CN108941445B - Application method of release agent for disc casting machine - Google Patents
Application method of release agent for disc casting machine Download PDFInfo
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- CN108941445B CN108941445B CN201810860759.5A CN201810860759A CN108941445B CN 108941445 B CN108941445 B CN 108941445B CN 201810860759 A CN201810860759 A CN 201810860759A CN 108941445 B CN108941445 B CN 108941445B
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000005266 casting Methods 0.000 title claims abstract description 38
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- 229910052802 copper Inorganic materials 0.000 claims abstract description 166
- 239000010949 copper Substances 0.000 claims abstract description 166
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 97
- 239000000843 powder Substances 0.000 claims abstract description 49
- 238000005245 sintering Methods 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000006082 mold release agent Substances 0.000 claims abstract description 30
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 27
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 26
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 26
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 239000005995 Aluminium silicate Substances 0.000 claims description 38
- 235000012211 aluminium silicate Nutrition 0.000 claims description 38
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 claims description 22
- 229910052849 andalusite Inorganic materials 0.000 claims description 22
- 229910052850 kyanite Inorganic materials 0.000 claims description 22
- 239000010443 kyanite Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 229920001353 Dextrin Polymers 0.000 claims description 5
- 239000004375 Dextrin Substances 0.000 claims description 5
- 235000019425 dextrin Nutrition 0.000 claims description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 11
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002955 isolation Methods 0.000 abstract description 6
- 229910052604 silicate mineral Inorganic materials 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 38
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
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- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 206010049040 Weight fluctuation Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009867 copper metallurgy Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D25/00—Special casting characterised by the nature of the product
- B22D25/02—Special casting characterised by the nature of the product by its peculiarity of shape; of works of art
- B22D25/04—Casting metal electric battery plates or the like
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Mold Materials And Core Materials (AREA)
Abstract
The invention discloses a using method of a mold release agent for a disc casting machine, and belongs to the field of copper anode plate casting. According to the application method of the release agent for the disc casting machine, when the release agent is used, the release agent is coated on the inner surface of the cavity of the copper mold cavity, and a sintering layer is formed between the copper liquid and the inner surface of the cavity of the copper mold cavity after the copper liquid is cast so as to isolate the copper anode plate from the cavity of the copper mold cavity; the release agent comprises an aluminum-silicon silicate mineral, sodium carboxymethylcellulose, composite superfine powder and an additive. The use method of the release agent for the disc casting machine forms the sintering layer between the copper mould and the copper anode plate, has an isolation effect on the copper mould and the copper anode plate, prolongs the service life of the copper mould, and improves the appearance quality of the copper anode plate.
Description
Technical Field
The invention relates to the field of copper anode plate casting, in particular to a using method of a mold release agent for a disc casting machine.
Background
In the existing copper smelting process, the casting of a copper anode plate is an important process, the ottoman disc casting is a process widely applied to the copper metallurgy industry at home and abroad at present, compared with the traditional manual casting, the casting process has the advantages of small weight fluctuation of a copper plate, continuous casting process, high casting efficiency and the like, and used molds are divided into steel molds and copper molds. The phenomenon of adhesion of the anode plate and the die can not occur to the steel die, a release agent is not needed, but a production enterprise can not repair the damaged steel die by self, so that the steel die is easy to damage, and the maintenance cost is high. Therefore, the copper mould is more widely applied to the copper smelting and casting process. However, because the copper water and the copper mould have larger temperature gradient in the casting process, the copper water is splashed during casting, the copper anode plate is bent and deformed during cooling and demoulding, the lug part of the copper anode plate is broken, and the lug part of the copper mould is twisted, so that the surface flatness of the copper anode plate is poor, and the like. And the heavy continuous operation pressure causes the service life of the copper mold to be remarkably reduced, so that a release agent must be used in the casting process.
The release agent is usually in a powder form, and is divided into two modes of directly coating dry powder or mixing the dry powder with water to form emulsion and then spraying in the using process. In the casting process, a large temperature gradient exists between the copper water and the copper mold, the copper mold is locally melted at high temperature, the anode plate is stuck to the mold, the anode plate and the copper mold can be separated by the release agent, the appearance of the anode plate can be improved by reasonably using the release agent, and the service life of the copper mold can be prolonged.
