WO2018182480A1 - Acier à outils pour travail à chaud - Google Patents

Acier à outils pour travail à chaud Download PDF

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Publication number
WO2018182480A1
WO2018182480A1 PCT/SE2018/050213 SE2018050213W WO2018182480A1 WO 2018182480 A1 WO2018182480 A1 WO 2018182480A1 SE 2018050213 W SE2018050213 W SE 2018050213W WO 2018182480 A1 WO2018182480 A1 WO 2018182480A1
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WO
WIPO (PCT)
Prior art keywords
steel
following requirements
steel according
temperature
fulfilling
Prior art date
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PCT/SE2018/050213
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English (en)
Inventor
Sebastian Ejnermark
Original Assignee
Uddeholms Ab
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Publication date
Application filed by Uddeholms Ab filed Critical Uddeholms Ab
Publication of WO2018182480A1 publication Critical patent/WO2018182480A1/fr

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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
    • 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
    • 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
    • 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
    • C21D1/26—Methods of annealing
    • 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
    • C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • 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
    • C21D2211/002—Bainite
    • 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 invention relates to a hot work tool steel.
  • Vanadium alloyed matrix tool steels have been on market for decades and attained a considerable interest because of the fact that they combine a high wear resistance with an excellent dimensional stability and because they have a good toughness. These steels have a wide range of applications such as for die casting and forging.
  • the steels are generally produced by conventional metallurgy followed by Electro Slag Remelting (ESR).
  • ESR Electro Slag Remelting
  • Uddeholm DIEVAR" 9 is a high performance chromium-molybdenum-vanadium steel, containing balanced carbon and vanadium contents as described in WO 99/50468 Al. It is a modified H13 premium hot work tool steel, which is machined in the soft annealed delivery condition.
  • the recommended soft annealing is heating to 850 °C in protecting atmosphere for 4 hours to obtain a uniform temperature followed by cooling at a rate of 10 °C/h to 600 °C and then freely in air. This results in a hardness of approximately 160 HB.
  • the object of the present invention is to provide a hot work tool steel having an improved property profile, i.e. the inventive steel should be superior over the modified H13 tool steel known in the art in at least one respect.
  • Another object of the present invention is to improve the machinability of the steel in the unhardened condition.
  • Fig. 1 shows the structure of the inventive steel 800 °C/6h according to the Example.
  • the length of the bar in the lower right corner is 20 ⁇ .
  • Fig. 2 shows the structure of the comparative subjected to conventional soft annealing according to the Example.
  • the length of the bar in the lower right corner is 20 ⁇ .
  • Fig. 3 shows the structure of the inventive steel 800 °C/6h according to the Example.
  • Fig. 4 shows the structure of the comparative subjected to conventional soft annealing according to the Example.
  • the amount of carbon should be controlled such that the amount of primary carbides of the type M23C6, M7C3 and Me in the steel is limited, preferably the steel is free from such primary carbides.
  • Si is commonly used for deoxidation. Si is present in the steel in a dissolved form and may positively influence the machinability. However, Si is a strong ferrite former and increases the carbon activity and therefore the risk for the formation of undesired carbides, which negatively affect the impact strength. Silicon is also prone to interfacial segregation, which may result in decreased toughness and thermal fatigue resistance. Si is therefore limited to 1.0 %. The upper limit may be 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.35 0.34, 0.32, 0.30, 0.28, 0.26, 0.24 or 0.22%. The lower limit may be 0.12, 0.14, 0.16, 0.18 and 0.20%. Preferred ranges are 0.10 - 0.25 % and 0.15 - 0.24%.
  • Manganese contributes to improving the hardenability of the steel and together with sulphur manganese contributes to improving the machinability by forming manganese sulphides.
  • Manganese shall therefore be present in a minimum content of 0.2 %, preferably at least 0.3, 0.35, 0.4, 0.45 or 0.5 %. At higher sulphur contents manganese prevents red brittleness in the steel.
  • the steel shall contain maximum 1.0 %, preferably maximum 0.8, 0.7, 0.6, 0.55 or 0.5 %.
  • Chromium is to be present in a content of at least 2.0 % in order to provide a good
  • the lower limit may be 2.0, 2.5, 3.0, 3.5, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8 or 4.9%.
  • the upper limit may be 6.0, 5.8, 5.6, 5.5, 5.4, 5.2 or 5.1 %.
  • Mo is known to have a very favourable effect on the hardenability. Molybdenum is essential for attaining a good secondary hardening response. The minimum content is 1.0 %, and may be set to 1,2, 1.4, 1.6, 1.8, 2.0, 2.1, 2.2, 2.25 or 2.3 %. Molybdenum is a strong carbide forming element and also a strong ferrite former. The maximum content of molybdenum is therefore 3.5 %. Mo may be limited to 3.4, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4 or 2.35 %. Vanadium (0.4 - 0.9 %)
