EP1852197B1 - Matériau pour la confection de noyaux de fonderie à base d'aérogel de silice contenant une argile gonflante - Google Patents

Matériau pour la confection de noyaux de fonderie à base d'aérogel de silice contenant une argile gonflante Download PDF

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Publication number
EP1852197B1
EP1852197B1 EP07106978A EP07106978A EP1852197B1 EP 1852197 B1 EP1852197 B1 EP 1852197B1 EP 07106978 A EP07106978 A EP 07106978A EP 07106978 A EP07106978 A EP 07106978A EP 1852197 B1 EP1852197 B1 EP 1852197B1
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EP
European Patent Office
Prior art keywords
sand
core material
clay
sol
aerogel
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
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EP07106978A
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German (de)
English (en)
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EP1852197A1 (fr
Inventor
Lorenz Prof. Ratke
Sabine Dr. Brück
Elmar Nolte
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Deutsches Zentrum fuer Luft und Raumfahrt eV
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Deutsches Zentrum fuer Luft und Raumfahrt eV
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/167—Mixtures of inorganic and organic binding agents

Definitions

  • the invention relates to a core material of clay-containing sand containing Aerogelsand and a process for its preparation.
  • Casting in bonded sand molds is a standard casting technique used to make workpieces of various alloys, especially aluminum, magnesium, titanium or cast iron alloys.
  • Models of castings are made of wood, styrofoam and other materials, fixed in suitable mold boxes and filled with sand, the sands are compacted.
  • the sands are usually chemically or thermally bound by organic binders (plastics), giving the sand mold sufficient strength.
  • organic binders plastics
  • 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 sands.
  • Disadvantage of today's conventional method for core production is that the removal of the cores from the casting, especially in light metal alloys is possible only with great effort (eg mechanical destruction, shaking, thermal decomposition), the distribution of the sands in the core is inhomogeneous and / or cracking germs Among other things, the break under thermal-mechanical Can lead to stress.
  • the thermal decomposition of the organic binder is problematic in light metal casting and not solved. As a rule, core fragments remain in the casting, which must be removed mechanically.
  • Aerogels are highly porous, open-pore solids, which are usually obtained via sol-gel processes via the gelation of colloidally disperse solutions and subsequent supercritical drying. For some years, it has also been possible to gel plastics using sol-gel processes and to convert them by supercritical drying into a highly porous organic solid (see, for example, US Pat DE 195 23 382 A1 . DE 694 09 161 T2 and US Patent No. 5,086,085 ). Pyrolysis of such plastic aerogels under inert gas or in vacuo at temperatures above 1000 ° C converts them into carbon aerogels.
  • plastic and carbon aerogels Like the oxidic 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 carbon aerogels are documented in the literature ( RW Pekala, CT Alviso, FM Kong, SS Hulsey; J. Non-Cryst. Solids 145 (1992) 90 ; RW Pekala, CT Alviso, Mat. Res. 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 preparation and use of highly porous, open-pored plastic and / or carbon aerogels obtainable by sol-gel polymerization of organic plastic materials.
  • the described aerogelsands can also be used as core materials, but the aerogelsands can be removed by oxidation at a temperature of less than 500 ° C.
  • Aerogelsands arise from the combination of conventional foundry sands and aerogels. If, in particular, RF aerogelsands are pyrolyzed, carbon aerogelsands are formed. Typically, carbon and carbonaceous products only burn at a noticeable rate at temperatures above 800 ° C. This means that carbon-bonded aerogelsands would be out of the question as a core material for aluminum casting. Carbon aerogelsands oxidize noticeably from 480 ° C ( DE 10200427382.0 ).
  • RF aerogelsands are made from foundry sands, resorcinol and formaldehyde. Resorcinol and formaldehyde are mixed as major constituents of the binder in a molar ratio of about 1.3: 1, and Na 2 Co 3 is added as a catalyst and deionized water. The sol is mixed with the sand and gelled under exclusion of air. Drying the mixture of wet gel and sand at 20-40 ° C produces the airgel sands.
  • Aerogelsande can be introduced at levels between 50 and 90 wt .-% in so-called Aerogelsande. Their shape and size as well as their chemical composition are the factors influencing the properties of a core.
  • Alodur ® - (96% Al 2 O 3), and Siliziumcarbidsand (SiC) are used. Aerogelsande have sufficient strengths that can be changed with the grain size of the sands but also the binder content.
  • the thermal conductivities are in the range of conventional mold and core material systems.
