EP3289109A1 - Acier inoxydable martensitique, procédé de fabrication d'un demi-produit en cet acier et outil de coupe réalisé à partir de ce demi-produit - Google Patents
Acier inoxydable martensitique, procédé de fabrication d'un demi-produit en cet acier et outil de coupe réalisé à partir de ce demi-produitInfo
- Publication number
- EP3289109A1 EP3289109A1 EP16724302.1A EP16724302A EP3289109A1 EP 3289109 A1 EP3289109 A1 EP 3289109A1 EP 16724302 A EP16724302 A EP 16724302A EP 3289109 A1 EP3289109 A1 EP 3289109A1
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- steel
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- temperature
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- 238000005520 cutting process Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000011265 semifinished product Substances 0.000 title claims abstract description 14
- 229910001105 martensitic stainless steel Inorganic materials 0.000 title claims abstract description 11
- 229910000831 Steel Inorganic materials 0.000 title claims description 51
- 239000010959 steel Substances 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910000734 martensite Inorganic materials 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 16
- 238000011282 treatment Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 5
- 238000005242 forging Methods 0.000 claims description 4
- 238000005097 cold rolling Methods 0.000 claims description 3
- 235000019589 hardness Nutrition 0.000 description 44
- 230000007797 corrosion Effects 0.000 description 34
- 238000005260 corrosion Methods 0.000 description 34
- 238000010791 quenching Methods 0.000 description 31
- 230000000171 quenching effect Effects 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 150000001247 metal acetylides Chemical class 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- 238000007711 solidification Methods 0.000 description 12
- 230000008023 solidification Effects 0.000 description 12
- 238000005498 polishing Methods 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 230000036541 health Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005496 tempering Methods 0.000 description 8
- 229910001566 austenite Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005088 metallography Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/005—Manufacture of stainless steel
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/068—Decarburising
- C21C7/0685—Decarburising of stainless steel
-
- 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
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
-
- 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
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
- C21D8/1222—Hot rolling
-
- 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
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- 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
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
-
- 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
-
- 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
-
- 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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- 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
- C22C38/46—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
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/18—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for knives, scythes, scissors, or like hand cutting tools
Definitions
- Martensitic stainless steel method of manufacturing a semi-finished product of this steel and cutting tool made from this semi-finished product
- the invention relates to a martensitic stainless steel.
- This steel is mainly intended for the manufacture of cutting tools, especially cutlery items, such as scalpels, scissors blades, or knife blades or blades of household robots.
- Steels for cutlery must have high corrosion resistance, polishing ability and hardness.
- the martensitic stainless steels currently used to make the blades of the cutting tools such as the steels of the types EN 1 .4021, EN 1 .4028 and EN 1 .4034, have Cr contents of less than or equal to 14 or 14, 5% by weight and variable C contents, ie 0.16% -0.25% for EN 1 4021, 0.26-0.35% for EN 1 4028 and 0.43-0.50. % for EN 1 4034.
- the hardness level of the steel depends mainly on this C content.
- the grade EN 1 .4419 at 0.36-0.42% C, 13.0-14.5% Cr and 0.60-1.00% of Mo can be used.
- these steels are typically made in an AOD or VOD converter, then continuously cast as slabs, blooms, or billets, and then hot-rolled to a reel, roll bar, or wire rod. They are then annealed to obtain a ferritic structure containing carbides, which is sufficiently soft to allow cold rolling for the flat products, or to facilitate sawing before forging the hot-rolled semi-finished product for long products.
- the product then undergoes recrystallization annealing.
- the product is cut to give it its final shape, for example that of a knife blade, before undergoing a heat treatment comprising a high temperature austenitization, typically between 950 ° C. and 1150 ° C, followed by quenching to room temperature which leads to a predominantly martensitic structure.
- the product has a high hardness, the higher the carbon content is important, but it also has great fragility.
- a tempering treatment typically between 100 ° C and 300 ° C, is then performed to reduce brittleness without too much lowering hardness.
