CN1071159C - Binder composition for casting mould, mould composition and mould manufacturing method - Google Patents
Binder composition for casting mould, mould composition and mould manufacturing method Download PDFInfo
- Publication number
- CN1071159C CN1071159C CN 96110934 CN96110934A CN1071159C CN 1071159 C CN1071159 C CN 1071159C CN 96110934 CN96110934 CN 96110934 CN 96110934 A CN96110934 A CN 96110934A CN 1071159 C CN1071159 C CN 1071159C
- Authority
- CN
- China
- Prior art keywords
- sand
- compound
- binding agent
- reclaimed
- sand mold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Abstract
To improve the strength of a casting mold formed of rebonded sand by composing a binder compsn. for the casting mold of a specific phenol aldehyde modified resin and a compd. contg. metal elements of specific groups of the periodic table as essential components. The phenol aldehyde modified resin A obtd. by copolymerization of >=1 kinds of compds. selected from the bisphenols expressed by the formula and an aldehyde compd. is used. In the formula, X denotes R1 -C-R2 , S, O, O=S=O. R1 and R2 denote hydrogen atoms, trifluooromethyl groups, 1 to 6c satd. or unsatd. alcohol, phenyl groups or the deriv. of the latter two. R3 and R4 denote hydrogen atoms, 1 to 6c satd. or unsatd. alkyl groups, phenyl groups or the deriv. of the latter two. The compd. B contains >=1 kinds of metal elements selected from groups IB to VIII of the period table. The binder compsn. for casting molds is composed of a resin A and the compd. B as the essential components. The pot life of the molding sand is improved.
Description
The binding agent that uses when the present invention relates to make sand mold.And relate to the molding sand composition that cooperates this binding agent, and use this binding agent to make the method for sand mold.In addition, the present invention relates to effectively utilize alkali reclaim sand, make the method for sand molds such as core in the moulding production line generation of various manufacturing processes.
As the molding of using the sand mold of organic binder bond manufacturing as main body sand mold and core, self-hardening property sand mold method, cold-box process sand mold method, the peaceful shell mouding method of clo (shell mould method) are known.Particularly organic self-hardening property method for filling molding sand is the center with the mechanical sand field of making, and goes out a little from the viewpoint of productivity ratio, sand spare quality, safety and sanitation, has become to replace inorganic system and widely used molding.
On the other hand, the past is widely used in the phenolic resins that is covered on the granular refractory material in order to make sand mold with middle and high speed, with so-called coated sand heat hardening, makes the peaceful shell mouding method of clo of sand mold.
But, province when making for sand mold can, in order to improve the sand mold speed of production, and then improve sand mold, sand spare quality, carry out the cold-box process sand mold method of cold(-)setting with gas shape or aerosol shape material, the sand mold autofrettage of the peaceful shell mouding method of clo is instead made industry at sand and is just conscientiously repaid examination and be introduced into.
Recently, in order to improve sand spare quality and operating environment, as the binding agent that in organic self-hardening property method for filling molding sand and gas hardening method for filling molding sand, uses, with water soluble phenol resin as binding agent, make the casting model powder binding agent of its sclerosis with organic ester, opening clear 50-130627 communique, spy by the spy, to open clear 58-154433 communique and the clear 58-154434 communique of Te Kai etc. be known.In addition, the phenolic aldehyde with bis-phenol and formaldehyde condensation polymer is that resin also is known as binding agent use (spy opens clear 62-40948 communique, the spy opens clear 63-40636 communique) with potash bis-phenol phenol copoly type phenol-formaldehyde A as binding agent use (spy opens flat 5-123818 communique).
In addition, recently as the method for filling molding sand of gas hardening, propose to use the method (special fair 1-224623 communique) of carbon dioxide.This method is compared with the gas of organic ester, and is little to the baneful influence of human body, because use carbon dioxide, from the viewpoint of safety and sanitation aspect, noticeable especially.
Use the method for filling molding sand of these binding agents, because sulfur atom-containing not in the binding agent, compare with the method for filling molding sand that uses the acid-curable resin, have by the another side that soaks the little feature of influence that sulphur causes, because resulting sand mold intensity is low, so it is very many to become the essential resin content of moulding, the gas flow that produces during cast is many, and the problem that occurs gas defects is easily arranged.And, known and known that the reproducibility of the casting model powder of this binding agent mode is extremely poor that its use is restricted, and expects its improvement strongly.
In addition, fire resistance aggregate and binding agent are mixed, be filled in the model, extremely the time of hardening again is commonly referred to as working life, particularly use greensand mold reclaimed sand, waterglass reclaimed sand, water soluble phenol resin, the reclaimed sand that obtains from the sand mold that hardens with carbon dioxide or organic ester etc. are selected more than one alkali reclaim sand, the mixture that contains the fire resistance aggregate of these reclaimed sands and this binding agent is in order to show practical sand mold intensity, the problem that becomes extremely short working life is arranged, therefore, expectation is to its improvement.
In more detail, if these alkali reclaim sand of narration etc., then general reclaimed sand is as the combination of the sand mold manufacture process of alkalize, known in the moulding of main body sand mold with greensand mold and the water-soluble phenol of ester constrictive type, with waterglass, the water-soluble phenol of ester constrictive type, oyster shell whiting, phenol urethane, water-soluble phenol of hardening carbon dioxide gas type as an example etc. uses as binding agent recently in core sand moulding.These sand molds that are shaped to reclaim after cast/regenerate and are reused, but each reclaimed sand becomes alkalescence because of the influence of the binding agent that becomes base.Is resin when carrying out the sand mold moulding with such alkali reclaim sand with hardening carbon dioxide gas type water soluble phenolic, hinders sclerosis owing to exist alkali source both to cause, causes the phenomenon that shortens working life again, remarkable when using greensand mold and waterglass reclaimed sand especially.Its reason derives from the bentonite (clay matter) as binding agent when the damp sand molding sand, form the result of the alkali glass matter (not activated clay composition) that is called " sedimentary deposit " because of the bentonite of cast sintering.In the occasion of water-glass sand, result from the residual binding agent sodium metasilicate that has.Except that greensand mold and waterglass, the residual calcination loss amount of the occasion of cited organic binder bond is brought baneful influence.
The present invention is the invention of making in view of the above problems.Such binding agent is because the sand mold intensity of gained is low, and in order to obtain necessary sand mold intensity, the volume of having to is added resin in moulding.And king-sized shortcoming as this binding agent, in case be the recovery sand of purpose and reusable reclaimed sand for several times as using to re-use after making with sand, be difficult to guarantee that sand mold intensity is more prone to be absorbed in respect to binding agent, the use quantitative change of the sand abominable circulations that wait more.And the thermal decomposition gas flow the when increase of the binder amount in the sand mold is with cast like this increases relevant, has simultaneously with the gas defects of sand spare to worsen defectives such as relevant with operating environment.Present situation is, in order to alleviate such defective a little, general residual organic matter and alkali branch in order to remove the sand surface when carrying out strong mechanical lapping regeneration and handling, increases the supply ratio of fresh sand, perhaps with sand etc. handle.Therefore when casting model powder regeneration was used, the limit of the regeneration rate of sand at most only was 85% degree (FOUNDRY TRADEJOURNAL-8/22 DECEMBER 1989).
About this sand reproducibility, to compare with the furane resins occasion of the general acid hardening type of popularizing, difference is more obvious.That is,, generally use the sand mold intensity of reclaimed sand to be understood that height, so the addition of binding agent will lack in reclaimed sand system than the fresh sand person in the occasion of acid hardening type furane resins.And, because do not need strong mechanical lapping regeneration to handle, so the rate of recovery of reclaimed sand is about more than 95%.But at the sand by the combination of utilization hardening binder, when making sand mold and core, the regeneration of sand is important economic problems.
For by sand mold or core reclaimed sand, after taking out sand spare, sand mold and the core that uses up carried out the vibration or the decomposition of machinery, make sand scattered, its piece or agglutination body are smashed to pieces, reclaim sand.Because have the combustion residue composition of binding agent on the surface of reclaiming sand, so the processing of then regenerating usually.The renovation process of reclaimed sand generally have approved three kinds of methods (machinery, wet type, heat).The wet type method of reproduction is because there be the discarded problem and the essential energy cost problem of dry sand of closing with clean water, so be more unfavorable method.In addition, the renovation process of heat, because the energy cost height of this method, so be more unfavorable method.In contrast, because the renovation process of machinery is most economical, so be the renovation process of popularizing of general use in the foundary industry.In the reclaimed sand that obtains like this, make the bonding process of water soluble phenol resin sclerosis with organic ester, there is the distinctive shortcoming of original method that can not get enough sand mold intensity as described above, with the occasion of the acid-curable furane resins of extensively popularizing are diverse phenomenons, therefore, strong expectation improvement.
Recently, use the sand mold intensity of reclaimed sand to be purpose to improve, reduce the method for the resin solid constituent concentration in the binding agent, open existing announcement the in the flat 1-262042 communique the spy, the method of with solution of silane reclaimed sand being carried out pre-treatment is in advance opened existing announcement the in the flat 1-262043 communique the spy in addition.But,, also can not get satisfied sand mold intensity though these methods make the intensity of reclaimed sand have some to improve.
In addition, open among flat 4-339537 and the flat 5-23781 of Te Kai, disclosed with water soluble phenol resin and polyvalent metal sand mold manufacture method, but the low problem of resulting sand mold intensity is arranged as essential composition the spy.
Have again, as the above-mentioned reclaimed sand in addition that shows alkalescence, obtaining containing with bentonite as the reclaimed sand of the greensand mold of binding agent, with the fire resistance aggregate of the waterglass reclaimed sand of carbon dioxide or ィ カ Le powder (dicalcium silicate powder) petrifying water glass etc. and the mixture of this binding agent, carry out in the process of sand mold moulding, also coexistence can not obtain the problem of abundant working life, can not get satisfied sand mold intensity as a rule.
