CN103857480A - Coating compositions for inorganic casting molds and cores, comprising formic acid esters, and use thereof - Google Patents
Coating compositions for inorganic casting molds and cores, comprising formic acid esters, and use thereof Download PDFInfo
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- CN103857480A CN103857480A CN201280049484.8A CN201280049484A CN103857480A CN 103857480 A CN103857480 A CN 103857480A CN 201280049484 A CN201280049484 A CN 201280049484A CN 103857480 A CN103857480 A CN 103857480A
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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
- B22C1/02—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
- B22C1/04—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 protection of the casting, e.g. against decarbonisation
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/12—Treating moulds or cores, e.g. drying, hardening
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- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mold Materials And Core Materials (AREA)
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The subject matter of the invention relates to coating compositions comprising formic acid esters, an aqueous carrier liquid and pulverulent refractory material, and to the use thereof for casting molds, in particular those produced using water glass as a binder.
Description
Technical field
The present invention relates to the sizing composition of a kind of conduct that comprises methyl formate for the coating material of mold.Sizing composition is suitable for core and mould, particularly at application waterglass manufactured this core and mould as adhesive in the situation that.
Background technology
Mold can be by refractory material, for example quartz sand in the case of being configured as mold and by obtaining applicable adhesive, to guarantee enough mechanical strengths of mold.Therefore apply fire-resistant mold base material and applicable adhesive for manufacturing mold.Fire-resistant mold base material is preferably can mobile mode existing, to such an extent as to it can be filled in applicable empty mould and be compressed at this place.Between the particle of mold base material, produce firmly bonding by adhesive, to such an extent as to mold obtains needed mechanical stability.
Not only can apply organic adhesive and also can apply inorganic adhesive in order to manufacture mold, the sclerosis of described adhesive can be undertaken by cold process or hot method respectively.At this, following method is called to cold process, described method is carried out substantially under the room temperature that does not need heated mold.Be hardened in this and mainly undertaken by chemical reaction, described chemical reaction for example triggers in the following way, is guided through mould to be hardened as the gas of catalyst.In hot method, moulding material mixture is heated in sufficiently high temperature after moulding, to for example remove the solvent that is included in adhesive or to start chemical reaction, for example harden by crosslinked by described chemical reaction adhesive.
All organic systems are jointly irrelevant with sclerosis mechanism, make their heat in the time that liquid metal is filled in mold pulverize and such as, can partly discharge Unidentified pyrolysis product at this harmful substance, benzene,toluene,xylene, phenol, formaldehyde etc.
Although successfully this Reducing exhaust emission is arrived to minimum degree by different measures, is organically discharging and can not avoid completely described in adhesive.
Although successfully this Reducing exhaust emission is arrived to minimum by different measures, can not fully avoid the in the situation that of organic adhesive.
For by the Reducing exhaust emission of the crushed products during casting process to minimum or avoid, can apply following adhesive, material or the described adhesive of described adhesive based on inorganic comprises the considerably less organic compound of content.These adhesive compositions are known for a long time always.Developed following adhesive composition, described adhesive composition hardens by the importing of gas.This class system is for example described in GB782205, and wherein using basic waterglass is as adhesive, and described alkaline water glass can be by importing CO
2sclerosis.In US6972059B1, describe the feed material of heat release, described feed material comprises subsilicate as adhesive.In addition developed following adhesive composition, described adhesive composition self-hardening at room temperature.These systems based on phosphoric acid or metal oxide are for example at US5, describe in 582,232.Finally known following inorganic adhesive composition also, described adhesive composition hardens at higher temperature, for example, in hot instrument, harden.The adhesive composition of these thermmohardenings is for example from US5, known in 474,606, wherein described the adhesive composition being made up of alkali formula waterglass and alumina silicate.
A kind of adhesive composition of the molding sand for the manufacture of core has been described in US7022178B1.Moisture absorption base, for example NaOH that adhesive composition based on waterglass adds by moisture subsilicate solution with the ratio of 1:4 to 1:6 form.Waterglass has 2.5 to 3.5 SiO
2/ M
2the coefficient of O and 20% to 40% solid share.For obtain also can be packed in complicated core can be mobile moulding material mixture and in order to control hygroscopicity, adhesive composition also comprises surfactant, as silicone oil, described silicone oil has >=boiling point of 250 ℃.Adhesive composition and applicable refractory material, mix as quartz sand, and then can be expelled in core box by core shooter.The sclerosis of moulding material mixture is undertaken by extracting the water still comprising out.Dry or the sclerosis of mold also can be carried out under the effect of microwave.