- the blade then undergoes various operations including sharpening and polishing to give it its cutting quality and aesthetic appearance. None of the four shades mentioned at the same time allows a good resistance to corrosion, a good surface condition and a high hardness, for a reasonable cost.
- the grade EN 1 .4419 has good corrosion resistance and high hardness, but it is prohibitively expensive due to the addition of Mo in large quantities.
- the grade EN 1 .4034 has a high hardness, but also a poor surface appearance after polishing, because of the presence in large numbers of undissolved carbides during austenitization, because of the high C content of this grade. .
- the corrosion resistance is insufficient because the Cr content is not high enough in the matrix, especially since part of the Cr is trapped in the undissolved carbides.
- the less loaded grades of C EN 1 4021 and 1 4028 have lower hardnesses, without having sufficient resistance to corrosion due to too low Cr contents.
- the present invention aims to solve the problems mentioned above.
- it aims to provide a martensitic stainless steel for cutting tool as economical as possible, which however has both good corrosion resistance, good polishing ability and high hardness.
- the invention relates to a martensitic stainless steel, characterized in that its composition consists of, in weight percentages:
- ⁇ C ⁇ 0.45% preferably 0.20% ⁇ C ⁇ 0.38%; better 0.20% ⁇ C ⁇ 0.35%; optimally 0.30% ⁇ C ⁇ 0.35%;
- Its microstructure preferably comprises at least 75% of martensite.
- the subject of the invention is also a process for producing a martensitic stainless steel semi-finished product, characterized in that:
- said semi-product is heated to a temperature greater than or equal to 1000 ° C .
- said sheet, said bar or said machine wire is annealed at a temperature of between 700 and 900 ° C .;
- Said half-product may be a sheet, and said forming operation may be cold rolling.
- Said half-product may be a bar or a wire rod, and said shaping operation may be forging.
- Said half-shaped product if its Cr content is between 15 and 17%, can then be austenitized between 950 and 1150 ° C, and then cooled to a speed of at least
- Said semi-finished product can then be austenitized between 950 and 950.
- the invention also relates to a cutting tool, characterized in that it was made from a semi-finished product prepared according to the preceding method.
- the cutting tool may be a cutlery article such as a knife blade, a food processor blade, a scalpel, or a scissors blade,
- the invention consists in using, in order to produce the cutting tool, a martensitic stainless steel of particular composition, free from expensive elements at high levels, but containing relatively large amounts of nitrogen located in a well defined range. Also, a particular balancing of the contents of Cr, C and N is necessary.
- FIG. 1 shows the evolution of the Vickers hardness of steel under a load of 1 kg, depending on the martensite rate after austenitization, quenching and tempering, of a steel according to the invention.
- the C content must therefore be at least 0.10% to obtain sufficient hardness and at most 0.45% to obtain good corrosion resistance and a satisfactory surface appearance after polishing.
- 0.20% ⁇ C ⁇ 0.38% better 0.20% ⁇ C ⁇ 0.35%, optimally 0.30% ⁇ C ⁇ 0.35%.
- the optimal range allows to have a high hardness while limiting the formation of carbides in acceptable proportions, the possible loss of hardness resulting from the lowering of the maximum content of C compared to the most general range which can be compensated by the presence of sufficient nitrogen for this purpose, as will be seen later.
- Mn is a so-called gammagenic element because it stabilizes the austenitic structure.
- An excessive content of Mn leads to an insufficient martensite rate after austenitization and quenching treatment, which leads to a decrease in hardness.
- the Mn content must be between traces resulting from the elaboration and 1.0%.
- Preferably its content is limited to 0.6% to help obtain an optimally low Ms temperature.
- Si is a useful element in the process of making steel. It is very reducing, and it therefore reduces the Cr oxides in the steel reduction phase following the decarburization phase in the AOD or VOD converter.
- the Si content in the final steel must be between traces and 1.0% since this element has a heat-setting effect which limits the possibilities of hot deformation during hot rolling or during forging.
- Preferably its content is limited to 0.6% to help obtain an optimally low Ms temperature.