The inventor must address the above problem, that furthers investigate found that, with phenolic modified resin as binding agent, make the wetting sand mold of its sclerosis with in the binding agent with organic ester and/or carbon dioxide, by in phenolic modified resin, using the metallic element of special ratios, especially increase substantially sand mold intensity and working life, reach thus and finish the present invention by the reclaimed sand moulding.
That is, the invention relates to the sand mold binding agent, it is characterized in that, with phenolic modified resin and the compound that contains more than one metallic elements of from periodic table I B-VIII family, selecting as must composition.
In addition, the invention relates to the molding sand composition, it is characterized in that, will mix obtaining by the fire resistance aggregate of 100 parts by weight with respect to the mixture that this above-mentioned sand mold of 0.1-15 parts by weight is formed with binding agent.
Especially the invention relates to the molding sand composition, it is characterized in that, make by 100 parts by weight with the carbon dioxide of 0.05-30 parts by weight and contain the fire resistance aggregate of alkali reclaim sand and the mixture cures formed with binding agent with respect to this above-mentioned sand mold of 0.1-15 parts by weight obtains.
Have again, the invention relates to the manufacture method of sand mold, it is characterized in that, use above-mentioned sand mold binding agent, and use organic ester and/or carbon dioxide as curing agent.
As more than one metallic elements from periodic table I B-VIII family, selected that use in the present invention, can enumerate Cu, Ag in the I B family, Mg in the II family, Ca, Sr, Ba, Zn, Cd, Sc in the III family, Y, Al, Ga, In, Tl, Ti in the IV family, Zr, Hf, Sn, Pb, the V in the V family, Nb, Ta, Bi, the Cr in the VI family, Mo, W, Po, Mn in the VII family, Tc, Re, the Fe in the VIII family, Co, Ni.
As supplying with the form that contains this metallic element compound of the present invention, various forms such as metal powder, oxide, hydroxide, inorganic acid salt, acylate, complex are arranged, but which kind of form can be used.Because this metallic element finally is included in the molding sand composition, so do not limit the compound form that contains metallic element at all.Below enumerate this metallic element and contain the object lesson of the compound of these metallic elements, but be not limited to these.
As metal powder, can enumerate Cu, Ag in the I B family, Mg in the II family, Ca, Sr, Ba, Zn, Cd etc., Sc in the III family, Al, Ga etc., the Ti in the IV family, Zr, Sn etc., the Sb in the V family, Bi etc., Cr in the VI family, Mo etc., Mn in the VII family, Tc etc., the Fe in the VIII family, Co, Ni etc. are unfavorable but be commonly referred to semimetallic B, Si, As, Te etc.And, can enumerate duralumin, mug(unit of measure) Na Liwumu almag, manganeisen etc. as alloyed powder.In addition, as the compounds represented that contains periodic table I B-VIII family metallic element, can enumerate salt and double salt, hydroxide, oxide, alkyl, the organo-metallic compound that alkyl such as aryl combine with metallic atom, nitride, metal alkoxides, hydride, carbide, metal imines, peroxide, sulfide, phosphide, nitration thing, anilid, phenolate, hexammine, two luxuriant iron and the similar compounds thereof of closing, dibenzene-chromium and similar compound thereof, inorganic heteropolymer, the metal carbonyl, metal contains enzyme, inclusion compound, metal complex, chelate compound, coordination high polymer etc.
In the compound of this metallic element that contains periodic table I B-VIII,, can seek the prolongation of working life and the raising of sand mold intensity satisfactorily by using the compound of representing with following general expression.
MaXb
(in the formula, a, b represent the positive number more than 1,
The metallic element of table I B-VIII family of M indication cycle,
X represents that hydrogen atom, carbon atom, alkyl, sulphur atom, nitrogen-atoms, phosphorus are former
Son, oxygen atom, halogen atom, hydroxyl, metal alkoxides, amino,
Imino group, nitro, inorganic anion atomic group, organic anion
Atomic group, demonstration metal ion block the atomic group of property.)
As M, with above-mentioned Cu, the Ag that can enumerate equally in the I B family, Mg in the II family, Ca, Sr, Ba, Zn, Cd etc., Sc in the III family, Al, Ga etc., the Ti in the IV family, Zr, Sn etc., the Sb in the V family, Bi etc., Cr in the VI family, Mo etc., Mn in the VII family, Tc etc., the Fe in the VIII family, Co, Ni post, and are unfavorable but be commonly referred to semimetallic B, Si, As, Te etc.
As X is the compound of the concrete example of hydrogen atom, can enumerate AlH
3, CaH
2, BaH
2Deng.
As X is the compound of the concrete example of carbon atom, can enumerate Al
4C
3, CaC
2Deng.
As X is the compound of the concrete example of alkyl, can enumerate the organo-metallic compound that alkyl such as alkyl, aryl combine with metallic atom, is following such compound: Al (CH
3)
3, Al (C
2H
5)
3, Al (C
6H
5)
3, (C
2H
5)
2AlI, (C
2H
5)
2AlH, (C
2H
5)
2AlCH, Al (i-C
4H
9)
3, (CH
2=CH
3) Al, Zn (C
6H
5)
2, (CH
2=CH)
2Zn, Ca (C
2H
5)
2And R-Mg-X Grignard reagents such as (R are an alkyl or aryl, and X is a halogen), the two luxuriant iron (Fe (C that close
5H
5)
2), Zn (C
5H
5)
2, Ni (C
5H
5)
2, Mn (C
5H
5)
2, V (C
5H
5)
2Deng two luxuriant iron and the similar compounds thereof of closing, Cr (C
6H
6)
2, Mo (C
6H
6)
2, V (C
6H
6) wait phenates such as dibenzene-chromium and similar compound thereof, Al-phenates, Zn-phenates, Ca-phenates.
As X is the compound of the concrete example of sulphur atom, can enumerate ZnS, Cu
2S, CnS etc.
As X is the compound of the concrete example of nitrogen-atoms, can enumerate aluminium nitride that contains the Al-N key etc.
As X is the compound of the concrete example of phosphorus atoms, can enumerate AlP etc.
As X is the compound of the concrete example of oxygen atom, can be used as oxide and enumerate magnesia, calcium oxide, barium monoxide, zinc oxide, aluminium oxide etc., but better being to use by the compound that constitutes more than two kinds of these oxides and the compound that constitutes by the oxide or the salt of above-mentioned oxide and other elements.
As the representative that such compound uses in the present invention, can enumerate following such compound.
As the cement class, blast furnace slag, magnesium refining slag, ferrochrome slag, bentonite that hydraulic lime, Roman cement, Parker's cement, Portland cement, alumina cement, blast-furance cement, tripoli cement, pulverized fuel ash cement, masonry cement, dilatancy cement, special cement etc. and blast furnace slag class are arranged, mullite synthesizings etc., its chemical constitution of mainly representing is mCaOnSiO
2, mCaOnAl
2O
3, mBaOnAl
2O
3, CaOmAl
2O
3NSiO
2, CaOmMgOnSiO
2, mCaCO
3NMgCO
3, mCaOnFe
2O
31CaOmAl
2O
3NFe
2O
3, mAl
2O
3NSiO
2(1, m, n represent the combination formed with the positive number more than 0 or 1).
Other have aluminium as zeolite, analcime, sodalite for phyllosilicates such as silicate, mica etc.
As peroxide, can enumerate CaO
2, BaO
2, BaO
4Deng.
As X is the compound of the concrete example of halogen atom, can enumerate potassium chloride, magnesium chloride, barium chloride, copper chloride, zinc chloride, KBr, aluminum fluoride, vanadium chloride, molybdenum chloride, manganese chloride, iron chloride, nickel chloride etc.
As X is the compound of the concrete example of hydroxyl, can enumerate aluminium hydroxide, potassium hydroxide, magnesium hydroxide, zinc hydroxide etc.
As X is the compound of the concrete example of metal alkoxides, can enumerate AL[OCH (CH
3)
2]
3, Zn (OCH
3)
2Deng.
As X is the compound of the concrete example of amino, can enumerate Ca (NH
2)
2Deng.
As X is the compound of the concrete example of imino group, can enumerate Al (NHPh)
3Deng.
As X is the compound of the concrete example of nitro, can enumerate CuNO
2Deng.
As X is the concrete example compound of the anion atoms group of inorganic acid, can enumerate SO
4, SO
3, S
2O
3, S
2O
6, SiF
6, MoO
4, MnO
4, NO
3, NO
2, ClO
3, ClO, CO
3, HCO
3, CrO
4, IO
3, PO
3, PO
4, HPO
3, HPO
4, H
2PO
4, P
2O
7, H
2PO
2, SiO
3, BO
2, BO
3, B
4O
7, Fe (CN)
6Deng.
As X is the compound of organic acid concrete example, can enumerate anion of carboxylic acid atomic groups such as formic acid, acetate, oxalic acid, tartaric acid, benzoic acid etc., also can enumerate the anion atoms group of organic sulfonic acids such as sulfamic acid, xylene monosulfonic acid, toluenesulfonic acid, phenol sulfonic acid, benzene sulfonic acid, alkyl benzene sulphonate.Also can enumerate the anion atoms group of organic phosphoric acids such as methyl acid phosphate, ethyl phosphonic acid etc.
As X is the compound that shows the concrete example of metal ion blockade property atomic group, can lift following compound.
