CN102146518A - Refining agent for atmosphere protected electro-slag re-melting - Google Patents
Refining agent for atmosphere protected electro-slag re-melting Download PDFInfo
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- CN102146518A CN102146518A CN201110084387XA CN201110084387A CN102146518A CN 102146518 A CN102146518 A CN 102146518A CN 201110084387X A CN201110084387X A CN 201110084387XA CN 201110084387 A CN201110084387 A CN 201110084387A CN 102146518 A CN102146518 A CN 102146518A
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Abstract
The invention provides a refining agent for atmosphere protected electro-slag re-melting. The refining agent comprises aluminum metal, calcium metal and electro-slag, wherein the specific gravity of the refining agent is greater than that of molten slag and smaller than that of molten alloy. The refining agent for the atmosphere protected electro-slag re-melting can be used for refining various products suitable for electro-slag re-melting process treatment such as carbon steel, alloy constructional steel, bearing steel, die steel, high-speed steel, stainless steel, heat resistant steel, ultrahigh-strength steel, high-temperature alloy, precision alloy, anticorrosive alloy, electric heating alloy and the like. The refining agent can effectively reduce the content of impurity elements such as O, S, P and the like of an alloy product on the premise that the conventional atmosphere protected electro-slag re-melting production process is not affected, can reduce nonmetallic inclusion content of the alloy and does not introduce new impurity elements, so as to improve the metallurgical quality of the alloy product.
Description
Technical field
The present invention relates to the electroslag remelting technique field, more particularly, relate to a kind of refining agent that is used for the atmosphere protection electroslag remelting process.
Background technology
When using traditional electroslag remelting process to smelt, consumable electrode and slag liquid level are exposed in the air, and the high temperature that electroslag produces makes the consumable electrode surface oxidation, and the FeO of generation passes oxygen to alloy liquid; FeO is exposed to air and then is oxidized to Fe in the slag
2O
3, Fe
2O
3Enter that slag is inner mutually to pass oxygen to alloy liquid, finally all can cause the rising of electroslag alloy pig total oxygen demand and also wherein original impurity element such as S, P also be difficult to control to ideal range.
With respect to traditional electroslag remelting process; when using the atmosphere protection electroslag remelting process to smelt; can secluding air and the contacting of consumable electrode and slag liquid level; there is not elemental gas links such as increasing oxygen, nitrogen in the smelting process, so improved the quality of esr processing back alloy product to a certain extent.Yet; for the atmosphere protection electroslag remelting process,, make the ESR system relative closure owing to adopted inert atmosphere protection in the whole electroslag remelting process process; do not add the effective ways of refining agent, thereby restricted the further raising of alloy product purity.In addition, under the esr working temperature, because dissolved aluminum, calcium and dissolved oxygen in the alloy liquid have reached balance, so if can not improve the content of dissolved aluminum, calcium, then dissolved oxygen is difficult to further reduce again.In addition, because the proportion (or density) of metallic aluminium, calcium is respectively 2.7g/cm
3And 1.54g/cm
3, they all are lower than or approach proportion (about 2.7~2.8g/cm of the used slag system of esr
3), and because can there be the problem of poor stability because of gasification in calcium metal when high temperature, thereby thereby metallic aluminium, calcium be difficult to enter the inner refining process of stably finishing alloy liquid of slag system.
Summary of the invention
The problems referred to above at the prior art existence, the present invention is directed to atmosphere protection esr process metallic aluminium, the difficult situation that adds slag system of calcium, developed the special-purpose aluminium calcium of atmosphere protection electroslag type refining agent, it is by metallic aluminium, calcium and treat that refinery feedstock (also can comprise slag charge) etc. makes (avoiding other materials to pollute), proportion is greater than liquid slag, and high-temperature stability is good; Aluminium calcium type refining agent descends with consumable electrode and enters melt cinder inside; alloy liquid molten bath upper surface slowly, stably the fusion; the metallic aluminium that discharges, calcium form aluminium, the higher relatively new slag blanket of calcium contents; metallic aluminium, calcium can react with alloy liquid droplet and alloy liquid molten bath; reaction product is absorbed by slag system; finally realized under the protective atmosphere condition refinery practice that takes off impurity elements removals such as O, S, P deeply of esr process.