  • the RF Aerogelsands are the necessary prerequisite to produce carbon aerogelsands. Pyrolysis can be used to produce carbon aerogelsands from them. In this case, bodies of RF airgel-bound sands are used in an oven; the furnace evacuated and flooded with argon. Heating the oven to above 1000 ° C and holding at this temperature for a few hours, depending on the size of the shaped body, converts the RF aerogels to carbon aerogels. After a cooling process, the C-aerogels or carbon-Aerogelsande be taken. The shaped bodies of sand and carbon airgel thus obtained do not lose their shape and are mechanically stable, comparable to the starting material - the plastic Aerogelsand.
  • clay has hitherto been added to the sand or natural sand types have been selected in which clay was already present in sufficient quantity (molding sand).
  • the clay-bound sands are generally bound with water.
  • these molding materials have no high strength and are therefore unsuitable for core production in principle.
  • cores are being made for molding with polymeric binders such as phenolic or furan resins.
  • polymeric binders such as phenolic or furan resins.
  • these can not be used in combination with natural sands, since they must necessarily have a high water content for swelling the layer material. This water would lead to a dilution of the resins and thus to a significant reduction in the binding capacity.
  • the swelling ability of clay materials depends on external circumstances, such as the water vapor pressure or electrolyte-containing pore waters. From 90 ° C, the interlayer water begins to escape, from about 250 ° C it is completely expelled. Upon cooling, rehydration already takes place again. The swelling also depends on the location of the cargoes. Charges in the O-layers are preferred over the T-layers.
  • the swelling depends on the charge of the elemental layers and the Z cations.
  • K + as Z-cation can lower the charge to 0.6 to 0.7 / O 10 (OH) 2 .
  • mica passes into smectitic structures, with other cations then from 0.9 onwards into vermiculite.
  • Smectite with i 0.2 to 0.7, such as montmorillonite and beidellite.
  • Montmorillonite has a low total charge, 0.25 to 0.5 / O 10 (OH) 2 .
  • the charge is predominantly generated by the Mg 2+ in the O-layers.
  • Diellit has the charge lying mostly in the T-layers.
  • He is the Al-richest smectite.
  • Trioctahedral smectite i 0.2 to 0.7. They rarely occur as weathering products under surface conditions. Mainly under marine conditions, for example saponite, a trioctahedral smectite with a high Mg content.
  • Bentonite is the term used to describe clayey rocks that have been formed by the weathering of volcanic ash. Bentonite was named after the first site of Fort Benton, Wyoming (USA). Its unusual properties are determined by the clay mineral montmorillonite. The name montmorillonite derives from the southern French town of Montmorillon, where clay also occurs.
  • Montmorillonite is an aluminum hydrosilicate belonging to the group of phyllosilicates (foliar structure silicates). Montmorillonite is the major representative in the group of three-layer silicates, also referred to as smectites. In practice, bentonite, smectite and montmorillonite are synonyms for Swellable multi-layer silicates used. Bentonite may also contain accompanying minerals such as quartz, feldspar, mica. Bentonite deposits are found throughout the world. However, due to the different genes, the mineralogical compositions and thus also the technical usability are very different. In general, a distinction is made between primary and secondary deposits. Primary deposits are the result of the local weathering of volcanic rocks (for example in the Westerwald). In secondary deposits (for example in Bavaria), volcanic ash was first transported, for example by wind, deposition and subsequent weathering.
  • the most important two-layer material is the kaolinite. Its elemental layer is composed of an SiO 2 tetrahedral layer and an Al 2 O 3 octahedron layer. In three-layer minerals, the elemental layer consists of two outer tetrahedral layers and one inner octahedral layer. This group includes the swellable montmorillonite or bentonite.
  • the swelling process is caused by the fact that water penetrates between the elemental layers and can change their distance.
  • intracrystalline swelling ie the widening of the distance of the elementary layers by the entry of excess water
  • osmotic swelling which results from concentration differences between “inner solution” and “outer solution”. If the swelling of a montmorillonite occurs within a limited volume (for example in a sealing layer), a swelling pressure is built up, which can reach several bar depending on the density. The swelling pressure prevents further penetration of water.
