EP2681340B1 - Hot-work tool steel and a process for making a hot-work tool steel - Google Patents
Hot-work tool steel and a process for making a hot-work tool steel Download PDFInfo
- Publication number
- EP2681340B1 EP2681340B1 EP12707998.6A EP12707998A EP2681340B1 EP 2681340 B1 EP2681340 B1 EP 2681340B1 EP 12707998 A EP12707998 A EP 12707998A EP 2681340 B1 EP2681340 B1 EP 2681340B1
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- EP
- European Patent Office
- Prior art keywords
- work tool
- low
- steel
- tool steel
- hot
- 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.)
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- 229910001315 Tool steel Inorganic materials 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 116
- 239000011651 chromium Substances 0.000 claims description 108
- 229910052757 nitrogen Inorganic materials 0.000 claims description 91
- 238000005496 tempering Methods 0.000 claims description 71
- 229910000831 Steel Inorganic materials 0.000 claims description 70
- 229910052804 chromium Inorganic materials 0.000 claims description 70
- 239000010959 steel Substances 0.000 claims description 70
- 239000000203 mixture Substances 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 238000010791 quenching Methods 0.000 claims description 9
- 230000000171 quenching effect Effects 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000005242 forging Methods 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 35
- 229910045601 alloy Inorganic materials 0.000 description 23
- 239000000956 alloy Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 22
- 229910052720 vanadium Inorganic materials 0.000 description 22
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 21
- 238000001556 precipitation Methods 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 13
- 239000011572 manganese Substances 0.000 description 12
- 229910052750 molybdenum Inorganic materials 0.000 description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 11
- 239000011733 molybdenum Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 229910001566 austenite Inorganic materials 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000001247 metal acetylides Chemical class 0.000 description 6
- -1 chromium carbides Chemical class 0.000 description 5
- 229910000734 martensite Inorganic materials 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000001934 delay Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- ZLANVVMKMCTKMT-UHFFFAOYSA-N methanidylidynevanadium(1+) Chemical class [V+]#[C-] ZLANVVMKMCTKMT-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910000997 High-speed steel Inorganic materials 0.000 description 2
- 241000976924 Inca Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229960005363 aluminium oxide Drugs 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000161 steel melt Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- 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
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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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
- 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
- C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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- C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
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- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0264—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
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- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
Definitions
- the present invention relates to a low-chromium hot-work tool steel and a process for making a low-chromium hot-work tool steel article.
- the term 'hot-work tools' is applied to a great number of different kinds of tools for the working or forming of metals at comparatively high temperatures, for example tools for die casting, such as dies, inserts and cores, inlet parts, nozzles, ejector elements, pistons, pressure chambers, etc.; tools for extrusion tooling, such as dies, die holders, liners, pressure pads and stems, spindles, etc.; tools for hot-pressing, such as tools for hot-pressing of aluminium, magnesium, copper, copper alloys and steel; moulds for plastics, such as moulds for injection moulding, compression moulding and extrusion; together with various other kinds of tools such as tools for hot shearing, shrink-rings/collars and wearing parts intended for use in work at high temperatures.
- tools for die casting such as dies, inserts and cores, inlet parts, nozzles, ejector elements, pistons, pressure chambers, etc.
- tools for extrusion tooling such as dies, die
- Low-alloyed hot-work tool steel is used in small to medium sized tools in applications where the demands on tempering resistance and thermal fatigue are high.
- Tempering resistance is the ability of a hot-work tool steel to keep its hardness at an elevated temperature for prolonged time.
- Hot-work tool steels are developed for strength and hardness during prolonged exposure to elevated temperatures and generally use a substantial amount of carbide forming alloys.
- High speed steels are used for cutting tools where strength and hardness must be retained at temperatures up to or exceeding 760 °C.
- tungsten and chromium e.g. 18 and 4 wt-%, respectively.
- molybdenum 5-10 wt-% were developed.
- High speed steel differs from hot-work steel in composition and price and cannot be used as a substitute for hot-work steel.
- One object of the present invention is to provide a low-chromium hot-work tool steel having an improved property profile, in particular an improved tempering resistance.
- the steels of the present invention is particular suitable for small tools which do not require a steel composition having a high hardenability for their manufacturing.
