EP3015188B1 - Sable de moulage et procédé de durcissement d'un tel sable - Google Patents

Sable de moulage et procédé de durcissement d'un tel sable Download PDF

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Publication number
EP3015188B1
EP3015188B1 EP14196636.6A EP14196636A EP3015188B1 EP 3015188 B1 EP3015188 B1 EP 3015188B1 EP 14196636 A EP14196636 A EP 14196636A EP 3015188 B1 EP3015188 B1 EP 3015188B1
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Prior art keywords
sand
starch
moulding
cms
binder
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EP14196636.6A
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German (de)
English (en)
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EP3015188A1 (fr
Inventor
Beata Grabowska
Karolina Kaczmarska
Dariusz Drozynski
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Akademia Gomiczo Hutnicza
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Akademia Gomiczo Hutnicza
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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
    • B22C1/20—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 organic agents
    • B22C1/26—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 organic agents of carbohydrates; of distillation residues therefrom
    • 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

Definitions

  • the present invention relates to moulding sand comprising a modified biopolymer and a method of curing thereof.
  • Moulding sands are used in the foundry industry for production of moulds and cores, which are then used to produce castings.
  • a typical process of producing a casting comprises filling a mould (prepared from a moulding sand) with a liquid material (such as metal alloy, gypsum, wax or plastic) in order to obtain a product having desired structure and properties. After the casting is solidified, the mould is subject to the process of striking, wherein the material of the mould is separated from the casting.
  • a liquid material such as metal alloy, gypsum, wax or plastic
  • the moulding sand is typically composed of a matrix, usually in the form of an inorganic, loose material, such as silica sand, and a binder for "connecting" the grains of the matrix; green sands additionally comprise water.
  • the main requirements for the moulding sands are the ability to be moulded while maintaining appropriate cohesion, as well as the strength of the bonds between sand grains - i.e. lack of tendency of the mould to be friable, both while waiting for filling, and during thermal and erosive impact on the mould of liquid material introduced into the mould.
  • moulds and cores made of moulding sand are highly influenced by the type of the binder applied.
  • One typical binder used for moulding sands is bentonite.
  • binders in the form of hydrocarbon resins wherein bonding process of the binder is carried out by a chemical reaction.
  • mixtures of synthetic polymers and biopolymers can be used as binders as well.
  • various types of additives can be introduced into moulding sands at the stage of their preparation, such as pulverised coal or sulphite lye, which are aimed at reducing mould friability and at reducing the tendency of casting defects to be formed, such as streaks, scars or dusting.
  • additives for moulding sands can be replaced by additives of natural origin, such as starch, cellulose or modifications thereof, including dextrins, carboxymethyl starch or carboxymethyl cellulose.
  • native starch can be used as an auxiliary substance which improves hardness and durability of moulding sands with bentonite, and reduces friability.
  • Native starch can also be introduced in the form of boiled starch, which helps to prevent casting defects associated with expansion.
  • a side effect of the presence of starch in the composition of the moulding sand is, however, deterioration in liquidity and in resistance of the sand to erosion and to penetration of metal into the mould.
  • Native starch is composed of glucose mers linked by ⁇ -1,4-glycosidic bonds in amylose, and by ⁇ -1,4- and ⁇ -1,6-glycosidic bonds in amylopectin.
  • Amylose forms viscous solutions at the temperature of 90°C
  • amylopectin forms hydrogel at the temperature of 70°C.
  • a disadvantage of native starch is its insolubility in cold water. Native starch begins to partially dissolve and swell at the temperature of about 70°C. In order to improve solubility of native starch in water, it is typically modified by introducing polar groups, such as hydroxyl groups.
  • the Polish Standard PN-87/A-74820 defines a modified starch as a natural starch in which one or more of its initial physical or chemical properties are changed by an appropriate treatment. Modification of starch aims at improving functional properties of starch or at giving it new characteristics.
  • Starch properties can be changed within a wide range by interacting with chemical agents, physical agents or enzymatically.
