WO2011070877A1 - Hot-pressed member and process for producing same - Google Patents
Hot-pressed member and process for producing same Download PDFInfo
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- WO2011070877A1 WO2011070877A1 PCT/JP2010/069644 JP2010069644W WO2011070877A1 WO 2011070877 A1 WO2011070877 A1 WO 2011070877A1 JP 2010069644 W JP2010069644 W JP 2010069644W WO 2011070877 A1 WO2011070877 A1 WO 2011070877A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J13/00—Details of machines for forging, pressing, or hammering
- B21J13/02—Dies or mountings therefor
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
Definitions
- the present invention relates to a hot press member manufactured by pressing a heated steel sheet, and more particularly, to a hot press member used in an undercarriage part or a vehicle body structure part of an automobile and a method for manufacturing the same.
- Patent Document 1 discloses a process called a hot press that enables both easy processing and high strength by simultaneously processing a heated steel sheet using a die and a punch and simultaneously cooling it.
- Technology has been proposed.
- the steel plate is heated to a high temperature of around 950 ° C. before hot pressing, so scale (Fe oxide) is generated on the steel plate surface, and the scale peels off during hot pressing.
- the mold is damaged or the surface of the member after hot pressing is damaged.
- the scale remaining on the surface of the member may cause poor appearance, reduced coating film adhesion (paintability), and corrosion resistance.
- the scale on the surface of the member is usually removed by processing such as pickling or shot blasting, but this complicates the manufacturing process and causes a decrease in productivity.
- Patent Document 2 discloses a coated steel sheet coated with Al or an Al alloy. It has been shown that by using this coated steel sheet, decarburization and oxidation are prevented during heating before hot pressing, and a hot pressed member having extremely high strength and excellent corrosion resistance can be obtained.
- Patent Document 3 discloses a Zn-Fe base that prevents corrosion and decarburization and has a lubrication function during hot pressing before hot pressing a steel sheet coated with Zn or a Zn base alloy.
- a hot pressing method in which an alloy compound such as the above compound or a Zn-Fe-Al-based compound is generated on the surface of a steel sheet is disclosed.
- a hot press member using a steel sheet coated with Zn-50 to 55 mass% Al a Zn-Al-Fe alloy layer is formed, and an excellent corrosion prevention effect is obtained.
- Patent Document 4 uses a steel plate mainly composed of Al or Zn, and is heated to an Ac 3 transformation point or higher and 1100 ° C. or lower in an atmosphere having a hydrogen concentration of 6% by volume or less and a dew point of 10 ° C. or less.
- a hot pressing method excellent in hydrogen embrittlement resistance by hot pressing after heating is disclosed. In this hot pressing method, the amount of hydrogen and water vapor in the atmosphere during heating is reduced to reduce the amount of hydrogen penetrating into the steel, thereby avoiding hydrogen embrittlement associated with high strength exceeding 1000 MPa. .
- Patent Documents 2 to 4 have the following problems. That is, die galling during hot pressing (a phenomenon in which the scale peeled off from the steel sheet surface does not damage the metal mold, but refers to a phenomenon in which the steel sheet and the metal mold stick together due to contact between metal surfaces). Inferior to hot pressability. When a steel plate coated with Al or an Al alloy is used, the weldable current range during spot welding is narrow and spot weldability is poor. When a steel sheet coated with Zn or a Zn alloy is used, Zn is volatilized and oxidized during heating before hot pressing, and is deposited on the surface of the steel sheet to reduce the paint adhesion of the hot pressed member. Rather than hydrogen penetration during heating before hot pressing, hydrogen embrittlement is caused by hydrogen penetration due to corrosion in the use environment.
- An object of the present invention is to provide a hot press member having excellent hot press properties, spot weldability, paint adhesion, and capable of suppressing hydrogen intrusion into steel due to corrosion, and a method for producing the same. To do.
- the present invention has been made on the basis of such knowledge, and has a Ni diffusion region with a Ni adhesion amount of 10 to 90000 mg / m 2 on the surface layer portion of the steel sheet constituting the member, and the inorganic diffusion region is formed on the Ni diffusion region.
- a hot press member comprising a compound is provided.
- an inorganic compound having a melting point of 500 to 1000 ° C. and containing an alkali-soluble component is preferable.
- the hot-pressed member of the present invention comprises a steel plate having a nickel-containing plating layer containing 10 to 90,000 mg / m 2 and an inorganic compound in order on the surface of the steel plate, with an Ac 3 transformation point of 1200 ° C. It can be manufactured by a method of hot pressing after heating to a temperature range.
- an inorganic compound having a melting point of 500 to 1000 ° C. and containing an alkali-soluble component is preferably used.
- C 0.15-0.5%
- Si 0.05-2.0%
- Mn 0.5-3%
- P 0.1% or less
- S in mass%. 0.05% or less
- Al 0.1% or less
- N 0.01% or less
- the balance being a steel plate having a component composition consisting of Fe and inevitable impurities, and further by mass%
- Cr At least one selected from 0.01 to 1%, Ti: 0.2% or less
- Sb 0.003 to 0.03% individually. Or it is preferable to use the steel plate contained simultaneously.
- the hot press member of the present invention is suitable for an automobile suspension member and a vehicle body structure member having a strength of 980 MPa or more.
- a Ni diffusion region is present in the surface layer portion of the steel plate constituting the member to suppress hydrogen intrusion into the steel due to corrosion.
- the reason for this is not necessarily clear, but can be considered as follows. That is, the hydrogen intrusion into the steel plate due to corrosion is related to the oxidation-reduction reaction of Fe rust in a wet environment, and it is necessary that the Fe rust is a stable rust that hardly changes to suppress the hydrogen intrusion. .
- Ni is effective for stabilizing Fe rust, and the presence of the Ni diffusion region suppresses hydrogen intrusion into the steel due to corrosion.
- the Ni diffusion region referred to here is a region where Ni is diffused in the steel from the plating layer during heating before hot pressing, or Co, Zn, Cr, Mn contained in the plating layer in addition to Ni, A region where metal elements such as Cu and Mo are diffused.
- the Ni adhesion amount per side in the Ni diffusion region is set to 10 mg / m 2 or more, preferably 50 mg / m 2 or more, more preferably 100 mg / m 2 or more.
- the Ni adhesion amount per side exceeds 90000 mg / m 2 , the effect is saturated and the cost is increased, so the Ni adhesion amount is 90000 mg / m 2 or less, preferably 10000 mg / m 2 or less, more preferably It is necessary to make it 5000 mg / m 2 or less.
- the Ni diffusion region is preferably present in the depth direction from 0.1 to 100 ⁇ m from the surface of the steel sheet constituting the member, more preferably present in the range of 1 to 50 ⁇ m, and present in the range of 3 to 10 ⁇ m. Further preferred.
- the Ni adhesion amount can be determined by fluorescent X-ray analysis or wet analysis.
- the depth of the Ni diffusion region can be obtained by analyzing the cross section in the thickness direction using EPMA (Electron Probe Micro Analyzer) or analyzing the depth direction using GDS (Glow Discharge Spectroscopy).
- the hot-pressed member of the present invention is manufactured by hot-pressing a steel plate having a plated layer containing Ni and an inorganic compound in order on the surface. Therefore, this inorganic compound remains on the surface of the member after hot pressing. However, this inorganic compound is then removed when the hot press member is subjected to chemical conversion treatment such as phosphate treatment or zirconium oxide treatment as a coating base treatment, particularly during alkaline degreasing. There is no.
- the hot-pressed member of the present invention comprises a steel plate having a nickel-plated layer containing 10 to 90,000 mg / m 2 of Ni and an inorganic compound in order on the surface of the steel plate. It can be produced by a method of hot pressing after heating to a temperature range of 3 transformation points to 1200 ° C.
- Ni in the plating layer diffuses into the steel sheet.
- a Ni diffusion region having a Ni adhesion amount of 10 to 90000 mg / m 2 is formed on the surface layer of the member, and hydrogen intrusion into the steel due to corrosion is suppressed.
- Such a plating layer containing Ni can be formed by an electroplating method or the like.
- the inorganic compound is present on the plating layer containing Ni and the inorganic compound is melted during heating before hot pressing, the sliding property during hot pressing can be remarkably improved by the fluid lubrication effect. No mold galling occurs and excellent hot pressability is obtained. For this reason, it is preferable to use an inorganic compound having a melting point of 500 to 1000 ° C. as the inorganic compound.
- the melting point of the inorganic compound is 500 ° C. or higher, since the inorganic compound does not melt at an early stage of the temperature rising process during heating before hot pressing, the molten inorganic compound does not adhere to the heating furnace, The amount of the inorganic compound in the molten state is not reduced, and the slidability during hot pressing is improved.
- the melting point of the inorganic compound is 1000 ° C. or lower, the inorganic compound does not melt during heating, or the melting is not insufficient, and the slidability during hot pressing is improved. It is more preferable to use an inorganic compound having a melting point of 500 to 900 ° C.
- the inorganic compound it is preferable to use an inorganic compound containing an alkali-soluble component so that it can be easily removed during alkali degreasing in chemical conversion treatment.
- the amount of the inorganic compound deposited on one side is 1 mg / m 2 or more, the amount of the inorganic compound in the molten state is not too small, and the slidability during hot pressing is sufficient, and is 5000 mg / m 2 or less.
- the adhesion amount of the inorganic compound can be measured by, for example, the following method.
- a method of measuring from a weight change before and after applying and drying an inorganic compound a method of measuring and measuring a weight change by dissolving and removing the inorganic compound with a solution capable of dissolving only the inorganic compound, and the plating layer on which the inorganic compound is adhered to the acid.
- the dissolved solution is analyzed by atomic absorption analysis or ICP (Inductively Coupled Plasma) analysis, and the amount of an element serving as a marker is quantified and converted to an inorganic compound amount.
- the ratio of the inorganic compound is preferably 50% by mass or more. Even if an organic compound coexists, since heating before hot pressing is performed at a high temperature of about 900 ° C., the organic compound reacts with oxygen in the atmosphere and disappears as oxygen dioxide and water, so that sliding property is eliminated. There is no effect on the plating layer.
- sodium tetraborate decahydrate having a melting point of 741 ° C. and a boiling point of 1575 ° C. is preferable.
- this sodium tetraborate decahydrate may change to an anhydride at 350 to 400 ° C and melt at 878 ° C if the temperature is further increased. Therefore, the use of this sodium tetraborate decahydrate is suitable when the heating temperature before hot pressing is 878 ° C. or higher.
- examples of inorganic compounds applicable to the present invention include ammonium sulfate, strontium nitrate, antimony (III) oxide, calcium hydroxide, sodium carbonate, sodium fluoride, and the like.
- a known method can be applied.
- a solution such as an aqueous solution containing an inorganic compound is applied to the surface of the plating layer and dried to evaporate moisture and solvent so that the inorganic compound exists on the plating layer.
- the coating method include a bar coater method, a brush coating method, a roll coater method, a dipping method, and a spray method.
- a steel sheet with high hardenability obtained after hot pressing with a strength of 980 MPa or more for example, in mass%, C: 0.15 to 0.5%, Si: 0.05 to 2.0%, Mn: 0.5 to 3%, P: 0.1% or less, S: 0.05% or less, Al: 0.1% or less, N: 0.01% or less
- C 0.15-0.5% C is an element that improves the strength of steel. In order to increase the TS of the hot pressed member to 980 MPa or more, the amount needs to be 0.15% or more. On the other hand, when the amount of C exceeds 0.5%, the blanking workability of the raw steel plate is significantly lowered. Therefore, the C content is 0.15 to 0.5%.
- Si 0.05 to 2.0% Si, like C, is an element that improves the strength of steel.
- the amount In order to increase the TS of the hot pressed member to 980 MPa or more, the amount needs to be 0.05% or more.
- the amount of Si exceeds 2.0%, the occurrence of surface defects called red scales during hot rolling is remarkably increased, the rolling load is increased, and the ductility of the hot-rolled steel sheet is deteriorated.
- the Si content exceeds 2.0%, the plating processability may be adversely affected when a plating process for forming a plating film mainly composed of Zn or Al on the steel sheet surface is performed. Therefore, the Si content is 0.05 to 2.0%.