- This object is obtained by providing a low-chromium hot-work tool steel as defined in claim 1, i.e. a steel consisting of (in wt-%): C 0.08-0.40 N 0.015-0.30 C+N 0.30-0.50 Cr 1-4 Mo 1.5-3 V 0.8-1.3 Mn 0.5-2 Si 0.1-0.5 optionally Ni ⁇ 3 Co ⁇ 5 B ⁇ 0.01 Fe balance apart from impurities.
- a low-chromium hot-work tool steel as defined in claim 1, i.e. a steel consisting of (in wt-%): C 0.08-0.40 N 0.015-0.30 C+N 0.30-0.50 Cr 1-4 Mo 1.5-3 V 0.8-1.3 Mn 0.5-2 Si 0.1-0.5 optionally Ni ⁇ 3 Co ⁇ 5 B ⁇ 0.01 Fe balance apart from impurities.
- Preferred embodiments of the low-chromium hot-work tool steel may fulfill one or more of the following conditions (in wt-%): C 0.25-0.35 preferably 0.27-0.34 N 0.04-0.30 preferably 0.04-0.10 C+N 0.38-0.42 Cr 1.3-2.5 preferably 1.4-2.3.
- More preferred embodiments of the low-chromium hot-work tool steel may fulfill one or more of the following conditions (in wt-%): N 0.042-0.15 preferably 0.045-0.12 C+N 0.39-0.41 Cr 1.3-2.3 preferably 1.4-2.1
- Even more preferred embodiments of the low-chromium hot-work tool steel may fulfill one or more of the following conditions (in wt-%): C 0.20-0.35 preferably 0.30-0.34 N 0.042-0.12 preferably 0.045-0.12 C+N 0.39-0.41 Cr 1.4-1.9 preferably 1.5-1.7 Mo/V 1.8-2.3 preferably 1.9-2.1 Cr/V ⁇ 2 preferably ⁇ 1.8
- the low-chromium hot-work tool steel may have a composition (in wt-%) according to the examples below: C 0.20-0.40 N 0.03-0.30 C+N 0.30-0.50 Cr 1.2-2.3 Mo 1-3 V 0.8-1.3 Mn 1-2 Si 0.1-0.4 Ni ⁇ 1 optionally Co 3-5 B 0.001-0.01 Mo/V 1.8-2.3 Cr/V ⁇ 2 Fe balance apart from impurities, or C 0.20-0.40 N 0.03-0.30 C+N 0.30-0.50 Cr 1.2-2.3 Mo 1.5-3 V 0.8-1.3 Mn 1-2 Si 0.1-0.4 Ni ⁇ 1 optionally Co 3-5 B 0.001-0.01 Mo/V 1.8-2.3 Cr/V ⁇ 2 Fe balance apart from impurities, or C 0.20-0.40 N 0.04-0.30 C+N 0.30-0.50 Cr 1.2-2.3 Mo 1-3 V 0.8-1.3 Mn 1-2 Si 0.1-0.4 Ni ⁇ 1 Co ⁇ 0.2 optionally B 0.001-0.01 Mo/V 1.8-2.3 Cr/
- Another object is to provide a low-chromium hot-work tool steel article having an improved property profile, in particular an improved tempering resistance.
- the total amount of carbon and nitrogen shall be regulated to 0.30 ⁇ (C+N) ⁇ 0.50, preferably 0,36 ⁇ (C+N) ⁇ 0.44.
- the nominal content shall be in the order of 0.40 wt-%.
- the preferred ranges are set out in the product claims.
- vanadium carbonitrides When the nitrogen content is balanced to about 0.05 to 0.10 wt-% vanadium carbonitrides will form, which will be partly dissolved during the austenitizing step and then precipitated during the tempering step as particles of nanometer size.
- the thermal stability of vanadium carbonitrides is better than that of vanadium carbides, and consequently the tempering resistance of the low-chromium hot-work tool steel article will be much improved. Further, by tempering at least twice, the tempering curve (showing hardness as a function of tempering temperature) will have a higher, secondary peak.
- the nitrogen content preferably is on the order of 0.05 wt-%. This value gives a better performance than higher values.
