EP1682291B1 - Aerogels contenant une matiere de charge - Google Patents

Aerogels contenant une matiere de charge Download PDF

Info

Publication number
EP1682291B1
EP1682291B1 EP04797542A EP04797542A EP1682291B1 EP 1682291 B1 EP1682291 B1 EP 1682291B1 EP 04797542 A EP04797542 A EP 04797542A EP 04797542 A EP04797542 A EP 04797542A EP 1682291 B1 EP1682291 B1 EP 1682291B1
Authority
EP
European Patent Office
Prior art keywords
casting
sand
core
binder
sol
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.)
Not-in-force
Application number
EP04797542A
Other languages
German (de)
English (en)
Other versions
EP1682291A1 (fr
Inventor
Lorenz Ratke
Sabine BRÜCK
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.)
Deutsches Zentrum fuer Luft und Raumfahrt eV
Original Assignee
Deutsches Zentrum fuer Luft und Raumfahrt eV
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 Deutsches Zentrum fuer Luft und Raumfahrt eV filed Critical Deutsches Zentrum fuer Luft und Raumfahrt eV
Publication of EP1682291A1 publication Critical patent/EP1682291A1/fr
Application granted granted Critical
Publication of EP1682291B1 publication Critical patent/EP1682291B1/fr
Not-in-force 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
    • B22C1/16—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
    • B22C1/183—Sols, colloids or hydroxide gels

