All-body travertine-imitating ceramic tile and preparation method thereof

Abstract

The invention relates to the field of architectural ceramics, and discloses a full-body travertine-imitating ceramic tile and a preparation method thereof.The preparation method comprises the following steps that S1, after green body powder and a pore forming agent are evenly mixed according to the mass ratio of 97-99: 1-3, the mixture is pressed into a green body; s2, drying the green body, wherein the drying temperature is 150-200 DEG C; and S3, feeding the dried green body into a kiln for firing, brushing and polishing, and edging, so as to obtain the full-body travertine-imitating ceramic tile. Wherein in the step S1, the raw materials of the pore-forming agent comprise paraffin, polyvinyl alcohol, low-melting-point glass powder and high-temperature frit; wherein the mass ratio of the paraffin to the polyvinyl alcohol to the low-melting-point glass powder to the high-temperature frit is (8-9.5): (0.1-0.5): (0.1-0.5): (0.1-1); and the melting temperature of the low-melting-point glass powder is 300-1000 DEG C. The travertine-imitated ceramic tile prepared by the invention successfully simulates a pore structure of a natural material, and artificial carving traces are avoided. Meanwhile, the proportion of all the components of the pore-forming agent is regulated and controlled, so that the low-melting-point glass powder and the high-temperature frit form a compact vitreous layer on the inner wall of a hole, and excellent stain resistance is obtained.

Description

Technical Field

[0001] This invention relates to the field of building ceramics, and in particular to a full-body imitation travertine ceramic brick and its preparation method. Background Technology

[0002] Travertine derives its name from the unevenly distributed and varied natural porous structure of its surface. In terms of color, travertine is primarily found in warm tones such as off-white, beige, and light brown, presenting a warm and soft aesthetic. Through different surface processing techniques, travertine can adapt to a variety of decorative styles, from modern minimalism to classic luxury. Due to its unique artistic appeal and historical and cultural significance, travertine is widely used in architecture and interior design. However, natural travertine, especially high-quality imported varieties, is quite expensive, directly limiting its practical application. Furthermore, its inherent porous structure easily attracts and retains stains, making cleaning and maintenance difficult, affecting not only aesthetics but also increasing long-term maintenance costs. Therefore, developing a natural travertine alternative that retains its unique aesthetic and decorative effects while possessing excellent stain resistance has always been an important goal for related fields. Ceramic tiles, due to their lower cost, good decorative performance, and stable physicochemical properties, are considered an ideal material for simulating natural travertine.

[0003] In existing technologies, the porous structure of travertine bricks is mainly achieved through two processes: one is to use a mold with protrusions to press and form the brick blank, creating holes corresponding to the protrusions; the other is to mix a pore-forming agent into the raw material, press and form it, and then heat-treat it, allowing the pore-forming agent to volatilize or decompose upon heating. However, travertine bricks prepared by the above-mentioned "molding and pore-forming" processes generally suffer from problems such as relatively regular hole shapes and obvious artificial traces, affecting the simulated natural texture. In addition, the open holes on the surface of the brick are prone to accumulating dirt and are difficult to clean. These factors collectively restrict the overall decorative effect of travertine bricks. Therefore, how to simultaneously achieve a unique travertine effect and excellent stain resistance on ceramic tiles has become a topic worthy of in-depth research. Summary of the Invention

[0004] The main objective of this invention is to propose a method for preparing a fully-through imitation travertine ceramic tile. The resulting imitation travertine ceramic tile not only has the original texture of imitating natural travertine, but also has excellent stain resistance inside the travertine.

[0005] To achieve the above objectives, in a first aspect, the present invention proposes a method for preparing a fully-through imitation travertine ceramic tile, comprising the following steps: S1. Mix the green body powder and the pore-forming agent evenly at a mass ratio of 97~99:1~3, and then press them into green bodies; S2. Dry the billet at a temperature of 150~200℃; S3. The dried green body is sent into a kiln for firing. After brushing, polishing and grinding the edges, the full-body imitation travertine ceramic brick is obtained. In step S1, the raw materials for the pore-forming agent include paraffin wax, polyvinyl alcohol, low-melting-point glass powder, and high-temperature frit; wherein the mass ratio of paraffin wax: polyvinyl alcohol: low-melting-point glass powder: high-temperature frit is 8~9.5:0.1~0.5:0.1~0.5:0.1~1. The melting temperature of the low-melting-point glass powder is 300~1000 ℃; The chemical composition of the high-temperature molten block, by mass percentage of oxides, includes: SiO2 37.49~42.97%, Al2O3 11.99~17.32%, Fe2O3 0.10~0.30%, TiO2 0.04~0.08%, CaO 3.78~8.53%, MgO 1.02~3.75%, K2O 0.46~2.31%, Na2O 2.61~5.94%, P2O5 0.06~0.20%, BaO 13.45~18.87%, ZnO 3.76~7.59%, SrO 0.05~1.34%, ZrO2 0.02~0.06%, and LOI 2.86~6.08%. In step S3, the firing temperature curve of the kiln is as follows: 200°C to intermediate temperature: 5-10 minutes; Intermediate temperature to maximum temperature: 18-20 minutes; Maximum temperature hold: 5-10 minutes; Cool to room temperature: 12-15 minutes; The intermediate temperature is 490~500 ℃; the maximum temperature is 1185~1205 ℃.

[0006] This invention selects various combustible / volatile substances with different geometric shapes and particle sizes, including paraffin wax and polyvinyl alcohol, to form pore-forming agents. These agents are then mixed with the raw materials of the green body. By controlling the drying temperature and firing curve, the pore-forming agents migrate, melt, and ultimately volatilize in stages and selectively, successfully simulating the pore structure of natural materials and avoiding traces of artificial carving. Simultaneously, by adjusting the proportions of each component of the pore-forming agent, low-melting-point glass powder and high-temperature frit form a dense glassy layer on the inner wall of the pores, thereby achieving excellent stain resistance.

