WO2015083876A1 - 용강 처리 장치 및 용강 처리 방법 - Google Patents
용강 처리 장치 및 용강 처리 방법 Download PDFInfo
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- WO2015083876A1 WO2015083876A1 PCT/KR2013/012127 KR2013012127W WO2015083876A1 WO 2015083876 A1 WO2015083876 A1 WO 2015083876A1 KR 2013012127 W KR2013012127 W KR 2013012127W WO 2015083876 A1 WO2015083876 A1 WO 2015083876A1
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- Prior art keywords
- molten steel
- liner
- value
- voltage
- current
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D21/00—Arrangement of monitoring devices; Arrangement of safety devices
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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
- B22D11/10—Supplying or treating molten metal
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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
- B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
- B22D1/007—Treatment of the fused masses in the supply runners
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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
- B22D11/10—Supplying or treating molten metal
- B22D11/11—Treating the molten metal
-
- 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
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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
- B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
- B22D41/50—Pouring-nozzles
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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
- B22D46/00—Controlling, supervising, not restricted to casting covered by a single main group, e.g. for safety reasons
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
- F27M2001/00—Composition, conformation or state of the charge
- F27M2001/02—Charges containing ferrous elements
Definitions
- the present invention relates to a molten steel processing apparatus and a molten steel processing method, and more particularly, to a molten steel processing apparatus and a molten steel processing method capable of quickly measuring a state of inclusions in a nozzle during an operation.
- Continuous casting equipment is a facility that produces cast steel by receiving refined molten steel from steelmaking equipment.
- a general continuous casting facility is a ladle containing molten steel refined in a steelmaking facility, a tundish disposed under the ladle to temporarily receive molten steel from the ladle, and a tumbled dish disposed under the tundish to receive molten steel from the tundish.
- a mold that solidifies into a shape and a segment disposed under the mold to perform a series of molding operations and to produce a cast. The tundish receives the molten steel of the ladle and supplies it to the mold.
- Tundish serves to separate the inclusions of the inclusions, stabilize the slag, prevent reoxidation of the molten steel, and distribute the molten steel to strands.
- the tundish is manufactured in the shape of a hollow container to provide a space for receiving molten steel therein.
- a tapping hole is formed at the bottom of the tundish, an upper nozzle is inserted into the tapping hole, and the upper nozzle is connected to a submerged entry nozzle provided below the tundish.
- a predetermined amount of molten steel is received, and the molten steel is introduced into the immersion nozzle through the tap hole and the upper nozzle connected thereto. Molten steel flowing into the immersion nozzle is supplied to the mold and solidified in the shape of a cast steel.
- the molten steel in the tundish may contain various inclusions such as alumina inclusions.
- the various inclusions incorporated in the molten steel are floated and removed in the tundish, but some remain in the molten steel without being removed. Residual inclusions are attached to the immersion nozzle in the process of molten steel passing through the immersion nozzle into the mold to form a now. Inclusions attached to the immersion nozzle irregularly reduce the inner diameter of the immersion nozzle, thereby irregularly changing the outgoing amount of the molten steel during operation. For this reason, the flow of molten steel in a mold generate
- Unstable flow of molten steel in the mold tends to cause defects in the solidification shell, which not only degrades cast quality, but also breaks out of the cast during operation.
- the nozzle may be clogged, which may cause the operation to be interrupted.
- an internal diameter of the immersion nozzle is irregularly reduced or the immersion nozzle is clogged due to the inclusions attached to the immersion nozzle as described above.
- 2005-066689 include an electrode attached to the immersion nozzle to be attached to the immersion nozzle.
- Disclosed is a continuous casting method for inducing an electrochemical deoxidation reaction. At this time, the current deoxidation reaction rate is changed according to the magnitude of the current applied to the electrode, and changing the magnitude of the applied current in response to the current adhesion state can more effectively suppress the nozzle clogging.
- the above-mentioned patent documents disclose a continuous casting method that can apply current of a certain magnitude to the inner wall of the immersion nozzle to suppress the current adhesion and to measure the inclusion state of the inclusions in the nozzle to correspond to the current adhesion state. It is not. Therefore, there is a need for a continuous casting method capable of quickly measuring the inclusion state in the nozzle in order to effectively remove the now adhered in response to the present attachment state.
- the present invention provides a molten steel processing apparatus and a molten steel processing method capable of quickly measuring the adhesion state of an inclusion in a nozzle during an operation.
- the present invention provides a molten steel processing apparatus and a molten steel processing method that can effectively suppress or prevent occurrence of nozzle clogging during operation.
- the present invention provides a molten steel treatment apparatus and a molten steel treatment method capable of improving the stability and productivity of the operation.
- the molten steel processing apparatus has a space for receiving molten steel, the storage container formed with a tap hole on the bottom surface to tap the molten steel; A nozzle having an inner space through which the molten steel passes and mounted to the tap hole; A liner made of an ion conductive material installed on at least a portion of an inner circumferential surface of the nozzle; A power supply for applying power to the molten steel and the liner; And a meter for measuring a voltage value or a current value between the molten steel and the liner.
- the power supply may apply DC current or DC voltage to the molten steel and the liner.
- the measuring device may measure a voltage value between the molten steel and the liner when the power supply applies a DC current to the molten steel and the liner, and when the power supply applies a DC voltage to the molten steel and the liner.
- the current value between the molten steel and the liner can be measured.
- the measuring device may measure a voltage value between the molten steel and the liner when the power supply applies a DC current to the molten steel and the liner, and uses the applied current value and the voltage value input from the power supply. Calculates a value, and when the power supply applies a DC voltage to the molten steel and the liner, measures a current value between the molten steel and the liner, and uses an applied voltage value and the current value input from the power supply. The resistance value can be calculated.
- the liner may comprise a solid electrolyte.
- It may further include a liner electrode disposed between the nozzle and the liner.
- the power supply may include a DC power supply capable of applying a DC current or a DC voltage to the molten steel and the liner, the negative terminal of the DC power supply may be connected to the molten steel, and both terminals of the DC power supply may be connected to the liner electrode. .
