US20030136482A1 - Inert material with increased hardness for thermally stressed parts - Google Patents

Inert material with increased hardness for thermally stressed parts Download PDF

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Publication number
US20030136482A1
US20030136482A1 US10/347,866 US34786603A US2003136482A1 US 20030136482 A1 US20030136482 A1 US 20030136482A1 US 34786603 A US34786603 A US 34786603A US 2003136482 A1 US2003136482 A1 US 2003136482A1
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hardness
alloy
weight
minus
elements
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US10/347,866
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Inventor
Gottfried Mayerbock
Johann Sammer
Gabriele Saller
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Voestalpine Boehler Edelstahl GmbH and Co KG
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Boehler Edelstahl GmbH and Co KG
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Assigned to BOHLER EDELSTAHL GMBH & CO KG reassignment BOHLER EDELSTAHL GMBH & CO KG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SALLER, GABRIELE, MAYERBOCK, GOTTFRIED, SAMMER, JOHANN
Publication of US20030136482A1 publication Critical patent/US20030136482A1/en
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of 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
    • C22C38/18—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
    • C22C38/50—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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • 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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • 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
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment

Definitions

  • the present invention relates to a material with high inertness, in particular high oxidation stability, and increased hardness for the manufacture of thermally resistant parts and tools.
  • a surface attack of objects is most often caused by an electrochemical corrosion in the presence of an ion conducting phase or by chemical corrosion and hot corrosion at elevated temperatures.
  • a corrosion attack can also occur in molten media at elevated temperature, e.g., in liquid glasses, with a change in the surface of a metal part in contact therewith.
  • Corrosion- and heat-resistant steels and alloys should have a cubic face-centered atomic lattice structure or an austenitic microstructure, respectively, also for a thermal resistance at temperatures above 600° C. In terms of alloy technology, this means that for increased strength and hardness at high temperatures, such materials have higher nickel and/or cobalt contents or are formed as nickel-based or cobalt-based alloys. However, for reasons of chemical corrosion they must have a chromium content of higher than 13% by weight.
  • a material with a high nickel concentration invariably shows an increased mechanical strength and high material hardness, respectively, which improves the performance characteristics of parts and tool parts at high temperature, for economical reasons there is a desire to reduce the nickel content to below 36% by weight and to increase the chromium content of the alloy to above 16% by weight in order to increase corrosion resistance.
  • an austenitic iron-based material having a nickel content of less than 36% by weight can withstand, if necessary, in combination with further elements inhibiting corrosion, a corrosion attack at high temperatures, e.g., at 600° C. and above, for a required minimum period, the material exhibits a low hardness and strength and a limited behavior under long period stressing.
  • alloys e.g., according to DIN material Nos. 1.2780 and 1.2782 and 1.2786, are used as tools for glass processing for reasons of cost effectiveness and for manufacturing reasons.
  • the present invention provides a material for the manufacture of parts and tools for use at elevated temperature.
  • the material comprises an alloy having a composition of, in % by weight: Carbon (C) 0.01 to 0.25 Silicon (Si) 0.35 to 2.5 Manganese (Mn) 0.4 to 4.3 Chromium (Cr) 16.0 to 28.0 Nickel (Ni) 15.0 to 36.0 Nitrogen (N) 0.01 to 0.29
  • the nickel content of the alloy is equal to or higher than the value formed by the chromium content plus 1.5 silicon minus 0.12 manganese minus 18 nitrogen minus 30 carbon minus the numerical value of 6:
  • the balance of the alloy is iron (Fe) and accompanying elements and impurities.
  • the material shows a hardness, provided by cold forming, of at least 230 HB.
  • the hardness of the material is higher than 250 HB, e.g., at least 300 HB.
  • the nickel content of the alloy is higher by not more than 4.8% than the value obtained according to the above equation.
  • the alloy comprises one or more (e.g., all) of the above elements in the following concentrations, in % by weight: C 0.02 to 0.20; Si 0.50 to 2.48; Mn 0.62 to 4.05; Cr 20.1 to 27.6; Ni 16.1 to 27.3; and N 0.014 to 0.23.