[0007] Preferably, the preparation process of the pore-forming agent is as follows: weigh the raw materials of the pore-forming agent according to the proportion, crush and mix them evenly, dry them at 70~90 ℃ for 5~10 min until the paraffin is completely melted, cool the molten liquid mixture naturally for 10~15 min, crush it to obtain the pore-forming agent.

[0008] Preferably, the particle size of the pore-forming agent is 1-6 mm. Pore-forming agents with different particle sizes and shapes can be obtained through the above method.

[0009] Preferably, the raw material formula of the green body powder, by mass parts, includes: 25-31 parts of new osmium powder, 0.5-2.5 parts of wollastonite, 2-6 parts of high-white talc, 3.5-6.5 parts of bentonite, 0.5-2.5 parts of high-clay, 18.5-25.5 parts of high-alumina mortar, 8.5-12.5 parts of high-white mortar, 0.5-2 parts of super-white sand, 0.5-2.5 parts of raw ore clay, 0.5-1.5 parts of ball clay, 3.5-7.5 parts of mortar, 3.5-7.5 parts of bauxite, and 8.5-13.5 parts of sodium silicate powder; The chemical composition of the green body powder, by mass percentage of oxides, includes: SiO2 58.36~70.86%, Al2O3 16.82~26.66%, Fe2O3 0.49~0.80%, TiO2 0.09~0.17%, CaO 0.72~1.73%, MgO 0.73~1.97%, K2O 1.84~2.52%, Na2O 1.95~2.76%, and LOI 4.61~7.92%.

[0010] Preferably, by weight, the green body powder comprises 100 parts of green body raw material, 35-50 parts of water, 0.1-0.3 parts of methylcellulose, 0.2-0.4 parts of sodium tripolyphosphate, 0.1-0.3 parts of degumming agent, and 0.2-0.6 parts of green body reinforcing agent; The particle size distribution of the green body powder is as follows: ≤3% for particles larger than 20 mesh, 45-55% for particles between 30 and 65 mesh, 80-95% for particles between 20 and 60 mesh, and ≤3% for particles smaller than 100 mesh.

[0011] Preferably, step S22 is further included between step S2 and step S3: inkjet printing a pattern on the surface of the blank and applying a protective glaze.

[0012] Preferably, the raw material formula of the protective glaze, by mass parts, includes: 8-12 parts calcined kaolin, 28-32 parts quartz, 6-10 parts potassium feldspar, 4-8 parts sodium feldspar, 7-12 parts calcite, 5-8 parts wollastonite, 8-11 parts alumina, 3-5 parts dolomite, 2-5 parts zinc oxide, 2-6 parts calcined talc, 1-4 parts high barium and high zinc frit, and 1-5 parts high sodium and high strontium frit; The chemical composition of the high-barium, high-zinc ingot, by mass percentage of oxides, includes: SiO2 38.63~44.52%, Al2O3 12.79~17.75%, Fe2O3 0.10~0.25%, TiO2 0.02~0.06%, CaO 6.22~10.06%, MgO 0.53~1.07%, K2O 0.96~2.84%, Na2O 1.05~2.92%, BaO 15.16~20.72%, SrO 0.81~1.73%, ZnO 8.16~12.18%, and LOI 0.11~0.54%. The chemical composition of the high-sodium, high-strontium ingot, by mass percentage of oxides, includes: SiO2 48.66~55.72%, Al2O3 14.26~19.71%, Fe2O3 0.05~0.16%, TiO2 0.02~0.07%, CaO 4.05~8.36%, MgO 0.59~2.11%, K2O 0.91~3.64%, Na2O 3.68~8.89%, BaO 0.09~0.26%, SrO 3.31~7.36%, ZnO 4.24~9.58%, and LOI 0.12~0.45%.

[0013] The protective glaze formula used in this invention achieves stable and continuous melting during the firing process through the synergistic effect of multiple components, promoting the complete transformation of the glaze into a glass phase, which is conducive to the discharge of air bubbles, and finally forming a glass body with uniform structure, no open pores, and a smooth surface, significantly improving the stain resistance of the tile surface.

[0014] Preferably, step S21 is further included between step S2 and step S22: applying a surface glaze to the blank.

[0015] Preferably, the raw material formula of the glaze, by mass parts, includes: 16-20 parts calcined kaolin, 32-36 parts quartz, 6-11 parts potassium feldspar, 3-8 parts sodium feldspar, 5-9 parts zirconium silicate, 4-9 parts wollastonite, 7-11 parts alumina, 1-4 parts nepheline, 2-4 parts barium carbonate, 1-3 parts zinc oxide, 1-3 parts calcined talc, and 2-4 parts frit; The chemical composition of the molten metal, by mass percentage of oxides, includes: SiO2 37.26~44.06%, Al2O3 17.88~24.43%, Fe2O3 0.08~0.25%, TiO2 0.04~0.08%, CaO 3.03~6.72%, MgO 0.06~0.27%, K2O 3.22~6.65%, Na2O 15.44~20.23%, ZrO2 3.53~7.98%, BaO 0.05~0.12%, P2O5 0.19~0.50%, and LOI 0.64~2.88%.

[0016] Secondly, this invention proposes a full-body imitation travertine ceramic tile, prepared using any of the above-mentioned preparation methods. The full-body imitation travertine ceramic tile prepared by this invention exhibits a natural, random, and original travertine effect, and also has good stain resistance within the travertine interior.

