JP2000063172A - Production of highly strong lightweight ceramic plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a highly strong lightweight ceramic plate from main components comprising fly ash and glass cullet whose treatments as wastes have become problems. SOLUTION: This method for producing the highly strong lightweight ceramic plate comprises mixing 100 pts.wt. of fly ash particles having a particle diameter of 5-50 μm with 3-50 pts.wt. of glass cullet particles having a particle diameter of 50-150 μm and 3-30 pts.wt. of a binder such as water glass, molding the obtained base material in a plate-like shape and subsequently sintering the molded plate at 850-1,200 deg.C. They are preferable to add a refractory fine aggregate such as silica particles, blast furnace slag particles or wollastonite powder to the base material, and to further add a nucleus-forming agent for crystallizing the glass. It is also preferable to further embed a heat-resistant material mesh sheet (for example, a stainless steel mesh net) in the base material. The obtained highly strong lightweight ceramic plate can suitably be used as a building material, a ceramic end tab or welding, or a ceramic surface cover for welding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-strength and lightweight ceramic plate mainly composed of industrial waste such as fly ash and glass cullet.

[0002]

2. Description of the Related Art Conventionally, the manufacturing and development of building boards using fly ash as a raw material has been continued, but generally the compounding ratio is about 10 to 30%, and the cement is generally used. Used as an admixture or as an alternative to clay raw materials. In recent years, the number of factories, public buildings, and private residences has been increasing, and the number of renovations has also increased dramatically. Conventionally, natural stone, artificial tile, cement, concrete / steel plate, wood, plywood, etc. have been used as the surface material for the interior and exterior of these buildings. However, today, due to lack of manpower and changes in architectural style, the shape of the material has become large,
It is necessary to solve the labor shortage, shorten the construction time, improve the appearance, and reduce the total construction cost.

On the other hand, the ceramic tile has a high firing temperature of about 1,200 ° C. during manufacture,
Products often warp or crack, and the raw materials cannot be abundantly supplied, resulting in high cost, and the large specific gravity of the materials increases the transportation cost of the products. Furthermore, a great deal of labor and time are required for processing, bonding and joining products. Under such circumstances, it has been desired to inexpensively supply a large amount of plate-like bodies that are lightweight, have high strength, and have good weather resistance.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above-mentioned problems, the present inventors have decided to produce a high-strength, lightweight ceramic plate with low water absorption and good weather resistance at low cost. Successful.

That is, the present invention is the following method of manufacturing a high-strength lightweight ceramic plate. (1) Fine fly ash powder 100 having a particle size of 5 to 50 μm
It is preferable that 3 to 50 parts by weight of glass cullet fine powder having a particle diameter of 50 to 150 μm and 3 to 30 parts by weight of a binder are added to and mixed in parts by weight, and the mixture is molded into a plate shape and then fired at 850 to 1200 ° C. A method for producing a high-strength, lightweight ceramic plate characterized by the above. (2) Fly ash fine powder 100 having a particle size of 5 to 50 μm
To 50 parts by weight, 3 to 50 parts by weight of glass cullet powder having a particle size of 50 to 150 μm, 5 to 20 parts by weight of silica powder, 5 to 20 parts by weight of blast furnace slag powder, and 3 to 30 parts by weight of binder are added and mixed. After forming the base material into a plate shape, 850-12
A method for manufacturing a high-strength lightweight ceramic plate, which comprises firing at 00 ° C. (3) Fine fly ash powder 100 having a particle size of 5 to 50 μm
3 to 50 parts by weight of glass cullet fine powder having a particle size of 50 to 150 μm, 5 to 20 parts by weight of fine clay mineral powder, 5 to 20 parts by weight of wollastonite powder, and 3 to 30 parts by weight of a binder are added and mixed in parts by weight. 850 after forming the base material into a plate shape
A method for manufacturing a high-strength lightweight ceramic plate, which comprises firing at ˜1200 ° C. (4) Fly ash fine powder 100 having a particle size of 5 to 50 μm
3 to 50 parts by weight of glass cullet fine powder having a particle size of 50 to 150 μm, 5 to 20 parts by weight of wollastonite powder, 5 to 20 parts by weight of fine powder of blast furnace slag, and 3 to 30 parts by weight of a binder are added and mixed in parts by weight. After forming the base material into a plate shape,
A method for producing a high-strength lightweight ceramic plate, which comprises firing at 0 to 1200 ° C.