Definitions

  • the invention relates to a method for producing a filler-containing airgel with a particularly short gelling and drying time.
  • Casting in ceramic shell molds and bonded sand molds is a standard casting technique to produce precision parts from a variety of alloys, particularly aluminum, magnesium, titanium or cast iron alloys.
  • alloys particularly aluminum, magnesium, titanium or cast iron alloys.
  • it is possible to cast in the correct shape and close to the final shape (J. Sprunk, W. Blank, W. Grossmann, E. Hauschild, H. Rieksmeier, HG Rosselnbruch, precision casting for all industrial sectors, 2nd edition, headquarters for casting use, Dusseldorf 1987, KA Krekeler, Feing manen, in: Handbuch der Vietnamesestechnik Bd. 1., Ed .: G. Speer, Hanser Verlag, Kunststoff 1981, W. Tilch, E. Flemming, Forming and Forming, German publishing house for primary industry, Leipzig / Stuttgart 1993).
  • the state of core manufacturing, as well as molding processes, is characterized by a variety of core forming processes, including various binder systems and equipment. Foundries, which have a large range of models, often have several procedures side by side apply.
  • the focus in the development of new core binder or core materials lies in the improvement of the specific strength of molded materials while reducing the binder content in order to protect the economic and ecological resources.
  • Thin-walled castings which can warp or bend during the grafting attempt, as well as a high sand-metal ratio are a problem that needs to be solved.
  • the emptying behavior of organically bound cores in aluminum casting depends on their mechanical strength. As the strength of the cores increased, the emptying behavior deteriorated. The usual way to achieve good decorability results in lower binder levels. The cores can then be removed more easily. At the same time, however, the stability of the core deteriorates, so that problems such as core breakage or core distortion can occur in the run-up to a casting.
  • the sand grains can only be sufficiently covered by the binder to a certain minimum limit, so that complete hardening is difficult.
  • Cores are today produced on so-called core shooters, i. a flowable mass of sand and binder is shot under high pressure into the core mold and then cured by addition of a curing agent (the curing can be done by addition of a chemical or by shooting in a preheated mold or a microwave can be initiated). Core production times today are in the seconds range when it comes to mass products, otherwise in the minute range.
  • Cavities within the mold must be preformed stable by means of a core.
  • Such cores are usually produced because of the prevailing high thermal and mechanical stress from plastic-bonded ceramic powders.
  • Disadvantage of today's conventional method for core production is that the removal of the cores from the casting is possible only with extremely high cost (eg combustion in an autoclave), the distribution of the sands in the core is inhomogeneous and cracking germs exist, including thermal break under thermal mechanical stress.
  • Aerogels are highly porous, open-pore oxidic solids, which are usually obtained by sol-gel process from metal alkoxides by polymerization, polycondensation to gels and subsequent supercritical drying. For some years now, it has also been possible to gel plastics by sol-gel processes and to convert them by supercritical drying into a highly porous organic solid (see, for example, DE 195 23 382 A1, DE 694 09 161 T2 and US Pat. No. 5,086,085). Pyrolysis of such plastic aerogels under inert gas or in a vacuum at temperatures above 1000 ° C, this converts to carbon aerogels.
  • plastic and carbon aerogels have extremely low effective thermal conductivities (of the order of a few mW / K / m) and are considerably lighter.
  • the physical and mechanical properties of plastic and cohort aerogels have been documented in the literature (RW Pekala, CT Alviso, FM Kong, SS Hulsey, J. Non-Cryst, Solids 145 (1992) 90, RW Pekala, CT Alviso, Mat Soc., Symp., Proc. 270 (1992) 3; R. Petricevic, G. Reichenauer, V. Bock, A. Emmerling, J. Fricke, J. Non-Cryst. Solids (1998)). They can be varied within a wide range by the starting materials, their mixture and the production process.
  • EP 1 077 097 A1 describes the use of plastic / carbon aerogels as core material.
  • the airgel described here may contain up to 60% filler.
  • the final gelling time is at least one day.
  • DE 30 04 466 A1 describes the production of a foundry core from a mixture of phenol-formaldehyde resin and carbon particles. These particles make up 99.5% of the core.
  • JP 04081243 A describes foundry cores consisting of carbon black foam. These cores also contain no fillers.
  • DE 196 47 368 A1 describes a composite material comprising a substrate and a nanocomposite, which is produced by a sol-gel process.
  • the object to be preserved is heated or tempered within a certain period of time.
  • JP 61108445 A describes the production of coated sand grains by adding urea to the heated sand.
  • JP 61003630 A describes the mixture of a product of a condensation reaction with preheated sand to obtain foundry sands.
  • the aging of the sol at room temperature takes place until the color of the sol turns from clear to white to white-pink or even brown.
  • the aging of the sol can generally be regarded as pre-gelation of the sol.
  • the upper limit of the temperature range of the fillers is 80 ° C, since from this temperature, the usual solvent evaporates water too quickly.
  • the gelation and drying of the mixture covers the period until a dimensionally stable gel filler body is formed. This can then be removed from its mold and transferred on further drying in a filler-containing airgel.
  • the foundry of today must meet many requirements. This includes the type and quantity of castings to be produced, the quality level required for the component, as well as energy-economic and ecological requirements. In comparison to other forming processes, casting has the greatest design freedom. Components with the most complicated structures and geometries can be produced directly from the melt by largely approximating the raw casting to the required shape and dimensions of the component. Not only the casting process as such is at the center of attention in this context and has a direct influence on the quality of the casting, but also on the production of molded parts. Appropriate selection of mold materials, molding techniques and equipment will affect the quality characteristics.
  • the quality parameters include dimensional accuracy, freedom from defects, the desired material parameters and the surface quality.
  • a pourable mold must be produced. It is in its dimensions and shape a negative form of the later component. Cavities of the casting are realized by cores.
  • the molding and core production uses different methods. Basically, a distinction is made between the permanent molds with service life of several hundred casts and the lost molds, which are to be used only for single use.
  • the quality of a shape is influenced by various parameters. In addition to the complete contour reproduction, it must be specially in Moment of pouring shape and contours stable, ie it must not warp or widen. It must meet pouring technology requirements such as gas permeability and thermal stability and the molding material used should be easily recovered after completion of casting. In interaction between the quality of the molding material flowing in the molding process, the processing technology and the production task, these properties must be coordinated with one another in such a way that the mold is able to cope with mechanical and thermal stresses during mold manipulation, casting and solidification. This so-called processing-technological behavior of the molding materials generally links material, technological and equipment influencing factors, which in each case take effect in a certain technological area.
  • the forms for single use include the sand molds. They have natural or synthetic sands with grain diameters of 0.02 to 2 mm as the basic molding material and form the framework of the mold. There are different types of sands. Besides that for cost reasons mainly used quartz sand, which can be used with certain restrictions for almost all binder systems, corundum, olivine, chromite and synthetic sands are used. The main requirement for sands is generally a high thermal stability, chemically inert behavior against the melt, low thermal expansion, good granulometric properties and sufficient thermal shock resistance.
  • the grain aggregate is responsible for the molding material behavior in combination with the binder used. The gas permeability and porosity as well as strength and chemical properties depend solely on the amount of binder used and the grain size of the sand.
  • the binder is applied to the sand grain surface.
  • the surface texture of the sands and granules used for the adhesive forces between binder shell and grain surface is of importance.
  • a rather splintery form has higher adhesion forces than a round sand mold.
  • the binder envelops the grain of sand.
