JPH01264950A - Production of building material such as tile - Google Patents

Abstract

PURPOSE:To obtain a tile which has color tones having a depth and has good performance and to make effective utilization of metal refining slag, etc., by adding clay to a ceramics mixture essentially consisting of iron oxide and silica and molding and calcining the mixture. CONSTITUTION:The mixture consisting of A) 100 parts ceramics mixture (50-90wt.% iron oxide, 10-30% silica, <=10% oxide of alkali or alkaline earth metal), B) >=3 parts clay, and an org. binder and/or water at need is extruded. This molding is calcined at 1,100-1,300 deg.C max. temp. in an oxidizing atmosphere to obtain the building material such as tile. The amt. of the clay to be added is specified to >=20 parts in case of press forming. A magnetization characteristic and electrical conductivity can be imparted to the calcined body if the clay is added at <=50 parts and the max. calcination temp. is kept at >=1,200 deg.C. Such material is useful as the building material for a clean room which requires an antistatic effect.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing building materials such as tiles, and particularly relates to a technology for manufacturing building materials such as tiles by effectively utilizing inexpensive ceramics such as metal smelting slag. Products include outer groove tiles, design tiles (oxidized style,
walnut finish), conductive tiles, electrocoated tiles and other tile products, building materials such as bricks, curbstones, wall stones, flooring materials,
It can also be used as flooring and wall materials in fields where static electricity is averse, such as in clean rooms.

Until now, metal smelting slag had been mainly reused as landfill material. However, landfilling is expensive, and because slag is generally fine-grained, it is difficult to compact, and there is a new danger that it may flow during an earthquake.

It was considered to be used as a raw material for cement, but its iron content hindered its usefulness.

There has been a desire to more actively utilize the properties of ceramics, and for example, an unfired molded body in which copper slag is bonded with phosphate has been proposed.

As mentioned above, an unfired molded product made by bonding copper slag with a phosphate has been proposed, and has achieved considerable profits, but in order to further expand its uses, the industry is developing new fired products. There is a desire to obtain something. Fired products have advantages over unfired products in terms of strength, appearance, water absorption, and other aspects, and if fired products are realized, they will have a wide range of uses for manufacturing building materials such as tiles. Be expected.

The purpose of the present invention is to
The goal is to establish a technology that makes it possible to manufacture building materials such as tiles by using ceramics, which are available in large quantities at low cost.

As a result of repeated studies for the above purpose, the present inventors have developed a method that mainly contains iron oxide and silica, as represented by iron concentrate, which is one of the slags produced in copper smelting. The ceramic mixture as a component exhibits good moldability and plasticity when clay is added, and the constituent minerals are mainly ferruginous stone and magnetite, which have the advantage of being extremely strong and chemically stable. Focusing on this aspect, we ventured into producing fired products, which had previously been considered difficult, and succeeded for the first time in developing products such as vine tiles that had a deep color tone and had satisfactory properties.

Based on the above findings, the present invention provides the following: 1) Iron oxide 50-90% by weight, silica 10-30% by weight
, 2 parts of clay per 100 parts of a ceramic mixture containing up to 10% by weight of alkali or alkaline earth metal oxides.
A step of adding an organic binder and/or water as necessary by adding 0 parts or more, a step of molding the resulting mixture to produce a molded object, and a step of heating the molded object to a maximum temperature of 1100 to 1
A method for producing building materials such as tiles, which includes the step of producing a fired product by firing in an oxidizing flame atmosphere at a temperature of 300°C, 2
) Iron oxide 50-90% by weight, silica 10-30% by weight,
20 parts of clay per 100 parts of a ceramic mixture containing up to 10% by weight of alkali or alkaline earth metal oxides.
a step of adding water and a deflocculant, a step of pulverizing and mixing the resulting mixture, adding an organic binder as necessary to the mixture, dehydrating and drying it, and then granulating it; A process for producing tiles, etc., which includes the steps of press-molding an object to produce a press-molded body, and firing the press-molded body in an oxidizing flame atmosphere at a maximum temperature of 1,100 to 1,300°C to produce a fired body. Manufacturing method of building materials and 3) Iron oxide 50-90% by weight, silica 10-30% by weight
, 3 parts of clay per 100 parts of a ceramic mixture containing up to 10% by weight of alkali or alkaline earth metal oxides.
a step of adding water and a deflocculant, a step of pulverizing and mixing the resulting mixture, adding an organic binder to the mixture, dehydrating and drying the mixture, and extruding the resulting mixture. A method for producing a building material such as a tile, which includes the steps of: producing an extruded body by heating the extruded body; and firing the extruded body in an oxidizing flame atmosphere at a maximum temperature of 1,100 to 1,300°C to produce a fired body. provide.

