JPS62235246A - Refractory fiber assembly and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention 88 [Field of Industrial Application] The present invention relates to a fiber aggregate made of fibers of a fire-resistant compound and a method for producing the same.

[Conventional technology]

Fiber aggregates made of refractory compounds are used in heat-resistant filters, chemical-resistant filters, catalyst carriers, etc. in order to take advantage of the heat resistance, corrosion resistance, and strength that are the inherent characteristics of refractory compounds. For example, the Journal of Industrial
Fabricoff (Journalof Industry)
New Fibers and Fabrics, Vol. 44-48, New Fibers and Fabrics
s in Ilotgas Fabrics Fil
The effectiveness of refractory fiber aggregates as high-temperature dust collecting filters is described in 2.

Several proposals have been made for fibers of fire-resistant compounds, fiber aggregates made of the fibers, and methods for producing them. For example, JP-A-49-35627 and JP-A-50-12335 disclose continuous filaments/short fibers and methods for producing the same. The fiber consists of a refractory crystalline oxide inner layer (core) and a glassy outer layer (sheath). Fiber aggregates made of these fibers have high strength and can be used simply in a straight line or when bent at a very small curvature. It is difficult to bend and use it. Therefore, in the manufacturing process of textiles, for example, the fibers are bent by guides, reeds, etc. during warping, causing the fibers to be cut. Furthermore, resins such as epoxy,
Even if fire-resistant fibers are protected and used with an oil agent, the problems in the process can be solved to some extent, but in terms of wood quality, the fabric must have a relatively simple structure and bends with small curvature. I couldn't weave it. Furthermore, knitted fabrics have a larger curvature than woven fabrics, so they can only be used as insert yarns. Similarly, when used in the form of a non-woven fabric, the fibers were cut due to the manufacturing method and the intertwined state of the fibers, and the strength of the fabric was not utilized. Similar results were obtained for spun yarn. As mentioned above, when using the above-mentioned refractory fiber aggregate, there is a drawback that its strength cannot be utilized effectively unless it is used in a straight line or bent with a small curvature.

US Pat. No. 3,385,915 discloses a method for producing a refractory oxide by impregnating an organic fiber aggregate with a metal compound and firing the impregnated organic fiber aggregate. Also, special public service 1976-9
No. 897 discloses that organic fiber aggregates are impregnated with a metal compound, and in the final stage of the firing atmosphere, nitrides are produced by contacting with a nitrogen-containing compound that forms a nitrogen compound. A method is disclosed in which a carbide is produced by impregnating a fiber aggregate with a metal compound and adjusting the firing atmosphere. In the above method, a complex fiber aggregate can be obtained because flexible organic fibers are used, but the method has a drawback that the strength, particularly the compressive strength, is very low.

[Problem that the invention seeks to solve]

An object of the present invention is to solve the problems of the prior art as described above, and to provide a refractory compound fiber assembly made of refractory compound fibers and having high compressive strength.

[Means for solving problems]

The above-mentioned problem is a fiber aggregate composed of fibers of a refractory compound, and the fibers have a two-layer structure consisting of an inner layer of a refractory crystalline compound and a refractory crystalline compound different from the crystalline compound. and the compressive strength of the fiber aggregate is 0.3 to 5.
The present invention is solved by a refractory fiber aggregate characterized in that the fibers are 0.00 for/-.

This refractory fiber aggregate is made by absorbing or reacting a precursor substance of the refractory compound into a fiber aggregate composed of organic fibers, and absorbing or reacting the precursor substance.
The fiber aggregate is fired in a controlled firing atmosphere to produce a fiber aggregate made of fibers of a refractory crystalline compound, and then a refractory compound different from the refractory compound or its precursor substance is added to the fiber aggregate. It is manufactured by coating the fibers constituting the fibers and then firing the coated fiber aggregate in a controlled atmosphere.

Examples of the organic fibers used for producing the fire-resistant compound fiber aggregate of the present invention include cellulose fibers, polyamide fibers, polyester fibers, polyacrylic fibers, polyolefin fibers, and polyurethane fibers. Among these, cellulose fibers are preferred. The fibers may be in the form of short fibers, long fibers, or a combination of both. Furthermore, the aggregate of organic fibers may be a knitted fabric, a woven fabric, or a nonwoven fabric.

The diameter of the fibers forming the fiber aggregate (fibers with a non-circular cross section is expressed as the diameter when the cross-sectional area is a circular cross-sectional area) is 1 μm to 5 μm.

If the diameter is larger than 5111, adsorption and reaction of the refractory compound to the fibers may not be uniform, or it will take a long time to achieve uniformity, which is not practical.

In addition, if it is thinner than 1 μm, it will be easily affected by the drying process after adsorbing and reacting the precursor of the refractory compound.
Fiber breakage is likely to occur.

The refractory compounds forming the inner layer (core) of the fibers constituting the refractory compound fiber aggregate of the present invention include BeO, Mg
O, CaO, SrO, BaO, 5C20z + YzO
+Y20z , LazOz l Cez031 Tl
0z + Zr0z 1)1fOz +V2O5+
NbzOi + NbzOs + Tag's + C
rzO= l 5iOz+MoO3, WO3, Mn0z
+ FezO3+ C0z(h + N1zO+ +
CuO, ZnO, CdO + Al2O:l + Caz
O+ + 5n021 pbo.

5bz03 + Th0z + 00. , Pu03
oxides such as TiC9) TFC, VC, NbC, T
aC+ Cr1C, + MozC, MoC.

WzC, WC, IC, UCz, ThC, ThCz
, PbC.

Carbides such as PbC2, B4C, 81acz + SiC, Si3N*.

Examples include nitrides such as AIN and BN.

The precursor substances for these refractory compounds are not particularly limited as long as they can be converted into these refractory compounds by heating. Inorganic compounds such as chlorides, hydroxides, sulfates, nitrates, basic hydrochlorides, basic sulfates, basic nitrates, ammonium salts, and organometallic compounds such as metal halides, metal oxyhalides, and silane compounds. ,
used. For example, inorganic compounds include aluminum chloride, basic aluminum chloride, basic aluminum nitrate, stannous chloride, tin chloride, zirconium tetrachloride,
Examples include zirconium oxychloride, yttrium chloride, titanium trichloride, nickel chloride, magnesium chloride, calcium chloride, and ammonium borate. Examples of organometallic compounds include silane compounds such as basic ammonium acetate, basic aluminum lactate, tributyltin acetate, aluminum acetate, zinc acetate, trimethylchlorosilane, and trimethoxymethylsilane, and aluminum compounds such as polyaluminoxane. .

In addition, two or more types of the above-mentioned fire-resistant compounds may constitute the inner layer of the fiber, and in this case, two or more types of compounds may form a compound or a solid solution.

In order to form a fiber aggregate made of fibers of a refractory compound, first, a precursor substance of the refractory compound is adsorbed or reacted with the organic fiber aggregate. The method is to apply the precursor material in an aqueous solution or in the form of a solution in J11 solvent. Further exposure to vapors of the precursor material may be performed. The method itself is not particularly limited as long as it is a method in which a large amount of the refractory compound is retained by adsorption or reaction on the organic fiber aggregate. Before applying the solution of the precursor material of the refractory compound, it can optionally be pretreated with a swelling agent in order to increase the absorption rate and/or amount of the precursor material. For example, cellulosic fibers are swollen prior to being immersed in an absorbing solution of a precursor material for a refractory compound.

Excess refractory compound precursor material solution is then removed from the fiber surface using known means such as centrifugal dehydrators, filter paper, suction dehydrators, and the like. Furthermore, the fiber assembly is dried to remove the solvent. Drying methods include hot air drying,
Examples include vacuum drying. Preferred methods and conditions may be selected depending on the properties of the fiber, the refractory compound precursor material, and the solvent.