  • the approach and contact with adjacent grains of the grain aggregate results in binder bridges which, in conjunction with the contact surface formed, result in complete bonding of the grains.
  • the wettability of the sand grain surfaces and the surface tension decisively influence the hardening reaction. Good wettability of the surfaces requires a low surface tension of the binder.
  • Binder cover In case of good wettability, the strength of the whole grain aggregate increases. With a maximum number of contact surfaces can be next to a good Binder cover a sufficiently high load capacity of the bond can be guaranteed. A distinction is made between a punctiform and a sheet-like bond. The strength of a bond depends on the elastic properties of the cured binder layer and the labor that must be expended to separate that layer from the grain surface. If cracks occur in the binder cover, this leads to a reduction of the load capacity. The binder layer thickness is therefore also an important influencing factor.
  • Synthetic resin binders include the condensation resins whose main representatives are phenolic, urea and furan resins. They are usually used in liquid form. The solidification takes place via a polycondensation. Here, identical or different monomers with the elimination of smaller molecules, such as water, to cross-linked macromolecules to. During the polycondensation, the resulting by-products must be removed for complete reaction. In contrast to the polymerization, the polycondensation proceeds more slowly and stepwise, ie it can be interrupted at any point.
  • the achievement of a certain degree of crosslinking at any point, for example, by changing the thermal boundary conditions stop and can then be continued, for example, by the action of strong acids to the formation of highly crosslinked macromolecules.
  • the polycondensation is an equilibrium reaction. If the cleavage product is removed, the reaction is shifted in favor of the polymer. In practice, can this will lead to negative effects. Higher water contents in the molding material mixture (condensation water, water content of the hardener) and high humidity make it difficult to release water from the molded part and delay the hardening process. As soon as the equilibrium reaction is disturbed by such a weakening, this can lead to hardening differences in the core cross-section. Core failure, gas porosity and other casting defects are the logical consequence.
  • Phenol resin binders are phenols or cresols that form linear or spatially crosslinked macromolecules with formaldehyde with a continuous increase in temperature. As with many other chemical reactions, the reaction process can be interrupted at any time by lowering the temperature. Phenol and formaldehyde are reacted with each other in a molar ratio of 1.2: 1. The reactions that take place are the addition of formaldehyde (HCHO) to phenol (C 6 H 5 OH) and the condensation of the adduct with another phenol molecule with elimination of water. The resulting product (novolak) consists of predominantly linear macromolecules. The subsequent curing by addition of hexamethylenetetraamine leads to a release of formaldehyde.
  • the novolak resins are used as binders for the production of resin-coated molding materials for the croning process.
  • phenol resins of the novolak type there are phenol resins of the Resol type. They are formed during condensation in alkaline medium.
  • the Starting products here are phenol and formaldehyde which undergo a reaction in a molar ratio of 1: 1.2 to 1.5 with the addition of sodium hydroxide or ammonia as the catalyst.
  • the ongoing reaction is characterized by the addition of formaldehyde at several points of the phenol molecule and the chain growth by further reaction with phenol with dehydration and formation of methylene bridges to the spatial crosslinking.
  • Resole resins which are cured by thermal and chemical treatment, form the basis for the cold-curing molding materials or molding processes.
  • Urea resins are formed by an initial reaction in alkaline, later in the acidic medium occurring reaction of formaldehyde and urea. This initially produces monomethylolurea and in the course of the condensation in various ways linearly crosslinked intermediates, which are still partially liquid and soluble. The further curing takes place by addition of formaldehyde in excess, wherein the hydrogen atoms bound to the nitrogen atoms of the amine react with formaldehyde and thus spatially crosslinked macromolecules are formed. Urea resins are used as molding material binder usually in combination with phenolic or furan resins.
  • Furan resins are formed on the basis of furfurol (furanaldehyde). Furfurol can be made to form a resin by a chemical reaction with phenol or urea via condensation reactions. Another possibility for resin formation is the hydrogenation and conversion of furfurol to furfuryl alcohol. It arises Furanpolymerisat with crosslinked macromolecules. Depending on the process, furan resins are cured in different ways. In the case of the thermosetting resins, a catalyst is added with simultaneous heat, in the case of cold curing resins, an acid is sufficient. In both cases, the curing process is characterized by condensation and polymerization reactions in which cleavage products are formed.
  • Furanharzbinder are usually a combination of different resins, such as furan-urea-formaldehyde.
  • the catalysts used are p-toluenesulfonic acid and with weaker action also phosphoric acid.
  • reaction resins for Sandform- and -kernher too are used in liquid or semi-liquid form.
  • the solidification is carried out by a polymerization or polyaddition reaction, usually with the addition of a catalyst (hardener, accelerator).
  • a catalyst hardener, accelerator
  • no fission products are formed.
  • an influence of the hardening reaction by liberated water is basically excluded. This ensures good curing.
  • the reaction resins include the epoxy resins, unsaturated polyester resins, polyureas and urethane resins.
  • Binders are usually the urethane resins, both as cold resin with fast-curing properties (Pep Set), but especially the resin binder for curing by fumigation by amines (cold box).
  • the urethane resins are characterized by the combination of polyisocyanate and Phenolic resin (Benzyletherpolyol) and the associated construction of highly crosslinked macromolecules formed.
  • a particular problem is the sensitivity of the hardened cores to moisture absorption and the associated decrease in strength. By processing in a preheated tool (for example 40 ° C to 80 ° C) improved hardness properties can be achieved (Cold Böx Plus method).
  • Short-cure urethane resins are cured with a catalyst additive which is a low-volatility pyridine derivative (Pep-Set method).
  • a catalyst additive which is a low-volatility pyridine derivative (Pep-Set method).
  • Pep-Set method a low-volatility pyridine derivative
  • curing ceases abruptly after a few minutes.
  • the addition of catalyst the solidification can be controlled.
  • Urethane resins for the cold-box process i. Resins which cure by gassing with amines are resins in which the two urethane reactants are present in a ratio of 1: 1.
  • the urethane resin is cured by a gaseous catalyst, a triethylamine (TEA) or dimethylamine (DEMA), which is passed through the molding material with air or an inert gas.
  • TAA triethylamine
  • DEMA dimethylamine
  • the sol is resorcinol and formaldehyde or a solution of these components.
  • plastic aerogels based on resorcinol / formaldehyde with a suitable composition and suitable content of basic catalyst can be converted at temperatures between 20 and 50 ° C. without supercritical drying into a microstructured plastic airgel.
  • the gelation reaction is adjustable so that, for example, first a highly viscous liquid is formed, which becomes stronger with time / temperature.
  • Foundry sands are advantageously suitable as fillers since they have a high temperature stability and are readily available for this application.
  • fillers having an average grain diameter in the range from 40 ⁇ m to 240 ⁇ m has proven to be particularly advantageous, since these lead to a particularly short finish gelation time and result in a particularly dimensionally stable gel sand body.
  • sands are advantageous, which have a splintered, polygonal shape and a high surface roughness, since so the strength of the molding material can be increased.
  • the gelling and drying time could be shortened particularly advantageous if the filler is preheated to a temperature in the range of 55 ° C to 65 ° C.
  • the evaporation of formaldehyde from the solution can be reduced when mixing with sand, since a large part of the formaldehyde has already reacted with the resorcinol.
  • the gelling and drying time is adjusted over a period of up to one hour.
  • the method described here for production processes with high throughput is accessible.
  • the short gelling and drying time could surprisingly be achieved, above all, by the use of preheated filler and aged sol.
  • the process is particularly advantageous when the airgel obtained by the above process is pyrolyzed.
  • the plastic airgel is converted into a carbon airgel, which is extremely temperature-resistant.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (7)