  • the alloy comprises one or more (e.g., all) of the above elements in the following concentrations, in % by weight: C 0.04 to 0.15; Si 1.22 to 2.36; Mn 1.00 to 3.95; Cr 23.9 to 26.5; Ni 17.9 to 25.45; and N 0.018 to 0.20.
  • the alloy comprises one or more (e.g., all) accompanying elements in the following concentrations, in % by weight: Molybdenum (Mo) less than 1.0; Vanadium (V) up to 0.5; Tungsten (W) up to 0.5; Copper (Cu) up to 0.5; Cobalt (Co) up to 6.5; Titanium (Ti) up to 0.5; Aluminum (Al) up to 1.5; Niobium (Nb) up to 0.5; Oxygen (O) up to 0.05; Phosphorus (P) up to 0.03; and Sulfur (S) up to 0.03.
  • Molybdenum (Mo) less than 1.0 Molybdenum (Mo) less than 1.0
  • Tungsten (W) up to 0.5 Copper
  • Cu up to 0.5
  • Cobalt (Co) up to 6.5 Titanium
  • Ti up to 0.5
  • the present invention also provides a process for producing a material for parts and tools for use at a temperature of up to 750° C.
  • the process comprises the provision of an initial product from an alloy having a composition of, in % by weight, as indicated above and the subsequent cold forming of the initial product to a hardness of at least 230 HB.
  • the initial product is formed by a process comprising hot forming and, subsequently, subjecting it to solution annealing or cooling down from the forming temperature, e.g., by forced cooling.
  • the cold forming is carried out over the whole circumference, and radially perpendicular to the longitudinal axis of the initial product.
  • the degree of cold forming is such that the hardness of the material is higher than 250 HB, e.g., at least 300 HB.
  • the degree of cold forming is at least 6%, for example, at least 12%.
  • a hot working tool which comprises a cold formed material of an alloy having a composition of, in % by weight, as indicated above.
  • the cold formed material has a hardness of at least 230 HB, e.g., higher than 250 HB.
  • the hot working tool of can be used at a working temperature of higher than 555° C., e.g., at a working temperature of higher than 602° C.
  • the working temperature may be up to 750° C.
  • the present invention additionally comprises a mold for machine pressed glass.
  • the mold is made, at least in part, from the cold formed material as indicated above.
  • a tool in the glass industry which comprises this material, as well as a process for the manufacture of a part or tool for use at elevated temperature. The process comprises providing the above cold formed material and making it into said part or tool.
  • the advantages obtained according to the invention lie, in particular, in the synergy of corrosion chemical resistance of the selected alloy and the properties of the material that can be achieved with this chemical composition by means of cold forming.
  • the cold forming or forming below the recrystallization temperature of the cubic face-centered austenite results in a strengthening of the material by a blocking of dislocations in the crystal lattice.
  • An increase in hardness and an increase in the strength of the material according to the invention associated therewith is retained even at use temperatures of above 600° C., which is surprising to those of skill in the art.
  • C 0.02 to 0.20, preferably 0.04 to 0.15
  • Si 0.50 to 2.48, preferably 1.22 to 2.36
  • Mn 0.62 to 4.05, preferably 1.00 to 3.95
  • Ni 16.1 to 27.3, preferably 17.9 to 25.45
  • N 0.014 to 0.23, preferably 0.018 to 0.20.
  • the alloy according to the invention should show concentrations, in % by weight, of Molybdenum (Mo) less than 1.0 Vanadium (V) up to 0.5 Tungsten (W) up to 0.5 Copper (Cu) up to 0.5 Cobalt (Co) up to 6.5 Titanium (Ti) up to 0.5 Aluminum (Al) up to 1.5 Niobium (Ni) up to 0.5 Oxygen (O) a max. of 0.05 Phosphorus (P) a max. of 0.03 Sulfur (S) a max. of 0.03.
  • an initial product is made from an alloy with a composition, in % by weight, of essentially Carbon (C) 0.01 to 0.25 Silicon (Si) 0.35 to 2.5 Manganese (Mn) 0.4 to 4.3 Chromium (Cr) 16.0 to 28.0 Nickel (Ni) 15.0 to 36.0 Nitrogen (N) 0.01 to 0.29
  • the nickel content of the alloy is equal to or higher, optionally by a maximum of 4.8% by weight, than the value formed by the chromium content plus 1.5 silicon minus 0.12 manganese minus 18 nitrogen minus 30 carbon minus the numerical value of 6:
  • the balance being iron (Fe) and accompanying elements and impurities.
  • This initial product is subsequently further processed by cold forming to produce a material with a hardness of higher than 230 HB.
  • the elasticity limit of the material can be increased to a tension level that is not reached even close to the working surface of the part or tool through a change in volume caused by alternating thermal stress. Accordingly, even in the area of the grain boundaries no zones occur that are plastically deformed during the temperature change, whereby a crack formation due to fatigue can be avoided. An attack at grain boundaries by chemical or hot corrosion can thus be largely avoided, so that, such as, e.g., with a glass mold, a high working surface or surface quality is retained over a long period even under high stress and with large production quantities.
