WO2009034282A1 - Acier inoxydable martensitique, procédé de fabrication de pièces réalisées en cet acier et pièces ainsi réalisées. - Google Patents
Acier inoxydable martensitique, procédé de fabrication de pièces réalisées en cet acier et pièces ainsi réalisées. Download PDFInfo
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- WO2009034282A1 WO2009034282A1 PCT/FR2008/051525 FR2008051525W WO2009034282A1 WO 2009034282 A1 WO2009034282 A1 WO 2009034282A1 FR 2008051525 W FR2008051525 W FR 2008051525W WO 2009034282 A1 WO2009034282 A1 WO 2009034282A1
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
- C21D1/22—Martempering
-
- 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
- C21D6/002—Heat treatment of ferrous alloys containing Cr
-
- 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
-
- 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
-
- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium 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
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
-
- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
Definitions
- the present invention relates to iron and steel, more specifically, martensitic stainless steels, intended for example for the manufacture of molds for the production of plastics by injection.
- the industry uses stainless steels of the AISI 420 family with a chromium content of 12 to 15% (in percentages by weight, like all the contents indicated in the rest of the text). , a silicon content of less than 1%, a manganese content of less than 1%, a carbon content of from 0.16 to 0.45%, and a nitrogen content which is that naturally resulting from the preparation and generally up to 0.03%.
- the vanadium content does not exceed 0.1% and results from the simple melting of the raw materials.
- the molybdenum content results from the melting of the raw materials and does not exceed 0.2%, unless 0.2 to 1.0% is added to improve the corrosion resistance. .
- the X40Cr14 nomenclature steel capable of exceeding a hardness of 50 HRC by virtue of its carbon content of 0.36-0.45%, offers an appreciable abrasion resistance.
- the performance of the material must be evaluated by obtaining a good compromise between the following properties:
- the desired wear resistance in order to be able to produce the maximum number of parts with a guaranteed geometrical regularity, including with plastics materials made abrasive by integrating fibers or other reinforcing additives; this resistance to wear is conferred by a high hardness;
- the object of the invention is the definition of an economic composition of steel for mold applications for the manufacture of plastic articles having compared with the references AISI 420 and X40Cr14, the following properties:
- the subject of the invention is a martensitic stainless steel, characterized in that it comprises, in weight percentages:
- traces Preferably ⁇ 0 ⁇ 0.0015% traces.
- traces ⁇ S Preferably ⁇ 0.003%.
- the invention also relates to a process for manufacturing a martensitic stainless steel part, characterized in that:
- a machining of said steel is carried out to give it the shape of said part; austenization of said machined steel is carried out at a temperature of 990-1040O, preferably 1000-1030O;
- quenching of the austenized steel is carried out at a rate of between 10 and 40OzmJn in the temperature range 800 to 400O; - Two incomes of hardened steel are realized to give it its final hardness.
- Said incomes can each be carried out at a temperature of 200 to 400 ° C., preferably 300 to 380 ° C., for a minimum of 2 hours, while maintaining the nominal temperature at least 1 hour at the core, so that obtain a hardness of 49 to 55 HRC.
- Said incomes can each be made at a temperature of 530 to 540 ° C for a minimum of 2 hours while maintaining a core temperature of the nominal temperature of at least 1 hour, so as to obtain a hardness between 42 and 50 HRC.
- the invention also relates to a piece of stainless steel magnetitic, characterized in that the element manufactured by the process is manufactured according to the preceding method.
- the invention is based on a steel composition whose carbon and chromium contents are simultaneously at the bottom of the ranges usually required, and sometimes even below for the chromium content, with the imposition of conditions. other elements present or to be limited or avoided. A manufacturing method is associated with this composition.
- the approach of the inventors has focused on the real consideration of the properties of the steel resulting from the manufacture, and in particular of the industrial treatment as described above, and not according to laboratory conditions.
- the research was carried out with the aim of optimizing the action of the alloying elements to limit the quantity introduced.
