WO2017133685A1 - 一种铸造水玻璃用固化剂及其制备方法和用途 - Google Patents

一种铸造水玻璃用固化剂及其制备方法和用途 Download PDF

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Publication number
WO2017133685A1
WO2017133685A1 PCT/CN2017/072892 CN2017072892W WO2017133685A1 WO 2017133685 A1 WO2017133685 A1 WO 2017133685A1 CN 2017072892 W CN2017072892 W CN 2017072892W WO 2017133685 A1 WO2017133685 A1 WO 2017133685A1
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Prior art keywords
curing agent
water glass
amorphous silica
water
ester
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PCT/CN2017/072892
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English (en)
French (fr)
Inventor
祝建勋
姚慧民
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济南圣泉集团股份有限公司
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Filing date
Publication date
Priority to AU2017214133A priority Critical patent/AU2017214133B2/en
Priority to CA3015239A priority patent/CA3015239C/en
Priority to RU2018131315A priority patent/RU2706078C1/ru
Priority to EP17747005.1A priority patent/EP3412376B1/en
Priority to US16/073,569 priority patent/US11305335B2/en
Priority to JP2018541340A priority patent/JP6736680B2/ja
Application filed by 济南圣泉集团股份有限公司 filed Critical 济南圣泉集团股份有限公司
Priority to BR112018015808-9A priority patent/BR112018015808B1/pt
Priority to MX2018009528A priority patent/MX2018009528A/es
Priority to KR1020187025561A priority patent/KR102143711B1/ko
Priority to ES17747005T priority patent/ES2890224T3/es
Publication of WO2017133685A1 publication Critical patent/WO2017133685A1/zh
Priority to ZA2018/05878A priority patent/ZA201805878B/en

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Classifications

    • 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
    • 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
    • B22C1/181—Cements, oxides or clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • C04B14/066—Precipitated or pyrogenic silica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/02—Alcohols; Phenols; Ethers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • C04B24/045—Esters, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00939—Uses not provided for elsewhere in C04B2111/00 for the fabrication of moulds or cores

Definitions

  • the invention relates to the technical field of casting sand modification, in particular to a curing agent for casting water glass, a preparation method thereof and use thereof.
  • Casting is the basic part of the equipment manufacturing industry, so the development of the foundry industry marks the production strength of a country. According to statistics in 2008, China's annual output of 33.5 million tons of castings is the world's largest casting country. Most of these castings are produced from self-hardening sand to form the mold and core.
  • the mold for preparing the metal molded body is basically prepared in two structural forms. The first is to form a so-called core or type from which it is assembled into a mold which is essentially the negative mold of the casting to be prepared.
  • the second type is the formation of a hollow body, a so-called feeder, which acts as a balancing reservoir which receives the liquid metal, whereby the corresponding measures ensure that the metal is more in comparison with the metal in the mold forming the female mold. Keep in the liquid phase for a long time. If the metal solidifies in the negative mold, the liquid metal may subsequently flow out of the equilibrium storage vessel to balance the volumetric shrinkage that occurs as the metal solidifies.
  • the mold is composed of a refractory material, such as quartz sand, and its granules are joined by a suitable binder after the mold is formed to ensure sufficient mechanical strength of the mold; and a refractory styling base material is also used for preparing the casting.
  • a refractory material such as quartz sand
  • a suitable binder is treated with a suitable binder.
  • the refractory styling base material is preferably present in a flowable form such that it can be filled into a suitable hollow form and compacted there. A strong bond between the particles of the molding base material by the binder results in the necessary mechanical stability of the mold.
  • the mold must meet a variety of different requirements. For the casting process itself, it must first have sufficient stability and temperature resistance to receive the liquid metal into a hollow type consisting of one or more castings. After the start of the solidification process, the mechanical stability of the mold is ensured by the solidified metal layer which is formed along the hollow wall. The material of the mould must then be decomposed in this way under the influence of the heat released by the metal, ie it loses its mechanical strength, ie the joint between the individual particles of the refractory material is eliminated. This is achieved, for example, by decomposition of the binder under the action of heat. In The casting which is vibrated and solidified after cooling, in which case the material of the mold is again decomposed into fine sand, which can be poured out from the cavity of the metal mold.
  • an organic binder In order to prepare a mold, not only an organic binder but also an inorganic binder can be used, and the hardening of the binder can be carried out by a cold method or a thermal method.
  • Casting is one of the most polluting industries in the machinery manufacturing industry, in which the binder for molding core is the main source of pollution.
  • organic binders such as furan resin and urethane resin are widely used in foundries. They are combusted and decomposed when liquid metal is poured into a mold, and may release toxic gases and harmful substances such as toluene, xylene, phenol, carbon monoxide and suspended matter.
  • toxic gases and harmful substances such as toluene, xylene, phenol, carbon monoxide and suspended matter.
  • a binder which is based on inorganic materials or contains at most very small amounts of organic compounds.
  • An exothermic feed composition comprising an alkali metal silicate as a binder is described in DE 19925167A.
  • a binder system has been developed which is self-hardening at room temperature.
  • phosphoric acid and metal oxide based system is described, for example, in US 5,582,232 A1.
  • inorganic binder system that hardens at higher temperatures, such as in a hot mold.
  • Such a thermosetting binder system is known, for example, from US Pat. No. 5,474,606 A1, the disclosure of which is incorporated herein by reference.
  • water glass is an inorganic binder synthesized from silica sand and soda ash. It is one of the most resource-rich substances on the earth and is the casting resin with the least impact on the environment. Since the introduction of the new water glass in 1999, the amount of water glass has been reduced to 1.8-3.0%. It has high strength, good collapsibility, and recyclable reuse of old sand. The recycling rate is 80-90%, and the use time is adjustable. It can be used in mechanized modeling production lines, and can also be used in single-piece small batch production.
  • water glass can meet the technical, economic and ecological requirements, and is a casting binder with a wide application prospect.
