EP4076784A1 - Procédé pour la construction en couches de corps comprenant un matériau de base de moulage réfractaire et des résols, corps tridimensionnels fabriqués à l'aide de ce procédé, et liant pour des corps de construction en trois dimensions - Google Patents

Procédé pour la construction en couches de corps comprenant un matériau de base de moulage réfractaire et des résols, corps tridimensionnels fabriqués à l'aide de ce procédé, et liant pour des corps de construction en trois dimensions

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Publication number
EP4076784A1
EP4076784A1 EP20841879.8A EP20841879A EP4076784A1 EP 4076784 A1 EP4076784 A1 EP 4076784A1 EP 20841879 A EP20841879 A EP 20841879A EP 4076784 A1 EP4076784 A1 EP 4076784A1
Authority
EP
European Patent Office
Prior art keywords
weight
phenol
molding material
ortho
binder
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.)
Pending
Application number
EP20841879.8A
Other languages
German (de)
English (en)
Inventor
Dennis BARTELS
Thomas Krey
Arkadius KAMINSKI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ASK Chemicals GmbH
Original Assignee
ASK Chemicals GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ASK Chemicals GmbH filed Critical ASK Chemicals GmbH
Publication of EP4076784A1 publication Critical patent/EP4076784A1/fr
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—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
    • B22C1/22—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 resins or rosins
    • B22C1/2233—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 resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2246—Condensation polymers of aldehydes and ketones
    • B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20

Definitions

  • the invention relates to a method for the layered construction of bodies comprising refractory basic molding material and resol resins as binders having ortho- and / or para-substituted phenols as monomer components and three-dimensional bodies produced by this method, as well as a binder for the 3-dimensional construction of bodies , especially of molds and cores for metal casting.
  • the hardening reaction can be triggered, for example, by flooding the entire component with a gaseous hardener or thermally.
  • EP 3137246 B1 discloses a method for building up bodies in layers comprising refractory basic molding material and resols. Alkaline resole resins are selectively applied via a print head and are cured during the process with an ester that was applied in layers together with the basic mold material.
  • Resoles or resole resins are phenoplasts and belong to the class of phenol-formaldehyde resins. These are produced by condensation of a Flydroxy aromatic and an aldehyde, in particular formaldehyde, in the presence of basic catalysts. Typically, formaldehyde and phenol are used as monomers for the production of the alkaline resole resins and subjected to a polycondensation reaction. The mostly overstoichiometric amounts of formaldehyde used (e.g. up to 2.5: 1) also form ether groups in addition to methylene groups to link the phenol monomers.
  • alkylphenols such as xylenols or cresols can also be used as monomer components for the production of resoles.
  • Resoles in the form of aqueous alkaline solutions are usually used as binders for the production of foundry molds and cores, but not with cresols as an additional monomer component, as these have a negative effect on price and odor.
  • the object of the present invention is to provide a storage-stable resole resin which remains more stable in viscosity over time, shows a smaller drop in gel time, and thus ensures the printability of the binding agent consisting of the resol resin over a longer period of time. Furthermore, the binding agent should bring about a sufficient level of strength of bound casting molds.
  • the method for building up bodies in layers comprises at least the following steps: a) bringing together at least one refractory molding base material and at least one ester to obtain an ester-impregnated molding material mixture, b) spreading out a thin layer with a layer thickness of 1 to 6, preferably 1 up to 5 and particularly preferably 1 to 3 grains of the ester-impregnated molding material mixture, c) printing selected areas of the thin layer with a binder comprising an alkaline resole resin to harden the areas, d) repeating steps b) and c) several times to complete a at least partially cured three-dimensional body, the alkaline resole resin is obtainable from the reaction of formaldehyde with at least phenol and at least ortho- and / or para-substituted phenol, where the substituent (each) is an aliphatic, branched or unbranched, saturated or unsaturated Hydrocarbon radical with 1 to 15 carbon atoms n, in particular 1 to 4 carbon atoms, and the
  • the binder for the 3-dimensional structure of molds and cores for the metal casting comprises (in particular consists of) at least one alkaline resol resin, it is available from the implementation of at least: a. Phenol; and b. at least phenol which carries at least one substituent in the ortho and / or para position, preferably one substituent, the substituent (possibly different) in each case being an aliphatic, branched or unbranched, saturated or unsaturated hydrocarbon radical with 1 to 15 C Atoms, so that at one or two of the remaining positions (2, 4, 6 or ortho / para) there is a bond to a further structural unit of the resol instead of a bond to hydrogen, with c. Formaldehyde.