- polishability and surface quality of the polished state of steel are degraded by:
- the toughness mediocre for this family of steels, is, for a given hardness, the lower the chromium content is high. It could be improved by balancing the composition, especially with additions of nickel and manganese to maintain a residue of austenite quenching. This solution, which also has no effect if the incomes are made above 500 ° C, proves unstable and handicaps the hardness. as much as it was not compatible with the desired lowering of the content of alloying elements.
- FIG. 1 shows micrographs of samples of a reference steel and of two steels according to the invention, showing the density and the distribution of the micrometric carbides in the state of use of these steels;
- FIG. 2 which shows the influence of the temperature of the two incomes on the corrosion resistance of a steel according to the invention
- FIG. 3 which shows the influence of the temperature of the incomes on the resistance to corrosion
- Table 1 groups the compositions of the samples studied.
- the "Reference" sample corresponds to a standard X40Cr14 type steel.
- the samples Exp.1 to Exp.7 are not in accordance with the invention but make it possible to identify the disadvantages of not complying with all the conditions required by the invention.
- Samples lnv.1 and lnv.2 are in accordance with the invention.
- the object of the invention is therefore to design an optimized steel intended to be treated according to the range of industrial quenching speeds, preferably with a subsequent double low temperature ( ⁇ 400 ° C.) for a hardness of 52 HRC with tenacity and a corrosion resistance equal to or better than that of the reference steel AISI 420 or X40Cr14 in its usual implementation.
- the invention has the objective of minimizing the addition of alloying elements, in particular metal elements, in order to reduce the cost of production, to prevent the presence of residual austenite after quenching, and to reduce the amplitude. interdendritic segregation is detrimental to the tenacity and quality of polish.
- the nitrogen content should be between 0.05% and 0.15% and preferably between 0.08% and 0.12%. This element is therefore systematically present at a high content, because it is essential to form carbonitrides of type V (C 1 N) able to prevent grain growth after austenization once the dissolved chromium carbides. An excessive content would, however, be detrimental by exceeding the solubility limit in the solid state and would be a source of metallurgical defects. Nitrogen combines with carbon to impart hardness and contributes to corrosion resistance. The nitrogen content can be adjusted by blowing nitrogen gas during the preparation of the liquid steel.
- Carbon mainly contributes to imparting the required hardness, associated with nitrogen. Given the hardness sought after low temperature income, the percentage must be between 0.22% and 0.32%. Moreover the sum C + N must be between 0.33% and 0.43% to allow, after income, to obtain the target hardness.
- Chrome gives steel its resistance to corrosion. Given the industrial quenching speeds practiced, and the income range chosen, and according to the mechanisms mentioned above, its content must be between 10 and 12.4% and preferably between 11, 0 and 12.4% .
- the vanadium must be present at a content of between 0.10% and 0.40% and preferably between 0.15% and 0.35%. Its presence is essential to form with carbon and nitrogen a sufficient density of micro- and nanoprepites able to prevent the growth of the grain. Too high a content would be detrimental by the excessive fixation of the carbon which would be lacking for the hardening, and by the formation, during solidification, of isolated carbides or clumps unfavorable to the tenacity and the quality of the polish.
- Molybdenum completes the action of chromium for corrosion resistance; it is present, by recycling or by voluntary addition, at percentages between 0.10 and 1.0%. A higher content would be detrimental by increasing the amplitude of interdendritic segregation, and by the risk of forming delta ferrite.
- Nickel may be present at levels below 1.0%, particularly because of the input by the raw materials. No favorable action of an addition within this limit for toughness was noted. On the other hand, a higher content would be likely to maintain residual austenite in the treated state.
- Silicon is naturally present for the elaboration and deoxidation of steel. Its content must be limited to 1.0% and preferably 0.5%, because it acts on the solidification process and the delta-gamma transformation and can therefore cause the presence of delta ferrite or local segregations consecutive to the presence of this phase at the end of solidification before filling.
- Tungsten may be present at levels below 1.0% without having a favorable or detrimental effect on the product. However, by its individual action or by synergy with molybdenum, it can promote the presence of delta ferrite in the state of use, or local precipitation or segregation originating from the presence of delta ferrite at any stage of the production. thermomechanical termination. It will be preferred to meet the condition 0.10% ⁇ Mo + W / 2 ⁇ 1, 20%.