But inorganic adhesive also has following shortcoming with respect to organic adhesive, example as is known inorganic adhesive has by means of the mold of its manufacture with respect to high air humidity or with respect to the low stability of water.Therefore within the longer time period, store mold, be not definitely feasible as common in organic adhesive.In cast(ing) surface, obtain better result with respect to the better durability of air humidity, higher initial strength and when the casting in order to obtain mold, in US7770629B2, propose a kind of moulding material mixture, described moulding material mixture also comprises the adhesive based on waterglass except fire-resistant mold base material.Moulding material mixture is added the granular metal oxide of certain share.Advantageous applications precipitated silica or fumed silica are as granular metal oxide.
In addition, on the described methodological principle for the manufacture of mold and core, comprise the fire-resistant mould coating also referred to as sizing material is at least applied on the surface contacting with casting metals of basic mode.Mould coating has following object on the one hand: mould part surface is exerted an influence, improved casting of appearance of cast, on metallurgy, foundry goods exerted an influence and/or avoid casting flaw.
Common applied sizing material for example comprises clay, quartz, diatomite, cristobalite, tridymite, alumina silicate, zirconium silicate, mica and/or fire clay and also has coke and graphite as mother metal.Described mother metal is the sizing material of the share of appointment, and these sizing materials cover die surfaces and sealing pore prevents cast metal infiltration.
Therefore also can coordinate mutually by the surface modification of mold and with the characteristic of pending metal by these coating.Therefore the outward appearance that can improve by sizing material foundry goods by following manner, produces level and smooth surface, because compensate the inhomogeneities being caused by the granular size of moulding material by sizing material.In addition, the sizing material of foundry goods can for example affect by the mode of optionally on the surface of foundry goods, additive being transferred in foundry goods via sizing material on metallurgy, the surface characteristic of described additive improved foundry goods.In addition sizing material has formed as lower floor, and described layer is chemically being isolated mold in the time of casting liquid metal.Prevented thus any adhesion between foundry goods and mold, to such an extent as to foundry goods can easily be removed from mold.But sizing material also can be used in the heat transmission of controlling targetedly between liquid metal and mold, to for example affect the formation of specific metal structure structure by cooling velocity.
The sclerosis of applied inorganic adhesive is carried out via the condensation reaction causing at Yin Gaowen now more and more, and wherein the formation of intermediate adhesive (Binderbr ü cken) is carried out via splitting water.If multiple chemical reactions are here reversible reactions, that is to say by with the contacting and react again cracking key (Bindung) of water, wherein the degree of this back reaction is relevant to the technological parameter that core is manufactured to a great extent.The in the situation that of common applied technological parameter in batch production (cycle, high temperature fast), mold is by contacting with water and partly also losing its intensity by contacting with alcohol, and surperficial deliquescing and mold lose its shape.
Summary of the invention
The present invention is based on following object, a kind of sizing material is proposed, can guarantee flawless as far as possible coating, particularly inorganic core and the coating of mould by described sizing material, and can not produce negative infringement and then can and not store processing and produce negative infringement the stability of core and mould.
The sizing composition of the feature of this object by having claim 1 is realized, and favourable design forms the theme of dependent claims or describes hereinafter.
Sizing composition according to the present invention provides with the form of cream or suspension according to a preferred form of implementation.In this form of implementation, sizing composition comprises carrying object.
Have been surprisingly found that, in the time specific additive being added to moisture sizing composition, the inorganic core of gluing and the quality of mould can be enhanced constantly, and for example can realize without any problems the bin stability of many days of core and mould.
As other additive part of sizing composition, can use the ester of formic acid (formic acid), wherein in the time of esterification, the chain length of applied alcohol or alcohol mixture is particularly on average less than 6 carbon atoms and is especially preferably less than 3 carbon atoms.Especially advantageous applications formic acid methyl ester (methyl formate) and formic acid ethyl ester (Ethyl formate).Also possible that, several in (or multiple) alcohol groups or alcohol groups carry one or two other group, as ether group, oh group, ester group or carboxylic group, or formic acid by second or trihydroxy group crosslinked, be for example cross-linked by condensation.
At this, above-mentioned additive level is counted 1 % by weight to 8 % by weight with sizing composition, preferably 2 % by weight to 8 % by weight and especially preferably 3 % by weight to 6 % by weight.
For example can use " the pure methyl formate " of BASF AG as additive.It has CAS numbering 107-31-3.
According to the desired application of sizing composition, for example, as basic coating or cover coating, and according to the desired layer thickness of the coating of being manufactured by described sizing composition, can regulate other characteristic parameter of sizing composition.
