WO2019085121A1 - Molten salt-based soluble core, preparation method therefor and application - Google Patents

Molten salt-based soluble core, preparation method therefor and application Download PDF

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Publication number
WO2019085121A1
WO2019085121A1 PCT/CN2017/113760 CN2017113760W WO2019085121A1 WO 2019085121 A1 WO2019085121 A1 WO 2019085121A1 CN 2017113760 W CN2017113760 W CN 2017113760W WO 2019085121 A1 WO2019085121 A1 WO 2019085121A1
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Prior art keywords
molten salt
nano
kno
sodium
salt
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PCT/CN2017/113760
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French (fr)
Chinese (zh)
Inventor
曾智勇
曾帆
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深圳市爱能森科技有限公司
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Publication of WO2019085121A1 publication Critical patent/WO2019085121A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/10—Cores; Manufacture or installation of cores
    • B22C9/105—Salt cores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds

Definitions

  • the invention belongs to the technical field of casting, and particularly relates to a soluble core based soluble core and a preparation method and application thereof.
  • the core is commonly called “mud core” and “core”.
  • the core sand used to form the internal structure of the casting usually made of raw sand and binder (water glass, resin, etc.), made in the core box by hand or machine (such as core blower, core shooter, etc.) .
  • the core box is made of wood or metal.
  • the device Before the casting, the device is placed in the mold, and the molten metal is poured into the condensed water, and is removed when the sand is discharged, and a cavity is formed in the casting.
  • a skeleton made of iron wire or cast iron is usually placed in the core, which is called “core bone” (commonly known as “mud core” or “core iron”).
  • core bone commonly used, and the metal is removed in time after solidification.
  • the cores are also used to form molds, which are called "core molding".
  • the core is used in the manufacture of parts in various fields.
  • the core can be further divided into a metal core, a ceramic core and a soluble core.
  • the metal core is often unable to core, and it is easy to scratch the surface for deep hole core pulling, or it is necessary to relax the machining allowance.
  • the ceramic core is capable of forming a cavity having a complicated shape and a small opening.
  • the preparation process of the ceramic core is long and complicated, and the cost is high.
  • the high-temperature alkali solution corrodes the surface of the aluminum alloy casting, so the aluminum alloy casting cannot use the ceramic core.
  • the soluble core is made of a material which is soluble in a solvent at normal temperature.
  • the core is placed in the molding cavity during molding and then waxed.
  • the prepared investment mold is placed in water or a solution to remove the core to form a cavity of the investment mold.
  • the use of a soluble core is simple, and it is possible to manufacture a cavity in which a metal core cannot be formed and to avoid the disadvantages of using a metal core.
  • Soluble cores can be divided into two categories according to their forming method: cast-formed and injection-formed.
  • the cast-formed soluble core is usually made of urea as the main raw material.
  • the urea core has high strength and small shrinkage, but has disadvantages such as large brittleness, strong hygroscopicity, high melting point and contaminated working environment.
  • the material used for the injection molded soluble core is a soluble mixture similar to a semi-solid wax.
  • the core has small brittleness, good storage, easy control of the dimensional accuracy and surface finish of the core, and is suitable for manufacturing complex cores.
  • the dimensions of the inner cavity of the aerospace industry are strictly required ( ⁇ 0.03 ⁇ 0.05mm), and the surface finish is high. In precision manufacturing, through mechanical processing and welding, such parts are of poor quality and low efficiency.
  • the soluble core is effective Solve the above problem.
  • the soluble core has higher strength than the general sand core, has good heat resistance, does not generate gas, can reduce the sand inclusion of the casting, the pore defect, the thermal conductivity is good, the cooling is fast, and the local stress is reduced.
  • the low melting point alloy is cast into a fusible core, which requires the use of induction coil heating to melt the core, and the process is complicated.
  • an object of the present invention is to provide a molten core-based soluble core and a preparation method and application thereof.
  • the soluble core provided by the invention has good dispersity and mechanical strength, can effectively improve the mechanical properties of the soluble core, and can conveniently clean the soluble core and the casting due to the good water solubility of the molten salt. Surface residue.
  • a soluble core characterized by comprising a molten salt, silica, silicic acid; the molten salt is a water-soluble molten salt, and has a melting point of 40-1500 ° C; the molten salt, silicon dioxide, The weight ratio of silicic acid is: 80-99 parts of molten salt; 1-20 parts of silica; 1-5 parts of silicic acid.
  • the molten salt is selected from the group consisting of a monomer molten salt, a binary composite molten salt, a ternary composite molten salt, or a multicomponent composite molten salt.
  • the silica is selected from the group consisting of nanosilica, and/or hydrated silica.
  • the monomer molten salt includes a monomeric nitrate, a monomeric carbonate, a monomeric sulfate, a monomeric silicate, or a monomeric chloride; or a respective aqueous crystalline salt thereof; the monomeric nitrate Including: potassium nitrate, sodium nitrate, sodium nitrite, lithium nitrate, or calcium nitrate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the calcium nitrate may be calcium nitrate tetrahydrate or the like;
  • the carbonate includes: potassium carbonate, sodium carbonate, or lithium carbonate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of sodium carbonate may be sodium carbonate monohydrate, sodium carbonate heptahydrate or sodium carbonate decahydrate;
  • the monomeric sulfate includes: magnesium sulfate, sodium sulfate, etc.
  • the hydrous crystalline salt of magnesium chloride may be magnesium chloride hexahydrate;
  • the binary composite molten salt comprises: KNO 3 -NaNO 3 system, K 2 CO 3 -Na 2 CO 3 system, KNO 3 a NaNO 2 system;
  • the ternary composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 system, NaNO 3 -KNO 3 -LiNO 3 system, KNO 3 -NaNO 3 -Ca(NO 3 ) 2 system;
  • the multi-component composite molten salt includes: KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 system, KNO 3 -NaNO 3 -NaNO 2 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -NaNO 2 -LiNO 3 system, KNO 3- NaNO 3 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3- NaNO 3 -Cs
  • a method for preparing a soluble core comprising: heating a molten salt to a molten state to form a molten molten salt system; adding silica and silicic acid to the molten molten salt system;
  • the molten salt is a water-soluble molten salt and has a melting point of 60-1200 ° C; the proportion by weight of the molten salt, silica, and silicic acid is: 80-99 parts of molten salt; 1-20 parts of silicon dioxide 1-5 parts of silicic acid.
  • the preparation method further comprises: adding silica and silicic acid to the molten molten salt system, and continuing to heat and heat for 12 hours.
  • the preparation method further comprises: forming a soluble core by solidifying a molten molten salt system to which silica and silicic acid are added; and forming the molten molten salt by stirring to form a uniform molten melting Salt system; the heating refers to a gradient heating to a molten state.
  • the molten salt is selected from the group consisting of a monomer molten salt, a binary composite molten salt, a ternary composite molten salt or a multicomponent composite molten salt;
  • the silica is selected from the group consisting of nano silica, and/or hydrated silica.
  • the monomer molten salt includes a monomeric nitrate, a monomeric carbonate, a monomeric sulfate, a monomeric silicate, or a monomeric chloride; or a respective aqueous crystalline salt thereof; the monomeric nitrate Including: potassium nitrate, sodium nitrate, sodium nitrite, lithium nitrate, or calcium nitrate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the calcium nitrate may be calcium nitrate tetrahydrate or the like;
  • the carbonate includes: potassium carbonate, sodium carbonate, or lithium carbonate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of sodium carbonate may be sodium carbonate monohydrate, sodium carbonate heptahydrate or sodium carbonate decahydrate;
  • the monomeric sulfate includes: magnesium sulfate, sodium sulfate, etc.
  • the hydrous crystalline salt of magnesium chloride may be magnesium chloride hexahydrate;
  • the binary composite molten salt comprises: KNO 3 -NaNO 3 system, K 2 CO 3 -Na 2 CO 3 system, KNO 3 a NaNO 2 system;
  • the ternary composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 system, NaNO 3 -KNO 3 -LiNO 3 system, KNO 3 -NaNO 3 -Ca(NO 3 ) 2 system;
  • the multi-component composite molten salt includes: KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 system, KNO 3 -NaNO 3 -NaNO 2 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -NaNO 2 -LiNO 3 system, KNO 3- NaNO 3 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3- NaNO 3 -Cs
  • the invention firstly provides a soluble core comprising a molten salt, silicon dioxide and silicic acid; the proportion by weight of the molten salt, silicon dioxide and silicic acid is: 80-99 parts of molten salt; 1-20 parts of silicon; 1-5 parts of silicic acid.
  • the invention adopts molten salt as the base material of the core, mainly adopts the molten salt to have good fluidity at high temperature, has low viscosity, can well fill the inner cavity structure of the core box, and can solidify and form hard after cooling. Solid, and the solid has a high strength, and the solid formed by solidification of the molten salt can be dissolved in water, that is, the core made of the base material containing the molten salt can be removed by water.
  • the bending strength of the core is improved by adding nano silica, silicic acid, and hydrated silica.
  • the melting point of the molten salt can be adjusted by adjusting the composition of the binary molten salt and the ternary molten salt to adjust the melting point of the corresponding molten salt system to meet the melting point characteristics of different casting materials.
  • the advantage of adding nano-silica, silicic acid, and hydrated silica is that the bending strength of the core can be improved.
  • the molten salt is selected from the group consisting of a monomeric molten salt or a multicomponent complex molten salt.
  • the silica is selected from the group consisting of nanosilica, and/or hydrated silica.
  • Another aspect of the present invention provides a method for preparing a soluble core, comprising: heating a molten salt to a molten state to form a molten molten salt system, and adding silica and silicic acid to the In the molten molten salt system; the molten salt is a water-soluble molten salt, and the melting point thereof is 40-1500 ° C; the proportion by weight of the molten salt, silica, and silicic acid is: molten salt 80-99 parts Silica 1-20 parts; 1-5 parts of silicic acid.
  • the method of preparation further comprises: adding silica and silicic acid to the molten molten salt system and continuing to heat for 12 hours.
  • the preparation method further comprises: forming the soluble core after the molten molten salt system to which silica and silicic acid are added is solidified.
  • the molten molten salt system forms a uniform molten molten salt system by agitation.
  • the heating refers to a gradient heating to a molten state.
