CN116023171B - Ceramic plate with skin-friendly texture and preparation method and application thereof - Google Patents
Ceramic plate with skin-friendly texture and preparation method and application thereof Download PDFInfo
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- CN116023171B CN116023171B CN202211566093.5A CN202211566093A CN116023171B CN 116023171 B CN116023171 B CN 116023171B CN 202211566093 A CN202211566093 A CN 202211566093A CN 116023171 B CN116023171 B CN 116023171B
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- 238000002360 preparation method Methods 0.000 title abstract description 12
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- 238000000034 method Methods 0.000 claims abstract description 21
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- 239000000047 product Substances 0.000 description 26
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 17
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
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Abstract
The invention provides a ceramic plate with skin-friendly texture, and a preparation method and application thereof, and relates to the technical field of ceramics. The ceramic plate with the skin-friendly texture adopts the blank layer to be matched with the ground coat layer, the overglaze layer and the transparent protective glaze layer, and the design mode ensures that the ceramic plate can realize the matte effect with the surface glossiness of 16-25 degrees, has soft and comfortable visual effect, realizes the surface roughness Ra=10-15 mu m, has better touch feeling, has the surface as fine and smooth as the skin of an infant and accords with the skin-friendly texture of human engineering. The invention also provides a preparation method of the ceramic plate with skin-friendly texture, which is simple and convenient to operate, stable in process and suitable for industrial mass production.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to a ceramic plate with skin-friendly texture, and a preparation method and application thereof.
Background
Along with the high-quality development of society and the trend of people for good life, in the decoration field, the used decoration materials are gradually changed from the traditional natural stone materials to the ceramic tile products produced in an industrialized standardized manner. In this process, those skilled in the art develop various ceramic tile products with various textures and different glossiness of the matching surfaces through various processes to meet different demands of consumers, and ceramic tile products with appropriate surface glossiness and silky and skin-friendly texture are increasingly favored by numerous consumers.
In the prior art, the method for manufacturing various ceramic tile products with proper luster and silky skin-friendly texture generally adopts the steps of firstly applying primer on a blank, printing patterns by ink jet, and then applying corresponding glaze. In order to ensure the silky and skin-friendly texture of ceramic tile products, the aluminum oxide content of the surface glaze in the formula components is set to be low (generally less than 18%), so that the firing temperature in the firing process is low, the initial melting point is low, if the surface glaze is directly distributed on a green body layer,compared with a thin glaze layer, the thickness of the blank layer is thick, the glaze with lower temperature is quickly melted and seals the lower blank layer in advance, so that the combination of the blank glaze is unsmooth in exhaust during firing, and prickly heat and bubbles are easy to occur, which is a remarkable quality defect. And if Al is lifted 2 O 3 The content increases the melting temperature of the glaze, and the Al is also caused by high temperature 2 O 3 The turbidity of the product reduces the visual effect of the surface, and particularly for dark products, the product is obvious in a hazy phenomenon and insufficient in transparency; in addition, the expansion coefficients of the low-temperature glaze layer and the relatively high-temperature blank layer are large in difference, so that the low-temperature glaze layer and the relatively high-temperature blank layer are easy to deform in the firing process, and the production controllability is poor. Therefore, there is a need to develop ceramic tile products with a certain gloss, silky and skin-friendly texture and more controllable operation in production.
In view of the above, the present invention has been made to solve at least one of the above-mentioned technical problems.
Disclosure of Invention
The first object of the present invention is to provide a ceramic board with skin-friendly texture, so as to solve at least one of the above technical problems.
The second object of the present invention is to provide a method for preparing the ceramic plate having skin-friendly texture.
A third object of the present invention is to provide an application of the above ceramic plate having skin-friendly texture.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the invention provides a ceramic plate with skin-friendly texture, which is mainly prepared from a green body layer and a skin glaze layer arranged on the surface of the green body layer, wherein the skin glaze layer comprises a ground glaze layer, a surface glaze layer and a transparent protective glaze layer which are sequentially arranged along the direction far away from the green body layer;
the surface glossiness of the ceramic plate is 16-25 degrees, and the surface roughness Ra of the ceramic plate is 10-15 mu m.
Furthermore, on the basis of the technical scheme of the invention, the green body for forming the green body layer comprises the following chemical components in percentage by mass:
SiO 2 65.5％-68.5％，Al 2 O 3 17％-20％，CaO 0.8％-1.6％，MgO 1％-2％，K 2 O 1.8％-3％，Na 2 O 2％-3％，Fe 2 O 3 1％-2.5％，TiO 2 0.1% -0.4% and the balance of burning and trace impurities.
Furthermore, on the basis of the technical scheme, the ground coat for forming the ground coat layer comprises the following chemical components in percentage by mass:
SiO 2 52％-56.6％，Al 2 O 3 27％-30.2％，CaO 0.8％-1.2％，MgO 0.9％-1.3％，K 2 O 4％-5.2％，Na 2 O 2.5％-3.3％，ZrO 2 4% -5.6% and the balance of burning and trace impurities.
Furthermore, on the basis of the technical scheme of the invention, the overglaze for forming the overglaze layer comprises the following chemical components in percentage by mass:
SiO 2 42％-45.3％，Al 2 O 3 16.5％-18.5％，CaO 4.7％-6％，MgO 3.2％-4.2％，K 2 O 3％-4％，Na 2 O 2.3％-3.2％，BaO 6.8％-8％，ZnO 4.8％-6％，ZrO 2 2.5 to 3.7 percent, and the balance of burning and trace impurities; at the same time, siO in the overglaze 2 With Al 2 O 3 The mass fraction ratio of (2.2-2.8): the sum of mass fractions of the CaO, the MgO, the BaO and the ZnO is 21-23%.
Furthermore, on the basis of the technical scheme, the transparent protective glaze for forming the transparent protective glaze layer comprises the following chemical components in percentage by mass:
SiO 2 44％-47％，Al 2 O 3 18％-20％，CaO 4.5％-6.3％，MgO 3％-4％，K 2 O1％-2％，Na 2 1.5 to 2.5 percent of O, 4 to 5 percent of BaO, 9 to 11 percent of ZnO, 1.5 to 2.5 percent of SrO and the balance of burning and trace impurities.
Further, on the basis of the technical scheme of the invention, the thermal expansion coefficient of the blank body for forming the blank body layer at 400 ℃ is(7.3-7.5)×10 -6 /℃；
Preferably, the primer used for forming the primer layer has a thermal expansion coefficient of (7.7-7.9). Times.10 at 400 DEG C -6 /℃；
Preferably, the overglaze used to form the overglaze layer has a coefficient of thermal expansion of (6.6-6.8) x 10 at 400 DEG C -6 /℃；
Preferably, the transparent protective glaze for forming the transparent protective glaze layer has a thermal expansion coefficient of (5.2-5.4). Times.10 at 400 DEG C -6 /℃。
Furthermore, on the basis of the technical proposal of the invention, the difference value of the thermal expansion coefficients of the ground coat and the green body at 400 ℃ is (0.3-0.5) multiplied by 10 -6 /℃；
Preferably, the difference between the thermal expansion coefficients of the base glaze and the overglaze at 400 ℃ is (1.0-1.2) multiplied by 10 -6 /℃；
Preferably, the difference in thermal expansion coefficient between the overglaze and the transparent protective glaze at 400 ℃ is (1.3-1.5) multiplied by 10 -6 /℃。
Furthermore, on the basis of the technical scheme of the invention, an ink-jet pattern layer is arranged between the overglaze layer and the transparent protective glaze layer.
The invention also provides a preparation method of the ceramic plate with skin-friendly texture, which comprises the following steps:
and sequentially forming a ground glaze layer, a surface glaze layer, an optional ink-jet pattern layer and a transparent protective glaze layer on the surface of the green body layer, then sintering and edging to obtain the ceramic plate with skin-friendly texture.