  • polymers are formed which link the phenol nuclei comprising at least phenol and substituted phenols (ortho- and / or para-substituted) via methylene groups and / or ether bridges (-CH2-O-CH2-).
  • refractory base molding material for short
  • quartz sand, zirconium sand or chrome ore sand, olivine, vermiculite, bauxite, chamotte and synthetic mold base materials for example based on mulite (sintered mullite), in particular more than 50% by weight of quartz sand based on the refractory mold base material, are suitable.
  • a basic molding material is understood to mean substances that have a high melting point (melting temperature).
  • the melting point of the refractory basic molding material is preferably greater than 600.degree. C., preferably greater than 900.degree. C., particularly preferably greater than 1200.degree. C. and particularly preferably greater than 1500.degree.
  • the refractory basic molding material has a free-flowing state.
  • the basic molding material preferably makes up more than 80% by weight, in particular more than 90% by weight, particularly preferably more than 95% by weight, of the molding material mixture.
  • the mean diameter of the refractory base molding materials is generally between 80 ⁇ m and 600 ⁇ m, preferably between greater than 100 ⁇ m and 400 ⁇ m and particularly preferably between 120 ⁇ m and 300 ⁇ m.
  • the particle size can be determined, for example, by sieving according to DIN ISO 3310. Particle shapes with the greatest length expansion to the smallest length expansion (at right angles to one another and in each case for all spatial directions) of 1: 1 to 1: 5 or 1: 1 to 1: 3, ie those which, for example, are not fibrous, are particularly preferred.
  • a special chromite sand sold under the name Spherichrome by Oregon Resources Corporation (ORC) is particularly suitable. In Europe, Spherichrome is sold by Possehl Erz sparkler GmbH, Lübeck.
  • Spherichrome differs in its grain shape from the previously known South African chrome ore sand. In contrast to the latter, Spherichrome has largely rounded grains. According to the preferred embodiment, spherichrome does not necessarily make up 100% by weight of the basic molding material; mixtures with other basic molding materials are also possible, especially quartz sand. The mixing ratio depends on the particular stress on the casting mold. As a rule, however, if quartz sand is used, this should contain at least 20% by weight of spherichrome, preferably at least 40% by weight, particularly preferably at least 60% by weight.
  • the Spherichrome molding base material has particle shapes in the ratio (mean) of the greatest length expansion to the smallest length expansion (at right angles to one another and in each case for all spatial directions) of in particular 1: 1 to 1: 3, particularly preferably of 1: 1 to 1: 3 on.
  • the binder consists of an alkaline resole resin.
  • the resol resin according to the invention is produced by condensation of at least phenol, ortho- or para-substituted phenol and formaldehyde in the presence of a basic catalyst.
  • the resoles are in the form of an aqueous alkaline solution, preferably with a solids content of 20 to 75% by weight. and a pH value of preferably greater than 11, particularly preferably greater than 12 (measured at 25 ° C.).
  • the resol resin is advantageously used in a concentration of 0.8% by weight to 8% by weight, preferably from 1% by weight to 7% by weight and particularly preferably from 1.5% by weight to 5% by weight, based in each case on the mold base material.
  • concentration of binding agent within the casting mold can vary. In the case of thicker parts of the mold, the proportion of binder can be lower than indicated above, while the binder content in thin and complex parts can exceed the limit value mentioned above.
  • Resoles in the context of the present invention are aromatics connected to one another via methylene groups (-CH2-) groups and / or via ether bridges (in particular -CH2-O-CH2-), each of which carries at least one -OH group (hydroxy aromatic).
