EP0646097A1 - Procede de preparation d'un materiau analogue a un aerogel de silice - Google Patents

Procede de preparation d'un materiau analogue a un aerogel de silice

Info

Publication number
EP0646097A1
EP0646097A1 EP92910393A EP92910393A EP0646097A1 EP 0646097 A1 EP0646097 A1 EP 0646097A1 EP 92910393 A EP92910393 A EP 92910393A EP 92910393 A EP92910393 A EP 92910393A EP 0646097 A1 EP0646097 A1 EP 0646097A1
Authority
EP
European Patent Office
Prior art keywords
alcogel
contact
silica
solution
drying
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.)
Ceased
Application number
EP92910393A
Other languages
German (de)
English (en)
Inventor
Mari-Ann Einarsrud
Siv Haereid
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.)
Sinvent AS
Original Assignee
Sinvent AS
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 Sinvent AS filed Critical Sinvent AS
Publication of EP0646097A1 publication Critical patent/EP0646097A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate

Definitions

  • This invention relates to a process for the preparation of a material similar to silica aerogel.
  • Silica aerogel is a porous material of a very low density and it contains up to 99% of air.
  • the type of silica aerogel prepared according to the present invention is normally called silica xerogel. Due its high porosity, the material has excellent heat insulating properties, and since the pore size of the material is smaller than the wave length of visible light, it is also transparent.
  • Typical properties of silica aerogel are as follows:
  • Pore size 10 - 20 nm
  • Silica aerogel has an insulating property which is approximately twice as good as that of rockwool, and since it is also transparent, it may be used as insulation in windows.
  • silica xerogel/aerogel Due to its porosity silica xerogel/aerogel has also a very high capacity for sucking up liquid and may also be used as starting material for composite materials and carrier for catalyst and liquids, e.g. electrolytes.
  • TMOS tetramethoxysilane
  • the alcogel formation takes place by a direct acid- and/or base-catalysed hydrolysis of TMOS in a so-called sol-gel technology.
  • the alcogel formed is a silica skeleton surrounded by aqeous methanol.
  • the problem which then arises is to remove the aqueous methanol from the silica skeleton to obtain the- aerogel.
  • silica xerogel will have a relatively high density, e.g. about 1,4 g/cm 3 .
  • preparation method a) will result in 10 an aerogel.
  • b> and c) there will be obtained a gel which may be described as silica cryogel and silica xerogel respectively, which may have approximately the same properties as silica aerogel.
  • Drying method b) is cheap, but due to volume expansion of the solvent during crystallisation (i.e. freezing) , the result may easily be cracking of the gel during the drying.
  • Drying method c) normally takes place with a large shrinkage of the gel due to a collapse of the gel structure.
  • the purpose of the present invention is to provide a process for preparing silica xerogel (aerogel) having a relatively low density (i.e. below 0.5 g/cm 3 ) and such that the material is suitable as a heat insulating material.
  • the process is characterised by the fact that the alcogel formed is contacted with a solution of a tetraalkoxysilane. The contact is maintained at or above room temperature to stabilise the silica skeleton, whereafter the alcogel is slowly dryed at or above room temperature and at above approximately atmospheric pressure.
  • the alcogel Before the alcogel is contacted with the solution of tetraalkoxysilane it may be suitable to contact the alcogel with a liquid to wash the gel (in order to change the composition of the aqueous alcohol surrounding the silica skeleton) and to replace functional groups on the surface.
  • This liquid may e.g. consist of a mixture of water and alcohol, preferably about 40% methanol. This liquid may also be replaced several times.
  • the liquid added for washing may have a temperature up to the boiling point, preferably room temperature.
  • tetrametoxysilane is used for preparing the alcogel, whereafter the gel formed is contacted with a solution of tetraethoxysilane, e.g. in a lower alcohol, particularly methanol.
  • the contact between the alcogel and the later added teraalkoxysilane is suitably maintained for a sufficiently long time for a strengthening of the gel network to take place, e.g. from 6 hours to 16 days, at a temperature which does not represent any risk for the alcogel, preferably from 20 to 200°C, particularly 40-80°C.
  • An increased ageing time results in the largest pores in the product, i.e the lowest density.
  • the washing of the alcogel with liquid, e.g aqueous alcohol results in less shrinking of the gel and larger pores.
  • the alcohol used is normally a mono-,, di- or trihydric alkanol, particularly with 1-10 C-atoms, preferably methanol. 5
  • Controlled drying may be accomplished by allowing it to take place in an atmosphere which contains components
  • the drying may e.g. take place in a chamber with such an atmosphere, or it may take place while the alcogel is kept almost completely covered, e.g. up to 99%, whereby the
  • the drying is suitably carried out at a temperature in the range 40 - 200°C.
  • the drying temperature may also be gradually varied from room temperature to the boiling point of aqueous alcohol.
  • the thereby formed xerogel has a low density (e.g. 0,5 g/cm 3 or lower) and has also a homogeneous structure.
  • Example 1 An alcogel was prepared by hydrolysis and polycondensation of
  • TEOS tetraethoxysilane
  • the mould was " removed from the bath after approximately 24 « hours, and the bath was then kept covered for additional 24
  • the surface area of the xerogel is in the range 600 - 650 m 2 /g.
  • the thermal conductivity of the silica xeroge? material formed has been measured down to 0.02 ⁇ 0.004 W. mK at 450C.
  • Example 2 An alcogel was prepared as described in Example 1. After up to several hours of standing in covered condition the mouled with the alcogel was immersed in liquid consisting of methanol and water (e.g. 30 volume % of water) . The liquid mixture was changed three times with 24 hours intervals. The alcogel in the liquid mixtures was kept at room temperature during the entire washing. After four days the washing solution was replaced by a solution of tetraethoxysilane as in Example l. The rest is as in Example 1.
  • the treatment of the alcogel in the solution of water and methanol causes less shrinkage of the alcogel during drying.
  • the shrinkage of the alcogel during drying is about 13%.
  • the thermal conductivity of the silica xerogel prepared has been measured down to 0.028 ⁇ 0.04W/mK.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

