JPH05238815A - Method for producing plate-shaped product by sintering serpentine - Google Patents

Abstract

(57) [Summary] [Purpose] It is an object to provide a method for producing a tile-like product or a plate-like product such as a tile, which has a natural texture, using serpentine as an unused resource produced as one of metamorphic rocks as a raw material. [Structure] The serpentine 1 is adjusted into a powder having an appropriate particle size by a powder adjusting means 2 to be a raw material, and the raw material is combined with a molding auxiliary material 3 and a sintering auxiliary material 4 and kneaded by a kneading means 5, A plate formed by sintering serpentine characterized in that it is press-formed into a plate shape under appropriate forming conditions preset in the press-forming unit 6 and is baked for a certain period of time by a baking unit 7 held at a predetermined temperature. A method for manufacturing a shaped product is provided.

Description

Detailed Description of the Invention

[0001]

The present invention uses serpentine as a main raw material,
The present invention relates to a plate-like product such as a stone roof tile or tile having a natural texture and a relatively low water absorption rate, and a method for producing the product.

[0002]

2. Description of the Related Art Roof tiles have been frequently used as roofing materials and decoration materials for construction since ancient times, but general roof tiles are usually made of plastic clay, and after molding this material by wet or dry means,
It is manufactured by firing. Further, tiles, which are ceramic products of ceramics, are manufactured by using the same clay, porcelain stone, feldspar, etc. as raw materials, molding these raw materials in the same manner as above, glazeing and firing. And it is roughly classified into ceramic tiles, stone tiles and porcelain tiles according to differences in properties such as firing temperature, material distribution, and water absorption.

[0003]

However, the plastic clay, porcelain stone, feldspar, etc., which are used as raw materials for such conventional roof tiles and tiles, are depleted in terms of resources, and the future supply of raw materials will be stable. There is a problem that it cannot be done by. In particular, it is extremely difficult to secure high-quality clay mineral resources that are frequently used as raw materials for a long period of time, and it is an urgent task to secure new materials from the viewpoint of resource saving.

On the other hand, serpentine is an unused resource available in Japan. This serpentine is a resource that is abundantly produced as a large rock body, but this serpentine has traditionally only been used as an auxiliary raw material for steelmaking, aggregate for construction, stone for decoration, and as a raw material for tiles and tiles. It has not been reported to have been used.

Therefore, the present invention focuses on the above serpentine as an unused resource, and an object thereof is to provide a method for producing a plate-like product such as a tile or tile having a natural texture using the serpentine as a raw material. Is.

[0006]

In order to achieve the above object, the present invention adjusts a serpentine produced as one of metamorphic rocks to a powder having an appropriate particle size as a raw material, and uses this raw material as a forming aid. , A method for producing a plate-shaped product in which a sintering aid is combined and kneaded, and then pressure-molded into a plate-like shape under preset appropriate molding conditions, and baked for a certain period of time in a baking furnace maintained at a predetermined temperature Is the basic means. The particle size range of the serpentine powder is 45 μm or less, and the average particle size is 3 μm to 10 μm.
It is adjusted to the value of μm, and the range of the press pressure is 100
kg / cm ² or more, and firing temperature is 1200 ° C to 130
It provides a configuration in the range of 0 ° C.

The above serpentine powder is mixed with coarse serpentine particles having a particle size of 45 to 300 μm at a mixing ratio of 40% by weight or less. Further, as a sintering aid, phosphate, carbonate or fluoride is added. 2.5 to 10% by weight of one or more selected from sodium silicate, waste glass powder and the like. Also,
A structure in which serpentine powder is calcined at about 600 ° C or higher to remove water of crystallization, and then pressure-molded into a plate shape. Manganese, nickel, cobalt, chrome, iron, etc. are used as coloring materials for plain powder of serpentine. The above composition is provided by adding various oxides, and as a pattern material, various rock powders and serpentine magnetized materials are decorated.