  • the corrosion resistance and hot strength can be further increased and a fatigue crack formation can effectively be suppressed if in the process according to the invention, a material having a hardness of higher than 250 HB, in particular 300 HB and higher, is formed by cold forming.
  • an initial product with a composition according to the invention is formed by means of hot forming, is subjected to a solution annealing or cooled down, optionally in a forced manner, from the forming temperature, and cold formed, a material with a particularly homogeneous microstructure and improved corrosion resistance can be produced.
  • the alloy of the invention advantageously contains one or more alloying elements in the following concentrations in % by weight
  • C 0.02 to 0.20, preferably 0.04 to 0.15
  • Si 0.05 to 2.48, preferably 1.22 to 2.36
  • Mn 0.62 to 4.05, preferably 1.00 to 3.95
  • Ni 16.1 to 27.3, preferably 17.9 to 25.45
  • N 0.014 to 0.23, preferably 0.018 to 0.2.
  • the concentrations of the individual alloying elements, in % by weight, in the iron-based alloy may be as follows: Carbon (C) up to 0.25 Silicon (Si) up to 2.5 Manganese (Mn) up to 4.3 Chromium (Cr) 16.0 to 28.0 Nickel (Ni) 15.0 to 36.0 Nitrogen (N) 0.01 to 0.29
  • the nickel content of the alloy is equal to or higher, optionally by a maximum of 4.8% by weight, than the value formed by the chromium content plus 1.5 silicon minus 0.12 manganese minus 18 nitrogen minus 30 carbon minus the numerical value of 6:
  • the balance being iron (Fe) and accompanying elements and impurities.
  • the alloy is strengthened to a material hardness of at least 230 HB, preferably higher than 250 HB, by cold forming the initial product made thereof, to result in a material for hot working tools with a working temperature of higher than 555° C., preferably higher than 602° C., in particular up to 750° C.
  • FIG. 1 shows the strength as a function of the degree of the cold forming of a material according to the invention at 604° C.
  • FIG. 2 shows the hardness curve at room temperature after a long-term thermal stress at 600° C.
  • FIG. 1 shows the strength of the material according to the invention at a test temperature of 604° C. as a function of the extent of the cold forming.
  • the test material was forged at a temperature of 1010° C. and cooled in a forced manner from the forming heat and subjected to a solution annealing at 1060° C.
  • a cold forming was carried out on parts of the material with a forming degree of 21%, 35%, 47% and 55%, respectively. Specimens for tensile tests were subsequently made from these materials.
  • the strength tests namely the determination of the 0.2% yield point and the tensile strength, were conducted at a temperature of 604° C., keeping the specimens at this temperature for 20 minutes.
  • FIG. 2 shows the fatigue strength of the material according to the invention at a temperature of 600° C., determined by a hardness test of the specimens in a cold state, compared with DIN materials Nos. 1.2083 and 1.4028.
  • This test block was hot formed to produce test material.
  • a solution annealing was carried out on the test material at 1060° C. with a subsequent quenching in water.
  • specimens with the designation H 5 unformed
  • specimens with the designation H 525 with a degree of cold forming of 35%) were subjected to a long-term annealing at 600° C.
  • the comparison materials Nos. 1.2083 and 1.4028 were hardened in oil from 1020° C., tempered at 630° C. and likewise subjected to the long-term annealing.
  • the test material was removed from the oven, allowed to cool, and the hardness of the material was determined. Thereafter, the samples were reinserted (with a temperature cycle stress).
  • the comparison material H 5 showed an expected hardness behavior, whereas the material H 525 according to the invention, cold-formed at 35%, exhibited an increased hardness of 315 HB and a high fatigue strength. At 600° C., no reduction of hardness and no creeping of the material could be detected even under alternating thermal stress. In contrast, a clear decrease in hardness was detected in the martensitic standard steels as a function of the annealing time of the samples.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Articles (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Powder Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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US10/347,866 2002-01-23 2003-01-22 Inert material with increased hardness for thermally stressed parts Abandoned US20030136482A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT107/2002 2002-01-23
AT0010702A AT410550B (de) 2002-01-23 2002-01-23 Reaktionsträger werkstoff mit erhöhter härte für thermisch beanspruchte bauteile

