EP1036610A1 - Investment and mould casting in carbon and organic aerogels - Google Patents
Investment and mould casting in carbon and organic aerogels Download PDFInfo
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- EP1036610A1 EP1036610A1 EP00104214A EP00104214A EP1036610A1 EP 1036610 A1 EP1036610 A1 EP 1036610A1 EP 00104214 A EP00104214 A EP 00104214A EP 00104214 A EP00104214 A EP 00104214A EP 1036610 A1 EP1036610 A1 EP 1036610A1
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- Prior art keywords
- wax
- gel
- sol
- temperature
- plastic
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 9
- 239000004964 aerogel Substances 0.000 title abstract description 11
- 238000005266 casting Methods 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000004793 Polystyrene Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims abstract description 3
- 229920002223 polystyrene Polymers 0.000 claims abstract description 3
- 239000010453 quartz Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract 4
- 239000002685 polymerization catalyst Substances 0.000 claims abstract 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract 2
- 239000004033 plastic Substances 0.000 claims description 31
- 229920003023 plastic Polymers 0.000 claims description 31
- 239000012778 molding material Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 239000004966 Carbon aerogel Substances 0.000 claims description 9
- 238000005058 metal casting Methods 0.000 claims description 7
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 5
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 239000012766 organic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 238000005495 investment casting Methods 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 239000001099 ammonium carbonate Substances 0.000 abstract 1
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 5
- 238000001879 gelation Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 229960001755 resorcinol Drugs 0.000 description 4
- 238000000352 supercritical drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003110 molding sand Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
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
- B22C1/165—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 in the manufacture of multilayered shell moulds
-
- 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
Definitions
- the invention relates to a molding material for the fine and mold casting of metals or metal alloys comprising plastic and / or carbon aerogels and a process for the production of corresponding molding materials.
- Investment casting in ceramic molded shells is a standard casting technique for precision parts to manufacture from various alloys.
- the shapes are in usually made using the lost wax technique; d. H. a wax body
- the part to be cast is wetted with a silica sol in several steps sanded, dried and then the shell is fired, whereby the wax is melted in an autoclave or burned.
- Means Modern casting processes make it possible to cast in line with the shape and close to the final shape (J. Sprunk, W. Blank, W. Grossmann, E. Hauschild, H. Rieksmeier, H.G. Rosselnbruch; Investment casting for all industrial sectors, 2nd edition, headquarters for casting use, Düsseldorf 1987; K.A. Krekeler, investment casting, in: manual of manufacturing technology Vol. 1., editor G. Speer, Hanser Verlag, Kunststoff 1981).
- Aerogels are highly porous, open-pored, oxidic solids that usually via sol-gel processes from metal alkoxides by polymerization, polycondensation to gels and subsequent supercritical drying. For some years now, it has also been possible to add plastics using sol-gel processes gel and by supercritical drying in a highly porous organic Convert solid body. Pyrolysis of such plastic aerogels under protective gas or in a vacuum at temperatures above 1000 ° C converts them into carbon aerogels around. Like the oxidic aerogels, plastic and carbon have aerogels extremely low effective thermal conductivities (order of magnitude some mW / K / m) and are considerably lighter. The physical and mechanical Properties of plastic and carbon aerogels are in the literature documented (R.W.
- a Molding material for the fine and mold casting of metals or metal alloys comprising highly porous, open-pore plastic and / or carbon aerogels, available through sol-gel polymerization of organic plastic materials optionally followed by partial or complete pyrolysis of the obtained Plastic aerogels.
- the molding material according to the invention is particularly suitable for use in lost wax processes and need not, as in the prior art for oxidic Gels can be applied in several steps.
- the molds obtained in this way are filled with melt using customary techniques and the melt starts.
- heat is dissipated over the mold shell or the molding sand.
- pour and freeze in
- aerogels mean, since carbon aerogels are quasi adiabatic, that the heat dissipation only via feeders and risers or specifically attached heat sink takes place, skillfully the risers and feeders can be used by yourself, but do not have to. That way is one fully controlled solidification is possible and the structure can accordingly required range of properties can be adjusted.
- the airgel forms produced according to the invention are particularly suitable for the casting of aluminum alloys (whereby the casting mold practically does not heat up must be, since no heat dissipation takes place by itself). This increases the economy because energy costs can be reduced. Magnesium and titanium alloys also do not react with carbon, so that these carbon airgel forms also for these alloys under protective gas or Offer vacuum as film material.
