EP3625046A1 - Acier résistant à l'usure ou acier de sécurité à trois couches, procédé de fabrication d'un élément et utilisation - Google Patents
Acier résistant à l'usure ou acier de sécurité à trois couches, procédé de fabrication d'un élément et utilisationInfo
- Publication number
- EP3625046A1 EP3625046A1 EP18722028.0A EP18722028A EP3625046A1 EP 3625046 A1 EP3625046 A1 EP 3625046A1 EP 18722028 A EP18722028 A EP 18722028A EP 3625046 A1 EP3625046 A1 EP 3625046A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- steel
- optional
- wear
- weight
- safety
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/007—Continuous casting of metals, i.e. casting in indefinite lengths of composite ingots, i.e. two or more molten metals of different compositions being used to integrally cast the ingots
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/008—Continuous casting of metals, i.e. casting in indefinite lengths of clad ingots, i.e. the molten metal being cast against a continuous strip forming part of the cast product
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/42—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for armour plate
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/04—Plate construction composed of more than one layer
- F41H5/0442—Layered armour containing metal
- F41H5/045—Layered armour containing metal all the layers being metal layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/30—Iron, e.g. steel
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2251/00—Treating composite or clad material
- C21D2251/02—Clad material
Definitions
- the invention relates to a three-layer wear steel or safety steel. Furthermore, the invention relates to a method for producing a component of the wear steel or safety steel and a corresponding use.
- the prior art wear steels and safety steels are hardened to 350 HBW hardness and more for their intended use, and accordingly have high strength in conjunction with limited ductility.
- the high hardness required of a security steel aims to provide high resistance to penetration by an impacting projectile, with the projectile expanding in diameter after impact, degrading energy and minimizing the penetration depth.
- the high hardness required for a wear steel aims at a sufficiently high resistance to abrasive wear.
- the object of the present invention is to provide a wear steel or safety steel with substantially improved properties, which in particular has no or a lower tendency to crack during molding with improved bending ability, and to provide a method for producing a component and a corresponding use.
- the inventors have found that by providing two cover layers of a softer compared to the core layer steel, wherein the cover layers by at least 20%, in particular by at least 50% lower hardness than the core layer in the cured or tempered state, which cohesively with a core layer of a steel, which in the hardened or tempered state has a hardness> 350 HBW, in particular> 400 HBW, preferably> 450 HBW, preferably> 500 HBW, more preferably> 550 HBW, particularly preferably> 600 HBW three-ply safety steel or wear steel with improved bendability can be provided.
- the bending radius r (inner radius) critical for comparable monolithic steels which are dependent on the material thicknesses t and are determined by the relationship r / t, can be reduced by at least 10% by the applied cover layers.
- the hardness of the softer steel is ⁇ 400 HBW, in particular ⁇ 350 HBW, preferably ⁇ 300 HBW, more preferably ⁇ 250 HBW, more preferably ⁇ 200 HBW.
- the composite material according to the invention is subjected before its intended use of a heat treatment for the purpose of hardening or tempering, wherein the heat treatment is tailored to the core layer.
- the hardness of the Deklagen is preferably determined in the state after this heat treatment.
- HBW corresponds to the Brinell hardness and is determined according to DIN EN ISO 6506-1. What the experts understand by "hardening” and “tempering” is regulated in DIN EN 10052: 1993.
- cover layers function according to the invention only as forming / bending aid and fulfill no function in the subsequent application or during use.
- a soft steel alone is in principle not suitable for the application considered or for the application considered, since the required functional properties, in particular a high hardness, can not be achieved. Both at a wear as well as an impact load z. B. by bombardment or blowing, the soft steel alloy is substantially penetrated without resisting.
- a wear steel or safety steel according to the invention must have a core layer whose thickness corresponds to a comparable monolithic steel, in order to ensure a comparable stability in the wear insert or a comparable bombardment resistance.
- the inventive wear steel or safety steel is designed for the same application with a slightly greater thickness than a comparable monolithic steel, since the cover layers are functionally negligible for the intended use. Investigations have shown that at the same bending radius due to the greater thickness of the wear steel or safety steel according to the invention compared to monolithic steel higher elongation in the edge fiber of the core layer respectively a higher elongation at the transition between the core and cover layer is present, so that an early failure of the hard Core situation was expected, which surprisingly did not occur.