  • Ortho- and / or para-substituted phenol are understood to mean compounds which, starting from the phenol at the ortho and / or para position (2,4,6), preferably an ortho position, by at least one aliphatic, branched or unbranched, saturated or unsaturated hydrocarbon radical with 1 to 15 carbon atoms, in particular 1 to 4 carbon atoms, are substituted and have a maximum of two radicals / substituents.
  • the aliphatic radical is preferably unbranched and saturated.
  • the substituted phenol is particularly preferably ortho- or para-cresol, more preferably ortho-cresol.
  • the hydrocarbon radical of the at least ortho- and / or para-substituted phenol is in particular one or more methyl groups, and the ortho- and / or para-substituted phenols in particular, for example, from the group include o-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol and mixtures thereof, and in particular o-cresol, are selected.
  • the ortho- and / or para-substituted phenol can additionally be meta-substituted.
  • greater than 90 mol%, in particular greater than 95 mol%, or all hydroxy aromatics in the resol resin are phenol and ortho- and / or para-substituted phenols or are based on such monomer units.
  • Formaldehyde can be used in various forms - for example in the form of a formalin solution (aqueous solution of formaldehyde) or paraformaldehyde.
  • the aldehyde used is preferably essentially exclusively formaldehyde.
  • the molar ratio of ortho- and / or para-substituted phenol (together) (A) to phenol (B) in the alkaline resol resin is from 1 to 1.5 (A: B) to 1 to 15 and preferably 1: 2 to 1 : 10 and most preferably from 1 in 4 to 1 in 6.
  • the molar ratio of the hydroxy aromatics to formaldehyde can vary in the range from 1: 1 to 1: 3, but is preferably between 1: 1.2 to 1: 2.6, particularly preferably between 1: 1.3 to 1: 2.5.
  • the hydroxy aromatics are preferably formed essentially exclusively from the phenol, the ortho-substituted phenol, the para-substituted phenol and the ortho- and para-substituted phenol, ie the ortho- and / or para-substituted phenol .
  • Resoles are preferred as part of the alkaline resole resin in which neighboring hydroxy aromatics are linked at the ortho and / or para position (relative to the hydroxy group of the built-in phenol / aromatic) via the methylene bridges and / or the ether bridges are, ie the majority of the links are para and / or ortho.
  • Both organic bases, such as amines or ammonium compounds, and inorganic bases, such as alkali metal hydroxides, can be used as basic catalysts. Preference is given to alkali metal hydroxides, particularly preferably sodium hydroxide and / or potassium hydroxide in the form of aqueous solutions. Mixtures of basic catalysts can also be used.
  • the molar ratio of hydroxy aromatics (such as phenol, also incorporated) to hydroxide ions in the binder system is preferably 1: 0.4 to 1: 1.2 and preferably 1: 0.5 to 1: 1.0.
  • the content of compounds with a molar mass greater than 5000 Dalton (g / mol) in the resol resin is preferably at most 3% by weight and particularly preferably at most 1% by weight.
  • the mean molar mass of the resol resin Mw (mass average) is in particular less than 1500 Daltons (g / mol), preferably less than 1400 Daltons (g / mol) and particularly preferably less than 1300 Daltons (g / mol).
  • the polydispersity of the resol resin D Mw (weight average) / Mn (number average) is in particular from 1.1 to 4, preferably 1.2 to 3.5 and particularly preferably from 1.5 to 3.
  • the specified molecular weights were determined by means of gel permeation chromatography. Due to the calibration, the molar masses given above are pullulan-dextran-equivalent molar masses. The following parameters were used:
  • PSS SECcurity 1260 autosampler with 20pL sample concentration: 1 g / l Temperature: injection volume 35 ° C Detector: PSS SECcurity 1260 UV / VIS (254nm)
  • resoles The production of resoles is disclosed, for example, in EP 0323096 B2 and EP 1228128 B1. Further binders based on resole are described, for example, in US Pat. No. 4,426,467 and US Pat. No. 4,474,904.
