EP1900838A1 - Stahl für eine mechanische struktur mit hervorragender festigkeit, biegbarkeit und härte sowie herstellungsverfahren dafür - Google Patents

Stahl für eine mechanische struktur mit hervorragender festigkeit, biegbarkeit und härte sowie herstellungsverfahren dafür Download PDF

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Publication number
EP1900838A1
EP1900838A1 EP06780846A EP06780846A EP1900838A1 EP 1900838 A1 EP1900838 A1 EP 1900838A1 EP 06780846 A EP06780846 A EP 06780846A EP 06780846 A EP06780846 A EP 06780846A EP 1900838 A1 EP1900838 A1 EP 1900838A1
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steel
ductility
mass
percent
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English (en)
French (fr)
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EP1900838A4 (de
Inventor
Keiichi JFE Steel Corporation MARUTA
Tohru JFE Steel Corporation HAYASHI
Nobutaka JFE Steel Corporation KUROSAWA
Hideto JFE Steel Corporation KIMURA
Takaaki JFE Steel Corporation TOYOOKA
Kazukuni JFE Steel Corporation HASE
Katsumi JFE Steel Corporation YAMADA
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JFE Steel Corp
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JFE Steel Corp
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Publication of EP1900838A4 publication Critical patent/EP1900838A4/de
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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
    • C21D9/46—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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • 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
    • C22C38/02—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
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite

Definitions

  • the present invention relates generally to steels for machine structural use, including components of automobiles and industrial machines.
  • the present invention relates to steels for machine structural use which have excellent strength, ductility, and toughness and are particularly suitable for metal belts, for example, used in continuously variable transmission (hereinafter abbreviated as CVT), which are currently produced with expensive steels such as maraging steel.
  • CVT continuously variable transmission
  • the present invention also relates to steel sheets for machine structural use and metal belts produced with such steels.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2000-345302
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. 2002-38251
  • Patent Document 3 Japanese Unexamined Patent Application Publication No. 2003-231921
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2002-53936
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2003-33803
  • an object of the present invention is to provide a steel and steel sheet for machine structural use which have high strength, high ductility, and high toughness with a minimal increase in production costs, and also provide a metal belt suitable as an endless metal belt for CVT at low cost.
  • the inventors have found a solution to the above problems. That is, the inventors have demonstrated that even a steel system that does not contain such a large amount of nickel or chromium as contained in maraging steel and austenitic stainless steel provides a better balance between tensile strength and elongation and higher toughness than maraging steel if the steel contains appropriate amounts of molybdenum and boron and is quenched and tempered to form a martensitic structure.
  • substructures Further studies on detailed structures constituting the martensitic structure (hereinafter referred to as substructures) have found that an especially excellent strength-elongation balance can be achieved by controlling blocks constituting the martensitic structure to a predetermined size or less. These studies have also found that excellent toughness can be ensure if dissolved boron is contained in at least a predetermined amount and is present at boundaries of prior austenite grains in a concentration at least 1.5 times that in the prior austenite grains.
  • the present invention can provide a steel for machine structural use which has excellent strength, ductility, and toughness without containing large quantities of expensive alloying elements, a metal sheet for machine structural use produced with the steel, and a metal belt produced with the metal sheet.
  • the steel can optionally contain the following elements:
  • the steel according to the present invention can further contain at least one of the following components:
  • incidental impurities include sulfur, phosphorus, nitrogen, and oxygen, which can be contained in amounts of up to 0.05%, up to 0.05%, up to 0.01%, and up to 0.01%, respectively.
  • dissolved boron is contained in the steel in an amount of at least 0.0005% and is present at boundaries of prior austenite grains in a concentration at least 1.5 times that in the grains after, for example, quenching
  • the steel according to the present invention provides stable mechanical properties if the distribution of dissolved boron is controlled as described below.
  • the content of boron is specified for obtaining improved quenching properties and grain boundary strengthening.
  • a sufficient amount of dissolved boron and the distribution thereof is very important to realize the effect of boron.
  • the amount of boron dissolved in the steel is decreased with, for example, formation of BN and M 23 (C,B) 6 (where M is a metal element). Addition of an element that combines readily with nitrogen, such as titanium, is effective to inhibit the formation of BN. In a carbon-rich steel system, however, the added element is dissolved in carbides by substitution and thus fails to provide the expected effect.
  • the dissolved boron is preferably present mainly at boundaries of prior austenite grains. Grain boundary strength, which significantly affects mechanical properties including strength, elongation, and toughness, is increased if the dissolved boron is present mainly at boundaries of prior austenite grains with a difference in concentration from the interior of the grains (i.e., grain boundary segregation). The grain boundary segregation of the dissolved boron will prevent grain boundary segregation of phosphorus, which could cause grain boundary embrittlement.
  • the studies by the inventors have confirmed that the steel can more reliably achieve stable toughness if the dissolved boron is contained in an amount of at least 0.0005% after final heat treatment, such as high-frequency heating quenching or low-temperature tempering at 400°C or less, and is present at boundaries of prior austenite grains in a concentration 1.5 times that in the prior austenite grains after the final heat treatment.
  • the amount of dissolved boron can be determined by subtracting the amount of precipitated boron from the amount of boron added.
  • the amount of precipitated boron is determined by extracting and separating boron-containing precipitates occurring as oxides, nitrides, carbides, or intermetallic compounds through electrolysis, for example, and directly measuring the content of boron in the precipitates.
  • the concentration distribution of dissolved boron in and at boundaries of prior austenite grains can be determined by, for example, secondary ion mass spectrometry (SIMS) to confirm that the ionic strength of the boundaries of the prior austenite grains is at least 1.5 times that of the interior of the grains if the grains have a grain size of 10 ⁇ m or more.
  • SIMS secondary ion mass spectrometry