  • Products of chemical modification of starch by esterification, etherification and oxidation are widely used in the industry, including products with modified molar mass, gelatinisation temperature, solubility, viscosity, water binding capacity, temperature stability and resistance to acids and enzymes.
  • Products of starch modification such as, for example, etherified starch, i.e. comprising hydroxyethyl, hydroxypropyl or carboxymethyl groups, for example, carboxymethyl starch, can be used as binder components of moulding sands in the form of multicomponent mixtures.
  • Modified biopolymers including modified products of starch and cellulose, introduced into binders due to their natural origin (as renewable raw materials), relatively low price and biodegradability, do not have a negative impact on the natural environment.
  • WMSB water-soluble modified starch binder
  • the sand after drying (self-curing under ambient conditions) has a tensile strength at the level of 0.7-2.5 MPa, depending on the amount of WMSB in the sand.
  • the sand has a tendency to absorb moisture from the environment and is a gas generant (14.2 ml/g).
  • CMS carboxymethyl starch
  • sand consists of bentonite 0.5%, pulverised graphite 0.3%, phosphate 0.01%, water 12-15% and synthetic residues of fatty acids 1.0%. Curing of the sand is carried out by heating the mould for 1h in the temperature of 160-180°C.
  • the sand is characterised by tensile strength after curing of 1.5-2.2 MPa, gas generation capacity at the level of 14-16 ml/g and coefficient of moisture absorption of 43-50%.
  • a publication " Synthesis and Application of Modified Starch as a Shell-Core Main Adhesive in a Foundry” (Xia Zhou, Jinzong Yang, Feng Qian,Guohui Qu, Journal of Applied Polymer Science, 116/5 (2010), pp. 2893-2900, DOI 10.1002/app.31781 ) describes a method for obtaining sand for the preparation of shell cores with the participation of corn-based binder CMS having DS of 0.25-0.78.
  • the sand consists of matrix, CMS, bentonite, graphite powder, phosphates, surfactants and water in the ratio of 100:4.0:0.5:0.3:0.01:0.03:(14-20).
  • the shell cores are prepared in a core box having the temperature of 100-200°C.
  • Mater. Sci. Technol., (20/05)2004,) pp. 617-621 describe a binder consisting of ⁇ -starch, kaolin, sodium silicate, dextrin, phosphate and water in the respective proportions of: 2.5-4.0%, 1.5-3.0%, 0.55%, 0.35%, 0.04% and 2.5-3.5%. Curing is carried out by annealing at the temperature of 160-200°C for 1 h. This sand is resistant to absorption of moisture from the environment and to high temperatures, bending strength of the sand at about 1000°C is maintained at the level of about 0.4 MPa.
  • 77- 84 describe a technology for preparing core sands of 4-12% of tapioca starch, 6-12% of water and 5% of locally occurring clay. Curing of the sand is carried out at the temperature of 180°C for 2 hours.
  • the maximum compressive strength of the sand (10% of water, 10% of starch) in wet state is 290 N/mm 2 , and that for the dried sand is, respectively, 4122 N/mm 2 .
  • compositions of moulding sands which contain biopolymers in the form of products of chemical modification of starch and cellulose.
  • a Japanese patent application JPS5731439 describes a binder for moulding sands which are obtained by esterification by adding, to the starch, chloroacetic acid and NaOH solution, and then cold water.
  • this publication does not relate to moulding sands as such and methods for their preparation and curing.
  • a Polish patent application PL285979 describes a moulding sand consisting of a matrix in the form of silica sand, carbon additive in the amount of 0-6% by weight, starch and cellulose formulations in the amount of 0.5-3.0% by weight, basaltic loam acting as a binder in the amount of 5-20% by weight and water.
  • a Polish patent application PL93595 describes an additive for moulding sands, based on silica sand, bentonite and water, reducing the tendency of the sand to friability.
  • the additive consists of formamyle in the amount of 40% by weight, flocculant in the amount of 30% by weight, glycol in the amount of 5% by weight and wood flour or harl flour in the amount of 25% by weight.
  • a Chineese patent application CN101898226 describes a use of carboxymethyl starch as an additive to the binder in the form of a multicomponent mixture for binding moulding sands.
  • the moulding sand consists of sand, modified starch, malt sugar, glycerine, sodium hydroxide, pulverised coal, iron oxide, starch, carboxymethyl cellulose and water. These components are of natural origin, which ensures lack of negative impact of the sand on the environment and its nontoxicity.
  • a Dutch patent application NL6913413 describes a moulding sand consisting of bentonite, water-soluble grafted polymer of acrylic acid on a base of carboxymethyl cellulose.
  • a Chinese patent application CN103521696 describes a composition of moulding sand, consisting of china clay, pulverised coal, aluminum powder, carboxymethyl cellulose, sodium hexametaphosphate, stearic acid, chlorinated paraffin, borax, boron oxide, boric acid and water.