- a nitrogen content on the order of 0.05 wt-% gives a higher potential for secondary hardening during quenching than higher contents do, thus giving the steel a high hardness.
- an amount in the order of 0.10 wt-% has shown to give a shift of the secondary hardening peak to somewhat higher tempering temperatures which is positive.
- the preferred ranges of are set out in the product claims.
- Chromium promotes the hardenability and corrosion resistance of steels. At too low contents the corrosion resistance will be adversely affected.
- a minimum chromium content in the steel therefore, is set to 1 wt-%.
- the maximum content is set to 4 wt-% in order to avoid undesired formation of chromium rich carbides/carbonitrides, e.g. M 23 C 6 ..
- the chromium content preferably shall not exceed 3 wt-%, and even more preferred preferably not exceed 2.6 wt-%. In one embodiment of the invention, the chromium content is 1.5-1.7 wt-%.
- the preferred ranges of are set out in the product claims.
- a low chromium content delays the precipitation of chromium carbides in the microstructure in favour of the more thermally stable vanadium-rich carbo-nitride. Thus the recovery is slowed down in the material and the tempering resistance becomes improved
- the steel shall contain vanadium in an amount of at least 0.8 wt-% in order to provide a sufficient precipitation potential and thus an adequate tempering resistance and desired high temperature strength properties.
- the upper limit of vanadium is 1.3 wt-%.
- vanadium is between 1.0 and 1.3 wt-%. The preferred ranges of are set out in the product claims.
- the ration Cr/V should preferably be less than 2, more preferably less than 1.8 in order to get the desired MC phase. The reason is that Cr can be considered as a poison for the MC phase.
- Silicon shall be present in the steel in an amount of between 0.1 - 0.5 wt-%, preferably 0.2 - 0.4 wt-%.
- Manganese is present in order to give the steel an adequate hardenability, particularly given the relatively low content of chromium and molybdenum in the steel.
- the content of manganese in the steel is between 0.5 and 2 wt-%, preferably between 1.0 and 2.0 wt-%. The preferred ranges of are set out in the product claims.
- Molybdenum shall be present in the steel in an amount of between 1.5 and 3 wt-%, preferably 2.2 - 2.8 wt-%, in order to provide a secondary hardening during tempering and to give a contribution to the hardenability.
- the preferred ranges of are set out in the product claims.
- Part of the molybdenum may be substituted for tungsten in a manner known per se but the steel shall preferably not contain any intentionally added amounts of tungsten, i.e. shall not contain tungsten in amounts exceeding impurity level, because of certain drawbacks related to the presence of that element.
- the ratio Mo/V should preferably lie in the range of 1.8 - 2.3, more preferably 1.9 -2.1 in order to get the desired precipitation sequence and precipitation potential of the secondary carbides. It is known that Mo stabilizes the M 2 C phase and by adjusting the contents of Mo and V to fall within the range of 1.8 -2.3 also the molybdenum rich M 2 C will form, which phase has a higher coarsening rate as compared to the vanadium rich MC phase.
- Nickel and cobalt are elements that may be included in the steel in amounts up to 3 wt-% and 5 wt-% respectively. Cobalt may increase the hardness at high temperatures which may be advantageous for some applications of the steel. If cobalt is added, an effective amount is about 4 wt. %. Nickel may increase the corrosion resistance, hardenability and toughness of the steel. The preferred ranges of are set out in the product claims.
- austenitizing may be carried out at a temperature between the soft annealing temperature 820 °C and the maximum austenitizing temperature 1200 °C, but the austenitizing of the steel article preferably is carried out at a temperature on the order of 1050 - 1150 °C, preferably at 1080 - 1150 °C, typically at 1100 °C.
- higher austenitizing temperatures shift the tempering hardness to higher temperatures, i.e. the secondary hardening peak will be shifted to higher temperatures, which means that the desired hardness will be reached at a higher initial tempering temperature.
- the material will obtain an improved tempering resistance and the work temperature of the tools could be elevated.
- the tempering of the quenched steel article preferably is carried out at least twice at a retention time of 2 hours at a temperature between 500 and 700 °C, preferably 550 and 680 °C. In the most preferred embodiment of the steel composition, the tempering is carried out at a temperature between 600 and 650 °C, preferably between 625 and 650 °C.