[0008]

According to such a method for manufacturing a plate-like product by sintering serpentine, the obtained stone roof tile or tile has a natural stone-like texture and can be used for a wide range of applications such as building materials. When the serpentine powder has a small particle size range and a small average particle size, it can be fired at a low temperature, but on the other hand, the shrinkage ratio increases and the bending strength decreases, so the powder particle size range is 4
Good products can be obtained by setting the average particle size to 5 μm or less and the average particle size to 3 μm to 10 μm. Further, by selecting such a value, the crushing cost can be reduced. Further, the pressing pressure of the serpentine powder is set to 100 kg / cm ² or more, and the firing temperature is set in the range of 1200 ° C to 1300 ° C, so that both the water absorption rate and the bending strength of the product are satisfied in good balance.

Further, it is possible to lower the overall sintering temperature by adding a sintering aid such as phosphate to the serpentine powder. The contraction rate is affected, and the effect that the product is decorated by adding the oxide and the pattern material to the plain powder of serpentine is obtained.

[0010]

EXAMPLE An example of a method for producing a plate-like product by sintering serpentine according to the present invention will be described below. First, the serpentine used as a raw material in this embodiment will be described. In other words, serpentinite is one of metamorphic rocks, which is a kind of igneous rock that has been altered by hydrothermal metamorphism and contains chrome iron ore or magnetite, but the main component is serpentine. Is. It is usually called a serpentine because it has a yellowish green or dark green color, a black color rarely a reddish brown mottled color, and has a fat luster and a greasy feel.

Since serpentinite is abundantly produced as a large rock body in metamorphic rock areas in various places and is easy to work, it has been used as a decorative stone material for construction since ancient times. In recent years, it has also been used as a slag material for blast furnaces.

In this embodiment, the above serpentine is adjusted into a powder having an appropriate particle size as a raw material, and this raw material is used as a forming aid,
A sintering furnace in which sintering aids are combined, decorated with pigments, etc., if necessary, and kneaded, and then pressure-molded into a plate shape with a preset appropriate press pressure, and kept at a predetermined temperature. The main purpose is to manufacture plate-like products such as stone roof tiles and tiles by firing for a certain period of time. The roof tile or tile according to this embodiment has a characteristic that it has a natural stone tone material feel and can be used for a wide range of purposes.

FIG. 1 is a block diagram showing a basic manufacturing process of the present embodiment. Reference numeral 1 in the figure is a serpentine produced as one of the metamorphic rocks, and this serpentine 1 is suitable for powder adjusting means 2. The raw material is prepared by adjusting it to powder with various particle sizes. This raw material is combined with a molding aid 3 and a sintering aid 4 and kneaded by a kneading means 5, and then pressure-molded by a pressure-molding means 6 to a plate shape with an appropriate press pressure set in advance and then fired. It is characterized in that the plate-shaped product is manufactured by firing for a certain period of time in the firing furnace kept at a predetermined temperature by means 7.

Specific examples of the present invention will be described below. [Example 1] In order to confirm the influence of the size of serpentine particles, 10.0% by weight of a CMC (carboxymethylcellulose) -1% by weight solution was added to serpentine powders having different particle size ranges and average particle diameters (μm). After kneading with a mixer and press-molding (pressing pressure 100 kg / cm ² ), firing is performed using an electric furnace (firing temperature is 1250 ° C, 1275 ° C, 1300
3 steps of ℃, heating rate: 250 ℃ / hr, 1 at a predetermined temperature
(Hr holding) to obtain a fired body. The results of measuring the physical properties of this fired body are shown in Table 1.

[0015]

[Table 1]

According to Table 1, when the particle size range and the average particle size are small, it is possible to sinter at a low temperature, but on the other hand, the shrinkage ratio increases and the bending strength decreases. It was also confirmed that when the particle size range and the average particle size are large, it becomes difficult to sinter and the bending strength is slightly weakened. Therefore, the serpentine fine particles have a particle size range of 45 μm or less and an average particle size of 3 μm to 1
It is judged that the value of 0 μm is preferable.