  • the moulding sand is characterised by good gas permeability and cohesiveness.
  • a Polish patent application PL396105 describes a composition of moulding sand with a biodegradable polymeric binder, consisting of 100 parts by weight of refractory matrix and of 1-5 parts by weight of organic binder.
  • the organic binder applied consists of a mixture of aqueous solutions of poly(acrylic acid) or poly(sodium acrylate) in the amount of 30-70% by weight and of biopolymer from the group of polysaccharides in the form of modified starch or dextrin in the amount of 30-70% by weight.
  • compositions of moulding sands with biopolymers are characterised by multicomponent nature of the binder, which is associated with the need to meet specific performance and strength parameters by the moulding sand.
  • a multicomponent nature of the binder negatively affects also prolongation of preparation of the sand and its price.
  • the object of the invention is a moulding sand and a method of curing a moulding sand according to the appended claims.
  • the moulding sand according to the invention comprises a single-component binder, a matrix and a solvent or it may contain a normally used binding material, such as an activated bentonite.
  • One of the sand components is a biodegradable sodium salt of carboxymethyl starch (CMS-Na), wherein depending on the amount of CMS-Na introduced into the moulding sand, it may serve only as an additive to the sand, improving certain utility properties, or it may serve as an additive and a binder.
  • CMS-Na carboxymethyl starch
  • silica sand is used, preferably acidic
  • the solvent is constituted by water capable of solvating CMS-Na, which is generally available, does not influence the environment negatively, and has a low price.
  • CMS-Na for the moulding sand according to the invention can be obtained in any known manner, for example by etherification of starch, for example potato starch, and then by neutralization of the etherification product by means of an aqueous solution of sodium hydroxide (NaOH), preferably having the concentration of: 2-10%, and more preferably having the concentration of 5%.
  • NaOH sodium hydroxide
  • Fig. 1 shows a reaction scheme for obtaining CMS-Na from starch by etherification of native starch slurry in ethyl alcohol by means of sodium salt of monochloroacetic acid in the presence of NaOH (Williamson synthesis). Products having different properties can be obtained, depending on the conditions for conducting modification. Changes that take place in the starch molecule are determined based on the degree of substitution (DS) which defines the average number of carboxymethyl groups (-CH 2 -COOH) or sodium carboxymethyl groups (-CH 2 -COONa) attributable to a single link of starch in each glucopyranose ring. Viscosity, water solubility and durability of CMS-Na increase proportionally to the degree of substitution (DS).
  • DS degree of substitution
  • CMS-Na is introduced in a loose form into the matrix, optionally with another loose material, such as for example activated bentonite, and all the components are stirred.
  • the time of stirring may be adapted depending on the needs, for example, depending on the efficiency of the stirrer applied.
  • the stirring time is 1 to 2 minutes, and more preferably the stirring time is 1 minute.
  • a polar solvent e.g. water
  • the stirring time of the loose components with water is 1 to 2 minutes, and more preferably the stirring time of the loose components with water is 2 minutes. Addition of the solvent ensures wetting of matrix grains, which provides appropriate adhesion of the binder-matrix system.
  • CMS-Na introduced into the sand as an additive in minor amounts, i.e. in the range of 0.2 to 2, and more preferably in the amount of 0.5 parts by weight per 100 parts by weight of the matrix, results in reduction of friability of the moulding sand. Further, it appeared that CMS-Na serves as a carrier of lustrous carbon in the moulding sand, and therefore it can be used as a bio-substitute for pulverised coal and hydrocarbon resins, which allows for achieving a simple composition of the moulding sand and ensures elimination of components from the sand, which could negatively affect the natural environment.
  • CMS-Na can also serve as a binder, when introduced into the moulding sand in the amount of 1.5 to 2.5 parts by weight per 100 parts by weight of the matrix - it exhibits the ability to bind the moulding sand permanently.
  • CMS-Na carboxymethyl starch
  • CMC carboxymethyl cellulose
  • CMS carboxymethyl starch
  • the degree of substitution (DS) has an impact on the binding properties of CMS-Na, wherein the best binding properties are achieved with the degree of substitution (DS) in the range of 0.2 to 0.9, and preferably 0.6 to 0.8.
  • DS degree of substitution
  • solubility of CMS-Na in polar solvents the higher DS (i.e. the greater share of side polar groups within a polymer chain - starch), the higher the solubility of CMS-Na in polar solvents. Therefore, an increase in solubility of CMS-Na improves the binding properties of this substance.