An aspect of of the present present invention provides a kind of atmosphere protection esr refining agent; described refining agent comprises metallic aluminium, the calcium metal of any proportioning and treats refinery feedstock, described metallic aluminium, calcium metal and treat refinery feedstock with the proportion of any proportioning combination and described refining agent greater than the proportion of slag liquid and less than the proportion of alloy liquid.
Another aspect of the present invention provides a kind of atmosphere protection esr refining agent; described refining agent comprises metallic aluminium, the calcium metal of any proportioning and is included in the proportion treated in the refinery feedstock greater than the heavy metal of slag liquor ratio, the proportion that described metallic aluminium, calcium metal and being included in treated in the refinery feedstock greater than the heavy metal of slag liquor ratio with the proportion of any proportioning combination and described refining agent greater than the proportion of slag liquid and less than the proportion of alloy liquid.
Atmosphere protection esr refining agent according to a further aspect of the invention, wherein, the described proportion treated in the refinery feedstock of being included in can be in iron, titanium, manganese, chromium, nickel, molybdenum, the cobalt one or more greater than the heavy metal of slag liquor ratio.
According to an aspect of the present invention or atmosphere protection esr refining agent on the other hand, wherein, described refining agent can also comprise slag charge.
According to an aspect of the present invention or atmosphere protection esr refining agent on the other hand, wherein, the proportion of described refining agent can be 3g/cm
3~6g/cm
3
According to an aspect of the present invention or atmosphere protection esr refining agent on the other hand, wherein, the metallic aluminium in the described refining agent and the weight ratio of calcium metal can be (0.5~1): (0.5~1).
According to an aspect of the present invention or atmosphere protection esr refining agent on the other hand, wherein, the shape of described refining agent can be particulate state, strip, sphere, elliposoidal or irregularly shaped.
According to an aspect of the present invention or atmosphere protection esr refining agent on the other hand, wherein, the particle diameter of described refining agent can be in the scope of 0.1mm~10mm.Preferably, the particle diameter of described refining agent can be in the scope of 0.7mm~3mm.
Compared with prior art, the invention has the beneficial effects as follows and provide a kind of high quality, high efficiency alloy product esr with aluminium calcium type refining agent.When carrying out the atmosphere protection electroslag remelting process; when aluminium calcium type refining agent of the present invention being continued to add in the slag liquid; because refining agent of the present invention can slowly and stably be melted in slag liquid and alloy liquid at the interface; can discharge simultaneously metallic aluminium, calcium so that purifying reaction is carried out in itself and alloy liquid droplet and alloy liquid molten bath, finally reach the purified purpose.In addition; the present invention can also be under the prerequisite of the production technique that does not influence existing atmosphere protection esr; reduce impurity contents such as alloy product O, S, P effectively; reduce in the alloy non-metallic inclusion content and do not introduce new impurity element, thereby further improved the metallurgical quality of alloy product.
Description of drawings
Fig. 1 shows and use the synoptic diagram of atmosphere protection esr according to the present invention with refining agent in the atmosphere protection electroslag remelting process.
Embodiment
Fig. 1 shows and use the synoptic diagram of atmosphere protection esr according to the present invention with refining agent in the atmosphere protection electroslag remelting process.As shown in Figure 1; in the atmosphere protection electroslag remelting process; when melting; consumable electrode 1 melted by heat forms molten drop; molten drop process slag liquid 2 is by refining; react to realize the deep removal to impurity elements such as the oxygen in the molten drop, sulphur, phosphorus with the fusion layer 4 that is formed by refining agent 3 fusions of the present invention then, last molten drop imports in the alloy molten bath 5 that is formed by alloy liquid.
Atmosphere protection esr according to a first aspect of the invention comprises metallic aluminium, the calcium metal of any proportioning and treats refinery feedstock with refining agent, and the proportion of described refining agent is greater than the proportion of slag liquid and less than the proportion of alloy liquid.In the present invention, metallic aluminium, calcium metal and treat that the amount of allocating into of refinery feedstock is all non-vanishing.
Atmosphere protection esr according to a second aspect of the invention comprises metallic aluminium, the calcium metal of any proportioning with refining agent and is included in the proportion treated in the refinery feedstock greater than the heavy metal of slag liquor ratio, and the proportion of described refining agent is greater than the proportion of slag liquid and less than the proportion of alloy liquid.In the present invention, the described refinery feedstock for the treatment of is identical with the composition of consumable electrode 1.Here, the described proportion treated in the refinery feedstock of being included in can be in iron, titanium, manganese, chromium, nickel, molybdenum, the cobalt one or more greater than the heavy metal of slag liquor ratio.
