WO2022163464A1 - 無機コーテッドサンド - Google Patents

無機コーテッドサンド Download PDF

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Publication number
WO2022163464A1
WO2022163464A1 PCT/JP2022/001786 JP2022001786W WO2022163464A1 WO 2022163464 A1 WO2022163464 A1 WO 2022163464A1 JP 2022001786 W JP2022001786 W JP 2022001786W WO 2022163464 A1 WO2022163464 A1 WO 2022163464A1
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WIPO (PCT)
Prior art keywords
mass
parts
inorganic
inorganic binder
coated sand
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Ceased
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PCT/JP2022/001786
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English (en)
French (fr)
Japanese (ja)
Inventor
宏明 青沼
佳祐 中根
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Kao Corp
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Kao Corp
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Priority to EP22745685.2A priority Critical patent/EP4286072A4/en
Priority to CN202280012044.9A priority patent/CN116801998A/zh
Publication of WO2022163464A1 publication Critical patent/WO2022163464A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
    • B22C1/186—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents contaming ammonium or metal silicates, silica sols
    • B22C1/188—Alkali metal silicates
    • 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
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • 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
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • B22C1/10—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
    • 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
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents

Definitions

  • the present invention relates to inorganic coated sand.
  • an inorganic coated sand having a refractory aggregate and an inorganic binder layer formed on the surface of the refractory aggregate is used to mold the desired shape.
  • Techniques related to such inorganic coated sand include, for example, those described in JP-A-2014-117740 (Patent Document 1) and International Publication No. 2015/194550 (Patent Document 2).
  • Patent Document 1 a coating layer of the caking material is formed on the surface of the refractory aggregate by mixing a specific water glass aqueous solution as a caking material with a heated refractory aggregate and evaporating the moisture.
  • a method for producing a dry coated sand having normal temperature fluidity is described.
  • Patent Document 2 a molding material mixture containing at least a caking material having refractory aggregate and water glass as essential components, and a carbonate and/or a borate is used and heated to a specific temperature.
  • a method of making a mold is described in which the mold is filled and held to harden.
  • a method of suppression is provided.
  • An inorganic coated sand having a refractory aggregate and an inorganic binder layer formed on the surface of the refractory aggregate,
  • the inorganic binder layer contains one or more selected from zinc oxide and magnesium oxide,
  • An inorganic coated sand is provided in which the total content of the zinc oxide and the magnesium oxide is 6 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the inorganic binder.
  • FIG. 4 is a cross-sectional view for explaining a method of measuring deformation of a mold in Examples.
  • the present invention provides a method for suppressing deformation of a mold made using inorganic coated sand during casting.
  • the present invention also provides an inorganic coated sand that suppresses mold deformation that occurs during casting.
  • the present inventors found that in a mold prepared using an inorganic coated sand having a refractory aggregate and an inorganic binder layer formed on the surface of the refractory aggregate, zinc oxide was added to the inorganic binder layer.
  • the inventors have found that the deformation of the mold during casting can be suppressed by containing magnesium oxide.
  • the present invention it is possible to provide a method for suppressing deformation of a mold made using inorganic coated sand during casting. Moreover, according to the present invention, it is possible to provide an inorganic coated sand that suppresses mold deformation during casting.
  • the method for suppressing deformation of the mold during casting is a mold made using inorganic coated sand having a refractory aggregate and an inorganic binder layer formed on the surface of the refractory aggregate.
  • the inorganic binder layer contains one or more selected from zinc oxide and magnesium oxide, and relative to 100 parts by mass of the inorganic binder, specifically relative to 100 parts by mass of the solid content of the inorganic binder
  • the total content of zinc oxide and magnesium oxide is 6 parts by mass or more and 70 parts by mass or less.
  • the reason why the effect of suppressing the deformation of the mold is exhibited is not clear, but it is considered as follows.
  • Zinc oxide or magnesium oxide forms a salt with alkali metal ions of alkali silicate or alkali metasilicate, releasing alkali metal ions that inhibit cross-linking of silicate chains from the system and promoting cross-linking of silicate chains. , to consolidate the silicate network.
  • the softening point of the inorganic binder rises, and even when the mold is exposed to the heat of the molten metal, it is thought that deformation due to the softening of the inorganic binder is less likely to occur.
  • the method for producing the inorganic coated sand and the mold will be described in more detail below.
  • the inorganic coated sand has a refractory aggregate and an inorganic binder layer formed on the surface of the refractory aggregate.
  • the inorganic binder layer contains one or more selected from zinc oxide and magnesium oxide.
  • the total content of zinc oxide and magnesium oxide is 6 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the inorganic binder, specifically with respect to 100 parts by mass of the solid content of the inorganic binder.
  • the inorganic coated sand is specifically composed of inorganic coated sand particle groups, and the refractory aggregate is specifically composed of refractory aggregate particle groups.
  • the inorganic coated sand is preferably spherical from the viewpoint of improving the fluidity and further improving the fillability of the molding die.
