JP2685121B2 - Functional ceramic film and method for manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a functional ceramics film having pores with uniform pore diameters on its surface, and the pore diameters changing from the surface to the inside, and a method for producing the same. It is a thing.

[0002]

2. Description of the Related Art Heretofore, as a ceramic material having voids and pores, that is, a ceramic porous material,
1) A powder containing internal pores such as zeolite or silica gel, 2) A sintered body such as alumina porcelain or a glass filter produced by sintering powder having pores, 3) A glass is produced by chemical treatment or perforation Porous glass, 4) fiber aggregates such as glass fiber and potassium titanate fiber,
5) Foams such as foam glass and cellular concrete are known (Yanagida Hiroaki, "Science of Ceramics", Gihodo Shuppan, p109 (1981)). However, these are all bulk materials, and the production of porous films of ceramics, especially porous thin films, has conventionally been very difficult, and it has been almost impossible to produce porous thin films having pores with uniform pore sizes. . Also,
There are also methods such as PVD, CVD, and sputtering, and methods of anodizing metal, but these methods are costly, and it is difficult to make a large area,
There have been problems such as difficulty in controlling the pores, limited useable metals, and limited ceramics that can be manufactured. Further, no production of a functional ceramics film having pores with uniform pore diameters on the surface and the pore diameters changing from the surface to the inside has been performed at all.

[0003]

In view of the above points, the present invention has a surface having pores with uniform pore diameters, and the pore diameters change from the surface to the inside, and the catalyst, the catalyst carrier, and the adsorption. It is an object of the present invention to provide a functional ceramic film having excellent properties as a material, a deodorizing / deodorizing material, a sustained release material, and the like, and a simple and economical method for producing the functional ceramic film.

[0004]

Means for Solving the Problems The present inventor has conducted extensive studies in order to achieve the above object. As a result, a sol solution of ceramics to which polyethylene glycol or polyethylene oxide having different molecular weights is added is sequentially coated on a substrate. Then, by heating and baking, or coating the sol solution of ceramics with different amounts of polyethylene glycol glycol or polyethylene oxide added to the substrate in order, by heating and baking, have pores with a uniform pore size on the surface, It was found that a functional ceramics film whose pore diameter changes from the surface to the inside can be produced, and the present invention has been completed.

[0005] The sol solution of ceramics used in the present invention can be prepared by suspending ultrafine ceramics in water, hydrolyzing alkoxides of metals obtained by the reaction of alcohols with metal salts or metals, or the like. It is prepared by hydrolyzing a metal salt dissolved in an alkoxide. At that time, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,
Addition of alcohol amines such as N-dimethyldiaminoethanol or diisopropanolamine or glycols such as diethylene glycol gives a uniform and transparent titania sol, and by using it, a functional ceramic film having excellent durability can be produced. You can

As the metal alkoxide for preparing the ceramic sol solution used in the present invention, all metal alkoxides are used.
B, Ba, Ca, Cd, Ce, Co, Cr, Cu, F
e, Ge, Hf, In, Li, Mg, Mn, Mo, N
b, Ni, P, Pb, Ru, Si, Sn, Sr, Ta,
Alkoxides of Ti, V, W, Y, Zr and alkoxides of mixtures thereof can be mentioned. Examples of the metal salts include organic acid salts of these metals, such as acetate, oxalate, 2-ethylhexanoate, stearate, lactate, and acetyl acetate.

The functional ceramic film of the present invention is a liquid prepared by adding polyethylene glycol or polyethylene oxide having different molecular weights to the ceramic sol solution thus obtained, or the addition amount of polyethylene glycol or polyethylene oxide is changed. Liquid is dip coating method or spin coating method,
It is obtained by sequentially coating the substrate by a coating method, a spray method, etc., and heating and baking. On this occasion,
When the substrate is coated in order such that the molecular weight or the addition amount of polyethylene glycol or polyethylene oxide increases and then heated and baked, it has pores with uniform pore diameters, and the pore diameters increase from the surface to the inside. It is possible to obtain a functional ceramics film that becomes smaller, that is, a functional ceramics film in which the pore diameter becomes larger toward the surface. On the contrary, when the substrate is coated in the order that the molecular weight or the addition amount of polyethylene glycol or polyethylene oxide is decreased and the mixture is heated and baked, it has fine pores with uniform pore diameter, and the pore diameter is It is possible to obtain a functional ceramics film that increases from the surface to the inside, that is, a functional ceramics film whose pore size decreases toward the surface.