The amount of precursor material applied to the organic fibers depends on the amount of absorption or reaction by the organic fibers. It also depends on the properties of the constituent materials and precursor materials of the organic fiber.

For example, if the concentration of the precursor substance becomes high, it may dissolve or decompose, making it impossible to maintain the form of the organic fiber aggregate, which is determined by the relationship between the organic fibers and the precursor substance. Generally, the amount of the refractory compound precursor is 10 weight percent or more and 300 weight percent or less of the weight of the organic fiber. In general, if the amount is less than 10% by weight, strength becomes a practical problem because the amount of precursor material that forms the refractory compound fiber after firing the organic fiber and decomposing and removing the organic fiber is small. For example, if a cellulose fiber aggregate is immersed in a 5% by weight aluminum chloride aqueous solution at room temperature for 50 hours, dehydrated in a centrifugal dehydrator, dried in a hot air dryer, and fired, the aluminum oxide fiber aggregate is However, since the amount of aluminum oxide that makes up the fibers is small, the strength of the fired product is very low. In addition, if the amount exceeds 300% by weight, the flexibility of the organic fibers will be lost, resulting in very poor handling properties.
Become. For example, by repeating the treatment steps of immersing a cellulose-based fiber aggregate in an aqueous solution of stannic chloride, washing with water, further immersing it in an aqueous solution of disodium hydrogen phosphate, and washing with water,
As a compound of tin, sodium, and phosphorus, the weight can be increased by about 430% compared to the original fiber weight.
A fiber aggregate with such a large weight increase lacks flexibility and becomes extremely brittle, resulting in very poor handling properties.

Next, the fiber aggregate is fired. Heating may be performed at a rate of temperature increase that does not ignite the organic matter. The firing atmosphere may be air, nitrogen, ammonia, hydrogen, helium, argon, neon, vacuum, under pressure, etc. as long as it meets the conditions for producing known refractory compounds. A mixture of more than one type of atmospheric gas may be used.

For example, in the case of an oxide, a method may be used in which heating is performed in an inert atmosphere in the initial stage of firing, and firing is performed in an oxidizing atmosphere in the latter half. In the case of nitrides, the firing may be carried out under an oxidizing atmosphere at the initial stage of firing, and at the final stage under an atmosphere of nitrogen-containing compounds (nitrogen gas, ammonia, organic amines, etc.). In the case of carbide, an oxidizing atmosphere may be used in the initial stage of firing, and an inert atmosphere may be used in the final stage.

Firing conditions such as heating temperature and heating time are set so that the organic matter is decomposed and removed and the fiber aggregate of the refractory compound is given sufficient strength to be handled in subsequent steps. For example, the heating temperature is 600°C to 800°C for SnO□,
For l2O, it is around 700°C, for ZrO□ it is 600°C ~
The temperature is 800°C. 1300'c~140 for Si3N4
At 0℃AIN, it is around 1200℃, and for SiC, it is 1400'
It is around C.

The refractory compound obtained as described above preferably has a diameter of 1 μm to 31111 μm (for fibers with a non-circular cross section, this is the diameter when the cross section is circular). In order to obtain a refractory compound with a diameter larger than that of the 3 dragons, it is necessary to use organic fibers with a fiber diameter of 51 mm or more, and with such thick fibers, the adsorption and reaction during the precursor treatment of the refractory compound cannot be uniformly performed. This creates a major drawback for refractory compound fibers.

Moreover, when the diameter becomes smaller than 1 μm, the strength of the fiber itself decreases, and the single fiber cannot withstand the treatment in the next step and breaks. Based on the above, the more preferable single fiber diameter of the refractory compound is 3 μm to 5 μm.

Further, the porosity of the refractory compound is 5% or more and less than 50%. It has been attempted to improve the strength of conventional fire-resistant compound fibers by reducing porosity and reducing fiber defects, but in the present invention, fire-resistant compound fibers with a certain degree of porosity The aim is to further improve tensile strength, tensile modulus, and compressive strength by filling a fire-resistant compound fiber inside the fiber and forming a fire-resistant crystalline compound coating on the fiber surface. It is said that When the porosity exceeds 50%, the strength of the refractory compound fiber is very low, and single fibers are likely to break during coating. On the other hand, if the porosity is less than 5%, the anchoring effect on the fibers will be small, and the crystalline coating of the film will act as a small rack, reducing the tensile strength, tensile modulus, and even compressive strength. From the above, the porosity is preferably 40% or less and 15% or more.

The fiber assembly is then coated with a refractory compound different from the refractory compound forming the inner layer, or a precursor thereof, or a mixture thereof.

In this specification, different refractory compounds, their precursor substances, or mixtures thereof include not only compounds with different chemical structures, but also compounds with the same chemical structure but with different crystal sizes. .

Refractory compounds to be coated include BeO, M
gO, CaO, SrO, BaO, 5CzOt, Y2
O.

YzO3, LazO3, CeO+, Cez031
Tio2, Zr0z.

HfO2, V2O5, Nb2O,, Nb2O3, Taz
Os, Crz03゜5tOz + MOO3+ 1
lI03+ MnO□+ Fe20s + COO3+
CO20:l, N1zO:+, CuO, ZnO
, CdO+ Al2O++ +CazOff, 5nO
z, PbO, 5b) BOff+ Th0z + [
Oxides such as IOi +Pup, TiC, HfC, VC
, NbC, TaC.

Crz':z + MO2C9MoCI LC, WC,
UC+ UCZ +ThC, ThCz, PbC, P
Examples include carbides such as bCz, B4C, and ^lac*1SiC, and nitrides such as 5iJa + AIN and BN.

The refractory compound to be coated, the precursor material of the refractory compound, or a mixture of both is different from the refractory compound constituting the fiber aggregate obtained as described above. Furthermore, it does not have to be a single refractory compound, but may be a mixture of two or more kinds. Furthermore, the refractory compound to be coated may form a solid solution with the refractory compound constituting the fiber aggregate. Further, it may or may not react. Furthermore, the coating agent may be in any form such as solid, liquid, or vapor upon coating, but preferably it should be in the form of particles with the size of molecules or colloid particles. Since most refractory compounds are insoluble in water, they can be easily applied as an aqueous dispersion of colloidal sized particles of the refractory compound. for example,
5in2゜AlzOl, Ti1t, 5nOz
+ Zr0z + MgO and PbO form a relatively stable dispersion under appropriate conditions (concentration, temperature, and particle size).

Precursors of refractory compounds are generally preferred that can conveniently and uniformly apply a coating to the fibers as a liquid or vapor.

As a precursor substance for a refractory compound, for example, basic aluminum lactate (AI(OH)3-x (LaC-Aci
d)
・C1・2H20), aluminum chloride, basic aluminum nitrate, basic aluminum acetate, chromium chloride 1.
Examples include chlorochromium hydroxide, zirconium tetrachloride, basic zirconium chloride, tin chloride, antimony chloride, yttrium chloride, monobasic aluminum phosphate, and other metal compounds.

When using a mixture of refractory compounds and precursor materials,
Unlike when used alone, the interaction between the refractory compound and the precursor material may lead to precipitation and failure to form a coating. Therefore, it is necessary to confirm the stability of the solution, and the refractory compound must be dispersed in the solution as a fine powder as much as possible. For this purpose, a dispersant or the like may be used.

Coating methods include exposure to a vapor of a refractory compound precursor, passing through a solution or dispersion of the refractory compound, a refractory compound precursor, or both, spray application, or coating. , coating with a gravure roll, or any other known method may be used. The appropriate coating method should be selected depending on the morphology of the refractory compound fiber aggregate.

Next, excess coating agent after coating is removed. This removal may be carried out by any method such as contacting with filter paper, centrifugal dehydration, suction dehydration, or scattering with compressed air.

