EP3551360A1 - Liant résol alcalin à fluidité améliorée - Google Patents

Liant résol alcalin à fluidité améliorée

Info

Publication number
EP3551360A1
EP3551360A1 EP17811304.9A EP17811304A EP3551360A1 EP 3551360 A1 EP3551360 A1 EP 3551360A1 EP 17811304 A EP17811304 A EP 17811304A EP 3551360 A1 EP3551360 A1 EP 3551360A1
Authority
EP
European Patent Office
Prior art keywords
molding material
material mixture
mixture according
sugar
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.)
Granted
Application number
EP17811304.9A
Other languages
German (de)
English (en)
Other versions
EP3551360B1 (fr
Inventor
Frank Lenzen
Christian Priebe
Melanie Mertscheit
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 EP3551360A1 publication Critical patent/EP3551360A1/fr
Application granted granted Critical
Publication of EP3551360B1 publication Critical patent/EP3551360B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • B22C1/10—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/162—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 use of a gaseous treating agent for hardening the binder
    • 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

Definitions

  • the invention relates to molding material mixtures for the production of molds, cores or feeders for metal casting comprising at least one refractory molding material, a binder based on an alkaline resole resin and at least one sugar surfactant. Furthermore, the invention relates to a process for the production of molds and cores using the molding material mixtures as well as molds, cores and feeders produced by this process.
  • Molds are essentially composed of molds and molds and cores, which represent the negative mold of the casting to be produced.
  • These forms and cores usually consist of a refractory base molding material, such as quartz sand, and a suitable binder, which gives the mold after removal from the mold sufficient mechanical strength.
  • the refractory molding base material is preferably in free-flowing form, so that it can be filled into a suitable mold after mixing with the binder, compacted and then cured. After curing, the binder provides for a firm cohesion between the particles of the molding base material, so that the casting mold obtains the required mechanical stability.
  • Molds form the outer wall of the casting during casting, cores are used to form cavities within the casting. It is not absolutely necessary that the forms and cores are made of the same material. For example, in die casting, the outer shape of the cast pieces is carried out using metallic permanent molds. Also possible is a combination of molds and cores made from differently blended molding compounds and by different processes. Feeders are voids in the mold, which are filled with liquid metal during casting together with the casting. The feeder keeps the metal in it liquid for a longer time and can thus compensate for a volume deficit in the solidification phase of the casting. If, in simplification terms, only kernels are discussed below, the statements apply to the same extent to molds and feeders based on the same molding material mixture and produced by the same process.
  • organic, inorganic and mixed organic / inorganic binder can be used, the curing of which can be done by cold or hot process.
  • Cold processes are those processes which are carried out essentially without heating the mold used for core production, generally at room temperature or at a temperature caused by a possible reaction.
  • the curing takes place, for example, in that a gas is passed through the molding mixture to be cured and thereby initiates a chemical reaction.
  • hot processes the molding material mixture is heated to a sufficiently high temperature after molding, for example by the heated mold, to expel the solvent contained in the binder and / or to initiate a chemical reaction by which the binder is cured.
  • alkaline phenolic resins as binders for molds is known per se and these are disclosed for example in EP 0323096 B2 and in EP 1228128 B1. These are alkaline resole resins that can be cured by introducing CO2.
  • Essential constituents of the binders described in said patents are oxyanions, e.g. the borate ion (EP 032096 B2) or the combination of borate and aluminate ion (EP 1228128 B1).
  • US 5376696 and WO 92/01016 A1 describe sand mixtures for ester-curing alkaline resole resins in which a surfactant solution for improving the flowability is added to the sand mixture.
  • EP 0399636 A2 describes ester-curing alkaline resole resins containing a fluorosurfactant, which may have an anionic, cationic, amphoteric or nonionic character. It improves the flowability of the molding material mixture.
  • sugar surfactants markedly improves the flowability of mixtures of alkaline resole resin and refractory molding base materials. This is surprising insofar as the surface tension of an alkaline resole resin is only insignificantly reduced by a sugar surfactant.
