CN117603592A - Blue-and-white pigment, blue-and-white ceramic ink, digital decorative blue-and-white ceramic plate and preparation method thereof - Google Patents

Blue-and-white pigment, blue-and-white ceramic ink, digital decorative blue-and-white ceramic plate and preparation method thereof Download PDF

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CN117603592A
CN117603592A CN202410099613.9A CN202410099613A CN117603592A CN 117603592 A CN117603592 A CN 117603592A CN 202410099613 A CN202410099613 A CN 202410099613A CN 117603592 A CN117603592 A CN 117603592A
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blue
white
parts
white ceramic
ink
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CN117603592B (en
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刘一军
梁铎
吴洋
陈鹏程
汪庆刚
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Monalisa Group Co Ltd
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Monalisa Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0009—Pigments for ceramics
    • C09C1/0012—Pigments for ceramics containing zirconium and silicon
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • 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
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Wood Science & Technology (AREA)
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Abstract

The invention belongs to the technical field of building ceramics, and particularly relates to a blue-and-white pigment, blue-and-white ceramic ink, a digital decorative blue-and-white ceramic plate and a preparation method thereof. The blue-white pigment comprises the following raw materials: 8-15 parts of cobalt oxide, 25-38 parts of frit, 1-5 parts of ferric oxide, 24-35 parts of water-washed kaolin, 1-5 parts of manganese oxide, 12-20 parts of pearl material and 1-4 parts of calcined talcum; the chemical composition of the frit comprises: in mass percent, siO 2 58‑70%、Al 2 O 3 6.0‑7.5%、Fe 2 O 3 0.1‑0.3%、CaO 13‑18%、MgO 1.0‑2.5%、K 2 O 2.5‑3.5%、Na 2 O 0.2‑2.5%、B 2 O 3 1 to 3 percent and 2.5 to 5.5 percent of ZnO. The blue and white ceramic plate with the blue and white effect can be obtained by creatively developing the blue and white pigment which is suitable for the building ceramic process, and the blue and white ceramic ink using the blue and white pigment is applied to the surface of a green body in a digital printing mode and then is combined with the transparent glaze, so that the blue and white ceramic plate with the blue and white effect can be used for preparing high-quality large-specification personalized digital decorative blue and white ceramic plates.

Description

Blue-and-white pigment, blue-and-white ceramic ink, digital decorative blue-and-white ceramic plate and preparation method thereof
Technical Field
The invention belongs to the technical field of building ceramics, and particularly relates to a blue-and-white pigment, blue-and-white ceramic ink, a digital decorative blue-and-white ceramic plate and a preparation method thereof.
Background
Blue and white porcelain is one of the ceramic varieties, and is popular and interesting for consumers due to the artistic characteristics of ink and wash painting. However, the blue and white porcelain in the current market is mainly prepared by manually drawing a layout and combining the procedures of decal and decoration firing. The traditional manufacture of blue-and-white ceramic plates generally adopts a teaching mode of teachers and students to carry out water splashing and green splashing processes, and long-time technical accumulation is needed to master the water splashing and green splashing processes. The current pattern transfer methods such as decal printing and the like easily cause the reduction of pattern fineness and color rendering effect. The decoration firing also easily causes low product yield and poor smoothness of the glaze, and the production of the high-quality large-specification decorative blue-and-white ceramic plate is difficult to realize. The blue-and-white color rendering effect of the blue-and-white ceramic plate, the product pattern updating and changing and the like are all to be improved.
Disclosure of Invention
Aiming at the problems, the invention creatively develops the blue-and-white pigment which is suitable for the building ceramic process, has good color development, and can be used for preparing high-quality large-specification personalized digital decorative blue-and-white ceramic plates by combining transparent glaze after the blue-and-white ceramic ink using the blue-and-white pigment is applied to the surface of a green body in a digital printing mode.
In a first aspect, the present invention provides a blue-and-white pigment. The blue-white pigment comprises the following raw materials: 8-15 parts of cobalt oxide, 25-38 parts of frit, 1-5 parts of ferric oxide, 24-35 parts of water-washed kaolin, 1-5 parts of manganese oxide, 12-20 parts of pearl material and 1-4 parts of calcined talcum; the chemical composition of the frit comprises: in mass percent, siO 2 58-70%、Al 2 O 3 6.0-7.5%、Fe 2 O 3 0.1-0.3%、CaO 13-18%、MgO 1.0-2.5%、K 2 O 2.5-3.5%、Na 2 O 0.2-2.5%、B 2 O 3 1-3%、ZnO 2.5-5.5%。
Preferably, the chemical composition of the bead comprises: in mass percent, siO 2 28-30%、Al 2 O 3 33-37%、Fe 2 O 3 2.0-3.5%、TiO 2 0.3-0.5%、CuO 0.7-0.9%、MgO 0.3-1.5%、CaO 0.3-0.5%、K 2 O 0.03-1%、Na 2 O 0.2-0.5%、MnO 22-24%、CoO 5-7%。
Preferably, the frit has an onset temperature of 1080-1115 ℃.