- Mn 0.5 to 3%
- Mn is an element effective for suppressing the ferrite transformation and improving the hardenability, and also reduces the Ac 3 transformation point, so that it is an effective element for lowering the heating temperature before hot pressing. is there. In order to exhibit such an effect, the amount needs to be 0.5% or more.
- the amount of Mn exceeds 3%, it segregates and the uniformity of the characteristics of the raw steel plate and the hot press member decreases. Therefore, the amount of Mn is 0.5 to 3%.
- P 0.1% or less
- the amount of P exceeds 0.1%, segregation occurs and the uniformity of the characteristics of the steel plate and the hot pressed member is reduced, and the toughness is also significantly reduced. Therefore, the P content is 0.1% or less.
- Al 0.1% or less When the Al amount exceeds 0.1%, blanking workability and hardenability of the steel plate as a material are lowered. Therefore, the Al content is 0.1% or less.
- N 0.01% or less
- the N content exceeds 0.01%, a nitride of AlN is formed during hot rolling or heating before hot pressing, and the blanking workability and hardenability of the raw steel sheet are improved. Reduce. Therefore, the N content is 0.01% or less.
- the balance is Fe and inevitable impurities, but at least selected from Cr: 0.01 to 1%, Ti: 0.2% or less, and B: 0.0005 to 0.08% for the following reasons.
- One kind or Sb: 0.003 to 0.03% is preferably contained individually or simultaneously.
- Cr 0.01 to 1% Cr is an element effective for strengthening steel and improving hardenability.
- the Cr content is preferably 0.01% or more.
- the upper limit is preferably 1%.
- Ti 0.2% or less Ti is an element effective for strengthening steel and improving toughness by refining. Further, it is also an element effective for forming a nitride in preference to B described below and exhibiting the effect of improving hardenability by solid solution B. However, if the amount of Ti exceeds 0.2%, the rolling load during hot rolling is extremely increased, and the toughness of the hot pressed member is reduced, so the upper limit should be 0.2% or less. Is preferred.
- B 0.0005 to 0.08%
- B is an element effective for improving the hardenability during hot pressing and toughness after hot pressing.
- the B content is preferably 0.0005% or more.
- the upper limit is preferably 0.08%.
- Sb 0.003 to 0.03%
- Sb has an effect of suppressing a decarburized layer generated in the steel sheet surface layer portion between the time when the steel plate is heated before hot pressing and the time when the steel plate is cooled by a series of processes of hot pressing. In order to exhibit such an effect, the amount needs to be 0.003% or more. On the other hand, if the Sb content exceeds 0.03%, the rolling load increases and the productivity is lowered. Therefore, the Sb amount is set to 0.003 to 0.03%.
- heating by an electric furnace or a gas furnace flame heating, current heating, high-frequency heating, induction heating, etc. can be exemplified, but not limited thereto.
- the rolled steel sheet was subjected to electroplating treatment at a current density of 10 A / dm 2 in a plating bath composed of 300 g / L nickel sulfate hexahydrate, 50 g / L sodium sulfate, and 30 g / L boric acid.
- Ni plating layers having different Ni adhesion amounts (per one side) shown were formed on both sides.
- some cold-rolled steel sheets include a plating bath comprising 300 g / L nickel sulfate hexahydrate, 10 g / L zinc sulfate heptahydrate, 50 g / L sodium sulfate, and 30 g / L boric acid.
- the electroplating treatment was performed at a current density of 50 A / dm 2 , and Ni-10 mass% Zn plating layers having the Ni adhesion amount shown in Table 1 were formed on both surfaces.
- an aqueous solution of an inorganic compound having a melting point as shown in Table 1 was applied by a bar coater, and then dried at 120 ° C. for 10 minutes, The amount of inorganic compound per one side shown in Table 1 was present.
- a 200 mm ⁇ 220 mm blank sampled from a steel sheet having a plated layer containing Ni and an inorganic compound on both surfaces thus prepared was heated for 10 minutes at the heating temperature shown in Table 1 in an electric furnace in an air atmosphere, and then in the furnace. 1 and immediately after drawing the surface containing the plating layer containing Ni and the inorganic compound as a non-punch contact surface by a pressing method as schematically shown in FIG. 1 to 15 were produced. At this time, the punch width was 70 mm, and the processing height was 30 mm.
- Hot pressability The non-punch contact surface side after hot pressing is visually observed, and the state of occurrence of scratches due to mold galling is evaluated according to the following criteria. I was doing it. ⁇ : There is no scratch on the member surface. ⁇ : There is a scratch on a part of the member surface. ⁇ : There is a scratch on the entire surface of the member.
- Spot weldability A sample is taken from the flat part of the member head, and spot is made by Kimura Denyu Co., Ltd. Using a welding machine, the same type of samples are welded together under the conditions of electrode tip used: DR6, electrode pressure: 2KN, squeeze time: 25 cycles / 50 Hz, welding time: 16 cycles / 50 Hz, holding time: 5 cycles / 50 Hz.
- the weldable current range (ACR) was measured. The evaluation was made according to the following criteria, and if ⁇ or ⁇ , the object of the present invention was satisfied. In addition, the non-punch contact surfaces were contacted and welded.
- ACR More than 2 times when ACR is Al-Si plated steel plate ⁇ : 1.5 times or more to less than 2 times when ACR is Al-Si plated steel plate ⁇ : ACR is equal to or more than Al-Si plated steel plate to 1 Less than 5 times coating adhesion:
- a sample was taken from the flat part of the head of the member, subjected to chemical conversion treatment under standard conditions using PB-L3020 manufactured by Nihon Parkerizing Co., Ltd. on the non-punch contact surface, and then Kansai Paint Co., Ltd.
- An electrodeposition paint GT-10HT gray manufactured by the company was formed into a film with a thickness of 20 ⁇ m under a baking condition of 170 ° C. for 20 minutes to prepare a coating test piece.
- the working electrode is a sample
- the counter electrode is platinum
- the ground surface is Ni-plated
- the hydrogen detection surface is set in the electrochemical cell schematically shown in FIG. 2, and the non-ground surface is corroded at room temperature in the atmosphere.
- the amount of hydrogen penetrating into the steel was measured by electrochemical hydrogen permeation method. That is, the hydrogen detection surface side is filled with 0.1M NaOH aqueous solution, the reference electrode (Ag / AgCl) is set through the salt bridge, and 0.5% by mass on the non-grinding surface (evaluation surface: non-punch contact surface) side.
- Hot press member No. 1 of the present invention. 1 to 13 are excellent in hot press property, spot weldability, paint adhesion, and hydrogen penetration resistance.
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Abstract
Provided are a hot-pressed member which has excellent hot-press formability, spot weldability, and coating adhesion and in which corrosion-induced penetration of hydrogen into the steel can be inhibited, and a process for producing the member. The hot-pressed member comprises a steel plate constituting the member, an Ni diffusion region formed on the surface layer of the steel plate in an amount of 10-90,000 mg/m2 in terms of deposited Ni amount, and an inorganic compound disposed on the Ni diffusion region.
Description
本発明は、加熱された鋼板をプレス加工して製造する熱間プレス部材、特に、自動車の足廻り部や車体構造部などで用いられる熱間プレス部材およびその製造方法に関する。
The present invention relates to a hot press member manufactured by pressing a heated steel sheet, and more particularly, to a hot press member used in an undercarriage part or a vehicle body structure part of an automobile and a method for manufacturing the same.
従来から、自動車の足廻り部材や車体構造部材などの多くは、所定の強度を有する鋼板をプレス加工して製造されている。近年、地球環境の保全という観点から、自動車車体の軽量化が熱望され、使用する鋼板を高強度化して、その板厚を低減する努力が続けられている。しかし、鋼板の高強度化に伴ってそのプレス加工性が低下するため、鋼板を所望の部材形状に加工することが困難になる場合が多くなっている。
Conventionally, many undercarriage members and body structure members of automobiles are manufactured by pressing a steel plate having a predetermined strength. In recent years, from the viewpoint of the preservation of the global environment, there has been a strong desire to reduce the weight of automobile bodies, and efforts have been made to increase the strength of steel sheets to be used and to reduce their thickness. However, as the strength of the steel plate increases, the press workability decreases, and it is often difficult to process the steel plate into a desired member shape.
そのため、特許文献１には、ダイとパンチからなる金型を用いて加熱された鋼板を加工すると同時に急冷することにより加工の容易化と高強度化の両立を可能にした熱間プレスと呼ばれる加工技術が提案されている。しかし、この熱間プレスでは、熱間プレス前に鋼板を９５０℃前後の高い温度に加熱するため、鋼板表面にはスケール（Ｆｅ酸化物）が生成し、そのスケールが熱間プレス時に剥離して、金型を損傷させる、または熱間プレス後の部材表面を損傷させるという問題がある。また、部材表面に残ったスケールは、外観不良や、塗膜密着性（塗装性）の低下や、耐食性の低下の原因にもなる。このため、通常は酸洗やショットブラストなどの処理を行って部材表面のスケールは除去されるが、これは製造工程を複雑にし、生産性の低下を招く。
For this reason, Patent Document 1 discloses a process called a hot press that enables both easy processing and high strength by simultaneously processing a heated steel sheet using a die and a punch and simultaneously cooling it. Technology has been proposed. However, in this hot press, the steel plate is heated to a high temperature of around 950 ° C. before hot pressing, so scale (Fe oxide) is generated on the steel plate surface, and the scale peels off during hot pressing. There is a problem that the mold is damaged or the surface of the member after hot pressing is damaged. In addition, the scale remaining on the surface of the member may cause poor appearance, reduced coating film adhesion (paintability), and corrosion resistance. For this reason, the scale on the surface of the member is usually removed by processing such as pickling or shot blasting, but this complicates the manufacturing process and causes a decrease in productivity.
このようなことから、熱間プレス前の加熱時にスケールの生成が抑制でき、耐食性や塗装密着性に優れた熱間プレス部材が要望され、表面にめっき層などの被膜を設けた熱間プレス用鋼板やそれを用いた熱間プレス方法が提案されている。例えば、特許文献２には、ＡｌまたはＡｌ合金が被覆された被覆鋼板が開示されている。この被覆鋼板を用いることにより、熱間プレス前の加熱時に脱炭や酸化が防止され、極めて高い強度と優れた耐食性を有する熱間プレス部材の得られることが示されている。また、特許文献３には、ＺｎまたはＺｎベース合金を被覆した鋼板を熱間プレスする際に、熱間プレス前の加熱時に、腐食や脱炭を防止するとともに、潤滑機能を有するＺｎ−Ｆｅベースの化合物やＺｎ−Ｆｅ−Ａｌベースの化合物などの合金化合物を鋼板表面に生成させる熱間プレス方法が開示されている。この方法で製造された部材、特に、Ｚｎ−５０~５５質量％Ａｌの被覆された鋼板を用いた熱間プレス部材では、Ｚｎ−Ａｌ−Ｆｅ合金層が形成され、優れた腐食防止効果の得られることが示されている。さらに、特許文献４には、ＡｌもしくはＺｎを主体とするめっきを施した鋼板を用い、水素濃度６体積％以下、露点１０℃以下の雰囲気中でＡｃ３変態点以上１１００℃以下の加熱温度に加熱後熱間プレスする耐水素脆性に優れた熱間プレス方法が開示されている。この熱間プレス方法では、加熱時に雰囲気中の水素や水蒸気の量を低減して鋼中に侵入する水素量を低減し、１０００ＭＰａを超える高強度化に伴う水素脆化の回避が図られている。
For this reason, there is a need for a hot press member that can suppress the formation of scale during heating before hot pressing, and has excellent corrosion resistance and paint adhesion, and for hot presses that have a coating such as a plating layer on the surface. Steel plates and hot pressing methods using the same have been proposed. For example, Patent Document 2 discloses a coated steel sheet coated with Al or an Al alloy. It has been shown that by using this coated steel sheet, decarburization and oxidation are prevented during heating before hot pressing, and a hot pressed member having extremely high strength and excellent corrosion resistance can be obtained. Patent Document 3 discloses a Zn-Fe base that prevents corrosion and decarburization and has a lubrication function during hot pressing before hot pressing a steel sheet coated with Zn or a Zn base alloy. A hot pressing method in which an alloy compound such as the above compound or a Zn-Fe-Al-based compound is generated on the surface of a steel sheet is disclosed. In a member manufactured by this method, in particular, a hot press member using a steel sheet coated with Zn-50 to 55 mass% Al, a Zn-Al-Fe alloy layer is formed, and an excellent corrosion prevention effect is obtained. It has been shown that Further, Patent Document 4 uses a steel plate mainly composed of Al or Zn, and is heated to an Ac 3 transformation point or higher and 1100 ° C. or lower in an atmosphere having a hydrogen concentration of 6% by volume or less and a dew point of 10 ° C. or less. A hot pressing method excellent in hydrogen embrittlement resistance by hot pressing after heating is disclosed. In this hot pressing method, the amount of hydrogen and water vapor in the atmosphere during heating is reduced to reduce the amount of hydrogen penetrating into the steel, thereby avoiding hydrogen embrittlement associated with high strength exceeding 1000 MPa. .