  • the sugar surfactant used according to the invention is either contained in the alkaline resole resin component or it is fed as pure or diluted second component directly to the molding material mixture before or during mixing.
  • the molding material mixture according to the invention thus comprises at least a) a refractory molding base material;
  • a sugar surfactant which may also be added as a sugar surfactant solution.
  • the invention relates to a method for producing a core comprising the following steps:
  • Molding material for obtaining a molding material mixture
  • the binder is alkaline Resolharze.
  • the resols are prepared by condensation of phenolic compounds and aldehyde compounds in the presence of a basic catalyst such as ammonium hydroxide or an alkali metal hydroxide. Preference is given to using alkali metal hydroxide catalysts.
  • the resoles are used in a concentration of about 0.8% by weight to about 10% by weight, preferably from about 1% by weight to about 5% by weight and more preferably from about 1% by weight to about 4% by weight, based in each case on the solids content of the resol (according to DIN EN ISO 3251) and the molding base material.
  • concentration of binder within the casting mold can vary.
  • Resoles in the sense of the present invention are aromatics which are linked to one another via methylene groups (-CH 2 -) groups and / or via ether bridges (especially -CH 2 -O-CH 2 -) and which each carry at least one -OH group (phenol compound).
  • Suitable phenol compounds are phenols, substituted phenols, such as, for example, cresols or nonylphenol, 1,2-dihydroxybenzene (pyrocatechol), 1,3-dihydroxybenzene (resorcinol), cashew nut shell oil, ie a mixture of caranol and cardol, or 1,4 Dihydroxybenzene (hydroquinone) or phenolic compounds such as bisphenol A.
  • aldehyde compounds examples include formaldehyde, paraformaldehyde and glyoxal and mixtures thereof. Particularly preferred is formaldehyde or mixtures containing predominantly formaldehyde (based on the molar amount of aldehydes).
  • the molar ratio of phenolic compound to aldehyde compound may vary in the range of 1.05: 1 to 1.05: 3, but is preferably between 1.05: 1.2 to 1.05: 2.6, more preferred between 1, 1: 1, 3 to 1, 1: 2.5.
  • resoles in which adjacent hydroxy aromatics are each linked to ortho and / or para (relative to the hydroxyl group of the incorporated phenol / aromatics) via the methylene bridges and / or the ether bridges, i. the majority of links are para and / or ortho.
  • Suitable oxyanions in the binder composition for the ReSO.sub.2 / CO2 process include borate, stannate and aluminate ions. Aluminate and borate ions are preferred.
  • the oxyanion may be used in the binder composition for the resole / CO2 process by the admixture of sodium tetraborate times x H2O, potassium tetraborate times x H2O, sodium metaborate, sodium pentaborate, sodium stannate trihydrate, sodium aluminate, potassium aluminate, aluminum hydroxide, alumina or ammonium oxyanion salt such as Ammonium borate be inserted. Borations can also be introduced by adding boric acid or boron oxide.
  • the molar ratio of the oxyanions (expressed as boron and / or aluminum and / or tin) to phenol group is preferably in the range of 0.1: 1 to 1: 1.
  • the molar ratio of boron to phenol is more preferably in the range 0.1: 1 to 0.5: 1.
  • organic aluminum, boron or tin compounds can also by introducing organic boron, aluminum and tin compounds such as aluminum alcoholates of the formula AI (OR) 3, wherein R can be independently a saturated or unsaturated, branched or unbranched hydrocarbon radical having 1 to 10 carbon atoms.
  • a solution of a boron compound such as boric acid or boric acid ester in brine is suitable as a solution of boron-containing oxyanion.
  • the solution used is a solution of a base in water, which is also used for mixing with the resole resin.
  • both organic bases e.g. Amines or ammonium compounds as well as inorganic bases such as e.g. Alkali metal hydroxides
  • alkali hydroxides e.g. Sodium hydroxide and potassium hydroxide used.
  • the molar ratio of hydroxide ions to the phenol group in the binder system is preferably 0.5: 1 to 3: 1, preferably 1, 0: 1 to 2.5: 1. It is not necessary that the entire amount of base is added already at the beginning of the condensation; Usually, the addition takes place in two or more substeps, wherein a part can be added only at the end of the manufacturing process. Mixtures of basic catalysts can also be used.
  • alkaline resoles The preparation of alkaline resoles is e.g. in EP 0323096 B2 and EP 1228128 B1. Further resol-based binders are described, for example, in US Pat. No. 4,426,467 and US Pat. No. 4,474,904.
  • the resole contains water, preferably in an amount of 15% by weight to 50% by weight, based on the binder.