[0017] Compared with the prior art, the present invention has the following beneficial effects: 1. A pore-forming agent is prepared by compounding various combustible / volatile substances with low-melting-point glass powder and high-temperature frit. Combined with a special drying method and firing regime curve, the raw materials of the pore-forming agent migrate, melt and finally volatilize in stages and selectively. This perfectly simulates the pore structure of natural materials during the formation process due to material loss or gas escape, avoiding traces of artificial carving and making the travertine effect of ceramic bricks present a natural randomness and original texture. 2. By adjusting the proportion of pore-forming agent raw materials, while achieving the effect of natural travertine, a dense glassy layer is formed on the inner wall of the travertine during the firing process, thus effectively preventing the travertine from becoming stained. 3. By using a specific protective glaze formula, a glaze with suitable surface tension and dense structure is formed on the ceramic surface after firing, which improves the stain resistance of the ceramic tile surface and ultimately achieves full stain resistance on the surface and inside of the travertine-like ceramic tile of this invention. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a schematic diagram of the surface of the fully-through imitation travertine ceramic tile prepared in Example 3; Figure 2 This is a schematic diagram of the cross-section of the full-body imitation travertine ceramic brick prepared in Example 3; Figure 3 This is a schematic diagram of the microstructure of the pores in the fully-through imitation travertine ceramic brick prepared in Example 3.

[0020] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of this application can be combined with each other. At the same time, the raw materials mentioned below, unless otherwise specified, are all commercially available products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to those skilled in the art.

[0022] This embodiment provides a method for preparing a full-body imitation travertine ceramic tile, including the following steps: S1. Mix the green body powder and the pore-forming agent evenly at a mass ratio of 97~99:1~3, and then press them into green bodies; the thickness of the green body can be 6~12 mm. The raw material formula for the body powder, by weight parts, includes: 25-31 parts of new osmium powder, 0.5-2.5 parts of wollastonite, 2-6 parts of high-whiteness talc, 3.5-6.5 parts of bentonite, 0.5-2.5 parts of high-clay, 18.5-25.5 parts of high-alumina mortar, 8.5-12.5 parts of high-whiteness mortar, 0.5-2 parts of super-white sand, 0.5-2.5 parts of raw ore clay, and 0.5-1 parts of ball clay. 0.5 parts, 3.5~7.5 parts, bauxite 3.5~7.5 parts, and sodium carbonate powder 8.5~13.5 parts; the chemical composition of the green body powder, in terms of the mass percentage of oxides, includes: SiO2 58.36~70.86%, Al2O3 16.82~26.66%, Fe2O3 0.49~0.80%, TiO2 0.09~0.17%, CaO 0.72~1.73%, MgO 0.73~1.97%, K2O 1.84~2.52%, Na2O 1.95~2.76%, and LOI 4.61~7.92%.

[0023] The green body powder comprises 100 parts of green body raw material, 35-50 parts of water, 0.1-0.3 parts of methylcellulose, 0.2-0.4 parts of sodium tripolyphosphate, 0.1-0.3 parts of degumming agent, and 0.2-0.6 parts of green body reinforcing agent. It should be noted that the above-mentioned green body powder is prepared by weighing the raw materials according to the specified proportions, crushing and mixing them.

[0024] The raw materials for the pore-forming agent include paraffin wax, polyvinyl alcohol, low-melting-point glass powder, and high-temperature frit; the melting temperature of the low-melting-point glass powder is 300~1000 ℃; the chemical composition of the high-temperature frit, in terms of the mass percentage of oxides, includes: SiO2 37.49~42.97%, Al2O3 11.99~17.32%, Fe2O3 0.10~0.30%, TiO2 0.04~0.08%, CaO 3.78~8.53%, MgO 1.02~3.75%, K2O 0.46~2.31%, Na2O 2.61~5.94%, P2O5 0.06~0.20%, BaO 13.45~18.87%, ZnO 3.76~7.59%, SrO 0.05~1.34%, ZrO2 0.02~0.06%, and LOI. 2.86~6.08%; wherein, the mass ratio of paraffin wax: polyvinyl alcohol: low melting point glass powder: high temperature frit is 8~9.5:0.1~0.5:0.1~0.5:0.1~1; S2. Dry the billet at a temperature of 150~200℃; S21: Apply a surface glaze to the blank and then dry it at a temperature of 160~200 ℃.

[0025] The raw material formula of the glaze, by mass parts, includes: 16-20 parts calcined kaolin, 32-36 parts quartz, 6-11 parts potassium feldspar, 3-8 parts sodium feldspar, 5-9 parts zirconium silicate, 4-9 parts wollastonite, 7-11 parts alumina, 1-4 parts nepheline, 2-4 parts barium carbonate, 1-3 parts zinc oxide, 1-3 parts calcined talc, and 2-4 parts frit; the chemical composition of the frit, by mass percentage of oxides, includes: SiO2 37.26-44.06%, Al2O3 17.88-24.43%, Fe2O3 0.08-0.25%, TiO2 0.04-0.08%, CaO 3.03-6.72%, MgO 0.06-0.27%, K2O 3.22-6.65%, Na2O 15.44~20.23%, ZrO23.53~7.98%, BaO 0.05~0.12%, P2O50.19~0.50% and LOI 0.64~2.88%.

[0026] S22: Print a pattern on the surface of the blank by inkjet printing, dry it at 160~200 ℃, apply a protective glaze, and dry it at 160~200 ℃.

[0027] The raw material formula of the protective glaze, by mass parts, includes: 8-12 parts calcined kaolin, 28-32 parts quartz, 6-10 parts potassium feldspar, 4-8 parts sodium feldspar, 7-12 parts calcite, 5-8 parts wollastonite, 8-11 parts alumina, 3-5 parts dolomite, 2-5 parts zinc oxide, 2-6 parts calcined talc, 1-4 parts high-barium and high-zinc frit, and 1-5 parts high-sodium and high-strontium frit. The chemical composition of the high-barium and high-zinc frit, by mass percentage of oxides, includes: SiO2 38.63-44.52%, Al2O3 12.79-17.75%, Fe2O3 0.10-0.25%, TiO2 0.02-0.06%, CaO 6.22-10.06%, MgO 0.53-1.07%, K2O 0.96-2.84%, Na2O The chemical composition of the high-sodium, high-strontium ingot, by mass percentage of oxides, includes: SiO₂ 48.66~55.72%, Al₂O₃ 14.26~19.71%, Fe₂O₃ 0.05~0.16%, TiO₂ 0.02~0.07%, CaO 4.05~8.36%, MgO 0.59~2.11%, K₂O 0.91~3.64%, Na₂O 3.68~8.89%, BaO 0.09~0.26%, SrO 3.31~7.36%, ZnO 4.24~9.58%, and LOI 0.11~0.54%. (Note: The original text contains some inconsistencies and inconsistencies in the chemical composition, which have been omitted from the translation.) 0.12~0.45%.

