Method for producing sintered artificial marble
By using fluorinated nano-silica and hydroxyalumina-modified graphene oxide composite materials in sintered artificial marble, the density and hardness of the glaze are enhanced, solving the problems of low hardness and easy scratching, and achieving wear resistance and self-cleaning properties.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGXI UNIV
- Filing Date
- 2024-05-28
- Publication Date
- 2026-06-23
Smart Images
Figure CN118702482B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for modifying artificial marble, specifically to a method for preparing sintered artificial marble. Background Technology
[0002] With socio-economic development, the market demand for processed natural stone as decorative items is increasing. However, the continuous mining of stone leads to environmental pollution and resource waste, which is detrimental to the sustainable development of natural resources. Artificial marble is mainly made by mixing natural marble, granite, or fragments of waste glass with a certain amount of clay and a small amount of filler. Compared to natural marble, artificial marble has lower mechanical strength, but it features rich colors, corrosion resistance, and high-temperature resistance.
[0003] Currently, artificial marble is mainly divided into four types: cement-based artificial marble, polyester-based artificial marble, composite artificial marble, and sintered artificial marble. Sintered artificial marble's main raw materials include natural quartz, clay, and expanding agents. It is produced using a sintering process, where the raw materials are melted at high temperatures to form a uniform crystalline structure. While this type of marble has a certain density and impermeability, because it is made by binding waste stone particles with clay and then sintering them, the bond strength between the waste stones is poor, resulting in low hardness and poor wear resistance.
[0004] Chinese invention application 201710859018.0 discloses an environmentally friendly lightweight artificial stone for building decoration and its preparation method. The method involves micronizing the stone and mixing it with a water-based binder and aluminum alloy powder to form a plastic material. This material is then molded into slabs in a mold, dried, and sintered and pressed at 660–750°C. This process melts and bonds the aluminum alloy powder to the marble powder, resulting in the environmentally friendly lightweight artificial stone. However, because aluminum alloy itself has relatively low hardness, adding only aluminum alloy can make the surface of the artificial marble more prone to scratches or wear. Summary of the Invention
[0005] To address the technical problems of low hardness, poor abrasion resistance, and susceptibility to scratches or wear in existing artificial marble, this invention provides a method for preparing sintered artificial marble. The aim is to obtain an artificial marble with high surface hardness, good wear resistance, and resistance to scratches after modification, and to form a hydrophobic surface.
[0006] To achieve the above objectives, the technical solution provided by the present invention is as follows:
[0007] A method for preparing sintered artificial marble includes the following steps:
[0008] (1) Preparation of filler: obtained by water bath heating, graphene oxide, polypyrrolidone and anhydrous ethanol are mixed, then ultrasonicated and stirred, kept at 60℃ for 30 min, ammonia water and distilled water are added, kept at 60℃ for 30 min, aluminum hydroxide is added, tetraethyl orthosilicate is added dropwise, kept at 60℃ for 30 min, 1H,1H,2H,2H-perfluorodecyltriethoxysilane is added dropwise, stirred continuously for 2 h, let stand for 1-2 days, filtered, washed and dried to obtain fluorinated nano silica and aluminum hydroxide modified graphene oxide composite material, which is the filler;
[0009] (2) Preparation of glaze: Add water softener and water to the filler prepared in step (1), mix and stir to obtain a mixture, add polishing powder and methyl compound powder to the mixture and ball mill to obtain composite glaze;
[0010] (3) Preparation of artificial marble blank: According to the mass ratio, 40-55 parts of quartz (main mineral raw material), 8-13 parts of albite, 20-30 parts of clay, 3-5 parts of cubic crystal powder, 0.3-0.5 parts of pigment, 0.3-0.5 parts of reinforcing agent and 0.3-0.5 parts of additive are uniformly mixed, and the artificial marble blank is obtained by molding and compression.
[0011] (4) Coating of glaze: The composite glaze obtained in step (2) is uniformly coated on the surface of the artificial marble blank prepared in step (3), and dried at 60-120℃ to obtain an artificial marble blank with surface glaze.
[0012] (5) The artificial marble blank with surface glaze obtained in step (4) is sintered, cooled, polished and modified to obtain sintered artificial marble.
[0013] Preferably, in step (1), the mass ratio of graphene oxide:polypyrrolidone:aluminum hydroxide is 1:1:1, the amount of anhydrous ethanol added is 30-80 mL; the mass ratio of ammonia water to distilled water is 1:1; the amount of tetraethyl orthosilicate added is 3-7 mL, and the amount of 1H,1H,2H,2H-perfluorodecyltriethoxysilane added is 200-500 μL.