- cover layers of the composite material according to the invention are removed very quickly, for example, when used in an abrasive environment by contact with abrasive media until the abrasive medium strikes the exposed hard core layer of the wear steel, and then analogously assume the task of a comparable, monolithic wear steel.
- security steel according to the invention the cover layer remains permanently on the later component, but is penetrated, for example, in the case of fire without or with low resistance, whereby the performance of the component does not change.
- the safety steel or wear steel may be band, plate or sheet-shaped respectively be fed to the further processing.
- the core layer has a predominantly martensitic and / or bainitic microstructure. Martensite, tempered martensite and / or bainite (less preferred) is at least 70 area%, in particular at least 80 area%, preferably at least 85 area%, more preferably at least 90 area%, more preferably at least 95 area% before. Due to the manufacturing process, the formation of the less desirable microstructural constituents ferrite, retained austenite, perlite or cementite can not always be reliably avoided. In an alternative embodiment of the core layer, up to 30% by area of more ductile phases such as retained austenite or ferrite may also be deliberately adjusted to increase ductility.
- the proportion of these phases is preferably set to a maximum of 20 area%, particularly preferably to a maximum of 10 area%.
- An increased ductility is particularly advantageous if a component of the wear-resistant steel according to the invention also experiences impact wear stress or if a component made of the security steel according to the invention should also be designed to be resistant to impact.
- a small proportion of not more than 10 area%, particularly preferably not more than 5 area% of cementite and / or perlite can be set in the structure.
- the high hardness of these phases can be used for example in the wear-resistant steel according to the invention, so that abrasive particles protrude on the surface during abrasive wear, after the surrounding material has been removed by wear. These protruding particles then reduce the effective contact surface between wear steel and abrasives and thus slow down the wear process.
- the core layer is in addition to Fe and production inevitable
- C is a strength-increasing alloying element and contributes to the increase in hardness to increase the hardness by either dissolved as an interstitial atom in austenite and the cooling contributes to the formation of harder martensite or forms with Fe, Cr, Ti, Nb, V or W carbides, the on the one hand harder than the surrounding matrix can be or at least distort it so that the hardness of the matrix increases.
- C is therefore present at levels of at least 0.1% by weight, in particular of at least 0.15% by weight, preferably of at least 0.2% by weight, in order to achieve or set the desired hardness.
- the brittleness increases, so that the content to a maximum of 0.6 wt .-%, in particular at most 0.55 wt .-%, preferably at most 0.5 wt .-%, more preferably at most 0.45 wt .-%, particularly preferably not more than 0.4 wt .-% is limited in order not to adversely affect the material properties, in particular the ductility, and to ensure sufficient weldability.
- N can be used as an alloying element, optionally with a minimum content of 0.003 wt .-% with similar effect as C, because its ability to nitride has a positive effect on the strength.
- Al aluminum nitrides are formed which enhance nucleation and impede grain growth.
- nitrogen increases the hardness of the martensite formed during curing.
- the nitrogen content for the melt analysis is limited to ⁇ 0.01% by weight.
- the optional alloying element Boron this is bound by nitrogen, if the aluminum or titanium content is not high enough.
- Si is an alloying element that contributes to solid solution hardening and, depending on the content, has a positive effect in increasing the hardness, so that optionally a content of at least 0.05% by weight is present. At lower levels, the effectiveness of Si is not clearly detectable, but Si also does not adversely affect the properties of the steel. Will that Adding too much silicon to steel has a negative impact on weldability, ductility and toughness properties.
- the alloying element is limited to at most 1.5% by weight, more preferably at most 0.9% by weight, to ensure sufficient rolling, and moreover, it is preferably limited to at most 0.5% by weight in order to obtain the To prevent the formation of Rotzunder safely, which can reduce in too large proportions the adhesion in the composite at the boundary layer between core layer and top layer.
- Si can be used for deoxidizing the steel, if the use of AI, for example, should be avoided to prevent unwanted setting z. B. of N to avoid.
- Mn is an alloying element which contributes to hardenability and is used in particular for setting S to MnS so that a content of at least 0.1 wt.%, In particular at least 0.3 wt.%, Is present. Manganese reduces the critical cooling rate, increasing hardenability.
- the alloying element is at most 2.5 wt .-%, in particular at most 1.9 wt .-%, to ensure sufficient weldability and a good forming behavior.
- Mn has a strong segregating effect and is therefore preferably limited to a maximum of 1.5% by weight.