  • the spherical inorganic coated sand means that the inorganic coated sand has a round shape like a ball.
  • the sphericity of the inorganic coated sand is preferably 0.75 or more, more preferably 0.75 or more, from the viewpoints of fluidity, mold quality and mold strength improvement, and from the viewpoint of ease of molding. It is 80 or more, more preferably 0.82 or more. Further, the upper limit of the sphericity is specifically 1 or less.
  • the sphericity of the inorganic coated sand is determined by image analysis of a particle image (photograph) obtained by an optical microscope or a digital scope (for example, VH-8000 manufactured by Keyence Corporation). and the perimeter of the cross section, then [the circumference of a perfect circle having the same area as the grain projected cross section (mm 2 )]/[perimeter of the grain projected cross section (mm)] can be calculated and averaged for any 50 particles.
  • the average particle size of the inorganic coated sand is preferably 0.05 mm or more, more preferably 0.1 mm or more, from the viewpoints of mold quality and mold strength improvement and ease of molding.
  • the average particle size of the inorganic coated sand is equal to or greater than the above lower limit, the amount of the inorganic binder layer used can be reduced during the production of the mold, making it easier to recycle the inorganic coated sand. It is also preferable in terms of The average particle size of the inorganic coated sand is preferably 2 mm or less, more preferably 1 mm or less, and even more preferably 0.5 mm or less, from the viewpoints of mold quality and mold strength improvement and ease of molding.
  • the average particle size of the inorganic coated sand is equal to or less than the above upper limit, the porosity is reduced during the production of the mold, which is also preferable in that the strength of the mold can be increased.
  • the average particle size of the inorganic coated sand and the later-described refractory aggregate can be specifically measured by the following method.
  • the major axis diameter and minor axis diameter of the particles are obtained by taking an image (photograph) of the particles with an optical microscope or a digital scope (eg, VH-8000 manufactured by Keyence Corporation) and analyzing the obtained image. can ask.
  • Materials for the refractory aggregate include one or more selected from the group consisting of natural sand and artificial sand.
  • natural sand examples include one or more selected from the group consisting of silica sand, chromite sand, zircon sand, olivine sand, and alumina sand containing quartz as a main component.
  • artificial sand examples include synthetic mullite sand, SiO2 - based foundry sand containing SiO2 as a main component, Al2O3 - based foundry sand containing Al2O3 as a main component , and SiO2 / Al2O3 .
  • the main component means the most abundant component among the components contained in sand.
  • the artificial sand is not foundry sand produced from nature, but foundry sand obtained by artificially preparing a metal oxide component and melting or sintering it.
  • recovered sand obtained by recovering used refractory aggregates and reclaimed sand obtained by subjecting recovered sand to reclaim treatment can also be used.
  • the refractory aggregate is preferably in the form of particles from the viewpoint of improving the fluidity of the inorganic coated sand and further improving the fillability of the molding die.
  • the average particle size of the refractory aggregate is preferably 0.05 mm or more, more preferably 0.1 mm or more, from the viewpoint of improving mold quality and mold strength, and from the viewpoint of ease of molding. .
  • the average particle size of the refractory aggregate is equal to or greater than the above lower limit, the amount of the inorganic binder layer used can be reduced when manufacturing the mold, making it easier to recycle the inorganic coated sand.
  • the average particle size of the refractory aggregate is preferably 2 mm or less, more preferably 1 mm or less, and still more preferably 0.5 mm or less, from the viewpoint of mold quality and mold strength improvement and from the viewpoint of ease of molding. is. Further, when the average particle size of the refractory aggregate is equal to or less than the above upper limit, the porosity is reduced during the production of the mold, which is also preferable in that the strength of the mold can be increased.
  • the inorganic binder layer specifically contains an inorganic binder and one or more selected from zinc oxide and magnesium oxide.
  • the inorganic binder layer is specifically a coating layer formed on the surface of the refractory aggregate.
  • the inorganic binder layer is, for example, a layer coated with a mixture of one or more selected from an inorganic binder, zinc oxide and magnesium oxide; A layer further coated with one or more compounds selected from magnesium; or zinc oxide and zinc oxide on a layer coated with a mixture of an inorganic binder and one or more compounds selected from zinc oxide and magnesium oxide.
  • the layer may be further coated with one or more compounds selected from magnesium.
  • the content of the inorganic binder layer in the inorganic coated sand is preferably 0.05% by mass or more, more preferably It is 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and particularly preferably 1.5% by mass or more.
  • the content of the inorganic binder layer in the inorganic coated sand is is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 6% by mass or less, even more preferably 4.5% by mass or less, and even more preferably 4% by mass or less.
  • the content of the inorganic binder layer refers to the content excluding water contained in the inorganic binder layer.
  • the content is calculated in terms of sodium metasilicate.
  • the content of the inorganic binder layer with respect to 100 parts by mass of the refractory aggregate in the inorganic coated sand is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass, from the viewpoint of improving mold strength. Above, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and most preferably 1.5 parts by mass or more.
