CN1212268C

CN1212268C - Silica dioxide aerogel membrane material preparation method

Info

Publication number: CN1212268C
Application number: CN 200310108722
Authority: CN
Inventors: 褚君浩; 马建华; 孟祥建; 孙璟兰; 王根水
Original assignee: Shanghai Institute of Technical Physics of CAS
Current assignee: Shanghai Institute of Technical Physics of CAS
Priority date: 2003-11-20
Filing date: 2003-11-20
Publication date: 2005-07-27
Anticipated expiration: 2023-11-20
Also published as: CN1544324A

Abstract

The present invention discloses a preparation method for material of silicon dioxide aerogel thin films, which is realized by combining a sol-gel technology of acid catalysis and base catalysis with an organic silanization process of colloidal particles and using chemical additives. The method of the present invention has the advantages that prepared precursor solutions can be stored for more than 9 months due to stable performance; prepared aerogel thin films are beneficial for commercial applications due to low cost; the prepared aerogel thin films can be used for insulating layers with a low dielectric constant and high efficiency heat-insulating layers of integrated devices due to a high pore rate.

Description

The silica aerogel preparation methods

Technical field

The present invention relates to a kind of porous oxide aerogel film material, specifically be meant a kind of silica aerogel preparation methods.

Background technology

Aerogel is the nano-meter porous amorphous solid material of a kind of novel lightweight, has characteristics such as nanostructure is controlled, specific refractory power is adjustable, specific surface area is big, is present specific refractory power minimum, and variable range is very big, the solid material that thermal conductivity, acoustic propagation velocity are extremely low.Aerogel has almost been inherited all excellent specific properties of block aerogel material, it can be used as wide band antireflective, Anti Glare Coatings, the thermal insulation layer, the specific acoustic resistance coupling material, low dielectric constant, and the very high speed integrated circuit substrate etc., therefore have broad application prospects in fields such as optics, calorifics, acoustics, electricity.

Sol-gel process is to prepare one of the most frequently used method of aerogel film material.Yet common sol-gel technology is in the drying process of film, and the capillary tension that the volatilization of hole internal solvent is caused will cause membrane structure to shrink, subside.Therefore membrane structure densification, the hole ratio of this method preparation are extremely low, are the xerogel film, do not possess the excellent specific property of aerogel.Then, people have invented supercritical process again, and the surface tension of eliminating the membrane pores internal solvent by high temperature, high pressure improves hole ratio.Yet, this method complex process, with high costs, the high temperature in the course of processing, high pressure have potential danger, and the discontinuity of film preparation is very restricted its practical application.In recent years, utilize the surface modification method of group under normal pressure, to prepare aerogel and obtained breakthrough, by the activity hydroxy on the alternative micelle surface of inactive alkyl, realize the structure bounce-back of film in drying process, and then keep the original vesicular structure of gel-film.The technological thought of this structure bounce-back has brought dawn for the commercial applications of aerogel, specifically consults UnitedStates Patent 5,948,482.But precursor solution instability, easily layering with this method obtains cause technology to repeat difficulty.

Summary of the invention

It is simple to the objective of the invention is to propose a kind of working method, and the synthetic precursor solution is stable, the silica aerogel preparation methods that the material hole ratio is high.

For achieving the above object, the present invention passes through to adopt the organic-silylation process of the sol-gel technology of acid/alkali two-step catalysis in conjunction with micelle, and realize at room temperature can stablizing the precursor sol of depositing more than 9 months by chemical additive, and under atmospheric environment the silica aerogel of preparation high hole rate.

Its concrete preparation process is as follows:

1. the preparation of precursor solution

Acid/alkali two-step catalysis method: the first step, with tetraethoxy (Si (OC ₂H ₅) ₄), deionized water (H ₂O), dehydrated alcohol (CH ₃CH ₂OH) and hydrochloric acid (HCl) mixed in molar ratio of pressing 0.8-1.2: 1.0-1.5: 3.5-4.5: 0.0005-0.0009, adopt heating in water bath 50-70 ℃ of following hydrolysis/condensation reaction 80-100 minute and constantly stir;

Second step is with dehydrated alcohol, ammoniacal liquor (NH ₄OH) and the mixed solution of deionized water slowly join in the above-mentioned solution, the mol ratio that makes tetraethoxy, deionized water, dehydrated alcohol, hydrochloric acid and ammoniacal liquor is 0.8-1.2: 3-4: 35-40: 0.0005-0.0009: 0.0016-0.0022, whole solution at room temperature stirred 25-35 minute, placed 50-60 ℃ thermostat container to wear out and gel 80-100 hour then.

The organic-silylation process of micelle: at first, clean the gel that obtains by aforesaid method with soaked in absolute ethyl alcohol, time 2-4 hour, to remove unnecessary material such as disacidify/alkaline catalysts; Then, soak the dehydrated alcohol that gel was replaced in the gel network structure in 3-5 hour with normal heptane; Then, gel is dipped in the finishing of carrying out silanization in the n-heptane solution that contains 4-7% trimethylchlorosilane volume ratio, the time is 18-24 hour; At last, use normal heptane soaking and washing 1.5-2.5 hour, remove the by product in the Silanization reaction process.Above soaking and washing and silanization process are all carried out in 50-60 ℃ thermostat container.

To adopt the normal heptane dilution through the gel behind soaking and washing and the silanization, the volume ratio of gel and normal heptane is 1: 0.7-0.9, and add an amount of stablizer, the volume ratio of gel and stablizer is 1: 0.5-0.6, with ultrasonic instrument it is carried out ultrasonicly shaking brokenly, make it become mobile colloidal sol, ultrasonic power is 200-250W, time is 20-30 minute, and this colloidal sol can at room temperature be stablized and deposits more than 9 months.

