A sintering-free porcelainized inorganic artificial stone by secondary excitation process and a preparation method thereof

Abstract

The present application relates to the technical field of artificial stone, especially to the field of C04B28 / 00, and more particularly to a sintering-free vitrification inorganic artificial stone prepared by secondary excitation process and a preparation method thereof. The preparation raw material of the artificial stone comprises 25-60 parts of inorganic gel material, 3-20 parts of adjusting auxiliary material, 2-10 parts of excitation agent 1, 2-10 parts of excitation agent 2, 30-70 parts of aggregate, 0.1-2 parts of additive, and 0.5-2 parts of additive material. The sintering-free vitrification inorganic artificial stone prepared by the secondary excitation process avoids the use of organic adhesive, can effectively improve the mechanical properties and high-temperature resistance of the material, reduces the pollution to the environment, and has good practical application prospect.

Description

Technical Field

[0001] This invention relates to the field of artificial stone technology, particularly to the field of C04B28 / 00, and more specifically to a secondary activation process for non-sintering vitrified inorganic artificial stone and its preparation method. Background Technology

[0002] With the increasing scarcity of building stone resources and the dual policy guidance of "transformation and upgrading" and "environmental protection" in the traditional construction industry, the production of pure natural stone has been significantly affected, leading to rising costs and prices. Therefore, artificial stone technology is receiving increasing attention in the building materials sector. Artificial stone is generally divided into two main categories: organic and inorganic. Organic artificial stone is further divided into resin-based and composite types. Resin-based artificial stone uses organic binders as its main raw material, which are mixed with natural marble chips, quartz sand, calcite, stone powder, or other inorganic fillers in a certain proportion, and then functional additives are added. The resulting products have vibrant and rich colors and excellent decorative effects. However, the higher the content of organic adhesive, the more the finished product resembles plastic, losing the natural texture of stone. Organic adhesives also soften and expand easily when heated, leading to significant thermal expansion and contraction, reduced frost resistance and heat resistance. When applied to the ground, the product is prone to bulging and cracking due to environmental changes. Furthermore, organic adhesives are flammable at high temperatures after curing, lowering the fire resistance and safety of the artificial stone, and emitting harmful VOC odors, posing a significant fire hazard. Excessive adhesive also results in low water absorption, preventing moisture from escaping from the bottom and causing it to accumulate at the base of the stone, leading to internal "disease" within the stone. Artificial stone typically includes organic pigments and other colorants to improve its appearance, but organic pigments have poor resistance to sunlight, heat, and weathering, easily fading over time, especially noticeable outdoors. Organic pigments also lack in terms of safety and environmental friendliness. Traditional inorganic artificial stone is made using cement as the main binder. However, cement production consumes a large amount of resources and energy, and emits large amounts of dust, CO2, CO, and NO. x Toxic and harmful waste gases such as SO2 pollute the ecological environment. The most common hydration products of silicate cement, apart from hydrated calcium silicate gel, include other components such as calcium hydroxide, hydrated calcium aluminate, and ettringite, which are not naturally occurring minerals. These hydration products are physically and chemically active substances that will gradually transform over time or undergo a series of chemical or physical reactions with the environmental medium, thereby adversely affecting the durability of cement-based materials. Silicate cement-based materials have poor volume stability and are prone to cracking, leading to premature structural deterioration.

[0003] Existing technology CN101570413A discloses acrylic artificial stone and its preparation method. The raw materials for preparation include acrylic resin monomers, thickeners, inorganic fillers, curing agents, unsaturated resins, etc. The raw materials are kneaded to obtain acrylic molding compound, and the molding compound is filled and cured to produce acrylic artificial stone. This artificial stone has excellent appearance and performance. Existing technology CN106277920A discloses an artificial stone patterned slab and its production method. The raw materials for preparation include resin, curing agents, coupling agents, etc. The resulting product has excellent light stability and weather resistance, bright and rich colors, strong processability, good decorative effect, and the processing process is simple, easy to form, with high slab strength and low production cost. However, the above-mentioned artificial stone raw materials contain a lot of organic resin, which will significantly affect the material's high temperature resistance, water absorption rate, mechanical strength, etc., thus limiting its practical application range. Summary of the Invention

