CN111533530B - Sanitary ceramic formula and preparation method - Google Patents

Sanitary ceramic formula and preparation method Download PDF

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Publication number
CN111533530B
CN111533530B CN202010250737.4A CN202010250737A CN111533530B CN 111533530 B CN111533530 B CN 111533530B CN 202010250737 A CN202010250737 A CN 202010250737A CN 111533530 B CN111533530 B CN 111533530B
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sanitary
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blank
borocalcite
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CN111533530A (en
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王彦庆
董志军
杨晖
宋子春
冯涛
李涛
马燕丽
董子红
杨艳云
汪丽敏
王海超
田磊
古利娜
高惠
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Huida Sanitary Ware Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/131—Inorganic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/24—Manufacture of porcelain or white ware
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/28—Slip casting
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3454—Calcium silicates, e.g. wollastonite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Abstract

The invention relates to the field of sanitary ceramic preparation processes, in particular to a sanitary ceramic formula and a preparation method, wherein the raw material composition of the formula is adjusted, and the chemical composition is optimized, so that the refractoriness of a blank body is improved, and the deformation degree of the blank body is reduced; in the mineral composition of the ordinary feldspar porcelain body, by introducing a proper amount of wollastonite raw materials, the content of anorthite crystal phase is increased on the basis of the original mullite and quartz crystal phase, and a proper amount of closed independent air holes are formed, so that the shrinkage rate and the volume density are reduced; the introduction of a proper amount of borocalcite flux can provide a (O = B-O-B = O) structure, ensure the integrity and tightness of a network structure around the air holes, and control the size of the independent air holes within a certain range so as to avoid the reduction of the firing strength.