[0014] Preferably, the washing in step (1) is washing with anhydrous ethanol and deionized water 3 to 5 times respectively; the drying is drying in a vacuum drying oven at 50 to 80°C for 12 hours.
[0015] Preferably, the softener mentioned in step (2) is at least one of sodium tartrate, pentasodium phosphate, sodium gluconate, disodium hydrogen phosphate, sodium pyrophosphate, disodium ethylenediaminetetraacetate, polyacrylic acid, sodium carbonate, trisodium phosphate, sodium hexametaphosphate, ethylenediaminetetraacetic acid, sodium tripolyphosphate, sodium hexametaphosphate, sulfonated coal, imine sulfonate, and sodium silicate.
[0016] Preferably, the methyl compound powder mentioned in step (2) is obtained by mixing any two components selected from 2-3-dimethylbenzoic acid, 2-methyl-6-nitrobenzoic acid, sodium trimethylsilicate, potassium trimethylsilicate, methylcellulose, carboxymethylcellulose, monomethylphthalic acid, N-methyltrifluoroacetamide, trimethylsilyl alcohol, or sodium carboxymethyl starch, with the mixing ratio of the two components being 1:1 to 1.5.
[0017] Preferably, in step (2), the filler obtained in step (1) consists of 5 to 16 parts, water softener 0.2 to 0.4 parts, water 24 to 28 parts, methyl compound powder 0.06 to 0.2 parts, and polishing powder 5 to 156 parts.
[0018] Preferably, the ball milling in step (2) is performed with a total mass ratio of grinding balls to the material in the grinding jar of 1:0.6 to 4, a ball milling speed of 260 to 450 rpm, and a ball milling time of 15 to 30 min.
[0019] Preferably, the adhesive in step (3) is one of kaolin, montmorillonite, illite, and green clay; the pigment is at least one of iron oxide red, chromium oxide green, or cobalt blue; and the additive is one of calcium carbonate, silica fume, or talc.
[0020] Preferably, the reinforcing agent mentioned in step (3) is carbon black, chopped carbon fiber, carbon nanotube, glass fiber, silicate reinforcing agent or aluminate reinforcing agent.
[0021] Preferably, the coating in step (4) is performed by spray glazing or scraping glazing; wherein the scraping glaze thickness is 0.25–0.80 mm and the scraping speed is 3–7 cm / s; and the spray glaze application amount is 0.05–0.32 g / cm³. 2 The specific gravity of the glaze is controlled at 1.70 to 1.77, and the glaze slurry flow rate is 23s to 28s.
[0022] Preferably, in step (4), the product is dried at 60–120°C for 12 hours.
[0023] Preferably, the sintering temperature in step (5) is 800-1200℃ and the sintering time is 70-90min.
[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0025] (1) This invention provides a method for preparing sintered artificial marble. Fluorinated nano-silica and graphene oxide modified with alumina hydroxyl oxide composite material synthesized by water bath heating enhance the glaze of artificial marble and significantly improve the density and scratch resistance of the artificial marble surface. Nano-silica can effectively fill the pores on the surface of artificial marble glaze. The fibrous alumina hydroxyl oxide and the sheet graphene oxide work together to form a network structure in the glaze, which improves the density and hardness of the glaze and further enhances the friction resistance and scratch resistance of the artificial marble surface.
[0026] (2) Fluorinated nano-silica and graphene oxide surfaces have superhydrophobic properties and can form a hydrophobic layer on the surface of artificial marble. The contact angle of water droplets on the marble surface can reach 157° and the roll-off angle is 4°. The water droplets flow freely on the surface, thereby improving the self-cleaning property of the artificial marble surface. Attached Figure Description
[0027] Figure 1 This is a process flow diagram of the graphene oxide composite material modified with fluorinated nano-silica and hydroxyalumina in the method of this invention.
[0028] Figure 2 This is a scanning electron microscope (SEM) image of the fluorinated nano-silica and hydroxyalumina-modified graphene oxide composite material prepared in step (1) of Example 2 of the present invention.
[0029] Figure 3 Scanning electron microscope (SEM) images at different magnifications of the fluorinated nano-silica modified graphene oxide composite material prepared in step (1) of Example 6 are shown. Detailed Implementation
[0030] The specific embodiments are described in detail below with reference to the accompanying drawings, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments. Unless otherwise specified, the raw materials and reagents used in the embodiments are commercially available.