- the nozzle contains an electrically conductive material
- the power supply includes a DC power source capable of applying a DC current or a DC voltage to the molten steel and the liner, the negative terminal of the DC power source is connected to the molten steel, the DC power source Both terminals of may be connected to the nozzle.
- the measuring device may include: a measuring part connected to the power supply and measuring a voltage value or a current value between the molten steel and the liner; A calculating unit connected to the measuring unit and calculating a resistance value using a voltage value or a current value input from the measuring unit and an applied current value or an applied voltage value input from the power supply; And a thickness of the inclusions connected to the calculation unit and attached to an interface between the molten steel and the liner in comparison with a resistance value input from the calculation unit and a preset reference resistance value, or a voltage value input from the measurement unit or And a determination unit determining a thickness of an inclusion attached to the interface by comparing a current value with a preset reference voltage value or a reference current value.
- Molten steel processing method the process for providing molten steel in the storage container; Tapping the molten steel provided in the storage container; Applying power to the liner installed on the inner circumferential surface of the nozzle for ejecting the molten steel and the molten steel; Measuring a voltage value or a current value between the molten steel and the liner; And determining a thickness of an inclusion adhered to an interface between the molten steel and the liner using the voltage value or the current value.
- a DC current is connected to the molten steel by connecting a negative terminal of the DC power source to the molten steel, and connecting both terminals of the DC power source to the liner electrode or the nozzle installed between the liner and the nozzle.
- a DC voltage can be applied.
- the step of calculating the resistance value between the molten steel and the liner After the step of measuring the voltage value or the current value, the step of calculating the resistance value between the molten steel and the liner; and in the step of calculating the resistance value, when a direct current is applied to the molten steel and the liner
- the resistance value may be calculated using the applied current value of the DC current and the voltage value, and when the DC voltage is applied to the molten steel and the liner, the resistance value may be calculated using the applied voltage value and the current value of the DC voltage. Can be.
- the process of determining the adhesion state of the inclusions of the interface Before the process of determining the thickness of the inclusions, the process of determining the adhesion state of the inclusions of the interface; and in the process of determining the attachment state of the inclusions, the voltage value or the current value or the resistance value and the Attaching the interface when the voltage value is greater than or equal to the reference voltage value, the current value is less than or equal to the reference current value, or the resistance value is greater than or equal to the reference resistance value in comparison to a set reference voltage value or reference current value or reference resistance value
- the interface may be determined as an inclusion free state.
- the thickness of the inclusions attached to the interface increases as the voltage value or the resistance value increases or the current value decreases.
- the thickness of the inclusions attached to the interface may decrease as the voltage value or the resistance value decreases or the current value increases.
- the embodiment of the present invention it is possible to form a measuring device that can quickly measure the inclusion state of the nozzle, by using this it is possible to quickly measure the state of inclusion in the nozzle during operation.
- the meter when applied to continuous casting equipment, the meter continuously measures the voltage value or current value between the molten steel and the liner in the nozzle during operation, and the measured value and the current value or voltage value of the power applied between the molten steel and the nozzle. Calculate the resistance value. By comparing this with the preset resistance value, it is possible to determine whether the inclusions in the nozzles and the increase and decrease of the thicknesses of the inclusions are quickly determined. This can be done quickly to eliminate the nozzle clogging. In detail, when the nozzle is clogged, the opening degree of the nozzle is increased to increase the tapping speed of the molten steel and promote separation of inclusions. It also increases the current value of the applied power source to promote electrochemical deoxidation of inclusions. In this way, nozzle clogging can be promptly eliminated.
- FIG. 1 is a schematic diagram of a molten steel processing apparatus according to an embodiment of the present invention.
- FIGS. 2 and 3 are schematic views of a molten steel treatment apparatus according to a modification of the present invention.
- FIG. 4 is a schematic diagram of an electric circuit provided in the molten steel processing apparatus according to the embodiment of the present invention.
- FIG. 5 is a conceptual diagram of an electric circuit provided in the molten steel processing apparatus according to the embodiment of the present invention.
- Figure 6 is a graph showing the results after performing a characteristic experiment of the solid electrolyte according to an embodiment of the present invention
- Figure 7 is a graph showing the results after performing the operation in accordance with an embodiment of the present invention.
- FIG. 1 is a schematic view showing a molten steel processing apparatus according to an embodiment of the present invention
- Figures 2 and 3 is a schematic view showing a molten steel processing apparatus according to a modification of the present invention
- Figure 4 is an embodiment of the present invention
- It is a schematic diagram which shows the electric circuit provided in the molten steel processing apparatus.
- 5 is a conceptual diagram which shows the electric circuit provided in the molten steel processing apparatus which concerns on embodiment of this invention.
- 2 is a schematic diagram showing a molten steel treatment apparatus according to a first modified example of the present invention
- FIG. 3 is a schematic diagram showing a molten steel treatment apparatus according to a second modified example of the present invention.
- Figure 4 (a) is a schematic diagram showing an electric circuit provided in the molten steel processing apparatus according to the embodiment and the second modification of the present invention
- Figure 4 (b) is a molten steel according to the first modification of the present invention
- It is a schematic diagram which shows the electric circuit provided in a processing apparatus
- FIG. 4 (c) shows the electric circuit provided in a molten steel processing apparatus when a current measuring part is applied to the measurement part of the molten steel processing apparatus which concerns on embodiment of this invention.
- the molten steel processing apparatus which concerns on embodiment of this invention is an apparatus which can process the to-be-processed object, such as molten steel, manufactured in the steel manufacturing equipment. More specifically, the molten steel treatment apparatus is a device for adjusting the amount of molten steel in the process of taking the molten steel and staying therein for a predetermined time and then tapping it.
- An embodiment of the present invention illustrates a continuous casting facility as a steel manufacturing facility to which the molten steel treatment apparatus is applied.
- the storage container 100 of the molten steel treatment apparatus may include a tundish used in a continuous casting facility, and the lower nozzle 220 may include a submerged entry nozzle (SEN) mounted at the tundish. It may include.