  • the resols are hardened with the aid of esters, the hardening being carried out by adding a liquid hardener, e.g. a lactone (US 4,426,467) or triacetin (US 4,474,904).
  • a liquid hardener e.g. a lactone (US 4,426,467) or triacetin (US 4,474,904).
  • the resole contains water, preferably in an amount of 25% by weight to 75% by weight, based on the weight of the composition.
  • the water can come from aqueous solutions that are used in the manufacture of the binder (in addition to the water produced by the polycondensation), on the other hand, it can also be added separately to the binder.
  • water also serves, for example, to give the binder an application-appropriate viscosity of in particular 3 mPas to 100 mPas, preferably from 4 mPas to 50 mPas and particularly preferably from 5 mPas to 20 mPas. The viscosity is determined using a Brookfield rotary viscometer, Small Sample, spindle no. 21 at 100 rpm and 25 ° C.
  • the binder can also contain up to approx. 50% by weight of additives such as alcohols, glycols, surfactants and silanes.
  • additives such as alcohols, glycols, surfactants and silanes.
  • silanes for example gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane, in concentrations of 0.1% by weight to 1.5% by weight, preferably 0.2% by weight to 1.3% by weight, has a particularly positive effect in this regard % By weight and particularly preferably from 0.2% by weight to 1.0% by weight, each based on the weight of the composition.
  • esters suitable for hardening the resoles are known to the person skilled in the art, e.g. from US Pat. No. 4,426,467, US Pat. No. 4,474,904 and US Pat. No. 5,405,881. They include lactones, organic carbonates and esters of C1 to C10 mono- and polycarboxylic acids with C1 to C10 mono- and polyalcohols.
  • esters and hardeners are gamma-butyrolactone, propylene carbonate, ethylene glycol diacetate, mono-, di- and triacetin and the dimethyl esters of succinic acid, glutaric acid and adipic acid, including their mixture known as DBE. Due to the different saponification rates of the individual esters, the rate of hardening of the resols varies depending on the ester used, which can also affect the strengths. The desired curing time can be varied within wide limits by mixing two or more esters.
  • ester component One possibility for modifying the ester component is to add benzyl ester resins according to US Pat. No. 4,988,745, epoxy compounds according to US Pat. No. 5,405,881 and / or polyphenol resins according to US Pat. No. 5,424,376, each in amounts of up to approx. 40% by weight, based on the ester component.
  • the ester component can hold up to about 50 wt.% Other ingredients ent such.
  • the amount of hardener added is usually 5% by weight to 50% by weight, preferably 5% by weight to 40% by weight and particularly preferably 5% by weight to 30% by weight, depending on the amount of binder, or in a concentration of 0.04% by weight to 4.0% by weight, preferably from 0.05% by weight to 3.5% by weight and particularly preferably from 0.08% by weight to 2.5% by weight. % used, each based on the basic mold material
  • the molding material mixtures can contain a proportion of an amorphous S1O2.
  • it is particulate amorphous S1O2.
  • Synthetically produced particulate amorphous silicon dioxide is particularly preferred.
  • the amorphous S1O2 can in particular be of the following types: a) amorphous S1O2 obtained by precipitation from an alkali silicate solution b) amorphous S1O2 obtained by flame hydrolysis of SiCL c) amorphous S1O2 obtained by reducing quartz sand with coke or anthracite to silicon monoxide with subsequent oxidation to S1O2 d) amorphous S1O2 obtained from the process of thermal decomposition of ZrSi04 to Zr ⁇ 2 and S1O2 e) amorphous S1O2 obtained by oxidation of metallic Si by means of an oxygen-containing gas f) amorphous S1O2 obtained by melting crystalline quartz with subsequent rapid cooling c ) includes both processes in which the amorphous S1O2 is specifically manufactured as the main product and processes in which it is obtained as a by-product, such as in the production of silicon or ferrosilicon.
  • amorphous S1O2 Both synthetically produced and naturally occurring silicas can be used as amorphous S1O2.
  • the latter are known, for example, from DE 102007045649, but are not preferred because they generally contain not inconsiderable crystalline proportions and are therefore classified as carcinogenic.