In a second aspect, the present invention provides a blue-and-white ceramic ink. Comprising the blue-and-white pigment.
Preferably, the blue-and-white ceramic ink comprises the following raw materials: the weight percentage of the blue-white pigment is 40-50%, the white oil is 15-30%, the isooctyl palmitate and/or the isopropyl laurate is 15-20%, the dispersant is 3-10%, and the defoamer is 0.2-0.6%.
In a third aspect, the invention provides a method for preparing a digital decorative blue-and-white ceramic plate. The preparation method comprises the following steps:
applying surface glaze on the surface of the blank;
printing the blue-and-white ceramic ink on the surface of the green body after the overglaze is applied according to a design layout;
the surface Shi Touming glaze of the green body after the blue-and-white ceramic ink is printed by ink jet;
and (3) sintering and polishing the green body subjected to transparent glaze application to obtain the digital decorative blue-and-white ceramic plate.
Preferably, the chemical composition of the transparent glaze comprises: the burning loss is 0 in mass percent.3-0.6%、SiO 2 59-61%、Al 2 O 3 12-14%、Fe 2 O 3 0.1-0.25%、CaO 10-12%、MgO 1.5-2.5%、K 2 O 5-7%、Na 2 O 1.5-2.5%、BaO 0.3-0.6 %、ZnO 4-6%、Li 2 O 0.4-0.8%。
Preferably, the specific gravity of the transparent glaze is 1.85-1.92 g/cm 3 The glazing quantity is 400-500 g/m 2 。
Preferably, the highest firing temperature is 1160-1210 ℃ and the firing time is 85-120 minutes.
In a fourth aspect, the invention provides a digital decorative blue-and-white ceramic plate. The digital decorative blue-and-white ceramic plate is obtained by a preparation method of the digital decorative blue-and-white ceramic plate.
The invention uses the specially customized blue-and-white pigment for blue-and-white ceramic ink, and organically combines with an ink-jet printing process, realizes the industrialized reproduction of large-specification blue-and-white artistic porcelain plates, overcomes the technical defects of manual blue-and-white painting, blue-and-white stained paper silk screen decal transfer printing and complex hanging firing process in the traditional blue-and-white porcelain plate making process, and meets the design requirements of new-era artistic diversification. In addition, the invention can realize batch, low-cost and high-quality preparation of the digital decorative blue-and-white ceramic plate under the existing building ceramic industrial conditions, can be widely applied to the aspects of background wall decoration, large-scale mural, large-scale print and the like of building ceramic, and greatly enhances the rendering effect of artistic design.
Drawings
FIG. 1 is a graph of the effect of the tile surface prior to firing in example 1;
fig. 2 is a brick surface effect diagram of the digital decorative blue-and-white ceramic plate of example 1;
FIG. 3 is a graph of the tile effect of comparative example 3.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof. Unless otherwise specified, each percentage refers to a mass percent.
Preparing blue-white pigment.
The blue-white pigment comprises the following raw materials: 8-15 parts of cobalt oxide, 25-38 parts of frit, 1-5 parts of ferric oxide, 24-35 parts of water-washed kaolin, 1-5 parts of manganese oxide, 12-20 parts of pearl material and 1-4 parts of calcined talcum. All the raw materials of the blue-white pigment are preferably technical-grade raw materials. The blue-and-white pigment is more suitable for the kiln rapid firing schedule of the existing building ceramics.
The chemical composition of the frit comprises: in mass percent, siO 2 58-70%、Al 2 O 3 6.0-7.5%、Fe 2 O 3 0.1-0.3%、CaO 13-18%、MgO 1.0-2.5%、K 2 O 2.5-3.5%、Na 2 O 0.2-2.5%、B 2 O 3 1 to 3 percent and 2.5 to 5.5 percent of ZnO. The frit is capable of promoting chemical reactions at high temperatures of coloring ions such as cobalt ions, chromium ions, manganese ions, etc. in pigments. The introduction of ZnO widens the color temperature range of coloring ions. Introduction of MgO and B 2 O 3 The high-temperature chemical reactivity of cobalt ions, manganese ions and iron ions in the blue-white pigment is increased. The initial melting temperature of the frit can be 1080-1115 ℃.