  • a montmorillonite crystal is composed of about 15 to 20 elemental layers. Between these layers are next to the crystal water exchangeable cations that compensate for the negative excess charges of the grid. These are not particularly tightly bound and can be replaced by other cations or by positively charged organic molecules. Bentonite or montmorillonite has a special ability for ion exchange and for the addition of positively charged particles. Because adsorption processes are surface reactions, the required adsorption capacity is significantly dependent on the specific surface area of the clay mineral. The specific surface area of montmorillonite can be up to 800 sqm / g. Object of the present invention is therefore to provide a core material of airgel and sand, which is much easier and cheaper to manufacture.
  • the object underlying the invention is achieved in a first embodiment by a core material of sand-containing airgel, characterized in that the core material clay-containing sand having a content of swellable phyllosilicates of 3 to 10%.
  • Clay sand in the sense of the invention is a sand (molding sand), which is moist on the one hand and on the other hand contains a substantial amount of clay.
  • Typical clay-containing sands contain, for example, between 5 and 15% by weight of clay.
  • Clay-containing sand in the sense of the invention is thus a clay mineral sand. This contains so-called clay minerals, in particular phyllosilicates in an amount of 3 to 10 wt.%, Such as illite, kaolinite or montmorillonite.
  • the core material of airgel and clay-containing sand compared to conventional core materials of airgel and foundry sand has a particularly high strength and cures quickly. This is possible This may be explained by the fact that polymer-based aerogels in particular naturally have a high water content and thus combine the high binding power of the clay mineral with the good binding properties of the airgel. Particularly advantageous in the subject matter of the present invention is also the special low price of clay-containing sand, which allows the production of cores for molding at a particularly low cost. Due to the high strength of the core material according to the invention, the core material can be manufactured with a significantly reduced binder content.
  • the water formation in the polycondensation reaction does not disturb here, but rather causes the gel to be formed better.
  • According to the invention can get the moisture out of the core body, because that is in the aerogels as opposed to the commercial binders prior art. Therefore, the use of sands with a high proportion of swellable phyllosilicates (vermiculite, montmorillonite, etc.) is a wonderful option that is not obvious to the skilled person and not even if he has knowledge about aerogels binder.
  • the airgel is advantageously a resorcinol-formaldehyde airgel.
  • These aerogels are obtained by drying a sol of resorcinol and formaldehyde. This material is therefore particularly advantageous because it is already used in the previous foundry technology as a non-porous and solid polymer-based binder resorcinol-formaldehyde resin.
  • the airgel is present as binder in a quantity range of 6 to 15 wt .-% in the core material. If the amount of the airgel is well below this range, increased abrasion and low strength of the core material are observed. If the proportion of airgel as a binder is well above 15% by weight, the gelling time in the production of the core material of a few minutes for the core material according to the invention is extended up to several hours for a core material containing more airgel.
  • the clay-containing sand is advantageously contained in a quantity range of 85 to 94 wt .-% in the core material.
  • a higher content of clay-containing sand leads to lower stability of the core material.
  • a lower content of clay-containing sand leads to a significantly longer gel time.
  • the strength of the core material is advantageously at least 100 N / cm 2 (1 MPa).
  • the mean grain diameter of the clay-containing sand is advantageously at least 100 microns.
  • the clay content of the clay-containing sand is advantageously in a range of 3 to 20 wt .-%, in particular 8 to 15 wt .-%.
  • the water content of the natural sand used is advantageously in a range of 3 to 10 wt .-%.
  • the thermal conductivity of the core material according to the invention is advantageously in a range of 0.1 to 0.5 W / mK.
  • the core material according to the invention can be used for applications such as aluminum casting and cast steel.
  • the process according to the invention differs above all in that a considerable shortening of the gelation time can be achieved with this process. While in the known method, the gelling was often several hours, can be achieved with the inventive method, surprisingly, a gelling time of only a few minutes. Due to the higher resulting strength of the core material, in contrast to the known methods, a significantly lower binding fraction can also be used.
  • clay-containing sand having a water content in a range from 3 to 10% by weight is used in the process according to the invention. At this water content it could be observed that a particularly high strength of the resulting core material could be achieved.
  • the object underlying the invention is achieved by the use of the core material according to the invention as a core material for molding.