Carrying object can partially or fully be made up of water.Carrying object is following part, described part under 160 ℃ and normal pressure, be can evaporate and thus current according to limit rather than solid containing thing.Carrying object comprise to be greater than 50 % by weight, the preferred water that is greater than if desired 95 % by weight 75 % by weight, that be particularly greater than 80 % by weight.
The part of other in carrying object can be organic solvent.Applicable solvent is alcohol, comprises polyalcohol and Aethoxy Sklerol.The alcohol of example is ethanol, normal propyl alcohol, isopropyl alcohol, butanols and ethylene glycol.
The solids content of available sizing composition is preferably set in the scope of 10 % by weight to 85 % by weight, or in the time selling (before dilution) particularly 30 % by weight to 70 % by weight.
Sizing material for example can comprise the combination as the specific clay that includes material of sizing material.Application
A) 1 parts by weight to 10 parts by weight, the palygorskite of 1 parts by weight to 5 parts by weight particularly;
B) 1 parts by weight to 10 parts by weight, the hectorite of 1 parts by weight to 5 parts by weight particularly; And
C) 1 parts by weight to 20 parts by weight, the particularly combination of the sodium bentonite of 1 parts by weight to 5 parts by weight (respectively about each other) is as clay material, particularly at palygorskite in 1 to 0.8 to 1.2 the weight ratio about hectorite, and at palygorskite together with hectorite in 1 to 0.8 to 1.2 the ratio about sodium bentonite.At this, sizing material accounts for the clay total content of above-mentioned clay and counts 0.1 % by weight to 4.0 % by weight with the solids content of sizing composition, preferably 0.5 % by weight to 3.0 % by weight and especially preferably 1.0 % by weight to 2.0 % by weight.The in the situation that of these clays of application, can further improve the bin stability of core and mould.
In addition sizing composition can comprise the magnesium that is greater than in the concentration of 1 % by weight in amounting to if desired of sizing composition and/or the slaine of manganese.Can especially compatibly use (multiple) sulfate ion and/or the chlorion anion as salt, wherein particularly use oxidation valency+2 or+4 magnesium, and/or the manganese of use oxidation valency+2, and the concentration of salt is particularly greater than 3 % by weight and is particularly greater than 5 % by weight in sizing composition.According to a design, the concentration of salt is the maximum saturated concentration corresponding to applied carrying object upwards, but or the concentration of salt be less than 10 % by weight in sizing composition.
Therefore sizing composition according to the present invention comprises at least one pulverous refractory material.This refractory material is used for: the pore of sealing mold infiltrates to prevent liquid metal.In addition realize the heat isolation between mold and liquid metal by refractory material.In metal casting, apply common refractory material as refractory material.The example of applicable refractory material is that quartz, aluminium oxide, zirconia, alumina silicate are as pyrophillite, kyanite, andalusite or fire clay, zircon sand, zirconium silicate, olivine, talcum, mica, coke, feldspar, diatomite, kaolin, calcined kaolin, kaolinite, metakaolinite, iron oxide and/or alumina.
Refractory material provides with Powdered.Granularity is selected as at this, makes in coating, to produce stable institutional framework, and sizing material is preferably distributed on the wall of mold without any problems by spraying equipment.Refractory material suitably have in the scope of 0.1 μ m to 500 μ m, the preferred particle mean size (measuring by means of the light scattering according to DIN/ISO13320) in the scope of 1 μ m to 200 μ m particularly.Have at least higher than the fusing point of 200 ℃ of the temperature of liquid metal and the special material not reacting with metal is independently to this suitable as refractory material.
The share (always only having contribution for solids content) of refractory material, is preferably selected as being greater than 70 % by weight in the solid share of sizing composition, is preferably greater than 80 % by weight, is especially preferably greater than 85 % by weight.
According to an embodiment (always only having contribution for solids content), the share of refractory material is less than 70 % by weight, is less than 60 % by weight and is less than 50 % by weight according to another embodiment according to another embodiment.
Can comprise at least one suspending agent (Stellmittel) according to a form of implementation according to sizing material of the present invention.Described suspending agent causes the raising of the viscosity of sizing material, to such an extent as to the part of the solid of sizing material in suspension does not decline or only marginally declines.In order to improve viscosity, not only can apply organic material and also can apply inorganic material or the mixture of these materials.The inorganic suspending agent being applicable to is for example the clay that can strongly expand, for example sodium bentonite.