- Nitrogen contents in the range of 0.05 - 0.10 wt-% may be obtained by incorporating the nitrogen by conventional casting methods to form a melt, casting the melt to form an ingot, and homogenizing the ingot by heat treatment. Nitrogen additions will produce large primary vanadium-rich M(C,N) precipitates, which in turn will give the material uneven hardness. However, the large primary carbo-nitrides will not occur if the nitrogen content is lowered and there is a homogenizing heat treatment prior to a subsequent forging.
- nitrogen may amount to up to 0.30 wt-%.
- conventional casting methods are insufficient.
- the nitrogen could be incorporated by first manufacturing a steel powder of essentially the desired composition, except for the nitrogen, then nitriding this powder in solid state by nitrogen containing fluid, e.g. nitrogen gas, thereafter hot pressing the powder isostatically at a temperature on the order of 1150 °C and a pressure on the order of 76 MPa to form an ingot.
- nitrogen containing fluid e.g. nitrogen gas
- the ingot is preferably forged at a temperature on the order of 1270 °C, and then soft annealed at a temperature on the order of 820 °C, followed by cooling at a rate of 10 °C per hour to a temperature of 650 °C and then free cooling in air to make it ready for austenitizing.
- the steel of the present inveintion has a much improved tempering resistance permitting a longer article life in hot-work applications.
- the nitrogen content preferably is on the order of 0.05 wt-% and the chromium content is preferably less than 3 wt-%, i.e 1.2 -2.6 or 1.3 - 2.3.
- the steel article of the present invention shall preferably also satisfy some of the following demands:
- Molybdenum and vanadium medium alloyed hot-work tool steels have good resistance to thermal fatigue, softening and high-temperature creep.
- An exemplary nominal chemical composition of such a prior art steel is presented in Table 1 (wt-%).
- FIG. 1 presents a tempering curve (hardness vs. tempering temperature) for the exemplary prior art tool steel.
- the samples were austenitized at 1030 °C, and then tempered two times at different temperatures; from 200 °C up to 700 °C for a tempering time of 2 + 2 hours.
- the interval 500 to 650 °C there is a pronounced secondary hardening peak at 550 °C.
- Later work has also shown that there is a significant precipitation of the meta-stable molybdenum-rich M 2 C in the exemplary prior art tool steel during tempering at 625 °C, which contributes to the secondary hardening effect.
- the tempering resistance can normally be connected to the initial tempering temperature; if the material is held at a temperature well below the initial tempering temperature it will not soften. At holding temperatures closer to or above the initial tempering temperature the softening will be more pronounced.
- the desired hardness e.g. 44-46 HRC
- the material would get an improved tempering resistance, and the work temperature of the tools could be raised.
- the substitution of nitrogen for part of the carbon is used to achieve a higher hardness of the martensitic steel matrix.
- the nitrogen addition initially causes a larger amount of retained austenite.
- this austenite can later be transformed to martensite by cold work, and it is possible to achieve hardness as high as 68 HRC in this manner.
- a low chromium content appears to have a positive effect on the tempering resistance.
- a comparison of two different hot-work tools steels with 1.5 and 5.0 wt-% chromium shows that the lower chromium content delays the precipitation of chromium carbides in the microstructure in favour of the more thermally stable vanadium-rich MC. Thus the recovery is slowed down in the material and the tempering resistance becomes improved.
- a low-chromium hot-work tool steel article having increased tempering resistance is made by carrying out the following process steps:
- vanadium carbo-nitrides when the nitrogen content is balanced to about 0.015 to 0.30 wt-% in a low-chromium steel, vanadium carbo-nitrides will form, which will be partly dissolved during the austenitizing step and then precipitated during the tempering step as particles of nanometer size.
- the particles are in the order of about 1 ⁇ m to about 10 ⁇ m.
- the average size of the particles are less than 1 ⁇ m.
- the thermal stability of vanadium carbo-nitrides is better than that of vanadium carbides, and consequently the tempering resistance of the low-chromium hot-work tool steel article will be much improved. Further, by tempering at least twice, the tempering curve (showing hardness as a function of tempering temperature) will have a higher, secondary peak.
