JPH0333059A - Composition for inorganic compacting and burning material - Google Patents

Abstract

PURPOSE:To permit the hardening by compacting without a biscuit-firing stage and to prevent the deterioration of the strength by glazing in the composition by blending it with a hydraulic cement-contg. material constituted of specified burning-treated products or melting-treated products. CONSTITUTION:The composition contains a hydraulic cement-contg. material constituted of at least one kind among the burning-treated products and melting- treated products of at least one kind among silicocarnotite, nagelschmitite and a CaO-P2O5-SiO2 series glass phase material. Furthermore, a melting assistant constituted of at least one kind among Na2O, K2O, MgO, Al2O3, Fe2O3 and CaF2 can be added to the above composition. The above hydraulic cement- contg. material is brought into reaction with water at an ordinary temp. and is hardened, and the hydrated and hardened body is stable to high temp. heating and is burnable at >=800 deg.C, preferably at a high temp. of 1000 to 1350 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a composition for inorganic molded and fired materials. More specifically, the present invention relates to compositions for inorganic molded and fired materials, such as tile materials widely used for the interior and exterior of buildings.

[Prior art/issues to be solved by the invention] Tile materials widely used in buildings are generally made by molding clay into a desired shape and size, drying it, and firing it to make unglazed ceramics.
After applying a glaze to this unglazed pottery and drying it, it is then fired again.

Such conventional tile manufacturing methods require two firing steps, resulting in high manufacturing costs. In this conventional method, there is a high probability that cracks and warpage will occur during the first firing step of producing unglazed clay from clay, which makes it particularly difficult to produce large tile products. Therefore, by using cement instead of clay as the raw material for tiles, the unglazing process can be omitted, and based on the properties of cement, it is possible to use molds in the forming process, which makes it possible to make large tiles. It will also be easier to manufacture products and tile products with complex shapes.

However, cement tiles have the significant drawback that they cannot be glazed and fired. That is, there are many types of cement, such as Portland cement, alumina cement, mixed cement, and gypsum, all of which form hardened bodies when hydrated. A common drawback of tile products made with these cements is that they lose strength upon heating. Such loss or reduction in tile strength is due to crystallization water of the hydrated and hardened cement that constitutes the cement tile being volatilized and lost by heating, resulting in alteration of the hardened cement. For this reason, it is impossible to apply a glaze to cement tiles and then fire them, and therefore, conventional cement tiles have been unsatisfactory in quality such as surface aesthetics and smoothness.

In view of the above circumstances, the present invention provides a composition for an inorganic molded and fired material that can be molded and hardened without a bisque firing process using a hydration-hardenable cementitious material, and that does not reduce its strength by glazing and firing. This is what we are trying to provide.

Further, the present invention uses a hydration hardenable cementitious material to
The large-size type is an inorganic material that can be molded into products with complex shapes without the need for bisque firing, and that the surface can be glazed and fired to improve the aesthetic appearance and smoothness of the surface without reducing strength. The present invention aims to provide a composition for shaping and firing materials.

[Means to solve the problem]

The composition for inorganic molded and fired materials of the present invention includes silicocarnotite, Nagelschmittite, CaOp, o,
It includes a hydraulic cement material made of at least one member selected from a sintered product of a 5iOz-based glass phase material and a melted product.

In addition, other compositions for inorganic molded and fired materials according to the present invention include:
Silicocarnotite, Nagelschmittite and C
A hydraulic cementitious material consisting of at least one selected from a sintering product and a melting product of at least one member of aO-hO, -5-SiO2-based glass phase material;
NaJ+ Kto, MgO9^120's.

A melting aid made of at least one selected from Fe, O, and CaFz.

In order to produce an inorganic molded and fired material, such as a tile material, from the inorganic molded and fired material composition of the present invention, a powder consisting of the composition of the present invention is mixed with water, phosphoric acid, a water-soluble phosphate,
It is mixed with at least one aqueous solution selected from sulfuric acid and at least one aqueous solution selected from water-soluble sulfates, this aqueous mixture is molded into a predetermined size and shape, and the molded product is cured.