In addition, preferably, the atmosphere protection esr of first aspect present invention or second aspect also can comprise slag charge with refining agent.Described slag charge fusing back forms slag liquid 2.
In the present invention, slag charge and treat that refinery feedstock is referred to as the electroslag material.
Preferably, the proportion of described refining agent can be 3g/cm
3~6g/cm
3
Since according to a first aspect of the invention or the proportion of the refining agent of second aspect greater than the proportion of slag liquid and less than the proportion of alloy liquid, so as shown in Figure 1, when in electroslag remelting process, using refining agent according to the present invention that alloy liquid is carried out refining, can enter the slag phase and float on alloy liquid molten bath upper surface (promptly according to refining agent of the present invention, be positioned at slag-Jin that slag liquid 2 contacts with alloy liquid at the interface), thereby metallic aluminium in the refining agent of the present invention and calcium metal can carry out purifying reaction fully with the alloy liquid in alloy molten drop and the alloy molten bath 5, thereby reduced oxygen in the alloy liquid effectively, sulphur, the content of impurity elements such as phosphorus has finally improved the quality of alloy product.
In addition, when refining agent according to the present invention enter slag mutually after, metallic aluminium, calcium are released and carry out purifying reaction with alloy liquid, purifying reaction comprises deoxygenation, dephosphorisation reaction, desulphurization reaction etc., and the reaction based on deoxygenation.Because can form low melting component between the purifying reaction product of aluminium and the purifying reaction product of calcium, so help the further removal of refining product, this has also further improved refining efficiency and effect, thereby the quality of alloy product is further improved.With the deoxidation products is example, and aluminum oxide and calcium oxide can form the low melting point composite oxides, and these low melting point composite oxides exist with liquid state under smelting temperature, and the come-up that helps deoxidation products is removed.Therefore, the weight ratio of metallic aluminium in the refining agent of the present invention and calcium metal is controlled at (0.5~1): in the scope of (0.5~1), can help impelling between the purifying reaction product of the purifying reaction product of aluminium and calcium forming low melting component.
In addition, because comprising with refining agent, the atmosphere protection esr of a second aspect of the present invention (for example is included in the proportion treated in the refinery feedstock greater than the heavy metal of slag liquor ratio, iron, titanium, manganese, chromium, nickel, molybdenum, cobalt etc.), so not only can the ratio of this refining agent is reconditioning, for greater than the proportion of slag liquid and less than the proportion of alloy liquid; And can in alloy liquid, not introduce under the prerequisite of other impurity, suitably regulate the composition of alloy product.Here, can assign to determine that the described proportion treated in the refinery feedstock of being included in is greater than the heavy metal of slag liquor ratio according to the one-tenth for the treatment of refinery feedstock.For example, according to the different kinds for the treatment of refined product, the described proportion treated in the refinery feedstock of being included in can be in the metals such as iron, titanium, manganese, chromium, nickel, molybdenum, cobalt one or more greater than the heavy metal of slag liquor ratio.
In addition, can be particulate state, strip, sphere, elliposoidal or different shape such as irregularly shaped according to atmosphere protection esr according to the present invention with the shape of refining agent.And, can be in the scope of 0.1mm~10mm according to the particle diameter of refining agent of the present invention.Preferably, the particle diameter of described refining agent can be in the scope of 0.7mm~3mm.Be controlled at by particle diameter in the scope of 0.1mm~10mm refining agent of the present invention, can guarantee that refining agent of the present invention at high temperature has satisfactory stability, thereby when refining agent of the present invention is used for the electroslag remelting process process, refining agent of the present invention can slowly and stably be dissolved in slag-Jin at the interface after entering slag system inside, this helps improving the utilization ratio of refining agent, can further improve refining effect and purifying reaction is carried out with moderate velocity-stabilization ground.In addition, when the particle diameter of refining agent during less than 0.1mm, it bad phenomenon such as the refining agent fusion is too fast, purifying reaction is too violent can occur in refining process; When the particle diameter of refining agent during greater than 10mm, it bad phenomenon such as intermittent type splash can occur in refining process.