しかしながら、上記の特許文献２~４に記載の技術では、以下のような問題がある。すなわち、熱間プレス時に型かじり（鋼板表面から剥離したスケールが金型を損傷させることではなく、金属面同士の接触により、鋼板と金型とがくっついてしまう現象をいう。）が発生しやすく、熱間プレス性に劣る。ＡｌまたはＡｌ合金が被覆された鋼板を用いると、スポット溶接時の溶接可能電流範囲が狭く、スポット溶接性に劣る。ＺｎまたはＺｎ合金が被覆された鋼板を用いると、熱間プレス前の加熱時にＺｎが揮発して酸化され、鋼板表面に析出して熱間プレス部材の塗料密着性を低下させる。熱間プレス前の加熱時における水素侵入よりむしろ使用環境中の腐食に伴う水素侵入により水素脆化を引き起こす。
However, the techniques described in Patent Documents 2 to 4 have the following problems. That is, die galling during hot pressing (a phenomenon in which the scale peeled off from the steel sheet surface does not damage the metal mold, but refers to a phenomenon in which the steel sheet and the metal mold stick together due to contact between metal surfaces). Inferior to hot pressability. When a steel plate coated with Al or an Al alloy is used, the weldable current range during spot welding is narrow and spot weldability is poor. When a steel sheet coated with Zn or a Zn alloy is used, Zn is volatilized and oxidized during heating before hot pressing, and is deposited on the surface of the steel sheet to reduce the paint adhesion of the hot pressed member. Rather than hydrogen penetration during heating before hot pressing, hydrogen embrittlement is caused by hydrogen penetration due to corrosion in the use environment.
本発明は、優れた熱間プレス性、スポット溶接性、塗料密着性を有するとともに、腐食に伴う鋼中への水素侵入を抑制可能な熱間プレス部材およびその製造方法を提供することを目的とする。
An object of the present invention is to provide a hot press member having excellent hot press properties, spot weldability, paint adhesion, and capable of suppressing hydrogen intrusion into steel due to corrosion, and a method for producing the same. To do.
本発明者らは、上記の目的とする熱間プレス部材について鋭意検討を行った結果、以下の知見を得た。
As a result of intensive studies on the above-mentioned hot pressed member, the present inventors have obtained the following knowledge.
ｉ）素材の鋼板として、ＮｉあるいはＮｉ合金めっき鋼板を用いることにより、優れたスポット溶接性や塗装密着性が得られる。
I) Excellent spot weldability and paint adhesion can be obtained by using a Ni or Ni alloy plated steel sheet as the material steel sheet.
ｉｉ）ＮｉあるいはＮｉ合金めっき鋼板上に無機化合物を存在させると、優れた熱間プレス性が得られる。
Ii) When an inorganic compound is present on the Ni or Ni alloy plated steel sheet, excellent hot pressability can be obtained.
ｉｉｉ）熱間プレス部材を構成する鋼板の表層部にＮｉ拡散領域を形成させると、腐食に伴う鋼中への水素侵入を効果的に抑制できる。
Iii) When the Ni diffusion region is formed in the surface layer portion of the steel plate constituting the hot press member, hydrogen intrusion into the steel due to corrosion can be effectively suppressed.
本発明は、このような知見に基づきなされたもので、部材を構成する鋼板の表層部に、Ｎｉ付着量が１０~９００００ｍｇ／ｍ２のＮｉ拡散領域を有し、前記Ｎｉ拡散領域上に無機化合物を有することを特徴とする熱間プレス部材を提供する。
The present invention has been made on the basis of such knowledge, and has a Ni diffusion region with a Ni adhesion amount of 10 to 90000 mg / m 2 on the surface layer portion of the steel sheet constituting the member, and the inorganic diffusion region is formed on the Ni diffusion region. A hot press member comprising a compound is provided.
本発明の熱間プレス部材の表面に存在する無機化合物としては、融点が５００~１０００℃で、アルカリ可溶成分を含む無機化合物が好ましい。
As the inorganic compound present on the surface of the hot press member of the present invention, an inorganic compound having a melting point of 500 to 1000 ° C. and containing an alkali-soluble component is preferable.
本発明の熱間プレス部材は、鋼板の表面に、順に、Ｎｉ付着量が１０~９００００ｍｇ／ｍ２のＮｉを含むめっき層と、無機化合物とを有する鋼板を、Ａｃ３変態点~１２００℃の温度範囲に加熱後熱間プレスする方法によって製造できる。
The hot-pressed member of the present invention comprises a steel plate having a nickel-containing plating layer containing 10 to 90,000 mg / m 2 and an inorganic compound in order on the surface of the steel plate, with an Ac 3 transformation point of 1200 ° C. It can be manufactured by a method of hot pressing after heating to a temperature range.
無機化合物としては、融点が５００~１０００℃で、アルカリ可溶成分を含む無機化合物を用いることが好ましい。また、鋼板としては、質量％で、Ｃ：０．１５~０．５％、Ｓｉ：０．０５~２．０％、Ｍｎ：０．５~３％、Ｐ：０．１％以下、Ｓ：０．０５％以下、Ａｌ：０．１％以下、Ｎ：０．０１％以下を含有し、残部がＦｅおよび不可避的不純物からなる成分組成を有する鋼板や、さらに、質量％で、Ｃｒ：０．０１~１％、Ｔｉ：０．２％以下、Ｂ：０．０００５~０．０８％のうちから選ばれた少なくとも１種や、Ｓｂ：０．００３~０．０３％を、個別にあるいは同時に含有する鋼板を用いることが好ましい。
As the inorganic compound, an inorganic compound having a melting point of 500 to 1000 ° C. and containing an alkali-soluble component is preferably used. Moreover, as a steel plate, C: 0.15-0.5%, Si: 0.05-2.0%, Mn: 0.5-3%, P: 0.1% or less, S in mass%. : 0.05% or less, Al: 0.1% or less, N: 0.01% or less, the balance being a steel plate having a component composition consisting of Fe and inevitable impurities, and further by mass%, Cr: At least one selected from 0.01 to 1%, Ti: 0.2% or less, B: 0.0005 to 0.08%, and Sb: 0.003 to 0.03% individually. Or it is preferable to use the steel plate contained simultaneously.
本発明により、優れた熱間プレス性、スポット溶接性、塗料密着性を有するとともに、腐食に伴う鋼中への水素侵入を抑制可能な熱間プレス部材を製造できるようになった。本発明の熱間プレス部材は、９８０ＭＰａ以上の強度を有する自動車の足廻り部材や車体構造部材に好適である。
According to the present invention, it has become possible to produce a hot press member that has excellent hot press properties, spot weldability, paint adhesion, and can suppress hydrogen intrusion into steel due to corrosion. The hot press member of the present invention is suitable for an automobile suspension member and a vehicle body structure member having a strength of 980 MPa or more.
１）熱間プレス部材
本発明の熱間プレス部材では、部材を構成する鋼板の表層部にＮｉ拡散領域を存在させて腐食に伴う鋼中への水素侵入を抑制している。この理由は必ずしも明確ではないが、次のように考えられる。すなわち、腐食による鋼板内部への水素侵入は湿潤環境下におけるＦｅ錆の酸化還元反応に関係しており、水素侵入を抑制するにはＦｅ錆が変化しにくい安定な錆であることが必要である。Ｆｅ錆の安定化にはＮｉ添加が有効であり、Ｎｉ拡散領域の存在が腐食に伴う鋼中への水素侵入を抑制することになる。なお、ここでいうＮｉ拡散領域とは、熱間プレス前の加熱時にめっき層からＮｉが鋼中に拡散している領域、あるいはＮｉに加えてめっき層に含まれるＣｏ、Ｚｎ、Ｃｒ、Ｍｎ、Ｃｕ、Ｍｏなどの金属元素が拡散している領域をいう。 1) Hot pressed member In the hot pressed member of the present invention, a Ni diffusion region is present in the surface layer portion of the steel plate constituting the member to suppress hydrogen intrusion into the steel due to corrosion. The reason for this is not necessarily clear, but can be considered as follows. That is, the hydrogen intrusion into the steel plate due to corrosion is related to the oxidation-reduction reaction of Fe rust in a wet environment, and it is necessary that the Fe rust is a stable rust that hardly changes to suppress the hydrogen intrusion. . Ni is effective for stabilizing Fe rust, and the presence of the Ni diffusion region suppresses hydrogen intrusion into the steel due to corrosion. The Ni diffusion region referred to here is a region where Ni is diffused in the steel from the plating layer during heating before hot pressing, or Co, Zn, Cr, Mn contained in the plating layer in addition to Ni, A region where metal elements such as Cu and Mo are diffused.
本発明の熱間プレス部材では、部材を構成する鋼板の表層部にＮｉ拡散領域を存在させて腐食に伴う鋼中への水素侵入を抑制している。この理由は必ずしも明確ではないが、次のように考えられる。すなわち、腐食による鋼板内部への水素侵入は湿潤環境下におけるＦｅ錆の酸化還元反応に関係しており、水素侵入を抑制するにはＦｅ錆が変化しにくい安定な錆であることが必要である。Ｆｅ錆の安定化にはＮｉ添加が有効であり、Ｎｉ拡散領域の存在が腐食に伴う鋼中への水素侵入を抑制することになる。なお、ここでいうＮｉ拡散領域とは、熱間プレス前の加熱時にめっき層からＮｉが鋼中に拡散している領域、あるいはＮｉに加えてめっき層に含まれるＣｏ、Ｚｎ、Ｃｒ、Ｍｎ、Ｃｕ、Ｍｏなどの金属元素が拡散している領域をいう。 1) Hot pressed member In the hot pressed member of the present invention, a Ni diffusion region is present in the surface layer portion of the steel plate constituting the member to suppress hydrogen intrusion into the steel due to corrosion. The reason for this is not necessarily clear, but can be considered as follows. That is, the hydrogen intrusion into the steel plate due to corrosion is related to the oxidation-reduction reaction of Fe rust in a wet environment, and it is necessary that the Fe rust is a stable rust that hardly changes to suppress the hydrogen intrusion. . Ni is effective for stabilizing Fe rust, and the presence of the Ni diffusion region suppresses hydrogen intrusion into the steel due to corrosion. The Ni diffusion region referred to here is a region where Ni is diffused in the steel from the plating layer during heating before hot pressing, or Co, Zn, Cr, Mn contained in the plating layer in addition to Ni, A region where metal elements such as Cu and Mo are diffused.
しかし、こうした水素侵入の抑制を効果的に図るには、Ｎｉ拡散領域における片面当たりのＮｉ付着量を１０ｍｇ／ｍ２以上、好ましくは５０ｍｇ／ｍ２以上、より好ましくは１００ｍｇ／ｍ２以上とする必要がある。一方、片面当たりのＮｉ付着量が９００００ｍｇ／ｍ２を超えると、その効果は飽和し、コスト増を招くので、Ｎｉ付着量は９００００ｍｇ／ｍ２以下、好ましくは１００００ｍｇ／ｍ２以下、より好ましくは５０００ｍｇ／ｍ２以下とする必要がある。また、Ｎｉ拡散領域は、部材を構成する鋼板の表面から深さ方向に０．１~１００μｍにわたって存在することが好ましく、１~５０μｍにわたって存在することがより好ましく、３~１０μｍにわたって存在することがさらに好ましい。
However, in order to effectively suppress such hydrogen intrusion, the Ni adhesion amount per side in the Ni diffusion region is set to 10 mg / m 2 or more, preferably 50 mg / m 2 or more, more preferably 100 mg / m 2 or more. There is a need. On the other hand, if the Ni adhesion amount per side exceeds 90000 mg / m 2 , the effect is saturated and the cost is increased, so the Ni adhesion amount is 90000 mg / m 2 or less, preferably 10000 mg / m 2 or less, more preferably It is necessary to make it 5000 mg / m 2 or less. Further, the Ni diffusion region is preferably present in the depth direction from 0.1 to 100 μm from the surface of the steel sheet constituting the member, more preferably present in the range of 1 to 50 μm, and present in the range of 3 to 10 μm. Further preferred.