Furthermore, by setting the clay content to 50 parts or less and setting the maximum firing temperature to 1200° C. or higher, magnetization and electrical conductivity can be imparted to the fired body.

The present invention uses 50 to 90% by weight of iron oxide and 10 to 30% by weight of silica.
The basic raw material is a ceramic mixture containing up to 10% by weight of alkali or alkaline earth metal oxides.

Although it can be prepared synthetically, it is convenient to
It can be obtained from metal smelting slag.

Here, we will explain copper smelting slag.

In copper smelting, depending on the smelting method, flash furnace slabs,
Various types of slag are produced, including reverberatory furnace slag, blast furnace slag, converter slag, and MI process slag. Approximately 2 million tons of such slag are produced annually. Taking the flash-smelting furnace method, which is currently widely used, as an example, copper concentrate is charged into the shaft of the flash-smelting furnace together with a small amount of solvent, and after melting and oxidation smelting in the shaft, a portion of the copper concentrate is Matte and slag are generated in the process. These slags are mainly composed of iron oxide and silica. The matte produced in the flash furnace is smelted in a converter, and in this case converter slag is generated. Since converter slag contains around 5% copper, it is sent to a beneficiation base to recover the copper, and the remaining slag is commonly referred to as "iron concentrate" due to its high iron content. This iron concentrate is one of the most suitable for use in the present invention, but as long as it falls within the above composition range, it is not limited to iron concentrate, and acid slag or a mixture of multiple types of slag may be used. can also be used.

In addition, in this specification, iron oxide refers to Fe01Fez
es, Fe, 04, FeO-Fears, n
It includes FeO-Sin□ (n is 1 to 3) existing in various forms. In particular, iron oxide present as n FeO.5iOz can be quantitatively determined by distinguishing it into FeO and SiO□ in ordinary quantitative analysis, so it is regarded as iron oxide here.

In order to obtain a robust and stable fired body, iron oxide must be 50 to 50%
90% by weight and 10-30% by weight of silica is required.High iron oxide content is key to the present invention.

Clay is incorporated to provide moldability to the ceramic mixture and to provide handling strength after molding until firing. For this purpose, at least 3 parts of clay are added to 100 parts of the ceramic mixture. The amount of clay required depends on the molding method and whether an organic binder is used. Clay is generally used as a raw material for ceramics.
Preferable examples include clay minerals containing bentonite, kaolinite, halloysite, and sericite, such as Obonbushi clay and Awaji clay.

An organic binder and water are added as necessary. The moldability and plasticity of the desired ceramic mixture can be improved using only clay.
If it is difficult to obtain sufficient handling strength after molding and before firing, an organic binder and/or water may be added as necessary for adjustment.

The use of an organic binder is effective in imparting plasticity to the material; for example, a polyacrylamide-based polymer flocculant is used. Practically speaking, it is more effective to use it by dissolving it in a solvent (for example, a paraffin emulsion and a surfactant) at a concentration of 5 to 60%, and then dissolving it in water. Distribute evenly throughout.

If press molding is desired, the above raw material components should be added to 100 parts of a ceramic mixture containing 50 to 90% by weight of iron oxide, 10 to 30% by weight of silica, and 10% by weight or less of an alkali or alkaline earth metal oxide. Add 20 parts or more of clay, further mix water and a deflocculant (for example, water glass),
The resulting mixture is pulverized and mixed, an organic binder is added to the mixture as required, and the mixture is dehydrated and dried, followed by granulation. Industrially, spray drying and granulation are useful. After this,
Press molding is carried out at a pressure of 200-300 kg/cm''. Press molding is suitable for producing simple surfaces such as tiles.

If extrusion is desired, 50-90% by weight iron oxide
A mixture obtained by adding 3 parts or more of clay to 100 parts of a ceramic mixture containing 10 to 30% by weight of silica and 10% by weight or less of an alkali or alkaline earth metal oxide, and further adding water and a deflocculant. are pulverized and mixed, an organic binder is added to the mixture, and the mixture is dehydrated and dried using a filter press, and the resulting mixture is extruded to produce an extrudate. Extrusion molding is more expensive, but it can be used for large products,
Suitable for manufacturing long products and special shaped products.

At these stages, water glass is used as the deflocculant.
Used at 0.05-2%. Grinding and mixing are carried out for 0.5 to 5 hours using a ball mill, for example. Put iron concentrate and clay into a ball mill, then add water and deflocculant. Afterwards, remove the organic binder to 0 in the storage tank.
．． Add 0.4 parts or more.

A flocculant such as bittern may be used with an organic binder.