- a particular advantage of the molding materials according to the invention is that the Sol-gel formation at room temperature, that is, in particular at temperatures completed below the pour point of the wax within a few hours can be.
- Supercritical drying as with the purely inorganic Gelling is not necessary. Nevertheless, it is possible to determine the pore size in the micrometer range adjust. When drying in the supercritical temperature range pore sizes in the nanometer range are also possible.
- the molding materials according to the invention can also be inorganic or contain organic filler materials. These are essentially Understand solid materials that are inert under solidification conditions.
- Inorganic Filler materials are selected, for example, from aluminum oxide, titanium dioxide and / or quartz, each in an amount of 5 to 30 vol .-%. used can be.
- Fillers for the purposes of the present invention further comprise Fiber materials that have a fiber reinforcement with organic, inorganic or allow carbon and / or SiC fibers with approximately equal volume fractions.
- organic fillers for example thermoplastic or thermosetting plastic particles, for example polystyrene and / or use organic (polyacrylonitrile) fibers.
- thermoplastic or thermosetting plastic particles for example polystyrene and / or use organic (polyacrylonitrile) fibers.
- these materials are also melted out during the pyrolysis of the plastic gels or be burned.
- using such materials is one Control of shrinkage possible during pyrolysis.
- Plastic aerogels based on resorcinol / formaldehyde used in suitable composition and suitable content of basic catalyst at temperatures between 20 and 50 ° C without supercritical drying in one microstructured plastic airgel can be transferred.
- the composition of the sol-gel polymerization can be set such that, for example First, a highly viscous liquid is created, which is applied to a wax mold can be applied. This is also possible in several work steps, so that the layer thickness is adapted to the needs of the applications in the foundry can be.
- the temperature of the conversion of the solution into a plastic airgel must be Melting point of the wax can be adjusted. After converting to a Plastic airgel can melt the wax and at the same time the conversion to a carbon airgel takes place in the absence of air.
- Dependent the composition of the starting solution, the gelation temperature, the density of the resulting porous body can be made into molds, as both plastic and carbon airgel, on a micrometer scale are smooth on the surface and reproduce sharp contours.
- the production of molds up to the plastic airgel usually takes 1 to 3 days, often only up to 24 hours.
- the pyrolysis time is determined by the thickness the mold shell; with a wall thickness of 1 cm, for example, the time is less than 24 hours, usually 10 hours.
- a glass container in which a wax model (weighted down with steel plates) of the Shaped body was filled with the solution until the model was complete was covered.
- the container was closed. Gelled within two hours the solution in an air circulator (Heraeus) at 40 ° 0. It became a color change the clear solution observed after ocher yellow / light brown. The drying of the gel was obtained in the air circulator over 24 hours. Subsequently the wax was melted out at a temperature of 60 ° C.
- the plastic airgel was placed in a cold muffle furnace brought in.
- the oven was slowly (3 hours) heated to 1050 ° 0, where continuous nitrogen (argon or another protective gas is possible analogously) was blown through to avoid oxidation.
- the temperature of 1050 ° C was maintained for 24 hours.
- the mixture was then cooled with a constant gas flow and the carbon dioxide airgel form taken.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Mold Materials And Core Materials (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
Gegenstand der Erfindung ist ein Formstoff für den Fein- und Formguss von Metallen oder Metall-Legierungen umfassend Kunststoff- und/oder Kohlenstoffaerogele sowie ein Verfahren zur Herstellung von entsprechenden Formstoffen.The invention relates to a molding material for the fine and mold casting of metals or metal alloys comprising plastic and / or carbon aerogels and a process for the production of corresponding molding materials.
