Construction Materials in Chemical Industry

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Construction Materials in Chemical Industry
¨ Hubert Grafen, Bayer AG, Leverkusen, Federal Republic of Germany Introduction . . . . . . . . . . . . . . Material Requirements . . . . . . . Processability and Joining . . . . . Mechanical Stability and its Dependence on Temperature . . . . . Corrosion Resistance . . . . . . . . Resistance to Wear . . . . . . . . . . Choice of Materials . . . . . . . . . Quality Assurance through Material Tests and Checking of Fabrication and Functioning . . . . . . . Properties and Applications of Materials . . . . . . . . . . . . . . . . Steels . . . . . . . . . . . . . . . . . . . Unalloyed and Low-Alloy Steels for Vessels and Pipelines . . . . . . . . . Steels with High-Temperature Strength . . . . . . . . . . . . . . . . . Heat-Resistant Steels . . . . . . . . . Steels for Low Temperatures . . . . Steels Resistant to Pressurized Hydrogen . . . . . . . . . . . . . . . . . . Stainless Steels . . . . . . . . . . . . . Technical Properties . . . . . . . . . . Chemical Properties . . . . . . . . . .

1. 2. 2.1. 2.2. 2.3. 2.4. 3. 4.

2 2 3 3 5 6 6

5.1.6.3. 5.2. 5.3. 5.3.1. 5.3.2. 5.3.3. 5.4. 5.5. 5.6. 5.7. 5.8. 5.9. 5.10. 5.10.1. 5.10.2. 5.10.3. 5.11. 5.11.1. 5.11.2. 5.11.3. 5.11.4. 6.

8 9 9 9 11 12 13 13 14 18 20

5. 5.1. 5.1.1. 5.1.2. 5.1.3. 5.1.4. 5.1.5. 5.1.6. 5.1.6.1. 5.1.6.2.

Development State of Stainless Cr – Ni Steels . . . . . . . . . . . . . . . . . Cast Iron . . . . . . . . . . . . . . . . Nickel and Nickel Alloys . . . . . . Nickel – Copper Alloys . . . . . . . . Nickel – Chromium Alloys . . . . . . Nickel – Molybdenum and Nickel – Molybdenum – Chromium Alloys . Aluminum and Aluminum Alloys Copper and Copper Alloys . . . . Lead and Lead Alloys . . . . . . . . Zinc and Zinc Alloys . . . . . . . . Tin and Tin Alloys . . . . . . . . . . Titanium, Zirconium, Niobium, and Tantalum . . . . . . . . . . . . . Organic Materials . . . . . . . . . . Selection Criteria . . . . . . . . . . . Properties and Application Criteria Thermosetting Plastics . . . . . . . . Inorganic Nonmetallic Materials Glass . . . . . . . . . . . . . . . . . . . Graphite . . . . . . . . . . . . . . . . . Refractory and Acid-Resistant Bricks . . . . . . . . . . . . . . . . . . Engineering Ceramics . . . . . . . . References . . . . . . . . . . . . . . .

24 25 26 26 27 27 28 31 33 34 35 35 38 39 39 41 42 42 43 43 44 45

1. Introduction
Components of chemical plant are generally subjected to thermal, chemical, and mechanical stresses. The combination of these stresses places very heavy demands on plant materials, especially with regard to corrosion. Thus even unalloyed and low-alloy steels have to meet very strict quality requirements. They must have high purity, for example, and their nonmetallic inclusions must be finely dispersed, since they affect the ability of plant to withstand corrosion cracking, such as stress corrosion cracking and damage by hydrogen. By far the most important materials are the highly alloyed stainless steels and nickel-based alloys, though aluminum, copper and their alloys, and refractory metals, and organic and inorganic materials are also important. In this article the applications of materials
c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.b01 07

in process plant manufacture are described and development trends are discussed.

2. Material Requirements
In the choice of materials for production plant in the chemical industry, there are three basic considerations: 1) The processibility of the material in its commercially available form (sheet, piping, profiles, etc.) 2) The ability of materials to withstand production processes. This is a complex property that includes mechanical stability and its dependence on temperature, resistance to corrosion, and possibly resistance to wear also. 3) The costs of materials, of their processing,

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Construction Materials in Chemical Industry and of the inspections of the chemical apparatus during its useful lifetime.

2.2. Mechanical Stability and its Dependence on Temperature [9]
Chemical apparatus in use is subjected to widely differing mechanical stresses. The possible variations of mechanical stress with time are shown schematically in Figure 1. These stresses may be monoaxial, biaxial, or triaxial.

As so many factors have to be taken into consideration, choosing materials is not easy, especially if the plant is to be used for a recently developed chemical process. The prospect of a suitable choice is best where the material scientist, chemical engineer, plant designer, and plant engineer have worked closely together [1], [2].

2.1. Processability and Joining
Shaping (e.g., bending, rounding, and flanging), separating (e.g., cutting and machining) and joining (e.g., welding, bonding, and pipe rolling) are particularly important processes in the fabrication of chemical plant. Coating and processes that modify the properties of materials (e.g., quenching, tempering, nitriding, age hardening) are also widely used. The choice of fabrication processes depends on the properties of the material concerned, e.g., on its suitability for cold shaping or welding. Fabrication must not affect materials so drastically that their resistance to the conditions of subsequent use is significantly impaired. Joint welding is by far the most important joining process in chemical plant fabrication, while build-up welding is used widely both for coating in original plant fabrication, and for repairs [3–5]. The weldability of a component depends on the weldability of the material and on the design and fabrication of the part [6]. Although each factor may be decisive on its own, the interplay of factors must never be overlooked. It is thus pointless to choose a steel with the highest possible yield strength unless one has checked that dangerous peak stress will not occur (through deficiencies of design) and that welding defects will not be caused by the use of welding techniques unsuited to the material. Bonding is used for materials that cannot be welded or whose properties are changed excessively by welding [7], [8]. As adhesive bonds cannot be exposed to elevated temperatures, this method of joining parts has acquired little importance for chemical apparatus.

Figure 1. Forms of the time function of mechanical stress

The behavior of materials under polyaxial stress – the states of stress in plant components are almost always of this kind – is seldom known as such, because strength data are usually available only as yield strength and tensile strength for loads exerted monoaxially in a tensile test. Therefore, where a particular exposure is concerned, the material’s mechanical stability must be assessed by comparing its known mechanical strength values with a stress calculated according to the appropriate theory of strength [10]. In the fabrication of chemical apparatus preference is given to materials that are easily shaped, since they react to the application of excessive force by undergoing energy-consuming changes of shape instead of simply breaking. Temperature has an important influence on the mechanical stability of materials. As the temperature rises, strength decreases, ease of shaping increases, and creep behavior becomes the main factor determining mechanical stability. Thus, above a limit temperature, which depends on the material, the yield strength or tensile strength at the envisaged operating temperature can no longer serve as a characteristic value for calculating the stress of a chemical apparatus (Fig. 2, see next page) [9]. The strength of metals increases with decreasing temperature. Therefore, components intended for use at room temperature might be expected to be more resistant to loads exerted at lower temperatures. That this is only partly true is explained by the deformation behavior of materials. The characteristic strain values of metals tend to drop suddenly as the tempera-

Construction Materials in Chemical Industry ture decreases, and this is accompanied by an increase in the tendency to undergo brittle fracture. The inherent risk of brittle fracture is not accounted for directly by strength calculations.

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Figure 2. Dependence of characteristic strength data on temperature (schematic)

Susceptibility to brittle fracture is represented by values for elongation at rupture and reduction of area in the tensile test, and also by the transition temperature obtained from a plot of the notched-bar impact energy versus temperature (Fig. 3) (see also → Mechanical Properties and Testing of Metallic Materials). In choosing a material to suit a particular set of requirements, adequate safety must be ensured by taking this transition temperature into consideration, as well as the influences exerted on the material during its production and processing. In the case of highstrength materials, it is also advisable to perform fracture toughness testing [11].

will enable a part to be designed so that it satisfies safety requirements is often difficult, because the combinations of loads exerted in practical use cannot be accounted for fully by measuring the alternating stress endurance limit (e.g., by the W¨ hler method). The shape and surface o condition of the part must also be considered (Fig. 4). More realistic criteria can be obtained by determining the resistance to service conditions of components themselves. The AD (Arbeitsgemeinschaft Druckbeh¨ lter) leaflets [12] a on calculations for pressure vessels or their components are based on the assumption that these vessels are normally subjected to static loads. If the pressure fluctuates, the resultant additional stresses can be taken into account according to AD leaflet S 1, in which allowance for them is made by reducing the permissible stresses (Fig. 5). Prediction of useful lifetime is particularly difficult when alternating stresses and creep stresses are superimposed.

Figure 4. Influence of the surface quality on alternating stress tests on high-presure tubes (nominal bore 6 mm; nominal pressure 250 MPa) made of alloy 30CrMoV9 (material no. 1.7707; HB30 ≈ 3000 MPa; tensile strength = 900 – 1100 MPa) a) Cold-worked; b) Nitrided; c) Electropolished; d) Nitrided; e) Polished; f) and g) As-delivered

Figure 3. Transition temperature T t of the notched-bar impact energy a) High level, fracture on working; b) Transition range, mixed fracture; c) Low level, brittle fracture

Where alternating stresses occur, determining suitable characteristic material values that

In such cases there is still no accepted method for prediction of useful life. It would also appear unrealistic to seek “universally valid” theories and better to simulate typical stress processes in test specimens similar to plant components, thus providing the design engineer with useful life data for particular kinds of materials and problems. According to the available experience it is best to design plant and components so that they

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Construction Materials in Chemical Industry iron-based and nickel-based alloys, this interrelation affects the static load fatigue resistance of parts exposed to corrosion processes at high temperatures.

can withstand the stress that gives the shortest useful life.

Figure 5. Admissible number of cycles for pressure vessels as a function of stress a) Range of alternating compressive stress = 90 %; b) Range of alternating compressive stress = 100 %

2.3. Corrosion Resistance (→ Corrosion)
The longevity of most apparatus depends not only on mechanical loads but also on the nature and spectrum of the corrosive ambient medium. As a rule the characteristic symptom of corrosion damage is not the loss of material but an impairment of function and load-bearing capacity. Uniform corrosion, for example, may cause a considerable loss of mass before the serviceability of a part begins to suffer. Localized or selective corrosion proceeds rapidly towards the inside of a part, such that a notching effect is exerted on parts that bear mechanical loads. Corrosion of this kind may rapidly cause vessels to leak, or parts to fail through low-ductility fracture. If the surface becomes creviced or pitted, the stress becomes nonuniform, and the operational stability of the component under alternating stresses is impaired. This also reduces the static fatigue resistance under constant load, as shown by the example in Figure 6 [13]. The static fatigue resistance of copper samples exposed simultaneously to corrosion and mechanical loading is impaired to a much greater extent that of precorroded samples that have already undergone a considerably greater loss of mass and are then stressed mechanically. This exemplifies the interaction between corrosion and creep. For

Figure 6. Creep rupture behavior of copper at 95 ◦ C a) 0.5 M H2 SO4 (air saturated); b) 0.5 M H2 SO4 (air); c) Air (precorroded in 0.5 M H2 SO4 ); d) Air ∆m = Mass loss, wt %

Basically it may be assumed that the behavior of a part exposed to corrosive influences depends largely on the stability of the material, which, in turn, depends mainly on the film which forms at the surface. Efforts are therefore being made to find alloys that can improve the conditions for surface film formation. It is also necessary to ensure that the microstructures of alloys remain as stable as possible, so that demixing (which, for example, could impair the passivation capability of alloys) cannot occur in welding, hot forming, etc. This is particularly important because precipitation may strengthen the tendency towards local activation (local removal of the passive layer), whereby local corrosion may be initiated. Highly localized corrosion that results from simultaneous chemical attack and mechanical stress is particularly serious. The criterion of failure here is the occurrence of lowductility fracture. Stress corrosion cracking, fatigue cracking, and water-induced cracking are phenomena of this kind. They are particularly important with regard to serviceability, useful life, and operational reliability. The special danger of anodic stress corrosion cracking and hydrogen-induced cracking is that they can rarely be detected while the cracks are spreading and before the apparatus starts to leak

The standardized calculation procedures based on strength and ductility data are intended to provide the designer with a proven basis on which to work. Not only do these operations call for definite properties on the part of materials. together with the need to use economical fabrication techniques. from initial planning to the detailed drawing of the finalized design. therefore.. experience in the operation of chemical plant has shown that much of the damage that occurs to chemical apparatus arises from the use of materials that are insufficiently resistant to corrosion under practical conditions. This is important at all stages. as a rule. and separation of phases. A shortlist of materials can be drawn up from corrosion tables. However. and its effects are more easily repaired. is particularly difficult for chemical plant. by build-up welding. Therefore. Resistance to Wear (see also → Abrasion and Erosion) Since all production processes. In the case of fatigue cracking the loss of fatigue strength for finite life and loss of fatigue strength have caused considerable difficulties in the dimensioning of parts. 5 2. for not only may severals kinds of wear occur simultaneously. however. the most extensive tables can never take into consideration all the conditions of a given practical case. conveyence. the metal itself retains its ductility. Nevertheless. Establishing and then interpreting the combination of mechanical and corrosion-chemical exposures. involve physical operations such as comminution. For a selection process. A basic procedure for the selection of materials for chemical plant is shown in Figure 7 (see next page). which give the corrosion behavior of specific materials [16]. only practical trials reveal the actual stress conditions involved. they may also affect the behavior of components under service conditions. and the variety of fabrication processes and range of materials available are growing. and that damage of purely mechanical origin is generally much less frequent [15]. Clearly the demands of the application and those of the fabrication process must be taken into account as fully as possible so that the overall requirements are correctly formulated and properly interpreted in the fixing of verifiable property data. that is not possible. Models of the various kinds of wear have been developed [14]. Compared to corrosion. here. wear is less problematic because it does not cause cracklike damage. however.Construction Materials in Chemical Industry or a part breaks. in practice. must be taken into consideration. The demands made on chemical plant in use are becoming increasingly strict. At the same time the behavior of materials under operating conditions and those of fabrication must be known so that one can judge reliably whether or not a given material is suitable for a given purpose. special design criteria must be worked out in each individual case. Thus. technical rules exist for designing and dimensioning apparatus to meet combined mechanical and thermal stresses. instead. the wear resistance of materials is important for many types of chemical apparatus. Frequently. 3. Although anodic stress corrosion cracks outwardly resemble brittle fractures. [17]. but overlap and interaction of wear and corrosion processes can also arise.g. however. The initiation of cracking by the various stress corrosion cracking mechanisms that result from the action of a given corrodent on a given material depends very much on the mechanical stresses involved. where wear processes (corrosion and abrasion) are concerned. These factors. but also the operations by which the components are fabricated from the material. Almost always there is more than one corrosive agent. the conditions are complex. Choice of Materials Designers of chemical apparatus must pay careful attention to materials as well as the purpose for which the apparatus is intended. have given the choice of materials a complexity that calls for systematic consideration. corrosion behavior is treated in the selection procedure as the decisive criterion. Often. all of which are often supplemented by wear. model experiments and serial testing are necessary as empirical aids to selection. except chemical reactions. not just the function and properties needed by the components. e. because chemi- . In many cases.4. these preconditions cannot be met entirely. In fact.

possibly because the stability of a material has been impaired by excessive cold forming or by excessive heat input in welding. however.6 Construction Materials in Chemical Industry Figure 7. pressure vessels. chemical engineers. chemists. and – where chemical apparatus subject to compulsory testing. It is therefore understandable that standardized corrosion tests are few in number or contain more general instructions. Frequently.g. corrosion may still occur. reactions are influenced by pressure and temperature. and terms such as resistant or nonresistant may be inappropriate in an actual application. they cover only the states of materials that are most favorable from the aspect of corrosion chemistry (that is to say the ho- . and solids that promote wear. is particularly desirable. Furthermore. intermediates and byproducts. often with unknown properties. Thus the corrosion behavior of materials cannot be given in tables with any degree of accuracy. Because corrosion reactions are so complex and depend on so many factors. The results of laboratory tests are consideraly more useful. Often.. Even in cases where tests have been carried out. or because the states of the material in the test plant and in the subsequently constructed chemical apparatus were not identical. False interpretations can be avoided and comparison improved if one has a good knowledge of the kinds of information provided by the chosen test method as well as knowing its limitations. In view of this complexity. e. such tests are very laborious. designers. an assessment of the corrosion behavior of a given material – corrodent system will differ greatly according to the method of investigation. Basic procedure for the choice of materials for chemical apparatus cal processes normally involve starting materials and end products. The most reliable predictions are those based on plant tests performed either in a plant engaged in practical production or in a pilot plant. close cooperation between material scientists. apparatus manufacturers. is concerned – the representatives of the officially recognized supervisory authorities.