In the raw material composition of the blue-and-white pigment, the excessive frit content can cause excessive reaction to generate a large amount of non-static substances when the blue-and-white pigment is presintered, and a large amount of colloid ions are generated when blue-and-white ceramic ink is prepared in the later period, so that the situation of blocking a spray head in the ink printing process can be caused, and the printing performance of the ink is affected; the too low frit content can lead to the failure of pre-uniformly dispersing coloring ions when the blue-and-white pigment is presintered, and can not ensure better coloring of the coloring ions such as cobalt, manganese and the like of the ink under a rapid firing system.
As an example, the chemical composition of the water-washed kaolin clay includes: in mass percent, the burning loss is 12.81 percent, siO 2 48.23%、Al 2 O 3 35.94%、Fe 2 O 3 0.8%、TiO 2 0.38 %、CaO 0.05%、MgO 0.12%、K 2 O 1.21%、Na 2 O 0.46%。
The chemical composition of the bead material comprises: in mass percent, siO 2 28-30%、Al 2 O 3 33-37%、Fe 2 O 3 2.0-3.5%、TiO 2 0.3-0.5%、CuO 0.7-0.9%、MgO 0.3-1.5%、CaO 0.3-0.5%、K 2 O 0.03-1%、Na 2 0.2-0.5% of O, 22-24% of MnO and 5-7% of CoO. The beading material is the primary color source of blue and white pigments and is capable of providing cobalt and manganese ions. The too high content of the bead material can cause the too high reaction temperature of the blue-and-white pigment, the incomplete color development in the rapid firing process can cause color shift and black development, and the color rendering effect of the blue-and-white pigment is not achieved; the too low content of the pearl material can cause the color development of the blue-and-white pigment to be lighter, and the blue-and-white color rendering effect can not reach the expected effect.
The chemical composition of the calcined talc comprises: 0.7 percent of burning loss and SiO in percentage by mass 2 65.8%、Al 2 O 3 1.87%、Fe 2 O 3 0.24%、TiO 2 0.07 %、CaO 0.99%、MgO 29.96%、K 2 O 0.16%、Na 2 O 0.21%。
Weighing according to the raw material composition of the blue and white pigment, ball milling and mixing uniformly until the granularity is controlled to be 325 meshes less than 2wt%, and marking the obtained material as material A. Heating the material A to 1150-1300 ℃ at 5-10 ℃/min (for example, 5 ℃/min) under the oxidizing atmosphere, sintering (presintering) for 2-4 hours at 1150-1300 ℃, and crushing to obtain the blue-white pigment. In the presintering process, the mixed inorganic powder fully and chemically reacts to obtain the blue-and-white pigment mainly comprising silicate-based compound. The pulverizing means includes, but is not limited to, mechanical pulverizing, jet milling, and the like. In some technical schemes, the particle size of the powder of the blue-white pigment is controlled at D 90 Preferably < 8. Mu.m.
The blue-and-white pigment meets the requirement of medium-temperature rapid firing of a roller kiln, simultaneously has the performance requirement of preparing blue-and-white ceramic ink, and introduces a high-temperature fluxing agent (frit) to reduce the color development temperature of the blue-and-white pigment and realize good color development. The blue-and-white pigment can be matched with the existing wrapping red ink and other decorations, and can realize the special decorative effects of rare blue-and-white porcelain varieties such as blue-and-white underglaze red.
And preparing blue-and-white ceramic ink. The blue-and-white ceramic ink comprises the following raw materials: the weight percentage of the blue-white pigment is 40-50%, the white oil is 15-30%, the isooctyl palmitate and/or the isopropyl laurate is 15-20%, the dispersant is 3-10%, and the defoamer is 0.2-0.6%. Dispersing agent and defoaming agent are commercially available. For example, the dispersant may be Lamberti 1028, lamberti 1087, BYK-AT203, BYK-AT204, BYK-9076, BYK-163, etc.; as the defoaming agent, ning Baidi DEFOMEX 108, a bright rainbow aid HF3107 fluorine-modified silicone type, a bright rainbow aid HF3012 special polymer and the like can be used. In the specific embodiment, BYK-AT203 is used as the dispersing agent, and HF3107 fluorine-modified organosilicon is used as the defoamer.