(5) 20 to 40 parts by weight of glass cullet fine powder having a particle size of 50 to 150 μm is added to 100 parts by weight of fly ash fine powder having a particle size of 5 to 50 μm. The method for producing a high-strength lightweight ceramic plate according to any one of items. (6) The method for producing a high-strength lightweight ceramic plate according to any one of items 1 to 5, wherein the binder is an inorganic binder. (7) The method for producing a high-strength lightweight ceramic plate according to any one of items 1 to 6, wherein the binder is an aqueous solution of an alkali metal silicate. (8) The method for producing a high-strength lightweight ceramic plate according to item 7, wherein the alkali metal silicate aqueous solution is a sodium silicate aqueous solution (water glass). (9) The method for producing a high-strength lightweight ceramic plate according to any one of items 1 to 8 above, wherein the binder is an inorganic binder or an organic binder. (10) The method for producing a high-strength lightweight ceramic plate according to any one of items 1 to 9 above, wherein the firing temperature is 1000 to 1150 ° C. (11) The method for producing a high-strength lightweight ceramic plate according to any one of the above items 1 to 10, wherein a nucleating agent for crystallizing glass is added to the substrate. (12) The method for producing a high-strength lightweight ceramic plate according to the above item 11, wherein a slow cooling treatment for promoting crystallization of glass is performed after firing of the base material. (13) The base material is added to 5 to 10 parts by weight of one or two or more kinds of metal fibers, glass fibers, carbon fibers and ceramic fibers with respect to 100 parts by weight of fly ash powder having a particle size of 5 to 50 μm. 13. The method for producing a high-strength lightweight ceramic plate according to any one of items 1 to 12 above, which is characterized by comprising:

(14) The heat-resistant material mesh sheet is embedded in the base material, compression-molded into a plate shape, and the molded body is fired. Manufacturing method of high strength and lightweight ceramic plate. (15) The method for producing a high-strength lightweight ceramic plate according to the above item 14, wherein the heat-resistant material mesh sheet is a stainless mesh sheet. (16) The total amount of the inorganic binder is one or two or more selected from the group consisting of the following (a) to (c): 3 to 30
16. The method for producing a high-strength lightweight ceramic plate according to any one of items 1 to 15 above, wherein the high-strength lightweight ceramic plate is parts by weight. (A) Sodium silicate aqueous solution (water glass No. 1),
(B) A mixed solution of sodium silicate, aluminum hydroxide, zinc oxide, wollastonite, kaolin, boric acid and sodium aluminate, and a solution obtained by mixing the solutions of (c) (a) and (b) with sodium alginate. (17) A method for producing a welding ceramic end dove, which comprises producing the welding ceramic end dove by forming the base material according to any one of the preceding items 1 to 16 into a plate shape and then firing the plate. (18) Manufacture of a ceramic ceramic backing material for welding, characterized in that the ceramic ceramic backing material for welding is manufactured by forming the base material according to any one of the above 1 to 16 into a plate shape and then firing the plate. Method.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Fly ash used as a main raw material in the present invention is residual ash produced after burning coal, petroleum pitch, etc., and is discharged in large quantities from thermal power plants and the like. Therefore, the utilization technology and the amount of utilization are small at present, and the utilization thereof is being studied earnestly in each field. Among them, fine fly ash powder having a particle size of 5 to 50 μm is used. The composition of fly ash is, for example, SiO ₂ : 50 to 68%, Al ₂ O ₃ :
_{20~35%, Fe 2 O 3:} 2~7%, CaO: 0.6
_{~7%, MgO: 0.2~2%,} Na 2 O: 0.1~2
%, K ₂ O: 0.3 to 1.5%, Ig. loss: 2
The fly ash particles are composed of 4% and are amorphous, and each fly ash particle is a spherical body having a particle size of 5 to 50 μm and the inside thereof is hollow. Therefore, the fly ash particles have good rolling properties, excellent filling properties, and good sinterability. Further, in the invention of the present application, the strength (bending strength) of the obtained product
In addition to increasing the water content, we are studying and adjusting the composition and firing temperature in order to achieve a reduction in water absorption. That is, it is characterized in that glass cullet fine powder is added to a blended composition based on fly ash fine powder and the mixture is baked in a specific baking temperature range.

