A water-based gel modified magnesite-based solid waste unfired ceramic decorative panel and a preparation method thereof

Abstract

This invention discloses a water-based gel-modified magnesite-based solid waste non-fired ceramic decorative panel and its preparation method in the field of building materials. It features non-fired operation and the absence of organic adhesives. The raw materials include: 60-80 parts of solid waste base material, 15-25 parts of inorganic modified filler, 6-10 parts of inorganic crosslinking activator, 1-5 parts of functional additives, and 3-6 parts of water. The solid waste base material is composed of steel slag tailings with a particle size of 0.02-0.06 mm, coal gangue fines with a particle size of 0.2-0.4 mm, and recycled construction waste aggregate with a particle size of 1-3 mm in a gradient gradation. The inorganic modified filler includes calcined attapulgite clay, silica fume powder, mica fragments, natural magnesite powder, and porous silica-coated hafnium carbonitride particles. The inorganic crosslinking activator includes aluminates, active silica sol, and composite basic salts. The base material of this invention uses a gradient-graded bulk solid waste and water as a dispersion medium. A gel network is spontaneously formed through a ternary inorganic crosslinking activator. No heating, pressurization, or adhesives are required. This chemically modifies natural magnesite powder and solid waste base material, giving the decorative board excellent performance.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, specifically to a water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel and its preparation method. Background Technology

[0002] The existing decorative panels on the market mainly have the following three major technical defects: (1) Sintered decorative materials (such as ceramic bricks and ceramic slabs): They need to be sintered at a high temperature of over 1100℃, which consumes a lot of energy, has high carbon emissions, and the finished products are brittle, have poor impact and crush resistance, high transportation and construction costs, and rely on non-renewable mineral resources. Conventional cement-based non-fired materials (such as ordinary non-fired bricks and artificial stone slabs): They have high porosity and high water absorption, and are prone to problems such as efflorescence, powdering, and cracking in humid environments. They have weak resistance to external damage, low solid waste utilization rate, and simple and rough decorative effects, which cannot meet the decoration standards of high-end places. (3) Organic composite non-fired materials: They contain a large amount of organic adhesives (such as resins and glues), and release harmful substances such as formaldehyde and TVOC in excess of the standard. They are easy to soften and deform when exposed to fire and release toxic gases. They are easy to age and delaminate after long-term soaking in water, and can only be used in indoor scenes with lower requirements.

[0003] In addition, existing solid waste non-fired building material technologies generally have the following limitations: they use only a single inorganic solid waste (such as construction waste, coal gangue, tailings, etc.), the formula is simple, and the material toughness and decorative properties are insufficient; or they use only organic solid waste such as sawdust, which is prone to mold, has poor thermal stability, and weak adhesion to inorganic substrates; they rely heavily on cement or conventional alkali activators, resulting in low density and low performance compliance rate after non-fired construction, and lack of special formulas and process optimizations for high-end decoration scenarios (such as high-end hotels). Summary of the Invention

[0004] The purpose of this invention is to provide a water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel and its preparation method. It uses bulk industrial solid waste and construction solid waste as the main raw materials and is a high-performance non-fired decorative composite material prepared through low-temperature inorganic cross-linking bonding mechanism and room-temperature pressureless molding process. This invention solves the defect that existing solid waste non-fired building material technology cannot be applied to high-end decoration scenarios.

[0005] The present invention achieves the above objectives through the following technical solutions:

[0006] A water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel, wherein the raw materials of the decorative panel, by weight, include:

[0007] Solid waste base material: 60-80 parts;

[0008] Inorganic modified filler: 15-25 parts;

[0009] Inorganic crosslinking activator: 6-10 parts;

[0010] Functional additives: 1-5 parts;

[0011] Water: 3-6 parts;

[0012] The solid waste base material is composed of steel slag tailings with a particle size of 0.02-0.06 mm, coal gangue fines with a particle size of 0.2-0.4 mm, and recycled construction waste aggregates with a particle size of 1-3 mm in a graded distribution. The inorganic modified filler includes calcined attapulgite, silica fume powder, mica fragments, natural magnesite powder, and porous silica-coated hafnium carbonitride particles. The inorganic crosslinking activator includes aluminates, active silica sol, and composite basic salts.

[0013] A further improvement is that the mass ratio of steel slag tailings powder, coal gangue fines and recycled construction waste aggregate in the solid waste base material is 10-14:8-10:15-18;

[0014] The mass ratio of calcined attapulgite clay, silica fume powder, mica fragments, natural magnesite powder, and porous silica-coated hafnium carbonitride particles in the inorganic modified filler is 7-9:5-7:1-3:2-3:1.5-2.5.

[0015] The mass ratio of aluminate, active silica sol, and composite basic salt in the inorganic crosslinking activator is 3-5:2-4:1-3.

[0016] A further improvement is that the aluminate is sodium aluminate or potassium aluminate, the active silica sol is acidic silica sol or alkaline silica sol, and the composite basic salt is at least two of sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, and potassium hydroxide.

[0017] A further improvement is that the functional additives include alkylsilane hydrophobic agents, low-temperature crosslinking regulators, pre-oxidized polyacrylonitrile short fibers, and mineral-based colorants, with a mass ratio of 7-9:5-7:6-8:3-5.

[0018] This invention also provides a method for preparing the aqueous gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel, the steps of which include:

[0019] S1. Solid waste activation pretreatment: Steel slag tailings powder, coal gangue fines and recycled construction waste aggregates are removed of impurities and ground to the target particle size, and then subjected to thermal activation treatment to obtain activated solid waste base material.

[0020] S2. Pre-crosslinked dry mix: Prepare porous silica-coated hafnium carbonitride particles and mix them with calcined attapulgite clay, silica fume powder, mica fragments, and natural magnesite powder to obtain an inorganic modified filler. Put the activated solid waste base material and the inorganic modified filler into a mixer and dry mix for 5-15 minutes at a speed of 20-60 r / min to ensure that the materials are evenly dispersed and obtain a dry mix.

[0021] S3. Preparation of activator slurry: Mix aluminate, active silica sol and composite basic salt with water, stir at 100-300 r / min for 2-10 min, control the temperature of the slurry at 15-35℃, let stand to remove bubbles for 1-5 min to obtain activator slurry.