Atmosphere protection esr of the present invention mainly has the following advantages with refining agent:
1) deoxidation products denaturing treatment; When only carrying out deoxidation with metallic aluminium or calcium metal, aluminum oxide or calcium oxide are present in alloy liquid inside with the form of solid phase inclusion, are unfavorable for the come-up removal; And can carry out complex deoxidization with metallic aluminium, calcium simultaneously according to refining agent of the present invention, not only involutory gold utensil has good deoxidation effect, simultaneously its deoxidation products (CaO and Al
2O
3) can form the low melting point composite oxides, the low melting point complex inclusion is easy to come-up can improve dust removal rate;
2) refining is in extensive range; Calcium metal can react with multiple alloy impurity element (S, P, Pb, Sn etc.), and reaction product is adsorbed removal mutually by slag, further improves the alloy purity;
3) do not influence existing production technique; The atmosphere protection esr process requires omnidistance atmosphere protection, adds very difficulty of metallic aluminium, calcium refining in the reflow process, and metallic aluminium proportion all is difficult to enter the inner and alloy liquid reaction of slag system less than liquid slag and calcium metal high-temperature gasification simultaneously; And refining agent of the present invention is the mixture of metallic aluminium, calcium and electroslag material, not only proportion is greater than liquid slag system, and high temperatures is good, in smelting process, refining agent is continued to add in the slag quantitatively, carry out smelting operation according to normal process, refining agent is from being advanced into melt cinder, and in the inner slowly fusion of slag system, discharge metallic aluminium, calcium and alloy liquid and carry out purifying reaction, in addition, because refining agent of the present invention is made up of metallic aluminium, calcium metal and electroslag material etc., so can not introduce extra impurity in electroslag remelting process;
4) suitable alloy kind is extensive; The present invention is the refining element with metallic aluminium, calcium, all is suitable for for the alloy kind of handling with metallic aluminium, calcium; Aluminium calcium type refining agent is a raw material with metallic aluminium, calcium and electroslag material, can not introduce the pollution of other elements to alloying constituent; And can reduce alloy material inner clamps foreign material and the impurity content that most metallic aluminiums, calcium are handled, thereby effectively improve the alloy material quality;
5) metallic aluminium, calcium add-on may command; Refining agent of the present invention is made according to specified proportion, can accurately control metallic aluminium, calcium add-on, refining agent according to the present invention will discharge an amount of metallic aluminium and calcium metal after mutually entering slag, and metallic aluminium is evenly distributed with calcium metal and can fully contact with interface, alloy liquid molten bath with alloy liquid molten drop, thereby improves refining efficiency.
The part of principle of the present invention is, make metallic aluminium, calcium and treat that purified electroslag material mixes the back and forms the refining agent of proportion greater than liquid slag proportion, thereby guarantee stably to be in slag-Jin at the interface (in other words after refining agent is in entering melt cinder, basically on upper strata, alloy liquid molten bath) and can stablize and be melted in the slag phase lentamente, in its fusion processes, refining agent slowly discharges metallic aluminium, calcium forms aluminium, the higher new slag blanket of calcium contents; Because metallic aluminium, calcium are immiscible two-phase with slag mutually, so metallic aluminium, calcium have higher reactive behavior; In esr process, alloy and melt cinder are subjected to the influence of electromagnetic force, and slag system internal motion complexity helps contacting and reaction between refining agent and alloy liquid in the slag system.
Specifically, atmosphere protection esr of the present invention mainly can be divided into two portions with the reaction mechanism of refining agent:
1) when alloy liquid droplet from top to bottom enters alloy liquid molten bath, through refining agent fusion layer, metallic aluminium, calcium carry out mass transfer and react with the impurity element that is melted in molten drop inside on electroslag material molten drop surface, and reaction product floats and absorbed by slag system;
2) metallic aluminium, calcium and the alloy liquid molten bath upper surface that discharge of refining agent fusion layer carry out mass transfer and with alloy in the impurity element reaction, reaction product floats and is absorbed by slag blanket.
Below, will describe the present invention in detail in conjunction with exemplary embodiment.