Acetate is the representative of aminocarboxylic acid type, can enumerate ethylenediamine tetra-acetic acid (EDTA) or its esters, NTA (NTA) or its esters, trans 1,2-1,2-diaminocyclohexane tetraacetic acid (CyDTA) or its esters, diethylene-triamine pentaacetic acid (DTPA) or its esters, triethylenetetraaminehexaacetic acid (TTHA) or its esters, glycoletherdiaminotetraacetic acid (GEDTA) or its esters, imido-acetic acid (IDA) or its esters, polyalkylene ethylenediamine tetraacetic acid (EDTA) or its esters and N-hydroxy alkylidene iminodiacetic acid or its esters; Phenyl is the representative of aminocarboxylic acid type, can enumerate 2-hydroxyphenyl imido-acetic acid or its esters, phenyl imido-acetic acid or its esters, 2-acrinyl imido-acetic acid or its esters, benzyl imido-acetic acid or its esters and N, N '-ethylenebis-[2-(salicyl)] amion acetic acid or its esters; Have the representative of the aminocarboxylic acid type of mercapto, can enumerate β-mercaptoethyliminodiacetic acid or its esters; Have the representative of the aminocarboxylic acid type of ehter bond, can enumerate glycoletherdiaminotetraacetic acid or its esters; Have the representative of the aminocarboxylic acid type of thioether bond, can enumerate Tiametonium Iodide tetraacethyl or its esters; Representative with sulfonic aminocarboxylic acid type can enumerate β-aminoethane sulfonic acid-N, N-oxalic acid or its esters; Representative with sulfonic aminocarboxylic acid type can enumerate nitrilo-oxalic acid-methylene phosphonic acid or its esters; Have the representative of the aminocarboxylic acid type of peptide bond, can enumerate N, N '-two glycyl ethylenediamine-N ', N ", N_, N
-tetraacethyl or its esters etc.: the representative of hydroxy acid type, can enumerate gluconic acid or its esters, citric acid or its esters, tartaric acid or its esters etc.: the representative that phosphatic type is arranged again, can enumerate tripolyphosphate or its esters, hydroxyl ethane di 2 ethylhexyl phosphonic acid (HEDP) or its esters, nitrilo-triphenylethylene phosphonic acids (NTP) or its esters, and acetylacetone,2,4-pentanedione etc.
Can enumerate the macromolecule that in molecule, has amino and/or azacyclo-and/or schiff bases and/or alcohol, carboxylic acid and/or ketone, ester, acid amides and/or amino carboxylic acid and/or phosphonic acids and/or phosphine and/or sulfo-etc. as having coordination high polymer that such metal ion blocks property.
As inclusion compound is cyclic polyether (crown ether), cyclic polyamines (azepine crown compound), the poly-thia ether (thia crown compound) of ring-type, the compound complex of giving body crown compound, multiple ring type crown compound (Network リ Block Application De), macromolecule crown compound, cyclic phenol (カ Network ス ア レ-Application), cyclodextrine derivatives etc.For example be dibenzo-18-hat-6 and Ca
2Complex, Network リ Block Application De [222] and Ca
2Complex etc.
Other can enumerate Ni (CO)
4, Mn
2(CO)
10Deng metalloenzyme such as metal carbonyl, Carboxypeptidase A, thermolysin and zirconium aluminium based compound etc.
In the compound of this metal that contains I B-VIII family that illustrates with these concrete examples, desirable metallic element is this metallic element of III-VIII family, and better is this metallic element of II, III, IV family, and wherein Zn, Ca, Mg, Al, Zr are desirable especially.
Have again,, can enumerate more than one that from aluminic acid compound, stannic acid compound, titanic acid compound and zirconic acid compound, select as the compound that contains periodic table I B-VIII family metallic element.As the aluminic acid compound, can enumerate magnesium aluminate, sodium aluminate, potassium aluminate, lithium aluminate etc.: as the stannic acid compound, can enumerate sodium stannate, potassium stannate, lithium stannate etc.: as titanic acid compound, can enumerate lithium titanate, sodium titanate, potassium titanate, barium titanate etc.:, can enumerate lithium zirconate, sodium zirconate, potassium zirconium etc. as the zirconic acid compound.Use simultaneously by these compounds and boronic acid compounds, can improve working life.
In addition, about in the sand and this metallic element in the binding agent quantitatively, as following, carry out usually.
This metallic element in the sand quantitatively
Sand is crushed to below 150 orders weighing 0.2-0.3g in the platinum diss of 100ml.Cross chloric acid to wherein adding 5ml concentrated hydrochloric acid, the dense hydrofluoric acid of 3ml, 10ml, make the Si volatilization after, add 10ml HCl (1+1)+10ml H
2O heats, and makes the dissolving of residue salt.With its filtration (No5C filter paper), with watery hydrochloric acid+warm water cleaning.In the platinum crucible of 30ml, put after carrying out ashing coldly with remaining in residue on the filter paper, add the 2g potassium pyrosulfate, carry out sour fusion at 800 ℃ in 900-1000 ℃.The material that to extract fused mass out merges with previous filtrate, in measuring bottle, be made into the solution of 100ml after, this metallic element of usefulness ICP (inductively coupled plasma luminesceence analysis) standard measure.So-called HCl (1+1) is that hydrochloric acid (36% concentration) and water are with the volume ratio mixed in equal amounts.
This metallic element in the binding agent quantitatively
Binding agent is fully mixed stirring, weighing 0.5-0.8g in the platinum diss of 100ml.To wherein adding after the 10ml red fuming nitric acid (RFNA) carries out acid and decompose, carry out weak thermal decomposition.Add the dense chloric acid of crossing of 10ml, carry out white cigarette and handle, make the dense chloric acid of crossing of 3ml.Put cold after, add 10mlHCl (1+1)+10ml H
2O carries out heating for dissolving.With its filtration (No5C filter paper), with watery hydrochloric acid+warm water cleaning.With remain in residue on the filter paper in the 30ml platinum crucible in 900-1000 ℃ carry out ashing after, put coldly, add the 2g potassium pyrosulfate, carry out fusion at 800 ℃.The material that to extract fused mass out merges with previous filtrate, in measuring bottle, be made into 100ml solution after, this metallic element of usefulness ICP (inductively coupled plasma luminesceence analysis) standard measure.
In order to make sand mold binding agent of the present invention, for phenolic modified resin, the solid constituent of phenolic modified resin is converted into metallic element relatively, uses relevant above-mentioned metallic element compound of the present invention of containing of 0.0005-5% (weight), best 0.001-3% (weight).If this compound is less than 0.0005% (weight), effect then of the present invention is insufficient, and on the contrary, if surpass 5% (weight), then effect is in saturation range.
As phenolic modified resin with contain the form of using simultaneously as above-mentioned metallic element compound, after can being dissolved in the compound that contains this metallic element in the phenol in advance or being blended in the phenol, carry out polycondensation reaction with aldehydes, also can carry out the dissolving of polycondensation reaction stage or mix the compound that contains this metallic element at phenol and aldehydes, can be contained in the phenolic modified resin or the aqueous solution, also can mix in organic ester, perhaps they also can be added in the fire resistance aggregate in addition.In addition, at this moment, also can be diluted in the known solvent and add, to improve Combination.
About sand mold binding agent of the present invention, no matter self-hardening property method for filling molding sand, or hardening method for filling molding sand is not done special restriction.
In order to use all binding agents of sand mold of the present invention, utilize the self-hardening property method for filling molding sand to make sand mold, in 100 parts by weight fire resistance aggregates, with known method mixing sand mold binding agent and curing agent organic ester, sand mold with aqueous solution, is 0.1-15 parts by weight, best 0.3-5 parts by weight as solid constituent with binding agent, and the curing agent organic ester is the 0.05-9 parts by weight, preferably the 0.1-5 parts by weight can intactly utilize self-hardening property sand mold modeling process in the past to make sand mold.
In addition, in the present invention, in order to utilize the gas hardening sand mold property made manufactured sand mold, at first in 100 parts by weight fire resistance aggregates, go into to add the mixed sand of sand mold with binding agent with hand-tamped, this binding agent is with aqueous solution, add 0.1-15 parts by weight, best 0.3-5 parts by weight as solid constituent, perhaps be filled in the model by the winding-up under the forced air, then be blown into the gas shape of 0.05-9 parts by weight or the organic ester of aerosol shape, make the phenolic modified resin sclerosis, make sand mold with this.
As the organic ester that uses in the present invention, can be used alone or as a mixture lactone or by the monobasic of carbon number 1-10 or polyalcohol and the organic ester of deriving by the organic carboxyl acid of carbon number 1-10, but in the self-hardening property method for filling molding sand, preferably use gamma-butyrolacton, propiolactone, 6-caprolactone, Ethyl formate, ethylene acetate, ethylene monoacetate, glycerol triacetate etc., in the gas hardening method for filling molding sand, preferably use methyl formate.In addition, for organic esters such as replacement gas shapes, when using carbon dioxide that sand mold is hardened with binding agent, in binding agent, add boronic acid compounds such as an amount of boric acid, borate, by the acting in conjunction of this boronic acid compounds and carbon dioxide, can make the phenolic modified resin sclerosis.At this moment, relative 100 parts by weight fire resistance aggregates, can be used for smashing into mixed sand, this mixed sand is added the sand mold binding agent of the boronic acid containing compound of 0.1-15 parts by weight, best 1-5 parts by weight, perhaps utilize the winding-up under the forced air, be filled in the model, then be blown into the carbon dioxide of 0.05-30 parts by weight, best 0.1-20 parts by weight, make the phenolic modified resin mixture cures with carbon dioxide, make sand mold with this.
As used boronic acid compounds, can enumerate boric acid (is to become borate in the resin at alkaline water soluble phenolic), sodium tetraborate 10 hydrates (borax), potassium borate 10 hydrates, methyl-boric acid sodium, potassium pentaborate, sodium pentaborate etc.Such boronic acid compounds, the phenolic modified resin aqueous solution can be the 0.1-30 parts by weight relatively, preferably can be the 3-15 parts by weight.The relative phenolic modified resin aqueous solution, if boronic acid compounds is less than 0.1 parts by weight, then the setting rate of sand mold and sand mold intensity are not enough, surpass 30 parts by weight, the proterties and the moisture that also are related to phenolic modified resin, usually resin viscosity and worsen with the intermiscibility of boronic acid compounds is seen producing sedimentary tendency.