  • Synthetic is understood to be non-naturally occurring amorphous S1O2, i.e. the production of which comprises a deliberately carried out chemical reaction as initiated by a person, e.g. the production of silica sols by ion exchange processes from alkali silicate solutions, precipitation from alkali silicate solutions, flame hydrolysis of silicon tetrachloride , the reduction of quartz sand with coke in an electric arc furnace in the production of ferrosilicon and silicon.
  • the amorphous Si0 2 produced by the last two processes mentioned is also referred to as pyrogenic S1O2.
  • amorphous silicon dioxide only refers to precipitated silica (CAS No. 112926-00-8) and S1O2 produced by flame hydrolysis (Pyrogenic Silica, Fumed Silica, CAS No. 112945-52-5), while that of Ferrosili -
  • the product resulting from the production of silicon or silicon is only referred to as amorphous silicon dioxide (Silica Fume, Microsilica, CAS No. 69012-64-12).
  • the product resulting from ferrosilicon or silicon manufacture is also understood as amorphous S1O2.
  • Amorphous silicon dioxide produced by thermal decomposition of ZrSi0 4 (described in DE 102012020509) and S1O2 produced by oxidation of metallic Si by means of an oxygen-containing gas are particularly preferred.
  • quartz glass powder mainly amorphous silicon dioxide, which was produced from crystalline quartz by melting and rapid cooling again, so that the particles are spherical and not splintery (described in DE 102012020511).
  • the mean primary particle size of the particulate amorphous silicon dioxide can be between 0.05 pm and 10 pm, in particular between 0.1 pm and 5 pm, particularly preferably between 0.1 pm and 2 pm.
  • the primary particle size can be determined, for example, with the aid of dynamic light scattering (for example Horiba LA 950) and checked by scanning electron microscope images (SEM images with, for example, Nova NanoSEM 230 from FEI). Furthermore, with the help of the SEM images, details of the primary particle shape down to the order of 0.01 mhi could be made visible.
  • the silicon dioxide samples were dispersed in distilled water and then applied to an aluminum holder covered with copper tape before the water was evaporated.
  • the specific surface area of the particulate amorphous silicon dioxide was determined using gas adsorption measurements (BET method) according to DIN 68131.
  • the specific surface of the particulate amorphous S1O2 is between 1 and 200 m 2 / g, in particular between 1 and 50 m 2 / g, particularly preferably less than 17 m 2 / g or even less than 15 m 2 / g. If necessary, the products can also be mixed, for example in order to obtain mixtures with specific particle size distributions in a targeted manner.
  • the particulate amorphous S1O2 can contain different amounts of by-products. Examples are:
  • the amount of amorphous S1O2 that is added to the molding material mixture according to the invention is usually between 0.05% by weight and 3% by weight, preferably between 0.1% by weight and 2.5% by weight and particularly preferably between 0 , 1% by weight and 2% by weight in each case based on the basic molding material.
  • the amorphous S1O2 can be added to the basic molding material in the form of an aqueous paste, as a slurry in water or as a dry powder. The latter is preferred.
  • the particulate amorphous S1O2 is preferably used as a powder (including dust).
  • the particulate amorphous silicon dioxide preferably used according to the present invention has a water content of less than 15% by weight, in particular less than 5% by weight and particularly preferably less than 1% by weight.
  • the amorphous S1O2 is preferably in particulate form.
  • the particle size of the particulate amorphous silicon dioxide is preferably less than 300 ⁇ m, preferably less than 200 ⁇ m, particularly preferably less than 100 ⁇ m and has, for example, an average primary particle size between 0.05 ⁇ m and 10 ⁇ m (primary particle size determined by dynamic light scattering).
  • the sieve residue of the particulate amorphous S1O2 when passing through a sieve with 125 ⁇ m mesh size (120 mesh) is preferably not more than 10% by weight, particularly preferably not more than 5% by weight and very particularly preferably not more than 2% by weight . Irrespective of this, the sieve residue on a sieve with a mesh size of 63 ⁇ m is less than 10% by weight, preferably less than 8% by weight.