Example 2 Next, in order to confirm the influence of the press pressure and the firing temperature, CM was added to the serpentine fine particles (45 μm or less, average particle size 6.5 μm) confirmed in Example 1 above.
Add 10.0% by weight of C-1% by weight solution, knead with a mixer, and press-mold (press pressure 50-1000 kg / c
m ² ), followed by firing using an electric furnace (the firing temperature is 125
3 stages of 0 ℃, 1275 ℃, 1300 ℃, heating rate: 2
50 degreeC / hr, 1 hour hold | maintained at the predetermined temperature), and the baked body was obtained. The results of measuring the physical properties of this fired body are shown in Table 2.

[0018]

[Table 2]

Regarding the relationship between the press pressure and the firing temperature and the characteristic value, when the degree of sintering is viewed as the change in shrinkage rate and water absorption rate, in order to promote the sintering, high temperature in the case of low pressure molding However, in the case of high-pressure molding, the influence of the firing temperature is small and the shrinkage rate is small. Further, the bending strength shows the highest strength at the time when the sintering is almost completed, and thereafter decreases with the generation of the glass phase due to over-firing, etc.
There is little merit in terms of strength and equipment. Therefore, in order to obtain a dense sintered body, the pressing pressure is 100 kg / c.
It was confirmed that m ² or more, preferably 200 to 400 kg / cm ² , and the firing temperature in the range of 1200 ° C. to 1300 ° C. are preferable.

[Embodiment 3] Next, in order to confirm the influence of the particle size of the serpentine coarse particles mixed with the serpentine fine particles in order to reduce the contraction rate, serpentine fine particles and serpentine coarse particles (45 to 300 μm)
m) is a fine: coarse mixing ratio of 100: 0,80: 20,
60:40 (wt%) classified into 3 stages and mixed, CM
After adding 10.0 wt% of C-1 wt% solution, kneading with a mixer, pressure molding (100 kg / cm ₂ ), firing using an electric furnace (firing temperature is 1250 ° C., 1275 ° C., 1
Three stages of 300 ° C., temperature rising rate: 250 ° C./hr, 1 hr holding at a predetermined temperature) were performed to obtain a fired body. The results of measuring the physical properties of this fired body are shown in Table 3.

[0021]

[Table 3]

The influence of the mixing of the above fine and coarse particles did not show a large difference in the water absorption rate. Overall, the mixing of coarse particles is effective in reducing the shrinkage rate, but if excessive mixing occurs, sintering may be impeded. If 40 or more (wt%) coarse particles are mixed, the appearance will be difficult. And increase the water absorption rate,
The mixing ratio of coarse serpentine grains is 4 because of deterioration of strength.
It is preferably 0 (% by weight) or less.

[Example 4] In order to confirm the influence of the sintering aid, 7.5 wt.
% By weight, and 2.5% by weight of glass powder and sodium carbonate (Na ₂ CO ₃ ) as a sintering aid, kneaded with a mixer, and then pressure-molded (100 kg / cm ₂ ) under the same conditions as above. Was fired using an electric furnace of No. 1 to obtain a fired body. The results of measuring the physical properties of this fired body are shown in Table 4.

[0024]

[Table 4]

Although there was no fundamental difference in the physical properties of the fired body, the sintering temperature should be lowered by 100 ° C. as a whole when the sintering aid is added and mixed as compared with the sample without addition. You can

Next, in order to confirm the effect of calcining the serpentine powder, the results of examining the firing shrinkage of the calcined serpentine powder compact are shown in FIG. In FIG. 2, as a comparative example, the firing shrinkage of a raw serpentine powder compact is shown. According to FIG. 2, it was confirmed that the serpentine powder was calcined at a temperature of about 600 ° C. or higher to remove the water of crystallization, and then it was effective in reducing the shrinkage rate.