  • water In the final part of the binder are resole, water, alkalis and oxyanion.
  • the water may originate from aqueous solutions which are used in binder preparation, but on the other hand it may also be added separately to the binder or be obtained as condensation water from the resol condensation.
  • water also serves, for example, to impart to the binder an application-specific viscosity (25 ° C.) of from 5 to 1200 mPas, preferably from 10 to 1100 mPas and particularly preferably from 10 to 950 mPas.
  • the viscosity is determined using a Brookfield Rotational Viscometer, Small Sample Method, Spindle No. 21 at 100 rpm and 25 ° C.
  • the alkaline resole preferably has a pH (at 25 ° C.) greater than 12.
  • the binder may contain up to about 50% by weight of additives such as e.g. Alcohols, glycols, and silanes may be added.
  • additives such as e.g. Alcohols, glycols, and silanes
  • the wettability of the molding material by the binder and its adhesion to the molding material can be increased, which in turn can lead to improved strength and increased moisture resistance.
  • silanes e.g. gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane
  • concentrations of from about 0.1 weight percent to about 4.0 weight percent, preferably from about 0.2 weight percent to about 3.0 weight percent, and especially preferably from about 0.3% by weight to about 2.5% by weight, in each case based on the weight of the molding composition.
  • esters suitable for curing the resols are known to those skilled in the art, e.g. from US 4426467, US 4474904 and US 5405881. They include lactones, organic carbonates and esters of C1 to C10 mono- and polycarboxylic acids with C1 to C10 mono- and polyalcohols. Preferred but non-limiting examples of these compounds 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 known under the name DBE mixture. Due to different saponification rates of the individual esters, the curing speed of the sole runs at different rates depending on the ester used, which can also influence the strengths. By mixing two or more esters, the desired cure time can be varied within wide limits.
  • sugar surfactants are nonionic surfactants in which sugars form the hydrophilic portion of the surfactant molecule.
  • the hydrophobic component is fatty alcohol or fatty acid residues.
  • Carbohydrates used are, for example, glucose, methyl glucose, fructose, methyl fructose, lactose, ribose, sucrose, xylenose, xylitol, mannose, mannitol, isosorbitol and sorbitol.
  • the sugar building blocks can be used as monomer or up to a degree of polymerization of 30.
  • the sugar units alpha or beta 1, 4 may be glycosidically linked.
  • the hydrophilic portion is formed by linking glucose, sucrose, fructose, isosorbitol and / or sorbitol, particular preference is given to sucrose and / or glucose.
  • Fatty acids can be esterified to the free hydroxyl groups or fatty alcohols, and / or fatty alcohol ethoxylates, fatty alcohol propoxylates and / or fatty alcohol ethoxylates / fatty alcohol propoxylates can be etherified, the chain length is between C6 and C32, in particular Cs and C22, and can be branched or straight-chain and saturated or be unsaturated. Both the sugar and the fat components can be mixed with each other. Preference is given to using alkylpolyglycosides (APG), in particular alkylpolyglucosides, which have the following exemplary structure.
  • APG alkylpolyglycosides
  • n is on average from 1 to 30, preferably on average from 2 to 25 and particularly preferably on average from 2 to 10.
  • n is a saturated or unsaturated, straight-chain or branched alkyl radical of on average 5 to 31 carbon atoms and particularly preferably of 7 to 21 carbon atoms.
  • Alkylpolyglycosides are industrially produced and marketed by BASF under the trade names Plantacare or Glucopon.
  • the sugar surfactants according to the invention are preferably added to the resole resin in a concentration of 0.05 to 5.0% by weight. Preferably in a range from 0.05 to 3.0% by weight, and more preferably from 0.05 to 2.0% by weight, relative to the binder.
  • the sugar surfactants according to the invention can be added directly to the molding material mixture. This can be done as pure substance or dissolved in a carrier medium (eg water). Based on the finished molding mixture 0.005 to 0.5 wt.%, Preferably 0.01 to 0.3 wt.% Sugar surfactant is added.
  • the sugar surfactants used preferably have an HLB value between 1 1 and 16 (HLB stands for English, hydrophilic-lipophilic balance).
  • molding base material materials customary for the production of casting molds can be used.
  • quartz sand, zircon sand or chrome ore sand, olivine, vermiculite, bauxite and chamotte or mixtures thereof are suitable. If there are no technological reasons, quartz sand is preferred for economic reasons. It is not necessary to use only new sands. In terms of resource conservation and to avoid landfill costs, it is even advantageous to use the highest possible proportion of regenerated used sand. Particularly suitable are regenerates, which are obtained by washing and subsequent drying. It is also possible to use regenerates obtained by thermo-mechanical or purely mechanical treatment.