At present, most copper smelting enterprises adopt precipitated barium sulfate or composite mold release agent containing the precipitated barium sulfate. Through retrieval, the name of the invention is: a method for using a release agent for casting a copper anode plate (application No. 201410475140.4, application date: 2014-09-17) discloses a method for using a release agent for casting a copper anode plate, which comprises the following steps: preparing a release agent emulsion; spraying release agent emulsion; forming a release agent protective layer by the release agent emulsion; sintering the release agent protective layer to form a release agent sintered layer; the release agent for casting the copper anode plate is a composite release agent, and comprises, by mass, 30% -70% of barium sulfate, 2.5% -15% of boron oxide, 20% -45% of silicon dioxide, 1% -8% of calcium oxide and 1% -7% of aluminum oxide. The application can reduce the adhesion between the copper mold and the anode plate to a certain extent, but the composite mold release agent used in the method still uses precipitated barium sulfate as a basic raw material, in the production process of the precipitated barium sulfate, most of the barium sulfate is used as a raw material, a large amount of particles, waste gas, waste water and waste residues are generated in the production process to pollute the environment, and the service life of the copper mold is required to be further improved.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to solve the problems of high manufacturing cost and environmental pollution of the release agent in the prior art, and provides a use method of the release agent for a disc casting machine.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention discloses a using method of a mold release agent for a disc casting machine, wherein when the mold release agent is used, the mold release agent is coated on the inner surface of a copper mold cavity, and a sintering layer is formed between copper liquid and the inner surface of the copper mold cavity after the copper liquid is cast so as to isolate a copper anode plate from the copper mold cavity; the release agent comprises aluminum-silicon silicate minerals, sodium carboxymethylcellulose, composite superfine powder and additives.
Preferably, the specific method of use of the release agent is as follows: adding water into a release agent to mix into suspension; preheating a copper mold, and heating a copper mold cavity; spraying the suspension on the inner surface of the copper mold cavity; evaporating the water of the suspension on the inner surface of the copper mold cavity to form a mold release agent drying layer; pouring copper liquid into the copper mold cavity, wherein the release agent drying layer forms a sintering layer between the copper liquid and the inner surface of the copper mold cavity; and solidifying the copper liquid into a copper anode, and separating the sintering layer from the copper anode.
Preferably, in the step of mixing the release agent with water to form the suspension, the mass water-solid ratio of the added water to the release agent is as follows: k: 1, the value range of K is 4.5-5.5, and the water temperature is 60-70 ℃.
Preferably, the copper mold is preheated, and in the step of heating the copper mold cavity, the temperature of the copper mold cavity is raised to 170-220 ℃.
Preferably, in the process of spraying the turbid liquid to the inner surface of the copper mold cavity, the amount of the turbid liquid sprayed on the inner surface of the copper mold cavity is 2.2-3.2 kg/m2。
Preferably, the release agent comprises kaolin, kyanite, andalusite, silicon micropowder, sodium carboxymethylcellulose, composite superfine powder and additives.
Preferably, the composite ultra-fine powder comprises active Al2O3Powder and fused SiO2And (5) micro-powder.
Preferably, the additives include sodium pyrophosphate and dextrin.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) the invention relates to a using method of a mold release agent for a disc casting machine, which is characterized in that when the mold release agent is used, the mold release agent is coated on the inner surface of a cavity of a copper mold cavity, and a sintering layer is formed between copper liquid and the inner surface of the cavity of the copper mold cavity after the copper liquid is cast so as to isolate a copper anode plate from the cavity of the copper mold cavity; the release agent comprises an aluminum-silicon silicate mineral, sodium carboxymethylcellulose, composite superfine powder and an additive; the use method of the release agent for the disc casting machine forms the sintering layer between the copper mould and the copper anode plate, has an isolation effect on the copper mould and the copper anode plate, prolongs the service life of the copper mould, and improves the appearance quality of the copper anode plate.
