CN105102142A - Thick steel plate manufacturing device and manufacturing method - Google Patents
Thick steel plate manufacturing device and manufacturing method Download PDFInfo
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- CN105102142A CN105102142A CN201480018472.8A CN201480018472A CN105102142A CN 105102142 A CN105102142 A CN 105102142A CN 201480018472 A CN201480018472 A CN 201480018472A CN 105102142 A CN105102142 A CN 105102142A
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- steel plate
- cooling
- cooling water
- descale
- partition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
- B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
- B21B45/0203—Cooling
- B21B45/0209—Cooling devices, e.g. using gaseous coolants
- B21B45/0215—Cooling devices, e.g. using gaseous coolants using liquid coolants, e.g. for sections, for tubes
- B21B45/0218—Cooling devices, e.g. using gaseous coolants using liquid coolants, e.g. for sections, for tubes for strips, sheets, or plates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
- B21B45/04—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing
- B21B45/08—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing hydraulically
-
- 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
- B21B15/00—Arrangements for performing additional metal-working operations specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
- B21B2015/0071—Levelling the rolled product
-
- 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
- B21B37/74—Temperature control, e.g. by cooling or heating the rolls or the product
- B21B37/76—Cooling control on the run-out table
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Heat Treatments In General, Especially Conveying And Cooling (AREA)
- Metal Rolling (AREA)
- Heat Treatment Of Strip Materials And Filament Materials (AREA)
Abstract
The purpose of the present invention is to provide a thick steel plate manufacturing device and manufacturing method in which, by leveling, in a descaling step, scale occurring on the surface of the thick steel plate, cooling is evenly performed in a cooling step, achieving excellent steel plate shape. In this thick steel plate manufacturing device, a hot-rolling device, a shape correction device, a descaling device and an accelerated cooling device are arranged in that order from the upstream side of the conveyance direction, wherein the energy density E of the cooling water sprayed at the surface of the thick steel plate by the descaling device is 0.10 J/mm<2> or greater.
Description
Technical field
The present invention relates to carry out steel plate hot rolling, the manufacturing equipment of steel plate of shape correction and controlled cooling model and manufacture method.
Background technology
In recent years, as the manufacturing process of steel plate, controlled cooling model be applied in expansion.But usually, the shape, surface texture etc. of hot-working steel plate are not necessarily uniform.Therefore, in steel plate, easily produce temperature in cooling uneven, it is uneven etc. that cooled steel plate can produce distortion, residual stress, material, causes bad, the operational trouble of quality thus.
Therefore, Patent Document 1 discloses following method: at least one situation in before the final passage being about to carry out finish rolling and after the final passage of just having carried out finish rolling, carry out descale, then carry out heat straightening, then carry out descale, and carry out pressure cooling.In addition, Patent Document 2 discloses following method: after carrying out finish rolling, heat straightening, after carrying out descale, carry out controlled cooling model again.In addition, Patent Document 3 discloses following method: before being about to carry out controlled cooling model, while the impact pressure of controlled cooling model water, carry out descale.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 9-57327 publication
Patent document 2: No. 3796133rd, Japan Patent
Patent document 3: Japanese Unexamined Patent Publication 2010-247228 publication
Summary of the invention
Invent problem to be solved
But in the method for above-mentioned patent document 1,2, when reality manufactures steel plate, there are the following problems: in descale, oxide skin can not be peeled off completely, can produce oxide skin inequality on the contrary, can not cool uniformly when controlled cooling model because of descale.In addition, in the method for patent document 3, in order to not produce oxide skin inequality, need high impact pressure.Therefore, there are the following problems: utilize during low impact pressure and can produce oxide skin inequality, consequently, can not cool uniformly when controlled cooling model.
Particularly in recent years, the level of the uniform in material required by steel plate becomes strict, the uneven harmful effect brought to the uniform in material of particularly steel plate width of cooling velocity when can not ignore the controlled cooling model produced because oxide skin is uneven as above.
Therefore, the an open question that the present invention is conceived to above-mentioned conventional example completes, and its object is to provide the homogenising by realizing the oxide skin produced on steel plate surface in descale operation and cools uniformly in refrigerating work procedure thus make manufacturing equipment and the manufacture method of the steel plate that steel plate shape is excellent.
For the method for dealing with problems
The present inventor conducts in-depth research the power causing oxide skin to peel off because of cooling water, found that, when carrying out descale after hot shape correction, if the energy density of the cooling water sprayed from descale device to steel plate is 0.10J/mm
2above, then the scale thickness that the surface after making product produces becomes even.Find consequently, when passing through from accelerated cooling device, producing the deviation of the surface temperature of the width position of steel plate hardly, can cool equably, form the steel plate that steel plate shape is excellent.
Purport of the present invention is as described below.
[1] a kind of manufacturing equipment of steel plate, it is characterized in that, by hot-rolling mill, shape correction device, descale device and accelerated cooling device with the configuration from carriage direction upstream side of this order, the energy density E that the cooling water that above-mentioned descale device is sprayed to the surface of steel plate has is 0.10J/mm
2above.
The manufacturing equipment of the steel plate [2] as described in [1], it is characterized in that, by from above-mentioned descale device to the travelling speed of above-mentioned accelerated cooling device be set to V [m/s], by cooling before steel plate temperature be set to T [K] time, the distance L [m] from above-mentioned descale device to above-mentioned accelerated cooling device meets formula L≤V × 5 × 10
-9× exp (25000/T).
The manufacturing equipment of the steel plate [3] as described in [2], is characterized in that, configures each device in the mode that the distance L made from above-mentioned descale device to above-mentioned accelerated cooling device is below 12m.
The manufacturing equipment of the steel plate [4] according to any one of [1] to [3], is characterized in that, makes the jet length H from the injection nozzle of above-mentioned descale device to the surface of above-mentioned steel plate be more than 40mm and below 200mm.