In the production of the high-strength lightweight ceramic plate of the present invention, first, in order to impart formability, a small amount of fly ash fine powder, glass cullet fine powder, and a small amount of a binder (binder) such as corn starch, CMC and water glass. ) Is added and mixed, and then pressure-molded into a desired plate shape. The binder for pressure molding is usually an organic material such as corn starch, CMC, sodium alginate, PVA,
Polyacrylic emulgin, polyhydric alcohol wax and the like are used, and water glass and inorganic material gel such as alumina gel are also used as a binder also serving as a sintering agent for sintering fly ash particles. Further, although glass cullet fine powder is blended and used in the present invention, glass cullet is generally a glass scrap produced in the disposal of used glass bottles, and is simply discarded as waste or usefully utilized as a raw material for manufacturing various products. Is required, and the composition thereof is, for example, SiO ₂ ; 60 to 70%, Ca
_{O; 10~15%, Na 2 O} ; 8~15%, Al
₂ O ₃ ; 1 to 8%, Fe ₂ O ₃ ; 1 to 8%, and other small amounts, which are finely pulverized to a particle size of 50 to 150 μm, are preferably used. In the present invention, it is utilized as a strength enhancer / sintering agent / water absorption reducing agent of the resulting high strength lightweight ceramic plate.

At this time, in addition to this, it is also preferable to add a nucleating agent in order to crystallize the glass and further enhance the strength, and fluorite, silver, gold, and the like used for producing crystallized glass. Known nucleating agents such as titania and zirconia can be added and used. When the crystallization agent is added and manufactured, the temperature should be controlled by slow cooling according to a cooling temperature pattern that produces good crystallization, according to a conventional method at the time of cooling after firing. As a result, it is possible to provide a high-strength, lightweight ceramic plate with significantly enhanced product strength.

In the present invention, a refractory fine aggregate may be further added. As such a refractory fine aggregate, for example, silica fine powder, blast furnace slag fine powder, clay mineral fine powder, wollastonite powder, chamotte powder, etc. can be adopted, and these refractory fine aggregates are added and sintered. The ceramic plate thus obtained has high mechanical strength and heat resistance. In the present invention, various reinforcing fibers such as metal fibers, glass fibers, carbon fibers and various ceramic fibers can be mixed.

Further, in the present invention, a mesh sheet made of a heat-resistant material, for example, a mesh sheet made of stainless steel, can be embedded in order to enhance the bending strength of the product and prevent scattering at the time of breakage. Although it depends on the thickness of the high-strength lightweight ceramic plate, the thickness of the stainless wire is 0.3 to 0.5 m at a thickness of about 6 mm.
m is preferable, and the opening of the mesh is preferably about 5 to 15 mm. The particle size range of the raw material used in the present invention is preferably fine powder, particle size of fly ash is 5 to 50 μm, wollastonite (wollastonite) is 40 to 70 μm, and particle size of blast furnace slag fine powder is 10 to 100 μm. The fine silica powder is preferably 1 μm or less.

The action of each of the blended raw materials used in the present invention will be described below. First, as described above, most of the particle size composition of the main powder raw materials is from submicron to about 70.
The moldability can be improved by having a particle size up to micron, and by making the maximum around 10 to 30 micron among them. In addition, a small amount of fine powder of blast furnace slag reacts with an alkaline solution to exhibit a kind of hydraulic property, and particularly in the presence of an alkaline solution, the presence of a small amount of fine powder causes the solidification to occur more quickly by heating and drying. Inorganic fibers such as carbon fibers and ceramic fibers are confused with the powder raw material in the vertical and horizontal directions to dramatically increase the bending strength and flexibility of the molded body, and the binder strengthens the bond with the powder raw material.

