WO2021085474A1 - 連続鋳造鋳片の二次冷却方法 - Google Patents
連続鋳造鋳片の二次冷却方法 Download PDFInfo
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- WO2021085474A1 WO2021085474A1 PCT/JP2020/040435 JP2020040435W WO2021085474A1 WO 2021085474 A1 WO2021085474 A1 WO 2021085474A1 JP 2020040435 W JP2020040435 W JP 2020040435W WO 2021085474 A1 WO2021085474 A1 WO 2021085474A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/12—Accessories for subsequent treating or working cast stock in situ
- B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/12—Accessories for subsequent treating or working cast stock in situ
- B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
- B22D11/1246—Nozzles; Spray heads
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/16—Controlling or regulating processes or operations
- B22D11/22—Controlling or regulating processes or operations for cooling cast stock or mould
- B22D11/225—Controlling or regulating processes or operations for cooling cast stock or mould for secondary cooling
Definitions
- the present invention relates to a secondary cooling method for continuously cast slabs.
- a general method for manufacturing a continuously cast slab will be described with reference to FIGS. 4 and 5 by taking a vertical bending type continuous casting facility as an example.
- the molten steel injected into the mold 3 from the tundish (not shown) is primarily cooled by the mold 3 to form a flat plate-shaped slab 5 forming a solidified shell, which is flat and descends from the vertical band 7 to the curved band 11. Proceed to. Then, at the bent portion 9 on the entry side of the curved band 11, the slab 5 is bent while being guided by a plurality of rolls (not shown) so as to maintain a constant radius of curvature.
- the straightening portion 13 is bent back (corrected) while gradually increasing the radius of curvature, and when the straightening portion 13 is exited, the slab 5 becomes flat again and proceeds to the horizontal band 15. After the solidification is completed in the horizontal band 15, the slab 5 is cut to a predetermined length by the gas cutting machine 17 installed on the outlet side of the continuous casting machine 1.
- the slab 5 is secondary using a water spray (water one-fluid spray or water-air two-fluid mixed mist spray) to complete solidification from the vertical band 7 to the horizontal band 15 to the center. Cooling is being carried out.
- a water spray water one-fluid spray or water-air two-fluid mixed mist spray
- the strength of the shell is secured by injecting a large flow rate of water in the vertical band 7 directly under the mold to perform strong cooling.
- the cooling is weakened, and the surface temperature is raised (reheated) by heat conduction from the high temperature portion inside. Then, the surface temperature of the straightening portion 13 is adjusted to be equal to or higher than the embrittlement temperature range to avoid the occurrence of lateral cracks.
- the casting speed is increased for the purpose of improving production efficiency, straightening is performed with the central part of the slab unsolidified, and strong cooling is performed in the horizontal band 15 at the end of continuous casting to complete solidification.
- the method of making it is also adopted.
- the cooling capacity is uneven in these strong cooling zones, a temperature deviation occurs on the surface of the slab, and surface cracks occur due to the thermal stress caused by the temperature deviation.
- the solidification completion position at the center of the slab becomes non-uniform due to uneven cooling, which affects the internal quality. Therefore, in order to stably realize high cooling capacity in the strong cooling zone, it is desirable that the cooling water maintains the nucleate boiling state on the surface of the slab.
- a plurality of guide rolls 19 are installed in the secondary cooling zone, and the cooling water is injected into the gaps between these guide rolls 19 (see FIG. 5).
- the cooling water is directly injected onto the surface of the slab.
- the contact portion with the guide roll 19 and the guide roll 19 block the cooling water to generate a non-direct irradiation region Y in which the cooling water does not directly hit.
- the cooling water is continuously supplied from the nozzle, so that the high cooling capacity is maintained, but in the non-direct irradiation region Y, only the contact with the guide roll 19 and the heat removal due to the accumulated water are performed, and the cooling capacity is lowered.
- the slab surface temperature rises significantly (reheat).
- the slab enters the direct irradiation region X between the next rolls and does not quickly reach the nucleate boiling state, and the boiling state changes unstable in the casting direction, causing a large temperature fluctuation.
- Patent Document 1 defines the ratio of the direct irradiation range length of the water spray in the casting direction to the distance between the guide rolls. , A technique for improving the uniformity of cooling capacity has been proposed.
