WO2017029922A1 - 高炭素冷延鋼板及びその製造方法 - Google Patents

高炭素冷延鋼板及びその製造方法 Download PDF

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WO2017029922A1
WO2017029922A1 PCT/JP2016/071133 JP2016071133W WO2017029922A1 WO 2017029922 A1 WO2017029922 A1 WO 2017029922A1 JP 2016071133 W JP2016071133 W JP 2016071133W WO 2017029922 A1 WO2017029922 A1 WO 2017029922A1
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steel sheet
mass
rolled steel
less
cold
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PCT/JP2016/071133
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English (en)
French (fr)
Japanese (ja)
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栄司 土屋
雄太 松村
佳弘 細谷
友佳 宮本
崇 小林
長滝 康伸
瀬戸 一洋
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株式会社特殊金属エクセル
Jfeスチール株式会社
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Priority to EP16836913.0A priority Critical patent/EP3216889B1/de
Priority to CN201680008133.0A priority patent/CN107208224B/zh
Priority to KR1020177014614A priority patent/KR101953495B1/ko
Publication of WO2017029922A1 publication Critical patent/WO2017029922A1/ja

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26Methods of annealing
    • C21D1/32Soft annealing, e.g. spheroidising
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226Hot rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236Cold rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0268Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment between cold rolling steps
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/004Dispersions; Precipitations
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/008Martensite

Definitions

  • the present invention relates to a high carbon cold-rolled steel sheet used as a material for various machine parts produced by quenching and tempering.
  • a solution treatment for a short time has both sufficient hardness (600 to 750HV) and excellent impact properties (toughness) after low temperature tempering treatment, and has further demands for durability and wear resistance.
  • the present invention relates to a high-carbon cold-rolled steel sheet with a thickness of less than 1.0 mm that can be applied to severe knitting needles.
  • short-time solution treatment means treatment in a temperature range of 760 to 820 ° C. for 3 to 15 minutes
  • low-temperature tempering treatment means treatment in a temperature range of 200 to 350 ° C. .
  • carbon steel materials for machine structure (SxxC) and carbon tool steel materials (SK) specified in JIS are used for various types of machine parts.
  • SxxC machine structure
  • SK carbon tool steel materials
  • hardness and toughness (impact characteristic) are provided.
  • High carbon cold-rolled steel sheets used as material for knitting needles are used for knitting needles for flat knitting machines when the thickness is 1.0 mm or more, and circular knitting machines and warp knitting machines when the thickness is less than 1.0 mm. Used for knitting needles. In knitting needles for circular knitting machines and warp knitting machines, thin yarns are knitted at high speed, so the thickness of the material used is often 0.4 to 0.7 mm. Furthermore, in addition to having excellent cold workability (hereinafter also referred to as secondary workability), the material for knitted needles is sufficiently processed after being processed into a needle shape (secondary work) and quenched and tempered. It is required to have sufficient hardness and toughness at the needle tip.
  • high carbon steel sheets such as carbon steel materials for machine structures (SxxC) and carbon tool steel materials (SK) specified in JIS are classified in detail according to the amount of C.
  • the high carbon steel plate with a C content greater than 1.1 mass% has excellent hardenability, but it contains a large amount of carbide (cementite).
  • cementite carbide
  • the cold workability is extremely inferior, and it is not suitable for knitting needle applications where precise and fine machining such as grooving is performed.
  • High carbon steel sheets with a C content greater than 1.1 mass% are limited to parts applications that require a simple shape and high hardness, such as blades and cold dies.
  • the material is subjected to quenching and tempering in order to ensure a predetermined hardness characteristic.
  • a low temperature tempering treatment in a temperature range of 200 to 350 ° C. is generally employed.
  • the above-mentioned low-temperature tempering treatment will sufficiently temper the martensite phase. In some cases, the impact characteristics (toughness) are not sufficiently improved or the toughness value varies.
  • Patent Documents 1 and 2 disclose techniques for adding a carbonitride-forming element such as Ti, Nb, V, etc., and refining the metal structure using the fine carbonitride of those elements. .
  • these elements are generally added as a measure for improving the toughness of steel having a hypoeutectoid composition with C of 0.8 mass% or less.
  • the influence (particularly the interaction) of the individual third elements on the impact properties of the martensite phase in the low-temperature tempered state at 200 to 350 ° C. has not been fully elucidated, and the effects of the individual elements are regarded as equivalent.
  • the ingredients were designed.