- Al contributes in particular to the deoxidation, which is why optionally a content of at least 0.01 wt .-%, in particular at least 0.015 wt .-% is set.
- the alloying element is limited to a maximum of 2.0 wt .-%, in particular a maximum of 1.0 wt .-% to ensure the best possible pourability, preferably at most 0.5 wt .-%, more preferably at most 0, 1 wt .-% in order to substantially reduce and / or avoid undesired precipitations in the material, in particular in the form of non-metallic oxidic inclusions, which may adversely affect the material properties.
- the content is adjusted between 0.02 and 0.06 wt .-%.
- AI can also be used to bind the nitrogen present in the steel, so that the optionally added boron can develop its strength-increasing effect.
- aluminum of more than 1.0% by weight to 2.0% by weight can be alloyed in a targeted manner in order to at least partially compensate for the weight increase of the additional cover layer to be applied by reducing the density.
- Cr may also contribute, as an optional alloying element, to the setting of the strength, in particular to a positive effect on the hardenability, with a content in particular of at least 0.05% by weight.
- Cr can be used alone or in combination with other elements as carbide formers. Because of the positive effect on the toughness of the material the Cr content can preferably be adjusted to at least 0.1% by weight, more preferably to at least 0.2% by weight.
- the alloying element is limited to a maximum of 1.5% by weight, in particular a maximum of 1.2% by weight, preferably a maximum of 1.0% by weight, in order to ensure sufficient weldability.
- B as an optional alloying element in atomic form, retards the microstructure transformation to ferritin / bainite and improves the hardenability and strength, in particular when N is bound by strong nitride formers such as Al or Nb, and can be used with a content in particular of at least 0.0001% by weight. % to be available.
- the alloying element is limited to a maximum of 0.01% by weight, in particular to a maximum of 0.005% by weight, since higher contents may adversely affect the material properties, in particular based on the ductility at grain boundaries, and a reduction in hardness and / or Strength would result.
- Ti, Nb, V and / or W can be alloyed as optional alloying elements singly or in combination for grain refining, moreover, Ti can be used for setting N. Above all, however, these elements can be used as micro-alloying elements to form strengthening carbides, nitrides and / or carbonitrides. To ensure their effectiveness Ti, Nb, V and / or W can be used at levels of at least 0.005 wt .-%. For complete setting of N, the content of Ti should be at least 3.42 * N.
- the alloying elements are limited in combination to a maximum of 0.2 wt .-%, in particular at most 0, 15 wt .-%, preferably at most 0, 1 wt .-%, since higher contents adversely affect the material properties, in particular adversely on the Toughness of the material.
- Mo can optionally be added to increase the strength and improve the through-hardenability. Furthermore, Mo has a positive effect on the toughness properties. Mo can be used as a carbide former to increase the yield strength and improve toughness. In order to ensure the effectiveness of these effects, a content of at least 0.1% by weight, preferably at least 0.2% by weight, is required. For reasons of cost, the maximum content is limited to 1% by weight, preferably 0.7% by weight.
- Cu as an optional alloying element can contribute to a hardness increase at a level of from 0.05% to 0.5% by weight by precipitation hardening.
- P is an iron companion, which has a strong toughening effect and is one of the undesirable accompanying elements in wear or safety steels. In order to use its strength-increasing effect, it can optionally be alloyed with contents of at least 0.005% by weight. P can lead to strong segregation due to its low diffusion rate during solidification of the melt. For these reasons, the element is set to max. 0, 15 wt .-%, in particular a maximum of 0.06 wt .-%, preferably a maximum of 0.03 wt .-% limited.
- S has a strong tendency to segregation in steel and forms undesirable FeS, which is why it must be set by Mn.
- the S content is therefore limited to a maximum of 0.03% by weight, in particular 0.02% by weight, preferably 0.01% by weight, particularly preferably 0.005% by weight.
- Ca may optionally be added to the melt as a desulfurizing agent and for selective sulphide imparting in amounts of up to 0.015% by weight, preferably up to 0.005% by weight, which leads to an altered plasticity of the sulphides in the hot rolling.
- the addition of calcium preferably also improves the cold forming behavior. The effects described are effective from 0.0015% by weight, and therefore this limit is chosen to be minimum when Ca is used.
- Ni which can optionally be alloyed up to a maximum of 5.0% by weight, positively influences the deformability of the material. By reducing the critical cooling rate, nickel also increases through-cure and throughput.