The invention also provides application of the ceramic plate with skin-friendly texture in the field of construction.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a ceramic plate with skin-friendly texture, which adopts a blank layer to be matched with a ground coat layer, a surface glaze layer and a transparent protective glaze layer, and the design mode ensures that the ceramic plate can realize a matte effect with the surface glossiness of 16-25 degrees, has soft and comfortable visual effect, realizes the surface roughness Ra=10-15 mu m, has better touch feeling, has fine and smooth surface like the skin of an infant, and accords with the skin-friendly texture of human engineering.
(2) The invention also provides a preparation method of the ceramic plate with skin-friendly texture, which has stable process and strong controllability and is suitable for industrial mass production.
(3) The invention provides application of the ceramic plate with skin-friendly texture, and the ceramic plate with skin-friendly texture has good application in the field of construction in view of the advantages of the ceramic plate with skin-friendly texture.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a ceramic plate with skin-friendly texture according to example 1 of the present invention;
FIG. 2 is a partial view of a ceramic plate with skin-friendly texture according to example 1 of the present invention;
FIG. 3 is a graph showing the data of the detection of the surface roughness Ra of the ceramic plate having skin-friendly texture according to example 1 of the present invention;
FIG. 4 is a firing graph of the green body and the primer of example 1 of the present invention;
fig. 5 is a partial view of a ceramic plate provided in comparative example 1 of the present invention.
Icon: 1-a blank layer; 2-a primer layer; 3-a surface glaze layer; 4-an inkjet pattern layer; 5-transparent protective glaze layer.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but it will be understood by those skilled in the art that the following embodiments and examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not specified, and the process is carried out according to conventional conditions or conditions suggested by manufacturers. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In order to achieve skin-friendly texture, the glaze layer of the surface layer is required to be soft and smooth, the most direct method is to adjust the glaze of the surface layer to be smooth, and the glaze layer is required to have a certain thickness so as to reflect soft and moist texture. On the other hand, if the glaze on the outermost layer is thickened, the glaze is not completely 100% transparent, and especially, the brightness is reduced and the glaze is not polished, and it is known in the industry that the thickened glaze inevitably causes transparency loss to affect the blurry and unclear visual effect of the pattern and color. The present invention has been made in order to improve the above-mentioned situation.
According to a first aspect of the present invention, there is provided a ceramic sheet having a skin-friendly texture, which is mainly made of a green body layer and a skin glaze layer provided on the surface of the green body layer, the skin glaze layer including a primer layer, a cover glaze layer and a transparent protective glaze layer provided in this order in a direction away from the green body layer;
the surface glossiness of the ceramic plate is 16-25 degrees, and the surface roughness Ra of the ceramic plate is 10-15 mu m.
The invention adopts the design mode that the green body layer is matched with the ground coat layer, the overglaze layer and the transparent protective glaze layer, realizes the matte effect with the surface glossiness of 16-25 degrees, has soft and comfortable visual effect, realizes the surface roughness Ra=10-15 mu m, has better touch feeling, has the surface as fine and smooth as the skin of infants, and accords with the skin-friendly texture of human engineering. The transparent protective glaze layer adopts a thin-layer high-transparency fine-sliding low-light effect, and the overglaze layer is prepared into a soft texture effect, so that the interaction achieves a surface skin-friendly effect with clear surface patterns, soft hand feeling and texture and a soft visual effect. The above effects are further improved for both visual effects and touch effects of matte products, and are more demanded in the market, and are more favorable for the widening of sales for dark color series products.
In addition, in order to solve the quality defect problem caused by brick shape of the ceramic plate and oxidation exhaust such as miliaria, bubble, etc., the invention designs the ground coat layer under the surface glaze layer, different mechanism effects are mutually combined and complemented, thus avoiding bubble and miliaria on the surface of the product, and because of the arrangement of the specific surface glaze layer and the transparent protective glaze layer, the combination effect on the ground coat layer and the blank layer is not great basically, so that the product is smoother in the firing process, the deformation degree after firing is smaller, the yield is higher, and the production cost is greatly saved.
In the ceramic plate of the present invention, if the surface roughness is less than 10 μm, the smoothness is higher, but the roughness is increased and the comfortable touch is decreased by more than 15 μm, so that the surface roughness needs to be controlled within a certain range of values. Typical, but non-limiting, surface roughness is 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm.
In the same way, if the surface glossiness of the ceramic plate is lower than 16 degrees, the surface of the plate is dull and dull, and a dull and deep feel is brought to people, and if the surface glossiness is higher than 25 degrees, a certain reflection phenomenon exists on the surface of the plate, the vision is not soft, and therefore the surface glossiness needs to be controlled within a specific numerical range. Typical, but non-limiting, surface gloss values are 16 °, 17 °, 18 °, 19 °, 20 °, 21 °, 22 °, 23 °, 24 °, or 25 °.
The composition of each glaze layer of the ceramic plate directly relates to the performance of the final product.
As an alternative embodiment of the present invention, the green body for forming the green body layer comprises the following chemical components in mass fraction:
SiO 2 65.5％-68.5％，Al 2 O 3 17％-20％，CaO 0.8％-1.6％，MgO 1％-2％，K 2 O 1.8％-3％，Na 2 O 2％-3％，Fe 2 O 3 1％-2.5％，TiO 2 0.1% -0.4% and the balance of burning and trace impurities.
SiO 2 Typical, but non-limiting, mass fractions are 65.5%, 66.0%, 66.5%, 67.0%, 67.5%, 68.0% or 68.5%; al (Al) 2 O 3 Typically butNon-limiting mass fractions are 17%, 18%, 19% or 20%; caO is typically, but not limited to, 0.8%, 1.0%, 1.2%, 1.4%, 1.5% or 1.6% by mass; mgO typically, but not limitatively, has a mass fraction of 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8% or 2.0%; k (K) 2 Typical but non-limiting mass fractions of O are 1.8%, 2.0%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8% or 3.0%; na (Na) 2 Typical but non-limiting mass fractions of O are 2.0%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8% or 3.0%; fe (Fe) 2 O 3 Typical but non-limiting mass fractions are 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4% or 2.5%; tiO (titanium dioxide) 2 Typical, but non-limiting, mass fractions are 0.1%, 0.2%, 0.3% or 0.4%.
There is also some optimization of the chemical composition of the primer forming the primer layer. As an alternative embodiment of the present invention, the primer used to form the primer layer comprises the following chemical components in mass percent:
SiO 2 52％-56.6％，Al 2 O 3 27％-30.2％，CaO 0.8％-1.2％，MgO 0.9％-1.3％，K 2 O 4％-5.2％，Na 2 O 2.5％-3.3％，ZrO 2 4% -5.6% and the balance of burning and trace impurities.
Wherein SiO is 2 Typical but non-limiting mass fractions are 52%, 53%, 54%, 55%, 56% or 56.6%; al (Al) 2 O 3 Typical, but non-limiting, mass fractions are 27%, 28%, 29%, 30% or 30.2%; caO is typically, but not limited to, 0.8%, 0.9%, 1.0%, 1.1% or 1.2% by mass; mgO typically, but not limitatively, has a mass fraction of 0.9%, 1.0%, 1.1%, 1.2% or 1.3%; k (K) 2 Typical but non-limiting mass fractions of O are 4%, 4.2%, 4.5%, 4.8%, 5.0% or 5.2%; na (Na) 2 Typical but non-limiting mass fractions of O are 2.5%, 2.6%, 2.8%, 3.0%, 3.2% or 3.3%; zrO (ZrO) 2 Typical, but non-limiting, mass fractions are 4%, 4.2%, 4.5%, 4.8%, 5.0%, 5.2%, 5.5% or 5.6%.
The raw materials of the primer are not particularly limited as long as the primer is made to have the above chemical composition. As an alternative embodiment of the invention, the primer is mainly prepared from the following raw materials in parts by weight: 15-19 parts of quartz, 38-42 parts of potassium feldspar, 7-9 parts of ball clay, 8-12 parts of nepheline, 18-22 parts of alumina, 1-3 parts of calcined talcum, 2-4 parts of dolomite and 9-11 parts of zirconium silicate.