[0028] S3. The dried green body is sent into a kiln for firing. After brushing, polishing and grinding the edges, the full-body imitation travertine ceramic brick is obtained. In step S3, the firing temperature curve of the kiln is as follows: 200°C to intermediate temperature: 5-10 minutes; Intermediate temperature to maximum temperature: 18-20 minutes; Maximum temperature hold: 5-10 minutes; Cool to room temperature: 12-15 minutes; The intermediate temperature is 490~500 ℃; the maximum temperature is 1185~1205 ℃.

[0029] It should be noted that the preparation process of the pore-forming agent used in this invention is as follows: the raw materials of the pore-forming agent are weighed according to the proportion, crushed and mixed evenly, dried at 70~90 ℃ for 5~10 min until the paraffin is completely melted, the molten liquid mixture is naturally cooled for 10~15 min, and then crushed to obtain the pore-forming agent. The particle size of the pore-forming agent is 1~6 mm.

[0030] The raw materials of the pore-forming agent used in this invention include paraffin wax with a melting temperature of 50-70 °C and an accelerated volatilization temperature ≥150 °C; polyvinyl alcohol powder with a melting temperature of 180-240 °C and an accelerated volatilization temperature ≥250 °C; low-melting-point glass powder with a melting temperature of 300-1000 °C; and high-temperature frit with a melting temperature ≥1000 °C. The pore-forming agent, composed of the above raw materials, forms a gradient range of melting and decomposition temperatures. Combined with segmented heat treatment, the melting and volatilization processes are sequentially achieved: during the drying stage, paraffin wax undergoes accelerated volatilization upon heating (≥150 °C) accompanied by volume expansion, causing polyvinyl alcohol, low-melting-point glass powder, and high-temperature frit to cover the inner wall of the pores in the blank. When the temperature reaches the melting point of polyvinyl alcohol (180-240 °C), polyvinyl alcohol melts and, through its own adhesive properties, adheres the low-melting-point glass powder, high-temperature frit, and itself to the inner wall of the pores. After entering the sintering stage, polyvinyl alcohol gradually volatilizes (≥250 ℃) and expands in volume. Low melting point glass powder begins to melt (300~1000 ℃), and then high temperature frit begins to melt (≥1000 ℃). Finally, low melting point glass powder and high temperature frit form a dense glassy layer on the inner wall of the pores.

[0031] This invention employs a pore-forming agent formulated as described above. During the pressing and molding stage, the pore-forming agent is randomly and non-directionally distributed within and on the surface of the preform. The design of the drying and firing process ensures that the melting or volatilization of paraffin wax, polyvinyl alcohol, low-melting-point glass powder, and high-temperature frit follows a preset controlled sequence, thereby achieving the functional gradient construction of the internal pore modification layer. During the drying process, as the temperature rises, the pore-forming agent migrates, melts, and ultimately volatilizes in stages and selectively, rather than synchronously. This differentiated phase transition process constructs a complex network of interconnected pores ranging from micrometers to millimeters in size and with varying pore shapes (including circular, elongated, and irregularly connected shapes) at its original sites. The entire process simulates the pore structure generated by material loss or gas escape during the formation of natural materials, thus fundamentally avoiding the artificial sculpting marks caused by uniform distribution, resulting in a finished product exhibiting natural randomness and original texture.

[0032] It should be noted that, in step S1, the green body powder, by mass fraction, comprises 100 parts of green body raw material, 35-50 parts of water, 0.1-0.3 parts of methylcellulose, 0.2-0.4 parts of sodium tripolyphosphate, 0.1-0.3 parts of desiccant, and 0.2-0.6 parts of green body reinforcing agent; the particle size distribution of the green body powder is: ≤3% for particles larger than 20 mesh, 45-55% for particles between 30 and 65 mesh, 80-95% for particles between 20 and 60 mesh, and ≤3% for particles smaller than 100 mesh. The preparation process of the green body powder adopts conventional ceramic powder preparation process. The preparation process includes, but is not limited to, the following: add 35-50 parts water, 0.1-0.3 parts methylcellulose, 0.2-0.4 parts sodium tripolyphosphate, 0.1-0.3 parts deflocculant, and 0.2-0.6 parts green body reinforcing agent to 100 parts of green body raw material, ball mill for 2-4 hours, then pass through a 180-250 mesh standard sieve, with a sieve residue of 0.6-0.9%, age for 8-12 hours, spray granulate, and then sieve again.

[0033] In step S21, the preparation process of the surface glaze adopts a conventional glaze slurry preparation process. This includes, but is not limited to: weighing the surface glaze raw materials according to the formula composition; adding 35-45 parts water, 0.2-0.4 parts methylcellulose, and 0.2-0.4 parts sodium tripolyphosphate to 100 parts of raw materials; ball milling for 2-4 hours; passing through a 180-200 mesh sieve; the residue on the sieve is 0.7-0.9%; and aging for 12-24 hours. The glaze is then applied to the surface of the body using a pouring method, with a specific gravity of 1.75-2.05 g / cm³. 3 The glaze application rate is 180~220 g / m². 2 .

[0034] In step S22, the protective glaze is prepared using a conventional glaze slurry preparation process. This includes, but is not limited to: weighing the protective glaze raw materials according to the formula; adding 40-50 parts water, 0.2-0.3 parts methylcellulose, and 0.2-0.4 parts sodium tripolyphosphate to 100 parts of raw materials; ball milling for 6-8 hours; passing the glaze through a 200-250 mesh sieve, with a residue of 0.6-0.8%; and aging for 12-24 hours. The glaze is then applied to the surface of the body using a pouring method, with a specific gravity of 1.23-1.30 g / cm³. 3 The glaze application rate is 80~100 g / m². 2 .