  • Patent Document 1 is limited to hypoeutectoid steel, and by adding carbonitride-forming elements such as V, Ti, Nb, etc., these fine carbonitrides are used in the past. This technology is expected to have the effect of refining austenite grains.
  • the technique described in Patent Document 1 is also a technique that improves the formability of the ferrite matrix because the carbon level is a hypoeutectoid composition. For this reason, it is difficult to apply this technique to mechanical parts such as knitted needles that require high hardness.
  • Patent Document 2 Mo, V, Ti, Nb, B, etc. are added to hypoeutectoid steel having a carbon content in the range of 0.67 to 0.81 mass%. This addition of Mo, V, Ti, Nb, B, etc. is clearly understood as an addition intended to improve the properties of hypoeutectoid steel.
  • Patent Document 2 there is no disclosure regarding the action of each third element in the steel having a carbon amount exceeding 0.81 mass% and its optimization.
  • Patent Document 2 regarding the addition amount of the third element, only an upper limit value that does not adversely affect the impact value is specified, and the lower limit value is not specified. Therefore, it can be said that Patent Document 2 does not disclose a technique in which the third element is added within the intended range and the impact characteristics are positively improved by the action of the added element.
  • Patent Document 1 and Patent Document 2 describe desired impact characteristics of high carbon cold rolled steel sheets by quenching with a short solution treatment holding time of 3 to 15 minutes and low temperature tempering at 200 to 350 ° C. Further, there is no disclosure of a technique that advantageously improves the predetermined hardness, and there is no disclosure of a technique that evaluates impact characteristics of a steel sheet having a thickness of less than 1.0 mm. Therefore, the present invention provides mechanical properties having an impact value of 5 J / cm 2 or more and a hardness in the range of 600 to 750 HV after quenching and low temperature tempering treatment after a short time solution treatment.
  • An object of the present invention is to provide a high carbon cold-rolled steel sheet (hereinafter also simply referred to as “cold-rolled steel sheet”) having a thickness of less than 1.0 mm that can be expressed.
  • the present inventors diligently studied the appropriate addition range of chemical components of the high-carbon cold-rolled steel sheet and the grain size and existence form of carbides in the steel.
  • the present invention is limited to C: 0.85 mass% or more and 1.10 mass% or less of carbon suitable for knitting needles from the viewpoint of workability, hardenability, hardness and toughness after low temperature tempering, etc.
  • Nb as a third element within a predetermined range and controlling the average particle size and degree of spheroidization of carbides is effective in developing the desired characteristics. At the heart.
  • the present inventors have developed a new test method for evaluating toughness (new impact test method) for steel sheets with a thickness of less than 1.0 mm, which has been difficult to evaluate toughness.
  • a new test method (new impact test method) is shown in FIGS.
  • the impact value in a quenched and tempered state of a high carbon cold rolled steel sheet with a thickness of less than 1.0 mm to which various third elements were added was investigated.
  • a new finding was obtained that the addition of a predetermined amount of Nb only satisfies the above-mentioned target characteristics.
  • the present invention has been made based on such knowledge.
  • the present inventors have intensively studied to solve the above-mentioned problems, and the basic components are C: 0.85 to 1.10 mass%, Mn: 0.50 to 1.0 mass%, Si: 0.10 to 0.35 mass%, P: 0.030 mass. %, S: 0.030 mass% or less, Cr: Addition of 0.005 to 0.020 mass% Nb to the high-carbon steel specified in the range of 0.35 to 0.45 mass%, It has been found that by controlling to a predetermined range, it is possible to obtain a high-carbon cold-rolled steel sheet that has both excellent hardenability and excellent toughness, and further it is possible to shorten the quenching time and lower the tempering temperature. It was.
  • the obtained cold-rolled steel sheet was subjected to a solution treatment in which the heating temperature was changed to two levels of 780 ° C. and 800 ° C. and the holding time was changed in the range of 0 to 16 minutes, followed by oil quenching and Vickers hardness. (HV) was measured.
  • the obtained results are shown in FIG. 3 (heating temperature: 800 ° C.) and FIG. 4 (heating temperature: 780 ° C.) in relation to the heat retention time (minutes) of the solution treatment and the quenching hardness (HV). 3 and 4, it can be seen that a cold rolled steel sheet having an Nb content of 0.010 mass% can secure a quenching hardness exceeding 700 HV in the shortest heat holding time.