- S and P are impurities that decrease hot ductility. P easily segregates at the grain boundaries and facilitates their decohesion. In addition, S reduces the resistance to pitting corrosion by forming compounds with Mn which serve as initiating sites for this type of corrosion. As such, the contents of S and P must respectively be between traces and, respectively, 0.01% and 0.04% by weight. Preferably, the S content does not exceed 0.005% to further ensure sufficient corrosion resistance.
- Cr is an essential element for corrosion resistance.
- its content must be limited because a high content may lower the temperature Mf (martensitic transformation end temperature) below ambient temperature. This would lead, after austenitization and quenching to room temperature, to a martensitic transformation that is too incomplete and to an insufficient hardness.
- the Cr content must be between 15.0% and 18.0% by weight.
- the Cr content it is advisable to limit the Cr content to 15.0-17.0%, better 15.2-17.0%, even better 15.5-16.0%, especially when a cryogenic treatment of steel is not carried out, so as not to have a temperature Ms of martensitic transformation start too high, and therefore not to leave too much residual austenite which would limit the hardness, so the tensile strength Rm, which is not desirable on a martensitic steel.
- the reduction in the corrosion resistance induced by the reduction in the maximum Cr content may be offset by a high N content within the limits otherwise prescribed.
- the solubility of N in the liquid metal decreases when the content of Cr decreases, so that it is no longer possible below 15% of Cr to keep enough dissolved N in the liquid metal at the solidification temperature of the steel, which leads to the formation of N 2 bubbles during solidification, and no longer allows N to compensate for the decline of Cr with respect to the corrosion resistance.
- This low Cr limit for the solubility of N also increases when the ferrostatic pressure at solidification decreases. It may be preferable to increase the minimum Cr content from 15.0% to 15.2% or 15.5% depending on the type of casting process and the casting conditions used to guard against any risk of formation. N 2 bubbles.
- the Cr content must also satisfy a formula linking it to the N and C contents as will be explained later.
- the elements Ni, Cu, Mo and V are expensive and also reduce the temperature Mf.
- the content of each of these elements must therefore be limited, between traces and 0.50% by weight, preferably at most 0.10% for Mo. It is therefore not necessary to add after the merger raw materials. It is even more favorable that the Mo content does not exceed 0.05%, to help obtain an optimally low Ms temperature. For the same reason, it is preferable that the Cu content does not exceed 0.3%, and that the V content does not exceed 0.2%.
- Nb, Ti and Zr are so-called “stabilizing" elements, which means that they form, in the presence of N and C and at high temperature, carbides and nitrides more stable than the carbides and nitrides of Cr.
- stabilizing elements which means that they form, in the presence of N and C and at high temperature, carbides and nitrides more stable than the carbides and nitrides of Cr.
- These elements are however undesirable because their respective carbides and nitrides, once formed during the manufacturing process, can no longer be easily dissolved during austenitization, which limits the levels of C and N in the austenite, and therefore the corresponding hardness of martensite after quenching. The content of each of these elements must therefore be between traces and 0.03%.
- the Al content must likewise be between traces and 0.010% to avoid forming nitrides of AI, whose dissolution temperature would be too high and which would reduce the N content of the austenite, hence the hardness. martensite after quenching.
- the O content results from the process of making the steel and its composition. It must be between traces and not more than 0.0080% (80 ppm), so as to avoid forming too many and / or too large oxide inclusions, which could constitute privileged sites of initiation of corrosion. by stitching, and also take off during polishing, so that the surface appearance of the product would not be satisfactory.
- the O content also influences the mechanical properties of the steel, and it may optionally, in a conventional manner, set a limit not to exceed lower than 80 ppm, depending on the requirements of users of the final product.
- Pb, Bi and Sn can be limited to traces resulting from the elaboration, and must not each exceed 0.02% so as not to make the hot transformations too difficult.
