US5409683A
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Method for producing metal oxide aerogels
Assignee: Lawrence Livermore National Security LLC
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Filing: 1994-07-07
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Granted: 1995-04-25
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Expires: 2014-07-07
Abstract
Abstract A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm 3 and greater than 0.27g/cm 3 . High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods.
Inventors
- 👤 Thomas M. Tillotson
- 👤 John F. Poco
- 👤 Lawrence W. Hrubesh
- 👤 Ian M. Thomas
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 23:38
CPC Classifications
B; B01; B01J; B01J13/00; B01J13/0091; C; C01; C01B; C01B33/00; C01B33/113; C01B33/12; C01B33/14; C01B33/157; C01B33/158; C01B33/1585; C03; C03C; C03C1/00; C03C1/006
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
135 words
A two-step reaction method for making metal oxide aerogels and porous glasses, comprising: (a) mixing a metal alkoxide with a hydrolysis rate reducing alcohol solvent, an additive, and a substoichiometric amount of water to form a solution; (b) reacting the metal alkoxide solution with an acid catalyst to form an oligomeric mixture of a partially condensed metal intermediate and a reaction-generated alcohol; (c) removing all reaction-generated and solvent alcohol; (d) adding a nonalcoholic solvent to the partially condensed metal intermediate to form a nonalcoholic solvated condensed metal intermediate; (e) reacting the nonalcoholic solvated condensed metal intermediate with a second catalyst and water to complete hydrolysis to form a condensed metal oxide product; (f) forming a gel from the condensed metal oxide product; and (g) removing the nonalcoholic solvent from the gel to form an aerogel.
Claim 2
Dependent Claim
135 words
A two-step reaction method for making metal oxide aerogels and porous glasses, comprising: (a) mixing a metal alkoxide with a hydrolysis rate reducing alcohol solvent, an additive, and a substoichiometric amount of water to form a solution; (b) reacting the metal alkoxide solution with an acid catalyst to form an oligomeric mixture of a partially condensed metal intermediate and a reaction-generated alcohol; (c) removing all reaction-generated and solvent alcohol; (d) adding a nonalcoholic solvent to the partially condensed metal intermediate to form a nonalcoholic solvated condensed metal intermediate; (e) reacting the nonalcoholic solvated condensed metal intermediate with a second catalyst and water to complete hydrolysis to form a condensed metal oxide product; (f) forming a gel from the condensed metal oxide product; and (g) removing the nonalcoholic solvent from the gel to form an aerogel.
Claim 3
Dependent Claim
37 words
A method as recited in claim 1, wherein the metal alkoxide is formed from a metal selected from the group consisting of silicon, zirconium, titanium, tantalum, germanium, boron, aluminum, strontium, iron, praseodymium, erbium, cerium, lithium, and magnesium.
Claim 4
Dependent Claim
23 words
A method as recited in claim 2, wherein the silicon alkoxide is selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
Claim 5
Dependent Claim
18 words
A method as recited in claim 1, wherein the metal alkoxide is of a purity greater than 98%.
Claim 6
Dependent Claim
30 words
A method as recited in claim 1, wherein the additive in Step (a) is selected from the group consisting of acetylacetone and any substituted acetylacetones, acetic acid, and hydrogen peroxide.
Claim 7
Dependent Claim
29 words
A method as recited in claim 1, wherein the alcohol solvent in Step (a) is selected from the group consisting of methanol, ethanol, propanol, butanol, and higher alkane alcohols.
Claim 8
Dependent Claim
42 words
A method as recited in claim 1, wherein the acid catalyst in Step (b) is selected from the group consisting of hydrochloric acid (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), and acetic acid (CH 3 COOH).
Claim 9
Dependent Claim
29 words
A method as recited in claim 1, wherein the removal of alcohol in Step (c) is performed by a method selected from the group consisting of distillation and evaporation.
Claim 10
Dependent Claim
30 words
A method as recited in claim 1, wherein the nonalcoholic solvent of Step (d) is selected from the group consisting of acetonitrile, acetone, ether, ethylene glycol, dimethylformamide, tetrahydrolfuran, and toluene.