- the equipment to which the molten steel treatment apparatus according to the embodiment of the present invention is applied is not particularly limited to the continuous casting equipment.
- the molten steel processing apparatus has a space for receiving molten steel M, and the storage container 100 and molten steel M having a tap hole 110 formed on the bottom surface thereof to tap the molten steel M.
- the liner 400, the nozzle 200, and the liner 400 made of an ion conductive material having an inner space therethrough and installed in at least a part of an inner circumferential surface of the nozzle 200 mounted on the tap hole 110.
- Meter 700 is included.
- a mold 10 is provided below the molten steel processing apparatus, and the mold 10 receives molten steel M that is discharged from the storage container 100 through the nozzle 200 of the molten steel processing apparatus. It solidifies into a slab shape.
- the storage container 100 for example, a tundish is a shape of a container in which a predetermined space for receiving molten steel M is provided, and the inside of the storage container 100 may be temporarily stored in the molten steel M supplied from a ladle (not shown). have.
- the storage container 100 penetrates the bottom surface of the storage container 100 in the vertical direction so as to tap the molten steel M received in the storage container 100 in a vertical direction, and the tapping hole 110 is formed in the storage container 110.
- the nozzle 200 is mounted.
- the nozzle 200 is mounted to penetrate the outlet 110 in the up and down direction from the lower side of the storage container 100.
- the nozzle 200 has a hollow tubular shape extending in the longitudinal direction and may be made of a refractory.
- the nozzle 200 is provided with an inner space through which the upper and lower portions are opened to allow the molten steel M to pass therethrough.
- the nozzle 200 includes an upper nozzle 210, a lower nozzle 220, for example, an immersion nozzle.
- the nozzle 200 has an upper nozzle 210 mounted through the tap hole 110, and a lower nozzle 220 is connected to the upper nozzle 210 to communicate with the storage container 100.
- the lower end of the lower nozzle 220 is provided with a discharge port so that the molten steel (M) can be pulled out.
- the molten steel M received in the storage container 100 is supplied into the mold 10 through the outlet 110, the inner space of the nozzle 200, and the outlet of the lower nozzle 220.
- One side of the nozzle 200 is provided with a sliding gate 300 to adjust the exit amount of the molten steel (M) passing through the internal space of the nozzle 200.
- the sliding gate 300 is disposed between the upper nozzle 210 and the lower nozzle 220, and adjusts the exit amount of the molten steel M by adjusting the opening degree of the nozzle 200.
- inclusions such as alumina inclusions may be mixed in the molten steel M.
- Inclusions mixed in the molten steel M may be attached to the nozzle 200 while the molten steel M is supplied to the mold 10 through the nozzle 200.
- Inclusions attached to the nozzle 200 irregularly reduce the inner diameter of the nozzle 200 to irregularly change the outgoing amount of the molten steel M passing through the nozzle 200. This phenomenon is called nozzle clogging.
- an inner conductive liner 400 which will be described later, is installed on the inner circumferential surface of the nozzle 200, and power is applied to the liner 400 to be attached to the nozzle 200. Is removed by deoxidation in an electrochemical manner.
- the deoxidation rate of the inclusions is changed according to the current value of the power applied, and in order to effectively remove the inclusions, it is necessary to quickly measure the inclusion state in the nozzle during operation and adjust the current value applied correspondingly.
- a measuring device 700 to be described later, it is possible to quickly measure the inclusion state and the thickness of the inclusions in the nozzle 200 through the measuring device 700.
- the liner 400 is in the shape of a film having a predetermined area and a predetermined thickness and is provided on at least a portion of the inner circumferential surface of the nozzle 200.
- the liner 400 may include a solid electrolyte, and the solid electrolyte may be, for example, zirconia (ZrO 2 ). Ions are movable inside the solid electrolyte, and the liner 400 has ion conductivity by the solid electrolyte. That is, a path through which ions can move may be formed on the inner circumferential surface of the nozzle 200 by the liner 400.
- the liner 400 is in contact with the molten steel M, and the interface 410 is formed on the inner circumferential surface of the liner 400 by the contact of the liner 400 with the molten steel M having different phases of the material. Is formed.
- Power is applied to the liner 400 during operation, and the electrochemical reduction reaction is applied to the inclusions 1, such as alumina inclusions (Al 2 O 3 ), which are attached to the interface 410 of the liner 400 during the operation by the applied power. Induced.
- the inclusion 1 is decomposed into oxygen ions and metal ions, the oxygen ions move toward the anode in the liner 400 to be removed from the molten steel M, and the metal ions are mixed in the molten steel M.
- the liner electrode 500 may be disposed between the liner 400 and the nozzle 200.
- the liner electrode 500 serves to apply power to the liner 400.
- power is applied to the molten steel M in response to the power applied to the liner electrode 500.
- a positive pole of direct current is applied to the liner electrode 500, and a negative pole of direct current is applied to the molten steel M.
- a DC voltage anode is applied to the liner electrode 500 and a cathode of DC voltage is applied to the molten steel M.
- the flow of electricity is formed in the liner 400 by the liner electrode 500 and the molten steel (M).
- the material of the liner electrode 500 may include a carbon material.
- the power supply 600 is provided at the outside of the storage container 100 and the nozzle 200, and serves to apply a power supply, for example, a DC current or a DC voltage, to the molten steel M and the liner 400.
- the power supply 600 may include a DC power source capable of applying a DC current or a DC voltage to the molten steel M and the liner 400.
- the negative terminal of the DC power supply is connected to the molten steel M, and both terminals of the DC power supply are connected to the liner electrode 500 or the nozzle 200. More specifically, when the liner electrode 500 is disposed between the nozzle 200 and the liner 400, both terminals of the DC power supply are connected to the liner electrode 500, and in other cases, both terminals of the DC power supply are nozzles.
- the nozzle 200 may contain 20 wt% or more of carbon based on the total weight, and thus the nozzle 200 may have a desired electrical conductivity.