- the control of the N content at a well defined level is an essential element of the invention. Like C, it allows, when in solid solution, to increase the hardness of martensite without having the disadvantage of forming precipitates during solidification. If it is not desired a C content too high not to form too much precipitates, an addition of N compensates for the loss of hardness. Nitrides are formed at lower temperatures than carbides, which makes them easier to dissolve during austenitization. The presence of N in solid solution also improves the resistance to corrosion.
- N 2 bubbles which form blisters (porosities) during the solidification of the steel, detrimental to the internal health of the metal .
- the N content must be between 0.10 and 0.20% by weight, preferably between 0.15 and 0.20% by weight.
- the N content must also satisfy various formulas that bind it to Cr contents and
- the hardness of the martensite depends on its contents in C and N.
- the inventors have shown that the hardening effects of these two elements are similar, and therefore that the hardness of the martensite is dependent on its overall content.
- C + N It has been established by the inventors that the hardness after quenching and tempering will be sufficient if the following formula is respected:
- C + N ⁇ 0.45% Three elements have an effect on the corrosion resistance. Cr and N are beneficial, while C has a negative effect because it is generally not possible to dissolve all the carbides of Cr during austenitization, for reasons of productivity and cost that limit in industrial practice the duration and the temperature of the treatment. Undissolved Cr carbides reduce the Cr content of the austenitic matrix, and thereby reduce the corrosion resistance.
- Steels according to the invention have been subjected to austenitization tests at different temperatures before quenching with water at 20 ° C. with a cooling rate greater than 100 ° C./s, followed by an income of 200 ° C. ° C, in order to vary the proportion of dissolved carbides, and consequently the carbon content in the austenite then in martensite after quenching.
- the martensite rate and the Vickers hardness were measured in order to plot the evolution of the hardness as a function of the martensite content, and the results are shown in FIG. 1, for a steel having the composition of Example 14 of table 1.
- the martensite rate of the steel after austenitization, quenching at a speed of at least 15 ° C / s up to a temperature below or equal to 20 ° C, and then returned to a temperature of 100 to 300 ° C, typically 200 ° C, is greater than or equal to 75%.
- Achieving a high martensite content of up to 100% can be better ensured if, after quenching up to 20 ° C or less, treatment is carried out cryogenic, that is to say the quenching in a very low temperature medium ranging from -220 to -50 ° C, typically in liquid nitrogen at -196 ° C or in dry ice at -80 ° C, before proceeding to 100-300 ° C.
- the remaining microstructure typically consists essentially of residual austenite. There may also be ferrite.
- compositions of the various samples of steel tested are shown in Table 1, expressed in% by weight.
- the underlined values are those which do not conform to the invention.
- the values of C + N, Cr + 16 N - 5 C and 17Cr + 500C + 500N were also reported for each sample.
- Invention 110 0.340 0.26 0.32 0.009 0.001 0.28 16.3 0.23 0.02 0.09
- these steels were heated to a temperature above 1100 ° C, hot rolled to a thickness of 3mm, annealed at a temperature of 800 ° C, and then pickled and cold rolled to a thickness of 1, 5mm.
- the steel sheets were then annealed at a temperature of 800 ° C.
- the annealed steel sheets were then subjected to a 15-minute austenitization treatment at 1050 ° C. followed by quenching with water to a temperature of 20 ° C.
- Table 2 shows the results of tests and observations made on these steels. The underlined values correspond to performances deemed insufficient.
- the martensite rate is measured after quenching with water at 20 ° C. and after a cryogenic quenching treatment at -80 ° C., this quenching, or the second of these quenchings, having been followed by a tempering at 200 ° C. .
- the martensite content is greater than or equal to 75% after quenching with water at 20 ° C.
- the other results given in Table 2 relate to the quenched state at 20 ° C. followed by the tempering at 200 ° C.
- the corrosion resistance is evaluated by an electrochemical pitting corrosion test in a medium composed of 0.02M NaCl, at 23 ° C. and at a pH of 6.6.
- the electrochemical test carried out on 24 samples to determine the potential E 0 .i for which the probability element of pitting is equal to 0.1 cm "2.