Claim 11
Dependent Claim
55 words
A method as recited in claim 1, wherein the second catalyst in Step (e) is selected from the group consisting of ammonia (NH 4 OH), sodium hydroxide (NaOH), potassium hydroxide (KOH), gaseous ammonia, fluoroboric acid (HBF 4 ), hydrochloric acid (HCl ), nitric acid (HNO 3 ), and sulfuric acid (H 2 SO 4 ).
Claim 12
Dependent Claim
33 words
A method as recited in claim 1, wherein the removal of nonalcoholic solvent in Step (g) is performed by a method selected from the group consisting of supercritical fluid extraction, freeze-drying, and evaporation.
Claim 13
Dependent Claim
20 words
A method as recited in claim 11, wherein a supercritical extraction of the solvent is performed using an inert gas.
Claim 14
Dependent Claim
47 words
A method as recited in claim 1, wherein the removal of nonalcoholic solvent in Step (g) comprises: (1) exchanging the nonalcoholic solvent for a liquefied gas; and (2) extracting the liquefied gas by a method selected from the group consisting of supercritical fluid extraction, freeze-drying, and evaporation.
Claim 15
Dependent Claim
23 words
A method as recited in claim 13, wherein the liquefied gas is selected from the group consisting of carbon dioxide, chlorofluorocarbons, and propane.
Claim 16
Dependent Claim
27 words
A method as recited in claim 1, wherein the water in Step (a) is formed from the reaction between the alcohol solvent and the additive during mixing.
Claim 17
Dependent Claim
21 words
A method as recited in claim 1, wherein the alcohol solvent and additive react to form the substoichiometric amount of water.
Claim 18
Independent Claim
92 words
A method for forming a partially condensed metal intermediate that can be stored and used to form an aerogel of a predetermined density, comprising: (a) mixing a metal alkoxide with a hydrolysis rate reducing alcohol solvent, an additive, and a substoichiometric amount of water to form a solution; (b) reacting the metal alkoxide solution with an acid catalyst to form an oligomeric mixture of a partially condensed metal intermediate and a reaction-generated alcohol; (c) removing all reaction-generated and solvent alcohol; and (d) diluting the partially condensed metal intermediate with a nonalcoholic solvent.
Claim 19
Independent Claim
92 words
A method for forming a partially condensed metal intermediate that can be stored and used to form an aerogel of a predetermined density, comprising: (a) mixing a metal alkoxide with a hydrolysis rate reducing alcohol solvent, an additive, and a substoichiometric amount of water to form a solution; (b) reacting the metal alkoxide solution with an acid catalyst to form an oligomeric mixture of a partially condensed metal intermediate and a reaction-generated alcohol; (c) removing all reaction-generated and solvent alcohol; and (d) diluting the partially condensed metal intermediate with a nonalcoholic solvent.
Claim 20
Dependent Claim
37 words
A method as recited in claim 17, wherein the metal alkoxide is formed from a metal selected from the group consisting of silicon, zirconium, titanium, tantalum, germanium, boron, aluminum, strontium, iron, praseodymium, erbium, cerium, lithium, and magnesium.
Claim 21
Dependent Claim
18 words
A method as recited in claim 17, wherein the metal alkoxide is of a purity greater than 98%.
Claim 22
Dependent Claim
30 words
A method as recited in claim 17, wherein the additive in Step (a) is selected from the group consisting of acetylacetone and any substituted acetylacetones, acetic acid, and hydrogen peroxide.
Claim 23
Dependent Claim
29 words
A method as recited in claim 17, wherein the alcohol solvent in Step (a) is selected from the group consisting of methanol, ethanol, propanol, butanol, and higher alkane alcohols.
Claim 24
Dependent Claim
42 words
A method as recited in claim 17, wherein the acid catalyst in Step (b) is selected from the group consisting of hydrochloric acid (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ) and acetic acid (CH 3 COOH).
Claim 25
Dependent Claim
29 words
A method as recited in claim 17, wherein the removal of alcohol in Step (c) is performed by a method selected from the group consisting of distillation and evaporation.
Claim 26
Dependent Claim
30 words
A method as recited in claim 17, wherein the nonalcoholic solvent of Step (d) is selected from the group consisting of acetonitrile, acetone, ether, ethylene glycol, dimethylformamide, tetrahydrolfuran, and toluene.
Claim 27
Dependent Claim
27 words
A method as recited in claim 17, wherein the water in Step (a) is formed from the reaction between the alcohol solvent and the additive during mixing.
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