  1. Procédé de fabrication d'un aérogel contenant une charge, caractérisé en ce qu'il comporte les étapes suivantes :
    a) laisser viellir durant 1 à 14 jours un liant qui est un sol à base de résine artificielle ;
    b) mélanger 1 à 6 parties en poids de ce sol vieilli avec 25 parties en poids de la charge, portée à une température de 40 à 80 °C;
    c) et faire en sorte que le mélange se gélifie et sèche.
  2. Procédé conforme à la revendication 1, caractérisé en ce que l'on emploie, en tant que sol, du résorcinol/formaldéhyde ou une solution de ces constituants.
  3. Procédé conforme à la revendication 1, caractérisé en ce que l'on emploie, en tant que charge, du sable de fonderie.
  4. Procédé conforme à la revendication 1, caractérisé en ce que l'on emploie une charge en particules de 40 à 240 µm de diamètre moyen.
  5. Procédé conforme à la revendication 1, caractérisé en ce que l'on emploie une charge portée à une température de 55 à 65 °C.
  6. Procédé conforme à la revendication 1, caractérisé en ce que l'on fait en sorte que le mélange se gélifie et sèche en un laps de temps allant jusqu'à une heure.
  7. Procédé conforme à la revendication 1, caractérisé en ce que l'on pyrolyse l'aérogel de matière artificielle ainsi obtenu.
EP04797542A 2003-11-11 2004-11-03 Aerogels contenant une matiere de charge Not-in-force EP1682291B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10352574A DE10352574A1 (de) 2003-11-11 2003-11-11 Füllstoff enthaltende Aerogele
PCT/EP2004/012401 WO2005046909A1 (fr) 2003-11-11 2004-11-03 Aerogels contenant une matiere de charge