- Cobalt and copper have no identified beneficial effect but may be present at levels less than or equal to 1.0%; higher grades may favor the presence of residual austenite.
- the total contents of Mn, Cu and Co is ⁇ 1, 8%, so as to limit the risk of presence of residual austenite.
- Titanium and niobium are very reactive elements that form very hard precipitates harmful to the quality of polishing. Their content must be kept as low as possible: at most 0.010%, preferably at most 0.003% for Ti, and at most 0.050%, preferably at most 0.010% for Nb.
- the added aluminum for the deoxidation of the steel can remain present in inclusions of oxides very harmful for the polishing.
- the level of addition must be adapted to the processing methods used. A maximum level of 0.050% is tolerable, provided that it does not lead to the presence of inclusions of alumina or silico-aluminates in large quantities which would lead to an exceedance of the acceptable O content (0.0040% better, 0.0015%).
- the sulfur is preferentially limited to a content of less than 0.003% to prevent the formation of sulphide inclusions.
- it may be chosen to make a voluntary addition in the range 0.003 to 0.020% preferably associated with another element (SE up to 0.010%, Ca up to 0.020%, La up to 0.040%). %, Ce up to 0.040%) promoting the formation of globular sulphides to improve machinability, to the detriment to a certain extent of the quality of the polish.
- Boron may be added to improve quenchability at a level not exceeding 0.0050%.
- the products must be manufactured in accordance with the state of the art for high-quality special steels for plastics molding applications, with the aim of limiting the inclusion content and the segregation of materials. obtaining a quality polish.
- the preparation must include, after melting, a phase of deoxidation and elimination of inclusions in a metallurgical reactor.
- a phase of deoxidation and elimination of inclusions in a metallurgical reactor.
- it will be practiced remelting by consumable electrode slag to improve the inclusion cleanliness and distribute the alloy elements, and above all the nitrogen, homogeneously throughout the mass.
- thermomechanical transformation by forging or rolling completed by annealing must follow to complete the homogeneity and compactness of the microstructure.
- the products After machining the workpiece to the final shape and before putting into operation, the products must, according to the preferred procedure, undergo a heat treatment comprising austenization at about 1020 ° C (990 to 1040 ° C, preferably 1000 ° C). 1030 ° C), a controlled quenching, for example under a pressure of neutral gas, at a speed of between 10 and 40OZmJn adapted to the size of the workpiece, then two incomes at a temperature of 200 to 400 ° C, preferably between 300 and 380 ° C to obtain a hardness close to 52 HRC _ + 2 HRC, and generally between 49 and 55 HRC.
- the steel defined by the invention can be treated with double-feed from 530 "C to 560" C for hardnesses less than or equal to 50 HRC and greater than or equal to at 42 HRC, conditions in which corrosion resistance is sufficient.
- the existing chromium carbides (M 23 C 6 ) in the delivery state are redissolved during the austenization that precedes quenching, and the holding temperature is limited to 1020/1030 "
- this solution temperature a significant amount of heterogeneously distributed carbides remain, with a substitution of about 0.10 to 0.15% of the content of the carbons. carbon by nitrogen, a reduction of about 2% of the chromium content and a simultaneous introduction of vanadium, it is observed at the adequate quenching temperature that the grain, fixed by nanometric precipitates of vanadium carbons; V (C 1 N) does not increase while most of the chromium carbides have dissolved.
- the effective density of the micrometric carbides observed on industrial products and illustrated in FIG. 1 effectively decreases significantly between the reference composition and the compositions of the invention, which constitutes a favorable factor for the quality of the polished state.
