosion problems involving caustic and caustic solutions are handled with nickel. Corrosion resistance of alloys to sodium hydroxide is roughly proportioned to their nickel content. Nickel generally shows good resistance to neutral and slightly acid solutions. Its is not resistant to strong oxidising solutions e.g. nitric acid and ammonia solutions. Nickel forms a good base for alloys requiring strength at high temperatures. However, nickel and its alloys are attacked and embrittled by sulphur bearing gases at elevated temperatures. Monel is a natural for hydrofluoric acid, Chlorimet and Hastelloy C are two of the most generally corrosion resistant alloys where oxidising conditions do not exist [3]. 7.11 Platinum Platinum is used as a lining due to its resistance to many oxidising environments, crucibles for chemical analytical work, combustion and reaction chambers for extremely corrosive environments at temperatures over 980C.

Contact with silica at very high temperatures embrittles the platinum. Platinum is attacked by aqua regia, hydriodic and hydrobromic acids, ferric chlorides, chlorine and bromine.

8.1 Composites Useful standards: BS 4994 : 1987, BS 6464, BS 7159. Glass reinforced plastics (GRP) is used as a piping material in process plants and as a lining for vessels. The nature of the composite allows lamination giving highest strength in a chosen plane. GRP is a poor conductor of heat and so may survive a fire where metal pipes would fail. A high coefficient of thermal expansion may cause problems where frequent temperature fluctuations are encountered. GRP are generally limited to water pipes and containers. 8.2 Glass Glass is generally used as a lining for vessels and generally has low strength, low ductility, fragile, high chemical resistance, high temperature resistance, limited resistance to rapid temperature changes. Borosilicate glass lined cast iron valves are widely used because of their good chemical resistance, particularly to acids [1]. 8.3 Plastics and Polymers Useful standards: BS 2782-830A. One of the most chemically inert polymers is PTFE (polytetrafluoroethylene), and valves are available lined with this material. It is, however, difficult to process as a lining. PTFE can withstand temperatures of about 250C, although approximately 10 times the cost of PVC. Injection moulded fluoropolymers such as PVDF (polyvinylidenefluoride), ETFE (ethylene/tetrafluoroethylene copolymer) and PFA (perfluoroalkoxy polymer). The chemical resistance of these materials approaches that of PTFE, and they are much tougher. All too rigid for diaphragm, best for this is PTFE/rubber composite [1]. PVC (polyvinylchloride) is resistant to attack in hydrochloric, sulphuric and chromic acid. It is unfortunately hard and brittle, but plasticised PVC is less useful for resistance to chemical attack [1]. Liquid crystal polymers are extremely resistant to chemical attack, they are tough and strong and operating temperatures can be as high as 190C. Fields of application have been identified in the handling of mineral acids, bases, alcohols, aromatics, hydrocarbons, esters, aldehydes, and organic acids [1]. 8.4 Rubber Useful standards: BS 5176. Rubber, as covered in its various forms by BS 5176 and ASTM D2000, has

many engineering uses and can be useful in chemical plant. Rubber withstands abrasion well, a high styrene/butadiene synthetic rubber can be used with dilute acids. The resistance to hot oil attack, allowable service temperature and overall resistance to hostile chemical environments increases through the range from natural rubber, chloroprene, neoprene, ethylene acrylic to acrylic and fluorosilicone, although in terms of chemical attack much will depend on the solvent involved. The silicone rubbers have high temperature service (~200C) but are considerably less oil resistant than the fluorosilicone. Nitrile rubbers, on the other hand, have limited service temperatures (~100C) but moderately good hot oil resistance. Bonding of rubbers to both metals and to polymers capable of withstanding short periods at 200C is readily achieved [3]. 8.5 Concrete Concrete is limited to water handling equipment or as a back-up for plastic or tiled linings. 8.6 Ceramics Useful standards: BS 7793, BS 1344-5, BS 1344-14, BS 1344-19 Ceramics are useful because they have high temperature resistance, high wear resistance and are chemically inert. Their use may be limited due to fabrication difficulties and chipping under certain conditions. Sintered silicon nitride is resistant to most chemicals, the main exceptions being hydrofluoric acid, phosphoric acid and molten caustic alkalis. Partially stabilised zirconia at fine grain size also has extremely good wear resistance, it also has a thermal expansion to steel. Zirconia is attacked by hydrofluoric acid but is otherwise generally resistant to chemicals [1]. Vitreous enamels coatings are used in protecting steel or iron in a wide range of chemical plant situations.