CN102517417A - Method for removing and controlling foreign substances in metal and alloy - Google Patents
Method for removing and controlling foreign substances in metal and alloy Download PDFInfo
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- CN102517417A CN102517417A CN2011104055052A CN201110405505A CN102517417A CN 102517417 A CN102517417 A CN 102517417A CN 2011104055052 A CN2011104055052 A CN 2011104055052A CN 201110405505 A CN201110405505 A CN 201110405505A CN 102517417 A CN102517417 A CN 102517417A
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Abstract
The invention discloses a method for removing and controlling foreign substances in metal and alloy. With the method, the foreign substances can be removed, or the sizes of the foreign substances can be reduced and the foreign substances can be dispersed. Therefore, a purpose for improving metal and alloy material qualities can be achieved. The method comprises steps that: metal and alloy requiring processing are fused, such that metal liquid is formed; the metal liquid is positioned in a vessel with a round cross section or a rectangular cross section; an anode and a cathode are directly inserted into the metal liquid; the anode and the cathode are connected with a power supply; a voltage of 1-100V is applied between the two electrodes; a direct current power supply, an alternating current power supply or a pulse power supply is adopted; graphite electrodes or metal ceramic electrodes which are stable under a high temperature of smelting are adopted as the electrodes; the electrodes are cylindrical electrodes or electrodes with rectangular cross sections. The method can be used for removing or controlling foreign substances in all metal and alloy systems, and can be performed in any vessels containing metal liquid. The method is simple, feasible, and is advantaged in high efficiency, low cost, and no pollution. With the method, industrial production can easily be realized.
Description
Technical field
The present invention relates to the method for metal and refining and modifying, the method for inclusion belongs to metallurgical technology field in especially a kind of removal, control metal and the alloy.
Background technology
Along with progress of science and technology, the user proposes higher requirement to the quality of metal, alloy material.Traditional production technology can not satisfy the specification of quality of user to these materials.For example for steel products, some Clean Steel proposes the impurity element summation less than 80ppm～150ppm to the cleanliness factor of steel.Even but reaching low like this impurity content, the content of inclusion also is appreciable.According to bibliographical information (R.Kiessling, Clean Steel-ADebatable Concept, p.2, in Clean Steel, Proceedings in English of the Second International Conference on Clean Steel, Jun.!～3; 1981; Hungary, Published in January 1983by The Metals Society), when containing [O] or [S] of 1ppm in the steel; If when the inclusion that generates was distributed in the steel with the different-grain diameter even dispersion, the mean distance of contained The amount of inclusions of steel per ton and inclusion particle was seen table 1.
The mean distance of table 1 inclusion size and inclusion number and inclusion particle
(oxygen content in steel or sulphur content are 1ppm)
And present smelting technology can not be realized the 1ppm impurity content at low cost on technology.Therefore, so-called " Clean Steel " in fact only contains " matrix material " of a large amount of small inclusiones.
Inclusion and steel have very big difference in nature; Though the existence of inclusion can make the continuity of metallic substance performance destroyed, material property is affected, and research shows; As long as the size of inclusion less than a certain critical size, just can not produce harm to the performance of steel.Therefore need only the inclusion size control in certain scope, just can not produce harm the performance of steel.In addition; The steel of different purposes must guarantee the performance to some particular requirement; And the kind of inclusion is different to the various performance impacts of steel; For example: because sulfide inclusion can cause hydrogen induced cracking(HIC) (HIC) and stress corrosion crack (SCC), so pipe line steel is strict to sulfide inclusion; Because Al
2O
3Be mingled with and have rigidity, Al in the deformation process of steel
2O
3Be mingled with not yielding, so cord steel is to Al
2O
3Be mingled with the requirement harshness; Because Al
2O
3Being mingled with to become the source of causing fracture, Al
2O
3Be mingled with the fatigue property that can significantly reduce steel, so steel grade such as bearing steel is to Al
2O
3Be mingled with strict.Therefore, for the steel grade of different purposes, in smelting process,, then can make the performance of steel be able to guarantee if can control or remove to those inclusiones that makes the performance of steel particular requirement produce harm.