the dependence of corrosion on potential is investigated and provides information on the effects of variables which alter the potential. A comparison of the sensitivities of unalloyed and low-alloyed steels to intergranular stress corrosion cracking is given in DIN 50 915. the testing of stainless steels for resistance to intergranular corrosion (DIN 50 914) or the testing of stainless steels in boiling nitric acid (DIN 50 921 and ASTM A 262-70). The differences arise because in chemical tests the corrosion potential may vary with time. and consequent falsification of measurements. In a distillation column. In electrochemical tests the potential is fixed. 2) By performing laboratory corrosion tests. production plants. so that. and not directly to the stresses that occur in practice. the parts of a pilot plant itself should be examined as a source of further information on corrosion behavior. and while it is in actual use. laboratory tests under conditions as close as possible to those of practice must be carried out. solid matter. it has been found advisable to remove a tube from time to time. For further details on chemical and electrochemical corrosion tests. These guidelines should be followed as a route to reciprocally comparable results that can be transferred to the plant component in question. before the apparatus is put into operation. impurities. As there are so many parameters. tests should use suitable specimens in a plant and under conditions as close as possible to those of practical use. The specimens should be placed at several representative locations. but not yet entirely satisfactory. The characteristic stability data needed in the choice of materials can be obtained in two ways: 1) By inserting suitable material specimens in pilot plants or in existing. General guidelines on the conduct of corrosion tests are given in DIN 50 905. and rate of flow. If stability tests cannot be performed in pilot installations. Supplementary chemical or electrochemical tests simulating the conditions that occur in practice are therefore necessary in the selection of materials. their practical value may be limited in others. 4. The shape of a specimen used depends on the types of corrosion expected. describing. temperature. If stress corrosion cracking is involved. To prevent polarization of specimens through contact with plant components. such as an agitator or a thermometer protection tube. For critical plant units such as heat exchangers. In addition to the exposure of test specimens. to cut it open. With regard to the corrosive medium in corrosion tests. whereas in electrochemical corrosion tests. At the stage of testing of materials when they leave the factory and arrive at the plant manufacturer’s establishment it is normally fairly easy to ascertain whether or not they are of the required . it is sufficient to use 7 welded sheets that have the surface quality of the parts to be used in practice. though they are more informative in some respects.Construction Materials in Chemical Industry mogeneous structural states existing at the time of delivery). They should also be carried out as a supplementary measure in cases where plant tests have not clearly revealed the time dependency of the corrosion processes. careful attention must be paid to a number of important factors. and severer conditions of attack may therefore help to complete the picture. Chemical tests are performed on samples exposed to gaseous and liquid corrodents at the operating pressure and temperature. see → Corrosion. Quality Assurance through Material Tests and Checking of Fabrication and Functioning To ensure that a chemical apparatus will be properly fabricated and that its functioning free from disturbances. The results of chemical corrosion tests and electrochemical corrosion tests may differ fundamentally. Where general corrosion predominates. such concentration. Material specimens are generally attached to interior parts. plastically and elastically stressed specimens or tuning fork specimens are used. many tests must be carried out before and during fabrication. dissolved gases. they should be placed in the pit. and in the head. the fixing screws are placed in insulating sheaths. for example. for example. in the vicinity of the feed point. and to examine the inside and outside surfaces for corrosion symptoms. A common feature of all investigation methods is that they refer to the material.

Steels (→ Steel) Steels are still the materials most commonly used for chemical plant. SS (Sweden).0562 1.1. Unalloyed and Low-Alloy Steels for Vessels and Pipelines Sheet and piping made of unalloyed and lowalloyed steels with carbon contents up to ca. Properties and Applications of Materials 5. in particular.1.8935 1. NF (France). Functioning tests check the behavior of the apparatus under conditions close to those of practice.0038 1. for example. storage vessels.8960 1.0 St 44.0425 1. Quality standards for unalloyed and low-alloy steels widely used in chemical plant Standard Short title Typical steels Short name DIN 17 100 DIN 1629 Steels for general structural purposes Seamless unalloyed circular steel tubes for special requirements Steel plates and strips for pressure purposes RSt 37 – 2 St 44 – 2 St 37. 5. or fabrication. The main standards and designations of several typical steels are compiled in Table 1. Of exceptional importance are the regular inspections of plant in use that are intended to reveal incipient damage early enough to ensure that plant shut-down can be avoided and any necessary repairs need not be undertaken in haste.0256 1. BS (Great Britain). visual inspection takes precedence.8 Construction Materials in Chemical Industry quality.0486 1.8961 DIN 17 155 DIN 17 102 Weldable.0 HI H II 15 Mo 3 StE 285 StE 355 WStE 460 St 35. this gives the tester an overall impression of the care taken by the manufacturer. Comparable steels with comparable properties are described in the standard specifications of other countries – see.0421 1.8 15 Mo 3 WTSt 37 – 2 WTSt 37 – 3 Material number 1. The same cannot be said of fabrication checks.0345 1. UNI (Italy) and NBN (Belgium). ASTM (United States). Their variety of alloy compositions and the range of variation of their properties permit an exceptional degree of adaptation to practical requirements. Much emphasis is also placed on nondestructive methods – thickness measurement. finegrained construction steels (normalized) Seamless tubes of heat-resistant steels DIN 17 175 Stahl-Eisen-Werkstoffblatt 087 – 81 Structural steels resistant to weathering .0305 1. checking the construction for compliance with the blueprints and examining the welding work. Checking compliance with legislation and official regulations is mainly the responsibility of the Technical Control Associations and the plant safety inspection departments of the large chemical firms. The steels are normally processed in the normalized state. as the required property data will have been agreed on the basis of quality standards or similar specifications.) and pipelines that are not exposed to particularly severe corrosion.25 wt % are used extensively in chemical plant for vessels (pressure vessels.5415 1. 0. Testing of plant in service also provides knowledge that may be useful in selecting materials for new chemical apparatus by revealing weaknesses of design. 5. It must be emphasized that the first step in fabrication testing should be a thorough visual inspection. Once again.0044 1. for example. which include.5415 1. etc. and tests that reveal initial cracking [18].0 St 52. SAE. materials. AISI.1. Owing to the introduction of weldable finegrained structuralsteels with yield strengths of Table 1. Here the test engineer has more latitude. especially in interpreting the results of nondestructive tests.0254 1.0405 1.8 St 45.

Construction Materials in Chemical Industry ≥ 360 MPa. Where damage occurs. They combine the excellent strength and toughness imparted by fine-grain hardening [25] with the advantages offered by modern ladle metallurgy in respect of purity and microalloying. c) ≥ 50 mm plate. together with the fine dispersion of their nonmetallic inclusions. the leak-beforefailure behavior imparted by high toughness is exceptionally favorable because the risk of sudden failure as a result of unstable crack propagation is practically eliminated. Specific welding guidelines must be adhered to increasingly as the alloy content and yield strength rise.010 % S.015 – 0. Influence of the TN process on the dynamic strength of steel StE 355 (stress ratio R = 0.002 % S Figure 9. Influence of sulfur content on the reduction of area at rupture in the thickness direction of StE 355 steel plates a) 40 – 55 mm plate. c) Normal . The high purity of fine-grained steels. ≤ 0. the anisotropy of the steel’s properties is reduced considerably. is used on a smaller scale than it was formerly. d) 20 – 50 mm plate. 0.054 % S. Figure 9 [26] shows that the fatigue resistance is also improved. is very favorable with regard to corrosion resistance. boiler plate consisting of unalloyed steels. weldability. The blast or shot injection of calcium compounds to reduce the sulfide content of steel (TN process) and the addition of cerium and zirconium to produce globular. Normalized fine-grained structural steels are now very popular. as may be seen from the percentage reductions of area at fracture of fine-grained structural steels in the thickness direction of the sheet (Fig. Processing guidelines for weldable fine-grained structural steels are compiled in DIN standards.005 %. and through the influence exerted on the nature of the precipitation. finely distributed sulfide inclusions should also be mentioned. B) Calcium treated (TN process). these guidelines can be found by consulting either the standards or manufacturers of steels and welding filler materials. TN treated. The use of high-strength heattreated structural steels with yield strengths of ≥ 700 MPa [19–23] will presumably increase. block segregation. Coarse sulfides promote the formation and growth of cracks both in hydrogen- 9 Figure 8. and toughness. In special cases. Steels are suitable for fusion welding by all processes. thickness of plate: 50 mm) A) Untreated. 0. Consequently. but the welding filler metals must be suited to the base material.006 % S. whose yield strengths are considerably lower. a) Transverse. ≤ 0. 8) [26]. b) 40 mm plate. these desulfurization methods enable the sulfur content to be reduced to below 0. b) Longitudinal. These processes improve purity. notably the sulfides. Pipes consisting of welded steel strip will be used increasingly instead of seamless pipes [24].

Steels with comparable yield strengths are also used on a large scale for pressure vessels and other chemical apparatus. piping) and for pressure vessels and tubes . and liquid ammonia. DIN 17 175 (pipes) and DIN 17 102 (finegrained structural steels) and are suitable for all fusion welding methods. and WStE 355 (1. Water quenching followed by tempering. 11 – 32 wt % nickel. 1. vanadium..10 Construction Materials in Chemical Industry operating at up to ca 800 ◦ C [29]. nickel.0345). and tungsten [30].2. Upon chemical exposure to aqueous solutions. whose main strength-related property is the high-temperature yield strength. Steels with High-Temperature Strength High-temperature structural steels are used in the chemical industry mainly for heavily stressed parts of steam boilers (e. 2) For temperatures of 400 – 550 ◦ C: unalloyed and low-alloy steels having good long-term. For greater safety. such as the pressure-bearing parts of multistory vessels.g.4961). Starting from steel St 52-3. tantalum.. DIN 17 175. 1. behaves favorably towards such crack-initiating media as alkalis. drums. 900 MPa. 5. But the scope for improvement in this way was limited by the fact that increasing the alloy content impairs the cold cracking resistance in welding. especially under the influence of the hydrolytic acidification that occurs in cracks.4981). and additions of molybdenum.0305).4922). though preheating and post-welding annealing may be necessary.8 (1. may be converted to H2 S. and other elements. is more favorable for steel needing high toughness. forgings) and in DIN 17 245 (steel castings). These materials are standardized in DIN 17 155. 4) Temperatures of 600 – 800 ◦ C: austenitic steels containing 16 – 21 wt % chromium. it has been possible to raise the yield strength from 355 to ca. 120 ◦ C and then immediately annealed. e. According to their maximum service temperatures that can be maintained for long periods. This steel is now a standard material for these media. induced crack formation and in stress corrosion cracking [27].3 wt %). niobium. high-temperature strength-related property values. air tempering is preferred. By far the most important representative of this group of steels in terms of quantity is StE 690. 3) For temperatures of 550 – 600 ◦ C: martensitic steels containing up to ca. 12 wt % chromium and additions of molybdenum. Considerably higher yield strengths. a typical representative is X 20 CrMoV 12 1 (1. These steels are suitable for fusion welding. X 8 CrNiMoNb 16 16 (material no. in particular. Typical steels belonging to this group are the grades HI (1. Agreement has therefore been reached that the yield strength of normalized steels should not exceed 500 MPa. In the case of heat-resistant structural steels.5 wt %). details of which can be found in the standards. after which they must be cooled to ca. These steels are standardized in DIN 17 155 (boiler plate types). these steels must be kept at 250 to 450 ◦ C during welding. pipes. the following groups are distinguished: 1) For temperatures up to ca. and DIN 17 245 (steel castings). St 35.0565). even at low alloy contents. The main alloying elements are manganese (up to 1. These materials are also very important in reactor technology. collectors. StE 890 has been used to an increasing extent since the mid 1980s [28].1.2 wt %). DIN 17 240 (nuts and bolts). and molybdenum (up to 1. Considerable progress has been made through efforts to improve the economy of structural steels by raising their strength. These steels are supplied in the quenched and tempered state. which is a vigorous promoter of hydrogen cracking.5 wt %). are obtainable by quenching and tempering. Being airhardenable. vanadium also being used occasionally (up to 0. 400 ◦ C: unalloyed steels. That would explain why steel StE 355. the sulfides. chromium (up to 2. on the other hand. the finished apparatus should be subjected to stress relief annealing. The first step in this direction consisted in raising the alloy contents of normalized structural steels. aluminum. X 8 CrNiNb 16 13 (material no.g. It is now believed that crack growth in anodic stress corrosion cracking is also promoted by hydrogen. whose minimum yield strength is 690 MPa (Euronorm 137). in some cases melted as fine-grained structural steels. tungsten. These are standardized in DIN 17 459 (sheet. nitrates.

1.4841). Resistance to scaling is obtained mainly by alloying with chromium. see also Section 5. the ferriticaustenitic steel X 20 CrNiSi25 4 (1. which are standardized in DIN 17 459.3. they are used only in the zones which reach the highest temperatures. which further reduce the toughness.4828).7380 1.5415 1. which causes severe embrittlement. and which are thus resistant to scaling [36]. For temperatures above 800 ◦ C only iron – chromium – nickel alloys and nonferrous alloys based on cobalt or nickel are suitable [32].4959). The highest service temperatures listed. which should be used only above 900 ◦ C. an intermetallic iron – chromium σ-phase.4724) and X 10 CrAl 24 (1. cracking units. They may be reduced greatly by admixtures to the air. followed by quenching. The steel most severely affected is X 15 CrNiSi 25 20 (1. It endangers particularly the weld interfaces.7335 1. These steels are welded with filler metals of the same composition. This so-called 475 ◦ C embrittlement can be eliminated by annealing briefly above 600 ◦ C.3. and muffle furnaces are examples of chemical plant in which these conditions arise. and at the lowest possible heat input to avoid hot cracking of the weld metal.Construction Materials in Chemical Industry Table 2. 1. Within the same temperature range. Distinctions are made between the ferritic steels.4762). [33].4961 1. The σ-phase and the carbides can be redissolved by annealing above 1000 ◦ C. The above-mentioned publication also gives long-term heat resistance values for periods of up to 105 h. e. heatresistant steels tend to become brittle.4981 Standard DIN 17 175 DIN 17 175 DIN 17 155 DIN 17 155 DIN 17 175 DIN 17 175 DIN 17 459 DIN 17 459 Approximate temperature. because the reaction products do not form sufficiently thick surface layers. which extend to 1200 ◦ C. such as X 10 CrAl 7 (1.4841) and X 10 CrNiAlTi 32 20 (1.8 St 45. and austenitic steels such as X 15 CrNiSi 20 12 (1. X 10 CrAl 13 (1. Long-term heat stability values are compiled in [34]. of water vapor or sulfur-containing or carburizing matter. austenitic steels precipitate chromium carbides. the importance of these values in calculating the useful lives of components subjected to this exposure is discussed in [35].0405 1. Ferritic steels with ≥ 12 wt % chromium do so between 400 and 530 ◦ C. but further improvements are possible if silicon and aluminum are added.8 15 Mo 3 13 CrMo 44 10 CrMo 9 10 X 20 CrMoV 12 1 X 8 CrNiNb 16 13 X 8 CrNiMoNb 16 16 Material number 1. X 15 CrNiSi 25 20 (1.. Approximate temperature limits for the use of steels in a weakly oxidizing flue-gas atmosphere Steel St 35. apply to air.0305 1. ◦ C 500 500 530 560 590 600 750 750 11 and X 8 NiCrAlTi 32 21 (material no. Heat-Resistant Steels Heat-resistant steels are those that have good strength-related property data and are distinguished by exceptional resistance to exposure for short or long periods to hot gases or combustion products at temperatures exceeding 550 ◦ C.g. Table 2 gives approximate figures for the highest temperatures at which a number of steels with high strength at elevated temperature can be used in a weakly oxidizing flue-gas atmosphere. In the case of ferritic steels with ≥ 17 wt % chromium and austenitic steels. Within certain temperature ranges. is formed between 600 and 900 ◦ C. .4922 1. Rotary furnaces. outside of which lowalloy steels are used. As austenitic steels are very expensive. 5.4876).4713). Special techniques have to be used to form welds between ferritic and austenitic steels because of the diffusion processes that occur in welding and because of the differences in thermal expansion [31].4828). The most commonly used heat-resistant steels are standardized in Stahl-Eisen-Werkstoffblatt 470-76.