Raw materials of the blue-and-white ceramic ink are mixed uniformly according to the proportion and then are ground in a sand mill, so that the blue-and-white ceramic ink with consistent and good stability is obtained. Particle diameter D of blue-and-white ceramic ink 90 ＜1μm。
The preparation method of the digital decorative blue-and-white ceramic plate is also exemplified.
Applying surface glaze on the surface of the blank body. Inkjet overglazes commonly used in the art may be employed. For example, the chemical composition of the overglaze includes: 3.0 to 4.0 percent of burning loss and SiO based on mass percent 2 52-60%、Al 2 O 3 20-26%、Fe 2 O 3 0.1-0.3%、CaO 0.1-0.3%、MgO 0.1-0.3%、K 2 O 2.0-5.0%、Na 2 O 1.0-3.0%、ZrO 2 4.0-6.0%. Overglaze may be applied by pouring the glaze. For example, the specific gravity of the overglaze is 1.86-1.88 g/cm 3 The glazing amount is 550-600 g/m 2 。
And printing the blue-and-white ceramic ink on the surface of the green body after the overglaze is applied according to a design layout by using an ink-jet printer. The blue-and-white ceramic ink and the ceramic ink with other colors can be used together, for example, the blue-and-white ceramic ink is used as a main color tone, and the inks with other colors such as red, yellow, blue, brown and the like are used together.
And (5) carrying out ink-jet printing on the surface Shi Touming glaze of the green body after the blue-and-white ceramic ink is printed. The chemical composition of the transparent glaze comprises: 0.3 to 0.6 percent of burning loss and SiO based on mass percent 2 59-61%、Al 2 O 3 12-14%、Fe 2 O 3 0.1-0.25%、CaO 10-12%、MgO 1.5-2.5%、K 2 O 5-7%、Na 2 O 1.5-2.5%、BaO 0.3-0.6 %、ZnO 4-6%、Li 2 O0.4-0.8%. Alkali metal oxides and alkaline earth metal oxides in the transparent glaze promote the development of blue-and-white pigmentsColor. The blue-and-white pigment and the transparent glaze are regulated and controlled to form anorthite equal crystals on the brick surface after firing, so that the blue-and-white pigment halation control method is an important mode for controlling blue-and-white pigment halation. The ZnO content of the transparent glaze can influence the transparency of the glaze layer and further influence the halation effect. Too high a ZnO content deteriorates the color development of the blue-and-white pigment. The transparent glaze provided by the invention can effectively reduce the high-temperature viscosity of the glaze, reduce bubbles in the glaze layer and well promote the color development of blue-and-white pigment. In addition, li 2 O can promote the appearance of a bluish hue.
As an example, the raw material composition of the transparent glaze includes: 15-25% of potassium feldspar, 15-20% of albite, 10-15% of quartz, 5-8% of kaolin, 10-20% of frit, 0.1-5% of barium carbonate, 0.1-13% of zinc oxide and 0.5-1% of lithium carbonate. The chemical composition of the frit may include: 0.3 to 0.1 percent of burning loss and SiO based on mass percent 2 50-60%、Al 2 O 3 12-18%、Fe 2 O 3 0.1-0.3%、CaO 5-8%、MgO 0.1-2.5%、K 2 O 3-5%、Na 2 O 1-2.5%、BaO 0.1-8%、ZnO 0.1-5%。
Glazing processes for transparent glazes include, but are not limited to, pouring, spraying, and the like. For example, the specific gravity of the transparent glaze is 1.85-1.92 g/cm 3 The glazing amount is 400-500 g/m 2 。
And (5) sintering the green body subjected to transparent glaze application in a roller kiln. The highest firing temperature is 1160-1210 ℃ and the firing time is 85-120 minutes. The firing temperature is too low to cause the firing of the glaze, and the blue-and-white pigment cannot give out vivid color; too high a firing temperature can cause the glaze to boil, and a large number of bubble defects appear. Under the firing system, the blue and white color normally scattered achieves the artistic effect of the ink and wash painting.