As suspending agent, alternatively or addedly, also can select organic thickener, because this thickener can be dried to and make it discharge hardly water in the time contacting with liquid metal after applying protection coating.For example can consider expandable polymer as organic suspending agent, as carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyethylcellulose and hydroxypropyl cellulose, natural plant gum, polyvinyl alcohol, PVP, pectin, gelatin, agar, polypeptide and/or alginates.
The share of suspending agent in whole sizing compositions preferably with 0.1 % by weight to 5 % by weight, preferably 0.5 % by weight to 3 % by weight, especially preferably 1 % by weight to 2 % by weight is selected.
According to a preferred form of implementation, sizing material according to the present invention comprises the part of at least one adhesive as other.Described adhesive can be realized on the wall that the protective finish of manufacturing by sizing material or by sizing material is better fixed on mold.In addition, improved the mechanical stability of protection coating by adhesive, to such an extent as to observed erosion lower under the effect of liquid metal.Preferred adhesive is irreversibly hardened, to such an extent as to obtains wear-resisting coating.Particularly preferably be following adhesive, described adhesive can again not soften in the time contacting with atmospheric moisture.Can comprise in fact all adhesives of applying in sizing material.Not only can apply inorganic adhesive at this and also can apply organic adhesive.For example can apply clay, particularly bentonite and/or kaolin as adhesive.
The share of adhesive preferably with the solid content meter of sizing composition 0.1 % by weight to 20 % by weight, especially preferably in the scope of 0.5 % by weight to 5 % by weight, select.
According to another preferred form of implementation, the graphite that sizing material comprises certain share.This auxiliary stratiform carbon is formed in the boundary face between foundry goods and mold.The share of graphite preferably with the solid content meter of sizing composition 1 % by weight to 30 % by weight, especially preferably in the scope of 5 % by weight to 15 % by weight, select.Graphite advantageously works to the surface quality of foundry goods in the time that iron is cast.
Also can also comprise if desired component common for sizing material, for example wetting agent, defoamer, pigment, dyestuff and antimicrobial according to sizing composition of the present invention.The share that these other part accounts for available coating material is preferably selected as being less than 10 % by weight, is preferably less than 5 % by weight and is especially preferably less than 1 % by weight.
Anion with surfactant non-anion, this surfactant particularly with the HSB value that is at least 7 for example can be used as wetting agent.The example of this class wetting agent is disodium dioctyl sodium sulfonate.Wetting agent is preferably in the amount of available sizing composition 0.01 % by weight to 1 % by weight, preferably 0.05 % by weight to 0.3 % by weight application %.
Can apply the defoamer also referred to as anti-foaming agent, to prevent formation of foam in the time manufacturing sizing composition or in the time applying described sizing composition.Formation of foam in the time of coating adhesive feed composition can cause inhomogeneous layer thickness and cause the hole in coating.For example can apply silicone oil or mineral oil as defoamer.Defoamer in available sizing composition preferably be contained in 0.01 % by weight to 1 % by weight, the preferred amount of 0.05 % by weight to 0.3 % by weight.
In sizing composition according to the present invention, can apply if desired common pigment and dyestuff.These pigment and dyestuff are added, to realize for example another contrast between different layers, or produce the stronger separating effect of sizing material and foundry goods.The example of pigment is red and yellow iron oxide and graphite.The example of dyestuff is commercially available dyestuff, as Ludwigshafen, Germany BASF AG
the dyestuff of chromatic series.Dyestuff and pigment preferably are contained in 0.01 % by weight to 10 % by weight, the preferred amount of 0.1 % by weight to 5 % by weight with the solid content meter of sizing composition.
According to another form of implementation, sizing composition comprises antimicrobial, to prevent bacterium invasion and then avoid bonding force and rheology on adhesive to produce negative impact.
In the time being included in carrying object in sizing composition and substantially being formed by water by weight, that is to say, in the time that sizing composition according to the present invention provides with the form of so-called water-based sizing material, this is especially preferred.The example of applicable antimicrobial is formaldehyde, MIT (MIT), CMIT (CIT) and BIT (BIT).Advantageous applications MIT, BIT or their mixture.Antimicrobial is applied conventionally with the weighing scale of available sizing composition in the amount of 50ppm to 500ppm 10ppm to 1000ppm, preferred.
Except already mentioned part, can comprise other common part for sizing material according to sizing composition of the present invention.
Can manufacture according to common method according to sizing composition of the present invention.For example manufactured in the following way according to sizing composition of the present invention, there is water and the in the situation that of application high-shear mixer, the clay that act as suspending agent divided in water.And then admix the additive of fire-resistant component, pigment and dyestuff and metal, until produce uniform mixture.Finally admix wetting agent, anti-foaming agent, antimicrobial and adhesive.