At this time, a firing step is not necessary. Next, after applying a glaze to a predetermined portion of this molded and cured body and drying, the glazed and cured body is subjected to a firing treatment at a specific temperature, for example, 700°C to 1200'C for 0.5 to 10 hours.

The main cementitious materials used in the present invention are silicocarnotite (CasPzSiO+z), Nagelschmittite (CatPzSizO+,) and CaO
High temperature of PzOs-3ing type glass phase material, e.g.
The product fired at 00 to 1600°C and the product melted at a high temperature, for example 1400 to 1500°C, are hydraulic cementitious materials that exhibit the property of being hardened by a hydration reaction in the aqueous slurry forming process. As described above, the powder of the hydraulic cementitious material of the present invention is dispersed in water or an aqueous solution of phosphoric acid, a water-soluble phosphate, sulfuric acid, or a water-soluble sulfate, and the resulting aqueous slurry (
For example, if the mixture is injected into a mold and molded, it will eventually be hydrated and hardened to obtain a molded and cured product. At this time, if phosphoric acid, water-soluble phosphate, sulfuric acid, or aqueous sulfate is present in the aqueous slurry, the hydration hardening reaction of the hydraulic cementitious material of the present invention is promoted. As the water-soluble phosphate used for this purpose, it is preferable to use sodium phosphate, sodium hydrogen phosphate, potassium phosphate, etc., and as the water-soluble sulfate, it is preferable to use sodium sulfate, potassium sulfate, etc. Further, the concentration of acid or salt in the aqueous slurry is preferably 10 to 1000 ppn+. Also, the hydraulic cement of the present invention in an aqueous slurry)! The concentration of the material is not particularly limited, but it is generally preferred to use a concentration of 10 to 90% (by weight).

The main cementitious material used in the present invention is basically CaO
It has a hos S-SiO2 system composition, and its fired or melted product is dicalcium silicate (CazSi04).
A continuous solid solution (Ca:+x+zy PzxSly O
++x+av'J. Such a continuous solid solution is silicocarnotite (CasPzSiO+
z), Nagelschmittite (CatPzSizO
+6) and CaO-P20s is formed in a hydraulic cementitious material by firing and melting a 5iOz-based glass phase material.

The material (hydraulic cement) of the present invention is cured by reacting with water at room temperature, and this hydrated cured product is stable against high temperature heating and is preferably heated to 800°C or higher, preferably LOOO~l,
It can be fired at a high temperature of 350″C.

However, this hydrated and hardened product does not undergo chemical changes, that is, continuous loss of crystallized water, even when fired at high temperatures as described above, and therefore does not suffer from a decrease in mechanical strength or deformation.

The composition for an inorganic molded and fired material of the present invention includes the above-mentioned hydraulic cementitious material and NazO + IhO, MgO, Al
tOff+Fe2O, and a melting aid consisting of at least 1 member selected from CaFz. This melting aid increases the mechanical strength of the obtained shaped and fired material, and also It is effective in improving the adhesion between the base material and the glaze. This melting aid is
It is preferably blended within a range of 20 to 80%, and preferably within a range of 30 to 70%, based on the weight of the main cementitious material. If the blending ratio of the melting aid is greater than 80%, melting may occur during firing of the resulting composition for molded and fired materials, resulting in blistering and melt dripping. When the blending ratio is less than 20%, the effect of increasing the strength of the obtained Kai-shaped Baking Kai material and the effect of improving the adhesion to the glaze are
It may be insufficient.

Furthermore, the calcined or melt-processed product of silicocarnotite (CazPzSi01□) is obtained by combining calcium raw materials such as calcium carbonate, phosphorus raw materials such as calcium dihydrogen phosphate, and silicate raw materials such as silicon dioxide. Mix the component elements so that the molar ratio corresponds to the above composition formula, and heat the mixture at 1450'C to 1500'C.
Obtained by firing or melting for ~50 hours.