Specifically, quartz is typically, but not limited to, 15, 16, 18 or 19 parts by mass; typical but non-limiting parts by weight of potassium feldspar are 38 parts, 40 parts or 42 parts; the typical, but non-limiting, parts by weight of the ball clay are 7, 8 or 9 parts; the typical, but nonlimiting, parts by weight of nepheline are 8, 9, 10, 11, or 12; typical, but non-limiting, parts by weight of alumina are 18 parts, 19 parts, 20 parts or 22 parts; the typical but non-limiting parts by mass of calcined talc are 1 part, 2 parts or 3 parts; dolomites typically but not limited to 2, 3 or 4 parts by mass; zirconium silicate is typically, but not limited to, 9, 10 or 11 parts by mass.
When the glaze blank is combined, the base glaze is set to have higher content of alumina than the blank, and the temperature is higher than that of the blank, so that the upper base glaze is not melted first and is closed when the blank is melted, and the blank has a certain space for oxidation and exhaust, thereby effectively reducing the generation rate of bubbles and prickly heat and avoiding the defect caused by bursting the upper layer glaze. Adding a proper amount of zirconium silicate into the raw materials of the base glaze, and whitening by utilizing the opacifying and whitening effects of the zirconium silicate to cover the low-whiteness green body of the lower layer; and an excellent glaze blank intermediate layer is formed between the matched ground glaze and the blank, so that the stress of the blank glaze is better relieved, and the glaze blanks are firmly combined.
There is also some optimization of the chemical composition of the overglaze forming the overglaze layer. As an alternative embodiment of the invention, the overglaze for forming the overglaze layer comprises the following chemical components in mass fraction:
SiO 2 42％-45.3％，Al 2 O 3 16.5％-18.5％，CaO 4.7％-6％，MgO 3.2％-4.2％，K 2 O 3％-4％，Na 2 O 2.3％-3.2％，BaO 6.8％-8％，ZnO 4.8％-6％，ZrO 2 2.5 to 3.7 percent, and the balance of burning and trace impurities; at the same time SiO in the overglaze 2 With Al 2 O 3 The mass fraction ratio of (2.2-2.8): the sum of mass fractions of the CaO, the MgO, the BaO and the ZnO is 21-23%.
Wherein SiO is 2 Typical but non-limiting mass fractions are 42%, 43%, 44%, 45% or 45.3%; al (Al) 2 O 3 Typical but non-limiting mass fractions are 16.5%, 17%, 17.5%, 18% or 18.5%; caO is typically, but not limited to, 4.7%, 4.8%, 5.0%, 5.2%, 5.5%, 5.6%, 5.8% or 6% by mass; mgO typically, but not limitatively, has a mass fraction of 3.2%, 3.5%, 3.8%, 4.0% or 4.2%; k (K) 2 Typical but non-limiting mass fractions of O are 3%, 3.2%, 3.5%, 3.8% or 4.0%; na (Na) 2 Typical but non-limiting mass fractions of O are 2.3%, 2.5%, 2.6%, 2.8%, 3.0% or 3.2%; typical but non-limiting mass fractions of BaO are 6.8%, 7.0%, 7.2%, 7.5%, 7.6%, 7.8% or 8%; the ZnO is typically, but not limited to, 4.8%, 5.0%, 5.2%, 5.5%, 5.6%, 5.8% or 6% by mass; zrO (ZrO) 2 Typical, but non-limiting, mass fractions are 2.5%, 2.6%, 2.8%, 3.0%, 3.2%, 3.5% or 3.7%.
In addition, the chemical components in the overglaze are ensured and simultaneously the SiO is also ensured 2 With Al 2 O 3 The mass fraction ratio of (2.2-2.8): 1, for example 2.2: 1. 2.3: 1. 2.4: 1. 2.5: 1. 2.6: 1. 2.7:1 or 2.8:1, a step of; the sum of the mass fractions of CaO, mgO, baO and ZnO is 21% -23%, and can be 21%, 21.5%, 22%, 22.5% or 23%, for example.
The raw materials for forming the overglaze are not particularly limited, and as an alternative embodiment of the invention, the overglaze is mainly prepared from the following raw materials in parts by mass:
23-27 parts of potassium feldspar, 16-20 parts of albite, 8-12 parts of calcite, 8-12 parts of kaolin, 4-6 parts of calcined kaolin, 8.5-11.5 parts of barium carbonate, 5-7 parts of zinc oxide, 10-14 parts of calcined talcum, 3-5 parts of aluminum oxide and 4.5-5.5 parts of zirconium silicate.
Typical but non-limiting parts by weight of potassium feldspar are 23 parts, 24 parts, 25 parts or 27 parts; typical but non-limiting parts by mass of albite are 16 parts, 18 parts, 19 parts or 20 parts; typical but non-limiting parts by mass of calcite are 8, 9, 10, 11 or 12 parts; typical, but non-limiting, parts by weight of kaolin are 8, 9, 10, 11 or 12 parts; the calcined kaolin is typically, but not limited to, 4 parts, 5 parts, or 6 parts by mass; typical but non-limiting parts by mass of barium carbonate are 8.5 parts, 9 parts, 10 parts, 11 parts or 11.5 parts; typical but non-limiting parts by mass of zinc oxide are 5 parts, 6 parts or 7 parts; typical but non-limiting parts by mass of calcined talc are 10 parts, 11 parts, 12 parts, 13 parts or 14 parts; typical, but non-limiting, parts by weight of alumina are 3 parts, 4 parts or 5 parts; typical but non-limiting parts by weight of zirconium silicate are 4.5 parts, 4.8 parts, 5 parts, 5.2 parts or 5.5 parts.
As an alternative embodiment of the invention, the surface of the overglaze layer is also formed with an inkjet pattern layer, i.e. the inkjet pattern layer is arranged between the overglaze layer and the transparent protective glaze layer. The ink-jet pattern layer may be formed on the surface of the overglaze layer by ink-jet printing.
Al contained in the overglaze of the invention 2 O 3 Is 16.5% -18.5% and SiO 2 With Al 2 O 3 Is controlled at SiO 2 ：Al 2 O 3 = (2.2-2.8): 1, the two become the basic direction for preparing the low-light glaze. Meanwhile, the high-content alkaline earth metal (CaO+MgO+BaO+ZnO=21-23%) flux promotes the glaze to be in a better molten state, and enables the overglaze layer to be molten earlier and also to further seal prickly heat bubbles and the like at the lower layer, which are combined and supplemented with different mechanisms of the base glaze, so that the prepared ceramic plate has fewer defects and effectively improves the color development of the inkjet pattern; in addition, due to the proper alumina content in the overglaze formula, surface ink can be integrated into the overglaze in the high-temperature firing process during ink-jet printing, and the visual effect is improved; and the addition of proper zirconium silicate in the surface glaze raw material can improve the color development of the pattern.
The chemical composition of the transparent protective glaze forming the transparent protective glaze layer is also optimized to a certain extent. As an alternative embodiment of the present invention, the transparent protective glaze for forming the transparent protective glaze layer includes the following chemical components in mass fraction:
SiO 2 44％-47％，Al 2 O 3 18％-20％，CaO 4.5％-6.3％，MgO 3％-4％，K 2 O1％-2％，Na 2 1.5 to 2.5 percent of O, 4 to 5 percent of BaO, 9 to 11 percent of ZnO, 1.5 to 2.5 percent of SrO and the balance of burning and trace impurities.