Ｎｉ付着量は蛍光Ｘ線分析または湿式分析によって求めることができる。Ｎｉ拡散領域の深さは、ＥＰＭＡ（Ｅｌｅｃｔｒｏｎ Ｐｒｏｂｅ Ｍｉｃｒｏ Ａｎａｌｙｚｅｒ）による厚み方向断面の分析やＧＤＳ（Ｇｌｏｗ Ｄｉｓｃｈａｒｇｅ Ｓｐｅｃｔｒｏｓｃｏｐｙ）による深さ方向の分析によって求めることができる。
The Ni adhesion amount can be determined by fluorescent X-ray analysis or wet analysis. The depth of the Ni diffusion region can be obtained by analyzing the cross section in the thickness direction using EPMA (Electron Probe Micro Analyzer) or analyzing the depth direction using GDS (Glow Discharge Spectroscopy).
本発明の熱間プレス部材は、表面に、順に、Ｎｉを含むめっき層と無機化合物とを有する鋼板を熱間プレスして製造される。そのため、熱間プレス後の部材表面にはこの無機化合物が残存する。しかし、この無機化合物は、その後、熱間プレス部材に塗装下地処理としてリン酸塩処理や酸化ジルコニウム処理などの化成処理を施す時、特にアルカリ脱脂時に除去されるので、塗料密着性などを損なうことはない。
The hot-pressed member of the present invention is manufactured by hot-pressing a steel plate having a plated layer containing Ni and an inorganic compound in order on the surface. Therefore, this inorganic compound remains on the surface of the member after hot pressing. However, this inorganic compound is then removed when the hot press member is subjected to chemical conversion treatment such as phosphate treatment or zirconium oxide treatment as a coating base treatment, particularly during alkaline degreasing. There is no.
２）製造方法
本発明の熱間プレス部材は、鋼板の表面に、順に、片面当たりのＮｉ付着量が１０~９００００ｍｇ／ｍ２のＮｉを含むめっき層と、無機化合物とを有する鋼板を、Ａｃ３変態点~１２００℃の温度範囲に加熱後熱間プレスする方法によって製造できる。 2) Manufacturing method The hot-pressed member of the present invention comprises a steel plate having a nickel-plated layer containing 10 to 90,000 mg / m 2 of Ni and an inorganic compound in order on the surface of the steel plate. It can be produced by a method of hot pressing after heating to a temperature range of 3 transformation points to 1200 ° C.
本発明の熱間プレス部材は、鋼板の表面に、順に、片面当たりのＮｉ付着量が１０~９００００ｍｇ／ｍ２のＮｉを含むめっき層と、無機化合物とを有する鋼板を、Ａｃ３変態点~１２００℃の温度範囲に加熱後熱間プレスする方法によって製造できる。 2) Manufacturing method The hot-pressed member of the present invention comprises a steel plate having a nickel-plated layer containing 10 to 90,000 mg / m 2 of Ni and an inorganic compound in order on the surface of the steel plate. It can be produced by a method of hot pressing after heating to a temperature range of 3 transformation points to 1200 ° C.
上記のようなＮｉ付着量が１０~９００００ｍｇ／ｍ２のＮｉを含むめっき層を有する鋼板をＡｃ３変態点~１２００℃の温度範囲に加熱することにより、めっき層のＮｉが鋼板内へ拡散し、部材の表層部にＮｉ付着量が１０~９００００ｍｇ／ｍ２のＮｉ拡散領域が形成され、腐食に伴う鋼中への水素侵入が抑制される。
By heating a steel sheet having a plating layer containing Ni having an Ni adhesion amount of 10 to 90000 mg / m 2 as described above to a temperature range of Ac 3 transformation point to 1200 ° C., Ni in the plating layer diffuses into the steel sheet. In addition, a Ni diffusion region having a Ni adhesion amount of 10 to 90000 mg / m 2 is formed on the surface layer of the member, and hydrogen intrusion into the steel due to corrosion is suppressed.
また、Ａｌや低沸点のＺｎではなく、高融点、高沸点のＮｉを含むめっき層、すなわちＮｉあるいはＮｉ合金のめっき層を有する鋼板を用いているため、スケールの発生もなく、優れたスポット溶接性や塗装密着性が得られる。
In addition, because it uses a steel plate having a high melting point and high boiling point Ni instead of Al or low boiling point Zn, that is, a plating layer of Ni or Ni alloy, there is no generation of scale and excellent spot welding. Properties and paint adhesion.
こうしたＮｉを含むめっき層は、電気めっき法などで形成できる。
Such a plating layer containing Ni can be formed by an electroplating method or the like.
Ｎｉを含むめっき層上に無機化合物を存在させ、熱間プレス前の加熱時にこの無機化合物を溶融させれば、流体潤滑効果により熱間プレス時の摺動性を著しく向上させることができるので、型かじりは発生せず、優れた熱間プレス性が得られる。このため、無機化合物としては、融点が５００~１０００℃の無機化合物を用いることが好ましい。無機化合物の融点を５００℃以上とすると、熱間プレス前の加熱時の昇温過程の早い段階で無機化合物が溶融することがないので、溶融した無機化合物が加熱炉に付着することがなく、溶融状態の無機化合物の量が減少せず、熱間プレス時の摺動性が向上する。一方、無機化合物の融点を１０００℃以下とすると、加熱時に無機化合物が溶融しないこと、または溶融が不十分であることがなく、熱間プレス時の摺動性が向上する。なお、融点が５００~９００℃の無機化合物を用いることがより好ましい。
If the inorganic compound is present on the plating layer containing Ni and the inorganic compound is melted during heating before hot pressing, the sliding property during hot pressing can be remarkably improved by the fluid lubrication effect. No mold galling occurs and excellent hot pressability is obtained. For this reason, it is preferable to use an inorganic compound having a melting point of 500 to 1000 ° C. as the inorganic compound. When the melting point of the inorganic compound is 500 ° C. or higher, since the inorganic compound does not melt at an early stage of the temperature rising process during heating before hot pressing, the molten inorganic compound does not adhere to the heating furnace, The amount of the inorganic compound in the molten state is not reduced, and the slidability during hot pressing is improved. On the other hand, when the melting point of the inorganic compound is 1000 ° C. or lower, the inorganic compound does not melt during heating, or the melting is not insufficient, and the slidability during hot pressing is improved. It is more preferable to use an inorganic compound having a melting point of 500 to 900 ° C.
無機化合物としては、また、化成処理のアルカリ脱脂時に容易に除去されるように、アルカリ可溶成分を含む無機化合物を用いることが好ましい。
As the inorganic compound, it is preferable to use an inorganic compound containing an alkali-soluble component so that it can be easily removed during alkali degreasing in chemical conversion treatment.
無機化合物の片面当りの付着量は、１ｍｇ／ｍ２以上とすると、溶融状態の無機化合物の量が少なすぎることがなく、熱間プレス時の摺動性が十分となり、５０００ｍｇ／ｍ２以下とすると、経済的に摺動性向上の効果が得られるばかりでなく、熱間プレス後に多くの無機化合物が残存することがないため、化成処理や塗装処理の不均一を招くことがなく、塗装密着性を向上させるので、１~５０００ｍｇ／ｍ２とすることが好ましい。ここで、無機化合物の付着量は、例えば、次に示す方法により測定できる。すなわち、無機化合物を塗布・乾燥する前後の重量変化から測定する方法、無機化合物のみを溶解可能な溶液により無機化合物を溶解除去し重量変化から測定する方法、無機化合物が付着しためっき層ごと酸に溶解してその溶解液を原子吸光分析またはＩＣＰ（Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌａｓｍａ）分析などにより分析してマーカーとなる元素の量を定量し無機化合物量に換算する方法などである。
When the amount of the inorganic compound deposited on one side is 1 mg / m 2 or more, the amount of the inorganic compound in the molten state is not too small, and the slidability during hot pressing is sufficient, and is 5000 mg / m 2 or less. As a result, not only the effect of improving the slidability can be obtained economically, but also many inorganic compounds do not remain after hot pressing, so there is no inhomogeneity of chemical conversion treatment and coating treatment, and coating adhesion From the standpoint of improving the properties, it is preferably 1 to 5000 mg / m 2 . Here, the adhesion amount of the inorganic compound can be measured by, for example, the following method. That is, a method of measuring from a weight change before and after applying and drying an inorganic compound, a method of measuring and measuring a weight change by dissolving and removing the inorganic compound with a solution capable of dissolving only the inorganic compound, and the plating layer on which the inorganic compound is adhered to the acid. For example, the dissolved solution is analyzed by atomic absorption analysis or ICP (Inductively Coupled Plasma) analysis, and the amount of an element serving as a marker is quantified and converted to an inorganic compound amount.
無機化合物をＮｉを含むめっき層上に固定するために、無機化合物に有機化合物を共存させることも可能である。ただし、熱間での摺動性を向上させる効果を有するのは無機化合物であるため、無機化合物と有機化合物を共存させる場合は、無機化合物の比率を５０質量％以上とすることが好ましい。なお、有機化合物を共存させても、熱間プレス前の加熱は９００℃前後の高温で行われるため、有機化合物は大気中の酸素と反応して二酸化酸素や水となり消失するため、摺動性やめっき層には何ら影響を与えることはない。
In order to fix the inorganic compound on the plating layer containing Ni, it is also possible to coexist the organic compound with the inorganic compound. However, since it is an inorganic compound that has the effect of improving hot slidability, when the inorganic compound and the organic compound coexist, the ratio of the inorganic compound is preferably 50% by mass or more. Even if an organic compound coexists, since heating before hot pressing is performed at a high temperature of about 900 ° C., the organic compound reacts with oxygen in the atmosphere and disappears as oxygen dioxide and water, so that sliding property is eliminated. There is no effect on the plating layer.
このような無機化合物として、例えば、融点が７４１℃、沸点が１５７５℃の四ホウ酸ナトリウム十水和物（硼砂）が好ましい。ただし、熱間プレス前の加熱条件によっては、この四ホウ酸ナトリウム十水和物が３５０~４００℃で無水物に変化し、さらに昇温を続けると８７８℃で溶融する場合がある。したがって、この四ホウ酸ナトリウム十水和物の使用は、熱間プレス前の加熱温度が８７８℃以上の場合に好適である。この他、本発明に適用できる無機化合物としては、硫酸アンモニウム、硝酸ストロンチウム、酸化アンチモン（ＩＩＩ）、水酸化カルシウム、炭酸ナトリウム、フッ化ナトリウムなどを挙げることができる。
As such an inorganic compound, for example, sodium tetraborate decahydrate (borax) having a melting point of 741 ° C. and a boiling point of 1575 ° C. is preferable. However, depending on the heating conditions before hot pressing, this sodium tetraborate decahydrate may change to an anhydride at 350 to 400 ° C and melt at 878 ° C if the temperature is further increased. Therefore, the use of this sodium tetraborate decahydrate is suitable when the heating temperature before hot pressing is 878 ° C. or higher. In addition, examples of inorganic compounds applicable to the present invention include ammonium sulfate, strontium nitrate, antimony (III) oxide, calcium hydroxide, sodium carbonate, sodium fluoride, and the like.