- the nitrogen content preferably is on the order of 0.05 percent by weight. This value gives a better performance than higher values. A nitrogen content on the order of 0.05 percent by weight gives a higher potential for secondary hardening during quenching than higher contents do.
- the chromium content preferably is 1.5-1.7 percent by weight.
- a low chromium content delays the precipitation of chromium carbides in the microstructure in favour of the more thermally stable vanadium-rich carbo-nitrides. Thus the recovery is slowed down in the material and the tempering resistance becomes improved.
- austenitizing may be carried out at a temperature between the soft annealing temperature 820 °C and the maximum austenitizing temperature 1200 °C.
- the austenitizing of the steel article preferably is carried out at a temperature on the order of 1050 - 1150 °C, preferably at 1100 °C.
- higher austenitizing temperatures shift the tempering hardness to higher temperatures, i.e. the secondary hardening peak will be shifted to higher temperatures, which means that the desired hardness will be reached at a higher initial tempering temperature.
- the material will get an improved tempering resistance and the work temperature of the tools will be raised.
- the tempering of the quenched steel article preferably is carried out at least twice at a retention time of 2 hours at a temperature between 500 and 700 °C, preferably 550 and 680 °C. In the most preferred embodiment of the steel composition, the tempering is carried out at a temperature between 600 and 650 °C, preferably between 625 and 650 °C.
- Nitrogen contents in the range of 0.05 - 0.10 percent by weight may be obtained by incorporating the nitrogen by conventional casting methods to form a melt, casting the melt to form an ingot, and homogenizing the ingot by heat treatment. Nitrogen additions will produce large primary vanadium-rich M(C,N) precipitates, which in turn will give the material uneven hardness. However, large primary carbo-nitrides will not occur if the nitrogen content is lowered and there is a homogenizing heat treatment prior to a subsequent forging.
- the nitrogen content preferably is on the order of 0.05 wt-%. This value gives a better performance than higher values.
- a nitrogen content on the order of 0.05 wt-% gives a higher potential for secondary hardening during quenching than higher contents do, thus giving the steel a high hardness.
- an amount in the order of 0.10 wt-% has shown to give a shift of the secondary hardening peak to somewhat higher tempering temperatures which is positive. Additionally, the performed tests and modelling calculations indicate that an increased austenitizing temperature is required in connection with increased nitrogen contents.
- nitrogen may amount to up to 0.30 wt-%.
- conventional casting methods are insufficient.
- the nitrogen then is incorporated preferably by first manufacturing a steel powder of essentially the desired composition, except for the nitrogen, then nitriding this powder in solid state by nitrogen gas, thereafter hot pressing the powder isostatically at a temperature on the order of 1150 °C and a pressure on the order of 76 MPa to form an ingot.
- the ingot is preferably forged at a temperature on the order of 1270 °C, and then soft annealed at a temperature on the order of 820 °C, followed by cooling at a rate of 10 °C per hour to a temperature of 650 °C and then free cooling in air to make it ready for austenitizing.
- N0.05 designates a material having a nitrogen content of 0.05 wt-%, and so on. Note that these are the actual compositions of the trial ingots.
- the aim was to keep the level of all alloying elements except carbon and nitrogen constant. Compared to the standard low chromium hot-work tool steel of Table 1, chromium was also slightly decreased. There was a small decrease in molybdenum content and an increase in manganese content. For carbon and nitrogen, the aim was to have a constant sum of around 0.40 wt-% of these elements, and this was relatively well achieved.
- the tempering stage concerns mainly meta-stable phases, and previous electron microscopy work has shown that they exist in standard low chromium hot-work tool steel at tempering temperature intervals, i.e. 400 to 700 °C.
- These carbide phases are mainly vanadium-rich MC (FCC) and molybdenum-rich M 2 C (HCP).
- FCC vanadium-rich MC
- HCP molybdenum-rich M 2 C
- Some amount of chromium-rich M 7 C 3 has also been found in the standard low chromium hot-work tool steel.
- the interesting temperature interval thus was between the soft annealing temperature, 820 °C and the set practically usable maximum austenitizing temperature, 1200 °C.
- M 6 C Since the molybdenum-rich M 6 C phase only dissolves carbon and no nitrogen, it suffers from the lower carbon content in N0.10 and N0.30, thus the amount of M 6 C decreases with decreasing carbon content. It should also be noted that all M 6 C is dissolved at the austenitizing temperatures used.