[0022] S4. Low-temperature crosslinking mixing: Add the dry mixture, activator slurry and functional additives to the mixer, and mix at a speed of 200-500 r / min for 8-20 min; control the material temperature to ≤35℃ and the moisture content to 10-20% during the mixing process to obtain the mixed material;

[0023] S5. Vibration molding: The mixture is evenly filled into the mold, the mold surface is coated with a release agent and then placed on a vibration table. After vibration molding, the surface is smoothed to obtain a blank.

[0024] S6. Demolding after standing: Take the blank and mold together and let it stand for 6-24 hours in an environment with a temperature of 15-35℃ and a relative humidity of 40-80%. Demold after the blank reaches the demolding strength.

[0025] S7. Natural steady-state curing: Place the demolded boards in a well-ventilated area away from direct sunlight, control the temperature at 15-35℃ and the relative humidity at 50-85%, and cure for 7-10 days.

[0026] A further improvement is that, in step S1, the temperature of the thermal activation treatment is 250-300℃, and the time is 1-4h.

[0027] A further improvement lies in the following step S2: the specific operation for preparing porous silica-coated hafnium carbonitride particles is as follows:

[0028] Hafnium carbonitride particles with a particle size of 2-3 μm were subjected to surface activation treatment;

[0029] A porous silica layer was coated onto the surface of hafnium carbonitride particles using the sol-gel method to obtain the coated body.

[0030] Add KH-550 coupling agent to an ethanol aqueous solution with a volume fraction of 60-80% at a ratio of 1g:8-10mL, and stir for 40-60min to obtain the treatment solution;

[0031] The coating is dispersed in 10-15 times its mass of ethanol and heated to 75-80°C. The treatment solution is then added dropwise, and the mass ratio of KH-550 coupling agent to hafnium carbonitride particles is controlled at 1:10-15. The mixture is refluxed for 4-6 hours. Finally, the mixture is centrifuged, washed, and vacuum dried to obtain porous silica-coated hafnium carbonitride particles.

[0032] A further improvement is that the surface activation treatment refers to: adding hafnium carbonitride particles to 8-12 times their mass of ethanol, ultrasonically dispersing for 20-30 minutes, then adding glacial acetic acid to adjust the pH to 4.0-4.5, stirring at 55-65℃ for 1-2 hours, and finally centrifuging, washing, and vacuum drying.

[0033] A further improvement is that the sol-gel method refers to: dispersing hafnium carbonitride particles in ethanol, adding hexadecyltrimethylammonium bromide and stirring to dissolve, then adding water and ammonia water in sequence and stirring for 15-25 min, then adding tetraethyl orthosilicate dropwise at a rate of 2-4 mL / min, reacting at 40-50℃ for 4-6 h, then aging at 58-62℃ for 8-12 h, centrifuging and washing, dispersing the obtained product in a 1:1 volume ratio ethanol / hydrochloric acid mixture, stirring at 55-65℃ for 4-6 h, repeating 2-3 times, and finally washing and drying.

[0034] In this process, for every 100g of hafnium carbonitride particles, the amount of ethanol used is 1500-2000mL, the amount of hexadecyltrimethylammonium bromide used is 3-5g, the amount of water used is 80-100mL, the amount of ammonia used is 20-30mL, the amount of tetraethyl orthosilicate used is 40-60mL, and the amount of ethanol / hydrochloric acid mixture used is 1000-1500mL.

[0035] A further improvement is that, in step S5, the vibration frequency of the vibration molding is 20-40Hz, the vibration time is 2-6min, and the amplitude is 0.3-1.5mm.

[0036] The beneficial effects of this invention are as follows:

[0037] (1) The base material of this invention adopts a gradient-graded bulk solid waste, uses water as a dispersion medium, and spontaneously forms a gel network through a self-developed ternary inorganic crosslinking activator, namely an interpenetrating network of aluminosilicate gel + magnesium hydrate gel. Without heating, pressurization, or adhesives, the natural magnesite powder and solid waste base material are chemically modified, thereby giving the non-fired ceramic decorative board excellent structural strength and durability.

[0038] (2) The final decorative board product of the present invention has the characteristics of being water-based, formaldehyde-free, TVOC-free, Class A flame retardant, low water absorption rate, moisture-resistant and non-alkali-returning. It is specially used for high-end indoor and outdoor decoration, outdoor landscape, humid environment and high flame retardant scene. It is different from traditional natural stone, ceramic board and ordinary non-fired building materials. It has comprehensive advantages such as environmental protection, high strength, water resistance and heat resistance, and realizes the high-value reuse of solid waste.

[0039] (3) This invention also uses porous silica-coated hafnium carbonitride particles as a filler for reinforcing and modifying the plate for the first time. Its coating layer can effectively reduce the density difference between the particles and the base material, reduce particle sedimentation, and facilitate dispersion. Its porous structure and coupling agent surface treatment can improve the interface anchoring effect with the base material, ultimately resulting in a significant increase in the strength of the plate. In addition, with reasonable dosage, it overcomes the problem caused by the excessive hardness of hafnium carbonitride itself and improves processability. Attached Figure Description

[0040] Figure 1 SEM image of porous silica-coated hafnium carbonitride particles. Detailed Implementation

[0041] The present application will now be described in further detail with reference to the accompanying drawings. It should be noted that the following specific embodiments are only used to further illustrate the present application and should not be construed as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application based on the above application content.

[0042] I. Main Materials

[0043] Table 1: Main Components of Solid Waste Base Material (wt%)

[0044] solid waste <![CDATA[SiO2]]> <![CDATA[Al2O3]]> <![CDATA[Fe2O3]]> CaO MgO Steel slag tailings 22.6% 17.4% 3.7% 26.4% 3.2% Coal gangue fines 52.3% 23.7% 10.2% 1.7% 1.9% Recycled aggregate from construction waste 31.6% 12.5% 4.1% 40.8% 5.3%

[0045] Unless otherwise specified, all other ingredients are commercially available products.