  • the moulding sand can be cured physically - by evaporating part of the water contained in the sand.
  • the evaporation can be performed by supplying energy in a thermal way, i.e. by heating the moulding sand until it solidifies.
  • the moulding sand can be annealed through thermal drying in the temperature of 80 to 150°C, and preferably in the temperature of 100°C.
  • the sand with CMS-Na binder can be subjected to electromagnetic radiation having a microwave frequency, preferably in the range of 2 to 3 GHz, and more preferably 2.45 GHz and with the power of 600 W to 1200 W, preferably 800 W. Radiation exposure time is selected depending on the amount and/or the weight of the sand.
  • the composition of the moulding sand which contains CMS-Na as an additive various types of typically used binding materials can be used, such as for example activated bentonite having montmorillonite content of 70 to 90%.
  • the moulding sand can be composed of 100 parts by weight of mineral matrix, 5-8 parts by weight of bentonite, 0.5-2 parts by weight of CMS-Na and 1.5-4 parts by weight of water.
  • the moulding sand according to the invention is its simple composition; the sand can be composed of only three components: CMS-Na binder, mineral matrix and solvent; introduction of CMS-Na as a binder allowed obtaining the effect of better binding of the matrix, and therefore obtaining moulds and cores having better functional parameters.
  • the simple composition of the moulding sand according to the invention is also related to the multifunctionality of CMS-Na in the sand.
  • This substance can simultaneously serve in the moulding sand as a binder and as an additive, providing reduction in friability of the bentonite-bound sand and allowing elimination from the system of substances such as pulverised coal or hydrocarbon resins, which significantly simplifies the composition of the sand.
  • CMS-Na binder such as degree of substitution (DS) or viscosity
  • starch modification provides additionally the possibility of producing, depending on the needs, the moulding sand with desired properties, such as bending strength or friability.
  • CMS-Na is a biodegradable polymer, and products of CMS-Na decomposition are substances which occur naturally in the environment and are harmless.
  • the moulding sand with CMS-Na according to the invention is characterised by allowing easy striking of the products out of the mould and by a high quality of the castings produced.
  • the moulding sand according to the invention is further characterised by good recoverability.
  • CMS-Na binder can be retrieved from the sand after a technological process.
  • CMS-Na bound sand is characterised by insignificant harmfulness to the environment and workers (the used sand can be utilised in the industry).
  • CMS-Na bound sand An important advantage of the CMS-Na bound sand is the possibility of its preparation with acidic matrices.
  • CMS-Na bound sand may be an alternative for the sands used in foundry industry due to the physicochemical characteristics of its components, and technological, ecological and economic aspects.
  • the starch component of CMS-Na sand can be produced from cheap raw materials, such as for example potato starch, or from vegetable waste containing starch (e.g. potato processing waste).
  • Modification of potato starch with the moisture content of up to 14.0% was conducted in a glass reactor equipped with a mechanical stirrer, a thermocouple and capillaries supplying nitrogen to the reaction system.
  • the starch was etherified in a mixture of isopropanol (IPOH) and water in a single-step process.
  • Monochloroacetic acid (MCA) was dissolved in IPOH in the reactor, and then was introduced in aqueous solution of NaOH.
  • the molar ratio of NaOH/(S)MCA was 2.25:1.
  • After stirring for 90 min and homogenisation of the mixture a fine fraction of NaOH was introduced into the reactor.
  • the reaction was conducted for the period of about 150 - 180 min in the temperature of 50°C.
  • the product obtained was filtered off and neutralised with acetic acid, then it was washed several times with methanol solution, once with pure methanol, and then it was left on a heated surface to be dried in the air.
  • CMS-Na The above example of the synthesis of CMS-Na should only be considered as illustrative, while CMS-Na to be used in further examples can be also obtained by other known methods.
  • the moulded pieces were subjected to curing under the influence of microwave radiation with power of 800W and frequency of 2.45 GHz for 120s, an then properties of the cured sand were examined.
  • the sand with the following properties was obtained:
  • the moulded pieces were subjected to curing under the influence of microwave radiation with power of 800W and frequency of 2.45 GHz for 120s, an then properties of the cured sand were examined.
  • the sand with the following properties was obtained:

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Mold Materials And Core Materials (AREA)

Claims (5)

  1. Sable de moulage comprenant de l'eau, un liant et une matrice de sable de silice, caractérisé en ce qu'il comprend en outre du sel de sodium de carboxyméthyl amidon (CMS-Na), ayant un degré de substitution (DS) dans la plage comprise entre 0,2 et 0,9, dans la quantité de 0,2 à 2,5 parties en poids pour 100 parties en poids de la matrice, la composition de sable de moulage ne comprenant pas de charbon pulvérisé et de résines de carbone.
  2. Sable de moulage selon la revendication 1, caractérisé en ce que CMS-Na est un liant dans la quantité de 1,5 à 2,5 parties en poids pour 100 parties en poids de la matrice.
  3. Sable de moulage selon la revendication 1, caractérisé en ce que le sable de moulage est un sable lié à la bentonite et CMS-Na est un additif dans la quantité de 0,2 à 2,0 parties en poids pour 100 parties en poids de matrice.
  4. Sable de moulage selon la revendication 3, caractérisé en ce qu'il comprend un liant sous forme de bentonite activée comprenant de la montmorillonite dans la quantité de 70 % à 90 % en poids.
  5. Procédé de durcissement d'un sable de moulage selon l'une quelconque des revendications 1 à 4 par évaporation de l'eau du sable en soumettant le sable de moulage à des ondes électromagnétiques de fréquence micro-onde dans la plage comprise entre 2 GHz et 3 GHz.
EP14196636.6A 2014-10-30 2014-12-05 Sable de moulage et procédé de durcissement d'un tel sable Active EP3015188B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PL409935A PL233870B1 (pl) 2014-10-30 2014-10-30 Masa formierska oraz sposób utwardzania masy formierskiej

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EP3015188A1 EP3015188A1 (fr) 2016-05-04
EP3015188B1 true EP3015188B1 (fr) 2020-03-04

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EP14196636.6A Active EP3015188B1 (fr) 2014-10-30 2014-12-05 Sable de moulage et procédé de durcissement d'un tel sable

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108723285B (zh) * 2018-07-11 2019-12-03 佛山市杨森化工有限公司 一种高湿压强度型砂粘结剂材料的制备方法
CN112317679A (zh) * 2020-11-07 2021-02-05 郑州远东耐火材料有限公司 一种电熔砖砂型专用新型改性树脂粘接剂及其制备方法

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Publication number Priority date Publication date Assignee Title
US2838406A (en) * 1954-10-06 1958-06-10 Mo Och Domsjoe Ab Methods of preparing sand cores and other sand mould parts for metal casting
GB1275618A (en) 1968-09-04 1972-05-24 Int Minerals & Chem Corp Clay and water soluble graft copolymer compositions
US3645937A (en) * 1968-09-04 1972-02-29 Int Minerals & Chem Corp Foundry sand compositions containing graft copolymers of acrylic acid with water-soluble polyhydroxy polymeric compounds
PL93595B1 (fr) 1974-08-30 1977-06-30
JPS5731439A (en) 1980-08-04 1982-02-19 Sintokogio Ltd Binder for molding sand
PL285979A1 (en) 1990-07-06 1992-01-13 Inst Odlewnictwa Moulding sand mix
CN101898226B (zh) 2010-08-16 2011-09-21 新蔡县东邦铸造有限责任公司 铸造配砂辅料
PL218966B1 (pl) 2011-08-29 2015-02-27 Akademia Górniczo Hutnicza Im Stanisława Staszica W Krakowie Masa formierska lub rdzeniowa wiązana biodegradowalnym spoiwem polimerowym
CN103521696A (zh) 2013-10-16 2014-01-22 合肥市田源精铸有限公司 一种压盘铸造的型砂及其制备方法

Non-Patent Citations (1)

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Title
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PL233870B1 (pl) 2019-12-31
PL409935A1 (pl) 2015-08-31

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