  • the average diameter of the molding materials is usually between 100 ⁇ and 600 ⁇ , preferably between 120 ⁇ and 550 ⁇ and more preferably between 150 ⁇ and 500 ⁇ .
  • the particle size can be e.g. by sieving in accordance with DIN ISO 3310.
  • synthetic molding materials can also be used as mold base materials, in particular as an additive to the above molding base materials, but also as exclusive molding base material, for example glass beads, glass granules, the spherical ceramic molding bases or aluminum silicate microbeads known under the name “Cerabeads” or “Carboaccucast” (US Pat. so-called microspheres).
  • Such aluminosilicate hollow microspheres are marketed, for example, by Omega Minerals Germany GmbH, Norderstedt, under the name “Omega Spheres.”
  • Corresponding products are also available from PQ Corporation (USA) under the name “Extendospheres”.
  • amorphous silicon dioxide to the molding base material.
  • an increase in strength is achieved.
  • This is i.a. disclosed in DE 102014106178.
  • the procedure is such that the refractory molding base material is initially charged and then the binder and the sugar surfactant are added together or successively with stirring.
  • the molding material mixture is then brought into the desired shape.
  • customary methods are used for the shaping.
  • the molding material mixture can be shot by means of a core shooter with the aid of compressed air into the tool.
  • Another possibility is to free-flow the molding material mixture from the mixer into the mold and to compact it there by shaking, stamping or pressing.
  • Preferred core manufacturing process is the Resol / CO2 process.
  • this does not preclude sparing with lower alkyl esters known under the name of Betaset, such as C1 to C3 alkyl formates, especially methyl formate, and liquid ester curing, known by the name Alphaset method.
  • Curing takes place in that the CO2, a CO2 / gas mixture (eg with air), a gas mixture (eg air) or gaseous methyl formate (Betaset method) successively (as described in detail in DE 102012103705.1) by the mold or by the molding material mixture contained therein is passed.
  • the gas stream has a temperature between 0 ° C to 140 ° C, preferably from 5 ° C to 120 ° C and more preferably from 6 ° C to 1 10 ° C.
  • Oleic acid technical oleic acid
  • Capstone FS 35 25% aqueous solution of a nonionic fluorosurfactant, manufacturer: Chemour
  • Plantacare 2000 UP 50% aqueous alkyl polyglucoside solution with C8-C16 fatty alcohol chains, manufacturer: BASF SE
  • Table 1 shows the surface tensions found (in mN / mm) at room temperature, which were obtained by adding the surfactants. If one considers the surface tension (comparison of the same amount of active substance, identification with " * "), it is surprisingly found that the APG type sugar surfactants according to the invention reduce the surface tension by only 2% (zero example to B2).
  • the oleic acid reduces the surface tension by 10% (zero example to A1), according to EP 0399 636 even a reduction by 27% is achieved (zero example to A8).
  • the reference water was 68.8 mN / mm. Determination of strength in N / cm 2 - Resol CO2 method
  • a sand mixture of quartz sand H 32, plus 3.0% NOVANOL 165 was homogeneously mixed for 2 minutes.
  • This sand mixture was transferred to a core shooter, model Laempe L 1 (opening at the sand outlet of the shooting head reduced to 5mm) and placed in a four core box (GF bar 220mm x 22.4mm x 22.4mm) with a shooting pressure of 2 bar by means of compressed air and a shooting time of 1 sec brought into the mold.
  • CO2 gas 2 liters / min for 30 sec
  • the flexural strengths were broken by means of a Biegeprüfös Fa. Multiserw after the specified time (average values of four determinations).
  • a sand mixture of quartz sand H 31, plus 2.3% AVENOL F 633 was mixed homogeneously for 2 minutes.
  • This sand mixture was transferred to a core shooter, Model Roeper H 1 (opening at the sand outlet of the shooting head 10 mm) and was placed in a two core box (GF bar 220mm x 22.4mm x 22.4 mm) with a shooting pressure of 3 bar by means of compressed air and a shooting time of 1 sec brought into the mold.
  • the sand was hardened by means of 60 ° C. warm methyl formate gas (2.0 ml liquid methyl formate, for 20 sec, 2 bar rinsing pressure).
  • the flexural strengths were determined by means of a Biegeprüfauss Fa. Multiserw after the specified time (average values of four determinations).
  • Plantacare 2000 UP the highest strengths in N / cm 2 and the highest packing density (indicated by the core weight) were achieved.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