Publications (2)

Publication Number Publication Date
EP1682291A1 EP1682291A1 (fr) 2006-07-26
EP1682291B1 true EP1682291B1 (fr) 2007-05-09

Family

ID=34584974

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04797542A Not-in-force EP1682291B1 (fr) 2003-11-11 2004-11-03 Aerogels contenant une matiere de charge

Country Status (4)

Country Link
EP (1) EP1682291B1 (fr)
AT (1) ATE361799T1 (fr)
DE (2) DE10352574A1 (fr)
WO (1) WO2005046909A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2308614A1 (fr) 2009-06-05 2011-04-13 Deutsches Zentrum für Luft- und Raumfahrt e.V. Aérosand résistant au vert
DK179276B1 (da) * 2013-06-19 2018-03-26 Dansk Skalform As Helstøbt højtalerkabinet med integreret basrefleks produceret ved sandstøbning i en grå støbejerns legering. CSRC

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006003198A1 (de) * 2006-01-24 2007-07-26 Deutsches Zentrum für Luft- und Raumfahrt e.V. Kerne für den Leichtmetall- und/oder den Feinguss
DE102006021151A1 (de) * 2006-05-06 2007-11-08 Deutsches Zentrum für Luft- und Raumfahrt e.V. Kernwerkstoff aus tonhaltigem Sand enthaltendem Aerogelsand