  • the heat retention time of solution treatment can be made into a short time. From this, it has been found that setting the Nb content in the range of 0.005 to 0.015 mass% is effective as a measure for preventing the variation in firing elongation and bending, which are problems in needle processing manufacturers. Further, a cold-rolled steel sheet having various Nb contents was subjected to a solution treatment with a heating temperature of 800 ° C. and a heating and holding time of 10 minutes, and after oil quenching, the steel was further tempered. In the tempering treatment, the tempering temperature was 150 ° C, 200 ° C, 250 ° C, 300 ° C, 350 ° C, and the holding time was 1 hour.
  • the impact properties were investigated.
  • the impact characteristics were measured using the new test method shown in FIGS.
  • the obtained result is shown in FIG.
  • the impact value was highest when the Nb content was 0.010 mass% when the tempering temperature was 200 ° C or higher.
  • the tempering temperature at which an impact value of 5 J / cm 2 is obtained is obtained and shown in FIG. 7 in relation to the Nb content.
  • the tempering temperature at which the impact value: 5 J / cm 2 is obtained is the lowest in the case of the steel sheet with Nb content: 0.010 mass%.
  • the tempering temperature at which an impact value of 5 J / cm 2 is obtained is on the high temperature side.
  • the tempering temperature becomes high, the hardness decreases, and the durability as a needle decreases.
  • Nb content was less than 0.005 mass%, in order to ensure a desired impact value, it discovered that it was necessary to make tempering temperature high. From FIG. 5 and FIG. 7, in order to combine high hardness after tempering and excellent impact properties, the Nb content is 0.005 mass% as the lower limit and 0.020 mass% as the upper limit. Furthermore, in order to shorten the heating and holding time of the solution treatment, it is preferable to set the upper limit of the Nb content to 0.015 mass%.
  • the present invention has been completed by further studies based on this finding. That is, the gist of the present invention is as follows.
  • the chemical composition of the steel sheet is C: 0.85 to 1.10 mass%, Mn: 0.50 to 1.0 mass%, Si: 0.10 to 0.35 mass%, P: 0.030 mass% or less, S: 0.030 mass% or less, Cr: 0.35 to 0.45 mass%, Nb: 0.005 to 0.020 mass%, consisting of the balance Fe and inevitable impurities, and the average particle size (d av ) and spheroidization rate (N SC / N TC ) of the carbides dispersed in the steel plate ⁇
  • a high carbon cold-rolled steel sheet characterized in that 100% satisfies the following formulas (1) and (2), respectively, and the thickness of the steel sheet is less than 1.0 mm.
  • the average particle diameter (d av ) in the formula (1) is the average value of the diameters of the individual circles (equivalent circle diameters) when assuming a circle having the same area as each carbide observed in the cross section of the steel sheet. It is.
  • N TC and N SC in the formula (2) are N TC : the total number of carbides per observation area 100 ⁇ m 2 , N SC : the number of carbides satisfying the condition that d L / d S is 1.4 or less, The major axis of the carbide is d L , and the minor axis is d S.
  • the chemical composition further contains one or two selected from Mo and V, and each content is 0.001 mass% or more and less than 0.05 mass%,
  • [3] In the method for producing a high carbon cold rolled steel sheet by repeatedly performing cold rolling and spheroidizing annealing on the hot rolled steel sheet having the chemical composition described in [1] or [2],
  • the average particle size (d av ) and the spheroidization ratio (N SC / N TC ) of the carbide dispersed in the above satisfy the following formulas (1) and (2), respectively, and the thickness of the high carbon cold-rolled steel sheet is 1.0
  • the manufacturing method of the high carbon cold-rolled steel plate characterized by being less than mm.
  • the average particle diameter (d av ) in the formula (1) is the average value of the diameters of the individual circles (equivalent circle diameters) when assuming a circle having the same area as each carbide observed in the cross section of the steel sheet. It is.
  • N TC and N SC in the formula (2) are N TC : the total number of carbides per observation area 100 ⁇ m 2 , N SC : the number of carbides satisfying the condition that d L / d S is 1.4 or less, The major axis of the carbide is d L , and the minor axis is d S.
  • the high carbon cold-rolled steel sheet according to the present invention is a thin high-carbon cold-rolled steel sheet having a thickness of less than 1.0 mm, particularly 0.4 to 0.7 mm, and the average particle size of carbide is set to 0.2 to 0.7 ⁇ m.
  • This steel plate is controlled and the spheroidization rate is controlled to 90% or more.
  • This steel sheet, hardening and heat treatment of tempering, quenching in solution treatment period as short as 3 to 15 minutes, good impact properties by heat treatment of low temperature tempering (impact value: 5 J / cm 2 or higher) and hardness properties (600-750 HV) is obtained.