[0031] The graphene oxide used in the following examples was prepared in our laboratory using the Hummers method. Hummers method for preparing graphene oxide: Flake graphite (1.0 g), NaNO3 (0.5 g), and H2SO4 (30 mL) were mixed in a beaker and stirred in an ice bath for 30 min. Then, KMnO4 (4.0 g) was slowly added, maintaining the temperature ≤15℃. The beaker was immediately transferred to an oil bath at 30℃ and heated and stirred for 2 h. 40 mL of deionized water was slowly added to avoid a rapid increase in reaction temperature, maintaining the temperature at 100℃ for 30 min. Finally, the mixture was centrifuged and filtered, washed with 10% HCl aqueous solution to remove metal ions. Then, the dispersed GO solution was sonicated for 30 min to obtain exfoliated GO.
[0032] The fluorinated nano-silica used in the examples was prepared by water bath heating. Anhydrous ethanol (10 mL), distilled water (5 mL), and ammonia (5 mL) were mixed, then sonicated and stirred. The mixture was kept at 60°C for 30 min, and tetraethyl orthosilicate (1 mL) was added dropwise. After keeping at 60°C for 30 min, 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise. The mixture was stirred continuously for 2 h, allowed to stand for 2 days, filtered, and the resulting material was washed four times with anhydrous ethanol and deionized water, respectively. After drying, fluorinated nano-silica was obtained.
[0033] The alumina hydroxya used in this example was prepared as follows: 6g of Al(NO3)3·9H2O and 0.9g of urea (CH4N2O) were dissolved in 30mL of deionized water, and the mixture was heated and stirred in a 50℃ water bath for 15min to obtain a mixed solution. The mixed solution was poured into a 50mL polytetrafluoroethylene reactor liner, which was then placed into a stainless steel reactor. A distinct white precipitate was obtained by hydrothermal drying at 180℃ for 12h. This precipitate was then filtered and vacuum dried at 60℃ for 12h to obtain fibrous alumina hydroxya.
[0034] Example 1
[0035] A method for preparing sintered artificial marble, comprising the following steps:
[0036] (1) Preparation of filler: 5g of graphene oxide, 5g of polypyrrolidone, and 50mL of anhydrous ethanol were mixed, then sonicated and stirred, poured into a round-bottom beaker, kept at 60℃ for 30min, 20g of ammonia and 20g of distilled water were added, kept at 60℃ for 30min, 5g of aluminum hydroxide was added, and then 5mL of tetraethyl orthosilicate was added dropwise. After keeping at 60℃ for 30min, 300mL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise, stirred continuously for 2h, and allowed to stand for 2 days. Then the mixture was filtered, the filtrate was removed, and the obtained substance was washed 4 times with anhydrous ethanol and deionized water respectively. After drying in a vacuum drying oven at 50℃ for 12h, the graphene oxide composite material modified with fluorinated nano silica and aluminum hydroxide was obtained, which is the filler.
[0037] (2) Preparation of glaze: Take 8.78g of the filler obtained in step (1), add 0.2g of water softener and 24g of distilled water to the filler and mix. Stir to obtain a mixture. Add 66.92g of polishing powder and 0.1g of methyl compound powder to the mixture and put it into a ball mill jar. Then add 50g of grinding balls. The total mass ratio of grinding balls to the material in the ball mill jar is 1:2. The ball mill speed is 260 rpm and the ball milling time is 30 min to obtain a composite glaze. The methyl compound powder is obtained by mixing 2-3-dimethylbenzoic acid and 2-methyl-6-nitrobenzoic acid in a mass ratio of 1:1.5. The water softener is obtained by mixing pentasodium phosphate and disodium hydrogen phosphate in a mass ratio of 1:1.
[0038] (3) Preparation of artificial marble blank: Weigh the following components in g: 40g of quartz (main mineral raw material), 8g of albite, 20g of montmorillonite, 3g of cubic crystal powder, 0.3g of iron oxide red, 0.3g of carbon black and 0.3g of calcium carbonate additive, mix them evenly, and obtain artificial marble blank by molding and compression.
[0039] (4) Glaze application: The composite glaze obtained in step (2) is uniformly applied to the surface of the artificial marble blank prepared in step (3), and dried at 100℃ for 12 hours to obtain the artificial marble blank with the glaze applied; the glaze is applied by spray glazing; the glaze application amount by spray glazing is 0.25 g / cm³. 2 The specific gravity of the glaze is controlled at 1.70, and the glaze slurry flow rate is 23s.