- the corrosion resistance is considered unsatisfactory if the potential E 0 is less .i 350 mV, measured against the saturated calomel electrode at KCI (350 mV / SCE). it is considered satisfactory if the potential E 0 .i is between 350 mV / SCE 450 mV / SCE. It is considered very satisfactory if the potential E 0 .i is greater than 450 mV / ECS.
- the Vickers hardness is measured in the thickness on a mirror-polished cut, under a load of 1 kg with a square base diamond pyramidal tip, according to EN ISO 6507.
- the average hardness obtained is calculated by making 10 impressions. Hardness is considered insufficient if the average hardness is less than 500 HV. It is considered satisfactory if the average hardness is between 500 HV and 550 HV. It is considered very satisfactory if the average hardness is between 551 and 600 HV. It is considered excellent if the average hardness is greater than 600 HV.
- polishability is evaluated by carrying out a flat polishing up to the mid-thickness of the sample, successively using the SiC papers 180, 320, 500, 800 and 1200 under a force of 30 N, then a polishing on a soaked cloth of diamond paste of particle size 3 ⁇ then 1 ⁇ under a force of 20 N. The surface is then observed under an optical microscope at the magnification of x100. Polishability is considered unsatisfactory if the density of defects conventionally called "comet tails" is greater than or equal to 100 / cm 2 . The polishability is considered satisfactory if this density is between 10 / cm 2 and 99 / cm 2 . The polishability is considered very satisfactory if this density is between 1 and 9 / cm 2 . The polishability is considered excellent if this density is less than 1 / cm 2 .
- the internal health is evaluated by observing the raw steel of solidification in section by optical metallography at magnification x25.
- the internal health is unsatisfactory and indicated by the value "0" in Table 2 if globular cavities (blowholes) reflecting the formation of nitrogen bubbles on solidification are observed. Otherwise the internal health is considered satisfactory and indicated by the value "1" in Table 2.
- the martensite rate is determined by X-ray diffraction by measuring the intensity of the lines characteristic of martensite compared to the intensity of the lines characteristic of austenite, knowing that, in all the samples examined, these are the only two phases in presence. In general, it would not be excluded that other phases are observed in the samples according to the invention. This is the martensite rate which is primarily to be considered in the context of the invention.
- Table 2 Results of the Tests on the Samples of Table 1
- the steels according to the invention 11 to 16, as well as the steels 18 to 19, combine good properties of resistance to corrosion, hardness and polishability, and exhibit good internal health, as well as a martensite rate greater than or equal to 75% after a quench at 20 ° C.
- the steel according to the invention 17 combines good properties of resistance to corrosion, hardness and polishability, and has good internal health and a martensite rate greater than or equal to 75%, but provided to perform cryogenic treatment at -80 ° C. Indeed, after a simple quenching with water at 20 ° C, the martensite rate is not yet sufficient, which is to relate to the presence of Cr at a higher level than other samples according to the invention.
- the reference steels R1 to R3 have Cr and N contents, as well as insufficient C + N and / or Cr + 16 N - 5 C sums, which does not allow a satisfactory corrosion resistance.
- the R4 and R5 reference steels have insufficient Cr contents. Without compensation by addition of N, the steel R4 also has a combination Cr + 16 N - 5 C insufficient leading to an unsatisfactory corrosion resistance.
- compensating for the lack of Cr by adding N restores a satisfactory corrosion resistance, but no longer allows to ensure good internal health because the Cr content is no longer sufficient to allow dissolution complete N in the liquid metal.
- the R6 reference steel has a high C content and an insufficient N content.
- the excessively high C content does not allow sufficient polishing ability due to excessive carbide formation.
- the reference steel R7 has too high a N content, which degrades internal health. It is the same for the reference steel R14.
- the R8 reference steel has an excessive C content, which leads to poor polishability and a low martensite rate even after cryogenic quenching at -80 ° C.
- the R9 reference steel contains too much Cr, which leads to an insufficient martensite rate even after cryogenic quenching at -80 ° C.