  • the high carbon cold-rolled steel sheet according to the present invention is a condition in which a so-called low temperature tempering at 200 to 350 ° C. is performed after a short solution treatment, quenching to a martensite phase containing an inevitable residual ⁇ phase.
  • a so-called low temperature tempering at 200 to 350 ° C. is performed after a short solution treatment, quenching to a martensite phase containing an inevitable residual ⁇ phase.
  • it has a clear advantage over the balance between hardness and impact properties (toughness) over conventional high carbon cold rolled steel sheets. That is, if the high carbon cold-rolled steel sheet according to the present invention is used, a machine tool part made of high carbon steel having excellent toughness after quenching and tempering while ensuring excellent hardenability can be obtained.
  • the cold-rolled steel sheet disclosed in the present invention requires not only a balance between hardness and toughness but also wear resistance and fatigue resistance, and applications that require excellent durability under harsh usage environments such as knitted needles. It is suitable for.
  • a steel sheet according to the present invention is obtained as a high-carbon cold-rolled steel sheet having a thickness of less than 1.0 mm by subjecting a hot-rolled steel sheet to soft annealing as needed, and repeatedly repeating cold rolling and spheroidizing annealing. It is. Thereafter, the high-carbon cold-rolled steel sheet is subjected to predetermined secondary processing and solution treatment, and is subjected to quenching and tempering treatments and used for members (mechanical parts) such as knitted needles.
  • the chemical composition of the steel sheet of the present invention is as follows: C: 0.85 to 1.10 mass%, Mn: 0.50 to 1.0 mass%, Si: 0.10 to 0.35 mass%, P: 0.030 mass% or less, S: 0.030 mass% or less, Cr: The reasons for specifying 0.35 to 0.45 mass% and Nb: 0.005 to 0.020 mass% will be described below.
  • the lower limit value can ensure a hardness of 600 to 750 HV with precision parts such as knitted needles, and the upper limit value can be controlled to a level of carbide that does not impede various types of cold work. Were determined. That is, the lower limit value was defined as 0.85 mass% in order to stably secure a hardness of 600 HV in a short time quenching and tempering treatment. Moreover, the upper limit was defined as 1.10 mass% as the upper limit that can withstand a wide variety of plastic processing such as punchability, swaging, bendability, and machinability.
  • C is specified in the range of 0.85 to 1.10 mass%. Preferably, it is 0.95 to 1.05 mass%.
  • Mn 0.50-1.0mass%
  • Mn is an element effective for deoxidation of steel, and is an element that can improve the hardenability of steel and stably obtain a predetermined hardness.
  • the target is a high carbon steel sheet applied to a severe use
  • the effect of the present invention becomes remarkable at 0.50 mass% or more. Therefore, the lower limit is defined as 0.50 mass%.
  • the upper limit is defined as 1.0 mass%.
  • Mn was specified in the range of 0.50 to 1.0 mass%. Preferably, it is 0.50 to 0.80 mass%.
  • Si 0.10 ⁇ 0.35mass% Since Si is a deoxidizing element of steel, it is an effective element for melting clean steel. Si is an element having martensite temper softening resistance. For this reason, the lower limit is defined as 0.10 mass%. Further, when added in a large amount, the tempering of martensite at low temperature tempering becomes insufficient and the impact characteristics are deteriorated. Therefore, the upper limit value is defined as 0.35 mass%. For this reason, Si was specified in the range of 0.10 to 0.35 mass%.
  • P 0.030 mass% or less
  • S 0.030 mass% or less
  • P and S are unavoidably present in the steel as impurity elements, and since both adversely affect impact properties (toughness), it is preferable to reduce as much as possible.
  • P contains up to 0.030 mass% and S contains up to 0.030 mass%. For this reason, P is specified to be 0.030 mass% or less, and S is specified to be 0.030 mass% or less. In order to maintain more excellent impact characteristics, it is preferable to contain P up to 0.020 mass% and S up to 0.010 mass%.
  • Cr 0.35-0.45 mass%
  • Cr is an element that improves the hardenability of steel, it dissolves in the carbide (cementite) and delays the remelting of the carbide in the heating stage. Therefore, if added in a large amount, the hardenability is adversely affected. Therefore, the upper limit value of Cr is regulated to 0.45 mass%. From the balance between hardness and impact characteristics after quenching and tempering, the lower limit value of Cr was defined as 0.35 mass%. For these reasons, Cr is specified in the range of 0.35 to 0.45 mass%.