Further, it is desirable that the heating and firing at that time be performed by gradually heating and raising the temperature from room temperature. To obtain a functional ceramic film that is durable and has excellent durability,
A thin film is formed by applying or spraying or spin-coating the ceramic sol solution to which polyethylene glycol or polyethylene oxide is added thinly and uniformly, or by dipping it at a slower pulling rate and pulling it up, then heating and baking it. It is desirable to produce a multilayer film by repeating the operation. As a result, it is possible to obtain a functional ceramic film that is thick, durable, and excellent in durability. At this time, by mixing and hydrolyzing two or more kinds of metal alkoxides, or by dissolving and hydrolyzing a salt of another metal in the metal alkoxide, the porous film of the composite oxide can be obtained. It can be manufactured. Further, by using two or more kinds of sol solutions and coating them alternately or sequentially, a multilayer film of different kinds of ceramics can be easily manufactured.

The polyethylene glycol or polyethylene oxide to be added to the ceramic sol solution used in the present invention preferably has a molecular weight of 1000 or more, and among them, the molecular weight is particularly 1000, 1500, 2
000, 3000, 6000, 8000, 11000,
13,000, 20,000, 100,000, 300,000, 2,000,000, 250
Thousands are preferred. When a molecular weight of less than 1000 is used, the finished functional ceramic film is likely to be peeled from the substrate, and a clean and durable film cannot be obtained.

The amount of polyethylene glycol or polyethylene oxide added to the ceramic sol solution used in the present invention is preferably less than its solubility. When added in excess of the solubility, the pores do not become uniform in size and a clean film cannot be formed.

The size of the pore diameter and the density of the pore distribution of the functional ceramic film of the present invention can be controlled by changing the addition amount or the molecular weight of polyethylene glycol or polyethylene oxide. When the amount of addition is small or when the one with a small molecular weight is used, the functional ceramic film with small pores is uniform, and when the addition is large or one with a large molecular weight is used, the large pores are formed. A uniform functional ceramics film can be obtained. When the added amount is small, a functional ceramics film having a fine pore distribution density is obtained, and when the added amount is large, a functional ceramics film having a fine pore distribution is obtained. Further, when polyethylene glycol or polyethylene oxide having a wide molecular weight distribution is added, a functional ceramic film in which pores of various pore sizes are mixed can be obtained.

The substrate used for producing the functional ceramics film of the present invention is glass, ceramics, concrete, metal, etc., as long as it can withstand the firing temperature.
Any material may be used. Also, its shape is plate-like,
It may have any shape such as a cylindrical shape, a prismatic shape, a conical shape, a spherical shape, a gourd shape, and a rugby ball shape. Also. The substrate may have a closed shape, may or may not have a lid, and may have a circular or square tubular shape, a fiber shape, or a hollow spherical shape such as a microballoon.

The thus-obtained functional ceramic film according to the present invention has excellent durability and is porous, and thus is suitable as a catalyst, a catalyst carrier, an adsorbent material, a deodorizing / deodorizing material, a sustained-release material and the like.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Among the embodiments of the present invention, particularly representative ones will be described below.

Example 1 0.1 mol of titanium tetraisopropoxide was added to 200 m.
It was diluted with 1 l of absolute ethanol, and 0.1 mol of diethanolamine and 0.1 mol of water were added with stirring.
Polyethylene glycol having a molecular weight of 2000, 6000, 11000, 20,000 and polyethylene oxide having a molecular weight of 100,000, 2 million were added to each of these to prepare 6 kinds of transparent sol solutions, and a length of 5 cm was prepared by a dip coating method. The surface of an aluminum plate having a width of 3 cm and a thickness of 1 mm was coated with three layers in this order. That is, the aluminum plate is immersed in this sol liquid and pulled up,
After drying, it was baked. This was repeated 3 times for a total of 18 times to form a 720 nm titania film on the surface of the aluminum plate. When the surface of the obtained titania film was coated, it was observed with an electron microscope.
0nm, 80nm, 150nm, 400nm, 900n
m of pores. The distribution of the pores was sparse in this order.

