A porcelain antique brick with gold-plated overflow color black gold vein and a preparation method thereof

Abstract

The present application relates to a kind of porcelain antique brick with gold overflow black gold vein and its preparation method, belong to ceramic tile production manufacturing technical field.The preparation method includes: applying antique face glaze on the surface of body;After applying antique face glaze, inkjet printing ordinary ink pattern on the surface of body;After inkjet printing ordinary ink pattern, inkjet printing metal glaze ink pattern on the surface of body;After inkjet printing metal glaze ink pattern, apply antique protective glaze on the surface of body;After applying antique protective glaze, the body is fired.The present application develops antique face glaze formula suitable for inkjet printing dark color texture, improves the drying efficiency of glaze and ink by face glaze coloring, solves the avoidance glaze defect of dark inkjet product, and introduces functional metal glaze ink, digital printing metal glaze ink combined with inkjet printing ordinary ink pattern texture shows metal luster effect.

Description

Technical Field

[0001] This invention relates to a porcelain antique-style tile with gilded and iridescent black-gold vein patterns and its preparation method, belonging to the field of ceramic tile production and manufacturing technology. Background Technology

[0002] Dark-textured ceramic tiles have become a popular product in the building decoration materials market in recent years. Their unique colors and textures have won the favor of many designers and consumers. However, the production process of dark-textured ceramic products is relatively difficult, and with the continuous development of the ceramic industry, building ceramic companies are constantly improving their technology to give ceramics surface effects and performance, especially functional added value such as ceramic mold effects, hardness, and slip resistance. Currently, there are many dark-textured ceramic products and products with metallic glaze processes on the market.

[0003] Patent CN109279779B describes a full-surface dark-colored ceramic tile where a base glaze layer, a colored glaze layer, a decorative pattern, and a top glaze layer are sequentially prepared on the surface of the ceramic body, followed by drying and firing to obtain the finished full-surface dark-colored ceramic tile. This method requires the use of roller printing to form the colored glaze layer, but roller printing requires different roller textures to be designed for different patterns, thus limiting the surface effect of dark-colored ceramic tiles.

[0004] Patent CN113754473B describes a metallic glaze slab where a base layer is formed on the surface of a green body. Ink of different gray levels is sequentially inkjet-printed onto the base glaze to form a first decorative pattern layer. A metallic glaze layer is then formed on the surface of this first decorative pattern layer. Finally, ink of different gray levels is sequentially inkjet-printed onto the surface of the metallic glaze to form a second decorative pattern layer. The slab is then fired in a kiln to obtain the metallic glaze slab. This method uses multiple inkjet printing processes, making the process relatively complex. Summary of the Invention

[0005] To address the aforementioned issues, this invention develops an antique-style glaze formula suitable for inkjet printing of dark textures. By adding color to the glaze, the drying efficiency of the glaze and ink is improved, solving the glaze avoidance defect in dark inkjet products. Furthermore, functional metallic glaze ink is introduced. The combination of digitally printed metallic glaze ink and inkjet printed ordinary ink patterns and textures creates a metallic luster effect, resulting in a strong three-dimensional effect on the pattern. This produces porcelain antique-style tiles with gilded and iridescent black and gold vein patterns, enhancing the core advantages of the product.

[0006] In a first aspect, the present invention provides a method for preparing a porcelain antique-style tile with gilded and iridescent black-gold vein patterns. The preparation method includes:

[0007] An antique-style glaze is applied to the surface of the body; the mineral composition of the antique-style glaze, by mass percentage, includes: 23-28% sodium feldspar, 13-17% alumina, 5-8% quartz, 4-7% kaolin, 2-5% calcined kaolin, 27-34% potassium feldspar, 2-5% talc, 4-7% zirconium silicate, 2-3% chromium black pigment, and 0.1-1% reddish-brown pigment;

[0008] Ordinary ink patterns are printed on the surface of the blank after applying an antique-style glaze.

[0009] A metallic glaze ink pattern is printed on the surface of a blank after a regular ink pattern has been printed using inkjet printing.

[0010] An antique-style protective glaze is applied to the surface of the blank after inkjet printing of a metallic glaze ink pattern; the mineral composition of the antique-style protective glaze, by mass percentage, includes: potassium feldspar 14-18%, sodium feldspar 28-35%, kaolin 15-20%, calcined kaolin 8-12%, barium carbonate 2-6%, talc 4-7%, dolomite 3-8%, zinc oxide 2-7%, and aluminum oxide 3-8%.

[0011] The body is fired after being coated with an antique-style protective glaze.