General Clean Steel all has strict restriction to the size of inclusion, and most of Clean Steel requires the size＜15 μ m of inclusion.
Inclusion is the inevitable outcome in the smelting process.In the smelting process of metal and alloy, larger-size inclusion can float entering top slag and be removed, and the less inclusion of size does not then have the sufficient time come-up and is retained in the molten metal.Because inclusion can produce harm to the performance of material, smelting process must manage to reduce the content of inclusion, and manages the size of inclusion is reduced to the degree that performance of material is not produced harm, to guarantee the performance requriements of material.For iron and steel metallurgical industry, be to adopt the refinery practices such as combination of Argon stirring, vacuum-treat (like RH, VD refining etc.), synthetic wash heat and these methods to reach the purpose of controlling or removing inclusion at present.
Chinese patent CN100543152C; The scheme that " a kind of process method of removing fine foreign matter in the molten steel " proposes is to finish the back in the RH refining to add compound ball, mainly is to decompose the small CO that produces through the carbonate in the compound ball (magnesiumcarbonate, lime carbonate or their mixture)
2The gas blow mixing molten steel, and through the high basicity in the compound ball, low-melting pre-melted slag the inclusion in the molten steel is carried out and add in the slag of top, thereby reach the purpose of removing inclusion.Chinese patent CN101323895B, " a kind of process method of removing fine foreign matter in the molten steel "; Chinese patent CN100582249C, " process method of fine foreign matter is removed in external refining "; It is the improvement of aforesaid method.Above scheme principle is identical, and effect is suitable.Chinese patent CN102019387A; " a kind of method of removing fine foreign matter in the molten steel " propose scheme be to offer a plurality of apertures on tundish long nozzle top; Be blown into rare gas element through these apertures; Perhaps be blown into pulvis as carrier gas and impel inclusion floating in the molten steel or the pulvis that is blown into to carry out, to reach the purpose of removing inclusion with rare gas element; Chinese patent CN101586177B, the scheme that " a kind of method that reduces titanium inclusion of molten steel " proposes is in cord steel is produced, molten steel to be carried out twice Argon to stir, and impels the inclusion floating in the molten steel, to reach the purpose of removing inclusion; Chinese patent CN101992280A, " a kind of method that reduces inclusion content in the strand " propose scheme be to adopt rare gas element and insulating covering agent secluding air, avoid the air-breathing and secondary oxidation of molten steel, to reach the purpose of removal inclusion.Above-mentioned these methods all are to adopt the means of external refining to manage to reduce the inclusion in the steel, though can obtain some effects, need be blown into rare gas element in the treating processes or add some pulvis, complicated operation and instability.
Summary of the invention
The invention provides the method for inclusion in a kind of control, removal metal and the alloy material, can remove inclusion or the inclusion size reduced and the disperse distribution, thereby reach the purpose that improves metal and alloy material quality.
Give birth in inclusion in metal and the alloy material can be divided into and be mingled with and two types of foreing impurityss: interior life is mingled with to be carried out producing in the operating process such as deoxidation, desulfurization and alloying in smelting process, foreing impuritys be since the refractory materials of the container of splendid attire molten metal at high temperature the refractory materials that gets off of melting loss some component and in ladle-to-ladle or casting process the volume slag caused.General foreing impuritys size is bigger, because its density has the comparison big difference with molten metal density, and in smelting process, can be through in the slag of come-up entering top and from molten metal, get rid of; And interior life is mingled with because size is less, in smelting, has quite a few and has little time to discharge and be retained in the molten metal, solidifies the back and is present in the metallic substance with the inclusion form.No matter be that interior life is mingled with or foreing impuritys, if size more mostly will produce serious harm to the performance of metallic substance.