[0004] To address the aforementioned problems, the first aspect of this invention provides a secondary activation process for non-sintering vitrified inorganic artificial stone, the raw materials of which, by mass parts, include: 25-60 parts inorganic gel material, 3-20 parts adjusting auxiliary materials, 2-10 parts activator 1, 2-10 parts activator 2, 30-70 parts aggregate, 0.1-2 parts additives, and 0.5-2 parts additives.

[0005] More preferably, the mass ratio of activator 1 to activator 2 is (1-3):1.

[0006] More preferably, the mass ratio of activator 1 to activator 2 is (1.5-2.5):1; as an implementable example, the mass ratio of activator 1 to activator 2 can be one of 3:2, 2:1 or 5:2.

[0007] Preferably, the activator 1 is an alkaline activator.

[0008] More preferably, the alkaline activator includes one or more of potassium silicate, sodium silicate, sodium sulfate, calcium sulfate, sodium hydroxide, and potassium hydroxide.

[0009] Preferably, the activator 2 is a phosphate activator.

[0010] More preferably, the phosphate activator includes one or more of the following: ammonium phosphate, potassium dihydrogen phosphate, potassium trihydrogen phosphate, potassium tetrahydrogen phosphate, aluminum dihydrogen phosphate, trisodium phosphate, sodium phosphate, sodium dihydrogen phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, aluminum tetrahydrogen phosphate, magnesium phosphate, and copper phosphate.

[0011] More preferably, the phosphate activator includes one or more of ammonium phosphate, aluminum dihydrogen phosphate, and trisodium phosphate.

[0012] Preferably, the inorganic gel material is an active mineral.

[0013] More preferably, the active minerals include one or more of the following: slag powder, fly ash, metakaolinite, silica fume, and active coal gangue powder.

[0014] Preferably, the conditioning additives include one or more of silica fume, nano-silica, and aluminum oxide.

[0015] Preferably, the aggregate includes one or more of the following: quartz sand, steel slag, and silica powder.

[0016] Preferably, the additives include one or more of the following: high-energy water-reducing agents, dispersants, setting regulators, and water-repellent agents.

[0017] More preferably, the high-energy water-reducing agent includes one or more of the following: polycarboxylate-based water-reducing agent, naphthalene-based water-reducing agent, sodium lignosulfonate, calcium lignosulfonate, and melamine.

[0018] More preferably, the dispersant includes one or more of hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and sodium hexametaphosphate.

[0019] More preferably, the setting agent includes one or more of glucose, sodium citrate, tartaric acid, sodium thiosulfate, sodium tripolyphosphate, and trisodium citrate.

[0020] More preferably, the hydrophobic agent includes one or more of the following: organosilicon hydrophobic agents and stearate hydrophobic agents.

[0021] Preferably, the additives include one or more of the following: toughening materials and colorants.

[0022] More preferably, the toughening material includes one or more of glass fiber, polypropylene fiber, and basalt fiber.

[0023] More preferably, the glass fiber includes one or more of the following: alkali-free glass fiber, medium-alkali glass fiber, and high-alkali glass fiber.

[0024] Preferably, the colorant is a metal oxide.

[0025] More preferably, the metal oxide includes one or more of the following: iron oxide, manganese oxide, iron(II,III) oxide, chromium oxide, cobalt oxide, nickel oxide, lead oxide, and zinc oxide.

[0026] The second aspect of this invention provides a method for preparing non-sintering vitrified inorganic artificial stone using a secondary activation process, comprising at least the following steps:

[0027] S1. Initial activation: Mix the inorganic cementitious materials, auxiliary materials and aggregates, and add the additives, auxiliaries, activator 1 and water. Mix evenly and stir at room temperature for 3-10 minutes. Then, carry out thorough mixing and initial activation treatment in a mixer.