[0046] II. Conducting the Experiment

[0047] Example 1

[0048] A water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel, wherein the raw materials of the decorative panel, by weight, include:

[0049] Solid waste base material: 60 parts;

[0050] Inorganic modified filler: 25 parts;

[0051] Inorganic crosslinking activator: 6 parts;

[0052] Functional additives: 1 part;

[0053] Water: 3 parts;

[0054] The solid waste base material is composed of steel slag tailings powder with a particle size of 0.02 mm, coal gangue fines with a particle size of 0.2 mm, and recycled construction waste aggregate with a particle size of 1 mm, in a gradient gradation ratio of 10:8:18. The inorganic modified filler includes calcined attapulgite, silica fume powder, mica fragments, natural magnesite powder, and porous silica-coated hafnium carbonitride particles, in a mass ratio of 7:5:1:2:2.5. The inorganic crosslinking activator includes sodium aluminate, acidic silica sol, and composite basic salt (mixed in equal mass ratios of sodium carbonate and potassium carbonate at 1:1), in a mass ratio of 3:2:3. The functional additives include alkylsilane hydrophobic agent (using n-octyltriethoxysilane powder), low-temperature crosslinking regulator (using organoboron crosslinking agent), pre-oxidized polyacrylonitrile short-cut fibers, and mineral-based colorant (using ochre powder), in a mass ratio of 7:5:6:5.

[0055] The preparation method of the aqueous gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel includes the following steps:

[0056] S1. Solid waste activation pretreatment: Steel slag tailings powder, coal gangue fines and recycled construction waste aggregates are removed of impurities and ground to the target particle size, and then subjected to thermal activation treatment (250℃, 4h) to obtain activated solid waste base material.

[0057] S2. Pre-crosslinked dry mix: Porous silica-coated hafnium carbonitride particles are prepared and mixed with calcined attapulgite clay, silica fume powder, mica fragments and natural magnesite powder to obtain inorganic modified filler. The activated solid waste base material and inorganic modified filler are put into a mixer and dry-mixed at 20 r / min for 15 min to ensure uniform dispersion of each material and obtain dry mix.

[0058] The specific steps for preparing porous silica-coated hafnium carbonitride particles are as follows:

[0059] Hafnium carbonitride particles with a particle size of about 2 μm were subjected to surface activation treatment. Specifically, the hafnium carbonitride particles were added to 8 times their mass of ethanol, ultrasonically dispersed for 20 min, then glacial acetic acid was added to adjust the pH to 4.0, and stirred at 55℃ for 2 h. Finally, the particles were centrifuged, washed, and vacuum dried.

[0060] A porous silica layer was coated onto the surface of hafnium carbonitride particles using the sol-gel method to obtain the coated body, specifically:

[0061] Hafnium carbonitride particles were dispersed in ethanol, and hexadecyltrimethylammonium bromide was added and stirred to dissolve. Water and ammonia were then added sequentially and stirred for 15 min. Tetraethyl orthosilicate was added dropwise at a rate of 2 mL / min. The reaction was carried out at 40 °C for 6 h, and then aged at 58 °C for 12 h. After centrifugation and washing, the resulting product was dispersed in a 1:1 ethanol / hydrochloric acid mixture and stirred at 55 °C for 6 h. This process was repeated twice (referring to the repeated steps of dispersing in the ethanol / hydrochloric acid mixture and stirring, the same below). Finally, the product was washed and dried. The amount of ethanol used per 100 g of hafnium carbonitride particles was 1500 mL, hexadecyltrimethylammonium bromide was 3 g, water was 80 mL, ammonia was 20 mL, tetraethyl orthosilicate was 40 mL, and the ethanol / hydrochloric acid mixture was 1000 mL (referring to the amount used each time, the same below).

[0062] Add KH-550 coupling agent to a 60% (v / v) ethanol aqueous solution at a ratio of 1g:8mL, and stir for 60min to obtain the treatment solution;

[0063] The coating is dispersed in 10 times its mass of ethanol and heated to 75°C. The treatment solution is then added dropwise, and the mass ratio of KH-550 coupling agent to hafnium carbonitride particles is controlled at 1:10. The mixture is refluxed for 6 hours and then centrifuged, washed, and vacuum dried to obtain porous silica-coated hafnium carbonitride particles.

[0064] S3. Preparation of activator slurry: Mix aluminate, active silica sol and composite basic salt with water, stir at 100 r / min for 10 min, control the temperature of the slurry at 15℃, let stand to remove bubbles for 5 min, and obtain activator slurry.

[0065] S4. Low-temperature crosslinking mixing: Add the dry mixture, activator slurry and functional additives to the mixer and mix at 200 r / min for 20 min. Control the material temperature to ≤35℃ and the moisture content to 10% during the mixing process to obtain the mixed material.

[0066] S5. Vibration molding: The mixture is evenly filled into the mold, the mold surface is coated with a release agent and then placed on a vibration table. After vibration molding, the surface is smoothed to obtain a blank. The vibration frequency of vibration molding is 20Hz, the vibration time is 6min, and the amplitude is 0.3mm.

[0067] S6. Demolding after standing: Take the blank and mold together and let it stand for 24 hours in an environment with a temperature of 15℃ and a relative humidity of 40%. Demold after the blank reaches the demolding strength.

[0068] S7. Natural steady-state curing: Place the demolded boards in a well-ventilated area away from direct sunlight, control the temperature at 15℃ and the relative humidity at 50%, and cure for 10 days.

[0069] Example 2

[0070] A water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel, wherein the raw materials of the decorative panel, by weight, include:

[0071] Solid waste base material: 70 parts;

[0072] Inorganic modified filler: 20 parts;

[0073] Inorganic crosslinking activator: 8 parts;

[0074] Functional additives: 3 parts;

[0075] Water: 5 parts;

[0076] The solid waste base material is composed of steel slag tailings powder with a particle size of 0.04 mm, coal gangue fines with a particle size of 0.3 mm, and recycled construction waste aggregate with a particle size of 2 mm, in a gradient gradation ratio of 12:9:16. The inorganic modified filler includes calcined attapulgite, silica fume powder, mica fragments, natural magnesite powder, and porous silica-coated hafnium carbonitride particles, in a mass ratio of 8:6:2:2.5:2. The inorganic crosslinking activator includes potassium aluminate, alkaline silica sol, and composite basic salt (mixed in equal mass ratios of sodium carbonate and potassium silicate at 1:1), in a mass ratio of 4:3:2. The functional additives include alkylsilane hydrophobic agent (using n-octyltriethoxysilane powder), low-temperature crosslinking regulator (using organoboron crosslinking agent), pre-oxidized polyacrylonitrile short-cut fibers, and mineral-based colorant (using ochre powder), in a mass ratio of 8:6:7:4.