  • Nb 0.005-0.020 mass%
  • Nb is an element that expands the non-recrystallization temperature range of steel during hot rolling and simultaneously precipitates as NbC to contribute to the refinement of austenite grains. For this reason, high carbon steel may be added in anticipation of the effect of refining the structure after the cold rolling step.
  • Nb is added in an amount of 0.005 to 0.020 mass% mainly for the purpose of restoring toughness by tempering at a low temperature after quenching. If a small amount of Nb is added, NbC that contributes to refinement of the structure is not formed, and Nb is in a dilute solid solution state.
  • Nb When Nb is added in excess of 0.020 mass%, the precipitation of NbC becomes remarkable, the Nb dilute solid solution state cannot be secured, and the effect of promoting the diffusion of C due to the Nb dilute solid solution state is observed. Disappear.
  • the upper limit of Nb addition amount was prescribed
  • the Nb addition amount is less than 0.005 mass%, the above-described effects cannot be expected. For this reason, the minimum of Nb addition amount was prescribed
  • Mo and V are basic components, in the present invention, one or two selected from Mo and V can be further contained as an optional selection element as required. Mo and V may inevitably be contained in each of Mo: less than 0.001 mass% and V: less than 0.001 mass%. Furthermore, in this invention, in order to improve hardenability and the impact characteristic after tempering as arbitrary selection elements, it can add more than the level which inevitably contains Mo and V. However, the addition effect of Mo or V exceeds a certain amount, the effect of Nb addition is lost. In order to maximize the effect of Nb addition, the content of Mo and V is limited within the following range. It is preferable to do.
  • Mo 0.001 mass% or more and less than 0.05 mass% Mo is an element effective in improving the hardenability of steel. However, if the addition amount is large, low temperature tempering at 200 to 350 ° C may deteriorate the impact characteristics. Therefore, when added, it is defined as 0.001 mass% or more, which is higher than the level of unavoidably contained, and less than 0.05 mass%, which is a range that does not inhibit the impact characteristics.
  • the addition of Mo is preferably 0.01 to 0.03 mass%.
  • V 0.001 mass% or more and less than 0.05 mass%
  • V is an element that is effective in improving impact characteristics by refining the steel structure, but it may deteriorate the hardenability. Therefore, when added, it is defined as 0.001 mass% or more higher than the level of unavoidably contained and less than 0.05 mass% within a range that does not impair hardenability.
  • the addition of V is preferably 0.01 to 0.03 mass%.
  • the balance other than the above components is Fe and inevitable impurities.
  • the average particle diameter (d av ) and spheroidization ratio (N SC / N TC ) of the carbide dispersed in the steel sheet satisfy the following expressions (1) and (2), respectively. It is necessary. 0.2 ⁇ d av ⁇ 0.7 ( ⁇ m) (1) (N SC / N TC ) ⁇ 100 ⁇ 90% (2)
  • the average particle diameter (d av ) ( ⁇ m) of the formula (1) is the diameter of each circle (equivalent circle diameter) when assuming a circle having the same area as each carbide observed in the cross section of the steel sheet. Average value.
  • the average particle diameter (d av ) When the average particle diameter (d av ) is in this range, the impact properties are excellent, and the desired quenching hardness can be easily achieved even with a solution treatment for a short time.
  • the average particle size (d av ) is less than 0.2 ⁇ m, experience shows that the load during secondary processing, which is processing into a needle shape, increases. The desired hardenability improvement is difficult to achieve, which is not preferable.
  • carbides defined in N TC and N SC of the spheroidization ratio is a ratio which is spheroidized (2).
  • NTC is the total number of carbides per 100 ⁇ m 2 observation area.
  • N SC is the number of carbide which can be regarded to be spheroidized in the same observation field, d L / d S: set to 1.4 following conditions are satisfied carbides number.
  • the major axis of the carbide was d L and the minor axis was d S.
  • the carbide is not necessarily formed into a perfect sphere, and is often observed as an ellipse depending on the observation surface. Therefore, the ratio of the major axis to the minor axis (d L / d S ) determines the spheroidization. The degree was specified. Under such circumstances, in the present invention, d L / d S: 1.4 satisfying the following conditions carbides were defined N SC is its number is regarded as being spheroidized. Further, the reason why the spheroidization ratio (N SC / N TC ) ⁇ 100 is 90% or more is because empirical knowledge has been found that the secondary workability of the steel sheet is good within this range. is there.