- the DC power source applies a cathode to the molten steel M and an anode to the liner electrode 500 or the nozzle 200.
- Measuring instruments 700 are connected to the power supply 600, measuring unit for measuring the voltage value or current value between the molten steel (M) and the liner 400, 710 (711, 712), measuring unit ( 710 is connected to the operation unit 720 and the operation unit 720 to calculate a resistance value using a voltage value or current value input from the measurement unit and an applied current value or an applied voltage value input from the power supply 600.
- the thickness of the inclusion 1 attached to the interface 410 between the molten steel M and the liner 400 is measured or measured by comparing the resistance value input from the calculator 720 and the preset reference resistance value.
- the measuring unit 710 may include a voltage measuring unit 711 capable of measuring a voltage value and a current measuring unit 712 capable of measuring a current value.
- the power supply 600 includes a voltage measuring unit 711, a calculating unit 720, and a determining unit 730 in response to the case where a DC current having a predetermined magnitude is applied to the molten steel M and the liner 400. 1, the meter 700a may be connected to the power supply 600 (see FIGS. 4A and 4B).
- the power supply 600 may be formed in the molten steel M and the liner 400.
- a second measuring device 700b including a current measuring unit 712, a calculating unit 720, and a determining unit 730 may be connected to the power supply 600. 4 (c))
- the first measuring unit 700a and the second measuring unit 700b are selectively applied to the molten steel treatment apparatus according to the embodiment of the present invention in response to the power applied from the power supply 600. Can be.
- the measuring device 700 is a voltage value between the molten steel (M) and the liner 400 when the power supply 600 applies a DC current to the molten steel (M) and the liner 400 using the measuring unit 710.
- the power supply 600 applies a DC voltage to the molten steel (M) and the liner 400
- the current value between the molten steel (M) and the liner 400 is measured.
- the measurer 700 may calculate a resistance value from the measured current value or the measured voltage value using the calculator 720. This is described below.
- the measuring unit 710 measures the voltage value between the molten steel (M) and the liner 400, and the calculating unit 720 The resistance value is calculated using the applied current value input from the power supply 600 and the measured voltage value input from the measuring unit 710. In addition, when the power supply 600 applies a DC voltage to the molten steel M and the liner 400, the measuring unit 710 measures a current value between the molten steel M and the liner 400, and calculates an operation unit 720. ) May calculate the resistance value using the applied voltage value input from the power supply 600 and the measured current value input from the measurement unit 710.
- the measuring unit 700 may quickly determine the thickness of the inclusions and the inclusion state of the inclusions attached to the interface 410 from the resistance value, the measured voltage value, or the measured current value calculated using the determination unit 730. have.
- the molten steel processing apparatus according to the present embodiment can quickly measure the inclusion state and the inclusion thickness in the nozzle 200 during operation.
- the meter 700 measures a current value or a voltage value between the molten steel M and the liner 400, calculates a resistance value, and includes an inclusion state and a thickness of an inclusion in the nozzle 200. Detailed description of the determination will be described below with reference to the molten steel treatment method according to the present embodiment.
- the molten steel processing apparatus may be configured in various forms including the following modified examples.
- FIGS. 2 and 4 (b) the molten steel treatment apparatus according to the first modification of the present invention will be described.
- FIGS. 3 and 4 (a) the second embodiment of the present invention will be described.
- the molten steel processing apparatus which concerns on a modification is demonstrated.
- the description will be made mainly on the features that are distinguished from the molten steel processing apparatus according to an embodiment of the present invention, the rest of which is similar to the configuration of the molten steel processing apparatus according to an embodiment of the present invention will be omitted below.
- both terminals of the DC power source may be connected to the nozzle 200. That is, the molten steel processing apparatus according to the first modification of the present invention may utilize the nozzle 200 as an electrode without separately providing an electrode.
- the nozzle 200 contains an electrically conductive material, the electrically conductive material being for example carbon.
- the content of carbon may be 20% by weight or more with respect to the total weight of the nozzle 200 in the nozzle 200.
- the liner 400 and the liner electrode 500 may be installed on a portion of the inner circumferential surface of the nozzle 200.
- the electric circuit provided in the molten steel processing apparatus according to the second modified example of the present invention is similar in configuration to the electric circuit provided in the molten steel processing apparatus according to the embodiment of the present invention, shown in Figure 4 (a).
- the liner 400 and the liner electrode 500 are installed at at least one or more desired positions on the inner circumferential surface of the nozzle 200, and the inclusion attachment state and the inclusion thickness at the installed position are determined. It can be measured quickly.
- the position where the liner 400 and the liner electrode 500 are installed is a position where a large amount of inclusions are attached in the nozzle 200, for example, the upper region or the molten steel M of the nozzle 200 flowing into the molten steel M is discharged. It may be a lower region of the nozzle 200.
- Figure 6 is a graph showing the results after performing a characteristic experiment of a solid electrolyte according to an embodiment of the present invention.
- a container of a predetermined size (hereinafter, a specimen) is formed of MgO stabilized ZrO 2 (MSZ), and a crucible containing molten steel is prepared.
- MSZ MgO stabilized ZrO 2
- the anode is connected to the specimen and the cathode is connected to the molten steel to form an electrochemical circuit.
- Apply a DC voltage to the constructed electrochemical circuit, increase the voltage value of the DC voltage, and measure the current value between the specimen and the molten steel.
- oxygen is supplied to the interface between the specimen and the molten steel to induce an inclusion (Al 2 O 3 ) to be formed between the specimen and the molten steel.
- an inclusion Al 2 O 3
- inclusions are attached to the specimen, and the inclusions act as a resistance that prevents current from flowing between the specimen and the molten steel. Therefore, the current value does not increase as the total resistance value of the electrochemical circuit increases and the voltage value increases after the attachment of the inclusions, and the slope of the measured voltage value and the current value is changed.