  • the content of the inorganic binder layer with respect to 100 parts by mass of the refractory aggregate in the inorganic coated sand is preferably 10. It is not more than 8 parts by mass, more preferably not more than 8 parts by mass, even more preferably not more than 6 parts by mass, still more preferably not more than 4.5 parts by mass, and even more preferably not more than 4 parts by mass.
  • the inorganic binder contains, for example, a silicic acid compound, preferably at least one selected from sodium silicate and sodium metasilicate, from the viewpoint of excellent productivity and availability.
  • the inorganic binder may further contain a water-soluble silicic acid compound other than the above as a main component.
  • silicate compounds other than sodium silicate and sodium metasilicate include potassium silicate, potassium metasilicate, lithium silicate, and ammonium silicate.
  • sodium silicate examples include one or more selected from the group consisting of sodium silicate Nos. 1 to 5.
  • sodium silicate is classified into Nos. 1 to 5 according to the molar ratio of SiO 2 /Na 2 O, and sodium silicate Nos. 1 to 3 are defined in JIS-K-1408.
  • the molar ratio of SiO 2 /Na 2 O in each item is as follows.
  • Sodium silicate No. 1: SiO 2 /Na 2 O molar ratio 2.0 to 2.3
  • Sodium silicate No. 2: SiO 2 /Na 2 O molar ratio 2.4 to 2.6
  • Sodium silicate No. 3: SiO 2 /Na 2 O molar ratio 2.8 to 3.3
  • SiO 2 /Na 2 O molar ratio 3.3 to 3.5
  • the molar ratio of SiO 2 /Na 2 O may be adjusted to a desired degree.
  • Sodium silicate is preferably at least one selected from No. 1 water glass and No. 3 water glass.
  • Sodium metasilicate is preferably a hydrate from the viewpoint of improving the productivity of the inorganic coated sand and the productivity of the casting mold. From the above viewpoint, the sodium metasilicate hydrate is preferably at least one selected from sodium metasilicate pentahydrate and sodium metasilicate nonahydrate, and more preferably sodium metasilicate nonahydrate.
  • the content of the inorganic binder in the inorganic binder layer is preferably 25% by mass with respect to the entire inorganic binder layer from the viewpoint of improving the strength of the mold and improving the surface shape of the mold. more preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more.
  • the content of the inorganic binder in the inorganic binder layer is preferably 94% by mass or less with respect to the entire inorganic binder layer, and more preferably. is 93% by mass or less.
  • the content of the inorganic binder in the inorganic binder layer refers to the content of the inorganic binder excluding water with respect to the entire components other than water in the inorganic binder layer.
  • the total content of sodium silicate and sodium metasilicate in the inorganic binder is preferably 80% by mass or more from the viewpoint of improving the mold strength, the viewpoint of excellent productivity, and the viewpoint of availability. It is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably substantially 100% by mass.
  • the term "substantially” means that it can contain unintentionally contained components, for example, components other than sodium silicate and sodium metasilicate contained in sodium silicate and sodium metasilicate which are raw materials.
  • the total content of sodium silicate and sodium metasilicate in the inorganic binder refers to the total content of sodium silicate and sodium metasilicate with respect to all components other than water in the inorganic binder.
  • the content of the inorganic binder in the inorganic coated sand is preferably 0.00% per 100 parts by mass of the refractory aggregate from the viewpoint of improving the strength of the mold and improving the surface shape of the mold.
  • 03 parts by mass or more more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, still more preferably 0.8 parts by mass or more, and most preferably 1 part by mass or more.
  • the content of the inorganic binder in the inorganic coated sand is preferably 5 parts by mass or less, more preferably 5 parts by mass or less with respect to 100 parts by mass of the refractory aggregate. is 4 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.
  • the properties of zinc oxide (ZnO) and magnesium oxide (MgO) are preferably fine particles from the viewpoint of enhancing reactivity with the inorganic binder.
  • the average particle size of zinc oxide and magnesium oxide is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, even more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less, from the viewpoint of enhancing reactivity with the inorganic binder. Even more preferably, it is 15 ⁇ m or less.
  • the average particle size of zinc oxide and magnesium oxide is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, and still more preferably 0.1 ⁇ m or more, from the viewpoint of ease of handling and availability. It is 5 ⁇ m or more, more preferably 1 ⁇ m or more.
  • the average particle size of zinc oxide and magnesium oxide can be determined using the following measuring method. (Method for measuring average particle size) It is the average particle diameter of 50% volume cumulative measured using a laser diffraction particle size distribution analyzer LA-960V2 (manufactured by HORIBA, Ltd.). Analysis conditions are as follows. ⁇ Measurement method: flow method ⁇ Dispersion medium: water ⁇ Dispersion method: stirring, built-in ultrasonic wave for 3 minutes ⁇ Sample concentration: 2 mg/100 mL ⁇ Refractive index: Refractive index of each oxide (zinc oxide: 2.00, magnesium oxide: 1.76)
  • the total content of zinc oxide and magnesium oxide in the inorganic binder layer is preferably 2 masses with respect to all components other than water in the inorganic binder layer. % or more, more preferably 3 mass % or more. Further, from the viewpoint of improving mold strength, the total content of zinc oxide and magnesium oxide in the inorganic binder layer is preferably 45% by mass or less with respect to the total components other than water in the inorganic binder layer. , more preferably 40% by mass or less, and still more preferably 35% by mass or less.
