FI125105B - Austenitic stainless steel with grain boundary corrosion and method of manufacture - Google Patents
Austenitic stainless steel with grain boundary corrosion and method of manufacture Download PDFInfo
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- FI125105B FI125105B FI20136077A FI20136077A FI125105B FI 125105 B FI125105 B FI 125105B FI 20136077 A FI20136077 A FI 20136077A FI 20136077 A FI20136077 A FI 20136077A FI 125105 B FI125105 B FI 125105B
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- stainless steel
- austenitic stainless
- heat treatment
- grain boundary
- plastic deformation
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Description
AUSTENITIC STAINLESS STEEL RESISTANT TO INTERGRANULAR CORROSION AND A METHOD FOR ITS PRODUCTION
This invention relates to an austenitic stainless steel that is resistant to intergranular corrosion caused by a phenomenon called as sensitization. The steel according to the invention differs from conventional austenitic stainless steels in that it is not susceptible to sensitization and intergranular corrosion though it contains high amount of carbon. The invention also relates to a method for producing the austenitic stainless steel.
Due to fluctuating nickel price the stainless steel industry is developing low-nickel and nickel-free alternatives for nickel-containing austenitic stainless steels. In these steels nickel is an important alloying element as it stabilises the austenite phase. Several alloying elements can be utilised to replace nickel, for instance: manganese, copper, nitrogen and carbon. Of these alloying elements manganese, copper and nitrogen are commonly used. Carbon, however, is considered to be an undesired impurity, because it has a tendency to form chromium carbides. Chromium carbides tend to form in particular at the grain boundaries of the steel, which leads to depletion of chromium in these regions. This phenomenon, called as sensitization, occurs if the material is subjected long enough time to temperatures at which the carbides tend to form, typically around 600-900°C. Sensitization may occur, for instance, during welding. Sensitization is harmful, as it can lead to rapid intergranular corrosion attack. In practice, risk of sensitization prevents utilisation of carbon as an alloying element. Instead, in modern stainless steels it is common that the maximum allowed carbon content is less than 0.03 weight %.
A method called as “grain boundary engineering” can be utilised to reduce materials' susceptibility to intergranular corrosion. The grain boundary engineering involves a modification of structure of grain boundaries by thermomechanical treatment including deformation at room temperature and subsequent heat treatment. The grain boundary engineering process may involve a single deformation and a heat treatment, or several such cycles. As the result of the grain boundary engineering process the regular random grain boundaries are replaced by a high fraction of special grain boundaries, referred to as coincidence site lattice (CSL) boundaries. Several patent publications relate to grain boundary engineering of austenitic stainless steels, for instance, US 5817193, JP 2003-253401, EP 2112237 A1.
However, none of these publications relate to utilization of grain boundary engineering in allowing use of carbon as an alloying element stabilising austenite and providing solid solution strengthening. No high carbon containing austenitic stainless steels utilising grain boundary engineering have been disclosed.
The object of the present invention is to prevent drawbacks of the prior art and to produce an austenitic stainless steel having good mechanical properties, low alloying costs and high resistance to intergranular corrosion. The present invention relates also to a production method of such a stainless steel. The essential features of the present invention are enlisted in the appended claims.
The present invention relates to an austenitic stainless steel in the form of a flat or long product, which stainless steel has high strength, low alloying costs and high resistance to intergranular corrosion. Such combination of desired properties is achieved with a manufacturing process according to the invention.
In accordance with the invention the stainless steel is an austenitic stainless steel containing in weight % 0.03 - 0.5 % C, 0.01 - 3 % Si, 0.01 - 20 % Mn, 10 -30 % Cr, 0.01 - 10 % Ni, 0.01 - 3 % Mo, 0.01 - 3 % Cu, 0.03 - 0.5 % N, 0.001 - 0.5 % Nb, 0.001 - 0.5 % Ti, 0.001 - 0.5 % V, the balance of Fe and inevitable impurities.
The stainless steel processed according to the method of the invention is advantageously in the form of a flat or long product such as a plate, a sheet, a strip, a coil, a bar, a rod or a wire.