Wherein SiO is 2 Typical but non-limiting mass fractions are 44%, 45%, 46% or 47%; al (Al) 2 O 3 Typical but non-limiting mass fractions are 18%, 19% or 20%; caO is typically, but not limited to, 4.5%, 4.8%, 5.0%, 5.2%, 5.5%, 5.6%, 5.8%, 6% or 6.3% by mass; mgO typically, but not limitatively, has a mass fraction of 3.0%, 3.2%, 3.5%, 3.8% or 4.0%; k (K) 2 O is typically, but not limited to, 1%, 1.5% or 2% by mass; na (Na) 2 Typical but non-limiting mass fractions of O are 1.5%, 1.8%, 2.0%, 2.2% or 2.5%; baO typically, but not limitatively, has a mass fraction of 4.0%, 4.2%, 4.5%, 4.8% or 5%; znO typically, but not by way of limitation, is 9.0%, 9.5%, 10%, 10.5% or 11%; srO is typically, but not limited to, 1.5%, 2% or 2.5% by mass.
The transparent protective glaze designs the formula of the same system for matching the overglaze, and also better ensures the basic consistency of the performances between the two without affecting the appearance of the glossiness of the overglaze layer, wherein the sum of the mass fractions of CaO and MgO in the chemical compositions of the two is larger than K 2 O and Na 2 The sum of the mass fractions of O can exert better extinction effect. In addition, the high-content calcium, magnesium, barium and zinc fluxes enable the surface layer to be lower in temperature and precipitate more crystals, so that more fine concave-convex is formed on the surface of the product, the touch feeling is finer and more comfortable, the surface roughness can reach 10-15 mu m, the comfortable fine and smooth skin-friendly texture is realized, and the matte effect can be better ensured. And a transparent protective glaze layer which is thin enough and sets Al in the transparent protective glaze 2 O 3 Content and overglaze Al 2 O 3 The content is 1% -2% of that of the surface glaze, and the color of the pattern is protected by the relatively proper high temperature without affecting the appearance of the skin-friendly texture of the surface glaze.
Through the further limitation to each glaze layer chemical composition for each glaze layer mutually cooperates, realizes the matte effect of surface glossiness 16 ~ 25, and the sensitivity is strong, and visual effect is soft comfortable, realizes surface roughness Ra=10 ~ 15 mu m simultaneously, and the sense of touch is better, and the surface is fine and smooth like baby's skin, accords with ergonomic parent skin feel.
Besides the optimization of the chemical composition of each glaze layer, the thermal expansion coefficients of the glazes forming the green body layer, the ground coat layer, the cover coat layer and the transparent protective glaze layer are also optimized to a certain extent.
As an alternative embodiment of the present invention, the green body used to form the green body layer has a coefficient of thermal expansion of (7.3-7.5). Times.10 at 400 DEG C -6 The temperature/DEG C may be, for example, 7.3X10 -6 /℃、7.4×10 -6 Per DEG C or 7.5X10 -6 /℃。
As an alternative embodiment of the present invention, the primer used to form the primer layer has a coefficient of thermal expansion of (7.7-7.9). Times.10 at 400 DEG C -6 The temperature/DEG C may be, for example, 7.7X10 -6 /℃、7.8×10 -6 Per DEG C or 7.9X10 -6 /℃。
As an alternative embodiment of the present invention, the overglaze used to form the overglaze layer has a coefficient of thermal expansion of (6.6-6.8). Times.10 at 400 DEG C -6 a/DEG C; for example, it may be 6.6X10 -6 /℃、6.7×10 -6 Per DEG C or 6.8X10 -6 /℃。
As an alternative embodiment of the present invention, the transparent protective glaze for forming the transparent protective glaze layer has a thermal expansion coefficient of (5.2-5.4). Times.10 at 400 DEG C -6 The temperature/DEG C may be, for example, 5.2X10 -6 /℃、5.3×10 -6 Per DEG C or 5.4X10 -6 /℃。
In the invention, the expansion coefficient of the overglaze and the protective glaze is smaller than that of the base glaze and the blank, and the combination of the base glaze and the blank is basically not greatly influenced, so that the deformation degree of the product after firing is less influenced.
The thermal expansion coefficients of the ground glaze, the overglaze and the transparent protective glaze in the skin glaze layer are set to be matched with each other, the shrinkage of the whole glaze layer is smaller than that of the green body in the firing process, the whole body has a compressive stress effect on the green body, the problem that the green body is easy to form a state with micro-warpage around at a higher bottom temperature under a kiln in the firing process is solved, the whole product tends to be flatter, and the actual production requirement can be met.
In addition, there is further optimization for the difference of the thermal expansion coefficients of different glazes.
As an alternative embodiment of the invention, the difference of the thermal expansion coefficients of the base glaze and the blank body at 400 ℃ is (0.3-0.5) multiplied by 10 -6 /℃；
Preferably, the difference in thermal expansion coefficient between the base glaze and the overglaze at 400 ℃ is (1.0-1.2) x 10 -6 /℃；
Preferably, the difference in thermal expansion coefficient between the overglaze and the transparent protective glaze at 400 ℃ is (1.3-1.5). Times.10 -6 /℃。
The expansion coefficients of the base glaze and the overglaze are close, and the material properties are the same, so that the influence on deformation of the blank glaze bonding layer is small, and better bonding matching can be realized between the base glaze and the overglaze.
According to a second aspect of the present invention, there is also provided a method for preparing the above ceramic plate having skin-friendly texture, comprising the steps of:
and sequentially forming a ground glaze layer, a surface glaze layer, an optional ink-jet pattern layer and a transparent protective glaze layer on the surface of the green body layer, then sintering and edging to obtain the ceramic plate with skin-friendly texture.
In the present invention, the "optional inkjet pattern layer" means that the inkjet pattern layer may be formed or may not be formed, that is, the inkjet pattern layer may be selectively provided.
In the invention, the step of sequentially forming the base coat layer, the overglaze layer, the optional ink-jet pattern layer and the transparent protective glaze layer on the surface of the green body layer means that the base coat layer is firstly formed on the surface of the green body, then the overglaze layer is formed on the surface of the base coat layer, and then the optional ink-jet pattern layer and the transparent protective glaze layer are formed on the surface of the overglaze layer.
The preparation method has stable process and strong operability, and is suitable for industrial mass production.
According to a third aspect of the present invention, there is also provided the use of the above-mentioned ceramic sheet material having skin-friendly texture in the field of construction.
In view of the advantages of the ceramic plate with skin-friendly texture, the ceramic plate has good application in the field of construction.
The present invention will be further described with reference to specific examples and comparative examples. Among them, the raw materials in each of the examples and comparative examples were commercially available.
Example 1
The embodiment provides a ceramic plate with skin-friendly texture, which is mainly prepared from a green body layer and a skin glaze layer arranged on the surface of the green body layer, wherein the skin glaze layer comprises a ground glaze layer 2, a surface glaze layer 3, an ink-jet pattern layer 4 and a transparent protective glaze layer 5 which are sequentially arranged along the direction away from the green body layer 1, and the specific structure is shown in figure 1.
The blank layer is mainly prepared from the following raw materials in parts by weight: 3 parts of silica sand, 2 parts of talcum, 3.5 parts of diopside, 46 parts of potassium sodium sand, 6 parts of high clay, 13 parts of potassium sodium stone powder, 15.5 parts of kaolin, 2 parts of environment-friendly mud and 9 parts of mud for dissolving. It should be noted that: the raw materials are conventional raw materials except environment-friendly mud and chemical sludge. The environment-friendly mud is waste residue mud generated after polishing and grinding ceramic bricks, and the main components of the environment-friendly mud are silicon oxide and aluminum oxide, wherein the silicon oxide accounts for 65-70% and the aluminum oxide accounts for 18-20%; the mud is used after impurity removal of low-price raw mud, and the main components of the mud are silicon oxide and aluminum oxide, wherein the silicon oxide accounts for 60% -64% and the aluminum oxide accounts for 22% -25%.
