Wear-resistant antifouling soft-light ceramic rock plate and preparation method thereof

Abstract

The invention provides a wear-resistant antifouling soft-light ceramic rock plate and a preparation method, and belongs to the technical field of ceramic, the soft-light ceramic rock plate is polished after being fired, and is strengthened after being polished, and the strengthening treatment comprises the steps of introducing and activating hydrogen bond functional groups into a brick body, immersing the brick body into a carbon nanotube suspension for dip-coating treatment, and drying the brick body to obtain the wear-resistant antifouling soft-light ceramic rock plate. Taking out the brick body, heating and drying, then immersing the brick body into tetrahydrofuran coating liquid containing a silane derivative and a curing agent, and curing to obtain a finished product, forming a micro-nano structure by using the carbon nanotubes in a hydrogen bond anchoring manner, and improving the mechanical strength of the ceramic rock plate by using the excellent mechanical properties of the carbon nanotubes. The wear resistance and the hardness of the ceramic rock plate are enhanced; by replacing aluminum sulfate octadecahydrate with the carbon nanotubes, various problems caused by aluminum sulfate octadecahydrate at high temperature can be avoided.

Description

Technical Field

[0001] This invention belongs to the field of ceramic technology, and particularly relates to a wear-resistant, stain-resistant, soft-light ceramic slab, and a method for preparing the wear-resistant, stain-resistant, soft-light ceramic slab. Background Technology

[0002] Soft-light ceramic slabs are a type of ceramic slab with a surface reflectivity between strong light and matte finish. They achieve soft light scattering through diffuse reflection technology, combining decorative and practical functions, making them suitable for living rooms, studies, and other spaces requiring a balance between visual comfort and spatial openness. Chinese patent application CN114276016A discloses a soft-light glazed ceramic slab and its preparation method. This invention achieves a natural soft-light effect by selecting a suitable ratio of SiO2 and Al2O3 and adding CaO, MgO, ZnO, and SrO as a composite fluxing matting agent. The surface is smooth and delicate, with a gloss level of 31°-38°, and excellent wear resistance. This technology simplifies the process of preparing soft-polished tiles, saving processing time and offering high efficiency and economic benefits. However, it still has shortcomings in terms of stain resistance and wear resistance. Although the surface of soft-light glazed ceramic slabs is smooth and delicate, it is easily contaminated by oil and stains and is difficult to clean.

[0003] Chinese patent application CN120664907A discloses a decorative ceramic slab and its manufacturing process. This invention utilizes a post-treatment process involving impregnation with aluminum sulfate octadechydrate to create a synergistic protective layer of micro-nano structures and a low surface energy coating on the ceramic slab surface. This significantly enhances the slab's anti-fouling and wear-resistance properties, achieving the highest levels in both stain resistance and wear resistance tests. However, after the aluminum sulfate octadechydrate impregnation treatment, calcination at 560℃ for 2 hours is required. Aluminum sulfate octadechydrate begins to lose its water of crystallization at around 250℃, and the resulting water vapor cannot escape smoothly during the glaze melting process. This easily forms bubbles and pinholes in the glaze layer, affecting surface smoothness and gloss, and reducing the mechanical strength and stain resistance of the glaze. Summary of the Invention

[0004] Based on the aforementioned problems in the existing technology, the present invention provides a wear-resistant, stain-resistant, soft-light ceramic slab. After firing, the soft-light ceramic slab undergoes polishing treatment, followed by strengthening treatment. The strengthening treatment includes activating hydrogen-bonded functional groups in the brick body, immersing it in a carbon nanotube suspension for dip coating treatment, removing the brick body, heating and drying it, and then immersing the brick body in a tetrahydrofuran coating solution containing silane derivatives and a curing agent for curing to obtain the finished product.

[0005] The carbon nanotube suspension comprises 0.5%-1% carbon nanotubes, 0.05%-0.1% sodium dodecyl sulfate, and 0.05%-0.1% hydroxypropyl cellulose.

[0006] The silane derivatives include one or more of methyltrimethoxysilane, perfluorodecyltriethoxysilane, and octamethylcyclotetrasiloxane.