[0035] In the formulation of the protective glaze of this invention, the synergistic effect of alkaline oxides (K₂O, Na₂O) and alkaline earth metal oxides (CaO, MgO, ZnO) enables stable and continuous melting during firing. This promotes the complete transformation of the glaze into a glassy phase, facilitates the removal of air bubbles, and ultimately forms a glassy body with a uniform structure, no open pores, and a smooth surface, achieving high stain resistance. The barium in the high-barium, high-zinc frit significantly improves the refractive index and density of the glaze, and enhances its mechanical properties. Zinc is a good fluxing agent, increasing the glaze's opacity and elasticity. Sodium in the high-sodium, high-strontium frit is a strong fluxing agent, ensuring excellent fluidity of the glaze at high temperatures, thus spreading it into a smooth and flat surface. Strontium improves chemical stability and is environmentally friendly. By introducing the two types of frits mentioned above, not only are some highly reactive components pre-synthesized, making firing more stable, but a strong fluxing effect and special divalent metal oxides (BaO, SrO) are also provided. These are all beneficial for forming a glaze with suitable surface tension and a dense structure at the final firing temperature. By using the above-mentioned protective glaze, the full-body imitation travertine ceramic tile of the present invention not only has high stain resistance inside the pores, but also has high stain resistance on the surface of the tile, achieving the superior performance of full stain resistance for imitation travertine ceramic tiles.

[0036] 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 in the following examples are merely one example within a suitable range; that is, those skilled in the art can make appropriate selections within the range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply.

[0037] The features and performance of the present invention will be further described in detail below with reference to embodiments. LOI represents loss on ignition. Oxides of elements such as C, N, S, and H are in a gaseous state under high-temperature conditions. Those skilled in the art should know that in the actual firing process, undetectable impurities may be present, resulting in the total weight of the raw material's chemical composition being less than 100%. Furthermore, because each oxide component is rounded to two decimal places, the sum of the percentages of various components may deviate slightly from 100%.

[0038] Example 1 A method for preparing a full-body imitation travertine ceramic tile includes the following steps: S1. Weigh the raw materials according to the formula to prepare green body powder. Add 40 parts water, 0.2 parts methylcellulose, 0.3 parts sodium tripolyphosphate, 0.2 parts degumming agent, and 0.4 parts green body reinforcing agent to 100 parts of green body raw materials. Ball mill for 3 hours, then pass through a 200-mesh standard sieve. The residue on the sieve is 0.8%. Aging is carried out for 10 hours, followed by spray granulation and sieving again. The particle size distribution of the powder is: ≤2% for particles above 20 mesh, 50% for particles 30~65 mesh, 85% for particles 20~60 mesh, and ≤2% for particles below 100 mesh. Mix the green body powder and pore-forming agent evenly at a mass ratio of 99:1, and then press into green bodies with a thickness of 9 mm. The raw material formula of the green body powder, by mass parts, includes: 29 parts of Xindong stone powder, 1.5 parts of wollastonite, 5 parts of high-whiteness talc, 4.5 parts of bentonite, 1 part of high-clay, 23.5 parts of high-alumina mortar, 10.5 parts of high-whiteness mortar, 1.5 parts of super-white sand, 1.5 parts of raw ore clay, 0.5 parts of ball clay, 5.5 parts of clay paste, 5.5 parts of bauxite, and 10.5 parts of sodium quartz powder. The chemical composition of the green body powder, by mass percentage of oxides, includes: 63.10% SiO2, 22.02% Al2O3, 0.66% Fe2O3, 0.13% TiO2, 1.26% CaO, 1.61% MgO, 2.24% K2O, 2.35% Na2O, and 6.46% LOI.

[0039] The raw materials for the pore-forming agent include paraffin wax, polyvinyl alcohol, low-melting-point glass powder, and high-temperature frit. The chemical composition of the high-temperature frit, by mass percentage of oxides, includes: SiO2 40.83%, Al2O3 15.77%, Fe2O3 0.19%, TiO2 0.06%, CaO 6.02%, MgO 2.13%, K2O 1.07%, Na2O 4.32%, P2O5 0.11%, BaO 17.04%, ZnO 6.64%, SrO 0.94%, ZrO2 0.04%, and LOI 4.61%. The mass ratio of paraffin wax:polyvinyl alcohol:low-melting-point glass powder:high-temperature frit is 8.7:0.3:0.2:0.8. The raw materials for the pore-forming agent are weighed according to the ratio, pulverized, and mixed evenly. Then, the mixture is placed in a drying oven at 80 ℃ for 10 min until the paraffin wax is completely melted. The liquid mixture was then cooled naturally for 10 minutes and then pulverized to obtain a pore-forming agent with a particle size of 1-4 mm.

[0040] S2. Dry the billet at a temperature of 180 ℃; S21: Weigh the glaze raw materials according to the formula. Add 45 parts water, 0.2 parts methylcellulose, and 0.3 parts sodium tripolyphosphate to 100 parts of the raw materials. Ball mill for 2 hours, then pass through a 180-mesh sieve. The residue on the sieve is 0.8%. Aging is carried out for 12 hours. Apply the glaze to the blank, with a specific gravity of 1.87 g / cm³.3 Glazing amount is 200 g / m 2 Then it is dried at a temperature of 200℃.