The manufacturing equipment of the steel plate [5] according to any one of [1] to [4], it is characterized in that, the collector that above-mentioned accelerated cooling device possesses the upper surface supply cooling water to above-mentioned steel plate, the cooling water injection nozzle of the bar-shaped cooling water of injection dangled from this collector and the partition be arranged between above-mentioned steel plate and above-mentioned collector, further, above-mentioned partition is provided with the admission port of the bottom of multiple interpolation above-mentioned cooling water injection nozzle and the cooling water drainage of the upper surface being supplied to above-mentioned steel plate is put into the discharge outlet above above-mentioned partition.
[6] a kind of manufacture method of steel plate, its order according to hot-rolled process, heat straightening operation and accelerating cooling operation manufactures steel plate, it is characterized in that, it is 0.10J/mm that energy density E is sprayed on the surface had between above-mentioned heat straightening operation and refrigerating work procedure to steel plate
2the descale operation of above cooling water.
The manufacture method of the steel plate [7] as described in [6], is characterized in that, terminates to meet formula t≤5 × 10 to the time t [s] above-mentioned accelerating cooling operation from above-mentioned descale operation
-9× exp (25000/T).Wherein, T is the steel plate temperature (K) before cooling.
Invention effect
According to the present invention, by realizing the homogenising of the oxide skin produced on steel plate surface in descale operation, can cool uniformly in accelerating cooling operation, the steel plate that steel plate shape is excellent can be manufactured.
Accompanying drawing explanation
Fig. 1 is the skeleton diagram of the example representing heavy plate rolling production line.
Fig. 2 is the energy density of the cooling water representing in descale device, spray and the figure of the relation of the scale thickness produced at the product surface of steel plate.
Fig. 3 be represent in descale device, the figure of the jet length of injection nozzle and the relation of fluid velocity.
Fig. 4 is the side view of the cooling device of an embodiment of the invention.
Fig. 5 is the side view of other cooling devices of an embodiment of the invention.
Fig. 6 is the figure be described the nozzle arrangement example of the partition of an embodiment of the invention.
Fig. 7 be to partition above the figure that is described of the flowing of cooling draining.
Fig. 8 be to partition above other figure of being described of flowing of cooling draining.
Fig. 9 is the figure be described the steel plate width Temperature Distribution of conventional example.
Figure 10 is the figure be described the flowing of the cooling water in accelerated cooling device.
Figure 11 be to the partition in accelerated cooling device above the figure that is described of the non-interfering of cooling draining.
Detailed description of the invention
Below, be described for implementing mode of the present invention with reference to accompanying drawing.It should be noted that, at this, be described for the situation of cooling the present invention being used for the steel plate in heavy plate rolling technique.
Fig. 1 is the skeleton diagram of an example of the heavy plate rolling production line represented for enforcement of the present invention.Utilize roll mill 3 to implement roughing and finish rolling on the steel billet taken out from heating furnace 2, be rolled into the steel plate 1 of regulation thickness of slab.Then, after utilizing descale device 4 oxide skin produced on the surface of steel plate 1 to be removed, steel plate 1 is transported to accelerated cooling device 6 with online mode.At this, be applicable by carrying out accelerating cooling for cooled steel plate shape after the shape that adjusts steel plate from the first shape correction device 5.In accelerated cooling device 6, utilize the cooling water sprayed from upper surface cooling device and lower surface cooling device that steel plate is cooled to set point of temperature.Then, the shape of the second shape correction device 7 pairs of steel plates is utilized to correct as required.
Descale device 4 is by the device of the oxide skin removing produced on the surface of steel plate 1.In descale device 4, the surface of steel plate 1 after making multiple injection nozzle utilize the first shape correction device 5 to carry out the shape correction of the distortion that steel plate 1 produces after rolling, sprays cooling water from these nozzles.
The present inventor obtains following opinion: fully can not carry out oxide skin stripping because of descale condition, can encourage oxide skin inequality on the contrary.So, the condition of fully carrying out oxide skin stripping is conducted in-depth research, result specify that: when carrying out descale after shape correction, as shown in Figure 2, and the energy density E of the cooling water that the surface from the injection nozzle of descale device 4 to steel plate 1 is sprayed is 0.10J/mm
2above, the scale thickness making it rear regeneration is thus less than 5 μm, and becomes even.This is presumably because, by descale, oxide skin is temporarily peeled off equably completely, then, and thin and regeneration oxide skin equably.
In the present invention, the energy density E of cooling water is made to be 0.10J/mm
2more than carry out descale, thus, by the oxide skin removing produced on the surface of steel plate 1.Then, accelerated cooling device 6 is utilized to carry out the accelerating cooling of steel plate 1.In the present invention, the scale thickness of steel plate is made to become thin by descale and evenly, therefore, when passing through from accelerated cooling device, produce the surface temperature deviation of the width position of steel plate hardly, can cool equably, form the steel plate that steel plate shape is excellent.
Its reason is as described below.For existing rolling equipment, when carrying out oxide skin removing in descale device after shape correction, the locality of oxide skin generation is sometimes peeled off.Like this, oxide skin can not evenly be peeled off, and therefore produces the deviation of the scale thickness distribution of about 10 μm ~ about 50 μm.In this case, be difficult to cool equably steel plate in accelerated cooling device afterwards.That is, when carrying out accelerating cooling to the steel plate of the deviation creating scale thickness distribution in existing rolling equipment, the deviation of the surface temperature of width position is large, can not cool equably.Consequently, steel plate shape is had an impact.
Therefore, by utilizing descale device 4 to make the energy density E of cooling water for 0.10J/mm
2more than carry out descale, the deviation of scale thickness distribution can not be produced, therefore, when utilizing accelerated cooling device 6 pairs of steel plates 1 to cool, produce the deviation of the surface temperature of width position hardly, can cool equably.Consequently, the excellent steel plate of steel plate shape 1 can be manufactured.In addition, in the present case, even if when impact pressure is low, by regulating travelling speed, the descale same with when using high impact pressure can also be realized.
At this, to the energy density E (J/mm of the cooling water that steel plate sprays
2) be by the index of descale except the ability of descale, define as shown in following (1) formula.