  • the molten salt is selected from the group consisting of a monomer molten salt, a binary composite molten salt, a ternary composite molten salt or a multicomponent composite molten salt;
  • the silica is selected from the group consisting of nano silica, and/or hydrated silica;
  • the monomer molten salt comprises a monomeric nitrate, a monomeric carbonate, a monomeric sulfate, a monomeric silicate, or a monomeric chloride; or a respective aqueous crystalline salt thereof;
  • the monomer nitrate includes: potassium nitrate, sodium nitrate, sodium nitrite, lithium nitrate, or calcium nitrate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the calcium nitrate may be calcium nitrate tetrahydrate (melting point 40 ° C), etc.;
  • the monomer carbonate includes: potassium carbonate (melting point 891 ° C), sodium carbonate (melting point 851 ° C), or lithium carbonate (melting point) 618 ° C) and the like; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of sodium carbonate may be sodium carbonate monohydrate, sodium carbonate heptahydrate, or sodium carbonate decahydrate;
  • the monomeric sulfate salt includes: magnesium sulfate (melting point 1124 ° C), sodium sulfate (melting point 884 ° C), etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium sulfate may be magnesium sulfate heptahydrate; The sodium sulfate may be sodium sulfate decahydrate;
  • the monomeric silicate comprises: sodium silicate (melting point 1089 ° C), lithium silicate (melting point 1255 ° C), sodium metasilicate (melting point 1088 ° C) or sodium disilicate pentoxide; or their respective water containing a crystalline salt; for example, the aqueous crystalline salt of the sodium metasilicate may be sodium metasilicate pentahydrate or sodium metasilicate pentahydrate;
  • the monomer chloride salt includes calcium chloride (melting point 782 ° C), sodium chloride (melting point 891 ° C), magnesium chloride (melting point 1412 ° C) and the like. Or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium chloride may be magnesium chloride hexahydrate (melting point 714 ° C);
  • the binary composite molten salt includes: a KNO 3 -NaNO 3 system, a K 2 CO 3 -Na 2 CO 3 system, and a KNO 3 -NaNO 2 system;
  • the ternary composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 system, NaNO 3 -KNO 3 -LiNO 3 system, KNO 3 -NaNO 3 -Ca(NO 3 ) 2 system;
  • the multi-component composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 system, KNO 3 -NaNO 3 -NaNO 2 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -NaNO 2 -LiNO 3 system , KNO 3 -NaNO 3 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -LiNO 3 -CsNO 3 system,
  • KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 -Ca(NO 3 ) 2 system KNO 3 -NaNO 3 -KNO 2 -CsNO 3 system
  • K 2 CO 3 -Na 2 CO 3 -NaCl-Li 2 CO 3 system K 2 CO 3 -Na 2 CO 3 -Li 2 CO 3 -NaCl-MgO-CaO system.
  • a third aspect of the invention provides the use of the soluble core and/or the preparation method described in the field of casting and moulding.
  • the preparation principle of the soluble core of the invention is to adjust the solidification temperature of the soluble core by using different eutectic point temperatures of different system molten salts, and is suitable for different temperature requirements.
  • the invention utilizes the molten salt to have good fluidity at high temperature, has low viscosity, and can well fill the inner cavity structure of the core box, and the solid has high strength after cooling.
  • the bending strength of the core is improved by adding nano silica, silicic acid, and hydrated silica.
  • the melting point of the molten salt can be adjusted by adjusting the composition of the binary molten salt and the ternary molten salt to adjust the melting point of the corresponding molten salt system to meet the melting point characteristics of different casting materials. Generally, the melting point of the molten salt system is higher than the melting point of the casting. To prevent the core from melting, damaging or Deformation, especially suitable for casting of low melting point casting materials.
  • silicic acid and hydrated silica have a hydroxyl group on the surface, hydrogen bonds can be formed, and the particles are arranged in a chain structure before, which can effectively reduce the shrinkage phenomenon of the molten salt during cooling and improve the quality of the casting.
  • Hydrated silica and silicic acid have good dispersion and mechanical strength, which can effectively improve the mechanical properties of the soluble core.
  • the molten salt has good water solubility and can easily clean the soluble core and the surface residue of the casting.
  • the core is made of a water-soluble molten salt system, the quality of the casting is high, the soluble core is easy to remove, can be removed by water at normal temperature, and the molten salt can be reused after removing water, and the cost is low, energy saving and environmental protection.
  • the present invention firstly provides a soluble core, wherein the matrix material of the soluble core comprises a molten salt, silica, silicic acid; the molten salt is a water-soluble molten salt, and the melting point thereof is 40 -1500 ° C.
  • the invention adopts molten salt as the base material of the core, mainly adopts the molten salt to have good fluidity at high temperature, has low viscosity, can well fill the inner cavity structure of the core box, and can solidify and form hard after cooling. Solid, and the solid has a high strength, and the solid formed by solidification of the molten salt can be dissolved in water, that is, the core made of the base material containing the molten salt can be removed by water.
  • the base material further comprises: the molten salt, silica, and silicic acid in a weight ratio of: 80-99 parts of molten salt; 1-20 parts of silicon dioxide; 5 servings.
  • the molten salt is selected from the group consisting of a monomer molten salt, a binary composite molten salt, a ternary composite molten salt, or a multicomponent composite molten salt.
  • the silica is selected from the group consisting of nanosilica, and/or hydrated silica.
  • the monomeric molten salt comprises a monomeric nitrate, a monomeric carbonate, a monomeric sulfate, a monomeric silicate, or a monomeric chloride; or their respective aqueous Crystalline salt;
  • the monomer nitrate includes: potassium nitrate, sodium nitrate, sodium nitrite, lithium nitrate, or calcium nitrate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the calcium nitrate may be calcium nitrate tetrahydrate (melting point 40 ° C), etc.;
  • the monomeric carbonate includes: potassium carbonate (melting point 891 ° C), sodium carbonate (melting point 851 ° C), or lithium carbonate (melting point 618 ° C), etc.; or their respective aqueous crystalline salts; for example, aqueous crystallization of sodium carbonate
  • the salt may be sodium carbonate monohydrate, sodium carbonate heptahydrate or sodium carbonate decahydrate;
  • the monomeric sulfate includes: magnesium sulfate (melting point 1124 ° C), sodium sulfate (melting point 884 ° C), etc.; or their respective An aqueous crystalline salt; for example, the aqueous crystalline salt of magnesium sulfate may be magnesium sulfate heptahydrate; the sodium sulfate may be sodium sulfate decahydrate;
  • the monomeric silicate comprises: sodium silicate (melting point 1089 ° C), lithium silicate (melting point 1255 ° C), sodium metasilicate (melting point 1088 ° C) or sodium disilicate pentoxide; or their respective water containing a crystalline salt; for example, the aqueous crystalline salt of the sodium metasilicate may be sodium metasilicate pentahydrate or sodium metasilicate pentahydrate;
  • the monomer chloride salt includes calcium chloride (melting point 782 ° C), sodium chloride (melting point 891 ° C), magnesium chloride (melting point 1412 ° C) and the like. Or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium chloride may be magnesium chloride hexahydrate (melting point 714 ° C);
  • the binary composite molten salt comprises: KNO 3 -NaNO 3 system (melting point 220 ° C), K 2 CO 3 -Na 2 CO 3 system, KNO 3 -NaNO 2 system (melting point 130 ° C);
  • the ternary composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 system (melting point 142 ° C), NaNO 3 -KNO 3 -LiNO 3 system (melting point 126 ° C), KNO 3 -NaNO 3 -Ca(NO 3 ) 2 system (melting point 120 ° C);
  • the multi-component composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 system, KNO 3 -NaNO 3 -NaNO 2 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -NaNO 2 -LiNO 3 system (melting point 250-550 ° C), KNO 3 -NaNO 3 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -LiNO 3 -CsNO 3 system, Ca(NO 3 ) 2 4H 2 O-KNO 3 -NaNO 3 -LiNO 3 system, KNO 3 -NaNO 3 -LiNO 3 -Ca(NO 3 ) 2 system,
  • KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 -Ca(NO 3 ) 2 system KNO 3 -NaNO 3 -KNO 2 -CsNO 3 system, K 2 CO 3 -Na 2 CO 3 -NaCl-Li 2 CO 3 system , K 2 CO 3 -Na 2 CO 3 -Li 2 CO 3 -NaCl-MgO-CaO system;
  • molten salts especially binary, ternary, and multi-component mixed molten salts, the melting points of which vary with the amount of each monomer component in the respective systems, but generally the melting points of various molten salts are in the range of 40 -1500 ° C.
  • Another aspect of the present invention provides a method for preparing a soluble core, comprising: heating a molten salt to a molten state to form a molten molten salt system, and adding silica and silicic acid to the In molten molten salt system.
  • the method of preparation further comprises: adding silica and silicic acid to the molten molten salt system and continuing to heat for 12 hours.
  • the preparation method further comprises: forming the soluble core after the molten molten salt system to which silica and silicic acid are added is solidified.
  • the parts by weight of the molten salt, silica, and silicic acid are: 80-99 parts of molten salt; 1-20 parts of silica; 1-5 parts of silicic acid;
  • the molten molten salt system forms a uniform molten molten salt system by stirring.
  • the heating refers to a gradient heating to a molten state.
  • the molten salt is a monomeric molten salt of calcium nitrate tetrahydrate; the silica is selected from the group consisting of nanosilica, and/or hydrated silica.
  • a third aspect of the present invention provides the use of the soluble core according to any one of the first group of embodiments and/or the preparation method provided by any one of the second embodiment, in casting and mold.
  • the manufacture, use, sale, and sale of a soluble core of the present invention for commercial purposes on any scale, and/or the use of the preparation methods described herein, are within the scope of the claimed invention.
  • the common feature is that the soluble core according to any one of the first group of embodiments of the present invention is placed in a commodity package, and/or the soluble core The product number, lot, trademark, and/or trade name are marked on it.
  • the molten salt is first placed in the corundum crucible, and mixed and stirred;
  • the function of this step is to determine the time when the molten sample flows into the mold according to the observed melting condition and viscosity characteristics of the sample, and whether the mold can be uniformly filled. .
  • the core of the invention is prepared, and the performance indexes of the core are determined according to the conventional detection methods in the art, and the same performance indexes of the two existing soluble cores are simultaneously measured, and the measured results are as follows: 2 is shown.
  • the soluble core product of the present invention represented by the embodiment 1-361 of Table 1, only the core products obtained by the formulations corresponding to the examples 143 and 294 have a core removal time of 8 respectively.
  • the moisture absorption rates of the core products of Examples 34 and 57 were 0.1% and 0.15%, respectively, in minutes and 10 minutes, and the core removal times of the soluble cores of the other examples were Between 2 and 7 minutes, the moisture absorption rate is between 0.06% and 0.08%.
  • the units corresponding to the performance indicators are generally understood and conventionally known by those skilled in the core field, and the test methods of the above various performance indicators are conventional testing methods in the field;
  • the dissolved core A is a commercially available brand and a batch of soluble core products;
  • the existing soluble core B is the best performance disclosed in the article "Research on M-84 soluble core mixture” Solvent core.
  • Table 1 herein merely exemplifies a list of hundreds of soluble core solutions of the present invention, the soluble cores claimed in the present invention are far more than these, and accordingly, each specific soluble core Corresponding performance data are also different, but the performance indexes of each specific soluble core claimed in the present invention are stably maintained at the level indicated by the data range described in the second row of Table 2, which is saving space.