  • the mechanical strength of ordinary water glass is lower than that of organic resin due to the specific strength of ordinary water glass ⁇ 0.3MPa (1%), and the poor collapsibility of water glass sand hinders its promotion. And application.
  • a water glass enhancer it is possible to increase its specific strength while limiting the amount of water glass.
  • CN104226890A discloses a water glass reinforcing agent for casting and a preparation method thereof.
  • the raw material of the water glass reinforcing agent comprises the following components in terms of parts by weight: 4-5 parts of polyenol; 0-0.5 parts of fluorosilicate; 0.1-8 parts of alcohol saccharides; 0.1-2 parts of inorganic acid.
  • the new water glass enhancer can greatly reduce the amount of water glass added, and can significantly increase the strength of the water glass sand, improve its mechanical properties, and make it more widely used, but it is stored for a long time after molding. The intensity improvement is very limited.
  • CN101027147A discloses a molding material mixture for preparing a mold for metal working, in order to prepare a mold, Using a refractory base material and a water glass based binder, and adding a proportion of particulate metal oxide to the binder selected from the group consisting of silica, alumina, titania and Zinc oxide.
  • a proportion of particulate metal oxide to the binder selected from the group consisting of silica, alumina, titania and Zinc oxide.
  • Yu Xinwei et al. reported the preparation and characterization of modified nano-silica-acrylate polyurethane emulsion, which has significant improvement on the hardness, water absorption and alcohol resistance of the paint film (Yu Xinwei, etc. Preparation and Characterization of Nano-Silica-Acrylate Polyurethane Emulsion, Electroplating and Finishing, No. 22, 2014) However, it does not disclose the use of this emulsion in the preparation of water glass self-hardening sand, which is not A reinforcing agent for casting water glass.
  • One of the objects of the present invention is to provide a novel curing agent for cast water glass containing: ester, amorphous silica and water; the amorphous silica It is a fumed amorphous silica and/or precipitated amorphous silica.
  • the curing agent of the present invention can be used for preparing a mold or a core, that is, the use of the molten water for curing the molten glass as a liquid enhancer for the use of water glass self-hardening sand.
  • the invention integrates the components of the curing agent into a suspension and then applies it to the preparation of the water glass self-hardening sand, thereby realizing the one-time addition of the curing agent for the cast water glass without powder pollution.
  • the utility model has the advantages of simple operation, convenient metering, convenient use and industrialized production; in addition, the use of the curing agent in the preparation of a mold or a core can significantly increase the strength of the water glass sand, and after molding, After a long period of storage, the strength is still maintained at a high level, which greatly improves the mechanical properties of the mold or core.
  • Consisting means that it may include, in addition to the components, other components which impart different characteristics to the curing agent.
  • the "contains” described in the present invention may also be replaced by a closed “for” or “consisting of”.
  • the curing agent for cast water glass contains a certain proportion of granular amorphous silica
  • the particle size of the particulate amorphous silica is preferably less than 50 ⁇ m, more preferably less than 10 ⁇ m, and particularly preferably less than 5 ⁇ m.
  • the particle size can be determined by screening analysis.
  • the sieving residue on the sieve having a mesh size of 10 ⁇ m is particularly preferably less than 7% by weight, preferably less than 4% by weight.
  • Pyrogenic amorphous silica or precipitated amorphous silica is equally applicable to the curing agent for cast water glass according to the present invention.
  • pyrogenic amorphous silica generally refers to being obtained by agglomeration from a gas phase at a high temperature; pyrogenic amorphous silica can be prepared, for example, by flame hydrolysis of silicon tetrachloride or in an electric arc. The furnace is carried out by reducing quartz sand with coke or anthracite to form SiO gas, followed by oxidation to silica; the pyrogenic amorphous silica prepared by the electric arc furnace method may further contain carbon.
  • Precipitation Amorphous silica is obtained by reacting an aqueous alkali metal silicate solution with a mineral acid, and then, the precipitate thus produced is separated and dried and ground.
  • the amorphous silica which is preferably formed by thermal decomposition of ZrSiO 4 , has a higher core weight than the amorphous silica of other sources in the same amount of addition. It indicates that the deposition of the mold particles is more compact.
  • the ester is monoglyceride, diacetin, triacetin, ethylene glycol diacetate, propylene carbonate or dibasic ester. Any one or a mixture of at least two, a typical but non-limiting example of which is a mixture of monoacetin and diacetin, a mixture of triacetin and ethylene glycol diacetate, diacetic acid A mixture of glycerides, triacetin, ethylene glycol diacetate and propylene carbonate.
  • the water in the curing agent for casting water glass may be tap water or the like, and is not particularly limited herein.
  • the ester and the amorphous silica are mixed in a suitable weight ratio, and the typical but non-limiting weight ratio is (0.3-4):1.
  • the Applicant states that the weight ratio of the above ester to amorphous silica is (0.3-4):1, and covers specific values of the range, and may be, for example, 0.3:1, 0.4:1, 0.45:1, 0.68.
  • the present invention is no longer exhaustive of the specific point values included in the scope. According to the present invention, however, it is preferably (0.68-2):1 for the weight ratio of the ester to the amorphous silica.
  • the curing agent for cast water glass contains: 20-40% of an ester by mass fraction; amorphous silica 30-60%; water 5-30%.
  • the ester may account for 20%, 22%, 23%, 23.5%, 24%, 25% of the mass of the curing agent.
  • the amorphous silica accounts for 30%, 32%, 33%, 33.5%, 34%, 35% of the mass of the curing agent.
  • the water content of the curing agent may be 5%, 6%, 8%, 10%, 12%, 13%, 13.5%, 14%, 15%, 16.5%, 20%, 22%, 23%, 25%, 28%, 30%, etc., and the specific values between the above values, limited by space and for conciseness For the consideration of the present invention, the specific point values included in the scope are not exhaustive.
  • the typical, but non-limiting, curing agent may contain, by mass fraction, ester 20%; amorphous silica 50%; water 30%; or ester 23%; amorphous silica 49%; Water 28% and so on.