At present, inclusion is reduced as far as possible, thereby make outside the inclusion total amount reduces as far as possible, also do not have suitable method control or remove to be mingled with except improving the smelting level.The method of inclusion is in smelting process, in molten metal, to insert positive and negative the two poles of the earth in this control that the present invention proposes or the removal metal or alloy; Between the two poles of the earth, apply voltage greater than the inclusion decomposition voltage; Destroy the stability of inclusion, make inclusion be dissociated into ion, these ions produce orientation movement under the effect of electrical forces; Negatively charged ion moves to anode, loses electronics generation gaseous product at anode and is excluded; Positively charged ion moves to negative electrode, obtains electronics at negative electrode and is reduced into metallic element, and these metals that are reduced are dissolved in again becomes alloying element in the molten metal.Like this, just can reach the method that adopts extra electric field and control or remove the purpose of the inclusion in the molten metal.
The know-why of present method is: the inclusion in the metal or alloy is that interior life is mingled with or foreing impuritys all is a certain component of slag, and at high temperature, inclusion is the same with slag can be thermodynamic(al)equilibrium with metal or alloy liquid.Ionic structure according to slag is theoretical, the ionic compound that slag is made up of the yin, yang ion.Obviously, inclusion is also the same with slag, is that the form with ionic compound is present in the molten metal.Under the hot conditions of smelting, the balance that the inclusion in the metal or alloy liquid exists is (is example with the divalence non-metallic inclusion) as follows:
For oxide inclusion, its balance can be represented with following reaction:
(MO)
Slag=(M
2+)
Slag+ (O
2-)
Slag
Under the hot conditions of smelting, there are following balance in inclusion and molten metal:
(M
2+)
Slag+ (O
2-)
Slag=[M]
Molten metal+ [O]
Molten metal
For sulfide inclusion, its balance can be represented with following reaction:
(MS)
Slag=(M
2+)
Slag+ (S
2-)
Slag
Under the hot conditions of smelting, there are following balance in inclusion and molten metal:
(M
2+) slag+(S
2-)
Slag=[M]
Molten metal+ [S]
Molten metal
Then there is similar following equilibrated form in situation for generating composite oxides:
(MnOSiO
2)
Slag=(MnO)
Slag+ (SiO
2)
Slag
(MnO)
Slag=(Mn
2+)
Slag+ (O
2-)
Slag
(MnS)
Slag+ [O]
Molten metal=(MnO)
Slag+ [S]
Molten metal
(O
2-)
Slag+ [S]
Molten metal=(S
2-)
Slag+ [O]
Molten metal
Obviously, in molten metal, insert yin, yang the two poles of the earth,, will destroy the stability of inclusion, make it be dissociated into negatively charged ion and positively charged ion as long as between the two poles of the earth, apply decomposition voltage greater than inclusion.These negatively charged ion and positively charged ion will move under the effect of extra electric field.When extra electric field is DC electric field, these inclusion disassociations becoming (M
2+), (O
2-), (S
2-) plasma, these ions all will carry out orientation and move under the effect of electrical forces, thereby will have destroyed above-mentioned balance: (O
2-), (S
2-) wait negatively charged ion to move to anode, after anode loses electronics, generate gaseous product and be excluded; (M
2+) wait positively charged ion to move to negative electrode, obtain electronics at negative electrode and be reduced into metallic element, being dissolved in again becomes alloying element in the molten metal.Like this, as long as keep voltage between the two poles of the earth greater than the decomposition voltage of inclusion, inclusion is constantly dissociated, consequently the size of inclusion constantly reduces, and becomes that size is littler, disperse is distributed in the inclusion in the molten metal.Adding under the situation of alternating-current; As long as the voltage between the two poles of the earth is greater than the decomposition voltage of inclusion, because ac period ground changes, above-mentioned balance also can be damaged periodically; Thereby make the inclusion size decreases, become disperse and be distributed in the minute sized inclusion in the molten metal.When extra electric field is pulsed electrical field, need only the decomposition voltage of pulsed voltage greater than inclusion, inclusion also will be crashed to pieces, and become littler particle, thereby disperse is distributed in the molten metal.Adopt above-mentioned multi-form extra electric field mode can obtain that size is small, disperse is distributed in the inclusion in the metal or alloy material, the inclusion that such size is small, disperse distributes can not produce harm to the performance and the quality of material.