[0077] The preparation method of the aqueous gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel includes the following steps:

[0078] S1. Solid waste activation pretreatment: Steel slag tailings powder, coal gangue fines and recycled construction waste aggregates are removed of impurities and ground to the target particle size, and then subjected to thermal activation treatment (280℃, 2h) to obtain activated solid waste base material.

[0079] S2. Pre-crosslinked dry mix: Porous silica-coated hafnium carbonitride particles are prepared and mixed with calcined attapulgite clay, silica fume powder, mica fragments and natural magnesite powder to obtain inorganic modified filler. The activated solid waste base material and inorganic modified filler are put into a mixer and dry-mixed at 40 r / min for 10 min to ensure uniform dispersion of each material and obtain dry mix.

[0080] The specific steps for preparing porous silica-coated hafnium carbonitride particles are as follows:

[0081] Hafnium carbonitride particles with a particle size of 2.5 μm were surface activated by adding the hafnium carbonitride particles to 10 times their mass of ethanol, ultrasonically dispersing for 25 min, then adding glacial acetic acid to adjust the pH to 4.2, stirring at 60 °C for 1.5 h, and finally centrifuging, washing, and vacuum drying.

[0082] A porous silica layer was coated onto the surface of hafnium carbonitride particles using the sol-gel method to obtain the coated body, specifically:

[0083] Hafnium carbonitride particles were dispersed in ethanol, and hexadecyltrimethylammonium bromide was added and stirred to dissolve. Water and ammonia were then added sequentially and stirred for 20 min. Tetraethyl orthosilicate was added dropwise at a rate of 3 mL / min. The mixture was reacted at 45 °C for 5 h, then aged at 60 °C for 10 h. After centrifugation and washing, the resulting product was dispersed in a 1:1 (v / v) ethanol / hydrochloric acid mixture and stirred at 60 °C for 5 h. This process was repeated three times. Finally, the mixture was washed and dried. The proportions were as follows: per 100 g of hafnium carbonitride particles, the amount of ethanol used was 1800 mL, the amount of hexadecyltrimethylammonium bromide used was 4 g, the amount of water used was 90 mL, the amount of ammonia used was 25 mL, the amount of tetraethyl orthosilicate used was 50 mL, and the amount of the ethanol / hydrochloric acid mixture used was 1200 mL.

[0084] Take KH-550 coupling agent and add it to a 70% (v / v) ethanol aqueous solution at a ratio of 1g:9mL, and stir for 50min to obtain the treatment solution;

[0085] The coating was dispersed in 12 times its mass of ethanol and heated to 78°C. The treatment solution was then added dropwise, and the mass ratio of KH-550 coupling agent to hafnium carbonitride particles was controlled at 1:14. The mixture was refluxed for 5 hours and then centrifuged, washed, and vacuum dried to obtain porous silica-coated hafnium carbonitride particles.

[0086] The microstructure of porous silica-coated hafnium carbonitride particles was scanned using a FEI Quanta 200 scanning electron microscope, such as... Figure 1 As shown, the particles are generally spherical with good coating effect and good dispersion, without obvious agglomeration. In addition, the particle surface has a porous network structure with uniform pore distribution.

[0087] S3. Preparation of activator slurry: Mix aluminate, active silica sol and composite basic salt with water, stir at 200 r / min for 2 min, control the temperature of the slurry at 25℃, let stand to remove bubbles for 3 min, and obtain activator slurry.

[0088] S4. Low-temperature crosslinking mixing: Add the dry mixture, activator slurry and functional additives to the mixer and mix at 400 r / min for 15 min. Control the material temperature to ≤35℃ and the moisture content to 15% during the mixing process to obtain the mixed material.

[0089] S5. Vibration molding: The mixture is evenly filled into the mold, the mold surface is coated with a release agent and then placed on a vibration table. After vibration molding, the surface is smoothed to obtain a blank. The vibration frequency of vibration molding is 30Hz, the vibration time is 4min, and the amplitude is 0.8mm.

[0090] S6. Demolding after standing: Take the blank and mold together and let it stand for 18 hours in an environment with a temperature of 25°C and a relative humidity of 60%. Demold after the blank reaches the demolding strength.

[0091] S7. Natural steady-state curing: Place the demolded boards in a well-ventilated area away from direct sunlight, control the temperature at 25℃ and the relative humidity at 65%, and cure for 8 days.

[0092] Example 3

[0093] A water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel, wherein the raw materials of the decorative panel, by weight, include:

[0094] Solid waste base material: 80 parts;

[0095] Inorganic modified filler: 15 parts;

[0096] Inorganic crosslinking activator: 10 parts;

[0097] Functional additives: 5 parts;

[0098] Water: 6 parts;

[0099] The solid waste base material is composed of steel slag tailings powder with a particle size of 0.06 mm, coal gangue fines with a particle size of 0.4 mm, and recycled construction waste aggregate with a particle size of 3 mm, in a gradient gradation ratio of 14:10:15. The inorganic modified filler includes calcined attapulgite, silica fume powder, mica fragments, natural magnesite powder, and porous silica-coated hafnium carbonitride particles, in a mass ratio of 9:7:3:3:1.5. The inorganic crosslinking activator includes sodium aluminate, acidic silica sol, and composite basic salt (mixed in equal mass ratios of sodium carbonate and sodium hydroxide in a 1:1 ratio), in a mass ratio of 5:4:1. The functional additives include alkylsilane hydrophobic agent (using n-octyltriethoxysilane powder), low-temperature crosslinking regulator (using organoboron crosslinking agent), pre-oxidized polyacrylonitrile short-cut fibers, and mineral-based colorant (using ochre powder), in a mass ratio of 9:7:8:3.

[0100] The preparation method of the aqueous gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel includes the following steps:

[0101] S1. Solid waste activation pretreatment: Steel slag tailings powder, coal gangue fines and recycled construction waste aggregates are removed and ground to the target particle size, and then subjected to thermal activation treatment (300℃, 1h) to obtain activated solid waste base material.