TTSt 35 (1. 2) Unalloyed and low-alloy weldable finegrained structural steels in the normalized state for service temperatures down to − 60 ◦ C.g. 4) Austenitic chromium – nickel steels for service temperatures extending close to absolute zero. Hence the lowest service temperature of a steel with good low-temperature tenacity is that at which the notch impact energy is still above this limit. e. V.g. The periodic alternation of the pressure subjects the components to a severe fatigueinducing stress.g. e. 12 Ni 19 (1. Steels Resistant to Pressurized Hydrogen [40].5 – 9 wt % Ni for service temperatures of − 100 to − 190 ◦ C. 5.. TStE 380 (1.5680). 2) Steels for components exposed to pressurized hydrogen at temperatures > 200 ◦ C. Heat-resistant cast steel. In the welding of steels for low temperatures it is necessary to use filler materials that give a weld metal whose strength and toughness are equal to those of the base material [37–39].. measured on DVM (Deutscher Verband f¨ r Materialu forschung und -pr¨ fung e. Suitable filler metals are listed in Stahl-Eisen-Werkstoffblatt 47076. for cast steel and other steels.. Berlin) longitudiu nal specimens. these are standardized in DIN 17 200 and in the case of large forgings. e. 3) Nickel-alloyed heat-treatable steels with 1. thus causing decarburization.g.. The relevant quality standards are DIN 17 173 and DIN 17 174 for groups 1 and 3 This reaction between hydrogen and cementite occurs mainly at the grain boundaries.8910). provided the guidelines for alloyed steels are followed.12 Construction Materials in Chemical Industry and DIN 17 102 for group 2.5.1. embrittlement.g. Their shape stability therefore depends decisively not just on the choice of materials. are formed at temperatures above 900 ◦ C. Notched-bar impact energies. Steels for low temperatures can be divided into four groups: 1) Unalloyed aluminum-killed steels for service temperatures down to − 50 ◦ C in the normalized state and − 80 ◦ C in the heat-treated state. ammonia synthesis and pressure hydrogenation) dissociates on the surface of many steels. coarse grains. and reacts with carbon to form methane. e. diffuses into the metal. in the fractional distillation of hydrocarbons or storage and transportation of liquid gases. and cracking: Fe3 C + 2 H2 → 3 Fe + CH4 The heat-resistant steels can be welded by the usual methods. If relatively good corrosion resistance is required.. Steels for Low Temperatures Refrigeration is very important in the chemical industry. e. but also on their being designed to suit the conditions of exposure as well as on satisfactory fabrication and installation [43]. in both cases at temperatures of ≤ 200 ◦ C. which is needed in many high-pressure syntheses (e. [41] Steels for high-pressure plant in the chemical industry can divided into the following two groups: 1) Steels for components subjected to purely mechanical loads or to pressurized hydrogen. The degree of low-temperature toughness depends particularly on the steel’s composition and heat treatment. mainly unalloyed and low-alloy heat-treatable steels are used. of ≥ 40 and ≥ 60 J/cm2 . For the conditions of group 1.g. the .4. Hot pressurized hydrogen.. for example. and Stahl-EisenWerkstoffblatt 685 – 82 for cast steel with good low-temperature toughness.1101).1. Steels for the pressure vessels must still have sufficient toughness at the lowest operating temperature. is standardized in Stahl-EisenWerkstoffblatt 471-76. as used in the manufacture of pipes by centrifugal casting. are regarded as evidence of sufficient low-temperature toughness. and occasionally hardenable stainless steels. It should be noted that in ferritic steels with ≥ 12 wt % chromium. as present in the production of low-density polyethylene (pressures of up to about 400 MPa). in Stahl-Eisen-Werkstoffblatt 550-76. are used instead [42]. 5. which can no longer be removed by heat treatment. respectively. stainless heat-treatable chromium and chromium – nickel steels according to DIN 17 440.. the steels specified in DIN 17 440 and DIN 17 441.

5/1.08/0.7766 1.15/0.0 3.80/1.0 Cr 0.28 0. The more highly alloyed corrosion-resistant (acid-resistant) steels must additionally withstand general corrosion and localized corrosion in relatively aggressive corrodents (salt solutions..07/0.7259 1.25 0.29 0.12 0.7779 1. the most important group comprises those that are chemically resistant.4988) tends to suffer hot cracking on welding.30 0. and heat treatment. The chromium steels have to be kept at 250 – 450 ◦ C throughout welding.30 0.20 2. acids.25 Cr 0.15/0.0 Mo steel.Construction Materials in Chemical Industry Table 3. molybdenum.85 Ni: 12.20 0.4922 1. d) 2.20/0.20/0. Together with the stresses exerted on the component and the loss of mechanical strength. Hydrogen and methane accumulate.5 1.10/0.5 Composition. as compiled by Nelson [44].20/0.5 Mo steel. g) 1. are molybdenum. Resistance diagram for the attack of pressurized hydrogen on steels (Nelson diagram) a) 1. and also in many cases 0.8 2.17/0. As an illustration. because the time factor is much too important and the attack of pressurized hydrogen on steels has a significant incubation period.20/0. Figure 10 gives stability limits for various steels. can be added to the steel to prevent the reaction between hydrogen and cementite.17/0.10/1.0/12. Short-term tests give very little indication of the limits to the use of steels of this kind.50/0.5 N: 0. The resistance of carbon steels to attack by pressurized hydrogen depends partly on the ambient conditions.0 2. wt % Mo 0.25/0.5 Mo steel. vanadium. .7218 1.5 wt % Mo. and niobium.60/0.10 Cr 0.6.35 0.5 Mo steel. provided that they are preheated.25 Cr 1.23 0. Stainless Steels [45] Among the highly alloyed steels. Characteristic alloying components. h) 0.50 V Others 13 0. they can be exposed to hydrogen throughout the range of temperatures used in normal high-pressure processes. Figure 10.20 0.5 Mo steel. apart from chromium and nickel.25 0.0 Cr 0.3. but also on the microstructure.04/0. and partially annealed immediately afterwards.g. It can be seen that even at low hydrogen partial pressures (e.0/3.5/17.1. 2 MPa) an unalloyed steel should be used only below 300 ◦ C.5/14.55 0.30 0. titanium. 9 % Ni have good resistance to pressurized hydrogen. such as chromium. i) Mild steel 5.5 Mo steel.5 15.3/2. b) 5.0 Cr 0.20 0.2 – 1.13 grains thus losing their cohesion.5 Mo steel.22/0.7281 1.60 0.20/0.22/0. As the steels of this group resist heat as well as chemicals. effects of welding. c) 8.4988 0.12/0.0 Cr 0.25 Cr 0. Composition of pressurized-hydrogen-resistant steels Steel type Material number C 25 CrMo 4 16 CrMo 9 3 26 CrMo 7 24 CrMo 10 10 CrMo 11 10 CrMoV 10 20 CrMoV 13 5 X 20 CrMoV 12 1 X 8 CrNiMoVNb 16 13 1. Austenitic steels with 18 % Cr and ca.0/2. e) 2. this results finally in pronounced brittle fracture. even at fairly high concentrations).30 0.45/0.40 0. copper. Elements that form stable carbides.1.3 11.7276 1. The low-alloy ferritic steels are suitable for fusion welding. Often they contain nickel in addition to chromium. impurities. cold working.6 2. f ) 1. The pressurized-hydrogen-resistant steels now in use contain up to 16 wt % Cr.20 1. Some types are additionally alloyed with up to 0.30/0.7273 1.7/3. this group also includes a considerable number of the heatresistant steels discussed in Section 5.5 Mo steel. giving rise to high pressure whose cleaving action leads to internal microcracks.23 0.85 wt % V (Table 3).90/1. tungsten. and in some cases silicon.7/3. The austenitic steel (1. They have chromium contents ≥ 14 wt %.

more nickel or nitrogen must be added to maintain the austenitic structure.14 Construction Materials in Chemical Industry sistance to stress corrosion cracking. it impairs the strength. which depends on composition and heat treatment. χ-phase. In the heat treatment. are unsatisfactory. Their mechanical and technical properties. are used in the solution-heat-treated state (solution heat treatment temperature 1000 – 1100 ◦ C). Pure iron has a ferritic structure. Stainless steels are divided according to microstructure into four groups: 1) Martensitic (hardenable) steels with > 0. silicon. molybdenum. They are hardened at temperatures > 1000 ◦ C (e. then it is also necessary to increase the content of austenitizers and/or to reduce the chromium content. 2) Ferritic steels with body-centered cubic lattice (α-phase). they tend to become coarse-grained and brittle. the tendency to segregate intermetallic compounds (σ-phase. If the precipitation tendency is strong enough. 18 wt % Cr and 10 wt % Ni. As the content of chromium increases. each being represented by a material number (DIN 17 007) or by chemical composition (DIN 17 006). Although this restores the corrosion resistance to some extent. increases greatly (see Fig. cutting steels). To equalize the chromium content of the ferritic matrix again it is necessary to anneal the steel for a fairly long time at elevated temperature. they undergo transgranular stress corrosion cracking. Fe2 Mo). Ternary phase diagram of Fe – Cr – Ni (section at 1100 ◦ C) With increasing chromium content. After being hardened they can be improved by tempering at 500 to 600 ◦ C – their strength thus being reduced to a desired lower level – and henceforth combine high strength with good ductility. The austenitic chromium – nickel steels. Nevertheless they have the advantage of resisting stress corrosion cracking in chloride-containing media. There are many kinds of steels and alloys. when welded. Particularly important are the austenitic chromium – nickel steels with ca. Their strength is relatively low and their ductility very good. however. nitrogen. and especially increasing molybdenum content. nickel. Those of greatest importance are the ferritic chromium steels with ca. a ferritic structure. If the content of molybdenum is raised. intermetallic compounds may already be precipitated during the . At solution heat treatment temperatures these steels are close to the boundary of the α + γ field in the iron – chromium – nickel phase diagram (Fig. The alloying elements that may be added to iron are either ferrite-forming (chromium.g. titanium) or austenite-forming (carbon. Fixation of chromium and the formation of chromium-depleted zones reduces the resistance to corrosion. They are therefore used mainly under conditions which may cause fatigue corrosion and stress corrosion cracking in austenitic steels. The mechanical properties of steels are determined by the microstructure. 11). with precipitated carbides of high chromium content of type M23 C6 or M7 C3 . manganese). In chloride-containing corrodents. 17 wt % chromium. 3) Austenitic steels with face-centered cubic lattice (γ-phase). with or without molybdenum. Laves phase.12 wt % C and ≤ 15wt % Cr. is formed. 4) Ferritic – austenitic steels combine good mechanical properties with improved re- Figure 11. however. the corrosion resistance after annealling procedure is still considerably poorer than that of the martensite. As some of the chromium is still bound as carbide. 12). but without addition of molybdenum.

important only in connection with the welded material. 18 wt % chromium this precipitation has no importance. In ferritic – austenitic steels. as well as improving the mechanical properties by introducing nitrogen atoms into interstices in the metal lattice. while in the case of molybdenum-free austenitic chromium – nickel steels it is. and are only important for the use of ferritic – austenitic steels in borderline cases. Being more resistant than commercial austenitic steels to stress corrosion cracking in neutral chloride solutions. the precipitation of phases and compounds that contain these elements exert strong effects. These differences of concentration are relatively slight. has a nickel content of about 5. A commonly used material of this group is X 2 CrNiMoN 22 5 (1. see next page). more nickel and less chromium and molybdenum. Unlike ferritic and austenitic steels. The segregation of chromium. [47]. Damage must be expected where a coherent δ-ferrite network is present (proportion of δ-ferrite in the structure > 10 %). σ. Hence the addition of molybdenum. however. In the case of austenitic chromium – nickel steels it is about 6 wt % Mo. has an upper limit. and of a complex nitride (Z-phase) for the steel X 2 CrNiMo 18 14 3 Addition of nitrogen retards the precipitation of the intermetallic phases and compounds considerably. By virtue of their high yield strength of at least 450 MPa. they are also being used increasingly to handle aggressive cooling water. In ferritic chromium steels and austenitic chromium – nickel steels. and reducing the austenite-stabilizing nickel content (Table 7.Construction Materials in Chemical Industry relatively short-lived heat exposure of welding. Owing to the special importance of chromium and molybdenum in imparting corrosion resistance to stainless steels.5 wt %. erosion) and vibration. For ferritic chromium steels with up to ca. in addition to about 22 wt % Cr. and an austenitic structure proportion of about 60 % [46]. The austenitic phase contains. Chemical engineering also uses a number of other special materials notable for their high resistance to pitting corrosion and stress corrosion cracking. nitrides. while exposed to corrosive media. which.4462). at the most. as well as to mineral acids (Table 5. which. The designations of the most important stainless steels for chemical plant are compiled in DIN 17 440 (Table 4. the chromium-rich σphase may precipitate on annealing at 600 – 900 ◦ C. steels of this kind are used for components which. Annealing within certain temperature ranges may cause carbides. In a corrosion exposure this decomposed δ-ferrite may be selectively dissolved. Particularly high molybdenum contents are present in the steels listed in Table 6 (see next page). ferritic – austenitic steels have a two-phase structure. . For reasons of welding technique (prevention of hot cracking) the welded material of normal austenitic steels almost always contains some δ-ferrite. molybdenum-rich Laves phase (Fe2 Mo).and molybdenumrich phases depletes the matrix in these elements. is obtained by raising the contents of ferrite-stabilizing elements. Nitrogenalloyed austenitic and ferritic – austenitic steels are therefore of industrial importance.and χ-phase. are additionally subjected to wear (cavitation. such as chromium and silicon. The stability of the austenite is due to nickel and nitrogen. in contrast to the composition of austenitic steels. whose nickel content is correspondingly depleted. which is desirable for reasons of corrosion chemistry. see page after next). The matrix therefore loses its resistance to corrosion. conversely. the ferritizers chromium and molybdenum are enriched in the ferrite phase. The alloy composition of these steels is also chosen such that the ferritic and austenitic phases are present in the structure in approximately equal proportions and the chromium content of the austenite is not less than 17 wt %. 15 Figure 12. see next page). an Mo content of about 3 wt %. which decomposes when the steel is annealed. Precipitation fields of chromium-rich carbides M23 C6 . and intermetallic compounds to be precipitated in the microstructure of stainless steels.

8 – 15.0 3.20 – 0.16 Awesta 254 SMO Nirosta 4529 VEW A 963 AC 6 X Trade mark .0 – 19.0 10.4113 1.0 17.10 <0.4116 1.4435 1.0 – 2.4311 1.60 V 0. Al Cu Al.08 0.1 6.12 – 0.10 – 0.4306 1.4429 12.30 0.50 0.5 – 18.0 17.4571 1.5 – 3.4529 0.0 – 11.0 17.5 – 15.22 0.15 <0.10 <0.0 12.10 <0.0 – 2.5 2.5 S 0.0 17. High-alloy stainless steels containing ≥ 6 wt % molybdenum DIN designation ASTM designation C S 31254 1.5 2.0 – 20. Composition of stainless steels Short name (DIN) US Standard (AISI) Material number Composition.7 ≤0.5 – 13.0 – 20.12 0.0 8.5 8.0 – 14.5 16.04 ≤0.90 – 1.45 – 0.15 0.0 – 19.5 16.10 <0.03 Si ≤1 ≤0.20 N 0.15 – 0.15 – 0.5 9.5 33.5 – 3.03 <0.5 Al 0.0 Cu 0.4305 1.10 <0.0 15.0 – 18.48 <0.02 ≤0.5 2.5 9. short name (DIN) X 3 CrNiMoN 17 13 5 X 2 NiCrAlTi 32 20 X 1 NiCrMoCu 25 20 X 1 CrNiMoN 25 25 2 X 1 NiCrMoCuN 31 27 NiCr21Mo Material number 1.12 – 0.0 – 14.02 0.5 17.5 – 13. wt % Ni 18 25 16 24 Mo 6.0 – 17.4563 2.5 3 Other N Ti.4002 1.4301 1.4057 1.7 ≤0.5 – 10.0 – 14.4465 1.02 ≤0.5 2.0 – 19.5 31 42 Mo 4.5 2.0 15.35 Ti > 5× % C Nb > 8× % C Ti > 5× % C Nb > 8× % C 2.08 – 0.16 Construction Materials in Chemical Industry Table 4.4550 1.5 6.0 – 12.4406 1.0 17.0 12.5 16.0 17.4541 1.5 – 18.22 Table 5.0 – 14.0 – 18.15 Ti ≥ 7× % C Nb ≥ 12× % C 0.4024 1.0 – 14.5 – 2.4021 1.02 0.0 12.30 1.5 – 18.08 <0.04 ≤0.35 S 0.4000 1.17 0. Al Table 6.07 <0.03 Cr 20 20 17 20 Composition.03 <0.0 2.0 10.4401 1.0 – 2.0 – 19.10 <0.0 – 20.0 – 18.5 21.0 17.4438 1.03 Cr Mo Ni Others 403 405 410 420 430 439 434 430 F 431 303 304 305/308 304 L 321 347 316 316 L 316 Ti 316 Cb 316 316 L 317 L 304 LN 316 LN 316 LN 1.23 <0.4104 1. wt % Cr 17.0 – 2.0 – 2.4580 1.0 10.5 Ni 13.5 20 25 27 21.4858 C ≤0.03 <0.0 12.0 15.0 9.5 – 18.5 – 17.0 16.40 – 0.3 3.0 N 0.02 ≤0.5 16.02 0.5 16.5 16.4404 1.42 – 0.5 2.0 16.0 – 19.20 N 0.0 – 14.0 – 14.5 16.5 – 14.5 – 18.0 – 10.0 2.6 N 0.4539 1.0 – 11.4034 1.2 0.0 13.4439 1.5 – 12.5 – 3.07 <0.5 – 18.5 – 17.5 Mn ≤2 ≤1 ≤2 ≤2 ≤2 ≤1 Composition.10 – 0.0 16.17 – 0.17 0.0 – 14.07 <0.4511 1.4558 1.4303 1.5 10.4006 1.0 – 4.07 0.15 – 0.5 12.20 0.03 <0.0 12. wt % C Ferritic and martensitic steels X 7 Cr 13 X 7 CrAl 13 X 10 Cr 13 X 15 Cr 13 X 20 Cr 13 X 40 Cr 13 X 45 CrMoV 15 X 8 Cr 17 X 8 CrTi 17 X 8 CrNb 17 X 6 CrMo 17 X 12 CrMoS 17 X 22 CrNi 17 Austenitic steels X 12 CrNiS 18 8 X 5 CrNi 18 9 X 5 CrNi 19 11 X 2 CrNi 18 9 X 10 CrNiTi 18 9 X 10 CrNiNb 18 9 X 5 CrNiMo 18 10 X 2 CrNiMo 18 10 X 10 CrNiMoTi 18 10 X 10 CrNiMoNb 18 10 X 5 CrNiMo 18 12 X 2 CrNiMo 18 12 X 2 CrNiMo 18 16 X 2 CrNiN 18 10 X 2 CrNiMoN 18 12 X 2 CrNiMoN 18 13 <0.0 16.03 <0.7 ≤1 ≤0.5 – 13.03 <0.0 – 11.3 6.5 10.4016 1.10 <0.5 – 13.14 – 0. Composition of special alloyed stainless steels Steel type.5 – 18.4510 1.5 – 18.10 – 0.5 11.5 11.07 <0.12 – 0.5 4.0 12.5 16.4436 1.5 10. Cu Cu Ti.7 1 1.0 – 18.5 25 23.