In addition, use the reclaimed sand (PH that fully mixes the supernatant of 100 parts by weight distilled water in relative 100 parts by weight reclaimed sands is that the reclaimed sand more than 8.0 is called the reclaimed sand that shows alkalescence) and the binding agent of the present invention that show the fire resistance aggregate alkalescence of enumerating as the problems referred to above, when obtaining as mixed sand, can fully obtain working life, even it is long to mix stand-by time, also can make fully high sand mold of sand mold intensity.This effect is effectively to using carbon dioxide to carry out the gas hardening method for filling molding sand especially, but about sand mold binding agent of the present invention, the self-hardening property method for filling molding sand still is that the gas hardening method for filling molding sand is not done special restriction.
The so-called reclaimed sand of alkalescence that shows is to use the reclaimed sand that shows alkaline binding agent, except the system sand that uses binding agent of the present invention, be to use bentonitic greensand mold reclaimed sand, make the waterglass reclaimed sand of waterglass sclerosis, make the reclaimed sand of water soluble phenol resin binding agent sclerosis with organic ester or carbon dioxide with carbon dioxide or dicalcium silicate ( ィ カ Le) powder.
Especially making the calcination loss amount % (LOI%) of the reclaimed sand of water soluble phenol resin binding agent sclerosis with organic ester or carbon dioxide is desirable for 0.1-15% (weight) scope, using the full clay component of the greensand mold reclaimed sand of bentonite etc. is desirable as 1-15% (weight), waterglass reclaimed sand is contained in the Na in this sand
2O is that 0.01-5% (weight) is desirable, be respectively from sand mold intensity and working life the aspect can improve the proterties of reclaimed sand.
In addition, also can use with hexane and make the shell mould reclaimed sand of novolac resin sclerosis, make the phenol urethane resin sclerosis reclaimed sand of phenol-formaldehyde A and oligomeric isocyanates sclerosis etc. with amine.
Have again, in the binding agent that the present invention uses, also can use gylcol ether.Usually, the relative 100 parts by weight phenolic modified resin aqueous solution cooperate and add the 1-20 parts by weight.As the kind of this gylcol ether, can enumerate diethylene glycol (DEG), triethylene glycol, DPG, tripropylene glycol, glycol monomethyl ether, ethylene glycol monoethylene glycol, ethylene glycol one propane diols, ethylene glycol monobutyl ether, diethylene glycol (DEG) monomethyl ether, diethylene glycol (DEG) monoethyl ether, diethylene glycol (DEG) one propyl ether, diethylene glycol-butyl ether, Glycol Monomethyl ether, DPG monomethyl ether etc.
The phenolic modified resin that the present invention uses, the resin that obtains with the aldehyde compound copolycondensation by more than one compounds that are selected from the bisphenols of following general formula (1) expression, the perhaps resin that obtains by more than one compounds that are selected from phenols, more than one compounds that are selected from the bisphenols of representing with above-mentioned general formula (1) and aldehyde compound copolycondensation.
(in the formula, X represents
S, O or
R
1And R
2Saturated or the unsaturated alkyl of expression hydrogen atom, three fluoro methyl, carbon number 1-6, phenyl or both derivatives of back.R
3And R
4Saturated or the unsaturated alkyl of expression hydrogen atom, carbon number 1-6, phenyl or both derivatives of back.)
Object lesson as the bisphenols of representing with general formula (1), can enumerate bisphenol-A, Bisphenol F, bisphenol-c, bis-phenol E, bisphenol Z, bisphenol S, bisphenol AF, bisphenol-ap, two sec-butyls-bisphenol-A, diisopropyl-bisphenol-A, 1,1-ethylidene-bis-phenol, methyl-ethyl-ethylidene-bisphenol-A, methyl-isobutyl group-ethylidene-bisphenol-A, methyl-hexyl-ethylidene-bis-phenol, methyl-phenyl-ethylidene-bis-phenol, 4,4 '-sulfo-diphenol etc. are used alone or as a mixture separately.
As phenol, use is selected from more than one in the compound of representing with following general formula (2)-(4).
(in the formula, R
5And R
6Expression hydrogen atom or the alkyl of carbon number below 2.)
(in the formula, R
7Expression hydrogen atom, hydroxyl or the alkyl of carbon number below 2.)
(in the formula, R
8Aliphatic alkyl or the aromatic hydrocarbyl of expression carbon number more than 3.)
In phenol,, can enumerate phenol, cresols, 3,5-xylenols etc. as the object lesson of the compound of representing with general formula (2).Compound with general formula (3) expression is a polyhydric phenols, can enumerate resorcinol, catechol etc. as object lesson.In addition, with the compound of general formula (4) expression, mainly be in the contraposition in conjunction with alkyl and the phenyl of carbon number more than 3, as object lesson, can enumerate nonyl phenol, p-t-butyl phenol, isopropenyl phenol, xenol etc.In addition, also can use various phenol mixtures as the cashew nut shell liquid.Especially, as phenol, the mixture of phenol and cresols is desirable.
In addition, be used alone or as a mixture formaldehyde, PARA FORMALDEHYDE PRILLS(91,95), furfural, glyoxal etc. as aldehyde compound.
When bisphenols or phenol and bisphenols and aldehyde compound copolycondensation, the mol ratio of each compound is desirable as described below.Promptly, the molal quantity of relative bisphenols, the perhaps total molal quantity of the molal quantity of the molal quantity of phenol and bisphenols, the mole ratio of aldehyde compound are the molal quantitys of the molal quantity+bisphenols of the molal quantity of 1.0-5.0[(bisphenols or phenol): the molal quantity of aldehyde compound=1: 1.0-5.0] be desirable.Especially, the mole ratio of aldehyde compound is that 1.5-3.0 is better.If the mole ratio less than 1.0 of aldehyde compound even use resulting phenolic modified resin to carry out moulding, also produces the tendency that can not fully improve sand mold intensity.On the contrary, if the mole ratio of aldehyde compound surpasses 5.0, then the aldehyde stink of resulting phenolic modified resin is strong, the danger that has operating environment to worsen.In addition, under the situation that phenol and bisphenols use simultaneously, the molal quantity of phenol relatively, the mole ratio of bisphenols is the (molal quantity of phenol: the molal quantity of bisphenols=1: be desirable 0.001-1000) about 0.001-1000.Especially, the mole ratio of bisphenols is that 0.01-90 is better.If the mole ratio of bisphenols less than 0.001, perhaps surpasses 1000, produce the tendency that resulting sand mold intensity can not fully improve.
Bisphenols, perhaps the copolycondensation of phenol and bisphenols and aldehyde compound is generally carried out in the aqueous solution, obtains phenolic modified resin.For example, in the aqueous solution of the bisphenols that dissolves ormal weight or phenol and bisphenols, the aldehyde compound of ormal weight is slowly added on the limit, and it is desirable that copolycondensation is carried out on the limit.At this moment, as catalysts, using potassium hydroxide (KOH), NaOH (NaOH), lithium hydroxide base catalysts such as (LiOH), is desirable but especially use NaOH.Phenolic modified resin among the present invention in order to be adjusted to alkaline aqueous solution, also can use the potassium hydroxide of ormal weight when copolycondensation, perhaps as catalysts, use minimal potassium hydroxide, after copolycondensation finishes, also can add the potassium hydroxide of ormal weight.In addition, after copolycondensation finishes, also can use NaOH and lithium hydroxide simultaneously, to form the alkalescence of regulation with potassium hydroxide.Have again, use acid catalyst to carry out copolycondensation after, then also can use base catalyst such as potassium hydroxide to carry out copolycondensation.In the alkaline aqueous solution of phenolic modified resin, the relative hydroxyl molal quantity of bisphenols, the perhaps total molal quantity of the hydroxyl molal quantity of the hydroxyl molal quantity of phenol and bisphenols, the mole ratio of full alkali is that 0.2-1.2 is desirable.In addition, the concentration of the phenolic modified resin in alkaline aqueous solution is that 30-75% (weight) is desirable.
In addition, phenolic modified resin, again by the copolycondensation alcohols, when mixing with the fire resistance aggregate, mixed sand mobile and become good to the filling of model.As alcohols, the monohydric alcohol of carbon number 2-10 is desirable, for example can enumerate ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol etc.Especially, as monohydric alcohol, it is optimal using propyl alcohol, isopropyl alcohol, butanols, isobutanol, sec-butyl alcohol or the tert-butyl alcohol.As the cooperation ratio, the relative molal quantity of bisphenols, the perhaps total molal quantity of the molal quantity of the molal quantity of phenol and bisphenols, 0.0001-0.5 doubly mole is desirable.Especially, alcohols is that 0.01-0.2 times of mole is better.The molal quantity of alcohols is as if 0.0001 times of mole of less than, and the effect of not adding alcohols on the contrary, if surpass 0.5 times of mole, produces the tendency that sand mold intensity can not fully improve.
As the fire resistance aggregate, can enumerate with quartziferous as the silica sand of principal component, chromite sand, zircon sand, olivine sand, aluminum oxide sand, artificial mullite synthesizing sand etc., but be not particularly limited. in the present invention, these fire resistance aggregates also can use any of fresh sand, reclaimed sand, and especially the raising effect of the sand mold intensity when using reclaimed sand is significant.When using reclaimed sand, use the reclaimed sand that obtains with common abrasion formula or the formula of fusing, but the method that obtains reclaimed sand is not particularly limited.
In addition, reclaimed sand that also can the above-mentioned alkalescence of mixed display in the fire resistance aggregate and using, also can use these reclaimed sand with any mixing ratio that contains more than one fresh sands, but when using the reclaimed sand of the demonstration alkalescence more than 10% (weight) in the fire resistance aggregate, it is desirable using sand mold binding agent of the present invention.
In binding agent of the present invention, as other additives, can use is known so far silane coupler.As its object lesson, can enumerate gamma-aminopropyl-triethoxy-silane and γ-(2-aminoethyl) aminopropyl trimethoxysilane, γ-glycidoxypropyl methoxy silane etc. as desirable coupling agent.In the present invention, these silane couplers and binding agent being used simultaneously, is desirable.As addition, relative 100 parts by weight fire resistance aggregates are 0.001-1 parts by weight, preferably the 0.002-0.5 parts by weight.