- the reference steels R10 and R1 1 have too low C contents as well as insufficient C + N sums, leading to too low hardnesses.
- the reference steels R12 and R13 would have compositions according to the invention on the individual contents of each element, but their sum Cr + 16 N - 5 C, which is less than 16.0%, is insufficient to guarantee a resistance to corrosion as high as that of steels which are in all respects according to the invention, including those which hardly exceed the value of 16.0% for this amount Cr + 16 N - 5 C.
- the steels according to the invention are used with advantage for the manufacture of cutting tools, such as for example scalpels, scissors, knife blades or circular blades of household robots.
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PCT/IB2015/053144 WO2016174500A1 (fr) | 2015-04-30 | 2015-04-30 | Acier inoxydable martensitique, procédé de fabrication d'un demi-produit en cet acier et outil de coupe réalisé à partir de ce demi-produit |
PCT/EP2016/059684 WO2016146857A1 (fr) | 2015-04-30 | 2016-04-29 | Acier inoxydable martensitique, procédé de fabrication d'un demi-produit en cet acier et outil de coupe réalisé à partir de ce demi-produit |
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US (1) | US20180127858A1 (fr) |
EP (1) | EP3289109B1 (fr) |
JP (1) | JP6767389B2 (fr) |
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CN (1) | CN107567507A (fr) |
BR (1) | BR112017023361B1 (fr) |
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RU (1) | RU2017137708A (fr) |
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BR112018071587B1 (pt) * | 2016-04-22 | 2022-03-29 | Aperam | Método para fabricação de uma peça de aço inoxidável martensítico |
CN106636893A (zh) * | 2016-11-25 | 2017-05-10 | 邢台钢铁有限责任公司 | 易切削不锈钢盘条及其制备方法 |
DE102017003965B4 (de) * | 2017-04-25 | 2019-12-12 | Zapp Precision Metals Gmbh | Martensitischer Chromstahl, Stahlfolie, perforierte und/oder gelochte Komponente aus einer Stahlfolie, Verfahren zum Herstellen einer Stahlfolie |
JP6918238B2 (ja) * | 2018-06-13 | 2021-08-11 | 日鉄ステンレス株式会社 | マルテンサイト系s快削ステンレス鋼 |
CN109022728B (zh) * | 2018-07-20 | 2020-05-26 | 西安建筑科技大学 | 一种亚稳态奥氏体不锈钢的高温淬火-深过冷-低温配分热处理方法及不锈钢 |
CN109666779B (zh) * | 2018-12-06 | 2021-01-01 | 南京理工大学 | 一种刃口马氏体强化医用手术剪刀及制作方法 |
EP3936629A4 (fr) * | 2019-03-06 | 2024-04-24 | Nippon Steel Corporation | Tôle d'acier laminée à chaud et procédé de production s'y rapportant |
CN110438404A (zh) * | 2019-09-09 | 2019-11-12 | 山东泰山钢铁集团有限公司 | 一种量具卡尺用钢的成分设计和控制技术 |
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SE301656B (fr) * | 1967-06-30 | 1968-06-17 | Sandvikens Jernverks Ab | |
US3575737A (en) * | 1968-06-25 | 1971-04-20 | Sandvikens Jernverks Ab | Razor blades and other thin cutting edge tools and method of manufacture of such tools |