E=Q/(d×W)×ρv
2/2×t…(1)
Wherein, Q is the injection flow [m of the deoxidation severe edema due to hypofunction of the spleen
3/ s], the d spray injection thickness [mm] that is flat burner, W be flat burner spray injection width [mm], fluid density ρ [kg/m
3], steel plate collision time fluid velocity v [m/s], collision time t [s] (t=d/1000/V, travelling speed V [m/s]).
But the mensuration of fluid velocity v during steel plate collision is not necessarily easy, therefore, if the energy density E that (1) formula of will strictly obtaining defines, then needs a large amount of labour.
Therefore, the present inventor is studied further, found that, as the energy density E (J/mm of the cooling water sprayed to steel plate
2) simple definition, water yield density × expulsion pressure × collision time can be adopted.At this, water yield density (m
3/ mm
2minute) be the value calculated with " the injection flow ÷ cooling water collision area of cooling water ".Expulsion pressure (N/m
2(=MPa)) define with the ejection pressure of cooling water.Collision time (s) is the value calculated with " travelling speed of the collision thickness ÷ steel plate of cooling water ".Utilize this energy density simply defining the cooling water calculated also same with Fig. 2 with the relation of the scale thickness produced at product surface, the energy density of cooling water is larger, then scale thickness is less.That is, energy density E is less than 0.10J/mm
2time, the deviation of the scale thickness of steel plate increases sometimes, can not cool equably, can not manufacture the steel plate that steel plate shape is excellent.On the other hand, energy density E is 0.10J/mm
2time above, such fault can be avoided.Therefore, in the present invention, the energy density E of cooling water is set as 0.10J/mm
2above, 0.15J/mm is more preferably
2above.
Then, the fluid velocity v of the present inventor to the cooling water that the injection nozzle from descale device 4 sprays investigates.Its result is recognized, the relation of fluid velocity v and jet length as shown in Figure 3.Fluid velocity as the longitudinal axis is obtained by resolving the equation of motion considering buoyancy and air drag.During arriving steel plate to cooling water, the fluid velocity v of cooling water slows down than when spraying.Therefore, jet length is less, then fluid velocity v during steel plate collision is larger, more can obtain large energy density.According to Fig. 3, when particularly jet length H is more than 200mm, decay increases, and therefore, jet length H is preferably set to below 200mm.
And jet length is shorter, then expulsion pressure, injection flow etc. for obtaining the energy density specified also can be less, can realize the reduction of the pump capacity of descale device 4.In an embodiment of the invention as shown in Figure 1, the steel plate 1 after utilizing the first shape correction device 5 to carry out shape correction moves in descale device 4, therefore, it is possible to make the injection nozzle of descale device 4 near the surface of steel plate 1.But consider the contact of injection nozzle and steel plate 1, the lower limit of jet length is preferably more than 40mm.Therefore, in the present invention, jet length H is preferably more than 40mm and below 200mm.
In addition, in descale device 4, the expulsion pressure of cooling water is preferably set to more than 10MPa, is more preferably set as more than 15MPa.Thereby, it is possible to the energy density of cooling water is set as 0.10J/mm when unduly reducing travelling speed
2above, be therefore effective.The higher limit of expulsion pressure is not particularly limited.But when improving expulsion pressure, the energy that the pump of supply water under high pressure consumes is huge, and therefore, expulsion pressure is preferably below 50MPa.
For bring impact to stability when utilizing the cooling of the steel plate 1 of accelerated cooling device 6, the oxide skin on the surface of steel plate 1, the growth of the oxide skin of steel plate 1 can control to arrange with diffusion rate usually, known Ru shown in following (2) formula.
ξ
2=a×exp(-Q/RT)×t…(2)
Wherein, ξ is scale thickness, a is constant, Q is activation energy, R is constant, T is steel plate temperature [K] before cooling, t is the time.
Therefore, consider the oxide scale growth after the oxide skin removing utilizing descale device 4, the simulated experiment of oxide scale growth is carried out under various temperature, time, experimentally derives the constant of above-mentioned (2) formula, and conducts in-depth research scale thickness and cooling stability further.Its result obtains following opinion: for cooling, stable when scale thickness is below 15 μm, more stable when scale thickness is below 10 μm, scale thickness be less than 5 μm highly stable.
When scale thickness is below 15 μm, based on above-mentioned (2) formula, following formula (3) can be derived.That is, when meeting following (3) formula from the time t [s] to the cooling of steel plate 1 utilizing accelerated cooling device 6 after utilizing the oxide skin of the steel plate 1 of descale device 4 to remove to terminate, the cooling of accelerated cooling device 6 is utilized to stablize.
t≤5×10
-9×exp(25000/T)…(3)
Wherein, T is the steel plate temperature [K] before cooling.
In addition, when scale thickness is below 10 μm, based on above-mentioned (2) formula, following formula (4) can be derived.Namely, removing from utilizing the oxide skin of the steel plate 1 of descale device 4 when meeting following (4) formula to the time t [s] of the cooling of steel plate 1 utilizing accelerated cooling device 6 after terminating, utilizing the cooling of accelerated cooling device 6 more stable.
t≤2.2×10
-9×exp(25000/T)…(4)
And then, when scale thickness is below 5 μm, based on above-mentioned (2) formula, following formula (5) can be derived.Namely, removing from utilizing the oxide skin of the steel plate 1 of descale device 4 when meeting following (5) formula to the time t [s] of the cooling of steel plate 1 utilizing accelerated cooling device 6 after terminating, utilizing the cooling of accelerated cooling device 6 highly stable.
t≤5.6×10
-10×exp(25000/T)…(5)
On the other hand, the distance L from the outlet side of descale device 4 to the entrance side of accelerated cooling device 6 sets in the mode meeting following (6) formula relative to the travelling speed V of steel plate 1 and time t (time from the operation that the operation of descale device 4 terminates to accelerated cooling device 6).
L≤V×t…(6)
Wherein, L be from descale device 4 to the distance (m) of accelerated cooling device 6, V be the travelling speed (m/s) of steel plate 1, t is the time (s)
Then, by above-mentioned (6) formula and above-mentioned (3) formula, following (7) formula can be derived.In the present invention, more preferably (7) formula is met.