Below, illustrate in greater detail the present invention according to embodiment, but the present invention is not limited only to these embodiment.
The sand mold adjusting of adhesive solution 1
In 50% potassium hydroxide aqueous solution, add with mol ratio shown in the table 1 quantitative phenol and bisphenols and alcohols, carry out stirring and dissolving.The limit remains on 80 ℃ with this solution, and add at leisure with the quantitative aldehyde compound of mol ratio shown in the table 1 on the limit.Then, the weight average molecular weight of the phenolic modified resin to the reaction solution reaches at 2500 o'clock, continues reaction at 80 ℃.Weight average molecular weight reaches 2500 o'clock judgement, is undertaken by the viscosity of assaying reaction solution.After reaction ends, cool to room temperature, then with the total molal quantity of the hydroxyl molal quantity of the hydroxyl molal quantity of relative phenol and bisphenols, it is 0.85 such that the mole ratio of potassium hydroxide is become, and adds 50% potassium hydroxide aqueous solution.Carry out as mentioned above, obtain the alkaline aqueous solution of phenolic modified resin.Then, in the aqueous solution, add the compound that contains the various metals shown in the table 1.(but, except that embodiment 8,9) relative 100 parts by weight phenolic modified resins, add gamma-aminopropyl-triethoxy-silane again in the 0.5 parts by weight aqueous solution.As mentioned above, be adjusted to the sand mold binder compound aqueous solution 1.Have, the content of the binding agent in the adhesive solution (phenolic modified resin, containing metal element compound) is 50% (weight) again.
The solid constituent amount of the phenolic modified resin aqueous solution among the present invention is by (2.0 ± 0.1g) measured in 100 ℃ of heating in 3 hours with the test portion of weighing in the air circulating type stove.
In addition, the A project in the table 1 is the molal quantity of aldehyde compound Pyrogentisinic Acid class, the molal quantity of bisphenols, perhaps the total mole ratio of the molal quantity of the molal quantity of phenol and bisphenols.Promptly, be [molal quantity of aldehyde compound/(molal quantity of the molal quantity+bisphenols of phenol].In addition, the B project is phenol and bisphenols and time spent, the mole ratio of the molal quantity Pyrogentisinic Acid class of bisphenols.That is, be (molal quantity of the molal quantity/phenol of bisphenols).Have, the C project is the ratio of total molal quantity of the molal quantity of the molal quantity of the molal quantity of molal quantity, bisphenols of the molal quantity Pyrogentisinic Acid class of alcohols or phenol and bisphenols again.That is, be [alcohols molal quantity/(molal quantity of the molal quantity of phenol+bisgallic acid class)].A-C in the following table is identical therewith.
The sand mold adjusting of adhesive solution 2
Except the weight average molecular weight of the phenolic modified resin in reaction solution reaches at 1800 o'clock and proceeds reaction, to be adjusted to sand mold usefulness adhesive solution 2 with the identical method of adhesive solution 1 with sand mold.In the mol ratio of reaction shown in the table 3 and the kind and the amount of the containing metal element compound of interpolation.
The sand mold adjusting of adhesive solution 3
Will be when sand mold to be used the adjusting of adhesive solution 2, the phenolic modified resin aqueous solution 25 parts by weight that reaction obtains after ending, sodium tetraborate 10 hydrates, 5 parts by weight and 50% potassium hydroxide, 5 parts by weight mix, and are adjusted to sand mold adhesive solution 3.The kind and the amount of the containing metal element compound of the mol ratio of reaction and interpolation shown in the table 5.
The modulator approach of reclaimed sand A
The fresh sand of relative 100 parts by weight Fremantle silica sands adds 1.5 parts by weight and contains the glycerol triacetate that 0.3 parts by weight are curing agents, the phenolic modified resin (solid constituent 49% (weight), weight average molecular weight 2300) of 0.5 parts by weight (phenolic ester modified resin relatively) gamma-aminopropyl-triethoxy-silane; Be mixed into mixture, use the sand mold by this mixture moulding, sand is made FC-250 (S/M=3.5), the sand that reclaims is added in the disintegrating machine, with Japan casting system M type rotary grinding device (ロ- リ-Network レ-マ) regenerate (A regeneration, 2 passages).Above process is repeated 5 times, resulting reclaimed sand is used for the modulation that following sand mold strength test is used.The calcination loss amount % (LDI) of gained reclaimed sand A is 0.8% (weight).
The modulator approach of reclaimed sand B
No. 5 fresh sand 100 parts by weight of homemade relatively silica sand add the above-mentioned sand mold of 3 parts by weight with adhesive solution 3, are mixed into mixture, and this mixture is filled in the gas hardening moulding model, are blown into 1.5 parts by weight carbon dioxide, obtain sand mold.Use this moulding, casting FC-250 (S/M=3.5) puts into disintegrating machine with the sand that reclaims, and uses Japan casting system M type rotary grinding device regenerate (A regeneration, 2 passages).Above process is repeated 5 times, resulting reclaimed sand is used for the modulation that following sand mold strength test is used.The LOI% of resulting reclaimed sand B is 0.9% (weight).
The modulator approach of reclaimed sand C
No. 6 fresh sands of the homemade silica sand of relative 100 parts by weight add 6 parts by weight waterglass (SiO
2/ Na
2O mol ratio 2.0,60 baume), be mixed into mixture, this mixture is filled in the gas hardening sand mold model, be blown into 3 parts by weight carbon dioxide, obtain sand mold.Use this sand casting FC-250 (S/M=3.5), the sand that reclaims is put into disintegrating machine, with Japan casting system M type rotary grinding device regenerate (A regenerates, 4 passages).Above process is repeated 5 times, and the reclaimed sand of gained is used for the modulation that following sand mold strength test is used.The Na of gained reclaimed sand C
2O% is 0.5% (weight).
The modulator approach of reclaimed sand D
No. 6 fresh sands of the homemade silica sand of relative 100 parts by weight, add 6.0 parts by weight bentonites, 3 parts by weight coal dusts, 1 parts by weight cornstarch, 3.5 parts by weight water, be mixed into mixture, this mixture is filled in the greensand mold model, obtain sand mold in the vibration molding mode.Use this sand casting FC-250 (S/M=10), the sand that reclaims is put into disintegrating machine, with Japan casting system M type rotary grinding device regenerate (B regenerates, 1 passage).Above process is repeated 5 times, the reclaimed sand of gained is regenerated once more (B regeneration, 5 passages), the reclaimed sand of gained is used for the modulation that following sand mold strength test is used.The full clay component of gained reclaimed sand D is 1.8% (weight).
The determination method of calcination loss amount %
Accurately weighing 10g puts into and is maintained at about 1000 ℃ electric furnace in advance according to the sample that JIS Z-2605 (the moisture test method of casting model powder) removes free moisture.Behind 1 hour heat-flash, take out crucible, in the drier of silica gel, put as drier be chilled to room temperature after, accurately weigh, calculate calcination loss amount % by following formula.
(in the formula, W
1Be the test portion weight (g) before the heat-flash, W
2Be the test portion weight (g) behind the heat-flash.)
Na
2The assay method of O% (weight)
About the Na in the waterglass reclaimed sand
2The determination method of O composition is according to " analytic approach (JISR-2212) of schamotte brick and clay matter fireclay mortar " of Japanese Industrial Standards (JIS) definition.
The assay method of full clay component
About the determination method of full clay component in the damp sand molding sand, according to the test method(s) of " sand is made the test method (JIS Z-2601-1993) of sand " of Japanese Industrial Standards (JIS) definition.
The assay method of compression strength
φ 50mm * high 50mm compressive strength of specimens with following embodiment moulding is measured, according to " sand is made the test method (JIS Z-2601-1993) of sand " of Japanese Industrial Standards (JIS) definition, with W/A[kgf/cm
2] obtain (W: the load (kgf) when sample destroys, A: the basal area (cm of sample
2)).
Embodiment 1-9 and comparative example 1-4
In the self-hardening property method for filling molding sand, estimate sand mold intensity.Promptly, relative 100 parts by weight reclaimed sand A, add 0.26 parts by weight glycerol triacetate, 1.3 parts by weight and contain the sand mold of containing metal compound of concentration shown in the table 1 (being converted into the metallic element concentration of relative resin solid composition) with adhesive solution 1, be mixed into mixture, the sample that this mixture is filled into φ 50mm * high 50mm is measured the compression strength after 24 hours with in the model.But the containing metal element compound that uses in embodiment 8 and 9 adds use in addition.
In addition, at the bottom erection support of the test tube of internal diameter 50mm, inner effective length 100mm,, mixed mixture roughstuff is charged in the test tube by 3mm purpose sieve.Then, the remaining mixture that has mixed in top is wiped off, put into the degree of packing exerciser of ジ ョ-ジ Off ィ Star シ ャ society system, with 10kg/cm
2Compacting press pressurization.The height that is determined at the mixture of mixing after this reduces, with this minimizing height Xmm[=C.B. (degree of packing)] as the flowability of the mixture that has mixed, the index of fillibility.In addition, X is more little, and the mixture that has mixed shows good flowability and fillibility more.
The results are shown in table 1.