[0028] S2, Secondary Activation: After the initial activation, activator 2 is added to the reaction system, and the reaction is stirred for 3-5 minutes.

[0029] S3, Fabric: The material obtained after secondary excitation is evenly distributed on the working surface for uniform fabrication;

[0030] S4. Block Forming: The material after the cloth is laid is formed. Vacuum forming method can be used, with a vacuum degree of -0.09 to 0.1 MPa.

[0031] S5. Curing and maintenance: After the molded material is covered with a film, it is transported to a high-temperature room for curing. The curing temperature is 60-100℃ and the curing time is 2-3 days.

[0032] S6. Cutting: Cut the cured raw blocks to a fixed thickness.

[0033] S7. Polishing: Polish the cut material with a polishing machine to obtain the secondary-excitation process non-sintering vitrified inorganic artificial stone.

[0034] Beneficial effects

[0035] 1. The raw materials prepared in this invention reduce the use of cement clinker, which is beneficial for energy conservation and emission reduction, and environmental protection, while also treating existing tailings waste.

[0036] 2. The non-sintering vitrified inorganic artificial stone produced by the secondary activation process of this invention is different from artificial inorganic stone prepared with cement as the main material. The secondary activation process produces chemical alkali ceramic with a zeolite-like network structure. It is significantly superior to organic and cement-based artificial stone in terms of durability and volume stability.

[0037] 3. In this invention, the initial activation process of alkali activation enables the raw materials to rapidly and fully dissolve silicon-oxygen tetrahedra [SiO4] and aluminum-oxygen tetrahedra [AlO4] under the action of alkali activator. At the same time, the dissolved aluminum-silicon complex diffuses from the surface of solid particles to the interparticle gaps, thereby accelerating the precursor reaction.

[0038] 4. In this invention, a secondary activation process induced by phosphate is used to introduce [PO4] tetrahedral groups during the polymerization reaction. These groups will polymerize with silicon-oxygen tetrahedrons [SiO4] and aluminum-oxygen tetrahedrons [AlO4] to form an oligomer gel phase. Then, the remaining moisture is gradually removed, and the material is solidified and hardened to form a mineral polymer material block with a highly condensed three-dimensional network structure. This process promotes the condensation reaction of the cementitious material by introducing phosphate, resulting in a denser condensate.

[0039] 5. The vitrified inorganic artificial stone produced by this invention does not require a sintering process, which reduces environmental pollution compared to ceramic materials.

[0040] 6. The vitrified inorganic artificial stone provided by this invention has good high temperature resistance. The vitrified inorganic artificial stone itself is an oxide network structure system, which does not oxidize or decompose between 1000℃ and 1200℃. At the same time, the dense oxide network system can isolate air and protect the internal materials from oxidation.

[0041] 7. The vitrified inorganic artificial stone produced by this invention has good durability. On the one hand, it is due to its stable network structure, and on the other hand, it can avoid the alkali-aggregate reaction caused by the migration of metal ions and the reaction of aggregates in ordinary cement. It does not expand (ordinary silicate cement concrete expands by 1.5 mm / m after 200 days due to alkali-aggregate reaction, which is a great safety hazard). Therefore, it has a strong ability to withstand natural damage. Detailed Implementation

[0042] Example 1

[0043] The first aspect of this embodiment provides a secondary activation process for non-sintering vitrified inorganic artificial stone, the raw materials for which are prepared by mass parts are: 40 parts inorganic gel material, 10 parts conditioning auxiliary material, 8 parts activator 1, 6 parts activator 2, 50 parts aggregate, 1 part auxiliary agent, and 1 part additive.

[0044] The inorganic gel material is metakaolin.

[0045] The regulating additive is 100-mesh nano-silica.

[0046] The activator 1 is sodium silicate and sodium hydroxide, with a mass ratio of 3:2.