Example 2 0.1 mol of aluminum triisopropoxide was added to 20 mol.
Dilute with 0 ml of isopropanol, add 0.1 mol of triethanolamine and 0.1 mol of water with stirring, and add to it a molecular weight of 13,000, 8000, 3000,
Four kinds of transparent sol liquids were prepared by adding 3 g of 1000 polyethylene glycol each. Then, in the same manner as in Example 1, a total of 16 layers of 4 layers in this order were coated on the surface of a quartz glass plate of 2 cm square and 1 mm in thickness by a dip coating method to form an alumina film having a thickness of 660 nm. When the surface of the obtained film was observed with an electron microscope each time it was coated, it was found that the substrate was approximately 70 nm, 50 nm
It was covered with 30 nm and 10 nm size pores.

EXAMPLE 3 50 mol of 0.2 mol of zirconium tetra-n-butoxide was used.
After diluting with 0 ml of absolute ethanol and adding 0.4 mol of diethylene glycol and 0.4 mol of water while stirring, 0.6 g of polyethylene glycol having a molecular weight of 3000 and 0.5 g of polyethylene glycol of 6000 were added.
g, 20,000 polyethylene glycol 0.4 g was added to prepare three kinds of transparent sol liquids. Then, in the same manner as in Example 1, a total of 21 layers of 7 layers in this order, 21 layers in total, were coated on the surface of the quartz glass plate of 2 cm square and 1 mm in thickness by the dip coating method to obtain a thickness of 900
A zirconia film of nm was made. When the surface of the obtained film was observed with an electron microscope each time it was coated, it was about 28 in order from the side closer to the quartz glass plate of the substrate.
It was covered with pores having sizes of 0 nm, 320 nm, and 350 nm, and the distribution of pores was sparse in this order.

Example 4 0.1 mol of titanium tetraisopropoxide and 0.1 mol of zirconium tetra n-butoxide were added to 500 ml of isopropanol, and 0.4 mol of diisopropanolamine and 0.4 mol of water were added with stirring. Polyethylene glycol 2 with a molecular weight of 3000
g and 4g, molecular weight 5000 polyethylene glycol 2
g and 4 g were added to prepare four kinds of transparent sol liquids.
Then, in the same manner as in Example 1, a total of 20 layers of 5 layers were coated in this order on the surface of a stainless plate having a length of 7 cm, a width of 3 cm, and a thickness of 1 mm by a dip coating method to form a total of 20 layers of zirconium titanate of 800 nm. Made a membrane. Each time the surface of the obtained film was coated, it was observed with an electron microscope. As a result, the substrate was closer to the stainless steel plate in order of about 15 nm, 30 nm, 50 nm,
It was covered with pores with a size of 90 nm.

Example 5 0.1 mol of titanium tetraisopropoxide and lead acetate
0.1 mol of trihydrate is added to 250 ml of isopropanol, and while stirring, 0.2 mol of diethanolamine is added.
And 0.6 mol of water were added. Molecular weight 2000,
20,000 polyethylene glycol, molecular weight 200,200
Each of 1.6 g of 10,000 polyethylene oxide was added to prepare four kinds of transparent sol liquids. And Example 1
Similarly to the above, a total of 28 layers of 7 layers in this order were coated on the surface of a heat-resistant glass plate of 2 cm square and 1 mm in thickness by a dip coating method to form a total of 28 layers of lead titanate having a thickness of 2200 nm. Each time the surface of the obtained film was coated, it was observed with an electron microscope.
It was covered with pores having a size of 0 nm, 500 nm, and 1000 nm. The distribution of the pores was sparse in this order.

Example 6 0.2 mol of niobium pentaethoxide was diluted with 500 ml of absolute ethanol, and 0.4 mol of N-ethyldiethanolamine and 0.4 mol of water were added with stirring. Add 0.1 g, 0.5 g, 1 g, 1.5 g and 2 g of polyethylene oxide having a molecular weight of 100,000 to obtain 5
Different types of transparent sol solutions were prepared. Then, in the same manner as in Example 1, a total of 45 layers of 9 layers were coated in this order on the surface of a quartz glass plate having a size of 2 cm and a thickness of 1 mm by a dip coating method to form a porous thin film of niobium oxide having a thickness of 2000 nm. Had made. The surface of the obtained film was observed with an electron microscope each time it was coated.
It was covered with pores having sizes of nm, 700 nm, 800 nm and 900 nm.