  • the total content of zinc oxide and magnesium oxide with respect to 100 parts by mass of the inorganic binder is preferably 6 parts by mass or more, more preferably 7 parts by mass or more, from the viewpoint of suppressing mold deformation at high temperatures. It is preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more.
  • zinc oxide and magnesium oxide are added after coating the refractory aggregate with an inorganic binder (external addition), dust scattering is suppressed.
  • the total content of zinc oxide and magnesium oxide with respect to 100 parts by mass of the inorganic binder is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 55 parts by mass or less, and still more Preferably, it is 50 parts by mass or less.
  • the inorganic binder layer may optionally contain various additives.
  • Other additives include humectants, moisture resistance improvers, coupling agents that strengthen the bond between the refractory aggregate and the inorganic binder, lubricants, surfactants, release agents, and the like.
  • moisturizing agents include polyhydric alcohols, water-soluble polymers, hydrocarbons, sugars, proteins, and inorganic compounds other than those mentioned above.
  • Moisture resistance improvers include metal oxides (excluding zinc oxide and magnesium oxide), carbonates, borates, sulfates, phosphates, and the like.
  • lubricants include waxes; fatty acid amides; alkylene fatty acid amides; stearic acid; stearyl alcohol; metal stearates such as lead stearate, zinc stearate, calcium stearate, and magnesium stearate; stearate; hydrogenated oil; Release agents include, for example, paraffin, wax, light oil, machine oil, spindle oil, insulating oil, waste oil, vegetable oil, fatty acid ester, organic acid, graphite fine particles, mica, vermiculite, fluorine-based release agent, and silicone-based release agent. stencil agents and the like.
  • the inorganic coated sand may further contain inorganic fine particles other than zinc oxide and magnesium oxide.
  • the inorganic fine particles preferably form part of the inorganic binder layer.
  • the inorganic binder layer preferably further contains inorganic fine particles on at least one of the layer and in the layer, and more preferably further contains inorganic fine particles on the layer.
  • the inorganic fine particles may be contained both on the inorganic binder layer and in the inorganic binder layer. By doing so, the particles of the inorganic coated sand are more firmly bound to each other via the inorganic fine particles, and as a result, the strength of the obtained template can be further improved.
  • the inorganic fine particles on the inorganic binder layer may be partially embedded in the inorganic binder layer.
  • inorganic fine particles include, but are not limited to, silica particles and silicon particles. From the viewpoint of improving the strength of the template, silica particles are preferred, and have a large specific surface area and are reactive with sodium silicate and sodium metasilicate. Amorphous silica particles are more preferable from the viewpoint of high These inorganic fine particles may be used singly or in combination of two or more.
  • the inorganic coated sand may further contain amorphous silica particles.
  • Amorphous silica particles preferably form part of the inorganic binder layer.
  • the degree of non-crystallization of the amorphous silica particles is preferably 80% or more, more preferably 90% or more, from the viewpoint of more firmly binding the particles of the inorganic coated sand through the amorphous silica particles. , more preferably 93% or more, even more preferably 95% or more, and particularly preferably 98% or more.
  • the upper limit of the degree of amorphousness of the amorphous silica particles is not limited, but is, for example, 100% or less, may be 99.8% or less, or may be 99% or less.
  • the degree of amorphousness of amorphous silica particles can be determined by the X-ray diffraction method shown below.
  • X-ray diffraction method Amorphous silica particles are pulverized in a mortar and pressed against an X-ray glass holder of a powder X-ray diffractometer for measurement.
  • the average particle diameter d50 in the weight-based particle size distribution of amorphous silica particles measured by a laser diffraction scattering particle size distribution measurement method is preferably 0.1 ⁇ m or more from the viewpoint of improving mold strength and improving handling properties. and more preferably 0.3 ⁇ m or more. Further, from the viewpoint of improving mold strength, the average particle diameter d50 of the amorphous silica particles is preferably 2.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, still more preferably 0.8 ⁇ m or less, and further preferably 0.8 ⁇ m or less. More preferably, it is 0.6 ⁇ m or less.
  • the average particle diameter d50 in the weight-based particle size distribution of the amorphous silica particles measured by the laser diffraction scattering particle size distribution measurement method is obtained, for example, by removing the inorganic binder layer from the inorganic coated sand by dissolving it with water and removing the non-crystalline silica particles. It can be obtained by taking out the crystalline silica particles and then measuring the particle size of the obtained amorphous silica particles by a laser diffraction scattering particle size distribution measurement method.