  • the measurement of the average particle size and the spheroidization ratio of the carbide described above was performed by observing the secondary electron image at a magnification of 2000 times using a scanning electron microscope.
  • Carbide cuts a plate-shaped test piece in a direction perpendicular to the rolling direction of the sample before heat treatment using a steel sheet after cold rolling, and performs processing such as resin embedding, and an observation area of 100 ⁇ m 2 near the center of the plate thickness.
  • the equivalent circle diameter, d L / d S ratio, N TC , and N SC were measured in the range, and the average value for five fields of view was calculated.
  • commercially available image analysis software “winroof” (trade name) was used.
  • the hot-rolled steel sheet used in the present invention may be obtained under normal manufacturing conditions.
  • a steel slab having the above-mentioned chemical composition (slab) is heated to 1050 to 1250 ° C, hot-rolled at a finishing temperature of 800 to 950 ° C, and coiled at a winding temperature of 600 to 750 ° C. it can.
  • board thickness of a hot-rolled steel plate so that it may become a suitable cold reduction rate from the plate
  • a high-carbon cold-rolled steel sheet with a thickness of less than 1.0 mm is manufactured by repeating cold rolling (25-65%) and spheroidizing annealing (640-720 ° C) multiple times. This cold rolling (25 to 65%) and spheroidizing annealing (640 to 720 ° C.) are preferably repeated 2 to 5 times, respectively.
  • cold rolling 25 to 65%
  • spheroidizing annealing 640 to 720 ° C.
  • the reason for this is that the average particle size (d av ) and spheroidization rate (N SC / N TC ) ⁇ 100 of the carbides are controlled so as to satisfy the above-described equations (1) and (2), respectively, as described below. It is to do.
  • cracks are introduced into the carbide by cold rolling, and the carbide that has just started to be spheroidized is spheroidized.
  • the cold rolling reduction ratio is preferably in the range of 25 to 65%.
  • the lower limit of the rolling reduction is not particularly limited.
  • the spheroidizing annealing temperature is preferably in the range of 640 to 720 ° C.
  • the holding time of the spheroidizing annealing can be appropriately selected at a temperature within this range within a range of 9 to 30 hours.
  • the same temperature range is preferable also about the softening annealing aiming at softening of the hot rolled steel sheet before cold rolling.
  • the above is the method for producing a high carbon cold-rolled steel sheet according to the present invention.
  • a mechanical part such as a knitted needle
  • the following heat treatment is performed after processing into a predetermined shape. It is preferable to carry out.
  • the heating temperature is 760 to 820 ° C.
  • the holding time is short 3 to 15 minutes. It is preferable to use oil for quenching (rapid cooling).
  • the tempering temperature is preferably 200 to 350 ° C. Further, it is more preferably 250 to 300 ° C. As a result, various machine parts having a hardness of 600 to 750 HV can be manufactured.
  • the upper limit of the solution treatment retention time is preferably 15 minutes.
  • the lower limit of the solution treatment holding time is preferably 3 minutes. More preferably, it is in the range of 5 to 10 minutes.
  • the tempering temperature is less than 200 ° C, the toughness recovery of the martensite phase is insufficient.
  • the tempering temperature exceeds 350 ° C., the impact value is recovered, but since the hardness is lower than 600 HV, durability and wear resistance become a problem. Therefore, the appropriate range of tempering temperature is preferably 200 to 350 ° C. More preferably, it is 250 to 300 ° C.
  • the tempering holding time can be appropriately selected within the range of 30 minutes to 3 hours.
  • FIG. 1 shows a state where the test piece is installed in the test apparatus
  • FIG. 2 shows the shape of the test piece. The reason for adopting such a test piece and test method is as follows.
  • the rated capacity of the test equipment is too large, at least 50 J, so accurate evaluation is possible. There was a problem that I could not.
  • a 1 J impact test device (model DG-GB, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used.
  • This test apparatus is a Charpy impact tester based on the Charpy impact test method (JIS K 7077) of carbon fiber reinforced plastic.
  • JIS K 7077 the Charpy impact test method of carbon fiber reinforced plastic.
  • This test apparatus was improved and the distance between the supports was changed from 60 mm to 40 mm. In this test apparatus, the distance between the support bases was changed from 60 mm to 40 mm in order to make the conditions close to the JIS standard (JIS Z 2242), which is a Charpy impact test method for metal materials.
  • a test piece having a notch depth of 2.5 mm, a notch radius of 0.1 mm (notch width of 0.2 mm), and a U-notch formed by electric discharge machining was used.