[0007] The carbon nanotubes are multi-walled carbon nanotubes with a purity >98% and a diameter of 4-6 nm.

[0008] This invention also provides a method for preparing a wear-resistant, stain-resistant, soft-light ceramic slab, which includes the following steps: Step S1: Fire the brick, which consists of a body layer, a base glaze layer, a top glaze layer, and an inkjet pattern layer from bottom to top. Step S2: Grind and polish the brick body, then spray an activation liquid onto the brick body surface and heat to dry; the activation liquid is an ethanol solution containing 1%-3% 3-aminopropyltriethoxysilane. Step S3, Functionalizing carbon nanotubes: Carbon nanotubes are added to deionized water at a mass ratio of 0.5%-1%, sodium dodecyl sulfate is added at a mass ratio of 0.05%-0.1%, and hydroxypropyl cellulose is added at a mass ratio of 0.05%-0.1%. The mixture is then ultrasonically dispersed to prepare a carbon nanotube suspension. Step S4: Immerse the brick treated in step S2 into the carbon nanotube suspension prepared in step S3 for immersion coating for 10-15 minutes. At the same time, perform ultrasonic vibration treatment. Remove the brick and dry it. Step S5: Immerse the brick in a tetrahydrofuran coating solution containing silane derivatives and curing agent. After 10-20 minutes, remove it and heat it to cure, thus obtaining the finished product.

[0009] In step S2, the spraying pressure is 0.35-0.45 MPa, the drying temperature is 90-110℃, and the drying time is 20-40 minutes.

[0010] In step S3, the ultrasonic frequency for ultrasonic dispersion treatment is 800 kHz - 1 MHz, and the processing time is 50-80 minutes; in step S4, the ultrasonic frequency for ultrasonic oscillation treatment is 80-100 kHz.

[0011] In step S4, the drying process involves air drying at room temperature for 20-40 minutes, followed by heating to 120-150°C for 1-2 hours.

[0012] The functionalized carbon nanotubes in step S3 include the following steps: Step S31: Mix carbon nanotubes with concentrated nitric acid at a mass ratio of 1:40-60, and heat under reflux for 4-6 hours. Step S32: Wash carbon nanotubes with deionized water by centrifugation until pH neutral, and vacuum dry at 75-85℃ for 11-13 hours.

[0013] In step S31, the concentrated nitric acid is 65-68% concentrated nitric acid, the reflux reaction temperature is 70-90℃, and the reflux stirring speed is 150-250 rpm.

[0014] The beneficial effects of this invention are as follows: 1. Carbon nanotubes are used to form micro-nano structures through hydrogen bonding, and the excellent mechanical properties of carbon nanotubes are utilized to improve the mechanical strength of ceramic slabs, thereby enhancing the wear resistance and hardness of ceramic slabs.

[0015] 2. Carbon nanotubes also have excellent thermal stability. By replacing aluminum sulfate octadecahydrate with carbon nanotubes, various problems caused by aluminum sulfate octadecahydrate at high temperatures can be avoided.

[0016] 3. Sodium dodecyl sulfate (SDS) and hydroxypropyl cellulose (HPC) exert their dispersing effects through electrostatic repulsion and steric hindrance, respectively. When used together, they can form a more stable "electrostatic-steric hindrance" dual stabilization mechanism, which enables the carbon nanotube suspension to have a better dispersion effect, more uniformly anchored to the ceramic slab, and improve the mechanical properties of the ceramic slab. Detailed Implementation

[0017] The present invention will now be described in detail with reference to specific embodiments.

[0018] Example 1: A wear-resistant, stain-resistant, soft-light ceramic slab.