[0102] S2. Pre-crosslinked dry mix: Porous silica-coated hafnium carbonitride particles are prepared and mixed with calcined attapulgite clay, silica fume powder, mica fragments and natural magnesite powder to obtain inorganic modified filler. The activated solid waste base material and inorganic modified filler are put into a mixer and dry-mixed at 60 r / min for 5 min to ensure uniform dispersion of each material and obtain dry mix.

[0103] The specific steps for preparing porous silica-coated hafnium carbonitride particles are as follows:

[0104] Hafnium carbonitride particles with a particle size of 3 μm were subjected to surface activation treatment. Specifically, the hafnium carbonitride particles were added to 12 times their mass of ethanol, ultrasonically dispersed for 30 min, then glacial acetic acid was added to adjust the pH to 4.5, and stirred at 65℃ for 1 h. Finally, the particles were centrifuged, washed, and vacuum dried.

[0105] A porous silica layer was coated onto the surface of hafnium carbonitride particles using the sol-gel method to obtain the coated body, specifically:

[0106] Hafnium carbonitride particles were dispersed in ethanol, and hexadecyltrimethylammonium bromide was added and stirred to dissolve. Water and ammonia were then added sequentially and stirred for 25 min. Tetraethyl orthosilicate was added dropwise at a rate of 4 mL / min. The reaction was carried out at 50 °C for 6 h, and then the temperature was raised to 62 °C for aging for 8 h. After centrifugation and washing, the resulting product was dispersed in a 1:1 volume ratio ethanol / hydrochloric acid mixture and stirred at 65 °C for 4 h. This process was repeated 3 times. Finally, the product was washed and dried. The amount of ethanol used per 100 g of hafnium carbonitride particles was 2000 mL, hexadecyltrimethylammonium bromide was 5 g, water was 100 mL, ammonia was 30 mL, tetraethyl orthosilicate was 60 mL, and the ethanol / hydrochloric acid mixture was 1500 mL.

[0107] Add KH-550 coupling agent to an 80% (v / v) aqueous ethanol solution at a ratio of 1g:10mL and stir for 40min to obtain the treatment solution;

[0108] The coating is dispersed in 15 times its mass of ethanol and heated to 80°C. The treatment solution is then added dropwise, and the mass ratio of KH-550 coupling agent to hafnium carbonitride particles is controlled at 1:15. The mixture is refluxed for 4 hours, and finally centrifuged, washed, and vacuum dried to obtain porous silica-coated hafnium carbonitride particles.

[0109] S3. Preparation of activator slurry: Mix aluminate, active silica sol and composite basic salt with water, stir at 300 r / min for 2 min, control the temperature of the slurry at 35℃, let stand to remove bubbles for 1 min, and obtain activator slurry.

[0110] S4. Low-temperature crosslinking mixing: Add the dry mixture, activator slurry and functional additives to the mixer and mix at a speed of 500 r / min for 8 min. Control the material temperature to ≤35℃ and the moisture content to 20% during the mixing process to obtain the mixed material.

[0111] S5. Vibration molding: The mixture is evenly filled into the mold, the mold surface is coated with a release agent and then placed on a vibration table. After vibration molding, the surface is smoothed to obtain a blank. The vibration frequency of vibration molding is 40Hz, the vibration time is 2min, and the amplitude is 1.5mm.

[0112] S6. Demolding after standing: Take the blank and mold together and let it stand for 6 hours in an environment with a temperature of 35℃ and a relative humidity of 80%. Demold after the blank reaches the demolding strength.

[0113] S7. Natural steady-state curing: Place the demolded boards in a well-ventilated area away from direct sunlight, control the temperature at 35℃ and the relative humidity at 85%, and cure for 7 days.

[0114] Comparative Example 1

[0115] A water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel, wherein the raw materials of the decorative panel, by weight, include:

[0116] Solid waste base material: 70 parts;

[0117] Inorganic modified filler: 20 parts;

[0118] Inorganic crosslinking activator: 8 parts;

[0119] Functional additives: 3 parts;

[0120] Water: 5 parts;

[0121] The solid waste base material is composed of steel slag tailings powder with a particle size of 0.3 mm, coal gangue fines with a particle size of 0.3 mm, and recycled construction waste aggregate with a particle size of 0.3 mm, in a gradient gradation ratio of 12:9:16. The inorganic modified filler includes calcined attapulgite, silica fume powder, mica fragments, natural magnesite powder, and porous silica-coated hafnium carbonitride particles, in a mass ratio of 8:6:2:2.5:2. The inorganic crosslinking activator includes potassium aluminate, alkaline silica sol, and composite basic salt (mixed in equal mass ratios of sodium carbonate and potassium silicate at 1:1), in a mass ratio of 4:3:2. The functional additives include alkylsilane hydrophobic agent (using n-octyltriethoxysilane powder), low-temperature crosslinking regulator (using organoboron crosslinking agent), pre-oxidized polyacrylonitrile short-cut fibers, and mineral-based colorant (using ochre powder), in a mass ratio of 8:6:7:4.

[0122] The preparation method of the water-based gel modified magnesium oxide-based solid waste non-fired ceramic decorative board is the same as that in Example 2.

[0123] Comparative Example 2

[0124] A water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel, wherein the raw materials of the decorative panel, by weight, include:

[0125] Solid waste base material: 70 parts;

[0126] Inorganic modified filler: 20 parts;

[0127] Inorganic crosslinking activator: 8 parts;

[0128] Functional additives: 3 parts;

[0129] Water: 5 parts;

[0130] The solid waste base material consists of steel slag tailings powder with a particle size of 0.04 mm, coal gangue fines with a particle size of 0.3 mm, and recycled construction waste aggregate with a particle size of 2 mm, in a mass ratio of 12:9:16. The inorganic modified filler includes calcined attapulgite clay, silica fume powder, mica fragments, natural magnesite powder, and porous silica-coated hafnium carbonitride particles, in a mass ratio of 8:6:2:2.5:2. The inorganic crosslinking activator is potassium aluminate as a single component. The functional additives include alkylsilane hydrophobic agent (selected as n-octyltriethoxysilane powder), low-temperature crosslinking regulator (selected as organoboron crosslinking agent), pre-oxidized polyacrylonitrile short-cut fibers, and mineral-based colorant (selected as ochre powder), in a mass ratio of 8:6:7:4.

