EP1599299B1 - Procede de traitement d'un produit en acier, et produit obtenu par ce traitement - Google Patents
Procede de traitement d'un produit en acier, et produit obtenu par ce traitement Download PDFInfo
- Publication number
- EP1599299B1 EP1599299B1 EP04710868A EP04710868A EP1599299B1 EP 1599299 B1 EP1599299 B1 EP 1599299B1 EP 04710868 A EP04710868 A EP 04710868A EP 04710868 A EP04710868 A EP 04710868A EP 1599299 B1 EP1599299 B1 EP 1599299B1
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- EP
- European Patent Office
- Prior art keywords
- steel product
- rolling
- steel
- product
- rolls
- 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.)
- Expired - Lifetime
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 175
- 239000010959 steel Substances 0.000 title claims abstract description 175
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000012545 processing Methods 0.000 title claims abstract description 23
- 238000005096 rolling process Methods 0.000 claims abstract description 112
- 230000002093 peripheral effect Effects 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000011282 treatment Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000009749 continuous casting Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910000859 α-Fe Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000734 martensite Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001563 bainite Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 description 91
- 239000000463 material Substances 0.000 description 21
- 230000009467 reduction Effects 0.000 description 20
- 230000008859 change Effects 0.000 description 8
- 238000010008 shearing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 229910001208 Crucible steel Inorganic materials 0.000 description 6
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 6
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- 230000008569 process Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 150000001247 metal acetylides Chemical class 0.000 description 5
- 238000003303 reheating Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
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- 230000007423 decrease Effects 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- -1 iron carbides Chemical class 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910000922 High-strength low-alloy steel Inorganic materials 0.000 description 2
- QFGIVKNKFPCKAW-UHFFFAOYSA-N [Mn].[C] Chemical compound [Mn].[C] QFGIVKNKFPCKAW-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
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- 229910052804 chromium Inorganic materials 0.000 description 2
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- 238000005097 cold rolling Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- UKGJZDSUJSPAJL-YPUOHESYSA-N (e)-n-[(1r)-1-[3,5-difluoro-4-(methanesulfonamido)phenyl]ethyl]-3-[2-propyl-6-(trifluoromethyl)pyridin-3-yl]prop-2-enamide Chemical compound CCCC1=NC(C(F)(F)F)=CC=C1\C=C\C(=O)N[C@H](C)C1=CC(F)=C(NS(C)(=O)=O)C(F)=C1 UKGJZDSUJSPAJL-YPUOHESYSA-N 0.000 description 1
- YGYGASJNJTYNOL-CQSZACIVSA-N 3-[(4r)-2,2-dimethyl-1,1-dioxothian-4-yl]-5-(4-fluorophenyl)-1h-indole-7-carboxamide Chemical compound C1CS(=O)(=O)C(C)(C)C[C@@H]1C1=CNC2=C(C(N)=O)C=C(C=3C=CC(F)=CC=3)C=C12 YGYGASJNJTYNOL-CQSZACIVSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 238000005496 tempering Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/02—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
- B21B1/026—Rolling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/16—Control of thickness, width, diameter or other transverse dimensions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
- B21B2001/225—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length by hot-rolling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
- B21B2001/383—Cladded or coated products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B2267/00—Roll parameters
- B21B2267/02—Roll dimensions
- B21B2267/06—Roll diameter
- B21B2267/065—Top and bottom roll have different diameters; Asymmetrical rolling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B2275/00—Mill drive parameters
- B21B2275/02—Speed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B2275/00—Mill drive parameters
- B21B2275/02—Speed
- B21B2275/04—Roll speed
- B21B2275/05—Speed difference between top and bottom rolls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B3/02—Rolling special iron alloys, e.g. stainless steel
-
- 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
-
- 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
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- 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
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
Definitions
- the invention relates to a method for processing a steel product, in which the steel product is passed between a set of rotating rolls of a rolling mill stand.
- This rolling mill stand may be part of a rolling mill device consisting of one or more rolling mill stands.
- Rolling is a very standard operation for imparting desired dimensions and properties to metal in general and steel in particular. Apart from obtaining the desired final geometry of the steel product, rolling also results in an improvement to the structure as a result of the metallurgical processes taking place during and after the rolling.
- the conventional rolling which for wide products is usually considered to be a plane strain compression process, results in a considerable change in thickness, which in some cases is undesirable or impossible.
- steel plate with a thickness of 60 to 150 mm for, inter alia, the production of off-shore platforms or bridges. Since cast steel slabs currently have a maximum thickness of less than 400 mm, the change in thickness caused by the rolling to 150 mm would only amount to approximately 60%.
- Each pass through a conventional rolling mill stand usually results in a change in thickness of 10 to 30%.
- the casting of slabs sometimes results in the formation of porosity in the slab, a characteristic which is inherent to the casting process.
- This porosity is closed up by the pressure applied as a result of the slabs being rolled a sufficient number of times.