- Patent Document 2 proposes a technique of providing a refrigerant guide plate close to the slab surface between guide rolls to spread cooling water to the slab surface.
- the spray pattern of the spray water used in the slab width direction is not described, it can be presumed to be a two-row oval shape. At this time, since the spray width and the water amount density of the end portion in the width direction of the spray water are lower than those of the central portion, the desired uniformity of the cooling capacity cannot be realized.
- the spray nozzle to be used has a plurality of injection ports, but the nozzle shape becomes complicated, the risk of nozzle clogging increases, and there is a high possibility that the ideal spray thickness cannot be secured.
- the present invention has been made to solve such a problem, and stably realizes and maintains a nucleate boiling state in both the casting direction and the width direction of the slab, and as a result, the equipment can be easily maintained and the cooling capacity can be increased. It is an object of the present invention to provide a secondary cooling method for continuously cast slabs capable of improving uniformity.
- the present invention has the following features.
- d unit: mm
- P unit: mm
- it is a secondary cooling method for continuously cast slabs in which spray nozzles having a square injection pattern are arranged in the slab width direction to cool the slabs.
- the distance L unit) between points A and B, which are two points where the water density of the cooling water sprayed from each of the spray nozzles is 50% of the maximum value of the water density in the casting direction.
- Mm A method for secondary cooling of continuously cast slabs, which comprises cooling while maintaining the nucleate boiling state in the range from the point A to the point B.
- the water density of the cooling water sprayed by each of the spray nozzles is 400 (L / m 2 ) / min or more and 2000 (L / m) per unit surface area of the slab in the cooling section by the spray nozzles. 2 )
- spray nozzles having a square injection pattern in the secondary cooling zone of a continuous casting machine are arranged in the width direction of the slab, and the maximum value of the distribution of the amount of cooling water sprayed from each spray nozzle in the casting direction is 50.
- the guide roll and the spray nozzle are arranged so that the relationship between the distance L (unit: mm) connecting the two points A and B, which is%, and the distance P between the axes satisfies L / P ⁇ 0.70.
- FIG. 1 is an explanatory diagram of an injection pattern and a flow rate distribution of a spray nozzle according to an embodiment of the present invention.
- FIG. 2 is an explanatory diagram illustrating the arrangement relationship between the spray nozzle and the guide roll according to the embodiment of the present invention.
- FIG. 3 is an explanatory diagram of the injection pattern and the flow rate distribution of the spray nozzle of Comparative Example 1 in the description of the embodiment.
- FIG. 4 is an explanatory diagram illustrating an outline of a conventional general continuous casting facility.
- FIG. 5 is an explanatory diagram of an arrangement of a guide roll and a spray nozzle and an injection state in a conventional general continuous casting facility.
- the secondary cooling method for the continuously cast slab according to the present embodiment is continuous casting composed of a vertical band 7, a bent portion 9, a curved zone 11, a straightening portion 13, and a horizontal band 15 from the upstream side in the casting direction.
- a radius d installed at an inter-axis distance P (unit: mm) in a part of the horizontal band 15 in the casting direction section or the entire horizontal band 15 in the casting direction section in the secondary cooling zone of the machine 1 (see FIG. 4).
- the relationship between the distance L (unit: mm) connecting the two points A and B, which is 50% of the maximum value of the horizontal water amount distribution in the casting direction of the cooling water sprayed from the spray nozzle 21, and the inter-axis distance P is the following equation (1).
- the guide roll 19 and the spray nozzle 21 are arranged so as to satisfy the above conditions, and the cooling is performed while maintaining the nuclear boiling state in the range of points A to B.
- a spray nozzle 21 having a quadrangular injection pattern is used.
- the reason for using the spray nozzle 21 having such a quadrangular injection pattern is as follows.
- the shape of the exposed slab surface is elongated (long in the slab width direction and in the casting direction). It becomes a rectangle (short).
- the spray nozzles 21 having a quadrangular injection pattern side by side in the slab width direction.
- the water density of the wrap portion is 50% or more and 100% or less of the maximum value of the water density when sprayed alone. It is desirable to set the lap allowance of the injection regions of the adjacent spray nozzles 21 so as to be.