[0012] Preferably, the chemical composition of the antique-style glaze, by mass percentage, includes: SiO2: 52.0–54.9%, Al2O3: 27.2–29.5%, Fe2O3: 2.21–3.25%, CaO: 0.77–0.95%, TiO2: 0.08–0.16%, MgO: 1.66–1.85%, K2O: 2.85–2.98%, Na2O: 2.16–2.31%, ZrO2: 3.81–3.98%, Cr2O3: 0.21–0.59%, MnO: 0.03–0.09%, and loss on ignition: 3.0–3.5%.

[0013] Preferably, an antique-style glaze is applied using a pouring glaze method; the specific gravity of the antique-style glaze is 1.86–1.88 g / cm³. 3 The glaze application amount is 430-460 g / m². 2 .

[0014] Preferably, the raw material composition of the metallic glaze ink, by mass percentage, includes: 32.5-34.2% iron phosphate, 37.1-43.6% high-phosphorus frit, 7.6-9.1% dispersant, and 17.5-18.8% diluent; the chemical composition of the high-phosphorus frit, by mass percentage, includes: 30.5-36.5% SiO2, 13.3-17.5% Al2O3, 18.2-23.7% P2O5, 2.16-4.53% Li2O, 3.29-6.33% Na2O, 5.12-8.64% K2O, 5.29-7.02% CaO, 5.36-6.98% MgO, and loss on ignition: 3.5-4.0%.

[0015] Preferably, the amount of the metallic glaze ink used is 60-75 g / m³. 2 .

[0016] Preferably, the chemical composition of the antique protective glaze, by mass percentage, includes: SiO2: 48.5–53.7%, Al2O3: 22.3–25.8%, Fe2O3: 0.22–0.36%, CaO: 2.86–4.11%, TiO2: 0.11–0.18%, MgO: 3.88–4.12%, K2O: 1.86–2.23%, Na2O: 3.27–3.84%, BaO: 3.12–3.47%, ZnO: 3.86–4.13%, and loss on ignition: 4.5–5.0%.

[0017] Preferably, an antique-style protective glaze is applied by spray glazing; the specific gravity of the antique-style protective glaze is 1.33–1.35 g / cm³. 3 The glaze application amount is 160-180g / m². 2 .

[0018] Preferably, the firing temperature is 1200–1220℃ and the firing cycle is 40–60 minutes.

[0019] Preferably, the glaze gloss of the porcelain antique-style tile with gilded black and gold vein patterns is 10 to 12 degrees.

[0020] Secondly, the present invention provides a porcelain antique-style tile with gilded and iridescent black-gold vein patterns. The porcelain antique-style tile with gilded and iridescent black-gold vein patterns is obtained by the preparation method described in any of the preceding claims. Attached Figure Description

[0021] Figure 1 This is a rendering of the brick surface from Example 1;

[0022] Figure 2 This is a comparison of scale 1, showing the brick surface effect.

[0023] Figure 3 This is a comparison of the brick surface effect in scale 2;

[0024] Figure 4 This is a comparison of the brick surface effect in scale 3. Detailed Implementation

[0025] The present invention is further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention. Unless otherwise specified, all percentage contents refer to mass percentages. The following exemplarily illustrates the preparation method of the porcelain antique-style tile with gilded and iridescent black-gold vein patterns according to the present invention.

[0026] Prepare the billet. The chemical composition of the billet is not limited; any commonly used billet chemical composition in this field may be used. For example, the chemical composition of the billet, by mass percentage, includes: SiO2: 67.3–71.2%, Al2O3: 16.1–20.8%, Fe2O3: 1.43–1.72%, TiO2: 0.21–0.29%, CaO: 0.48–0.59%, MgO: 0.09–1.12%, K2O: 2.42–2.63%, Na2O: 1.76–1.88%, and loss on ignition: 4.5–5.5%.

[0027] Any raw material formulation that results in the green body's chemical composition falling within the aforementioned range is applicable. A solid waste utilization formulation is preferred. This solid waste utilization formulation incorporates lepidolite tailings, polishing filter residue, and waste ceramic powder into the ceramic green body to achieve resource reuse.

[0028] As an example, the mineral composition of the ceramic body, by mass percentage, includes: bentonite 8–12%, raw ore slime 9–13%, polishing and filter press residue 3–6%, montmorillonite 1–4%, lepidolite tailings 30–36%, washed mud 8–11%, black talc 3–5%, waste porcelain powder 2–6%, medium-temperature sand 12–18%, and bauxite 4–8%. By utilizing solid waste and incorporating lepidolite tailings into the ceramic body, waste can be turned into treasure, greatly improving economic benefits.