  • the curing agent for cast water glass may further contain an alcohol, which is mainly used for accelerating the dissolution of each component of the curing agent, and other known organic solvents may be used.
  • a typical but non-limiting alcoholic solvent may be selected from any one or at least two of ethanol, methanol, propanol, isopropanol, butanol, isobutanol, benzyl alcohol, ethylene glycol or polyethylene glycol.
  • a mixture but preferably ethanol.
  • ethanol is used as the organic solvent, it is capable of making the suspension of the curing agent more uniform and stable. Ethanol is the best choice for the stability, economy and environmental protection of the suspension.
  • the curing agent may contain, by mass fraction, ester: 20-40%; amorphous silica 30-60%; alcohol 2-12%; water 3-18%.
  • ester 20% amorphous silica 60%; alcohol 2%; water 18%; or ester 32%; amorphous silica 50%; alcohol 3%; water 15% Or, ester 35%; amorphous silica 48%; alcohol 5%; water 12% and the like.
  • Another object of the present invention is to provide a method for preparing a curing agent for casting water glass, which comprises the following steps:
  • the ester, water, amorphous silica or alcohol used in the preparation method is referred to according to the weight ratio, mass fraction and specific selection in one of the objects of the present invention as described above. The amount will not be repeated here.
  • the present invention is formulated into a uniform suspension by subjecting each component of the curing agent comprising an ester, amorphous silica and water to high-speed shearing, uniformly stirring and mixing.
  • the uniform suspension can be implemented into one Sub-addition, effectively avoiding powder pollution, simpler operation, convenient metering, addition and use, can be used for large-scale industrial production, greatly improving production efficiency.
  • the rotational speed of step (2) is set to 800 rpm or more, for example, it can be appropriately adjusted within the range of 900-1000 rpm, for example, 950 rpm, 955 rpm, 960 rpm. / min, 965 rev / min, 970 rev / min, 980 rev / min, 985 rev / min, 990 rev / min, 1000 rev / min, and the specific value between the above values, limited space and for concise It is contemplated that the present invention is no longer exhaustive of the specific point values included in the scope.
  • the method for preparing the curing agent for cast water glass may include, for example, the following steps:
  • the preparation method of the curing agent for casting water glass may include, for example, the following steps:
  • the ester in the preparation of the curing agent for casting water glass, it is preferred to first add the ester to the stirring tank for stirring, and then add other components.
  • the order of addition can more effectively avoid dust pollution when the materials are mixed, and is more favorable for the uniformity of the slurry.
  • a third object of the present invention is also to provide a use of a curing agent for casting water glass, which is to use a curing agent which is one of the objects of the present invention for preparing a mold and a core.
  • the mould and core are preferably used for metal casting, in particular for cast iron and cast steel.
  • the addition of the curing agent can not only increase the strength of the water glass sand, but also improve the mechanical properties thereof, and can effectively avoid powder pollution, so that the operation is simple, the metering, It is convenient to add and use, and can realize industrial production. It has long-term significance for the promotion and application of water glass self-hardening sand.
  • a fourth object of the present invention is to provide a water glass self-hardening sand which comprises 95-98% of quartz sand, 1.8-2.5% of water glass, and 0.6-2.5 of liquid enhancer by mass fraction. %; wherein the liquid reinforcing agent is a curing agent for cast water glass according to one of the objects of the present invention.
  • the water glass self-hardening sand contains: mass fraction of quartz sand: 95-98%; water glass 1.8-2.5%; liquid
  • the body enhancer is 0.6-1.6%, and its typical but non-limiting combination is: quartz sand 96%; water glass 2.5%; liquid enhancer 1.5%; or, quartz sand 96%; water glass 2.4%; liquid enhancer 1.6 %; or, quartz sand 97.2%; water glass 2.2%; liquid enhancer 0.6%; or, quartz sand 97.5%; water glass 1.8%; liquid enhancer 0.7%, etc., limited space and for concise considerations, this The invention is not exhaustive of the specific point values included in the scope.
  • the present invention has at least the following beneficial effects:
  • the present invention realizes by preparing a suspension of a curing agent containing an ester, amorphous silica and water by high-speed shear mixing, and then applying it to the preparation of water glass self-hardening sand.
  • the one-time addition of the curing agent for casting water glass has no powder pollution, the operation is simple, the metering, the addition and the use are convenient, and the industrial production is realized.
  • the present invention can significantly increase the strength of the water glass sand by adding amorphous silica, especially the addition of silicon fine powder, in the curing agent, and the strength remains after the storage for a long time after molding.
  • the high level greatly improves the mechanical properties of the mold or core, so that the tensile strength of the mold or core after molding for 24 hours can reach 0.605 MPa.
  • Water glass self-hardening sand liquid enhancer a i.e., a curing agent for cast water glass of the present invention.
  • Example 1 (1) according to the components in Example 1, the ratio, except that the ethanol is replaced by polyethylene glycol;
  • Example 1-9 The water glass prepared in Example 1-9 was subjected to stability test from a hard sand liquid enhancer, and the results are shown in Table 1.
  • a representative curing agent sample was poured into a dry graduated cylinder to a level of 100 ml.
  • the static state according to the specific requirements of different types of curing agent detection for 5h, read the area of the clear layer, accurate to 1ml.
  • Example 1 As can be seen from Table 1, in comparison with Examples 2-8, when Example 1 used ethanol as an organic solvent, it was able to make the suspension of the curing agent more stable; compared with Example 9, Example 1 8 After adding an alcohol solvent, the prepared liquid enhancer can be formed into a suspension and has strong stability.
  • Example 10 The preparation process is the same as in Example 10, and the water glass self-hardening liquid liquid enhancer c (i.e., the curing agent for cast water glass of the present invention) is obtained.