After coating, heat drying is performed. The heating temperature is determined by the solvent and diluent used.

It is also possible to stack these coated refractory compound fiber aggregates and fire them.

To fire the coated refractory compound fiber aggregate, the atmosphere, firing temperature, and time are selected to be sufficient for the coated refractory compound or its precursor to transform into a refractory compound and crystallize. For example, the firing atmosphere may be air, nitrogen, ammonia, hydrogen, helium, argon, neon, or vacuum, as long as it meets the conditions for producing known refractory compounds.
A mixture of two or more types of atmospheric gases may be used. For example, in the case of an oxide, a method may be used in which heating is performed in an inert atmosphere in the initial stage of firing, and firing is performed in an oxidizing atmosphere in the latter half. In the case of nitrides, the firing may be carried out under an oxidizing atmosphere at the initial stage of firing, and at the final stage under an atmosphere of nitrogen-containing compounds (nitrogen gas, ammonia, organic amines, etc.). In the case of carbide, the firing may be carried out under an oxidizing atmosphere in the initial stage and then in an inert atmosphere in the final stage, or in an atmosphere containing a carbon component. Appropriate temperature and time are maintained under the above-adjusted atmosphere.

When the two-layer structure of the refractory fiber obtained in this way is composed of two or more different refractory compounds, point analysis of the cross section of the refractory fiber is performed using an X-ray microanalyzer. A and B in Figure 1.

By performing the evaluation at points such as C, D, and E, evaluation can be made from the concentration gradient of one or more constituent elements.

In addition, even when the crystal size of the same refractory compound differs, changes in crystal size can be observed using a scanning electron microscope.
It can be evaluated by measuring at points shown as A, B, C, D, and E in the figure.

Next, whether or not the fire-resistant fiber is crystalline is evaluated using wide-angle X-cotton. The X-ray diffraction peak of a single fiber is obtained by reflection or transmission method. This can be clarified by identifying the crystal from this X-ray diffraction peak.

Furthermore, more accurate evaluation can be made by examining the identification of the crystal together with the results of the elemental analysis using the X-ray microanalyzer.

As can be seen from the analysis results using the aforementioned X-ray microanalyzer etc. (elements forming the inner layer near the surface of the single fibers were detected), in the single fibers in the refractory fiber aggregate according to the present invention, is not clearly separated into two layers, the outer layer and the inner layer, but the refractory crystalline compound applied as the inner layer penetrates into the outer layer, while the refractory crystalline compound applied as the outer layer Single fibers are formed in a state where the fibers permeate into the inner layer. This is the monofilament 1 according to the present invention.
If we look at Figure 1, which shows a model cross-section of The applied refractory crystalline compound 3 is also present near the center of the single fiber 1, as shown by 3a.

In addition, the refractory compound fiber aggregate fired after coating may partially adhere to adjacent fibers, may adhere to laminated portions, or may even become a mixture of both.

The refractory compound fiber aggregate obtained as described above has very high strength, especially compressive strength of 0.3 to 500 kg/ca.

Here, the compressive strength is J [SI? -2227.

〔Example〕

The present invention will be specifically described below with reference to Examples.

In addition, in the examples, the tensile strength and elastic modulus are JISL
-1013. However, the sample length was 20, and the tensile speed was 1 cm/min (constant elongation).

Porosity is calculated by the following formula:

The apparent specific gravity is obtained using an air vicinometer and a sample size of approximately 0.1 g. The fiber assembly is heated to 600° C. for 2 minutes before testing. The fibers are then ground to powder using a mortar and pestle to a length of not more than five times the average diameter of the fibers, minimizing the content of any closed voids, and having an apparent density equal to or approximately equal to the true specific gravity of the sample. obtains the value of specific gravity.

To measure bulk specific gravity, the fibers are straightened in a propane flame so that the length of the fibers can be easily measured. Fiber length is measured by noting the movement required to sweep the entire length of the sample using a microscope equipped with a micrometer. In addition, if the refractory compounding process causes changes in a propane flame, the total length of the sample may be measured by taking a photograph of the fiber and enlarging it.

2. Measure the diameter using a microscope equipped with an eyepiece to insert the thread.
Measure with an accuracy of 5 x 10-''. Weigh with a balance that can measure up to 1 x lO-'?g. The minimum amount of fiber used is 1 x
l0-'g.

The bulk specific gravity of a circular cross-sectional area is calculated using the following formula.

Example 1: A fiber knitted structure consisting of a crystalline alumina inner layer and a crystalline alumina/mullite outer layer for those having a non-circular cross section.

2. Viscose method rayon 120d/8f. Using,
A rubber knitted fabric was created using a l0GG horizontal stripe machine. The density is 17
It was 1 piece/inch x 14 wales/inch. This knitted fabric is immersed in water for 1 hour to pre-swell, and then the water-containing knitted fabric is centrifugally dehydrated (250 Or, p, m
) for 5 minutes to remove excess water. This knitted fabric is 2
．． The knitted fabric was immersed in an 8 mol/l aluminum chloride aqueous solution at room temperature for 50 hours, taken out, and dehydrated for 5 minutes in a centrifugal dehydrator to remove excess solution. This mass was then dried at 50°C.

Next, this knitted fabric was placed in a box-shaped electric furnace and heated to 400°C in the air.
The temperature was raised over 50 hours to remove organic substances.

After confirming that no carbon remained, the temperature was raised to 800°C and held for 5 hours. A knitted structure made of white aluminum oxide fibers was obtained.

The strength of the knitted fabric was so weak that it was impossible to measure it. The compressive strength is considered to be less than 50 g/cat. When I applied a little force, the shape of the knitted fabric broke and turned into powder. However, if handled carefully, it could be used in the next step. The density of the knitted fabric was 25 coats/inch x 23 wales/inch, and the thickness was 0.7 mm.

This knitted fabric is made of a mixture of aluminum lactate and silicon dioxide (
Alz03/SiO□/26.5%/12% as lactic acid
/27%) (aluminum lactate is dissolved in water. SiO□ is finely dispersed in water) and the excess solution was removed by contacting with filter paper. Next, this area was dried in a hot air dryer at 100°C. This metal material was placed in an electric furnace, heated to 800° C. over 8 hours to remove carbon, and then held at 1500° C. for 20 hours to be fired.

The crystalline aluminum oxide fiber structure thus obtained, on which a film of crystalline alumina and mullite was formed, had a very high strength of 3 kg/ctA. Further, the density was 27 cos/inch x 25 wale/inch, and the thickness was 0.71*. It was found that the knitted fabric had a shrunken appearance as it was originally knitted, and that each filament was separated and coated uniformly. Furthermore, when the transparency of the fibers before and after coating was measured, when the transparency before coating was 1, the transparency after coating was 0.6.

The obtained crystalline aluminum oxide fiber knitted structure with a film of crystalline alumina and mullite has high strength and is extremely useful as a variety of filter media and catalyst carriers that have the appearance of a knitted fabric. Met.

Example 2 Fiber woven structure consisting of an inner layer of crystalline tin oxide and an outer layer of crystalline alumina/mullite A three-dimensional structure fabric having a pile configuration according to the following fabric design was prepared using a double bell head loom.