  • the average particle diameter d50 in the weight-based particle size distribution of the amorphous silica particles measured by the laser diffraction scattering particle size distribution measurement method is obtained by measuring the particle size of the raw material amorphous silica particles by the laser diffraction scattering particle size distribution measurement method. can also be obtained by doing
  • the average particle size of the amorphous silica particles obtained from the observation image of the scanning electron microscope is preferably 0.1 ⁇ m or more, more preferably 0.1 ⁇ m or more, from the viewpoint of improving mold strength per unit mass and improving handling properties. is 0.3 ⁇ m or more.
  • the average particle size of the amorphous silica particles obtained from the observation image of the scanning electron microscope is preferably 2.0 ⁇ m or less, more preferably 1.0 ⁇ m. Below, more preferably 0.8 ⁇ m or less, still more preferably 0.6 ⁇ m or less.
  • various image analysis techniques can be used to determine the average particle size of the amorphous silica particles obtained from the observation image of the scanning electron microscope.
  • Random particle sorting may be performed as a pretreatment. For example, after judging the inorganic binder layer and the amorphous silica particles based on the elements, 100 arbitrary amorphous silica particles are selected, their particle diameters are measured, and 10 particles are counted from the maximum particle diameter.
  • the content of the amorphous silica particles in the inorganic binder layer is specifically 0% by mass or more with respect to the total components other than water in the inorganic binder layer. , preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more.
  • the content of the amorphous silica particles in the inorganic binder layer is is preferably 55% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.
  • the content of the amorphous silica particles is specifically 0 parts by mass or more, preferably 20 parts by mass or more with respect to 100 parts by mass of the inorganic binder, from the viewpoint of improving the mold strength. , more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more, and even more preferably 60 parts by mass or more.
  • the content of the amorphous silica particles is preferably 150 parts by weight or less with respect to 100 parts by weight of the inorganic binder. More preferably 120 parts by mass or less, still more preferably 100 parts by mass or less, even more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less.
  • the content of water in the inorganic binder layer contained in the inorganic coated sand is preferably 5 parts by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the inorganic binder. is 10 parts by mass or more, more preferably 20 parts by mass or more.
  • the content of water in the inorganic binder layer contained in the inorganic coated sand is , preferably 180 parts by mass or less, more preferably 160 parts by mass or less, still more preferably 150 parts by mass or less, and even more preferably 140 parts by mass or less.
  • the water content in the inorganic binder layer contained in the inorganic coated sand can be adjusted according to the type of inorganic binder.
  • the content of water in the inorganic binder layer is preferably 5 parts by mass or more with respect to 100 parts by mass of sodium silicate from the viewpoint of obtaining a high-strength mold. , more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more.
  • the content of water in the inorganic binder layer contained in the inorganic coated sand is It is preferably 55 parts by mass or less, more preferably 50 parts by mass or less.
  • the water content in the inorganic binder layer is 100 parts by mass of sodium metasilicate, from the viewpoint of obtaining a high-strength mold and from the viewpoint of easy production of the mold.
  • the amount is preferably 180 parts by mass or less, more preferably 160 parts by mass or less, still more preferably 150 parts by mass or less, and even more preferably 140 parts by mass or less.
  • the inorganic binder constituting the inorganic binder layer is only sodium metasilicate pentahydrate
  • the content of water is 74 parts by mass with respect to 100 parts by mass of sodium metasilicate.
  • the content of water in the case of only nonahydrate is 133 parts by mass with respect to 100 parts by mass of sodium metasilicate.
  • the method for producing the inorganic coated sand can be selected, for example, according to the type of inorganic binder.
  • the inorganic binder contains sodium silicate
  • an aqueous solution of water glass as the inorganic binder is kneaded or mixed uniformly with the heated refractory aggregate, together with additives if necessary. By mixing them together, coating the surface of the refractory aggregate with the aqueous solution of water glass, and allowing the water in the aqueous solution of water glass to evaporate, it is possible to obtain a dry inorganic coated sand having fluidity at room temperature.
  • the inorganic binder contains sodium metasilicate hydrate
  • the inorganic binder layer can be crystallized, so that an inorganic coated sand having excellent fluidity can be obtained as compared with the conventional production method.
  • it is not necessary to use an aqueous solution of sodium metasilicate hydrate there is no need for a dehydration step, and the method for producing the inorganic coated sand can be simplified.
  • the surface of the refractory aggregate is coated with the fluidized sodium metasilicate hydrate at a temperature equal to or higher than the melting point of the sodium metasilicate hydrate.
  • a method of mixing the refractory aggregate and the sodium metasilicate hydrate at a temperature higher than the melting point of the sodium metasilicate hydrate for example, a refractory aggregate heated to a temperature higher than the melting point of the sodium metasilicate hydrate
  • the method of adding the heat-melted sodium metasilicate hydrate to the refractory aggregate and mixing them is preferable from the viewpoint of shortening the coating time. From the same point of view, it is preferable to mix the sodium metasilicate hydrate without making it into an aqueous solution in advance in the step of obtaining the mixture. It is also preferred that the step of obtaining the mixture does not include the step of intentionally adding water. Mixing conditions such as stirring speed and treatment time when the refractory aggregate and sodium metasilicate hydrate are mixed can be appropriately determined according to the treatment amount of the mixture.