Procédé de préparation d'un xérogel de silice par hydrolyse et polycondensation d'un tétraalcoxysilane, afin d'obtenir un alcogel, qui est une ossature de silice entourée par un méthanol aqueux supprimé ensuite par évaporation. L'alcogel obtenu est mis en contact avec une solution de tétraalcoxysilane; on maintient le contact à température ambiante ou au-dessus de ladite température, afin de solidifier l'ossature de silice et on fait sécher ensuite le gel lentement à température ambiante ou au-dessus et environ à la pression atmosphérique. Avant de mettre l'alcogel en contact avec la solution de tétraalcoxysilane, on peut le laver avec une solution (par exemple, un méthanol aqueux), afin de modifier les groupes fonctionnels de la surface de l'alcogel.
EP92910393A 1991-05-24 1992-05-22 Procede de preparation d'un materiau analogue a un aerogel de silice Ceased EP0646097A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NO912006A NO912006D0 (no) 1991-05-24 1991-05-24 Fremgangsmaate for fremstilling av et silika-aerogel-lignende materiale.
NO912006 1991-05-24
PCT/NO1992/000096 WO1992020623A1 (fr) 1991-05-24 1992-05-22 Procede de preparation d'un materiau analogue a un aerogel de silice

Publications (1)

Publication Number Publication Date
EP0646097A1 true EP0646097A1 (fr) 1995-04-05

Family

ID=19894166

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92910393A Ceased EP0646097A1 (fr) 1991-05-24 1992-05-22 Procede de preparation d'un materiau analogue a un aerogel de silice

Country Status (7)

Country Link
EP (1) EP0646097A1 (fr)
JP (1) JPH06510268A (fr)
BR (1) BR9206051A (fr)
CA (1) CA2109715A1 (fr)
FI (1) FI935203A (fr)
NO (2) NO912006D0 (fr)
WO (1) WO1992020623A1 (fr)