US4180420A (en) * | 1977-12-01 | 1979-12-25 | The Gillette Company | Razor blades |
JPS6134161A (ja) * | 1984-07-25 | 1986-02-18 | Kawasaki Steel Corp | 刃物用ステンレス鋼 |
JPH07110970B2 (ja) * | 1987-12-26 | 1995-11-29 | 新日本製鐵株式会社 | 耐応力腐食割れ性の優れた針状フェライトステンレス鋼の製造方法 |
JPH07113126B2 (ja) * | 1987-12-26 | 1995-12-06 | 新日本製鐵株式会社 | 耐応力腐食割れ性の優れたステンレス鋼の製造方法 |
FR2708939B1 (fr) * | 1993-08-11 | 1995-11-03 | Sima Sa | Acier martensitique à l'azote à faible teneur en carbone et son procédé de fabrication. |
JP3219128B2 (ja) * | 1996-03-19 | 2001-10-15 | 日新製鋼株式会社 | 抗菌性に優れた高強度マルテンサイト系ステンレス鋼 |
GB2324305B (en) * | 1997-04-16 | 2000-05-24 | Nsk Ltd | Rolling member |
JP3965779B2 (ja) * | 1998-05-22 | 2007-08-29 | 大同特殊鋼株式会社 | プラスチック成形金型用鋼 |
JP2000144332A (ja) * | 1998-11-02 | 2000-05-26 | Sanyo Special Steel Co Ltd | 耐食性と鏡面仕上性に優れたプラスチック用金型用鋼 |
US6273973B1 (en) * | 1999-12-02 | 2001-08-14 | Ati Properties, Inc. | Steelmaking process |
JP3452354B2 (ja) * | 2000-01-20 | 2003-09-29 | 日本高周波鋼業株式会社 | ピストンリング用マルテンサイト系ステンレス鋼及びピストンリング用異形線 |
FR2896514B1 (fr) * | 2006-01-26 | 2008-05-30 | Aubert & Duval Soc Par Actions | Acier martensitique inoxydable et procede de fabrication d'une piece en cet acier, telle qu'une soupape. |
JP4857811B2 (ja) * | 2006-02-27 | 2012-01-18 | Jfeスチール株式会社 | 刃物用鋼 |
JP5368887B2 (ja) * | 2008-09-01 | 2013-12-18 | ミネベア株式会社 | マルテンサイト系ステンレス鋼および転がり軸受 |
CN101768700A (zh) * | 2009-02-01 | 2010-07-07 | 裘德鑫 | 抗菌马氏体不锈钢应用于五金行业 |
KR101318274B1 (ko) * | 2009-12-28 | 2013-10-15 | 주식회사 포스코 | 쌍롤식 박판 주조공정에 의해 제조된 마르텐사이트계 스테인리스강 및 그 제조방법 |
CN102337461B (zh) * | 2010-07-23 | 2013-10-16 | 宝山钢铁股份有限公司 | 一种高硬度马氏体不锈钢及其制造方法 |
KR101239589B1 (ko) * | 2010-12-27 | 2013-03-05 | 주식회사 포스코 | 고내식 마르텐사이트 스테인리스강 및 그 제조방법 |
CN102168226B (zh) * | 2011-04-02 | 2013-04-10 | 裘德鑫 | 一种马氏体抗菌不锈钢及其制造方法 |
KR101423826B1 (ko) * | 2012-07-16 | 2014-07-25 | 주식회사 포스코 | 마르텐사이트계 스테인리스강 및 그 제조방법 |
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2015
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- 2016-04-29 US US15/570,574 patent/US20180127858A1/en not_active Abandoned
- 2016-04-29 EP EP16724302.1A patent/EP3289109B1/fr active Active
- 2016-04-29 CA CA2984514A patent/CA2984514A1/fr not_active Abandoned
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UA120119C2 (uk) | 2019-10-10 |
JP2018521215A (ja) | 2018-08-02 |
ES2796354T3 (es) | 2020-11-26 |
RU2017137708A (ru) | 2019-04-30 |
RU2017137708A3 (fr) | 2019-10-21 |
EP3289109B1 (fr) | 2020-03-04 |
WO2016146857A1 (fr) | 2016-09-22 |
CA2984514A1 (fr) | 2016-09-22 |
WO2016174500A1 (fr) | 2016-11-03 |
BR112017023361B1 (pt) | 2021-07-13 |
KR20170141250A (ko) | 2017-12-22 |
US20180127858A1 (en) | 2018-05-10 |
CN107567507A (zh) | 2018-01-09 |
MX2017013834A (es) | 2018-03-21 |
BR112017023361A2 (pt) | 2018-07-17 |
JP6767389B2 (ja) | 2020-10-14 |
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