- the inclusions attached to the interface formed between the molten steel and the solid electrolyte may be correlated with the resistance value between the molten steel and the solid electrolyte. Therefore, in the molten steel processing apparatus and the molten steel processing method according to the present embodiment, it is possible to effectively determine the attachment state of the inclusions and the thickness of the inclusions during the operation, and accordingly adjust the operating conditions to effectively suppress or prevent the nozzle clogging. .
- the molten steel treatment method according to an embodiment of the present invention, the process of providing the molten steel (M) in the storage container 100, the process of tapping the molten steel (M) provided in the storage container 100, the molten steel (M) and The process of applying power to the liner 400 installed on the inner circumferential surface of the nozzle 200 for tapping the molten steel (M), the process of measuring the voltage value or current value between the molten steel (M) and the liner 400, and the measurement And determining the thickness of the inclusion 1 attached to the interface 410 between the molten steel M and the liner 400 using the obtained voltage value or current value.
- the molten steel processing apparatus includes a storage container 100 capable of taking molten steel and a nozzle 200 mounted to a tap hole 110 provided in the storage container 100, and a liner electrode (sequentially) is disposed on an inner circumferential surface of the nozzle 200. 500 and a liner 400 are provided.
- One side of the nozzle 200 is equipped with a slide gate 300 that can adjust the opening degree of the nozzle 200.
- the power supply 600 is provided on the outside of the nozzle 200 to apply power to the molten steel (M) and the liner 400, the electrochemical including the power supply 600, the molten steel (M) and the liner 400
- the circuit is constructed.
- a measuring device 700 capable of measuring a voltage value or a current value between the molten steel M and the liner 400 is connected to an electrochemical circuit including the power supply 600 and the molten steel M and the liner 400.
- the mold 10 is provided below the molten steel processing apparatus described above, and the molten steel M in the storage container 100 is supplied into the mold 10 by the nozzle 200.
- molten steel M is provided in the storage container 100.
- a transport container (not shown) for transporting molten steel M, for example, a ladle, is moved above the storage container 100, and then the molten steel is tilted to prepare molten steel in the storage container 100.
- the molten steel M provided in the storage container 100 is tapped out.
- the molten steel M is pulled out by opening the nozzle 200 using the slide gate 300 mounted to the nozzle 200.
- the slide gate 300 may adjust the tapping amount and tapping speed of the molten steel M tapping by adjusting the opening degree of the nozzle 200.
- both terminals of the DC power supply may be connected to the nozzle 200 (see FIG. 4 (b)) to apply a DC current or a DC voltage to the molten steel M and the liner 400.
- an electrochemical circuit including the power supply 600, the molten steel M, and the liner 400 will be described with reference to FIGS. 4 and 5.
- an electrochemical circuit provided in a molten steel treatment apparatus includes both terminals of a DC power supply, a liner electrode 500, a liner 400, and an interface 410.
- molten steel (M) and the negative terminal of the DC power supply each of which is electrically connected to each other.
- the resistances R 1, R 3, and R 4 which are the resistances of the molten steel M, the liner 400, and the liner electrode 500, may be given or measurable constant values according to the electrical properties of the respective materials. Resistance is a variable value that varies with inclusions attached during operation. This is simplified and shown in FIG. 5.
- the total resistance of the electrochemical circuit is the sum of R1 resistance, which is the resistance of the molten steel M, R2 resistance, which is the resistance of the interface 410, R3 resistance, which is the resistance of the liner 400, and R4 resistance, which is the resistance of the liner electrode 410. Becomes total resistance.
- a measuring device 700 is connected to the electrochemical circuit described above.
- the configuration of the measuring device 700 is as follows.
- the measuring device 710 is connected to an electrochemical circuit, and is connected to the measuring unit 710 measuring the voltage value or the current value, the measuring unit 710, and calculating the resistance unit 720 and the calculating unit 720. Is connected, and includes a determination unit 730 for determining the thickness of the inclusions attached to the interface 410.
- the measuring unit 710 includes a voltage measuring unit 711 such as a voltmeter and a current measuring unit 712 such as an ammeter, and corresponds to a power applied from a DC power source, and the voltage measuring unit 711 and the current measuring unit 712. Is selected and connected to the electrochemical circuit.
- the voltage measuring unit 711 includes an electrochemical circuit such that the voltage measuring unit 711 is connected in parallel with the DC power supply, as shown in FIG. 4A or 4B.
- the current measuring unit 712 is connected to an electrochemical circuit such that the current measuring unit 712 is connected in series with the DC power supply, as shown in FIG.
- the current value and the voltage value measured in the electrochemical circuit are used to calculate the R2 resistance, which is the resistance of the interface 410.
- the total resistance value of the electrochemical circuit may be calculated from the voltage value measured by the voltage measuring unit 711 and the applied current value of the DC current applied from the DC power supply, and R1 having a given value from the total resistance value.
- the resistance value of the R2 resistance which is the resistance of the interface 410, excluding the resistance values of the resistance, the R3 resistance, and the R4 resistance, may be calculated.
- the total resistance value of the electrochemical circuit can be calculated from the current value measured by the current measuring unit 712 and the applied voltage value of the DC voltage applied from the DC power supply, the R1 resistance having a given value from the total resistance value,
- the resistance value of the R2 resistance which is the resistance of the interface 410, excluding the resistance values of the R3 and R4 resistors, can be calculated.
- a voltage value or a current value between the molten steel M and the liner 400 is measured.
- a direct current is applied to the molten steel M and the liner 400
- the voltage value between the molten steel M and the liner 400 is measured, and the molten steel M and
- a DC voltage is applied to the liner 400
- the current value between the molten steel M and the liner 400 is measured.
- the measurement of the voltage value or the current value is performed in real time, and may be continuously performed at regular time intervals. For example, the voltage value or the current value can be continuously measured at intervals of 0.2 seconds while the operation is in progress.
- a process of calculating the resistance value between the molten steel M and the liner 400 may be performed.
- the resistance value is calculated using, for example, Ohm's law using the applied current value of the DC current and the measured voltage value, and the molten steel.
- the resistance value may be calculated using the applied voltage value of the DC voltage and the measured current value.