  • the specific soluble core schemes other than Table 1 are not exhaustively described herein, and the individual performance values of the soluble cores are not listed here.

Abstract

A molten salt-based soluble core, a preparation method therefor and an application. A base material of the soluble core comprises a molten salt, silicon dioxide and silicic acid, the molten salt being a water soluble molten salt having a melting point of 40-1500°C, the proportions of the molten salt, silicon dioxide and silicic acid being 80-99 parts by weight of the molten salt, 1-20 parts by weight of silicon dioxide and 1-5 parts by weight of silicic acid. The core made from the molten salt having good water solubility has high casting quality and can be removed by water at normal temperature, and the removed molten salt is reusable. The present invention is low-cost and environmentally friendly.

Description

一种基于熔盐的可溶型芯及其制备方法与应用Soluble salt based soluble core and preparation method and application thereof 技术领域Technical field
本发明属于铸造技术领域，特别是涉及一种基于熔盐的可溶型芯及其制备方法与应用。The invention belongs to the technical field of casting, and particularly relates to a soluble core based soluble core and a preparation method and application thereof.
背景技术Background technique
型芯俗称“泥芯”、“芯子”。铸造时用以形成铸件内部结构，常由原砂和粘结剂(水玻璃、树脂等)配成的芯砂，在芯盒中手工或机器(如吹芯机、射芯机等)制成。The core is commonly called "mud core" and "core". The core sand used to form the internal structure of the casting, usually made of raw sand and binder (water glass, resin, etc.), made in the core box by hand or machine (such as core blower, core shooter, etc.) .
芯盒用木材或金属制成。在浇铸前装置在铸型内，金属液浇入冷凝后，出砂时将它清除，在铸件中即可形成空腔。为增加型芯强度，通常在型芯内安置由铁丝或铸铁制成的骨架，称“芯骨”(俗称“泥芯骨”或“芯铁”)。在金属型铸造中，常用金属制的型芯，在金属凝固后及时拔除。在成批或大量生产较复杂的铸件(如气缸头等)、生产大型铸件时，型芯亦用以组成铸型，即称“组芯造型”。过去常用黏土、植物油、合脂作型芯黏结剂，现已组逐步被淘汰。现在，小批量生产铸件用自硬树脂、自硬水玻璃组作型芯黏结剂，大批量生产铸件用热芯盒、冷芯盒、覆膜砂工艺做型芯。The core box is made of wood or metal. Before the casting, the device is placed in the mold, and the molten metal is poured into the condensed water, and is removed when the sand is discharged, and a cavity is formed in the casting. In order to increase the core strength, a skeleton made of iron wire or cast iron is usually placed in the core, which is called "core bone" (commonly known as "mud core" or "core iron"). In metal casting, a metal core is commonly used, and the metal is removed in time after solidification. When producing large-scale castings in batches or in large quantities, such as cylinder heads, etc., the cores are also used to form molds, which are called "core molding". In the past, clay, vegetable oil and fat-binding core binders were used, and the group has been gradually eliminated. At present, small-scale production of castings is made of self-hardening resin and self-hardening water glass as core-bonding agent, and mass-produced castings are made of hot core box, cold core box and coated sand.
型芯被应用于各个领域的零件制造中。型芯又可分为金属型芯、陶瓷型芯和可溶型芯。对于开口小的内腔，金属型芯往往无法抽芯，而且对于深孔抽芯时容易划伤表面,或需放宽加工余量。The core is used in the manufacture of parts in various fields. The core can be further divided into a metal core, a ceramic core and a soluble core. For a cavity with a small opening, the metal core is often unable to core, and it is easy to scratch the surface for deep hole core pulling, or it is necessary to relax the machining allowance.
陶瓷型芯能够形成形状复杂、开口细小的内腔。然而陶瓷型芯的制备过程长而复杂，成本高，型芯从铸件脱除时，采用高温碱溶液会腐蚀铝合金铸件的表面，所以铝合金铸件不能采用陶瓷型芯。The ceramic core is capable of forming a cavity having a complicated shape and a small opening. However, the preparation process of the ceramic core is long and complicated, and the cost is high. When the core is removed from the casting, the high-temperature alkali solution corrodes the surface of the aluminum alloy casting, so the aluminum alloy casting cannot use the ceramic core.
可溶型芯是采用能在常温下溶于溶剂的材料制成的。型芯在制模时放入压型型腔，然后注蜡。制好的熔模放在水或溶液里把型芯除掉，形成熔模的内腔。可溶型芯的使用工艺简单，可以制造金属型芯无法形成的内腔和避免使用金属型芯所带来的缺点。The soluble core is made of a material which is soluble in a solvent at normal temperature. The core is placed in the molding cavity during molding and then waxed. The prepared investment mold is placed in water or a solution to remove the core to form a cavity of the investment mold. The use of a soluble core is simple, and it is possible to manufacture a cavity in which a metal core cannot be formed and to avoid the disadvantages of using a metal core.
可溶型芯按其成形方法可分成两类：浇注成形的和压注成形的。浇注成形的可溶型芯通常是用尿素作主要原料。尿素型芯的强度高，收缩率小，但存在脆性大，吸湿性强，熔点高和污染作业环境等缺点。压注成形的可溶性型芯使用的材料是类似半固态蜡料的可溶性混合料。这种型芯脆性小，存放性好，型芯的尺寸精度和表面光洁度容易控制，适用于制造形状复杂的型芯。Soluble cores can be divided into two categories according to their forming method: cast-formed and injection-formed. The cast-formed soluble core is usually made of urea as the main raw material. The urea core has high strength and small shrinkage, but has disadvantages such as large brittleness, strong hygroscopicity, high melting point and contaminated working environment. The material used for the injection molded soluble core is a soluble mixture similar to a semi-solid wax. The core has small brittleness, good storage, easy control of the dimensional accuracy and surface finish of the core, and is suitable for manufacturing complex cores.
航天工业中所用的零件内腔尺寸精度要求严(±0.03～0.05mm)，表面光洁度要求高，精密制造中，通过机械加工，焊接成型，这样的部件质量差，效率低。而可溶性型芯可有效的 解决上述问题。可溶芯比一般砂芯的强度高，耐热性好，不发气，可降低铸件的夹砂，气孔缺陷，导热性好，冷却快，减少局部应力的产生。低熔点合金铸造成可熔型芯，需要使用感应线圈加热的方式熔化掉型芯，过程复杂。The dimensions of the inner cavity of the aerospace industry are strictly required (±0.03~0.05mm), and the surface finish is high. In precision manufacturing, through mechanical processing and welding, such parts are of poor quality and low efficiency. The soluble core is effective Solve the above problem. The soluble core has higher strength than the general sand core, has good heat resistance, does not generate gas, can reduce the sand inclusion of the casting, the pore defect, the thermal conductivity is good, the cooling is fast, and the local stress is reduced. The low melting point alloy is cast into a fusible core, which requires the use of induction coil heating to melt the core, and the process is complicated.
因此，本领域亟需开发基于全新材料的可溶型芯，在保证尺寸精度高、表面光洁度好的同时，方便溶解脱芯，以便能更加便捷广泛地应用于各类制造行业，尤其是航天领域。Therefore, there is an urgent need in the art to develop a soluble core based on a new material, which is convenient for dissolving and decoupling while ensuring high dimensional accuracy and good surface finish, so that it can be more conveniently and widely used in various manufacturing industries, especially in the aerospace field. .
发明内容Summary of the invention
基于本领域存在的上述客观问题及需求，本发明的目的在于提供一种基于熔盐的可溶型芯及其制备方法与应用。本发明所提供的可溶型芯具有很好的分散度、机械强度，能有效的提高可溶芯的机械性能，同时由于熔盐的水溶性好，能够方便的清洗掉可溶型芯和铸件表面残留物。Based on the above objective problems and needs existing in the art, an object of the present invention is to provide a molten core-based soluble core and a preparation method and application thereof. The soluble core provided by the invention has good dispersity and mechanical strength, can effectively improve the mechanical properties of the soluble core, and can conveniently clean the soluble core and the casting due to the good water solubility of the molten salt. Surface residue.
本发明的技术方案如下：The technical solution of the present invention is as follows:
一种可溶型芯，其特征在于，包括熔盐、二氧化硅、硅酸；所述熔盐为水溶性熔盐，且其熔点为40-1500℃；所述熔盐、二氧化硅、硅酸的重量份配比为：熔盐80-99份；二氧化硅1-20份；硅酸1-5份。A soluble core characterized by comprising a molten salt, silica, silicic acid; the molten salt is a water-soluble molten salt, and has a melting point of 40-1500 ° C; the molten salt, silicon dioxide, The weight ratio of silicic acid is: 80-99 parts of molten salt; 1-20 parts of silica; 1-5 parts of silicic acid.
所述熔盐选自单体熔盐、二元复合熔盐、三元复合熔盐、或多元复合熔盐。The molten salt is selected from the group consisting of a monomer molten salt, a binary composite molten salt, a ternary composite molten salt, or a multicomponent composite molten salt.
所述二氧化硅选自纳米二氧化硅，和/或水合二氧化硅。The silica is selected from the group consisting of nanosilica, and/or hydrated silica.