L≤V×5×10
-9×exp(25000/T)…(7)
In addition, by above-mentioned (6) formula and above-mentioned (4) formula, following (8) formula can be derived.In the present invention, preferably (8) formula is met further.
L≤V×2.2×10
-9×exp(25000/T)…(8)
And then, by above-mentioned (6) formula and above-mentioned (5) formula, following (9) formula can be derived.In the present invention, preferably (9) formula is met.
L≤V×5.6×10
-10×exp(25000/T)…(9)
According to above-mentioned (7) ~ (9) formula, such as when making the temperature of the steel plate 1 before utilizing accelerated cooling device 6 to cool be 820 DEG C, making the travelling speed of steel plate 1 be 0.28 ~ 2.50m/s, from descale device 4 to the distance L of accelerated cooling device 6 be more than 12m and below 107m time cooling stable, distance L be more than 5m and below 47m time cooling more stable, distance L be more than 1.3m and below 12m time cool highly stable.
Thus, when making to be below 12m from descale device 4 to the distance L of accelerated cooling device 6, even if cooling is also stablized when travelling speed V slow (such as the V=0.28m/s) of steel plate 1, otherwise, cool highly stable when travelling speed V fast (such as the V=2.50m/s) of steel plate 1, therefore preferably.It should be noted that, more preferably from descale device 4 to the distance L of accelerated cooling device 6 be below 5m.
And then generally speaking, if consider to need the most travelling speed V of the steel plate 1 of controlled cooling model to be more than 0.5m/s, then preferred highly stable condition, i.e. the distance L of cooling under this travelling speed V is set as below 2.5m further.
It should be noted that, at this, be that the situation of 820 DEG C is illustrated to making the temperature of the steel plate 1 before utilizing accelerated cooling device 6 to cool.Be situation beyond 820 DEG C for making the temperature of the steel plate 1 before utilizing accelerated cooling device 6 to cool also be same, make to be preferably below 12m from descale device 4 to the distance L of accelerated cooling device 6, be more preferably below 5m, more preferably below 2.5m, can stably cool thus.This is because, when the temperature of the steel plate 1 before utilizing accelerated cooling device 6 to cool is lower than 820 DEG C, the value on the right of above-mentioned (7) formula, above-mentioned (8) formula, above-mentioned (9) formula increases respectively compared with the situation of T=820 DEG C, therefore, if for suitably set for the situation of T=820 DEG C from descale device 4 to the distance L of accelerated cooling device 6, then will inevitably meet above-mentioned (7) formula, above-mentioned (8) formula, above-mentioned (9) formula.Otherwise, when the temperature of the steel plate 1 before utilizing accelerated cooling device 6 to cool is higher than 820 DEG C, by suitably regulating lower by the travelling speed V of steel plate 1, above-mentioned (7) formula, above-mentioned (8) formula, above-mentioned (9) formula still can be met.
Then, as shown in Figure 4, accelerated cooling device 6 of the present invention preferably possess upper header 11 from the upper surface supply cooling water to steel plate 1, from the cooling water injection nozzle 13 of the bar-shaped cooling water of injection of this upper header 11 pendency and the partition 15 that is arranged between steel plate 1 and upper header 11, further, the admission port 16 partition 15 being provided with the bottom of multiple interpolation cooling water injection nozzle 13 and the discharge outlet 17 cooling water drainage of the upper surface being supplied to steel plate 1 is put into above partition 15.
Specifically, upper surface cooling device possess to steel plate 1 upper surface supply cooling water upper header 11, from this upper header 11 pendency cooling water injection nozzle 13 and be horizontally disposed with at whole steel plate width between upper header 11 and steel plate 1 and there is the partition 15 of multiple through hole (admission port 16 and discharge outlet 17).Further, cooling water injection nozzle 13 is formed by spraying the pipe nozzle 13 of bar-shaped cooling water, be inserted in its front end be arranged at above-mentioned partition 15 through hole (admission port 16) in and the mode more closer to the top than the bottom of partition 15 arrange.It should be noted that, for cooling water injection nozzle 13, blocking, preferably with in the mode injection upper header 11 making its upper end outstanding to the inside of upper header 11 to prevent the foreign matter of the bottom sucked in upper header 11.
At this, bar-shaped cooling water in the present invention refers to from the nozzle ejiction opening of circular (also comprising ellipse, polygon) with the cooling water sprayed by the state after to a certain degree pressurizeing, and is be more than 6m/s from the jet velocity of the cooling water of nozzle ejiction opening ejection, be preferably more than 8m/s and the cross section of the current ejected from nozzle ejiction opening roughly keeps the circular cooling water with the current of continuity and craspedodrome.That is, different from the free-falling stream sprayed from pipe laminar flow nozzle, the current that spray with the drop state as spraying.
To be inserted within the front end of cooling water injection nozzle 13 in through hole and the mode more closer to the top than the bottom of partition 15 arrange be because, even if when the steel plate of front end warpage upward enters, partition 15 also can be utilized to produce damage to prevent cooling water injection nozzle 13.Thus, cooling water injection nozzle 13 can cool chronically under good state, therefore, need not carry out equipment repairing etc., can prevent the generation of the temperature inequality of steel plate.
In addition, be inserted in through hole in the front end of pipe nozzle 13, therefore, as shown in figure 11, the width of the discharge water 19 of the dotted arrow that can not flow with the upper surface from partition 15 flows and interferes.Therefore, the cooling water ejected from cooling water injection nozzle 13 independently can arrive steel plate upper surface comparably with width position, can cool uniformly in the direction of the width.
If illustrate partition 15 one example, as shown in Figure 6, on partition 15 with on steel plate width on 80mm, carriage direction for the spacing of 80mm offers with the trellis of chessboard the through hole that multiple diameter is 10mm.Further, in admission port 16, the cooling water injection nozzle 13 that external diameter is 8mm, internal diameter is 3mm, length is 140mm is inserted with.Cooling water injection nozzle 13 arranges with staggered clathrate, and the through hole that cooling water injection nozzle 13 does not pass through is the discharge outlet 17 of cooling water.Like this, multiple through holes that the partition 15 of accelerated cooling device of the present invention is arranged are made up of the admission port 16 of roughly the same quantity and discharge outlet 17, the effect of sharing separately, function.