Feingießen in keramischen Formschalen ist eine Standardgusstechnik, um Präzisionsteile aus verschiedensten Legierungen herzustellen. Die Formen werden in der Regel über das Wachsausschmelzverfahren hergestellt; d. h. ein Wachskörper des zu gießenden Teils wird mit einem Silica-Sol benetzt, in mehreren Schritten besandet, getrocknet und anschließend wird die Formschale gebrannt, wobei das Wachs in einem Autoklaven ausgeschmolzen wird oder verbrennt. Mittels moderner Gussverfahren ist es möglich, konturgerecht und endformnah zu gießen (J.Sprunk, W. Blank, W. Grossmann, E. Hauschild, H. Rieksmeier, H.G. Rosselnbruch; Feinguss für alle Industriebereiche, 2. Auflage, Zentrale für Gussverwendung, Düsseldorf 1987; K.A. Krekeler, Feingießen, in: Handbuch der Fertigungstechnik Bd. 1., Herausgeber G. Speer, Hanser Verlag, München 1981).Investment casting in ceramic molded shells is a standard casting technique for precision parts to manufacture from various alloys. The shapes are in usually made using the lost wax technique; d. H. a wax body The part to be cast is wetted with a silica sol in several steps sanded, dried and then the shell is fired, whereby the wax is melted in an autoclave or burned. Means Modern casting processes make it possible to cast in line with the shape and close to the final shape (J. Sprunk, W. Blank, W. Grossmann, E. Hauschild, H. Rieksmeier, H.G. Rosselnbruch; Investment casting for all industrial sectors, 2nd edition, headquarters for casting use, Düsseldorf 1987; K.A. Krekeler, investment casting, in: manual of manufacturing technology Vol. 1., editor G. Speer, Hanser Verlag, Munich 1981).
Aerogele sind hochporöse, offenporige oxidische Festkörper, die in der Regel über Sol-Gel-Verfahren aus Metallalkoxiden durch Polymerisation, Polykondensation zu Gelen und anschließender überkritischer Trocknung gewonnen werden. Seit einigen Jahren ist es gelungen, auch Kunststoffe über Sol-Gel-Verfahren zu gelieren und durch überkritische Trocknung in einen hochporösen organischen Festkörper umzuwandeln. Pyrolyse solcher Kunststoffaerogele unter Schutzgas oder im Vakuum bei Temperaturen oberhalb 1000 °C wandelt diese in Kohlenstoffaerogele um. Wie die oxidischen Aerogele haben Kunststoff- und Kohlenstoffaerogele extrem geringe effektive Wärmeleitfähigkeiten (Größenordnung einige mW/K/m) und sind erheblich leichter. Die physikalischen und mechanischen Eigenschaften von Kunststoff- und Kohlenstoffaerogelen sind in der Literatur dokumentiert (R.W. Pekala, C.T. Alviso, F.M. Kong, S.S. Hulsey; J. Non-Cryst. Solids 145 (1992) 90; R.W. Pekala, C.T. Alviso, Mat. Res. Soc. Symp. Proc. 270 (1992) 3; R. Petricevic, G. Reichenauer, V. Bock, A. Emmerling, J. Fricke; J.Non-Cryst.Solids (1998)). Sie lassen sich durch die Ausgangsstoffe, ihr Gemisch und das Herstellungsverfahren in weiten Grenzen variieren.Aerogels are highly porous, open-pored, oxidic solids that usually via sol-gel processes from metal alkoxides by polymerization, polycondensation to gels and subsequent supercritical drying. For some years now, it has also been possible to add plastics using sol-gel processes gel and by supercritical drying in a highly porous organic Convert solid body. Pyrolysis of such plastic aerogels under protective gas or in a vacuum at temperatures above 1000 ° C converts them into carbon aerogels around. Like the oxidic aerogels, plastic and carbon have aerogels extremely low effective thermal conductivities (order of magnitude some mW / K / m) and are considerably lighter. The physical and mechanical Properties of plastic and carbon aerogels are in the literature documented (R.W. Pekala, C.T. Alviso, F.M. Kong, S.S. Hulsey; J. Non-Cryst. Solids 145 (1992) 90; R.W. Pekala, C.T. Alviso, Mat. Res. Soc. Symp. Proc. 270 (1992) 3; R. Petricevic, G. Reichenauer, V. Bock, A. Emmerling, J. Fricke; J.Non-Cryst. Solids (1998)). You can be through the source materials, you Mixture and the manufacturing process vary within wide limits.
Es ist daher Aufgabe der vorliegenden Erfindung die im Stand der Technik bekannten Verfahren zur Herstellung von Formstoften für den Fein- und Formguss von Metallen und Metall-Legierungen zu vereinfachen, insbesondere die Verfahrensdauer der Trocknung zu reduzieren.It is therefore an object of the present invention to be known in the prior art Process for the production of molding materials for fine and mold casting of metals and metal alloys, in particular to simplify the process time to reduce drying.