所述单体熔盐包括单体硝酸盐、单体碳酸盐、单体硫酸盐、单体硅酸盐、或单体氯化盐；或它们各自的含水结晶盐；所述单体硝酸盐包括：硝酸钾、硝酸钠、亚硝酸钠、硝酸锂、或硝酸钙等；或它们各自的含水结晶盐；例如，所述硝酸钙的含水结晶盐可以是四水硝酸钙等；所述单体碳酸盐包括：碳酸钾、碳酸钠、或碳酸锂等；或它们各自的含水结晶盐；例如，碳酸钠的含水结晶盐可以是一水碳酸钠、七水碳酸钠、或十水碳酸钠；所述单体硫酸盐包括：硫酸镁、硫酸钠等；或它们各自的含水结晶盐；例如，硫酸镁的含水结晶盐可以是七水硫酸镁；所述硫酸钠可以是十水合硫酸钠；所述单体硅酸盐包括：硅酸钠、硅酸锂、偏硅酸钠或二硅五氧酸钠等；或它们各自的含水结晶盐；例如，所述偏硅酸钠的含水结晶盐可以是五水偏硅酸钠、或九水偏硅酸钠；所述单体氯化盐包括：氯化钙、氯化钠、氯化镁等。或它们各自的含水结晶盐；例如，氯化镁的含水结晶盐可以是六水氯化镁；所述二元复合熔盐包括：KNO3-NaNO3体系、K2CO3-Na2CO3体系、KNO3-NaNO2体系；所述三元复合熔盐包括：KNO3-NaNO3-NaNO2体系、NaNO3-KNO3-LiNO3体系、KNO3-NaNO3-Ca(NO3)2体系；所述多元复合熔盐包括：KNO3-NaNO3-NaNO2-CsNO3体系、KNO3-NaNO3-NaNO2-Ca(NO3)2体系、KNO3-NaNO3-NaNO2-LiNO3体系、KNO3-NaNO3-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-LiNO3-CsNO3体 系、Ca(NO3)24H2O-KNO3-NaNO3-LiNO3体系、KNO3-NaNO3-NaNO2-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-KNO2-CsNO3体系、K2CO3-Na2CO3-NaCl-Li2CO3体系、K2CO3-Na2CO3-Li2CO3-NaCl-MgO-CaO体系。The monomer molten salt includes a monomeric nitrate, a monomeric carbonate, a monomeric sulfate, a monomeric silicate, or a monomeric chloride; or a respective aqueous crystalline salt thereof; the monomeric nitrate Including: potassium nitrate, sodium nitrate, sodium nitrite, lithium nitrate, or calcium nitrate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the calcium nitrate may be calcium nitrate tetrahydrate or the like; The carbonate includes: potassium carbonate, sodium carbonate, or lithium carbonate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of sodium carbonate may be sodium carbonate monohydrate, sodium carbonate heptahydrate or sodium carbonate decahydrate; The monomeric sulfate includes: magnesium sulfate, sodium sulfate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium sulfate may be magnesium sulfate heptahydrate; the sodium sulfate may be sodium sulfate decahydrate; The monomeric silicate comprises: sodium silicate, lithium silicate, sodium metasilicate or sodium disilicate, or the like; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the sodium metasilicate may It is sodium metasilicate pentahydrate or sodium metasilicate pentahydrate; Chloride salts of said monomers comprising: calcium chloride, sodium chloride and magnesium chloride. Or their respective aqueous crystalline salts; for example, the hydrous crystalline salt of magnesium chloride may be magnesium chloride hexahydrate; the binary composite molten salt comprises: KNO 3 -NaNO 3 system, K 2 CO 3 -Na 2 CO 3 system, KNO 3 a NaNO 2 system; the ternary composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 system, NaNO 3 -KNO 3 -LiNO 3 system, KNO 3 -NaNO 3 -Ca(NO 3 ) 2 system; The multi-component composite molten salt includes: KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 system, KNO 3 -NaNO 3 -NaNO 2 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -NaNO 2 -LiNO 3 system, KNO 3- NaNO 3 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -LiNO 3 -CsNO 3 system, Ca(NO 3 ) 2 4H2O-KNO3-NaNO3-LiNO3 system, KNO 3 -NaNO 3 - NaNO 2 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -KNO 2 -CsNO 3 system, K 2 CO 3 -Na 2 CO 3 -NaCl-Li 2 CO 3 system, K 2 CO 3 - Na 2 CO 3 -Li 2 CO 3 -NaCl-MgO-CaO system.
一种可溶型芯的制备方法，其特征在于，包括：将熔盐加热至熔融状态，形成熔融的熔盐体系；将二氧化硅和硅酸添加至所述熔融的熔盐体系中；所述熔盐为水溶性熔盐，且其熔点为60-1200℃；所述熔盐、二氧化硅、硅酸的重量份配比为：熔盐80-99份；二氧化硅1-20份；硅酸1-5份。A method for preparing a soluble core, comprising: heating a molten salt to a molten state to form a molten molten salt system; adding silica and silicic acid to the molten molten salt system; The molten salt is a water-soluble molten salt and has a melting point of 60-1200 ° C; the proportion by weight of the molten salt, silica, and silicic acid is: 80-99 parts of molten salt; 1-20 parts of silicon dioxide 1-5 parts of silicic acid.
所述的制备方法还包括：将二氧化硅和硅酸添加至所述熔融的熔盐体系中后继续加热保温12小时。The preparation method further comprises: adding silica and silicic acid to the molten molten salt system, and continuing to heat and heat for 12 hours.
所述的制备方法还包括：待添加了二氧化硅和硅酸的熔融的熔盐体系凝固后即制成所述可溶型芯；所述熔融的熔盐体系通过搅拌形成均一的熔融的熔盐体系；所述加热指梯度加热至熔融状态。The preparation method further comprises: forming a soluble core by solidifying a molten molten salt system to which silica and silicic acid are added; and forming the molten molten salt by stirring to form a uniform molten melting Salt system; the heating refers to a gradient heating to a molten state.
所述熔盐选自单体熔盐、二元复合熔盐、三元复合熔盐或多元复合熔盐；所述二氧化硅选自纳米二氧化硅，和/或水合二氧化硅。The molten salt is selected from the group consisting of a monomer molten salt, a binary composite molten salt, a ternary composite molten salt or a multicomponent composite molten salt; the silica is selected from the group consisting of nano silica, and/or hydrated silica.
所述单体熔盐包括单体硝酸盐、单体碳酸盐、单体硫酸盐、单体硅酸盐、或单体氯化盐；或它们各自的含水结晶盐；所述单体硝酸盐包括：硝酸钾、硝酸钠、亚硝酸钠、硝酸锂、或硝酸钙等；或它们各自的含水结晶盐；例如，所述硝酸钙的含水结晶盐可以是四水硝酸钙等；所述单体碳酸盐包括：碳酸钾、碳酸钠、或碳酸锂等；或它们各自的含水结晶盐；例如，碳酸钠的含水结晶盐可以是一水碳酸钠、七水碳酸钠、或十水碳酸钠；所述单体硫酸盐包括：硫酸镁、硫酸钠等；或它们各自的含水结晶盐；例如，硫酸镁的含水结晶盐可以是七水硫酸镁；所述硫酸钠可以是十水合硫酸钠；所述单体硅酸盐包括：硅酸钠、硅酸锂、偏硅酸钠或二硅五氧酸钠等；或它们各自的含水结晶盐；例如，所述偏硅酸钠的含水结晶盐可以是五水偏硅酸钠、或九水偏硅酸钠；所述单体氯化盐包括：氯化钙、氯化钠、氯化镁等。或它们各自的含水结晶盐；例如，氯化镁的含水结晶盐可以是六水氯化镁；所述二元复合熔盐包括：KNO3-NaNO3体系、K2CO3-Na2CO3体系、KNO3-NaNO2体系；所述三元复合熔盐包括：KNO3-NaNO3-NaNO2体系、NaNO3-KNO3-LiNO3体系、KNO3-NaNO3-Ca(NO3)2体系；所述多元复合熔盐包括：KNO3-NaNO3-NaNO2-CsNO3体系、KNO3-NaNO3-NaNO2-Ca(NO3)2体系、KNO3-NaNO3-NaNO2-LiNO3体系、KNO3-NaNO3-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-LiNO3-CsNO3体系、Ca(NO3)24H2O-KNO3-NaNO3-LiNO3体系、KNO3-NaNO3-NaNO2-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-KNO2-CsNO3体系、K2CO3-Na2CO3-NaCl-Li2CO3体系、K2CO3-Na2CO3-Li2CO3-NaCl-MgO-CaO体系。 The monomer molten salt includes a monomeric nitrate, a monomeric carbonate, a monomeric sulfate, a monomeric silicate, or a monomeric chloride; or a respective aqueous crystalline salt thereof; the monomeric nitrate Including: potassium nitrate, sodium nitrate, sodium nitrite, lithium nitrate, or calcium nitrate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the calcium nitrate may be calcium nitrate tetrahydrate or the like; The carbonate includes: potassium carbonate, sodium carbonate, or lithium carbonate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of sodium carbonate may be sodium carbonate monohydrate, sodium carbonate heptahydrate or sodium carbonate decahydrate; The monomeric sulfate includes: magnesium sulfate, sodium sulfate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium sulfate may be magnesium sulfate heptahydrate; the sodium sulfate may be sodium sulfate decahydrate; The monomeric silicate comprises: sodium silicate, lithium silicate, sodium metasilicate or sodium disilicate, or the like; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the sodium metasilicate may It is sodium metasilicate pentahydrate or sodium metasilicate pentahydrate; Chloride salts of said monomers comprising: calcium chloride, sodium chloride and magnesium chloride. Or their respective aqueous crystalline salts; for example, the hydrous crystalline salt of magnesium chloride may be magnesium chloride hexahydrate; the binary composite molten salt comprises: KNO 3 -NaNO 3 system, K 2 CO 3 -Na 2 CO 3 system, KNO 3 a NaNO 2 system; the ternary composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 system, NaNO 3 -KNO 3 -LiNO 3 system, KNO 3 -NaNO 3 -Ca(NO 3 ) 2 system; The multi-component composite molten salt includes: KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 system, KNO 3 -NaNO 3 -NaNO 2 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -NaNO 2 -LiNO 3 system, KNO 3- NaNO 3 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -LiNO 3 -CsNO 3 system, Ca(NO 3 ) 2 4H2O-KNO3-NaNO3-LiNO3 system, KNO 3 -NaNO 3 - NaNO 2 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -KNO 2 -CsNO 3 system, K 2 CO 3 -Na 2 CO 3 -NaCl-Li 2 CO 3 system, K 2 CO 3 - Na 2 CO 3 -Li 2 CO 3 -NaCl-MgO-CaO system.
所述的可溶型芯和/或所述的制备方法在铸造、模具领域的应用。The use of the soluble core and/or the preparation method described in the field of casting and moulding.
本发明首先提供一种可溶型芯，其包括熔盐、二氧化硅、硅酸；所述熔盐、二氧化硅、硅酸的重量份配比为：熔盐80-99份；二氧化硅1-20份；硅酸1-5份。本发明采用熔盐作为型芯的基体材料，主要利用熔盐在高温下具有很好的流动性，粘度低，能很好的填充芯盒内腔结构，而在冷却后，又能凝固形成坚硬固体，且固体具有很高的强度这一特性，同时熔盐凝固后形成的固体又能溶解于水，即基于包含熔盐的基体材料制成的型芯通过水就能达到清除的目的。The invention firstly provides a soluble core comprising a molten salt, silicon dioxide and silicic acid; the proportion by weight of the molten salt, silicon dioxide and silicic acid is: 80-99 parts of molten salt; 1-20 parts of silicon; 1-5 parts of silicic acid. The invention adopts molten salt as the base material of the core, mainly adopts the molten salt to have good fluidity at high temperature, has low viscosity, can well fill the inner cavity structure of the core box, and can solidify and form hard after cooling. Solid, and the solid has a high strength, and the solid formed by solidification of the molten salt can be dissolved in water, that is, the core made of the base material containing the molten salt can be removed by water.