  • the water glass self-hardening liquid liquid enhancer c i.e., the curing agent for cast water glass of the present invention
  • the water glass obtained from Examples 1 and 10-11 is used in the preparation of water glass self-hardening sand, and the specific operation is as follows:
  • Example 1 (1) According to the components in Example 1, the ratio is not except that silicon micropowder, ethanol and water are not added;
  • Example 10 (1) According to the components in Example 10, except that no silicon micropowder, ethanol and water were added;
  • Example 11 (1) According to the components in Example 11, the ratio is not except that silicon micropowder, ethanol and water are not added;
  • Examples 1, 10-11 By comparing Examples 1, 10-11 with Comparative Examples 1-3, respectively, it can be seen that in Examples 1, 10-11, by adding silicon fine powder to the organic ester component, the water glass prepared by using the same is self-hardening.
  • the water glass prepared from the sand liquid enhancer has a significant improvement in the tensile strength, and the strength of the self-hardening sand of the water glass can be significantly increased after molding for 1 hour, even after storage for a long time after molding.
  • the prepared water glass can maintain the strength of the hard sand at a relatively high level, and thus, the mechanical properties of the mold or the core are greatly improved.
  • the water glass obtained from Examples 12-18 was used in the preparation of water glass self-hardening sand from the hard sand liquid reinforcing agent, and the specific operation was as follows:
  • the strength of the prepared water glass can be maintained at a high level, and the tensile strength can reach between 0.586-0.605 when molded for 24 hours. Improve the mechanical properties of the mold or core.
  • the present invention achieves the preparation of a slurry of a water-glass self-hardening sand by mixing the components of the curing agent containing an ester, amorphous silica and water into a slurry by high-speed shear mixing.
  • the one-time addition of the curing agent for casting water glass has no powder pollution, the operation is simple, the metering, the addition and the use are convenient, and the industrial production is realized.
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Abstract

一种铸造水玻璃用固化剂，包含：酯、无定形二氧化硅和水，无定形二氧化硅为热解法无定形二氧化硅和/或沉淀法无定形二氧化硅。还公开了一种铸造水玻璃用固化剂在制备铸型和型芯中的用途，将包含酯、无定形二氧化硅和水的固化剂各组分高速混合配制成悬浮液，再将其应用于水玻璃自硬砂的制备中，无粉体污染，计量、添加方便。还公开了一种铸造水玻璃用固化剂制备方法和一种水玻璃自硬砂。

Description

一种铸造水玻璃用固化剂及其制备方法和用途