[0040] (5) The artificial marble blank with surface glaze obtained in step (4) is sintered at 1000℃ for 70 minutes, cooled, and the surface of the sintered marble is polished and corrected by a high-speed polishing machine (polishing method: first wet the marble surface with water, then use a water suction machine to remove the water from the marble surface, wax the marble surface, and then polish and correct it by a high-speed polishing machine). The sintered artificial marble is obtained.
[0041] Example 2
[0042] A method for preparing sintered artificial marble, comprising the following steps:
[0043] (1) Preparation of filler: 5g of graphene oxide, 5g of polypyrrolidone, and 50mL of anhydrous ethanol were mixed, then sonicated and stirred, poured into a round-bottom beaker, kept at 60℃ for 30min, 20g of ammonia and 20g of distilled water were added, and kept at 60℃ for another 30min. 5g of aluminum hydroxide was added, followed by 5mL of tetraethyl orthosilicate. After keeping at 60℃ for 30min, 300mL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added, and the mixture was stirred continuously for 2h. After standing for 2 days, the mixture was filtered, the filtrate was removed, and the resulting material was washed 4 times with anhydrous ethanol and deionized water, respectively. After drying in a vacuum drying oven at 60℃ for 12h, a graphene oxide composite material modified with fluorinated nano-silica and aluminum hydroxide was obtained, which was the filler. The obtained graphene oxide composite material modified with fluorinated nano-silica and aluminum hydroxide was scanned using a scanning electron microscope (SEM). The results are as follows: Figure 2 As shown, through Figure 2 It can be seen that fluorinated nano-silica was successfully generated on the surface of graphene oxide and aluminum hydroxide, forming a micro-nano structure on the composite surface;
[0044] (2) Preparation of glaze: Take 5g of the filler obtained in step (1), add 0.3g of water softener and 24g of water to the filler and mix. Stir to obtain a mixture. Add 45.64g of polishing powder and 0.06g of methyl compound powder to the mixture and put it into a ball mill jar. Then add 50g of grinding balls. The total mass ratio of grinding balls to the material in the ball mill jar is 1:1.5. The ball mill speed is 300 rpm and the ball milling time is 25 min to obtain a composite glaze. The methyl compound powder is obtained by mixing sodium trimethylsilicate and potassium trimethylsilicate in a mass ratio of 1:1. The water softener is obtained by mixing sodium pyrophosphate and sodium carbonate in a mass ratio of 1:1.
[0045] (3) Preparation of artificial marble blank: Weigh the following components in g: 48g of quartz (main mineral raw material), 10g of albite, 25g of kaolin, 4g of cubic crystal powder, 0.4g of chromium oxide green, 0.4g of carbon nanotubes and 0.4g of calcium carbonate additive, mix them evenly, and obtain artificial marble blank by molding and compression.
[0046] (4) Glaze application: The composite glaze obtained in step (2) is uniformly applied to the surface of the artificial marble blank prepared in step (3), and dried at 100℃ for 12 hours to obtain the artificial marble blank with the glaze applied; the glaze is applied by spray glazing; the glaze application amount by spray glazing is 0.25 g / cm³. 2 The specific gravity of the glaze is controlled at 1.77, and the glaze slurry flow rate is 25s.
[0047] (5) The artificial marble blank with surface glaze obtained in step (4) is sintered at 1000℃ for 80 minutes, cooled, and the surface of the sintered marble is polished and corrected by a high-speed polishing machine (polishing method: first wet the marble surface with water, then use a water suction machine to remove the water from the marble surface, wax the marble surface, and then polish and correct it by a high-speed polishing machine). The sintered artificial marble is obtained.
[0048] Example 3
[0049] A method for preparing sintered artificial marble, comprising the following steps:
[0050] (1) Preparation of filler: 5g of graphene oxide, 5g of polypyrrolidone, and 80mL of anhydrous ethanol were mixed, then sonicated and stirred, poured into a round-bottom beaker, kept at 60℃ for 30min, 20g of ammonia and 20g of distilled water were added, kept at 60℃ for 30min, 5g of aluminum hydroxide was added, and then 5mL of tetraethyl orthosilicate was added dropwise. After keeping at 60℃ for 30min, 300mL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise, stirred continuously for 2h, stood for 1 day, then filtered, the filtrate was removed, and the obtained substance was washed 5 times with anhydrous ethanol and deionized water respectively. After drying in a vacuum drying oven at 80℃ for 12h, the graphene oxide composite material modified with fluorinated nano silica and aluminum hydroxide was obtained, which is the filler;
[0051] (2) Preparation of glaze: Take 16g of the filler obtained in step (1), add 0.4g of water softener and 28g of water to the filler and mix. Stir to obtain a mixture. Add 155.4g of polishing powder and 0.2g of methyl compound powder to the mixture and put it into a ball mill jar. Then add 50g of grinding balls. The total mass ratio of grinding balls to the material in the ball mill jar is 1:4. The ball mill speed is 350 rpm and the ball milling time is 20 min to obtain a composite glaze. The methyl compound powder is obtained by mixing methylcellulose and carboxymethylcellulose in a mass ratio of 1:1. The water softener is obtained by mixing trisodium phosphate and sodium hexametaphosphate in a mass ratio of 1:1.