- the rolling only closes up the pores in the outermost layers of the slab, and not those in the core of the material.
- the pores in the core of the material are highly disadvantageous for the mechanical properties of the material, in particular for the toughness properties of the plate.
- grain refinement only occurs in the outermost layers of the plate.
- the degree of rolling through the thick slab therefore has to be high, whereas the combination of starting thickness of the slab and final thickness of the steel product do often not allow a large thickness reduction.
- the method is particularly intended to prevent the formation of coarse grains in austenitic stainless steel plates having a thickness of more than 50 mm.
- JP 55045507 a method is proposed wherein a shearing deformation is imparted to a metal cast piece by means of rolling between an upper and a lower roll having a different peripheral speed.
- Yet another object of the invention is to provide a method for processing a steel product which results in grain refinement in the product which is thereby produced.
- Yet another object of the invention is to provide a method for processing continuously cast steel by means of which the properties of the slab or strip are improved.
- steel should be considered to comprise all ferrous alloys for example ultra-low carbon steels, low-carbon steels, medium to high carbon steels, electrical steels, and stainless steels.
- a steel product in the context of this invention comprises ingots, slabs, blooms, billets, bar, rod, strip and profiled sections.
- a method for processing a continuously cast steel product in which the steel is passed between a set of rotating rolls of a rolling mill stand in order to roll the steel product, wherein the rolls of the rolling mill stand have different peripheral velocities such that one roll is a faster moving roll and the other roll is a slower moving roll, wherein the peripheral velocity of the faster moving roll is at least 5% and at most 100% higher that that of the slower moving roll, wherein the thickness of the steel product is reduced by at most 15% for each pass, and wherein that the rolling takes place at a maximum temperature of 1350°C.
- shearing occurs in the steel product and has been found to occur throughout the entire thickness of the product. It has been found that this requires a velocity difference of at least 5%.
- the shearing leads to pores in the continuously cast material being closed up to a considerable extent. This does not require a major change in thickness, but rather a change in thickness of at most 15% can suffice.
- this thickness reduction is at most 8% and more preferable at most 5%. This is particularly advantageous in the processing of those steel products where the dimensions of the steel product at the start of the process do not allow a singificant reduction in the thickness direction, because the thickness is substantially retained.
- the rolling according to the invention can result in a grain refinement which occurs throughout the entire thickness of the rolled material, which is advantageous for the mechanical properties of the slab or strip.
- the strength of the material increases.
- the beneficial effects of smaller grain sizes are commonly known.
- the rolling is preferably carried out at an elevated temperature.
- the maximum temperature is limited to 1350°C because the formation of low melting oxides on the surface of the steel product to be produced has to be avoided.
- the elevated temperature makes the rolling run more smoothly.
- the peripheral velocity of the faster moving roll is preferably at most 50% higher and more preferably at most 20% higher than that of the slower moving roll. If there is a high difference in velocity, there is a considerable risk of slipping between the rolls and the steel product, which would result in uneven shearing.
- the rolling mill is designed in such a manner that the rolls have different diameters. This makes it possible to obtain the desired difference in peripheral velocity.
- the rolls have a different rotational speed. This too makes it possible to obtain the desired difference in rotational speed.
- the steel product is introduced between the rolls at an angle of between 5 and 45° with respect to the perpendicular to the plane through the center axes of the rolls.
- Introducing the steel product between the rolls at an angle makes it easier for the rolls to grip the steel product, with the result that the change in thickness can be kept as low as possible.
- the steel product is preferably fed in at an angle of between 10 and 25°, and more preferably at angle of between 15 and 25°, since with such an angle the steel product comes out of the rolling mill with a good level of straightness. It should be noted that the latter effect is also dependent on the reduction in the size of the steel product, the type of steel product and the alloy and the temperature.
- the processing operating is preferably repeated one or more times.
- sufficiently good grain refinement is obtained by carrying out the processing operating according to the invention three times.
- the number of times that the processing operation has to be carried out depends on the thickness of the steel product, the difference in peripheral velocity of the rolls and the desired grain refinement. It is desirable for the steel product to be introduced between the rolls at an angle of between 5 and 45°, preferably between 10 and 25° and more preferably between 15 and 25° during each processing operation.
- the steel product can be passed through the rolling mill stand in opposite directions for each pass.
- the steel product then changes direction after each rolling operation and is always passed through the same rolling mill stand.
- the rolls have to rotate in opposite directions for each pass.
- the steel product is successively passed through two or more rolling mill stands.
- This method is suitable primarily for strip material, which in this way can undergo the desired processing operation very quickly.
- the rolling is carried out on a steel product of which at least a skin layer has a substantially austenitic structure, and preferably on a steel product having a substantially austenitic structure throughout.
- Typical minimum temperatures range from 900 °C for an ultra low carbon steel to 800-870 °C for a low carbon steel (depending on the chemical composition of course) to about 723 °C for a steel with 0.8 %C. In all cases the maximum temperature is 1350 °C. In case of rolling an austenitic stainless steel, the rolling always takes place on an austenitic structure.