According to sizing composition of the present invention can as can with by formula manufacture sizing material carry out produce and market.But also can carry out produce and market with the form concentrating according to sizing material of the present invention.In this case, for available sizing material is provided, add a certain amount of carrying object, described carrying object is essential, to regulate desired viscosity and the density of sizing material.In addition, also can carry out produce and market with the form of cover group according to sizing composition of the present invention, wherein for example solid constituent and solvent composition are present in the container of separation each other simultaneously.Solid constituent can be provided at container independently as pulverous solid mixture.The liquid composition of if desired to be applied other, for example adhesive, wetting agent, penetrant (Netzer)/defoamer, pigment, dyestuff and antimicrobial can again be present in the container of separation in this cover group.Solvent composition or can comprise if desired component additionally to be applied, for example component in a common container, or it can be present in independently in container dividually with other optional part.
In order to manufacture available sizing material, solid constituent, optionally other component and together with the applicable amount of solvent composition is mixed with each other.
Sizing composition according to the present invention is suitable for to mold coating.Applied statement here " mold " comprises all types of base substrates, described base substrate for foundry goods, as the manufacture of core, mould and die be important.The application according to the present invention of sizing composition also comprises mould portion ground coating.Sizing material is for the mold for metal processing, described sizing material can be obtained by inorganic moulding material mixture, comprise at least one fire-resistant mold base material, adhesive based on waterglass and preferably include the metal oxide of certain share, described metal oxide is selected from silica, particularly amorphous silica, aluminium oxide, titanium oxide or zinc oxide and their mixture, wherein this metal oxide preferred exist granularly and particularly have be less than 300 μ m(screen analysises) particle size.Amorphous carbon dioxide for example starts to obtain via depositing technology from waterglass, and the quartz sand that described waterglass can have sodium carbonate or potash by division obtains.Therefore according to process conditions by produced SiO
2be called precipitated silica
another kind of important manufacture flexible program be in oxyhydrogen flame the chlorosilane from fluid, start to produce so-called gas phase SiO as silicon tetrachloride
2.
Moulding material mixture and for manufacturing method for the mold of metal processing at WO2006/024540(=US7770629B2 in the case of the moulding material mixture of application sclerosis) describe and put described open source literature about this and be incorporated to this paper by reference.Preferred moulding material mixture is the theme of the claim of WO2006/024540.Therefore the mold for the treatment of coating typically comprises:
A) be greater than the fire-resistant mold base material (comprising additive, the performance of described additive as fire-resistant mold base material) of 80 % by weight;
B) waterglass of the sclerosis of 0.01 % by weight to 5 % by weight is as adhesive;
C) above-mentioned one or more metal oxides of 0 % by weight to 5 % by weight if desired.
In addition the present invention relates to a kind of method of manufacturing the mold of the gluing of processing for metal in the case of sizing material being applied on the above-mentioned inorganic moulding material mixture partially or fully hardening.Applying or providing of sizing material can be carried out as follows:
In the time immersing as applying method, mold is immersed in container and continues to reach about 2 seconds to 2 minutes, in the mould cavity of described mold, be applied with if desired basic coating, described container by can with, sizing composition according to the present invention fills.Mold takes out subsequently from sizing composition, and unnecessary sizing composition is flowed out from mold.After immersing, defer to the outflow performance of applied sizing composition for flowing out the time of unnecessary sizing composition.
In the time spraying as applying method, apply commercially available forbay spraying equipment.Here sizing composition is filled in forbay with the state of dilution.Via overvoltage to be arranged, sizing material can be pressed in spray gun, states sizing material spray by means of independent regulatable atomizing air in this place.In the time of spraying, preferably condition is chosen as, the pressure for sizing composition and atomizing air on rifle is adjusted to, injected sizing composition is mapped on mould or core still moisteningly, apply but produce uniformly.
When using flow coat as applying method, mold by means of flexible pipe, spray gun or similarly instrument with can with sizing composition according to the present invention pour into, in the mould cavity of described mold, be applied with if desired basic coating.Mold is fully covered by sizing composition at this, and unnecessary sizing composition flows out from mold.After flow coat, defer to the outflow performance of applied sizing composition for flowing out the time of unnecessary sizing composition.
In addition, sizing material also can apply by smearing.
And then the carrying object being included in sizing material is evaporated, to such an extent as to obtains dry sizing material layer.As drying means, can apply all traditional drying means, for example air drying, by the air after dehumidifying be dried, by microwave or infra-red radiation be dried, in convection oven dry and similarly method as drying means.