Warp Viscose method rayon 100d150f
Density 80 zero/inch Weft 〃〃〃 Pile yarn 〃 〃
4o pieces/inch pile height
A 20% fabric was immersed in a 30% by weight aqueous solution of tin chloride at room temperature for 1 hour, washed with water, further immersed in a 7% by weight aqueous sodium hydrogen phosphate solution at 60°C, and further washed with water. By repeating this operation five times, the fabric weight increased to 256% of the original fabric weight. Furthermore, it was immersed in 4% by weight sodium silicate (No. 1) at 60°C for 1 hour. Furthermore, excess sodium silicate was removed by washing with water. As a result,
Fabric weight increased to 273%. This fabric was dried in a hot air dryer at 100℃, placed in a box-shaped electric furnace, and dried in the air for 4 hours.
The temperature was raised to 00°C in 15 hours to remove carbon, and further,
The temperature was raised to 800°C and held for 20 hours. After cooling, a fabric with a three-dimensional fiber structure mainly made of tin oxide was obtained, the front and back sides of which were connected by pile threads. The strength of the woven fabric is very low, and the compressive strength is thought to be 50 g/cut or less. however,
If handled carefully, it could be used in the next step. The pile height of the double-woven fabric is 14■l, and the warp density is 105 threads/inch.
The weft density was 106 threads/inch, and the pile density was 53 threads/inch. This double woven fabric is mixed with aluminum lactate and S
The mixture of iO□ (same as in Example 1) was immersed in a 20% aqueous solution, and after removing the excess aqueous solution by suction,
It was dried at 0°C.

This fabric was placed in a box-shaped electric furnace, heated to 800℃ in 8 hours, carbon removed, then heated to 1200℃ in 30 minutes, further heated to 1400℃ in 2 hours, and then heated for 1 hour. It was maintained at that temperature and cooled.

The fibrous three-dimensional structure mainly composed of tin oxide obtained in this way was coated with alumina and mullite.
It had a high strength of kg/cal.

The thickness of the double woven fabric is 13 fins, the warp density is 110 threads/inch, the weft thread density is 109 threads/1' inch, and the pile density is 55.
It was wood/inch. It was white in color and showed a shrunken appearance with the initial double-woven fabric, and each filament was separated, indicating that the coating was uniform. Furthermore, when the transparency of the fibers before and after coating was measured, when the transparency before coating was 1, the transparency after coating was 0.2. The color of the double fabric was white.

The resulting fibrous three-dimensional structure fabric mainly composed of crystalline tin oxide had high strength and was extremely useful as various filter media and catalyst supports having three-dimensional structure fabrics.

Example 3 A fiber woven structure consisting of a crystalline tin oxide inner layer and a crystalline zirconia/yttrium outer layer Using copper ammonium method rayon 75 d 150 f, a warp density of 107 yarns/inch, a weft yarn density of 70 yarns/inch, and an Mi weave were produced. A plain weave fabric was created. This fabric was immersed in a 30% by weight aqueous solution of tin chloride at room temperature for one sowing period, washed with water, further immersed in a 7% by weight aqueous sodium hydrogen phosphate solution at 60° C., and further washed with water. By repeating this operation four times, the fabric weight increased to 186% of the original fabric weight. This fabric was dried in a hot air dryer at 100°C. The fabric has a warp density of 118 threads/inch and a weft density of 8
It has 6 fins/inch and the thickness ranges from 0.1 fin to 0.15 fin. This fabric was placed in a box-shaped electric furnace and heated in air for 40 minutes.
The temperature was raised to 0°C over 3 hours, held for an additional 1 hour, further raised to 700°C, held for 5 hours, and then cooled.

Thus, a white tin oxide fiber fabric was obtained.

The strength of the fabric is very weak, with a compressive strength of 50 g/c
It is considered to be below J. However, if handled carefully, it could be used in the next step. The woven fabric had a warp density of 154 threads/inch, a weft density of 129 threads/inch, and a thickness of 0.12 threads.

This fabric was immersed in an aqueous solution of 2 mol/β zirconium chloride and 0.06 mol/l yttrium chloride at room temperature for 5 minutes, excess aqueous solution was removed on a filter paper, then immersed in water and then dried with hot air at 100°C. Machine dried. This woven fabric was placed in a box-shaped electric furnace, and the temperature was raised to 1200° C. in 1 hour, and further raised to 1400° C. in 1 hour and 30 minutes, held for 1 hour, and cooled. The color of the obtained fabric was white. The warp density of the woven fabric was 125 threads/inch, the weft thread density was 98 threads/inch, and the thickness was 0.13 m. The fabric remained the original double-woven fabric with a shrunken appearance, and the individual filaments were found to be separated and evenly coated. In addition, when we measured the transparency of the fibers before and after coating, we found that when the transparency before coating is 1, it is 0.
．． It was 1. The compressive strength of a crystalline coating layer of zirconium oxide and indium oxide formed on this tin oxide fiber was 4.5 kg/cM, which was extremely disappointing.

Example 4 Viscose method rayon 250 d/10 f as thread
A rubber knitted fabric was created using a 5CG flat knitting machine.

The density was 6 coats/inch x 5 wales/inch. This knitted fabric was immersed in a 30% by weight aqueous solution of tin chloride at room temperature for one hour, washed with water, further immersed in a 7% by weight aqueous disodium hydrogen phosphate solution at 60° C. for one hour, and further washed with water. By repeating this operation 5 times, the weight of the knitted fabric is
It increased to 214%. Furthermore, it was immersed in 4% by weight sodium silicate (No. 1) at 60°C for one hour. Furthermore, excess sodium silicate was removed by washing with water. As a result, the weight of the knitted fabric increased to 245%. This knitted fabric was dried in a hot air dryer at 80°C, placed in a box-shaped electric furnace, and heated in air for 400°C.
The temperature was raised to 800°C over 50 hours, and the temperature was further raised to 800°C, held for 5 hours, and then cooled. The knitted fabric was white and had shrunk more than the original knitted fabric, but maintained its shape. The strength of the obtained knitted fabric was so weak that it was impossible to measure it, but the compressive strength is thought to be 50 g/ad or less. When a little force was applied to the knitted fabric, the shape of the knitted fabric broke and it became powder-like. However, if handled carefully, it could be used in the next step.

This fiber knitted structure mainly composed of tin oxide is made of a mixture of aluminum lactate and silicon dioxide (AI203/SjO□
/contains 26.5%/12%/27% as lactic acid) of 10
Weight% cloudy aqueous solution (aluminum lactate is dissolved in water, 5i
Oz is dispersed in fine particles in water), and excess solution was removed by contacting with filter paper. This knitted fabric was dried in a hot air dryer at 100℃, placed in a box-type electric furnace, and dried in air for 40 minutes.
The temperature was raised to 0°C over 5 hours, and further raised to 1350°C, maintained for 1 hour, and cooled.

The resulting knitted fabric was white in color and exhibited a shrunken appearance of the initial weave.

In addition, as a comparative example, a dimethylpolysiloxane modified product [Shin-Etsu Chemical - POLON M
It was immersed in a 20% by weight aqueous solution of R) and brought into contact with filter paper to remove excess solution. The knitted fabric was dried in a hot air dryer at 100°C and heated in a propane-air flame for 5 seconds to vitrify the coating.

The fibers of the yarns in the crystalline-coated knitted fabric and the yarn in the vitrified-coated knitted fabric of the present invention were observed using an optical microscope using transmitted light. Crystalline-coated knitted fabrics appear black in photographs because the transmitted light is diffusely reflected by the microcrystalline layer on the fiber surface. On the other hand, the vitrified coated knitted fabric was transparent because it did not diffusely reflect the transmitted light.

Furthermore, the results of wide-angle X-ray and X-ray microanalyzer revealed that mullite and alumina crystals were still formed on the fiber surface layer. Table 1 shows the results of point analysis at a total of five points A to E in FIG. 1 using an X-ray microanalyzer.

The compressive strength of the crystalline-coated knitted fabric and the vitrified-coated knitted fabric of the present invention was measured. In addition, yarns were taken from the same knitted fabric before firing and subjected to the same process as the knitted fabric to create crystalline coated yarn and vitrified coated yarn, and the tensile strength and tensile modulus were also measured. . The results are as shown in Table 2.
Compressive strength, tensile strength, and tensile modulus were greatly improved.