  • the reason why the notch radius is reduced is that the deflection of the plate becomes a problem in the case of a thin plate of less than 1.0 mm during the Charpy impact test. Therefore, increasing the stress concentration factor minimizes the deflection of the plate during the Charpy impact test.
  • Example 1 The effects of various additive elements on the cross-sectional hardness and impact value after oil quenching and tempering after solution treatment were confirmed.
  • the test results are shown in Tables 3 and 4 together with chemical components.
  • the condition of 5A (Table 1) was used for both.
  • the rolling reduction was controlled within the range described in Table 1.
  • the cross section hardness was measured at the center of the plate thickness by embedding a test piece cut in the direction perpendicular to the rolling direction into a resin, polishing the cross section.
  • the impact value was measured using an impact test piece taken in the rolling parallel direction.
  • the obtained results (hardness, impact value) are shown in Tables 3 and 4.
  • the evaluation when the impact value is larger than 5 J / cm 2 and the hardness satisfies 600 to 750 HV is “ ⁇ ”, and the case where any of the above target values of the impact value and the hardness is not satisfied is evaluated as “X”.
  • the impact value and the quenching and tempering hardness were outside the target values for the case where the C amount was outside the lower limit (steel type No. 1).
  • the quenching and tempering hardness exceeded the target value of 600 to 750 HV, and the impact value was below the target value of 5 J / cm 2 .
  • Nb-free materials have a C amount of 0.85 mass% (steel grade No. 2, comparative example) and a C amount of 1.10 mass% (steel grade No. 4, comparative example). The value was below 5 J / cm 2 and the evaluation was x.
  • the steel plates corresponding to the chemical components of the inventive examples (steel types No. 3, 5, 7, 8, 9, 10) had quenching and tempering hardness within the target range and excellent impact characteristics.
  • the steel plates with the chemical composition corresponding to the inventive examples all have a quenching and tempering hardness satisfying the target value of 600 to 750 HV and excellent impact properties. It was. Nb not added (steel grade No. 11), Nb not added and V added amount exceeding 0.05 mass% (steel grade No. 12), Nb not added and Mo added amount exceeding 0.05 mass% ( Steel type No. 13), Nb + Mo composite addition with Nb addition less than 0.005 mass% (steel grade No. 14), Nb + Mo composite addition with Nb addition over 0.020 mass% (steel type No.
  • Nb + Mo composite When the addition of Mo is greater than 0.05 mass% (steel grade No. 20), and when Nb + Mo + V is added and the addition of V is greater than 0.05 mass% (steel grade No. 22), the quenching and tempering hardness is 600 ⁇ Although it meets 750 HV, or impact properties are inferior, either but impact properties are satisfied the target value 5 J / cm 2 are reduced quenching and tempering hardness, quenching and tempering hardness and impact properties are both desired value It was below the lower limit of.
  • Example 2 Using a hot-rolled steel sheet having the chemical composition of steel type No. 3 (Table 3), the production conditions for cold rolling and spheroidizing treatment shown in Table 1 were changed, and cold-rolled steel sheets having the thicknesses shown in Table 5 were used.
  • Table 5 shows the spheroidization ratio and carbide average particle size of the obtained cold-rolled steel sheet. Furthermore, the obtained cold-rolled steel sheet was subjected to oil quenching and low-temperature tempering after solution treatment under the conditions shown in Table 2 as in Example 1. The cross-sectional hardness and impact value of the obtained cold-rolled steel sheet after solution treatment and quenching and tempering were measured in the same manner as in Example 1, and are shown in Table 5.
  • the spheroidizing annealing temperature is 600 to 635 ° C and the cold rolling reduction ratio is 70 to 85% and repeated twice, the impact characteristics are sufficient, but the average particle size of the carbide falls outside the lower limit, and quenching and tempering treatment. The later hardness exceeded the target value (Manufacturing condition No. 2C).
  • the spheroidizing annealing temperature is 640 to 720 ° C and the cold rolling reduction ratio is 10 to 20% and each is repeated twice, the spheroidization is sufficient, but the average particle size of the carbide exceeds the upper limit of the target value, and the impact characteristics Was inferior (production conditions No. 2D). This is because if the carbide is too large, the undissolved carbide in the martensite substrate becomes larger during quenching, and the area of the interface between the undissolved carbide and the martensite substrate that tends to be the starting point for fracture is large, so the impact characteristics are inferior. It seems to have become.