(2) The invention relates to a method for using a mold release agent for a disc casting machine, which adopts aluminum-silicon materials such as kaolin and the like with wide natural sources to replace the traditional precipitated BaSO with higher price and high pollution in the production process4And a certain amount of composite additive is added to prepare the release agent meeting the production requirements, thereby achieving good environmental protection and economic benefits.
(3) Compared with the precipitated barium sulfate release agent used in the same industry, the release agent used in the method has the advantages that the release agent consumed by one ton of copper is reduced by 15-20% in the same ratio, the production cost is greatly reduced, and the obvious economic benefit is achieved; has wide market popularization prospect, and is particularly suitable for the copper mold casting process of the copper anode plate.
Drawings
FIG. 1 is a schematic view of a copper mold structure according to the present invention;
FIG. 2 is a flow chart of the method of using the mold release agent for a disc caster of the present invention.
The reference numerals in the schematic drawings illustrate:
100. copper mold; 110. a copper mold cavity.
Detailed Description
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which form a part hereof, and in which is shown by way of illustration exemplary embodiments in which the invention may be practiced. Although these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it should be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the present invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the invention is to be limited only by the following claims.
The detailed description and exemplary embodiments of the invention will be better understood when read in conjunction with the appended drawings, where the elements and features of the invention are identified by reference numerals.
Example 1
Referring to fig. 1 and 2, the method for using the mold release agent for the disc casting machine of the present invention comprises:
adding water into a release agent to mix into suspension; the method comprises the following specific steps: the mass water-solid ratio of water to the release agent is K: 1, the value range of K is 4.5-5.5, and the water temperature is 60-70 ℃; in the embodiment, the water-solid ratio is 5.0: 1, and the water temperature is 65 ℃; then uniformly stirring the water and the release agent together, and continuously stirring in the mixing process to avoid the release agent from precipitating; the above-described release agent was used in this example;
preheating the copper mold 100, and heating the copper mold cavity 110; the method comprises the following specific steps: preheating the copper mold 100, and heating the mold cavity 110 to 170-220 ℃, wherein in the embodiment, the temperature of the mold cavity 110 is heated to 185 ℃;
spraying the suspension on the inner surface of the cavity of the mold cavity 110; the method comprises the following specific steps: then connecting the prepared release agent turbid liquid with a spraying device above a disc casting machine, when the preheated copper mold 100 reaches the position below the spraying device, starting the spraying device to uniformly spray the turbid liquid on the inner surface of the cavity body of the mold cavity 110, so that the cavity body of the mold cavity 110 is covered with the turbid liquidThe suspension covered with the release agent, and the amount of the suspension sprayed on the inner surface of the cavity 110 of the die cavity is 2.2-3.2 kg/m2In this example, the amount of the suspension sprayed was 2.7kg/m2。
Evaporating the water content of the suspension on the inner surface of the cavity of the mold cavity 110 to form a mold release agent drying layer; the method comprises the following specific steps: the temperature of the inner surface of the cavity 110 of the preheated copper mold 100 is high, when a mold release agent suspension is in contact with the inner surface of the cavity 110 of the mold cavity, water in the mold release agent suspension begins to evaporate, the mold release agent after evaporation and drying is uniformly distributed on the inner surface of the cavity 110 of the mold cavity in a solid form, the mold release agent suspension evaporates on the inner surface of the cavity 110 of the mold cavity to form a mold release agent drying layer, the upper surface of the mold release agent drying layer is flat, the time interval from spraying of the suspension to casting is 140-160 s, and in the embodiment, the time interval is 155 s;
pouring copper liquid into the cavity of the mold cavity 110, wherein the release agent drying layer forms a sintering layer between the copper liquid and the inner surface of the cavity of the mold cavity 110; the method comprises the following specific steps: the copper mold 100 moves to a casting station of a disc casting machine, copper liquid is cast into the mold cavity 110, the casting temperature of the copper liquid is 1100-1250 ℃, the copper liquid is connected with the copper mold 100 covered with the release agent drying layer, the release agent drying layer is sintered to form a smooth and compact sintering layer, and the sintering layer plays a role in isolation protection between the copper liquid and the inner surface of the cavity of the mold cavity 110;
solidifying the copper liquid into a copper anode plate, and separating the sintered layer from the copper anode plate; the method comprises the following specific steps: and ejecting the solidified copper anode plate through an ejector rod, and separating the sintered layer from the copper anode plate.