[0019] A wear-resistant, stain-resistant, soft-light ceramic slab comprises, from bottom to top, a body layer, a base glaze layer, a top glaze layer, and an inkjet pattern layer. The body layer is made of the following raw materials by weight percentage: 40% wollastonite, 18% quartz sand, 10% potassium feldspar powder, 5% mica powder, 5% bauxite, 4% pyrophyllite, 2% sodium borate, 6% zirconium oxide ceramic sand, 6% diopside, 3% high-clay, 0.5% ceramic dispersant, and 0.5% sodium silicate. The base glaze layer is made of the following raw materials by weight percentage: 30% sodium feldspar, 30% quartz, 15% nepheline syenite, 10% kaolinite, 7% dolomite, and 8% calcium feldspar; The surface glaze is made from the following raw materials by weight percentage: nepheline syenite 33%, spodumene 14%, wollastonite 14%, diopside 10%, apatite 5%, barium feldspar 3%, quartz 9%, calcined α-alumina powder 4%, calcined zinc oxide 5%, and strontium carbonate 3%; The inkjet pattern layer is formed by digital inkjet printing on the surface of the glaze layer.

[0020] Following high-temperature firing using existing processes, the bricks undergo edge grinding and polishing, followed by a strengthening treatment. This strengthening treatment includes activating the bricks by introducing hydrogen-bonded functional groups, immersing them in a carbon nanotube suspension for coating, removing the bricks, heating and drying them, and then immersing them in a tetrahydrofuran coating solution containing a silane derivative and a curing agent for curing, resulting in the finished product. The carbon nanotube suspension comprises 0.8% carbon nanotubes, 0.08% sodium dodecyl sulfate, and 0.06% hydroxypropyl cellulose. The silane derivative is methyltrimethoxysilane, and the carbon nanotubes are multi-walled carbon nanotubes with a purity >98% and a diameter of 4-6 nm.

[0021] Example 2: A wear-resistant, stain-resistant, soft-light ceramic slab.

[0022] The difference between this embodiment and Embodiment 1 is that the silane derivative is octamethylcyclotetrasiloxane.

[0023] Example 3: A wear-resistant, stain-resistant, soft-light ceramic slab.

[0024] The difference between this embodiment and Embodiment 1 is that the silane derivative is perfluorodecyltriethoxysilane.

[0025] Example 4: A wear-resistant, stain-resistant, soft-light ceramic slab.

[0026] The difference between this embodiment and Embodiment 1 is that the silane derivative is a mixture of methyltrimethoxysilane, perfluorodecyltriethoxysilane and octamethylcyclotetrasiloxane.

[0027] Example 5: A method for preparing a wear-resistant, stain-resistant, soft-light ceramic slab.

[0028] A method for preparing a wear-resistant, stain-resistant, soft-light ceramic slab includes the following steps: Step S1: Fire the brick according to the formula of Example 1, which includes the body layer, the base glaze layer, the top glaze layer and the inkjet pattern layer from bottom to top. Step S2: Grind and polish the brick body, then spray the activation liquid onto the brick body surface at a spraying pressure of 0.4 MPa, and then heat to 100°C to dry the brick body for 30 minutes; the activation liquid is an ethanol solution containing 2% 3-aminopropyltriethoxysilane, with 3-aminopropyltriethoxysilane (APTES) as a coupling agent. Step S3 includes the process of functionalizing carbon nanotubes. This step can be carried out simultaneously with steps S1-2. It includes step S31, in which carbon nanotubes are mixed with concentrated nitric acid of 65% concentration at a mass ratio of 1:50, heated to 80°C with a temperature control accuracy of ±2°C, and stirred under reflux for 5 hours at a stirring speed of 150-250 rpm to generate carboxylic acid functional groups on the surface of carbon nanotubes. Step S32: Wash carbon nanotubes with deionized water by centrifugation until pH is neutral, and then vacuum dry at 80°C for 12 hours. Carbon nanotubes were then added to deionized water at a mass ratio of 1%, sodium dodecyl sulfate at a mass ratio of 0.08%, and hydroxypropyl cellulose at a mass ratio of 0.05%. The mixture was then ultrasonically dispersed to prepare a carbon nanotube suspension. The ultrasonic frequency for the dispersion treatment was 900 kHz, and the treatment time was 60 minutes. The purpose of the ultrasonic dispersion treatment was to improve the dispersion effect of the carbon nanotubes. SDS, an anionic surfactant, adsorbs its hydrophobic ends onto the hydrophobic surface of carbon nanotubes, while its negatively charged hydrophilic ends extend into the water. This creates a negatively charged molecular layer on the carbon nanotube surface, making it difficult for the nanotubes to aggregate due to electrostatic repulsion. Studies have shown that the addition of SDS significantly reduces the zeta potential of the carbon nanotube surface from approximately -28 mV to approximately -48 mV, indicating a substantial enhancement in the electrostatic stability of the dispersion system. HPC is a nonionic cellulose ether whose long molecular chains can extend in water. It can interact with the surface of carbon nanotubes through some hydrophobic segments or functional groups, or it can wrap its molecular chains around the carbon nanotubes to form a thick polymeric protective layer. This protective layer generates a strong steric hindrance effect, physically preventing the carbon nanotubes from approaching each other and thus preventing aggregation. The addition of HPC can effectively improve the uniform intercalation of carbon nanotubes in three-dimensional composite structures.