The ceramic plate after firing may also be polished. Polishing includes rough polishing, medium polishing, and fine polishing. For example, the parameters of rough polishing are: belt running frequency 40 HZ, head swing 35HZ; the grinding block combination used for rough polishing is 240 mesh 9 group, 240 mesh 10 group and 320 mesh 1 group. For example, parameters of the mid-throw are: belt running frequency 53.5 HZ, head swing 35HZ; the grinding block combination used in the polishing is 320 meshes of 2 groups, 240 meshes of 3 groups, 400 meshes of 2 groups, 600 meshes of 1 group, 800 meshes of 4 groups, 1000 meshes of 3 groups, 1200 meshes of 2 groups and 1500 meshes of 3 groups. For example, the parameters of polishing are: a belt: 35.6 HZ, swing 35HZ; the grinding block combination used for fine polishing is 2000 mesh 2 group, 3000 mesh 3 group, 6000 mesh 2 group, 8000 mesh 1 group.
The polished digital decorative blue-and-white ceramic plate can be subjected to super-clean and bright waxing treatment and then packaged into a finished product.
The present invention will be described in more detail by way of examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
The preparation method of the digital decorative blue-and-white ceramic plate comprises the following steps:
1. applying surface glaze on the surface of the blank body. The chemical composition of the overglaze comprises: in mass percent, the burning loss is 4.14 percent, siO 2 58.54%、Al 2 O 3 24.24%、Fe 2 O 3 0.2%、CaO 0.23%、MgO 0.17%、K 2 O 4.42%、Na 2 O 2.24%、ZrO 2 5.82%. The glazing process of the overglaze is glazing, and the specific gravity is 1.87. 1.87 g/cm 3 Glazing amount is 580 g/m 2 。
2. And preparing blue-and-white ceramic ink. 8 parts of cobalt oxide, 35 parts of frit, 3 parts of ferric oxide, 34 parts of water-washed kaolin, 2 parts of manganese oxide, 15 parts of pearl material and 3 parts of calcined talcum are uniformly mixed by ball milling until the discharge granularity is controlled to be 325 meshes less than 2 weight percent, and the obtained material is marked as material A. The chemical composition of the frit comprises: in mass percent, siO 2 68.5%、Al 2 O 3 6.15%、Fe 2 O 3 0.13%、CaO 15.42%、MgO 1.1%、K 2 O 2.97%、Na 2 O 0.35%、B 2 O 3 1.1% and 4.28% of ZnO. The chemical composition of the bead comprises: in mass percent, siO 2 28.33%、Al 2 O 3 35.96%、Fe 2 O 3 2.80%、TiO 2 0.35%、CuO 0.83%、MgO 1.45%、CaO 0.37%、K 2 O 0.05%、Na 2 0.3% of O, 23.54% of MnO and 6.02% of CoO. Heating the material A to 1200 ℃ at 5 ℃/min under the oxidizing atmosphere, sintering for 3 hours at 1200 ℃, and crushing to obtain the blue-white pigment. The blue-and-white ceramic ink comprises the following raw materials: the paint comprises, by mass, 40% of blue-white pigment, 30% of white oil, xin Zhizhi% of palmitic acid, 9.8% of a dispersing agent and 0.2% of a defoaming agent. And (3) uniformly mixing the raw materials of the blue-and-white ceramic ink, and grinding the mixture in a sand mill to obtain the blue-and-white ceramic ink. Particle diameter D of blue-and-white ceramic ink 90 ＜1μm。
3. And (3) carrying out ink-jet printing on the surface of the green body after the overglaze is applied according to the design pattern to form the blue-and-white artistic porcelain design pattern.
4. And (5) carrying out ink-jet printing on the surface Shi Touming glaze of the green body after the blue-and-white ceramic ink is printed. The transparent glaze is applied by adopting a glaze spraying mode. The chemical composition of the transparent glaze comprises: 0.37 percent of burning loss and SiO in percentage by mass 2 59.9%、Al 2 O 3 12.4%、Fe 2 O 3 0.13%、CaO 10.58%、MgO 1.85%、K 2 O 6.15%、Na 2 O 2.18%、BaO 0.46%、ZnO 5.39%、Li 2 O0.59%. The specific gravity of the transparent glaze is 1.86 g/cm 3 The glazing amount is 410 g/m 2 。
5. And (5) sintering the green body subjected to transparent glaze application in a roller kiln. The highest firing temperature was 1200 ℃, and the firing time was 95 minutes.
6. Polishing the ceramic plate after firing to obtain the digital decorative blue-and-white ceramic plate. The specification is 900 mm multiplied by 1800 multiplied by mm multiplied by 5.5mm thick.