無機化合物をＮｉを含むめっき層上に存在させるには、公知の方法が適用可能である。例えば、無機化合物を含む水溶液などの溶液をめっき層表面に塗布し、乾燥することにより水分や溶媒を蒸発させて、無機化合物をめっき層上に存在させる方法を挙げられる。塗布方法としては、バーコーター法、ハケ塗り法、ロールコーター法、浸漬法、スプレー法を挙げることができる。
In order for the inorganic compound to be present on the plating layer containing Ni, a known method can be applied. For example, there is a method in which a solution such as an aqueous solution containing an inorganic compound is applied to the surface of the plating layer and dried to evaporate moisture and solvent so that the inorganic compound exists on the plating layer. Examples of the coating method include a bar coater method, a brush coating method, a roll coater method, a dipping method, and a spray method.
本発明の熱間プレス部材の製造方法では、熱間プレス前に鋼板温度がＡｃ３変態点~１２００℃になるように加熱する必要があるが、加熱方法としては、電気炉やガス炉などによる加熱、火炎加熱、通電加熱、高周波加熱、誘導加熱などを適用できる。
In the method for producing a hot-pressed member of the present invention, it is necessary to heat the steel plate so that the steel plate temperature becomes Ac 3 transformation point to 1200 ° C. before hot pressing. Heating, flame heating, electric heating, high frequency heating, induction heating, etc. can be applied.
本発明である熱間プレス部材用の鋼板としては、熱間プレス後に９８０ＭＰａ以上の強度の得られる焼入れ性に富む鋼板、例えば、質量％で、Ｃ：０．１５~０．５％、Ｓｉ：０．０５~２．０％、Ｍｎ：０．５~３％、Ｐ：０．１％以下、Ｓ：０．０５％以下、Ａｌ：０．１％以下、Ｎ：０．０１％以下を含有し、残部がＦｅおよび不可避的不純物からなる成分組成を有する鋼板や、さらに、質量％で、Ｃｒ：０．０１~１％、Ｔｉ：０．２％以下、Ｂ：０．０００５~０．０８％のうちから選ばれた少なくとも１種や、Ｓｂ：０．００３~０．０３％を、個別にあるいは同時に含有する鋼板を用いることが好ましい。
As the steel sheet for a hot press member according to the present invention, a steel sheet with high hardenability obtained after hot pressing with a strength of 980 MPa or more, for example, in mass%, C: 0.15 to 0.5%, Si: 0.05 to 2.0%, Mn: 0.5 to 3%, P: 0.1% or less, S: 0.05% or less, Al: 0.1% or less, N: 0.01% or less And a steel plate having a composition comprising Fe and inevitable impurities as the balance, and further, in mass%, Cr: 0.01 to 1%, Ti: 0.2% or less, B: 0.0005 to 0. It is preferable to use a steel plate containing at least one selected from 08% or Sb: 0.003 to 0.03% individually or simultaneously.
各成分元素の限定理由を、以下に説明する。ここで、成分の含有量を表す「％」は、特に断らない限り「質量％」を意味する。
The reasons for limitation of each component element will be described below. Here, “%” representing the content of a component means “% by mass” unless otherwise specified.
Ｃ：０．１５~０．５％
Ｃは、鋼の強度を向上させる元素であり、熱間プレス部材のＴＳを９８０ＭＰａ以上にするには、その量を０．１５％以上とする必要がある。一方、Ｃ量が０．５％を超えると、素材の鋼板のブランキング加工性が著しく低下する。したがって、Ｃ量は０．１５~０．５％とする。 C: 0.15-0.5%
C is an element that improves the strength of steel. In order to increase the TS of the hot pressed member to 980 MPa or more, the amount needs to be 0.15% or more. On the other hand, when the amount of C exceeds 0.5%, the blanking workability of the raw steel plate is significantly lowered. Therefore, the C content is 0.15 to 0.5%.
Ｃは、鋼の強度を向上させる元素であり、熱間プレス部材のＴＳを９８０ＭＰａ以上にするには、その量を０．１５％以上とする必要がある。一方、Ｃ量が０．５％を超えると、素材の鋼板のブランキング加工性が著しく低下する。したがって、Ｃ量は０．１５~０．５％とする。 C: 0.15-0.5%
C is an element that improves the strength of steel. In order to increase the TS of the hot pressed member to 980 MPa or more, the amount needs to be 0.15% or more. On the other hand, when the amount of C exceeds 0.5%, the blanking workability of the raw steel plate is significantly lowered. Therefore, the C content is 0.15 to 0.5%.
Ｓｉ：０．０５~２．０％
Ｓｉは、Ｃ同様、鋼の強度を向上させる元素であり、熱間プレス部材のＴＳを９８０ＭＰａ以上にするには、その量を０．０５％以上とする必要がある。一方、Ｓｉ量が２．０％を超えると、熱間圧延時に赤スケールと呼ばれる表面欠陥の発生が著しく増大するとともに、圧延荷重が増大したり、熱延鋼板の延性の劣化を招く。さらに、Ｓｉ量が２．０％を超えると、ＺｎやＡｌを主体としためっき皮膜を鋼板表面に形成するめっき処理を施す際に、めっき処理性に悪影響を及ぼす場合がある。したがって、Ｓｉ量は０．０５~２．０％とする。 Si: 0.05 to 2.0%
Si, like C, is an element that improves the strength of steel. In order to increase the TS of the hot pressed member to 980 MPa or more, the amount needs to be 0.05% or more. On the other hand, when the amount of Si exceeds 2.0%, the occurrence of surface defects called red scales during hot rolling is remarkably increased, the rolling load is increased, and the ductility of the hot-rolled steel sheet is deteriorated. Furthermore, if the Si content exceeds 2.0%, the plating processability may be adversely affected when a plating process for forming a plating film mainly composed of Zn or Al on the steel sheet surface is performed. Therefore, the Si content is 0.05 to 2.0%.
Ｓｉは、Ｃ同様、鋼の強度を向上させる元素であり、熱間プレス部材のＴＳを９８０ＭＰａ以上にするには、その量を０．０５％以上とする必要がある。一方、Ｓｉ量が２．０％を超えると、熱間圧延時に赤スケールと呼ばれる表面欠陥の発生が著しく増大するとともに、圧延荷重が増大したり、熱延鋼板の延性の劣化を招く。さらに、Ｓｉ量が２．０％を超えると、ＺｎやＡｌを主体としためっき皮膜を鋼板表面に形成するめっき処理を施す際に、めっき処理性に悪影響を及ぼす場合がある。したがって、Ｓｉ量は０．０５~２．０％とする。 Si: 0.05 to 2.0%
Si, like C, is an element that improves the strength of steel. In order to increase the TS of the hot pressed member to 980 MPa or more, the amount needs to be 0.05% or more. On the other hand, when the amount of Si exceeds 2.0%, the occurrence of surface defects called red scales during hot rolling is remarkably increased, the rolling load is increased, and the ductility of the hot-rolled steel sheet is deteriorated. Furthermore, if the Si content exceeds 2.0%, the plating processability may be adversely affected when a plating process for forming a plating film mainly composed of Zn or Al on the steel sheet surface is performed. Therefore, the Si content is 0.05 to 2.0%.
Ｍｎ：０．５~３％
Ｍｎは、フェライト変態を抑制して焼入れ性を向上させるのに効果的な元素であり、また、Ａｃ３変態点を低下させるので、熱間プレス前の加熱温度を低下するにも有効な元素である。このような効果の発現のためには、その量を０．５％以上とする必要がある。一方、Ｍｎ量が３％を超えると、偏析して素材の鋼板および熱間プレス部材の特性の均一性が低下する。したがって、Ｍｎ量は０．５~３％とする。 Mn: 0.5 to 3%
Mn is an element effective for suppressing the ferrite transformation and improving the hardenability, and also reduces the Ac 3 transformation point, so that it is an effective element for lowering the heating temperature before hot pressing. is there. In order to exhibit such an effect, the amount needs to be 0.5% or more. On the other hand, when the amount of Mn exceeds 3%, it segregates and the uniformity of the characteristics of the raw steel plate and the hot press member decreases. Therefore, the amount of Mn is 0.5 to 3%.
Ｍｎは、フェライト変態を抑制して焼入れ性を向上させるのに効果的な元素であり、また、Ａｃ３変態点を低下させるので、熱間プレス前の加熱温度を低下するにも有効な元素である。このような効果の発現のためには、その量を０．５％以上とする必要がある。一方、Ｍｎ量が３％を超えると、偏析して素材の鋼板および熱間プレス部材の特性の均一性が低下する。したがって、Ｍｎ量は０．５~３％とする。 Mn: 0.5 to 3%
Mn is an element effective for suppressing the ferrite transformation and improving the hardenability, and also reduces the Ac 3 transformation point, so that it is an effective element for lowering the heating temperature before hot pressing. is there. In order to exhibit such an effect, the amount needs to be 0.5% or more. On the other hand, when the amount of Mn exceeds 3%, it segregates and the uniformity of the characteristics of the raw steel plate and the hot press member decreases. Therefore, the amount of Mn is 0.5 to 3%.
Ｐ：０．１％以下
Ｐ量が０．１％を超えると、偏析して素材の鋼板および熱間プレス部材の特性の均一性が低下するとともに、靭性も著しく低下する。したがって、Ｐ量は０．１％以下とする。 P: 0.1% or less When the amount of P exceeds 0.1%, segregation occurs and the uniformity of the characteristics of the steel plate and the hot pressed member is reduced, and the toughness is also significantly reduced. Therefore, the P content is 0.1% or less.
Ｐ量が０．１％を超えると、偏析して素材の鋼板および熱間プレス部材の特性の均一性が低下するとともに、靭性も著しく低下する。したがって、Ｐ量は０．１％以下とする。 P: 0.1% or less When the amount of P exceeds 0.1%, segregation occurs and the uniformity of the characteristics of the steel plate and the hot pressed member is reduced, and the toughness is also significantly reduced. Therefore, the P content is 0.1% or less.
Ｓ：０．０５％以下
Ｓ量が０．０５％を超えると、熱間プレス部材の靭性が低下する。したがって、Ｓ量は０．０５％以下とする。 S: 0.05% or less When the amount of S exceeds 0.05%, the toughness of the hot pressed member is lowered. Therefore, the S amount is 0.05% or less.
Ｓ量が０．０５％を超えると、熱間プレス部材の靭性が低下する。したがって、Ｓ量は０．０５％以下とする。 S: 0.05% or less When the amount of S exceeds 0.05%, the toughness of the hot pressed member is lowered. Therefore, the S amount is 0.05% or less.
Ａｌ：０．１％以下
Ａｌ量が０．１％を超えると、素材の鋼板のブランキング加工性や焼入れ性を低下させる。したがって、Ａｌ量は０．１％以下とする。 Al: 0.1% or less When the Al amount exceeds 0.1%, blanking workability and hardenability of the steel plate as a material are lowered. Therefore, the Al content is 0.1% or less.
Ａｌ量が０．１％を超えると、素材の鋼板のブランキング加工性や焼入れ性を低下させる。したがって、Ａｌ量は０．１％以下とする。 Al: 0.1% or less When the Al amount exceeds 0.1%, blanking workability and hardenability of the steel plate as a material are lowered. Therefore, the Al content is 0.1% or less.
Ｎ：０．０１％以下
Ｎ量が０．０１％を超えると、熱間圧延時や熱間プレス前の加熱時にＡｌＮの窒化物を形成し、素材の鋼板のブランキング加工性や焼入れ性を低下させる。したがって、Ｎ量は０．０１％以下とする。 N: 0.01% or less When the N content exceeds 0.01%, a nitride of AlN is formed during hot rolling or heating before hot pressing, and the blanking workability and hardenability of the raw steel sheet are improved. Reduce. Therefore, the N content is 0.01% or less.
Ｎ量が０．０１％を超えると、熱間圧延時や熱間プレス前の加熱時にＡｌＮの窒化物を形成し、素材の鋼板のブランキング加工性や焼入れ性を低下させる。したがって、Ｎ量は０．０１％以下とする。 N: 0.01% or less When the N content exceeds 0.01%, a nitride of AlN is formed during hot rolling or heating before hot pressing, and the blanking workability and hardenability of the raw steel sheet are improved. Reduce. Therefore, the N content is 0.01% or less.
