EP2449143A1 - Cryogenic treatment of martensitic steel with mixed hardening - Google Patents
Cryogenic treatment of martensitic steel with mixed hardeningInfo
- Publication number
- EP2449143A1 EP2449143A1 EP10742187A EP10742187A EP2449143A1 EP 2449143 A1 EP2449143 A1 EP 2449143A1 EP 10742187 A EP10742187 A EP 10742187A EP 10742187 A EP10742187 A EP 10742187A EP 2449143 A1 EP2449143 A1 EP 2449143A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- steel
- temperature
- traces
- ppm
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 119
- 239000010959 steel Substances 0.000 title claims abstract description 119
- 229910000734 martensite Inorganic materials 0.000 title claims abstract description 36
- 238000011282 treatment Methods 0.000 title description 8
- 230000009466 transformation Effects 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 229910001566 austenite Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 7
- 238000012423 maintenance Methods 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000004663 powder metallurgy Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000012530 fluid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- 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
- C21D6/04—Hardening by cooling below 0 degrees Celsius
-
- 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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/30—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for crankshafts; for camshafts
-
- 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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
-
- 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
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
Definitions
- the present invention relates to a process for treating a martensitic steel which comprises contents of other metals such that it is capable of being hardened by a precipitation of intermetallic compounds and carbides, with an Al content of between 0.4% and 3%, and which has a martensitic transformation end temperature Mf of less than 0 0 Q this heat treatment process comprising the following steps:
- composition of such a steel is given in FR 2,885,142 as follows (percentages by weight): 0.18 to 0.3% C, 5 to 7% Co, 2 to 5% Cr, 1 to 2 % Al, 1 to 4% Mo + W / 2, traces at 0.3% V, traces at 0.1% Nb, traces at 50 ppm B, 10.5 to 15% Ni with Ni> 7 + 3.5 Al, traces at 0.4% Si, traces at 0.4% Mn, traces at 500 ppm Ca, traces at 500 ppm rare earth, traces at 500 ppm Ti, traces at 50 ppm O (elaboration from liquid metal) or at 200 ppm O (elaboration by metallurgy of the powders), traces at 100 ppm of N, traces at 50 ppm of S, traces at 1% of Cu, traces at 200 ppm P, the remainder being Fe.
- This steel has a very high mechanical strength (breaking load ranging from 2000 to 2500 MPa) and at the same time a very good resilience (180 * IQ 3 J / m 2 ) and toughness (40 to 60 MPa * -Jm), and good fatigue resistance.
- cryogenic means temperatures below 0 ° C.
- the purpose of placing such steels in a cryogenic enclosure is to minimize the remaining austenite content in the steel, that is to say to optimize the transformation of austenite to martensite in steel. Indeed, the strength properties of steel increase inversely to its austenite content.
- the temperature Mf at the end of martensitic transformation is between -30 ° C. and -40 ° C., estimated under conditions of thermodynamic equilibrium. To ensure optimal transformation of the austenite martensite, it is generally considered that the temperature in the cryogenic chamber must be slightly below the temperature Mf.
- the temperature in the cryogenic chamber must be less than -40 ° C., and that the optimal martensite transformation is carried out when the hottest steel have reached this temperature. The steel is then removed from the cryogenic enclosure.
- the present invention aims to remedy these disadvantages.
- the aim of the invention is to propose a process for treating this type of steel which makes it possible to reduce the dispersions in its mechanical properties, which gives dispersions which follow normal statistical laws, and which on average increases these mechanical properties,
- the temperature Ti in 0 C with a tolerance of +/- 5 0 C
- the time ti in hours with a tolerance of +/- 5%
- the steel is placed in the cryogenic environment less than 70 hours after the temperature at the surface of the part during cooling in step (b) reaches the temperature of 80 ° C.
- the maximum conversion rate of austenite to martensite that can be achieved in steel by placing it in a cryogenic environment is as high as possible.