FIG. 1 is a graph showing the effect of the brick surface before firing in example 1. The green color of the green brick surface before being burned is dull. Fig. 2 is a graph showing the effect of the tile surface of the digital decorative blue-and-white ceramic plate of example 1. The digital decorative blue-and-white ceramic plate has a color development foundation similar to that of a blue-and-white porcelain imitating a primordial generation.
Example 2
The preparation method of the digital decorative blue-and-white ceramic plate comprises the following steps:
1. on the surface of the blankApplying surface glaze. The chemical composition of the overglaze comprises: in mass percent, the burning loss is 4.14 percent, siO 2 58.54%、Al 2 O 3 24.24%、Fe 2 O 3 0.2%、CaO 0.23%、MgO 0.17%、K 2 O 4.42%、Na 2 O 2.24%、ZrO 2 5.82%. The glazing process of the overglaze is glazing, and the specific gravity is 1.87. 1.87 g/cm 3 Glazing amount is 580 g/m 2 。
2. And preparing blue-and-white ceramic ink. 10 parts of cobalt oxide, 38 parts of frit, 1 part of ferric oxide, 24 parts of water-washed kaolin, 5 parts of manganese oxide, 20 parts of pearl material and 2 parts of calcined talcum are uniformly mixed by ball milling until the discharge granularity is controlled to be 325 meshes less than 2 weight percent, and the obtained material is marked as material A. The chemical composition of the frit comprises: in mass percent, siO 2 68.5%、Al 2 O 3 6.15%、Fe 2 O 3 0.13%、CaO 15.42%、MgO 1.1%、K 2 O 2.97%、Na 2 O 0.35%、B 2 O 3 1.1% and 4.28% of ZnO. The chemical composition of the bead comprises: in mass percent, siO 2 28.33%、Al 2 O 3 35.96%、Fe 2 O 3 2.80%、TiO 2 0.35%、CuO 0.83%、MgO 1.45%、CaO 0.37%、K 2 O 0.05%、Na 2 0.3% of O, 23.54% of MnO and 6.02% of CoO. Heating the material A to 1230 ℃ at 10 ℃/min under the oxidation atmosphere, sintering at 1230 ℃ for 3 hours, and crushing to obtain the blue-white pigment. The blue-and-white ceramic ink comprises the following raw materials: the paint comprises, by mass, 40% of blue-white pigment, 30% of white oil, xin Zhizhi% of palmitic acid, 9.8% of a dispersing agent and 0.2% of a defoaming agent. And (3) uniformly mixing the raw materials of the blue-and-white ceramic ink, and grinding the mixture in a sand mill to obtain the blue-and-white ceramic ink. Particle diameter D of blue-and-white ceramic ink 90 ＜1μm。
3. And (3) carrying out ink-jet printing on the surface of the green body after the overglaze is applied according to the design pattern to form the blue-and-white artistic porcelain design pattern.
4. And (5) carrying out ink-jet printing on the surface Shi Touming glaze of the green body after the blue-and-white ceramic ink is printed. The transparent glaze is applied by adopting a glaze spraying mode. The chemical composition of the transparent glaze comprises: 0.37 percent of burning loss and SiO in percentage by mass 2 59.9%、Al 2 O 3 12.4%、Fe 2 O 3 0.13%、CaO 10.58%、MgO 1.85%、K 2 O 6.15%、Na 2 O 2.18%、BaO 0.46%、ZnO 5.39%、Li 2 O0.59%. The specific gravity of the transparent glaze is 1.88 g/cm 3 The glazing amount is 500 g/m 2 。
5. And (5) sintering the green body subjected to transparent glaze application in a roller kiln. The highest firing temperature is 1210 ℃, and the firing time is 95 minutes.
6. Polishing the ceramic plate after firing to obtain the digital decorative blue-and-white ceramic plate. The specification is 900 mm multiplied by 1800 multiplied by mm multiplied by 5.5mm thick.
The digital decorative blue-and-white artistic ceramic plate prepared in the embodiment 2 presents a purple blue tone with more gorgeous color development and has a blue-and-white porcelain-like basic tone.