  • the spheroidizing annealing temperature is 640 to 720 ° C and the cold rolling reduction ratio is 25 to 65% and repeated twice each
  • the spheroidizing ratio, carbide grain size, and hardness after quenching and tempering are the target values, respectively. It was within the range and had excellent impact characteristics (manufacturing condition No. 2B).
  • Example 3 Using the hot-rolled steel sheet having the chemical composition of steel type No. 16 (Table 4), the production conditions shown in Table 1 were changed to obtain cold-rolled steel sheets having the thicknesses shown in Table 6.
  • Table 6 shows the spheroidization ratio and carbide average particle size of the obtained cold-rolled steel sheet. Furthermore, the obtained cold-rolled steel sheet was subjected to oil quenching and low-temperature tempering after solution treatment under the conditions shown in Table 2 as in Example 1.
  • the cross-sectional hardness and impact value of the obtained cold-rolled steel sheet after solution treatment and quenching and tempering were measured in the same manner as in Example 1 and are shown in Table 6.
  • Steel sheets with chemical components within the scope of the present invention are hardened by Nb addition and impact properties after heat treatment are improved, so they are suitable for machine tool parts used in harsh environments with hypereutectoid steels. Yes.
  • a hypereutectoid steel sheet having a C of 0.85 to 1.10 mass% is suitable for applications that require a balance between hardness and toughness in harsh usage environments such as knitted needles.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135111A1 (ja) * 2017-01-17 2018-07-26 トクセン工業株式会社 針用の線
CN113099723A (zh) * 2019-11-08 2021-07-09 株式会社特殊金属超越 高碳冷轧钢板及其制造方法以及高碳钢制机械部件

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* Cited by examiner, † Cited by third party
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SE543422C2 (en) * 2019-06-07 2021-01-12 Voestalpine Prec Strip Ab Steel strip for flapper valves
CN110306027A (zh) * 2019-07-02 2019-10-08 浙江豪环新材料有限公司 一种t8碳素钢冷轧生产工艺
KR102502011B1 (ko) * 2020-12-21 2023-02-21 주식회사 포스코 Qt열처리된 고탄소 열연강판, 고탄소 냉연강판, qt열처리된 고탄소 냉연강판 및 이들의 제조방법
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003147485A (ja) * 2001-11-14 2003-05-21 Nisshin Steel Co Ltd 加工性に優れた高靭性高炭素鋼板およびその製造方法
JP2005139534A (ja) * 2003-11-10 2005-06-02 Kobe Steel Ltd 過共析鋼
JP2006063384A (ja) * 2004-08-26 2006-03-09 Nisshin Steel Co Ltd 衝撃特性に優れた高炭素鋼部材及びその製造方法
JP2009215612A (ja) * 2008-03-11 2009-09-24 Nisshin Steel Co Ltd 加工性に優れた中・高炭素鋼板およびその製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4161090B2 (ja) * 1999-03-16 2008-10-08 日新製鋼株式会社 打抜き性に優れた高炭素鋼板
JP5030280B2 (ja) 2007-07-20 2012-09-19 日新製鋼株式会社 焼入れ性、疲労特性、靭性に優れた高炭素鋼板及びその製造方法
CN102851579A (zh) * 2012-09-07 2013-01-02 首钢总公司 一种含Nb微合金化高碳钢热轧盘条及制造方法
KR101799712B1 (ko) * 2013-11-22 2017-11-20 신닛테츠스미킨 카부시키카이샤 고탄소 강판 및 그 제조 방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003147485A (ja) * 2001-11-14 2003-05-21 Nisshin Steel Co Ltd 加工性に優れた高靭性高炭素鋼板およびその製造方法
JP2005139534A (ja) * 2003-11-10 2005-06-02 Kobe Steel Ltd 過共析鋼
JP2006063384A (ja) * 2004-08-26 2006-03-09 Nisshin Steel Co Ltd 衝撃特性に優れた高炭素鋼部材及びその製造方法
JP2009215612A (ja) * 2008-03-11 2009-09-24 Nisshin Steel Co Ltd 加工性に優れた中・高炭素鋼板およびその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135111A1 (ja) * 2017-01-17 2018-07-26 トクセン工業株式会社 針用の線
JP2018115353A (ja) * 2017-01-17 2018-07-26 トクセン工業株式会社 針用の線
CN113099723A (zh) * 2019-11-08 2021-07-09 株式会社特殊金属超越 高碳冷轧钢板及其制造方法以及高碳钢制机械部件

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