- a content of at least 0.2 wt .-% is alloyed.
- Sn, As and / or Co are alloying elements which, individually or in combination, can be counted as impurities if they are not deliberately alloyed to set specific properties.
- the contents are limited to a maximum of 0.05% by weight of Sn, to a maximum of 0.02% by weight of Co, to a maximum of 0.02% by weight of As.
- oxide deposits in particular on the separating layer between core and cover layer, prevent the diffusion between the deliberately differently alloyed steels. hinders, as described for example in the document DE 10 2016 204 567.9.
- the maximum content of oxygen is given as 0.005% by weight, preferably 0.002% by weight.
- the element hydrogen is therefore reduced to a content of not more than 0.001% by weight, in particular not more than 0.0006% by weight, preferably not more than 0.0004% by weight, more preferably not more than 0.0002% by weight.
- the cover layers for providing the bending / forming aid consist of a soft, ductile steel, which can be easily reshaped and in particular has a high elongation at break.
- the steel for the cover layers is selected so that it has the lowest possible hardenability.
- Steels are alloyed so that in particular nitrogen and carbon are completely bonded by elements such as Ti, Nb, V, W and / or Cr.
- Mn 0.05 to 2.5%
- the optional alloying elements N, Si, Mn, Al, Cr, B, Ti, Nb, V, W, Mo, Cu, P, Ca, Ni may alternatively also be present as an impurity at lower levels.
- the cover layer C is limited as an alloying element to a maximum of 0, 15 wt .-%, in particular at most 0, 10 wt .-%, preferably at most 0.06 wt .-%.
- the topsheet is ULC steels in which the maximum carbon content is limited to 0.03 wt%.
- IF steels are used as the cover layer, for which a C content of not more than 0.01% by weight is specified.
- a maximum content of 0.005 wt .-%, particularly preferably 0.003 wt .-% is preferably set. Due to the process, a minimal content of C can not be economically avoided. Therefore, the lower limit for the C content is given as 0.001 wt%.
- N also increases the hardenability of the steel as an optional alloying element in dissolved form, but can optionally also be used specifically for nitride or carbonitride formation with Al, B, Ti, Nb, V, W, Cr and / or Mo.
- nitrogen content is limited to a maximum of 0.01 wt .-%, preferably 0.005 wt .-%. Due to the process, a minimal content of N can not be economically avoided. Therefore, the optional lower limit for the N content is given as 0.001 wt%.
- Si, Mn, P, Mo, Cr, Cu and Ni are optional alloying elements that can be used in an alternative embodiment of the inventive concept to increase the strength of the cover layer to reduce the hardness difference between the core layer and cover layer and the durability of the cover layer z , B. to increase against abrasive wear.
- Mn also serves to bind S to MnS.
- Al can be used optionally for deoxidation, wherein a content of at least 0.005 wt .-%, in particular with 0.01 wt .-% may be present.
- the content is limited to a maximum of 0.5 wt .-%, especially at most 0, 1 wt .-%, preferably at most 0.05 wt .-%, so as not to adversely affect the material properties.
- B may optionally contribute to hardenability as an alloying element in a less preferred embodiment of the present invention, especially when N is set and may be present at a level in particular of at least 0.0001% by weight, preferably 0.0005% by weight, particularly preferably 0.0010% by weight.
- the alloying element is at most 0.01 wt .-%, in particular to a maximum of 0.005 wt .-%, since higher contents have an adverse effect on the material properties and lead to excessive unwanted hardening of the cover layer.
- Ti, Nb, V, W, Cr and Mo can be alloyed as alloying elements singly or in combination for grain sizeening and / or C and N setting, the use of Ti, Nb and V preferably being preferred for cost reasons becomes.
- Ti, Nb and / or V can be used at levels of at least 0.001 wt .-%, preferably 0.005 wt .-%, particularly preferably 0.01 wt .-%.
- the stoichiometry sets the contents of Ti, Nb, V, W, Cr and Mo such that
- the alloying elements Ti, Nb, V and W are limited in combination to a maximum of 0.3% by weight, in particular not more than 0.2% by weight Ti + Nb + V + W is limited to a maximum of 0.15% by weight, particularly preferably 0.1% by weight, since higher contents have a disadvantageous effect on the material properties, in particular on the toughness of the material optional alloying elements Cr and Mo have already been given above.