In particular, water glass (sodium silicate aqueous solution)
The binder containing the above-mentioned material greatly promotes the dissolution and gelation of the particle surface of the fly ash powder raw material, and exerts the function of strongly sintering the powder particles as the firing temperature rises while uniformly enclosing the particles, and 850 It becomes a strong adhesive component for forming a ceramic body exhibiting sufficiently high strength at a firing temperature of up to 1200 ° C. The viscosity of the binder containing water glass is preferably adjusted by adding a clay mineral, for example, kaolin fine powder.

[0015]

EXAMPLE Next, an example of manufacturing a high-strength lightweight ceramic plate according to the present invention will be described. Example 1: Fly ash fine powder (average particle size 20 μm)
100 parts by weight of glass cullet fine powder (average particle size 7
0 μm) 30 parts by weight and binder (38Be water glass) 16
The base formed by adding and mixing parts by weight is roll-formed to 6
Thickness of 6 mm, width of 3 by rolling at a pressure of 0 kgf / cm ^2.
It was molded into a plate having a length of 00 mm and a length of 300 mm, dried, baked at 1150 ° C. for 2 hours, and allowed to cool. The bending strength of the ceramic plate obtained by cooling is 210 kgf / cm.
^{It had} a high strength of ² and a light weight with a bulk specific gravity of 1.9.

Example 2: Fine fly ash powder (average particle size 10 μm) 83% by weight, kaolin 11% by weight, wollastonite (wollastonite)
A fly ash base material comprising 5% by weight and 1% by weight of dextrin. ． Glass cullet fine powder (average particle size 9
0 μm) ,. A base material obtained by mixing and kneading water glass with various compounding compositions (specimen No. A1 to A5) shown in Table 1 was press-molded at a pressure of 60 kgf / cm ² ,
An unfired plate body having a thickness of 6 mm, a width of 200 mm and a length of 200 mm was produced.

[0017]

[Table 1]

Next, the green plate was baked at various temperatures and allowed to cool to obtain a high strength lightweight ceramic plate. The results are shown in Table 2 and FIGS.

[0019]

[Table 2]

It can be seen from Table 2 and FIGS. 1 to 4 that the material obtained by firing the glass cullet-added material has a high bending strength, a low water absorption rate and a low firing weight loss rate. In particular, it was found that the one having a firing temperature of 1000 to 1150 ° C. had high bending strength.

Example 3: A fly ash base material comprising 79% by weight of fine fly ash powder (average particle size 10 μm), 6% by weight silica fine powder, 9% by weight fine blast furnace slag powder, and 6% by weight kaolin. ． Glass cullet fine powder (average particle size 100 μm)
When,. Water glass and various compounding compositions shown in Table 3 (specimen No. B1 to B5) were mixed and kneaded to obtain 60 kgf / cm.
Press-molded at a pressure of ² , thickness 6mm x width 200mm
× An unfired plate having a length of 200 mm was produced.

[0022]

[Table 3]

Next, the green plate was baked at various temperatures and allowed to cool to obtain a high strength lightweight ceramic plate. The results are shown in Table 4 and FIGS.

[0024]

[Table 4]

It can be seen from Table 4 and FIGS. 5 to 8 that the material obtained by firing the glass cullet-added material has a high bending strength, a low water absorption rate and a low firing weight loss rate. In particular, it was found that the one having a firing temperature of 1000 to 1150 ° C. had high bending strength.

Example 4 Next, the compound (A3) material 1 used in Example 2 in the hopper 8 was placed on the molding line using the high-strength lightweight ceramic plate molding apparatus shown in FIG. On the left side, the sheet was adjusted to a thickness of 15 to 20 mm by the leveling plate 4 on the conveyor sheet 3 being fed, and at the same time, the stainless mesh sheet 2 was inserted into the material 1 on the conveyor sheet 3. . At this time, the stainless mesh sheet 2 is inserted into the material 1 from a position slightly floating from the surface of the conveyor sheet 3. After that, the stainless mesh sheet 2 is sandwiched between the materials 1 from above and below by a leveling plate 4 to form a sandwich, and the thickness is adjusted.
Rolled at ~ 70 kgf / cm ² and then cut with a cutter (not shown), thickness 6 mm x width 900 mm x length 9
After making a plate of 00 mm, it is transferred to the drying device 6 and
It is dried at 00 to 120 ° C, and further dried at 250 ° C.
By the above-mentioned rolling compaction, adjustment of width and thickness, firm adhesion with the stainless mesh sheet, partial defoaming by the roller in the first row and homogenization of the base composition were achieved. Finally, the dried composite plate 7 obtained as described above was transferred to a heating device (not shown) such as a tunnel kiln and fired at a high temperature. In this way, a high-strength lightweight ceramic composite plate having a stainless mesh sheet embedded therein was manufactured.