- the calculation of the resistance value is performed in real time corresponding to the process of measuring the voltage value or the current value, and may be continuously performed at predetermined time intervals. For example, when the measurement of the voltage value or the current value is performed continuously at 0.2 second intervals, the calculation of the resistance value may also be performed continuously at 0.2 second intervals.
- the process of determining the thickness of the inclusions attached to the interface 410 between the molten steel (M) and the liner 400 do.
- the time when the flow of the molten steel (M) in the nozzle 200 is stabilized means a time when the flow of the molten steel (M) uniformly passes through the entire region in the nozzle 200 to stabilize the flow.
- the process of determining the inclusion state of the interface 410 is performed prior to the process of determining the thickness of the inclusion 1.
- the process of determining the attachment state of the inclusions is performed in real time while the operation is in progress, and may be continuously performed at predetermined time intervals.
- the measured voltage value is greater than or equal to the reference voltage value by comparing the measured voltage value or measured current value or calculated resistance value with a predetermined reference voltage value or reference current value or reference resistance value. If the measured current value is equal to or less than the reference current value or the calculated resistance value is equal to or greater than the reference resistance value, the interface 410 is determined to be in the state of inclusions, and the measured voltage value is less than the reference voltage value or the measured current value is a reference value. If the current value is greater or the calculated resistance value is less than the reference resistance value, the interface 410 is determined as an inclusion free state. By using this, the inclusion state in the nozzle 200 can be quickly measured while the operation is in progress.
- the molten steel treatment operation is repeatedly performed by applying the molten steel treatment apparatus according to the present embodiment. As the operation is repeated, the measured voltage value, current value, and calculated resistance value are quantified. Quantified values are analyzed over time, that is, time series, to inductively deduce the time of inclusion inclusions. For example, when the flow of molten steel M is stabilized after the tapping of the molten steel M starts, the voltage value measured by applying a constant current value and the calculated resistance value have a constant value within a predetermined range. However, a sudden increase in the voltage value occurs, which can be determined by the increase in the resistance value. In addition, it may be determined that the increase in the resistance value increases with the inclusion of inclusions at the interface 410 of the liner 400.
- FIG. 7 is a graph showing the results after performing the operation according to an embodiment of the present invention.
- a method of setting the reference voltage value, the reference current value, and the reference resistance value will be described with reference to FIG. 7.
- Operation conditions of operation are as follows. 10 tons of high alumina high titanium molten steel was repeatedly performed five times at a casting speed of 0.8 m / min. At this time, a 1.0 A DC current was applied to the molten steel M and the liner 400 using the power supply 600, and the voltage was measured using the measuring device 700. The measurement interval at this time is 0.2 seconds. Then, the total resistance was calculated using the measured voltage value. The amount of increase in voltage and the amount of increase in resistance at this time are quantified in time series as shown in FIG. 7. Referring to Figure 7, the flow through the non-uniform flow (A) of the initial casting molten steel passes through the section (B) to stabilize the flow of the molten steel.
- the resistance value is maintained within a predetermined range.
- a section C in which the resistance value suddenly increases or decreases occurs. It can be inferred that the point at which the resistance value suddenly increases or decreases is the point of attachment.
- the casting speed, molten steel discharge amount, and nozzle inner diameter of the nozzle 200 are information given according to operating conditions. Accordingly, it is possible to quantify the change in the inner diameter of the nozzle 200, that is, the thickness of the inclusions to be attached, through the molten steel discharge amount and the nozzle inner diameter information when the resistance value increases.
- the database can be constructed by securing the attachment state of the inclusion and the thickness information of the inclusion corresponding to the resistance value.
- the voltage value, the current value, and the resistance value when the inclusion is attached to the nozzle are set as the reference voltage value, the reference current value, and the reference resistance value.
- a process of determining the thickness of the inclusion is performed.
- the inclusions attached to the interface 410 as the measured voltage value or the measured resistance value increases or the measured current value decreases. It may be determined that the thickness of the electrode increases, and as the measured voltage value or the measured resistance value decreases or the measured current value increases, it may be determined that the thickness of the inclusions attached to the interface decreases.
- the increase or decrease of the thickness of the inclusions attached to the interface 410 may be determined using the result value.
- the operation is repeated to quantify and quantify the relationship between the result value and the thickness of the inclusions, it is of course possible to determine not only the thickness change of the inclusions but also the thickness values of the inclusions.
- the process of determining the thickness of the inclusions it is natural that the thickness of the inclusions is not determined when the interface 410 is determined to be non-inclusion state in the previous process.
- the interface 410 in performing the process of determining the thickness of the inclusions, when the voltage value or the resistance value decreases to decrease below the reference voltage value or the reference resistance value, the interface 410 is determined to be non-inclusion state, and then the process proceeds to the previous process. Go back and determine the attachment state.
- the process of determining the thickness of the inclusions when the current value increases and exceeds the reference current value, after determining the interface 410 as the non-inclusion state, the process returns to the previous process to determine the inclusion state Perform the process.
- a process of performing a subsequent process according to the thickness of the inclusions is performed.
- the tapping speed of the molten steel M is increased or the current value between the molten steel M and the liner 400 is increased.
- the inclusions attached to the interface 410 are removed, thereby eliminating nozzle clogging caused by the inclusions.
- the tapping speed of the molten steel M is maintained or the current value between the molten steel M and the liner 400 is maintained.
- the method of increasing the tapping speed of the molten steel (M) has a method of increasing the opening degree of the nozzle 200 by using the slide gate 300, for example.
- the tapping speed of the molten steel M is increased, the inclusions attached to the nozzle 200 may be desorbed.
- the current value between the molten steel (M) and the liner 400 using the power supply 600, it is possible to increase the decomposition rate of the inclusions by increasing the electrochemical deoxidation phenomenon.
- the inclusions attached to the interface 410 are quickly removed to insert the inclusions of the interface 410, that is, the nozzles.