Table 1 □ Table 2 Example 5 Using two pieces of viscose method rayon 120d/8f, l
A rubber knitted fabric was created using 0GG woven fabric. The density was 17 coats/inch x 14 wales/inch. This knitted fabric was pre-swollen by immersing it in water, and then the water-containing knitted fabric was dehydrated for 5 minutes using a centrifugal dehydrator (250 rpm) to remove excess water.

This knitted fabric was immersed in a 2.8 mol/l aluminum chloride aqueous solution at room temperature for 50 hours, taken out, and dehydrated for 5 minutes in a centrifugal dehydrator to remove excess solution. This knitted fabric is 5
It was dried in a hot air dryer at 0°C.

Next, this knitted fabric was placed in a box electric furnace and heated in air for 400 minutes.
The temperature was raised to ℃ over 50 hours to remove carbon.

Furthermore, the temperature was raised to 800°C and held for 5 hours. The knitted fabric is
A white aluminum oxide fiber knitted structure was obtained. The density of the knitted fabric was 25 coats/inch x 20 wales/inch, and the thickness was 0.7 mm.

Although the strength of the obtained composite material was so weak that it was impossible to measure it, the compressive strength is thought to be less than 50 g/ctA. When a little force was applied to the knitted fabric, the form of the attached fabric broke and became powder-like. However, if handled carefully, it could be used in the next step.

Aluminum lactate + silicon dioxide mixture (Example 4) was added to the aluminum oxide fiber knitted structure thus obtained.
The sample was immersed in a 10x4% white cloudy aqueous solution (same as above), and the excess solution was removed by contacting it with filter paper. Next, this knitted fabric is 1
It was dried in a hot air dryer at 00°C. Next, this knitted fabric was placed in a box-shaped electric furnace and heated to 800° C. over 8 hours to remove carbon, heated to 1500° C., held for 20 hours, and cooled.

The aluminum oxide fiber knitted structure thus obtained, in which a crystalline coating of aluminumite was formed, had a high compressive strength of 3 kg/crl. Further, the density of the knitted fabric was 27 coats/inch x 25 wales/inch. The appearance of the knitted fabric remained the same as the original knitted fabric, but showed a shrunken appearance, and it was found that each filament was separated and coated uniformly.

Example 6 Using two pieces of viscose method rayon 120d/8f, l
A rubber knitted fabric was created using 0GG horizontal fabric. The density was 17 coats/inch by 14 wales/inch. This knitted fabric was pre-swollen by immersing it in water, and then the water-containing knitted fabric was dehydrated for 5 minutes using a centrifugal dehydrator (2500 rpm) to remove excess water.

This knitted fabric was immersed in a 2.8 mol/2 aluminum chloride aqueous solution at room temperature for 50 hours, taken out, and dehydrated for 5 minutes in a centrifugal dehydrator to remove excess solution. Next, this knitted fabric was dried in a hot air dryer at 50°C. Next, this knitted fabric was placed in a box-shaped electric furnace, and the temperature was raised to 400° C. over 50 hours in air to remove carbon. Furthermore, the temperature was raised to 800°C and held for 5 hours. A white aluminum oxide fiber knitted fabric structure was obtained as a knitted fabric. The density of the knitted fabric is 25 coats/inch x 20 wales/inch, and the thickness is 0.7
It was n+. The strength of the obtained knitted fabric was so weak that it was impossible to measure it, but the compressive strength is thought to be 50 g/cJA or less. When I applied a little pressure to the knitted fabric, the shape of the knitted fabric broke and turned into powder. However, if handled carefully, it could be used in the next step.

The aluminum oxide fiber knitted structure thus obtained was immersed in a 30% by weight aqueous solution of tin chloride, and the excess solution was removed by bringing a filter paper into contact with it. Then, it was washed with a 1% ammonia aqueous solution to form a tin hydroxide gel film on the fiber surface of the aluminum oxide fiber knitted structure. This knitted fabric was dried in a hot air dryer at 100°C. Next, this material was placed in a box-type electric furnace and heated to 800°C in 8 hours.
The temperature was raised to 1200°C, maintained for 10 hours, and then cooled.

The aluminum oxide fiber knitted structure obtained in this way is coated with a tin oxide crystalline coating.
It had a high compressive strength of 2 kg/cnl. Further, the density of the knitted fabric was 29 coats/inch x 23 wales/inch. The appearance of the knitted fabric remained the same as the original knitted fabric, but showed a shrunken appearance, and it was found that each filament was separated and coated uniformly.

Example 7 A rubber knitted fabric was created using a 10CG flat knitted fabric using two pieces of 120'd/8 ft of viscose method rayon. The density is
It was 17 coats/inch x 14 wales/inch.

This knitted fabric is pre-swollen by soaking it in water, and then the water-containing knitted fabric is heated in a centrifugal dehydrator (2500 rpm) for 50 minutes.
Dehydrated for a minute to remove excess water.

2 moles/! of this knitted fabric! The knitted fabric was immersed in an aqueous solution of zirconium chloride and 0.06 mol/l yttrium chloride at room temperature for 30 hours, and the knitted fabric was taken out and dehydrated for 5 minutes in a centrifugal dehydrator to remove excess solution. Next, this knitted fabric was dried in a hot air dryer at 50°C. Next, this knitted fabric was placed in a box-shaped electric furnace, and the temperature was raised to 400° C. over 50 hours in air to remove carbon. Furthermore, the temperature was raised to 600°C and held for 5 hours. A white zirconium oxide fiber knitted fabric structure was obtained as a knitted fabric.

The density of the knitted fabric was 28 coats/inch x 22 wales/inch, and the thickness was 0.71. The strength of the obtained knitted fabric was very weak and impossible to measure, but the compressive strength was 5.
It is considered to be less than 0 g/crA.

When a little force was applied to the knitted fabric, the shape of the knitted fabric broke and it became powder-like. However, if handled carefully, it could be used in the next process.

The thus obtained zirconium oxide fiber knitted structure was immersed in a 20% aqueous solution of aluminum lactate, and the excess solution was removed by suction. Next, this knitted fabric is
Dry in a hot air dryer at ℃.

Next, this knitted fabric was placed in a box-shaped electric furnace and heated to 800°C for 8 hours to remove carbon, and then heated to 1600°C.
It was held for 10 hours and cooled.

The thus obtained zirconium oxide fiber knitted structure is coated with alumina crystalline coating.
It had a high compressive strength of 4.5 kg/ad. The density of the knitted fabric was 27 coats/inch x 25 wales/inch. The appearance of the knitted fabric remained the same as the original knitted fabric, but showed a shrunken appearance, and each filament was found to be separated and coated uniformly.

Example 8 Using double velvet 'tVam, a three-dimensional structure fabric having a pile structure with the following textile design was created using viscose process rayon for the pile yarn and copper ammonium process rayon for the warp and weft.

Thread usage Density Warp yarn 100 d / 60 f 80 pieces / inch Weft yarn 100 d / 60 f 80 pieces / inch Pile yarn 120 d / 44 f 4
0 pieces/inch This fabric was immersed in a 30% tin chloride aqueous solution at room temperature for one hour, washed with water, further immersed in a 7% by weight aqueous disodium hydrogen phosphate solution at 60'C for 1 hour, and further washed with water. did. By repeating this operation five times, the weight of the fabric increased to 256%. Furthermore, the fabric was washed with 4% by weight sodium silicate (No. 1) at 60"C for 1 hour. Furthermore, the fabric was washed with water to remove excess sodium silicate. As a result, the fabric weight increased to 273%. This fabric was dried in a hot air dryer at 80°C, placed in a box-type electric furnace, heated in air to 400”C for 50 hours, and further heated to 80°C.
The temperature was raised to 00"C, held for 5 hours, and then cooled. The fabric was white and had shrunk more than the original fabric, but it maintained the form of a three-dimensional fabric structure with the front and back sides connected by pile threads. .