- the corrosion resistance capacity is, theoretically according to the basic knowledge, primarily related to the chromium content available in the matrix; thermodynamic calculations show that carbons undissolved in austenization set about 0.9% chromium. This amount of chromium unavailable for corrosion resistance becomes less than 0.1% for vanadium and nitrogen alloyed experimental grades. According to the following formula:
- the electrochemical method performed according to the ASTM G 108 standard consists, in a 1% by weight aqueous H 2 SO 4 solution, of polarizing the sample for 15 minutes at a potential of -550mV / ECS and then carrying out a forward scan. and back to 60mV / min from -55OmV to + 50OmV.
- the intensity-potential curves at the return can have two peaks, one (Pic1) due to the dissolution of the matrix, the second (Pic 2), at a higher potential, connected to the dissolution at the right of carbide precipitates of chromium.
- Figure 2 shows for the INV1 casting the steel sensitizes strongly vis-à-vis corrosion for revenue generated in the curing zone to 500 0 C. If the corrosion resistance is a characteristic preferable for imperative the applications envisaged, we will therefore favor low-temperature incomes (200-380 0 C).
- compositions of the invention make it possible to obtain the hardness of 52 HRC or more after quenching under industrial conditions and double-tempered at 380 ° C., despite the softening experienced in this field for this steel family from crude. quenching, as shown in Figure 5.
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- 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)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08830336A EP2188402B1 (fr) | 2007-09-10 | 2008-08-25 | Acier inoxydable martensitique, procédé de fabrication de pièces réalisées en cet acier et pièces ainsi réalisées. |
CN200880106281A CN101861407A (zh) | 2007-09-10 | 2008-08-25 | 马氏体不锈钢、由其制成的部件的生产方法和由此生产出的部件 |
CA2698889A CA2698889A1 (fr) | 2007-09-10 | 2008-08-25 | Acier inoxydable martensitique, procede de fabrication de pieces realisees en cet acier et pieces ainsi realisees. |
JP2010523562A JP2010539325A (ja) | 2007-09-10 | 2008-08-25 | マルテンサイト系ステンレス鋼、この鋼から作られる部品の製造方法及びこの方法で製造される部品 |
US12/677,464 US20100276038A1 (en) | 2007-09-10 | 2008-08-25 | Martensitic stainless steel, method for making parts from said steel and parts thus made |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0757451 | 2007-09-10 | ||
FR0757451A FR2920784B1 (fr) | 2007-09-10 | 2007-09-10 | Acier inoxydable martensitique, procede de fabrication de pieces realisees en cet acier et pieces ainsi realisees |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009034282A1 true WO2009034282A1 (fr) | 2009-03-19 |
Family
ID=39272694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2008/051525 WO2009034282A1 (fr) | 2007-09-10 | 2008-08-25 | Acier inoxydable martensitique, procédé de fabrication de pièces réalisées en cet acier et pièces ainsi réalisées. |
Country Status (9)
Country | Link |
---|---|
US (1) | US20100276038A1 (fr) |
EP (1) | EP2188402B1 (fr) |
JP (1) | JP2010539325A (fr) |
KR (1) | KR20100059965A (fr) |
CN (1) | CN101861407A (fr) |
CA (1) | CA2698889A1 (fr) |
FR (1) | FR2920784B1 (fr) |
RU (1) | RU2010114173A (fr) |
WO (1) | WO2009034282A1 (fr) |
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US10508327B2 (en) * | 2016-03-11 | 2019-12-17 | Daido Steel Co., Ltd. | Mold steel and mold |
AU2017252037A1 (en) * | 2016-04-22 | 2018-11-22 | Aperam | A process for manufacturing a martensitic stainless steel part from a sheet |