- the two alloys N0.05 and N0.10 were conventionally cast as small ingots of 50 kg. N0.10 was the first trial and there was no homogenizing treatment done on this ingot before the forging process. The second trial, N0.05, a homogenizing treatment at 1300°C for 15 hours was applied before forging. The third alloy, N0.30 had a too high nitrogen content to be manufactured by conventional casting. Therefore this alloy was produced using powder metallurgy. First the steel powder was manufactured and then this powder was nitrided in solid state by pressurized N 2 -gas. The powder was then hot isostatically pressed (HIP) at 1150 °C with the pressure of 76 MPa.
- HIP hot isostatically pressed
- Fig. 6 The results from the hardness measurements are presented in Fig. 6 . As can be seen, all three alloys have a secondary hardening peak in the temperature interval 500 to 650 °C. All tempering was done for 2 + 2 hours. N0.05 has the highest hardness in the asquenched condition (53HRC), while N0.10 and N0.30 had somewhat lower hardness. However, all three alloys are regarded as hardenable. The hardness curve of N0.05 is very similar to that of the standard low-chromium hot-work tool steel with a maximum of around 54 HRC as shown in Fig. 1 .
- the secondary hardening peak of N0.10 seems to be somewhat shifted to a higher temperature with peak hardness at 600 °C.
- the peak hardness for both N0.05 and N0.30 was at 550 °C.
- the undissolved M(C,N) particles in the conventionally cast N0.05, the alloy with the lowest nitrogen content, have an average size smaller than 1 ⁇ m. This is comparable with ordinary undissolved carbides in steel.
- Another phase that is easily found in N0.05 is the mixture of aluminium-oxide and manganese-sulphide, see Fig. 7 , which is a SEM image (back-scattered) showing small undissolved M(C,N) precipitates 2 and a globular mixed oxide-sulphide particle 1 in N0.05.
- the sample was austenitized at 1100 °C for 30 min and tempered at 625 °C for 2 + 2 hours.
- the most common size of the M(C,N) particles in N0.10 is between 5 and 10 ⁇ m Equivalent Circle Diameter (ECD) after austenitizing at 1150 °C for 30 minutes and tempering at 625 °C for 2 + 2 hours. Larger, primary carbides 3 (precipitated in the melt) are frequently found in former austenite grain boundaries, see Fig. 8 , which is a back-scattered SEM image revealing undissolved, primary M(C,N) at former austenite grain boundaries in alloy N0.10. The sample was austenitized at 1150 °C for 30 min and tempered at 625 °C for 2 + 2 hours.
- ECD Equivalent Circle Diameter
- Fig. 9 is a detail SEM micrograph of primary M(C,N) particles 4 in N0.10. They were discovered automatically in SEM using the INCA Feature software from Oxford Instruments. Their sharp edges indicated that they had precipitated from the melt. The white areas in the image are molybdenum-rich M 6 C particles 5. Note that in this case the sample was soft annealed N0.10.
- the undissolved M(C,N) particles 6 had a size distribution (ECD) between 1 to 5 ⁇ m with the most common size 2 ⁇ m, thus the particles were small even though the nitrogen content was high.
- the particles were homogeneously distributed in the microstructure, see Fig. 10 . However, as shown in Fig. 11 , some clusters 7 of M(C,N) were found.
- the process and the low-chromium hot-work tool steel of the present invention are applicable where it is desired to get hot-work steel tools, which can be utilized at increased temperatures for an extended period of time.