[0029] The chemical composition of the raw ore slime, by mass percentage, may include: SiO2: 63.8–69.0%, Al2O3: 18.7–20.2%, Fe2O3: 1.36–1.58%, TiO2: 0.81–0.86%, CaO: 0.55–0.61%, MgO: 0.47–0.52%, K2O: 1.49–1.57%, Na2O: 0.54–0.59%, and loss on ignition: 8.72–8.95%.

[0030] The chemical composition of the polished filter residue, by mass percentage, may include: SiO2: 69.5–71.4%, Al2O3: 18.9–21.6%, Fe2O3: 1.02–1.18%, TiO2: 0.13–0.18%, CaO: 0.76–0.89%, MgO: 0.79–0.91%, K2O: 3.22–3.36%, Na2O: 2.08–2.16%, and loss on ignition: 1.35–1.45%.

[0031] The chemical composition of the lepidolite tailings, by mass percentage, may include: SiO2: 77.1–79.4%, Al2O3: 12.6–14.0%, Fe2O3: 0.19–0.25%, TiO2: 0.02–0.06%, CaO: 0.35–0.59%, MgO: 0.06–0.15%, K2O: 2.32–2.71%, Na2O: 3.88–4.56%, and loss on ignition: 1.02–1.35%.

[0032] The chemical composition of the washed mud, by mass percentage, may include: SiO2: 46.5–49.8%, Al2O3: 31.9–34.3%, Fe2O3: 2.31–2.59%, TiO2: 0.15–0.21%, CaO: 0.16–0.21%, MgO: 0.14–0.22%, K2O: 1.21–1.49%, Na2O: 0.22–0.35%, and loss on ignition: 10.25–13.85%.

[0033] The chemical composition of the waste ceramic powder, by mass percentage, may include: SiO2: 69.5–73.6%, Al2O3: 18.3–20.8%, Fe2O3: 1.22–1.48%, TiO2: 0.21–0.29%, CaO: 0.66–0.93%, MgO: 0.71–0.93%, K2O: 3.11–3.88%, Na2O: 1.42–2.01%, and loss on ignition: 0.22–0.45%.

[0034] The chemical composition of the medium-temperature sand, by mass percentage, may include: SiO2: 69.8–74.7%, Al2O3: 15.2–18.3%, Fe2O3: 0.77–1.02%, TiO2: 0.08–0.21%, CaO: 0.15–0.36%, MgO: 0.18–0.29%, K2O: 4.31–4.97%, Na2O: 1.24–1.59%, and loss on ignition: 2.56–3.45%.

[0035] Weigh each raw material according to the composition of the brick body, add water and mix evenly, perform wet ball milling, and spray dry into powder to obtain brick body powder. Press the brick body powder into shape. Dry pressing can be used. For example, in the embodiments and comparative examples, the brick body powder is filled into a mold with micro-textured material, and then dry pressed using a press to obtain the brick body. Combining the molded brick body can give the brick surface texture a three-dimensional feel.

[0036] Dry the billets. The billets can be placed in a drying kiln for drying. The moisture content of the dried billets should ideally be controlled below 0.4% wrt%.

[0037] An antique-style glaze is applied to the surface of the dried body. The chemical composition of the antique-style glaze, by mass percentage, includes: SiO2: 52.0–54.9%, Al2O3: 27.2–29.5%, Fe2O3: 2.21–3.25%, CaO: 0.77–0.95%, TiO2: 0.08–0.16%, MgO: 1.66–1.85%, K2O: 2.85–2.98%, Na2O: 2.16–2.31%, ZrO2: 3.81–3.98%, Cr2O3: 0.21–0.59%, MnO: 0.03–0.09%, and loss on ignition: 3.0–3.5%.

[0038] The mineral composition of the antique-style glaze, by mass percentage, includes: 23-28% sodium feldspar, 13-17% alumina, 5-8% quartz, 4-7% kaolin, 2-5% calcined kaolin, 27-34% potassium feldspar, 2-5% talc, 4-7% zirconium silicate, and 2-4 wt% colorant. The colorant in the antique-style glaze includes cobalt black and reddish-brown pigments. In some technical solutions, the mineral composition of the antique-style glaze, by mass percentage, includes: 23-28% sodium feldspar, 13-17% alumina, 5-8% quartz, 4-7% kaolin, 2-5% calcined kaolin, 27-34% potassium feldspar, 2-5% talc, 4-7% zirconium silicate, 2-3% chrome black, and 0.1-1% reddish-brown. The antique-style fabric of this invention does not use frit; by adding color through the glaze, the drying efficiency of ink and glaze is improved, making the production of dark-colored products more stable.