  • the step of cooling the mixture by cooling the mixture obtained in the step of obtaining the mixture to a temperature below the melting point of the sodium metasilicate hydrate, the fluidity of the sodium metasilicate hydrate is reduced and the refractory bone is obtained.
  • a sodium metasilicate hydrate layer ie, an inorganic binder layer is formed.
  • inorganic coated sand there are no restrictions on the method of adding zinc oxide or magnesium oxide.
  • one or more selected from zinc oxide and magnesium oxide, optionally amorphous silica particles, and other additives may be coated.
  • the refractory aggregate may be coated with one or more selected from an inorganic binder, zinc oxide and magnesium oxide, optionally amorphous silica particles, and other additives.
  • Zinc oxide or magnesium oxide can be in solid form or in aqueous dispersion and mixed with refractory aggregates, inorganic binders and the like. Moreover, zinc oxide or magnesium oxide may be added all at once, or may be added in multiple batches.
  • the inorganic coated sand in this embodiment can be obtained. Also, the obtained inorganic coated sand can be used alone or in combination with other known refractory aggregates and other additives to form desired molds.
  • the mold is made using the inorganic coated sand in this embodiment described above.
  • the molding method of the mold include a molding method using a heated molding die, and a molding method in which steam is passed through the heated molding die and then hot air is passed through the mold.
  • the inorganic binder layer contains sodium metasilicate hydrate
  • a method of molding by filling a heated molding die with inorganic coated sand is preferred.
  • the inorganic binder layer contains sodium silicate, a method of adding water to the inorganic coated sand, kneading it, and then filling it into a heated molding die for molding, or molding the inorganic coated sand into a heated molding die. It is preferable to mold by blowing water vapor after filling the mold, and then blowing hot air.
  • the inorganic coated sand is first filled into the molding die that provides the desired mold.
  • the molding die is preferably heated in advance to keep it warm before filling with the inorganic coated sand.
  • the heating temperature at this time is preferably 100° C. or higher, more preferably 150° C. or higher, and preferably 300° C. or lower, from the viewpoint of improving mold productivity and improving mold strength. , more preferably 250° C. or less.
  • the mold After filling with the inorganic coated sand, the mold is heated without passage of water vapor to cure the inorganic coated sand.
  • the inorganic binder layer contains sodium metasilicate hydrate
  • the inorganic coated sand can be hardened without using the step of adding water to the inorganic coated sand and kneading, or the step of passing water vapor. Equipment or the like for ventilating water vapor becomes unnecessary.
  • the heating temperature is preferably 100° C. or higher, more preferably 150° C. or higher, and preferably 300° C. or lower, from the viewpoint of improving mold productivity and improving mold strength. It is preferably 250° C. or less.
  • the heating time is preferably 30 seconds or longer, more preferably 60 seconds or longer, and preferably 600 seconds or shorter, from the viewpoint of obtaining stable mold strength.
  • the inorganic binder layer contains sodium silicate
  • water is added to the inorganic coated sand, kneaded, and then filled into a heated molding die.
  • water vapor is passed through, for example, water vapor is blown in after the inorganic coated sand is filled in the molding die that provides the desired mold. The aeration of water vapor wets the packed phase of the inorganic coated sand to a wet state. Then, hot air is passed through the molding die heated to 90 to 200° C. to dry and harden the inorganic coated sand.
  • the inorganic coated sand in this embodiment can also be used in the additive manufacturing method.
  • the present invention further discloses a method for suppressing mold deformation and an inorganic coated sand described below.
  • a mold made using an inorganic coated sand having a refractory aggregate and an inorganic binder layer formed on the surface of the refractory aggregate, wherein the inorganic binder layer is selected from zinc oxide and magnesium oxide. are contained, and the total content of the zinc oxide and the magnesium oxide is 6 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the inorganic binder, so that deformation of the mold during casting is suppressed. How to suppress.
  • the inorganic binder layer contains one or more selected from zinc oxide and magnesium oxide, The total content of the zinc oxide and the magnesium oxide is 6 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the inorganic binder,
  • the inorganic caking agent contains at least one selected from the group consisting of sodium silicate and sodium metasilicate in a total amount of 80 mass% or more of sodium silicate and sodium metasilicate,
  • the inorganic binder layer contains one or more selected from zinc oxide and magnesium oxide, The total content of the zinc oxide and the magnesium oxide is 6 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the inorganic binder,
  • the inorganic caking agent contains at least one selected from the group consisting of sodium silicate and sodium metasilicate in total of 98% by mass or more of sodium silicate and sodium metasilicate, ⁇ 1> or ⁇ 2>, wherein the content of the inorganic binder layer with respect to 100 parts by mass of the refractory aggregate in the inorganic coated sand is 1 part by mass or more and 4.5 parts by mass or less.