The release agent used in the using method of the release agent for the disc casting machine comprises an aluminum-silicon silicate mineral, sodium carboxymethyl cellulose, composite superfine powder and an additive. The specific components of the release agent comprise kaolin, kyanite, andalusite, silicon micropowder, sodium carboxymethylcellulose, composite superfine powder and additives. The mixture ratio in the embodiment is as follows: 60-70 parts of kaolin, 4-5 parts of kyanite, 9-10 parts of andalusite, 14-15 parts of silicon micropowder and 0.15 part of sodium carboxymethylcellulose.
The concrete mass ratio of the embodiment is as follows: 63kg of kaolin, 5kg of kyanite, 9kg of andalusite, 15kg of silicon micropowder and 0.15kg of sodium carboxymethylcellulose. It is to be noted that in this example, the kaolin component is SiO2≥40％，Al2O3≥35％，Fe2O3≤0.15％，K2O≤0.1％，Na2Less than or equal to 0.1 percent of O, less than or equal to 1.5 percent of loss on ignition and the balance of impurities. Wherein: the proportion of the granularity of the silicon micropowder is less than 600 meshes and is 95-98%. Wherein the silicon micropowder component is SiO2≥99.3％，Fe2O3≤0.1％，K2O≤0.1％，Na2O is less than or equal to 0.1 percent, and the balance is impurities. The reason why the aluminum-silicon silicate mineral such as kaolin is used as the matrix of the whole mold release agent is that kaolin has better sintering property and fire resistance, and in the using process, when copper liquid with higher temperature is poured into the copper mold cavity 110, the mold release agent containing kaolin between the copper mold cavity 110 and crude copper liquid is sintered at high temperature, so that a sheet-shaped sintering layer with certain hardness is formed; on one hand, the sheet-shaped sintering layer plays a role in isolating the copper mold cavity 110 from the copper liquid, so that the copper anode plate produced by the copper liquid can be prevented from being bonded with the copper mold 100, and the copper anode plate can be conveniently taken out of the copper mold 100; on the other hand, as the copper liquid and the copper mold 100 have a larger temperature gradient during casting, a series of problems such as copper water splashing, bending deformation of the copper anode plate, ear fracture of the copper anode plate, ear distortion of the copper mold 100, partial melting of the copper mold 100, poor surface flatness of the copper anode plate and the like easily occur, and the sheet sintering layer can reduce the damage of thermal stress generated by the temperature gradient to the copper mold 100 and the copper anode plate to a certain extent, so that the service life of the copper mold 100 and the quality of the copper anode plate are improved; in addition, the kaolin material has low price and low economic cost.
The proportion of the kaolin with the particle size of less than 600 meshes is 75-80%, and the proportion of the kaolin with the particle size of less than 800 meshes is 15-20%. The kaolin has proper granularity, so that the kaolin and the silica powder have higher free energy and have larger contact angles with other particles. The release agent is rapidly sintered to form an even flaky sintering layer when high-temperature copper liquid is poured in, and the even flaky sintering layer covers the inner surface of the copper mold cavity 110 flatly, so that a cast copper anode plate is more flat, the release agent is not easy to be washed away by the copper liquid, and the mold sticking effect of the release agent and the flatness of the surface of the copper anode plate are improved.