- S has a strong tendency to segregation in steel and forms undesirable FeS, which is why it must be set by Mn.
- the S content is therefore limited to a maximum of 0.03% by weight, in particular 0.02% by weight, preferably 0.01% by weight, particularly preferably 0.005% by weight.
- the melt may optionally be added to the melt as desulfurizing agent and for selective sulphide-influencing in amounts of up to 0.015% by weight, in particular up to 0.005% by weight, which leads to an altered plasticity of the sulphides in the hot rolling.
- the addition of calcium preferably also improves the cold forming behavior. The described effects are effective from 0.0015% by weight, therefore this limit is chosen as minimum with optional use of Ca.
- Sn, As and / or Co are alloying elements, individually or in combination, if they are not specifically added to set specific properties, to the impurities can be counted.
- the contents are limited to a maximum of 0.05% by weight of Sn, to a maximum of 0.02% by weight of As, to a maximum of 0.02% by weight of Co.
- 0 is usually undesirable, but may also be beneficial in the lowest levels in the present invention, since oxide occupations particularly on the interface between the core and cover layer hinders the diffusion between the deliberately differently alloyed steels, such as in the document DE 10 2016 204 567.9 described.
- the maximum content of oxygen is given as 0.005% by weight, preferably 0.002% by weight.
- the element hydrogen is therefore reduced to a content of not more than 0.001% by weight, in particular not more than 0.0006% by weight, preferably not more than 0.0004% by weight, more preferably not more than 0.0002% by weight.
- All mentioned optional alloying elements can be present in contents below the specified minimum value as impurities without disturbing effect in the cover layer of the wear or security steels according to the invention.
- unalloyed steels, low-alloyed steels, microalloyed steels or IF steels can be used as exemplary representatives for the cover layers of both the wear-resistant steel according to the invention and the safety steel according to the invention.
- the cover layers of the soft, ductile steel each have a material thickness between 1% and 12%, in particular between 2% and 10%, preferably between 3% and 8%, particularly preferably 3% and 6% per Page related to the total material thickness of the wear steel or safety steel.
- the total material thickness is between 2.0 and 40.0 mm, in particular between 3.0 and 30.0 mm and preferably between 6.0 and 20.0 mm.
- the wear steel or safety steel may have a symmetrical or asymmetrical structure in relation to the specified outer layer portions.
- the wear or safety steel on one or both sides of a metallic corrosion protection coating in particular based on zinc.
- a metallic corrosion protection coating in particular based on zinc.
- the wear steel or safety steel depending on the design one or both sides. provided with an electrolytic zinc coating.
- the performance of an electrolytic coating has the advantage that the properties, in particular of the core layer, are not adversely affected, in particular by thermal influences, as occur, for example, when a hot dip coating is carried out.
- the wear steel or safety steel can be provided on one or both sides with an organic coating, preferably with a lacquer. As a result, wear steels or safety steels with improved appearance of lacquer can be provided.
- the wear steel or safety steel is produced by means of plating, in particular roll cladding or by casting.
- the wear-resistant steel or safety steel according to the invention is preferably produced by means of hot-roll cladding, as described, for example, in German Patent DE 10 2005 006 606 B3. Reference is made to this patent application, the content of which is hereby incorporated by reference in this application, wherein the production step of the hasp to a coil is to be regarded as an optional process step.
- the method for producing the composite material according to the invention in particular for thicknesses from about 10 mm, this takes place completely in plate or sheet form.
- An additional contribution to the delay of crack initiation can be achieved by the diffusion of core layer and cover layers, which takes place in the hot layer cladding, since a kind of edge decarburization in the core layer takes place in the boundary layer region of the core layer as a result of the migration of the carbon from the core layer into the cover layers, whereby locally a comparison is achieved to the remaining area of the core layer more ductile area arises. Due to the diffusion processes, there is also a substantially continuous and no sudden transition of the material properties (hardness / strength) between the core layer and the cover layers.
- the cover layers in the hot state advantageously have a reduced resistance to deformation compared to the core layer due to the higher ductility, so that they deform during hot roll plating respectively hot rolling in the direction of the core layer and thus in particular production-related defects, such as air pockets between the layers can close by the rolling assembly.
- This is especially advantageous for later use or use, so that it can not come in the case of wear and tear to outbreaks or in the case of impact stress to unwanted shock wave due to the defects.