The pile height is 14 dragons, and the warp density is 105 threads/inch.
The weft density was 106 threads/inch and the pile density was 53 threads/inch. The strength of this fabric made mainly of tin oxide was extremely weak and impossible to measure, but the compressive strength was 50
It is considered to be less than g/-. When a little force was applied to the fabric, its form broke and it became powder-like. However, if handled carefully, it could be used in the next step.

This fibrous fabric structure mainly composed of tin oxide was immersed in a 20% by weight aqueous solution of aluminum lactate, and excess solution was removed by suction. This fabric was dried in a hot air dryer at 100°C, placed in a box electric furnace, heated in air to 400°C in 5 hours, and after removing carbon, heated to 1200°C in 30 minutes. Furthermore, the temperature was raised to 1400° C. over 2 hours, maintained for 1 hour, and then cooled.

The resulting fabric was white in color and exhibited the shrunken appearance of the original fiber three-dimensional fabric structure.

The thus obtained fiber three-dimensional fabric structure mainly composed of tin oxide was coated with alumina crystalline coating, and a high strength of 4 kg/cut was obtained. The pile height is 13 pieces, the warp density is 110 pieces/inch, the weft density is 109 pieces/inch, and the pile density is 55 pieces/inch.
It was inches. It was found that each filament was separated and coated uniformly.

Example 9 Using a double velvet loom, a three-dimensional structure fabric having a pile structure with the following textile design was created using viscose rayon as the pile yarn and copper ammonium rayon as the warp and weft.

Thread usage Density Warp yarn 100 d / 60 f 80 pieces / inch Weft yarn 100 d / 60 f 80
Thread/inch pile yarn 120 d/44 r
40 yarns/inch This fabric is pre-swollen by soaking in water, and then the water-laden knitted fabric is placed in a centrifugal dehydrator (250 yarns/inch).
Orpm) for 5 minutes to remove excess water. This knitted fabric was immersed in a 2.8 mol/l aluminum chloride aqueous solution at room temperature for 50 hours, then taken out and placed in a centrifugal dehydrator for 50 hours.
It was dehydrated for a minute and the excess solution was removed. Next, this knitted fabric was dried in a hot air dryer at 50°C, placed in a box-type electric furnace, and heated to 400°C in air for 50 hours, and further heated to 800°C.
The temperature was raised to , maintained for 5 hours, and then cooled. The woven fabric was white and had shrunk more than the original woven fabric, but it maintained the form of a three-dimensional woven fabric structure with the front and back sides connected by pile threads. The pile height was Ion, the warp density was 115 threads/inch, the weft density was 116 threads/inch, and the pile density was 65 threads/inch. The strength of the resulting fabric was so weak that it was impossible to measure it, but the compressive strength is thought to be 50 g/CTA or less. When a little force was applied to the fabric, its form broke and it became powder-like. However, if handled carefully, it could be used in the next step.

This fiber fabric structure mainly composed of aluminum oxide is mixed with 20% aluminum lactate and 0.05% magnesium chloride.
It was immersed in a 1% by weight aqueous solution and the excess solution was removed by suction. This fabric was dried in a hot air dryer at 100°C, placed in a box-shaped electric furnace, and heated in air to 400°C in 5 hours. After removing carbon, the temperature was raised to 1500°C in 30 minutes. Then, the temperature was further warmed to 1650°C for 2 hours, maintained for 3 hours, and cooled. The resulting fabric was white in color and exhibited the shrunken appearance of the original fiber three-dimensional fabric structure.

The aluminum oxide fiber three-dimensional fabric structure thus obtained, in which an alumina crystalline coating was formed, had a high compressive strength of 35 kg/cot. The pile height was 8 pieces, the warp density was 128 threads/inch, the weft density was 124 threads/inch, and the pile density was 78 threads/inch. It was found that each filament was separated and coated uniformly.

Example 10 A nonwoven fabric was prepared by needle punching using short fibers of 1.5 d x 38 mm.

The thickness was 7 mm, and the basis weight was 450 g/m. This nonwoven fabric was preswollen by immersing it in water, and then the water-containing nonwoven fabric was dehydrated for 5 minutes using a centrifugal dehydrator (250 rpm) to remove excess water. 2. This nonwoven fabric.
The nonwoven fabric was immersed in an 8 mol/l aluminum chloride aqueous solution at room temperature for 24 hours, taken out, and dehydrated in a centrifugal dehydrator for 5 minutes to remove excess solution.

Next, this nonwoven fabric was dried in a hot air dryer at 50°C, placed in a box-shaped electric furnace, and heated in air to 400°C in 50 hours, further heated to 800°C, held for 5 hours, and cooled. did. The nonwoven fabric was white and had shrunk more than the original nonwoven fabric, but maintained the form of a fibrous nonwoven fabric structure. The thickness is 5 dragons,
The eye size was 420 g/m. The strength of the obtained aluminum oxide nonwoven fabric was so weak that it was impossible to measure it, but the compressive strength is thought to be 50 g/c++I or less. When a little force was applied to the nonwoven fabric, its form broke and it became powder-like.

However, if handled carefully, it could be used in the next process.

This fibrous nonwoven fabric structure mainly composed of aluminum oxide was immersed in a 2 mol/2 zirconium chloride and 0.06 mol/l yttrium chloride aqueous solution, and excess solution was removed by suction. This nonwoven fabric was dried in a hot air dryer at 100°C, placed in a box electric furnace, heated in air to 400°C in 5 hours, heated to 1500°C in 30 minutes, and further heated to 1600°C in 30 minutes.
The temperature was raised to ℃ over 2 hours, maintained for 4 hours, and then cooled.

The resulting nonwoven fabric was white in color and exhibited the shrunken appearance of the original fiber three-dimensional nonwoven structure. The nonwoven fabric thus obtained had a high compressive strength of 25 kg/cJ.

The thickness was 5 mm and the basis weight was 480 g/m. It was found that each filament was separated and coated uniformly.

Example 11 A fiber knitted structure consisting of an inner layer of crystalline tin oxide and an outer layer of crystalline alumina/mullite. Using two pieces of viscose method rayon 120d/8f, l
A rubber knitted fabric was created using a 0GG flat knitting machine. The density was 17 coats/inch x 14 wales/inch. This knitted fabric was soaked in 30wt.1% stannic chloride in water for one hour at room temperature, then washed with water, and further immersed in a 7wt.% disodium hydrogen phosphate aqueous solution at 60°C for one hour and washed with water. . By repeating this operation five times, the weight of the knitted fabric increased by 256% compared to the original weight of the knitted fabric. Furthermore, it was immersed in a 4-fold 1% aqueous solution of sodium silicate (number -) at 60°C for one hour.

Furthermore, excess sodium silicate was removed by washing with water. As a result, the weight of the knitted fabric increased to 273% of the original weight of the knitted fabric. This knitted fabric was dried in a hot air dryer at 100°C, placed in a box-shaped electric furnace, heated in air to 400°C for 15 hours to decompose and remove organic matter, and then heated to 800°C. , and held for 20 hours. After cooling, a refractory compound fiber aggregate mainly composed of tin oxide was obtained which retained the form of the initial fiber knitted structure. The strength of this fiber aggregate is very low, and the compressive strength is thought to be 50 g/cJ or less. However, if handled carefully, it could be used in the next step.

This knitted fabric is made of a mixture of aluminum lactate and silicon dioxide (
AhO, /SiO□/26.5%/12%/ as lactic acid
27% (manufactured by Tamoto Kagaku Co., Ltd.)), and after removing the excess aqueous solution by suction,
Dry in a hot air dryer.