Example 3
The preparation method of the digital decorative blue-and-white ceramic plate comprises the following steps:
1. applying surface glaze on the surface of the blank body. The chemical composition of the overglaze comprises: in mass percent, the burning loss is 4.14 percent, siO 2 58.54%、Al 2 O 3 24.24%、Fe 2 O 3 0.2%、CaO 0.23%、MgO 0.17%、K 2 O 4.42%、Na 2 O 2.24%、ZrO 2 5.82%. The glazing process of the overglaze is glazing, and the specific gravity is 1.87. 1.87 g/cm 3 Glazing amount is 580 g/m 2 。
2. And preparing blue-and-white ceramic ink. 11 parts of cobalt oxide, 36 parts of frit, 4 parts of ferric oxide, 26 parts of water-washed kaolin, 3 parts of manganese oxide, 18 parts of pearl material and 2 parts of calcined talcum are uniformly mixed by ball milling until the discharge granularity is controlled to be 325 meshes less than 2 weight percent, and the obtained material is marked as material A. The same frit and bead as in example 1 was used. Heating the material A to 1230 ℃ at 10 ℃/min under the oxidation atmosphere, sintering at 1230 ℃ for 3 hours, and crushing to obtain the blue-white pigment. The blue-and-white ceramic ink comprises the following raw materials: the paint comprises, by mass, 40% of blue-white pigment, 30% of white oil, xin Zhizhi% of palmitic acid, 9.8% of a dispersing agent and 0.2% of a defoaming agent. And (3) uniformly mixing the raw materials of the blue-and-white ceramic ink, and grinding the mixture in a sand mill to obtain the blue-and-white ceramic ink. Particle diameter D of blue-and-white ceramic ink 90 ＜1μm。
3. And (3) carrying out ink-jet printing on the surface of the green body after the overglaze is applied according to the design pattern to form the blue-and-white artistic porcelain design pattern.
4. And (5) carrying out ink-jet printing on the surface Shi Touming glaze of the green body after the blue-and-white ceramic ink is printed. The transparent glaze is applied by adopting a glaze spraying mode. The chemical composition of the transparent glaze comprises: 0.37 percent of burning loss and SiO in percentage by mass 2 59.9%、Al 2 O 3 12.4%、Fe 2 O 3 0.13%、CaO 10.58%、MgO 1.85%、K 2 O 6.15%、Na 2 O 2.18%、BaO 0.46%、ZnO 5.39%、Li 2 O0.59%. The specific gravity of the transparent glaze is 1.88 g/cm 3 The glazing amount is 500 g/m 2 。
5. And (5) sintering the green body subjected to transparent glaze application in a roller kiln. The highest firing temperature is 1210 ℃, and the firing time is 95 minutes.
6. Polishing the ceramic plate after firing to obtain the digital decorative blue-and-white ceramic plate. The specification is 900 mm multiplied by 1800 multiplied by mm multiplied by 5.5mm thick.
The blue-and-white pigment of example 3 has better blue-and-white color development under the firing schedule of the invention, because the blue-and-white pigment has relatively lower aluminum content in the formula, and the content of flux-type raw materials such as calcium oxide, potassium oxide, sodium oxide and the like in the frit is higher, cobalt ions can be better melted in the glaze layer at high temperature, and the blue-and-white pigment is favorable for presenting better blue-and-white color development state.
Comparative example 1
Substantially the same as in example 1, the only difference is that: the blue-white pigment comprises the following raw materials: the composite material comprises, by mass, 16 parts of cobalt oxide, 20 parts of a frit, 1 part of ferric oxide, 42 parts of water-washed kaolin, 6 parts of manganese oxide, 10 parts of a bead-made material and 5 parts of calcined talc. The same frit and bead as in example 1 was used.
The blue-and-white pigment of comparative example 1 was blackened under the firing schedule of the present invention, and the brick face did not exhibit a blue hue. This is because the blue-and-white pigment of comparative example 1 has a relatively high content of high-temperature oxides such as cobalt oxide and aluminum oxide and a low content of flux-like raw materials such as frit, and thus the blue-and-white pigment has a relatively high color development temperature, and cannot develop a bright blue-and-white color tone at the conventional firing temperature of 1160 to 1210 ℃.
Comparative example 2
Substantially the same as in example 1, the only difference is that: the chemical composition of the transparent glaze comprises: 0.15 percent of burning loss and SiO in percentage by mass 2 53.4%、Al 2 O 3 18.31%、Fe 2 O 3 0.12%、CaO 14.65%、MgO 3.21%、K 2 O 4.12%、Na 2 O 3.14%、BaO 1.53 %、ZnO 1.25%、Li 2 O 0.12%。
The brick surface of comparative example 2 is frosted because the transparent glaze has high content of barium oxide, aluminum oxide and the like, the transparent glaze has high-temperature viscosity, and crystallization is easy to form a matte glaze in the kiln firing and cooling stage, so that the blue-and-white pigment is frosted.