The green body for forming the green body layer comprises the following chemical components in percentage by mass: siO (SiO) 2 67％、Al 2 O 3 18.5％、CaO 1.2％、MgO 1.5％、K 2 O 2.4％、Na 2 O 2.5％、Fe 2 O 3 1.75％、TiO 2 0.25%, 4.9% of burning and trace impurities; the thermal expansion coefficient of the blank body is 7.4 multiplied by 10 -6 /℃(400℃)。
The ground coat layer is mainly prepared from the following raw materials in parts by weight: 17 parts of quartz, 40 parts of potassium feldspar, 8 parts of ball clay, 10 parts of nepheline, 20 parts of alumina, 2 parts of calcined talcum, 3 parts of dolomite and 10 parts of zirconium silicate;
the primer used for forming the primer layer comprises the following chemical components in percentage by mass: siO (SiO) 2 54.31％、Al 2 O 3 28.60％、CaO 1.01％、MgO 1.11％、K 2 O 4.63％、Na 2 O 2.92％，ZrO 2 4.83%, burning and trace impurity 2.59%; the thermal expansion coefficient of the primer is 7.8X10 -6 /℃(400℃)；
The overglaze layer is mainly prepared from the following raw materials in parts by weight: 25 parts of potassium feldspar, 18 parts of albite, 10 parts of calcite, 10 parts of kaolin, 5 parts of calcined kaolin, 12 parts of calcined talcum, 4 parts of aluminum oxide, 10 parts of barium carbonate, 6 parts of zinc oxide and 5 parts of zirconium silicate;
the overglaze for forming the overglaze layer comprises the following chemical components in percentage by mass: siO (SiO) 2 43.65％、Al 2 O 3 17.20％、CaO 5.35％、MgO 3.70％、K 2 O 3.47％、Na 2 O 2.75％、BaO7.41％、ZnO 5.33％、ZrO 2 3.08%, 8.06% of burning and trace impurities; siO in overglaze 2 And Al 2 O 3 The mass ratio is 2.5:1, the sum of mass fractions of CaO, mgO, baO and ZnO is 21.79%; the thermal expansion coefficient of the overglaze was 6.7X10 -6 /℃(400℃)；
The transparent protective glaze layer is mainly prepared from the following raw materials in parts by weight: 18 parts of potassium feldspar, 25 parts of albite, 10 parts of dolomite, 5 parts of calcite, 8 parts of kaolin, 7 parts of calcined kaolin, 5 parts of calcined talcum, 7 parts of barium carbonate, 10 parts of zinc oxide and 5 parts of strontium carbonate;
The transparent protective glaze for forming the transparent protective glaze layer comprises the following chemical components in percentage by mass: siO (SiO) 2 45.5％、Al 2 O 3 19.5％、CaO 5.4％、MgO 3.5％、K 2 O 1.5％、Na 2 2% of O, 4.5% of BaO, 10% of ZnO, 2% of SrO, and 6.1% of burning and trace impurities; the thermal expansion coefficient of the transparent protective glaze is 5.3 multiplied by 10 -6 /℃(400℃)。
The preparation method of the ceramic plate with skin-friendly texture provided by the embodiment comprises the following steps:
(a) Preparation of the blank layer
Mixing the raw materials of the green body layer, adding a debonder (DuramaxD-3019, accounting for 0.3% of the total mass of the raw materials of the green body layer), an alkaline water agent (sodium silicate, accounting for 0.3% of the total mass of the raw materials of the green body layer), a reinforcing agent (vinyl acetate, accounting for 0.4% of the total mass of the raw materials of the green body layer), mixing with water at a mass ratio of 3:1, adding into a ball mill, ball milling, and preparing the green body material through a spray tower; wherein, the moisture percentage by mass of the blank material obtained by testing is 6.5%, and the grain size of the blank material is more than 95% after passing through a 100-mesh sieve;
placing the green body material under a ceramic press for compression molding and drying to obtain a green body layer;
(b) Preparation of ground glaze, overglaze and transparent protective glaze
Mixing the raw materials of the ground glaze (110 parts), adding 33 parts of water, 0.17 part of methyl cellulose and 0.4 part of sodium tripolyphosphate, ball milling for 6 hours, sieving with a 325-mesh sieve to obtain a screen residue of 0.5%, and aging for 32 hours after sieving with the 325-mesh sieve to obtain the ground glaze; the specific gravity of the obtained ground coat is (1.88+ -0.02) g/cm 3 The outflow time was 35s (using a "paint-4 viscosity cup");
mixing the raw materials of the overglaze (105 parts), adding 30 parts of water, 0.16 part of methyl cellulose and 0.37 part of sodium tripolyphosphate, ball milling for 6 hours, sieving with a 325-mesh sieve to obtain the overglaze with the screen residue of 0.5%, and aging for 32 hours after sieving with the 325-mesh sieve to obtain the overglaze; the specific gravity of the obtained overglaze was (1.88.+ -. 0.02) g/cm 3 The run-out time was 35s (using a "paint-4 viscosity cup").
Mixing the raw materials of the transparent protective glaze (100 parts), adding 38 parts of water, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate, ball milling for 6 hours, sieving with a 325-mesh sieve to obtain a screen residue of 0.5%, and aging for 32 hours after sieving with the 325-mesh sieve to obtain the transparent protective glaze; the specific gravity of the obtained transparent protective glaze is (1.18+/-0.02) g/cm 3 。
(c) Applying a bottom on the surface of the blank layerGlaze, forming a ground coat, wherein the spraying amount of the ground coat is 460g/m 2 ；
(d) Applying overglaze on the surface of the base glaze layer to form an overglaze layer, wherein the overglaze application amount is 390g/m 2 ；
(e) Ink-jet printing on the surface of the overglaze layer to obtain an ink-jet pattern layer;
(f) Spraying transparent protective glaze on the surface of the ink-jet pattern layer to form a transparent protective glaze layer, wherein the spraying amount of the transparent protective glaze is 185g/m 2 ；
(g) And (3) firing the ceramic plate in a kiln with the highest temperature of 1180 ℃ for 50 minutes, and then grinding edges to obtain the ceramic plate with skin-friendly texture.
Example 2
The embodiment provides a ceramic plate with skin-friendly texture, which is mainly prepared from a green body layer and a skin glaze layer arranged on the surface of the green body layer, wherein the skin glaze layer comprises a ground glaze layer, a surface glaze layer, an ink-jet pattern layer and a transparent protective glaze layer which are sequentially arranged along the direction far away from the green body layer.