L'invention concerne des mélanges de matières à mouler pour la fabrication de moules, de masselottes ou de noyaux pour la coulée de métaux, les mélanges comprenant au moins une matière à mouler de base réfractaire, un liant à base d'une résine résol alcaline et au moins un tensio-actif de sucre. L'invention concerne en outre un procédé de fabrication de moules et de noyaux au moyen de mélanges de matières à mouler ainsi que des moules, des masselottes ou des noyaux fabriqué(e)s selon ce procédé.
EP17811304.9A 2016-12-07 2017-12-07 Liant résol alcalin à fluidité améliorée Active EP3551360B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016123661.6A DE102016123661A1 (de) 2016-12-07 2016-12-07 Alkalische Resolbinder mit verbesserter Fließfähigkeit
PCT/EP2017/081934 WO2018104493A1 (fr) 2016-12-07 2017-12-07 Liant résol alcalin à fluidité améliorée

Publications (2)

Publication Number Publication Date
EP3551360A1 true EP3551360A1 (fr) 2019-10-16
EP3551360B1 EP3551360B1 (fr) 2020-11-25

Family

ID=60627646

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17811304.9A Active EP3551360B1 (fr) 2016-12-07 2017-12-07 Liant résol alcalin à fluidité améliorée

Country Status (3)

Country Link
EP (1) EP3551360B1 (fr)
DE (1) DE102016123661A1 (fr)
WO (1) WO2018104493A1 (fr)

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2473032A1 (fr) 1980-01-07 1981-07-10 Banquy David Procede de production d'ammoniac et du gaz de synthese correspondant
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
AU605943B2 (en) 1987-12-24 1991-01-24 Foseco International Limited Production of articles of bonded particulate material and binder compositions for use therein
US4996249A (en) 1989-04-27 1991-02-26 Acme Resin Corporation Method to improve flowability of resin coated sand
US5077323A (en) 1989-10-10 1991-12-31 Acme Resin Corporation Method to improve flowability of alkaline phenolic resin coated sand
US5376696A (en) 1990-07-13 1994-12-27 Ashland Oil, Inc. Foundry mixes based upon reclaimed sand
AU8328191A (en) 1990-07-13 1992-02-04 Ashland Oil, Inc. Three component foundry binder system
TW256851B (fr) 1992-11-18 1995-09-11 Ashland Oil Inc
JP3250915B2 (ja) * 1994-09-30 2002-01-28 花王株式会社 鋳型用粘結剤組成物、鋳型組成物および鋳型の製造方法
DE19938043C2 (de) 1999-08-12 2001-12-06 Ashland Suedchemie Kernfest Aluminiumhaltiges Bindemittelsystem auf Resolbasis, Verfahren zur Herstellung und Verwendung sowie Formmasse
JP2001219242A (ja) * 2000-02-08 2001-08-14 Hodogaya Ashland Kk 鋳物砂用粘結剤組成物及び鋳型組成物
DE102007051850B4 (de) * 2007-10-30 2025-08-28 Ask Chemicals Gmbh Verfahren zur Herstellung von Gießformen für die Metallverarbeitung unter Verwendung einer Formstoffmischung mit verbesserter Fliessfähigkeit
DE102012103705A1 (de) 2012-04-26 2013-10-31 Ask Chemicals Gmbh Verfahren zur Herstellung von Formen und Kernen für den Metallguss sowie nach diesem Verfahren hergestellte Formen und Kerne
DE102012104934A1 (de) * 2012-06-06 2013-12-12 Ask Chemicals Gmbh Forstoffmischungen enthaltend Bariumsulfat
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