Comparative example 3
Substantially the same as in example 1, the only difference is that: the chemical composition of the transparent glaze comprises: 0.15 percent of burning loss and SiO in percentage by mass 2 61.4%、Al 2 O 3 10.31%、Fe 2 O 3 0.12%、CaO 14.65%、MgO 3.21%、K 2 O 4.12%、Na 2 O 3.14%、BaO 1.53 %、ZnO 1.25%、Li 2 O 0.12%。
The glaze of comparative example 3 appeared a large number of bubbles and the blue-and-white pigment developed color difference. The transparent glaze has low alumina content, high content of high-temperature fluxed oxides such as calcium oxide, magnesium oxide and the like, so that the melting temperature of the glaze is low, the glaze is easy to burn in the stage of melting to form a transparent glass phase, and a large number of bubbles are generated on the glaze layer, so that the transparency and blue-and-white color of the brick surface are poor.

Claims (10)

1. The blue-and-white pigment is characterized by comprising the following raw materials in percentage by weight: 8-15 parts of cobalt oxide, 25-38 parts of frit, 1-5 parts of ferric oxide, 24-35 parts of water-washed kaolin, 1-5 parts of manganese oxide, 12-20 parts of pearl material and 1-4 parts of calcined talcum; the chemical composition of the frit comprises: in mass percent, siO 2 58-70%、Al 2 O 3 6.0-7.5%、Fe 2 O 3 0.1-0.3%、CaO 13-18%、MgO 1.0-2.5%、K 2 O 2.5-3.5%、Na 2 O 0.2-2.5%、B 2 O 3 1-3%、ZnO 2.5-5.5%。
2. The blue-and-white pigment according to claim 1, wherein the chemical composition of the bead comprises: in mass percent, siO 2 28-30%、Al 2 O 3 33-37%、Fe 2 O 3 2.0-3.5%、TiO 2 0.3-0.5%、CuO 0.7-0.9%、MgO 0.3-1.5%、CaO 0.3-0.5%、K 2 O 0.03-1%、Na 2 O 0.2-0.5%、MnO 22-24%、CoO 5-7%。
3. The blue pigment according to claim 1 or 2, wherein the onset temperature of the frit is 1080-1115 ℃.
4. A blue-and-white ceramic ink, characterized in that the blue-and-white ceramic ink comprises the blue-and-white pigment according to any one of claims 1 to 3.
5. The blue-and-white ceramic ink according to claim 4, wherein the raw material composition of the blue-and-white ceramic ink comprises: the weight percentage of the blue-white pigment is 40-50%, the white oil is 15-30%, the isooctyl palmitate and/or the isopropyl laurate is 15-20%, the dispersant is 3-10%, and the defoamer is 0.2-0.6%.
6. The preparation method of the digital decorative blue-and-white ceramic plate is characterized by comprising the following steps of:
applying surface glaze on the surface of the blank;
printing the blue-and-white ceramic ink according to claim 4 or 5 on the surface of a green body after overglaze application according to a design layout;
the surface Shi Touming glaze of the green body after the blue-and-white ceramic ink is printed by ink jet;
and (3) sintering and polishing the green body subjected to transparent glaze application to obtain the digital decorative blue-and-white ceramic plate.
7. The method of manufacturing according to claim 6, wherein the chemical composition of the transparent glaze comprises: 0.3 to 0.6 percent of burning loss and SiO based on mass percent 2 59-61%、Al 2 O 3 12-14%、Fe 2 O 3 0.1-0.25%、CaO 10-12%、MgO 1.5-2.5%、K 2 O 5-7%、Na 2 O 1.5-2.5%、BaO 0.3-0.6 %、ZnO 4-6%、Li 2 O 0.4-0.8%。
8. The method according to claim 6, wherein the specific gravity of the transparent glaze is 1.85-1.92 g/cm 3 The glazing quantity is 400-500 g/m 2 。
9. The method according to claim 6, wherein the maximum firing temperature is 1160 to 1210℃and the firing time is 85 to 120 minutes.
10. A digital decorated blue-and-white ceramic plate, characterized in that it is obtained by the method for producing a digital decorated blue-and-white ceramic plate according to any one of claims 6 to 9.
CN202410099613.9A 2024-01-24 2024-01-24 Blue-and-white pigment, blue-and-white ceramic ink, digital decorative blue-and-white ceramic plate and preparation method thereof Active CN117603592B (en)

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