- FIG. 2 shows the variation of the austenite content remaining in a steel as a function of the temperature Ti in the cryogenic enclosure for different times during which the steel is maintained in this chamber after the hottest part of the steel reaches a temperature below the martensitic transformation temperature Mf,
- FIG. 3 shows the variation of the hardness in a steel as a function of the temperature Ti in the cryogenic enclosure for different times during which the steel is maintained in this enclosure after the hottest part of the steel reaches a temperature lower than the martensitic transformation temperature Mf,
- FIG. 4 shows the variation of the remaining austenite ratio in a steel as a function of the time separating the end of the cooling of this steel from its austenization temperature, and the placement of this steel in the cryogenic chamber, for different time ti during which the steel is maintained in this chamber after the hottest part of the steel reaches a temperature below the Martensitic transformation temperature Mf.
- a steel object of the present application is subjected to the following treatment with the aim of minimizing its residual austenite content: the steel is heated and maintained above its austenization temperature until its temperature is substantially homogeneous, the steel is then cooled to about room temperature, then the steel is placed and maintained in a chamber where there is a cryogenic temperature.
- the inventors have carried out tests on such steels having undergone the above treatment. These steels have the following composition; 0.200% to 0.250% C, 12.00% to 14.00% Ni, 5.00% to 7.00% Co, 2.5% to 4.00% Cr, 1.30 to 1, 70% in AI, 1.00% to 2.00% in MB.
- FIG. 2 shows, according to the results of these tests, the variation of the austenite content remaining in a steel as a function of the temperature Ti in the cryogenic chamber for different times ti, where ti is the duration during which this steel is maintained in this cryogenic chamber after the hottest part of the steel reaches a temperature below the martensitic transformation temperature Mf.
- the temperature of the enclosure is equal to or lower than about -71 ° C and -67 ° C, respectively, so that the residual austenite level is minimal.
- the curve Ti / (ti) gives the temperature Ti (expressed in 0 C) in the cryogenic chamber where the steel must be maintained for a time ti (expressed in hours) after the hottest part of the steel reaches a temperature below the martensitic transformation temperature Mf so that all the regions of the steel are converted to a maximum of martensite, and therefore have a minimum and homogeneous residual austenite content.
- the first derivative of the function / with respect to t, / '(t), is positive, and the second derivative of / with respect to t, / "(t), is negative.
- the shape of this curve is valid for all the steels of this family and is translated in the vertical direction (variation in temperature) according to the chemical composition of the steel.
- the horizontal asymptote of this equation (the temperature Ti for which a holding time infinite ti is necessary, that is to say the highest possible temperature for the enclosure) is a function of the chemical composition of the steel (This composition has a direct influence on the Ms start and end Mf martensitic transformation temperatures). For the present steel, this temperature is approximately equal to -40 ° C.
- the minimum maintenance time ti necessary is approximately equal to 1 hour, and is substantially constant for all the steels of this family.
- the austenite content in the steel is minimized, and consequently the mechanical properties of the steel are increased on average.
- the minimum austenite content in a region of a steel workpiece is reached only when this region has reached a temperature below the temperature Mf and is maintained there long enough, as shown in the curve of FIG. .
- the steel is kept in the cryogenic enclosure long enough after the hottest part of the steel reaches a temperature below the martensitive transformation temperature Mf, which ensures a transformation. optimal in martensite of this part.
- the method according to the invention which makes it possible to obtain a residual level of austenite in steel which is homogeneous and minimum, the dispersion of the values of the mechanical properties is minimized, as found by the inventors .
- the average hardness of the treated steel is 560 Hv with statistically a minimum at 535 Hv and a maximum at 579 Hv.
- the average hardness of the treated steel is 575 Hv with statistically a minimum at 570Hv and a maximum at 579 Hv.
- step (b) Before placing it in the cryogenic enclosure, the steel undergoes, in step (b), a quenching in a fluid (a medium) in order to cool the steel to ambient temperature.
- a fluid a medium
- this fluid has a drasticity at least equal to that of air.
- this fluid is air.