03 0.5 6 3. In the meantime a variant has been developed for extremely severe HNO3 exposure (5. Technical Properties The mechanical properties of the four groups of stainless steels are shown in Table 9. As Figure 13 shows. . b) X 2 CrNi 18 9. 2) molybdenum-containing steels with 18 wt % Cr.65 1. its advantages are particularly pronounced at HNO3 concentrations above 75 %. Because the mechanical properties of the welded joints were unsatisfactory. Stabilized ferritic steels should be of particular interest in connection with the handling of corrosive media.34 1. where it is superior to stainless steels of all other types [48].8 Cr 22. 0. and availability as semifinished products.7 N 0.3 Ni 5. especially those used for chemical pumps. the commercial types used until now were rarely chosen for chemical plant.4 1. which.1 2.14 0.3 wt % Si.1. although the proportions of the aforementioned interstitial elements have been lowered.015 wt % (superferrites). Figure 13. stainless cast steel is often preferred to stainless rolled and wrought steels as a material for chemical plant.4460 A 905 X 2 CrNiMoN 22 5 3 X 2 CrNiMoCu 25 5 G–X 3 CrNiMoCuN 24 6 X 3 CrMnNiMoN 25 4 4 0. as compared with that of a conventional Cr steel. and 3) stabilized molybdenumand nickel-containing ferritic steels with high Cr contents. 5. such as X 1 CrNiMoNb 28 4 2 (Remanit 4575) and X 2 CrNiMoTi 25 4 4 (Monit).1. and in all cases with a C + N content limited to 0. owing to their good corrosion properties.5 5. river water). Area-related mass loss rate of stainless steels in boiling nitric acid (exposure time: 50 – 90 d) a) X 2 CrNiSi 18 15. suitability for welding.4 1. 1.019 0. as well as for economic reasons [51]. Table 8 lists several important types.Construction Materials in Chemical Industry Table 7. The chemical composition and mechanical properties of stainless cast steels are fairly similar to those of the rolled and wrought steels.3 3.7 5. without nickel. For reasons of cost.6. and because of certain design problems. The superior toughness of the last-mentioned steel types. Progress in the field of ferritic steels has been marked by the use of special methods for obtaining low C + N contents in their manufacture (ELI = extra low interstitial steels) [50]. are additionally stabilized with titanium or niobium.1 26 25 26 Mo 3.2 + 0.4361) and has already undergone trials under practical conditions has remarkably good resistance to highly concentrated nitric acid and chromic acid. wt % Mn 0.4462 Ferralium 255 Noridur 9.012 0.g. d) X 1 CrNi 25 21 Ferritic steels have also undergone special development. 17.034 Si 0. A substantial improvement may be expected from the titaniumstabilized chromium and chromium – molybdenum steels of low carbon and nitrogen content and from the nickel-alloyed chromium – molybdenum steels. Three groups can now be distinguished: 1) steels with 25 – 28 wt % Cr. is illustrated by the transition temperature of the notch impact strength.5 wt % Ni.015 wt % C) [49]. Composition of ferritic – austenitic (duplex) steels Name/material number Short designation (DIN) C 1.36 17 A specially developed austenitic steel that contains about 4 wt % Si (X 2 CrNiSi 18 15. especially chloride-containing cooling waters (e.0 3.5 Typical composition. c) X 1 CrMo 26 1.. in some cases with an addition of Mo.

cooling in oil or air. Martensitic steels exist only in the pearlitic and martensitic forms. 300 450 – 650 ca. 750 ca.04 4. and more resistant to chloride-containing solutions. Having good resistance to erosion and cavitation as well as high fatigue strength.0 ≤1. c Solution annealed. The production of a fine-grained structure requires forming at temperatures below 800 ◦ C.5 2.4313 1.18 Construction Materials in Chemical Industry Table 8.2 % yield strength.0 19.5 ≤1. e 0. Mechanical properties of the four main steel types Steel type Yield strength.08 ≤1. depending on carbon content.5 ≤0. Quenched and annealed.09 ≤1. They are hardened by heating to 980 – 1100 ◦ C. d Annealed at 1100 ◦ C and quenched. These steels cannot be hardened by heat treatment.3 2.0 Ni 1. and cooling.0 ≤1. MPa Tensile strength. thus embrittling the steel and causing precipitation of carbides. as well as for heat exchangers and condensers.0 2.0 6.5 ≤0. Between their melting points and room temperature. % Notch impact energy.0 4. without intermediate stages.5 ≤1.07 ≤2. Austenitic steels with low chromium and nickel contents are so unstable that martensite may be formed at low temperatures or through cold . 500 f ca. and tempering at a temperature above 600 ◦ C.4008 1. Being less expensive than austenitic steels.0 13.05 2.4448 1.0 ≤0.0 11.5 ≤1.4460 Si Mn ≤1.5 ≤1.5 ≤2. Heating above 1000 ◦ C (welding) enlarges the grain. The steels containing less than 0.0 25.0 25.4408 1. Certain types are resistant to very high temperatures and to pressurized water.0 ≤2.0 17.07 ≤1.0 13.0 ≤0. wt % Cr 13.08 ≤1.5 4.06 ≤1.0 10.0 ≤0. annealed.1 2.0 Mo ≤0. Cast stainless and special steels Steel type Designation Material number C Cast ferritic stainless steel Cast martensitic stainless steel Cast austenitic stainless steel G-X 8 CrNi 13 G-X 5 CrNi 13 4 G-X 6 CrNi 18 9 G-X 6 CrNiMo 18 10 G-X 6 CrNiMo 1713 G-X 5 CrNiNb 18 9 G-X 5 CrNiMoNb 18 10 G-X 7 CrNiMoCuNb 18 18 Cast special austenitic G-X 7 NiCrMoCuNb 25 20 steel G-X 3 CrNiSiN 2013 Cast G-X 3 CrNiMoCu 24 6 ferritic – austenitic stainless steel 1.5 20. they are used also for propellers and impellers.0 ≤0.5 ≤0.5 ≤2.5 2.06 ≤1.1 Nb ≥ 8× % C Nb ≥ 8× % C Nb ≥ 8× % C Nb ≥ 8× % C N N Table 9.0 17.0 19.5 ≤0. 25 30 – 55 Martensitic b 450 – 600 600 – 950 14 – 18 Austenitic c ca.5 4.5 ≤0.5 10.0 ≤0.0 13. they are used for pipelines intended for chloridecontaining waters. Temperatures above 1100 ◦ C affect the structure to such an extent that the steel breaks when subsequently loaded.4308 1.04 ≤1.4 wt % carbon serve as heattreatable materials with good mechanical properties.0 11.5 20.0 19.0 20.0 19. J g a b Ferritic a ca.4585 1.07 ≤1.5 ≤0. 150 Austenitic – ferritic d ca. longitudinal. MPa Fracture strain.4500 9. 230 e ca. ferritic steels are pure or mainly ferritic.5 ≤0.7 Cu Others ≤0. heating beyond 800 ◦ C. g DVM specimen.4581 1. f 1 % yield strength.5 Composition. while those with higher carbon contents are used as hardened steels.4306 9.3 3.4 3. 600 45 ca.4552 1.07 ≤1. 30 Normal steels with 16 – 18 wt % Cr.

even in mild corrodents. resistance welding (spot or seam welding). heat resistance. It is therefore advisable to use thin electrodes and low currents. chromium reduces the passivation current density and the residual current density of the steel in the passive state. In view of the marked grain growth tendency. Ferritic. additions of stabilizing elements also improve the resistance to pitting corrosion. as little heat as possible should be introduced. and submerged-arc welding. stability diagrams. Hardening by heat treatment is not possible. and loss of chemical resistance through separation into phases of high iron and chromium content [52] and σ-phase formation). MIG. In particular. In this connection. MIG) process. High chromium contents favor the formation of ferritic structures. for example. Apart from using steels that have no intergranular susceptibility after welding (stabilized steels and ELC types) it is particularly important to avoid hot cracking and loss of corrosion resistance through precipitation of intermetallic phases. the surface quality can be improved by subsequent grinding. protective gas should be used to prevent scale formation on welding. in comparison with purely austenitic steels. and a tendency to creep. 2 . If. apply only to chemically pure corrodents. and copper are also significant.1 g m−2 h−1 ) represents the highest degree of corrosion resistance attainable under practical conditions. and the plasma arc welding and electron beam welding are particularly suitable for ferritic chromium steels. resistance to pressurized water. Their applications include pump manufacture. The final heat treatment consists of heating to 1000 – 1100 ◦ C and quenching in water or air. In austenitic – ferritic steels the ratio of ferrite to austenite is determined by the composition and heat treatment. as well as to the fact that. Although the latter benefit from heat treatment. for reasons of corrosion (particularly the risk of stress corrosion cracking). Austenitic chromium – nickel steel is recommended as the electrode material in addition to material of the same composition as the base. of which Figure 14 is an example. The most conspicuous properties of these steels are a low yield strength. The grain-growth rate is much lower than that of ferritic steel. 5. either of these materials cannot be used. The main effect of molybdenum is a reduction of the passivation current density and facilitation of repassivation. Where the de- 19 mands are particularly severe. Often. chromium is particularly important.6. however. Cleanliness of the seam. It increases with the annealing temperature and rate of cooling. stabilized grades should be used. as in the case of components subjected to vibration. austenitic. molybdenum. Appropriate recommendations can be found in the processing guidelines. Corresponding data can be found in stability tables and diagrams and in manufacturers’ literature. which must be without splashes and undercutting. these steels are less sensitive to stress corrosion cracking. In general it is considered that a corrosion rate of 0. The principal welding methods for austenitic steels are TIG. As scale formation may be accompanied by the formation of chromium-depleted surface zones.1. Unstabilized 17 wt % chromium steels that have been welded must always be annealed since they are otherwise sensitive to intergranular corrosion. and ferritic – austenitic stainless steels can be welded by practically all the well-known methods. which promotes the transition from the active to the passive state. In the case of sulfuric acid.2. high strength at elevated temperatures. Where this treatment is impracticable. the strength is improved by cold or hot – cold forming. Apart from imparting resistance to intergranular corrosion. Chemical Properties The resistance of stainless steels to corrosive media is determined by their passive behavior. permanent strain at low loads. Special grades with high wear resistance are used for bushings. is also important. but the effects of nickel. loss of toughness. Fine granulation results from recrystallization during hot forming. Attention is drawn to the risk of 475 ◦ C embrittlement (hardness increase. The argon arc (TIG. which depends in turn on the alloying elements and their concentrations. high resistance to fracture. Stabilized steels and molybdenum-containing steels also exhibit lower growth tendency.1 mm/a (0.Construction Materials in Chemical Industry forming. An important application is the fabrication of pressure vessels. it is not absolutely necessary. even relatively small amounts of oxidizing agents(NO− . an austenitic filler can serve for the lower layers and a ferritic filler for the cover pass.

the susceptibility of metallic materials to localized corrosion increases with the resistance to general corrosion. Intergranular corrosion is a selective process in which the areas close to the grain boundaries are corroded.g. Therefore. The corrosion may penetrate even relatively thick components within a short time. Normally.g. pitting corrosion (pit formation). Uniform surface corrosion is of relatively minor importance for stainless steels.20 Construction Materials in Chemical Industry Fe3+ ) permit the use of stainless steels in sulfuric acid at concentrations up to ca. silicon.g. 2) Chemical attack on precipitates at the grain boundaries. e. 20 % Cr. and fatigue corrosion (corrosion fatigue cracking). e. 3 % Mo. which occur with virtually no loss of mass. the local anodic dissolution current density is very high. Isocorrosion curves of chromium – nickel – molybdenum stainless steels in sulfuric acid A) 0.. and boron (which Figure 14. B) 0. however.. these precipitates may be formed in the heat-affected zones bordering on the weld seams.. In all cases it has one of the following causes: 1) Depletion of alloying elements important to chemical resistance in areas close to grain boundaries. 50 % and temperatures considerably higher than those shown in Figure 14. and of the state of motion (e.05 % C.05 % C. The types of localized corrosion that are most important in stainless steels are intergranular corrosion (grain-boundary attack). In joint welding. in which these elements have accumulated. Damage caused to passive materials by stress corrosion cracking and fatigue corrosion. 17 % Cr. 25 % Ni. stress corrosion (corrosion cracking). 13 % Ni. the corrodent’s oxygen content. laminar or turbulent flow) must be taken into account also. Thus figures for resistance to pure corrodents should in many cases be regarded as initial approximations.e. at the grain boundaries. In localized corrosion of stainless steels. 3) Preferential attack by accumulations of accompanying and trace elements in the steel. i. The influences of ventilation. by concentrated nitric acid on precipitates of titanium carbonitrides in titanium-stabilized steels. may lead quickly to component failure even where the corrosion rate is low. Localized corrosion. 2 % Cu . is particularly hazardous. phosphorus. caused by formation of precipitates. the locally active areas are very small compared to the area of the passive surface. 5 % Mo.. and must therefore be avoided as far as possible.

and especially titanium. 4) Cell formation between the matrix and precipitates at the grain boundaries. see above). c) Intergranular corrosion The susceptibility to intergranular corrosion is indicated by the grain-boundary corrosion fields in the plot of annealing time versus annealing temperature (Fig. however. In ferritic chromium steels. When the temperature falls after welding. the depletion of the alloying elements chromium and molybdenum resulting from precipitation of carbides with high chromium and molybdenum contents is the most important cause of intergranular corrosion in industry. In stainless steels. are formed round the precipitated carbides. the rate at which chromium-rich carbides are precipitated is very high. the very high diffusion rates permitted by the body-centered cubic lattice of the α mixed crystal causes rapid replenishment of chromium by diffusion from the chromiumrich matrix into the chromium-depleted grain boundary areas. 21 highest temperature that still causes susceptibility to intergranular corrosion and by the shortest annealing time leading to sensitization of grain boundaries. the steel’s nitrogen content. as well as its carbon content. Through the precipitation of chromium-rich carbides (75 – 90 wt % Cr) the chromium content in the vicinity of the grain boundaries falls below the so-called resistance limit of ca. stabilization. As a reduction of the carbon content would not eliminate intergranular susceptibility until an extremely low level had been reached (< 0. It is therefore also known as chloride corrosion. They form special carbides or carbonitrides of the type M (C. The carbon dissolved in the austenitic solid solution at high annealing temperatures may precipitate at the grain boundaries at lower annealing temperatures as a carbide of type M23 C6 with high chromium and molybdenum content. must be taken into account in calculating the stabilization ratio. The following steps are taken to make the steel resistant to intergranular corrosion after welding: 1) The carbon content is reduced to levels at which neither temperature nor the exposure time causes sensitization (ELC steels). even of ferritic chromium steels.005 wt %). which grow together to form coherent chromium-depleted areas as the carbide precipitation progresses. The shape and sizes of these fields are best described by the . This shortest annealing time (represented by the “nose” of the grain-boundary corrosion field) is situated in the temperature range around 650 ◦ C for molybdenum-free austenitic steels and in the range around 750 ◦ C for molybdenum-containing steels. The affinity of these alloying elements for carbon is greater than that of chromium. Figure 15. In this way zones of depleted chromium and molybdenum content. it passes through the range in which austenitic chromium – nickel steels become susceptible to intergranular corrosion. Pitting corrosion of stainless steels occurs only when they are in the passive state. has great industrial importance. Diagram of grain-boundary disintegration a) Solubility limit for carbon. In the temperature range around 800 ◦ C. After annealing at temperatures above 850 ◦ C. At low temperatures the solubility of carbon in austenitic chromium – nickel steels and nickel – chromium alloys is very low. and is then caused almost exclusively by chloride ions in aqueous solution.Construction Materials in Chemical Industry stimulate the anodic metal dissolution at the grain boundaries). but it increases markedly as the temperatures rises. N). 15. even very rapid cooling cannot prevent their precipitation. 2) Stabilization with additions of the carbide-forming element titanium or niobium/tantalum. by addition of niobium/tantalum. and the formation of a structure susceptible to intergranular corrosion. b) Precipitation of chromiumrich carbides. Due to the affinity of both elements for nitrogen. 12 wt % chromium.

no SCC Under conditions that cause stress corrosion cracking the following materials can be used instead of normal stainless austenitic 18 Cr 10 Ni steels: stainless ferritic chromium steels with 17 – 28 wt % chromium.22 Construction Materials in Chemical Industry Stress corrosion cracking of stainless steels with mainly transgranular progression of the corrosion cracks may occur in the following corrodents: 1) Chloride solutions (threshold temperature 50 ◦ C). The basic prerequisites of stress corrosion cracking are as follows: 1) The action of a specific corrodent on a material susceptible to stress corrosion cracking. with the help of the pitting resistance equivalent PRE [54]: PRE = wt %Cr + 3. With regard to the attacking medium. on the other hand. 100 ◦ C). In the presence of a corrosive medium. Figure 16. the alloying elements nickel and manganese. whose use is restricted in some cases to temperatures below 300 ◦ C. with or without molybdenum. Pitting corrosion only occurs when the potential exceeds the pitting potential. an alloying element that decisively improves the stress corrosion cracking resistance . austenitic – ferritic steels (duplex steels). In the pitting corrosion of stainless steels. possibly superimposed by infrequent dynamic loads. SCC. intergranular cracking occurs at high temperatures in dilute alkaline solutions. In addition. The effects of chromium and molybdenum are described. 16) [55]. the pitting potential can be shifted towards more positive potentials by raising the chromium content and especially the molybdenum content. With regard to the material. the presence of a critical material/corrodent system. If the steel is in the sensitized state in which it is susceptible to intergranular cracking. Apart from molybdenum. in as far as the structure is that given by solution annealing. the main factors by which the pitting potential is lowered (and therefore the risk of pitting corrosion heightened) are increase of chloride concentration and temperature. e. SCC. water at high temperatures (Fig.g. and the tensile stress and potential exceed critical values. 2) Static tensile stresses. accounts for most of the damage suffered by stainless steels. Stress corrosion cracking. have practically no influence. no SCC. austenitic steels with increased nickel and/or molybdenum content.. and reduction of pH [53].e. Pressure does not cause stress corrosion cracking. whereupon the passivity breaks down. 2) Alkaline solutions (threshold temperature at 40 – 50 wt % NaOH. in fact. in many cases it is an effective means of preventing corrosion of this type. In the initiating step of pitting corrosion chloride ions are adsorbed locally by the passive layer. Only tensile loads are effective.3 × wt %Mo Over a wide range of percentages of these elements.. Applied stresses in excess of yield strength and test times in excess of 1000 h. ◦ = Sensitized. The mechanism of this corrosion has not yet been fully explained. and the resistances of the various alloys estimated. intergranular stress corrosion cracking occurs also in. the pitting potential depends linearly on the pitting resistance equivalent. i. = Annealed. Deviations are attributable to homogenization of the structure by relatively high nitrogen contents. = Annealed. or strain rates greater than 10−5 s−1 • = Sensitized. the influence of potential is important. Concentration ranges of dissolved oxygen and chloride that may lead to stress corrosion cracking (SSC) of type 304 stainless steels in water at temperatures in the range 260 – 300 ◦ C. and nickel-based alloys. pitting corrosion therefore occurs only if the corrosion potential of the steel is more positive than the pitting potential. which is likewise initiated mainly by chlorides.