The produced high-strength ceramic composite plate has a bulk specific gravity of 1.89 g / cm ³ , a water absorption rate of 4.8% or less, a bending strength of 215 kgf / cm ^{2, a} heat resistant temperature of 1200 ° C., and a freeze-thaw. The test results were good. On the other hand, when the stainless mesh sheet was not embedded, the bending strength was 1
It was reduced by about 0%.

The high-strength lightweight ceramic plate or high-strength lightweight ceramic composite plate manufactured as described above is lightweight and has relatively high strength and low water absorption, so that it can be used as an interior or exterior material in a building, or as a ceramic for welding. It was preferable as an end tab and a ceramic surface covering material for welding.

[0029]

The high-strength, lightweight ceramic plate of the present invention as described above exhibits the following excellent operational effects. ． Fly ash and glass cullet are the main raw materials, and due to their amorphous nature (glassy), 850-12
Sintering can be sufficiently performed at 00 ° C, and fuel cost can be significantly reduced. ． The high-strength lightweight ceramic plate obtained by the present invention is
Since the glass cullet fine powder is present as a molten glass-like matrix between the fly ash particles, it becomes a relatively high-strength product and also has good water resistance. ． The high-strength lightweight ceramic plate obtained by the present invention with the mesh sheet interposed therebetween is hard to be destroyed because the reinforcing effect by the mesh sheet is exerted even when subjected to a physical impact, and even if it is destroyed, it is scattered as a fragment. It is safe because it never happens. ． Since the high-strength lightweight ceramic plate obtained by the present invention uses inexpensive fly ash and glass cullet as main raw materials, the product manufacturing cost can be significantly reduced as compared with the conventional product. The present invention also opens a great way to effectively utilize fly ash and glass cullet, which have been conventionally discarded in large quantities.

[Brief description of drawings]

FIG. 1 is a graph showing a change in water absorption of a high-strength lightweight ceramic plate obtained in an example of the present invention.

FIG. 2 is a graph showing a change in water absorption of a high-strength lightweight ceramic plate obtained in an example of the present invention.

FIG. 3 is a graph showing the change in bending strength of the high-strength lightweight ceramic plate obtained in the example of the present invention.

FIG. 4 is a graph showing the change in bending strength of the high-strength lightweight ceramic plate obtained in the example of the present invention.

FIG. 5 is a graph showing the change in water absorption of the high-strength lightweight ceramic plate obtained in the example of the present invention.

FIG. 6 is a graph showing changes in water absorption of the high-strength lightweight ceramic plate obtained in the example of the present invention.

FIG. 7 is a graph showing the change in bending strength of the high-strength lightweight ceramic plate obtained in the example of the present invention.

FIG. 8 is a graph showing a change in bending strength of the high-strength lightweight ceramic plate obtained in the example of the present invention.

FIG. 9 is a side view of an apparatus for manufacturing a high-strength lightweight ceramic plate according to an embodiment of the present invention.

[Explanation of symbols]

1: substrate 2: Stainless mesh sheet, 3: Conveyor sheet, 4: Leveling board, 5: Rolling roller, 6: Drying device, 7: Dry composite plate 8: Hopper

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Claims (18)