Now, the total sectional area of discharge outlet 17 is fully greater than the total sectional area of the internal diameter of the pipe nozzle 13 of cooling water injection nozzle 13, ensure that about 11 times of the total sectional area of the internal diameter of pipe nozzle 13, as shown in Figure 4, the cooling water being supplied to steel plate upper surface riddles between steel plate surface and partition 15, pass through from discharge outlet 17 and be conducted to the top of partition 15, and being quickly discharged.Fig. 7 be to partition above steel plate width end near the front view that is described of the flowing of cooling draining.The drainage direction of discharge outlet 17 is the upward direction contrary with cooling water injection direction, and the cooling draining passing the top of partition 15 changes direction outside steel plate width, flows through the drainage flow path between upper header 11 and partition 15 and is discharged.
On the other hand, the example shown in Fig. 8 makes discharge outlet 17 in steel plate width surface thereof, drainage direction is set as towards the example of the incline direction outside width towards the mode outside steel plate width.Thus, the steel plate width flowing of the discharge water 19 above partition 15 becomes smooth, and draining is promoted, therefore preferably.
At this, as shown in Figure 9, when discharge outlet and admission port are arranged in same through hole, after cooling water collision steel plate, be difficult to the top passing partition 15, thus to steel plate width endwall flow between steel plate 1 and partition 15.Like this, the end of flow more close to plate width of the cooling draining between steel plate 1 and partition 15 is then more, therefore, in plate width end, sprays the through delay moisture film of cooling water 18 and the power that arrives steel plate is more hindered.
When thin plate, plate width is about 2m to the maximum, and therefore its impact is limited.But particularly when plate width is the slab of more than 3m, its impact can not be ignored.Therefore, the cooling of steel plate width end dies down, and the Temperature Distribution of steel plate width now becomes uneven Temperature Distribution.
On the other hand, accelerated cooling device of the present invention has been provided separately admission port 16 and discharge outlet 17 as shown in Figure 10, shares the effect of feedwater and draining, therefore, makes cooling draining pass through from the discharge outlet 17 of partition 15 and successfully flow to the top of partition 15.Therefore, cooled draining is got rid of from steel plate upper surface rapidly, and therefore, the cooling water of follow-up supply can easily through delay moisture film, can obtain sufficient cooling capacity.The Temperature Distribution of steel plate width now becomes uniform Temperature Distribution, can obtain uniform Temperature Distribution in the direction of the width.
By the way, when the total sectional area of discharge outlet 17 is more than 1.5 times of the total sectional area of the internal diameter of pipe nozzle 13, the discharge of cooling water is carried out fast.Such as, partition 15 offers the hole larger than the external diameter of pipe nozzle 13, enable the number of discharge outlet identical with the number of admission port or more than it time realize above-mentioned effect.
When the total sectional area of discharge outlet 17 is less than 1.5 times of the total sectional area of the internal diameter of pipe nozzle 13, the flow resistance of discharge outlet increases, and occluded water is difficult to be discharged, and the cooling water inflow that result allows to through delay moisture film and arrives steel plate surface significantly reduces, cooling capacity reduces, therefore not preferred.Be more preferably more than 4 times.On the other hand, when discharge outlet too much or the diameter of section of discharge outlet is excessive, the rigidity of partition 15 reduces, and easily produces damage when steel plate is collided.Therefore, the total sectional area of discharge outlet and the ratio of the total sectional area of the internal diameter of pipe nozzle 13 are preferably the scope of 1.5 to 20.
In addition, the gap being inside inserted in the outer peripheral face of the pipe nozzle 13 in the admission port 16 of partition 15 and the inner peripheral surface of admission port 16 is preferably set to below 3mm.When this gap is large, due to the impact with stream of the cooling water that sprays from pipe nozzle 13, the cooling draining of discharging to the upper surface of partition 15 be introduced in admission port 16 with in the gap of the outer peripheral face of pipe nozzle 13, be again supplied on steel plate, therefore cooling effectiveness is deteriorated.In order to prevent above-mentioned situation, more preferably make the external diameter of pipe nozzle 13 roughly the same with the size of admission port 16.But consider operating accuracy, alignment error, the gap affecting in fact little below 3mm allows.More preferably below 2mm is set as.
In addition, in order to make cooling water can through delay moisture film and arrive steel plate, need to make the jet velocity of the internal diameter of pipe nozzle 13, length, cooling water, nozzle distance also reach best.
That is, nozzle inside diameter is preferably 3 ~ 8mm.When being less than 3mm, the water bundle sprayed from nozzle attenuates, and the flow of water dies down.On the other hand, when nozzle diameter is more than 8mm, flow velocity is slack-off, and the power of through delay moisture film weakens.
The length of pipe nozzle 13 is preferably 120 ~ 240mm.The length of pipe nozzle 13 described herein refer to from the inflow entrance of the to a certain degree upper end of nozzle of injection collector inside to the length of the lower end of the interior nozzle be inserted in the admission port of partition.Pipe nozzle 13 than 120mm in short-term, the distance of collector lower surface and partition upper surface become too short (such as, collector thickness is set to 20mm, the overhang that upper end of nozzle is outstanding in collector is set to 20mm, when nozzle lower end is set to 10mm to the insertion that partition inserts, above-mentioned distance is less than 70mm), therefore, from partition, the drainage space of upside reduces, and cooling draining can not successfully be discharged.On the other hand, time longer than 240mm, the pressure loss of pipe nozzle 13 increases, and the power of through delay moisture film weakens.。
Need for more than 6m/s from the jet velocity of the cooling water of nozzle ejection, be preferably more than 8m/s.This is because when being less than 6m/s, the power of cooling water through delay moisture film is extremely weak.When for more than 8m/s, larger cooling capacity can be guaranteed, therefore preferably.In addition, 30 ~ 120mm can be set as from the distance on lower end to the surface of steel plate 1 of the cooling water injection nozzle 13 of upper surface cooling.When being less than 30mm, the frequency that steel plate 1 and partition 15 collide is very big, is difficult to carry out plant maintenance.During more than 120mm, the power of cooling water through delay moisture film is extremely weak.