通过加入纳米二氧化硅、硅酸、水合二氧化硅提高型芯的抗弯强度。熔盐的熔点则可以通过调节二元熔盐和三元熔盐的组分，调节相应熔盐体系的熔点，以适应不同铸件材料的熔点特性需求。加入纳米二氧化硅、硅酸、水合二氧化硅的好处在于可提高型芯的抗弯强度。The bending strength of the core is improved by adding nano silica, silicic acid, and hydrated silica. The melting point of the molten salt can be adjusted by adjusting the composition of the binary molten salt and the ternary molten salt to adjust the melting point of the corresponding molten salt system to meet the melting point characteristics of different casting materials. The advantage of adding nano-silica, silicic acid, and hydrated silica is that the bending strength of the core can be improved.
在具体的实施例中，所述熔盐选自单体熔盐或多元复合熔盐。In a specific embodiment, the molten salt is selected from the group consisting of a monomeric molten salt or a multicomponent complex molten salt.
在一些优选的实施例中，所述二氧化硅选自纳米二氧化硅，和/或水合二氧化硅。In some preferred embodiments, the silica is selected from the group consisting of nanosilica, and/or hydrated silica.
本发明的另一个方面还提供一种可溶型芯的制备方法，其特征在于，包括：将熔盐加热至熔融状态，形成熔融的熔盐体系，将二氧化硅和硅酸添加至所述熔融的熔盐体系中；所述熔盐为水溶性熔盐，且其熔点为40-1500℃；所述熔盐、二氧化硅、硅酸的重量份配比为：熔盐80-99份；二氧化硅1-20份；硅酸1-5份。Another aspect of the present invention provides a method for preparing a soluble core, comprising: heating a molten salt to a molten state to form a molten molten salt system, and adding silica and silicic acid to the In the molten molten salt system; the molten salt is a water-soluble molten salt, and the melting point thereof is 40-1500 ° C; the proportion by weight of the molten salt, silica, and silicic acid is: molten salt 80-99 parts Silica 1-20 parts; 1-5 parts of silicic acid.
在进一步的实施例中，所述制备方法还包括：将二氧化硅和硅酸添加至所述熔融的熔盐体系中后继续加热保温12小时。In a further embodiment, the method of preparation further comprises: adding silica and silicic acid to the molten molten salt system and continuing to heat for 12 hours.
在更进一步的实施例中，所述制备方法还包括：待添加了二氧化硅和硅酸的熔融的熔盐体系凝固后即制成所述可溶型芯。In still further embodiments, the preparation method further comprises: forming the soluble core after the molten molten salt system to which silica and silicic acid are added is solidified.
在一些实施例中，所述熔融的熔盐体系通过搅拌形成均一的熔融的熔盐体系。In some embodiments, the molten molten salt system forms a uniform molten molten salt system by agitation.
在另一些实施例中，所述加热指梯度加热至熔融状态。In other embodiments, the heating refers to a gradient heating to a molten state.
在具体的实施例中，所述熔盐选自单体熔盐、二元复合熔盐、三元复合熔盐或多元复合熔盐；In a specific embodiment, the molten salt is selected from the group consisting of a monomer molten salt, a binary composite molten salt, a ternary composite molten salt or a multicomponent composite molten salt;
所述二氧化硅选自纳米二氧化硅，和/或水合二氧化硅；The silica is selected from the group consisting of nano silica, and/or hydrated silica;
优选地，所述单体熔盐包括单体硝酸盐、单体碳酸盐、单体硫酸盐、单体硅酸盐、或单体氯化盐；或它们各自的含水结晶盐；Preferably, the monomer molten salt comprises a monomeric nitrate, a monomeric carbonate, a monomeric sulfate, a monomeric silicate, or a monomeric chloride; or a respective aqueous crystalline salt thereof;
所述单体硝酸盐包括：硝酸钾、硝酸钠、亚硝酸钠、硝酸锂、或硝酸钙等；或它们各自的含水结晶盐；例如，所述硝酸钙的含水结晶盐可以是四水硝酸钙(熔点40℃)等；The monomer nitrate includes: potassium nitrate, sodium nitrate, sodium nitrite, lithium nitrate, or calcium nitrate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the calcium nitrate may be calcium nitrate tetrahydrate (melting point 40 ° C), etc.;
所述单体碳酸盐包括：碳酸钾(熔点891℃)、碳酸钠(熔点851℃)、或碳酸锂(熔点 618℃)等；或它们各自的含水结晶盐；例如，碳酸钠的含水结晶盐可以是一水碳酸钠、七水碳酸钠、或十水碳酸钠；The monomer carbonate includes: potassium carbonate (melting point 891 ° C), sodium carbonate (melting point 851 ° C), or lithium carbonate (melting point) 618 ° C) and the like; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of sodium carbonate may be sodium carbonate monohydrate, sodium carbonate heptahydrate, or sodium carbonate decahydrate;
所述单体硫酸盐包括：硫酸镁(熔点1124℃)、硫酸钠(熔点884℃)等；或它们各自的含水结晶盐；例如，硫酸镁的含水结晶盐可以是七水硫酸镁；所述硫酸钠可以是十水合硫酸钠；The monomeric sulfate salt includes: magnesium sulfate (melting point 1124 ° C), sodium sulfate (melting point 884 ° C), etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium sulfate may be magnesium sulfate heptahydrate; The sodium sulfate may be sodium sulfate decahydrate;
所述单体硅酸盐包括：硅酸钠(熔点1089℃)、硅酸锂(熔点1255℃)、偏硅酸钠(熔点1088℃)或二硅五氧酸钠等；或它们各自的含水结晶盐；例如，所述偏硅酸钠的含水结晶盐可以是五水偏硅酸钠、或九水偏硅酸钠；The monomeric silicate comprises: sodium silicate (melting point 1089 ° C), lithium silicate (melting point 1255 ° C), sodium metasilicate (melting point 1088 ° C) or sodium disilicate pentoxide; or their respective water containing a crystalline salt; for example, the aqueous crystalline salt of the sodium metasilicate may be sodium metasilicate pentahydrate or sodium metasilicate pentahydrate;
所述单体氯化盐包括：氯化钙(熔点782℃)、氯化钠(熔点891℃)、氯化镁(熔点1412℃)等。或它们各自的含水结晶盐；例如，氯化镁的含水结晶盐可以是六水氯化镁(熔点714℃)；The monomer chloride salt includes calcium chloride (melting point 782 ° C), sodium chloride (melting point 891 ° C), magnesium chloride (melting point 1412 ° C) and the like. Or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium chloride may be magnesium chloride hexahydrate (melting point 714 ° C);
所述二元复合熔盐包括：KNO3-NaNO3体系、K2CO3-Na2CO3体系、KNO3-NaNO2体系；The binary composite molten salt includes: a KNO 3 -NaNO 3 system, a K 2 CO 3 -Na 2 CO 3 system, and a KNO 3 -NaNO 2 system;
所述三元复合熔盐包括：KNO3-NaNO3-NaNO2体系、NaNO3-KNO3-LiNO3体系、KNO3-NaNO3-Ca(NO3)2体系；The ternary composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 system, NaNO 3 -KNO 3 -LiNO 3 system, KNO 3 -NaNO 3 -Ca(NO 3 ) 2 system;
所述多元复合熔盐包括：KNO3-NaNO3-NaNO2-CsNO3体系、KNO3-NaNO3-NaNO2-Ca(NO3)2体系、KNO3-NaNO3-NaNO2-LiNO3体系、KNO3-NaNO3-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-LiNO3-CsNO3体系、The multi-component composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 system, KNO 3 -NaNO 3 -NaNO 2 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -NaNO 2 -LiNO 3 system , KNO 3 -NaNO 3 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -LiNO 3 -CsNO 3 system,
Ca(NO3)2·4H2O-KNO3-NaNO3-LiNO3体系、Ca(NO3)2·4H2O-KNO3-NaNO3-LiNO3 system,
KNO3-NaNO3-NaNO2-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-KNO2-CsNO3体系、K2CO3-Na2CO3-NaCl-Li2CO3体系、K2CO3-Na2CO3-Li2CO3-NaCl-MgO-CaO体系。KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -KNO 2 -CsNO 3 system, K 2 CO 3 -Na 2 CO 3 -NaCl-Li 2 CO 3 system , K 2 CO 3 -Na 2 CO 3 -Li 2 CO 3 -NaCl-MgO-CaO system.
本文中记载的各项化学式、各类化学物质的中文名称都具有化学领域普通技术人员通常理解的含义；各项化学式指代的是化学领域普通技术人员常规理解的该化学式对应的化学物质；各类化学物质则相应地具有化学领域普通技术人员常规理解的该化学物质对应的规范的化学式。The chemical formulas and the Chinese names of various chemical substances described herein have the meanings commonly understood by those of ordinary skill in the chemical arts; each chemical formula refers to a chemical substance corresponding to the chemical formula conventionally understood by those skilled in the chemical arts; The chemistry of the class correspondingly has the chemical formula corresponding to the specification of the chemical substance as generally understood by those skilled in the chemical arts.
本发明的第三个方面提供所述可溶型芯和/或所述的制备方法在铸造、模具领域的应用。A third aspect of the invention provides the use of the soluble core and/or the preparation method described in the field of casting and moulding.
本发明可溶型芯的制备原理是利用不同体系熔盐不同的共晶点温度调整可溶型芯的凝固温度，适用于不同温度需求。The preparation principle of the soluble core of the invention is to adjust the solidification temperature of the soluble core by using different eutectic point temperatures of different system molten salts, and is suitable for different temperature requirements.
本发明利用熔盐在高温下具有很好的流动性，粘度低，能很好的填充芯盒内腔结构，在冷却后，固体具有很高的强度。The invention utilizes the molten salt to have good fluidity at high temperature, has low viscosity, and can well fill the inner cavity structure of the core box, and the solid has high strength after cooling.
通过加入纳米二氧化硅、硅酸、水合二氧化硅提高型芯的抗弯强度。熔盐的熔点则可以通过调节二元熔盐和三元熔盐的组分，调节相应熔盐体系的熔点，以适应不同铸件材料的熔点特性需求，一般要求熔盐体系的熔点高于铸件熔点，防止芯子在铸造过程熔化，损坏或者 变形，特别适合低熔点铸件材料的铸造。并且，硅酸和水合二氧化硅由于表面有羟基基团，能够形成氢键，粒子之前呈链状结构排列，能有效的减少熔盐在冷却过程中产生的收缩现象，提高铸件的品质。水合二氧化硅和硅酸具有很好的分散度，机械强度，能有效的提高可溶芯的机械性能。熔盐的水溶性好，能够方便的清洗掉可溶型芯和铸件表面残留物。The bending strength of the core is improved by adding nano silica, silicic acid, and hydrated silica. The melting point of the molten salt can be adjusted by adjusting the composition of the binary molten salt and the ternary molten salt to adjust the melting point of the corresponding molten salt system to meet the melting point characteristics of different casting materials. Generally, the melting point of the molten salt system is higher than the melting point of the casting. To prevent the core from melting, damaging or Deformation, especially suitable for casting of low melting point casting materials. Moreover, since silicic acid and hydrated silica have a hydroxyl group on the surface, hydrogen bonds can be formed, and the particles are arranged in a chain structure before, which can effectively reduce the shrinkage phenomenon of the molten salt during cooling and improve the quality of the casting. Hydrated silica and silicic acid have good dispersion and mechanical strength, which can effectively improve the mechanical properties of the soluble core. The molten salt has good water solubility and can easily clean the soluble core and the surface residue of the casting.