- the rolling is carried out on a steel product of which at least a skin layer has a substantially austenitic-ferritic two-phase structure, and preferably on a steel product having a substantially austenitic-ferritic two-phase structure throughout.
- Typical temperatures range for a low carbon steel from 723 °C ending at 800-870 °C. The temperature range decreases with increasing carbon contents to reduce to an eutectoid point of about 723 °C for a steel with 0.8 %C.
- the rolling is carried out on a steel product of which at least a skin layer has a substantially ferritic structure, and preferably on a steel product having a substantially ferritic structure throughout.
- a steel product of which at least a skin layer has a substantially ferritic structure, and preferably on a steel product having a substantially ferritic structure throughout.
- the maximum temperature is about 723 °C, whereas for steels with lower carbon contents such as ultra low carbon steels the maximum temperature is about 850 °C.
- these temperature boundaries for the ferritic, ferritic-austenitic and austenitic region depend on the composition of the steel and on the thermomechanical history of the steel.
- the phase transformation is not instantaneous once a critical temperature is exceeded and therefore a transforming steel may have a skin layer of a different phase compared to the centre layer of the steel product.
- the rolling is performed at temperatures between 0 °C and 720°C.
- This comprises not only the cold rolling of the ferritic steel product, but also the advantageous rolling of steel with a martensitic structure or the austenitic stainless steel structure.
- a steel product is produced according to a method comprising the steps of:
- the most commonly used method to produce steel slabs is by continuous casting of a steel strand and cutting it into steel slabs with a thickness of between 200 and 400 mm. After casting, these slabs are usually allowed to cool down to ambient temperatures before being introduced in the furnaces of a hot strip mill. In some cases the slabs can be introduced into the furnace while it is still warm or hot from casting (respectively so-called “hot-charging” or “direct-charging”).
- the thickness of the continuously cast strand is preferably below 150 mm, more preferably below 100 mm and even more preferably below 80 mm for thin slab casting.
- the cast strand may be cut after casting by means of a cutting device.
- the thus obtained slabs may be stored for later processing and allowed to cool down or they may be processed immediately.
- the slabs may require reheating prior to rolling, in the latter case the slabs may require to be homogenised in temperature.
- After finish rolling the rolled product may be cooled using accelerated cooling and optionally coiled.
- After the final processing step the steel product cools or is cooled to ambient temperatures.
- the cast strand is not cut into slabs, but processed immediately by continuous, endless or semi-endless rolling, the rolled product will be cut in a later stage of the rolling process e.g. before the optional coiler. It will be obvious that the rolling according to the invention may take place anywhere between the casting step and the final cooling step, or even thereafter.
- the steel product Prior to coiling the steel product may be subjected to accelerated cooling. After the final processing step the steel product cools or is cooled to ambient temperatures.
- the thickness of the continuously cast strand is preferably below 20 mm, more preferably below 10 mm and even more preferably below 5 mm.
- the cast strand having a cast microstructure may be cut after casting by means of a cutting device.
- the thus obtained slabs may be stored for later processing and allowed to cool down or they may be processed immediately.
- the slabs may require reheating prior to rolling, or they may be used as final product.
- the slabs may require to be homogenised in temperature.
- One drawback of the strip-cast steel products is that the end product still largely has the cast microstructure, since the strip has scarcely been rolled. Consequently, the mechanical properties of the end products are relatively poor, and consequently the use of the end products is limited and do not meet the standards of the products obtained through the conventional thick slab or even the more recent thin slab route.
- the microstructure is transformed from a casting structure to a wrought microstructure without substantial reduction in thickness thereby improving the final properties of the steel product significantly.
- finish rolling the rolled product may be cooled using accelerated cooling and optionally coiled.
- the steel product cools or is cooled to ambient temperatures.
- the cast strand is not cut into slabs, but processed immediately by continuous, endless or semi-endless rolling, the rolled product will be cut in a later stage of the rolling process e.g. before the optional coiler.
- the rolled product may be cooled using accelerated cooling.
- the steel product cools or is cooled to ambient temperatures.
- a further advantage is obtained if the steel product to be processed according to the previous two embodiments is a stainless steel.
- stainless steel comprises both ferritic, austenitic-ferritic duplex steels and austenitic stainless steels. These steels are commonly applied in application where the corrosion resistance of unalloyed or low-alloy steel is inadequate. The combination of corrosion resistance, high strength and good ductility usually associated with the duplex stainless steels results in applications where the formability of ferritic and austenitic stainless steels is inadequate.
- Typical examples of a ferritic stainless steels according to EN 10088 (1995) are X2CrNi12- 1.4003 (410) X6Cr14 - 1.4016 (430), and of austenitic stainless steels are X5CrNiMo17-12-2 1.4401 (316) X5CrNi18-10 - 1.4301 (304). These steels are typically used as general-purpose stainless steels in plate, strip, semi-, bar, rod and applied as construction steels for buildings, pipelines, kitchenware, components in pumps and valves etc.