In the present embodiment, treat that refinery feedstock is the H13 steel, its proportion is about 7.8g/cm
3, its total oxygen content is 30ppm, and sulphur content is 88ppm, and phosphorus content is 120ppm.The H13 steel is a hot-work die steel, operative norm GB/T1299-2000.Slag charge is by 60% Calcium Fluoride (Fluorspan) (CaF
2), 20% calcium oxide (CaO) and 20% aluminium sesquioxide (Al
2O
3) form, in the time of 1600 ℃, the proportion of this slag charge is about 2.7g/cm
3With calcium metal powder, metallic aluminium powder, H13 powdered steel and slag charge according to weight ratio meter 1: 1: 3: 1 proportioning mixes; the appointment mould of packing into then; use the cold isostatic pressure machine with 150MPa pressure extrusion 1 hour; after the shaping; 700 ℃ of following argon shield roastings 24 hours, forming particle diameter was the particulate state refining agent of 0.1mm.The proportion of the refining agent that makes in the present embodiment, is 3g/cm
3This specific gravity value is greater than the proportion (2.7g/cm of slag liquid in the electroslag remelting process
3) and less than the proportion (7.8g/cm by the alloy liquid that after the refining of slag phase, forms of H13 steel of fusion
3).
In the present embodiment, the atmosphere protection electroslag remelting process carries out in capacity is the Reaktionsofen of 5t.Use the refining agent of forming as mentioned above to come refining H13 steel, the add-on of refining agent is 25 kilograms.After finishing the esr refining process, elements such as the oxygen in the H13 steel, sulphur and phosphorus are detected, draw total oxygen content in the H13 steel and reduce to that 8ppm, sulphur content reduce to about 19ppm, phosphorus content is reduced to about 98ppm.
In the present embodiment, treat that refinery feedstock is the H13 steel, its proportion is about 7.8g/cm
3, its total oxygen content is 30ppm, and sulphur content is 70ppm, and phosphorus content is 100ppm.Slag charge is by 70% CaF
2With 30% Al
2O
3Form, in the time of 1600 ℃, the proportion of this slag charge is about 2.8g/cm
3With calcium metal powder, metallic aluminium powder, H13 powdered steel and slag charge according to weight ratio meter 2: 1: 5.3: 1 proportioning mixes; the appointment mould of packing into then; use the cold isostatic pressure machine with 180MPa pressure extrusion 1 hour; after the shaping; 700 ℃ of following argon shield roastings 24 hours, forming particle diameter was the particulate state refining agent of 10mm.The proportion of the refining agent that makes in the present embodiment, is 5g/cm
3The proportion of the alloy liquid that this specific gravity value forms after the refining of slag phase greater than the proportion of slag liquid in the electroslag remelting process and less than the H13 steel by fusion.
In the present embodiment, the atmosphere protection electroslag remelting process carries out in capacity is the Reaktionsofen of 5t.Use the refining agent of forming as mentioned above to come refining H13 steel, the add-on of refining agent is 25 kilograms.After finishing the esr refining process, elements such as the oxygen in the H13 steel, sulphur and phosphorus are detected, draw total oxygen content in the H13 steel and reduce to that 7ppm, sulphur content reduce to about 17ppm, phosphorus content is reduced to about 94ppm.
In the present embodiment, treat that refinery feedstock is the S136 steel, its proportion is about 7.8g/cm
3, its total oxygen content is 28ppm, and sulphur content is 62ppm, and phosphorus content is 92ppm.Slag charge is by 60% CaF
2, 20% CaO and 20% Al
2O
3Form, in the time of 1600 ℃, the proportion of this slag charge is 2.7g/cm
3With calcium metal powder, metallic aluminium powder, S136 powdered steel and slag charge according to weight ratio meter 1: 2: 6.6: 0.8 proportioning mixes; the appointment mould of packing into then; use the cold isostatic pressure machine with 140MPa pressure extrusion 1.2 hours; after the shaping; 720 ℃ of following argon shield roastings 24 hours, forming particle diameter was the particulate state refining agent of 3mm.The proportion of the refining agent that makes in the present embodiment, is 6g/cm
3The proportion of the alloy liquid that this specific gravity value forms after the refining of slag phase greater than the proportion of slag liquid in the electroslag remelting process and less than the S136 steel by fusion.