本申请要求中国发明专利申请201610082019.4(申请日：2016年02月05日；发明名称：一种铸造水玻璃用固化剂及其制备方法和用途)的优先权，其全部内容通过援引并入本说明书。
技术领域
本发明涉及铸造型砂改性技术领域，尤其涉及一种铸造水玻璃用固化剂及其制备方法和用途。
背景技术
铸件是装备制造业的基础件，因此铸造业的发展标志着一个国家的生产实力。据2008年统计，我国年产铸件3350万吨，是世界铸造第一大国。这些铸件的生成大多采用自硬砂制备铸型和型芯。
用于制备金属成型体的铸型基本上以两种结构形式制备。第一种是形成所谓的型芯或型，由其装配成铸型，其基本上是所要制备的铸件的阴模。第二种是形成空心体，所谓的给料器，其起平衡储备容器的作用，该容器接收液态金属，在此通过相应的措施确保金属与处于构成阴模的铸型中的金属相比更长时间地保持在液相下。如果金属在阴模中凝固，那么液态金属可能从平衡储备容器中随后流出，以平衡在金属凝固时出现的体积收缩。
铸型由耐火的材料，例如石英砂构成，它的颗粒在铸型成形后通过合适的粘结剂而接合，以保证铸型具有足够的机械强度；也应用耐火的造型基础材料用于制备铸型，该造型基础材料被用合适的粘结剂处理。耐火的造型基础材料优选以可流动的形式存在，使得其可填充入合适的空心型中和在那里被紧实。通过粘结剂在造型基础材料的颗粒之间产生牢固的接合，使得铸型获得必要的机械稳定性。
铸型必须满足各种不同的要求。对于浇铸过程本身，其首先必须具有足够的稳定性和耐温度性，以将液态的金属接收到由一个或多个铸(分)型所构成的空心型中。在凝固过程开始后，铸型的机械稳定性通过凝固的金属层而保证，该金属层沿着空心型的壁形成。铸型的材料这时必须在由金属所释放的热量的影响下以这种方式分解，即其失去它的机械强度，也即在耐火材料的单个颗粒之间的接合被消除。这通过例如粘结剂在热的作用下分解而达到。在 冷却后振动凝固的铸件，在此在理想的情况下，铸型的材料再次分解成细砂，其可以从金属模具的空腔中倒出。
为了制备铸型，不仅可使用有机的粘结剂，而且可以使用无机的粘结剂，所述粘结剂的硬化各自可通过冷法或热法进行。铸造是机械制造业中污染最严重的一个行业，其中造型制芯用粘结剂是造成污染的主要根源。目前，铸造厂广泛采用呋喃树脂、脲烷树脂等有机粘结剂，它们在液态金属浇入铸型时燃烧分解可能释放出甲苯、二甲苯、苯酚、一氧化碳和悬浮物等有毒气体和有害物质。随着国家法律、法规对铸造厂环保要求的日益提高，水玻璃自硬砂越来越多的受到人们的关注。
为了避免在浇铸过程期间分解产物的排放，必须应用这样的粘结剂，即，其基于无机的材料或最多含有非常少量的有机化合物。在DE19925167A中描述了一种放热的给料组合物，其含有碱金属硅酸盐作为粘结剂。此外已研发出了这种粘结剂体系，其是在室温下自硬化的。一种这样的基于磷酸和金属氧化物的体系例如描述在US5,582,232A1中。还有一种无机粘结剂体系，其在较高温度下硬化，例如在热的模具中硬化。这样的热硬化性粘结剂体系例如从US5,474,606A1中是已知的，在此文献中描述了由碱金属水玻璃和硅酸铝构成的粘结剂体系。
典型地，水玻璃是硅砂和纯碱合成的无机粘结剂，是地球上资源最丰富的物质之一，是对环境影响最小的铸造树脂。新型水玻璃自1999年问世，到现在水玻璃加入量降低至1.8-3.0％，其具有强度高、溃散性好、旧砂可再生回用，回用率达80-90％，使用时间可调，可用于机械化造型生产线，也可用于单件小批量生产等优点。
水玻璃作为型(芯)砂粘结剂，能较好地满足技术、经济和生态方面的要求，是一种具有广泛应用前途的铸造用粘结剂。但是，水玻璃粘结剂在相同加入量下，由于普通水玻璃的比强度≤0.3MPa(1％)，其力学性能还是低于有机树脂，加上水玻璃砂溃散性差，阻碍了它的推广和应用。然而通过加入水玻璃增强剂，却可以在限制水玻璃用量的前提下提高它的比强度。
CN104226890A公开了一种铸造用的水玻璃增强剂及其制备方法。按照重量份数计，该水玻璃增强剂的原料包括以下组分：聚烯醇4-5份；氟硅酸盐0-0.5份；醇糖类0.1-8份；无机酸0.1-2份。该新型水玻璃增强剂能够大大减少水玻璃的加入量，并且可显著地增加水玻璃砂的强度，提高其力学性能，使其应用范围更加广泛，然而其对于成型后经较长时间的贮存后的强度改善十分有限。
CN101027147A公开了一种用于制备金属加工用铸型的造型材料混合物，为制备铸型，使 用耐火的造型基础材料以及基于水玻璃的粘结剂，并将一定比例的颗粒状金属氧化物加入到粘结剂中，该颗粒状金属氧化物选自二氧化硅、氧化铝、氧化钛和氧化锌。虽然其对于成型后铸型的强度有了很大提高，然而固体粉料加入的连续性较差、加料时粉尘飞扬恶化了工作环境，尤其是在酯硬化水玻璃砂使用时，多组分分别加入增加了操作的复杂性，从而不利于产业化。
于欣伟等报道了改性纳米二氧化硅-丙烯酸酯聚氨酯乳液的制备及表征，该乳液对于漆膜的硬度、吸水率和耐醇性等性能均有明显改善(于欣伟等，改性纳米二氧化硅-丙烯酸酯聚氨酯乳液的制备及表征，电镀与涂饰，第22期，2014年)，然而，其并未公开将该乳液用于水玻璃自硬砂的制备中，未将其作为一种铸造水玻璃用的增强剂。
因此，开发一种铸造水玻璃用增强剂，其除了能更好地提高水玻璃砂的力学性能外，还能避免粉体污染，使操作简单，计量、添加使用方便，并能实现工业化生产，对水玻璃自硬砂推广应用具有长远意义。
发明内容
针对现有技术的不足，本发明的目的之一在于提供了一种新型的铸造水玻璃用固化剂，所述固化剂含有：酯、无定形二氧化硅和水；所述无定形二氧化硅为热解法无定形二氧化硅和/或沉淀法无定形二氧化硅。
本发明所述固化剂可用于制备铸型或型芯中，即将所述铸造水玻璃用固化剂作为液体增强剂用于水玻璃自硬砂的用途。
本发明通过将固化剂的各组分混合均匀配制成悬浮液，然后再将其应用于水玻璃自硬砂的制备中，从而实现了铸造水玻璃用固化剂的一次性加入，无粉体污染，操作简单，计量、添加使用方便，实现了工业化生产；除此以外，将所述固化剂用于铸型或型芯的制备中，可以显著增加水玻璃砂的强度，并在成型后经较长时间的贮存后其强度仍保持在较高水平，大大改善了铸型或型芯的力学性能。