采用水溶性好的熔盐体系制作成芯，铸件的质量高，可溶型芯容易清除，常温下通过水即可清除，且熔盐除去水后可重复使用，成本低，节能环保。The core is made of a water-soluble molten salt system, the quality of the casting is high, the soluble core is easy to remove, can be removed by water at normal temperature, and the molten salt can be reused after removing water, and the cost is low, energy saving and environmental protection.
具体实施方式Detailed ways
下面结合附图和具体实施方式对本发明作进一步的详细说明，但并不限制本发明的范围。如无特殊说明，下述实施例中采用的操作步骤均为本领域常规操作手段，所采用的原材料均可以商购获得。The invention is further described in detail below with reference to the drawings and specific embodiments, without limiting the scope of the invention. Unless otherwise stated, the procedures used in the following examples are all conventional means of operation in the art, and the raw materials used are commercially available.
第1组实施例：本发明的可溶型芯Group 1 embodiment: soluble core of the present invention
本发明首先提供一种可溶型芯，其特征在于，所述可溶型芯的基体材料包括熔盐、二氧化硅、硅酸；所述熔盐为水溶性熔盐，且其熔点为40-1500℃。本发明采用熔盐作为型芯的基体材料，主要利用熔盐在高温下具有很好的流动性，粘度低，能很好的填充芯盒内腔结构，而在冷却后，又能凝固形成坚硬固体，且固体具有很高的强度这一特性，同时熔盐凝固后形成的固体又能溶解于水，即基于包含熔盐的基体材料制成的型芯通过水就能达到清除的目的。The present invention firstly provides a soluble core, wherein the matrix material of the soluble core comprises a molten salt, silica, silicic acid; the molten salt is a water-soluble molten salt, and the melting point thereof is 40 -1500 ° C. The invention adopts molten salt as the base material of the core, mainly adopts the molten salt to have good fluidity at high temperature, has low viscosity, can well fill the inner cavity structure of the core box, and can solidify and form hard after cooling. Solid, and the solid has a high strength, and the solid formed by solidification of the molten salt can be dissolved in water, that is, the core made of the base material containing the molten salt can be removed by water.
在一些实施例中，所述基体材料还包括：所述熔盐、二氧化硅、硅酸的重量份配比为：熔盐80-99份；二氧化硅1-20份；硅酸1-5份。In some embodiments, the base material further comprises: the molten salt, silica, and silicic acid in a weight ratio of: 80-99 parts of molten salt; 1-20 parts of silicon dioxide; 5 servings.
在具体的实施例中，所述熔盐选自单体熔盐、二元复合熔盐、三元复合熔盐、或多元复合熔盐。In a specific embodiment, the molten salt is selected from the group consisting of a monomer molten salt, a binary composite molten salt, a ternary composite molten salt, or a multicomponent composite molten salt.
在一些优选的实施例中，所述二氧化硅选自纳米二氧化硅，和/或水合二氧化硅。In some preferred embodiments, the silica is selected from the group consisting of nanosilica, and/or hydrated silica.
在更具体的一些实施例中，所述单体熔盐包括单体硝酸盐、单体碳酸盐、单体硫酸盐、单体硅酸盐、或单体氯化盐；或它们各自的含水结晶盐；In more specific embodiments, the monomeric molten salt comprises a monomeric nitrate, a monomeric carbonate, a monomeric sulfate, a monomeric silicate, or a monomeric chloride; or their respective aqueous Crystalline salt;
所述单体硝酸盐包括：硝酸钾、硝酸钠、亚硝酸钠、硝酸锂、或硝酸钙等；或它们各自的含水结晶盐；例如，所述硝酸钙的含水结晶盐可以是四水硝酸钙(熔点40℃)等；The monomer nitrate includes: potassium nitrate, sodium nitrate, sodium nitrite, lithium nitrate, or calcium nitrate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the calcium nitrate may be calcium nitrate tetrahydrate (melting point 40 ° C), etc.;
所述单体碳酸盐包括：碳酸钾(熔点891℃)、碳酸钠(熔点851℃)、或碳酸锂(熔点618℃)等；或它们各自的含水结晶盐；例如，碳酸钠的含水结晶盐可以是一水碳酸钠、七水碳酸钠、或十水碳酸钠；The monomeric carbonate includes: potassium carbonate (melting point 891 ° C), sodium carbonate (melting point 851 ° C), or lithium carbonate (melting point 618 ° C), etc.; or their respective aqueous crystalline salts; for example, aqueous crystallization of sodium carbonate The salt may be sodium carbonate monohydrate, sodium carbonate heptahydrate or sodium carbonate decahydrate;
所述单体硫酸盐包括：硫酸镁(熔点1124℃)、硫酸钠(熔点884℃)等；或它们各自的 含水结晶盐；例如，硫酸镁的含水结晶盐可以是七水硫酸镁；所述硫酸钠可以是十水合硫酸钠；The monomeric sulfate includes: magnesium sulfate (melting point 1124 ° C), sodium sulfate (melting point 884 ° C), etc.; or their respective An aqueous crystalline salt; for example, the aqueous crystalline salt of magnesium sulfate may be magnesium sulfate heptahydrate; the sodium sulfate may be sodium sulfate decahydrate;
所述单体硅酸盐包括：硅酸钠(熔点1089℃)、硅酸锂(熔点1255℃)、偏硅酸钠(熔点1088℃)或二硅五氧酸钠等；或它们各自的含水结晶盐；例如，所述偏硅酸钠的含水结晶盐可以是五水偏硅酸钠、或九水偏硅酸钠；The monomeric silicate comprises: sodium silicate (melting point 1089 ° C), lithium silicate (melting point 1255 ° C), sodium metasilicate (melting point 1088 ° C) or sodium disilicate pentoxide; or their respective water containing a crystalline salt; for example, the aqueous crystalline salt of the sodium metasilicate may be sodium metasilicate pentahydrate or sodium metasilicate pentahydrate;
所述单体氯化盐包括：氯化钙(熔点782℃)、氯化钠(熔点891℃)、氯化镁(熔点1412℃)等。或它们各自的含水结晶盐；例如，氯化镁的含水结晶盐可以是六水氯化镁(熔点714℃)；The monomer chloride salt includes calcium chloride (melting point 782 ° C), sodium chloride (melting point 891 ° C), magnesium chloride (melting point 1412 ° C) and the like. Or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium chloride may be magnesium chloride hexahydrate (melting point 714 ° C);
所述二元复合熔盐包括：KNO3-NaNO3体系(熔点220℃)、K2CO3-Na2CO3体系、KNO3-NaNO2体系(熔点130℃)；The binary composite molten salt comprises: KNO 3 -NaNO 3 system (melting point 220 ° C), K 2 CO 3 -Na 2 CO 3 system, KNO 3 -NaNO 2 system (melting point 130 ° C);
所述三元复合熔盐包括：KNO3-NaNO3-NaNO2体系(熔点142℃)、NaNO3-KNO3-LiNO3体系(熔点126℃)、KNO3-NaNO3-Ca(NO3)2体系(熔点120℃)；The ternary composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 system (melting point 142 ° C), NaNO 3 -KNO 3 -LiNO 3 system (melting point 126 ° C), KNO 3 -NaNO 3 -Ca(NO 3 ) 2 system (melting point 120 ° C);
所述多元复合熔盐包括：KNO3-NaNO3-NaNO2-CsNO3体系、KNO3-NaNO3-NaNO2-Ca(NO3)2体系、KNO3-NaNO3-NaNO2-LiNO3体系(熔点250-550℃)、KNO3-NaNO3-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-LiNO3-CsNO3体系、Ca(NO3)24H2O-KNO3-NaNO3-LiNO3体系、KNO3-NaNO3-LiNO3-Ca(NO3)2体系、The multi-component composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 system, KNO 3 -NaNO 3 -NaNO 2 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -NaNO 2 -LiNO 3 system (melting point 250-550 ° C), KNO 3 -NaNO 3 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -LiNO 3 -CsNO 3 system, Ca(NO 3 ) 2 4H 2 O-KNO 3 -NaNO 3 -LiNO 3 system, KNO 3 -NaNO 3 -LiNO 3 -Ca(NO 3 ) 2 system,
KNO3-NaNO3-NaNO2-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-KNO2-CsNO3体系、K2CO3-Na2CO3-NaCl-Li2CO3体系、K2CO3-Na2CO3-Li2CO3-NaCl-MgO-CaO体系；KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -KNO 2 -CsNO 3 system, K 2 CO 3 -Na 2 CO 3 -NaCl-Li 2 CO 3 system , K 2 CO 3 -Na 2 CO 3 -Li 2 CO 3 -NaCl-MgO-CaO system;
上述各类型熔盐中，尤其是二元、三元、多元复合熔盐，它们的熔点随各自体系中的各单体组分量的变化而变化，但总体上各种熔盐的熔点范围处于40-1500℃。Among the above various types of molten salts, especially binary, ternary, and multi-component mixed molten salts, the melting points of which vary with the amount of each monomer component in the respective systems, but generally the melting points of various molten salts are in the range of 40 -1500 ° C.
上述实施例中，所述二元复合熔盐的具体体系配方记载于中国专利ZL201310731924、ZL201310732781、ZL201310733403、ZL201310733405以及中国专利申请CN201310732738中；In the above embodiments, the specific system formula of the binary composite molten salt is described in Chinese patents ZL201310731924, ZL201310732781, ZL201310733403, ZL201310733405, and Chinese patent application CN201310732738;
所述三元复合熔盐的具体体系配方记载于中国专利ZL201310029569、ZL201310732785和中国专利申请CN201310040070中；The specific system formula of the ternary composite molten salt is described in Chinese patents ZL201310029569, ZL201310732785 and Chinese patent application CN201310040070;
所述多元复合熔盐的具体体系配方记载于中国专利ZL201310053597、ZL201310731924、ZL201310732816、ZL201310731910及中国专利申请CN201310040909中。The specific system formulation of the multi-component composite molten salt is described in Chinese patents ZL201310053597, ZL201310731924, ZL201310732816, ZL201310731910 and Chinese patent application CN201310040909.