Description

Sanitary ceramic formula and preparation method
Technical Field
The invention relates to the field of sanitary ceramic preparation processes, in particular to a sanitary ceramic formula and a preparation method.
Background
With the steady development of national economy, the living standard of people is continuously improved. The consumer's view and aesthetic concept of people are also changing. The use of materials pursuing high quality and high specification is also reflected in the bathroom industry. In the production process of sanitary ceramics, some large products such as toilet bowls and basins (more than 1 meter) are easy to deform and crack in the firing process. This not only reduces the first order rate of the product, but also affects the regularity of the product. Meanwhile, the product is heavy, and the weight of the product is 20-60 Kg. This not only increases workman's intensity of labour in the production handling process, also brings inconvenience for the construction simultaneously. At present, in order to improve the regularity of products, some large products such as basins are made of slurry made of FFC materials. The slurry has small deformation degree and sintering shrinkage, and can improve the appearance regularity. However, the material has high water absorption rate, and can cause later-stage moisture absorption expansion to crack the glaze surface of the product. Meanwhile, the strength of the material is lower than that of the VC material, and potential safety hazards exist.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a sanitary ceramic formula with low deformation, low shrinkage and low density and a preparation method thereof.
The invention is realized by the following technical scheme:
the sanitary ceramic formula is characterized by comprising the following components in parts by weight: 15 to 25 percent of porcelain stone, 20 to 30 percent of porcelain clay, 15 to 20 percent of ball clay, 5 to 15 percent of washing kaolin, 5 to 14 percent of feldspar, 5 to 20 percent of wollastonite and 2 to 6 percent of borocalcite,
the china clay is filtered by washing and pressing, the granularity of the wollastonite is less than or equal to 10 mu m and is 20 to 30 percent, and the borocalcite is pre-sintered at the temperature of 550 ℃.
Preferably, the weight ratio of the components comprises: 18% of porcelain stone, 30% of porcelain clay, 18% of ball clay, 8% of washing kaolin, 8% of feldspar, 14% of wollastonite and 4% of borocalcite.
The preparation method of the sanitary ceramic is characterized by comprising the following steps:
grinding 15-25 parts of porcelain stone, 20-30 parts of porcelain clay, 15-20 parts of ball clay, 5-15 parts of washing kaolin, 5-14 parts of feldspar, 5-20 parts of wollastonite and 2-6 parts of borocalcite according to the weight parts, adding a debonding agent and water, and carrying out ball milling to obtain slurry;
after the slurry is aged for seven days, injecting the slurry into a mold by adopting the grouting pressure less than 0.02MPa, and drying to obtain a blank;
and glazing the blank body, and then putting the blank body into a kiln to be fired to obtain the sanitary ceramic.
Preferably, the method comprises the following steps:
grinding 18 parts of porcelain stone, 30 parts of porcelain clay, 18 parts of ball clay, 8 parts of washing kaolin, 8 parts of feldspar, 14 parts of wollastonite and 4 parts of borocalcite according to the weight components, adding a debonding agent and water, and carrying out ball milling to prepare slurry;
after the slurry is aged for seven days, injecting the slurry into a mold by adopting the grouting pressure less than 0.02MPa, and drying to obtain a blank;
and glazing the blank, and then putting the blank into a kiln for firing to obtain the sanitary ceramic.
Preferably, the chemical composition of the slurry comprises, by mass percent: 6-8% LOI, 52-58% SiO 2 、18～26％AL 2 O 3 、0.5～2.5％B 2 O 3 、0～1.5％Fe 2 O 3 、0～1.0％TiO 2 CaO 3-11.5%, mgO 0.5-1.0%, and K3.5-5.5% 2 O+Na 2 O。
Preferably, the mud has a granularity of less than or equal to 10 microns of 50-60 percent in a temperature environment of 28-32 ℃, fineness of 3-6 percent in a 350-mesh sieve residue, concentration of 350-360 g/200ml and yield value of 8-12 dyn/cm 2 The fluidity is 35 to 55s/100ml.
Preferably, the sanitary ceramics are sintered in the tunnel kiln in the oxidizing atmosphere for one time, the sintering period is 14 to 20 hours, the maximum sintering temperature is 1180 to 1220 ℃, and the heat preservation time is 30 to 45 minutes.
Preferably, the sanitary ceramic has a volume density of 2.0 to 2.1g/cm 3 The deformation degree is less than 10mm, the shrinkage rate is less than 4 percent, and the firing strength is 70-80 MPa. .
The invention has the beneficial effects that:
according to the invention, by adjusting the raw material composition of the formula and optimizing the chemical composition, the refractoriness of the blank body is improved, and the deformation degree of the blank body is reduced; in the mineral composition of the ordinary feldspar porcelain body, by introducing a proper amount of wollastonite raw materials, the content of anorthite crystal phase is increased on the basis of the original mullite and quartz crystal phase, and a proper amount of closed independent air holes are formed, so that the shrinkage rate and the volume density are reduced; the introduction of a proper amount of borocalcite flux can provide a (O = B-O-B = O) structure, ensure the integrity and tightness of a network structure around the air holes, and control the size of the independent air holes within a certain range so as to avoid the reduction of the firing strength.
Drawings
FIG. 1 is a table of the composition of the raw materials for each example.
FIG. 2 is a table of parameters for sanitary ware performance for each example.
FIG. 3 is a table of the chemical composition of the slurries of the present invention.
FIG. 4 is a table of the performance parameters of the slurries of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments.
As shown in figure 1, raw material components in each embodiment are ground, and proper debonder and water ball grinding are added to prepare slurry, wherein the used raw material of the borocalcite is a hydrous calcium borate mineral which is formed by sodium boronatrocite and borax, crystals are short column-shaped, a certain flocculation phenomenon can be generated when the boronatrocite is directly added into the slurry, the physical use performance of the boronatrocite is influenced, in each embodiment, the boronatrocite is pre-sintered at 550 ℃ before use, the structural water content of the boronatrocite is eliminated, the boronatrocite can be directly used, the slurry can be smoothly debonded, the sintering strength of a blank can be improved, the used raw material of the wollastonite is a fibrous white fine powdery mineralized raw material, the particle size (less than or equal to 10 mu m) is controlled to be 20-30 percent, and the wollastonite is a calcium carbide provider of a crystalline phase in mineral composition, closed independent air holes are formed, and the volume density is reduced. The main chemical composition of the prepared mud is shown in figure 3, the main performance parameters are shown in figure 4,
after the slurry is aged for seven days, injecting the slurry into a mold by adopting the grouting pressure less than 0.02MPa, and drying to obtain a blank;
and glazing the blank, and then putting the blank into a kiln for firing to obtain the sanitary ceramic.
The slurry of each example was tested to produce a product having a bulk density of 2.4 (g/cm) of that of a conventional ceramic, as shown in FIG. 2 3 ) Reduced to 2.0-2.1 (g/cm) 3 ) The weight is reduced by 12 to 16 percent;
the deformation degree is reduced to about 10mm from 18-25 mm of common ceramics, and the appearance regularity is obviously improved;
the firing shrinkage is reduced to about 4% from 8-12% of common ceramics, and the incidence rate of cracking defects of products is greatly reduced;
the firing strength is improved to 70-80 Mpa from 35-55 Mpa of FFC ceramic, thereby achieving the strength of common VC ceramic and improving the safety and usability of the product.
The sanitary ceramic obtained in the embodiment 4 has better forming performance on the whole, and each index can reach the optimized performance, namely the sanitary ceramic is the best embodiment of the invention.
According to the invention, by adjusting the raw material composition of the formula and optimizing the chemical composition, the refractoriness of the blank body is improved, and the deformation degree of the blank body is reduced; in the mineral composition of the ordinary feldspar porcelain body, by introducing a proper amount of wollastonite raw materials, the content of anorthite crystal phase is increased on the basis of the original mullite and quartz crystal phase, and a proper amount of closed independent air holes are formed, so that the shrinkage rate and the volume density are reduced; the introduction of a proper amount of borocalcite flux can provide a (O = B-O-B = O) structure, ensure the integrity and tightness of a network structure around the air holes, and control the size of the independent air holes within a certain range so as to avoid the reduction of the firing strength.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (3)