本发明所述的“含有”，意指其除所述组分外，还可以包括其他组分，这些其他组分赋予所述固化剂不同的特性。除此之外，本发明所述的“含有”，还可以替换为封闭式的“为”或“由……组成”。
根据本发明，所述铸造水玻璃用固化剂中含有一定比例的颗粒状的无定形二氧化硅，该 颗粒状无定形二氧化硅的粒度优选为小于50μm，更优选为小于10μm，特别优选为小于5μm。粒度可以通过筛分分析而确定。在具有10μm的筛孔尺寸的筛上的筛分残留物特别优选为小于7重量％，优选为小于4重量％。
根据本发明，优选应用热解法无定形二氧化硅或沉淀法无定形二氧化硅中的任意一种或至少两种的混合物作为颗粒状的无定形二氧化硅。
热解法无定形二氧化硅或沉淀法无定形二氧化硅对于根据本发明的铸造水玻璃用固化剂是同样适用的。其中，热解法无定形二氧化硅通常是指是在高温下通过从气相中凝聚而得到的；热解法无定形二氧化硅的制备例如可通过四氯化硅的火焰水解，或在电弧炉中通过用焦炭或无烟煤将石英砂还原生成一氧化硅气体，随后氧化成二氧化硅而进行；按电弧炉法制备的热解法无定形二氧化硅还可含有碳。沉淀法无定形二氧化硅是通过碱金属硅酸盐水溶液与无机酸的反应而得到的，随后，在此产生的沉淀物中被分离出并对其进行干燥和研磨。
根据本发明，所述无定形二氧化硅优选ZrSiO4热分解而形成的无定形二氧化硅，在加入量相同的情况下比其它来源的无定形二氧化硅获得了更高的型芯重量，表明铸型粒子的堆积更加紧密。
根据本发明，所述铸造水玻璃用固化剂中，所述酯为单乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、乙二醇二乙酸酯、碳酸丙烯酯或二元酯中的任意一种或至少两种的混合物，所述混合物典型但非限制性的实例为单乙酸甘油酯和二乙酸甘油酯的混合物，三乙酸甘油酯和乙二醇二乙酸酯的混合物，二乙酸甘油酯、三乙酸甘油酯、乙二醇二乙酸酯和碳酸丙烯酯的混合物。
根据本发明，所述铸造水玻璃用固化剂中的水可以采用自来水等，在此不做特别限定。
根据本发明，所述铸造水玻璃用固化剂中，酯和无定形二氧化硅是以合适的重量配比进行混合的，其典型但非限制性的重量比为(0.3-4)∶1。申请人声明，上述酯和无定形二氧化硅的重量比为(0.3-4)∶1，涵盖了该范围的各具体点值，例如可以是0.3∶1、0.4∶1、0.45∶1、0.68∶1、0.8∶1、0.92∶1、1∶1、1.2∶1、1.3∶1、1.6∶1、1.8∶1、2∶1等，以及上述数值之间的具体点值，比如0.7∶1、1.4∶1等，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。然而根据本发明，对于酯和无定形二氧化硅的重量配比，其优选为(0.68-2)∶1。
根据本发明，所述铸造水玻璃用固化剂按质量分数含有：酯20-40％；无定形二氧化硅 30-60％；水5-30％。申请人声明，上述各组分的含量范围，涵盖了该范围的各具体点值，例如酯占所述固化剂的质量分数可以是20％、22％、23％、23.5％、24％、25％、26.5％、27％、28％、29％、30％等；无定形二氧化硅占所述固化剂的质量分数可以是30％、32％、33％、33.5％、34％、35％、36.5％、37％、38％、39％、40％、41％、42％、43％、43.5％、44％、45％、46.5％、47％、48％、49％、50％、51％、52％、53％、54％、55％、56％、58％、60％等；水占所述固化剂的质量分数可以是5％、6％、8％、10％、12％、13％、13.5％、14％、15％、16.5％、20％、22％、23％、25％、28％、30％等，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
根据本发明，典型但非限制性的所述固化剂按质量分数可以含有：酯20％；无定形二氧化硅50％；水30％；或者，酯23％；无定形二氧化硅49％；水28％等等。
根据本发明，所述铸造水玻璃用固化剂中还可以含有醇，其主要是用于加速固化剂各组分的溶解，也可以采用公知的其它有机溶剂。典型但非限制性的醇类溶剂可以选自乙醇、甲醇、丙醇、异丙醇、丁醇、异丁醇、苯甲醇、乙二醇或聚乙二醇中的任意一种或至少两种的混合物，但优选为乙醇。采用乙醇作为有机溶剂时，其能够使所述固化剂的悬浮液更加均一稳定。乙醇无论是悬浮液的稳定性、经济性、环保性都是最优的选择。
根据本发明，所述固化剂按质量分数可以含有：酯20-40％；无定形二氧化硅30-60％；醇2-12％；水3-18％。典型但非限制性的组合有：酯20％；无定形二氧化硅60％；醇2％；水18％；或者，酯32％；无定形二氧化硅50％；醇3％；水15％；或者，酯35％；无定形二氧化硅48％；醇5％；水12％等等。
本发明的目的之二还在于提供了一种铸造水玻璃用固化剂的制备方法，其包括以下步骤：
(1)先将按配比称量的酯加入高速搅拌机搅拌罐内，启动搅拌；
(2)投入按配比称量好的水，任选地，再投入按配比称量好的醇；调节转速在800转/分以上，加入无定形二氧化硅，继续搅拌10-20min，使其成为悬浮液，得到所述的铸造水玻璃用固化剂。
根据本发明，所述制备方法中用到的酯、水、无定形二氧化硅或者醇，都是依据如前所述本发明目的之一中的重量配比、质量分数以及具体选择来进行称量的，在此不再赘述。
本发明通过将包含酯、无定形二氧化硅和水的固化剂各组分通过高速剪切，均匀搅拌混合从而配制成均一的悬浮液。在水玻璃自硬砂的制备过程中，可以将该均一的悬浮液实行一 次性加入，有效避免了粉体污染，操作更加简单，计量、添加使用方便，可用于大规模的工业化生产，大大提高了生产效率。
根据本发明，步骤(2)的转速设置为800转/分以上，例如可以在900-1000转/分的范围内进行适当的调整，例如可以是950转/分、955转/分、960转/分、965转/分、970转/分、980转/分、985转/分、990转/分、1000转/分，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
根据本发明，所述铸造水玻璃用固化剂的制备方法例如可以包括以下步骤：
(1)先将按配比称量的酯加入高速搅拌机搅拌罐内，启动搅拌；