  • Vanadium forms evenly distributed primary precipitated carbides and carbonitrides of the type V(N,C) in the matrix of the steel.
  • This hard phase may also be denoted MX, wherein M is mainly V but Cr and Mo may be present and X is one or more of C, N and B. Vanadium shall therefore be present in an amount of 0.4 - 0.9%.
  • the upper limit may be set to 0.9, 0.8, 0.7, 0.6, 0.58, 0.56 or 0.55 %.
  • the lower limit may be 0.42, 0.44, 0.46, 0.48, 0.50 or 0.52%. Aluminium (0.001 - 0.06 %)
  • Aluminium is an optional element and may be used for deoxidation in combination with Si and Mn.
  • the lower limit may be set to 0.001, 0.003, 0.005 or 0.007% in order to ensure a good deoxidation.
  • the upper limit is restricted to 0.06% for avoiding precipitation of undesired phases such as AIN.
  • the upper limit may be 0.05, 0.04, 0.03, 0.02 or 0.015%.
  • Nitrogen is restricted to 0.08 % in order to obtain the desired type and amount of hard phases, in particular V(C,N).
  • vanadium rich carbonitrides V(C,N) will form. These 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 considered to be better than that of vanadium carbides, hence the tempering resistance of the tool steel may be improved and the resistance against grain growth at high austenitizing temperatures is enhanced.
  • the lower limit may be 0.001, 0.004, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016 or 0.017%.
  • the upper limit may be 0.07, 0.06, 0.05, 0.04, 0.03 or 0.01 %.
  • Hydrogen is known to have a deleterious effect on the properties of the steel and to cause problems during processing.
  • the upper limit can be set to 0.0004% (4 ppm) and it may be limited to 3, 2.5, 2, 1.5 or 1 ppm.
  • Nickel may be present in an amount of ⁇ 1.5 %. It gives the steel a good hardenability and toughness. However, because of the expense, the nickel content of the steel should be limited.
  • the upper limit may therefore be set to 1.0, 0.8, 0.5 or 0.3%.
  • the lower limit may be set to 0.05, 0.10, 0.15 or 0.20 %.
  • Cu is an optional element, which may contribute to increasing the hardness and the corrosion resistance of the steel. If used, the preferred range is 0.02 - 1%.
  • the lower limit may beset to 0.05, 0.1 or 0.15 %.
  • the upper limit may be set to 0.6, 0.4 0.3 or 0.2 %.
  • Co is an optional element. Co causes the solidus temperature to increase and therefore provides an opportunity to raises the hardening temperature, which may be 15 - 30 °C higher than without Co. During austenitization it is therefore possible to dissolve larger fraction of carbides and thereby enhance the hardenability. Co also increases the M s temperature.
  • the maximum amount is 8 % and, if added, an effective amount may be 2 - 6 %, in particular 4 to 5 %. However, for practical reasons, such as scrap handling, deliberate additions of Co is not made.
  • the maximum impurity content may then be set to 1 % or 0.3 %.
  • molybdenum may be replaced by twice as much with tungsten because of their chemical similarities.
  • tungsten is expensive and it also complicates the handling of scrap metal.
  • the maximum amount is therefore limited to 1 %, preferably 0.5 %, more preferably 0.3 % and most preferably no deliberate additions are made.
  • Niobium is similar to vanadium in that it forms carbonitrides of the type M(N,C) and may in principle be used to replace part of the vanadium but that requires the double amount of niobium as compared to vanadium.
  • Nb results in a more angular shape of the
  • M(N,C) The maximum amount is therefore 0.5%, preferably 0.05 % and most preferably no deliberate additions are made.
  • These elements are carbide formers and may be present in the alloy in the claimed ranges for altering the composition of the hard phases. However, normally none of these elements are added.
  • B may be used in order to further increase the hardness of the steel.
  • the amount is limited to 0.01%, preferably ⁇ 0.005%.
  • a preferred range for the addition of B is 0.001 - 0.004 %.
  • Selenium may be added to the steel in an amount of ⁇ 0.05% in order to further improve the machinability of the steel.
  • Y may optionally be added in an amount of up to 1 % in order to improve adherence of the oxide scale and thereby improving the wear resistance of the steel.
  • the addition is particularly effective when evenly distributed in the steel matrix.
  • Y is therefore preferably added to steels produced by powder metallurgy.
  • the lower limit may be set to 0.2, 0.3 or 0.4 %.
  • the upper limit may be set to 0.9, 0.8, 0.7 or 0.6 %.
  • REM is here defined to consist of the elements 57 to 71 in the periodic table.
  • P, S and O are the main impurities, which have a negative effect on the mechanical properties of the steel.
  • P may therefore be limited to 0.03%, preferably to 0.01%.
  • S may be limited to 0.03, 0.01, 0.00 5, 0.003, 0.001, 0.0008, 0.0005 or even 0.0001%.
  • O may be limited to 0.0015, 0.0012, 0.0010, 0.0008, 0.0006 or 0.0005%.
  • the invention provides a steel for hot working having a composition consisting of in weight % (wt.%):
  • the steel is in an annealed condition, has a hardness of not more than 360 HB and a microstructure comprising:
  • the steel should fulfil at least one of the following requirements c 0.30-0.38
  • the steel should fulfil at least one of the following requirements
  • the steel should fulfil at least one of the following requirements