18).4565 are as follows: . are formed. 123 ◦ C) The steel X 3 CrNiMnMoNbN 23 17 5 3 (1. for whose occurrence specific corrodents are responsible. In boiling seawater all the steels achieved times to failure of more than 1000 h at loads above the 0. In the active state numerous cracks are formed. Damage to stainless steel plant through fatigue cracking is.3. Figure 18. [58].6. which is without Nb and therefore free from precipitation. whereas in the passive state few cracks. This is achieved by renitrogenizing the steel under pressure and simultaneously adding alloying elements that increase the nitrogen’s solubility [57]. With a pitting resistance equivalent of about 48 (in which the high nitrogen content is taken into account) it is more resistant to pitting corrosion than any other stainless steel (cf. Figure 17. Corrosion fatigue is the term used for crack damage which occurs in a component exposed simultaneously to alternating mechanical stress and a corrodent. Only NiCr 22 Mo 9 Nb. 5. the latter is superior in respect of strength-related properties in consequence of precipitation hardening by a finely dispersed intermetallic Z-phase (0. Development State of Stainless Cr – Ni Steels The corrosion resistance of stainless steels is benefitting from the attainment of particularly high degrees of purity. To make possible the increases in Cr and Mo content on which these improvements depend it is necessary to increase the nitrogen content. manganese.Construction Materials in Chemical Industry of stainless austenitic steels is nickel (at nickel contents exceeding about 40 wt %.1. It may be caused in all metallic materials by unspecific corrodents.. Stress corrosion behavior of nitrogen-containing stainless steels in boiling MgCl2 solution (35 wt %. 500 MPa. At the same time the strength-related properties are being improved without loss of ductility. The main symptom of corrosion fatigue is the loss of endurance strength.4565) is commercially available. relatively rare [56]. is superior in ductility (notch impact energy at room temperature > 300 J). Of two steels now undergoing trials. stress corrosion cracking no longer occurs). This steel.2 % yield strength of ca. > 300 MPa). for example. however. The steel 23 with the highest N content is the one most resistant to boiling 35 % MgCl2 solution.g. Pitting resistance equivalent (PRE) and critical pitting corrosion temperature for various steels and Incoloy 625 in a 10 wt % solution of FeCl3 · 6 H2 O Some mechanical properties of alloy 1. Fatigue cracking of stainless steels differs according to whether they are in the active or passive states.2 % yield strength [60]. e. The stress corrosion cracking behavior of steels of this type is shown in Figure 17. better known as Incoloy 625. 250 MPa [59]. or perhaps just a single precrack. differing in this respect very much from stress corrosion cracking. Fig. as given by electroslag remelting. at 500 ◦ C. namely X 3 CrNiMoNoN 23 27 6 4 and X 3 CrNiMnMoNbN 23 17 8 4. though at 500 ◦ C it still has a 0.2 % yield strength at room temperature ca. performs comparably well.

Mean tensile strength of gray cast iron versus the section thickness of the casting (according to DIN 1691) A special grade that withstands hot nitric acid and hot sulfuric acid is the iron – silicon material containing 14 – 18 wt % silicon. [63] withstand corrosion by alkalis and sulfuric acid. ferritic – pearlitic. Its hardness and brittleness constitute a great disadvantage because they restrict the choice of shaping techniques to casting and grinding. for unalloyed and lowalloy lamellar graphite cast iron. MPa 100 – 450 400 – 800 140 – 280 390 – 500 Fracture strain. DIN 1693. 2 – 5 wt % carbon and 0. The exceptionally low plastic deformability and impact strength of lamellar graphite cast iron in comparison with nodular graphite cast iron are explained by the graphite lamellae. for unalloyed and low-alloy spheroidal graphite cast iron. J 9 – 14 (−20 ◦ C) 7 – 34 . for example. The strength of gray cast iron depends on the thickness of the casting’s cross section (wall thickness). lowalloy. but also austenitic. 0. 0. Lamellar and nodular graphite cast iron can be welded hot with filler materials of the same Tensile strength σ u . The austenitic grades that withstand moderately high and high temperatures are used for pumps. and highly alloyed iron – carbon cast materials containing ca. and plastics industries as well as for pipes and vessels. waste-gas pipes. for austenitic cast iron. The main alloying elements are nickel. The filler metals used for them at present are relatively highly alloyed nickelbased materials of the Ni – Mo – Cr type. Cast Iron [60]. artificial silk. and DIN 1694.6676) and the low-temperature ductility of GGG(nodular)NiMn 23 4 (material no. Figure 19. Empirical values for the strength of castings are given in Figure 19. Mechanical properties of the various types of cast iron are listed in Table 10.7673).2. The fundamental structure of unalloyed and low-alloy cast iron is ferritic. Depending on their composition and the form of the graphite. The main quality standards are DIN 1691. Mention should also be made of the thermal shock stability of GGL(laminar)NiCr 30 3 (material no. Mechanical properties of the various types of cast iron Cast iron type Unalloyed and low-alloyed laminar Unalloyed and low-alloyed nodular Austenitic laminar Austenitic nodular furic acid and pure phosphoric acid. and copper. and furnace parts.2 % Yield strength 0. Unalloyed and low-alloy lamellar graphite cast iron and nodular graphite cast iron are attacked only slightly by pure sulTable 10. these materials have good welding behavior. Their resistance to soil corrosion and seawater attack is also good. austenitic cast materials [62]. chromium. which act as internal notches. or pearlitic. The corrosion-resistant grades are used in the food. valves. [61] (→ Steel) The term cast iron is used for unalloyed. % <1 2 – 22 1–3 1 – 40 Notch impact energy. 5. that of highly-alloyed cast iron may be any of these.8 – 3 wt % silicon. the carbon being mainly in the form of graphite.2 % Yield strength at 300 ◦ C Notch impact energy at − 269 ◦ C Elongation Reduction of area As the nitrogen contents of the aforementioned steels in the molten state are below the solubility limit.24 Construction Materials in Chemical Industry ≥ 500 N/mm2 ≥ 300 N/mm2 ≥200 J > 50 % at room temperature > 70 % at room temperature 0. cylinder linings.

and nickel – copper. The nickel content (according to DIN 17 740) may include up to 1 wt % cobalt. wires. except submerged-arc welding [74].0 wt %. and nickel – molybdenum alloys. Figure 20. [65]. namely NiCu30Fe (2.6 wt %.6 (2. pipe. which has a maximum carbon content of 0. and manganese to improve the flow of the molten metal and density of the castings. solutions of nonoxi- . LC-Ni 99 (2. nickel and its alloys are of growing importance in chemical engineering. Corrosion resistance of pure nickel in sodium hydroxide. related to concentration and temperature [72] All the welding methods normally used for steel. It can also be exposed to dry chlorine or hydrogen chloride at temperatures up to 535 ◦ C.6 (2.3. the carbon may be precipitated as grain boundary graphite. rods.2 up to 0. strip.6 wt %. LC-Ni 99. have good high-temperature strength by virtue of their high creep strengths.4375). nickel content ≥ 99. Plant consisting of nickel or nickel-plated steels is used mainly to produce and process alkalis [71]. Ni – Cr alloys. Up to about 300 ◦ C its yield strength and tensile strength undergo practically no change [69].4360.2 (2. Ni 99. [72]. The surface must therefore be cleaned thoroughly before welding and each annealing treatment. nickel content ≥ 99. silicon. [70].Construction Materials in Chemical Industry composition.2 wt %. The most important unalloyed nickel grades are Ni 99. Both are sold as sheets. Nickel is very sensitive to sulfur and sulfur compounds [69]. 5. seawater. Nickel and Nickel Alloys [66–68] (→ Nickel. The good resistance of pure nickel to sodium hydroxide solution can be seen in Figure 20. nickel content ≥ 99. copper – nickel. Sulfur-free lubricants must be used in hot and cold forming. and Ni 99. Nickel parts can also be joined by brazing and soldering. Suitable weld filler materials are available for combinations with unalloyed or low-alloy steels. Above 400 ◦ C sulfur penetrates nickel along the grain boundaries and forms a eutectic mixture of nickel and nickel sulfide. austenitic stainless steels. which are standardized in DIN 17 743. after prolonged exposure to temperatures above about 300 ◦ C. and fatty acids. [71]. → Nickel Alloys) Owing to their excellent corrosion resistance to various aggressive media. thus making the material brittle [69].4060). Frequent use is therefore made of LC (lowcarbon) Ni. embrittling the material.4061). are suitable for nickel.02 wt % [70]. nickel content ≥ 99.3. dilute airfree and nonoxidizing mineral acids and salt solutions. [74]. and cold with filler materials of different composition [64]. Nickel – Copper Alloys In chemical engineering only two alloys with more than 50 wt % nickel have gained importance. 25 5. The alloy NiCu30Fe can be exposed to seawater and brackish water.4066).1. Furthermore. This process is rapid at 550 – 650 ◦ C. the furnace atmosphere should be slightly oxidizing.4060). but is always slightly alloyed with carbon. Cast nickel [70] has the characteristic properties of forged nickel. Nickel is also used to handle acid halides [73]. especially those with additions of silicon and aluminum.08 wt % carbon. The furnace atmosphere for heat treatment should be sulfur-free and reducing or neutral.1 wt % carbon. Ni 99. Inconel alloy 400) and NiCu30Al (2. brackish water. if freedom from sulfur cannot be ensured. Nickel has good high-temperature strength.6 may contain up to 0. and good heat-resistance to hot gases and combustion products. and forgings.

Like pure nickel and the other nickel alloys. Table 11. hot gases. 5.4641 2. cooling water. Nickel – Chromium Alloys [68] Nickel – chromium alloys. are normally used where the corrosion resistance of highly alloyed stainless steels is inadequate. phosphoric acid seawater. Like pure nickel. has good resistance to caustic alkalis. 5. is envisaged. cold or warm nonoxidizing acids [73]. This explains their good resistance to acids and salt solutions.3.g. Because of the risk of stress corrosion cracking it should be used in the age-hardened state. together with their main applications. Nickel – chromium alloys DIN designation NiCr15Fe NiCr23Fe NiCr29Fe LC-NiCr15Fe NiCr20CuMo NiCr21Mo NiCr21Mo6Cu NiCr22Mo6Cu NiCr22Mo7Cu NiCr22Mo9Nb NiCr21Fe18Mo Material no. alkalis sulfuric acid. Soft soldering is less frequently used. Chromium – nickel casting alloys (60/40.4816 alkalis sulfuric acid. Nickel – chromium – iron – molybdenum alloys combine the good resistance of nickel – molybdenum alloys under reducing conditions with the good resistance of nickel – chromium alloys under oxidizing conditions.4603 U. phosphoric acid.4619 2. combustion products as 2.3. they are sensitive to sulfur and its compounds at temperatures above ca. stress relief annealing should be carried out at 550 ◦ C. by welding. alkalis. 400 ◦ C. Both materials are weldable by the usual methods. even surpassing it in this respect under oxidizing conditions in consequence of its high chromium content [77]. trade name Inconel alloy 600 Inconel alloy 601 Inconel alloy 690 Carpenter 20 Cb-3 Inconel alloy 825 Exposure tolerated seawater. with various iron contents and up to ca. both alloys are sensitive to sulfur and sulfur compounds above ca. 9 wt % molybdenum and 2 wt % copper. The types most important in chemical engineering. HNO3 – HF pickling acid Hastelloy alloy G-3 Inconel alloy 625 Hastelloy alloy G-30 . as well as to a lesser extent in the liquid phase.4618 2. seawater. cooling water acids. Nickel – Molybdenum and Nickel – Molybdenum – Chromium Alloys Nickel – molybdenum and nickel – molybdenum – chromium alloys are among the chemically most resistant metallic materials. NiCr15Fe. 50/50 and 35/65) are used in chemical engineering and have good resistance to corrosion by fuel ash [78].5851 2.4642 2. crevice corrosion. With the low-carbon grades and those stabilized with titanium or niobium there is virtually no risk of intergranular corrosion. and followed by slow cooling in the furnace. seawater. they can also be brazed. Where there is a risk of stress corrosion cracking. NiCr23Fe and NiCr29Fe have greater high-temperature strength than nickel and can be exposed to oxidizing sulfur-free atmospheres at temperatures up to 1100 ◦ C.4816 2. like nickel. NiCu30Al is an age-hardenable alloy with similar corrosion behavior to NiCu30Fe. Stress corrosion cracking has been caused in these alloys by corrosive media containing mercury or its compounds. and to reducing sulfur-free atmospheres at up to 1150 ◦ C.4858 2. The main dizing salts.4641 acids. 400 ◦ C.26 Construction Materials in Chemical Industry The molybdenum-free alloy NiCr15Fe.4856 2.S. this must be taken into account where processing. though stress corrosion cracking may occur in hydrofluoric acid vapors containing air.2. however.3. and dry bromine. e. are listed in Table 11. 2. and in exceptional cases at up to 650 ◦ C. it cannot be exposed to hydrofluoric acid. alkalis [75].4817 2.4660 2. and stress corrosion cracking. As NiCu30Fe is expensive. They exhibit good resistance to acids and to pitting corrosion. cooling water as 2. solid sheet is often replaced in the manufacture of process plant by steel sheet plated with this alloy. It is also resistant to hydrofluoric acid [76]. These alloys are also used in nitriding gases (480 – 600 ◦ C) and under carburizing conditions (800 – 950 ◦ C). cooling water.. mixed acids acids.