In the present embodiment, the atmosphere protection electroslag remelting process carries out in capacity is the Reaktionsofen of 5t.Use the refining agent of forming as mentioned above to come refining S136 steel, the add-on of refining agent is 25 kilograms.After finishing the esr refining process, elements such as the oxygen in the S136 steel, sulphur and phosphorus are detected, draw wherein total oxygen content and reduce to that 5ppm, sulphur content reduce to about 15ppm, phosphorus content is reduced to about 60ppm.
In the present embodiment, treat that refinery feedstock is the S136 steel, its proportion is about 7.8g/cm
3, its total oxygen content is 25ppm, and sulphur content is 56ppm, and phosphorus content is 136ppm.Slag charge is by 70% CaF
2With 30% Al
2O
3Form, in the time of 1600 ℃, the proportion of this slag charge is about 2.8g/cm
3With calcium metal powder, metallic aluminium powder, S136 powdered steel and slag charge according to weight ratio meter 2: 3: 5.2: 1 proportioning mixes; the appointment mould of packing into then; use the cold isostatic pressure machine with 140MPa pressure extrusion 1.2 hours; after the shaping; 700 ℃ of following argon shield roastings 24 hours, forming particle diameter was the particulate state refining agent of 0.7mm.The proportion of the refining agent that makes in the present embodiment, is 5.5g/cm
3The proportion of the alloy liquid that this specific gravity value forms after the refining of slag phase greater than the proportion of slag liquid in the electroslag remelting process and less than the S136 steel by fusion.
In the present embodiment, the atmosphere protection electroslag remelting process carries out in capacity is the Reaktionsofen of 5t.Use the refining agent of forming as mentioned above to come refining S136 steel, the add-on of refining agent is 25 kilograms.After finishing the esr refining process, elements such as the oxygen in the S136 steel, sulphur and phosphorus are detected, draw wherein total oxygen content and reduce to that 7ppm, sulphur content reduce to about 18ppm, phosphorus content is reduced to about 90ppm.
In the present embodiment, treat that refinery feedstock is nickeliferous high temperaturesteel, its proportion is about 7.78g/cm
3, its total oxygen content is 22ppm, and sulphur content is 66ppm, and phosphorus content is 98ppm.Calcium metal powder, metallic aluminium powder and S136 powdered steel are mixed according to 2: 3: 4.2 proportioning of weight ratio meter; the appointment mould of packing into then; use the cold isostatic pressure machine with 170MPa pressure extrusion 1.5 hours; after the shaping; 750 ℃ of following argon shield roastings 20 hours, forming particle diameter was the particulate state refining agent of 1.8mm.The proportion of the refining agent that makes in the present embodiment, is 4.4g/cm
3The proportion of the alloy liquid that this specific gravity value forms after the refining of slag phase greater than the proportion of slag liquid in the electroslag remelting process and less than the nickeliferous high temperaturesteel by fusion.
In the present embodiment, the atmosphere protection electroslag remelting process carries out in capacity is the Reaktionsofen of 5t.Use the refining agent of forming as mentioned above to come the described nickeliferous high temperaturesteel of refining, the add-on of refining agent is 24 kilograms.After finishing the esr refining process, the elements such as oxygen, sulphur and phosphorus in the described nickeliferous high temperaturesteel are detected, draw wherein total oxygen content and reduce to that 6ppm, sulphur content reduce to about 17ppm, phosphorus content is reduced to about 70ppm.
Embodiment 6
In the present embodiment, treat that refinery feedstock is nickeliferous high temperaturesteel, its proportion is about 7.82g/cm
3, its total oxygen content is 23ppm, and sulphur content is 46ppm, and phosphorus content is 98ppm.Calcium metal powder, metallic aluminium powder and metallic iron powder are mixed according to 2: 3: 4.1 proportioning of weight ratio meter; the appointment mould of packing into then; use the cold isostatic pressure machine with 180MPa pressure extrusion 1 hour; after the shaping; 760 ℃ of following argon shield roastings 24 hours, forming particle diameter was the particulate state refining agent of 2.5mm.The proportion of the refining agent that makes in the present embodiment, is 4.3g/cm
3The proportion of the alloy liquid that this specific gravity value forms after the refining of slag phase greater than the proportion of slag liquid in the electroslag remelting process and less than the nickeliferous high temperaturesteel by fusion.