The blank layer is mainly prepared from the following raw materials in parts by weight: 2 parts of silica sand, 1.5 parts of talcum, 2.5 parts of diopside, 43 parts of potassium sodium sand, 8 parts of high clay, 12 parts of potassium sodium stone powder, 18 parts of kaolin, 3 parts of environment-friendly mud and 10 parts of chemical pulping mud;
the green body for forming the green body layer comprises the following chemical components in percentage by mass: siO (SiO) 2 65.8％、Al 2 O 3 19.6％、CaO 1.5％、MgO 1.8％、K 2 O 2.1％、Na 2 O 2.2％、Fe 2 O 3 1.5％、TiO 2 0.2%, 5.3% of burning and trace impurities; the thermal expansion coefficient of the blank body is 7.5 multiplied by 10 -6 /℃(400℃)；
The ground coat layer is mainly prepared from the following raw materials in parts by weight: 15 parts of quartz, 38 parts of potassium feldspar, 9 parts of ball clay, 10.5 parts of nepheline, 21.5 parts of alumina, 2.5 parts of calcined talcum, 3.5 parts of dolomite and 9 parts of zirconium silicate;
the primer used for forming the primer layer comprises the following chemical components in percentage by mass: siO (SiO) 2 52.5％、Al 2 O 3 29.8％、CaO 1.1％、MgO 1.2％、K 2 O 4.2％、Na 2 O 2.6％，ZrO 2 4.33%, and 4.27% of burning and trace impurities; the thermal expansion coefficient of the primer is 7.9 multiplied by 10 -6 /℃(400℃)；
The overglaze layer is mainly prepared from the following raw materials in parts by weight: 23.5 parts of potassium feldspar, 16.5 parts of albite, 11 parts of calcite, 11.5 parts of kaolin, 5.5 parts of calcined kaolin, 13 parts of calcined talcum, 4.5 parts of aluminum oxide, 9 parts of barium carbonate, 5.5 parts of zinc oxide and 5 parts of zirconium silicate;
The overglaze for forming the overglaze layer comprises the following chemical components in percentage by mass: siO (SiO) 2 42.4％、Al 2 O 3 18.2％、CaO 5.7％、MgO 3.9％、K 2 O 3.18％、Na 2 O 2.44％、BaO 7.1％、ZnO 5.12％、ZrO 2 3.08%, 8.88% of burning and trace impurities; siO in overglaze 2 And Al 2 O 3 The mass ratio is 2.33:1, the sum of mass fractions of CaO, mgO, baO and ZnO is 21.82%; the thermal expansion coefficient of the overglaze is 6.8X10 -6 /℃(400℃)；
The transparent protective glaze layer is mainly prepared from the following raw materials in parts by weight: 17 parts of potassium feldspar, 24 parts of albite, 10.5 parts of dolomite, 5.5 parts of calcite, 10 parts of kaolin, 8.5 parts of calcined kaolin, 4.5 parts of calcined talcum, 6 parts of barium carbonate, 9 parts of zinc oxide and 5 parts of strontium carbonate;
SiO 2 44.5％、Al 2 O 3 19.7％、CaO 6％、MgO 3.8％、K 2 O 1.2％、Na 2 1.7% of O, 4.2% of BaO, 9% of ZnO, 2% of SrO, and 7.9% of burning and trace impurities; the thermal expansion coefficient of the transparent protective glaze is 5.4 multiplied by 10 -6 /℃(400℃)。
The method for preparing the ceramic plate with skin-friendly texture of the embodiment is the same as that of the embodiment 1.
Example 3
The embodiment provides a ceramic plate with skin-friendly texture, which is mainly prepared from a green body layer and a skin glaze layer arranged on the surface of the green body layer, wherein the skin glaze layer comprises a ground glaze layer, a surface glaze layer, an ink-jet pattern layer and a transparent protective glaze layer which are sequentially arranged along the direction far away from the green body layer.
The blank layer is mainly prepared from the following raw materials in parts by weight: 3 parts of silica sand, 2.5 parts of talcum, 4 parts of diopside, 48 parts of potassium sodium sand, 5 parts of high clay, 14.5 parts of potassium sodium stone powder, 13.5 parts of kaolin, 1.5 parts of environment-friendly mud and 8 parts of mud;
The green body for forming the green body layer comprises the following chemical components in percentage by mass: siO (SiO) 2 68％、Al 2 O 3 17.5％、CaO 0.91％、MgO 1.2％、K 2 O 2.7％、Na 2 O 2.8％、Fe 2 O 3 2％、TiO 2 0.35%, 4.54% of burning and trace impurities; the thermal expansion coefficient of the blank body is 7.3 multiplied by 10 -6 /℃(400℃)；
The ground coat layer is mainly prepared from the following raw materials in parts by weight: 18.5 parts of quartz, 41.5 parts of potassium feldspar, 7.5 parts of ball clay, 9.5 parts of nepheline, 18.5 parts of alumina, 1.8 parts of calcined talcum, 2.7 parts of dolomite and 10.5 parts of zirconium silicate;
the primer used for forming the primer layer comprises the following chemical components in percentage by mass: siO (SiO) 2 55.8％、Al 2 O 3 27.2％、CaO 0.9％、MgO 1％、K 2 O 4.8％、Na 2 O 2.9％，ZrO 2 5.13%, 2.27% of burning and trace impurities; the thermal expansion coefficient of the primer is 7.7X10 -6 /℃(400℃)；
The overglaze layer is mainly prepared from the following raw materials in parts by weight: 26.5 parts of potassium feldspar, 19.5 parts of albite, 9 parts of calcite, 9 parts of kaolin, 4.5 parts of calcined kaolin, 11 parts of calcined talcum, 3.5 parts of aluminum oxide, 11 parts of barium carbonate, 6 parts of zinc oxide and 5 parts of zirconium silicate;
the overglaze for forming the overglaze layer comprises the following chemical components in percentage by mass: siO (SiO) 2 44.9％、Al 2 O 3 16.8％、CaO 5.56％、MgO 3.3％、K 2 O 3.87％、Na 2 O 3％、BaO 7.78％、ZnO 5.63％、ZrO 2 3.08%, 6.64% of burning and trace impurities; siO in overglaze 2 And Al 2 O 3 The mass ratio is 2.67:1, the sum of mass fractions of CaO, mgO, baO and ZnO is 21.71%; the thermal expansion coefficient of the overglaze is 6.6X10 -6 /℃(400℃)；
The transparent protective glaze layer is mainly prepared from the following raw materials in parts by weight: 19 parts of potassium feldspar, 26 parts of albite, 9.5 parts of dolomite, 4.5 parts of calcite, 7 parts of kaolin, 6 parts of calcined kaolin, 5 parts of calcined talcum, 8 parts of barium carbonate, 10 parts of zinc oxide and 5 parts of strontium carbonate;
The transparent protective glaze for forming the transparent protective glaze layer comprises the following chemical components in percentage by mass: siO (SiO) 2 46.5％、Al 2 O 3 18.6％、CaO 5％、MgO 3.3％、K 2 O 1.7％、Na 2 2.3% of O, 4.8% of BaO, 10% of ZnO, 2% of SrO, and 5.8% of burning and trace impurities; the thermal expansion coefficient of the transparent protective glaze is 5.2 multiplied by 10 -6 /℃(400℃)。
The method for preparing the ceramic plate with skin-friendly texture of the embodiment is the same as that of the embodiment 1.
Comparative example 1
This comparative example provides a ceramic sheet that differs from example 1 only in the primer layer.
The ground coat layer is mainly prepared from the following raw materials in parts by weight: 21 parts of quartz, 40 parts of potassium feldspar, 6 parts of ball clay, 11 parts of nepheline, 16 parts of alumina, 2.5 parts of calcined talcum, 3.5 parts of dolomite and 10 parts of zirconium silicate;
the primer used for forming the primer layer comprises the following chemical components in percentage by mass: siO (SiO) 2 57.5％、Al 2 O 3 25.3％、CaO 0.91％、MgO 1.18％、K 2 O 4.8％、Na 2 O 3％，ZrO 2 4.83%, 2.48% of burning and trace impurities; the thermal expansion coefficient of the primer is 8.2 multiplied by 10 -6 /℃(400℃)；
The ceramic plate of this comparative example was prepared in the same manner as in example 1.
Comparative example 2
This comparative example provides a ceramic panel that differs from example 1 only in the overglaze layer.
The overglaze layer is mainly prepared from the following raw materials in parts by weight: 26 parts of potassium feldspar, 19 parts of albite, 6 parts of calcite, 12.5 parts of kaolin, 6 parts of calcined kaolin, 8 parts of calcined talcum, 6.5 parts of aluminum oxide, 10 parts of barium carbonate, 6 parts of zinc oxide and 5 parts of externally added zirconium silicate;
The overglaze for forming the overglaze layer comprises the following chemical components in percentage by mass: siO (SiO) 2 41％、Al 2 O 3 19.8％、CaO 5.53％、MgO 3.81％、K 2 O 3.87％、Na 2 O 3％、BaO 7.41％、ZnO5.33％、ZrO 2 3.08%, 6.99% of burning and trace impurities; siO in overglaze 2 And Al 2 O 3 The mass ratio is 2.07:1, the sum of mass fractions of CaO, mgO, baO and ZnO is 22.08 percent; the thermal expansion coefficient of the overglaze is 6.3X10 -6 /℃(400℃)。
The ceramic plate of this comparative example was prepared in the same manner as in example 1.