  • the sieve residue is determined using the machine sieving method described in DIN 66165 (Part 2), with a chain ring being used as a sieving aid.
  • the order in which the amorphous SiC is added to the binder and / or to the mold base is immaterial. It can take place both before, after, or together with the binder.
  • the amorphous S1O2 is preferably added first and then the binder is added.
  • the basic mold material can, if necessary, be mixed in with other additives that are customary in the foundry industry, such as ground wood fibers or mineral additives such as iron oxide, etc., their proportion usually being 0% by weight to 6% by weight, preferably 0% by weight to 5% by weight .% and particularly preferably 0% by weight to 4% by weight, based on the basic molding material.
  • additives that are customary in the foundry industry, such as ground wood fibers or mineral additives such as iron oxide, etc.
  • the invention relates to a method for producing a casting mold or a core (or body in general) comprising the steps of a) mixing the refractory basic molding material with the ester component and, if necessary, with the inorganic additive and, if necessary, the other additives to obtain a molding material mixture, b) spreading a thin layer with a layer thickness of 1 to about 6, preferably 1 to about 5 and particularly preferably 1 to 3 grains of the molding material mixture produced in a) on a defined work surface, c) selective printing of the thin layer of the molding material mixture with the binder at the locations specified by the CAD data, the binder at least partially hardening through contact with the ester, d) repeating steps b) and c) several times up to Completion of the casting mold, e1) post-curing of the at least partially hardened casting mold in an oven or by means of a microwave without prior removal of the unbound molding material mixture or alternatively to e1) e2) removal of the unbound molding material mixture from the at least partly hard
  • the unbound molding material mixture can be removed from the casting mold after step e1) and this can be used for further treatment, e.g. preparation for metal casting.
  • the casting mold can, if necessary, be post-cured by conventional measures such as storage at elevated temperatures or by means of microwaves. As soon as the strengths allow, the mold can be used for further treatment, e.g. preparation for metal casting.
  • the unbound molding material mixture can be fed to a further casting mold after removal from the at least partially hardened casting mold for production.
  • alkaline resole resins with different contents of phenol and o-cresol were produced.
  • the alkaline resole resins were set in the viscosity range of 40-60 mPas.
  • the resoles can be adjusted to an application viscosity of 5 to 20 mPas using suitable solvents, such as ethanol and water.
  • suitable solvents such as ethanol and water.
  • the influence of the proportions of o-cresol in the resols on the strengths was then tested using conventional test specimens, the so-called Georg Fischer test bars.
  • Resin 1 contained exclusively phenol as a hydroxy-aromatic monomer unit.
  • Resins 2-6 contained 12-51% by weight of o-cresol based on the total amount of phenol and o-cresol.
  • the resin was obtained as a clear solution and had a viscosity (Brookfield Rota tion viscometer, Small Sample, spindle no. 21 at 100 rpm and 25 ° C.) of 49 mPas.
  • the resin was obtained as a clear solution and had a viscosity (Brookfield Rota tion viscometer, Small Sample, spindle no. 21 at 100 rpm and 25 ° C.) of 47 mPas.
  • the resin was obtained as a clear solution and had a viscosity (Brookfield rotary viscometer, Small Sample, spindle no. 21 at 100 rpm and 25 ° C.) of 51 mPas.
  • the resin was obtained as a clear solution and had a viscosity (Brookfield Rota tion viscometer, Small Sample, spindle no. 21 at 100 rpm and 25 ° C.) of 51 mPas.
  • the resin was obtained as a clear solution and had a viscosity (Brookfield Rota tion viscometer, Small Sample, spindle no. 21 at 100 rpm and 25 ° C.) of 51 mPas.
  • the resin was obtained as a clear solution and had a viscosity (Brookfield Rota tion viscometer, Small Sample, spindle no. 21 at 100 rpm and 25 ° C.) of 51 mPas.
  • the molding material was poured into the bowl of a mixer from Beba (model L 7). While stirring, the hardener and then the binder were then added and mixed intensively with the basic molding material for 1 minute.