Table 1
| Embodiment and comparative example | Phenol | Bisphenols | Alcohols | Aldehyde compound | Mol ratio | The containing metal element compound | This metallic element concentration (ppm) | Compression strength (just mixing) back moulding) (kg/cm 2) | The CB value | ||
| A | B | C | |||||||||
| Embodiment 1 | Phenol/metacresol=1/1 | Bisphenol-A | Isopropyl alcohol | Formaldehyde | 2.0 | 0.4 | 0.01 | MgCl 2 | 500 | 33.3 | 25.3 |
| Embodiment 2 | P-t-butyl phenol | ＂ | ＂ | ＂ | 2.0 | 5 | 0.1 | Calcium acetate | 2,000 | 34 2 | 25.7 |
| Embodiment 3 | Metacresol | ＂ | Butanols | ＂ | 2.0 | 10 | 0.1 | ZnCl 2 | 100 | 31.6 | 25.3 |
| Embodiment 4 | - | ＂ | Propyl alcohol | Formaldehyde/furfural=9/1 | 2.0 | - | 0.01 | AlCl 3 | 20 | 36.2 | 25.2 |
| Embodiment 5 | Phenol | Bisphenol F | ＂ | Formaldehyde | 2.0 | 0.2 | 0.2 | EDTA·Na 2Nl | 5,000 | 31.4 | 25.8 |
| Embodiment 6 | Phenol/metacresol=1/1 | Bisphenol-A | Isopropyl alcohol | ＂ | 2.0 | 1 | 0.02 | Aluctyl | 1,000 | 35.9 | 26.7 |
| Embodiment 7 | ＂ | ＂ | - | ＂ | 2.0 | 1 | - | ＂ | 1,000 | 35.8 | 28.8 |
| Embodiment 8 | ＂ | ＂ | Isopropyl alcohol | ＂ | 2.0 | 1 | 0.02 | Aluminium powder | 3,000 | 33.2 | 26.5 |
| Embodiment 9 | ＂ | ＂ | - | ＂ | 2.0 | 1 | - | ＂ | 3,000 | 33.0 | 28.4 |
| Comparative example 1 | ＂ | ＂ | ＂ | ＂ | 2.0 | 1 | 0.02 | Do not have | - | 10.5 | 26.7 |
| Comparative example 2 | ＂ | - | ＂ | ＂ | 2.0 | - | 0.02 | Do not have | - | 7.2 | 26.8 |
| Comparative example 3 | - | Bisphenol-A | ＂ | ＂ | 2.0 | - | 0.02 | Do not have | - | 9.3 | 27.0 |
| Comparative example 4 | Phenol/metacresol=1/1 | - | ＂ | ＂ | 2.0 | - | 0.02 | AlCl 2 | 20 | 29.2 | 25.4 |
Embodiment 10-16 and comparative example 5-7
The sand mold intensity of alkali reclaim sand shown in the evaluation table 2 in the self-hardening property method for filling molding sand.Evaluation method is only measured sand mold intensity, changes except shown in table 2 kind of fire resistance aggregate, carries out equally with embodiment 1-9 and comparative example 1-4.But the containing metal element compound that uses in embodiment 12 adds use in addition.The results are shown in table 2.
Table 2
| Embodiment and comparative example | Binding agent | The kind of fire resistance aggregate and mixing ratio | Compression strength (just having mixed the back moulding) (kg/cm 2) | |||
| Homemade silica sand fresh sand | Reclaimed sand B | Reclaimed sand C | Reclaimed sand D | |||
| Embodiment 10 | Embodiment 1 user | 10 | 90 | 32.5 | ||
| Embodiment 11 | Embodiment 1 user | 50 | 50 | 33.8 | ||
| Embodiment 12 | Embodiment 6 users | 20 | 80 | 28.2 | ||
| Embodiment 13 | Embodiment 6 users | 60 | 40 | 29.5 | ||
| Embodiment 14 | Embodiment 8 users | 100 | 30.0 | |||
| Embodiment 15 | Embodiment 8 users | 30 | 70 | 32.5 | ||
| Embodiment 16 | Embodiment 4 users | 25 | 75 | 28.0 | ||
| Comparative example 5 | Comparative example 1 user | 10 | 90 | 13.5 | ||
| Comparative example 6 | Comparative example 2 users | 20 | 80 | 9.5 | ||
| Comparative example 7 | Comparative example 3 users | 100 | 8.2 | |||
Embodiment 17-23 and Bi Jiao example 8-11
The sand mold intensity of evaluation in methyl formate gas hardening method for filling molding sand.Promptly, relative 100 parts by weight reclaimed sand A, the sand mold that 2.0 parts by weight is contained the containing metal element compound of concentration shown in the table 3 (being converted into the metallic element concentration of relative resin solid composition) is filled into the gas hardening of φ 50mm * high 50mm with in the sample usefulness model with adhesive solution 2.In this model, inject 1.5 parts by weight gas shape methyl formates, measure the compression strength after 24 hours.The results are shown in table 3.
Table 3
| Embodiment and comparative example | Phenol | Bisphenols | Alcohols | Aldehyde compound | Mol ratio | The containing metal element compound | This metallic element concentration (ppm) | Compression strength (just having mixed the back moulding) (kg/cm 2) | ||
| A | B | C | ||||||||
| Embodiment 17 | Phenol/metacresol=1/1 | Bisphenol-A | Isopropyl alcohol | Formaldehyde | 2.0 | 0.4 | 0.01 | CaCl 2 | 5,000 | 36.0 |
| Embodiment 18 | P-t-butyl phenol | ＂ | ＂ | ＂ | 2.0 | 5 | 0.1 | Aluctyl | 2,000 | 37.5 |
| Embodiment 19 | Metacresol | ＂ | Butanols | ＂ | 2.0 | 10 | 0.1 | Magnesium acetate | 3,000 | 36.8 |
| Embodiment 20 | - | ＂ | Propyl alcohol | Formaldehyde/furfural=9/1 | 2.0 | - | 0.01 | Zn(OH) 2 | 10,000 | 35.1 |
| Embodiment 21 | Phenol | Bisphenol F | ＂ | Formaldehyde | 2.0 | 0.2 | 0.2 | MgCl 2 | 1,000 | 34.6 |
| Embodiment 22 | Phenol/metacresol=1/1 | Bisphenol-A | Isopropyl alcohol | ＂ | 2.0 | 1 | 0.02 | AlCl 3 | 50 | 35.2 |
| Embodiment 23 | ＂ | ＂ | ＂ | ＂ | 2.0 | 1 | 0.02 | Aluminium acetate | 500 | 38.2 |
| Comparative example 8 | ＂ | ＂ | ＂ | ＂ | 2.0 | 1 | 0.02 | Do not have | - | 11.3 |
| Comparative example 9 | ＂ | - | ＂ | ＂ | 2.0 | - | 0.02 | Do not have | - | 7.8 |
| Comparative example 10 | - | Bisphenol-A | ＂ | ＂ | 2.0 | - | 0.02 | Do not have | - | 10.1 |
| Comparative example 11 | Phenol/metacresol=1/1 | - | ＂ | ＂ | 2.0 | - | 0.02 | Aluminium acetate | 500 | 30.9 |
Embodiment 24-30 and comparative example 12-14
In methyl formate gas hardening method for filling molding sand, the sand mold intensity of alkali reclaim sand shown in the evaluation table 4.Evaluation method is only measured sand mold intensity, changes except shown in table 4 kind of fire resistance aggregate, carries out equally with embodiment 17-23 and comparative example 8-11.The results are shown in table 4.
Table 4
| Embodiment and comparative example | Binding agent | The kind of fire resistance aggregate and mixing ratio | Compression strength (just having mixed the back moulding) (kg/cm 2) | |||
| Homemade silica sand fresh sand | Reclaimed sand B | Reclaimed sand C | Reclaimed sand D | |||
| Embodiment 24 | Embodiment 18 users | 100 | 35.0 | |||
| Embodiment 25 | Embodiment 18 users | 25 | 75 | 36.2 | ||
| Embodiment 26 | Embodiment 18 users | 100 | 31.2 | |||
| Embodiment 27 | Embodiment 18 users | 30 | 70 | 33.0 | ||
| Embodiment 28 | Embodiment 20 users | 10 | 90 | 30.0 | ||
| Embodiment 29 | Embodiment 20 users | 10 | 90 | 28.9 | ||
| Embodiment 30 | Embodiment 23 users | 20 | 80 | 28.5 | ||
| Comparative example 12 | Comparative example 8 users | 100 | 8.2 | |||
| Comparative example 13 | Comparative example 8 users | 10 | 90 | 5.5 | ||
| Comparative example 14 | Comparative example 10 users | 20 | 80 | 6.2 | ||
Embodiment 31-36 and comparative example 15-17
The sand mold intensity of evaluation in the hardening carbon dioxide gas method for filling molding sand.Promptly, relative 100 parts by weight reclaimed sand A, add the sand mold adhesive solution 3 that 3.5 parts by weight contain the containing metal element compound of concentration shown in the table 5 (being converted into the metallic element concentration of relative resin solid composition), be mixed into mixture, the gas that this mixture is filled in φ 50mm * high 50mm is with in the sample sandbox, feed carbon dioxide 2 minutes with 10 liters/minute flows, be shaped to sand mold.Measure the compression strength after 24 hours.The results are shown in table 5.