[0039] The chemical composition of the chromium black pigment, by mass percentage, includes: SiO2: 0.51–0.63%, Al2O3: 4.73–4.95%, Fe2O3: 65.6–69.9%, CaO: 0.11–0.16%, TiO2: 0.21–0.29%, MgO: 3.52–3.96%, K2O: 0.01–0.02%, Na2O: 0.26–0.35%, Cr2O3: 18.6–19.9%, MnO: 1.98–2.35%, and loss on ignition: 0.6–1.2%. For example, the chemical composition of the chromium black pigment used in the examples and comparative examples, by mass percentage, includes: SiO2: 0.52%, Al2O3: 4.73%, Fe2O3: 69.4%, CaO: 0.11%, TiO2: 0.21%, MgO: 3.52%, K2O: 0.01%, Na2O: 0.26%, Cr2O3: 18.6%, MnO: 1.98%, and loss on ignition: 0.66%.

[0040] The chemical composition of the reddish-brown material, by mass percentage, includes: SiO2: 0.01–0.03%, Al2O3: 0.01–0.03%, Fe2O3: 94.3–99.7%, CaO: 0.01–0.02%, TiO2: 0.01–0.02%, MgO: 0.01–0.02%, K2O: 0.01–0.02%, Na2O: 0.01–0.02%, MnO: 2.11–2.18%, and loss on ignition: 0.2–0.8%. For example, the chemical composition of the reddish-brown material, by mass percentage, includes: SiO2: 0.03%, Al2O3: 0.01%, Fe2O3: 97.6%, CaO: 0.01%, TiO2: 0.01%, MgO: 0.01%, K2O: 0.01%, Na2O: 0.01%, MnO: 2.11%, and loss on ignition: 0.2%.

[0041] If no pigment is introduced into the antique-style glaze, a large amount of ordinary ink for inkjet printing needs to be applied during the inkjet printing process to add color. However, excessive ink usage leads to a large amount of ink being difficult to dry. This invention, by adding pigment to the antique-style glaze, avoids printing defects such as streaks, color marks, and uneven coloring that are prone to occur when inkjet printing large amounts of ordinary ink to form dark patterns and textures. In addition, it can improve the drying efficiency of ink and glaze, stabilizing production operations.

[0042] Weigh each raw material according to the mineral composition of the antique glaze, mix it with sodium tripolyphosphate, sodium carboxymethyl cellulose, and water, ball mill until homogeneous, and sieve to remove iron to obtain the antique glaze slurry. For example, the antique glaze slurry includes, by mass percentage: 60-80% glaze minerals, 0.1-0.4% sodium tripolyphosphate, 0.1-0.4% sodium carboxymethyl cellulose, and 20-40% water. The residue of the antique glaze slurry after passing through a 325-mesh sieve is ≤0.8wt%. Water can also be added to the antique glaze slurry during application to adjust the final desired specific gravity.

[0043] An antique-style glaze is applied using a pouring method. In some technical solutions, the specific gravity of the antique-style glaze is 1.86–1.88 g / cm³. 3 The glaze application amount is 430-460 g / m². 2 Applying too much glaze to the antique-style glaze can affect the moisture content of the blanks entering the kiln. If the blanks drain too quickly during the preheating stage at the kiln head, glaze cracks are likely to form.

[0044] A pattern in regular ink is printed onto the surface of the ceramic body after applying an antique-style glaze. This creates a texture resembling dark stone. Digital inkjet printers can be used. For example, the stone pattern can be created as a vector file, then imported into a computer and the inkjet printer controlled for printing. Regular ink colors include, but are not limited to, blue, brown, orange, black, lemon yellow, and red.

[0045] A metallic glaze ink pattern is then printed onto the surface of the blank after a regular ink pattern has been printed. This can be done using a digital inkjet printer. The principle of printing a metallic glaze ink pattern is the same as that of printing a regular ink pattern. Preferred positioning is used for printing the metallic glaze ink pattern. Positioning here refers to the correspondence between the regular ink pattern and the metallic glaze ink pattern; that is, the metallic glaze ink is printed on the areas where a metallic luster is desired.

[0046] The solid phase components of the metallic glaze ink are mainly iron phosphate and high-phosphorus frit. The raw material composition of the metallic glaze ink, by mass percentage, includes: 32.5–34.2% iron phosphate, 37.1–43.6% high-phosphorus frit, 7.6–9.1% dispersant, and 17.5–18.8% diluent.

[0047] The chemical composition of the high-phosphorus frit, by mass percentage, includes: SiO2: 30.5–36.5%, Al2O3: 13.3–17.5%, P2O5: 18.2–23.7%, Li2O: 2.16–4.53%, Na2O: 3.29–6.33%, K2O: 5.12–8.64%, CaO: 5.29–7.02%, MgO: 5.36–6.98%, and loss on ignition: 3.5–4.0%.