The reason for adding kyanite to the refractory matrix kaolin is: decomposition of kyanite at high temperatures to yield mullite and SiO2Meanwhile, gaps are generated and volume expansion occurs, and on one hand, the generated gaps can enable a sheet sintering layer generated by the release agent at a high temperature to have a stronger heat insulation effect; on the other hand, the refractory matrix kaolin can generate volume shrinkage in the sintering process, and the sintering expansion characteristic of the kaolin after adding the kyanite can offset the shrinkage of the kaolin to a certain degree, so that the thickness and the isolation performance of a sheet sintering layer are ensured; further, kyanite also accelerates the drying of the water in the water-applied release agent on the copper mold cavity 110. The reasons for adding andalusite to the refractory base kaolin are: the density and volume of andalusite before and after calcination are kept unchanged, and the internal porosity of the andalusite is also unchanged, so that the density of the release agent is not greatly changed in the sintering process by adding the andalusite into the refractory matrix kaolin, and the volume of the matrix composed of the kaolin, the kyanite and the andalusite is kept stable in the sintering process.
In the embodiment, the release agent is also added with the silica powder, and the silica powder has the characteristics of high hardness and good thermal stability. The release agent can play a role in filling and sintering assistance on a matrix containing kaolin during the sintering use process.
It is worth to be noted that sodium carboxymethyl cellulose is also added into the release agent, the sodium carboxymethyl cellulose is a polymer agglomeration agent, molecules of the sodium carboxymethyl cellulose contain a large amount of hydrophilic groups, and the sodium carboxymethyl cellulose has strong wetting performance, and a small amount of sodium carboxymethyl cellulose is added into the release agent to strengthen the mixing effect of the release agent; in addition, after the sodium carboxymethyl cellulose is added, the surface of a sintering layer formed by components such as kaolin and the like in the release agent in the sintering process is smoother, so that the produced copper anode plate has better surface quality. In the prior art, a certain amount of glass water is added in the mixing process to strengthen the mixing effect, but the use cost of the release agent is increased, the price of the sodium carboxymethyl cellulose is low, and a good mixing effect can be realized by adding a small amount of the glass water in the mixing process.
In this embodiment, through multiple empirical summaries, the mass parts of the composite ultrafine powder added can be calculated by the following formula:
wherein: b is the mass part of kaolin added; c is the mass portion of the added kyanite; d is the mass portion of andalusite added; e is the mass part of the added silicon micropowder; f is the added mass portion of the composite superfine powder. By calculation, the mass portion of the composite superfine powder added in the embodiment is 3.86 kg. The composite ultrafine powder includes active Al2O3Powder and fused SiO2The micro powder and the composite ultra-micro powder are active Al in percentage by mass2O340-50% of powder and molten SiO250% -60% of micro powder, wherein the active Al is2O3Powder and fused SiO2The mass ratio of the micro powder is 0.667-1, and the active Al in the composite ultra-fine powder is in the embodiment2O3The mass percent of the powder is 45 percent, and SiO is melted2The mass percentage of the micro powder is 55 percent.
The mass part of the additive is 0.75kg of g ═ e + f) x k, k is 0.03-0.05, and the mass part of the additive is 0.04; wherein: e is the mass part of the added silicon micropowder; f is the mass portion of the composite superfine powder; g is the mass portion added by the additive.
The additive comprises 25-30% of sodium pyrophosphate and 70-75% of dextrin by mass, wherein the mass ratio of the sodium pyrophosphate to the dextrin is 0.3-0.33, the sodium pyrophosphate is 27% and the dextrin is 74% in the embodiment. The additive promotes the sintering of the release agent and strengthens the formation of a sintering layer and the adhesion capability thereof.
The release agent used in the embodiment is formed by taking kaolin as a refractory matrix and silica micropowder as a filler and a sintering aid to replace precipitated BaSO in the prior art4Mainly composed ofThe traditional release agent avoids serious harm to the environment caused by a large amount of particles, waste gas, waste water and waste residues generated in the process of producing precipitated barium sulfate.