Table 5
| Embodiment and comparative example | Phenol | Bisphenols | Alcohols | Aldehyde compound | Mol ratio | The containing metal element compound | This metallic element concentration (ppm) | Compression strength (just having mixed the back moulding) (kg/cm 2) | ||
| A | B | C | ||||||||
| Embodiment 31 | Phenol/metacresol=1/1 | Bisphenol-A | Isopropyl alcohol | Formaldehyde | 2.0 | 0.4 | 0.01 | ZnCl 2 | 300 | 25.1 |
| Embodiment 32 | P-t-butyl phenol | ＂ | ＂ | ＂ | 2.0 | 5 | 0.1 | AlCl 3 | 50 | 26.0 |
| Embodiment 33 | Metacresol | ＂ | Butanols | ＂ | 2.0 | 10 | 0.1 | Calcium acetate | 100 | 25.0 |
| Embodiment 34 | - | ＂ | Propyl alcohol | Formaldehyde/furfural=9/1 | 2.0 | ＂ | 0.01 | Aluctyl | 500 | 27.3 |
| Embodiment 35 | Phenol | Bisphenol F | ＂ | Formaldehyde | 2.0 | 0.2 | 0.2 | MgCl 2 | 1,500 | 26.2 |
| Embodiment 36 | Phenol/metacresol=1/1 | Bisphenol-A | Isopropyl alcohol | ＂ | 2.0 | 1 | 0.02 | CaCl 2 | 3,000 | 24.8 |
| Comparative example 15 | ＂ | ＂ | ＂ | ＂ | 2.0 | 1 | 0.02 | Do not have | - | 8.0 |
| Comparative example 16 | ＂ | - | ＂ | ＂ | 2.0 | ＂ | 0.02 | Do not have | - | 6.8 |
| Comparative example 17 | - | Bisphenol-A | ＂ | ＂ | 2.0 | - | 0.02 | Do not have | - | 7.5 |
Embodiment 37-42 and comparative example 18-20
The sand mold intensity of evaluation in the hardening carbon dioxide gas method for filling molding sand.Promptly, relative 100 parts by weight reclaimed sand B, add the sand mold adhesive solution 3 that 3.5 parts by weight contain the containing metal element compound of concentration shown in the table 6 (being converted into the metallic element concentration of relative resin solid composition), be mixed into mixture, the gas that this mixture is filled in φ 50mm * high 50mm is with in the sample sandbox, feed carbon dioxide 2 minutes with 10 liters/minute flows, be shaped to sand mold.Measure the compression strength after 24 hours.
In addition, in order to investigate the influence of working life, just will mix the mixture sealing of above-mentioned binding agent with polymer pouches after firm mixing, after 4 hours, the gas hardening that is filled into φ 50mm * high 50mm is equally used in the model with sample.In this model, feed carbon dioxide 2 minutes with 10 liters/minute flows, be shaped to sand mold.Measure the compression strength behind 24 hours of this sand mold.
The results are shown in table 6.
Table 6
| Embodiment and comparative example | Phenol | Bisphenols | Alcohols | Aldehyde compound | Mol ratio | The containing metal element compound | This metallic element concentration (ppm) | Compression strength | |||
| (just having mixed the back moulding) (kg/cm 2) | Mix moulding (kg/cm after 4 hours 2) | ||||||||||
| A | B | C | |||||||||
| Embodiment 37 | Phenol/metacresol=1/1 | Bisphenol-A | Isopropyl alcohol | Formaldehyde | 2.0 | 0.4 | 0.01 | ZnCl 2 | 300 | 23.2 | 21.2 |
| Embodiment 38 | P-t-butyl phenol | ＂ | ＂ | ＂ | 2.0 | 5 | 0.1 | AlCl 3 | 50 | 23.5 | 22.0 |
| Embodiment 39 | Metacresol | ＂ | Butanols | ＂ | 2.0 | 10 | 0.1 | Calcium acetate | 100 | 21.5 | 20.0 |
| Embodiment 40 | - | ＂ | Propyl alcohol | Formaldehyde/furfural=9/1 | 2.0 | - | 0.01 | Aluctyl | 500 | 25.2 | 23.7 |
| Embodiment 41 | Phenol | Bisphenol F | ＂ | Formaldehyde | 2.0 | 0.2 | 0.2 | MgCl 2 | 1,500 | 24.2 | 22.5 |
| Embodiment 42 | Phenol/metacresol-1/1 | Bisphenol-A | Isopropyl alcohol | ＂ | 2.0 | 1 | 0.02 | CaCl 2 | 3,000 | 23.5 | 21.5 |
| Comparative example 18 | ＂ | ＂ | ＂ | ＂ | 2.0 | 1 | 0.02 | Do not have | - | 7.0 | 1.3 |
| Comparative example 19 | ＂ | ＂ | ＂ | ＂ | 2.0 | - | 0.02 | Do not have | - | 5.2 | 1.0 |
| Comparative example 20 | ＂ | Bisphenol-A | ＂ | ＂ | 2.0 | - | 0.02 | Do not have | - | 6.0 | 0 |
Embodiment 43-49 and comparative example 21-24
The sand mold intensity of evaluation in the hardening carbon dioxide gas method for filling molding sand.Promptly, use homemade silica sand fresh sand, reclaimed sand A-D, be modulated into the compound of the aggregate of fire resistance shown in the table 7 mixing ratio (weight %) as the fire resistance aggregate, relative this compound of 100 parts by weight adds the sand mold binding agent shown in the 3.0 weight portion numerical tables 7, be mixed into mixture, the gas that this mixture is filled in φ 50mm * high 50mm is with in the sample sandbox, in this model, inject 1.5 parts by weight carbon dioxides, measure the compression strength after 24 hours.
In addition,, after firm mixing, just will be mixed with the mixture sealing of above-mentioned binding agent, take out this mixture after 4 hours, obtain sample, measure the compression strength after 24 hours with molding same as described above with polymer pouches in order to investigate the influence of working life.
The results are shown in table 7.
Table 7
| Embodiment and comparative example | Binding agent | The kind of fire resistance aggregate and mixing ratio | Compression strength | |||||
| Homemade silica sand fresh sand | Reclaimed sand A | Reclaimed sand B | Reclaimed sand C | Reclaimed sand D | Just mixed back moulding (kg/cm 2) | Mix moulding (kg/cm after 4 hours 2) | ||
| Embodiment 43 | Embodiment 40 users | 100 | 24.0 | 22.0 | ||||
| Embodiment 44 | Embodiment 40 users | 30 | 70 | 26.2 | 23.2 | |||
| Embodiment 45 | Embodiment 41 users | 20 | 80 | 24.2 | 21.0 | |||
| Embodiment 46 | Embodiment 40 users | 100 | 23.2 | 21.5 | ||||
| Embodiment 47 | Embodiment 40 users | 20 | 80 | 22.5 | 20.0 | |||
| Embodiment 48 | Embodiment 42 users | 25 | 75 | 24.2 | 21.5 | |||
| Embodiment 49 | Embodiment 42 users | 50 | 50 | 23.0 | 20.2 | |||
| Comparative example 21 | Comparative example 18 users | 100 | 19.2 | 7.5 | ||||
| Comparative example 22 | Comparative example 19 users | 100 | 18.2 | 8.0 | ||||
| Comparative example 23 | Comparative example 20 users | 25 | 75 | 15.2 | 8.5 | |||
| Comparative example 24 | Comparative example 20 users | 50 | 50 | 13.2 | 8.0 | |||
Embodiment 50-56 and comparative example 25-29
The sand mold intensity of evaluation in the hardening carbon dioxide gas method for filling molding sand.That is, use homemade silica sand fresh sand, reclaimed sand A-D, be modulated into the compound of the aggregate of fire resistance shown in the table 8 mixing ratio (weight %), relative this compound of 100 parts by weight as the fire resistance aggregate.Add 3.0 parts by weight sand molds with adhesive solution 3 (but not containing the containing metal element compound), and add the containing metal element compound of concentration shown in the table 8 (being converted into the metallic element concentration of resin solid composition) in addition with binding agent, be mixed into mixture, the gas that this mixture is filled in φ 50mm * high 50mm is with in the sample model, in this model, inject 1.5 parts by weight carbon dioxides, measure the compression strength after 24 hours.
In addition,, after just mixing, just be mixed with the mixture of above-mentioned binding agent, take out this mixture after 4 hours, obtain sample, measure the compression strength after 24 hours with molding same as described above with the polymer pouches sealing in order to investigate the influence of working life.
The results are shown in table 8.
Table 8
| Embodiment and comparative example | Containing metal element compound and this metallic element concentration | The kind of fire resistance aggregate and mixing ratio | Compression strength | |||||
| Homemade silica sand fresh sand | Reclaimed sand A | Reclaimed sand B | Reclaimed sand c | Reclaimed sand D | Just mixed back moulding (kg/cm 2) | Mix moulding (kg/cm after 4 hours 2) | ||
| Embodiment 50 | Aluctyl 4000ppm | 20 | 80 | 22.8 | 21.0 | |||
| Embodiment 51 | ZnCl 2 700ppm | 10 | 90 | 24.8 | 22.5 | |||
| Embodiment 52 | Sodium aluminate 45000ppm | 100 | 19.8 | 18.2 | ||||
| Embodiment 53 | MgCl 2 110ppm | 50 | 50 | 21.0 | 20.8 | |||
| Embodiment 54 | CaF 2 800ppm | 100 | 19.8 | 18.9 | ||||
| Embodiment 55 | Potassium stannate 49000ppm | 30 | 70 | 18 7 | 18.0 | |||
| Embodiment 56 | Aluminium powder 50000ppm | 15 | 85 | 21.0 | 19.7 | |||
| Comparative example 25 | Do not have | 20 | 80 | 13.9 | 5.9 | |||
| Comparative example 26 | Do not have | 10 | 90 | 12.2 | 4.0 | |||
| Comparative example 27 | Do not have | 100 | 11.9 | 4.2 | ||||
| Comparative example 28 | Do not have | 50 | 50 | 10.0 | 3.7 | |||
| Comparative example 29 | Do not have | 100 | 8.0 | 3.0 | ||||
The invention effect
The sand of fire resistance aggregate moulding being made with in the manufacture method of sand mold, use hardening sand mold binding agent of the present invention, can improve significantly sand mold intensity and working life by the reclaimed sand moulding.
Claims (18)
1. the binding agent that sand mold is used is characterized in that, it contains phenolic modified resin (A) and the essential component of compound (B) conduct,
Described phenolic modified resin (A) is that more than one bisphenol compound and the aldehyde by formula (I) expression carries out copolycondensation and the phenolic modified resin that obtains,
Wherein, (in the formula, X represents
S, O or
R
1And R
2Saturated or the unsaturated alkyl of expression hydrogen atom, trifluoromethyl, carbon number 1-6, phenyl or both derivatives of back;
R
3And R
4Saturated or the unsaturated alkyl of expression hydrogen atom, carbon number 1-6, phenyl or both derivatives of back;
Described compound (B) is to contain more than one the compound of metallic element that is selected from periodic table of elements I B family to the VIII family.