[0048] The mineral composition of the high-phosphorus frit, by mass percentage, includes: 32-48% aluminum dihydrogen phosphate, 20-28% phosphate rock powder, 9-11% sodium carbonate, 5-8% potassium carbonate, 6-10% calcined kaolin, 3-5% washed clay, and 11-14% alumina. The raw materials are weighed according to the composition of the high-phosphorus frit, mixed evenly, and melted at 1000-1150℃ for 2-5 hours to obtain a glass melt. The glass melt is then quenched with water and broken to obtain the high-phosphorus frit. The mesh size of the high-phosphorus frit can be less than or equal to 325 mesh.

[0049] The chemical composition of the phosphate rock powder, by mass percentage, includes: SiO2: 25.1–27.9%, Al2O3: 1.36–1.77%, P2O5: 26.5–29.9%, Li2O: 3.12–5.75%, K2O: 5.12–8.64%, CaO: 34.6–39.3%, MgO: 0.52–0.86%, and loss on ignition: 3.5–4.0%.

[0050] The dispersant can be a commonly used dispersant in digital metallic enamel inks, including but not limited to styrene-maleic anhydride copolymers, polyethylene glycol, EO-PO block copolymers, and EO-PO-EO triblock copolymers. Commercially available dispersants such as HLD-18 / AJ (Silcona, Germany) can also be used. In the examples and comparative examples, PEG4000 was specifically used as the dispersant.

[0051] The diluent may be a commonly used diluent for digital metallic enamel inks. This includes, but is not limited to, one or more of diethylene glycol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, glycerol, D-sorbitol, 1,2,6-hexanetriol, trimethylolpropane, 1,2-propanediol, polyols, polyol ethers, and polysaccharides. In the examples and comparative examples, the diluent specifically used was a mixture of ethylene glycol and 1,3-propanediol in a 1:1 volume ratio.

[0052] The metallic glaze ink is obtained by uniformly mixing all the raw materials. The amount of metallic glaze ink used is 60-75 g / m³. 2 If the amount of metallic glaze ink used exceeds this range, the inkjet printer will output too much ink, leading to excessive ink buildup and potentially causing ink leakage and glaze concavity. Controlling the amount of metallic glaze ink used within this range allows for the simultaneous and appropriate regulation of the glaze gloss and firing temperature, resulting in a superior metallic glaze effect. The metallic glaze ink, after firing, possesses a unique decorative effect with a golden metallic luster.

[0053] Prefer multi-channel inkjet printing inks for metallic enamel printing, such as dual-channel inkjet printing inks. This promotes more stable production.

[0054] An antique-style protective glaze is applied to the surface of the blank after inkjet printing of a digital metallic glaze ink pattern. The chemical composition of the antique-style protective glaze, by mass percentage, includes: SiO2: 48.5–53.7%, Al2O3: 22.3–25.8%, Fe2O3: 0.22–0.36%, CaO: 2.86–4.11%, TiO2: 0.11–0.18%, MgO: 3.88–4.12%, K2O: 1.86–2.23%, Na2O: 3.27–3.84%, BaO: 3.12–3.47%, ZnO: 3.86–4.13%, and loss on ignition: 4.5–5.0%.

[0055] The mineral composition of the antique protective glaze, by mass percentage, includes: 14-18% potassium feldspar, 28-35% sodium feldspar, 15-20% kaolin, 8-12% calcined kaolin, 2-6% barium carbonate, 4-7% talc, 3-8% dolomite, 2-7% zinc oxide, and 3-8% aluminum oxide.

[0056] The antique-style protective glaze of this invention does not use frit. By adjusting the composition of the antique-style protective glaze and using it in combination with the antique-style surface glaze, the surface gloss of the ceramic tile is controlled at a soft gloss level of 10-12 degrees. If the glaze gloss is too low, the surface of the metallic glaze ink will be dull and the metallic luster will be low, resulting in a poor effect; if the glaze gloss is too high, the luster of the metallic glaze ink will be covered by the luster of the tile surface, and the metallic refraction effect will not be prominent. Within the range of 10-12 degrees, the surface decoration effect of the metallic glaze ink is good.