Thirty pieces of this knitted fabric were layered and heated to 800℃ in 8 hours in a box-type electric furnace. After removing organic matter, the temperature was increased to 1200℃ for 3 hours.
The temperature was raised in 0 minutes, further raised to 1400°C in 2 hours, maintained at that temperature for 3 hours, and cooled.

The fiber knitted structure obtained by forming a film of alumina and mullite on the monofilament mainly composed of tin oxide thus obtained exhibited a compressive strength of 380 kg/crA. The appearance of the fibrous woven structure was white and maintained the initial two-dimensional structure of the knitted fabric in a contracted form, indicating that the structure was not conscious of the laminated state. Moreover, some of the single fibers of the fiber knitted structure were adhered to adjacent single fibers.

Example 12 Laminated structure of a fiber knitted structure consisting of a crystalline alumina inner layer and a crystalline alumina/mullite outer layer, and a fiber knitted structure consisting of a crystalline tin oxide inner layer and a crystalline alumina/mullite outer layer Viscose method Rayon 120d/8ft -Use two pieces,
A rubber knitted fabric was created using a l0GG flat knitting machine. The density is 17
It was 1 piece/inch x 14 wales/inch. This knitted fabric is pre-swollen by soaking it in water for one hour at room temperature, and then the water-containing knitted fabric is placed in a centrifugal dehydrator (250 Or,
p, m) for 5 minutes to remove excess water. This knitted fabric is 2.8 mol#! After being immersed in an aluminum chloride aqueous solution at room temperature for 50 hours, the knitted fabric was taken out and dehydrated for 5 minutes in a centrifugal dehydrator (2500 r, p, m) to remove excess solution. Next, this knitted fabric was dried in a hot air dryer at 50°C, placed in a box-shaped electric furnace, and heated in air to 250°C for 10 minutes.
The temperature is raised for 800 hrs, and the organic matter is decomposed and removed.
The temperature was raised to 0.degree. C. and maintained for 5 hours. After cooling, an aluminum oxide refractory compound fiber aggregate was obtained which retained the form of the initial fiber knitted structure. The strength of this fiber aggregate is very low, and the compressive strength is thought to be 50 g/cd or less. However, if handled carefully, it could be used in the next step.

This knitted fabric is made of a mixture of aluminum lactate and silicon dioxide (
After the excess aqueous solution was removed by suction, the sample was dried in a hot air dryer at 100°C.

Thirty sheets of this knitted fabric and the dried knitted fabric coated with the tin oxide-based fiber structure used in Example 11 were alternately laminated and heated to 800°C in 8 hours in a box electric furnace. After removing organic matter, the temperature was raised to 1200°C in 30 minutes, further raised to 1400°C in 2 hours, maintained at that temperature for 3 hours, and cooled.

The thus obtained fibrous structure mainly composed of tin oxide on which a film of alumina and mullite was formed and the knitted alumina fiber structure on which a film of alumina and mullite were formed were compressed at 150 kg/-. It showed strength. The appearance of the fiber knitted structure was white and maintained the initial knitted structure in a contracted form, indicating that the structure was not conscious of the laminated state. Further, some of the single fibers of the fiber knitted structure were adhered to adjacent single fibers.

Example 13 A fibrous fabric structure consisting of a crystalline silicon carbide inner layer and a crystalline alumina outer layer A double velvet loom was used to use a three-dimensional fabric having a pile configuration according to the following fabric design.

Warp Piece course method rayon 1ood150f
Density 80/inch weft yarn

〃Pile thread〃
〃 40 pieces/inch Bile height 20 m The fabric was pre-swollen by soaking it in water at room temperature for one hour, and then the water-containing fabric was placed in a centrifugal dehydrator (2500 r,
p, m) for 5 minutes to remove excess water. This fabric was immersed in liquid silicon tetrachloride for 1 hour, and by evaporation,
Dry. Place in a tube furnace and heat in air to 400°C for 50
The temperature was raised over time to remove volatile organic matter, and a carbonaceous fiber residue was obtained. Next, the air in the tube furnace was replaced with nitrogen, and the temperature was raised to 1400°C with dry hydrogen gas flowing.
Holds time.

After cooling, a silicon carbide fibrous woven structure was obtained which retained the morphology of the initial fibrous woven structure. The strength of this fiber m-material structure is very low, and the compressive strength is thought to be less than 50 g/ct. However, if handled carefully, it could be used in the next step. This fabric was immersed in an aqueous solution of 10% by weight of aluminum lactate (manufactured by Tamoto Kagaku Co., Ltd.) and 0.5% by weight of magnesium chloride, and after removing the excess aqueous solution with a filter paper, it was dried in a hot air dryer at 100°C. .

The coated and dried fabric is heated in a box-type electric furnace for 8
The temperature was raised to 00°C over 8 hours, the organic matter was removed, and then the temperature was further raised to 1100°C over 2 hours, and the temperature was maintained at that temperature for 3 hours, followed by cooling.

The fiber fabric structure obtained by forming an alumina film on the silicon carbide single fiber thus obtained has a weight of 80 kg/cnl.
showed a compressive strength of The appearance of the fibrous fabric structure was gray in color and a shrunken version of the original fabric structure. Moreover, some of the single fibers of the fiber woven structure were adhered to adjacent single fibers.

Example 14 Fiber fabric structure consisting of crystalline zirconia inner layer and crystalline silicon carbide outer layer Using a double velvet loom, a three-dimensional fabric having a pile configuration of the following fabric design was used.

Warp piece course method rayon 100d150f
Density: 80 fine threads
〃〃 Vile thread 〃 〃
40 pieces/inch pile height
Pre-swell the 20m fabric by soaking it in water for one hour at room temperature, then place the water-laden fabric in a centrifugal dehydrator (250Or,
p, m) for 5 minutes to remove excess water. This fabric was mixed with 2 mol #2 of basic zirconium chloride and 0.06 mol #2 of yttrium chloride/(30 mol #2 in an aqueous solution of
Soak the fabric for an hour, take it out, and transfer the water-containing fabric to a centrifugal dehydrator (
The sample was dehydrated at 2500 r, p, m for 5 minutes to remove excess water and dried. Place in a box electric furnace and heat at 400° in air.
The temperature was raised to C in 50 hours, organic matter was decomposed and removed, and
The temperature was raised to 0.degree. C. and maintained for 5 hours. After cooling, a zirconium oxide fiber aggregate was obtained that retained the morphology of the initial fiber fabric structure. The strength of this fiber aggregate is very low, and the compressive strength is thought to be 50 g/a+1 or less. however,
If handled carefully, it could be used in the next step. This fabric is exposed to an atmosphere of 95% R1+ at 60° C. for 5 hours to adsorb moisture. The fabric was then soaked in liquid silicon tetrachloride for 1 hour and dried by evaporation. This fabric was placed in a tube furnace, heated to 1400° C. in -carbon oxide, maintained for 5 hours, and cooled.

A fiber fabric structure obtained by forming a silicon carbide film on the zirconium oxide single fiber obtained in this way weighs 40 kg.
showed a compressive strength of /ctM. The appearance of the fibrous woven structure was gray and a shrunken version of the original woven structure. Moreover, some of the single fibers of the fiber woven structure were adhered to adjacent single fibers.