The calcined or melted product of Nagelschmittite (CatPzSiJ+i) is prepared by mixing the raw materials of each element in the same manner as above, and calcining or melting this at a temperature of 1450'C to 1500'C for 0.5 to 20 hours. obtained by doing.

Also, CaO-1'20. - The fired or melted Sing-based glass phase material is produced by mixing each elemental raw material with NazO, K2O, CaF, etc. in the same manner as above, and heating the mixture at 1300°C to 1500°C. Obtained by melting and assimilating at temperature for 5-20 hours.

To produce the composition of the present invention, the main cementitious material of a predetermined composition is mixed with a predetermined amount of a predetermined type of melting aid, if necessary, and calcined at a temperature of 1300°C-1600'C. Alternatively, it is melted, then solidified, and then ground to a predetermined particle size.

〔Example〕

The invention will be further illustrated by the following examples.

(Example 1) 3 mol of calcium dihydrogen phosphate, 7 mol of calcium carbonate, and 0.5 mol of silicon oxide were mixed, and this mixture was calcined at 1500°C for 16 hours to form silicocarnotite ( 5CaO.P2O, .S-SiO2) was produced.

This fired product was ground into powder having a particle size of 44 mm or less using a ball mill. For 100 g of this main cementitious material powder, 100 g of alumina (Al zo
o) was added, and this mixture was further added to 60 g of a 1% aqueous sodium hydrogen phosphate solution and kneaded.

The above-mentioned kneaded material was poured into a tile forming mold, and the mixture was cured in humid air for 2 hours at 60" CI to cure it. This tile cured product was removed from the mold. It was taken out, a frit glaze was applied to its surface, and it was dried.

This cured glazed tile body was fired at 1000°C for 1 hour. The obtained tile had sufficient mechanical strength for practical use, and its surface had sufficient aesthetic appearance and gloss for practical use.

(Example 2) The same operation as in Example 1 was performed. However, Schnagelschmittite was used instead of silicocarnotite.

This Schenergelstite was produced by calcining a mixture of 2 moles of calcium hydrogen phosphate, 5 moles of calcium carbonate, and 1 mole of silicon oxide at 1500° C. for 10 hours. Also, alumina was not used.

The obtained tile had practically sufficient mechanical strength and surface appearance and smoothness.

(Example 3) The same operation as in Example 1 was performed. However, instead of silicocarnotite, a mixture of 3 moles of calcium dihydrogen phosphate, 7 moles of calcium carbonate, 1 mole of silicon oxide, and 3 moles of CaF2 was melt-treated at 1400 °C for 12 hours. CaOpros Sing-based glass phase material powder obtained by the above method was used.

The obtained tile had practically sufficient mechanical strength, surface smoothness, and aesthetic appearance.

〔Effect of the invention〕

The composition for an inorganic molded and fired material of the present invention has a hydraulic green cementitious material as a main component, and therefore the bisque firing process can be omitted in the molded product. Furthermore, since the hydrated and cured product obtained from this composition has high heat resistance, even if it is fired after being glazed, there is no loss in strength, and a product with excellent aesthetics and smoothness can be obtained. Furthermore, the present invention facilitates the manufacture of products of large dimensions and complex shapes, which were difficult to manufacture using the prior art.

Claims (2)

[Claims] 1. An inorganic material containing a hydraulic cementitious material consisting of at least one calcination product selected from silicocarnotite, Nagelschmittite, and at least one member of CaO-P_2O_5-SiO_2-based glass phase material, and a melt-processed product. Composition for shaping and firing materials. 2. A hydraulic cementitious material consisting of at least one member selected from silicocarnotite, Nagelschmittite, and a calcined product of at least one member of CaO-P_2O_5-SiO_2-based glass phase material, and a melt-processed product, and Na_2O , K_2O, MgO, Al_2O
_3, Fe_2O_3, and a melting aid consisting of at least one selected from CaF_2.