[Claims] 1. A base material comprising 100 parts by weight of fine fly ash powder having a particle size of 5 to 50 μm, 3 to 50 parts by weight of glass cullet powder having a particle size of 50 to 150 μm, and 3 to 30 parts by weight of a binder. 850-1200 after being formed into a plate
A method for manufacturing a high-strength lightweight ceramic plate, which comprises firing at ℃. 2. 100 parts by weight of fly ash fine powder having a particle size of 5 to 50 μm, 3 to 50 parts by weight of glass cullet fine powder having a particle size of 50 to 150 μm, 5 to 20 parts by weight of silica fine powder and 5 to 5 parts of blast furnace slag fine powder. 850 after molding a substrate formed by adding 20 parts by weight and 3 to 30 parts by weight of a binder into a plate shape
A method for manufacturing a high-strength lightweight ceramic plate, which comprises firing at ˜1200 ° C. 3. 100 parts by weight of fly ash fine powder having a particle size of 5 to 50 μm, 3 to 50 parts by weight of glass cullet fine powder of 50 to 150 μm, 5 to 20 parts by weight of clay mineral fine powder, and 5 of wollastonite powder. ~ 20 parts by weight and binder 3 ~ 3
After forming a green body by adding and mixing 0 parts by weight into a plate,
A method for producing a high-strength lightweight ceramic plate, which comprises firing at 850 to 1200 ° C. 4. 100 parts by weight of fly ash fine powder having a particle size of 5 to 50 μm, 3 to 50 parts by weight of glass cullet fine powder having a particle size of 50 to 150 μm, and 5 to 20 wollastonite powder.
5 parts by weight and blast furnace slag fine powder 5 to 20 parts by weight and binder 3 to
A method for producing a high-strength lightweight ceramic plate, which comprises forming a base material obtained by adding and mixing 30 parts by weight into a plate shape, and then firing the plate-shaped base material at 850 to 1200 ° C. 5. A glass cullet fine powder having a particle diameter of 50 to 150 μm is added in an amount of 20 to 40 parts by weight to 100 parts by weight of fly ash fine powder having a particle diameter of 5 to 50 μm. The method for producing a high-strength lightweight ceramic plate according to any one of items. 6. The method for producing a high-strength lightweight ceramic plate according to claim 1, wherein the binder is an inorganic binder. 7. The method for producing a high-strength lightweight ceramic plate according to claim 1, wherein the binder is an alkali metal silicate aqueous solution. 8. The method for producing a high-strength lightweight ceramic plate according to claim 7, wherein the alkali metal silicate aqueous solution is a sodium silicate aqueous solution (water glass). 9. The method for producing a high-strength, lightweight ceramic plate according to claim 1, wherein the binder is an inorganic binder or an organic binder. 10. The method for producing a high-strength lightweight ceramic plate according to claim 1, wherein the firing temperature is 1000 to 1150 ° C. 11. The method for producing a high strength lightweight ceramic plate according to claim 12, wherein a nucleating agent for crystallizing glass is added to the base material. 12. A gradual cooling treatment for promoting crystallization of glass is performed after firing of the base material.
A method for producing the high-strength lightweight ceramic plate described. 13. A base material is 5 to 10 parts by weight of one or two or more kinds of metal fibers, glass fibers, carbon fibers and ceramic fibers with respect to 100 parts by weight of fly ash powder having a particle size of 5 to 50 μm. The method for producing a high-strength lightweight ceramic plate according to claim 1, wherein the high-strength lightweight ceramic plate is added. 14. The heat-resistant material mesh sheet is embedded in a base material, compression-molded into a plate shape, and then the molded body is fired, according to claim 1. Manufacturing method of high strength and lightweight ceramic plate. 15. The method for producing a high-strength lightweight ceramic plate according to claim 14, wherein the heat-resistant material mesh sheet is a stainless mesh sheet. 16. A total amount of one or more inorganic binders selected from the group consisting of the following (a) to (c): 3
The method for producing a high-strength lightweight ceramic plate according to any one of claims 1 to 15, characterized in that the amount is -30 parts by weight. (A) Sodium silicate aqueous solution (water glass No. 1),
(B) A mixed solution of sodium silicate, aluminum hydroxide, zinc oxide, wollastonite, kaolin, boric acid and sodium aluminate, and a solution obtained by mixing the solutions of (c) (a) and (b) with sodium alginate. 17. A ceramic end dove for welding, which is produced by forming the base material according to any one of claims 1 to 16 into a plate shape and then firing it. Production method. 18. A ceramic ceramic backing material for welding, which is produced by forming the base material according to any one of claims 1 to 16 into a plate and then firing it. Method of manufacturing wood.