Die vorgenannte Aufgabe wird in einer ersten Ausführungsform gelöst durch einen Formstoff für den Fein- und Formguss von Metallen oder Metall-Legierungen umfassend hochporöse, offenporige Kunststoff- und/oder Kohlenstoffaerogele, erhältlich durch Sol-Gel-Polymerisation von organischen Kunststoffmaterialien gegebenenfalls gefolgt von teilweise oder vollständiger Pyrolyse des erhaltenen Kunststoffaerogels.The aforementioned object is achieved in a first embodiment by a Molding material for the fine and mold casting of metals or metal alloys comprising highly porous, open-pore plastic and / or carbon aerogels, available through sol-gel polymerization of organic plastic materials optionally followed by partial or complete pyrolysis of the obtained Plastic aerogels.
Der erfindungsgemäße Formstoff eignet sich besonders zum Einsatz in Wachsausschmelzverfahren und muß nicht, wie im Stand der Technik bei oxidischen Gelen, in mehreren Schritten aufgebracht werden.The molding material according to the invention is particularly suitable for use in lost wax processes and need not, as in the prior art for oxidic Gels can be applied in several steps.
Die so gewonnenen Formen werden nach üblichen Techniken mit Schmelze gefüllt und die Schmelze erstant. Bei den üblichen Gusstechniken, erfolgt die Wärmeableitung über die Formschale oder den Formsand. Gießen und Erstarren in Aerogelen bedeutet hingegen, da Kohlenstoffaerogele quasi adiabatisch sind, dass die Wärmeabfuhr einzig über Speiser und Steiger beziehungsweise speziell angebrachte Kühlkörper erfolgt, wozu geschickterweise die Steiger und Speiser selbst verwendet werden können, aber nicht müssen. Auf diese Weise ist eine vollständig gelenkte Erstarrung möglich und das Gefüge kann entsprechend dem erforderlichen Eigenschaftsspektrum angepasst werden. The molds obtained in this way are filled with melt using customary techniques and the melt starts. With the usual casting techniques, heat is dissipated over the mold shell or the molding sand. Pour and freeze in By contrast, aerogels mean, since carbon aerogels are quasi adiabatic, that the heat dissipation only via feeders and risers or specifically attached heat sink takes place, skillfully the risers and feeders can be used by yourself, but do not have to. That way is one fully controlled solidification is possible and the structure can accordingly required range of properties can be adjusted.
Die erfindungsgemäß hergestellten Aerogelformen eignen sich insbesondere für das Gießen von Aluminiumlegierungen (wobei die Gussform praktisch nicht aufgeheizt werden muß, da keine Wärmeableitung durch sie selbst erfolgt). Dies erhöht die Wirtschaftlichkeit, da Energiekosten gesenkt werden können. Magnesium- und Titanlegierungen reagieren mit Kohlenstoff ebenfalls nicht, so dass sich diese Kohlenstoffaerogelformen auch für diese Legierungen unter Schutzgas oder Vakuum als Fomistoff anbieten.The airgel forms produced according to the invention are particularly suitable for the casting of aluminum alloys (whereby the casting mold practically does not heat up must be, since no heat dissipation takes place by itself). This increases the economy because energy costs can be reduced. Magnesium and titanium alloys also do not react with carbon, so that these carbon airgel forms also for these alloys under protective gas or Offer vacuum as film material.
Ein besonderer Vorteil der erflndungsgemäßen Formstoffe besteht darin, dass die Sol-Gel-Bildung bei Raumtemperatur, das heißt insbesondere bei Temperaturen unterhalb des Fließpunktes des Wachses innerhalb weniger Stunden abgeschlossen werden kann. Eine überkritische Trocknung, wie bei den rein anorganischen Gelen ist nicht erforderlich. Dennoch ist es möglich, die Porengröße im Mikrometerbereich einzustellen. Bei Trocknung im überkritischen Temperaturbereich sind darüber hinaus auch Porengrößen im Nanometerbereich möglich.A particular advantage of the molding materials according to the invention is that the Sol-gel formation at room temperature, that is, in particular at temperatures completed below the pour point of the wax within a few hours can be. Supercritical drying, as with the purely inorganic Gelling is not necessary. Nevertheless, it is possible to determine the pore size in the micrometer range adjust. When drying in the supercritical temperature range pore sizes in the nanometer range are also possible.