They are weldable by all the commonly used methods. solution annealing at 1150 ◦ C. test for intercrystalline corrosion in accordance with ASTM G28 Hot and cold forming of these high-nickel materials is difficult owing to their high water resistance and work-hardening tendency. is recommended [79]. and they are often used for this purpose. precipitation of intermetallic compounds containing these elements may make the materials susceptible to intergranular corrosion. therefore. minimization of the silicon and carbon contents (< 0.4610) and NiCr21Mo14W (2. and therefore resistant to corrosion under these conditions also. Al 99.4617 2.5. 2. above all. for which molybdenum is responsible. If the design and size of a component permit heat treatment.4 (b). NiCr21Mo14W has proved itself under severely oxidizing conditions. they can be used under reducing and oxidizing conditions. however. 26 – 30 wt % molybdenum and 5 – 7 wt % iron withstands hydrochloric acid at all concentrations. 5.4. like all materials with high nickel contents. followed by water quenching. for example). Above 400 ◦ C they are sensitive to sulfur and sulfur compounds.99. Nickel – molybdenum alloys of this kind cannot be used under oxidizing conditions. The alloy NiMo30 (2. [83]. Their good resistance to reducing acids is explained by the low rate of corrosion in the active state. in spite of its very negative standard electrode . 21). Since the corrosion resistance of nickel – molybdenum and nickel – molybdenum – chromium alloys depends on molybdenum and/or chromium.4608).Construction Materials in Chemical Industry representatives of this group are listed in Table 12. Steel can be explosion-cladded with any of these alloys.4608 Designation NiMo28 NiMo16Cr16Ti NiMo16Cr15W NiCr21Mo14W US trade name Hastelloy alloy B-2 Hastelloy alloy C-4 Hastelloy alloy C-276 Hastelloy alloy C-22 27 strated by the time – temperature precipitation diagram of Hastelloy alloy C-4 (Fig. Aluminum and Aluminum Alloys (→ Aluminum. because even atmospheric oxygen increases the rate of corrosion considerably.03 wt %) and additional stabilization [80]. Precipitation of molybdenum-rich compounds leads to intergranular susceptibility in the active state (in hydrochloric acid. The good corrosion resistance of aluminum. for example. annealing. however.4610 2. depends more on its corrosion behavior [82].8. In addition they retain their low rates of corrosion in the active state. consisting of nickel. Pure and very pure aluminum according to DIN 1712 comprise the grades Al 99. give alloys that tolerate hot forming. to start by making a thin root pass and then to weld the filler and cover passes while cooling the root side of the weld. Alloying with chromium makes them passive in oxidizing corrodents. [81]. Nickel – molybdenum and nickel – molybdenum – chromium alloys Material no. Nickel – molybdenum alloys are not passifiable. but. since they contain no chromium. this must be taken into account in connection with annealing and welding. and welding without acquiring intergranular sensitivity. this is demon- Figure 21. and Al 99.4810). like NiMo16Cr16Ti (2. while precipitation of compounds rich in chromium causes susceptibility to intergranular corrosion and intergranular crack formation in the passive state [79]. Al 99. → Aluminum Alloys) The high strength and low density of aluminum make it highly suitable for lightweight structures. Exact proportioning of the alloying elements. Its economic value in the chemical industry. Time – temperature sensitization diagrams for Hastelloy alloy C-276 (a) and Hastelloy alloy C. in the interest of good corrosion resistance. Table 12.4819 2. In the production of weld joints it is advisable.

relatively thick corrosion-inhibiting Al2 O3 layers can be produced by anodic oxidation. apparatus 2 3–5 Cooling machines Cooling plant ∗ 1 = good resistance. is due to the formation of nonconducting Al2 O3 passive films. Al – Mg – Si. Table 13. 6 = not resistant . They consist of a very thin and almost nonporous dielectric underlayer (barrier film) and Figure 23. 4 = still usable. 5 = barely resistant. The corrosion behavior and the main applications are listed in Table 13 [82].5 wt % Al.8 (Fig. The corrosion resistance depends on the purity of the material. cars Shipbuilding Tanks. wet Distilled water Freon Ice Seawater Corrosion resistance∗ AlMg AlCuMg Application 1–2 5 1 1–2 1 2–3 1–2 1 1 3–6 1–2 1 1 2–3 2–3 1–2 1 3–2 1 1 1 1–2 1 1 1–2 3 3–5 1 1–3 Pressure bottles Cooling elements Pressure bottles Construction. produced by anodizing High-purity aluminum is used in chemical engineering mainly as a cladding material. dry Liquid ammonia.28 Construction Materials in Chemical Industry a fine-pored top layer (Fig. which for chemical plant should not be below 99. 23). Structure of an oxide film on aluminum.5 – 8. which can be dyed and compacted [84]. 3 = low resistance. 22). Apart from aluminum itself. potential of − 1. dry Ethane Atmosphere industrial marine Benzene Gasoline leaded. aluminum materials have very good resistance to corrosion in approximately neutral aqueous media. As the protective Al2 O3 surface layer is largely insoluble in the pH range of 4. 2 = resistant. Hard anodizing is an anodic oxidation process that gives particularly hard and wear-resistant oxide films for technical purposes [85]. Al – Mn. Figure 22. Influence of pH on the solubility of the Al2 O3 film on aluminum Because the Al2 O3 passive film is nonconducting. Examples for the corrosion behavior of aluminum alloys in various media Corrosive environment Al 99. and Al – Zn – Mg are suitable for hard anodizing.66 V.5 Ethanol water-containing dry Acetylene. numerous wrought and cast alloys based on Al – Mg.

5Mn. AlMgSi0. AlMg3. Wrought alloys are standardized in DIN 1725. they reduce the resistance to intergranular corrosion by causing the formation of heterogeneous grain boundary precipitates. b) AlMg7 phase with grain boundary precipitates.8 – 4. they are particularly susceptible to stress corrosion cracking [89].4 – 3. 25). These materials. c) AlMg7 phase. Figure 24. AlCu4Mg2: σ u = 440 MPa) but low corrosion resistance. the alloys based on Al – Zn – Mg. Their corrosion resistance is approximately equal to that of pure aluminum (Al99. A Figure 25. Part 1. it is preferable to choose materials with low silicon contents (e. with increasing magnesium content (especially for Mg >5 wt %). Part 2.5 wt % Mn are easy to process and exhibit corrosion resistance similar to that of pure aluminum. and AlMg4.g.. whose strength is further improved by cold forming. Corrosion behavior of Al 99. where corrosion is expected.5).8. Si.3 – 1.5 wt % Mg. Zn. even at high temperatures. are not fully resistant to pitting and intergranular corrosion in media with high chloride contents. Aluminum – manganese alloys are of the selfhardening type.8 – 1. After artificial ageing. . and especially Al – Zn – Mg – Cu. Table 13). Both groups include self-hardening (alloy hardening) and hardenable (precipitation hardening) materials. Although relatively high silicon contents raise the strength. the susceptibility of Al – Mg alloys to intergranular corrosion increases through the formation of Al8 Mg5 grain-boundary precipitates (Fig. There is also a risk of susceptibility to stress corrosion cracking [87].5Mn therefore belong to the group of aluminum materials known as seawater resistant..5).5 in nitric acid The main alloying elements that are used to increase the strength of aluminum are Mg.g. The stability can be raised by reducing the magnesium content and adding manganese. Cu. Breakthrough potentials for intergranular corrosion a) Al8 Mg5 . and Mn.Construction Materials in Chemical Industry Super-pure aluminum and AlSi 12 are outstandingly resistant to highly concentrated nitric acid (Fig. 0. however. which has good strength-related properties and corrosion resistance and is used both for purposes involving seawater contact and in chemical engineering.8 wt % Cu. AlMg2Mn0. which they even surpass where seawater is concerned (cf. 24). and cast alloys in DIN 1725. AlMg5. Additions of Mn and Cr improve the resistance to chloride-induced pitting corrosion [88]. 29 typical representative of the materials obtained in this way is AlMg4. homogenized Age-hardenable Al – Cu – Mg alloys (2.4 – 1. They also withstand concentrated acetic acid well [86].8 wt % Mg) have high strength (e. Alloys containing 0. Apart from having little resistance to atmospheric corrosion. The main representatives of the selfhardening materials are Al – Mg alloys. Age-hardenable Al – Mg – Si alloys with good heat forming behavior (0.5 wt % Si) are more resistant to corrosion than Al – Cu – Mg alloys. Therefore. However. 0.

condensers. or Sn. Another possibility is the use of impressed current or sacrificial anodes (zinc) to reduce the potential below the values at which the risk of pitting or intergranular corrosion is critical [84]. is plant for drinking. In nonoxidizing acids in the absence of oxygen and at room temperature this rate remains low. too. especially aqueous media containing NO− . Copper and Copper Alloys [90]. In approximately neutral solutions capable of forming surface films. heat exchangers in seawater desalination plants. strength-related properties. and for many other purposes are explained not only by good resistance to corrosion but also by their good workability.34 V) copper (DIN 1787) has good resistance to corrosion. Sb. and high thermal and electrical conductivity. Dezincification of the α-phase alloys is counteracted by adding As. which has the higher Zn content. this explains its use in the construction industry. 5. and industrial water [82]. Important cast aluminum alloys for mechanical and chemical plant are those based on Al – Si (5 to 20 % Si). including resistance to seawater. Various treatments and methods are used to protect aluminum from corrosion. Sn. Their many outdoor applications as fresh water pipes. copper is substantially resistant. however. The (α + β)-alloys tend to suffer preferential attack on the β-phase. in oxidizing acids such as sulfuric acid. raises the strength of copper. The alloys of both types. Al – Mg (3 to 10 % Mg). cannot be entirely excluded [93]. but above all the (α + β)-alloys.5. even on the part of pure copper. they are distinguished by good corrosion resistance. High-strength aluminum alloys. Nonmetallic inorganic coatings such as chromate and phosphate increase the corrosion resistance and also serve as primers for paints [83]. CuZn20Al is remarkable also for its good resistance to seawater and also to erosion – corrosion. In aqueous ammonia solutions under conditions in which surface films are not formed (high alkalinity). are frequently plated with pure aluminum (Al99. and water at high temperatures. suffer dezincification corrosion in chloride-containing waters (Fig. and P as additional alloying elements [94]. Al. condenser. In cooling water containing NH3 or H2 S there is a risk of stress corrosion cracking. some susceptibility to stress cor2 rosion cracking. as do high-copper alloys. apart from having high strength and adequate ductility. In the case of Cu – Zn alloys (DIN 17 660) single phase α-phase alloys (Zn ≤ 37 wt %) and (α + β)alloys (37 – 46 wt % Zn) are distinguished. CuZn28Sn and CuZn20Al (2 wt % Al) have been used successfully for many years as materials for cooler. In inorganic and organic acids the corrosion rate depends largely on the presence of oxidizing agents. Among the ternary alloys. industrial water. it has good resistance. In accordance with its position in the electrochemical series (standard potential Cu/Cu+ = 0. 26. see next page).30 Construction Materials in Chemical Industry containing NH3 ) results from the formation of oxide films which consist of Cu2 O or CuO (depending on the nature of the medium and the corrosion potential) and which afford good protection.5). but they are susceptible to pitting and intergranular corrosion in chloride-containing media. Here. cooling. fittings. though under unfavorable conditions (as when deposits are formed or the nature of the water is unsuitable) pitting corrosion cannot be entirely ruled out [92]. particularly with Zn. Ni. for example. Its main field of application. The critical stress for ammonia-inducedstress corrosion have higher strength (up to 530 MPa) than all other aluminum materials. Alloying. [91] (→ Copper and → Copper Alloys) The good corrosion behavior of copper and copper-based alloys has led to their extensive use under moist atmospheric conditions and in the handling of drinking water. as a result of which an AlOOH (boehmite) layer with a thickness of 1 – 2 µm is formed above the Al2 O3 barrier layer [84]. In outdoor applications. the former being more resistant to corrosion. and heat exchanger tubes in cooling waters with relatively low contamination levels. or Al – Mg – Si or Al – Si – Mg. including those in marine climates. it increases with the oxygen content. The thickness of the natural oxide film on aluminum can be increased by boiling the metal in deionized water or by steaming it. in chemical apparatus. copper is attacked severely. The good resistance to approximately neutral to alkaline aqueous media (not including water .

. CuAl11Ni. With favorable working properties and resistance to alternating stresses. In addition to the increased Al content. Dezincification of α-brass in tap water Figure 27. Owing to their lubrication properties. but also preferential dealuminization. Fe. and condenser tubing. the homogeneous α-alloys (Al ≤ 7. including those of seawater pumps. worm gears. Their strength depends on the tin content and degree of cold forming. depending on whether they are wrought alloys or cast alloys [82]. which. Residual stresses in components that have not been sufficiently annealed may therefore suffice to initiate crack formation. examples being CuAl5. and is only about 10 MPa for Cu70Zn30 (Fig. b) CuNi. and process plant. they show heightened susceptibility to ammonia-induced stress corrosion cracking. and turbine blades. pipes (CuSn6) and chemical plant components (CuSn4. The heterogeneous multiphase alloys (Al >10 wt %). this applies particularly to Cu – Al materials with about 4 wt % Al (Fig. Although the homogeneous α-alloys are those most resistant to uniform corrosion and dealuminization.g. c) CuZn Upper curves: tensile strength. In their resistance to seawater they even surpass pure copper [82]. and Mn improve the corrosion behavior of the heterogeneous alloys (e. Influence of the content of alloying elements on ammonia-induced SCC of copper alloys a) CuAl. Aluminum bronzes are used in process plant manufacture. but are sensitive to selective corrosion [95]. Cast materials consisting of binary Cu – Sn bronzes and multicomponent alloys with additions of Pb (Sn – Pb bronzes) or Zn (gun metal) have proved themselves in marine technology. Lower curves: SCC treshold stress cracking in Cu – Zn materials decreases with increasing Zn content. The two-phase (α + β)-alloys (Al >7. respectively. . CuSn6). 27) [95]. CuAl10Fe. also contain the γ2 -phase and (depending on the heat treatment) martensitic phases. toothed wheels. To prevent stress corrosion cracking. Of the Cu – Al alloys standardized in DIN 17 665. have good resistance to stress corrosion cracking. etc. highly protective oxide films that contain Cu2 O and Al2 O3 [96]. where their applications include pump parts (gears) and fittings. followed by testing for residual stresses according to DIN 50 916. Additions of Ni. springs (CuSn2). CuAl5As and CuAl8. The heterogeneous materials with Al >8 wt %. is necessary. suffer not only corrosion at relatively high rates. Technically interesting Cu – Sn materials (tin bronzes) standardized in DIN 17 662 contain up to 9 wt % and up to 14 wt % Sn. they are used for screws. apart from the αphase. on the other hand. CuAl9Mn).8 wt %) are less resistant. machinery. they are used for bearings. their improved resistance results from the formation of adherent. 27).8 wt %) are among those that withstand corrosion. screws.Construction Materials in Chemical Industry 31 Figure 26. which are outstanding in some cases. together with resistance to corrosion in neutral salt solutions and alkaline solutions (except those containing NH3 ). pumps. stress relief annealing.

valves. It has also been demonstrated that the stress corrosion cracking behavior is determined exclusively by the hardness of the material [97]. Lead and Lead Alloys [82]. The good corrosion resistance of the frequently used materials CuNi10Fe and CuNi30Fe results from the formation of oxidic surface films consisting of Cu2 O on the metal side and complex corrosion products with high percentages of Fe and Ni on the solution side [97]. which gives them further strength (hard lead). 5.5 in ammonia-containing solutions have shown. In outdoor applications and approximately neutral waters the protection from corrosion arises from the formation of basic lead carbonates of low solubility (Pb(OH) 2 · 2 PbCO3 ). These alloys also withstand erosion – corrosion and cavitation well. and other mechanical components and also for leadings (reaction vessels. pipes. which generally contain iron and manganese additions. which improves their corrosion behavior. These alloys are used particularly where mechanical stresses must be withstood in addition to corrosion. 28). pumps.5 wt %. or chromate surface films [99]. Hence the homogenized state has always been preferred for component fabrication. For greater strength and finer grain. Lead – antimony alloys can be age hardened (precipitation hardening). are among the copperbased materials most resistant to corrosion. and impellers [82]. The Cu – Ni materials of technical interest (CuNi10. firmly adherent surface films consisting of lead sulfates.5 – 13 wt % Sb). or oxides. precipitation-free materials are those most resistant to intergranular stress corrosion cracking. The high corrosion resistance of Cu – Ni – Fe materials. lead is alloyed with antimony (0. At levels of up to about 1. phosphate. The variety of copper-based materials is such that reliable usedepends on very careful choice: Figure 28. it is assumed that the homogenized. but also in ammonia-containing media (brackish water). that specific heat treatments are capable of producing material states considerably superior to the homogeneous states [97] (Fig. b) Aged (50 h. 29). pump parts. this results from the low solubility of the sulfate. carbonates. 50 ◦ C) as a function of the electrode potential a) Homogenized. however. Lead is therefore a useful material for fittings. The corrosion resistance can be further improved by small additions of As and Se. depending on the corrosive medium [99]. Mean crack velocity v of CuNi10Fe1.5 in 1 M [(NH4 )2 SO4 + NH3 ] (pH 9. [100]. 27). In acids and alkalis. which may also contain lead sulfates. As the Cu – Ni – Fe alloys of technical interest tend to form Fe – Ni-rich grain boundary precipitates at 350 – 650 ◦ C [98]. iron further improves the corrosion behavior. and heat exchangers [82]. In comparison with other copper-based materials. .6. However. [99](→ Lead and → Lead Alloys) Lead owes its good corrosion resistance to its ability to form dense. it is distinguished by outstanding resistance to sulfuric acid and good resistance to phosphoric acid and chromic acid. CuNi20. coolers. Cu – Ni – Fe alloys with Ni contents of ≥ 10 % exhibit substantially better resistance to ammoniainduced intergranular stress corrosion cracking (Fig. explains their growing importance in marine technology (seawater desalination plants) and as tube materials for condensers.32 Construction Materials in Chemical Industry Copper – nickel alloys (DIN 17 664 and DIN 17 658) form a continous mixed-crystal series. They are immune to stress corrosion cracking in chloride-containing media [97]. lead normally suffers severe surface corrosion (Fig. 500 ◦ C) the material must be exactly suited to the conditions of use. as in the case of accumulator plates. electrolysis tanks) [82]. Investigations into the influence of the state of precipitation on the stress corrosion cracking behavior of the alloy CuNi10Fe1. especially in seawater. Chloride-induced pitting corrosion occurs occasionally under unfavorable conditions. CuNi30).