本发明更具体的一些实施例所提供的可溶型芯的配方如下表1所示：The formulation of the soluble core provided by some more specific embodiments of the present invention is shown in Table 1 below:
表1Table 1
Figure PCTCN2017113760-appb-000001
Figure PCTCN2017113760-appb-000001
Figure PCTCN2017113760-appb-000002
Figure PCTCN2017113760-appb-000002
Figure PCTCN2017113760-appb-000003
Figure PCTCN2017113760-appb-000003
Figure PCTCN2017113760-appb-000004
Figure PCTCN2017113760-appb-000004
Figure PCTCN2017113760-appb-000005
Figure PCTCN2017113760-appb-000005
Figure PCTCN2017113760-appb-000006
Figure PCTCN2017113760-appb-000006
Figure PCTCN2017113760-appb-000007
Figure PCTCN2017113760-appb-000007
Figure PCTCN2017113760-appb-000008
Figure PCTCN2017113760-appb-000008
Figure PCTCN2017113760-appb-000009
Figure PCTCN2017113760-appb-000009
Figure PCTCN2017113760-appb-000010
Figure PCTCN2017113760-appb-000010
第2组实施例：本发明可溶型芯的制备方法Group 2 embodiment: Preparation method of soluble core of the present invention
本发明的另一个方面还提供一种可溶型芯的制备方法，其特征在于，包括：将熔盐加热至熔融状态，形成熔融的熔盐体系，将二氧化硅和硅酸添加至所述熔融的熔盐体系中。Another aspect of the present invention provides a method for preparing a soluble core, comprising: heating a molten salt to a molten state to form a molten molten salt system, and adding silica and silicic acid to the In molten molten salt system.
在进一步的实施例中，所述制备方法还包括：将二氧化硅和硅酸添加至所述熔融的熔盐体系中后继续加热保温12小时。In a further embodiment, the method of preparation further comprises: adding silica and silicic acid to the molten molten salt system and continuing to heat for 12 hours.
在更进一步的实施例中，所述制备方法还包括：待添加了二氧化硅和硅酸的熔融的熔盐体系凝固后即制成所述可溶型芯。In still further embodiments, the preparation method further comprises: forming the soluble core after the molten molten salt system to which silica and silicic acid are added is solidified.
在一些实施例中，所述熔盐、二氧化硅、硅酸的重量份配比为：熔盐80-99份；二氧化硅1-20份；硅酸1-5份；In some embodiments, the parts by weight of the molten salt, silica, and silicic acid are: 80-99 parts of molten salt; 1-20 parts of silica; 1-5 parts of silicic acid;
所述熔融的熔盐体系通过搅拌形成均一的熔融的熔盐体系。The molten molten salt system forms a uniform molten molten salt system by stirring.
在另一些实施例中，所述加热指梯度加热至熔融状态。In other embodiments, the heating refers to a gradient heating to a molten state.
在具体的实施例中，所述熔盐为单体熔盐四水硝酸钙；所述二氧化硅选自纳米二氧化硅，和/或水合二氧化硅。In a specific embodiment, the molten salt is a monomeric molten salt of calcium nitrate tetrahydrate; the silica is selected from the group consisting of nanosilica, and/or hydrated silica.
第3组实施例：本发明可溶型芯的应用Group 3 embodiment: application of the soluble core of the present invention
本发明的第三个方面提供第1组实施例任一项方案所述的可溶型芯和/或第2组实施例任一项方案提供的制备方法在铸造、模具方面的应用。任何规模地出于商业目的制造、使用、销售、许诺销售本发明所述的可溶型芯、和/或，使用本发明所述的制备方法的行为，均落入本发明请求保护的范围。A third aspect of the present invention provides the use of the soluble core according to any one of the first group of embodiments and/or the preparation method provided by any one of the second embodiment, in casting and mold. The manufacture, use, sale, and sale of a soluble core of the present invention for commercial purposes on any scale, and/or the use of the preparation methods described herein, are within the scope of the claimed invention.
在本组所有的实施例中，都具有如下共同特征：将本发明第1组实施例任一项方案所述的可溶型芯放入商品包装内，和/或，所述可溶型芯上标记有商品编号、批次、商标和/或商品名。 In all of the embodiments of the present group, the common feature is that the soluble core according to any one of the first group of embodiments of the present invention is placed in a commodity package, and/or the soluble core The product number, lot, trademark, and/or trade name are marked on it.
实验例、本发明可溶型芯与现有可溶型芯的性能对比Experimental example, performance comparison between the soluble core of the present invention and the existing soluble core
制备过程：Preparation Process:
(1)按上述实施例表1提供的配方先将熔盐放入刚玉坩埚内，混合搅拌；(1) according to the formulation provided in Table 1 of the above embodiment, the molten salt is first placed in the corundum crucible, and mixed and stirred;
(2)将混合后的熔盐置于烘箱中，搅拌状态下梯度加热至熔融状态后，继续搅拌，使熔盐成为均一熔融的液体体系；(2) placing the mixed molten salt in an oven, heating the mixture to a molten state under stirring, and continuing to stir, so that the molten salt becomes a uniformly molten liquid system;
(3)根据上述实施例表1记载的配比，取一定比例的纳米二氧化硅、硅酸、水合二氧化硅加入到液态的熔融盐液体中，继续在所述熔点温度加热保温12小时。(3) According to the ratios shown in Table 1 of the above examples, a certain proportion of nano silica, silicic acid, and hydrated silica were added to the liquid molten salt liquid, and heating was continued for 12 hours at the melting point temperature.
(4)在不同温度条件下，观察混合样品的熔化情况和粘度特性，这一步的作用是根据观察到的样品熔化情况和粘度特性，初步确定熔融样品流入模具的时间，是否能均匀的充满模具。(4) Observe the melting condition and viscosity characteristics of the mixed sample under different temperature conditions. The function of this step is to determine the time when the molten sample flows into the mold according to the observed melting condition and viscosity characteristics of the sample, and whether the mold can be uniformly filled. .
(5)冷却后制得本发明的型芯，并按本领域常规检测方法测定型芯的各项性能指标，同时测定2种现有的可溶型芯的相同性能指标，测得结果如下表2所示。(5) After cooling, the core of the invention is prepared, and the performance indexes of the core are determined according to the conventional detection methods in the art, and the same performance indexes of the two existing soluble cores are simultaneously measured, and the measured results are as follows: 2 is shown.
表2Table 2
Figure PCTCN2017113760-appb-000011
Figure PCTCN2017113760-appb-000011
需要特别说明的是：在表1的实施例1-361所代表的本发明可溶型芯产品中，只有和实施例143、实施例294对应配方获得的型芯产品的脱芯时间分别为8分钟和10分钟，实施例34和57的型芯产品的吸湿率分别为0.1％和0.15％，其它实施例的可溶型芯的脱芯时间均在 2-7分钟之间，吸湿率在0.06％-0.08％之间。It should be particularly noted that in the soluble core product of the present invention represented by the embodiment 1-361 of Table 1, only the core products obtained by the formulations corresponding to the examples 143 and 294 have a core removal time of 8 respectively. The moisture absorption rates of the core products of Examples 34 and 57 were 0.1% and 0.15%, respectively, in minutes and 10 minutes, and the core removal times of the soluble cores of the other examples were Between 2 and 7 minutes, the moisture absorption rate is between 0.06% and 0.08%.
上表2中，各项性能指标对应的单位是型芯领域普通技术人员通常理解并常规知晓的，并且上述各项性能指标的测试方法为本领域常规测试手段；上表2中，现有可溶型芯A为市售的某品牌、某批次可溶型芯产品；现有可溶型芯B为《M-84可溶型芯混合料的研究》一文披露的具有最优性能的可溶型芯。由于本文的表1仅仅是例举性地罗列了数百种本发明的可溶型芯方案，而本发明请求保护的可溶型芯远不止这些，因此相应地，各具体的可溶型芯对应的性能数据也均不相同，但本发明请求保护的各个具体的可溶型芯的各项性能指标都稳定保持在上表2第2行所记载的数据范围所表征的水平，处于节约篇幅的目的，本文不再穷尽式地例举表1以外其它各项具体可溶型芯方案，也不在此一一罗列各项可溶型芯的单独的性能数值。 In Table 2 above, the units corresponding to the performance indicators are generally understood and conventionally known by those skilled in the core field, and the test methods of the above various performance indicators are conventional testing methods in the field; The dissolved core A is a commercially available brand and a batch of soluble core products; the existing soluble core B is the best performance disclosed in the article "Research on M-84 soluble core mixture" Solvent core. Since Table 1 herein merely exemplifies a list of hundreds of soluble core solutions of the present invention, the soluble cores claimed in the present invention are far more than these, and accordingly, each specific soluble core Corresponding performance data are also different, but the performance indexes of each specific soluble core claimed in the present invention are stably maintained at the level indicated by the data range described in the second row of Table 2, which is saving space. For the purpose of this article, the specific soluble core schemes other than Table 1 are not exhaustively described herein, and the individual performance values of the soluble cores are not listed here.

Claims (10)

  1. 一种可溶型芯，其特征在于，包括熔盐、二氧化硅、硅酸；所述熔盐为水溶性熔盐，且其熔点为40-1500℃；a soluble core characterized by comprising a molten salt, silica, silicic acid; the molten salt is a water-soluble molten salt, and its melting point is 40-1500 ° C;
    所述熔盐、二氧化硅、硅酸的重量份配比为：熔盐80-99份；二氧化硅1-20份；硅酸1-5份。The proportion by weight of the molten salt, silica, and silicic acid is: 80-99 parts of molten salt; 1-20 parts of silica; 1-5 parts of silicic acid.
  2. 根据权利要求1所述的可溶型芯，其特征在于，所述熔盐选自单体熔盐、二元复合熔盐、三元复合熔盐、或多元复合熔盐。The soluble core according to claim 1, wherein the molten salt is selected from the group consisting of a monomer molten salt, a binary composite molten salt, a ternary composite molten salt, or a multicomponent composite molten salt.
  3. 根据权利要求1所述的可溶型芯，其特征在于，所述二氧化硅选自纳米二氧化硅，和/或水合二氧化硅。A soluble core according to claim 1 wherein the silica is selected from the group consisting of nanosilica, and/or hydrated silica.