Die erlindungsgemäßen Formstoffe können darüber hinaus auch anorganische oder organische Füllstoffmaterialien enthalten. Hierunter werden im wesentlichen bei Erstarrungsbedingungen inerte stabile Materialien verstanden. Anorganische Füllstoffmaterialien sind beispielsweise ausgewählt aus Aluminiumoxid, Titandioxid und/oder Quarz, die jeweils in einer Menge von 5 bis 30 Vol.-%. eingesetzt werden können. Füllstoffe im Sinne der vorliegenden Erfindung umfassen weiterhin Fasermaterialien, die eine Faserverstärkung mit organischen, anorganischen oder Kohlenstoff- und/oder SiC-Fasern bei etwa gleichen Volumenanteilen erlauben.The molding materials according to the invention can also be inorganic or contain organic filler materials. These are essentially Understand solid materials that are inert under solidification conditions. Inorganic Filler materials are selected, for example, from aluminum oxide, titanium dioxide and / or quartz, each in an amount of 5 to 30 vol .-%. used can be. Fillers for the purposes of the present invention further comprise Fiber materials that have a fiber reinforcement with organic, inorganic or allow carbon and / or SiC fibers with approximately equal volume fractions.
In gleicher Weise ist es aber auch möglich, organische Füllstoffe, beispielsweise thermoplastische oder duroplastische Kunststoffpartikel, beispielsweise Polystyrol und/oder organische (Polyacrylnitril) Fasern einzusetzen. Hierbei ist jedoch zu beachten, dass bei der Pyrolyse der Kunststoffgele diese Materialien mit ausgeschmolzen oder verbrannt werden. Mit Hilfe solcher Materialien ist jedoch eine Kontrolle der Schrumpfung während der Pyrolyse möglich. In the same way, however, it is also possible to use organic fillers, for example thermoplastic or thermosetting plastic particles, for example polystyrene and / or use organic (polyacrylonitrile) fibers. However, this is too note that these materials are also melted out during the pyrolysis of the plastic gels or be burned. However, using such materials is one Control of shrinkage possible during pyrolysis.
Besonders bevorzugt im Sinne der vorliegenden Erfindung werden für den Formstoff Kunststoffaerogele auf der Basis Resorcin/Formaldehyd eingesetzt, die bei geeigneter Zusammensetzung und geeignetem Gehalt an basischem Katalysator bei Temperaturen zwischen 20 und 50 °C ohne überkritisches Trocknen in ein mikrostrukturiertes Kunststoffaerogel überführt werden können. Durch Auswahl der Zusammensetzung ist die Sol-Gel-Polymerisation so einstellbar, dass beispielsweise zunächst eine hochviskose Flüssigkeit entsteht, die auf eine Wachsform aufgebracht werden kann. Dies ist auch in mehreren Arbeitsgängen möglich, so dass die Schichtdicke den Bedürfnissen der Anwendungen in der Gießerei angepasst werden kann.For the purposes of the present invention, particular preference is given to the molding material Plastic aerogels based on resorcinol / formaldehyde used in suitable composition and suitable content of basic catalyst at temperatures between 20 and 50 ° C without supercritical drying in one microstructured plastic airgel can be transferred. By selection The composition of the sol-gel polymerization can be set such that, for example First, a highly viscous liquid is created, which is applied to a wax mold can be applied. This is also possible in several work steps, so that the layer thickness is adapted to the needs of the applications in the foundry can be.
Somit besteht eine weitere Ausführungsform der vorliegenden Erfindung in einem
Verfahren zur Herstellung von Gussformen für den Fein- und Formguss von Metallen
oder Metall-Legierungen und der Verwendung von hochporösen, offenporigen
Kunststoff- und/oder Kohlenstoffaerogelen, wobei man
Eine alternative Verfahrensweise zur Herstellung der Gussform besteht darin,
dass man
Somit ist es möglich, den Wachsformkörper einfach in einen geeigneten Behälter einzubringen, mit der Ausgangslösung für die Kunststoffaerogele aufzufüllen und dann das Verfahren der Aerogelherstellung durchzuführen.It is therefore possible to simply place the shaped wax body in a suitable container bring in, fill up with the starting solution for the plastic aerogels and then carry out the airgel manufacturing process.
Auf diese Weise lassen sich analog zum bekannten Block-Mold-Verfahren (das im wesentlichen Gips verwendet) massive, aber leichte quasi-adiabatische Formen herstellen.In this way, analogous to the well-known block-mold process (which in the essential plaster used) massive but light quasi-adiabatic forms produce.