- the thickness of the slab or strip is preferably reduced by at most 15% for each pass, and preferably by at most 8% and more preferably by at most 5% for each pass. Since the shearing and therefore the grain refinement are brought about by the difference in peripheral velocity between the rolls, the reduction in thickness of the material is not required to obtain grain refinement. The reduction in thickness is required primarily in order to enable the rolls to grip the material. This only requires a slight change in thickness, which is advantageous in the case of thin continuously cast steel slab, strip cast material and strip material. The smaller the reduction, the thicker the slab or strip remains after each pass. The possible applications of continuously cast slabs and strip material increase as a result.
- HSLA-steels high strength, low alloy
- the continuously cast slabs that are used to start the rolling process with usually have a fixed thickness of between 200 and 350 mm, for example 225 mm.
- the rolling mills also usually are divided in a roughing section where the slab is rolled down in a number of passes, for example 5 passes, to a chosen thickness of, for example, 36 mm.
- This so-called transfer bar thickness is usually a fixed thickness within a given hot strip mill and the deviations from this fixed value are minimal. Deviations from this value by increasing its value usually results in rolling forces or torques in the finishing mill which exceed operational limits, thereby causing risks to the rolling mill or resulting in unacceptable changes in the shape and profile of the product. Decreasing the thickness of the transfer bar usually results in rolling forces or torques in the roughing mill which exceed operational limits.
- the fixed value of the transfer bar also causes a problem because it results in different values of reduction for a thick strip of for example 18 mm and a thin strip of for example 4 mm. In the first case the total reduction in the finishing mill is 50%, in the second case it is 89%.
- the degree of deformation of the steel product can be increased without the need to increase the transfer bar thickness, or the degree of deformation can be kept unchanged while the final thickness of the steel product is increased.
- steel billets which are rolled into profiled sections such as H-sections
- steel billets for sections usually have a gauge between 200 and 400 mm, for example 230 mm or 310 mm. These are rolled in the slab/bloom/billet stage after reheating to a temperature of maximal 1350°C. Finish rolling occurs usually at a temperature where the steel is austenitic and flange thicknesses range from 10 to 150 mm.
- Non-limitative examples for typical steel grades used for these sections comprise CMn-steels and HSLA-steels.
- the process according to the invention allows a finer grainsize of the billet because of the larger degree of deformation in the billet, and also allows a reduction in the pore size of the billet, resulting in better fracture toughness.
- the average grainsize of the steel product obtained is preferably smaller than 5 ⁇ m, more preferably smaller than 2 ⁇ m and even more preferably smaller than 1 ⁇ m.
- the properties of complex phase steels are unexpectedly improved because of the accumulation of strain in the steel without substantially reducing the thickness.
- the large degree of accumulated deformation allows the steel to transform to a very fine ferrite grain in combination with a very finely distributed fine-grained second phase consisting of bainite or martensite.
- a small amount of carbides may also be present.
- the ferrite content of this steel product is preferably at least 60%, more preferably at least 70% and even more preferably at least 80%.
- the average grainsize of the steel product obtained is preferably smaller than 5 ⁇ m, more preferably smaller than 2 ⁇ m and even more preferably smaller than 1 ⁇ m.
- the starting point is a continuously cast slab with a typical thickness between 200 and 350 mm. These slabs are reheated in a reheating furnace to a temperature between 1000 and 1350°C. After reheating these slabs are rolled to a thickness of between 30 to 200 mm, preferably 40 to 150 mm and held at temperature, for instance by shielding it against cooling. During this holding period at high temperature grain growth takes place as a result of which the final mechanical properties of the finished plate may also deteriorate. It is common knowledge that a larger grain size decreases the ductility properties and the toughness of a steel product.
- the plate receives a heat treatment during the production process.
- This may for example be a normalisation treatment wherein the slab is reheated into the austenite region and allowed to cool down in still air or a tempering anneal or stress relief anneal which both aim to reduce the level of internal stresses.
- a heat treatment is the speroidisation treatment in which elongated carbides are transformed into more or less spheroidal particles. These carbides may be iron carbides (e.g. cementite) or other metal carbides like chromium carbides. This type of annealing treatment is used often in steels with carbon contents in excess of 0.8%. Unfortunately, the majority of these heat treatments and particularly the spheroidisation treatments take a long time and frequently lead to decarburisation of the surface part of the strip thereby adversely affecting the properties.
- the rolling according to the invention can also be carried out at low temperatures between 0 and 720 °C. Special benefits from the rolling can be expected when performed at low temperatures (i.e. cold rolling) because of the resulting breaking up of undesired particles. As a result of the break up of the particles the final properties of the steel product are improved.
- the shearing as a result of the rolling process breaks up the particles in the steel products, for example metal carbides like cementite or chromium carbides which may result in an improved toughness.