(2)投入按配比称量好的水；调节转速在800转/分以上，加入无定形二氧化硅，继续搅拌10-20min，使其成为均匀的液体，得到所述的铸造水玻璃用固化剂。
作为进一步优选的技术方案，所述铸造水玻璃用固化剂的制备方法例如可以包括以下步骤：
(1)先将按配比称量的酯加入高速搅拌机搅拌罐内，启动搅拌；
(2)投入按配比称量好的水和醇；调节转速在800转/分以上，加入无定形二氧化硅，继续搅拌10-20min，使其成为均匀的液体，得到所述的铸造水玻璃用固化剂。
根据本发明，在进行铸造水玻璃用固化剂的制备时，优选先将酯加入搅拌罐进行搅拌，然后再加入其它组分。该加入顺序可以更有效地避免物料掺混时的粉尘污染，也更有利于浆料的均一。
本发明的目的之三还在于提供了一种铸造水玻璃用固化剂的用途，所述用途是指将本发明目的之一的固化剂用于制备铸型和型芯。
根据本发明，所述铸型和型芯优选用于金属铸造，尤其是用于铸铁和铸钢。
本发明在制备铸型和型芯时，所述固化剂的加入，除了能更好地增加水玻璃砂的强度，提高其力学性能外，还能有效避免粉体污染，使操作简单，计量、添加使用方便，并能实现工业化生产，对水玻璃自硬砂推广应用具有长远意义。
本发明的目的之四还在于提供了一种水玻璃自硬砂，所述水玻璃自硬砂按质量分数含有：石英砂95-98％；水玻璃1.8-2.5％；液体增强剂0.6-1.6％；其中，所述液体增强剂即为本发明目的之一所述的铸造水玻璃用固化剂。
根据本发明，所述水玻璃自硬砂按质量分数含有：石英砂95-98％；水玻璃1.8-2.5％；液 体增强剂0.6-1.6％，其典型但非限制性的组合为：石英砂96％；水玻璃2.5％；液体增强剂1.5％；或者，石英砂96％；水玻璃2.4％；液体增强剂1.6％；或者，石英砂97.2％；水玻璃2.2％；液体增强剂0.6％；或者，石英砂97.5％；水玻璃1.8％；液体增强剂0.7％等等，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
与现有技术相比，本发明至少具有以下有益效果：
(1)本发明通过将包含酯、无定形二氧化硅和水的固化剂各组分通过高速剪切混合配制成悬浮液，再将其应用于水玻璃自硬砂的制备中，从而实现了铸造水玻璃用固化剂的一次性加入，无粉体污染，操作简单，计量、添加使用方便，实现了工业化生产。
(2)本发明通过在固化剂中添加无定形二氧化硅，尤其是硅微粉的加入，可以显著增加水玻璃砂的强度，并在成型后经较长时间的贮存后其强度仍保持在较高水平，大大改善了铸型或型芯的力学性能，使其成型24h后的铸型或型芯的抗拉强度能达到0.605MPa。
具体实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
组分  配比(质量/g)
二乙酸甘油酯  30
乙二醇二乙酸酯  60
三乙酸甘油酯  300
碳酸丙烯酯  10
硅微粉  600
乙醇  30
水  50
制备工艺
1、称取二乙酸甘油酯、乙二醇二乙酸酯、三乙酸甘油酯和碳酸丙烯酯，将其加入高速搅拌机搅拌罐内，启动搅拌，搅拌60min；
2、加入乙醇和水，调整搅拌转速在900-1100转/分，加入硅微粉，继续搅拌10min，得 水玻璃自硬砂液体增强剂a(即本发明的铸造水玻璃用固化剂)。
实施例2
(1)按照实施例1中的各组分进行配比，除了将乙醇替换为甲醇外；
(2)制备工艺同实施例1。
实施例3
(1)按照实施例1中的各组分进行配比，除了将乙醇替换为丙醇外；
(2)制备工艺同实施例1。
实施例4
(1)按照实施例1中的各组分进行配比，除了将乙醇替换为异丙醇外；
(2)制备工艺同实施例1。
实施例5
(1)按照实施例1中的各组分进行配比，除了将乙醇替换为丁醇外；
(2)制备工艺同实施例1。
实施例6
(1)按照实施例1中的各组分进行配比，除了将乙醇替换为苯甲醇外；
(2)制备工艺同实施例1。
实施例7
(1)按照实施例1中的各组分进行配比，除了将乙醇替换为乙二醇外；
(2)制备工艺同实施例1。
实施例8
(1)按照实施例1中的各组分进行配比，除了将乙醇替换为聚乙二醇外；
(2)制备工艺同实施例1。
实施例9
(1)按照实施例1中的各组分进行配比，除了不加乙醇外；
(2)制备工艺同实施例1。
将实施例1-9制备得到的水玻璃自硬砂液体增强剂进行稳定性测试，其结果如表1所示。
表1
Figure PCTCN2017072892-appb-000001
稳定性测试标准：参考JB/T5107-91《砂型铸造用涂料》
操作步骤
把代表性固化剂样品倒入干燥的量筒中，使其达到100ml标高处。在静止状态下，按不同型号固化剂检测要求的具体放置5h，读取澄清层面积，准确至1ml。
结果计算
Figure PCTCN2017072892-appb-000002
式中：
C------固化剂的悬浮率，％
V------量筒中固化剂柱上面澄清层的面积，ml
通过表1可以看出，与实施例2-8相比，实施例1采用乙醇作为有机溶剂时，其能够使所述固化剂的悬浮液更加稳定；与实施例9相比，实施例1-8采用添加醇类溶剂后，能使所制备的液体增强剂形成悬浮液，并具有较强的稳定性。
实施例10
组分  配比(质量/g)
二乙酸甘油酯  37.5
乙二醇二乙酸酯  75
三乙酸甘油酯  375
碳酸丙烯酯  12.5
硅微粉  500
乙醇  60
水  20
制备工艺
1、称取二乙酸甘油酯、乙二醇二乙酸酯、三乙酸甘油酯、碳酸丙烯酯，将其加入高速搅拌机搅拌罐内，启动搅拌，搅拌60min；
2、加入乙醇和水，调整搅拌转速在900-1100转/分，加入硅微粉，继续搅拌10min，得水玻璃自硬砂液体增强剂b(即本发明的铸造水玻璃用固化剂)。
实施例11
(1)按照实施例10中的各组分进行配比，除了按以下质量调整酯组分的加入量外；
二乙酸甘油酯  30g
乙二醇二乙酸酯  70g
三乙酸甘油酯  400g
(2)制备工艺同实施例10，得水玻璃自硬砂液体增强剂c(即本发明的铸造水玻璃用固化剂)。
将实施例1、10-11得到的水玻璃自硬砂液体增强剂用于水玻璃自硬砂的制备中，具体操作为：