- the wear steel or safety steel of the present invention may be produced by casting, and a possibility for its production is disclosed in Japanese Patent Laid-Open Publication JP-A 03 133 630.
- Metallic composite fabrication is generally known in the art.
- the accelerated cooling takes place in a preferred embodiment, directly after the hot roll plating or hot rolling without prior cooling from the rolling heat.
- the cooling is terminated at a temperature below the martensite start temperature Ms of the core layer, preferably below the martensite finish temperature of Mf of the core layer, more preferably at most 100 ° C above room temperature.
- the curing may also take place as follows: after hot rolling, the material initially cools to temperatures below 500 ° C., in order to avoid undesired effects such as grain growth or coarsening of precipitates.
- the cooling can take place both in the coil or as a plate in air and by exposure to a cooling medium such as water or oil.
- a cooling medium such as water or oil.
- cooling to below 100 ° C. is preferred, more preferably to a temperature close to room temperature.
- the composite material is at least partially austenitized and heated to a temperature at least above A cl of the core layer.
- a complete austenitization and a corresponding heating to at least A c3 of the core layer are carried out.
- the austenitizing temperature is limited to a maximum of 1100 ° C, to avoid unwanted Austenitkorn growth preferably to a maximum (Ac3 + 200 ° C), particularly preferably to a maximum (Ac3 + 100 ° C), wherein A c3 refers to the core layer ,
- the material composite for curing is accelerated to a temperature of less than 500 ° C., preferably less than 300 ° C., more preferably less than 100 ° C.
- a temperature of less than 500 ° C. preferably less than 300 ° C., more preferably less than 100 ° C.
- the methods for tempering treatment correspond to the usual procedures disclosed in the prior art for single-layer materials for an alloy concept which corresponds to the respective core layer of the composite material according to the invention.
- the material composite can optionally be rolled up into a coil for logistical reasons and then rewound in preparation for the next production step.
- the invention relates to a method for producing a component having a ballistic protective effect, wherein a security steel according to the invention is cold-formed. Since the cover layers of the security steel according to the invention are particularly readily deformable, optimum bending properties, in particular in the edge fiber, are present, and the security steel according to the invention can be formed with a smaller bending radius than a monolithic security steel having the same composition.
- the manufactured component is used to protect living beings in vehicles or buildings.
- the invention relates to a method for producing a component which is to be exposed to high abrasive wear, wherein a wear-resistant steel according to the invention is cold-formed. Since the cover layers of the security steel according to the invention are particularly well deformable, optimum bending properties are present and the wear steel according to the invention can be formed with a smaller bending radius than a monolithic wear steel having the same composition.
- the manufactured component is used in construction, agricultural, mining or transport machines, especially in dump trucks.
- Figure 1 shows a schematic section through a wear steel according to the invention respectively safety steel.
- the three-layer wear steel or safety steel (1) according to the invention comprises a core layer (1.1) made of a steel which, when hardened or tempered, has a hardness> 350 HBW, in particular> 400 HBW, preferably> 500 HBW, more preferably> 550 HBW, more preferably> 600 HBW and two cohesively bonded to the core layer (1.1) cover layers (1.2) made of a softer steel, wherein the cover layers (1.2) have at least 20% lower hardness than the core layer (1.1) in the cured or tempered state, with a hardness ⁇ 400 HBW, in particular ⁇ 350 HBW, preferably ⁇ 300 HBW, particularly preferably ⁇ 250 HBW, further preferred given ⁇ 200 HBW.
- the wear steel or safety steel (1) can have a metallic corrosion protection coating (1.3) on both sides.
- the core layer (1.1) is in addition to Fe and production-related unavoidable impurities in wt .-% of
- the cover layers (1.2) consist of Fe and production-related unavoidable impurities in% by weight
- Mn 0.05 to 2.5%
- the material thickness of the cover layers (1.2) can be between 1% and 12%, in particular between 2% and 10%, preferably between 3% and 8% per side based on the total material thickness of the wear steel or safety steel (1).
- a security steel according to the invention and a wear steel according to the invention were produced by means of hot-rolled cladding, each of which had a three-layer material composite.
- the top layers used were each a micro-alloyed steel designated S315MC or an IF steel designated DC05, and the core layer was a steel designated XAR®500 or XAR®600 for the production of wear steel and a steel designated SECURE500 or SECU-RE600 or SECURE 650 used for the production of safety steel.