[0131] The preparation method of the water-based gel modified magnesium oxide-based solid waste non-fired ceramic decorative board is the same as that in Example 2.

[0132] Comparative Example 3

[0133] A water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel, wherein the raw materials of the decorative panel, by weight, include:

[0134] Solid waste base material: 70 parts;

[0135] Inorganic modified filler: 20 parts;

[0136] Inorganic crosslinking activator: 8 parts;

[0137] Functional additives: 3 parts;

[0138] Water: 5 parts;

[0139] The solid waste base material is composed of steel slag tailings powder with a particle size of 0.04 mm, coal gangue fines with a particle size of 0.3 mm, and recycled construction waste aggregate with a particle size of 2 mm, in a gradient gradation ratio of 12:9:16. The inorganic modified filler includes calcined attapulgite, silica fume powder, mica fragments, natural magnesite powder, and commercially available hafnium carbonitride particles, in a mass ratio of 8:6:2:2.5:2. The inorganic crosslinking activator includes potassium aluminate, alkaline silica sol, and composite basic salt (mixed in equal mass ratios of sodium carbonate and potassium silicate at 1:1), in a mass ratio of 4:3:2. The functional additives include alkylsilane hydrophobic agent (using n-octyltriethoxysilane powder), low-temperature crosslinking regulator (using organoboron crosslinking agent), pre-oxidized polyacrylonitrile short-cut fibers, and mineral-based colorant (using ochre powder), in a mass ratio of 8:6:7:4.

[0140] The preparation method of the aqueous gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel includes the following steps:

[0141] S1. Solid waste activation pretreatment: Steel slag tailings powder, coal gangue fines and recycled construction waste aggregates are removed of impurities and ground to the target particle size, and then subjected to thermal activation treatment (280℃, 2h) to obtain activated solid waste base material.

[0142] S2. Pre-crosslinked dry mix: Take hafnium carbonitride particles and calcined attapulgite clay, silica fume powder, mica fragments and natural magnesite powder to obtain inorganic modified filler. Put the activated solid waste base material and inorganic modified filler into a mixer and dry mix for 10 minutes at a speed of 40 r / min to make the materials evenly dispersed and obtain dry mix.

[0143] S3. Preparation of activator slurry: Mix aluminate, active silica sol and composite basic salt with water, stir at 200 r / min for 2 min, control the temperature of the slurry at 25℃, let stand to remove bubbles for 3 min, and obtain activator slurry.

[0144] S4. Low-temperature crosslinking mixing: Add the dry mixture, activator slurry and functional additives to the mixer and mix at 400 r / min for 15 min. Control the material temperature to ≤35℃ and the moisture content to 15% during the mixing process to obtain the mixed material.

[0145] S5. Vibration molding: The mixture is evenly filled into the mold, the mold surface is coated with a release agent and then placed on a vibration table. After vibration molding, the surface is smoothed to obtain a blank. The vibration frequency of vibration molding is 30Hz, the vibration time is 4min, and the amplitude is 0.8mm.

[0146] S6. Demolding after standing: Take the blank and mold together and let it stand for 18 hours in an environment with a temperature of 25°C and a relative humidity of 60%. Demold after the blank reaches the demolding strength.

[0147] S7. Natural steady-state curing: Place the demolded boards in a well-ventilated area away from direct sunlight, control the temperature at 25℃ and the relative humidity at 65%, and cure for 8 days.

[0148] Comparative Example 4

[0149] A water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel, wherein the raw materials of the decorative panel, by weight, include:

[0150] Solid waste base material: 70 parts;

[0151] Inorganic modified filler: 20 parts;

[0152] Inorganic crosslinking activator: 8 parts;

[0153] Functional additives: 3 parts;

[0154] Water: 5 parts;

[0155] The solid waste base material is composed of steel slag tailings powder with a particle size of 0.04 mm, coal gangue fines with a particle size of 0.3 mm, and recycled construction waste aggregate with a particle size of 2 mm, in a gradient gradation ratio of 12:9:16. The inorganic modified filler includes calcined attapulgite, silica fume powder, mica fragments, and natural magnesite powder, in a mass ratio of 8:6:2:2.5. The inorganic crosslinking activator includes potassium aluminate, alkaline silica sol, and composite basic salt (mixed in equal mass ratios of sodium carbonate and potassium silicate at 1:1), in a mass ratio of 4:3:2. The functional additives include alkylsilane hydrophobic agent (using n-octyltriethoxysilane powder), low-temperature crosslinking regulator (using organoboron crosslinking agent), pre-oxidized polyacrylonitrile short-cut fibers, and mineral-based colorant (using ochre powder), in a mass ratio of 8:6:7:4.

[0156] The preparation method of the aqueous gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel includes the following steps:

[0157] S1. Solid waste activation pretreatment: Steel slag tailings powder, coal gangue fines and recycled construction waste aggregates are removed of impurities and ground to the target particle size, and then subjected to thermal activation treatment (280℃, 2h) to obtain activated solid waste base material.

[0158] S2. Pre-crosslinked dry mix: Take calcined attapulgite clay, silica fume powder, mica fragments and natural magnesite powder and mix them to obtain inorganic modified filler. Put the activated solid waste base material and inorganic modified filler into a mixer and dry mix for 10 minutes at a speed of 40 r / min to make the materials evenly dispersed and obtain dry mix.

[0159] S3. Preparation of activator slurry: Mix aluminate, active silica sol and composite basic salt with water, stir at 200 r / min for 2 min, control the temperature of the slurry at 25℃, let stand to remove bubbles for 3 min, and obtain activator slurry.

[0160] S4. Low-temperature crosslinking mixing: Add the dry mixture, activator slurry and functional additives to the mixer and mix at 400 r / min for 15 min. Control the material temperature to ≤35℃ and the moisture content to 15% during the mixing process to obtain the mixed material.