Comparative example 3
This comparative example provides a ceramic sheet which differs from example 1 only in the transparent protective glaze layer.
The transparent protective glaze layer is mainly prepared from the following raw materials in parts by weight: 15 parts of potassium feldspar, 22.5 parts of albite, 11.5 parts of dolomite, 6 parts of calcite, 11 parts of kaolin, 9 parts of calcined kaolin, 4 parts of calcined talcum, 6.5 parts of barium carbonate, 9.5 parts of zinc oxide and 5 parts of strontium carbonate;
the transparent protective glaze for forming the transparent protective glaze layer comprises the following chemical components in percentage by mass: siO (SiO) 2 42.89％、Al 2 O 3 21.2％、CaO 5.56％、MgO 3.6％、K 2 O 1.44％、Na 2 1.8% of O, 4.4% of BaO, 9.5% of ZnO, 2% of SrO, and 7.61% of burning and trace impurities; the thermal expansion coefficient of the transparent protective glaze is 5 multiplied by 10 -6 /℃(400℃)。
Comparative example 4
This comparative example provides a ceramic sheet that differs from example 1 in the overglaze layer and the transparent protective glaze layer.
The composition of the overglaze layer was the same as in comparative example 2, and the composition of the transparent protective glaze layer was the same as in comparative example 3.
The ceramic plate of this comparative example was prepared in the same manner as in example 1.
Comparative example 5
This comparative example provides a ceramic panel that differs from example 1 only in the overglaze layer.
The overglaze layer is mainly prepared from the following raw materials in parts by weight: 27.5 parts of potassium feldspar, 20.5 parts of albite, 13 parts of calcite, 7 parts of kaolin, 3.5 parts of calcined kaolin, 10 parts of calcined talcum, 2.5 parts of aluminum oxide, 10 parts of barium carbonate, 6 parts of zinc oxide and 5 parts of zirconium silicate;
the overglaze for forming the overglaze layer comprises the following chemical components in percentage by mass: siO (SiO) 2 46.2％、Al 2 O 3 15.6％、CaO 5.55％、MgO 3.8％、K 2 O 4.03％、Na 2 O 3.24％、BaO 7.41％、ZnO 5.33％、ZrO 2 3.08%, 8.84% of burning and trace impurities; siO in overglaze 2 And Al 2 O 3 The mass ratio is 2.96:1, the sum of mass fractions of CaO, mgO, baO and ZnO is 22.09%; the thermal expansion coefficient of the overglaze is 7.2 multiplied by 10 -6 /℃(400℃)。
The ceramic plate of this comparative example was prepared in the same manner as in example 1.
Comparative example 6
This comparative example provides a ceramic sheet which differs from example 1 only in the transparent protective glaze layer.
The transparent protective glaze layer is mainly prepared from the following raw materials in parts by weight: 19.5 parts of potassium feldspar, 26.5 parts of albite, 10.5 parts of dolomite, 5.5 parts of calcite, 6 parts of kaolin, 5 parts of calcined talcum, 7 parts of barium carbonate, 10 parts of zinc oxide and 5 parts of strontium carbonate;
The transparent protective glaze for forming the transparent protective glaze layer comprises the following chemical components in percentage by mass: siO (SiO) 2 48.1％、Al 2 O 3 17.2％、CaO 5.44％、MgO 3.6％、K 2 O 1.86％、Na 2 2.41% of O, 4.5% of BaO, 10% of ZnO, 2% of SrO, and 6.1% of burning and trace impurities; the thermal expansion coefficient of the transparent protective glaze is 5.7X10 -6 /℃(400℃)。
The ceramic plate of this comparative example was prepared in the same manner as in example 1.
Comparative example 7
This comparative example provides a ceramic sheet that differs from example 1 in the overglaze layer and the transparent protective glaze layer.
The composition of the overglaze layer was the same as in comparative example 5, and the composition of the transparent protective glaze layer was the same as in comparative example 6.
The ceramic plate of this comparative example was prepared in the same manner as in example 1.
Comparative example 8
This comparative example provides a ceramic panel that differs from example 1 only in the overglaze layer.
The overglaze layer is mainly prepared from the following raw materials in parts by weight: 28 parts of potassium feldspar, 21 parts of albite, 6 parts of calcite, 13 parts of kaolin, 6.5 parts of calcined kaolin, 8 parts of calcined talcum, 5 parts of aluminum oxide, 8 parts of barium carbonate, 4.5 parts of zinc oxide and 5 parts of zirconium silicate;
the overglaze for forming the overglaze layer comprises the following chemical components in percentage by mass: siO (SiO) 2 45.51％、Al 2 O 3 18.72％、CaO 4.41％、MgO 3.23％、K 2 O 4.03％、Na 2 O 3.05％、BaO6.15％、ZnO 4.27％、ZrO 2 3.08%, 7.55% of burning and trace impurities; siO in overglaze 2 And Al 2 O 3 The mass ratio is 2.4:1, the sum of mass fractions of CaO, mgO, baO and ZnO is 18.06%; the thermal expansion coefficient of the overglaze is 6.6X10 -6 /℃(400℃)；
The ceramic plate of this comparative example was prepared in the same manner as in example 1.
Comparative example 9
This comparative example provides a ceramic sheet material having the same structure as in example 1 except that a transparent protective glaze layer is not provided.
The preparation method of the ceramic plate of the comparative example was the same as in example 1 except that the transparent protective glaze was not sprayed on the surface of the inkjet pattern layer (i.e., step (f) was not performed).
In order to verify the technical effects of the above examples and comparative examples, the following experimental examples were specially set.
Experimental example 1
The ceramic plates produced in examples 1 to 3 and comparative examples 1 to 9 were examined for glossiness, surface roughness, deformation and surface quality. Wherein, the glossiness is tested according to the specification in GB/T13891 by adopting a glossiness meter, the surface roughness Ra is tested by adopting an ultra-high-definition microscope, the deformation degree is tested by adopting the specification in GB/T39156, the surface quality defect is tested by adopting the specification in GB/T3810.14, and the specific test results are shown in Table 1.
TABLE 1
As can be seen from the data in examples 1-3 of the table, the glossiness of the ceramic plate prepared by adopting the technical scheme of the invention is between 16 and 25 degrees, the surface of the product has no obvious strong reflected light, no dull and dull phenomenon, a soft visual effect is realized, and the surface has no defects such as bubbles, prickly heat and the like (see fig. 2, no surface flaws are caused). When the ceramic plate of example 1 is observed under an ultra-high-definition microscope, fig. 3 is a graph of the detection data of the surface roughness Ra of the ceramic plate with skin-friendly texture provided by example 1, the surface roughness Ra of the plate product is between 12.37 and 14.22 μm, and the surface is fine and smooth like the skin of an infant, so that the comfortable fine skin-friendly texture is realized. FIG. 4 is a firing graph of the green body and the primer of example 1 of the present invention.
As can be seen from the data of example 1 and comparative example 1, when the primer formulation of comparative example 1 adopts a high silicon low aluminum scheme, the surface roughness Ra value of the two sheet products is relatively close to that of the sheet products, but the Al in the primer 2 O 3 The content is lower than that, and the melting is earlier, so that the blank body is not oxidized and exhausted smoothly, and the surface is easy to form defects such as bubbles, miliaria and the like (see fig. 5, the surface has obvious defects of bubbles and miliaria); and the expansion coefficient is also increased, and the brick shape can be influenced to a certain extent. The setting of the formula of the primer high-alumina is described, so that the blank body has sufficient oxidation and exhaust space, thereby effectively reducing the generation rate of bubbles and miliaria and avoiding the defect that the blank body breaks through the upper surface glaze. In addition, the expansion coefficient of the base glaze is close to that of the green body, so that an excellent glaze intermediate layer is easier to form, the stress of the green glaze is better relieved, and the glaze blanks are firmly combined.
