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Creep resistant steels

Creep resistant steels are steels designed to withstand a constant load at high temperatures. The most important application of creep resistant steels is components of steam power plants operating at elevated temperatures (boilers, turbines, steam lines). The major part of the industrial uses of high creep-resistant alloys at elevated temperatures and fairly high stresses has been due to the development of the gas turbine and the jet-propulsion engines. Although Howe' as far back as 185 made investigation on the extension of metals as function of time , and creep data were reported by Andrade2 in 1911, there was very little technical interest in the phenomena of creep or in creep-resistant metals and alloys until shortly after World War I, when better materials were required for aero-engine parts, for the petroleum and chemical industries at fairly high temperatures ( 400- 600C.) and sometimes under severely corrosive conditions, for parts of industrial furnaces at high temperatures and for steam turbines. The demand of materials resistant to creep steadily increased during World War II. But the greatest resistance to creep at high temperatures and fairly high stresses have been due to the development of gas turbine and jet-propulsion engines. An attempt has been made in this paper to indicate briefly some of the metallurgical factors involved in the development of high creep-resistant alloy steels with particular reference to turbine materials 9-12 Cr martensitic creep resistant steels Creep resistance of 9-12 Cr steels is provided by the presence of the chromium carbides Cr23C6. One of the most popular ferritic/martensitic 9-12 Cr Creep resistant steels widely used in subcritical steam power plats is P91 developed in USA in 1970s. P91 is differs from the previous 9-12 Cr steel by additions of niobium (Nb) and a controlled amount of Nitrogen (N). Niobium and vanadium react with carbon and nitrogen during heat treatment forming precipitating particles of carbides and nitrides (V,Nb)(C,N). Creep resistance of the 9-12 Cr steels was further enhanced in the steel P92 by introduction of tungsten (W) and boron (B). Boron inhibits coarsening M23C6 (eg. Cr23C6) carbides. Tungsten in P92 causes hardening the steel due to both solid solution hardening and formation of Laves phase particles (Fe2W), which are more stable than molybdenum Laves phase characteristic for the microstructure of P91 steel. Further improvement of creep resistance of ferritic/martensitic 9-12 Cr steels was achieved (steels T/P122, NF12, SAVE12) by an increase of Cr content from 9 to 11%. In order to prevent incomplete austenitization during normalizing treatment caused by larger amount of ferrite stabilizing Cr, austenite stabilizing elements such as cobalt or copper are added. Despite of its excellent austenite stabilizing effect nickel leads to coarsening M23C6 particles and therefore is not used in the martensitic 9-12 Cr steel. Besides higher creep resistance the steels containing 11% of Cr has also better

oxidation resistance particularly in the steam containing atmosphere at a temperature above 1112F (600C). Increase of the chromium content from 9 to 11% results in better oxidation resistance of the steel due to the formation of a tightly adherent protective Cr reach oxide scale. Oxidation resistance may be also improved by additions of other (than chromium) oxidizing elements (silicone, manganese) combined with special surface treatments (pre-oxidation, Shot peening). Typical heat treatment of 9-12 Cr ferritic/martensitic steels includes Normalizing for 2-3 hours at 1922F (1050C) with air cooling followed by Tempering at 12561436F (680-780C). During normalizing the steel structure becomes austenitic. Most of carbides and nitrides dissolve in austenite at this stage. Air cooling after normalizing results in transformation of austenite into hard and brittle martensite, which is then soften during tempering. Carbide and nitride particles precipitate along the grains of prior austenite. 9-12 martensitic steels are used in the applications with operating temperature up to 1148F (620C). Chemical compositions of some 9-12 Cr martensitic creep resistant steels Designation AST M EN Chemical composition, % Japan C Si Mn C C Cr Ni Mo W V u o ma 9.0 x. 0.4 9.0 0.2 5 1.0 1.0 1.0 Nb Nd Ta B N 0.0 5

T/P9 X10CrMoVN 1 b9-1 E911 X11CrMoWV Nb9-1

0.1 0.3 0.4 0 5 5 0.1 0.3 0.4 1 0 5

0.2 0.0 0 8 0.2 0.0 0 8

0.0 0.0 03 7 0.0 0.0 04 5

ma T/P9 X10CrMoWV NF61 0.1 x. 0.4 2 Nb9-2 6 0 0.5 5 0 T/P1 22 ma HCM1 0.1 x. 2A 0 0.5 0

ma 9.0 x. 0.4

0.4 1.7 0.2 0.0 5 5 0 7

ma ma x. 1. 11. x. 0.7 0 0 0.4 0 11. 0 11. 0

0.4 1.7 0.2 0.0 5 5 0 7

0.0 0.0 03 7 0.0 0.0 04 5 0.0 5

NF12 0.0 0.2 0.5 SAVE 0.1 0.3 0.2 12 0 0 to top Austenitic creep resistant steels

2. 0.2 0.0 0.2 2.6 5 0 7 3 3

0.2 0.0 0.0 0.0 0 7 4 7

Austenitic Creep resistant steels contain chromium (Cr) and nickel (Ni). Chromium increases the resistance to oxidation and corrosion. However chromium is ferrite stabilizing element therefore it inhibits austenitization. Nickel is added into the

austenitic creep resistant steel in order to stabilize the austenitic structure in the presence of large amount of chromium. Titanium (Ti) and niobium (Nb) form carbides and nitrides enhancing creep resistance of the steels. Molybdenum (Mo) and tungsten (W) harden the steel due to both effects solid solution hardening and formation of strengthening   and Laves phases. Aluminium (Al) and silicon (Si) improve the oxidation resistance promoting together with chromium the formation of a protective oxide film on the steel surface. Austenitic creep resistant steels may be used at the operating temperatures up to 1202-1292F (650-700C). Nickel base superalloys (eg. Inconel 617, Inconel 671, Inconel 740, Haynes 230) combine high creep resistance with good Corrosion and oxidation resistance and may be used even at higher temperatures. The disadvantages of the austenitic creep resistant steels as compared to the martensitic steels: Lower thermal conductivity; Greater coefficient of thermal expansion; Higher cost. Chemical compositions of some austenitic creep resistant steels