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KR20160108529A (ko) * | 2014-01-16 | 2016-09-19 | 우데홀름스 악티에보라그 | 스테인리스 강 및 스테인리스 강제의 절삭 공구 본체 |
SE539646C2 (en) * | 2015-12-22 | 2017-10-24 | Uddeholms Ab | Hot work tool steel |
CN107604257B (zh) * | 2016-08-25 | 2019-03-29 | 北京机科国创轻量化科学研究院有限公司 | 一种hm3粉末钢及其制备工艺 |
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JPS5450421A (en) * | 1977-09-30 | 1979-04-20 | Daido Steel Co Ltd | Hot tool steel |
SE426177B (sv) * | 1979-12-03 | 1982-12-13 | Uddeholms Ab | Varmarbetsstal |
JPH02125840A (ja) * | 1988-11-01 | 1990-05-14 | Hitachi Metals Ltd | 熱間加工用工具鋼 |
SU1659520A1 (ru) * | 1989-07-04 | 1991-06-30 | Производственное Объединение "Гомсельмаш" | Инструментальна сталь |
SU1767019A1 (ru) * | 1991-01-25 | 1992-10-07 | Запорожский машиностроительный институт им.В.Я.Чубаря | Штампова сталь |
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JP2952245B2 (ja) * | 1998-07-24 | 1999-09-20 | 日立金属株式会社 | 熱間加工用工具鋼 |
JP2001158937A (ja) * | 1999-09-22 | 2001-06-12 | Sumitomo Metal Ind Ltd | 熱間加工用工具鋼とその製造方法および熱間加工用工具の製造方法 |
SE516622C2 (sv) * | 2000-06-15 | 2002-02-05 | Uddeholm Tooling Ab | Stållegering, plastformningsverktyg och seghärdat ämne för plastformningsverktyg |
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AU2003292572A1 (en) * | 2003-12-19 | 2005-07-14 | Daido Steel Co., Ltd | Hot work tool steel and mold member excellent in resistance to melting |
JP2006104519A (ja) * | 2004-10-05 | 2006-04-20 | Daido Steel Co Ltd | 高靭性熱間工具鋼およびその製造方法 |
JP2007100194A (ja) * | 2005-10-07 | 2007-04-19 | Daido Steel Co Ltd | 熱間工具鋼の製造方法 |
JP4992344B2 (ja) * | 2006-08-30 | 2012-08-08 | 大同特殊鋼株式会社 | 熱疲労特性に優れた金型用鋼 |
CN101563470B (zh) * | 2006-12-27 | 2011-05-11 | 日立金属株式会社 | 工具钢的制造方法 |
JP5444938B2 (ja) * | 2009-08-24 | 2014-03-19 | 大同特殊鋼株式会社 | 金型用鋼 |
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- 2012-03-01 JP JP2013557046A patent/JP5837945B2/ja not_active Expired - Fee Related
- 2012-03-01 BR BR112013022606A patent/BR112013022606A2/pt active Search and Examination
- 2012-03-01 KR KR1020157009651A patent/KR102012950B1/ko active IP Right Grant
- 2012-03-01 PL PL12707998T patent/PL2681340T3/pl unknown
- 2012-03-01 KR KR1020177025271A patent/KR20170105138A/ko not_active Application Discontinuation
- 2012-03-02 TW TW101106919A patent/TWI535863B/zh not_active IP Right Cessation
-
2016
- 2016-01-06 US US14/989,469 patent/US20160115573A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
KR20150047636A (ko) | 2015-05-04 |
CN103703150B (zh) | 2015-12-23 |
KR20140015445A (ko) | 2014-02-06 |
TW201303043A (zh) | 2013-01-16 |
US20140056749A1 (en) | 2014-02-27 |
PL2681340T3 (pl) | 2015-10-30 |
PT2681340E (pt) | 2015-08-25 |
JP5837945B2 (ja) | 2015-12-24 |
US20160115573A1 (en) | 2016-04-28 |
WO2012119925A1 (en) | 2012-09-13 |
BR112013022606A2 (pt) | 2016-12-06 |
JP2014512456A (ja) | 2014-05-22 |
KR20170105138A (ko) | 2017-09-18 |
CN103703150A (zh) | 2014-04-02 |
ES2540905T3 (es) | 2015-07-14 |
SE1150200A1 (sv) | 2012-09-05 |
SI2681340T1 (sl) | 2015-10-30 |
CA2828962A1 (en) | 2012-09-13 |
RU2013142584A (ru) | 2015-04-10 |
TWI535863B (zh) | 2016-06-01 |
DK2681340T3 (en) | 2015-06-29 |
SE536596C2 (sv) | 2014-03-18 |
CA2828962C (en) | 2018-11-06 |
KR102012950B1 (ko) | 2019-08-21 |
EP2681340A1 (en) | 2014-01-08 |
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