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2561553B1 (fr) * 1984-03-23 1987-06-19 Harborchem Inc Composition de liant refractaire et son procede d'obtention
JPS60227944A (ja) * 1984-04-27 1985-11-13 Nissan Motor Co Ltd 鋳物砂用粘結剤
JPS613630A (ja) * 1984-06-16 1986-01-09 Nissan Motor Co Ltd 鋳砂の製造方法
JPS61108445A (ja) * 1984-10-31 1986-05-27 Aisin Chem Co Ltd シエルモ−ルド用樹脂被覆砂粒の製造方法
US5014763A (en) * 1988-11-30 1991-05-14 Howmet Corporation Method of making ceramic cores
US5086085A (en) * 1991-04-11 1992-02-04 The United States Of America As Represented By The Department Of Energy Melamine-formaldehyde aerogels
US5582231A (en) * 1995-04-28 1996-12-10 General Motors Corporation Sand mold member and method
DE19523382C2 (de) * 1995-06-30 2003-04-30 Jochen Fricke Kohlenstoffaerogele und Verfahren zu deren Herstellung
DE19533564A1 (de) * 1995-09-11 1997-03-13 Hoechst Ag Faserhaltiges Aerogel-Verbundmaterial
DE19606114A1 (de) * 1996-02-20 1997-08-21 Hoechst Ag Aerogelbeschichtete Folie
DE19647368A1 (de) * 1996-11-15 1998-05-20 Inst Neue Mat Gemein Gmbh Verbundwerkstoffe
DE19911847A1 (de) * 1999-03-17 2000-09-28 Deutsch Zentr Luft & Raumfahrt Fein- und Formguß in Kunststoff/Kohlenstoff-Aerogelen
DE19939062A1 (de) * 1999-08-18 2001-02-22 Deutsch Zentr Luft & Raumfahrt Verwendung von Kunststoff/Kohlenstoff-Aerogelen als Kernwerkstoff
DE10126865B4 (de) * 2001-06-01 2005-09-08 Neue Materialien Würzburg GmbH Substrat und Verwendung des Substrats
DE10216464B4 (de) * 2002-04-12 2004-04-15 Deutsches Zentrum für Luft- und Raumfahrt e.V. Silica gebundene Kernwerkstoffe, Verfahren zu deren Herstellung und deren Verwendung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2308614A1 (fr) 2009-06-05 2011-04-13 Deutsches Zentrum für Luft- und Raumfahrt e.V. Aérosand résistant au vert
DK179276B1 (da) * 2013-06-19 2018-03-26 Dansk Skalform As Helstøbt højtalerkabinet med integreret basrefleks produceret ved sandstøbning i en grå støbejerns legering. CSRC

Also Published As

Publication number Publication date
EP1682291A1 (fr) 2006-07-26
WO2005046909A1 (fr) 2005-05-26
ATE361799T1 (de) 2007-06-15
DE10352574A1 (de) 2005-06-16
DE502004003801D1 (de) 2007-06-21