  • EELS electron energy loss spectrum
  • ATE ⁇ -ray track etching
  • SIMS is the most suitable in terms of detection sensitivity and quantitative determination for a trace amount of boron.
  • grain boundary embrittlement can be avoided if the dissolved boron is contained in an amount of at least 0.0005% and is present mainly at boundaries of prior austenite grains.
  • the strength and total elongation of the steel according to the present invention are limited to the above ranges because the steel requires at least such strength and ductility levels to achieve properties comparable to those of maraging steel, a currently expensive steel intended to be replaced with the steel according to the present invention. If the steel has the composition and structure described above, it can achieve a tensile strength of 2,000 MPa or more, a total elongation of 10% or more, and high toughness. The studies by the inventors have also demonstrated that a metal belt for CVT produced with a steel having the above composition, a tensile strength of 2,000 MPa or more, and a total elongation of 10% or more has durability comparable to that of a metal belt produced with a conventional maraging steel.
  • the steel is produced by quenching and tempering a steel material having the above composition.
  • the rate of temperature rise in quenching and tempering temperature which are important in the present invention, must be controlled as follows:
  • the rate of temperature rise in heating for quenching falls below 100°C/s, the blocks of martensitic structure grow to a size exceeding 1.5 ⁇ m. In this case, the steel cannot have a good strength-ductility balance. Hence, the rate of temperature rise in heating for quenching must be 100°C/s or more.
  • Tempering temperature 100°C to 400°C
  • the tempering temperature falls within the range of 100°C to 400°C, the boron contained in the steel is concentrated at the grain boundaries without diffusion or precipitation, thus contributing to grain boundary strengthening. If the tempering temperature is 400°C or less, the steel maintains its high strength, high ductility, and high toughness in synergy with a fine grain effect. Excessive tempering temperatures result in decreased strength and decreased concentration of boron at the grain boundaries, thus significantly decreasing toughness. From this viewpoint, the tempering temperature must be 400°C or less. If the tempering temperature is less than 100°C, the steel exhibits insufficient elongation and fails to provide a total elongation of 10% or more. Accordingly, the tempering temperature should fall within the range of 100°C to 400°C.
  • the steel material used can be one prepared by subjecting a steel ingot with the above composition to hot or cold working, such as rolling or forging.
  • the steel ingot with the above composition can be one produced by converter melting or vacuum melting.
  • the steel material used is a steel sheet
  • a steel ingot or a continuously cast slab is subjected to hot rolling with heating, scale removal by pickling, and cold rolling to produce a steel sheet with a predetermined thickness.
  • a metal belt is to be produced with the steel sheet, the sheet is cold-rolled to a thickness of 0.5 mm or less, is cut into a predetermined width and length, and is formed into an annular shape to produce a metal belt.
  • the above steel material (including a steel sheet and a metal belt) is subjected to quenching and tempering to form a martensitic structure.
  • the heating means used for these treatments can be high-frequency heating, furnace heating, infrared heating, or electrical heating.
  • the steel thus produced (including a steel sheet and a metal belt) has a strength-ductility balance comparable to that of maraging steel despite low production costs and can be used for automobile parts requiring high strength, high ductility, and high toughness.
  • a metal belt produced with the steel is suitable for use as an endless metal belt for CVT, which is currently produced with maraging steel.
  • the structures of the steels, which are to be subjected to high-frequency heating quenching, after the final heat treatment are expected to contain only a martensitic phase formed by transformation from the austenite temperature range, an untransformed ferrite phase that can result from insufficient heating, and undissolved inclusions and precipitates such as carbides.
  • These phases can be discriminated by developing the structures by nital etching, one of the generally used methods, and observing them using an optical microscope. Accordingly, the volume percentage of martensitic structure was determined by the method described below. The above materials were cut to a size of 20 mm x 20 mm, were heated to 920°C by high-frequency heating, were quickly quenched, and were tempered at 170°C for 20 minutes to prepare samples.
  • the surfaces of the samples were etched with nital and were observed using an optical microscope to determine the area percentage of the region of phases other than martensitic phase which were discriminated by optical microscopy (i.e., untransformed ferrite phase and undissolved inclusions and precipitates such as carbides).
  • the volume percentage of martensitic phase in the examples was determined by converting the area percentage of the region of the phases other than the martensitic phase to volume percentage and subtracting it from 100%.
  • the martensitic phase accounted for most of the structure because the temperature for high-frequency quenching was 920°C, which falls within the austenite range.
  • Blocks one of the substructures of martensitic structure, were evaluated by the method described below.