In the cooling of steel plate upper surface, can not arrange except damping roller (water cuts ロ ー Le) 20 along the mode of steel plate length direction expansion in the front and back of upper header 11 to make cooling water.Thus, cooling zone consistent length, temperature controls to become easy.At this, utilize except the flowing of the cooling water of steel plate carriage direction stops by damping roller 20, therefore, cooling draining is to steel plate width flows outside.But, be easily detained cooling water except near damping roller 20.
Therefore, preferably as shown in Figure 5, in the row of the pipe nozzle 13 that steel plate width arranges, the cooling water injection nozzle of side, the most upstream row of steel plate carriage direction tilts 15 ~ 60 degree to the updrift side of steel plate carriage direction, and the cooling water injection nozzle of the most downstream side of steel plate carriage direction row is to the downstream direction inclination 15 ~ 60 degree of steel plate carriage direction.Thus, also can supply cooling water close to the position except damping roller 20, can not be detained cooling water near damping roller 20, cooling effectiveness improves, therefore preferably.
The distance of upper header 11 lower surface and partition 15 upper surface is arranged in the mode of more than 1.5 times of the total sectional area that the steel plate width flow path cross sectional area made in the space that surrounded by collector lower surface and partition upper surface is cooling water injection nozzle internal diameter, such as, be about more than 100mm.When this steel plate width flow path cross sectional area does not reach more than 1.5 times of the total sectional area of cooling water injection nozzle internal diameter, the cooling draining of discharging from the discharge outlet 17 be arranged at partition to partition 15 upper surface can not successfully be discharged along steel plate width.
In accelerated cooling device of the present invention, the scope that can play the water yield density of effect is 1.5m
3/ m
2more than minute.When water yield density is lower than above-mentioned scope, being detained moisture film can not be so thick, even if application makes bar-shaped cooling water freely fall the known technology cooled steel plate, the temperature inequality of width also can not be so large sometimes.On the other hand, even if in water yield density higher than 4.0m
3/ m
2minute when, use technology of the present invention to be also effective, but the problem of the practical aspects such as equipment cost rising can be there is, therefore, therefore 1.5 ~ 4.0m
3/ m
2minute be the most practical water yield density.
Apply cooling technology of the present invention for situation about configuring except damping roller is effective especially in the front and back of cooling manifold.But, also can apply when not removing damping roller.Such as, also can be applied to collector longer in the longitudinal direction (when there is about 2m ~ about 4m), spray the water spray of purging in the front and back of this collector and prevent the cooling device leaked to non-water-cooled district.
It should be noted that, in the present invention, the cooling device for steel plate lower face side is not particularly limited.In the embodiment shown in Fig. 4,5, show the example of the cooling lower collector pipe 12 possessing the pipe nozzle 14 same with the cooling device of upper surface side.In the cooling of steel plate lower face side, the cooling water ejected falls after colliding steel plate naturally, therefore, also can not there is the partition 15 of cooling draining being discharged along steel plate width as upper surface side cooling.In addition, the known technology of supply membranaceous cooling water, vaporific misting cooling water etc. can also be used.
As mentioned above, the manufacturing equipment of steel plate of the present invention is by being set as 0.10J/mm by the energy density E sprayed to the surface of steel plate 1 from the injection nozzle of descale device 4
2above, the homogenising of the oxide skin that steel plate 1 produces can be realized, accelerated cooling device 6 can be utilized to realize uniform cooling.Consequently, the excellent steel plate of steel plate shape 1 can be manufactured.
In addition, by the shape correction utilizing the first shape correction device 5 to carry out steel plate 1, the injection nozzle of descale device 4 can be made close to the surface of steel plate 1.
In addition, make jet length H (distance on the injection nozzle of descale device 4 and the surface of steel plate 1) for more than 40mm and below 200mm time, descale ability improve.In addition, less also passable for the expulsion pressure, injection flow etc. obtaining the energy density E specified, therefore, it is possible to realize the reduction of the pump capacity of descale device 4.
In addition, by making to meet L≤V × 5 × 10 from descale device 4 to the distance L of accelerated cooling device 6
-9× exp (25000/T), can make the cooling of the steel plate 1 utilizing accelerated cooling device 6 stablize.
In addition, for accelerated cooling device 6 of the present invention, as shown in Figure 4, cool via the upper surface of cooling water to steel plate 1 that admission port 16 supplies from top cooling water injection nozzle 13 and become the draining of high temperature, flow from the top of partition 15 along the width of steel plate 1 using the discharge outlet 17 of not inserting top cooling water injection nozzle 13 as drainage flow path, cooled draining is got rid of rapidly from steel plate 1, therefore, the cooling water flowed via admission port 16 from top cooling water injection nozzle 13 contacts with steel plate 1 in turn, thus, fully and in the direction of the width uniform cooling capacity can be obtained.
It should be noted that, the result that the present inventor carries out studying is known, and the temperature inequality of having carried out the width of the steel plate of accelerating cooling when not carrying out the descale as the present invention reaches about 40 DEG C.Known on the other hand, use descale device 4 of the present invention and make the energy density of cooling water for 0.10J/mm
2the temperature inequality of having carried out the width of the steel plate of accelerating cooling after more than carrying out descale is reduced to about 10 DEG C.Known further, after utilizing descale device 4 to implement descale, the temperature inequality using the accelerated cooling device 6 shown in Fig. 4 to implement the width of the steel plate of accelerating cooling is reduced to about 4 DEG C.In addition, the temperature about steel plate is uneven, utilizes sweep type thermometer to measure the surface of steel plate Temperature Distribution after accelerating cooling, and the temperature being calculated width by its measurement result is uneven.