[0041] The raw material formula of the glaze, by mass parts, includes: 18 parts calcined kaolin, 34 parts quartz, 9 parts potassium feldspar, 6 parts sodium feldspar, 7 parts zirconium silicate, 6 parts wollastonite, 10 parts alumina, 2 parts nepheline, 2 parts barium carbonate, 1 part zinc oxide, 2 parts calcined talc, and 3 parts frit; the chemical composition of the frit, by mass percentage of oxides, includes: SiO2 41.51%, Al2O3 21.90%, Fe2O3 0.18%, TiO2 0.06%, CaO 5.29%, MgO 0.15%, K2O 4.59%, Na2O 17.93%, ZrO2 6.40%, BaO 0.08%, P2O5 0.32%, and LOI 1.34%. The chemical composition of the glaze, by mass percentage of oxides, includes: SiO2 60.41%, Al2O3 22.11%, Fe2O3 0.20%, TiO2 0.20%, CaO 2.96%, MgO 0.99%, K2O 1.46%, Na2O 1.84%, ZrO2 4.73%, BaO 1.54%, ZnO 0.99%, P2O5 0.01%, and LOI 2.43%.

[0042] S22: Inkjet print a pattern on the surface of the blank and dry it at 180 ℃; weigh the protective glaze raw materials according to the formula, add 50 parts water, 0.2 parts methylcellulose, and 0.3 parts sodium tripolyphosphate to 100 parts of the raw materials, ball mill for 6 hours, pass through a 250-mesh sieve, the residue is 0.6%, and age for 24 hours; apply the protective glaze with a specific gravity of 1.25 g / cm³. 3 Glazing amount is 90 g / m 2 Dry at 180℃.

[0043] The raw material formula of the protective glaze, by mass parts, includes: 10 parts calcined kaolin, 29 parts quartz, 8 parts potassium feldspar, 5 parts sodium feldspar, 11 parts calcite, 7 parts wollastonite, 11 parts alumina, 5 parts dolomite, 4 parts zinc oxide, 6 parts calcined talc, 2 parts high-barium high-zinc frit, and 2 parts high-sodium high-strontium frit. The chemical composition of the high-barium high-zinc frit, by mass percentage of oxides, includes: SiO2 42.30%, Al2O3 15.80%, Fe2O3 0.15%, TiO2 0.04%, CaO 8.00%, MgO 0.70%, K2O 1.85%, Na2O 1.47%, BaO 17.31%, SrO 1.31%, ZnO 10.51%, and LOI. 0.32%; The chemical composition of the high-sodium, high-strontium ingot, by mass percentage of oxides, includes: SiO2 52.78%, Al2O3 17.68%, Fe2O3 0.10%, TiO2 0.04%, CaO 6.15%, MgO 1.26%, K2O 2.12%, Na2O 6.21%, BaO 0.18%, SrO 5.43%, ZnO 7.46%, and LOI 0.22%. The chemical composition of the protective glaze, by mass percentage of oxides, includes: SiO2 50.57%, Al2O3 18.94%, Fe2O3 0.16%, TiO2 0.13%, CaO 10.40%, MgO 3.58%, K2O 1.16%, Na2O 1.03%, BaO 0.35%, SrO 0.14%, ZnO 4.45%, and LOI 8.73%.

[0044] S3. The dried green body is sent into a kiln for firing. After brushing, polishing and grinding the edges, the full-body imitation travertine ceramic brick is obtained. In step S3, the firing temperature curve of the kiln is as follows: 200~500 ℃: 6 minutes; 500~1202 ℃: 20 minutes; 1202 ℃ heat preservation: 8 minutes; Cool to room temperature: 14 minutes.

[0045] Example 2 The difference between this embodiment and Embodiment 1 is that the mass ratio of paraffin wax, polyvinyl alcohol, low-melting-point glass powder, and high-temperature frit in the pore-forming agent raw materials is adjusted to 9:0.3:0.2:0.5.

[0046] Example 3 The difference between this embodiment and Embodiment 2 is that the raw material composition of the protective glaze is adjusted to (parts by weight): 10 parts calcined kaolin, 30 parts quartz, 9 parts potassium feldspar, 6 parts sodium feldspar, 10 parts calcite, 7 parts wollastonite, 8 parts alumina, 4 parts dolomite, 3 parts zinc oxide, 6 parts calcined talc, 4 parts high-barium and high-zinc frit, and 3 parts high-sodium and high-strontium frit. The chemical composition of the protective glaze, in terms of the mass percentage of oxides, includes: SiO2 54.86%, Al2O3 17.41%, Fe2O3 0.10%, TiO2 0.11%, CaO 9.97%, MgO 3.53%, K2O 1.34%, Na2O 1.23%, BaO 0.70%, SrO 0.22%, ZnO 3.63%, and LOI 6.09%.

[0047] Comparative Example 1 The difference between this comparative example and Example 3 is that the firing temperature curve of the kiln is adjusted as follows: 200~500 ℃: 6 minutes; 500~1178 ℃: 18 minutes; 1178 ℃ heat preservation: 7 minutes; Cool to room temperature: 12 minutes.

[0048] Comparative Example 2 The difference between this comparative example and Example 3 is that the mass ratio of paraffin wax, polyvinyl alcohol, low melting point glass powder, and high temperature frit in the pore-forming agent raw materials was adjusted to 7.9:0.1:0.8:1.2.

[0049] Comparative Example 3 The difference between this comparative example and Example 3 is that polyvinyl alcohol was not added to the pore-forming agent raw material.

[0050] Comparative Example 4 The difference between this comparative example and Example 3 is that low-melting-point glass powder and high-temperature frit were not added to the pore-forming agent raw materials.

[0051] Comparative Example 5 The difference between this comparative example and Example 3 is that polyvinyl alcohol, low-melting-point glass powder, and high-temperature frit were not added to the pore-forming agent raw materials.

[0052] Comparative Example 6 The difference in this comparative example 3 is that no high-temperature frit was added to the pore-forming agent raw material.

[0053] Comparative Example 7 The difference between this comparative example and Example 3 is that no high-barium and high-zinc frit was added to the protective glaze raw material.