  • the above materials were cut into samples with a size of 20 mm x 20 mm. These samples were heated to 920°C by high-frequency heating, were quickly quenched, and were tempered at 170°C for 20 minutes. Subsequently, the samples were cut into samples for microscopy with a size of 10 mm x 10 mm. These samples were evaluated for blocks by orientation imaging microscopy.
  • Crystal orientation information was obtained at a total of about 11,000 points in two fields of view of 10 ⁇ m x 10 ⁇ m regions on each sample. In each field of view, the boundaries of closed regions of the same colors were recognized as blocks. The size of the blocks in the field of view was determined by the same intercept method as generally used for determination of average grain size. The simple arithmetic average of all measurements of the fields of view was determined as the average size of the blocks of the material.
  • the content of dissolved boron in each steel was determined by subtracting the amount of precipitated boron from the amount of boron added.
  • the amount of precipitated boron was determined by electrolytic extraction analysis. First, the above materials were cut into samples with a size of 30 mm x 30 mm. These samples were heated to 920°C by high-frequency heating, were quickly quenched, and were tempered at 170°C for 20 minutes. Subsequently, 1 g of each tempered sample was electrolyzed in a 10% acetylacetone electrolytic solution, and electrolysis residues were filtered out to determine the amount of precipitated boron.
  • the concentration distribution of dissolved boron in each sample was measured by the method described below.
  • the samples with a size of 10 mm x 10 mm used in the evaluation of block size were mirror-polished again for concentration distribution measurement by SIMS.
  • the primary ions O 2 + were used to obtain two fields of view of ion images of the secondary ions BO 2 - with a mass number of 43 from regions with a field stop of 150 ⁇ m (in diameter).
  • Average secondary ion strengths at boundaries of grains and in the interior of the grains in each field of view were determined, and the ratio therebetween was determined. Finally, the arithmetic average of the ion strength ratios of the two fields of view was determined as the concentration distribution ratio of the sample.
  • Boundaries of prior austenite grains were inspected as follows.
  • the samples with a size of 10 mm x 10 mm used in the measurement of concentration distribution of dissolved boron were used as samples for microscopy.
  • L-shaped cross sections, parallel to the rolling direction, of the samples used in the measurement of concentration distribution of dissolved boron were mirror-polished and were exposed to an etchant to develop boundaries of prior austenite grains.
  • the etchant was prepared by dissolving 50 g of picric acid in 500 g of water and adding 11 g of sodium dodecylbenzenesulfonate, 1 g of ferrous chloride, and 1.5 g of oxalic acid to the picric acid aqueous solution.
  • the boundaries of prior austenite grains were inspected using an optical microscope at a magnification of x1,000.
  • the materials were cut into tensile test pieces (JIS No. 5) by electrical discharge machining.
  • the test pieces were heated to 920°C by high-frequency heating, were quickly quenched, and were tempered at 170°C for 20 minutes.
  • the test pieces were subjected to a tensile test.
  • a maraging steel (Fe-18Ni-10Co-5Mo-0.4Ti) was processed until cold rolling and was cut into a test piece with the same shape as above.
  • the test piece was heated to 820°C, was quenched by air cooling, and was subjected to aging by heating being to 520°C.
  • the steels were hot-rolled to a thickness of 15 mm and were cut into charpy test pieces with U-notches extending in the C direction of the rolled sheets.
  • the test pieces were heated to 920°C by high-frequency heating, were quickly quenched, and were tempered at 170°C for 30 minutes.
  • the test pieces were subjected to a charpy test, which was conducted under two different conditions, namely, test temperatures of -40°C and 40°C, and the measured absorption energies were compared.
  • Table 1 shows measurements of the volume percentage of martensitic structure, tensile strength, total elongation, and toughness. According to Table 1, the steels within the scope of the present invention had a better strength-ductility balance than the maraging steel and also had high toughness.
  • Example 1 The effect of the rate of temperature rise in heating for quenching was examined.
  • a steel having the same composition as Steel No. 1-4 of Example 1 was subjected to furnace heating rather than high-frequency heating and was tempered under the same conditions as used in Example 1. This steel was examined for structure and properties.
  • Table 4 shows a comparison of the rates of temperature rise, structures, and properties of the steel subjected to furnace heating (Steel No. 4-1) with the steel subjected to high-frequency heating (Steel No. 1-4 in Table 1).
  • Table 5 shows that the tempering temperature exceeding 400°C resulted in a decreased concentration of boron at grain boundaries and significantly decreased toughness.
  • a steel according to the present invention has a better balance between tensile strength and elongation and higher toughness than maraging steel and can therefore be used for components that to date have been conventionally produced with maraging steel.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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EP06780846A 2005-07-05 2006-06-30 Stahl für eine mechanische struktur mit hervorragender festigkeit, biegbarkeit und härte sowie herstellungsverfahren dafür Withdrawn EP1900838A4 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005195739 2005-07-05
JP2005326844 2005-11-11
JP2006079070A JP2007154305A (ja) 2005-07-05 2006-03-22 強度、延性及び靱性に優れた機械構造用鋼およびその製造方法
PCT/JP2006/313521 WO2007004707A1 (ja) 2005-07-05 2006-06-30 強度、延性及び靭性に優れた機械構造用鋼およびその製造方法