[0161] S5. Vibration molding: The mixture is evenly filled into the mold, the mold surface is coated with a release agent and then placed on a vibration table. After vibration molding, the surface is smoothed to obtain a blank. The vibration frequency of vibration molding is 30Hz, the vibration time is 4min, and the amplitude is 0.8mm.

[0162] S6. Demolding after standing: Take the blank and mold together and let it stand for 18 hours in an environment with a temperature of 25°C and a relative humidity of 60%. Demold after the blank reaches the demolding strength.

[0163] S7. Natural steady-state curing: Place the demolded boards in a well-ventilated area away from direct sunlight, control the temperature at 25℃ and the relative humidity at 65%, and cure for 8 days.

[0164] S8. Take the decorative board obtained after curing and apply a conventional spraying process to spray a porous silica-coated hafnium carbonitride particle coating on both surfaces of the board. The preparation method and amount of the porous silica-coated hafnium carbonitride particles used in the coating are the same as in Example 2.

[0165] III. Performance Testing

[0166] (1) Bending strength

[0167] Referring to GB / T 4741-1999 "Test Method for Bending Strength of Ceramic Materials", the bending strength was tested using a Xi'an LCSC WDW-10 universal testing machine. Specifically, the decorative panels prepared in Examples 1-3 and Comparative Examples 1-4 were cut into cuboid samples with a length of 120 mm and a width-to-thickness ratio of 1:1. The samples were placed in an oven at 110℃ ± 5℃ and dried to constant weight. Then, they were cooled to room temperature in a desiccator. The samples were then placed on support blades, and the distance between the blades was adjusted so that the length of the sample outside the blades was 10 mm. The two support blades must be in the same plane and parallel to each other, with the loading blade positioned in the center of the two blades. The bending strength testing machine was then turned on. Care was taken to avoid impact when the loading blades contacted the sample. A constant load was applied at an average speed of 30 N / s until failure. The maximum load at failure was recorded, and the width and thickness of the fracture point were measured with calipers to an accuracy of 0.1 mm. Finally, the flexural strength of each sample was calculated using the following formula:

[0168]

[0169] In the formula, δ is the bending strength, MPa; F is the load at which the sample breaks, N; L is the distance between the supporting blades, mm; b is the width of the sample fracture, mm; and h is the thickness of the sample fracture, mm.

[0170] (2) Water absorption rate

[0171] Referring to the standard "ISO 9425:1989 Determination of Moisture Content in Wood-based Panels", the decorative panels prepared in Examples 1-3 and Comparative Examples 1-4 were first cut into 100mm × 100mm × 10mm samples and placed in a room temperature environment of 20℃±2℃ and relative humidity of 65%±5%. The samples were weighed using a balance and recorded as m1. Then, the samples were immersed in water with a pH of 7 and a temperature of 20℃±2℃ for 24h±15min. Next, the samples were removed, the surface was wiped with absorbent paper, and weighed again using a balance and recorded as m2 (the test process was completed within 10 minutes). Finally, the water absorption rate W of each sample was calculated using the following formula:

[0172]

[0173] (3) Heat resistance

[0174] These decorative panels generally possess excellent flame-retardant properties. However, in high-temperature environments, significant thermal expansion can lead to further distortion, deformation, and detachment, failing to meet application requirements in terms of reliability and safety. Therefore, this study will test the expansion rate of the decorative panels in high-temperature environments to verify their heat resistance. The specific testing procedure is as follows: First, the decorative panels prepared in Examples 1-3 and Comparative Examples 1-4 are cut into 100mm×100mm×20mm samples. The initial sample thickness L0 (20mm in this case) is measured and recorded using a US-50 thickness gauge. Then, the samples are fired in an electric heating oven at 350℃ for 10 minutes. After the samples have fully expanded, the sample thickness L is measured and recorded. Finally, the expansion ratio η of each sample is calculated using the following formula:

[0175]

[0176] IV. Results Analysis

[0177] The test results for flexural strength, water absorption, and heat resistance are summarized in Table 2 below:

[0178] Table 2: Performance Test Results

[0179] Group Flexural strength / MPa Water absorption rate / % Heat resistance (ratio of thermal expansion) / % Example 1 34.1 2.35 0.95 Example 2 32.9 2.29 0.84 Example 3 31.4 2.47 0.88 Comparative Example 1 25.5 6.11 0.93 Comparative Example 2 21.8 10.65 1.26 Comparative Example 3 26.4 2.23 0.86 Comparative Example 4 26.2 2.07 0.82

[0180] As can be seen from Table 2 above, the water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panels prepared in Examples 1-3 of the present invention exhibit excellent performance in terms of bending strength, water absorption rate, and heat resistance. Among them, the bending strength reaches more than 31.4 MPa, the water absorption rate is less than 2.47%, and the thermal expansion rate is less than 0.95%.

[0181] Comparative Examples 1-4 were all based on Example 2 with process adjustments. Comparative Example 1 did not use graded solid waste base material (uniform particle size 0.3mm), which resulted in poor internal density of the board, increased porosity, and a significant decrease in flexural strength, a significant increase in water absorption, and an increase in thermal expansion rate. Comparative Example 2 used only a single-component inorganic crosslinking activator (potassium aluminate), resulting in insufficient crosslinking, a loose structure, the lowest flexural strength, and the highest water absorption and thermal expansion rate, resulting in the worst overall performance. Comparative Example 3 used ordinary hafnium carbonitride particles instead of porous silica-coated hafnium carbonitride particles, which affected the interfacial bonding and dispersion effect, significantly reducing flexural strength, while water absorption and thermal expansion rate remained almost unchanged. Comparative Example 4 used a spray coating method to add porous silica-coated hafnium carbonitride particles, resulting in a lack of reinforcing phase inside the board, significantly reducing flexural strength. However, the dense coating reduced water absorption to some extent, resulting in a slight decrease in water absorption and thermal expansion rate, with minimal impact.

[0182] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively 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.