  4. 根据权利要求1或2所述的可溶型芯，其特征在于，所述单体熔盐包括单体硝酸盐、单体碳酸盐、单体硫酸盐、单体硅酸盐、或单体氯化盐；或它们各自的含水结晶盐；The soluble core according to claim 1 or 2, wherein the monomer molten salt comprises a monomeric nitrate, a monomeric carbonate, a monomeric sulfate, a monomeric silicate, or a monomer. Chloride salts; or their respective aqueous crystalline salts;
    所述单体硝酸盐包括：硝酸钾、硝酸钠、亚硝酸钠、硝酸锂、或硝酸钙等；或它们各自的含水结晶盐；例如，所述硝酸钙的含水结晶盐可以是四水硝酸钙等；The monomer nitrate includes: potassium nitrate, sodium nitrate, sodium nitrite, lithium nitrate, or calcium nitrate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the calcium nitrate may be calcium nitrate tetrahydrate Wait;
    所述单体碳酸盐包括：碳酸钾、碳酸钠、或碳酸锂等；或它们各自的含水结晶盐；例如，碳酸钠的含水结晶盐可以是一水碳酸钠、七水碳酸钠、或十水碳酸钠；The monomeric carbonate includes: potassium carbonate, sodium carbonate, or lithium carbonate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of sodium carbonate may be sodium carbonate monohydrate, sodium carbonate heptahydrate, or ten Sodium carbonate of water;
    所述单体硫酸盐包括：硫酸镁、硫酸钠等；或它们各自的含水结晶盐；例如，硫酸镁的含水结晶盐可以是七水硫酸镁；所述硫酸钠可以是十水合硫酸钠；The monomer sulfate includes: magnesium sulfate, sodium sulfate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium sulfate may be magnesium sulfate heptahydrate; the sodium sulfate may be sodium sulfate decahydrate;
    所述单体硅酸盐包括：硅酸钠、硅酸锂、偏硅酸钠或二硅五氧酸钠等；或它们各自的含水结晶盐；例如，所述偏硅酸钠的含水结晶盐可以是五水偏硅酸钠、或九水偏硅酸钠；The monomeric silicate comprises: sodium silicate, lithium silicate, sodium metasilicate or sodium disilicate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the sodium metasilicate It may be sodium metasilicate pentahydrate or sodium metasilicate pentahydrate;
    所述单体氯化盐包括：氯化钙、氯化钠、氯化镁等。或它们各自的含水结晶盐；例如，氯化镁的含水结晶盐可以是六水氯化镁；The monomer chloride salt includes calcium chloride, sodium chloride, magnesium chloride and the like. Or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium chloride may be magnesium chloride hexahydrate;
    所述二元复合熔盐包括：KNO3-NaNO3体系、K2CO3-Na2CO3体系、KNO3-NaNO2体系；The binary composite molten salt includes: a KNO 3 -NaNO 3 system, a K 2 CO 3 -Na 2 CO 3 system, and a KNO 3 -NaNO 2 system;
    所述三元复合熔盐包括：KNO3-NaNO3-NaNO2体系、NaNO3-KNO3-LiNO3体系、KNO3-NaNO3-Ca(NO3)2体系；The ternary composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 system, NaNO 3 -KNO 3 -LiNO 3 system, KNO 3 -NaNO 3 -Ca(NO 3 ) 2 system;
    所述多元复合熔盐包括：KNO3-NaNO3-NaNO2-CsNO3体系、KNO3-NaNO3-NaNO2-Ca(NO3)2体系、KNO3-NaNO3-NaNO2-LiNO3体系、KNO3-NaNO3-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-LiNO3-CsNO3体系、Ca(NO3)24H2O-KNO3-NaNO3-LiNO3体系、KNO3-NaNO3-NaNO2-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-KNO2-CsNO3体系、K2CO3-Na2CO3-NaCl-Li2CO3体系、K2CO3-Na2CO3-Li2CO3-NaCl-MgO-CaO体系。The multi-component composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 system, KNO 3 -NaNO 3 -NaNO 2 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -NaNO 2 -LiNO 3 system , KNO 3 -NaNO 3 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -LiNO 3 -CsNO 3 system, Ca(NO 3 ) 2 4H2O-KNO3-NaNO3-LiNO3 system, KNO 3 -NaNO 3- NaNO 2 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -KNO 2 -CsNO 3 system, K 2 CO 3 -Na 2 CO 3 -NaCl-Li 2 CO 3 system, K 2 CO 3- Na 2 CO 3 -Li 2 CO 3 -NaCl-MgO-CaO system.
  5. 一种可溶型芯的制备方法，其特征在于，包括：将熔盐加热至熔融状态，形成熔融的熔盐体系；将二氧化硅和硅酸添加至所述熔融的熔盐体系中； A method for preparing a soluble core, comprising: heating a molten salt to a molten state to form a molten molten salt system; adding silica and silicic acid to the molten molten salt system;
    所述熔盐为水溶性熔盐，且其熔点为60-1200℃；The molten salt is a water-soluble molten salt, and has a melting point of 60-1200 ° C;
    所述熔盐、二氧化硅、硅酸的重量份配比为：熔盐80-99份；二氧化硅1-20份；硅酸1-5份。The proportion by weight of the molten salt, silica, and silicic acid is: 80-99 parts of molten salt; 1-20 parts of silica; 1-5 parts of silicic acid.
  6. 根据权利要求5所述的制备方法，其特征在于，还包括：将二氧化硅和硅酸添加至所述熔融的熔盐体系中后继续加热保温12小时。The method according to claim 5, further comprising: adding silica and silicic acid to the molten molten salt system and continuing to heat and hold for 12 hours.
  7. 根据权利要求5或6所述的制备方法，其特征在于，还包括：待添加了二氧化硅和硅酸的熔融的熔盐体系凝固后即制成所述可溶型芯；The preparation method according to claim 5 or 6, further comprising: forming a soluble core after the molten molten salt system to which silica and silicic acid are added is solidified;
    所述熔融的熔盐体系通过搅拌形成均一的熔融的熔盐体系；The molten molten salt system forms a uniform molten molten salt system by stirring;
    所述加热指梯度加热至熔融状态。The heating refers to heating the gradient to a molten state.
  8. 根据权利要求5-7任一所述的制备方法，其特征在于，所述熔盐选自单体熔盐、二元复合熔盐、三元复合熔盐或多元复合熔盐；The preparation method according to any one of claims 5 to 7, wherein the molten salt is selected from the group consisting of a monomer molten salt, a binary composite molten salt, a ternary composite molten salt or a multicomponent composite molten salt;
    所述二氧化硅选自纳米二氧化硅，和/或水合二氧化硅。The silica is selected from the group consisting of nanosilica, and/or hydrated silica.
  9. 根据权利要求8所述的制备方法，其特征在于，所述单体熔盐包括单体硝酸盐、单体碳酸盐、单体硫酸盐、单体硅酸盐、或单体氯化盐；或它们各自的含水结晶盐；The preparation method according to claim 8, wherein the monomer molten salt comprises a monomer nitrate, a monomer carbonate, a monomer sulfate, a monomer silicate, or a monomer chloride; Or their respective aqueous crystalline salts;
    所述单体硝酸盐包括：硝酸钾、硝酸钠、亚硝酸钠、硝酸锂、或硝酸钙等；或它们各自的含水结晶盐；例如，所述硝酸钙的含水结晶盐可以是四水硝酸钙等；The monomer nitrate includes: potassium nitrate, sodium nitrate, sodium nitrite, lithium nitrate, or calcium nitrate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the calcium nitrate may be calcium nitrate tetrahydrate Wait;
    所述单体碳酸盐包括：碳酸钾、碳酸钠、或碳酸锂等；或它们各自的含水结晶盐；例如，碳酸钠的含水结晶盐可以是一水碳酸钠、七水碳酸钠、或十水碳酸钠；The monomeric carbonate includes: potassium carbonate, sodium carbonate, or lithium carbonate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of sodium carbonate may be sodium carbonate monohydrate, sodium carbonate heptahydrate, or ten Sodium carbonate of water;
    所述单体硫酸盐包括：硫酸镁、硫酸钠等；或它们各自的含水结晶盐；例如，硫酸镁的含水结晶盐可以是七水硫酸镁；所述硫酸钠可以是十水合硫酸钠；The monomer sulfate includes: magnesium sulfate, sodium sulfate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium sulfate may be magnesium sulfate heptahydrate; the sodium sulfate may be sodium sulfate decahydrate;
    所述单体硅酸盐包括：硅酸钠、硅酸锂、偏硅酸钠或二硅五氧酸钠等；或它们各自的含水结晶盐；例如，所述偏硅酸钠的含水结晶盐可以是五水偏硅酸钠、或九水偏硅酸钠；The monomeric silicate comprises: sodium silicate, lithium silicate, sodium metasilicate or sodium disilicate, etc.; or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of the sodium metasilicate It may be sodium metasilicate pentahydrate or sodium metasilicate pentahydrate;
    所述单体氯化盐包括：氯化钙、氯化钠、氯化镁等。或它们各自的含水结晶盐；例如，氯化镁的含水结晶盐可以是六水氯化镁；The monomer chloride salt includes calcium chloride, sodium chloride, magnesium chloride and the like. Or their respective aqueous crystalline salts; for example, the aqueous crystalline salt of magnesium chloride may be magnesium chloride hexahydrate;
    所述二元复合熔盐包括：KNO3-NaNO3体系、K2CO3-Na2CO3体系、KNO3-NaNO2体系；The binary composite molten salt includes: a KNO 3 -NaNO 3 system, a K 2 CO 3 -Na 2 CO 3 system, and a KNO 3 -NaNO 2 system;
    所述三元复合熔盐包括：KNO3-NaNO3-NaNO2体系、NaNO3-KNO3-LiNO3体系、KNO3-NaNO3-Ca(NO3)2体系；The ternary composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 system, NaNO 3 -KNO 3 -LiNO 3 system, KNO 3 -NaNO 3 -Ca(NO 3 ) 2 system;
    所述多元复合熔盐包括：KNO3-NaNO3-NaNO2-CsNO3体系、KNO3-NaNO3-NaNO2-Ca(NO3)2体系、KNO3-NaNO3-NaNO2-LiNO3体系、KNO3-NaNO3-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-LiNO3-CsNO3体系、Ca(NO3)24H2O-KNO3-NaNO3-LiNO3体系、 KNO3-NaNO3-NaNO2-CsNO3-Ca(NO3)2体系、KNO3-NaNO3-KNO2-CsNO3体系、K2CO3-Na2CO3-NaCl-Li2CO3体系、K2CO3-Na2CO3-Li2CO3-NaCl-MgO-CaO体系。The multi-component composite molten salt comprises: KNO 3 -NaNO 3 -NaNO 2 -CsNO 3 system, KNO 3 -NaNO 3 -NaNO 2 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -NaNO 2 -LiNO 3 system , KNO 3 -NaNO 3 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -LiNO 3 -CsNO 3 system, Ca(NO 3 ) 2 4H2O-KNO3-NaNO3-LiNO3 system, KNO 3 -NaNO 3- NaNO 2 -CsNO 3 -Ca(NO 3 ) 2 system, KNO 3 -NaNO 3 -KNO 2 -CsNO 3 system, K 2 CO 3 -Na 2 CO 3 -NaCl-Li 2 CO 3 system, K 2 CO 3- Na 2 CO 3 -Li 2 CO 3 -NaCl-MgO-CaO system.
  10. 权利要求1-4任一所述的可溶型芯和/或权利要求5-9任一所述的制备方法在铸造、模具领域的应用。 Use of the soluble core of any of claims 1-4 and/or the preparation method of any of claims 5-9 in the field of casting and moulding.
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