The stainless steel and its production method according to the invention is based on the utilization of grain boundary engineering for modification of grain boundary structure of the steel. According to invention the grain boundary structure of the stainless steel is modified by at least one thermomechanical processing consisting of at least one plastic deformation stage, preferably for instance cold rolling or tensile straining, and at least one subsequent heat treatment stage. The thermomechanical processing can be repeated several times. After the thermomechanical processing stages the desired fraction of special grain boundaries in the microstructure of the stainless steel is achieved to exceed at least 60%, and preferably at least 80%. The thermomechanical processing in accordance with the invention contains at least one deformation stage and at least one subsequent heat treatment step. The deformation degree in a single deformation stage is at the range of 0.1 - 40 % dependent on the chemical composition of the stainless steel to be treated. The subsequent heat treatment is carried out at the temperature range of 800 -1200°C the time for this treatment being from 1 second to 72 hours depending on the preceding deformation degree and the chemical composition of the stainless steel to be treated. When more than one deformation stage is used, an equal number of the subsequent heat treatment stages is also carried out. If the thermomechanical processing consists of one deformation stage and one heat treatment, the deformation degree is typically rather low, order of 0.1-10% and the subsequent heat treatment is carried out at lower regime of the indicated temperature range and in the upper regime of the indicated time range. If the thermomechanical processing consists of several deformation stages and heat treatments, the deformation degrees during a single deformation stage are typically higher, the heat treatment temperatures higher and the heat treatment durations shorter. The deformation degrees and respectively the heat treatment conditions are the same in two or more thermomechanical processings or the reduction degrees and respectively the heat treatment conditions are different from each other in two or more thermomechanical processings.
The thermochemical processing in accordance with the invention makes possible to utilise carbon as an austenite stabilising and austenite forming element, and to utilise carbon as an alloying element providing solid solution strengthening. Therefore, the stainless steel contains 0.03 - 0.5 % carbon (C), preferably 0.1 - 0.5 % carbon (C). This high content of carbon is beneficial due to two main reasons: carbon improves mechanical properties of the steel, and carbon is also a cost efficient austenite stabilising element that enables lower use of expensive nickel. An additional benefit is that allowing higher carbon content in the stainless steel enables shorter process time for instance in costly argon-oxygen decarburization (AOD) process, and also enables use of carbon-containing ferromanganese as a source of manganese, which is also utilised as a cost-efficient austenite-forming element.
The stainless steel according to the invention is advantageously produced via the conventional stainless steel process route including among others melting in an electric arc furnace, AOD (Argon Oxygen Decarburization) converter treatment and ladle treatment, continuous casting, hot rolling, possibly cold rolling, annealing and pickling. After the conventional processing of the stainless steel to a flat or long product manufactured for instance by hot rolling, cold rolling, drawing, extrusion, forging, the material is thermomechanically processed by deforming and subsequent heat treating according to the invention to modify the grain boundary structure of the stainless steel.
The present invention is described in more details referring to the following drawings, in which
Fig. 1a shows the microstructure of a conventional stainless steel,
Fig. 1b shows the microstructure of a stainless steel according to the invention,
Fig. 2 shows corrosion rate of a conventional stainless steel and the stainless steel according to the invention in a Streicher test in both non-sensitized and sensitized condition,
Fig. 3a shows scanning electron microscope image of the surface of a conventional stainless steel after a Streicher test, and
Fig. 3b shows scanning electron microscope image of the surface of the stainless steel according to the invention after a Streicher test.
The stainless steel of the invention was tested by performing various cold rolling and heat treatment experiments. Examples of microstructures are shown in Fig. 1a for a conventional austenitic stainless steel without any thermomechanical processing and in Fig. 1b for the stainless steel according to the invention after the thermomechanical processing consisting of cold rolling with the reduction degree 1 % and the subsequent heat treatment at the temperature 947°C for 24 hours. The desired special grain boundaries are shown in light gray and random grain boundaries in dark grey in Fig. 1a and in Fig. 1b. In the stainless steel according to the invention the fraction of the desired special grain boundaries is 82% compared to only 38% in the conventional steel.