[0052] (3) Preparation of artificial marble blank: Weigh the following components in g: 55g of quartz (main mineral raw material), 13g of albite, 30g of kaolin, 5g of cubic crystal powder, 0.5g of cobalt blue, 0.5g of carbon black and 0.5g of calcium carbonate additive, mix them evenly, and obtain artificial marble blank by molding and compression.
[0053] (4) Glaze application: The composite glaze obtained in step (2) is uniformly applied to the surface of the artificial marble blank prepared in step (3), and dried at 100℃ for 12 hours to obtain the artificial marble blank with the glaze applied; the glaze is applied by spray glazing; the glaze application amount by spray glazing is 0.25 g / cm³. 2The specific gravity of the glaze is controlled at 1.73, and the glaze slurry flow rate is 26s.
[0054] (5) The artificial marble blank with surface glaze obtained in step (4) is sintered at 1000℃ for 90 minutes, cooled, and the surface of the sintered marble is polished and corrected by a high-speed polishing machine (polishing method: first wet the marble surface with water, then use a water extractor to remove the water from the marble surface, wax the marble surface, and then polish and correct it by a high-speed polishing machine). The sintered artificial marble is obtained.
[0055] Example 4
[0056] A method for preparing sintered artificial marble, comprising the following steps:
[0057] (1) Preparation of filler: 5g of graphene oxide, 5g of polypyrrolidone, and 30mL of anhydrous ethanol were mixed, then sonicated and stirred, poured into a round-bottom beaker, kept at 60℃ for 30min, 20g of ammonia and 20g of distilled water were added, kept at 60℃ for 30min, 5g of aluminum hydroxide was added, and then 3mL of tetraethyl orthosilicate was added dropwise. After keeping at 60℃ for 30min, 200mL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise, stirred continuously for 2h, and allowed to stand for 2 days. Then the mixture was filtered, the filtrate was removed, and the obtained substance was washed 4 times with anhydrous ethanol and deionized water respectively. After drying in a vacuum drying oven at 70℃ for 12h, the graphene oxide composite material modified with fluorinated nano silica and aluminum hydroxide was obtained, which is the filler.
[0058] (2) Preparation of glaze: Take 16g of the filler obtained in step (1), add 0.2g of water softener and 28g of water to the filler and mix. Stir to obtain a mixture. Add 5.7g of polishing powder and 0.1g of methyl compound powder to the mixture and put it into a ball mill jar. Then add 50g of grinding balls. The total mass ratio of grinding balls to the material in the ball mill jar is 1:1. The ball mill speed is 400 rpm and the ball milling time is 15 min to obtain a composite glaze. The methyl compound powder is obtained by mixing monomethyl phthalic acid and N-methyltrifluoroacetamide in a mass ratio of 1:1. The water softener is obtained by mixing ethylenediaminetetraacetic acid and sodium tripolyphosphate in a mass ratio of 1:1.
[0059] (3) Preparation of artificial marble blank: Weigh the following components in g: 49g quartz (main mineral raw material), 10g albite, 26g kaolin, 4g cubic crystal powder, 0.2g cobalt blue, 0.2g iron oxide red, 0.5g carbon black and 0.4g calcium carbonate additive, mix them evenly, and obtain artificial marble blank by molding and compression.
[0060] (4) Glaze application: The composite glaze obtained in step (2) is uniformly applied to the surface of the artificial marble blank prepared in step (3), and dried at 100℃ for 12 hours to obtain the artificial marble blank with the glaze applied; the glaze is applied by spray glazing; the glaze application amount by spray glazing is 0.25 g / cm³. 2 The specific gravity of the glaze is controlled at 1.75, and the glaze slurry flow rate is 26s.