[0057] Weigh each raw material according to the mineral composition of the antique protective glaze, mix it with sodium tripolyphosphate, sodium carboxymethyl cellulose, and water, ball mill until uniform, and sieve to remove iron to obtain the antique protective glaze slurry. For example, the antique protective glaze slurry includes, by mass percentage: 60-80% antique protective glaze minerals, 0.1-0.4% sodium tripolyphosphate, 0.1-0.4% sodium carboxymethyl cellulose, and 20-40% water. The residue of the antique protective glaze slurry after passing through a 325-mesh sieve is ≤0.8wt%. When applying the antique protective glaze, water can be added to the glaze slurry to adjust the final desired specific gravity.

[0058] An antique-style protective glaze is applied using a spray glazing method. In some technical solutions, the specific gravity of the antique-style protective glaze is 1.33–1.35 g / cm³. 3 The glaze application amount is 160-180g / m². 2 If the amount of glaze applied to the antique-style protective glaze exceeds the above range, it will result in an excessively thick glaze layer, which is prone to glaze shrinkage and may also obscure the refractive effect of the metallic glaze ink. If the amount of glaze applied to the antique-style protective glaze is too small, the glaze layer will be too thin, resulting in rough marks on the glaze surface after firing, poor glaze gloss, and a dull surface effect for the metallic glaze ink.

[0059] The body is then dried a second time after the antique-style protective glaze has been applied. For example, the drying temperature is 95℃ and the drying time is 8 minutes.

[0060] Firing. Rapid firing can be achieved using a roller kiln. The firing temperature can be 1200–1220℃, and the firing cycle can be 40–60 minutes.

[0061] Edge grinding and grading. Packing and warehousing.

[0062] This invention, through the development of antique-style glaze and protective glaze formulas, innovatively introduces a specially formulated metallic glaze ink to precisely apply patterns, resulting in a uniquely glossy, gilded black-gold effect on black porcelain tiles. In other words, this invention uses inkjet printing with ordinary ink to create a texture resembling dark marble, while simultaneously applying metallic glaze ink to the pattern texture, resulting in a uniquely glossy, gilded black-gold effect on black porcelain tiles. This interplay between the dark pattern and the metallic glaze ink gives the antique-style porcelain tiles a unique charm and rustic beauty, perfectly replicating the natural effect of high-end dark marble, more closely resembling the texture of stone, and with a more delicate feel.

[0063] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0064] Example 1

[0065] The preparation method of porcelain antique-style tiles with gilded and iridescent black-gold vein patterns includes the following steps:

[0066] Step 1. Prepare and dry the green body. The chemical composition of the green body, by mass percentage, includes: SiO2: 69.4%, Al2O3: 18.3%, Fe2O3: 1.51%, TiO2: 0.25%, CaO: 0.51%, MgO: 1.08%, K2O: 2.51%, Na2O: 1.82%, and loss on ignition: 4.62%.

[0067] Step 2. Apply an antique-style glaze to the dried body surface. The raw material composition of the antique-style glaze, by weight percentage, includes: sodium feldspar 25%, alumina 15.5%, quartz 6.5%, kaolin 6%, calcined kaolin 4%, potassium feldspar 30%, talc 4%, zirconium silicate 6%, chrome black pigment 2.5%, and reddish-brown pigment 0.5%. The chemical composition of the antique-style glaze, by weight percentage, includes: SiO2: 53.0%, Al2O3: 28.8%, Fe2O3: 2.39%, CaO: 0.82%, TiO2: 0.12%, MgO: 1.79%, K2O: 2.92%, Na2O: 2.23%, ZrO2: 3.94%, Cr2O3: 0.49%, MnO: 0.06%, and loss on ignition: 3.44%. The specific gravity of the antique-style glaze is 1.86 g / cm³. 3 The glaze application amount is 430g / m² 2 .

[0068] Step 3. Print a regular ink pattern on the surface of the blank after applying the antique glaze.

[0069] Step 4. Inkjet print a metallic glaze ink pattern onto the surface of the blank after inkjet printing a regular ink pattern. The raw material composition of the metallic glaze ink, by mass percentage, includes: 33.9% iron phosphate, 38.7% high-phosphorus frit, 8.8% dispersant, and 18.6% diluent. The chemical composition of the high-phosphorus frit, by mass percentage, includes: SiO2: 34.0%, Al2O3: 15.1%, P2O5: 19.2%, Li2O3: 3.17%, Na2O: 5.21%, K2O: 6.81%, CaO: 6.31%, MgO: 6.25%, and loss on ignition: 3.95%.