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EP1900838A1 true EP1900838A1 (de) 2008-03-19
EP1900838A4 EP1900838A4 (de) 2009-03-25

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US (1) US20080017283A1 (de)
EP (1) EP1900838A4 (de)
JP (1) JP2007154305A (de)
KR (1) KR100945313B1 (de)
TW (1) TWI321590B (de)
WO (1) WO2007004707A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8163108B2 (en) 2008-03-27 2012-04-24 Nippon Steel Corporation High-strength cold-rolled steel sheet, high-strength galvanized steel sheet, and high-strength alloyed hot-dip galvanized steel sheet having excellent formability and weldability, and methods for manufacturing the same
JP2016196697A (ja) * 2015-04-06 2016-11-24 トヨタ自動車株式会社 金属リング及びその製造方法
EP3081661A4 (de) * 2013-12-12 2017-06-21 Aichi Steel Corporation Ringelement für stufenloses getriebe und verfahren zur herstellung davon

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EP1956108A4 (de) * 2005-10-31 2015-03-11 Jfe Steel Corp Hochfester stahl mit hervorragender beständigkeit gegen verzögerte fraktur und metallbolzen
KR101129370B1 (ko) * 2007-10-24 2012-03-26 신닛뽄세이테쯔 카부시키카이샤 고온에서의 면압 피로 강도가 우수한 침탄 질화 고주파 담금질 강 부품 및 그 제조 방법
JP5425675B2 (ja) * 2010-03-18 2014-02-26 愛知製鋼株式会社 無段変速機ベルト及び無段変速機ベルト用鋼
JP5410466B2 (ja) * 2011-03-01 2014-02-05 株式会社神戸製鋼所 ステンレス鋼フラックス入りワイヤ
WO2012153009A1 (fr) * 2011-05-12 2012-11-15 Arcelormittal Investigación Y Desarrollo Sl Procede de fabrication d'acier martensitique a tres haute resistance et tole ainsi obtenue
WO2012153008A1 (fr) 2011-05-12 2012-11-15 Arcelormittal Investigación Y Desarrollo Sl Procede de fabrication d'acier martensitique a tres haute resistance et tole ou piece ainsi obtenue
CN104988391A (zh) * 2015-07-07 2015-10-21 河北钢铁股份有限公司 一种1200MPa级冷轧Q&P钢及其制造方法
CN105256246A (zh) * 2015-10-22 2016-01-20 南京钢铁股份有限公司 一种生产薄规格高强度耐大气腐蚀结构钢板的方法
CN105296885B (zh) * 2015-11-19 2017-07-18 攀钢集团攀枝花钢铁研究院有限公司 含钛高铬耐候钢及其制备方法
CN116219279B (zh) * 2022-12-23 2024-04-16 鞍钢股份有限公司 一种高强度高韧性核反应堆安全壳用钢及其制造方法

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EP1553197A1 (de) * 2002-10-18 2005-07-13 JFE Steel Corporation Stahlmaterial für mechanische konstruktionen mit hervorragender walzbarkeit, abschreckungsrissfestigkeit und torsionseigenschaft und antriebswelle
EP1669469A1 (de) * 2003-09-29 2006-06-14 JFE Steel Corporation Stahlteile für eine maschinenkonstruktion, material dafür und herstellungsverfahren dafür
EP1770181A1 (de) * 2004-07-16 2007-04-04 JFE Steel Corporation Komponente für eine maschinenstruktur, verfahren zu deren herstellung und material für hochfrequenzhärtung

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JPH1036937A (ja) * 1996-07-19 1998-02-10 Daido Steel Co Ltd 高周波焼入れ部品
US20050034795A1 (en) * 2001-08-17 2005-02-17 Takashi Motoyoshi Highly impact-resistant steel pipe and method for producing the same
EP1553197A1 (de) * 2002-10-18 2005-07-13 JFE Steel Corporation Stahlmaterial für mechanische konstruktionen mit hervorragender walzbarkeit, abschreckungsrissfestigkeit und torsionseigenschaft und antriebswelle
EP1669469A1 (de) * 2003-09-29 2006-06-14 JFE Steel Corporation Stahlteile für eine maschinenkonstruktion, material dafür und herstellungsverfahren dafür
EP1770181A1 (de) * 2004-07-16 2007-04-04 JFE Steel Corporation Komponente für eine maschinenstruktur, verfahren zu deren herstellung und material für hochfrequenzhärtung

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8163108B2 (en) 2008-03-27 2012-04-24 Nippon Steel Corporation High-strength cold-rolled steel sheet, high-strength galvanized steel sheet, and high-strength alloyed hot-dip galvanized steel sheet having excellent formability and weldability, and methods for manufacturing the same
EP3081661A4 (de) * 2013-12-12 2017-06-21 Aichi Steel Corporation Ringelement für stufenloses getriebe und verfahren zur herstellung davon
US10948046B2 (en) 2013-12-12 2021-03-16 Aichi Steel Corporation CVT ring member and method for manufacturing the same
JP2016196697A (ja) * 2015-04-06 2016-11-24 トヨタ自動車株式会社 金属リング及びその製造方法

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JP2007154305A (ja) 2007-06-21
TW200710227A (en) 2007-03-16
KR100945313B1 (ko) 2010-03-08
US20080017283A1 (en) 2008-01-24
TWI321590B (en) 2010-03-11
EP1900838A4 (de) 2009-03-25
WO2007004707A1 (ja) 2007-01-11

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