As can be seen from the data of example 1 and comparative example 2, siO is present in the overglaze 2 With Al 2 O 3 When the mass percentage ratio of (2) is too small, the glossiness value is reduced, and the surface roughness is increased, so that the comfortable touch feeling of the surface of the product is reduced; at the same time, the low silicon high aluminum scheme causes the expansion coefficient to be reduced, so that the brick shape is slightly influenced.
As can be seen from the data of example 1 and comparative example 3, when the transparent protective glaze adopts the low silicon high aluminum scheme, the gloss value is reduced, and the surface roughness is also increased, resulting in reduced comfortable touch feeling of the product surface; meanwhile, the expansion coefficient is also reduced due to the low-silicon high-aluminum scheme, but the protective glaze layer is thinner, and the influence on the brick shape is not obvious.
As can be seen from the data of example 1 and comparative example 4, when the overglaze and the transparent protective glaze are simultaneously used in a low silicon high aluminum scheme, the gloss value is significantly reduced, and the surface roughness is increased, resulting in a reduction in the pleasant touch feeling of the surface of the article; at the same time, the low silicon high aluminum solution causes the expansion coefficient to be too small, thereby affecting the brick shape.
As can be seen from the data of example 1 and comparative example 5, siO is present in the overglaze 2 With Al 2 O 3 When the mass percentage ratio of the glass is too large, the glossiness value is increased, the surface roughness is reduced, and the smoothness is increased; at the same time, the high silicon low aluminum scheme causes the expansion coefficient to be increased, so that the brick shape is slightly influenced.
As can be seen from the data of example 1 and comparative example 6, when the transparent protective glaze adopts a high silicon low aluminum scheme, the gloss value is increased to some extent, and the surface roughness is reduced, resulting in an increase in smoothness; although the high silicon low aluminum solution results in a slightly larger expansion coefficient, the protective glaze layer is thinner and has no obvious effect on brick shape.
As can be seen from the data of example 1 and comparative example 7, when the overglaze and the transparent protective glaze are simultaneously used in a high silicon low aluminum scheme, the gloss value is significantly increased and the surface roughness is reduced, resulting in an increased smoothness and a lack of fine touch; at the same time, the high silicon low aluminum scheme leads to an increase in expansion coefficient, thereby affecting the brick shape.
As can be seen from the data of example 1 and comparative example 8, when the sum of the mass percentages of CaO, mgO, baO and ZnO in the overglaze is too small, the fluxing process is slow, and correspondingly, the formation process of the glass phase substance is slow, so that the surface glossiness of the product is low, the glaze is dull and sinking, and the molten state is poor, so that the prickly heat and bubbles on the lower layer are difficult to seal in advance.
As can be seen from the data of example 1 and comparative example 9, when the transparent protective glaze is not sprayed on the surface of the inkjet pattern layer, the protection of the transparent protective glaze layer is not performed, and pores and pinholes are formed on the surface, so that the antifouling effect is poor.
The technical scheme of the blank layer, the ground coat layer, the overglaze layer, the ink-jet pattern layer and the protective glaze layer provided by the invention is described above, the protective glaze layer can be kept to have a thin-layer high-transmittance thin-sliding low-light effect, and the overglaze layer is prepared into a soft texture effect, so that the interaction achieves the effects of clear surface pattern, soft hand feeling and texture, a soft skin-friendly effect and a soft visual effect. In order to solve the quality defect problems caused by brick shapes and oxidation and exhaust such as miliaria, bubbles and the like, the invention designs the ground coat layer under the surface glaze, and different mechanisms act mutually and complementarily, so that the generation of bubbles and miliaria on the surface of a product is controlled, and the expansion coefficients of the surface glaze and the protective glaze are smaller than those of the ground coat and the green body, so that the combination of the ground coat and the green body is basically not greatly influenced, and the deformation degree of the product after firing is less influenced. From the above, the technical solutions of the present invention work synergistically with each other.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (7)
1. The ceramic plate with the skin-friendly texture is characterized by being mainly prepared from a green body layer and a skin glaze layer arranged on the surface of the green body layer, wherein the skin glaze layer comprises a ground glaze layer, a surface glaze layer and a transparent protective glaze layer which are sequentially arranged along the direction far away from the green body layer;
the surface glossiness of the ceramic plate is 16-25 degrees, and the surface roughness Ra of the ceramic plate is 10-15 mu m;
the green body for forming the green body layer comprises the following chemical components in percentage by mass:
SiO 2 65.5%-68.5%，Al 2 O 3 17%-20%，CaO 0.8%-1.6%，MgO 1%-2%，K 2 O 1.8%-3%，Na 2 O 2%-3%，Fe 2 O 3 1%-2.5%，TiO 2 0.1% -0.4%, and the rest is burning and trace impurities;
the primer used for forming the primer layer comprises the following chemical components in percentage by mass:
SiO 2 52%-56.6%，Al 2 O 3 27%-30.2%，CaO 0.8%-1.2%，MgO 0.9%-1.3%，K 2 O 4%-5.2%，Na 2 O 2.5%-3.3%，ZrO 2 4% -5.6%, and the rest is burning and trace impurities;
the overglaze for forming the overglaze layer comprises the following chemical components in percentage by mass:
SiO 2 42%-45.3%，Al 2 O 3 16.5%-18.5%，CaO 4.7%-6%，MgO 3.2%-4.2%，K 2 O 3%-4%，Na 2 O 2.3%-3.2%，BaO 6.8%-8%，ZnO 4.8%-6%，ZrO 2 2.5 to 3.7 percent, and the balance of burning and trace impurities; at the same time, siO in the overglaze 2 With Al 2 O 3 The mass fraction ratio of (2.2-2.8): 1, wherein the sum of mass fractions of CaO, mgO, baO and ZnO is 21-23%;
the transparent protective glaze for forming the transparent protective glaze layer comprises the following chemical components in percentage by mass:
SiO 2 44%-47%，Al 2 O 3 18%-20%，CaO 4.5%-6.3%，MgO 3%-4%，K 2 O 1%-2%，Na 2 1.5 to 2.5 percent of O, 4 to 5 percent of BaO, 9 to 11 percent of ZnO, 1.5 to 2.5 percent of SrO and the balance of burning and trace impurities;
the green body for forming the green body layer has a thermal expansion coefficient of (7.3-7.5) x 10 at 400 DEG C -6 /℃；
The primer used for forming the primer layer has a thermal expansion coefficient of (7.7-7.9) x 10 at 400 DEG C -6 /℃；
The overglaze for forming the overglaze layer has a thermal expansion coefficient of (6.6-6.8) x 10 at 400 DEG C -6 /℃；
The thermal expansion coefficient of the transparent protective glaze for forming the transparent protective glaze layer is (5.2-5.4) multiplied by 10 at 400 DEG C -6 /℃。
2. The skin-friendly ceramic board according to claim 1, wherein the difference between the thermal expansion coefficients of the primer and the green body at 400 ℃ is (0.3-0.5) x 10 -6 /℃。
3. The skin-friendly ceramic board according to claim 1, wherein the difference of thermal expansion coefficients of the under-glaze and the over-glaze at 400 ℃ is (1.0-1.2) x 10 -6 /℃。
4. The skin-friendly ceramic board according to claim 1, wherein the difference in thermal expansion coefficient between the overglaze and the transparent protective glaze at 400 ℃ is (1.3-1.5) ×10 -6 /℃。
5. The ceramic board with skin-friendly texture according to claim 1, wherein an inkjet pattern layer is further arranged between the overglaze layer and the transparent protective glaze layer.
6. The method for preparing a ceramic plate having skin-friendly texture as claimed in any one of claims 1 to 5, comprising the steps of:
and sequentially forming a ground glaze layer, a surface glaze layer, an optional ink-jet pattern layer and a transparent protective glaze layer on the surface of the green body layer, then sintering and edging to obtain the ceramic plate with skin-friendly texture.
7. Use of the skin-friendly ceramic board according to any one of claims 1 to 5 in the construction field.
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