WO2019002924A1 (fr) * | 2017-06-30 | 2019-01-03 | Aperam | Procédé de soudage par points de tôles d'acier inoxydable martensitique |
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EP0178334A1 (fr) * | 1984-10-11 | 1986-04-23 | Kawasaki Steel Corporation | Aciers inoxydables martensiques pour tubes d'acier sans soudure |
JPH10110248A (ja) * | 1996-10-03 | 1998-04-28 | Hitachi Metals Ltd | 耐孔食性の優れた高硬度マルテンサイト系ステンレス鋼 |
EP1288316A1 (fr) * | 2001-08-29 | 2003-03-05 | Kawasaki Steel Corporation | Procédé de fabrication de tubes sans soudure en acier inoxydable martensitique à résistance et tenacité éléveés |
WO2006016043A2 (fr) * | 2004-07-12 | 2006-02-16 | Industeel Creusot | Acier inoxydable martensitique pour moules et carcasses de moules d'injection |
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JP2007277639A (ja) * | 2006-04-07 | 2007-10-25 | Daido Steel Co Ltd | マルテンサイト鋼 |
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JPS54115617A (en) * | 1978-02-28 | 1979-09-08 | Hitachi Metals Ltd | Corrosion and abrasion resistant alloy steel |
JP2968844B2 (ja) * | 1995-01-13 | 1999-11-02 | 日立金属株式会社 | 耐孔食性の優れた高硬度マルテンサイト系ステンレス鋼 |
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US7520942B2 (en) * | 2004-09-22 | 2009-04-21 | Ut-Battelle, Llc | Nano-scale nitride-particle-strengthened high-temperature wrought ferritic and martensitic steels |
-
2007
- 2007-09-10 FR FR0757451A patent/FR2920784B1/fr not_active Expired - Fee Related
-
2008
- 2008-08-25 CA CA2698889A patent/CA2698889A1/fr not_active Abandoned
- 2008-08-25 WO PCT/FR2008/051525 patent/WO2009034282A1/fr active Application Filing
- 2008-08-25 JP JP2010523562A patent/JP2010539325A/ja active Pending
- 2008-08-25 EP EP08830336A patent/EP2188402B1/fr not_active Revoked
- 2008-08-25 CN CN200880106281A patent/CN101861407A/zh active Pending
- 2008-08-25 US US12/677,464 patent/US20100276038A1/en not_active Abandoned
- 2008-08-25 RU RU2010114173/02A patent/RU2010114173A/ru unknown
- 2008-08-25 KR KR1020107007729A patent/KR20100059965A/ko not_active Application Discontinuation
Patent Citations (6)
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EP0178334A1 (fr) * | 1984-10-11 | 1986-04-23 | Kawasaki Steel Corporation | Aciers inoxydables martensiques pour tubes d'acier sans soudure |
JPH10110248A (ja) * | 1996-10-03 | 1998-04-28 | Hitachi Metals Ltd | 耐孔食性の優れた高硬度マルテンサイト系ステンレス鋼 |
EP1288316A1 (fr) * | 2001-08-29 | 2003-03-05 | Kawasaki Steel Corporation | Procédé de fabrication de tubes sans soudure en acier inoxydable martensitique à résistance et tenacité éléveés |
WO2006016043A2 (fr) * | 2004-07-12 | 2006-02-16 | Industeel Creusot | Acier inoxydable martensitique pour moules et carcasses de moules d'injection |
WO2007063210A1 (fr) * | 2005-11-29 | 2007-06-07 | Aubert & Duval | Acier pour outillage a chaud, et piece realisee en cet acier, son procede de fabrication et ses utilisations. |
JP2007277639A (ja) * | 2006-04-07 | 2007-10-25 | Daido Steel Co Ltd | マルテンサイト鋼 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103097555A (zh) * | 2010-09-14 | 2013-05-08 | 斯奈克玛 | 马氏体不锈钢可加工性的优化处理 |
CN104087854A (zh) * | 2014-06-17 | 2014-10-08 | 江苏金石铸锻有限公司 | 马氏体不锈钢钢材 |
Also Published As
Publication number | Publication date |
---|---|
CA2698889A1 (fr) | 2009-03-19 |
KR20100059965A (ko) | 2010-06-04 |
RU2010114173A (ru) | 2011-10-20 |
CN101861407A (zh) | 2010-10-13 |
FR2920784B1 (fr) | 2010-12-10 |
US20100276038A1 (en) | 2010-11-04 |
EP2188402A1 (fr) | 2010-05-26 |
FR2920784A1 (fr) | 2009-03-13 |
EP2188402B1 (fr) | 2012-05-23 |
JP2010539325A (ja) | 2010-12-16 |
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