[0070] Step 5. Spray an antique-style protective glaze onto the surface of the blank after inkjet printing the metallic glaze ink pattern. The mineral composition of the antique-style protective glaze, by mass percentage, includes: potassium feldspar 16%, sodium feldspar 32%, kaolin 18%, calcined kaolin 10%, barium carbonate 4%, talc 5%, dolomite 6%, zinc oxide 4%, and aluminum oxide 5%. The chemical composition of the antique-style protective glaze, by mass percentage, includes: SiO2: 50.3%, Al2O3: 23.8%, Fe2O3: 0.31%, CaO: 3.75%, TiO2: 0.15%, MgO: 4.02%, K2O: 2.01%, Na2O: 3.43%, BaO: 3.35%, ZnO: 3.93%, and loss on ignition: 4.95%. The specific gravity of the antique-style protective glaze is 1.33 g / cm³. 3 Glazing amount is 160g / m 2 .

[0071] Step 6. Perform a second drying on the body after spraying the antique protective glaze. The drying temperature is 95℃ and the drying time is 8 minutes.

[0072] Step 7. Firing. Firing is performed rapidly using a roller kiln. The firing temperature is 1200℃, and the firing cycle is 40 minutes.

[0073] Step 8. Edge grinding and grading. Pack and store in the warehouse.

[0074] Figure 1 This is an image showing the brick surface effect of Example 1. The surface gloss of the ceramic tile is approximately 12 degrees. It can be seen that a unique gilded black-gold effect is achieved on the black porcelain tile.

[0075] Comparative Example 1

[0076] The preparation process of this comparative example is the same as in Example 1, with the main difference being: the raw material composition of the antique glaze, by mass percentage, includes: sodium feldspar 21%, alumina 14.5%, quartz 6.5%, kaolin 6%, calcined kaolin 4%, potassium feldspar 30%, talc 4%, zirconium silicate 6%, chrome black pigment 4.5%, and reddish-brown pigment 3.5%. The chemical composition of the antique glaze, by mass percentage, includes: SiO2: 52.1%, Al2O3: 27.7%, Fe2O3: 4.06%, CaO: 0.79%, TiO2: 0.13%, MgO: 1.82%, K2O: 2.92%, Na2O: 2.16%, ZrO2: 3.94%, Cr2O3: 0.91%, MnO: 0.15%, and loss on ignition: 3.32%. The specific gravity of the antique glaze is 1.86 g / cm³. 3 The glaze application amount is 430g / m² 2 .

[0077] Figure 2 This is a rendering of the brick surface as shown in Comparative Example 1. Comparative Example 1 increases the content of chromium black and reddish-brown pigments in the antique-style glaze, resulting in a darker glaze color. The lighter transition colors in the inkjet-printed patterns are masked by the glaze color. At the same time, with the increase in pigment content, the pigment homogenization is relatively poor, making it easy to produce uneven colors, and pigment particles can be seen on the glaze surface.

[0078] Comparative Example 2

[0079] The preparation process of this comparative example is the same as in Example 1, the main difference being the inkjet printing pattern and the antique protective glaze. The raw material composition of the antique protective glaze, by mass percentage, includes: 10% potassium feldspar, 34% sodium feldspar, 18% kaolin, 10% calcined kaolin, 4% barium carbonate, 5% talc, 4% dolomite, 2% zinc oxide, and 13% aluminum oxide. The chemical composition of the antique protective glaze, by mass percentage, includes: SiO2: 49.6%, Al2O3: 28.8%, Fe2O3: 0.33%, CaO: 2.51%, TiO2: 0.15%, MgO: 3.08%, K2O: 1.85%, Na2O: 3.54%, BaO: 3.35%, ZnO: 1.97%, and loss on ignition: 4.82%. The specific gravity of the antique protective glaze is 1.34 g / cm³. 3 Glazing amount is 170g / m 2 .

[0080] Figure 3 This is a rendering of the brick surface from Comparative Example 2. The glaze gloss of Comparative Example 2 is around 6, the metallic luster is dull, and the glaze surface has defects such as pinholes and unevenness.

[0081] Comparative Example 3

[0082] The preparation process of this comparative example is the same as that of Comparative Example 2, with the main difference being the different antique-style protective glaze. The raw material composition of the antique-style protective glaze, by mass percentage, includes: potassium feldspar 16%, sodium feldspar 33%, kaolin 18%, calcined kaolin 10%, barium carbonate 4%, talc 5%, dolomite 3%, zinc oxide 10%, and aluminum oxide 1%. The chemical composition of the antique-style protective glaze, by mass percentage, includes: SiO2: 51.1%, Al2O3: 20.9%, Fe2O3: 0.32%, CaO: 2.52%, TiO2: 0.16%, MgO: 3.21%, K2O: 2.09%, Na2O: 3.52%, BaO: 3.35%, ZnO: 7.89%, and loss on ignition: 4.94%. The specific gravity of the antique-style protective glaze is 1.34 g / cm³. 3 Glazing amount is 170g / m 2 .