In the present embodiment, the atmosphere protection electroslag remelting process carries out in capacity is the Reaktionsofen of 5t.Use the refining agent of forming as mentioned above to come the described nickeliferous high temperaturesteel of refining, the add-on of refining agent is 24 kilograms.After finishing the esr refining process, the elements such as oxygen, sulphur and phosphorus in the described nickeliferous high temperaturesteel are detected, draw wherein total oxygen content and reduce to that 6ppm, sulphur content reduce to about 17ppm, phosphorus content is reduced to about 72ppm.
Embodiment 7
In the present embodiment, treat that refinery feedstock is the titaniferous stainless steel, its proportion is about 7.85g/cm
3, its total oxygen content is 20ppm, and sulphur content is 56ppm, and phosphorus content is 88ppm.Slag charge is by 60% CaF
2, 20% CaO and 20% Al
2O
3Form, in the time of 1600 ℃, the proportion of this slag charge is about 2.7g/cm
3With calcium metal powder, metallic aluminium powder, slag charge and titanium valve according to weight ratio meter 1: 1: 1: 6.2 (proportioning mix; the appointment mould of packing into then; use the cold isostatic pressure machine with 150MPa pressure extrusion 1 hour; after the shaping; 750 ℃ of following argon shield roastings 24 hours, forming particle diameter was the particulate state refining agent of 2.8mm.The proportion of the refining agent that makes in the present embodiment, is 3.5g/cm
3The proportion of the alloy liquid that this specific gravity value forms after the refining of slag phase greater than the proportion of slag liquid in the electroslag remelting process and less than the titaniferous stainless steel by fusion.In the present embodiment, can finely tune alloying constituent in this titaniferous stainless steel by in refining agent, allocating an amount of titanium valve into.
In the present embodiment, the atmosphere protection electroslag remelting process carries out in capacity is the Reaktionsofen of 5t.Use the refining agent of forming as mentioned above to come the described titaniferous stainless steel of refining, the add-on of refining agent is 24 kilograms.After finishing the esr refining process, the elements such as oxygen, sulphur and phosphorus in the described titaniferous stainless steel are detected, draw wherein total oxygen content and reduce to that 7ppm, sulphur content reduce to about 15ppm, phosphorus content is reduced to about 65ppm.
Embodiment 8
In the present embodiment, treat that refinery feedstock is a chromium stainless steel, its proportion is about 7.85g/cm
3, its total oxygen content is 24ppm, and sulphur content is 76ppm, and phosphorus content is 97ppm.Slag charge is by 60% CaF
2, 20% CaO and 20% Al
2O
3Form, in the time of 1600 ℃, the proportion of this slag charge is about 2.7g/cm
3With calcium metal powder, metallic aluminium powder, chromium stainless steel powder, slag charge and chromium powder according to weight ratio meter 2: 3: 3.5: 1: 1 proportioning mixes; the appointment mould of packing into then; use the cold isostatic pressure machine with 150MPa pressure extrusion 1 hour; after the shaping; 750 ℃ of following argon shield roastings 24 hours, forming particle diameter was the particulate state refining agent of 2.5mm.The proportion of the refining agent that makes in the present embodiment, is 4.8g/cm
3The proportion of the alloy liquid that this specific gravity value forms after the refining of slag phase greater than the proportion of slag liquid in the electroslag remelting process and less than the chromium stainless steel by fusion.In the present embodiment, can finely tune alloying constituent in this chromium stainless steel by in refining agent, allocating an amount of chromium powder into.
In the present embodiment, the atmosphere protection electroslag remelting process carries out in capacity is the Reaktionsofen of 5t.Use the refining agent of forming as mentioned above to come the described chromium stainless steel of refining, the add-on of refining agent is 22 kilograms.After finishing the esr refining process, elements such as the oxygen in the described chromium stainless steel, sulphur and phosphorus are detected, draw wherein total oxygen content and reduce to that 6ppm, sulphur content reduce to about 15ppm, phosphorus content is reduced to about 70ppm.
Those skilled in the art should understand that; atmosphere protection esr of the present invention can be used for the product that the various suitable electroslag remelting process of refining are handled with refining agent; for example, carbon steel, structural alloy steel, bearing steel, die steel, rapid steel, stainless steel, high temperature steel, ultrahigh-strength steel, superalloy, Precise Alloy, non-corrosive metal and electrical heating alloys etc.