[0061] (5) The artificial marble blank with surface glaze obtained in step (4) is sintered at 1000℃ for 80 minutes, cooled, and the surface of the sintered marble is polished and corrected by a high-speed polishing machine (polishing method: first wet the marble surface with water, then use a water suction machine to remove the water from the marble surface, wax the marble surface, and then polish and correct it by a high-speed polishing machine). The sintered artificial marble is obtained.
[0062] Example 5
[0063] A method for preparing sintered artificial marble, comprising the following steps:
[0064] (1) Preparation of filler: 5g of graphene oxide, 5g of polypyrrolidone, and 50mL of anhydrous ethanol were mixed, then sonicated and stirred, poured into a round-bottom beaker, kept at 60℃ for 30min, 20g of ammonia and 20g of distilled water were added, kept at 60℃ for 30min, 5g of aluminum hydroxide was added, and then 7mL of tetraethyl orthosilicate was added dropwise. After keeping at 60℃ for 30min, 500mL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise, stirred continuously for 2h, and allowed to stand for 2 days. Then the mixture was filtered, the filtrate was removed, and the obtained substance was washed 3 times with anhydrous ethanol and deionized water respectively. After drying in a vacuum drying oven at 60℃ for 12h, the graphene oxide composite material modified with fluorinated nano silica and aluminum hydroxide was obtained, which is the filler.
[0065] (2) Preparation of glaze: Take 5g of the filler obtained in step (1), add 0.2g of water softener and 28g of water to the filler and mix. Stir to obtain a mixture. Add 66.74g of polishing glaze powder and 0.06g of methyl compound powder to the mixture and put it into a ball mill jar. Then add 50g of grinding balls. The total mass ratio of grinding balls to the material in the ball mill jar is 1:2. The ball mill speed is 400 rpm and the ball milling time is 15 min to obtain a composite glaze. The methyl compound powder is obtained by mixing trimethylsilanol and sodium carboxymethyl starch in a mass ratio of 1:1. The water softener is obtained by mixing sodium pyrophosphate and sodium carbonate in a mass ratio of 1:1.
[0066] (3) Preparation of artificial marble blank: Weigh the following components in g: 53g of quartz (main mineral raw material), 11g of albite, 22g of kaolin, 4g of cubic crystal powder, 0.2g of iron oxide red, 0.2g of chromium oxide green, 0.4g of carbon black and 0.4g of silica fume additive, mix them evenly, and obtain artificial marble blank by molding and compression;
[0067] (4) Glaze application: The composite glaze obtained in step (2) is uniformly applied to the surface of the artificial marble blank prepared in step (3), and dried at 100℃ for 12 hours to obtain the artificial marble blank with the glaze applied; the glaze is applied by spray glazing; the glaze application amount by spray glazing is 0.25 g / cm³. 2 The specific gravity of the glaze is controlled at 1.75, and the glaze slurry flow rate is 28s.
[0068] (5) The artificial marble blank with surface glaze obtained in step (4) is sintered at 1000℃ for 80 minutes, cooled, and the surface of the sintered marble is polished and corrected by a high-speed polishing machine (polishing method: first wet the marble surface with water, then use a water suction machine to remove the water from the marble surface, wax the marble surface, and then polish and correct it by a high-speed polishing machine). The sintered artificial marble is obtained.
[0069] Comparative Example 1
[0070] A method for preparing artificial marble, comprising the following steps:
[0071] In this embodiment, the preparation of filler in step (1) of Example 2 is omitted. No filler is added in step (2) of glaze preparation; the remaining operations are the same as in Example 2.
[0072] Comparative Example 2
[0073] A method for preparing artificial marble, comprising the following steps:
[0074] In this embodiment, the preparation of filler in step (1) of Example 2 is omitted. In step (2) of glaze preparation, "5g of filler" is replaced with "2.5g of fluorinated nano silica powder and 2.5g of aluminum hydroxide" for reaction. The rest of the operation is the same as in Example 2.
[0075] Comparative Example 3
[0076] A method for preparing artificial marble, comprising the following steps:
[0077] In this embodiment, the preparation of filler in step (1) of Example 2 is omitted. In the preparation of glaze in step (2), "5g of filler" is replaced with "5g of graphene oxide prepared by Hummers method". The rest of the operation is the same as in Example 2.
[0078] Comparative Example 4
[0079] A method for preparing artificial marble, comprising the following steps:
[0080] In this embodiment, the preparation of filler in step (1) of Example 2 is omitted. In the preparation of glaze in step (2), "5g of filler" is replaced with "5g of a mixture of nano silica powder, graphene oxide and alumina hydroxyl (mass ratio of the three is 1:1:1)". The rest of the operation is the same as in Example 2.