- the cover layers each had a material thickness of 10% per side based on the total material thickness of the wear steel, whereas the material thicknesses of the cover layers of the safety steel each amounted to 5% per side based on the total material thickness of the safety steel. Both the safety steel and the wear-resistant steel were combined with all specified variants of the cover layer in all specified variants of the core layer.
- Sheet metal blanks having two cover layers and a core layer arranged therebetween were stacked on top of each other, which were connected to one another in a cohesive manner at least in regions along their edges, preferably by means of welding.
- the precoat was brought to a temperature> 1100 ° C and hot rolled in several steps to a composite material with a total material thickness of 6 mm.
- the material composite was then coated on both sides with a zinc-based coating a layer thickness of 20 ⁇ electrolytically coated.
- the layer thicknesses can be between 5 and 30 ⁇ .
- All boards which had a size of 6000 mm ⁇ 1200 mm, were heated to austenitizing temperature, in particular above A c3 based on the core layer in an oven for about 180 minutes and soaked and were then to adjust the desired hardness in the Core situation deterred. Before quenching, the boards were clamped in a cooling unit, a so-called quette, to ensure a substantially distortion-free thermal treatment. The quenching was carried out by exposure to water. Other liquid media for deterrence are also usable. The cooling rates in the core of the composite were controlled by previously introduced thermocouples and were> 20 K / s.
- the core layers of the security steel according to the invention and the wear-resistant steel according to the invention had a structure of predominantly martensite and / or bainite, in particular substantially martensite.
- cover layers in the case of the top layer S315MC, a mixed structure with proportions of ferrite, bainite and partly martensite has been established.
- cover layer DC05 In the case of the cover layer DC05, a substantially ferritic microstructure with small amounts of bainite and / or martensite was observed, which is attributed to carbon diffusion from the core layer.
- the monolithic reference steels had comparable properties to the corresponding core layers with the same composition.
- the critical bending radius r of the monolithic SECURE 500 safety steel with the DC05 support material was determined to be approximately 30 mm, with narrower bending radii leading to surface cracking in the bending area
- the critical bending radius r for the monolithic wear steel XAR 500 with the bearing material DC05 was determined to be about 23.5 mm, while smaller bending radii resulted in cracking of the surface in the bending region even with monolithic wear steel 21 mm, bending radii could be implemented without difficulty in the inventive wear steel
- the possibility of implementing a smaller bending radius is greater in the case of the wear steel according to the invention in comparison to the safety steel according to the invention, which is the result of the slight ig greater material thickness of the top layers is owed.
- a reduction of the critical bending radius in the case of wear steels and safety steels according to the invention in comparison to monolithic reference steels with the same properties is accompanied by a slight increase
- the wear steel or safety steel according to the invention can also be formed from a tailored product, for example a tailored blank and / or tailored roiled blank.
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- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Heat Treatment Of Articles (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
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Abstract
Applications Claiming Priority (2)
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DE102017208252.6A DE102017208252A1 (de) | 2017-05-16 | 2017-05-16 | Dreilagiger Verschleißstahl oder Sicherheitsstahl, Verfahren zur Herstellung einer Komponente und Verwendung |