[0054] The raw material composition of the protective glaze is as follows (parts by weight): 10 parts calcined kaolin, 30 parts quartz, 9 parts potassium feldspar, 6 parts sodium feldspar, 10 parts calcite, 7 parts wollastonite, 8 parts alumina, 4 parts dolomite, 3 parts zinc oxide, 6 parts calcined talc, and 3 parts high-sodium, high-strontium frit. The chemical composition of the protective glaze, in terms of the mass percentage of oxides, includes: SiO2 54.76%, Al2O3 16.85%, Fe2O3 0.16%, TiO2 0.14%, CaO 9.92%, MgO 3.51%, K2O 1.32%, Na2O 1.22%, BaO 0.01%, SrO 0.17%, ZnO 3.34%, and LOI 8.34%.

[0055] Comparative Example 8 The difference between this comparative example and Example 3 is that no high-sodium, high-strontium frit was added to the protective glaze raw material.

[0056] The raw material composition of the protective glaze is as follows (parts by weight): 10 parts calcined kaolin, 30 parts quartz, 9 parts potassium feldspar, 6 parts sodium feldspar, 10 parts calcite, 7 parts wollastonite, 8 parts alumina, 4 parts dolomite, 3 parts zinc oxide, 6 parts calcined talc, and 4 parts high-barium and high-zinc frit. The chemical composition of the protective glaze, in terms of the mass percentage of oxides, includes: SiO2 54.41%, Al2O3 16.78%, Fe2O3 0.16%, TiO2 0.14%, CaO 9.96%, MgO 3.46%, K2O 1.31%, Na2O 1.07%, BaO 0.71%, SrO 0.06%, ZnO 3.51%, and LOI 8.13%.

[0057] The stain resistance of the ceramic tiles prepared in Examples 1-3 and Comparative Examples 1-8 was tested according to GB / T3810.14-2016 "Ceramic Tiles - Test Methods - Part 14: Determination of Stain Resistance". In the stain resistance test, standard contaminants such as light oil containing a green staining agent, 13 g / L iodine tincture, and olive oil were used to contaminate the glaze and pores of the ceramic tiles. After 24 hours, the tiles were cleaned, and the stain resistance level was assessed according to a 5-level standard. The stain resistance level grading method is shown in Table 1. The test results and pore effects are shown in Table 2.

[0058] Table 1. Stain Resistance Rating Method Table 2. Stain resistance test results and pore effect of Examples 1-3 and Comparative Examples 1-8 As shown in Table 2, the stain resistance level of the travertine-like ceramic tiles prepared in Examples 1-3 all reached level 5 inside the pores, and the stain resistance level of the tile surface reached level 4 or above. The pores are natural and the simulation is extremely high. Among them, the technical solution of Example 3 has the best effect, with a smooth and delicate glaze and a stain resistance level of level 5. Figure 1 As shown, the tiles have a natural appearance. (Refer to...) Figure 2 A cross-sectional diagram shows no material accumulation inside the cavity. (See diagram for example.) Figure 3 As shown in the microscopic structure diagram, the pores in the ceramic tile are highly similar to those in natural pores.

[0059] The sintering temperature of Comparative Example 1 was too low, which led to a decrease in the stain resistance level of the glaze and the inside of the pores, but it still had a certain degree of stain resistance.

[0060] Comparative Example 2 adjusted the raw material ratio of the pore-forming agent, reduced the amount of paraffin and polyvinyl alcohol used, and increased the amount of low melting point glass powder and high temperature frit used, which resulted in a decrease in the stain resistance inside the pores and a large amount of raw material accumulation at the bottom of the pores, making the pores unnatural.

[0061] After adjusting the raw material composition of the pore-forming agent in Comparative Examples 3 to 6, the results showed that the stain resistance of the inner wall of the pores decreased significantly, and there were phenomena such as a lot of raw material accumulation or unnatural pores at the bottom of the pores. This indicates that the components of the pore-forming agent have a synergistic effect, rather than a single effect.

[0062] After adjusting the formula of the protective glaze in Comparative Examples 7 and 8, the stain resistance of the glaze surface decreased.

[0063] In summary, the fully-fledged travertine-like ceramic tiles produced using this invention exhibit a natural and highly realistic porous structure, with excellent stain resistance on the inner walls of the pores. Furthermore, the protective glaze formula ensures that the tile surface also possesses good stain resistance, achieving comprehensive stain resistance for the fully-fledged travertine-like ceramic tiles. In particular, the optimal appearance of the pores and the best stain resistance are achieved when the mass ratio of the pore-forming agent's raw materials—paraffin wax, polyvinyl alcohol, low-melting-point glass powder, and high-temperature frit—is 8.7~9:0.2~0.5:0.2~0.5:0.5~0.8.

[0064] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for preparing a fully-through imitation travertine ceramic tile, characterized in that, Includes the following steps: S1. Mix the green body powder and the pore-forming agent evenly at a mass ratio of 97~99:1~3, and then press them into green bodies; S2. Dry the billet at a temperature of 150~200℃; S3. The dried green body is sent into a kiln for firing. After brushing, polishing and grinding the edges, the full-body imitation travertine ceramic brick is obtained. In step S1, the raw materials for the pore-forming agent include paraffin wax, polyvinyl alcohol, low-melting-point glass powder, and high-temperature frit; wherein the mass ratio of paraffin wax: polyvinyl alcohol: low-melting-point glass powder: high-temperature frit is 8~9.5:0.1~0.5:0.1~0.5:0.1~1. The melting temperature of the low-melting-point glass powder is 300~1000 ℃; The chemical composition of the high-temperature molten block, by mass percentage of oxides, includes: SiO2 37.49~42.97%, Al2O3 11.99~17.32%, Fe2O3 0.10~0.30%, TiO2 0.04~0.08%, CaO 3.78~8.53%, MgO 1.02~3.75%, K2O 0.46~2.31%, Na2O 2.61~5.94%, P2O5 0.06~0.20%, BaO 13.45~18.87%, ZnO 3.76~7.59%, SrO 0.05~1.34%, ZrO2 0.02~0.06%, and LOI 2.86~6.08%. In step S3, the firing temperature curve of the kiln is as follows: 200°C to intermediate temperature: 5-10 minutes; Intermediate temperature to maximum temperature: 18-20 minutes; Maximum temperature hold: 5-10 minutes; Cool to room temperature: 12-15 minutes; The intermediate temperature is 490~500 ℃; the maximum temperature is 1185~1205 ℃.