Also Published As

Publication number Publication date
DE102016123661A1 (de) 2018-06-07
EP3551360B1 (fr) 2020-11-25
WO2018104493A1 (fr) 2018-06-14

Similar Documents

Publication Publication Date Title
EP3137246B1 (fr) Procédé de fabrication par couches de corps comprenant un produit de départ de moulage réfractaire et des résols
EP3606690B1 (fr) Procédé de production de moules de coulée, de noyaux et de matières de base de moulage régénérées à partir de ces derniers
EP3137245B1 (fr) Mélanges de matériaux de moulage contenant des résols et du dioxyde de silicium amorphe, moules et noyaux fabriqués à partir de ces mélanges et procédé pour les fabriquer
EP2209572B1 (fr) Mélange de matériaux de moulage de fluidité améliorée
EP2014392B1 (fr) Mélange de matière à mouler, pièce brute pour des besoins de fonderie et procédé de fabrication d'une pièce brute
EP3634726B1 (fr) Procédé de fabrication de corps façonnés stratifiés en trois dimensions
DE69706193T2 (de) Sandregenerierung
DE1096029B (de) Verfahren zur Herstellung von verformbaren Kunstharzmassen
EP1228128B1 (fr) Systeme de liant a base de resol, contenant de l'aluminium et du bore
EP3551360B1 (fr) Liant résol alcalin à fluidité améliorée
EP3558559A1 (fr) Système d'éléments destiné à la fabrication de noyaux et de moules
EP1417060B1 (fr) Moule et son procede de fabrication
EP3478428B1 (fr) Composition alcaline aqueuse comme liant, à durcissement au dioxyde de carbone, son utilisation, mélange de matières moulables correspondant pour la fabrication d'un corps moulé de fonderie, corps moulé de fonderie correspondant et procédé de fabrication d'un corps moulé de fonderie
EP4519036B1 (fr) Procédé de construction couche par couche d'articles construits avec un liant à viscosité modifiée
WO2018002129A1 (fr) Composition alcaline aqueuse de liant, à durcir avec du dioxyde de carbone, son utilisation, mélange de matières à mouler correspondant pour la fabrication d'un corps de moule de fonderie, corps de moule de fonderie correspondant et procédé de fabrication d'un corps moule de fonderie
DE10136365A1 (de) CO¶2¶-härtbares Bindemittelsystem auf Resolbasis
DE102005024524B4 (de) Form und Verfahren zu deren Herstellung
DE102019135605A1 (de) 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
EP0032596B1 (fr) Procédé pour fabriquer des moules perdus
DE2713115A1 (de) Mischung zur herstellung von giessereikernen und -formen
DE1095516B (de) Verfahren zur Herstellung von waermehaertbaren Kunstharzmassen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190618

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: PRIEBE, CHRISTIAN

Inventor name: MERTSCHEIT, MELANIE

Inventor name: LENZEN, FRANK

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200722

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502017008405

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1337701

Country of ref document: AT

Kind code of ref document: T

Effective date: 20201215

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20201125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210325

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210225

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210325

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210225

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502017008405

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201231

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201207

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201207

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

26N No opposition filed

Effective date: 20210826

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210325

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20211207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211207

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230517

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20231218

Year of fee payment: 7

Ref country code: FR

Payment date: 20231219

Year of fee payment: 7

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1337701

Country of ref document: AT

Kind code of ref document: T

Effective date: 20221207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221207

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20241231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20260226

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20260410

Year of fee payment: 5