- the break up of the particles also affects the heat treatment response of the steel product. Different heating and cooling regimes can be employed leading to improved throughput through the heat treatment stage, e.g. a spheroidisation annealing treatment, or an improved product.
- the method according to the invention is also possible for the method according to the invention to be preceded or followed by a heat treatment of the steel product.
- heat treatments are the well known normalising treatment, stress relief annealing treatment, temper annealing treatment or spheroidisation annealing treatment.
- a steel product also comprises a steel where one or both steel surfaces which are to be rolled are covered with one or more layers prior to rolling according to the invention.
- This combination of a steel product covered on one or both surfaces with one or more layers of metal is commonly referred to as cladded plate or strip.
- cladded plate In producing clad plate there are three options by which the covering metal is bonded to the steel substrate: explosive bonding, roll bonding and weld overlay.
- One of the important factors affecting the quality of clad plate is the quality of the adhesion between the substrate and the cladding layer.
- a surface of the steel product which is to be rolled is covered by one or more layers prior to rolling.
- the covering layer can be a metal, preferably another steel, e.g. a steel with a different composition or a stainless steel, Titanium, Nickel, Copper, Aluminium or alloys thereof.
- laminated material such as what is known as clad material for use in, for example, pipes and pipe lines, chemical plants, power plants, vessels, pressure vessels.
- the invention also relates to an improved metal plate or strip which has been produced by continuous casting, preferably with the aid of the method according to the first aspect of the invention, in which the pores in the core of the plate or strip have a maximum dimension of less than 200 ⁇ m, preferably less than 100 ⁇ m, more preferably less than 20 ⁇ m and even more preferably less than 10 ⁇ m.
- continuously cast plate and strip material always has pores which can be significantly larger than 200 ⁇ m.
- the standard rolling operations can only close up these pores in the core to a slight extent or cannot do so at all.
- the rolling operation according to the invention makes it possible to provide continuously cast plate and strip material having pores which are much smaller.
- the invention also relates to an improved metal plate or strip which is produced by continuous casting, preferably with the aid of the method according to the first aspect of the invention, in which the metal plate or strip, after recrystallisation, has a substantially homogenous degree of recrystallisation over its entire thickness.
- the starting point is a steel ingot
- the pores in the core of the product preferably have a maximum dimension of less than 200 ⁇ m, more preferably less than 100 ⁇ m, still more preferably less than 20 ⁇ m and even more preferably less than 10 ⁇ m as well as to a steel product produced by continuous casting and processed according to the invention, in which the pores in the core of the plate or strip have a maximum dimension of less than 200 ⁇ m, more preferably less than 100 ⁇ m, still more preferably less than 20 ⁇ m and even more preferably less than 10 ⁇ m.
- the invention also relates to a steel strip produced according to the invention for use in for example parts of automobiles, transport equipment, piling, buildings, construction and to a clad steel product for use in for example pipes, chemical plants, power plants, vessels, pressure vessels and to a steel strip wherein the steel is a HSLA-steel comprising at least one of the elements niobium, titanium, vanadium or boron, or wherein the steel is an ultra low carbon steel, preferably at least partly stabilised, preferably with at least one of the elements titanium, niobium or boron.
- the slabs were introduced at different angles varying between 5° and 45°.
- the temperature of the slabs when they were introduced into the rolling device was approximately 1000 °C.
- the two rolls were driven at a speed of 5 revolutions per minute.
- the slabs After rolling, the slabs had a certain curvature, which is highly dependent on the angle of introduction.
- the straightness of the slab after rolling can to a large extent be determined by the angle of introduction, in which context the optimum angle of introduction will be dependent on the degree of reduction of the slab, the type of material and alloy, and the temperature.
- an optimum introduction angle is approximately 20°.
- the rolling using the method according to the invention results in an equivalent strain which is three to four times higher than with conventional rolling without any difference in peripheral velocity.
- a high equivalent strain means less porosity in the slab, greater recrystalization and therefore greater grain refinement, and more extensive breaking up of the second-phase particles (constituent particles) in the slab. These effects are generally known to the person skilled in this field of engineering if the equivalent strain increases. Therefore, the rolling according to the invention means that the resulting properties of the material are greatly improved as a result of the use of the method according to the invention.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Metal Rolling (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
Claims (26)
- Procédé pour traiter un produit en acier, dans lequel le produit en acier est amené à passer entre un ensemble de cylindres en rotation d'une cage de laminoir afin de laminer le produit en acier, les cylindres de la cage de laminoir ayant des vitesses périphériques différentes de telle sorte qu'un premier cylindre est un cylindre à mouvement plus rapide et que l'autre cylindre est un cylindre à mouvement plus lent, caractérisé en ce que la vitesse périphérique du cylindre à mouvement plus rapide est supérieure d'au moins 5%, et au maximum supérieure de 100% à celle du cylindre à mouvement plus lent, en ce que l'épaisseur du produit en acier est réduite d'au moins 15% par passe et en ce que le laminage a lieu à une température maximale de 1350°C.