The release agent on the inner surface of the copper mold cavity 110 forms a proper sintering layer in the casting process, the adhesion of the sintering layer is firm, the release agent is promoted to be sintered and molded under the combined action of the composite superfine powder and the additive, the smooth and compact sintering layer can be formed through sintering, the adhesive force is strong, and the inner surface of the copper mold cavity 110 is prevented from being washed by high-temperature copper liquid. Through compound superfine powder, additive and carboxymethylcellulose sodium combined action for release agent evenly distributed can play thermal-insulated effect at copper die cavity 110 internal surface, the isolation layer that forms between copper die cavity 110 internal surface and the anode plate, thereby reduce copper mould 100 and influence the quality of copper anode plate because the temperature field risees the reduction repeatedly, and then improve copper mould 100's life, improve anode plate appearance quality, make this release agent have high temperature resistant, easy sintering, meet the advantage of easy and anode plate separation behind the water.
The preparation method of the release agent for the disc casting machine comprises the following steps:
adding the aluminosilicate mineral, the sodium carboxymethylcellulose, the composite superfine powder and the additive into a stirrer, and uniformly mixing for more than 30min, wherein the specific steps of uniformly mixing are as follows:
(1) mixing kaolin, kyanite and andalusite, and stirring for more than 10 min;
(2) mixing and stirring kaolin, kyanite and andalusite, adding sodium carboxymethylcellulose, and mixing and stirring for more than 15 min;
(3) adding sodium carboxymethylcellulose, mixing, adding the composite superfine powder and additive, and stirring for more than 5 min.
By adjusting different water-solid concentration ratios in the process of uniformly mixing the release agent and different spraying amounts of the release agent on the copper mold 100, the test mold is cast by using the release agent, and the front mold and the rear mold adopt the existing BaSO4The base mold release agent was cast and the results of the experiment are shown in table 1. As can be seen from the table, the mold temperatures of the front mold, the rear mold and the test mold were substantially the same.
TABLE 1 mould temp. COMPARATIVE TABLE
The records of the quality parameters of the copper anode plate produced by the comparison die and the test die are shown in table 2, and the specific quality parameters comprise white board ratio, porosity and service life. As can be seen from the table, the blank plate rate of the copper anode plate produced by the test die is obviously lower than that of the comparison die; the porosity of the copper anode plate produced by adopting the test die is lower than that of the comparison die; the service life of the copper anode plate produced by the test die reaches 85-100 days, which is obviously longer than that of the copper anode plate produced by the comparison die.
TABLE 2 comparison table of quality parameters of copper anode
| Quality parameter | BaSO4Radical release agent | Kaolin-based mold release agent |
| White board rate | 17％-32％ | 12％-23％ |
| Porosity of the alloy | 10％-19％ | 4％-10％ |
| Service life | 50-60 days | 85-100 days |
Example 2
The present embodiment is basically the same as embodiment 1, except that: the mass portion ratio of the release agent in the embodiment is 60kg of kaolin, 5kg of Suzhou soil, 5kg of kyanite, 9kg of andalusite and 14kg of silicon micropowder, and the compound ultramicro powder is prepared by the formula
The additive is 0.71kg of (e + f) x k, 0.15kg of sodium carboxymethylcellulose and Suzhou soil with a formula g, the sintering layer formed by the additive has good insulating property, the white board rate of the copper anode plate produced by the release agent prepared by the mixture ratio is 10-15%, the porosity is 2.5-7%, and the service life is 90-103 days.
Example 3
The present embodiment is basically the same as embodiment 1, except that: in the embodiment, the mass part ratio of the release agent is 70kg of kaolin, 6kg of attapulgite, 5kg of kyanite, 9kg of andalusite, 15kg of silicon micropowder and composite superfine powder according to a formula
The additive is 0.59kg of (e + f) x k and 0.15kg of sodium carboxymethylcellulose according to a formula g, the attapulgite also has good sintering performance, a formed sintering layer has excellent isolation performance, the white board rate of a copper anode plate produced by using the release agent prepared according to the proportion is 8-17%, the porosity is 3.2-8%, and the service life is 90-107 days.
