KR20070111706A - Modified clay complex comprising organic or inorganic plasticizer, and method for preparing the same - Google Patents

Abstract

A modified clay composite comprising an organic/inorganic plasticizer is provided to realize easily controllable plastic property, excellent moldability, low shrinkage and high deformation stability, and to produce low-weight large-size ceramic ware. A modified clay composite comprises a clay mineral substance having no layered structure, and an organic plasticizer or an inorganic plasticizer. The clay mineral substance includes at least one selected from the group consisting of clay, kaolin and porcelain clay. The organic or inorganic plasticizer includes at least one plasticizer selected from the group consisting of polyethylene glycol, dodecyl amine, silica, alumina and metal oxalates, and is used in an amount of 0.1-20 wt%.

Description

Ceramic clay modified clay composite containing organic-inorganic plasticizer, and manufacturing method therefor {MODIFIED CLAY COMPLEX COMPRISING ORGANIC OR INORGANIC PLASTICIZER, AND METHOD FOR PREPARING THE SAME}

1 is a process chart showing the manufacturing process of the modified clay composite of the present invention.

[Industrial use]

The present invention relates to a modified clay composite, and a method for manufacturing the same, and more particularly, to possess a new type of ceramics (eg, kitchenware, sanitary ware, tiles, etc.), that is, plasticity capable of producing thin, light, and large-scale ceramic products. And a clay mineral modification having excellent moldability.

[Private Technology]

Ceramics, such as kitchenware, sanitary ware and tiles, require products with light, thin and large new physical properties. In addition, existing ceramic raw materials have difficulty in producing such specialized products.

The reason for reforming the clay is that the clay mineral resources of the raw material requirements and excellent characteristics are gradually depleted to manufacture new specialized products. Industrially, the application of clay minerals was mainly used as additives for flame retardants, high strength composites, and the like, mainly using montmorillonite, a layered compound.

However, research on the modification of clay minerals by adding clays as a main component and organic matters has been reported mainly in Japan with respect to interlayer clay minerals.

Dimethyl sulfoxide, normal methyl formamide and the like were intercalated into a layered kaolinite mineral interlayer to form a compound, followed by washing with water (Japanese Patent Publication No. 6-60013), and then plasticity and molding. Polyglycol, polyacrylic emulsion binder, additives, and water were kneaded to prepare a base having good properties (Japanese Patent Laid-Open No. 7-138066).

Clay minerals were compounded by compounding thermoplastic and thermosetting polymer matrices such as smectite, montmorillonite, saponite, biderite and mica having a layered structure as a method of complexing clay minerals (Japanese Patent Laid-Open No. 2001-172014).

However, since the clay minerals having the layered structure reported above are rarely used as raw materials for the ceramic field such as kitchenware, sanitary ware, tiles, etc., it is difficult to expect the effect of ceramic material plasticity control by improving these plasticity.

In addition, the reforming method reported above is a technique of inserting an organic compound between layers by mainly intercalating clay minerals having a layered structure, and after the addition of the organic compound, evaluation of specific plasticity and moldability is not made, and thus the plasticizer of the organic compound is The role as a role was not identified.

Moreover, since the clay minerals applied to the products of the ceramic field are atomized through continuous grinding rather than structurally having an interlayer structure, the intercalation technique is not suitable as a method of modifying the clay minerals of fine particles having such a structure.

The present invention is to solve the above problems, an object of the present invention is to provide a modified clay composite having a plasticity suitable for the production of ceramic products utilizing various organic plasticizers and inorganic nano plasticizers.

Another object of the present invention is to provide a method for producing the modified clay composite.

The present invention provides a modified clay composite comprising a clay mineral having no layered structure, and an organic plasticizer or an inorganic nanoplasticizer to achieve the above object.

The present invention also comprises the steps of mixing the clay mineral with an organic plasticizer or inorganic nano plasticizer; And it provides a method for producing a modified clay composite comprising the step of aging the mixture for more than 7 days in the state of inhibiting water evaporation.

Hereinafter, the present invention will be described in more detail.

In the present invention, 'clay mineral' is used to mean silicate minerals of extremely fine mineral particles, and 'clay' is used as a term of a sub-concept belonging to the 'clay mineral'.

In the present invention, the surface of mineral particles such as clay, kaolin, and pottery, which are important materials of ceramic products, is modified with an organic plasticizer or an inorganic nanoplasticizer to control plasticity and moldability.

Plasticity of the clay mineral in the present invention can be adjusted according to the type and amount of the plasticizer, the interparticle bonding, the water content and the like can be adjusted according to the addition of the plasticizer.

Clay minerals have been used as materials of various products, and depending on the purpose of use, chemical composition, particle structure and shape, and allowable impurities amount are different, but they have high plasticity for producing the most popular and profitable high-quality ceramic products. It must contain a small amount of iron.