1. The preparation method of the sanitary ceramic is characterized by comprising the following steps: grinding 15-25 parts of porcelain stone, 20-30 parts of porcelain clay, 15-20 parts of ball clay, 5-15 parts of washing kaolin, 5-14 parts of feldspar, 5-20 parts of wollastonite and 2-6 parts of borocalcite according to the weight parts of the components, wherein the total amount of all the components is 100 parts, and then adding a debonding agent and a water ball mill to prepare slurry; after the slurry is aged for seven days, injecting the slurry into a mold by adopting the grouting pressure less than 0.02MPa, and drying to obtain a blank; glazing the blank, and then putting the blank into a kiln for firing to obtain sanitary ceramics; the chemical composition of the mud comprises the following components in percentage by mass: 6-8% LOI, 52-58% SiO 2 、18～26％Al 2 O 3 、0.5～2.5％B 2 O 3 、0～1.5％Fe 2 O 3 、0～1.0％TiO 2 CaO 3-11.5%, mgO 0.5-1.0%, and K3.5-5.5% 2 O+Na 2 O; the mud has a granularity of less than or equal to 10 mu m and 50-60 percent in a temperature environment of 28-32 ℃, has a fineness of 350 meshes and a screen residue of 3-6 percent, a concentration of 350-360 g/200ml and a yield value of 8-12 dyn/cm 2 The fluidity is 35 to 55s/100ml; the sanitary ceramics are sintered in a tunnel kiln at one time under an oxidizing atmosphere, the sintering period is 14 to 20 hours, the maximum sintering temperature is 1180 to 1220 ℃, and the heat preservation time is 30 to 45 minutes; the volume density of the sanitary ceramic is 2.0-2.1 g/cm 3 The deformation degree is less than 10mm, the shrinkage rate is less than 4 percent, and the firing strength is 70-80 Mpa; the porcelain clay is washed by water and filtered by pressure, the particle size of the wollastonite is less than or equal to 10 mu m and is 20-30%, and the borocalcite is pre-sintered at the temperature of 550 ℃.
2. The preparation method of sanitary ceramics according to claim 1, characterized by comprising the following components by weight: 18 parts of porcelain stone, 30 parts of porcelain clay, 18 parts of ball clay, 8 parts of washing kaolin, 8 parts of feldspar, 14 parts of wollastonite and 4 parts of borocalcite.
3. The sanitary ware produced by the method for producing a sanitary ware according to claim 1 or 2.
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CN112279627B (en) * 2020-09-30 2022-11-08 湖南省醴陵市环宇陶瓷实业有限公司 Ceramic milk cup and processing technology thereof
CN112552036B (en) * 2020-12-24 2022-07-05 景德镇陶瓷大学 Wollastonite tailing reinforcing and toughening low-temperature ceramic tile and preparation method thereof
CN113929437B (en) * 2021-11-05 2022-08-05 河北工业大学 Low-temperature sintered sanitary ceramic body and preparation method thereof
CN115536361B (en) * 2022-11-28 2023-05-02 蒙娜丽莎集团股份有限公司 High-strength ceramic sheet and preparation method thereof

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CN101811858B (en) * 2010-03-10 2013-05-22 惠达卫浴股份有限公司 Fine-pottery sanitary ceramic body and manufacturing method thereof
CN101844910B (en) * 2010-05-17 2012-01-18 唐山惠达陶瓷(集团)股份有限公司 Thin-wall light-weighted sanitary ceramic body and manufacturing method thereof
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