In a preferred form of implementation of the present invention, the mold of coating, at 20 ℃ in 250 ℃, is preferably dried in 50 ℃ to 180 ℃ in convection oven.
In the time of application alcohol sizing material, be preferably dried by burn off alcohol or alcohol mixture according to sizing composition of the present invention.Here the mold of coating additionally heats by calory burning.In another preferred form of implementation, the processing that the mold of coating has not needed other is dry at air drying or in applied microwave in the situation that.
Sizing material can be applied in the mode of the layer of multiple stack settings with the form of independent layer or also.In its constituent, can be same or different at this each layer.For example first can manufacture basic coating by commercially available sizing material, described commercially available sizing material does not comprise the additives according to metal of the present invention.As basic coating, for example, can apply glue material or also can apply ethanol sizing material.But also possible that, manufacture all sizing materials by sizing composition according to the present invention.But the layer contacting with liquid metal afterwards is always manufactured by sizing material according to the present invention.In the time applying multiple layers, each layer can fully or partly be dried after applying.
The coating of being manufactured by sizing composition preferably has at least 0.1mm, preferably 0.2mm at least, especially preferably 0.45mm at least, especially preferably the drying layer thickness of 0.55mm at least.According to a form of implementation, the thickness of coating is selected as being less than 1.5mm.Here drying layer thickness is the layer thickness of dry coating, described dry coating by by substantially remove completely solvent composition and if desired and then sclerosis be dried sizing composition and obtain.The drying layer thickness of basis coating and covering coating is preferably by measuring and determine by means of wet layer thickness comb.
And then mold can intactly be assembled if desired.Casting is preferred for the manufacture of cast iron base substrate and cast steel base substrate.
The specific embodiment
In this example, the salt pair impact of the intensity of the core of gluing in check sizing material.Applied core sizing material 1 to 3 have table 1 to 3 in explanation constituent.
Table 1: the constituent of sizing material
Die casting sizing material is manufactured as follows: water is provided and and then pulverizes clay at least 15 minutes by the agitator of application high shear therein.And then admix fire-resistant component, pigment and dyestuff at least 15 minutes, until produce uniform mixture.Be that methyl formate or Ethyl formate add in sizing material 1 and 2 by two kinds of additives together with described refractory material.Finally admix additive as wetting agent, defoamer and anticorrisive agent and adhesive.
Sizing material is adjusted to and is suitable for viscosity application, in the scope of 0.6Pas for following test.Described adjusting by give original constituent add the water of respective amount and and then homogenising carry out.Principal character variable is viscosity at this, and described viscosity is measured by Brookfield viscometer (DIN EN ISO2555) and DIN4mm viscosity flow cup (DIN EN ISO2431) at 20 ℃.
Table 2: application parameter
| ? | Sizing material 1 | Sizing material 2 | Sizing material 3 |
| Bu Shi [Pas] | 0.6 | 0.6 | 0.6 |
| Delivery time [s] | 15.5 | 15.5 | 15.5 |
| Solids content [%] | 66.9 | 66.9 | 66.9 |
| Immersion depth [mm] | 2 | 2 | 2 |
| ? | According to the present invention | According to the present invention | Not according to the present invention |
Being included in methyl formate in sizing material 1 can also react with the inorganic adhesive dissolving during gluing process except other characteristic.The higher stability that this causes the sclerosis of the inorganic adhesive having dissolved and then causes the core of gluing.Otherwise the decline of the content in sizing material causes the loss of strength in core.What be suitable for equally is the Ethyl formate using in sizing material 2.Be described in more detail below the execution of corresponding experimental series, described experimental series is as the basis of described knowledge.
Comparable performance equally can realizing by the ester chemically close.
The Computer-Assisted Design, Manufacture And Test of moulding material sample:
For two kinds of different core geometries of experiment purpose research.A kind of geometry, the performance of the sample that so-called George's Fischer prod illustrates gluing in thicker core geometry, another kind of geometry, the performance of the sample that so-called long core illustrates gluing in thin geometry.George's Fischer prod is interpreted as to prod rectangular-shaped, that have 150mm × 22.36mm × 22.36mm size.Long core has the size of 13mm × 20mm × 235mm.