[0083] Figure 4 This is a rendering of the brick surface as shown in Comparative Example 3. The glaze gloss of Comparative Example 3 is approximately 22 degrees, which is too high and masks the refractive effect of the metallic ink. Visually, there is no obvious contrast between the glaze gloss and the metallic luster, and the expected gilded and iridescent black-gold vein pattern cannot be formed.

Claims

1. A method for preparing a porcelain antique tile with gilded and highlighted black gold veins, characterized by the fact that, The preparation method includes: An antique-style glaze is applied to the surface of the blank; the mineral composition of the antique-style glaze, by mass percentage, includes: 23%~28% albite, 13%~17% alumina, 5%~8% quartz, 4%~7% kaolin, 2%~5% calcined kaolin, 27%~34% potassium feldspar, 2%~5% talc, 4%~7% zirconium silicate, 2%~3% chrome black pigment, and 0.1%~1% reddish-brown pigment; Ordinary ink patterns are printed on the surface of the blank after applying an antique-style glaze. A metallic glaze ink pattern is inkjet printed onto the surface of a blank after inkjet printing a pattern with ordinary ink. The raw material composition of the metallic glaze ink, by mass percentage, includes: 32.5%~34.2% iron phosphate, 37.1%~43.6% high-phosphorus frit, 7.6%~9.1% dispersant, and 17.5%~18.8% diluent. The chemical composition of the high-phosphorus frit, by mass percentage, includes: SiO2: 30.5%~36.5%, Al2O3: 13.3%~17.5%, P2O5: 18.2%~23.7%, Li2O: 2.16%~4.53%, Na2O: 3.29%~6.33%, K2O: 5.12%~8.64%, CaO: 5.29%~7.02%, MgO: 5.36%~6.98%, and loss on ignition: 3.5%~4.0%. An antique-style protective glaze is applied to the surface of the blank after inkjet printing of a metallic glaze ink pattern; the mineral composition of the antique-style protective glaze, by mass percentage, includes: potassium feldspar 14%~18%, sodium feldspar 28%~35%, kaolin 15%~20%, calcined kaolin 8%~12%, barium carbonate 2%~6%, talc 4%~7%, dolomite 3%~8%, zinc oxide 2%~7%, aluminum oxide 3%~8%; The body is fired after being coated with an antique-style protective glaze.

2. The production method according to claim 1, characterized by, The chemical composition of the antique-style glaze, by mass percentage, includes: SiO2: 52.0%~54.9%, Al2O3: 27.2%~29.5%, Fe2O3: 2.21%~3.25%, CaO: 0.77%~0.95%, TiO2: 0.08%~0.16%, MgO: 1.66%~1.85%, K2O: 2.85%~2.98%, Na2O: 2.16%~2.31%, ZrO2: 3.81%~3.98%, Cr2O3: 0.21%~0.59%, MnO: 0.03%~0.09%, and loss on ignition: 3.0%~3.5%.

3. The production method according to claim 1, characterized by, The antique surface glaze is applied by glaze pouring, the specific gravity of the antique surface glaze is 1.86-1.88 g / cm 3 , and the glaze application amount is 430-460 g / m 2 .

4. The production method according to claim 1, characterized by, The metal glaze ink is used in an amount of 60 to 75 g / m 2 .

5. The preparation method according to claim 1, characterized in that, The chemical composition of the antique protective glaze, by mass percentage, includes: SiO2: 48.5%~53.7%, Al2O3: 22.3%~25.8%, Fe2O3: 0.22%~0.36%, CaO: 2.86%~4.11%, TiO2: 0.11%~0.18%, MgO: 3.88%~4.12%, K2O: 1.86%~2.23%, Na2O: 3.27%~3.84%, BaO: 3.12%~3.47%, ZnO: 3.86%~4.13%, and loss on ignition: 4.5%~5.0%.

6. The production method according to claim 1, characterized by, The antique protective glaze is applied by spraying, and the specific gravity of the antique protective glaze is 1.33-1.35 g / cm 3 , and the glaze application amount is 160-180 g / m 2 .

7. The preparation method according to claim 1, characterized in that, The firing temperature is 1200~1220℃, and the firing cycle is 40~60min.

8. The preparation method according to claim 1, characterized in that, The porcelain antique-style tile with gilded and iridescent black-gold vein patterns has a glaze gloss of 10-12 degrees.

9. A porcelain antique tile having a gold highlighted black gold vein, characterized in that, The porcelain antique-style tile with gilded and iridescent black and gold vein patterns is obtained by the preparation method according to any one of claims 1 to 8.

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