Example 15 Laminated structure of fiber knitted fabric structure consisting of crystalline alumina inner layer and crystalline aluminum nitride outer layer Two pieces of viscose method rayon 120d/8f were used to make l
A rubber knitted fabric was created using a 0CG flat knitting machine. The density was 17 coats/inch x 14 wales/inch. This knitted fabric was pre-swollen by soaking it in water for one hour at room temperature, and then the water-laden fabric was placed in a centrifugal dehydrator (2500r, p
, m) for 5 minutes to remove excess water. This knitted fabric was coated with 2.8 mol/g aluminum chloride + 0.3 m
After immersing the fabric in a magnesium chloride aqueous solution of
p, m) for 5 minutes to remove excess solution. Next, this knitted fabric was dried in a hot air dryer at 50°C, placed in a box-shaped electric furnace, and heated to 400°C in air for 50 hours.
The organic matter was decomposed and removed, and the temperature was further raised to 800°C and held for 5 hours. After cooling, an aluminum oxide refractory compound fiber aggregate was obtained which retained the form of the initial fiber knitted structure. The strength of this fiber aggregate is very low, and the compressive strength is thought to be 50 g/ant or less. However, if handled carefully, it could be used in the next step. This knitted fabric was immersed in a 10-weight aqueous solution of aluminum lactate (manufactured by Taki Kagaku Co., Ltd.), and after removing the excess aqueous solution by suction, the ioo
It was dried in a hot air dryer.

10 pieces of this knitted fabric were placed in a tube furnace, first the atmosphere was replaced with nitrogen, and then dry ammonia gas was passed through the furnace for 4 hours.
Raise the temperature to 00℃ in 3 hours, remove volatile organic substances,
Next, the temperature was raised to 1400° C. over 2 hours, maintained at that temperature for 2 hours, and cooled.

The appearance of the alumina fiber aggregate obtained in this way with an aluminum nitride film formed on it shows an aggregate that maintains the original knitted structure in a contracted form and is not aware of the laminated state. Ta. Further, some of the single fibers of the fiber aggregate were adhered to adjacent single fibers. Compressive strength is 8kg
/ci.

Example 16 A fiber fabric structure consisting of an inner layer of crystalline silicon nitride and an outer layer of crystalline alumina. Using two pieces of viscose method rayon 120d/8f, l
A rubber knitted fabric was created using a 0GG flat knitting machine. The density was 17 coats/inch x 14 wales/inch.

Pre-swell the fabric by soaking it in water for one hour at room temperature, then place the water-laden fabric in a centrifugal dehydrator (250 Or,
p, m) for 5 minutes to remove excess water. The fabric was soaked in trimethylchlorosilane for 1 hour and dried by evaporation. Place in a tube furnace and heat under nitrogen atmosphere for 40 minutes.
The temperature was raised to 0° C. over 2 hours and maintained at that temperature for 2 hours to remove volatile organic matter and obtain a carbonaceous fiber residue. next,
Flow ammonia gas mixed with nitrogen and heat to 1200℃ for 1 hour.
The temperature was raised to 1400℃ for 15 hours, and then the temperature was raised to 1400℃ for 15 hours.
Holds time. A silicon nitride fiber fabric structure was obtained which retained the morphology of the initial fiber fabric structure after cooling. The strength of this fiber fabric structure is very weak, with a compressive strength of 50 g/c.
It is considered to be less than j. However, if handled carefully, it could be used in the next step. This fabric was mixed with 10% by weight of aluminum lactate (manufactured by Taki Chemical Co., Ltd.) and 0% by weight of magnesium chloride.
The sample was immersed in a 5% by weight mixed aqueous solution, and after removing the excess aqueous solution using a filter paper, it was dried in a hot air dryer at 100°C.

The coated and dried fabric is heated in a box-type electric furnace for 8
The temperature was raised to 00°C over 8 hours, organic matter was removed, and then the temperature was further raised to 1100°C over 2 hours, and the temperature was maintained at that temperature for 3 hours to allow the mixture to lubricate.

A fiber fabric structure obtained by forming an alumina film on the silicon nitride single fiber obtained in this way has a 0.5ksr/-
showed a compressive strength of The appearance of the fiber aggregate was gray and had the structure of the initial fabric shrunk. Furthermore, the single fibers in the fiber aggregate were clearly separated.

Example 17 Using four pieces of viscose method rayon 120d/8 flc, a Milano Rip knitted fabric was created using a 7CG flat knitting machine. 16
It was 1 piece/inch x 10 wales/inch. This knitted fabric is pre-swollen by soaking it in water for one hour at room temperature, and then the water-containing knitted fabric is placed in a centrifugal dehydrator (2,50 or
, p, m) for 5 minutes to remove excess water. This knitted fabric is 2.8 mol/j! After being immersed in an aluminum chloride aqueous solution for 50 hours, the knitted fabric was taken out and dehydrated for 5 minutes in a centrifugal dehydrator (2,50 Or, p, m) to remove excess solution. Next, this knitted fabric was dried in a hot air dryer at 50℃, placed in a tubular electric furnace, and dried in nitrogen gas for 40 minutes.
The temperature was raised to 0°C in 10 hours, to 1300°C in 3 hours, and further to 1400°C in 40 hours. After cooling, an aluminum nitride refractory compound fiber aggregate was obtained which retained the form of the initial fiber knitted structure. The strength of this fiber aggregate is very weak, with a compressive strength of 50 g/cI
It is considered to be 11 or less. However, if handled carefully, it could be used in the next step. This knitted fabric was allowed to adsorb moisture for 24 hours in an atmosphere of 40° C. and relative humidity of 95% RH, and then placed in a desiccator, and after being evacuated to a vacuum, it was reacted for 1 hour in a trimethylchlorosilane atmosphere. After taking out this knitted fabric from the desiccator, it was dried at 100°C.

This knitted fabric was placed in a tubular electric furnace and heated to 1300°C in 10 hours in a mixed gas of nitrogen and ethanol.
The temperature was raised to 1400°C over 3 hours, and the temperature was further maintained at 1400°C for 5 hours, followed by cooling. The appearance of the fiber aggregate made of aluminum nitride lamb single fibers coated with silicon carbide thus obtained maintained the structure of the original knitted fabric in a contracted form. Furthermore, the single fibers of the fiber aggregate were clearly separated. The compressive strength of this structure is 0,8 kg/c
It was rA.

Table 3 shows the results of a total of five point analyzes A to E in FIG. 1 using an X-ray microanalyzer. Furthermore, when we used wide-angle X-rays to identify the crystal peaks, we found that
It turned out to be silicon carbide/aluminum nitride crystals. From the above results and the results of the X-ray microanalyzer described above, it was found that a fiber aggregate having a two-layer structure of a refractory crystalline compound was obtained.

Table 3 [Effects of the Invention] Since the refractory compound fiber aggregate of the present invention is constructed as described above, it does not easily break even when the constituent fibers are used after being bent at a large curvature. Therefore, this fiber aggregate is useful as various filter media, catalyst carriers, etc.

[Brief explanation of drawings]

FIG. 1 is a diagram schematically showing the arrangement of refractory crystalline compounds in the inner and outer layers in a cross section of a single fiber in a refractory fiber aggregate according to the present invention. ■...Single fiber, 2.2a...Refractory crystalline compound for inner layer, 3.3a
...Refractory crystalline compound for outer layer.

Claims (1)

[Claims] 1. A fiber aggregate composed of fibers of a refractory compound, the fibers comprising an inner layer of a refractory crystalline compound and an inner layer of a refractory crystalline compound different from the refractory crystalline compound. It has a two-layer structure consisting of an outer layer, and the compressive strength of the fiber aggregate is 0.3 to 50.
A fire-resistant fiber aggregate characterized by having a weight of 0 kg/cm^2. 2. A fiber aggregate composed of organic fibers is made to absorb or react with a precursor substance of a refractory compound, and the fiber aggregate that has absorbed or reacted with the precursor substance is fired in a controlled firing atmosphere to create a refractory compound. A fiber assembly consisting of fibers of a polycrystalline compound is prepared, and the fibers constituting the fiber assembly are further coated with a refractory compound different from the refractory compound or its precursor substance, and then the fiber assembly is coated. The fiber is composed of a two-layer structure consisting of an inner layer of a refractory crystalline compound and an outer layer of a refractory crystalline compound different from the refractory crystalline compound, characterized in that the body is fired in a controlled atmosphere. A method for producing a fire-resistant fiber aggregate.