2. The method for preparing a full-body imitation travertine ceramic tile according to claim 1, characterized in that, The preparation process of the pore-forming agent is as follows: weigh the raw materials of the pore-forming agent according to the proportion, crush and mix them evenly, dry them at 70~90 ℃ for 5~10 min until the paraffin is completely melted, cool the molten liquid mixture naturally for 10~15 min, crush it to obtain the pore-forming agent.

3. The method for preparing a full-body imitation travertine ceramic tile according to claim 1, characterized in that, The particle size of the pore-forming agent is 1~6 mm.

4. The method for preparing a full-body imitation travertine ceramic tile according to claim 1, characterized in that, The raw material formula of the blank powder, by mass parts, includes: 25-31 parts of new osmium powder, 0.5-2.5 parts of wollastonite, 2-6 parts of high-white talc, 3.5-6.5 parts of bentonite, 0.5-2.5 parts of high-clay, 18.5-25.5 parts of high-alumina mortar, 8.5-12.5 parts of high-white mortar, 0.5-2 parts of super-white sand, 0.5-2.5 parts of raw ore, 0.5-1.5 parts of ball clay, 3.5-7.5 parts of mortar, 3.5-7.5 parts of bauxite, and 8.5-13.5 parts of sodium silicate powder; The chemical composition of the green body powder, by mass percentage of oxides, includes: SiO2 58.36~70.86%, Al2O3 16.82~26.66%, Fe2O3 0.49~0.80%, TiO2 0.09~0.17%, CaO 0.72~1.73%, MgO 0.73~1.97%, K2O 1.84~2.52%, Na2O 1.95~2.76%, and LOI 4.61~7.92%.

5. The method for preparing a full-body imitation travertine ceramic tile according to claim 1, characterized in that, By weight, the green body powder comprises 100 parts of green body raw material, 35-50 parts of water, 0.1-0.3 parts of methylcellulose, 0.2-0.4 parts of sodium tripolyphosphate, 0.1-0.3 parts of degumming agent and 0.2-0.6 parts of green body reinforcing agent; The particle size distribution of the green body powder is as follows: ≤3% for particles larger than 20 mesh, 45-55% for particles between 30 and 65 mesh, 80-95% for particles between 20 and 60 mesh, and ≤3% for particles smaller than 100 mesh.

6. The method for preparing a full-body imitation travertine ceramic tile according to claim 1, characterized in that, Between steps S2 and S3, there is also step S22: inkjet printing a pattern on the surface of the blank and applying a protective glaze.

7. The method for preparing a full-body imitation travertine ceramic tile according to claim 6, characterized in that, The raw material formula of the protective glaze, by mass parts, includes: 8-12 parts calcined kaolin, 28-32 parts quartz, 6-10 parts potassium feldspar, 4-8 parts sodium feldspar, 7-12 parts calcite, 5-8 parts wollastonite, 8-11 parts alumina, 3-5 parts dolomite, 2-5 parts zinc oxide, 2-6 parts calcined talc, 1-4 parts high barium and high zinc frit, and 1-5 parts high sodium and high strontium frit; The chemical composition of the high-barium, high-zinc ingot, by mass percentage of oxides, includes: SiO2 38.63~44.52%, Al2O3 12.79~17.75%, Fe2O3 0.10~0.25%, TiO2 0.02~0.06%, CaO 6.22~10.06%, MgO 0.53~1.07%, K2O 0.96~2.84%, Na2O 1.05~2.92%, BaO 15.16~20.72%, SrO 0.81~1.73%, ZnO 8.16~12.18%, and LOI 0.11~0.54%. The chemical composition of the high-sodium, high-strontium ingot, by mass percentage of oxides, includes: SiO2 48.66~55.72%, Al2O3 14.26~19.71%, Fe2O3 0.05~0.16%, TiO2 0.02~0.07%, CaO 4.05~8.36%, MgO 0.59~2.11%, K2O 0.91~3.64%, Na2O 3.68~8.89%, BaO 0.09~0.26%, SrO 3.31~7.36%, ZnO 4.24~9.58%, and LOI 0.12~0.45%.

8. The method for preparing a full-body imitation travertine ceramic tile according to claim 6, characterized in that, The step between step S2 and step S22 also includes step S21: applying a surface glaze to the blank.

9. The method for preparing a full-body imitation travertine ceramic tile according to claim 8, characterized in that, The raw material formula of the glaze, by mass parts, includes: 16-20 parts calcined kaolin, 32-36 parts quartz, 6-11 parts potassium feldspar, 3-8 parts sodium feldspar, 5-9 parts zirconium silicate, 4-9 parts wollastonite, 7-11 parts alumina, 1-4 parts nepheline, 2-4 parts barium carbonate, 1-3 parts zinc oxide, 1-3 parts calcined talc, and 2-4 parts frit; The chemical composition of the fused block, by mass percentage of oxides, includes: SiO2 37.26~44.06%, Al2O3 17.88~24.43%, Fe2O3 0.08~0.25%, TiO2 0.04~0.08%, CaO 3.03~6.72%, MgO 0.06~0.27%, K2O 3.22~6.65%, Na2O 15.44~20.23%, ZrO2 3.53~7.98%, BaO 0.05~0.12%, P2O5 0.19~0.50%, and LOI 0.64~2.88%.

10. A fully-through imitation travertine ceramic tile, characterized in that, The ceramic tile is prepared using the method described in any one of claims 1 to 9 for a full-body imitation travertine ceramic tile.

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