Die Temperatur der Umwandlung der Lösung in ein Kunststoffaerogel muß dem Schmelzpunkt des Wachses angepasst werden. Nach Umwandlung in ein Kunststoffaerogel kann das Wachs ausgeschmolzen werden und gleichzeitig dabei unter Luftabschluss die Konversion zu einem Kohlenstoffaerogel erfolgen. Abhängig von der Zusammensetzung der Ausgangslösung, der Gelierungstemperatur, der Dichte des entstehenden porösen Körpers lassen sich Gussformen herstellen, sowohl als Kunststoff- wie auch als Kohlenstoffaerogel, die auf einer Mikrometerskala oberflächlich glatt sind und konturscharf abbilden. Erfindungsgemäß benötigt die Herstellung von Formen bis zum Kunststoffaerogel meist 1 bis 3 Tage, häufig nur bis zu 24 Stunden. Die Pyrolysedauer ist bestimmt durch die Dicke der Gussformschale; bei einer Wanddicke von 1 cm beträgt die Zeit beispielsweise weniger als 24 Stunden, meist 10 Stunden. Im Vergleich zur Herstellung von typischen Feingussschalen unter Einsatz oxidischer Sol-Gel-Prozesse sind die Herstellungszeiten kurz und damit wirtschaftlich. Die Schrumpfung erfolgt in den beiden Prozessschritten immer isotrop und variiert von wenigen Prozent bis 20 % und ist daher beherrschbar. Sie lässt sich durch die Zusammensetzung des Sols, die Trocknungsbedingungen, das Formmaterial und Füllstoffe reduzieren und beeinflussen und ist somit beherrschbar. The temperature of the conversion of the solution into a plastic airgel must be Melting point of the wax can be adjusted. After converting to a Plastic airgel can melt the wax and at the same time the conversion to a carbon airgel takes place in the absence of air. Dependent the composition of the starting solution, the gelation temperature, the density of the resulting porous body can be made into molds, as both plastic and carbon airgel, on a micrometer scale are smooth on the surface and reproduce sharp contours. According to the invention the production of molds up to the plastic airgel usually takes 1 to 3 days, often only up to 24 hours. The pyrolysis time is determined by the thickness the mold shell; with a wall thickness of 1 cm, for example, the time is less than 24 hours, usually 10 hours. Compared to producing Typical investment cast shells using oxidic sol-gel processes are the Manufacturing times short and therefore economical. The shrinkage takes place in the both process steps always isotropic and varies from a few percent to 20% and is therefore manageable. It can be determined by the composition of the sol, reduce and influence drying conditions, molding material and fillers and is therefore manageable.
Beispielhaft sind die jeweiligen Verfahrensschritte zur Herstellung von Kunststoffaerogelformen
wie folgt charakterisiert:
Eine Lösung aus 110 g Resorcin (Merck), 162 g Formaldehyd-Lösung (37 %ig, Merck), 0,075 g Na2CO3 und 750 ml Wasser wurde bei Zimmertemperatur mechanisch gerührt.A solution of 110 g resorcinol (Merck), 162 g formaldehyde solution (37%, Merck), 0.075 g Na 2 CO 3 and 750 ml water was mechanically stirred at room temperature.
Ein Glasbehälter, in dem sich ein Wachsmodell (mit Stahlplatten beschwert) des Formkörpers befand, wurde mit der Lösung aufgefüllt, bis das Modell vollständig bedeckt war. Der Behälter wurde verschlossen. Innerhalb von zwei Stunden gelierte die Lösung in einem Luftumwälzer (Heraeus) bei 40 °0. Es wurde ein Farbumschlag der klaren Lösung nach ockergelb/hellbraun beobachtet. Die Trocknung des Gels wurde im Luftumwälzer im Verlauf von 24 Stunden erhalten. Anschließend wurde bei einer Temperatur von 60 °C das Wachs ausgeschmolzen.A glass container in which a wax model (weighted down with steel plates) of the Shaped body was filled with the solution until the model was complete was covered. The container was closed. Gelled within two hours the solution in an air circulator (Heraeus) at 40 ° 0. It became a color change the clear solution observed after ocher yellow / light brown. The drying of the gel was obtained in the air circulator over 24 hours. Subsequently the wax was melted out at a temperature of 60 ° C.