- the water density of the wrap is less than 50% of the maximum value, the water density of the wrap is insufficient and the nucleate boiling state does not occur during cooling, causing temperature unevenness in the width direction.
- it is larger than 100%, the lap range is too wide, and the cooling waters of the adjacent spray nozzles 21 interfere with each other. Will increase.
- the distance L (unit: mm) connecting the two points A and B, which is 50% of the maximum value of the casting direction water amount distribution of the cooling water sprayed from each spray nozzle 21, and the shaft distance.
- the guide roll 19 and the spray nozzle 21 are arranged so that the relationship of the distance P satisfies L / P ⁇ 0.70.
- the area to be the non-directly shining part is narrow, and the cooling water flowing from the direct shining part to the non-directly shining part is sufficient enough not to hinder the cooling of the slab, so that the temperature unevenness Does not occur.
- the cooling water that collides with the slab flows from the direct irradiation part toward the surroundings.
- the flow in the casting direction is dammed by the gap between the guide roll and the slab, and a flow in the slab width direction is formed and drained. Therefore, when the water density is high and the range of the non-directly shining portion is too small, the flow during rolling and the direct shining portion may interfere with each other. Therefore, it is desirable that the relationship between the distance L connecting the two points A and B and the distance P between the axes satisfies L / P ⁇ 0.90.
- the spray pattern of the spray nozzle 21 of the present embodiment is quadrangular, the spray thickness does not change in the slab width direction, and the L / P can be kept within the specified range in the entire width direction.
- the spray thickness of the direct irradiation portion becomes small at the end portion in the slab width direction, and the L / P value is obtained in the entire width direction. Is difficult to keep within the specified range.
- the water density is also an important factor in realizing and maintaining this nucleate boiling state. If the water density is not sufficient, the slab 5 does not immediately reach the nucleate boiling state even if it enters the cooling water direct irradiation portion, but transitions to the nucleate boiling after the temperature drops due to the film boiling.
- the cooling rate differs depending on the width direction position (center of slab width, slab corner), and the transition point from film boiling to nucleate boiling is affected by the surface texture, so the starting point of nucleate boiling is the slab. It varies in the width direction. Therefore, a large temperature deviation occurs in the width direction, surface cracking due to thermal stress and variation in the internal solidification completion position in the width direction occur, which causes surface and internal defects.
- the reason why the water density is required to be 400 (L / m 2 ) / min or more is as follows.
- the cooling water becomes a film boiling state on the slab surface and a steam film is generated.
- the jet water density is less than 400 (L / m 2 ) / min, the water density is small, so the steam film does not collapse immediately due to the collision of cooling water, and the film boiling state is maintained until the slab surface temperature drops to some extent. To. After that, when the surface temperature drops and the transition from film boiling to nucleate boiling occurs, cooling progresses rapidly.
- the boiling state also differs depending on the slab surface position, and as a result, the temperature unevenness further increases.
- the water volume density is 400 (L / m 2 ) / min or more, even if a steam film is generated on the surface of the slab, the steam film immediately collapses due to the collision of the cooling water, so that the nucleate boiling state is rapidly entered. Therefore, the boiling state is made uniform depending on the surface position of the slab, and temperature unevenness does not occur.
- the cooling by boiling becomes dominant, and the dependence of the cooling capacity on the water density becomes smaller. Therefore, if the water density is greater than 2000 (L / m 2 ) / min, the cooling capacity cannot be expected to improve significantly, and the total amount of cooling water used becomes excessive, resulting in a large capital investment for water treatment equipment. It is appropriate that the water density of the water is in the range of 400 (L / m 2 ) / min or more and 2000 (L / m 2 ) / min or less.
- the water density is in the range of 400 (L / m 2 ) / min or more and 2000 (L / m 2 ) / min or less depending on the operating conditions (slab surface temperature, collision pressure of cooling water, etc.). It is not essential to do so, and the water density should be set so that the nucleate boiling state occurs.
- the boiling state should be monitored. It is necessary to increase the amount of water while doing so to ensure the achievement and maintenance of the nucleate boiling state.