12.10) a Accordingly.10) Pb Cu Sn Pd (0.29 0.1) Pb Cu Sn Pd (0. 0. these alloying elements are present in the precipitated state. g) Pb 99. Through outdoor exposure and even mild chemical exposure (contact with drinking water.10) Pb Te Sn Pd (0.12). The precipitates are .985 – 0.5 and Zn 97. A fairly high corrosion rate can also be expected in industrial air containing SO2 [82].10. 30) [101]. of lead and palladium.19 1. have improved resistance to corrosion by hot and boiling sulfuric acid [101]. for example) zinc forms protective surface films that consist mainly of basic zinc carbonates and which adhere to the metallic zinc fairly firmly. Sn (0.01 0. Zinc and Zinc Alloys (→ Zinc Alloys) In DIN 1706 a distinction is made between highpurity zinc (Zn 99.86 0. Dependence of the corrosion behavior of lead in aqueous solutions on pH a) HNO3 .80 3.01 0.23 0. 0. Potential – time curves of lead alloys in boiling 70 % H2 SO4 a) Pb Cu Sn Pd (0. Zinc is not resistant to acids and strong alkalis.1) Pb Cu Au (0.10. e) Pb Cu Sn (0. f) Pb 99. 0.1 Au. or where particularly good corrosion resistance is needed. 5.17 0.10 0.01 – 0. b) Acetic acid.1).12 0.04 0. 0.05.10 wt %).21 0.1) Pb Sb Pd (1. and fine dispersion of the particles is beneficial.13. b) Pb 99. Linear corrosion rate of multicomponent lead alloys in boiling sulfuric acid Alloy Corrosion rate.1 Pd.23 0.19 0. As the solubilities of Cu and Pd in lead are extremely low.04.12 0. alloys consisting of highpurity lead and copper.09 0.06. where it is used mainly in the form of metallic coatings. see Table 14.05 0. alloys based on Pb – Cu or Pb – Cu – Sn. The most important zinc alloys are the die casting alloys GD-ZnAl 4 and GD-ZnAl 4Cu 1.95) and technical zinc (Zn 99. Zn 99. 0. 0. are used for chemical apparatus. thus shifting the potential of the metal into the passive range and consequently improving its corrosion resistance (Fig. 0.15 0.7.985 Figure 29.985 – 0.9 Cu – 0. Zn 98. and also alloys of the Pb – Cu – Sn – Pd type with extremely low contents of Cu (0.10.1).995. The main use of zinc is the protection of steel from corrosion.05 – 1.Construction Materials in Chemical Industry 33 capable of reducing the hydrogen overvoltage and accelerating oxygen reduction. Zn 99.5).9 Cu.12 wt %). 0.10.99.1. d) Pb Cu Sn Au (0. The Pb – Cu – Sn – Pd alloys also have relatively high creep strength [101]. 0.1 Pd. Table 14.05 0. c) Pb 99. 0.95 2. 0.22 0. Zinc is severely attacked by hot water and steam.06. Figure 30.26 0.12 1. and Pd (0.30 a 0.10.5. 0.1 wt %). mm/a 50 % 70 % H2 SO4 H2 SO4 Pb 99.10) Pb Ni Sn Pd (0. 80 % H2 SO4 a 0. 0.09 8. d) NaOH Compared to pure lead.05 0.10 0.50 Dissolves. h) Pb 99. but also as sacrificial anodes.05.9 Cu Pb Cu Pd (0.2) Pb Cu Sn Au (0. c) Ba(OH)2 .48 0.28 0.

013 Yield strength (1 %).40 0.015 0.03 0.4 Mo 0. 1 – 3 wt % Pb). niobium.10 0.18 0.15 0.-Mo + Ni Ticorex-A∗ ∗ Nippon Mining Co. maleic. C.015 0. It also has good resistance to corrosion by organic acids (acetic.30 0.and nickel-containing 5. tantalum.03 0.P.05 C 0.6 – 0.10 0.7065 0.05 0.35 Max.10 0. citric.03 0.-Pd C.013 0.05 0. Tin is used mainly in the food industry as a protective metallic coating on appliances and containers. U.-Pd C. [103] The refractory metals of groups 4 and 5 of the periodic table have now gained considerable importance in the fabrication of chemical plant. which results from the formation of oxidic surface films.20 0. 5. Titanium.25 0.30 0.12 0. C.9 Ni 0. Grades of unalloyed titanium Material Material number Fe Ti I Ti II Ti III Ti IV 3. are used as soft solders (DIN 1707).015 0. Two palladium-alloyed titanium types are termed grade 7 and grade 11.25 0.20 0.05 0.P. wt % N 0. Niobium. especially in the absence of oxygen.015 0.15 – 0. ¨ In VdTUV-Werkstoffblatt 230/1 unalloyed titanium is allocated to four groups having different degrees of purity and strength (Table 15).06 0.05 0.8. impurity content.P. and zirconium are outstandingly resistant to many media.05 Ru 0. and Tantalum [102]. and lactic acid). only those belonging to groups I to III are normally used in chemical engineering.7035 3.P. possibly with additions of Sb and Cu.015 0.5 Ni .12 – 0. 1 2 3 4 7 11 12 Fe 0.g.30 O 0.10 0. MPa 200 270 350 410 Table 16.25 0. It is substantially resistant to numerous foods and drinks.015 0. The corrosion resistance of these types can be improved by alloying with 0.) C 0. Classification of titanium Type ASTM B-265-79 grade C. PbSn50.35 0. tartaric.10 0.08 0.Tin is attacked severely by halogens.06 H 0. The high price of Pd explains the introduction of the molybdenum.10 0. PbSn40). Having excellent passivity. tin has good corrosion behavior in outdoor applications and in water [82].34 Construction Materials in Chemical Industry in plant manufacture they are of only minor importance.25 0. such materials as titanium.7025 3. As the forming behavior of types belonging to group IV is limited. see Table 16) but the percentages of permissible additives are greater ¨ than those laid down in VdTUV-Werkstoffblatt 230/1.013 0. unalloyed titanium (C.05 0.P.25 0. Tin and Tin Alloys (→ Tin Alloys) The purity requirements for tin as specified in DIN 1704 range from 98 to 99. Tin – lead alloys with 30 – 60 wt % Sn (e. C.013 0. C.P. examples are Sn80Sb12 (5 – 7 wt % Cu..18 0.30 0. wt % (max. SnPb40. 1 – 3 wt % Pb) and Sn80Sb18 (16 – 20 wt % Sb. Zirconium. Due to the formation of oxidic surface films of low solubility. and alkalis.25 0.30 0.015 0.90 wt % Sn.25 wt % palladium [104].12 – 0. 11 – 13 wt % Sb.0015 Pd Others 0.2 – 0.7055 3. Ti = commercially pure titanium) is classified in four groups (grades 1 to 4. Table 15.S. Tin alloys with Sn contents of 80 – 91 wt % are important bearing materials (sliding bearings).25 0.03 0. In the United States.008 Composition.P.18 0.06 0.20 0.03 0.05 N 0. halogen compounds.50 0.P.004 H 0.9.06 0.03 O 0.

g/cm3 mp. which is the most favorable material in this group with respect to density. are compiled in Tables 17 and 18.7055 group III 470 – 600 360 170 130 18 1600 Zirconium grade 702 Tantalum 35 brackish water. bleaching solutions. GPa Titanium 3. MPa 400 – 550 280 150 110 22 1400 Titanium 3. Table 17. It has improved resistance to nitric acid. Titanium and zirconium cannot be used in fuming nitric acid. particular attention must be drawn to its resistance to chlorides and oxidizing agents. % Hardness HB 30. The mechanical properties of titanium. In hot. It is also highly resistant to hydrochloric acid and phosphoric acid and has no pyrophoric tendency in 295 – 442 197 – 295 176 117 25 – 35 1180 – 1570 274 196 255 225 15 825 – 1470 Table 18. Corrosion resistance data for titanium. zirconium. and tantalum Property 3. which. Mechanical properties of titanium. Some physical properties of tianium. is in preparation. and tantalum are compiled in Table 19 (see next page).176 . MPa Hardness HV 30. MPa 250 ◦ C (105 h). zirconium. In the case of titanium. Of the refractory metals. chlorine dioxide.5 1 975 17 108 Zirconium Tantalum (Ta-ES) 16.25 172. and improves the resistance to crevice corrosion [104]. MPa 0. concentrated sulfuric acid its corrosion resistance is comparable with that of glass or cast ferrosilicon and is surpassed only by that of noble metals such as gold and platinum. The use of palladium as an alloying element extends the range of applications of titanium in acids with reducing effects. and tantalum Property Density. apart from hydrofluoric acid. For example. like the ruthenium. tantalum has by far the best corrosion behavior in hot. zirconium and tantalum. acetic acid.5 tungsten. sodium chlorate.and nickel-containing alloy Ticorex A.6 3 271 55.Construction Materials in Chemical Industry alloy grade 12.5 6. zirconium.7035 group II Tensile strength. Finally. mention should be made of a titanium alloy containing 5 % tantalum which has been developed to the production stage in Japan. J m−1 s−1 K−1 Modulus of elasticity (300 K). and also a selection of their physical data. such as sulfuric acid and hydrochloric acid. nitric acid. K Thermal conductivity. A Werkstoffblatt for the alloy tantalum – 2. titanium has been used successfully for heat exchangers exposed to seawater. moist chlorine. chromic acid. A common feature of the special metals is a pronounced sensitivity to hydrofluoric acid and fluorides. MPa Elongation. its resistance to these media can be improved considerably by adding oxidizing agents.1 % Yield strength. Titanium cannot be used in hydrochloric acid or sulfuric acid. MPa Creep strength 150 ◦ C (105 h). in which growing interest is being shown on account of its strength. is superior to unalloyed titanium in crevice corrosion resistance. with a risk of hydrogen embrittlement in the case of extreme exposures. concentrated mineral acids. However.53 2 125 21 94. and sodium chlorite. because of the possibility of pyrophoric reactions and stress corrosion cracking. The fundamental corrosion-chemical properties of these materials for chemical plant are 1) The stability of titanium under oxidizing conditions 2) The stability of zirconium under reducing and alkaline conditions 3) The stability of tantalum under oxidizing and reducing conditions.7025 4.

001 <0. Comparison of the corrosion resistance of tantalum and Hastelloy alloy B in hydrochloric acid Figure 31.08 <0. zirconium. and also by hot alkaline solutions. MPa 225 290 0. If. is possible. however.001 resistant not resistant 1.36 Construction Materials in Chemical Industry T .001 10 40 20 35 35 35 35 all 100 80 <0.5W. in air not resistant <0.05 <0. and tantalum Medium Concentration. The alloy most favorable in this respect is Ta2.05 <0.5 W TaNb 60/40 276 193 25 Nb type 2 Tensile strength. The range of conditions under which tantalum is at risk through hydrogen embrittlement is shown in Figure 32. Although it has high ductility. attacked by oleum. Table 20. Mechanical properties of tantalum.2 % Yield strength.05 Tantalum <0. in air not resistant <0.0 not resistant Hydrochloric acid (aerated) Sulfuric acid (aerated) Nitric acid (fuming) Sodium hydroxide 5 15 37 10 40 0. its strength can be increased considerably by alloying with 2 – 10 wt % W. Alloying tantalum with niobium gives favorably priced materials with similar resistance to corrosion that have a good chance of becoming established in the chemical industry and of playing a part similar in importance to that of tantalum itself. tantalum alloys.05 2. and finally through hydrogen embrittlement. damage through hydrogen absorption.0 1. which may be seen in Figure 31 [105]. the rate of corrosion increases with the niobium content. however.05 <0. Tantalum – tungsten alloys exhibit good resistance to sulfuric acid. tantalum alloys.1 fuming nitric acid. only alloys containing up to 40 wt % Nb are of technical interest. Figure 32. % 15 25 170 105 25 . Figure 33 shows the corrosion rates of tantalum – niobium alloys in sulfuric acid (70 %) at 165 ◦ C. Tantalum is.2 8. As. and niobium Property Ta Ta 2.4 15. This applies particularly to use in nitric acid. wt % Corrosion rate.08 <0. Corrosion resistance of titanium. ◦C Titanium Table 19. and niobium are shown in Table 20. however.001 <0.05 inflamm.05 <0. MPa 140 205 Elongation. with little effect on the corrosion resistance.001 <0.001 <0. hydrochloric acid is handled under pressure in tantalum apparatus. An autoclave insert failed in consequence of hydrogen embrittlement after being in use for only 8 h.5 wt % tungsten are completely resistant to hydrochloric acid at all concentrations and temperatures [106].5 inflamm. mm/a Zirconium <0. even at room temperature. Corrosion rates of tantalum – tungsten alloys in sulfuric acid (96 %) At normal pressure tantalum and its alloy with 2. The mechanical properties of tantalum.

Refractory metals have a wide range of applications in the chemical industry. Corrosion of zirconium in hydrochloric acid a) 5 mm/a. 34). especially after welding. for example. zirconium is resistant to hot alkaline solutions and is therefore the most suitable material for these media in many cases. copper) [110]. For critical corrosion conditions. that must also function reliably under adverse conditions are protected by cladding with special metals. In many cases nonadherent lining or sheathing of the substrate material is sufficient. for example. They are used for reactors. c) Ta–50 Nb. 5. In this respect the chemical nature of organic materials gives them certain advantages over metallic and inorganic nonmetallic materials. fittings. or tube bundles are used to cool or heat corrosive media. Organic Materials [113–115] To an increasing extent the growing requirements on the availability and reliability of chemically exposed plant components are necessitating the use of particularly corrosion-resistant materials. such as Fe(III) or Cu(II) compounds. Sensing heads. next page) [112].. cladding is appropriate where heavy loads are exerted. d) Ta–40 Nb.6×10−4 mm/a to 7. is resistant to many organic acids. f) Ta Figure 34. Although special metals have good welding behavior.10. At 30 ◦ C and an acid concentration of 32 %. Fig. Unlike the other refractory metals. e) Ta– 25 Nb. or negative pressure exists.Construction Materials in Chemical Industry 37 Figure 33. As the special metals tend to form intermetallic phases with steel at high temperatures (1000 ◦ C). is roughly twice as high as that of steel. are not present. Its resistance to nonoxidizing media nevertheless greatly exceeds that of titanium. c) 0. like titanium. b) Ta–60 Nb. 35. candle-shaped elements. good heat transmission is needed. fluoride-free sulfuric acid.g. as little as 5 ppm of such a compound increases the corrosion rate ten-fold (from 7. Zirconium is thus practically passive in hot. Heat exchangers made from special metals and consisting of coils. heat treatment for 3 h at 750 – 790 ◦ C. and pumps. [108]. bellows. magnetic floats and membranes. b) 0. their reactions with atmospheric gases must be taken into account. Since the melting point of tantalum. The components may consist entirely of the special metal or of suitable composites. though it is vital to ensure that oxidizing agents. provided the operating temperatures do not reach critical levels. specially designed butt-welds are necessary in the processing of explosion-cladded metal sheet (cf. Corrosion rates of tantalum – niobium in boiling 70 vol% sulfuric acid at 165 ◦ C a) Ta–75 Nb. Zirconium. they are normally applied by explosion cladding. such as thermo-feelers.5 mm/a. columns. Hence welding is only possible under an inert gas or in high vacuum. but is severely attacked by hydrofluoric acid. is advisable in order to maximize the resistance [109].6×10−3 mm/a) [107].13 mm/a Under oxidizing conditions zirconium is often less resistant than titanium. In many cases they . [111]. pipelines. possibly with intermediate layers (e. agitators. Zirconium also has good resistance to corrosion by hydrochloric acid (Fig. rods. It is essential to avoid alloying with iron-based materials in welding.