残部はＦｅおよび不可避的不純物であるが、以下の理由により、Ｃｒ：０．０１~１％、Ｔｉ：０．２％以下、Ｂ：０．０００５~０．０８％のうちから選ばれた少なくとも１種や、Ｓｂ：０．００３~０．０３％を、個別にあるいは同時に含有させることが好ましい。
The balance is Fe and inevitable impurities, but at least selected from Cr: 0.01 to 1%, Ti: 0.2% or less, and B: 0.0005 to 0.08% for the following reasons. One kind or Sb: 0.003 to 0.03% is preferably contained individually or simultaneously.
Ｃｒ：０．０１~１％
Ｃｒは、鋼を強化するとともに、焼入れ性を向上させるのに有効な元素である。こうした効果の発現のためには、Ｃｒ量を０．０１％以上とすることが好ましい。一方、Ｃｒ量が１％を超えると、著しいコスト高を招くため、その上限は１％とすることが好ましい。 Cr: 0.01 to 1%
Cr is an element effective for strengthening steel and improving hardenability. In order to exhibit such an effect, the Cr content is preferably 0.01% or more. On the other hand, if the Cr content exceeds 1%, the cost is significantly increased, so the upper limit is preferably 1%.
Ｃｒは、鋼を強化するとともに、焼入れ性を向上させるのに有効な元素である。こうした効果の発現のためには、Ｃｒ量を０．０１％以上とすることが好ましい。一方、Ｃｒ量が１％を超えると、著しいコスト高を招くため、その上限は１％とすることが好ましい。 Cr: 0.01 to 1%
Cr is an element effective for strengthening steel and improving hardenability. In order to exhibit such an effect, the Cr content is preferably 0.01% or more. On the other hand, if the Cr content exceeds 1%, the cost is significantly increased, so the upper limit is preferably 1%.
Ｔｉ：０．２％以下
Ｔｉは、鋼を強化するとともに、細粒化により靭性を向上させるのに有効な元素である。また、次に述べるＢよりも優先して窒化物を形成して、固溶Ｂによる焼入れ性の向上効果を発揮させるのに有効な元素でもある。しかし、Ｔｉ量が０．２％を超えると、熱間圧延時の圧延荷重が極端に増大し、また、熱間プレス部材の靭性が低下するので、その上限は０．２％以下とすることが好ましい。 Ti: 0.2% or less Ti is an element effective for strengthening steel and improving toughness by refining. Further, it is also an element effective for forming a nitride in preference to B described below and exhibiting the effect of improving hardenability by solid solution B. However, if the amount of Ti exceeds 0.2%, the rolling load during hot rolling is extremely increased, and the toughness of the hot pressed member is reduced, so the upper limit should be 0.2% or less. Is preferred.
Ｔｉは、鋼を強化するとともに、細粒化により靭性を向上させるのに有効な元素である。また、次に述べるＢよりも優先して窒化物を形成して、固溶Ｂによる焼入れ性の向上効果を発揮させるのに有効な元素でもある。しかし、Ｔｉ量が０．２％を超えると、熱間圧延時の圧延荷重が極端に増大し、また、熱間プレス部材の靭性が低下するので、その上限は０．２％以下とすることが好ましい。 Ti: 0.2% or less Ti is an element effective for strengthening steel and improving toughness by refining. Further, it is also an element effective for forming a nitride in preference to B described below and exhibiting the effect of improving hardenability by solid solution B. However, if the amount of Ti exceeds 0.2%, the rolling load during hot rolling is extremely increased, and the toughness of the hot pressed member is reduced, so the upper limit should be 0.2% or less. Is preferred.
Ｂ：０．０００５~０．０８％
Ｂは、熱間プレス時の焼入れ性や熱間プレス後の靭性向上に有効な元素である。こうした効果の発現のためには、Ｂ量を０．０００５％以上とすることが好ましい。一方、Ｂ量が０．０８％を超えると、熱間圧延時の圧延荷重が極端に増大し、また、熱間圧延後にマルテンサイト相やベイナイト相が生じて鋼板の割れなどが生じるので、その上限は０．０８％とすることが好ましい。 B: 0.0005 to 0.08%
B is an element effective for improving the hardenability during hot pressing and toughness after hot pressing. In order to exhibit such an effect, the B content is preferably 0.0005% or more. On the other hand, if the amount of B exceeds 0.08%, the rolling load at the time of hot rolling is extremely increased, and a martensite phase and a bainite phase are generated after hot rolling, resulting in cracking of the steel sheet. The upper limit is preferably 0.08%.
Ｂは、熱間プレス時の焼入れ性や熱間プレス後の靭性向上に有効な元素である。こうした効果の発現のためには、Ｂ量を０．０００５％以上とすることが好ましい。一方、Ｂ量が０．０８％を超えると、熱間圧延時の圧延荷重が極端に増大し、また、熱間圧延後にマルテンサイト相やベイナイト相が生じて鋼板の割れなどが生じるので、その上限は０．０８％とすることが好ましい。 B: 0.0005 to 0.08%
B is an element effective for improving the hardenability during hot pressing and toughness after hot pressing. In order to exhibit such an effect, the B content is preferably 0.0005% or more. On the other hand, if the amount of B exceeds 0.08%, the rolling load at the time of hot rolling is extremely increased, and a martensite phase and a bainite phase are generated after hot rolling, resulting in cracking of the steel sheet. The upper limit is preferably 0.08%.
Ｓｂ：０．００３~０．０３％
Ｓｂは、熱間プレス前に鋼板を加熱してから熱間プレスの一連の処理によって鋼板を冷却するまでの間に鋼板表層部に生じる脱炭層を抑制する効果を有する。このような効果の発現のためにはその量を０．００３％以上とする必要がある。一方、Ｓｂ量が０．０３％を超えると、圧延荷重の増大を招き、生産性を低下させる。したがって、Ｓｂ量は０．００３~０．０３％とする。 Sb: 0.003 to 0.03%
Sb has an effect of suppressing a decarburized layer generated in the steel sheet surface layer portion between the time when the steel plate is heated before hot pressing and the time when the steel plate is cooled by a series of processes of hot pressing. In order to exhibit such an effect, the amount needs to be 0.003% or more. On the other hand, if the Sb content exceeds 0.03%, the rolling load increases and the productivity is lowered. Therefore, the Sb amount is set to 0.003 to 0.03%.
Ｓｂは、熱間プレス前に鋼板を加熱してから熱間プレスの一連の処理によって鋼板を冷却するまでの間に鋼板表層部に生じる脱炭層を抑制する効果を有する。このような効果の発現のためにはその量を０．００３％以上とする必要がある。一方、Ｓｂ量が０．０３％を超えると、圧延荷重の増大を招き、生産性を低下させる。したがって、Ｓｂ量は０．００３~０．０３％とする。 Sb: 0.003 to 0.03%
Sb has an effect of suppressing a decarburized layer generated in the steel sheet surface layer portion between the time when the steel plate is heated before hot pressing and the time when the steel plate is cooled by a series of processes of hot pressing. In order to exhibit such an effect, the amount needs to be 0.003% or more. On the other hand, if the Sb content exceeds 0.03%, the rolling load increases and the productivity is lowered. Therefore, the Sb amount is set to 0.003 to 0.03%.
熱間プレス前の加熱方法としては、電気炉やガス炉などによる加熱、火炎加熱、通電加熱、高周波加熱、誘導加熱などを例示できるが、これらに限定されるものではない。
As a heating method before hot pressing, heating by an electric furnace or a gas furnace, flame heating, current heating, high-frequency heating, induction heating, etc. can be exemplified, but not limited thereto.
質量％で、Ｃ：０．２３％、Ｓｉ：０．１２％、Ｍｎ：１．５％、Ｐ：０．０１％、Ｓ：０．０１％、Ａｌ：０．０３％、Ｎ：０．００５％、Ｃｒ：０．４％、Ｂ：０．００２２％を含み、残部がＦｅおよび不可避的不純物からなる成分組成を有し、Ａｃ３変態点が８１８℃で、板厚１．６ｍｍの冷延鋼板に、３００ｇ／Ｌの硫酸ニッケル六水和物、５０ｇ／Ｌの硫酸ナトリウム、３０ｇ／Ｌのホウ酸からなるめっき浴中で電流密度１０Ａ／ｄｍ２で電気めっき処理を施し、表１に示すＮｉ付着量（片面当たり）の異なるＮｉめっき層を両面に形成した。また、一部の冷延鋼板には、３００ｇ／Ｌの硫酸ニッケル六水和物、１０ｇ／Ｌの硫酸亜鉛七水和物、５０ｇ／Ｌの硫酸ナトリウム、３０ｇ／Ｌのホウ酸からなるめっき浴中で電流密度５０Ａ／ｄｍ２で電気めっき処理を施し、表１に示すＮｉ付着量のＮｉ−１０質量％Ｚｎめっき層を両面に形成した。次に、形成したＮｉめっき層あるいはＮｉ−１０質量％Ｚｎめっき層上に、表１に示すような融点の無機化合物の水溶液をバーコーターにより塗布後、１２０℃で１０分間の乾燥を行って、表１に示す片面当りの付着量の無機化合物を存在させた。
In mass%, C: 0.23%, Si: 0.12%, Mn: 1.5%, P: 0.01%, S: 0.01%, Al: 0.03%, N: 0.00. 005%, Cr: 0.4%, B: 0.0022%, the balance is a component composition consisting of Fe and inevitable impurities, the Ac 3 transformation point is 818 ° C., and the thickness is 1.6 mm. The rolled steel sheet was subjected to electroplating treatment at a current density of 10 A / dm 2 in a plating bath composed of 300 g / L nickel sulfate hexahydrate, 50 g / L sodium sulfate, and 30 g / L boric acid. Ni plating layers having different Ni adhesion amounts (per one side) shown were formed on both sides. Also, some cold-rolled steel sheets include a plating bath comprising 300 g / L nickel sulfate hexahydrate, 10 g / L zinc sulfate heptahydrate, 50 g / L sodium sulfate, and 30 g / L boric acid. In particular, the electroplating treatment was performed at a current density of 50 A / dm 2 , and Ni-10 mass% Zn plating layers having the Ni adhesion amount shown in Table 1 were formed on both surfaces. Next, on the formed Ni plating layer or Ni-10 mass% Zn plating layer, an aqueous solution of an inorganic compound having a melting point as shown in Table 1 was applied by a bar coater, and then dried at 120 ° C. for 10 minutes, The amount of inorganic compound per one side shown in Table 1 was present.
このようにして作製した両面にＮｉを含むめっき層と無機化合物を有する鋼板から採取した２００ｍｍ×２２０ｍｍのブランクを、大気雰囲気の電気炉内で表１に示す加熱温度で１０分間加熱後、炉内から取り出し、直ちに図１に模式的に示したようなプレス方法でＮｉを含むめっき層と無機化合物を有する面を非ポンチ接触面として絞り加工し、熱間プレス部材Ｎｏ．１~１５を作製した。このとき、ポンチ幅は７０ｍｍ、加工高さは３０ｍｍとした。なお、比較のために、無機化合物を存在させないＮｉめっき層を有する鋼板、片面当たりのめっき付着量が４００００ｍｇ／ｍ２のＡｌ−１０質量％Ｓｉめっき鋼板、冷延鋼板を用いて、同様な方法で熱間プレス部材Ｎｏ．１６~１８を作製した。なお、比較材として用いた冷延鋼板Ｎｏ．１８は熱間プレスの際の加熱によるスケール発生が著しいため、熱間プレス後にショットブラストで表面のスケールを除去した後に以後の評価を実施した。
A 200 mm × 220 mm blank sampled from a steel sheet having a plated layer containing Ni and an inorganic compound on both surfaces thus prepared was heated for 10 minutes at the heating temperature shown in Table 1 in an electric furnace in an air atmosphere, and then in the furnace. 1 and immediately after drawing the surface containing the plating layer containing Ni and the inorganic compound as a non-punch contact surface by a pressing method as schematically shown in FIG. 1 to 15 were produced. At this time, the punch width was 70 mm, and the processing height was 30 mm. For comparison, a similar method using a steel plate having a Ni plating layer that does not contain an inorganic compound, an Al-10 mass% Si-plated steel plate having a plating adhesion amount of 40,000 mg / m 2 per side, and a cold-rolled steel plate. Hot press member No. 16-18 were produced. In addition, the cold-rolled steel plate No. used as a comparative material. In No. 18, since scale generation due to heating during hot pressing was significant, the surface scale was removed by shot blasting after hot pressing, and the subsequent evaluation was performed.