For this reason, various studies have been attempted to improve the physical properties by modifying low-cost plastic clay, but the results satisfying both technical and economic aspects have not been reported. Moreover, the main subject of the study is montmorillonite mineral having a layered structure rather than a ceramic material, which is limited to use in the ceramic and ceramic industries.

In general, clay minerals are minerals produced by the reaction of water with water in the surface environment and are fine particles and hydrous silicates having a layered lattice structure. Clay has a large surface area per unit weight and exhibits colloidal behavior and is susceptible to changes in environment due to its sensitivity to environmental changes.

The crystal structure of clay consists of SiO ₄ tetrahedral layer and M _2-3 (OH) ₆ octahedral layer. Si and Al, which are the central ions of tetrahedron and octahedron, are easily substituted with Mg and Zn, and the surface of clay mineral is electrically negative. These clay properties have been widely applied to the adsorption of trace heavy metal ions with positive valences, and the surface of polar clay minerals does not facilitate the adsorption of nonpolar organic materials through hydrogen bonding and dipole reactions.

In the present invention, by using an organic plasticizer or an inorganic nano plasticizer by using these characteristics, to control the physical properties of the clay mineral.

Modified clay composites of the present invention include clay minerals and organic plasticizers or inorganic nanoplasticizers. The clay mineral may include one or more selected from the group consisting of clay, kaolin, and pottery stone. The organic plasticizer may be selected from the group consisting of polyethylene glycols, alkyl amines, and metal oxalates. It is preferable to include at least one species, and the inorganic nano plasticizer preferably contains at least one species selected from the group consisting of silica sol and alumina sol. Further, the metal oxalate is more preferably an alkali metal oxalate, most preferably sodium oxalate.

The organic plasticizer or inorganic nano-plasticizer to modify the surface of the clay mineral to have excellent plasticity, in order to exhibit the most desirable effect is preferably contained in 0.1 to 20% by weight in the modified clay composite.

The modified clay composite of the present invention may be prepared by mixing a clay mineral with a certain amount of an organic plasticizer or an inorganic nanoplasticizer, and then aging at room temperature for 7 days or more in a state in which evaporation of moisture is suppressed. , And ion exchange methods may be used. 1 is a process chart showing a manufacturing process of the modified clay of the present invention.

Referring to the manufacturing method of the modified clay composite as an example, after mixing a plasticizer aqueous solution containing an organic plasticizer or an inorganic nano plasticizer with a clay mineral, and then aged at room temperature for at least 7 days in a closed space that can prevent evaporation of moisture It can be prepared by. At this time, the final moisture content of the clay mineral mixture is preferably 20 to 30% by weight, and the mixing time is preferably 5 minutes to 5 hours. However, the manufacturing method of the modified clay composite of the present invention is not limited only to the above method.

The modified clay composite may be used as a raw material for the manufacture of ceramic products such as tableware, sanitary ware, tiles, etc., and has an effect of shortening the drying time in the ceramic product manufacturing process and improving molding performance, and making light ceramic products possible. There is an advantage.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

EXAMPLE

In the following example, after drying for 24 hours in an oven 100 ℃, using a clay mineral cooled to room temperature in a desiccator. The clay minerals used afterwards were experimented under the condition that they are used in the absence of moisture.

Comparative Example 1

After adding 26 g of water to 74 g of the prepared dry clay, the mixture was mixed for 15 minutes using auto trigger.

The mixed specimen was prepared in a well-sealed plastic container that prevents evaporation of moisture and ripens for 7 days to prepare a base having a water content of 26% by weight.

Example 1

To 71 g of the dried clay, a mixed solution of 26 g of water and 3 g of polyethylene glycol was added, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 2

To 71 g of the dried clay, a mixed solution of 26 g of water and 3 g of dodecyl amine was added, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 3

To 71 g of the dried clay, a mixed solution of 26 g of water and 3 g of silica sol was added, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 4

To 71 g of the dried clay, a mixed solution of 26 g of water and 3 g of alumina sol was added, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 5

To 71 g of the dried clay, a mixed solution of 26 g of water and 3 g of sodium oxalate was added, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Comparative Example 2

23 g of water was added to 77 g of the prepared dried kaolin, followed by mixing for 15 minutes using auto trigger.

The mixed specimen was prepared in a well-sealed plastic container that prevents evaporation of moisture and ripens for 7 days to prepare a base having a water content of 26% by weight.

Example 6

74 g of the prepared dried kaolin was added with a mixed solution of 23 g of water and 3 g of polyethylene glycol, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 7

To 74 g of dried kaolin, a mixed solution of 23 g of water and 3 g of dodecyl amine was added, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 8

A mixed solution of 23 g of water and 3 g of silica sol was added to 74 g of the dried kaolin prepared, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 9

A mixture of 23 g of water and 3 g of alumina sol was added to 74 g of the dried kaolin prepared, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 10

To 74 g of dried kaolin, a mixed solution of 23 g of water and 3 g of sodium oxalate was added, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Comparative Example 3

20 g of water was added to 80 g of the prepared dry stone, followed by mixing for 15 minutes using auto trigger.