[0081] Comparative Example 5
[0082] A method for preparing artificial marble, comprising the following steps:
[0083] (1) Preparation of filler: Graphene oxide is mixed with deionized water to prepare a graphene oxide slurry with a solid content of 4.33%, which is the filler;
[0084] The remaining operations are the same as in Example 2.
[0085] Comparative Example 6
[0086] A method for preparing artificial marble, comprising the following steps:
[0087] (1) Preparation of the filler: 5g of graphene oxide, 5g of polypyrrolidone, and 50mL of anhydrous ethanol were mixed, then sonicated and stirred. The mixture was poured into a round-bottom beaker and kept at 60℃ for 30min. 20g of ammonia and 20g of distilled water were added, and the mixture was kept at 60℃ for another 30min. 5mL of tetraethyl orthosilicate was added dropwise, and the mixture was kept at 60℃ for another 30min. 300mL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added dropwise, and the mixture was stirred continuously for 2h. After standing for 2 days, the mixture was filtered, and the filtrate was removed. The resulting material was washed four times with anhydrous ethanol and deionized water, respectively. After drying in a vacuum drying oven at 50℃ for 12h, fluorinated nano-silica modified graphene oxide composite material was obtained, which is the filler. The obtained filler was scanned using a scanning electron microscope (SEM). Figure 3 As shown;
[0088] The remaining operations are the same as in Example 2.
[0089] The artificial marbles prepared in Examples 1-5 and Comparative Examples 1-6 were subjected to Mohs hardness testing on their surfaces using the Mohs hardness pen scratch test. The abrasion resistance of the artificial marbles prepared in Examples 1-5 and Comparative Examples 1-6 was also tested using a glaze abrasion tester. The experimental results are shown in Table 1 below.
[0090] Table 1.
[0091] project Mohs hardness abrasion resistance Example 1 7.0 Level 5 Example 2 7.0 Level 5 Example 3 7.0 Level 5 Example 4 7.0 Level 5 Example 5 7.0 Level 5 Comparative Example 1 5.0 Level 2 Comparative Example 2 6.0 Level 4 Comparative Example 3 6.0 Level 3 Comparative Example 4 6.0 Level 4 Comparative Example 5 6.0 Level 4 Comparative Example 6 7.0 Level 4
[0092] Antifouling performance test:
[0093] Anti-fouling performance tests were conducted on the artificial marble surface. Ink was dripped onto the artificial marble surface and then rinsed with water. For the artificial marble surfaces prepared in Examples 1-5, the ink was completely removed by rinsing with water, and no water droplets accumulated on the marble surface. For the artificial marble surfaces prepared in Comparative Examples 2 and 6, the ink could be removed by rinsing with water. For the artificial marble surfaces prepared in Comparative Examples 1, 3, 4, and 5, there was obvious ink residue on the marble surface after rinsing with water. The anti-fouling performance test showed that the artificial marble surfaces prepared in Examples 1-5 and Comparative Examples 2 and 6 had good anti-fouling performance, while the marble surfaces prepared in Comparative Examples 1, 3, 4, and 5 had poor anti-fouling performance.
[0094] The performance test results above show that the method of the present invention, through the synthesis of fluorinated nano-silica and aluminum oxide-modified graphene oxide composite material by water bath heating, enhances the glaze of artificial marble and significantly improves the density and scratch resistance of the artificial marble surface. Nano-silica can effectively compensate for defects inside and on the surface of artificial marble, while the addition of graphene oxide greatly increases the hardness of the artificial marble surface, further enhancing its abrasion resistance and scratch resistance. The fluorinated nano-silica and graphene oxide surfaces possess superhydrophobic properties, forming a hydrophobic layer on the artificial marble surface. Contact angle testing shows that the water droplet contact angle can reach 157°, allowing the liquid to flow freely on its surface, thereby improving the self-cleaning properties of the artificial marble surface.
[0095] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.