  • a method of suppressing deformation of the mold during casting ⁇ 4> The method for suppressing deformation of the mold during casting according to any one of ⁇ 1> to ⁇ 3>, wherein the inorganic coated sand has an average particle size of 0.05 mm or more and 2 mm or less.
  • ⁇ 6> Suppressing deformation of the mold during casting according to any one of ⁇ 1> to ⁇ 5>, wherein the content of the inorganic binder layer in the inorganic coated sand is 1.0% by mass or more and 4.5% by mass or less. how to.
  • ⁇ 7> The method for suppressing deformation of the mold during casting according to any one of ⁇ 1> to ⁇ 6>, wherein the content of the inorganic binder in the inorganic binder layer is 35% by mass or more and 94% by mass or less.
  • ⁇ 8> Suppressing deformation of the mold during casting according to any one of ⁇ 1> to ⁇ 7>, wherein the total content of sodium silicate and sodium metasilicate in the inorganic binder is substantially 100% by mass.
  • ⁇ 11> The deformation of the mold during casting according to any one of ⁇ 1> to ⁇ 10>, wherein the total content of zinc oxide and magnesium oxide in the inorganic binder layer is 2% by mass or more and 40% by mass or less. How to suppress.
  • ⁇ 12> Deformation of the mold during casting according to any one of ⁇ 1> to ⁇ 11>, wherein the total content of the zinc oxide and the magnesium oxide is 20 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the inorganic binder how to suppress ⁇ 13>
  • the content of water in the inorganic binder layer is 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the inorganic binder.
  • An inorganic coated sand having a refractory aggregate and an inorganic binder layer formed on the surface of the refractory aggregate,
  • the inorganic binder layer contains one or more selected from zinc oxide and magnesium oxide,
  • the inorganic coated sand wherein the total content of the zinc oxide and the magnesium oxide is 6 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the inorganic binder.
  • the inorganic binder layer contains one or more selected from zinc oxide and magnesium oxide,
  • the total content of the zinc oxide and the magnesium oxide is 6 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the inorganic binder,
  • the inorganic caking agent contains at least one selected from the group consisting of sodium silicate and sodium metasilicate in a total amount of 80 mass% or more of sodium silicate and sodium metasilicate,
  • the inorganic coated sand according to ⁇ 14> wherein the content of the inorganic binder layer with respect to 100 parts by mass of the refractory aggregate in the inorganic coated sand is 0.05 parts by mass or more and 10 parts by mass or less.
  • the inorganic binder layer contains one or more selected from zinc oxide and magnesium oxide,
  • the total content of the zinc oxide and the magnesium oxide is 6 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the inorganic binder,
  • the inorganic caking agent contains at least one selected from the group consisting of sodium silicate and sodium metasilicate in total of 98% by mass or more of sodium silicate and sodium metasilicate,
  • ⁇ 17> The inorganic coated sand according to any one of ⁇ 14> to ⁇ 16>, wherein the inorganic coated sand has an average particle size of 0.05 mm or more and 2 mm or less.
  • ⁇ 18> The inorganic coated sand according to any one of ⁇ 14> to ⁇ 17>, wherein the refractory aggregate has an average particle size of 0.05 mm or more and 2 mm or less.
  • ⁇ 19> The inorganic coated sand according to any one of ⁇ 14> to ⁇ 18>, wherein the content of the inorganic binder layer in the inorganic coated sand is 1.0% by mass or more and 4.5% by mass or less.
  • ⁇ 20> The inorganic coated sand according to any one of ⁇ 14> to ⁇ 19>, wherein the content of the inorganic binder in the inorganic binder layer is 35% by mass or more and 94% by mass or less.
  • ⁇ 21> The inorganic coated sand according to any one of ⁇ 14> to ⁇ 20>, wherein the total content of sodium silicate and sodium metasilicate in the inorganic binder is substantially 100% by mass.
  • ⁇ 22> Any one of ⁇ 14> to ⁇ 21>, wherein the content of the inorganic binder in the inorganic coated sand is 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the refractory aggregate. Inorganic coated sand.
  • ⁇ 23> The inorganic coated sand according to any one of ⁇ 14> to ⁇ 22>, wherein the zinc oxide and magnesium oxide have an average particle size of 0.5 ⁇ m or more and 30 ⁇ m or less.
  • ⁇ 24> The inorganic coated sand according to any one of ⁇ 14> to ⁇ 23>, wherein the total content of zinc oxide and magnesium oxide in the inorganic binder layer is 2% by mass or more and 40% by mass or less.
  • ⁇ 25> The inorganic coated sand according to any one of ⁇ 14> to ⁇ 24>, wherein the total content of the zinc oxide and the magnesium oxide is 20 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the inorganic binder.
  • ⁇ 26> The inorganic coated sand according to any one of ⁇ 14> to ⁇ 25>, wherein the content of water in the inorganic binder layer is 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the inorganic binder. . ⁇ 27> ⁇ 14> to ⁇ , wherein the inorganic coated sand contains amorphous silica particles, and the content of the amorphous silica particles is 50 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the inorganic binder. 26> The inorganic coated sand according to any one of the above.