- cameras will be installed in each section to monitor the amount of water smoke generated by visual observation or measurement with a transmissometer.
- a threshold value for the amount of water smoke generated to distinguish between nucleate boiling and film boiling By conducting an experiment in advance to obtain a threshold value for the amount of water smoke generated to distinguish between nucleate boiling and film boiling, and confirming whether or not the amount of water smoke generated exceeds the threshold value, the nucleate boiling state can be determined in a predetermined section. You can check if you have achieved it. Then, if the nucleate boiling state has not been achieved, the amount of cooling water is adjusted to be increased. This ensures that the nucleate boiling state can be achieved and maintained.
- the fluid temperature and the solid temperature are locally equal at the point of contact between them. Since the temperature of liquid water rises only to the boiling point under atmospheric pressure, it is considered that the surface temperature of the slab is about 100 ° C. if nucleate boiling is realized. Therefore, the nucleate boiling state is achieved by measuring the temperature of the slab surface and the surrounding cooling water using a contact-type thermometer having a small probe and confirming that the temperature is stable at around 100 ° C. Can be confirmed. Then, if the nucleate boiling state has not been achieved, the amount of cooling water is adjusted to be increased. This ensures that the nucleate boiling state can be achieved and maintained.
- a water spray having a square injection pattern is used, and the length of the cooling water direct irradiation portion between the guide rolls 19 is the roll interval.
- the angle (injection angle) ⁇ (unit: degree) formed by the straight line CA and the straight line CB with the center of the nozzle injection port as the point C is 100 degrees or less in order to maintain the uniformity of the water amount distribution. Is desirable.
- the distance L connecting the two points A and B which is 50% of the maximum value of the water amount distribution in the casting direction of the cooling water sprayed from the spray nozzle 21, (hereinafter referred to as “direct irradiation portion length L”) is expressed by the formula (1). ), It is necessary to set the injection angle ⁇ .
- the conditions under which the injection angle ⁇ should be satisfied will be described.
- the injection angle ⁇ needs to be set within a range in which the straight lines CA and CB do not come into contact with the guide roll 19. Therefore, when the straight line CA (or the straight line CB) circumscribes the guide roll 19, the following equation (5) holds for the triangle DAE.
- the range of the height h (unit: mm) from the slab surface is also determined in the same manner. This point will be described below.
- the upper limit of the height h is the position where the straight lines CA and CB come into contact with the guide roll 19, the equation (8) holds. Therefore, when the equation (6) is substituted into the equation (8) and deformed with respect to the height h, the upper limit of the height h is expressed as the equation (9). Therefore, the range of height h is as shown in equation (3).
- the size of the direct irradiation portion length L becomes 70% or more of the guide roll interval P, and the direct irradiation portion The range can be widened sufficiently and local fluctuations in the slab surface temperature can be prevented.
- the cooling device (see FIGS. 1 and 2) according to the embodiment of the present invention is used to perform strong cooling in the horizontal zone 15.
- the slab 5 was manufactured.
- the length of the continuous casting machine 1 is 45 m, and a thermometer and a gas cutting machine 17 for measuring the temperature distribution on the surface of the slab are installed at the end of the machine.
- a slab is manufactured by changing the radius and spacing of the guide roll 19, the injection angle of the spray nozzle 21 to be used, the pitch of the spray nozzle in the slab width direction, the spray nozzle installation height and casting speed, and the water volume density, and the temperature during cooling. The surface texture, internal defects, and manufacturing cost of the slab after unevenness and casting were evaluated.
- the thickness of the cast slab was unified to 235 mm.
- Table 1 shows the casting conditions and results.
- Comparative Example 1 and Examples 1 and 2 are examples of casting by applying the conditions of the prior art and the technique of the present invention, respectively.
- a water spray having an elliptical shape of the injection pattern (see FIG. 3) was used.
- the water density was 400 (L / m 2 ) / min, and the casting speed was increased to 3.0 m / s.
- Example 2 the equipment arrangement is the same as that in Example 1, and the density of the cooling water is 2000 (L / m 2 ) / min. As a result, temperature fluctuations in the casting direction could be suppressed, and a boiling state could be quickly realized and maintained in the slab width direction. When the slabs after casting were inspected, no defects were found on the surface or inside, and high-quality slabs could be produced with high efficiency.