- Procédé selon la revendication 1, dans lequel l'épaisseur du produit en acier est réduite tout au plus de 8% à chaque passe, et de préférence plutôt plus de 5% à chaque passe.
- Procédé selon la revendication 1 ou 2, dans lequel la vitesse périphérique du cylindre à mouvement plus rapide est supérieure tout au plus de 50%, et de préférence supérieure tout au plus de 20% à celle du cylindre à mouvement plus lent.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le laminoir est conçu de façon que les cylindres aient des diamètres différents.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel les cylindres ont des vitesses de rotation différentes.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le produit en acier est introduit entre les cylindres suivant un angle de 5 à 45° par rapport à la perpendiculaire au plan passant par les axes centraux des cylindres, de préférence suivant un angle de 10 à 25° et de préférence encore suivant un angle de 15 à 25°.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le laminage est répété une ou plusieurs fois après le laminage initial.
- Procédé selon la revendication 7, dans lequel le produit en acier est amené à passer dans la cage de laminoir dans des directions opposées pour chaque passe.
- Procédé selon la revendication 7, dans lequel le produit en acier est amené à passer successivement par deux ou plus de deux cages de laminoir.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le laminage décrit dans l'une des revendications 1 à 9 est précédé ou suivi d'un laminage qui est effectué à l'aide d'un laminoir dans lequel les cylindres ont des vitesses périphériques sensiblement identiques.
- Procédé selon l'une quelconque des revendications 1 à 10, dans lequel le laminage est effectué sur un produit en acier dont au moins une couche superficielle a une structure sensiblement austénitique, et de préférence sur un produit en acier ayant partout une structure sensiblement austénitique.
- Procédé selon l'une quelconque des revendications 1 à 10, dans lequel le laminage est effectué sur un produit en acier dont au moins une couche superficielle a une structure à deux phases sensiblement austénitique-ferritique, et de préférence sur un produit en acier ayant partout une structure à deux phases sensiblement austénique-ferritique.
- Procédé selon l'une quelconque des revendications 1 à 10, dans lequel le laminage est effectué sur un produit en acier dont au moins une couche superficielle a une structure sensiblement ferritique, et de préférence sur un produit en acier ayant partout une structure sensiblement ferritique.
- Procédé selon l'une quelconque des revendications 1 à 10, dans lequel le laminage est effectué tandis que la température du produit en acier est supérieure à 0°C et inférieure à 720°C.
- Procédé selon la revendication 14, dans lequel le laminage est effectué sur un produit en acier à structure sensiblement martensitique.
- Procédé pour réaliser un produit en acier, comprenant les étapes consistant à :• couler en continu une barre d'acier ;• éventuellement chauffer et/ou rendre homogène la température de la barre d'acier entre une machine de coulée et un dispositif de laminage;• éventuellement laminer le produit en acier dans une ou plusieurs cages de laminoir du dispositif de laminage, les cylindres ayant des vitesses périphériques sensiblement identiques;• éventuellement réaliser un refroidissement accéléré après la dernière passe de laminage ;• éventuellement découper le produit en acier en brames ou en bobines avant ou après le laminage ;• éventuellement enrouler en bobine le produit en acier ;• refroidir le produit en acier.caractérisé en ce que, entre la coulée de la barre et le refroidissement accéléré ou le bobinage ou le refroidissement ou après le refroidissement, le produit en acier est soumis au procédé selon l'une quelconque des revendications 1 à 10.
- Procédé pour réaliser un produit en acier selon la revendication 16, caractérisé en ce que l'épaisseur de la barre coulée est inférieure à 150 mm, de préférence inférieure à 100 mm, de préférence encore inférieure à 80 mm.
- Procédé pour réaliser un produit en acier selon la revendication 16, caractérisé en ce que l'épaisseur de la barre coulée est inférieure à 20 mm, de préférence inférieure à 10 mm, de préférence encore inférieure à 5 mm.
- Procédé selon la revendication 16 ou 18, dans lequel le produit en acier réalisé est un produit en acier inoxydable.
- Procédé pour réaliser un produit en acier selon les revendications 16 à 19, caractérisé en ce que le laminage est effectué sur un produit en acier à structure sensiblement austénitique, en ce que l'acier est ensuite soumis à un refroidissement accéléré, en ce que le produit en acier est sensiblement constitué de ferrite, de bainite et/ou de martensite, et en ce que la teneur en ferrite après refroidissement est de préférence d'au moins 60%, de préférence supérieure à 70% et de préférence encore supérieure à 80%.
- Procédé pour réaliser un produit en acier selon les revendications 16 à 20, dans lequel la taille moyenne des grains du produit en acier est inférieure à 5 µm, de préférence inférieure à 2 µm et de préférence encore inférieure à 1 µm.