The explanation in table 3 of the constituent of moulding material mixture.Carry out following steps in order to manufacture George's Fischer prod: the component of enumerating is mixed in laboratory arm stirrer (Hagen, Germany Vogel & Schemmann AG company) in table 3.First this provided to quartz sand and in the situation that stirring, add waterglass.As waterglass, application has the sodium silicate of the potassium of certain share.The SiO of waterglass
2: M
2o coefficient is about 2.2, and wherein M represents the summation of sodium and potassium.After mixture has been stirred one minute, under further stirring, add amorphous silica if desired.Amorphous silica is the aerosil of RW Silicium company.And then mixture still stirs one minute in addition.
Moulding material mixture is transferred in storage bin, and German Fil is gloomy
in the hot box core shooter of H2.5 of Gie β ereimaschinen limited company, the mould of described moulding material mixture is heated to 180 ℃.Moulding material mixture is introduced in mould and in mould and keeps 35 seconds in addition by means of compressed air (5bar).For the sclerosis of accelerating mixture, during latter 20 seconds, hot-air (2bar in the time entering mould, 150 ℃) is guided through mould.Open mould and take out prod.
Clad compositions is applied on prod by dipping, and application parameter is listed in table 2.Prod or from mould take out after immediately coating or after the cool time of 30 minutes coating.The prod of coating is deposited 30 minutes applying after coating in drying box at 150 ℃.
In order to determine bending strength, prod inserted in George's Fischer ruggedness test equipment that is equipped with three-point bending device (the DISA Industrie joint-stock company of Schaffhausen, Switzerland) and measure the power that causes prod to fracture.
The bending strength of the prod of coating is not measured according to following proposal:
-in latter 10 seconds of taking-up (calorific intensity)
-in latter 1 hour of taking-up (cold strength)
Prod carrys out coating according to following proposal:
-at latter 1 minute coating (hot coating) of taking-up
-at latter 30 minutes coating (cold coating) of taking-up
The bending strength of the prod of coating is measured according to following proposal:
-taking out latter 10 seconds (calorific intensity, hot coating) from drying box
-at latter 30 minutes coating (cold strength, hot coating, directly from baking oven takes out) of taking-up
-taking out latter 10 seconds (calorific intensity, cold coating, 20 ℃ of room temperatures) from drying box
-at latter 30 minutes coating (cold strength, cold coating) of taking-up
Table 3: the constituent of moulding material mixture
Table 4: the intensity of George's Fischer prod
Table 5: the intensity on long core
Result:
Containing the application of the coating of alcohol owing to forming the shortcoming of emission during casting technique but less desirable.In the case of the coating agent based on water of application standard, the sample being made up of the moulding material agent that comprises waterglass loses intensity (sizing material 4) consumingly.
Suppress to come from the possibility of reacting between the water of coating and the adhesive of moulding material by searching, be surprisingly found out that, the ester that adds formic acid in coating suppresses described effect significantly.Strength retention is constant.Can use the ester with different chain length and structure, for example the ester in sizing material 1 and 2 in example 1.Compared with core with sizing material 3 gluings, high intensity is the proof of positive effect.
Claims (12)
1. a sizing composition, comprises:
(A) ester of formic acid;
(B) carrying object that comprises water or formed by water; And
(C) refractory material.
2. sizing composition according to claim 1, is characterized in that, (multiple) alcohol groups of the ester of described formic acid has respectively and is less than 10 carbon atoms, is preferably less than 6 carbon atoms and is especially preferably less than 3 carbon atoms.
3. sizing composition according to claim 1 and 2, the concentration of the ester of the described formic acid in wherein said sizing composition is 1 % by weight to 8 % by weight, preferably 2 % by weight to 8 % by weight, and 3 % by weight to 6 % by weight especially.
4. according to one or more described sizing composition in the claims, wherein said carrying object comprises the water that is greater than 50 % by weight, and preferably comprise in addition alcohol, comprise polyalcohol and Aethoxy Sklerol, and particularly until can fully evaporate 160 ℃ and 1013mbar in the situation that.
5. according to one or more described sizing composition in the claims, the solids content of wherein said sizing composition is 30 % by weight to 70 % by weight.
6. according to one or more described sizing composition in the claims, the refractory material that wherein said sizing composition comprises 10 % by weight to 85 % by weight with the described solid content meter of described sizing composition.
7. according to one or more described sizing composition in the claims, wherein said refractory material is the mixture of quartz, aluminium oxide, zirconia, alumina silicate, zircon sand, zirconium silicate, olivine, talcum, mica, coke, feldspar, diatomite, calcined kaolin, kaolinite, metakaolinite, iron oxide, alumina and/or above-mentioned material.
8. according to one or more described sizing composition in the claims, wherein said refractory material is measured by means of the light scattering according to DIN/ISO13320, has the granularity of 0.1 μ m to 500 μ m, especially the granularity of 1 μ m to 200 μ m.