- the drasticity of a quenching medium is understood to mean the capacity of this medium to absorb the calories in the layers closest to the part which is immersed therein and to diffuse them into the rest of the medium. This capacity conditions the rate of cooling of the surface of the room immersed in this medium.
- Figure 4 shows the results of these tests.
- the residual austenite content in the steel can reach its minimum after maintenance in the cryogenic chamber according to the conditions of the invention.
- the steel is placed in the cryogenic environment more than 70 hours after this moment, then the residual content in austenite can not reach its minimum, regardless of the subsequent duration of maintenance and the temperature in the cryogenic chamber.
- the minimum of the residual austenite content is of the order of 2.5% for the grade of steel tested in the tests. More generally, for the type of steel according to the invention, the minimum of the residual austenite content is less than 3%.
- time ti For other families of steel, the minimum values of time ti vary. For example, the time ti may be greater than 2 hours, or greater than 3 hours, or greater than 4 hours.
- the temperature Ti below which the temperature of the chamber must be is, for example, equal to -50 ° C. or -60 ° C., or -70 ° C.
- the invention also relates to a piece made of a steel obtained according to a process according to the invention, the residual austenite content in this steel being less than 3%.
- this part is a turbomachine shaft.
Landscapes
- 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 Articles (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0954577A FR2947565B1 (en) | 2009-07-03 | 2009-07-03 | CRYOGENIC TREATMENT OF A MARTENSITIC STEEL WITH MIXED CURING |
PCT/FR2010/051402 WO2011001126A1 (en) | 2009-07-03 | 2010-07-02 | Cryogenic treatment of martensitic steel with mixed hardening |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2449143A1 true EP2449143A1 (en) | 2012-05-09 |
EP2449143B1 EP2449143B1 (en) | 2018-09-05 |
Family
ID=41612378
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10742187.7A Active EP2449143B1 (en) | 2009-07-03 | 2010-07-02 | Cryogenic treatment of martensitic steel with mixed hardening |
Country Status (9)
Country | Link |
---|---|
US (1) | US10174391B2 (en) |
EP (1) | EP2449143B1 (en) |
JP (1) | JP5996427B2 (en) |
CN (1) | CN102471854B (en) |
BR (1) | BR112012000128B1 (en) |
CA (1) | CA2766788C (en) |
FR (1) | FR2947565B1 (en) |
RU (1) | RU2554836C2 (en) |
WO (1) | WO2011001126A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2947566B1 (en) * | 2009-07-03 | 2011-12-16 | Snecma | PROCESS FOR PRODUCING A MARTENSITIC STEEL WITH MIXED CURING |
JP5692623B2 (en) * | 2013-02-12 | 2015-04-01 | 日立金属株式会社 | Method for producing martensitic steel |
JP5692622B1 (en) * | 2013-03-26 | 2015-04-01 | 日立金属株式会社 | Martensite steel |
FR3072392B1 (en) * | 2017-10-18 | 2019-10-25 | Safran Landing Systems | PROCESS FOR PROCESSING A STEEL |
CN115478212A (en) * | 2021-05-31 | 2022-12-16 | 宝武特种冶金有限公司 | Carbide and intermetallic compound composite reinforced ultrahigh-strength steel and bar preparation method thereof |
CN115329475B (en) * | 2022-07-15 | 2023-04-25 | 华中科技大学 | Part preparation method and equipment based on zoned multistage cryogenic treatment |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1056561A (en) * | 1962-10-02 | 1967-01-25 | Armco Steel Corp | Chromium-nickel-aluminium steel and method for heat treatment thereof |