[0029] When SDS and HPC coexist, they interact with each other. HPC molecular chains may bind to SDS molecules adsorbed on the carbon nanotube surface through hydrophobic interactions. This interaction can cause the HPC molecular chains to extend further onto the SDS adsorption layer, forming a thicker and more robust composite protective layer. This provides the carbon nanotubes with dual protection from electrostatic repulsion and steric hindrance, significantly improving both dispersion and long-term stability. Step S4: Immerse the brick treated in step S2 into the carbon nanotube suspension prepared in step S3 for 15 minutes. The functionalized carbon nanotubes are firmly anchored to the surface of the ceramic tile through hydrogen bonding. During the immersion treatment, ultrasonic vibration is performed. The purpose of ultrasonic vibration is to maintain the dispersion effect of carbon nanotubes and to force out the air in the pores on the surface of the ceramic slab through ultrasonic energy, so that the carbon nanotubes can be better anchored to the surface of the ceramic slab. The ultrasonic frequency of ultrasonic vibration is 90 kHz. After removing the brick, air dry it at room temperature for 30 minutes to allow the moisture to evaporate slowly. Then heat it to 130℃ and dry it for 1.5 hours to promote the formation of hydrogen bond network and improve adhesion. In step S5, 1.5 parts of silane derivative and 0.3 parts of curing agent are added to 90 parts of tetrahydrofuran and stirred evenly to obtain a coating liquid. The brick treated in step S4 is immersed in the coating liquid for 15 minutes, and then taken out and cured at 110°C for 1 hour to obtain the finished product.

[0030] Example 6: Stain resistance and abrasion resistance test of ceramic slabs.

[0031] Stain resistance test method: The stain resistance performance was tested in accordance with the national standard GB / T 3810.14-2016 "Test Methods for Ceramic Tiles Part 14: Determination of Stain Resistance". The stain resistance performance of the ceramic slabs prepared in the experimental group and the control group was tested. The test principle is to contact the front of the ceramic slab with the staining agent (chrome green, iodine and olive oil, etc.) and let it act for a certain period of time. Then, the front of the ceramic slab was cleaned according to the prescribed cleaning method. The surface changes were observed to determine the stain resistance of the brick. The grades were divided into 1 to 10, with grade 10 having the best stain resistance performance.

[0032] Wear resistance test method: The ceramic rock plates prepared by the experimental group and the control group were subjected to wear test using a reciprocating friction and wear tester under the test conditions of 50N test load, 4mm stroke, 2Hz frequency and 40min duration. The friction and wear performance was measured and the wear resistance was measured by the wear volume.

[0033] Except for the distinguishing conditions in the table, all experimental and control groups followed the conditions of Examples 1 and 5. The test results are as follows: As shown in the table above, experimental group 1 received the highest ratings for both stain resistance and abrasion resistance, with its abrasion resistance being significantly higher than that of control group 1. Referring to the contact measurement method in the national standard GB / T 39156-2020 "Technical Requirements and Test Methods for Large-Size Ceramic Plates," a stylus profilometer was used to directly measure the surface profile of the ceramic slabs in experimental group 1 and control group 1. It was found that pinholes were present on the surface of the ceramic slab in control group 1, while no pinholes were found on the surface of the ceramic slab in experimental group 1. This demonstrates that using carbon nanotube suspension can bring superior mechanical properties to ceramic slabs, and experimental group 1 requires less time and energy.