Example 4
The present embodiment is basically the same as embodiment 1, except that: the component proportion of the release agent in the embodiment is 63kg of kaolin, 5kg of kyanite, 9kg of andalusite, 14kg of silica micropowder, 0.4kg of fly ash and the formula of composite superfine powder
The additive is prepared by the formula of g ═ (e + f) x k ═ 0.54kg, sodium carboxymethylcellulose 0.15kg, and a small amount of silicon micropowder can increase demouldingThe quantity of pores of a sintering layer formed by the agent is increased, the heat insulation effect of the sintering layer is improved, the crushing of the sintering layer after the use is convenient, the white board rate of a copper anode plate produced by using the release agent prepared according to the proportion is 15-18%, the porosity is 5-8%, and the service life is 83-96 days.
Example 5
The present embodiment is basically the same as embodiment 1, except that: the component proportion of the release agent in the embodiment is that kaolin of 75kg, kyanite of 5kg, andalusite of 9kg, silica micropowder of 14kg, steel slag of 0.2kg and composite superfine powder pass through a formula
The additive is prepared by the formula g (e + f) x k (0.58 kg), the sodium carboxymethylcellulose is 0.15kg, the steel slag granularity is 87-95% of 500 meshes, a small amount of steel slag in the release agent can properly improve the strength of a sintering layer formed by the release agent, the release agent after dehydration is prevented from being locally cracked due to impact of copper liquid, the white board rate of a copper anode plate produced by the release agent prepared by the proportion is 7-15%, the porosity is 7-13%, and the service life is 92-108 days.
Example 6
The present embodiment is basically the same as embodiment 1, except that: kaolin, kyanite, andalusite, silicon micropowder, sodium carboxymethylcellulose, composite superfine powder and additives. In the embodiment, the mixture ratio is that 60-70 parts by mass of kaolin is added, 4-5 parts by mass of kyanite is added, 9-10 parts by mass of andalusite is added, 14-15 parts by mass of silicon micropowder is added, and 0.15 part by mass of sodium carboxymethylcellulose is added.
The calculation formula of the added mass parts of the composite superfine powder is f, and f is as follows:
wherein:
b is the mass part of kaolin added; c is the mass portion of the added kyanite; d is the mass portion of andalusite added; e is the mass part of the added silicon micropowder; f is the mass portion of the composite superfine powder; the value of alpha is 47-49, and in the embodiment, the value of alpha is 47, and the specific mass ratio is as follows: 67kg of kaolin, 4kg of kyanite, 9kg of andalusite, 14kg of fine silica powder, 0.15kg of sodium carboxymethylcellulose, 1-gamma and 4.79kg of f;
the mass part of the additive is g ═ e + f) x k, k is 0.03-0.05, in this example 0.04; wherein: e is the mass part of the added silicon micropowder; f is the mass portion of the composite superfine powder; g is the mass portion added by the additive, and the g is 0.75kg by calculation. The white board rate of the copper anode plate produced by using the release agent prepared according to the proportion is 9-20%, the porosity is 2-8%, and the service life is 90-102 days.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined (e.g., between various embodiments), adapted and/or substituted as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Claims (5)
1. The use method of the release agent for the disc casting machine is characterized by comprising the following steps:
when the release agent is used, the release agent is coated on the inner surface of the cavity of the copper mold cavity (110), and a sintering layer is formed between the copper liquid and the inner surface of the cavity of the copper mold cavity (110) after the copper liquid is cast to isolate the copper anode plate from the cavity of the copper mold cavity (110); the release agent comprises kaolin, kyanite, andalusite, silicon micropowder, sodium carboxymethylcellulose, composite superfine powder and an additive; the composite superfine powder comprises active Al2O3Powder and fused SiO2Micro-powder; wherein the mass parts of the composite superfine powder can be calculated by the following formula: f = (b × (b + c + d + e))/100 e, where: b is the mass part of kaolin added; c is the mass portion of the added kyanite; d is the mass portion of andalusite added; e is the mass part of the added silicon micropowder; f is the mass portion of the composite superfine powder;
the specific application method of the release agent is as follows:
adding water into a release agent to mix into suspension;
preheating the copper mold (100), and heating the copper mold cavity (110);
spraying the suspension on the inner surface of the cavity of the copper mold cavity (110);
evaporating the water of the suspension on the inner surface of the copper mold cavity (110) to form a mold release agent drying layer;
pouring copper liquid into the cavity of the copper mold cavity (110), wherein the release agent drying layer forms a sintering layer between the copper liquid and the inner surface of the cavity of the copper mold cavity (110);
and solidifying the copper liquid into a copper anode, and separating the sintering layer from the copper anode.