Said stablizer is methyl ethyl diketone (CH ₃COCH ₂COCH ₃).

The preparation of 2 thin-film materials

Adopt the spin-coating method plated film, substrate is a monocrystalline silicon piece.Rotating speed is 1500-4000 rev/min, and the time is 20-30 second, and the film after the spin coating was through 400-500 ℃ of slow annealing 60-80 minute, and intensification and rate of temperature fall are 5-10 ℃/minute.Repeat the aerogel that said process can make desired thickness.

The SiO of the inventive method preparation ₂Aerogel film material has following effect:

1. Pei Zhi precursor solution stable performance can be deposited more than 9 months;

2. Zhi Bei aerogel cost is low, helps commercial applications;

3. Zhi Bei aerogel hole ratio height can be used for the low dielectric constant and the effectively insulating layer of integrated device.

Description of drawings

Fig. 1 is the SiO of the inventive method preparation ₂The type looks figure of aerogel, a figure are surface type looks figure, and b figure is the section type looks figure of aerogel.

Specific implementation method

Embodiment

1.SiO ₂The preparation of precursor solution

The 0.1 milliliter of hydrochloric acid that is 1 mol with 30.5 milliliters of tetraethoxys, 30.5 milliliters of dehydrated alcohol, 2.4 ml deionized water and concentration adds in the flask successively, stirring at room 30 minutes, and 60 ℃ of heating in water bath are 90 minutes then.Get 10 milliliters of above-mentioned solution, add 1 milliliter of ammoniacal liquor that 44 milliliters of dehydrated alcohols and concentration are 0.05 mol, stirring at room 30 minutes.Place 50 ℃ thermostat container to wear out and gelation 96 hours whole solution.

The gel that is obtained by aforesaid method cleaned 3 hours with soaked in absolute ethyl alcohol earlier, soaked 4 hours with normal heptane then, then gel is soaked in that to contain the trimethylchlorosilane volume ratio be in 5% the n-heptane solution 20 hours, uses normal heptane soaking and washing gel 2 hours at last.Above process is all carried out in 50 ℃ thermostat container.At last, with the mixed solution sonic oscillation dilution gel of the methyl ethyl diketone of 40 milliliters normal heptanes and 30 milliliters, ultrasonic power 250W, ultrasonic time 25 minutes can become the mobile colloidal sol that is suitable for film preparation.

2.SiO ₂The preparation of aerogel

Adopt spin-coating method to prepare SiO ₂Aerogel.Get SiO with glue head dropper ₂About 0.5 milliliter of precursor solution drops on the substrate of rotation, and rotating speed is 2000 rev/mins, 20 seconds time.To obtain gel-film and place a slow annealing stove, and anneal 60 minutes for 450 ℃, intensification and rate of temperature fall are 8 ℃/minute.Repeat said process and obtain the desired thickness film.

3. material is identified

The SiO of present method preparation ₂The type looks figure of aerogel sees Fig. 1, and a figure is surface type looks figure, and b figure is the section type looks figure of aerogel.

Performance perameter is as follows:

Specific refractory power 1.06-1.08;

Hole ratio 85-89%;

Thermal conductivity (Wm ^-1K ^-1) (during 300K) 0.019-0.025;

Specific inductivity 1.46-1.54.

Claims

1. silica aerogel preparation methods is characterized in that this preparation method in turn includes the following steps:

A. the preparation of precursor solution

The first step, tetraethoxy, deionized water, dehydrated alcohol and hydrochloric acid are pressed 0.8-1.2: 1.0-1.5: 3.5-4.5: the mixed in molar ratio of 0.0005-0.0009, adopt heating in water bath in 50-70 ℃ of following hydrolysis/condensation reaction 80-100 minute and constantly stirring;

Second step, the mixed solution of dehydrated alcohol, ammoniacal liquor and deionized water is slowly joined in the above-mentioned solution, the mol ratio that makes tetraethoxy, deionized water, dehydrated alcohol, hydrochloric acid and ammoniacal liquor is 0.8-1.2: 3-4: 35-40: 0.0005-0.0009: 0.0016-0.0022, whole solution at room temperature stirred 25-35 minute, placed 50-60 ℃ thermostat container to wear out and gel 80-100 hour then;

Then, clean the gel that obtains by aforesaid method, time 2-4 hour with soaked in absolute ethyl alcohol; Soak the dehydrated alcohol that gel was replaced in the gel network structure in 3-5 hour with normal heptane again; Then, gel is dipped in the finishing of carrying out silanization in the n-heptane solution that contains 4-7% trimethylchlorosilane volume ratio, the time is 18-24 hour; At last, use normal heptane soaking and washing 1.5-2.5 hour; Above process is all carried out in 50-60 ℃ thermostat container;

To adopt the normal heptane dilution through the gel behind soaking and washing and the silanization, the volume ratio of gel and normal heptane is 1: 0.7-0.9, and add an amount of stablizer, the volume ratio of gel and stablizer is 1: 0.5-0.6, with ultrasonic instrument to its carry out ultrasonic shake broken, make it become mobile colloidal sol, ultrasonic power is 200-250W, and the time is 20-30 minute;

B. the preparation of thin-film material

Adopt the spin-coating method plated film, substrate is a monocrystalline silicon piece, and rotating speed is 1500-4000 rev/min, time is 20-30 second, film after the spin coating was through 400-500 ℃ of slow annealing 60-80 minute, and intensification and rate of temperature fall are 5-10 ℃/minute, repeated the aerogel that said process can make desired thickness.

2. according to a kind of silica aerogel preparation methods of claim 1, it is characterized in that: said stablizer is a methyl ethyl diketone.