  • VZ The processing time (VZ), i.e. H. the time within which a mixture can be compacted without any problems was determined visually. You can tell that the processing time has been exceeded by the fact that a mixture no longer flows freely, but rolls off like clods. The processing times of the individual mixtures are given in Tab.
  • AZ disconnection time
  • the flexural strengths were determined according to the following scheme:
  • resol resins 1 to 5 described under 1 were stored at room temperature. The viscosity and the gel time were checked immediately after production and at fixed intervals after storage. Resole resin 6 was classified as unfavorable due to its longer stripping time and low flexural strengths determined in accordance with point 3 and was not investigated further.
  • the viscosity of the resol resins was determined using a Brookfield rotary viscometer, small sample, spindle no. 21 at 100 rpm and 25 ° C. The results are shown in Tab. 3.
  • the gel time of the resol resins was determined by means of a Gelnorm Geltimer from Gel Instruments AG (type Geltimer-m and ST 1) at 25 ° C. For this purpose, 18 g of resol resin and 2 g of 5090 catalyst (ASK Chemicals GmbH) triacetin were mixed in a test tube and the time until the mixture hardened was determined with the gel timer.
  • Test bars which were produced with resol resins 2 - 5, containing o-cresol and phenol, showed comparable or higher strengths than test bars made from the comparison resol resin 1 without o-cresol.
  • Resole resins 2 - 5 produced with o-cresol showed a lower increase in viscosity and a longer gel time, especially after storage, than a comparison resol resin 1 produced without o-cresol.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Ceramic Engineering (AREA)
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Abstract

L'invention concerne : un procédé pour la construction en couches de corps comprenant un matériau de base de moulage réfractaire et des résols en tant que liants, ayant, en plus du phénol, des phénols ortho- et/ou para-substitués en tant qu'éléments structuraux monomères ; des corps tridimensionnels fabriqués à l'aide de ce procédé ; et un liant pour des corps de construction en trois dimensions, en particulier des moules et des noyaux pour la coulée de métaux.
EP20841879.8A 2019-12-20 2020-12-18 Procédé pour la construction en couches de corps comprenant un matériau de base de moulage réfractaire et des résols, corps tridimensionnels fabriqués à l'aide de ce procédé, et liant pour des corps de construction en trois dimensions Pending EP4076784A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019135605.9A DE102019135605A1 (de) 2019-12-20 2019-12-20 Verfahren zum schichtweisen Aufbau von Körpern umfassend feuerfesten Formgrundstoff und Resole, nach diesem Verfahren hergestellte dreidimensionale Körper sowie ein Bindemittel für den 3-dimensionalen Aufbau von Körpern
PCT/DE2020/101080 WO2021121487A1 (fr) 2019-12-20 2020-12-18 Procédé pour la construction en couches de corps comprenant un matériau de base de moulage réfractaire et des résols, corps tridimensionnels fabriqués à l'aide de ce procédé, et liant pour des corps de construction en trois dimensions

Publications (1)

Publication Number Publication Date
EP4076784A1 true EP4076784A1 (fr) 2022-10-26

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EP20841879.8A Pending EP4076784A1 (fr) 2019-12-20 2020-12-18 Procédé pour la construction en couches de corps comprenant un matériau de base de moulage réfractaire et des résols, corps tridimensionnels fabriqués à l'aide de ce procédé, et liant pour des corps de construction en trois dimensions

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US (1) US20230042686A1 (fr)
EP (1) EP4076784A1 (fr)
JP (1) JP2023511497A (fr)
KR (1) KR20220116286A (fr)
CN (1) CN114829034A (fr)