In einem weiteren Schritt wurde das Kunststoffaerogel in einem kalten Muffelofen eingebracht. Der Ofen wurde langsam (3 Stunden) auf 1050 °0 aufgeheizt, wobei kontinuierlich Stickstoff (Argon oder ein anderes Schutzgas ist analog möglich) zur Vermeidung der Oxidation durchgeblasen wurde. Die Temperatur von 1050 °C wurde für 24 Stunden beibehalten.In a further step, the plastic airgel was placed in a cold muffle furnace brought in. The oven was slowly (3 hours) heated to 1050 ° 0, where continuous nitrogen (argon or another protective gas is possible analogously) was blown through to avoid oxidation. The temperature of 1050 ° C was maintained for 24 hours.
Anschließend wurde unter stetigem Gasfluss abgekühlt und die Kohlestoffaerogelform entnommen.The mixture was then cooled with a constant gas flow and the carbon dioxide airgel form taken.
Claims (10)
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DE19911847A DE19911847A1 (en) | 1999-03-17 | 1999-03-17 | Fine and molded casting in plastic / carbon aerogels |
DE19911847 | 1999-03-17 |
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EP1036610A1 true EP1036610A1 (en) | 2000-09-20 |
EP1036610B1 EP1036610B1 (en) | 2005-08-31 |
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EP00104214A Expired - Lifetime EP1036610B1 (en) | 1999-03-17 | 2000-03-01 | Investment and mould casting in carbon and organic aerogels |
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US (2) | US6599953B1 (en) |
EP (1) | EP1036610B1 (en) |
AT (1) | ATE303214T1 (en) |
DE (2) | DE19911847A1 (en) |
Cited By (9)
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EP1077097A1 (en) * | 1999-08-18 | 2001-02-21 | DLR Deutsches Zentrum für Luft- und Raumfahrt e.V. | Use of plastic and/or carbon aerogels as core material |
DE10216403A1 (en) * | 2002-04-12 | 2003-11-13 | Deutsch Zentr Luft & Raumfahrt | Molding material used for casting molds for casting metals or metal alloys contains open pore plastic aerogels and inorganic silicon carbide fillers |
WO2005046909A1 (en) * | 2003-11-11 | 2005-05-26 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Filler-containing aerogels |
DE102004027382A1 (en) * | 2004-06-04 | 2006-01-05 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Carbon aerogel sand used as a core material for dead-mold casting to produce cylinder heads and hydraulic lines contains foundry sand and has a specified temperature of thermal decomposition of in the presence of an oxidant |
EP2204246A3 (en) * | 2008-11-12 | 2012-01-04 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Foundry core with improved gutting properties I |
CN102343285A (en) * | 2011-07-18 | 2012-02-08 | 南京工业大学 | Preparation method of blocky silicon-carbon composite aerogel |
CN102351506A (en) * | 2011-07-18 | 2012-02-15 | 南京工业大学 | Preparation method of block high temperature resistant silicon-charcoal composite aerogel material |
WO2017102231A1 (en) * | 2015-12-15 | 2017-06-22 | Robert Bosch Gmbh | Feeder for castings consisting in particular of cast iron |
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US6806299B2 (en) * | 2001-05-18 | 2004-10-19 | The Regents Of The University Of California | Preparation of hydrophobic organic aeorgels |
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US8293657B2 (en) | 2010-11-05 | 2012-10-23 | Honeywell International Inc. | Sacrificial layers made from aerogel for microelectromechanical systems (MEMS) device fabrication processes |
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WO2005046909A1 (en) * | 2003-11-11 | 2005-05-26 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Filler-containing aerogels |
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DE102004027382B4 (en) * | 2004-06-04 | 2006-03-09 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Carbon aerogel sand used as a core material for dead-mold casting to produce cylinder heads and hydraulic lines contains foundry sand and has a specified temperature of thermal decomposition of in the presence of an oxidant |
EP2204246A3 (en) * | 2008-11-12 | 2012-01-04 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Foundry core with improved gutting properties I |
CN102343285A (en) * | 2011-07-18 | 2012-02-08 | 南京工业大学 | Preparation method of blocky silicon-carbon composite aerogel |
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CN109675620B (en) * | 2017-10-18 | 2021-07-09 | 中国石油化工股份有限公司 | Cobalt-containing catalyst, preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
US6887915B2 (en) | 2005-05-03 |
US6599953B1 (en) | 2003-07-29 |
DE19911847A1 (en) | 2000-09-28 |
DE50011046D1 (en) | 2005-10-06 |
EP1036610B1 (en) | 2005-08-31 |
US20030212152A1 (en) | 2003-11-13 |
ATE303214T1 (en) | 2005-09-15 |
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