Chemical composition, % Designatio C Si n 0.1 SAVE25 0 0.1 max Super 0 . 0.3 304H 347 HFG Mn Cu Cr Ni Co Mo W 23. 18. 0 0 max 18. 3.0 9.0 0 . 1.0 3.0 18. 13. 0 0 20. 0 24. 0 31. 0 37. 0 Nb Al Ti B N 0.2

1.5 0.45 1.5 0.45

0.01 5 -

0.00 0.0 5 9 -

max 0.0 max . 8 . 2.0 0.75 0.1 -

Nb+T a 8xC 1.0 0.4 0.25 -

HR3C NF709 800HT HR120

25. 0 0.0 20. 7 0 0.0 max 20. 0.4 1.25 8 . 0.5 0 0.0 25. 0.6 0.7 5 0

1.5 -

max max max 0.7 . 3 . 2.5 . 2.5

0.2 5 0.00 0.1 0.1 5 5 0.4 0.45 5 0.00 0.1 4 -

In practice to improve the properties of Creep-resistant-steels one modifies the metals by alloying them with specified small additions of elements like Chromium, Molybdenum, Vanadium, and other materials having definite influence on favorable modifications of metallurgical microstructure. The accepted criterion for evaluating different Creep-resistant-steels is the stress that, if applied continuously on specified specimens at the given temperatures for one hundred thousand hours (corresponding to slightly more than eleven years), will cause in that time period an elongation not exceeding 1% of its basic gauge length. This will be the reference for establishing safe design stresses. Creep-resistant-steels for high temperature service are those suitable for applications that require exposures between 345 and 815 0C (650 and 1500 0F). For each one of the approved materialsExcluding austenitic stainless steels the other Creep-resistant-steels listed above, in particular those containing Chromium and Molybdenum are all martensitic, that is they will harden upon quick cooling from elevated temperatures like those found in welding. The usual precaution, to avoid cracking as a consequence of shrinking stresses, is to apply preheating before welding to decrease the cooling rate, and then to relieve the stresses as soon as possible after welding especially for thick materials and/or for constrained structures. Filler metals are generally similar in composition to the base Creep-resistantsteels except if post weld heat treatment cannot be performed. In that case austenitic filler metals may be preferred to provide more ductility in the weld. While base metals Creep-resistant-steels may be quite acceptable for elevated temperature service, it must be noted that welded joints are a potential source of weaker behavior in creep due to their intrinsic lack of homogeneity and possibly to the presence of weld discontinuities. the usual Code establishes the allowable design stress at service temperature.

Factors Affecting the Creep Properties Creel) properties are affected by (1) temperature, ( 2) stress, (3) structure , ( 4) treatment, ( 5) environment , and (6) composition. (1) Temperature -. In connection with the effects of temperature it may be noted that: (i) At a lower temperature there is a prolonged stage of constant rate secondary creep and fracture may not occur if load be low; (ii) With increasing temperatures the stage of secondary creep rapidly decreases

(iii) at high temperatures the primary stage of decelerating creep rate is soon followed with a point of inflection by the rapidly accelerating rate of tertiary creep. The secondary creep may be altogether absent. (2) Stress - The effects of increasing stresses on creep curves are more or less similar to those of increasing temperatures. Different theoretical and empirical relations have been developed by various investigators as indicated before. It should be noted here that most of the alloys undergo structural changes when subjected to stress and high temperature for long periods of time and hence do not obey any of the empirical relations. It is extremely unsafe, therefore , to rely on extrapolated data from short -time creep tests. To obtain the correct design data at high temperatures and stresses it is essential that creep tests are carried out for periods at least equal to those for which the material will be stressed in service. (3) Structure - Creep is highly structure sensitive property and is affected by minor variations to it greater extent than any other mechanical property. Some of the common structural factors affecting the creep properties are grain size, soluble elements due to soluble impurities anchor alloy additions, insoluble phases due to insoluble impurities, phase changes and/or precipitation and allied phenomena. (4) Treatment - From what has been discussed before it will be evident that for services at low temperatures when atomic migrations due to recovery or recr_ystallization are small, the heat treatment which corresponds to maximum strength and hardness also corresponds to maximum resistance against creep (e.g. quenching or quenching followed by ageing to maximum hardness ). For higher temperatures, however, when atomic diffusion is large resulting in the socalled 'Place-change-plasticity' and causing recovery, recrystallization, phase changes and/or precipitation, the heat treatment should be directed towards attaining strainfree and metallurgically stable phases. For heat-treatable alloy steels, normalizing at comparatively high temperatures and for longer periods of time, and quenching followed by tempering is usually recommended. For age-hardening type alloys, solution heat treatment at high temperatures ensuring complete homogenization and large grain growth followed by stabilization of the precipitate at about the operating temperatures is recommended. (5) Environment - The atmosphere to which a metal or alloy is exposed in service seriously affects its creep properties. Selective oxidation or corrosion of the grain boundaries and/or elements in the alloy may cause accelerated rate of creep. Since the surface properties of the alloys are primarily responsible for such reactions, the alloys in question are often given a protective treatment to inhibit surface reactions. (6) Composition - Detailed quantitative knowledge about the effects of different elements (either individually or in combination) on the creep strength of steel is rather not enough. Elements in general affect the creep properties in two ways which may he looked upon as- (i) solid-solution effect, and (ii) precipitation effect.