称取大林标准砂1000g，加入叶片式实验室用混砂机，加水玻璃自硬砂液体增强剂8.64g，搅拌1min，加水玻璃SQ-1 20g，搅拌1min，出砂，打制标准“8”形试块，检测1h，4h和24h抗拉强度，其结果如表2所示。
对比例1
(1)按照实施例1中的各组分进行配比，除了不加硅微粉、乙醇和水外；
(2)制备工艺同实施例1。
对比例2
(1)按照实施例10中的各组分进行配比，除了不加硅微粉、乙醇和水外；
(2)制备工艺同实施例10。
对比例3
(1)按照实施例11中的各组分进行配比，除了不加硅微粉、乙醇和水外；
(2)制备工艺同实施例11。
将上述对比例1-3得到的有机酯用于水玻璃自硬砂的制备中，具体操作为：
称取大林标准砂1000g，加入叶片式实验室用混砂机，加有机酯SG-257.5g，搅拌1min，加水玻璃SQ-130g，搅拌1分钟，出砂，打制标准“8”形试块，检测1h，4h和24h的抗拉强度，执行标准GB-2684，其结果如表2所示。
表2
Figure PCTCN2017072892-appb-000003
通过将实施例1、10-11分别与对比例1-3进行对比可以看出，实施例1、10-11中通过在有机酯组分中增加硅微粉，采用其配制成的水玻璃自硬砂液体增强剂制备得到的水玻璃自硬砂在抗拉强度上得到了明显改善，在成型1h后即可显著增加水玻璃自硬砂的强度，即使在成型后经较长时间的贮存，其制备的水玻璃自硬砂强度仍能保持在较高的水平，因而，其大大改善了铸型或型芯的力学性能。
实施例12
组分  配比(质量/g)
单乙酸甘油酯  90
三乙酸甘油酯  300
碳酸丙烯酯  10
硅微粉  600
甲醇  30
水  50
制备工艺同实施例1。
实施例13
组分  配比(质量/g)
三乙酸甘油酯  300
碳酸丙烯酯  100
硅微粉  600
丙醇  30
水  50
制备工艺同实施例1。
实施例14
组分  配比(质量/g)
碳酸丙烯酯  400
硅微粉  600
丁醇  30
水  50
制备工艺同实施例1。
实施例15
组分  配比(质量/g)
碳酸丙烯酯  400
硅微粉  600
水  80
制备工艺同实施例1。
实施例16
组分  配比(质量/g)
乙二醇二乙酸酯  112.5
三乙酸甘油酯  375
碳酸丙烯酯  12.5
硅微粉  500
乙醇  60
水  20
制备工艺同实施例1。
实施例17
组分  配比(质量/g)
二乙酸甘油酯  60
三乙酸甘油酯  410
硅微粉  500
甲醇  60
水  20
制备工艺同实施例1。
实施例18
组分  配比(质量/g)
三乙酸甘油酯  470
硅微粉  500
丙醇  60
水  20
制备工艺同实施例1。
将实施例12-18得到的水玻璃自硬砂液体增强剂用于水玻璃自硬砂的制备中，具体操作为：
称取大林标准砂1000g，加入叶片式实验室用混砂机，加水玻璃自硬砂液体增强剂8.64g，搅拌1min，加水玻璃SQ-1 20g，搅拌1min，出砂，打制标准“8”形试块，检测1h，4h和24h抗拉强度。经检测，采用其配制成的水玻璃自硬砂液体增强剂制备得到的水玻璃自硬砂，在成型1h后即可显著增加水玻璃自硬砂的强度，使其抗拉强度在0.395-0.408之间，即使在成型后经较长时间的贮存，其制备的水玻璃自硬砂强度仍能保持在较高的水平，在成型24h时，其抗拉强度能达到0.586-0.605之间，大大改善了铸型或型芯的力学性能。
此外，本发明通过将包含酯、无定形二氧化硅和水的固化剂各组分通过高速剪切混合配制成浆状体，再将其应用于水玻璃自硬砂的制备中，从而实现了铸造水玻璃用固化剂的一次性加入，无粉体污染，操作简单，计量、添加使用方便，实现了工业化生产。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (9)

  1. 一种铸造水玻璃用固化剂，其特征在于，所述固化剂含有：酯、无定形二氧化硅和水；所述无定形二氧化硅为热解法无定形二氧化硅和/或沉淀法无定形二氧化硅。
  2. 根据权利要求1所述的固化剂，其特征在于，所述酯为单乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、乙二醇二乙酸酯、碳酸丙烯酯或二元酯中的任意一种或至少两种的混合物。
  3. 根据权利要求1或2所述的固化剂，其特征在于，所述酯和无定形二氧化硅的重量比为(0.3-4)∶1，优选为(0.68-2)∶1。
  4. 根据权利要求1-3任一项所述的固化剂，其特征在于，所述固化剂按质量分数含有：酯20-40％；无定形二氧化硅30-60％；水5-30％。
  5. 根据权利要求1-4任一项所述的固化剂，其特征在于，所述固化剂还含有醇；所述醇优选为乙醇、甲醇、丙醇、异丙醇、丁醇、异丁醇、苯甲醇、乙二醇或聚乙二醇中的任意一种或至少两种的混合物，进一步优选为乙醇。
  6. 根据权利要求5所述的固化剂，其特征在于，所述固化剂按质量分数含有：酯20-40％；无定形二氧化硅30-60％；醇2-12％；水3-18％。
  7. 根据权利要求1-6任一项所述的铸造水玻璃用固化剂的制备方法，其特征在于，包括以下步骤：
    (1)先将按配比称量的酯加入高速搅拌机搅拌罐内，启动搅拌；
    (2)投入按配比称量好的水，任选地，再投入按配比称量好的醇；调节转速在800转/分以上，加入无定形二氧化硅，继续搅拌10-20min，使其成为悬浮液，得到所述的铸造水玻璃用固化剂。
  8. 根据权利要求1-6任一项所述的铸造水玻璃用固化剂的用途，其特征在于，将所述固化剂用于制备铸型和型芯；
    优选地，所述铸型和型芯用于金属铸造，尤其是用于铸铁和铸钢。
  9. 一种水玻璃自硬砂，其特征在于，所述水玻璃自硬砂按质量分数含有：石英砂95-98％；水玻璃1.8-2.5％；液体增强剂0.6-1.6％；
    其中，所述液体增强剂为权利要求1-6任一项所述的铸造水玻璃用固化剂。
PCT/CN2017/072892 2016-02-05 2017-02-04 一种铸造水玻璃用固化剂及其制备方法和用途 WO2017133685A1 (zh)

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