  • ⁇ 28> The inorganic coated sand according to ⁇ 27>, wherein the content of the amorphous silica particles in the inorganic binder layer is 20% by mass or more and 45% by mass or less.
  • ⁇ 29> The inorganic according to ⁇ 27> or ⁇ 28>, wherein the amorphous silica particles have an amorphous degree of 90% or more and an average particle diameter of 0.1 ⁇ m or more and 2.0 ⁇ m or less. coated sandwich.
  • ⁇ 30> ⁇ 14> to ⁇ including a step of coating a refractory aggregate with an inorganic binder, and a step of coating the refractory aggregate coated with the inorganic binder with at least one selected from zinc oxide and magnesium oxide. 29> The method for producing an inorganic coated sand according to any one of the above.
  • Examples 1 to 4 Mikawa Silica Sand R6 (100 parts by mass) was put into a stirrer as a refractory aggregate. Then, sodium metasilicate nonahydrate (4.00 parts by mass) melted by heating to 80° C. was added to a stirrer and kneaded for 4 minutes, and then amorphous silica fine particles (1.20 parts by mass). ) was added and kneaded for 2 minutes. Next, zinc oxide or magnesium oxide in the amount shown in Table 1 was added and kneaded for 2 minutes to obtain inorganic coated sands of Examples 1-4. Table 1 shows the composition of the inorganic coated sand.
  • Examples 5 to 12 ⁇ Examples 5 to 12> Mikawa Silica Sand R6 (100 parts by mass) heated to about 120° C. was put into a stirrer as a refractory aggregate. Next, No. 150 water glass (4.00 parts by mass) was put into a stirrer and kneaded to evaporate water, and stirred for about 3 minutes until the sand grain lumps collapsed. Further, zinc oxide or magnesium oxide (the amount shown in Table 2) was added and kneaded for 2 minutes to obtain inorganic coated sands of Examples 5-12. Table 2 shows the composition of the inorganic coated sand.
  • Example 13 ⁇ Example 13> Lunamos MS#60 (100 parts by mass) heated to about 120° C. was put into a stirrer as a refractory aggregate. Next, No. 150 water glass (2.00 parts by mass) was put into a stirrer and kneaded to evaporate water, and stirred for about 3 minutes until the sand grain lumps collapsed. Further, zinc oxide (0.19 parts by mass) was added and kneaded for 2 minutes to obtain an inorganic coated sand of Example 13. Table 2 shows the composition of the inorganic coated sand.
  • Examples 14 and 16 > Mikawa Silica Sand R6 (100 parts by mass) heated to about 120° C. was put into a stirrer as a refractory aggregate. Next, No. 3 water glass (4.00 parts by mass) and zinc oxide or magnesium oxide (0.41 parts by mass) are put into a stirrer and kneaded to evaporate the water content. After stirring for a minute, inorganic coated sands of Examples 14 and 16 were obtained. Table 3 shows the composition of the inorganic coated sand.
  • Examples 15 and 17 > Mikawa Silica Sand R6 (100 parts by mass) heated to about 120° C. was put into a stirrer as a refractory aggregate. Next, No. 3 water glass (4.00 parts by mass) was put into a stirrer and kneaded to evaporate water, and stirred for about 3 minutes until the sand grain lumps collapsed. Further, zinc oxide or magnesium oxide (0.41 parts by mass) was added and kneaded for 2 minutes to obtain inorganic coated sands of Examples 15 and 17.
  • FIG. 1(a) and FIG. 1(b) are sectional views for explaining a method of measuring the deformation of the mold.
  • the template test piece of each example obtained by the above method was left in a constant temperature room at 25° C./55% RH for 1 hour, and then cut into a plate-shaped test piece 10 of 5 ⁇ 22.3 ⁇ 90 mm.
  • Metal pedestals 11a and 11b (13 mm ⁇ 13 mm, height 13 mm) are arranged on an iron plate of appropriate size so that the distance between the centers is 90 mm, and a plate-shaped test piece 10 is placed on it. It was placed so as to be positioned at the center of the pedestal (Fig. 1(a)).
  • a weight 13 (4.7 g) was put on the center of the plate-shaped test piece 10 .
  • the iron plate on which the plate-shaped test piece 10 was placed was heated in a muffle furnace heated under the conditions described later. After a predetermined time had elapsed, the plate-shaped test piece 10 was taken out from the muffle furnace and allowed to stand for 1 hour to cool. After that, the amount of deformation of the plate-shaped test piece 10 was measured. The deformation amount was defined as the maximum vertical distance from the straight line connecting both ends of the plate-shaped test piece 10 to the curved portion (FIG. 1(b)).
  • the heating conditions were 500° C. and 10 minutes for all of Examples 1-17 and Comparative Examples 1-4.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
PCT/JP2022/001786 2021-01-29 2022-01-19 無機コーテッドサンド Ceased WO2022163464A1 (ja)

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CN202280012044.9A CN116801998A (zh) 2021-01-29 2022-01-19 无机覆膜砂

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