Claims
1. A method for preparing sintered artificial marble, characterized in that, Includes the following operations: (1) Preparation of filler: Graphene oxide, polypyrrolidone and ethanol are mixed, then ultrasonicated and stirred, kept at 60℃ for 30 min, ammonia and water are added, kept at 60℃ for 30 min, aluminum hydroxide is added, then tetraethyl orthosilicate is added, kept at 60℃ for 30 min, 1H,1H,2H,2H-perfluorodecyltriethoxysilane is added, stirred continuously for 2 h, and allowed to stand for 1-2 days. After filtration, washing and drying, a composite material of fluorinated nano silica and aluminum hydroxide modified graphene oxide is obtained, which is the filler. (2) Preparation of glaze: Add water softener and water to the filler prepared in step (1), mix and stir to obtain a mixture, add polishing powder and methyl compound powder to the mixture and ball mill to obtain composite glaze; (3) Preparation of artificial marble blank: According to the mass ratio, 40-55 parts of quartz, 8-13 parts of albite, 20-30 parts of clay, 3-5 parts of cubic crystal powder, 0.3-0.5 parts of pigment, 0.3-0.5 parts of reinforcing agent and 0.3-0.5 parts of additive are evenly mixed, and the artificial marble blank is obtained by molding and compression. (4) Coating of glaze: The composite glaze obtained in step (2) is coated on the surface of the artificial marble blank prepared in step (3), and dried at 60~120℃ to obtain an artificial marble blank with surface glaze; (5) The artificial marble blank with surface glaze obtained in step (4) is sintered, cooled, polished and modified to obtain sintered artificial marble.
2. The method for preparing sintered artificial marble according to claim 1, characterized in that: In step (1), the mass ratio of graphene oxide: polypyrrolidone: alumina hydroxide is 1:1:1, the amount of ethanol added is 30~80mL; the mass ratio of ammonia water to water is 1:1; the amount of tetraethyl orthosilicate added is 3~7mL, and the amount of 1H,1H,2H,2H-perfluorodecyltriethoxysilane added is 200~500μL.
3. The method for preparing sintered artificial marble according to claim 1, characterized in that: The washing described in step (1) involves washing with ethanol and water 3 to 5 times respectively; the drying described is vacuum drying at 50 to 80°C for 12 hours.
4. The method for preparing sintered artificial marble according to claim 1, characterized in that: The water softener mentioned in step (2) is at least one of sodium tartrate, pentasodium phosphate, sodium gluconate, disodium hydrogen phosphate, sodium pyrophosphate, disodium ethylenediaminetetraacetate, polyacrylic acid, sodium carbonate, trisodium phosphate, sodium hexametaphosphate, ethylenediaminetetraacetic acid, sodium tripolyphosphate, sodium hexametaphosphate, sulfonated coal, imine sulfonate, and sodium silicate.
5. The method for preparing sintered artificial marble according to claim 1, characterized in that: The methyl compound powder mentioned in step (2) is obtained by mixing any two of the following components: 2-3-dimethylbenzoic acid, 2-methyl-6-nitrobenzoic acid, sodium trimethylsilicate, potassium trimethylsilicate, methylcellulose, carboxymethylcellulose, monomethylphthalic acid, N-methyltrifluoroacetamide, trimethylsilyl alcohol, or sodium carboxymethyl starch, with a mixing ratio of 1:1 to 1.
5.
6. The method for preparing sintered artificial marble according to claim 1, characterized in that: In step (2), the filler obtained in step (1) consists of 5 to 16 parts, water softener 0.2 to 0.4 parts, water 24 to 28 parts, methyl compound powder 0.06 to 0.2 parts, and polishing powder 5 to 156 parts.
7. The method for preparing sintered artificial marble according to claim 1, characterized in that: The ball milling in step (2) is as follows: the total mass ratio of the grinding balls to the material in the grinding jar is 1:0.6~4, the ball milling speed is 260~450 rpm, and the ball milling time is 15~30 min.
8. The method for preparing sintered artificial marble according to claim 1, characterized in that: The clay mentioned in step (3) is one of kaolin, montmorillonite, illite, and green clay; the pigment is at least one of iron oxide red, chromium oxide green, or cobalt blue; the additive is one of calcium carbonate, silica fume, or talc; and the reinforcing agent is carbon black, chopped carbon fiber, carbon nanotubes, glass fiber, silicate reinforcing agent, or aluminate reinforcing agent.
9. The method for preparing sintered artificial marble according to claim 1, characterized in that: The coating process in step (4) involves either spray glazing or scraping glazing. The scraping glaze thickness is 0.25~0.80 mm, and the scraping speed is 3~7 cm / s. The spray glaze application rate is 0.05~0.32 g / cm³. 2 The specific gravity of the glaze is controlled at 1.70~1.77, and the glaze slurry flow rate is 23s~28s; in step (4), it is dried at 60~120℃ for 12h.
10. The method for preparing sintered artificial marble according to claim 1, characterized in that: The sintering temperature in step (5) is 800~1200℃ and the sintering time is 70~90min.