- the inclusion state of the interface 410 that is, the nozzle clogging
- the resistance of the interface 410 is reduced. Accordingly, the voltage value or the resistance value is reduced to form the value in the range below the reference voltage value or the reference resistance value, and the current value increases to form the value in the range above the reference current value. This can be measured from the measurement unit 710 during the operation, the measurement value is fed back can be used for accurate determination of the inclusion state of the interface 410.
- the tapping speed of the molten steel M and the current value between the molten steel M and the liner 400 are gradually increased to attach the inclusions of the interface 410. The state can be resolved more effectively.
- the molten steel treatment method performed as described above includes a process of measuring a current value or a voltage value during an operation for processing molten steel, a process of determining an inclusion state, a process of determining a thickness of an inclusion, and a subsequent process.
- the process of carrying out is carried out continuously at regular time intervals, thereby quickly measuring the occurrence of nozzle clogging of the equipment. Because of this, if the clogging of the nozzle during the operation proceeds to facilitate the separation and decomposition of the inclusions attached to the nozzle can be quickly eliminated. Thus, the stability and productivity of the operation can be improved.
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Abstract
Description
Claims (16)
- 용강을 수강하는 공간을 가지고, 상기 용강을 출강하도록 바닥면에 출강구가 형성된 저장용기;상기 용강이 통과하는 내부공간을 가지고, 상기 출강구에 장착되는 노즐;상기 노즐의 내주면의 적어도 일부에 설치되는 이온 전도성 재질의 라이너;상기 용강과 상기 라이너에 전원을 인가하는 전원공급기; 및상기 용강과 상기 라이너 사이의 전압값 또는 전류값을 측정하는 측정기;를 포함하는 용강 처리 장치.
- 청구항 1에 있어서,상기 전원공급기는 상기 용강과 상기 라이너에 직류전류 또는 직류전압을 인가하는 용강 처리 장치.
- 청구항 2에 있어서,상기 측정기는,상기 전원공급기가 상기 용강과 상기 라이너에 직류전류를 인가하는 경우 상기 용강과 상기 라이너 사이의 전압값을 측정하고,상기 전원공급기가 상기 용강과 상기 라이너에 직류전압을 인가하는 경우 상기 용강과 상기 라이너 사이의 전류값을 측정하는 용강 처리 장치.
- 청구항 2에 있어서,상기 측정기는,상기 전원공급기가 상기 용강과 상기 라이너에 직류전류를 인가하는 경우 상기 용강과 상기 라이너 사이의 전압값을 측정하고, 상기 전원공급기로부터 입력되는 인가전류값과 상기 전압값을 이용하여 저항값을 산출하며,상기 전원공급기가 상기 용강과 상기 라이너에 직류전압을 인가하는 경우 상기 용강과 상기 라이너 사이의 전류값을 측정하고, 상기 전원공급기로부터 입력되는 인가전압값과 상기 전류값을 이용하여 저항값을 산출하는 용강 처리 장치.
- 청구항 1에 있어서,상기 라이너는 고체전해질을 포함하는 용강 처리 장치.
- 청구항 1에 있어서,상기 노즐과 상기 라이너 사이에 배치되는 라이너 전극;을 더 포함하는 용강 처리 장치.
- 청구항 6에 있어서,상기 전원공급기는 상기 용강과 상기 라이너에 직류전류 또는 직류전압을 인가 가능한 DC전원을 포함하며,상기 DC전원의 음단자는 상기 용강에 연결되고,상기 DC전원의 양단자는 상기 라이너 전극에 연결되는 용강 처리 장치.
- 청구항 1에 있어서,상기 노즐은 전기 전도성 물질을 함유하고,상기 전원공급기는 상기 용강과 상기 라이너에 직류전류 또는 직류전압을 인가 가능한 DC전원을 포함하며,상기 DC전원의 음단자는 상기 용강에 연결되고,상기 DC전원의 양단자는 상기 노즐에 연결되는 용강 처리 장치.
- 청구항 1에 있어서,상기 측정기는,상기 전원공급기에 연결되고, 상기 용강과 상기 라이너 사이의 전압값 또는 전류값을 측정하는 측정부;상기 측정부에 연결되고, 상기 측정부로부터 입력되는 전압값 또는 전류값과 상기 전원공급기로부터 입력되는 인가전류값 또는 인가전압값을 이용하여 저항값을 산출하는 연산부;상기 연산부에 연결되고, 상기 연산부로부터 입력되는 저항값과 기 설정된 기준 저항값을 대비하여 상기 용강과 상기 라이너 사이의 계면에 부착되는 개재물의 두께를 판단하거나, 상기 측정부로부터 입력되는 전압값 또는 전류값과 기 설정된 기준 전압값 또는 기준 전류값을 대비하여 상기 계면에 부착되는 개재물의 두께를 판단하는 판단부;를 포함하는 용강 처리 장치.
- 용강을 저장용기 내에 마련하는 과정;상기 저장용기 내에 마련된 용강을 출강하는 과정;상기 용강 및 상기 용강을 출강하는 노즐의 내주면에 설치된 라이너에 전원을 인가하는 과정;상기 용강과 상기 라이너 사이의 전압값 또는 전류값을 측정하는 과정; 및상기 전압값 또는 전류값을 이용하여 상기 용강과 상기 라이너 사이의 계면에 부착되는 개재물의 두께를 판단하는 과정;을 포함하는 용강 처리 방법.
- 청구항 10에 있어서,상기 전원을 인가하는 과정에 있어서,상기 용강에 DC전원의 음단자를 연결하고, 상기 라이너와 상기 노즐 사이에 설치된 라이너 전극 또는 상기 노즐에 DC전원의 양단자를 연결하여 상기 용강과 상기 라이너에 직류전류 또는 직류전압을 인가하는 용강 처리 방법.
- 청구항 11에 있어서,상기 전압값 또는 전류값을 측정하는 과정에 있어서,상기 용강과 상기 라이너에 직류전류가 인가되는 경우 상기 용강과 상기 라이너 사이의 전압값을 측정하고,상기 용강과 상기 라이너에 직류전압이 인가되는 경우 상기 용강과 상기 라이너 사이의 전류값을 측정하는 용강 처리 방법.