Similar Documents

Publication Publication Date Title
EP3079871B1 (fr) Procédé d'infiltration dans des pièces en 3d
EP1633509B1 (fr) Procede de realisation de modeles par couches
EP1697273B1 (fr) Production d'aerogels contenant une charge
DE102006056093B4 (de) Kernwerkstoff aus Aerogelsand enthaltend Additivsand und dessen Verwendung
DE3221357A1 (de) Verfahren zur herstellung von formen und kernen fuer giesszwecke
EP3548200B1 (fr) Mélange de matière de moulage contenant un acide aminé pour la fabrication de corps de moulage pour l'industrie de la fonderie
EP0917499B1 (fr) Procede de production d'ebauches de noyaux et de sable a noyaux de recyclage pour la fonderie
EP1567576A1 (fr) Procede de production de corps moules, notamment de noyaux, de moules et de masselottes pour la fonderie
EP1852197B1 (fr) Matériau pour la confection de noyaux de fonderie à base d'aérogel de silice contenant une argile gonflante
EP1682291B1 (fr) Aerogels contenant une matiere de charge
DE102008056842A1 (de) Gießereikerne mit verbesserten Entkernungseigenschaften II
EP2308614B1 (fr) Aérosand résistant au vert
EP3006136A1 (fr) Utilisation d'une composition basique en tant que moyen d'infiltration pour la matiere a mouler d'un moule destine a eviter des depots blancs (surfaces piquees) sur des elements en coulee, procede correspondant, moules et kits
DE2235668A1 (de) Bindermasse
EP1752235B1 (fr) Procédé de fabrication de noyau de coulée ou de moule
EP0143954B1 (fr) Procédé de fabrication de parties de moule, selon le procédé en boîte froide et appareil de moulage utilisé
WO2019121637A1 (fr) Procédé de fabrication d'une pièce de fonte métallique ou d'une pièce moulée durcie au moyen de polymères aliphatiques comprenant des groupes hydroxy
DE10216403B4 (de) Aerogelgebundene Formstoffe mit hoher Wärmeleitfähigkeit
EP3265254B1 (fr) Procédé de durcissement de liants au polyuréthane dans des mélanges de matériaux ce moulage par introduction d'amines tertiaires et de solvants et kit pour la mise en uvre du procédé
DE4442884B4 (de) Verfahren zur Herstellung eines Formkörpers
WO2023217325A1 (fr) Procédé de construction couche par couche d'articles construits avec un liant à viscosité modifiée
DE10136365A1 (de) CO¶2¶-härtbares Bindemittelsystem auf Resolbasis
DE102008056856A1 (de) Gießereikerne mit verbesserten Entkernungseigenschaften I
DE2324313A1 (de) Verfahren bzw. werkstoff zur herstellung von giessformteilen
DE1571320C (de) Verfahren zum Herstellen einer Dauer gießform aus Kohlenstoff

Legal Events

Date Code Title Description
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

17P Request for examination filed

Effective date: 20060504

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LU MC NL PL PT RO SE SI SK TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LU MC NL PL PT RO SE SI SK TR

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

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: 20070509

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: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: RITSCHER & PARTNER AG

REF Corresponds to:

Ref document number: 502004003801

Country of ref document: DE

Date of ref document: 20070621

Kind code of ref document: P

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

Ref country code: SE

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: 20070809

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: 20070820

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20070809

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: 20070909

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
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: 20070509

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

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: 20070809

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: 20070509

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: 20070509

Ref country code: IE

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: 20070509

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: 20070509

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: 20070509

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: 20071009

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: 20070509

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

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCAR

Free format text: RITSCHER & PARTNER AG;RESIRAIN 1;8125 ZOLLIKERBERG (CH)

26N No opposition filed

Effective date: 20080212

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

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: 20070810

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

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: 20070509

BERE Be: lapsed

Owner name: DEUTSCHES ZENTRUM FUR LUFT- UND RAUMFAHRT E.V.

Effective date: 20071130

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 NON-PAYMENT OF DUE FEES

Effective date: 20071130

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: 20071130

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

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: 20070509

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

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: 20070509

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: 20071103

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

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: 20070509

Ref country code: HU

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: 20071110

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

Ref country code: AT

Payment date: 20101022

Year of fee payment: 7

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

Ref country code: GB

Payment date: 20101022

Year of fee payment: 7

Ref country code: IT

Payment date: 20101120

Year of fee payment: 7

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

Ref country code: CH

Payment date: 20111026

Year of fee payment: 8

Ref country code: FR

Payment date: 20111103

Year of fee payment: 8

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 361799

Country of ref document: AT

Kind code of ref document: T

Effective date: 20121103

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

Effective date: 20121103

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: 20121130

Ref country code: AT

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

Effective date: 20121103

Ref country code: LI

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

Effective date: 20121130

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20130731

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

Ref country code: IT

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

Effective date: 20121103

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: 20121130

Ref country code: GB

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

Effective date: 20121103

REG Reference to a national code

Ref country code: DE

Ref legal event code: R084

Ref document number: 502004003801

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R084

Ref document number: 502004003801

Country of ref document: DE

Effective date: 20150221

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

Ref country code: DE

Payment date: 20161130

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502004003801

Country of ref document: DE

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

Ref country code: DE

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

Effective date: 20180602