The intergranular corrosion resistance of the conventional stainless steel and the stainless steel according to the invention are compared in Fig. 2. Fig. 2 presents results of the Streicher test (according to the standard ASTM A262-85 Practice B). In accordance with this corrosion rate test the materials were boiled for 120 hours in an 1 liter Erlenmeyer flask the conditions containing 50 % sulfuric acid and 25 grams of ferric sulfate in order to determine the sensitization effect in the materials. A measure of sensitization effect was weight loss due to the intergranular corrosion, which was determined by measuring weight of samples with 24 hour intervals. In Fig. 2 results are presented for both non-sensitized and sensitized stainless steels. The sensitized test samples were sensitized by a heat treatment at 745°C for 30 min. The stainless steel according to the invention clearly outperformed the conventional stainless steel both in sensitized and non-sensitized conditions. In the sensitized condition the intergranular corrosion attack was so severe in the conventional stainless steel that the sample dissolved entirely before the first weighing of the sample.
Surfaces of the conventional stainless steel (Fig. 3a) and the stainless steel according to the invention (Fig. 3b) after 120 h exposure to Streicher test are shown in Fig. 3a and in Fig. 3b. These samples were not sensitized before the test. Flowever, it can be seen that the conventional stainless steel was clearly attacked at the grain boundaries, whereas no signs of corrosion attack can be seen in the stainless steel thermomechanically processed according to the invention.
Claims (13)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI20136077A FI125105B (en) | 2013-11-04 | 2013-11-04 | Austenitic stainless steel with grain boundary corrosion and method of manufacture |
PCT/FI2014/050822 WO2015063374A1 (en) | 2013-11-04 | 2014-11-03 | Austenitic stainless steel resistant to intergranular corrosion and a method for its production |
TW103138169A TW201522661A (en) | 2013-11-04 | 2014-11-04 | Austenitic stainless steel resistant to intergranular corrosion and a method for its production |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FI20136077A FI125105B (en) | 2013-11-04 | 2013-11-04 | Austenitic stainless steel with grain boundary corrosion and method of manufacture |
FI20136077 | 2013-11-04 |
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FI20136077A FI20136077A (en) | 2015-05-05 |
FI125105B true FI125105B (en) | 2015-06-15 |
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FI20136077A FI125105B (en) | 2013-11-04 | 2013-11-04 | Austenitic stainless steel with grain boundary corrosion and method of manufacture |
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FI (1) | FI125105B (en) |
TW (1) | TW201522661A (en) |
WO (1) | WO2015063374A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US11268177B2 (en) * | 2015-09-30 | 2022-03-08 | Nippon Steel Corporation | Austenitic stainless steel |
KR102160735B1 (en) * | 2018-08-13 | 2020-09-28 | 주식회사 포스코 | Austenitic stainless steel with improved strength |
CN111334700A (en) * | 2018-12-18 | 2020-06-26 | 财团法人金属工业研究发展中心 | High-nitrogen low-nickel austenitic stainless steel alloy and manufacturing method thereof |
CN113025919A (en) * | 2019-12-24 | 2021-06-25 | 南通耀龙金属制造有限公司 | High-strength anti-bending anti-corrosion stainless steel alloy material and preparation method thereof |
EP3960881A1 (en) * | 2020-09-01 | 2022-03-02 | Outokumpu Oyj | Austenitic stainless steel |
CN115679225A (en) * | 2021-07-28 | 2023-02-03 | 叶均蔚 | High chromium silicon corrosion resistant steel and use thereof |
CN114457288A (en) * | 2022-01-20 | 2022-05-10 | 山西太钢不锈钢股份有限公司 | High-nitrogen austenitic stainless steel and preparation method of middle plate thereof |
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JP2009287104A (en) * | 2008-05-30 | 2009-12-10 | Hitachi-Ge Nuclear Energy Ltd | Thin sheet of austenitic stainless steel and manufacturing method therefor |
JP2010275569A (en) * | 2009-05-26 | 2010-12-09 | Hitachi-Ge Nuclear Energy Ltd | Austenitic stainless steel and method of manufacturing the same |
JP2011168819A (en) * | 2010-02-17 | 2011-09-01 | Hitachi-Ge Nuclear Energy Ltd | Austenitic stainless steel and method for manufacturing the same |
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2013
- 2013-11-04 FI FI20136077A patent/FI125105B/en not_active IP Right Cessation
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2014
- 2014-11-03 WO PCT/FI2014/050822 patent/WO2015063374A1/en active Application Filing
- 2014-11-04 TW TW103138169A patent/TW201522661A/en unknown
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Publication number | Publication date |
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TW201522661A (en) | 2015-06-16 |
FI20136077A (en) | 2015-05-05 |
WO2015063374A1 (en) | 2015-05-07 |
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