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US (1) US20030136482A1 (da)
EP (1) EP1420077B1 (da)
KR (1) KR100540851B1 (da)
CN (1) CN1434146A (da)
AT (1) AT410550B (da)
BR (1) BR0300116A (da)
CA (1) CA2416950C (da)
DE (1) DE50208351D1 (da)
DK (1) DK1420077T3 (da)
ES (1) ES2273992T3 (da)
RU (1) RU2246553C2 (da)
TW (1) TWI225102B (da)

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US20090053100A1 (en) * 2005-12-07 2009-02-26 Pankiw Roman I Cast heat-resistant austenitic steel with improved temperature creep properties and balanced alloying element additions and methodology for development of the same
US11884997B2 (en) 2009-07-22 2024-01-30 Arcelormittal Hot rolled plate or forging of an austenitic steel
US12465991B2 (en) 2018-07-02 2025-11-11 Höganäs Ab (Publ) Wear-resistant iron-based alloy compositions comprising nickel

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EP1605072B1 (en) * 2003-03-20 2012-09-12 Sumitomo Metal Industries, Ltd. Stainless steel for high pressure hydrogen gas, vessel and equipment comprising the steel
JP4329883B1 (ja) * 2008-02-27 2009-09-09 住友金属工業株式会社 耐浸炭性金属材料
UA100460C2 (uk) * 2008-11-19 2012-12-25 Сандвік Інтеллекчуал Проперті Аб Сплав на основі нікелю, здатний утворювати оксид алюмінію
RU2415962C2 (ru) * 2009-01-11 2011-04-10 Федеральное государственное унитарное предприятие "Государственный космический научно-производственный центр имени М.В. Хруничева" (ФГУП "ГКНПЦ им. М.В. Хруничева") Аустенитная дисперсионно-твердеющая высокопрочная сталь, стойкая к сероводородному растрескиванию под напряжением
ES2418135T3 (es) 2009-02-17 2013-08-12 Mec Holding Gmbh Aleación resistente al desgaste
CN101921967A (zh) * 2010-08-12 2010-12-22 江苏新华合金电器有限公司 一种新型奥氏体耐热不锈钢
CN102650023A (zh) * 2011-02-23 2012-08-29 宝山钢铁股份有限公司 一种油套管用含铜铁镍铬合金
US9347121B2 (en) * 2011-12-20 2016-05-24 Ati Properties, Inc. High strength, corrosion resistant austenitic alloys
CN110520551B (zh) * 2017-03-03 2022-01-07 博格华纳公司 具有增强的高温抗氧化性的镍和铬基铁合金
CN110724873A (zh) * 2018-07-17 2020-01-24 宝钢特钢有限公司 一种高耐磨模锻模具钢及其制造方法
RU2703318C1 (ru) * 2019-04-15 2019-10-16 Акционерное Общество "Российский Концерн По Производству Электрической И Тепловой Энергии На Атомных Станциях" (Ао "Концерн Росэнергоатом") Радиационно-стойкая аустенитная сталь для внутрикорпусной выгородки ввэр
AT17259U1 (de) * 2020-11-13 2021-10-15 Plansee Se Hochtemperatur-umformwerkzeug

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CA2416950C (en) 2007-08-28
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EP1420077A1 (de) 2004-05-19
CA2416950A1 (en) 2003-07-23
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