2. The method of using a mold release agent for a disc caster as defined in claim 1, wherein: in the step of mixing the release agent with water to form the suspension, the mass water-solid ratio of the added water to the release agent is as follows: k: 1, the value range of K is 4.5-5.5, and the water temperature is 60-70 ℃.
3. The method of using a mold release agent for a disc caster as defined in claim 1, wherein: preheating the copper mold (100), and in the step of heating the copper mold cavity (110), heating the copper mold cavity (110) to 170-220 ℃.
4. The method of using a mold release agent for a disc caster as defined in claim 1, wherein: in the process of spraying the suspension on the inner surface of the copper mold cavity (110), the amount of the suspension sprayed on the inner surface of the copper mold cavity (110) is 2.2-3.2 kg/m2。
5. The use method of the mold release agent for a disc caster as described in any one of claims 1 to 4, wherein: the additives include sodium pyrophosphate and dextrin.
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| CN114951544A (en) * | 2022-07-08 | 2022-08-30 | 江西铜业（清远）有限公司 | Special release agent for steel die and spraying process thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5542141A (en) * | 1978-09-19 | 1980-03-25 | Sumitomo Metal Ind Ltd | Coat die forming method of large-sized cast iron casting |
| CN102105242A (en) * | 2008-05-28 | 2011-06-22 | 阿什兰-苏德舍米-克恩费斯特有限公司 | Coating compositions for casting moulds and cores for avoiding maculate surfaces |
| CN103170610A (en) * | 2013-04-10 | 2013-06-26 | 广西有色再生金属有限公司 | Device for casting anode copper mould by using dual-mode disk casting machine tundish and casting method applicable to device |
| JP5274415B2 (en) * | 2009-09-08 | 2013-08-28 | 本田技研工業株式会社 | Application method of coating agent in casting mold |
| CN103537613A (en) * | 2012-12-17 | 2014-01-29 | 机械科学研究总院先进制造技术研究中心 | Mold-releasing type complexing agent with effects of resisting high temperature, insulating heat and demolding |
| CN104226896A (en) * | 2014-09-17 | 2014-12-24 | 云南铜业股份有限公司 | Compound release agent for copper anode casting and preparation method of compound release agent |
| CN104226895A (en) * | 2014-09-17 | 2014-12-24 | 昆明理工大学科技产业经营管理有限公司 | Using method of release agent for copper anode plate casting |
-
2018
- 2018-07-31 CN CN201810860759.5A patent/CN108941445B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5542141A (en) * | 1978-09-19 | 1980-03-25 | Sumitomo Metal Ind Ltd | Coat die forming method of large-sized cast iron casting |
| CN102105242A (en) * | 2008-05-28 | 2011-06-22 | 阿什兰-苏德舍米-克恩费斯特有限公司 | Coating compositions for casting moulds and cores for avoiding maculate surfaces |
| JP5274415B2 (en) * | 2009-09-08 | 2013-08-28 | 本田技研工業株式会社 | Application method of coating agent in casting mold |
| CN103537613A (en) * | 2012-12-17 | 2014-01-29 | 机械科学研究总院先进制造技术研究中心 | Mold-releasing type complexing agent with effects of resisting high temperature, insulating heat and demolding |
| CN103170610A (en) * | 2013-04-10 | 2013-06-26 | 广西有色再生金属有限公司 | Device for casting anode copper mould by using dual-mode disk casting machine tundish and casting method applicable to device |
| CN104226896A (en) * | 2014-09-17 | 2014-12-24 | 云南铜业股份有限公司 | Compound release agent for copper anode casting and preparation method of compound release agent |
| CN104226895A (en) * | 2014-09-17 | 2014-12-24 | 昆明理工大学科技产业经营管理有限公司 | Using method of release agent for copper anode plate casting |
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