- Procédé selon l'une quelconque des revendications 1 à 21, dans lequel le produit en acier est soumis à un traitement thermique avant ou après le laminage, par exemple à un traitement de normalisation, un recuit complet, un recuit de détente ou un traitement de recuit de sphéroïdisation.
- Procédé selon l'une quelconque des revendications 1 à 21, dans lequel une surface du produit en acier destiné à être laminé est couverte par une ou plusieurs couches avant le laminage.
- Procédé selon la revendication 23, dans lequel la couche de couverture est un métal, de préférence un autre acier, par exemple un acier à composition différente ou un acier inoxydable, du titane, du nickel, du cuivre, de l'aluminium ou des alliages de ceux-ci.
- Produit en acier réalisé suivant le procédé selon l'une quelconque des revendications 1 à 10, dans lequel on part d'un lingot d'acier, les pores de la partie centrale de ce produit en acier ayant de préférence une taille maximale inférieure à 200 µm, de préférence inférieure à 100 µm, de préférence encore inférieure à 20 µm et de préférence même inférieure à 10 µm.
- Produit en acier selon la revendication 25, caractérisé en outre en ce que le produit en acier est une tôle, un feuillard ou une billette d'acier réalisé par coulée continue.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04710868A EP1599299B1 (fr) | 2003-02-24 | 2004-02-13 | Procede de traitement d'un produit en acier, et produit obtenu par ce traitement |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03075546A EP1449596A1 (fr) | 2003-02-24 | 2003-02-24 | Méthode pour le traitement d'un produit en acier et produit fabriqué utilisant cette méthode |
EP03075546 | 2003-02-24 | ||
EP04710868A EP1599299B1 (fr) | 2003-02-24 | 2004-02-13 | Procede de traitement d'un produit en acier, et produit obtenu par ce traitement |
PCT/EP2004/001502 WO2004073900A1 (fr) | 2003-02-24 | 2004-02-13 | Procede de traitement d'un produit en acier, et produit obtenu par ce traitement |
Publications (2)
Publication Number | Publication Date |
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EP1599299A1 EP1599299A1 (fr) | 2005-11-30 |
EP1599299B1 true EP1599299B1 (fr) | 2007-07-04 |
Family
ID=32731582
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP03075546A Withdrawn EP1449596A1 (fr) | 2003-02-24 | 2003-02-24 | Méthode pour le traitement d'un produit en acier et produit fabriqué utilisant cette méthode |
EP04710868A Expired - Lifetime EP1599299B1 (fr) | 2003-02-24 | 2004-02-13 | Procede de traitement d'un produit en acier, et produit obtenu par ce traitement |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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EP03075546A Withdrawn EP1449596A1 (fr) | 2003-02-24 | 2003-02-24 | Méthode pour le traitement d'un produit en acier et produit fabriqué utilisant cette méthode |
Country Status (15)
Country | Link |
---|---|
US (1) | US20070051439A1 (fr) |
EP (2) | EP1449596A1 (fr) |
JP (1) | JP2006520692A (fr) |
KR (1) | KR20050100701A (fr) |
CN (1) | CN1767910A (fr) |
AT (1) | ATE366149T1 (fr) |
AU (1) | AU2004213135A1 (fr) |
BR (1) | BRPI0407621B1 (fr) |
DE (1) | DE602004007362D1 (fr) |
MX (1) | MXPA05008979A (fr) |
PT (1) | PT1599299E (fr) |
RU (1) | RU2005129721A (fr) |
UA (1) | UA85550C2 (fr) |
WO (1) | WO2004073900A1 (fr) |
ZA (1) | ZA200506720B (fr) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
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NL1018815C2 (nl) * | 2001-08-24 | 2003-02-25 | Corus Technology B V | Werkwijze voor het bewerken van een metalen plak of knuppel, en daarmee vervaardigd product. |
EP1846584B2 (fr) | 2005-02-02 | 2022-12-14 | Tata Steel IJmuiden B.V. | Acier austénitique à haute résistance et procédé pour sa fabrication et son utilisation |