BR (1) BR112022011484A2 (fr)
DE (2) DE102019135605A1 (fr)
MX (1) MX2022007651A (fr)
WO (1) WO2021121487A1 (fr)

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4426467A (en) 1981-01-12 1984-01-17 Borden (Uk) Limited Foundry molding compositions and process
US4474904A (en) 1982-01-21 1984-10-02 Lemon Peter H R B Foundry moulds and cores
JPH0673714B2 (ja) * 1987-12-24 1994-09-21 住友デュレズ株式会社 鋳型用粘結剤組成物
AU605943B2 (en) 1987-12-24 1991-01-24 Foseco International Limited Production of articles of bonded particulate material and binder compositions for use therein
US4988745A (en) 1989-04-27 1991-01-29 Acme Resin Corporation Ester hardeners for phenolic resin binder systems
TW256851B (fr) 1992-11-18 1995-09-11 Ashland Oil Inc
US5424376A (en) 1993-10-04 1995-06-13 Ashland Inc. Ester cured no-bake foundry binder system
DE19938043C2 (de) 1999-08-12 2001-12-06 Ashland Suedchemie Kernfest Aluminiumhaltiges Bindemittelsystem auf Resolbasis, Verfahren zur Herstellung und Verwendung sowie Formmasse
DE102007045649B4 (de) 2007-09-25 2015-11-19 H2K Minerals Gmbh Verfahren zur Herstellung einer Form und/oder eines Kernes unter Verwendung von zerkleinerten natürlichen partikulären amorphen Kieselsäurematerialien im Gießereibereich und Binderzusammensetzung
DE102012020511A1 (de) 2012-10-19 2014-04-24 Ask Chemicals Gmbh Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
DE102012020510B4 (de) 2012-10-19 2019-02-14 Ask Chemicals Gmbh Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
DE102012020509A1 (de) 2012-10-19 2014-06-12 Ask Chemicals Gmbh Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
DE102014106177A1 (de) * 2014-05-02 2015-11-05 Ask Chemicals Gmbh Formstoffmischung enthaltend Resole und amorphes Siliciumdioxid, aus diesen hergestellte Formen und Kerne und Verfahren zu deren Herstellung
DE102014106178A1 (de) * 2014-05-02 2015-11-05 Ask Chemicals Gmbh Verfahren zum schichtweisen Aufbau von Körpern umfassend feuerfesten Formgrundstoff und Resole und Formen oder Kerne hergestellt nach diesem Verfahren
WO2016165916A1 (fr) * 2015-04-14 2016-10-20 Huttenes Albertus France Composition de résine phénolique pour une utilisation dans le procédé boîte froide de polyurethane et/ou le procédé durcissant à froid et systèmes de liant à deux composants correspondants, applications et procédé
DE102016211971A1 (de) * 2016-06-30 2018-01-04 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Wässrige alkalische Bindemittelzusammensetzung zur Aushärtung mit Kohlendioxidgas sowie deren Verwendung, eine entsprechende Formstoffmischung zur Herstellung eines Gießereiformkörpers, ein entsprechender Gießereiformkörper sowie ein Verfahren zur Herstellung eines Gießereiformkörpers
DE102016115947A1 (de) * 2016-08-26 2018-03-01 Ask Chemicals Gmbh Verfahren zum schichtweisen Aufbau von Formkörpern mit einem Phenolharz-Polyurethan-basiertem Bindersystem
DE102016123051A1 (de) * 2016-11-29 2018-05-30 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Aminosäure enthaltende Formstoffmischung zur Herstellung von Formkörpern für die Gießereiindustrie
DE102016125624A1 (de) * 2016-12-23 2018-06-28 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Phenolharz zur Verwendung in der Phenolharzkomponente eines Zweikomponenten- Bindemittelsystems
DE102016125700A1 (de) * 2016-12-23 2018-06-28 Ask Chemicals Gmbh Bindemittel auf Basis von Phenolharzen vom Benzylethertyp enthaltend freies Phenol und freie Hydroxybenzylalkohole

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Publication number Publication date
DE112020006262A5 (de) 2023-01-12
US20230042686A1 (en) 2023-02-09
DE102019135605A1 (de) 2021-06-24
BR112022011484A2 (pt) 2022-08-23
KR20220116286A (ko) 2022-08-22
WO2021121487A1 (fr) 2021-06-24
JP2023511497A (ja) 2023-03-20
MX2022007651A (es) 2022-07-19
CN114829034A (zh) 2022-07-29

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