In addition, as the present invention, the first shape correction device 5 distortion produced in rolling is utilized to correct, descale device 4 is utilized to carry out the descale of steel plate 1, the controlling of cooling is stablized, therefore, the steel plate 1 that the second shape correction device 7 be utilized to correct is originally high with regard to flatness, and the temperature of steel plate 1 is also even.Therefore, the rectification reaction force of the second shape correction device 7 is without the need to too high.In addition, the distance of accelerated cooling device 6 and the second shape correction device 7 can be longer than the maximum length of the steel plate 1 manufactured in rolling manufacturing line.Thus, in most cases also utilize the second shape correction device 7 to implement oppositely to correct, therefore, it is possible to expect following effect: prevent the steel plate 1 oppositely transported from beating in transport roller and with the fault such as accelerated cooling device 6 collides; Make the small temperature deviation homogenising produced in the cooling in accelerated cooling device 6, thus the generation of the warpage caused because of temperature deviation after avoiding correcting.
Embodiment 1
The thickness of slab 30mm making to utilize roll mill 3 to roll out, the steel plate 1 of width 3500mm pass through from the first shape correction device 5 and descale device 4, then carry out the controlled cooling model from 820 DEG C to 420 DEG C.At this, for the condition that cooling is stable, when calculating according to above-mentioned (3), (4), (5) formula, the time t removed from utilizing the oxide skin of the steel plate 1 of descale device 4 to the cooling of steel plate 1 utilizing accelerated cooling device 6 after terminating is preferably below 42s, is more preferably below 19s, more preferably below 5s.
In descale device 4, the expulsion pressure of nozzle is set as 17.7MPa, the injection flow of each root nozzle is set as 50L/ minutes (=8.3 × 10
-4m
3/ s), jet length (distance on the injection nozzle of descale device 4 and the surface of steel plate 1) is set as 130mm, nozzle spray angle is set as 32 °, the nozzle angle of attack is set as 15 °, to make the jeting area of adjacent nozzle be arranged in 1 row in the direction of the width in a certain degree overlapping mode, spray injection thickness is 3mm, spray injection width is 77mm.At this, the energy density of cooling water is the value defined with above-mentioned water yield density × expulsion pressure × collision time.Collision time (s) is the time of spraying the deoxidation severe edema due to hypofunction of the spleen to steel plate surface, by obtaining divided by travelling speed with spray injection thickness.
Accelerated cooling device 6 is for being provided with the equipment of following stream: make the cooling water flow being supplied to steel plate upper surface to the top of partition as shown in Figure 4, can discharge as shown in Figure 7 further from steel plate width side.Partition offers with the trellis of chessboard the hole that diameter is 12mm, and as shown in Figure 6, interpolation top cooling water injection nozzle in the admission port arranged with staggered clathrate, is used as discharge outlet by remaining hole.The distance of upper header lower surface and partition upper surface is 100mm.
The top cooling water injection nozzle of accelerated cooling device 6 is set as internal diameter 5mm, external diameter 9mm, length 170mm, makes its upper end outstanding in collector.In addition, the jet velocity of bar-shaped cooling water is made to be 8.9m/s.The injector spacing of steel plate width is 50mm, in the region of roller-way spacing 1m, arrange 10 row nozzles in the longitudinal direction.The water yield density of upper surface is 2.1m
3/ m
2minute.The nozzle lower end of upper surface cooling is arranged in the mode in the centre position becoming the upper and lower surface of the partition of thickness of slab 25mm, and the distance to steel plate surface is 80mm.
It should be noted that, for lower surface cooling device, use as shown in Figure 4 except not possessing cooling device except partition, same with upper surface cooling device, make the jet velocity of bar-shaped cooling water and water yield density be 1.5 times of upper surface.
Then, as shown in table 1, make to carry out various change from descale device 4 to the travelling speed V of the distance L of accelerated cooling device 6, steel plate and from descale device 4 to the time t of accelerated cooling device 6.
For steel plate shape, evaluate with additional restitution factor (%).Specifically, it is qualified that warpage on warpage in the whole length of steel plate and/or the whole width of steel plate is judged as when being within a reference value specified in the product standard corresponding with its steel plate, be judged as when exceeding a reference value adding correcting and implement material, add restitution factor and calculate in the mode of (adding the radical corrected and implement material)/(total radical of subject material) × 100.
For the example of the present invention 1 ~ 5 of table 1, energy density is 0.10J/mm
2above, therefore, the additional restitution factor that shape defect causes is low, obtains good result.Think that this is when utilizing accelerated cooling device 6 to cool, there is the deviation of the surface temperature of width position hardly and be cooled equably, the flatness being considered to be caused by the Temperature Distribution of steel plate is excellent, and consequently, the additional restitution factor that shape defect causes is low.In addition, example 1 ~ 5 of the present invention all eliminates oxide skin, and surface texture is also good.It should be noted that, in the evaluation of surface texture, use the image being cooled to the steel plate surface of room temperature, the image procossing according to the hue difference utilizing oxide skin residual part and stripping portion determines whether oxide skin, and evaluates.
Particularly, for make from descale device 4 to the distance of accelerated cooling device 6 be for the example of the present invention 1 ~ 3 of 5m, removing from utilizing the oxide skin of the steel plate 1 of descale device 4 after terminating and have nothing to do to the time t of cooling of steel plate 1 utilizing the accelerated cooling device 6 and travelling speed V of steel plate, is the condition, i.e. below the 19s that utilize the cooling of accelerated cooling device 6 more stable.Therefore, additional restitution factor is less than 5%, is good.
In addition, in example 5 of the present invention, even if the high impact pressure (1.0MPa) not needing patent document 1, patent document 2 such, by making energy density within the scope of the present invention, have also been obtained good result.
On the other hand, for when not implementing to have carried out when utilizing the oxide skin of descale device 4 to remove for the comparative example 1 of the cooling utilizing accelerated cooling device 6, the flatness being considered to be caused by the Temperature Distribution of steel plate is deteriorated, and additional restitution factor is 40%.
In addition, be 25L/ minutes (=4.2 × 10 for making based on the injection flow imposed a condition as hydraulic pressure 9MPa, each root nozzle of descale device 4
-4m
3/ s), other conditions are identical with example 2 of the present invention and make energy density be 0.08J/mm
2comparative example 2, oxide skin generating portion is peeled off, and thus, the Temperature Distribution of steel plate width is deteriorated, and accompany therewith, the flatness of steel plate is also deteriorated, and therefore adding restitution factor is 70%.