EP1942995B1 (fr) | 2005-09-26 | 2012-08-15 | University Of Leeds | Extincteur d'incendie |
ES2583143T3 (es) * | 2006-07-27 | 2016-09-19 | The University Of Tokyo | Acero de varias capas y procedimiento de producción de acero de varias capas |
WO2009135514A1 (fr) * | 2008-05-09 | 2009-11-12 | Ady Palti | Outil chirurgical destiné notamment à l'usinage d'os pour la pose d'un implant dentaire |
US8522471B2 (en) * | 2010-06-25 | 2013-09-03 | Pacific Aerospace & Electronics, Inc. | Firearms and firearm components comprising bonded multi-metallic materials; methods of manufacture |
KR101230139B1 (ko) * | 2010-12-28 | 2013-02-05 | 주식회사 포스코 | 스테인리스강의 연속 냉간 압연 방법 |
CN102154537A (zh) * | 2011-02-14 | 2011-08-17 | 南京润邦金属复合材料有限公司 | 碳素工具钢/普碳钢高耐磨高均匀性高寿命冶金用复合衬板 |
KR101342487B1 (ko) | 2011-06-29 | 2013-12-17 | 포항공과대학교 산학협력단 | 층상 구조를 구비한 강판의 제조 방법 |
JP5382257B1 (ja) * | 2013-01-10 | 2014-01-08 | 大日本印刷株式会社 | 金属板、金属板の製造方法、および金属板を用いて蒸着マスクを製造する方法 |
JP5455099B1 (ja) | 2013-09-13 | 2014-03-26 | 大日本印刷株式会社 | 金属板、金属板の製造方法、および金属板を用いてマスクを製造する方法 |
JP5516816B1 (ja) | 2013-10-15 | 2014-06-11 | 大日本印刷株式会社 | 金属板、金属板の製造方法、および金属板を用いて蒸着マスクを製造する方法 |
JP5641462B1 (ja) | 2014-05-13 | 2014-12-17 | 大日本印刷株式会社 | 金属板、金属板の製造方法、および金属板を用いてマスクを製造する方法 |
KR101857382B1 (ko) | 2015-02-10 | 2018-05-11 | 다이니폰 인사츠 가부시키가이샤 | 증착 마스크의 제조 방법, 증착 마스크를 제작하기 위해 사용되는 금속판 및 그 제조 방법 |
PL3445507T3 (pl) * | 2016-05-11 | 2020-11-30 | Nucor Corporation | Kontrola zmiany temperatury taśmy przy bezpośrednim odlewaniu taśm |
Family Cites Families (4)
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AT357587B (de) * | 1976-02-18 | 1980-07-25 | Voest Alpine Ag | Verfahren zum herstellen von blechen aus aus- tenitischen staehlen mit feinem korn |
JPS5913281B2 (ja) * | 1978-09-25 | 1984-03-28 | 新日本製鐵株式会社 | 金属鋳片の熱間圧延方法 |
JPS6044104A (ja) * | 1983-08-22 | 1985-03-09 | Nippon Kokan Kk <Nkk> | 調質圧延方法 |
JPS6152317A (ja) * | 1984-08-20 | 1986-03-15 | Kobe Steel Ltd | 低温靭性にすぐれた熱延鋼板の製造方法 |
-
2003
- 2003-02-24 EP EP03075546A patent/EP1449596A1/fr not_active Withdrawn
-
2004
- 2004-02-13 WO PCT/EP2004/001502 patent/WO2004073900A1/fr active IP Right Grant
- 2004-02-13 RU RU2005129721/02A patent/RU2005129721A/ru not_active Application Discontinuation
- 2004-02-13 EP EP04710868A patent/EP1599299B1/fr not_active Expired - Lifetime
- 2004-02-13 KR KR1020057015675A patent/KR20050100701A/ko not_active Application Discontinuation
- 2004-02-13 JP JP2006501871A patent/JP2006520692A/ja not_active Withdrawn
- 2004-02-13 AU AU2004213135A patent/AU2004213135A1/en not_active Abandoned
- 2004-02-13 UA UAA200509038A patent/UA85550C2/ru unknown
- 2004-02-13 BR BRPI0407621-4A patent/BRPI0407621B1/pt not_active IP Right Cessation
- 2004-02-13 CN CNA2004800086191A patent/CN1767910A/zh active Pending
- 2004-02-13 US US10/546,192 patent/US20070051439A1/en not_active Abandoned
- 2004-02-13 AT AT04710868T patent/ATE366149T1/de not_active IP Right Cessation
- 2004-02-13 ZA ZA200506720A patent/ZA200506720B/en unknown
- 2004-02-13 MX MXPA05008979A patent/MXPA05008979A/es active IP Right Grant
- 2004-02-13 PT PT04710868T patent/PT1599299E/pt unknown
- 2004-02-13 DE DE602004007362T patent/DE602004007362D1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE602004007362D1 (de) | 2007-08-16 |
RU2005129721A (ru) | 2006-04-27 |
UA85550C2 (ru) | 2009-02-10 |
ATE366149T1 (de) | 2007-07-15 |
AU2004213135A1 (en) | 2004-09-02 |
JP2006520692A (ja) | 2006-09-14 |
BRPI0407621A (pt) | 2006-02-21 |
US20070051439A1 (en) | 2007-03-08 |
WO2004073900A1 (fr) | 2004-09-02 |
CN1767910A (zh) | 2006-05-03 |
EP1449596A1 (fr) | 2004-08-25 |
KR20050100701A (ko) | 2005-10-19 |
MXPA05008979A (es) | 2006-04-27 |
BRPI0407621B1 (pt) | 2014-06-17 |
PT1599299E (pt) | 2007-09-11 |
ZA200506720B (en) | 2006-11-29 |
EP1599299A1 (fr) | 2005-11-30 |
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