PCT/EP2018/061341 WO2018210574A1 (fr) | 2017-05-16 | 2018-05-03 | Acier résistant à l'usure ou acier de sécurité à trois couches, procédé de fabrication d'un élément et utilisation |
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EP3625046A1 true EP3625046A1 (fr) | 2020-03-25 |
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EP18722028.0A Withdrawn EP3625046A1 (fr) | 2017-05-16 | 2018-05-03 | Acier résistant à l'usure ou acier de sécurité à trois couches, procédé de fabrication d'un élément et utilisation |
Country Status (9)
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US (1) | US20200061971A1 (fr) |
EP (1) | EP3625046A1 (fr) |
KR (1) | KR20200004839A (fr) |
AU (1) | AU2018268764A1 (fr) |
BR (1) | BR112019023531A2 (fr) |
CA (1) | CA3056409A1 (fr) |
DE (1) | DE102017208252A1 (fr) |
MX (1) | MX2019013272A (fr) |
WO (1) | WO2018210574A1 (fr) |
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BR112019024206A2 (pt) * | 2017-05-16 | 2020-06-02 | Thyssenkrupp Steel Europe Ag | Material de moldagem a quente, componente e emprego |
DE102018220116A1 (de) * | 2018-11-23 | 2020-05-28 | Thyssenkrupp Ag | Ballistisches Produkt und seine Verwendung |
DE102019215055A1 (de) * | 2019-09-30 | 2021-04-01 | Thyssenkrupp Steel Europe Ag | Verfahren zur Herstellung eines Stahlproduktes sowie ein entsprechendes Stahlprodukt |
CN112496036A (zh) * | 2020-11-12 | 2021-03-16 | 太原理工大学 | 一种通过轧制制备金属梯度材料的方法 |
EP4309838A1 (fr) * | 2021-03-31 | 2024-01-24 | JFE Steel Corporation | Tôle d'acier plaquée, élément et procédés de production associés |
KR20230153445A (ko) * | 2021-03-31 | 2023-11-06 | 제이에프이 스틸 가부시키가이샤 | 클래드 강판 및 부재, 그리고, 그것들의 제조 방법 |
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JPH03133630A (ja) | 1989-10-20 | 1991-06-06 | Nippon Steel Corp | 耐デント性、耐面歪性に優れた良成形性クラッド鋼板 |
JPH0639656B2 (ja) * | 1990-02-02 | 1994-05-25 | 新日本製鐵株式会社 | 加工性および溶接性に優れた耐摩耗複合鋼板 |
JPH106037A (ja) * | 1996-06-25 | 1998-01-13 | Sumitomo Metal Ind Ltd | 刃物用クラッド鋼板の製造方法 |
DE102005006606B3 (de) | 2005-02-11 | 2006-03-16 | Thyssenkrupp Steel Ag | Verfahren zum Herstellen von walzplattiertem Warmband zur Weiterverarbeitung zu Kaltband und gewickeltes Coil aus solchem Warmband |
JP4960289B2 (ja) * | 2008-03-27 | 2012-06-27 | 国立大学法人 東京大学 | 複層鋼 |
ES2709433T3 (es) * | 2008-05-07 | 2019-04-16 | Thyssenkrupp Steel Europe Ag | Material compuesto con efecto de protección balística |
EP2886332B1 (fr) * | 2013-12-20 | 2018-11-21 | ThyssenKrupp Steel Europe AG | Produit en acier plat, et procédé de fabrication d'un composant d'une carrosserie de véhicule automobile et d'une carrosserie de véhicule automobile. |
DE102016204567A1 (de) | 2016-03-18 | 2017-09-21 | Thyssenkrupp Ag | Verfahren zum Herstellen eines warmwalzplattierten Werkstoffverbundes, Flachproduktpaket, warmwalzplattierter Werkstoffverbund sowie seine Verwendung |
CN107310218B (zh) * | 2016-04-26 | 2019-03-29 | 宝山钢铁股份有限公司 | 一种复合防弹钢板及其制造方法 |
CN107310219B (zh) * | 2016-04-26 | 2019-03-29 | 宝山钢铁股份有限公司 | 一种冷弯加工性能优良的防弹钢板及其制造方法 |
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2017
- 2017-05-16 DE DE102017208252.6A patent/DE102017208252A1/de not_active Withdrawn
-
2018
- 2018-05-03 MX MX2019013272A patent/MX2019013272A/es unknown
- 2018-05-03 CA CA3056409A patent/CA3056409A1/fr not_active Abandoned
- 2018-05-03 KR KR1020197035018A patent/KR20200004839A/ko unknown
- 2018-05-03 BR BR112019023531A patent/BR112019023531A2/pt not_active Application Discontinuation
- 2018-05-03 AU AU2018268764A patent/AU2018268764A1/en not_active Abandoned
- 2018-05-03 US US16/611,637 patent/US20200061971A1/en not_active Abandoned
- 2018-05-03 EP EP18722028.0A patent/EP3625046A1/fr not_active Withdrawn
- 2018-05-03 WO PCT/EP2018/061341 patent/WO2018210574A1/fr unknown
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CA3056409A1 (fr) | 2018-11-22 |
WO2018210574A1 (fr) | 2018-11-22 |
KR20200004839A (ko) | 2020-01-14 |
BR112019023531A2 (pt) | 2020-05-19 |
DE102017208252A1 (de) | 2018-11-22 |
US20200061971A1 (en) | 2020-02-27 |
AU2018268764A1 (en) | 2019-10-17 |
MX2019013272A (es) | 2020-01-13 |
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