The mixed specimen was prepared in a well-sealed plastic container that prevents evaporation of moisture and ripens for 7 days to prepare a base having a water content of 26% by weight.

Example 11

To 77 g of the prepared dry coating, a mixed solution of 20 g of water and 3 g of polyethylene glycol was added, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 12

A mixture of 20 g of water and 3 g of dodecyl amine was added to 77 g of the prepared dried stone, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 13

A mixed solution of 20 g of water and 3 g of a silica sol was added to 77 g of the prepared dried stone, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 14

To 77 g of the prepared dry stone, a mixed solution of 20 g of water and 3 g of alumina sol was added, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

Example 15

To 77 g of the prepared dry stone, a mixed solution of 20 g of water and 3 g of sodium oxalate was added, followed by mixing for 15 minutes using auto trigger.

The mixed specimens were prepared by aging for 7 days in a well-sealed plastic container that prevents evaporation of moisture and well ripens.

90 g of the base material prepared according to Comparative Examples 1 to 3 and Examples 1 to 15 were taken to prepare a test piece in a mold (Φ 30 × 40 cylinder) by compression molding, and then plasticity was obtained using a rheometer Rheo GX6000. Measured.

The Rheo GX6000 is a pin-type rheometer with the sample placed just below the pin so that the pin moves downwards and automatically records the load on the specimen over time. The smaller the load applied to the specimen, the better the plasticity.

The plasticity measurement results are summarized in Table 1 below.

TABLE 1

Clay minerals Plasticizer Plasticity (N) Water content (% by weight) Comparative Example 1 clay - 0.6 26 Example 1 clay Polyethylene glycol 0.2 26 Example 2 clay Dodecyl amine 1.1 26 Example 3 clay Silica sol 0.3 26 Example 4 clay Alumina sol 0.7 26 Example 5 clay Sodium oxalate 0.3 26 Comparative Example 2 china clay - 8.1 23 Example 6 china clay Polyethylene glycol 5.2 23 Example 7 china clay Dodecyl amine 16 23 Example 8 china clay Silica sol 3.2 23 Example 9 china clay Alumina sol 8.9 23 Example 10 china clay Sodium oxalate 3.2 23 Comparative Example 3 Pottery - 0.7 20 Example 11 Pottery Polyethylene glycol 0.2 20 Example 12 Pottery Dodecyl amine 1.2 20 Example 13 Pottery Silica sol 0.3 20 Example 14 Pottery Alumina sol 0.8 20 Example 15 Pottery Sodium oxalate 0.3 20

As shown in Table 1, Examples 1, 6, and 11 comprising polyethylene glycol; Examples 3, 8, and 13 including silica sol; Examples 5, 10, and 15 containing sodium oxalate showed 50 to 70% improved plasticity compared to those of Comparative Examples 1 to 3, which did not include a plasticizer, and an organic plasticizer containing dodecyl amine. It can be seen that the plasticity was reduced for Examples 2, 6, and 10 and for Examples 4, 8, and 12, including alumina sol, an inorganic nano plasticizer.

As such, the organic plasticizer and the inorganic nanoplasticizer according to the present invention can increase or decrease the plasticity of the clay for producing ceramic products, and the modified clay of the present invention can be improved in plasticity by varying the type and content of the plasticizer according to the use. You can manufacture new specialty ceramic products such as flake ceramics.

 The present invention relates to clay mineral modification for producing thin and large ceramic products, wherein clay, kaolin, pottery and the like have been modified using organic plasticizer and inorganic nano plasticizer. The clay-plastic composite with enhanced plasticity can produce a ceramic-carrying body in which particles are uniformly mixed, thereby producing a low shrinkage, strain stability, and densified ceramic sintered body. In addition, the modified clay composite of the present invention can control the hydrophilicity, hydrophobicity and plasticity according to the type and loading of each clay mineral and nano plasticizer, which possesses ceramic products according to the use of future products (liver, sanitary ware, tile, etc.) Moisture control included in it is expected to shorten the drying time, improve molding performance, and affect the manufacture of lightweight ceramic products.

Claims (5)

A modified clay composite comprising a clay mineral having no layered structure, and an organic plasticizer or an inorganic nanoplasticizer. The modified clay composite of claim 1, wherein the clay mineral comprises one or more selected from the group consisting of clay, kaolin, and cobblestone. The modified clay composite of claim 1, wherein the organic plasticizer or the inorganic nanoplasticizer comprises one or more selected from the group consisting of polyethylene glycol, dodecylamine, silica, alumina, and metal oxalate. The modified clay composite of claim 1, wherein the organic plasticizer or the inorganic nanoplasticizer is included in an amount of 0.1 to 20 wt%. Mixing a clay mineral with an organic plasticizer or an inorganic nanoplasticizer to prepare a mixture including 20 to 30% by weight of water; And Method for producing a modified clay composite comprising the step of aging the mixture for at least 7 days in the condition that water evaporation is suppressed.

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