Table 5 shows the weight of the product of the present invention and the existing target product.
(kg / 3.3m ² ), water absorption rate (%) and bending strength (kg / cm ² ) are shown in comparison with existing products such as natural slate tile, clay tile and stoneware interior tile. It is clear that both the weight and the water absorption of the product of the present invention are small, and the bending strength of the product of the present invention is much higher.

The serpentine fired product obtained in this example is
As shown in FIG. 3, since it is a far-infrared radiator that exhibits a high emissivity of around 80% in the wavelength range of 4 to 20 μm, it can be used as a plate for grilled meat or tableware for cooking with these characteristics taken into consideration. In addition, the bending strength shown in Table 6,
It can be used as an insulating material because of its thermal expansion coefficient and electromagnetic characteristics.

[0029]

[Table 6]

FIG. 4 is a differential heat curve of serpentinite, and FIG. 5 is a graph showing the same X-ray diffraction pattern. After dehydration of contained brucite at around 400 ° C. and dehydration of crystal water at around 700 ° C., It is understood that at around 820 ° C., antigorite is transformed into forsterite, and at higher temperatures, a part of enstatite is formed, and as the temperature rises, sintering progresses and becomes dense.

From the above description, by making the serpentine powder into fine particles of at least 45 μm or less, it is effective to lower the temperature of sintering, but an average particle diameter of 3 to 10 μm is an energy cost for pulverization. It is preferable from the aspect. Further, in order to reduce the firing shrinkage rate, 45 to 300 μ
It is effective to mix about 30% by weight of coarse particles of m, but in this case, the mixing of coarse particles having a maximum dimension of 300 μm or more and mixing of 40% by weight or more result in a rough surface of the fired body, There is a drawback that it is not preferable in appearance. Note that calcination of serpentine at 600 ° C. or higher to remove water of crystallization is also effective in reducing the firing shrinkage rate.

The molding is carried out by an ordinary mechanical pressure press or a vibration pressure press, and the press pressure is preferably 100 kg / cm ² or more from the viewpoint of strength and densification of the molded product, and the higher the pressure, the higher the pressure. It is good. In addition, mixing with water, coarse particles, molding aids, binders, sintering aids, decorating materials, etc. is performed by a mixer, but the water content of these raw materials naturally varies depending on the molding method and pressing pressure. From the viewpoint of handling and physical properties of the obtained molded product, it is necessary to set it in an optimum range, and most is 5 to 10% by weight. When the raw materials are mixed and adjusted by a wet method, granulation and drying with a spray dryer are effective.

Firing is carried out in an oxidizing or reducing atmosphere in an ordinary electric furnace or gas furnace, but in order to lower the firing temperature, sintering aids such as phosphates, carbonates, fluorides, sodium silicate, waste glass powder, etc. are used. It is preferable to add 2.5 to 10% by weight of the material, and most preferably 2.5% by weight of sodium carbonate is added.

By mixing a small amount (10% or less) of bentonite or high-quality plastic clay as a molding aid, the molding process and the properties of the molded body and the fired body can be improved. In addition, serpentine contains a few weight percent of iron,
Even if it is baked alone, it has a good color tone with a sense of texture,
In some cases, oxides of manganese, nickel, cobalt, chrome, iron, etc., which are usually used as coloring materials, should be added, and as a patterning material, various rock powders, serpentine magnetized materials, etc. should be decorated. You can

[0035]

As described in detail above, according to the method for producing a plate-like product by sintering serpentine according to the present invention,
Plate-shaped products such as roof tiles and tiles can be obtained from serpentine, which has only been used as an auxiliary raw material for steelmaking, aggregate for construction, and stone for decoration, as a raw material. Effective utilization of unused resources abundant in Japan It is possible to make full use of it. Therefore, it can be used as a substitute for depleted resources such as plastic clay, porcelain stone, and feldspar, which have been used as the above-mentioned raw materials, and it also has the great effect of stabilizing the supply of raw materials in the future. To do.