A comprehensive account of the design of plastic components. Only when the various factors have been established can a list of foreseeably suitable materials be drawn up for more detailed consideration. oxidizing agents). in nonstructural plastics. amines. In general no risk arises if the physical properties of a coating or facing consisting of a synthetic material are impaired through the action of a medium. and in a number of other cases. waters. Composite and surface coating materials are being used increasingly too (see → Corrosion). The stability data published in manufacturers’ and other literature are usually based on swelling tests. and the static and dynamic loads. e. caustic soda solution. the action of liquid media on organic materials leads mainly to swelling. Figure 35. and the quality of joints relatively unimportant. of rubber or plastics. – – – Hardness curve in copper intermediate layer One of the most important processing methods for plastics is welding. The main types of organic materials are thermoplastics. is contained in VDITaschenbuch T 21 [117]. must receive special attention. with detailed consideration of strength calculations and dimensioning.g. As important parameters. swelling and stress corrosion cracking may be nonhazardous.. The permeability of polymers is less serious in components than in coatings.2. glass-fiberreinforced plastics. Thus the envisaged conditions of use must be carefully considered before materials are chosen. and foamed plastics. Unlike the surface removal corrosion of metallic materials.Hardness curve in tantalum cladding. sulfuric acid. compounds with high vapor pressures. Selection Criteria The stability required of plastics varies according to whether a plastic component must simply withstand corrosion. namely hydrochloric acid. or critical. or fulfil structural functions also. hypochlorite solution. but hazardous. elastomers.10. swelling tests alone must be considered tentative. the maximum and long-term service temperatures. caused by absorption of the medium. but the same process in a statically or dynamically stressed part may lead to its premature failure. including all their consituents (such as solvents. in those with structural functions. especially those on metallic substrates. These data are adequate where coatings or linings. and salt solutions of all kinds. Properties and Application Criteria are well suited for plant that handles the media most commonly encountered at chemical works. Design of a butt-weld for explosion-cladded sheet (mild steel/tantalum with copper intermediate layer) – · – Hardness curve in tantalum cover strip. the solutions to which the components will be exposed.1. 5. phenols.38 Construction Materials in Chemical Industry 5. enabling one merely to draw up . Similarly. the pressures and vacuum conditions. thermosetting plastics. In many cases the degree of swelling of an organic material in individual media and the dependence of swelling on time and temperature as well as its possible reversibility constitute adequate criteria for the determination of suitability. Where static or dynamically loaded parts are concerned. A survey of the welding methods is given in [116]. —.10. are concerned.

but falls with increasing molecular mass. rotary filters. The thermoplastics most widely used in chemical engineering are PVC [poly(vinyl chloride)]. or 80 ◦ C if glass fibers are incorporated. in other cases it is largely independent of them. organic acids. In common with hard polyethylene it has a certain permeability to organic media. like that of metals. but greater impact. PP (polypropylene) and PB (polybutene).g. The upper service temperature limit is 60 ◦ C. notched impact. The most favorable deformation range is 110 – 130 ◦ C. and oxidizing media. or 100 ◦ C if glass fibers are present. The swelling caused by hydrocarbons leads to losses of strength that can be taken into account with the aid of resistance factors. The resistance to nonoxidizing media is excellent. by internal and external stresses. It can be shaped thermoplastically at temperatures above 130 ◦ C and welded at ca. Polypropylene (PP) has properties similar to those of polyethylene. Tests are performed in various media and at various temperatures on panels or pipes subjected to constant deformation or constant stress in the long period tensile creep test [118]. extrusion. High molecular mass material is less easily processed. Polypropylene is almost as resistant to chemicals as hard polyethylene. Polybutene (PB) is one of the more recent polymeric materials that have gained acceptance in chemical engineering. In some media this ratio depends on the mechanical stresses exerted on the sample. occurs exclusively in the presence of tensile stresses. A resistance factor is the ratio of the time to failure in the test medium to the time to failure in water [118]. Here it is far more important to ascertain how the strength of materials is affected by prolonged exposure to chemicals.Construction Materials in Chemical Industry a shortlist of materials for further consideration. by prolonged exposure to high temperatures in processing. The term is used only where cracking caused by exposure to chemicals. internal chimney tubing. Its long period creep resistance exceeds even that of polypropylene. − 100 ◦ C. The applications of polypropylene include exhaust ducts. Losses of long period creep resistance caused by liquid media are preferably expressed as resistance factors. Susceptibility to stress corrosion cracking is increased by exposure to wetting agents. In many cases the sensitivity of finished parts to stress corrosion cracking can be reduced by thermal after-treatment. Above its softening temperature of 80 ◦ C. by temperature alteration. High-density polyethylene is preferred for chemical plant because it has greater strength and stiffness than the lowdensity types. hydrocyclones. and its properties may suffer if it is exposed to elevated processing temperatures for long periods. or welding) requires higher temperatures. especially at temperatures below 0 ◦ C. separators. for example) [119]. poly(vinyl chloride) can be shaped by plastic deformation. Although polybutene is soluble in several organic . or possibly a lower temperature. 200 ◦ C. and by notching. by shaping and jointing operations. and shock resistance. The upper service temperature limit is 60 ◦ C. but more sensitive to oxidizing media and more strongly swelling in organic solvents. Poly(vinyl chloride) has been used for decades due to its outstanding resistance to chemicals. It is harder and tougher than other thermoplastics. depending on the chemical exposure. 39 Original shaping (e. with diffusion and swelling processes and internal and/or external stresses playing a major part [120]. however. Resistance factors for glass-reinforced plastics can be derived from the differences in creep behavior in tensile tests under various ambient conditions (as ratios between creep moduli. the degree to which creep occurs. Polyethylene is a partly crystalline material with high impact strength at temperatures down to ca. The stress corrosion cracking of organic polymers is generally an entirely physical process. and whether or not the conditions are favorable to stress corrosion cracking. solvents. however (170 – 200 ◦ C).. The susceptibility to stress corrosion cracking increases with the degree of crystallization. Its strength properties lie between those of soft polyethylene (LD-PE) and polypropylene. but at temperatures below 20 ◦ C it has less impact strength than polyethylene (PE) and polybutene (PB). by injection molding. and gas scrubbers. The upper service temperature limit is 80 ◦ C. filter fabrics and pressure plates. PE (polyethylene).

furane. if glass-filled. seals. [82] are used mainly for surface protection (see → Corrosion).10. The upper service temperature limits extend to about 120 ◦ C.3. its susceptibility to stress corrosion cracking is low. They are filled with glass fibers. vibration dampers. Elastomers and ebonite based on natural or synthetic rubber [121]. Having high cross-link density. PVDF is resistant to most organic and inorganic acids. hot molding compounds. in which the proportion of glass is low. filter pressure plates. Its service temperature range extends from − 200 to 250 ◦ C. 0 = conditionally resistant. thermosetting plastics are insoluble and cannot be melted. especially pipes for waste water and waste air disposal. Individual parts can be joined to one another with catalytically hardening cements. and their strength and long period creep resistance are without the marked dependence on temperature exhibited by thermoplastics and elastomers. hoses. Solid parts made from glass-reinforced reaction resins are distinguished not only by chemical stability but also by relatively low weight. they are rarely Resistance towards Type of resin Acids Alkalis Solvents Oxidizing agents + + +/− 0/− Polyester Vinyl ester Epoxy Furane +/0 +/0 0/− + +/− + + + 0/− 0/− +/0 + ∗ + = resistant. acts as a barrier to corrosion and protects the loadbearing. conveyor belts. vinyl ester. Applications include pipe linings. parts consisting entirely of glass-reinforced plastics usually receive an at least 2. and pumps. and filter fabrics. vinyl ester. tube bundle heat exchangers. down-pipes. and Moineau pump stators. Table 21. transportation and storage containers. pump parts. Thermosetting Plastics The main materials in this group are phenolic. glass-reinforced structure from the action of destructive media. Its main application is in pipelines used to convey acids. or quartz and processed to tamping compositions. steam release nozzles. The outstanding abhesive behavior and exceptionally favorable sliding properties deserve special mention. vats. hoses. Chemical resistance of reaction resins ∗ solvents at elevated temperatures. It can be used at temperatures up to 100 ◦ C. However. Poly(vinylidene fluoride) (PVDF) is a partly crystalline plastic of high thermal stability. bellows. For exposure to aggressive media. The main applications of polybutene are high-temperature pressure pipes. Being brittle. epoxy. fillers added to the plastic to improve its extrudability or mechanical strength may reduce its resistance to chemicals. up to about 120 ◦ C. It is chemically resistant to virtuallly all media except molten alkalis and elemental fluorine. The upper service temperature limit is 90 ◦ C.40 Construction Materials in Chemical Industry used directly for mechanically stressed parts unless reinforcing materials and fillers have been incorporated. as well as being used for space-saving folding containers for the transportation of corrosive materials by land and sea. − = not resistant . stacks. Glassfiber-reinforced resins are used for corrosionresistant articles of all kinds. filter pressure plates. and putties. and frames. Polytetrafluorethylene (PTFE) is the thermally and chemically most resistant plastic used in chemical engineering. and by good emergency running behavior. it tends to suffer stress corrosion cracking. bellows. depending on the resin in question. 5. membranes. They are being used increasingly for composite structures exploiting the high stability and heat resistance of glassfiber-reinforced reactive resins with the superior chemical resistance of thermoplastic coatings and linings. Table 21 gives a general idea of the corrosion resistance of reaction resins used in the fabrication of apparatus and pipes. epoxy. Elastomers also have many applications in chemical engineering as seals. This protective coating. stripwound vessels. sheet.5 mm thick coating consisting mainly of resin. In alkalis. together with high strength. The resins used are unsaturated polyester. or. especially caustic soda solution. or furane resins. stuffing box packings. graphite. siphons. and unsaturated polyester (UP) resins.

parts consisting of glass-reinforced plastics are provided with linings. The normal welding techniques are hot gas. UP-GF tanks and pipes with PVC liners. apparatus. and even to complex heat exchangers and their accessories. Other advantages include the smoothness of its surfaces. ranging from simple pipe sections and moldings to fittings. heated tool. catalytic inertness. highly corrosion-resistant nickel alloys. 41 are described in [123]. Glass can be combined with other materials – plastics and metals. vessels and column components. In the fabrication of composite structures.11. Inorganic Nonmetallic Materials 5. seen here as a demonstration exhibit with parts removed to show structural details. [125] Pipelines. consisting of UP-GF tanks and pipes with PVC liners. processing. Borosilicate glass has a very wide range of uses and can be exposed permanently to temperatures up to 200 ◦ C. however. Above 200 ◦ C it is attacked fairly severely by all acids. The use of organic materials in the form of corrosion-resistant coatings and linings represents an important application in chemical engineering (see → Corrosion). Pumps and valves of all kinds can be sealed with polytetrafluoroethylene components. Figure 37. Glass apparatuses for heating purposes can be provided with elements consisting of stainless steel. is now commercially available.1. Another application is shown in Figure 37. or tantalum. The lining materials most widely used at present are the thermoplastics polypropylene (PP).Construction Materials in Chemical Industry More frequently. unplasticized polyvinyl chloride (PVC-U) and polyvinylidene fluoride (PVDF). PVC-lined UP-GF apparatus Figure 36 depicts a PVC-lined UP-GF apparatus. especially phosphoric acid [126]. Properties. It is permanently stable to virtually all media except hydrofluoric acid and strong alkalis. and even entire plants are now being produced increasingly from borosilicate glass in order to solve exceptionally critical corrosion problems. containing HCl and NaOCl solutions 5. for example – thus opening up a wide range of technical possibilities.11. A complete range of glass parts for assembly by the user. The design of parts consisting of glass-reinforced plastics is described in [122]. thermoplastic liners are normally produced as a first step and than reinforced with a glass-filled reaction resin. and applications . Thermoplastic linings consisting of sheet material are placed end to end and joined by welding. titanium. PTFE is also used in the form Figure 36. Glass [124]. and hot gas extrusion welding. and nontoxicity. This is a storage facility for solutions containing HCl and NaOCl.

to protect tanks. 5. and withstands even severe temperature shocks. Refractory and Acid-Resistant Bricks [129–132] This term covers ceramic materials that are still free from deformation at temperatures exceeding 1600 ◦ C and still do not soften at those exceeding 1800 ◦ C. alternative impregnating agents. has high thermal conductivity.3. In view of the variety of these conditions they must be chosen for then intended application in accordance with their chemical and technological properties. the effect of this treatment being that all the pores are closed. tiles. alumina-based materials. or moldings. resistance to temperature alternation.11. made from vitreous enamels and partly crystalline enamels. such as pipes. Important applications of borosilicate glass include distillation and rectification units. centrifugal pumps.42 Construction Materials in Chemical Industry chemical engineering. the parts must be so designed that tensile and shear stresses are avoided as far as possible. observation windows). 5. neutral refractory products. [128] Graphite has been used as a special material in chemical engineering since the mid-1930s. nitric acid concentrators. but are sometimes used in the form of castings. can be produced from impregnated graphite (hardfired carbon or electrographite). and upper service temperature limits (which are in the region of 165 ◦ C). shape stability. and other organic compounds. which are then decomposed thermally. Bricks are normally shaped and fired. Resin-impregnated electrographite is the synthetic carbon material most widely used in . [127]. simply cemented together from panels and strip. The resulting material has good corrosion resistance and a high service temperature limit. As the various graphite production methods give porous materials. absorbers and gas scrubbers. The quality of the finished material depends on the properties of the chosen resin. thermal conductivity. and small parts of many kinds. and profiles. all structural elements. basic refractory bricks. Carbon filling of the pores in graphite can be carried out by impregnating with cokable materials. pipelines. valves. its high cost limits technical use to special articles (e. and slagging tendency are of great importance. Sealing and insulating layers may be used additionally between the wall of the apparatus and the lining. The main applications of graphite are heat exchangers of all kinds. carbon bricks. The use of graphite in plant for production of dry hydrogen chloride and in the treatment of waste water and waste air deserves special mention. and piping. It is easily worked. corrosion resistance. pipelines.11. Now. For greater stability and higher service temperature limits. As graphite is a brittle material with practically no plastic deformation.2. and silicon carbide bricks. The use of enamel coatings. abrasion resistance. The following classification of refractory materials is based on their main consituents: products of high silica content. impregnation with phenol – formaldehyde or furane condensation resins by the vacuum-pressure process is necessary if impermeability to gases and liquids is required. Refractory bricks serve to enclose spaces in which reactions take place and must last as long as possible under the given conditions.g. pumps and other items from corrosion is described in → Corrosion). solid and hollow cylinders. columns. are used. Although quartz glass is very resistant to thermal shock due to its extremely low coefficient of thermal expansion. These are attached to the wall or to one another with mortar or putty. columns. For corrosion protection in difficult cases. such as polytetrafluorethylene. this treatment being repeated several times. acid recovery plant. apparatus. alkalis. chemical apparatus can be lined with corrosionresistant bricks. such properties as softening under pressure. but is less strong and more brittle than the resinimpregnated grades. alcohols and many solvents. chemical resistance. slabs. Apart from refractoriness. of bellows to compensate for thermal expansion and to damp vibration.. were the first application. panels. Graphite [82]. sprinkling coolers. It is highly resistant to corrosion by organic and inorganic acids. cleaning units. Heat exchangers. This applies particularly to the permeability.

As silicon nitride meets these requirements.1 – 0. Silicon Carbide. On the other hand the impact strength (unnotched) of 0. g/cm3 Bending strength. 800 ◦ C. copper and their alloys. glass. and zirconium dioxide as a rocket material. and high strength at temperatures up to ca. molten metals.. especially where high rotation speeds occur. Al2 O3 . SiC thermocouple protection tubes are used in contact with liquid aluminum in aluminum holding furnaces. and for tank linings.g. roller bearings. among other things. Beryllium oxide has applications as a moderator in nuclear reactors. 0. aluminum. Its use is therefore leading to the replacement of conventional stuffing boxes on rotating shafts by mechanical seals.9 300 2500 <0. Aluminum oxide can be used in oxidizing and reducing atmospheres .5 620 1600 80 5 43 and under vacuum at working temperatures of up to 1950 ◦ C. SiC heating elements are used in oxidizing atmospheres at temperatures up to 1500 ◦ C. and Alumina has very good corrosion resistance. it is used as a structural material for components subjected to severe thermal and chemical loads.4.1 390 1750 30 8 WC Hard metal with 6 % Co 14. A conspicuous property of Al2 O3 is its great hardness. Table 22. and ceramics. and heat resistance. nonferrous metals. The most important oxide ceramic material is aluminum oxide. but also a low coefficient of thermal expansion of only 4. The strength values are practically constant over a wide temperature range. is low compared to the notched impact strength of 100 J/cm2 for structural steel. together with the low friction coefficient (µ = 0. Silicon carbide is used mainly as a grinding agent. Thus Al2 O3 is a brittle material. which. and slag. These properties explain the very good resistance of silicon carbide products to changes of temperature. materials are needed that are not wetted by the molten metal. The most remarkable properties of silicon nitride include good resistance to chemical attack by acids and molten nonferrous metals. it is used for. With good electrical conductivity at high temperatures.2). At 1000 ◦ C dense silicon nitride still has a 100h long-term creep resistance of 200 MPa. The hardness of silicon nitride gives it high wear resistance. Engineering Ceramics [133]. MPa Breaking elongation in compression test. for grey cast iron. coupled with resistance to oxidation. have good resistance to temperature fluctuation.Construction Materials in Chemical Industry 5. GPa Vickers hardness Thermal conductivity. [134] Oxide Ceramics. It has advantages over metals particularly where corrosive and thermal stresses are superimposed on mechanical stresses. In the case of the aluminum industry. resistance to temperature fluctuation (coefficient of thermal expansion 3×10−6 K−1 ). Since silicon carbide also has excellent resistance to corrosion. 10−6 /K Al2 O3 ceramic 3. favors its use as a material for bearings and sliding contacts. thermocouple protection tubes and ascending pipes in low-pressure casting. This is because the increase in plasticity (and hence in the ability to dissipate local peak stresses) which occurs as the temperature rises compensates for the thermally induced loss of strength.8×10−6 K−1 and a high thermal conductivity of 42 W K−1 m−1 . One of the commonest applications of alumina ceramics is therefore the sealing of passages leading into vessels and spaces in which corrosive media are present. Properties of Al2 O3 ceramic and a hard metal Property Density.2 J/cm2 at 20 ◦ C. % Modulus of elasticity. Silicon carbide has not only high strength (bending strength up to 650 MPa). Silicon Nitride. In the form of slide rings and mechanical seals alumina is superior to all other materials in resistance to corrosion and wear.9 1900 5000 ca. The bending strength of hot-pressed silicon nitride is about 700 MPa at 20 ◦ C and still as high as 290 MPa at 1400 ◦ C. With great resistance to temperature alternation and corrosion.11. withstanding acids. MPa Compression strength. Slide rings. Silicon carbide products are used for the muffles of indirectly heated smelting furnaces for zinc. e. In Table 22 the main mechanical and thermal properties of aluminum oxide are compared with those of hard metal. many glasses. W m−1 K−1 Coefficient of thermal expansion.

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