After this, when it is desired to give the surface a design or to increase the hardness of the surface according to a special purpose, glazing may be applied. The glaze that is generally used for ceramics may be used. However, in the present invention, a beautiful color tone is basically achieved without glazing. ' The molded body, which is glazed as necessary, can be heated to a maximum temperature of 1100~
It is fired in an oxidizing flame atmosphere at a temperature of 1300°C. Firing sinters the particles and develops the strength of the structure. As the firing temperature increases, the color tone of the fired product changes from reddish to black. In order to reduce the water absorption to 0.5% or less, a high temperature of 1100° C. or higher is required. 130
If the temperature exceeds 0°C, melting tends to occur. The firing temperature is determined by taking into account the composition of the raw materials, the type of clay, the color tone of the fired product, the physical characteristics of the product, etc. The heating rate is 100-20
The holding time at the maximum temperature is preferably about 0"C/hour. The holding time at the maximum temperature is determined in relation to the physical strength, color tone, etc. of the final product depending on the temperature, and is generally in the range of 1 to 4 hours.

As the equipment used for firing, a boat-based firing kiln can be used. Preference is given to using a roller hearth kiln. The roller hearth kiln maintains the inside of the kiln at a predetermined temperature distribution curve along its longitudinal direction, and has rollers arranged inside for conveying the objects to be fired.Six objects to be fired are placed on a setter and moved on the rollers.

When cooling from the firing stage, smoking treatment may be performed if necessary.

The clay content is 50 parts or less, and the maximum firing temperature is 1200.
By controlling the temperature to be above .degree. C., it is possible to impart magnetization and electrical conductivity to the fired body. If the amount of clay exceeds 50 parts, magnetization becomes difficult to obtain. By setting the temperature to 1200°C or higher, the thermal decomposition of Fe20s −+Fe, 04 progresses,
0 Magnetism, where magnetism is expressed, refers to the property of being attached to a magnet. Electric conductivity means having a resistivity of 104 to 106 ΩCm. This is useful for building materials for clean rooms and the like that require anti-static properties.

Fruit 11''1 Three types of tiles were manufactured using a raw material containing 80 parts of iron concentrate, 20 parts of clay (honbushi clay), and about 5% water. The iron concentrate used is in a dehydrated cake state, containing 47% Fe, 310225% Fe as the main components, Al2O3CaO etc. as trace components, true specific gravity 4.1, average particle size 18.4 microns, and maximum particle size. It was 128 microns or less. Honbushi clay is grade 1 Onada Honbushi clay, and the unprepared product was used as it was mined. Water content is 19-21%
It is.

A mixture of iron concentrate and clay with a moisture content of approximately 50% (internally)
Add water so that
% was added and mixed by pulverization in a ball mill for 4 hours. No organic binder was used.

0.1% bittern was added to the storage tank as a flocculant.

It was dried at 100 to 105°C in a drying oven. The dried material was crushed and sieved into pieces of 2 mm or less.

The raw material powder was filled into a mold and press-molded using a 50-ton hydraulic press at a maximum pressure of 250 kgf/cma.

The press-formed body was baked in a roller hearth kiln at a maximum firing temperature of 100-b°C. Koguchihira (118X65X
12.2 mm), 150 square and 300 square tiles were manufactured. The water absorption rate of the fired body was 1%.

The color tone was a beautiful black-gray tone.

In Example 1, the iron concentrate was reduced to 60 parts, 40 parts of Awaji clay was used as the clay, the firing temperature was 1200° C., and the tiles were press-molded and fired under the same conditions. Oxidized tiles were obtained.

K 巖■1 Here, extrusion molding was carried out. As an organic binder,
Polyacrylamide-based polymer flocculant is used as a solvent at a concentration of 40
% was used to prepare the following mixture.

Iron concentrate 11 basake water 75 0.04 25
13% (honbushi clay) (incl.) 1000.5 3 13% (bentonite) (incl.) These mixtures are dehydrated in a filter press, mixed in a vacuum clay machine, and then extruded to form large bricks and hollow blocks. was created. Good molding, 1200-1280℃
The baking time was also sufficient.

[According to Example 1, JISA-
Abrasion tests were carried out by dropping 10 kg of sand in accordance with No. 5209. The abrasion loss was 10 mg. On the other hand, commercially available unglazed tiles and glazed tiles are twice as expensive.
mg・iΔ仇夛由亘亇I Various tests were conducted on fired tiles made by adding bentonite to iron concentrate.