そして、部材頭部の平坦部から試料を採取し、上記の方法で、非ポンチ接触面のＮｉ拡散領域の深さを測定した。また、次の方法により、熱間プレス性、スポット溶接性、塗装密着性、耐水素侵入性を調査した。
熱間プレス性：熱間プレス後の非ポンチ接触面側を目視で観察し、型かじりに起因する傷発生の状態を以下の基準で評価し、○、△であれば本発明の目的を満足しているとした。○：部材表面に傷なし
△：部材表面の一部に傷あり
×：部材表面の全面に傷有り
スポット溶接性：部材頭部の平坦部から試料を採取し、木村電熔（株）製スポット溶接機を用いて、使用電極チップ：ＤＲ６、電極加圧力：２ＫＮ、スクイズ時間：２５サイクル／５０Ｈｚ、溶接時間：１６サイクル／５０Ｈｚ、保持時間：５サイクル／５０Ｈｚの条件で同種試料同士を溶接し、溶接可能電流範囲（ＡＣＲ）を測定した。以下の基準で評価し、◎、○であれば本発明の目的を満足しているとした。なお、非ポンチ接触面同士を接触させて溶接した。
◎：ＡＣＲがＡｌ−Ｓｉめっき鋼板の場合の２倍以上
○：ＡＣＲがＡｌ−Ｓｉめっき鋼板の場合の１．５倍以上~２倍未満
×：ＡＣＲがＡｌ−Ｓｉめっき鋼板と同等以上~１．５倍未満
塗装密着性：部材頭部の平坦部から試料を採取し、非ポンチ接触面に日本パーカライジング株式会社製ＰＢ−Ｌ３０２０を使用して標準条件で化成処理を施した後、関西ペイント株式会社製電着塗料ＧＴ−１０ＨＴグレーを１７０℃×２０分間の焼付け条件で膜厚２０μｍ成膜して、塗装試験片を作製した。そして、作製した試験片に対してカッターナイフで碁盤目（１０×１０個、１ｍｍ間隔）の鋼素地まで到達するカットを入れ、接着テープにより貼着・剥離する碁盤目テープ剥離試験を行った。以下の基準で評価し、○、△であれば本発明の目的を満足しているとした。
○：剥離なし
△：１~１０個の碁盤目で剥離
×：１１個以上の碁盤目で剥離
耐水素侵入性：部材頭部の平坦部から試料を採取し、一方の面（ポンチ接触面）を鏡面研削して板厚を１ｍｍとした。次に、作用極を試料、対極を白金とし、研削面にＮｉめっきを行い水素検出面として、図２に模式的に示す電気化学セルにセットし、非研削面を大気中、室温で腐食させながら鋼中に侵入する水素量を電気化学的水素透過法で測定した。すなわち、水素検出面側には０．１ＭＮａＯＨ水溶液を充填し、塩橋を通じて参照電極（Ａｇ／ＡｇＣｌ）をセットして、非研削面（評価面：非ポンチ接触面）側に０．５質量％ＮａＣｌ溶液を滴下し、大気中、室温で腐食させ、水素検出面側の電位が０ＶｖｓＡｇ／ＡｇＣｌになるようにして、１回／日の頻度で腐食部に純水を滴下しながら水素透過電流値を連続的に５日間測定し、その最大電流値から腐食に伴う耐水素侵入性を、以下の基準で評価した。○、△であれば本発明の目的を満足しているとした。なお、熱間プレス時のスケールの生成が著しい部材に対しては、ショットブラストで表面のスケールを除去してから試験を行った。
○：最大電流値が冷延鋼板の場合の１／１０以下
△：最大電流値が冷延鋼板の場合の１／１０超~１／２以下
×：最大電流値が冷延鋼板の場合の１／２超~冷延鋼板と同じ
結果を表１に示す。本発明である熱間プレス部材Ｎｏ．１~１３は、熱間プレス性、スポット溶接性、塗料密着性、耐水素侵入性に優れていることがわかる。 And the sample was extract | collected from the flat part of the member head, and the depth of the Ni diffusion area | region of a non-punch contact surface was measured by said method. In addition, hot pressability, spot weldability, paint adhesion, and hydrogen penetration resistance were investigated by the following methods.
Hot pressability: The non-punch contact surface side after hot pressing is visually observed, and the state of occurrence of scratches due to mold galling is evaluated according to the following criteria. I was doing it. ○: There is no scratch on the member surface. Δ: There is a scratch on a part of the member surface. ×: There is a scratch on the entire surface of the member. Spot weldability: A sample is taken from the flat part of the member head, and spot is made by Kimura Denyu Co., Ltd. Using a welding machine, the same type of samples are welded together under the conditions of electrode tip used: DR6, electrode pressure: 2KN, squeeze time: 25 cycles / 50 Hz, welding time: 16 cycles / 50 Hz, holding time: 5 cycles / 50 Hz. The weldable current range (ACR) was measured. The evaluation was made according to the following criteria, and if ◎ or ○, the object of the present invention was satisfied. In addition, the non-punch contact surfaces were contacted and welded.
◎: More than 2 times when ACR is Al-Si plated steel plate ○: 1.5 times or more to less than 2 times when ACR is Al-Si plated steel plate ×: ACR is equal to or more than Al-Si plated steel plate to 1 Less than 5 times coating adhesion: A sample was taken from the flat part of the head of the member, subjected to chemical conversion treatment under standard conditions using PB-L3020 manufactured by Nihon Parkerizing Co., Ltd. on the non-punch contact surface, and then Kansai Paint Co., Ltd. An electrodeposition paint GT-10HT gray manufactured by the company was formed into a film with a thickness of 20 μm under a baking condition of 170 ° C. for 20 minutes to prepare a coating test piece. And the cut which reaches | attains the steel base of a grid (10x10 piece, 1mm space | interval) with a cutter knife was put with respect to the produced test piece, and the grid tape peeling test which sticks and peels with an adhesive tape was done. Evaluation was made according to the following criteria, and it was considered that the object of the present invention was satisfied if it was ○ or Δ.
○: No peeling Δ: Peeling with 1 to 10 grids ×: Peeling with 11 or more grids Hydrogen penetration resistance: Sample is taken from the flat part of the member head, and one surface (punch contact surface) Was mirror-polished to a plate thickness of 1 mm. Next, the working electrode is a sample, the counter electrode is platinum, the ground surface is Ni-plated and the hydrogen detection surface is set in the electrochemical cell schematically shown in FIG. 2, and the non-ground surface is corroded at room temperature in the atmosphere. The amount of hydrogen penetrating into the steel was measured by electrochemical hydrogen permeation method. That is, the hydrogen detection surface side is filled with 0.1M NaOH aqueous solution, the reference electrode (Ag / AgCl) is set through the salt bridge, and 0.5% by mass on the non-grinding surface (evaluation surface: non-punch contact surface) side. Drop the NaCl solution, corrode at room temperature in the atmosphere, hydrogen permeation current value while dripping pure water to the corroded part once a day so that the potential on the hydrogen detection surface side becomes 0VvsAg / AgCl Was continuously measured for 5 days, and the hydrogen penetration resistance accompanying corrosion was evaluated from the maximum current value according to the following criteria. ○ and Δ are considered to satisfy the object of the present invention. In addition, it tested after removing the surface scale by shot blasting to the member which the production | generation of the scale at the time of a hot press was remarkable.
○: 1/10 or less when the maximum current value is cold-rolled steel sheet Δ: 1/10 or more to 1/2 or less when the maximum current value is cold-rolled steel sheet ×: 1 when the maximum current value is cold-rolled steel sheet Table 1 shows the same results as those of over / 2 steel sheets. Hot press member No. 1 of the present invention. 1 to 13 are excellent in hot press property, spot weldability, paint adhesion, and hydrogen penetration resistance.
熱間プレス性：熱間プレス後の非ポンチ接触面側を目視で観察し、型かじりに起因する傷発生の状態を以下の基準で評価し、○、△であれば本発明の目的を満足しているとした。○：部材表面に傷なし
△：部材表面の一部に傷あり
×：部材表面の全面に傷有り
スポット溶接性：部材頭部の平坦部から試料を採取し、木村電熔（株）製スポット溶接機を用いて、使用電極チップ：ＤＲ６、電極加圧力：２ＫＮ、スクイズ時間：２５サイクル／５０Ｈｚ、溶接時間：１６サイクル／５０Ｈｚ、保持時間：５サイクル／５０Ｈｚの条件で同種試料同士を溶接し、溶接可能電流範囲（ＡＣＲ）を測定した。以下の基準で評価し、◎、○であれば本発明の目的を満足しているとした。なお、非ポンチ接触面同士を接触させて溶接した。
◎：ＡＣＲがＡｌ−Ｓｉめっき鋼板の場合の２倍以上
○：ＡＣＲがＡｌ−Ｓｉめっき鋼板の場合の１．５倍以上~２倍未満
×：ＡＣＲがＡｌ−Ｓｉめっき鋼板と同等以上~１．５倍未満
塗装密着性：部材頭部の平坦部から試料を採取し、非ポンチ接触面に日本パーカライジング株式会社製ＰＢ−Ｌ３０２０を使用して標準条件で化成処理を施した後、関西ペイント株式会社製電着塗料ＧＴ−１０ＨＴグレーを１７０℃×２０分間の焼付け条件で膜厚２０μｍ成膜して、塗装試験片を作製した。そして、作製した試験片に対してカッターナイフで碁盤目（１０×１０個、１ｍｍ間隔）の鋼素地まで到達するカットを入れ、接着テープにより貼着・剥離する碁盤目テープ剥離試験を行った。以下の基準で評価し、○、△であれば本発明の目的を満足しているとした。
○：剥離なし
△：１~１０個の碁盤目で剥離
×：１１個以上の碁盤目で剥離
耐水素侵入性：部材頭部の平坦部から試料を採取し、一方の面（ポンチ接触面）を鏡面研削して板厚を１ｍｍとした。次に、作用極を試料、対極を白金とし、研削面にＮｉめっきを行い水素検出面として、図２に模式的に示す電気化学セルにセットし、非研削面を大気中、室温で腐食させながら鋼中に侵入する水素量を電気化学的水素透過法で測定した。すなわち、水素検出面側には０．１ＭＮａＯＨ水溶液を充填し、塩橋を通じて参照電極（Ａｇ／ＡｇＣｌ）をセットして、非研削面（評価面：非ポンチ接触面）側に０．５質量％ＮａＣｌ溶液を滴下し、大気中、室温で腐食させ、水素検出面側の電位が０ＶｖｓＡｇ／ＡｇＣｌになるようにして、１回／日の頻度で腐食部に純水を滴下しながら水素透過電流値を連続的に５日間測定し、その最大電流値から腐食に伴う耐水素侵入性を、以下の基準で評価した。○、△であれば本発明の目的を満足しているとした。なお、熱間プレス時のスケールの生成が著しい部材に対しては、ショットブラストで表面のスケールを除去してから試験を行った。
○：最大電流値が冷延鋼板の場合の１／１０以下
△：最大電流値が冷延鋼板の場合の１／１０超~１／２以下
×：最大電流値が冷延鋼板の場合の１／２超~冷延鋼板と同じ
結果を表１に示す。本発明である熱間プレス部材Ｎｏ．１~１３は、熱間プレス性、スポット溶接性、塗料密着性、耐水素侵入性に優れていることがわかる。 And the sample was extract | collected from the flat part of the member head, and the depth of the Ni diffusion area | region of a non-punch contact surface was measured by said method. In addition, hot pressability, spot weldability, paint adhesion, and hydrogen penetration resistance were investigated by the following methods.
Hot pressability: The non-punch contact surface side after hot pressing is visually observed, and the state of occurrence of scratches due to mold galling is evaluated according to the following criteria. I was doing it. ○: There is no scratch on the member surface. Δ: There is a scratch on a part of the member surface. ×: There is a scratch on the entire surface of the member. Spot weldability: A sample is taken from the flat part of the member head, and spot is made by Kimura Denyu Co., Ltd. Using a welding machine, the same type of samples are welded together under the conditions of electrode tip used: DR6, electrode pressure: 2KN, squeeze time: 25 cycles / 50 Hz, welding time: 16 cycles / 50 Hz, holding time: 5 cycles / 50 Hz. The weldable current range (ACR) was measured. The evaluation was made according to the following criteria, and if ◎ or ○, the object of the present invention was satisfied. In addition, the non-punch contact surfaces were contacted and welded.