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

Claims (9)

  1. Matériau de noyau en aérogel contenant du sable, caractérisé en ce que ledit matériau de noyau contient du sable argileux ayant une teneur en phyllosilicates gonflables de 3 à 10 pour cent.
  2. Matériau de noyau selon la revendication 1, caractérisé en ce que l'aérogel est un aérogel de résorcine/formaldéhyde.
  3. Matériau de noyau selon la revendication 1, caractérisé en ce que l'aérogel est contenu dans le matériau de noyau en une quantité comprise entre 6 et 15 pour cent en poids.
  4. Matériau de noyau selon la revendication 1, caractérisé en ce que le sable argileux est contenu dans le matériau de noyau en une quantité comprise entre 85 et 94 pour cent en poids.
  5. Matériau de noyau selon la revendication 1, caractérisé en ce que sa résistance est au moins 100 N/cm2.
  6. Matériau de noyau selon la revendication 1, caractérisé en ce que le diamètre moyen des grains du sable argileux est au moins 100 µm.
  7. Procédé pour préparer le matériau de noyau selon la revendication 1, comprenant les étapes consistant à :
    a. préparer un sol,
    b. mélanger le sol avec du sable argileux,
    c. faire gélifier le sol pour former un gel, et
    d. sécher le gel.
  8. Procédé selon la revendication 7, caractérisé en ce que du sable argileux ayant une teneur en eau comprise entre 3 et 10 pour cent en poids est utilisé.
  9. Utilisation du matériau de noyau selon la revendication 1 comme matériau de noyau pour le moulage.
EP07106978A 2006-05-06 2007-04-26 Matériau pour la confection de noyaux de fonderie à base d'aérogel de silice contenant une argile gonflante Not-in-force EP1852197B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102006021151A DE102006021151A1 (de) 2006-05-06 2006-05-06 Kernwerkstoff aus tonhaltigem Sand enthaltendem Aerogelsand

Publications (2)

Publication Number Publication Date
EP1852197A1 EP1852197A1 (fr) 2007-11-07
EP1852197B1 true EP1852197B1 (fr) 2011-09-21

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EP07106978A Not-in-force EP1852197B1 (fr) 2006-05-06 2007-04-26 Matériau pour la confection de noyaux de fonderie à base d'aérogel de silice contenant une argile gonflante

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EP (1) EP1852197B1 (fr)
AT (1) ATE525153T1 (fr)
DE (1) DE102006021151A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008056856A1 (de) * 2008-11-12 2010-05-20 Deutsches Zentrum für Luft- und Raumfahrt e.V. Gießereikerne mit verbesserten Entkernungseigenschaften I
DE102008056842A1 (de) * 2008-11-12 2010-05-20 Deutsches Zentrum für Luft- und Raumfahrt e.V. Gießereikerne mit verbesserten Entkernungseigenschaften II
DE102009024013A1 (de) 2009-06-05 2010-12-09 Deutsches Zentrum für Luft- und Raumfahrt e.V. Grünfeste Aerosande
US20120231251A1 (en) * 2011-03-09 2012-09-13 Samsung Electronics Co., Ltd. Composition for clay-aerogel composite, clay-aerogel composite, and method of making the same
DE102011077714A1 (de) * 2011-06-17 2012-12-20 E.G.O. Elektro-Gerätebau GmbH Gusskern für ein Gießverfahren und Verfahren zum Entfernen eines Gusskerns
DE102011077711A1 (de) * 2011-06-17 2012-12-20 E.G.O. Elektro-Gerätebau GmbH Gießwerkzeug und Verfahren zur Herstellung eines Gießwerkzeugs
CN109575510B (zh) * 2018-12-12 2021-04-20 河北工业大学 一种纳米纤维矿物增强酚醛树脂三维气凝胶材料的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19939062A1 (de) * 1999-08-18 2001-02-22 Deutsch Zentr Luft & Raumfahrt Verwendung von Kunststoff/Kohlenstoff-Aerogelen als Kernwerkstoff
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
US6719835B2 (en) * 2002-11-08 2004-04-13 Wyo-Ben, Inc. Sand casting foundry composition and method using shale as anti-veining agent
DE10352574A1 (de) * 2003-11-11 2005-06-16 Deutsches Zentrum für Luft- und Raumfahrt e.V. Füllstoff enthaltende Aerogele
DE102004027382B4 (de) * 2004-06-04 2006-03-09 Deutsches Zentrum für Luft- und Raumfahrt e.V. Thermisch zersetzbare Kohlenstoff-Aerogelsande

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Publication number Publication date
EP1852197A1 (fr) 2007-11-07
DE102006021151A1 (de) 2007-11-08
ATE525153T1 (de) 2011-10-15

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