Claims

1. A water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel, characterized in that, The raw materials of the decorative panel, by weight, include: Solid waste base material: 60-80 parts; Inorganic modified filler: 15-25 parts; Inorganic crosslinking activator: 6-10 parts; Functional additives: 1-5 parts; Water: 3-6 parts; The solid waste base material is composed of steel slag tailings with a particle size of 0.02-0.06 mm, coal gangue fines with a particle size of 0.2-0.4 mm, and recycled construction waste aggregates with a particle size of 1-3 mm in a graded distribution. The inorganic modified filler includes calcined attapulgite, silica fume powder, mica fragments, natural magnesite powder, and porous silica-coated hafnium carbonitride particles. The inorganic crosslinking activator includes aluminates, active silica sol, and composite basic salts.

2. The water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel according to claim 1, characterized in that, The mass ratio of steel slag tailings, coal gangue fines, and recycled construction waste aggregate in the solid waste base material is 10-14:8-10:15-18. The mass ratio of calcined attapulgite clay, silica fume powder, mica fragments, natural magnesite powder, and porous silica-coated hafnium carbonitride particles in the inorganic modified filler is 7-9:5-7:1-3:2-3:1.5-2.

5. The mass ratio of aluminate, active silica sol, and composite basic salt in the inorganic crosslinking activator is 3-5:2-4:1-3.

3. The water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel according to claim 1, characterized in that, The aluminate is sodium aluminate or potassium aluminate, the active silica sol is acidic silica sol or alkaline silica sol, and the composite basic salt is at least two of sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, and potassium hydroxide.

4. The water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel according to claim 1, characterized in that, The functional additives include alkylsilane hydrophobic agents, low-temperature crosslinking regulators, pre-oxidized polyacrylonitrile short fibers, and mineral-based colorants, with a mass ratio of 7-9:5-7:6-8:3-5.

5. A method for preparing aqueous gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panels as described in any one of claims 1-4, characterized in that the steps include... include: S1. Solid waste activation pretreatment: Steel slag tailings powder, coal gangue fines and recycled construction waste aggregates are removed of impurities and ground to the target particle size, and then subjected to thermal activation treatment to obtain activated solid waste base material. S2. Pre-crosslinked dry mix: Prepare porous silica-coated hafnium carbonitride particles and mix them with calcined attapulgite clay, silica fume powder, mica fragments, and natural magnesite powder to obtain an inorganic modified filler. Put the activated solid waste base material and the inorganic modified filler into a mixer and dry mix for 5-15 minutes at a speed of 20-60 r / min to ensure that the materials are evenly dispersed and obtain a dry mix. S3. Preparation of activator slurry: Mix aluminate, active silica sol and composite basic salt with water, stir at 100-300 r / min for 2-10 min, control the temperature of the slurry at 15-35℃, let stand to remove bubbles for 1-5 min to obtain activator slurry. S4. Low-temperature crosslinking mixing: Add the dry mixture, activator slurry and functional additives to the mixer, and mix at a speed of 200-500 r / min for 8-20 min; control the material temperature to ≤35℃ and the moisture content to 10-20% during the mixing process to obtain the mixed material; S5. Vibration molding: The mixture is evenly filled into the mold, the mold surface is coated with a release agent and then placed on a vibration table. After vibration molding, the surface is smoothed to obtain a blank. S6. Demolding after standing: Take the blank and mold together and let it stand for 6-24 hours in an environment with a temperature of 15-35℃ and a relative humidity of 40-80%. Demold after the blank reaches the demolding strength. S7. Natural steady-state curing: Place the demolded boards in a well-ventilated area away from direct sunlight, control the temperature at 15-35℃ and the relative humidity at 50-85%, and cure for 7-10 days.

6. The preparation method of the aqueous gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel according to claim 5, characterized in that, In step S1, the temperature of the thermal activation treatment is 250-300℃, and the time is 1-4h.

7. The preparation method of the aqueous gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel according to claim 5, characterized in that, In step S2, the specific operation for preparing porous silica-coated hafnium carbonitride particles is as follows: Hafnium carbonitride particles with a particle size of 2-3 μm were subjected to surface activation treatment; A porous silica layer was coated onto the surface of hafnium carbonitride particles using the sol-gel method to obtain the coated body. Add KH-550 coupling agent to an ethanol aqueous solution with a volume fraction of 60-80% at a ratio of 1g:8-10mL, and stir for 40-60min to obtain the treatment solution; The coating is dispersed in 10-15 times its mass of ethanol and heated to 75-80°C. The treatment solution is then added dropwise, and the mass ratio of KH-550 coupling agent to hafnium carbonitride particles is controlled at 1:10-15. The mixture is refluxed for 4-6 hours. Finally, the mixture is centrifuged, washed, and vacuum dried to obtain porous silica-coated hafnium carbonitride particles.

8. The method for preparing water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panels according to claim 7, characterized in that, The surface activation treatment refers to: adding hafnium carbonitride particles to 8-12 times their mass of ethanol, ultrasonically dispersing for 20-30 minutes, then adding glacial acetic acid to adjust the pH to 4.0-4.5, stirring at 55-65℃ for 1-2 hours, and finally centrifuging, washing, and vacuum drying.

9. The preparation method of the water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panel according to claim 7, characterized in that, The sol-gel method refers to the following steps: Hafnium carbonitride particles are dispersed in ethanol, hexadecyltrimethylammonium bromide is added and stirred to dissolve, then water and ammonia are added sequentially and stirred for 15-25 min, then tetraethyl orthosilicate is added dropwise at a rate of 2-4 mL / min, the reaction is carried out at 40-50℃ for 4-6 h, then the temperature is raised to 58-62℃ and aged for 8-12 h, centrifuged and washed, the resulting product is dispersed in a 1:1 volume ratio ethanol / hydrochloric acid mixture, stirred at 55-65℃ for 4-6 h, repeated 2-3 times, and finally washed and dried. In this process, for every 100g of hafnium carbonitride particles, the amount of ethanol used is 1500-2000mL, the amount of hexadecyltrimethylammonium bromide used is 3-5g, the amount of water used is 80-100mL, the amount of ammonia used is 20-30mL, the amount of tetraethyl orthosilicate used is 40-60mL, and the amount of ethanol / hydrochloric acid mixture used is 1000-1500mL.

10. The method for preparing water-based gel-modified magnesium oxide-based solid waste non-fired ceramic decorative panels according to claim 5, characterized in that, In step S5, the vibration frequency of the vibration molding is 20-40Hz, the vibration time is 2-6min, and the amplitude is 0.3-1.5mm.

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