Test conditions: Pennite addition amount 5% Water addition amount 5% Press molding pressure 300 kg/cm2 Firing temperature 1000°C 1100°C 1200°C Holding time 1 hour Measurement method Shrinkage rate Calculated bending strength by borrowing the dimensions before and after firing with a caliper Caliper Water absorption measured by a testing machine (Shimadzu Autograph AG-500A) Measure the difference between dry weight and wet weight and calculate as a percentage of dry weight Warp For two diagonals, 415 or more of the diagonal length on the diagonal. The vertical distance from the midpoint connecting both base points to the tile surface was measured using a dial gauge.The color tone visual results are shown in Table 1.

From the above results, the following points were understood.

1. The higher the firing temperature, the greater the bending strength. Even if the firing temperature is 1000℃, it still meets JIS standards (12kg/am for floors)
There are more than twice as many. The bending strength of this tile is perfect.

2. The higher the firing temperature, the larger the bulk specific gravity and the lower the water absorption rate. A major feature of this tile is that it has virtually zero water absorption. This is because the higher the firing temperature, the lower the porosity. It was also confirmed by microscopic observation.

3. Warpage tends to increase as the firing temperature increases, but it is based on the JIS standard (stoneware warpage 0.9
mm) or less.

4. The color is reddish brown at a firing temperature of 1000°C, but becomes darker as the temperature rises.

Table 1 Shrinkage rate 0. ．． 0 2.8 7.0 Bending strength 25.8 30.7 40.4 Water absorption rate
'19 1.5 0.0 warp
0.25 0.40 0.45 Appearance
The building material of the present invention has the following effects and is widely expected to be used as a new building material.

1. Technology that focuses on the unique characteristics of metal smelting slag that contains large amounts of iron oxide, such as iron concentrate (fine grain size, composition that includes olivine and magnetite), and utilizes these to their advantage. As a result of this search, we opened the way to its effective use in building materials such as tiles.

2. The tiles according to the present invention have physical properties equivalent to or better than commercially available porcelain tiles. In particular, the water absorption rate can be reduced to virtually zero. Low water absorption means no damage from freezing.

3. It can produce unique and beautiful colors that cannot be seen in conventional tiles. In particular, blacks such as oxidized and blackish shades cannot be produced using conventional manufacturing methods that use pigments.Incidentally, commercially available porcelain tiles require black pigments (oxides of Fe, Mn, Co, and Cr) to produce black colors. ) is required as much as 20%.

4. The graphite on the surface of commercially available oxidized products easily peels off. With the present invention, the oxidized finish can be achieved without smoking.
Resistant to wear.

5. Plasticity is imparted by using a small amount of clay and a small amount of organic binder, and it can be manufactured using the same equipment as regular ceramics, making extrusion molding possible, making it easy to create large, irregularly shaped, and long items. Manufactured in vines.

6. It can be produced cheaply and in large quantities.

7. It is possible to create tiles that have both magnetization and conductivity, which are not found in conventional tiles.

Claims (1)

[Claims] 1) Iron oxide 50-90% by weight, silica 10-30% by weight
, 3 parts of clay per 100 parts of a ceramic mixture containing up to 10% by weight of alkali or alkaline earth metal oxides.
a step of blending an organic binder and/or water as necessary; a step of molding the resulting mixture to produce a molded body; and a step of molding the molded body at a maximum temperature of 1100 to 13
A method for producing building materials such as tiles, which includes the steps of: - producing a fired product by firing in an oxidizing atmosphere at a temperature of 00°C. 2) Iron oxide 50-90% by weight, silica 10-30% by weight
, 2 parts of clay per 100 parts of a ceramic mixture containing up to 10% by weight of alkali or alkaline earth metal oxides.
A step of adding 0 parts or more and further blending water and a deflocculant, a step of pulverizing and mixing the obtained mixture, adding an organic binder to the mixture as necessary, and granulating it after dehydration and drying.
The method includes a step of press-molding the granules to produce a press-molded body, and a step of firing the press-molded body in an oxidizing atmosphere at a maximum temperature of 1,100 to 1,300°C to produce a fired body. A manufacturing method for building materials such as tiles. 3) Iron oxide 50-90% by weight, silica 10-30% by weight
, 3 parts of clay per 100 parts of a ceramic mixture containing up to 10% by weight of alkali or alkaline earth metal oxides.
a step of adding water and a deflocculant, a step of pulverizing and mixing the resulting mixture, adding an organic binder to the mixture, dehydrating and drying the mixture, and extruding the resulting mixture. A method for producing building materials such as tiles, which includes the steps of producing a molded body and firing the extruded body in an oxidizing atmosphere at a maximum temperature of 1,100 to 1,300°C to produce a fired body. 4) The clay content is 50 parts or less, and the maximum firing temperature is 12
4. The method according to any one of claims 1 to 3, wherein the temperature is set at 00°C or higher to impart magnetization and electrical conductivity to the fired body.