◎: More than 2 times when ACR is Al-Si plated steel plate ○: 1.5 times or more to less than 2 times when ACR is Al-Si plated steel plate ×: ACR is equal to or more than Al-Si plated steel plate to 1 Less than 5 times coating adhesion: A sample was taken from the flat part of the head of the member, subjected to chemical conversion treatment under standard conditions using PB-L3020 manufactured by Nihon Parkerizing Co., Ltd. on the non-punch contact surface, and then Kansai Paint Co., Ltd. An electrodeposition paint GT-10HT gray manufactured by the company was formed into a film with a thickness of 20 μm under a baking condition of 170 ° C. for 20 minutes to prepare a coating test piece. And the cut which reaches | attains the steel base of a grid (10x10 piece, 1mm space | interval) with a cutter knife was put with respect to the produced test piece, and the grid tape peeling test which sticks and peels with an adhesive tape was done. Evaluation was made according to the following criteria, and it was considered that the object of the present invention was satisfied if it was ○ or Δ.
○: No peeling Δ: Peeling with 1 to 10 grids ×: Peeling with 11 or more grids Hydrogen penetration resistance: Sample is taken from the flat part of the member head, and one surface (punch contact surface) Was mirror-polished to a plate thickness of 1 mm. Next, the working electrode is a sample, the counter electrode is platinum, the ground surface is Ni-plated and the hydrogen detection surface is set in the electrochemical cell schematically shown in FIG. 2, and the non-ground surface is corroded at room temperature in the atmosphere. The amount of hydrogen penetrating into the steel was measured by electrochemical hydrogen permeation method. That is, the hydrogen detection surface side is filled with 0.1M NaOH aqueous solution, the reference electrode (Ag / AgCl) is set through the salt bridge, and 0.5% by mass on the non-grinding surface (evaluation surface: non-punch contact surface) side. Drop the NaCl solution, corrode at room temperature in the atmosphere, hydrogen permeation current value while dripping pure water to the corroded part once a day so that the potential on the hydrogen detection surface side becomes 0VvsAg / AgCl Was continuously measured for 5 days, and the hydrogen penetration resistance accompanying corrosion was evaluated from the maximum current value according to the following criteria. ○ and Δ are considered to satisfy the object of the present invention. In addition, it tested after removing the surface scale by shot blasting to the member which the production | generation of the scale at the time of a hot press was remarkable.
○: 1/10 or less when the maximum current value is cold-rolled steel sheet Δ: 1/10 or more to 1/2 or less when the maximum current value is cold-rolled steel sheet ×: 1 when the maximum current value is cold-rolled steel sheet Table 1 shows the same results as those of over / 2 steel sheets. Hot press member No. 1 of the present invention. 1 to 13 are excellent in hot press property, spot weldability, paint adhesion, and hydrogen penetration resistance.
Claims (9)
- 部材を構成する鋼板の表層部に、Ｎｉ付着量が１０~９００００ｍｇ／ｍ２のＮｉ拡散領域を有し、前記Ｎｉ拡散領域上に無機化合物を有することを特徴とする熱間プレス部材。 A hot pressed member having a Ni diffusion region having a Ni adhesion amount of 10 to 90000 mg / m 2 on a surface layer portion of a steel plate constituting the member, and having an inorganic compound on the Ni diffusion region.
- 前記無機化合物の融点が５００~１０００℃であることを特徴とする請求項１に記載の熱間プレス部材。 The hot-pressed member according to claim 1, wherein the inorganic compound has a melting point of 500 to 1000 ° C.
- 前記無機化合物がアルカリ可溶成分を含むことを特徴とする請求項１または２に記載の熱間プレス部材。 The hot press member according to claim 1 or 2, wherein the inorganic compound contains an alkali-soluble component.
- 鋼板の表面に、順に、Ｎｉ付着量が１０~９００００ｍｇ／ｍ２のＮｉを含むめっき層と、無機化合物とを有する鋼板を、Ａｃ３変態点~１２００℃の温度範囲に加熱後熱間プレスすることを特徴とする熱間プレス部材の製造方法。 On the surface of the steel sheet, a steel sheet having a Ni-containing plating layer containing 10 to 90,000 mg / m 2 of Ni and an inorganic compound are heated in the temperature range of Ac 3 transformation point to 1200 ° C. and then hot pressed. A method for producing a hot-pressed member.
- 前記無機化合物として、融点が５００~１０００℃の無機化合物を用いることを特徴とする請求項４に記載の熱間プレス部材の製造方法。 The method for producing a hot press member according to claim 4, wherein an inorganic compound having a melting point of 500 to 1000 ° C is used as the inorganic compound.
- 前記無機化合物として、アルカリ可溶成分を含む無機化合物を用いることを特徴とする請求項４または５に記載の熱間プレス部材の製造方法。 The method for producing a hot press member according to claim 4 or 5, wherein an inorganic compound containing an alkali-soluble component is used as the inorganic compound.
- 前記鋼板として、質量％で、Ｃ：０．１５~０．５％、Ｓｉ：０．０５~２．０％、Ｍｎ：０．５~３％、Ｐ：０．１％以下、Ｓ：０．０５％以下、Ａｌ：０．１％以下、Ｎ：０．０１％以下を含有し、残部がＦｅおよび不可避的不純物からなる成分組成を有する鋼板を用いることを特徴とする請求項４から６のいずれか１項に記載の熱間プレス部材の製造方法。 As the steel sheet, C: 0.15 to 0.5%, Si: 0.05 to 2.0%, Mn: 0.5 to 3%, P: 0.1% or less, S: 0% by mass A steel plate containing 0.05% or less, Al: 0.1% or less, N: 0.01% or less, and the balance being composed of Fe and inevitable impurities is used. The manufacturing method of the hot press member of any one of these.
- さらに、質量％で、Ｃｒ：０．０１~１％、Ｔｉ：０．２％以下、Ｂ：０．０００５~０．０８％のうちから選ばれた少なくとも１種を含有する鋼板を用いることを特徴とする請求項７に記載の熱間プレス部材の製造方法。 Furthermore, a steel sheet containing at least one selected from Cr: 0.01 to 1%, Ti: 0.2% or less, and B: 0.0005 to 0.08% by mass% is used. The manufacturing method of the hot press member of Claim 7 characterized by the above-mentioned.
- さらに、質量％で、Ｓｂ：０．００３~０．０３％を含有する鋼板を用いることを特徴とする請求項７または８に記載の熱間プレス部材の製造方法。 Furthermore, the manufacturing method of the hot press member of Claim 7 or 8 using the steel plate which contains Sb: 0.003-0.03% by mass%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020127010874A KR101361227B1 (en) | 2009-12-11 | 2010-10-28 | Hot-pressed member and process for producing same |
| CN2010800485163A CN102686779B (en) | 2009-12-11 | 2010-10-28 | Hot-pressed member and process for producing same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009281154A JP5110073B2 (en) | 2009-12-11 | 2009-12-11 | Hot pressed member and method for manufacturing the same |
| JP2009-281154 | 2009-12-11 |
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| WO2011070877A1 true WO2011070877A1 (en) | 2011-06-16 |
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| PCT/JP2010/069644 WO2011070877A1 (en) | 2009-12-11 | 2010-10-28 | Hot-pressed member and process for producing same |
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| Country | Link |
|---|---|
| JP (1) | JP5110073B2 (en) |
| KR (1) | KR101361227B1 (en) |
| CN (1) | CN102686779B (en) |
| TW (1) | TWI421351B (en) |
| WO (1) | WO2011070877A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6303580B2 (en) * | 2014-02-19 | 2018-04-04 | 新日鐵住金株式会社 | Steel plate for heat treatment and manufacturing method thereof |
| KR101665804B1 (en) * | 2014-12-23 | 2016-10-13 | 주식회사 포스코 | Steel sheet for hot press forming, method for manufacturing hot pressed part and hot pressed part manufactured thereby |
| WO2017187215A1 (en) * | 2016-04-29 | 2017-11-02 | Arcelormittal | Carbon steel sheet coated with a barrier coating |
| WO2020070545A1 (en) * | 2018-10-04 | 2020-04-09 | Arcelormittal | A press hardening method |
| CN111801436B (en) | 2019-02-05 | 2021-10-29 | 日本制铁株式会社 | Steel member, steel sheet, and method for producing same |
| WO2020162513A1 (en) | 2019-02-05 | 2020-08-13 | 日本製鉄株式会社 | Coated steel member, coated steel sheet, and methods for producing same |
| DE102021118765A1 (en) | 2021-07-20 | 2023-01-26 | Kamax Holding Gmbh & Co. Kg | Component with integrated nickel diffusion layer |
| WO2023153099A1 (en) * | 2022-02-08 | 2023-08-17 | Ｊｆｅスチール株式会社 | Steel sheet for hot pressing, hot-pressed member and method for producing hot-pressed member |
| WO2024053207A1 (en) * | 2022-09-05 | 2024-03-14 | Ｊｆｅスチール株式会社 | Steel sheet for hot pressing, hot-pressed member and method for producing hot-pressed member |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61227181A (en) * | 1985-03-30 | 1986-10-09 | Sumitomo Metal Ind Ltd | Highly corrosion resistant surface treated steel material |
| JPH03104855A (en) * | 1989-09-20 | 1991-05-01 | Nippon Steel Corp | Ni diffusion-treated steel sheet, ni-plated steel sheet, and production of ni-plated steel sheet |
| JP2005290395A (en) * | 2000-12-04 | 2005-10-20 | Jfe Steel Kk | Zinc-base plated steel sheet and method for producing the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4707415A (en) * | 1985-03-30 | 1987-11-17 | Sumitomo Metal Industries, Ltd. | Steel strips with corrosion resistant surface layers having good appearance |
| CN100462481C (en) * | 2000-12-04 | 2009-02-18 | 杰富意钢铁株式会社 | Zinc-based metal plated steel and method for production thereof |
| CA2683739C (en) * | 2007-04-11 | 2013-02-19 | Nippon Steel Corporation | Hot dip plated high strength steel sheet for press forming use superior in low temperature toughness and method of production of the same |
| JP2008297601A (en) * | 2007-05-31 | 2008-12-11 | Nisshin Steel Co Ltd | Austenitic stainless steel for press plate |
| EP2072630A1 (en) * | 2007-12-21 | 2009-06-24 | ArcelorMittal Commercial RPS S.à r.l. | Corrosion resistant steel for marine applications |
| JP4849186B2 (en) * | 2009-10-28 | 2012-01-11 | Ｊｆｅスチール株式会社 | Hot pressed member and method for manufacturing the same |
-
2009
- 2009-12-11 JP JP2009281154A patent/JP5110073B2/en not_active Expired - Fee Related
-
2010
- 2010-10-28 WO PCT/JP2010/069644 patent/WO2011070877A1/en active Application Filing
- 2010-10-28 KR KR1020127010874A patent/KR101361227B1/en active IP Right Grant
- 2010-10-28 TW TW099136873A patent/TWI421351B/en not_active IP Right Cessation
- 2010-10-28 CN CN2010800485163A patent/CN102686779B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61227181A (en) * | 1985-03-30 | 1986-10-09 | Sumitomo Metal Ind Ltd | Highly corrosion resistant surface treated steel material |
| JPH03104855A (en) * | 1989-09-20 | 1991-05-01 | Nippon Steel Corp | Ni diffusion-treated steel sheet, ni-plated steel sheet, and production of ni-plated steel sheet |
| JP2005290395A (en) * | 2000-12-04 | 2005-10-20 | Jfe Steel Kk | Zinc-base plated steel sheet and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101361227B1 (en) | 2014-02-10 |
| CN102686779A (en) | 2012-09-19 |
| CN102686779B (en) | 2013-11-13 |
| TW201127967A (en) | 2011-08-16 |
| KR20120065428A (en) | 2012-06-20 |
| JP2011122207A (en) | 2011-06-23 |
| JP5110073B2 (en) | 2012-12-26 |
| TWI421351B (en) | 2014-01-01 |
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