  • the steel should fulfil at least one of the following requirements
  • the steel should fulfil the following requirements:
  • the packets of the tempered martensite and/or bainite should have a maximum size of 40 ⁇ , preferably 20 ⁇ , more preferably 15 ⁇ .
  • the hard phase comprises Me , M7C3, M23C6 and MC, wherein M is one or more metals of Cr, Mo, V and Nb and wherein the hard phase, apart from C, may comprise N and B.
  • the amount of hard phase is 3-8 vol. % and/or the maximum size of the hard phase ⁇ 5 3 ⁇ .
  • the steel in the annealed condition has a hardness of not more than 300 HB, preferably not more than 250 HB.
  • a preferred hardness range is 180-250 HB, preferably 190-230 HB.
  • the steel fulfils the machinability value V1000 (HSS) > 35 m/min.
  • a method of producing a steel comprising the steps of:
  • the method of producing a steel fulfils at least one of the following requirements: the temperature in step c) is 980-1030 °C, the reheating temperature in step e) is A c i-50 °C to Aci-10 °C and the holding time is 4-8 hours.
  • the method of producing a steel may further comprise the step of:
  • a tool steel having the claimed chemical composition can be produced by conventional metallurgy including melting in an Electric Arc Furnace (EAF) and further refining in a ladle and vacuum treatment.
  • ESR Electro Slag Remelting
  • the steel is subjected to hardening and tempering before being used e.g. in a mould for die casting.
  • Austenitizing may then be performed at an austenitizing temperature (TA) in the range of 1000-1070 °C, preferably about 1000-1030 °C.
  • TA austenitizing temperature
  • a typical T A is 1025 °C with a holding time of 30 minutes followed by rapid quenching.
  • the tempering temperature is chosen according to the hardness requirement and is performed at least twice at 550 - 650 °C for 2 hours (2x2h) followed by cooling in air. This results in a hardness of 44 - 54 HRC.
  • HBW10/3000 i.e. a 10 mm diameter tungsten carbide ball indenter and a load of 3000 kgf. Accordingly, in this application HB is the same as HBW10/3000.
  • the inventors of the present invention has surprisingly found that if the conventional soft annealing is replaced by an alternate high temperature annealing slightly below the Aci temperature it is possible to improve the machinability of the steel by providing the steel with a completely different microstructure.
  • packets of tempered martensite and/or bainite refers to a structure of carbon depleted packets of tempered martensite and/or bainite with carbides distributed in the grain- and sub-grain boundaries as well as to a packet structure of ferrite having most of the carbides distributed in the grain- and sub-grain boundaries.
  • a steel was produced by EAF-melting, ladle refining, and vacuum degassing followed by uphill casting.
  • the ingots were subjected to forging to the dimension 799x379 mm. Test pieces of were taken for examination.
  • the steel had the following composition in weight % (wt.%): C: 0.35, Si: 0.18, Mn: 0.45, Cr: 5.0, Mo 2.3, V: 0.6 and Al:0.01.
  • the Aci for this composition is 820 °C.
  • the steel sample according to the invention was subjected to annealing at 800 °C, which is slightly below the Aci temperature. This resulted in a hardness value of 213 HB.
  • the hardness of the sample subjected to conventional soft annealing above the Aci temperature was 164 HB. The results are shown in Table 1.
  • Fig. 1 discloses the microstructure of the inventive steel, Light Optical Microscope (LOM).
  • Fig. 2 discloses the microstructure of the comparative steel, which was subjected to conventional soft annealing (LOM). The length of the bar in the lower right corner in Figures 1 and 2 is 20 ⁇ . It can be seen that the inventive steel has a much finer and more homogeneous structure as well as a finer and more uniform carbide distribution than the soft annealed steel. These differences can be more clearly recognized in the pictures taken in the Scanning Electron Microscope (SEM).
  • Fig. 3 discloses a SEM picture of the inventive steel consisting of packets of carbon depleted tempered martensite and carbides mainly distributed in the grain- and sub- grain boundaries.
  • Fig. 4 discloses the structure of the comparative steel having coarse carbides uniformly distributed in a matrix of polygonal ferrite.
  • Machinability was examined by drilling, since this is one of the toughest operations in tool body manufacture.
  • the tests were carried out on a MODIG 7000 machining center.
  • the steels were subjected to V1000 drilling test. This test gives the cutting speed for a cutting length of 1000 mm.
  • the drills used were HSS Wedevag Double-X 05 mm.
  • Table 2 discloses the result according to the invention and Table 3 for the comparative steel.
  • the results of the drilling tests were used to derive the VIOOO-values for the steels examined.
  • the inventive steel had a V1000 value of 40 m/min and the comparative steel a V1000 value of 30 m/min. Accordingly, the inventive steel revealed a remarkable improved machinability in this test.
  • a result of this microstructure is that the hardness of the annealed material increases from about 160 HB to e.g. about 210 HB.
  • it has surprisingly been found that the new structure give rise to a very much improved machinability.
  • the tool steel of the present invention is particular useful in large dies requiring a good hardenability and a good machinability in the unhardened condition.