In addition, although comparative example 3 is in the scope of the high impact pressure as patent document 1, patent document 2, but energy density is outside scope of the present invention, therefore, oxide skin generating portion is peeled off, thus, the Temperature Distribution of steel plate width is deteriorated, accompany therewith, the flatness of steel plate is also deteriorated, and therefore adding restitution factor is 65%.
Symbol description
1 steel plate
2 heating furnaces
3 roll mills
4 descale devices
5 first shape correction devices
6 accelerated cooling devices
7 second shape correction devices
11 upper headers
12 lower collector pipe
Cooling water injection nozzle (pipe nozzle) on 13
14 times cooling water injection nozzles (pipe nozzle)
15 partitions
16 admission ports
17 discharge outlet
18 spray cooling water
19 discharge water
20 except damping roller
21 except damping roller
Claims (7)
1. the manufacturing equipment of a steel plate, it is characterized in that, by hot-rolling mill, shape correction device, descale device and accelerated cooling device with the configuration from carriage direction upstream side of this order, the energy density E that the cooling water that described descale device is sprayed to the surface of steel plate has is 0.10J/mm
2above.
2. the manufacturing equipment of steel plate as claimed in claim 1, it is characterized in that, by from described descale device to the travelling speed of described accelerated cooling device be set to V [m/s], by cooling before steel plate temperature be set to T [K] time, the distance L [m] from described descale device to described accelerated cooling device meets formula L≤V × 5 × 10
-9× exp (25000/T).
3. the manufacturing equipment of steel plate as claimed in claim 2, is characterized in that, configure each device in the mode that the distance L made from described descale device to described accelerated cooling device is below 12m.
4. the manufacturing equipment of steel plate as claimed any one in claims 1 to 3, is characterized in that, make the jet length H from the injection nozzle of described descale device to the surface of described steel plate be more than 40mm and below 200mm.
5. the manufacturing equipment of the steel plate according to any one of Claims 1-4, it is characterized in that, the collector that described accelerated cooling device possesses the upper surface supply cooling water to described steel plate, the cooling water injection nozzle of the bar-shaped cooling water of injection dangled from this collector and the partition be arranged between described steel plate and described collector, and
Described partition is provided with the admission port of the bottom of cooling water injection nozzle described in multiple interpolation and the cooling water drainage of the upper surface being supplied to described steel plate is put into the discharge outlet above described partition.
6. the manufacture method of a steel plate, its order according to hot-rolled process, heat straightening operation and accelerating cooling operation manufactures steel plate, it is characterized in that, it is 0.10J/mm that energy density E is sprayed on the surface had between described heat straightening operation and refrigerating work procedure to steel plate
2the descale operation of above cooling water.
7. the manufacture method of steel plate as claimed in claim 6, is characterized in that, terminates to meet formula t≤5 × 10 to the time t [s] described accelerating cooling operation from described descale operation
-9× exp (25000/T), wherein, T is the steel plate temperature (K) before cooling.
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PCT/JP2014/001615 WO2014156086A1 (en) | 2013-03-27 | 2014-03-20 | Thick steel plate manufacturing device and manufacturing method |
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JP (1) | JP5962849B2 (en) |
KR (1) | KR101742607B1 (en) |
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CN111194245A (en) * | 2017-09-28 | 2020-05-22 | 杰富意钢铁株式会社 | Steel sheet manufacturing facility and steel sheet manufacturing method |
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JP6377550B2 (en) * | 2015-03-06 | 2018-08-22 | 株式会社神戸製鋼所 | Thick steel plate cooling method and thick steel plate cooling device |
JP2016182622A (en) * | 2015-03-26 | 2016-10-20 | Jfeスチール株式会社 | Method and apparatus for removing excess scale on plug for piercing seamless steel tube material and method of using the plug |
US11033942B2 (en) * | 2016-08-09 | 2021-06-15 | Toshiba Mitsubishi-Electric Industrial Systems Corporation | Rolling mill exit side temperature control system |
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JP3796133B2 (en) | 2000-04-18 | 2006-07-12 | 新日本製鐵株式会社 | Thick steel plate cooling method and apparatus |
KR100496607B1 (en) * | 2000-12-27 | 2005-06-22 | 주식회사 포스코 | Method And Device For Manufacturing A Hot Rolled Steel Strip |
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2014
- 2014-03-20 WO PCT/JP2014/001615 patent/WO2014156086A1/en active Application Filing
- 2014-03-20 JP JP2015508047A patent/JP5962849B2/en active Active
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- 2014-03-20 KR KR1020157030446A patent/KR101742607B1/en active IP Right Grant
- 2014-03-20 EP EP14775597.9A patent/EP2979770B1/en active Active
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JPS59144513A (en) * | 1983-02-09 | 1984-08-18 | Mitsubishi Heavy Ind Ltd | Cooling device of steel sheet |
JPH10113713A (en) * | 1996-10-09 | 1998-05-06 | Kobe Steel Ltd | Production of steel plate of controlled cooling |
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US20120017660A1 (en) * | 2009-03-25 | 2012-01-26 | Jfe Steel Corporation | Steel plate manufacturing facility and manufacturing method |
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Cited By (2)
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CN111194245B (en) * | 2017-09-28 | 2022-03-01 | 杰富意钢铁株式会社 | Steel sheet manufacturing facility and steel sheet manufacturing method |
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EP2979770B1 (en) | 2018-08-22 |
TW201501829A (en) | 2015-01-16 |
EP2979770A4 (en) | 2016-03-16 |
KR20150138269A (en) | 2015-12-09 |
EP2979770A1 (en) | 2016-02-03 |
CN105102142B (en) | 2018-06-12 |
JPWO2014156086A1 (en) | 2017-02-16 |
WO2014156086A1 (en) | 2014-10-02 |
TWI565541B (en) | 2017-01-11 |
KR101742607B1 (en) | 2017-06-01 |
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