In sum, the invention provides a kind of high quality, high efficiency alloy product esr aluminium calcium type refining agent.Use the refining agent of the present invention can be under the prerequisite of the production technique that does not influence existing atmosphere protection esr; reduce impurity contents such as alloy product O, S, P effectively; reduce in the alloy non-metallic inclusion content and do not introduce new impurity element, thereby improved the metallurgical quality of alloy product.
Although described the present invention above, it will be apparent to those skilled in the art that and in not breaking away from the of the present invention spiritual scope that limits by claim and equivalent thereof, can carry out various modifications and change embodiment in conjunction with exemplary embodiment.
Claims (9)
1. atmosphere protection esr refining agent; it is characterized in that; comprise metallic aluminium, calcium metal and treat refinery feedstock, described metallic aluminium, calcium metal and treat refinery feedstock with the proportion of combination of any proportioning and described refining agent greater than the proportion of slag liquid and less than the proportion of alloy liquid.
2. atmosphere protection esr refining agent; it is characterized in that; comprise metallic aluminium, the calcium metal of any proportioning and be included in the proportion treated in the refinery feedstock greater than the heavy metal of slag liquor ratio, the proportion that described metallic aluminium, calcium metal and being included in treated in the refinery feedstock greater than the heavy metal of slag liquor ratio with the proportion of any proportioning combination and described refining agent greater than the proportion of slag liquid and less than the proportion of alloy liquid.
3. atmosphere protection esr refining agent as claimed in claim 2 is characterized in that, the described proportion treated in the refinery feedstock of being included in is in iron, titanium, manganese, chromium, nickel, molybdenum, the cobalt one or more greater than the heavy metal of slag liquor ratio.
4. as any described atmosphere protection esr refining agent in the claim 1 to 3, it is characterized in that described refining agent also comprises slag charge.
5. as any described atmosphere protection esr refining agent in the claim 1 to 3, it is characterized in that the proportion of described refining agent is 3g/cm
3~6g/cm
3
6. as any described atmosphere protection esr refining agent in the claim 1 to 3, it is characterized in that the metallic aluminium in the described refining agent and the weight ratio of calcium metal are (0.5~1): (0.5~1).
7. as any described atmosphere protection esr refining agent in the claim 1 to 3, it is characterized in that, described refining agent be shaped as particulate state, strip, sphere, elliposoidal or irregularly shaped.
8. as any described atmosphere protection esr refining agent in the claim 1 to 3, it is characterized in that the particle diameter of described refining agent is in the scope of 0.1mm~10mm.
9. atmosphere protection esr refining agent as claimed in claim 8 is characterized in that the particle diameter of described refining agent is in the scope of 0.7mm~3mm.
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CN103667731A (en) * | 2013-11-19 | 2014-03-26 | 东南大学 | Production method of high-plasticity high-speed steel |
CN105925916A (en) * | 2016-06-24 | 2016-09-07 | 东北大学 | Method for calcium and aluminum nitrogen increase and deoxygenation in pressurized electroslag remelting process of high-nitrogen steel |
CN109880960A (en) * | 2019-04-10 | 2019-06-14 | 鞍钢实业集团有限公司原燃料生产服务分公司 | A kind of environment-friendly type slag modifier and preparation method thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN103667731A (en) * | 2013-11-19 | 2014-03-26 | 东南大学 | Production method of high-plasticity high-speed steel |
CN103667731B (en) * | 2013-11-19 | 2015-09-09 | 东南大学 | A kind of production method of high-ductility rapid steel |
CN105925916A (en) * | 2016-06-24 | 2016-09-07 | 东北大学 | Method for calcium and aluminum nitrogen increase and deoxygenation in pressurized electroslag remelting process of high-nitrogen steel |
CN105925916B (en) * | 2016-06-24 | 2017-11-03 | 东北大学 | A kind of method of calcium aluminium nitrogen pick-up deoxidation during electroslag remelting high nitrogen steel of pressurizeing |
CN109880960A (en) * | 2019-04-10 | 2019-06-14 | 鞍钢实业集团有限公司原燃料生产服务分公司 | A kind of environment-friendly type slag modifier and preparation method thereof |
CN109880960B (en) * | 2019-04-10 | 2021-06-22 | 鞍钢实业集团有限公司原燃料生产服务分公司 | Environment-friendly slag modifier and preparation method thereof |
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