Abstract

L'invention concerne un acier à outils pour travail à chaud. L'acier comprend les constituants principaux suivants (en % en poids) : C 0,27 à 0,40, Si 0,10 à 0,35, Mn 0,2 à 1,0, Cr 4,0 à 6,0, Mo 1,0 à 3, V 0,4 à 0,9, le reste étant constitué d'éléments facultatifs, de fer et d'impuretés, l'acier, à l'état recuit, présentant une microstructure comprenant : a) au moins 75 % en volume de paquets de martensite et/ou de bainite revenue, et b) 1 à 20 % en volume d'une phase dure comprenant des carbures, des nitrures et des carbonitrures.
PCT/SE2018/050213 2017-03-29 2018-03-07 Acier à outils pour travail à chaud WO2018182480A1 (fr)

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SE1750368-1 2017-03-29
SE1750368 2017-03-29

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CN110157984A (zh) * 2019-05-29 2019-08-23 唐山志威科技有限公司 一种高均匀性高抛光型塑料模具钢zw636及其制备方法
WO2020070917A1 (fr) * 2018-10-05 2020-04-09 日立金属株式会社 Acier pour outil de travail à chaud et outil de travail à chaud
CN113604730A (zh) * 2021-07-05 2021-11-05 昆山东大特钢制品有限公司 一种耐高温和高韧性的热作模具钢及其生产工艺
CN113699446A (zh) * 2021-08-20 2021-11-26 天津钢研海德科技有限公司 一种超细化型高韧性模具钢及其制备方法
US11319621B2 (en) * 2018-04-02 2022-05-03 Daido Steel Co., Ltd. Steel for mold, and mold
CN114990423A (zh) * 2021-11-22 2022-09-02 上海双舜科技发展有限公司 一种强韧性热作模具钢的生产方法
CN115896594A (zh) * 2022-11-09 2023-04-04 成都先进金属材料产业技术研究院股份有限公司 一种铝挤压用高强韧性h13模具钢及其制备方法
CN115896634A (zh) * 2022-12-19 2023-04-04 湖北志联模具科技有限公司 一种耐高温有色金属压铸成型模具钢材料及其制备方法
JP7305483B2 (ja) 2019-08-19 2023-07-10 山陽特殊製鋼株式会社 靱性に優れた熱間工具鋼

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CN109371329B (zh) * 2018-12-24 2021-02-02 黄石华中模具材料研究所 一种耐高温人工水晶成型模具钢材料及其制备方法
WO2022153790A1 (fr) * 2021-01-13 2022-07-21 日鉄ステンレス株式会社 Matériau en acier inoxydable à base de martensite et son procédé de production

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JP2014177710A (ja) * 2008-12-25 2014-09-25 Hitachi Metals Ltd 鋼の焼入方法

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