- 청구항 12에 있어서,상기 전압값 또는 전류값을 측정하는 과정 이후에,상기 용강과 상기 라이너 사이의 저항값 산출 과정;을 수행하고,상기 저항값 산출 과정에 있어서,상기 용강과 상기 라이너에 직류전류가 인가되는 경우 상기 직류전류의 인가전류값과 상기 전압값을 이용하여 저항값을 산출하고, 상기 용강과 상기 라이너에 직류전압이 인가되는 경우 상기 직류전압의 인가전압값과 상기 전류값을 이용하여 저항값을 산출하는 용강 처리 방법.
- 청구항 13에 있어서,상기 개재물의 두께를 판단하는 과정 이전에,상기 계면의 개재물 부착 상태를 판단하는 과정;을 수행하고,상기 개재물 부착 상태를 판단하는 과정에 있어서,상기 전압값 또는 상기 전류값 또는 상기 저항값과 기 설정된 기준 전압값 또는 기준 전류값 또는 기준 저항값을 대비하여 상기 전압값이 상기 기준 전압값 이상이거나 상기 전류값이 상기 기준 전류값 이하이거나 상기 저항값이 상기 기준 저항값 이상일 경우 상기 계면을 개재물 부착 상태로 판단하고, 상기 전압값이 상기 기준 전압값 미만이거나 상기 전류값이 상기 기준 전류값 초과이거나 상기 저항값이 상기 기준 저항값 미만일 경우 상기 계면을 개재물 미부착 상태로 판단하는 용강 처리 방법.
- 청구항 14에 있어서,상기 개재물의 두께를 판단하는 과정에 있어서,상기 계면을 개재물 부착 상태로 판단하는 경우 상기 전압값 또는 상기 저항값이 증가하거나 상기 전류값이 감소함에 따라 상기 계면에 부착되는 개재물의 두께가 증가한다고 판단하고, 상기 전압값 또는 상기 저항값이 감소하거나 상기 전류값이 증가함에 따라 상기 계면에 부착되는 개재물의 두께가 감소한다고 판단하는 용강 처리 방법.
- 청구항 15에 있어서,상기 개재물의 두께를 판단하는 과정 이후에,상기 개재물의 두께에 따라 후속공정을 수행하는 과정;을 수행하고,상기 후속공정을 수행하는 과정에 있어서,상기 계면을 개재물 부착 상태로 판단하는 경우 상기 용강의 출강속도를 증가시키거나 상기 용강과 상기 라이너 사이의 전류값을 증가시키고, 상기 계면을 개재물 미부착 상태로 판단하는 경우 상기 용강의 출강속도를 유지시키거나 상기 용강과 상기 라이너 사이의 전류값을 유지시키는 용강 처리 방법.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15/036,196 US9927177B2 (en) | 2013-12-06 | 2013-12-24 | Molten steel treatment apparatus and molten steel treatment method |
| CN201380080929.3A CN105745041B (zh) | 2013-12-06 | 2013-12-24 | 熔融金属处理设备及熔融金属处理方法 |
| JP2016526901A JP6208346B2 (ja) | 2013-12-06 | 2013-12-24 | 溶鋼の処理装置及び溶鋼の処理方法 |
| EP13898865.4A EP3078434B1 (en) | 2013-12-06 | 2013-12-24 | Molten metal treating apparatus and molten metal treating method |
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| KR10-2013-0151566 | 2013-12-06 | ||
| KR20130151566A KR101489377B1 (ko) | 2013-12-06 | 2013-12-06 | 용강 처리 장치 및 용강 처리 방법 |
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| WO2015083876A1 true WO2015083876A1 (ko) | 2015-06-11 |
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| US (1) | US9927177B2 (ko) |
| EP (1) | EP3078434B1 (ko) |
| JP (1) | JP6208346B2 (ko) |
| KR (1) | KR101489377B1 (ko) |
| CN (1) | CN105745041B (ko) |
| WO (1) | WO2015083876A1 (ko) |
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| EP3381587A4 (en) * | 2015-11-27 | 2018-10-03 | Posco | Nozzle, casting device, and casting method |
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| KR101489377B1 (ko) * | 2013-12-06 | 2015-02-03 | 주식회사 포스코 | 용강 처리 장치 및 용강 처리 방법 |
| CN109759573A (zh) * | 2019-03-19 | 2019-05-17 | 东北大学 | 一种利用脉冲电流以抑制浸入式水口内壁结瘤的方法 |
| CN109732072B (zh) * | 2019-03-19 | 2021-05-25 | 东北大学 | 一种施加同性电荷以抑制浸入式水口内壁结瘤的方法 |
| TWI810064B (zh) * | 2022-09-14 | 2023-07-21 | 中國鋼鐵股份有限公司 | 導體材料電阻值量測系統及方法 |
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- 2013-12-24 EP EP13898865.4A patent/EP3078434B1/en not_active Not-in-force
- 2013-12-24 JP JP2016526901A patent/JP6208346B2/ja not_active Expired - Fee Related
- 2013-12-24 CN CN201380080929.3A patent/CN105745041B/zh not_active Expired - Fee Related
- 2013-12-24 WO PCT/KR2013/012127 patent/WO2015083876A1/ko not_active Ceased
- 2013-12-24 US US15/036,196 patent/US9927177B2/en not_active Expired - Fee Related
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| CN108778568A (zh) * | 2015-11-27 | 2018-11-09 | 株式会社Posco | 水口、铸造装置和铸造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3078434A4 (en) | 2016-10-12 |
| KR101489377B1 (ko) | 2015-02-03 |
| JP6208346B2 (ja) | 2017-10-04 |
| EP3078434A1 (en) | 2016-10-12 |
| CN105745041B (zh) | 2017-09-19 |
| US20160298906A1 (en) | 2016-10-13 |
| JP2017501037A (ja) | 2017-01-12 |
| CN105745041A (zh) | 2016-07-06 |
| EP3078434B1 (en) | 2018-06-13 |
| US9927177B2 (en) | 2018-03-27 |
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