The stoneware tiles and tiles thus obtained have a natural stone-like texture, and can be used in a wide range of applications such as building materials. At the time of production, it is possible to adjust the firing temperature and the shrinkage rate of the product by selecting the particle size range and average particle size of the serpentine powder, and further adding a sintering aid such as phosphate to the serpentine powder. It is possible to lower the overall sintering temperature by changing the shrinkage ratio of the product depending on the fine: coarse mixing ratio of the serpentine powder. Since the product can be decorated by adding
By selecting various manufacturing conditions, it is possible to obtain an effect that a desired quality product can be obtained.

[Brief description of drawings]

FIG. 1 is a block diagram showing a basic manufacturing process of the present invention.

FIG. 2 is a graph showing firing shrinkage rates of calcined serpentine powder and raw serpentine powder compacts.

FIG. 3 is a graph showing emissivity of a serpentine fired body in a specific wavelength range.

FIG. 4 is a differential heat curve graph of serpentine.

FIG. 5 is a graph showing an X-ray diffraction pattern of serpentine.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Serpentine rock 2 ... Powder adjusting means 3 ... Forming auxiliary material 4 ... Sintering auxiliary material 5 ... Kneading means 6 ... Pressure forming means 7 ... Firing means

[Table 5]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jun Yamamoto 3992, Fushida, Kochi City, Kochi Prefecture Kochi Prefecture Industrial Technology Center (72) Inventor, Kazuhide Hamada 3992, Fushida Kochi City, Kochi Prefecture Kochi Prefecture Industrial Technology Inside the center (72) Inventor Haruyuki Nishiyama 4-3 Shonoshiba-cho, Aki-shi, Kochi Nagano Kawarauchi Co., Ltd.

Claims (9)

[Claims] 1. A serpentine produced as one of metamorphic rocks is adjusted to a powder having an appropriate particle size as a raw material, and the raw material is preliminarily set after being combined with a forming aid and a sintering aid. A method for producing a plate-shaped product by sintering serpentine, which comprises press-molding into a plate-like shape under appropriate molding conditions and firing in a firing furnace maintained at a predetermined temperature for a certain period of time. 2. The method for producing a plate-like product by sintering serpentine according to claim 1, wherein the particle size range of the serpentine powder is 45 μm or less and the average particle size is adjusted to a value of 3 μm to 10 μm. 3. The method for producing a plate-shaped product by sintering serpentine according to claim 1, wherein the molding condition is a pressing pressure of 100 kg / cm ² or more. 4. The firing temperature is 1200 ° C. to 1300 ° C.
The method for producing a plate-like product by sintering serpentinite according to claim 1, wherein 5. The method for producing a plate-like product by sintering serpentine according to claim 1, wherein the molding condition is a pressing pressure of 100 kg / cm ² or more, and the firing temperature is in the range of 1200 ° C. to 1300 ° C. .. 6. Sintering of serpentine according to claim 1, 2, 3, 4, 5 wherein serpentine powder is mixed with serpentine coarse particles having a particle size of 45 to 300 μm at a mixing ratio of 40% by weight or less. For manufacturing plate-shaped products. 7. A sintering aid containing 2.5 to 10% by weight of one or more selected from phosphates, carbonates, fluorides, sodium silicate, waste glass powder and the like. ，
A method for producing a plate-like product by sintering the serpentine according to 2, 3, 4, 5, 6. 8. Serpentine powder is calcined at about 600 ° C. or higher,
The plate-shaped pressure molding is performed after removing water of crystallization.
A method for producing a plate-like product by sintering the serpentine according to 2, 3, 4, 5, 6, 7. 9. A method in which an oxide of manganese, nickel, cobalt, chrome, iron, etc. is added as a coloring material to a plain powder of serpentine and further decorated with various rock powders and magnetites of serpentine as a patterning material. Items 1, 2, 3, 4, 5, 6, 7, 8
A method for producing a plate-like product by sintering the serpentine as described.