It is thus clear that under the effect of extra electric field, the stability of inclusion is destroyed, as long as keep the decomposition voltage of the voltage of extra electric field greater than inclusion, just can be through the method control or the removal inclusion of extra electric field.As long as the decomposition voltage of general inclusion is 1～3V, therefore at the voltage that applies between the two poles of the earth more than 1～3V, just can control or remove non-metallic inclusion.Obvious this method is simple, and efficient is high, and is with low cost, pollution-free, easy realization of industrial production, and the production of suitable any metal and alloy material.
The essence of this method be adopt add that electric work destroys or the hierarchy of control in the method for compound stability reach the purpose of removing inclusion.This method can be used for the removal or the control of the inclusion of all metals and alloy system, is particularly useful for the production of Clean Steel.
The method of the inclusion in a kind of removal provided by the invention, control metal and the alloy comprises following content:
Behind the pending metal and alloy molten, form molten metal, be contained in the container of rounded section or square-section; Directly insert the positive and negative electrode in the molten metal; Positive and negative the two poles of the earth are connected with power supply, between the two poles of the earth, apply the voltage of 1～100V, and power supply adopts direct supply or the AC power or the pulse power; Electrodes use Graphite Electrodes or cermet electrodes, the electrode that is shaped as cylindrical electrode or square-section of electrode.
The container of described splendid attire molten metal adopts containers of circular cross section; The electrode that inserts is a negative electrode, 1～4 anode, and decoration form is: when electrode is a negative electrode, an anode; Two electrodes are along the bulge medullary ray, near layout of wall of container one side; When electrode is a negative electrode, during 2～4 anodes, cathode electrode is arranged in container center, and anode electrode is along container perimeter, near the wall of container disposed at equal distance.
The container of described splendid attire molten metal adopts rectangular section vessels; The electrode that inserts is a negative electrode, 1～2 anode, and decoration form is: when electrode is a negative electrode, an anode; Two electrodes are along the rectangular vessel medullary ray, near the layout in wall of container one side; When electrode is a negative electrode, during two anodes, cathode electrode is arranged in container center, and two anodes are along container center lines, near layout of wall of container one side.
The method of the inclusion in a kind of removal provided by the invention, control metal and the alloy is compared with existing method, and its significant beneficial effect is:
1. the inventive method is simple, and efficient is high, and cost is low, and is pollution-free, easy realization of industrial production.
The essence of the inventive method be adopt add that electric work destroys or the hierarchy of control in the method for compound stability reach the purpose of removing inclusion; This method can be used for the removal or the control of the inclusion of all metals and alloy system, is particularly useful for the production of Clean Steel.
3. method provided by the present invention can be carried out in the container of any splendid attire molten metal, for example, in steel smelting procedure, can on LF, RH, VD, tundish, mold, adopt.
Embodiment
Specifically describe the present invention with embodiment below.
Embodiment 1
Behind the pending metal and alloy molten, form molten metal, be contained in the container of rounded section; The positive and negative electrode is inserted in the molten metal; Positive and negative the two poles of the earth are connected with power supply, between the two poles of the earth, apply the voltage of 1～100V, and power supply adopts direct supply or AC power; The electrodes use Graphite Electrodes, electrode be shaped as cylindrical electrode.The electrode that inserts is a negative electrode, three anodes, and decoration form is: cathode electrode is arranged in container center, and anode electrode is along container perimeter, near the wall of container disposed at equal distance.
Embodiment 2
Behind the pending metal and alloy molten, form molten metal, be contained in the container of square-section; The positive and negative electrode is inserted in the molten metal; Positive and negative the two poles of the earth are connected with power supply, between the two poles of the earth, apply the voltage of 1～100V, and power supply adopts the AC power or the pulse power; The electrodes use cermet electrodes, the electrode that is shaped as the square-section of electrode.The electrode that inserts is a negative electrode, an anode, and decoration form is: two electrodes are along the rectangular vessel medullary ray, near the layout in wall of container one side.