- Example 3 the injection height is changed based on the conditions of Example 1.
- the range of the injection height h is 97 to 101 mm from the equation (3).
- Examples 5 and 6 are the cases where the lower limit and the upper limit of the injection height h are set, respectively, and L / P ⁇ 0.70 is satisfied under both conditions. No defects were found inside, and high-quality slabs could be manufactured with high efficiency.
- Comparative Example 5 is an example in which the water density is reduced to 350 (L / m 2 ) / min by using the same spray nozzle 21 as in Example 1. At this time, since the nucleate boiling state could not be stably realized as in Comparative Example 4, when the slab after casting was confirmed, surface cracks and internal defects were confirmed.
- Comparative Example 6 and Example 7 are examples in which the same spray nozzle 21 as in Example 1 is used and the radius d and the interval P of the guide roll 19 are changed to 80 mm and 250 mm.
- spray nozzles 21 were arranged in a straight line in parallel with the rolls at intervals of 250 mm (width pitch 250 mm) in the gaps between the support rolls of the secondary cooling zone (without staggered arrangement). Further, in Example 7, the spray nozzles 21 were arranged at intervals of 210 mm. Under these conditions, the water density of the wrap portion was within the range of 50% or more and 100% or less of the maximum value in all cases, and no defect was observed as described above.
- Comparative Example 7 only the width pitch of the spray nozzle 21 was changed to 275 mm with respect to Example 1, and the water density of the lap portion was 40% of the maximum value, so that the nucleate boiling state was stably maintained. It has not been realized.
- temperature unevenness in the width direction was visually apparent along the arrangement of the spray nozzles 21.
- vertical cracks were generated on the surface of the slab, which was considered to be caused by temperature unevenness in the width direction.
- the spray nozzle 21 it is preferable to arrange the spray nozzle 21 so that the water density of the wrap portion is in the range of 50% or more and 100% or less of the maximum value.
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Abstract
Description
[1] 連続鋳造機の二次冷却帯における水平帯の鋳造方向全区間または一部区間において、軸間距離P(単位:mm)で設置された半径d(単位:mm)のガイドロールの間に、噴射パターンが四角形となるスプレーノズルを鋳片幅方向に並べて、鋳片を冷却する連続鋳造鋳片の二次冷却方法であって、
前記スプレーノズルの各々から噴霧される冷却水の水量密度が、該水量密度の前記鋳造方向における最大値の50%となる2つの地点である、A地点とB地点との間の距離L(単位:mm)と、前記軸間距離Pとの関係が、下式(1)を満たすとともに、
前記A地点~前記B地点の範囲で核沸騰状態を維持しながら冷却することを特徴とする連続鋳造鋳片の二次冷却方法。
[2] 前記スプレーノズルのノズル噴射口と前記A地点とを結ぶ直線と、前記ノズル噴射口と前記B地点とを結ぶ直線とが成す角度θ(単位:度)が式(2)を満たすとともに、前記ノズル噴射口の前記鋳片からの高さであるノズル高さh(単位:mm)が式(3)を満たすことを特徴とする[1]に記載の連続鋳造鋳片の二次冷却方法。