2. binding agent according to claim 1, wherein, more than one oxybenzene compound and the aldehyde that described phenolic modified resin (A) still is selected from formula (2), (3) or (4) expression carries out copolycondensation and the phenolic modified resin that obtains,
In the formula,
R
5And R
6Expression hydrogen atom or the alkyl of carbon number below 2,
In the formula,
R
7Expression hydrogen atom, hydroxyl or the alkyl of carbon number below 2,
In the formula,
R
8Aliphatic group or the aryl of expression carbon number more than 3.
3. binding agent according to claim 1 and 2, wherein, described bisphenol compound is bisphenol-A or Bisphenol F.
4. according to claim 2 or 3 described binding agents, wherein, described oxybenzene compound is the mixture of phenol and cresols.
5. according to each described binding agent among the claim 1-4, wherein, described phenolic modified resin (A) still carries out copolycondensation with alcohols and the phenol-modified resin that obtains.
6. according to each described binding agent among the claim 1-5, wherein, described metallic element is selected from periodic table II-VIII family.
7. molding sand composition, the mixture of the binding agent that it is used by any one described sand mold among fire resistance aggregate 100 weight portions and the claim 1-6 mix and obtain.
8. molding sand combination according to claim 7, wherein, described composition also comprises organic ester curing agent 0.05-9 weight portion.
9. according to claim 7 or 8 described molding sand compositions, wherein, the key component of described fire resistance aggregate is the aggregate after regeneration back and/or the recovery.
10. the manufacture method of a sand mold, it is characterized in that, it comprises adopts any one described binding agent 0.1～15 weight portion among fire resistance aggregate 100 weight portions and the claim 1-6, employing organic ester 0.05～9 weight portion and/or carbon dioxide 0.05-30 weight portion as curing agent, hardens to make sand mold.
11. molding sand composition according to claim 7, wherein, described fire resistance aggregate contains alkali reclaim sand.
12. manufacture method according to claim 10 wherein, adopts carbon dioxide gas to harden.
13. molding sand composition according to claim 7, wherein, described mixture also comprises boronic acid compounds.
14. binding agent according to claim 1, wherein, described compound (B) is more than one the compound that is selected from aluminic acid compound, stannic acid compound, titanic acid compound and the zirconic acid compound.
15. molding sand composition according to claim 11, wherein, described alkali reclaim sand is to be selected to adopt greensand mold reclaimed sand, waterglass reclaimed sand and water soluble phenol resin, more than one in the reclaimed sand that reclaims from the sand mold that makes it to harden with carbon dioxide gas or organic ester.
16. manufacture method according to claim 12 wherein, is added into respectively in the fire resistance aggregate that contains alkali reclaim sand with claim 1 or 2 described (A) with (B).
17. manufacture method according to claim 16 wherein, is also added boronic acid compounds.
18. manufacture method according to claim 16, wherein, described alkali reclaim sand is selected more than one reclaimed sand in the reclaimed sand that is reclaimed by sand mold, described sand mold is with greensand mold reclaimed sand, waterglass reclaimed sand and water-soluble phenolic resin, the sand mold that makes it to harden and form with carbon dioxide gas and/or organic ester.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07290094A JP3115518B2 (en) | 1994-12-16 | 1995-11-08 | Binder composition for mold, mold composition and method for producing mold |
| JP290094/95 | 1995-11-08 | ||
| JP290094/1995 | 1995-11-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1150070A CN1150070A (en) | 1997-05-21 |
| CN1071159C true CN1071159C (en) | 2001-09-19 |
Family
ID=17751727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96110934 Expired - Lifetime CN1071159C (en) | 1995-11-08 | 1996-06-14 | Binder composition for casting mould, mould composition and mould manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1071159C (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE50206490D1 (en) * | 2001-09-14 | 2006-05-24 | Hydro Aluminium Mandl & Berger | METHOD FOR PRODUCING CASTINGS, FORMING SAND AND ITS USE FOR THE IMPLEMENTATION OF THE PROCESS |
| JP4571693B2 (en) * | 2006-11-30 | 2010-10-27 | 株式会社ビーエムジー | Self-degradable powder-liquid and powder-powder two-reactor type medical adhesive |
| CN101977709B (en) * | 2008-03-19 | 2013-03-20 | 旭有机材工业株式会社 | Phenol resin composition for shell mold, resin-coated sand for shell mold, and mold obtained by using the same |
| CN101941045B (en) * | 2009-07-10 | 2012-10-03 | 湖北工业大学 | Preparation method and application of phosphate inorganic casting binder suspension curing agent |
| WO2011097818A1 (en) * | 2010-02-11 | 2011-08-18 | 济南圣泉集团股份有限公司 | Phenolic resin binder composition |
| CN101992259B (en) * | 2010-12-13 | 2012-07-04 | 四川海科机械制造有限公司 | Sand casting adhesive and preparation method thereof |
| CN102559132A (en) * | 2011-12-26 | 2012-07-11 | 吴江德邦科技化工有限公司 | Ceramic binding agent and production method |
| CN103056284B (en) * | 2013-01-09 | 2015-10-21 | 山东建筑大学 | The application of clay holomorphosis sand modifier, method of modifying and modifier |
| CN104338892A (en) * | 2013-07-31 | 2015-02-11 | 见得行股份有限公司 | Stabilizing agent added to green sand mold |
| CN103521709B (en) * | 2013-08-22 | 2015-12-02 | 内蒙古第一机械集团有限公司 | A kind of CO 2air hardening is from hard coupling Hardening Sodium Silicate sand core core-making method |
| CN103495694A (en) * | 2013-10-16 | 2014-01-08 | 合肥市田源精铸有限公司 | Yellow-soil foundry sand and preparation method thereof |
| CN104030708B (en) * | 2014-06-17 | 2015-12-02 | 张希君 | A kind of precision casting sand and preparation method thereof |
| CN104226889B (en) * | 2014-09-24 | 2017-02-15 | 西峡县西泵特种铸造有限公司 | Casting molding sand with regenerated dedusting ash and preparation technology of casting molding sand |
| CN104588569B (en) * | 2014-12-29 | 2017-09-29 | 北京仁创科技集团有限公司 | A kind of fast curable type high temperature resistant binder and its precoated sand and preparation method |
| CN105414464A (en) * | 2015-11-23 | 2016-03-23 | 合肥李诺新材料贸易有限公司 | Composite modified sodium silicate sand for thin, small and high-smoothness pump valve steel castings, and preparation method thereof |
| CN105414465A (en) * | 2015-11-23 | 2016-03-23 | 合肥李诺新材料贸易有限公司 | High-activity composite modified sodium silicate sand for pump valve castings, and preparation method thereof |
| CN108348986B (en) * | 2015-11-27 | 2020-08-28 | 花王株式会社 | Casting mold molding kit |
| CN109465391B (en) * | 2018-12-20 | 2020-10-27 | 青岛连山铸造有限公司 | Preparation method of molding sand for casting 350km axle box |
| MX2021011818A (en) * | 2019-03-29 | 2021-10-22 | Asahi Yukizai Corp | Mold material composition and method for manufacturing mold using same. |
| JP6798059B1 (en) * | 2019-09-09 | 2020-12-09 | 花王株式会社 | Binder composition for molding |
| CN112743036B (en) * | 2020-12-24 | 2022-06-24 | 南阳仁创再生资源有限公司 | Curing agent for inorganic precoated sand and inorganic precoated sand core containing curing agent |
| CN113351824B (en) * | 2021-06-09 | 2022-09-23 | 山东交通学院 | Bionic casting binder and preparation method thereof |
| CN114406181B (en) * | 2022-01-21 | 2023-10-20 | 金耐源(河南)工业科技有限公司 | Warm core box binder and preparation method thereof |
-
1996
- 1996-06-14 CN CN 96110934 patent/CN1071159C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1150070A (en) | 1997-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1071159C (en) | Binder composition for casting mould, mould composition and mould manufacturing method | |
| CN1100631C (en) | Mould manufacturing method, mould composition and binding agent composition for moulds | |
| KR950010603B1 (en) | Process for producing sand mold | |
| KR960004413B1 (en) | Composition for mold, casting mold and the method of production thereof | |
| JP2020516460A (en) | Method for producing mold, core and mold base material regenerated therefrom | |
| CN1117514A (en) | Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold | |
| JP3115518B2 (en) | Binder composition for mold, mold composition and method for producing mold | |
| JP3453469B2 (en) | Binder composition for curing carbon dioxide | |
| JP2954398B2 (en) | Resin composition for producing ester-curable mold and method for producing mold | |
| JP3092981B2 (en) | Resin composition for mold, binder composition for mold, mold composition, and method for producing mold | |
| JP3092985B2 (en) | Hardener composition for curable mold and method for producing mold | |
| JP3453491B2 (en) | Binder composition for curing carbon dioxide | |
| JP2504638B2 (en) | Curable mold manufacturing additive and method for manufacturing mold | |
| JP2999299B2 (en) | Binder composition for producing curable mold and method for producing mold | |
| JP2898795B2 (en) | Resin composition for producing curable mold and method for producing mold | |
| JP3092982B2 (en) | Resin composition for mold, binder composition for mold, composition for mold, and method for producing mold | |
| JP3453485B2 (en) | Method for treating casting sand and method for producing mold | |
| JP4216104B2 (en) | Method for regenerating synthetic mullite sand and method for producing mold | |
| JP2504638C (en) | ||
| JPH0669597B2 (en) | Low expansion mold material | |
| JP2015123500A (en) | Manufacturing method for mold composition, and manufacturing method for mold | |
| JPH04118149A (en) | Binder composition for molding sand | |
| JPH05228575A (en) | Resin composition for casting mold and production of casting mold by using this resin | |
| JPH0966346A (en) | Molding method and mold composition | |
| FR2546509A1 (en) | Cement for the manufacture of foundry cores and moulds and process for its manufacture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20010919 |
|
| EXPY | Termination of patent right or utility model |