GB1089934A (en) * | 1964-10-28 | 1967-11-08 | Republic Steel Corp | High strength steel alloy composition |
SU1553564A1 (en) * | 1987-12-30 | 1990-03-30 | Предприятие П/Я Г-4778 | Method of heat treatment of martensite-ageing steels |
US5393488A (en) * | 1993-08-06 | 1995-02-28 | General Electric Company | High strength, high fatigue structural steel |
US6238455B1 (en) * | 1999-10-22 | 2001-05-29 | Crs Holdings, Inc. | High-strength, titanium-bearing, powder metallurgy stainless steel article with enhanced machinability |
BR0208714A (en) * | 2001-03-27 | 2004-07-20 | Crs Holdings Inc | Ultra-high strength precipitation hardenable stainless steel alloy |
US7475478B2 (en) * | 2001-06-29 | 2009-01-13 | Kva, Inc. | Method for manufacturing automotive structural members |
RU2260061C1 (en) * | 2004-07-23 | 2005-09-10 | Открытое акционерное общество "Тульский оружейный завод" | Method for manufacturing parts of electromagnetic steering drive of guided missile |
FR2885142B1 (en) * | 2005-04-27 | 2007-07-27 | Aubert & Duval Soc Par Actions | CURED MARTENSITIC STEEL, METHOD FOR MANUFACTURING A WORKPIECE THEREFROM, AND PIECE THUS OBTAINED |
FR2885141A1 (en) * | 2005-04-27 | 2006-11-03 | Aubert & Duval Soc Par Actions | Hardened martensitic steel contains amounts of carbon, cobalt, chrome and aluminum with traces of other minerals |
FR2887558B1 (en) | 2005-06-28 | 2007-08-17 | Aubert & Duval Soc Par Actions | MARTENSITIC STAINLESS STEEL COMPOSITION, PROCESS FOR MANUFACTURING A MECHANICAL PART THEREFROM, AND PIECE THUS OBTAINED |
US8968495B2 (en) * | 2007-03-23 | 2015-03-03 | Dayton Progress Corporation | Methods of thermo-mechanically processing tool steel and tools made from thermo-mechanically processed tool steels |
WO2009007562A1 (en) * | 2007-07-10 | 2009-01-15 | Aubert & Duval | Hardened martensitic steel having a low or zero content of cobalt, process for manufacturing a part from this steel, and part thus obtained |
FR2933990B1 (en) * | 2008-07-15 | 2010-08-13 | Aubert & Duval Sa | LOW-COBALT HARDENED CURED MARTENSITIC STEEL, METHOD FOR MANUFACTURING A WORKPIECE THEREFROM, AND PIECE THUS OBTAINED |
-
2009
- 2009-07-03 FR FR0954577A patent/FR2947565B1/en active Active
-
2010
- 2010-07-02 EP EP10742187.7A patent/EP2449143B1/en active Active
- 2010-07-02 BR BR112012000128-0A patent/BR112012000128B1/en active IP Right Grant
- 2010-07-02 WO PCT/FR2010/051402 patent/WO2011001126A1/en active Application Filing
- 2010-07-02 JP JP2012518125A patent/JP5996427B2/en active Active
- 2010-07-02 CN CN201080030278.3A patent/CN102471854B/en active Active
- 2010-07-02 RU RU2012103658/02A patent/RU2554836C2/en active
- 2010-07-02 US US13/382,052 patent/US10174391B2/en active Active
- 2010-07-02 CA CA2766788A patent/CA2766788C/en active Active
Non-Patent Citations (1)
Title |
---|
See references of WO2011001126A1 * |
Also Published As
Publication number | Publication date |
---|---|
BR112012000128B1 (en) | 2021-03-23 |
WO2011001126A1 (en) | 2011-01-06 |
CA2766788A1 (en) | 2011-01-06 |
RU2012103658A (en) | 2013-08-10 |
CN102471854B (en) | 2015-04-22 |
FR2947565B1 (en) | 2011-12-23 |
BR112012000128A2 (en) | 2016-03-15 |
CA2766788C (en) | 2019-06-18 |
JP2012531525A (en) | 2012-12-10 |
EP2449143B1 (en) | 2018-09-05 |
US10174391B2 (en) | 2019-01-08 |
JP5996427B2 (en) | 2016-09-21 |
RU2554836C2 (en) | 2015-06-27 |
FR2947565A1 (en) | 2011-01-07 |
CN102471854A (en) | 2012-05-23 |
US20120168039A1 (en) | 2012-07-05 |
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