7P/[20tan(θ/2)]≦h≦[P-2dtan{(180-θ)/4}]/[2tan(θ/2)]・・・(3)
[3] 前記スプレーノズルの各々が噴射する前記冷却水の水量密度が、前記スプレーノズルによる冷却区間内にある前記鋳片の単位表面積当たり400(L/m2)/min以上2000(L/m2)/min以下であることを特徴とする[1]又は[2]に記載の連続鋳造鋳片の二次冷却方法。
本実施の形態では、図1に示すように、噴射パターンが四角形となるスプレーノズル21を用いている。このような噴射パターンが四角形となるスプレーノズル21を用いた理由は以下の通りである。
3 鋳型
5 鋳片
7 垂直帯
9 曲げ部
11 湾曲帯
13 矯正部
15 水平帯
17 ガス切断機
19 ガイドロール
21 スプレーノズル
A、B スプレーノズルから噴霧される冷却水の鋳造方向水量分布が最大値の50%となる地点
C ノズル噴射口
θ 直線ABと直線BCとが成す角度
P ガイドロールの軸間距離
d ガイドロールの半径
Claims (3)
- 連続鋳造機の二次冷却帯における水平帯の鋳造方向全区間または一部区間において、軸間距離P(単位:mm)で設置された半径d(単位:mm)のガイドロールの間に、噴射パターンが四角形となるスプレーノズルを鋳片幅方向に並べて、鋳片を冷却する連続鋳造鋳片の二次冷却方法であって、
前記スプレーノズルの各々から噴霧される冷却水の水量密度が、該水量密度の前記鋳造方向における最大値の50%となる2つの地点である、A地点とB地点との間の距離L(単位:mm)と、前記軸間距離Pとの関係が、下式(1)を満たすとともに、
前記A地点~前記B地点の範囲で核沸騰状態を維持しながら冷却することを特徴とする連続鋳造鋳片の二次冷却方法。
L/P≧0.70・・・(1) - 前記スプレーノズルのノズル噴射口と前記A地点とを結ぶ直線と、前記ノズル噴射口と前記B地点とを結ぶ直線とが成す角度θ(単位:度)が下式(2)を満たすとともに、前記ノズル噴射口の前記鋳片からの高さであるノズル高さh(単位:mm)が下式(3)を満たすことを特徴とする請求項1に記載の連続鋳造鋳片の二次冷却方法。
180-4tan-1[3P/(20d)]≦θ≦100・・・(2)
7P/[20tan(θ/2)]≦h≦[P-2dtan{(180-θ)/4}]/[2tan(θ/2)]・・・(3) - 前記スプレーノズルの各々が噴射する前記冷却水の水量密度が、前記スプレーノズルによる冷却区間内にある前記鋳片の単位表面積当たり400(L/m2)/min以上2000(L/m2)/min以下であることを特徴とする請求項1又は2に記載の連続鋳造鋳片の二次冷却方法。
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EP20882570.3A EP4052815B1 (en) | 2019-10-29 | 2020-10-28 | Secondary cooling method for continuous cast strand |
JP2021552134A JP7052931B2 (ja) | 2019-10-29 | 2020-10-28 | 連続鋳造鋳片の二次冷却方法 |
KR1020227013451A KR102631495B1 (ko) | 2019-10-29 | 2020-10-28 | 연속 주조 주편의 2 차 냉각 방법 |
CN202080076092.5A CN114641356B (zh) | 2019-10-29 | 2020-10-28 | 连续铸造铸片的二次冷却方法 |
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- 2020-10-28 WO PCT/JP2020/040435 patent/WO2021085474A1/ja unknown
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- 2020-10-28 CN CN202080076092.5A patent/CN114641356B/zh active Active
- 2020-10-28 KR KR1020227013451A patent/KR102631495B1/ko active IP Right Grant
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JP2005103628A (ja) * | 2003-10-01 | 2005-04-21 | Sanyo Special Steel Co Ltd | 連続鋳造ブルームの均一冷却方法およびその冷却水注水ノズル |
JP2006315044A (ja) * | 2005-05-13 | 2006-11-24 | Nippon Steel Corp | 連続鋳造におけるスプレー冷却方法 |
JP2013022620A (ja) * | 2011-07-21 | 2013-02-04 | Nippon Steel & Sumitomo Metal Corp | 連続鋳造鋳片の冷却方法 |
JP2018015781A (ja) | 2016-07-28 | 2018-02-01 | 新日鐵住金株式会社 | 連続鋳造の二次冷却方法及び二次冷却装置 |
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KR102631495B1 (ko) | 2024-01-30 |
EP4052815A4 (en) | 2022-10-19 |
CN114641356B (zh) | 2024-04-05 |
TWI770652B (zh) | 2022-07-11 |
CN114641356A (zh) | 2022-06-17 |
KR20220069059A (ko) | 2022-05-26 |
JP7052931B2 (ja) | 2022-04-12 |
EP4052815A1 (en) | 2022-09-07 |
EP4052815B1 (en) | 2023-08-30 |
JPWO2021085474A1 (ja) | 2021-12-09 |
TW202133967A (zh) | 2021-09-16 |
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