Example 7 Zirconium tetra-n-butoxide (0.1 mol) and lead acetate / trihydrate (0.1 mol) were added to 500 ml of isopropanol, and 0.2 m of diethanolamine was added with stirring.
and 0.6 mol of water were added. This has a molecular weight of 20,000,
Four kinds of transparent sol liquids were prepared by adding 0.1 g of 100,000, 300,000 and 2 million polyethylene oxides respectively. Then, in the same manner as in Example 1, a total of 40 layers of 10 layers were coated in this order on the surface of a quartz glass plate of 2 cm square and 1 mm thick to form a lead zirconate film having a thickness of 1600 nm. It was When the surface of the obtained film was observed with an electron microscope each time it was coated, it was found that the substrate was closer to the quartz glass plate in order of about 100 nm, 300 nm, 500 nm,
It was covered with pores having a size of 1100 nm, and the distribution of pores was sparse in this order.

Example 8 0.1 mol of titanium tetraisopropoxide, 0.1 mol of zirconium tetra-n-butoxide and 0.2 mol of lead acetate trihydrate were added to 500 ml of isopropanol, and 0.4 mol of diethanolamine and water were added with stirring. 1.2 mol was added. 0.3 g of polyethylene oxide having a molecular weight of 200,000, 0.25 g, 0.2
g, 0.15 g, and 0.1 g were added to prepare 5 kinds of transparent sol liquids. Then, in the same manner as in Example 1, a total of 25 layers of 5 layers in this order were coated on the surface of a quartz glass plate having a size of 2 cm and a thickness of 1 mm by a dip coating method in total of 25 layers, and a film of lead zirconate titanate having a thickness of 1000 nm was formed. made. When the surface of the obtained film was observed with an electron microscope each time it was coated, it was found that the substrate was approximately 900 nm, 850 nm, 800 n
m, 750 nm, 700 nm.

[0023]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a functional ceramic film having pores with uniform pore diameters, the pore diameters of which change from the surface toward the inside, and a simple and economical method for producing the same. The purpose is to provide. A sol solution of ceramics to which polyethylene glycol or polyethylene oxide having different molecular weights is added, or a sol solution of ceramics to which polyethylene glycol or polyethylene oxide is added in different amounts is coated on a substrate in order, and a simple method of heating and baking, It is possible to manufacture a functional ceramics film that has pores with uniform pore diameters, and the pore diameter changes from the surface to the inside. By varying the addition amount of polyethylene glycol or polyethylene oxide, the distribution density of pores can be increased. It can be controlled easily. According to this method, it is possible to fabricate a nano-order ceramic porous film whose pore diameter changes from the surface to the inside, which is impossible with the conventional method, and the pore size is as desired. It is possible to produce a ceramic porous film having a sheath distribution density. Then, two or more kinds of metal alkoxides are mixed and hydrolyzed, a salt of another metal is dissolved in the metal alkoxide to be hydrolyzed, and two or more kinds of sol solutions are used. This makes it possible to easily manufacture a porous thin film of a composite oxide or a multilayer film of different ceramics. Furthermore, this method requires a lower sintering temperature than conventional methods, and is therefore energy saving and economical. The obtained functional ceramic film has excellent heat resistance and durability, is suitable for catalysts, catalyst carriers, adsorbent materials, deodorizing / deodorizing materials, sustained-release materials, etc., and can be applied to a wide range of fields. The ripple effect is great. In particular, if the pore size decreases from the surface to the inside, it is used as an adsorbent for molecules of various sizes, and if the pore size increases from the surface to the inside, the fragrance or drug is gradually released. It is useful as a sustained release material.

Claims (6)

(57) [Claims] 1. A functional ceramics film having pores of uniform pore diameter, the pore diameter varying from the surface to the inside. 2. The functional ceramic film according to claim 1, wherein the pores have a diameter of 1 nm to 2 μm. 3. A method for producing a functional ceramics film, which comprises sequentially coating a substrate with a sol solution of ceramics to which polyethylene glycol or polyethylene oxide having different molecular weights are added, followed by heating and baking. 4. A method for producing a functional ceramics film, which comprises sequentially coating a substrate with a sol solution of ceramics having different amounts of polyethylene glycol or polyethylene oxide added thereto, followed by heating and baking. 5. The method for producing a functional ceramic film according to claim 3, wherein polyethylene glycol or polyethylene oxide having a molecular weight of 1000 or more is used. 5. The method for producing a functional ceramic film according to claim 3, wherein the amount of polyethylene glycol or polyethylene oxide added to the ceramic sol solution is not more than its solubility. 6. The ceramic sol solution is prepared from a ceramic alkoxide and alcohol amines or glycols.
And the method for producing the functional ceramics film according to 4.