[0034] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A wear-resistant, stain-resistant, soft-light ceramic slab, wherein the soft-light ceramic slab is polished after firing, characterized in that... After polishing, a strengthening treatment is carried out, which includes introducing and activating hydrogen-bonded functional groups into the brick, immersing it in a carbon nanotube suspension for dip coating, removing the brick and heating and drying it, and then immersing the brick in a tetrahydrofuran coating solution containing silane derivatives and curing agents for curing to obtain the finished product.

2. The wear-resistant, stain-resistant, soft-light ceramic slab according to claim 1, characterized in that, The carbon nanotube suspension comprises 0.5%-1% carbon nanotubes, 0.05%-0.1% sodium dodecyl sulfate, and 0.05%-0.1% hydroxypropyl cellulose.

3. The wear-resistant, stain-resistant, soft-light ceramic slab according to claim 2, characterized in that, The silane derivatives include one or more of methyltrimethoxysilane, perfluorodecyltriethoxysilane, and octamethylcyclotetrasiloxane.

4. The wear-resistant, stain-resistant, soft-light ceramic slab according to claim 2, characterized in that, The carbon nanotubes are multi-walled carbon nanotubes with a purity >98% and a diameter of 4-6 nm.

5. A method for preparing a wear-resistant, stain-resistant, soft-light ceramic slab, characterized in that, It includes the following steps: Step S1: Fire the brick, which consists of a body layer, a base glaze layer, a top glaze layer, and an inkjet pattern layer from bottom to top. Step S2: Grind and polish the brick body, then spray an activation liquid onto the brick body surface and heat to dry; the activation liquid is an ethanol solution containing 1%-3% 3-aminopropyltriethoxysilane. Step S3, Functionalizing carbon nanotubes: Carbon nanotubes are added to deionized water at a mass ratio of 0.5%-1%, sodium dodecyl sulfate is added at a mass ratio of 0.05%-0.1%, and hydroxypropyl cellulose is added at a mass ratio of 0.05%-0.1%. The mixture is then ultrasonically dispersed to prepare a carbon nanotube suspension. Step S4: Immerse the brick treated in step S2 into the carbon nanotube suspension prepared in step S3 for immersion coating for 10-15 minutes. At the same time, perform ultrasonic vibration treatment. Remove the brick and dry it. Step S5: Immerse the brick in a tetrahydrofuran coating solution containing silane derivatives and curing agent. After 10-20 minutes, remove it and heat it to cure, thus obtaining the finished product.

6. The method for preparing a wear-resistant, stain-resistant, soft-light ceramic slab according to claim 5, characterized in that, In step S2, the spraying pressure is 0.35-0.45 MPa, the drying temperature is 90-110℃, and the drying time is 20-40 minutes.

7. The method for preparing a wear-resistant, stain-resistant, soft-light ceramic slab according to claim 5, characterized in that, In step S3, the ultrasonic frequency for ultrasonic dispersion treatment is 800 kHz - 1 MHz, and the treatment time is 50-80 minutes; in step S4, the ultrasonic frequency for ultrasonic oscillation treatment is 80-100 kHz.

8. The method for preparing a wear-resistant, stain-resistant, soft-light ceramic slab according to claim 5, characterized in that, The drying process in step S4 involves air drying at room temperature for 20-40 minutes, followed by heating to 120-150℃ for 1-2 hours.

9. The method for preparing a wear-resistant, stain-resistant, soft-light ceramic slab according to claim 5, characterized in that, The functionalized carbon nanotubes in step S3 include the following steps: Step S31: Mix carbon nanotubes with concentrated nitric acid at a mass ratio of 1:40-60, and heat under reflux for 4-6 hours. Step S32: Wash carbon nanotubes with deionized water by centrifugation until pH neutral, and vacuum dry at 75-85℃ for 11-13 hours.

10. The method for preparing a wear-resistant, stain-resistant, soft-light ceramic slab according to claim 9, characterized in that, The concentrated nitric acid in step S31 is 65-68% concentrated nitric acid, the reflux reaction temperature is 70-90℃, and the reflux stirring speed is 150-250 rpm.