Claims (3)
1. the method for the inclusion in a removal, control metal and the alloy is characterized in that this method comprises following content:
Behind the pending metal and alloy molten, form molten metal, be contained in the container of rounded section or square-section; The positive and negative electrode is inserted in the molten metal; Positive and negative the two poles of the earth are connected with power supply, between the two poles of the earth, apply the voltage of 1～100V, and power supply adopts direct supply or the AC power or the pulse power; Electrodes use Graphite Electrodes or cermet electrodes, the electrode that is shaped as cylindrical electrode or square-section of electrode.
2. the method for the inclusion in removal according to claim 1, control metal and the alloy; It is characterized in that wherein the container of splendid attire molten metal adopts containers of circular cross section; The electrode that inserts is a negative electrode, 1～4 anode, and decoration form is: when electrode is a negative electrode, an anode; Two electrodes are along the bulge medullary ray, near layout of wall of container one side; When electrode is a negative electrode, during 2～4 anodes, cathode electrode is arranged in container center, and anode electrode is along container perimeter, near the wall of container disposed at equal distance.
3. the method for the inclusion in removal according to claim 1, control metal and the alloy; The container that it is characterized in that wherein said splendid attire molten metal adopts rectangular section vessels; The electrode that inserts is a negative electrode, 1～2 anode, and decoration form is: when electrode is a negative electrode, an anode; Two electrodes are along the rectangular vessel medullary ray, near the layout in wall of container one side; When electrode is a negative electrode, during two anodes, cathode electrode is arranged in container center, and two anodes are along container center lines, near layout of wall of container one side.
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|---|---|---|---|
| CN2011104055052A CN102517417A (en) | 2011-12-08 | 2011-12-08 | Method for removing and controlling foreign substances in metal and alloy |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436655A (en) * | 2013-05-23 | 2013-12-11 | 沈阳东大高温材料有限公司 | Method for removing and refining inclusion and bubble from molten metal |
| CN104668526A (en) * | 2015-03-12 | 2015-06-03 | 东北大学 | Method for improving steel ingot casting quality |
| CN104772452A (en) * | 2015-03-12 | 2015-07-15 | 东北大学 | Method for preventing steel billet continuous casting nozzle from blocking |
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| CN201501902U (en) * | 2009-09-27 | 2010-06-09 | 上海大学 | Adjustable anode device applicable to pollution-free deoxidation of external electric field of slag metal room |
| CN201660668U (en) * | 2010-02-08 | 2010-12-01 | 鞍钢股份有限公司 | VD refining device for pollution-free deoxidation |
| CN102140565A (en) * | 2010-01-29 | 2011-08-03 | 上海大学 | Method for pollution-free deoxygenation refining by externally applying electric field to tundish |
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2011
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Patent Citations (5)
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| CN1453371A (en) * | 2002-04-25 | 2003-11-05 | 上海大学 | Electrochemical pollution-free metal liquid deoxygenating process |
| CN101235430A (en) * | 2008-02-29 | 2008-08-06 | 上海大学 | Impressed electric field pollution-free deoxygenation refining method and device for ladle furnace |
| CN201501902U (en) * | 2009-09-27 | 2010-06-09 | 上海大学 | Adjustable anode device applicable to pollution-free deoxidation of external electric field of slag metal room |
| CN102140565A (en) * | 2010-01-29 | 2011-08-03 | 上海大学 | Method for pollution-free deoxygenation refining by externally applying electric field to tundish |
| CN201660668U (en) * | 2010-02-08 | 2010-12-01 | 鞍钢股份有限公司 | VD refining device for pollution-free deoxidation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436655A (en) * | 2013-05-23 | 2013-12-11 | 沈阳东大高温材料有限公司 | Method for removing and refining inclusion and bubble from molten metal |
| CN104668526A (en) * | 2015-03-12 | 2015-06-03 | 东北大学 | Method for improving steel ingot casting quality |
| CN104772452A (en) * | 2015-03-12 | 2015-07-15 | 东北大学 | Method for preventing steel billet continuous casting nozzle from blocking |
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Application publication date: 20120627 |