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4439217A1 (de) * 1994-11-03 1996-05-09 Hoechst Ag Verfahren zur Herstellung von Aerogelen
DE19538333A1 (de) * 1995-10-14 1997-04-17 Basf Ag Verfahren zur unterkritischen Herstellung von Aerogelen
US6764690B2 (en) 1996-05-29 2004-07-20 Delsitech Oy Dissolvable oxides for biological applications
DE19718740A1 (de) 1997-05-02 1998-11-05 Hoechst Ag Verfahren zur Granulierung von Aerogelen
DE19718741A1 (de) 1997-05-02 1998-11-05 Hoechst Ag Verfahren zur Kompaktierung von Aerogelen
DE19756633A1 (de) 1997-12-19 1999-06-24 Hoechst Ag Verfahren zur unterkritischen Trocknung von Lyogelen zu Aerogelen
DE19801004A1 (de) 1998-01-14 1999-07-15 Cabot Corp Verfahren zur Herstellung von im wesentlichen kugelförmigen Lyogelen in wasserunlöslichen Silylierungsmitteln
DE59811774D1 (de) 1998-06-05 2004-09-09 Cabot Corp Nanoporöse interpenetrierende organisch-anorganische netzwerke
US6239243B1 (en) 1999-06-10 2001-05-29 Dow Corning Corporation Method for preparing hydrophilic silica gels with high pore volume
ES2174680B1 (es) * 1999-09-03 2004-09-16 Consejo Superior De Investigaciones Cientificas Materiales termohibridos inorganico-organicos de baja densidad y su procedimiento de obtencion.
GB0025940D0 (en) * 2000-10-24 2000-12-13 Secr Defence Solvogels & a method of manufacturing the same
JP4170734B2 (ja) 2002-11-13 2008-10-22 信越化学工業株式会社 多孔質膜形成用組成物、多孔質膜とその製造方法、層間絶縁膜及び半導体装置
US8034749B2 (en) 2002-12-31 2011-10-11 Baker Hughes Incorporated Aerogels effective to reduce drilling fluid density
AU2005217169B2 (en) 2004-02-27 2011-09-01 Delsitech Oy Method for preparing adjustably bioresorbable sol-gel derived SiO2
FR2873677B1 (fr) * 2004-07-29 2007-08-17 Armines Ass Pour La Rech Et Le Procede d'elaboration de serogels de silice hydrophobes
PT103257B (pt) 2005-04-05 2007-05-31 Inst Superior Tecnico Método de produção subcrítica de xerogéis e aerogéis monolíticos híbridos de sílica e látex modificado com grupos alcoxissilano
CA2619860A1 (fr) * 2005-08-25 2007-03-01 Robert R. Keller, Sr. Aerogel et son procede de fabrication
DE102008056987A1 (de) * 2008-11-12 2010-05-20 Rwe Power Ag Isolierkassette
DE102009053784A1 (de) * 2009-11-19 2011-05-26 BSH Bosch und Siemens Hausgeräte GmbH Verfahren zur Herstellung eines porösen SiO2-Xerogels mit charakteristischer Porengröße durch ein Bottom-Up-Verfahren über eine Vorstufe mit organischen Festkörperskelettstützen
DE102009053782A1 (de) * 2009-11-19 2011-06-01 BSH Bosch und Siemens Hausgeräte GmbH Poröses SiO2-Xerogel mit charakteristischer Porengröße, dessen trocknungsstabile Vorstufen und dessen Anwendung
PT106781A (pt) 2013-02-15 2014-08-18 Inst Superior Técnico Aerogéis híbridos flexíveis preparados em condições subcríticas e processo de preparação dos mesmos
JP6191012B2 (ja) * 2013-12-12 2017-09-06 パナソニックＩｐマネジメント株式会社 断熱材
US10889501B2 (en) 2016-02-24 2021-01-12 Massachusetts Institute Of Technology Solar thermal aerogel receiver and materials therefor
KR102092769B1 (ko) 2016-09-12 2020-03-24 주식회사 엘지화학 실리카 에어로겔의 제조방법 및 이에 의해 제조된 실리카 에어로겔
KR102092770B1 (ko) * 2016-09-12 2020-03-24 주식회사 엘지화학 실리카 에어로겔의 제조방법 및 이에 의해 제조된 실리카 에어로겔
EP3677618A4 (fr) * 2017-09-01 2021-05-26 AGC Inc. Procédés de production de gel humide et de xérogel
WO2019210051A1 (fr) 2018-04-25 2019-10-31 Massachusetts Institute Of Technology Rénovation de fenêtres d'insonorisation à faible consommation d'énergie

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* Cited by examiner, † Cited by third party
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SE422045C (sv) * 1979-04-30 1985-03-18 Guy Von Dardel Sett att framstella silikaaerogel i form av ett vesentligen sprickfritt, foretredesvis transparent block samt anvendning av detsamma i solpaneler
US4402927A (en) * 1980-04-22 1983-09-06 Dardel Guy Von Silica aerogel
DE3616133A1 (de) * 1985-09-25 1987-11-19 Merck Patent Gmbh Kugelfoermige sio(pfeil abwaerts)2(pfeil abwaerts)-partikel
DD283701A7 (de) * 1988-09-26 1990-10-24 Veb Leuna-Werke "Walter Ulbricht",Dd Verfahren und vorrichtung zur herstellung organisch modifizierter silikagele

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9220623A1 *

Also Published As

Publication number Publication date
WO1992020623A1 (fr) 1992-11-26
AU1785292A (en) 1992-12-30
NO912006D0 (no) 1991-05-24
BR9206051A (pt) 1994-11-15
NO934233L (no) 1993-11-23
CA2109715A1 (fr) 1992-11-26
AU662147B2 (en) 1995-08-24
FI935203A (fi) 1994-01-13
JPH06510268A (ja) 1994-11-17
NO934233D0 (no) 1993-11-23
FI935203A0 (fi) 1993-11-23

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