9. according to one or more described sizing composition in the claims, wherein said sizing composition with the described solid content meter of described sizing composition comprise 0.1 % by weight to 20 % by weight, at least one adhesive of 0.5 % by weight to 5 % by weight especially.
10. according to one or more described sizing composition in the claims, wherein said sizing composition comprises bright carbon forming agent or graphite, particularly 0.1 % by weight to 10 % by weight, particularly 0.5 % by weight to 3 % by weight.
The 11. one application for coating moulding material mixture according to one or more described sizing composition in the claims, described moulding material mixture is hardened by the waterglass as adhesive, is hardened if desired after at least with water dilution.
12. application according to claim 11, wherein said moulding material mixture comprises the mixture of silica, aluminium oxide, titanium oxide or zinc oxide and/or above-mentioned material and particularly amorphous silica.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011115024A DE102011115024A1 (en) | 2011-10-07 | 2011-10-07 | Coating compositions for inorganic casting molds and cores comprising formic acid esters and their use |
| DE102011115024.6 | 2011-10-07 | ||
| PCT/DE2012/000973 WO2013050023A2 (en) | 2011-10-07 | 2012-10-05 | Coating compositions for inorganic casting molds and cores, comprising formic acid esters, and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103857480A true CN103857480A (en) | 2014-06-11 |
Family
ID=47115089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280049484.8A Pending CN103857480A (en) | 2011-10-07 | 2012-10-05 | Coating compositions for inorganic casting molds and cores, comprising formic acid esters, and use thereof |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20140242269A1 (en) |
| EP (1) | EP2763806B1 (en) |
| JP (1) | JP2014534075A (en) |
| KR (1) | KR20140077196A (en) |
| CN (1) | CN103857480A (en) |
| BR (1) | BR112014008377A2 (en) |
| DE (1) | DE102011115024A1 (en) |
| IN (1) | IN2014KN00957A (en) |
| MX (1) | MX2014004211A (en) |
| RU (1) | RU2014118127A (en) |
| WO (1) | WO2013050023A2 (en) |
| ZA (1) | ZA201402090B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108246977A (en) * | 2018-01-16 | 2018-07-06 | 中国船舶重工集团公司第十二研究所 | A kind of restorative procedure of Ti alloy casting graphite mould surface hole defect |
| CN109641261A (en) * | 2016-06-30 | 2019-04-16 | 胡坦斯·阿尔伯图斯化学厂有限公司 | In the mold wash component for being used to manufacture mold coating on iron casting and the non-permanent mold or type core of steel casting |
| CN110446571A (en) * | 2017-01-04 | 2019-11-12 | 胡坦斯·阿尔伯图斯化学厂有限公司 | In foundary industry includes the coating composition of organic esters and granular amorphous silica |
| CN110997179A (en) * | 2017-07-18 | 2020-04-10 | Ha国际有限责任公司 | Composition and method for fire resistant coatings with ester carriers |
| CN113905837A (en) * | 2019-06-07 | 2022-01-07 | 日油株式会社 | Surfactant composition for foamed sand |
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| DE102010013999A1 (en) * | 2010-04-07 | 2011-10-13 | Vautid Gmbh | A method for producing a cast workpiece having at least partially increased wear protection |
| DE102017107655A1 (en) | 2017-01-04 | 2018-07-05 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Use of an acid-containing sizing composition in the foundry industry |
| DE102017107658A1 (en) | 2017-01-04 | 2018-07-05 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | A sizing composition for the foundry industry containing particulate amorphous silica and acid |
| DE102018117651A1 (en) | 2018-07-20 | 2020-01-23 | Ask Chemicals Gmbh | Sizing composition for casting molds for metal casting, their use and the casting composition provided with the sizing composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20140242269A1 (en) | 2014-08-28 |
| WO2013050023A2 (en) | 2013-04-11 |
| IN2014KN00957A (en) | 2015-10-09 |
| KR20140077196A (en) | 2014-06-23 |
| DE102011115024A1 (en) | 2013-04-11 |
| MX2014004211A (en) | 2014-05-28 |
| EP2763806A2 (en) | 2014-08-13 |
| ZA201402090B (en) | 2015-06-24 |
| BR112014008377A2 (en) | 2017-04-11 |
| WO2013050023A3 (en) | 2013-05-30 |
| JP2014534075A (en) | 2014-12-18 |
| RU2014118127A (en) | 2015-11-20 |
| EP2763806B1 (en) | 2016-07-06 |
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