[0047] The activator 2 is aluminum dihydrogen phosphate.

[0048] The aggregate is steel slag.

[0049] The additives are sodium lignosulfonate (a high-performance water-reducing agent), hydroxypropyl methylcellulose (a dispersant), sodium tripolyphosphate (a setting regulator), and sodium stearate (a water-repellent agent); the mass ratio of sodium lignosulfonate, hydroxypropyl methylcellulose, sodium tripolyphosphate, and sodium stearate is 1:1:1:1.

[0050] The additives are alkali glass fiber as a toughening agent and iron oxide as a colorant, with a mass ratio of 3:2.

[0051] The second aspect of this embodiment provides a method for preparing non-sintering vitrified inorganic artificial stone using a secondary activation process, specifically comprising the following steps:

[0052] S1. Initial activation: Mix the inorganic cementitious materials, auxiliary materials and aggregates, and add the additives, auxiliaries, activator 1 and water. Mix evenly and stir at room temperature (25°C) for 8 minutes. Then, perform thorough mixing and initial activation treatment in a mixer.

[0053] S2, Secondary Activation: After the initial activation, activator 2 is added to the reaction system, and the reaction is stirred for another 5 minutes.

[0054] S3. Fabric: The material obtained after secondary excitation is evenly distributed on the working surface using a scraper.

[0055] S4. Block Forming: The material after the cloth is laid is formed using a vacuum pressing method with a vacuum degree of 0.1MPa.

[0056] S5. Curing and maintenance: After the molded material is covered with a film, it is transported to a high-temperature room for curing at 80℃ for 3 days.

[0057] S6. Cutting: Cut the cured raw blocks to a fixed thickness.

[0058] S7. Polishing: Polish the cut material with a polishing machine to obtain the secondary-excitation process non-sintering vitrified inorganic artificial stone.

[0059] Example 2

[0060] The first aspect of this embodiment provides a secondary activation process for non-sintering vitrified inorganic artificial stone, the raw materials for which are prepared by mass parts are: 25 parts inorganic gel material, 5 parts adjusting auxiliary material, 6 parts activator 1, 3 parts activator 2, 30 parts aggregate, 0.8 parts auxiliary agent, and 0.8 parts additive.

[0061] The inorganic gel material is fly ash.

[0062] The regulating additive is silica fume.

[0063] The activator 1 is calcium sulfate and potassium hydroxide in a mass ratio of 2:3.

[0064] The activator 2 is aluminum dihydrogen phosphate.

[0065] The aggregate is quartz sand.

[0066] The additives are melamine (a high-performance water-reducing agent), hydroxyethyl cellulose (a dispersant), trisodium citrate (a setting regulator), and sodium methylsilicate (a water-repellent agent); the mass ratio of melamine (a high-performance water-reducing agent), hydroxyethyl cellulose (a dispersant), trisodium citrate (a setting regulator), and sodium methylsilicate (a water-repellent agent) is 1:1:1:1.

[0067] The additives are alkali glass fiber as a toughening agent and iron oxide as a colorant, with a mass ratio of 3:2.

[0068] The second aspect of this embodiment provides a method for preparing non-sintering vitrified inorganic artificial stone using a secondary activation process, specifically comprising the following steps:

[0069] S1. Initial activation: Mix the inorganic cementitious materials, auxiliary materials and aggregates, and add the additives, auxiliaries, activator 1 and water. Mix evenly and stir at room temperature (25°C) for 8 minutes. Then, perform thorough mixing and initial activation treatment in a mixer.

[0070] S2, Secondary Activation: After the initial activation, activator 2 is added to the reaction system, and the reaction is stirred for another 5 minutes.

[0071] S3. Fabric: The material obtained after secondary excitation is evenly distributed on the working surface using a scraper.

[0072] S4. Block Forming: The material after the cloth is laid is formed using a vacuum pressing method with a vacuum degree of 0.1MPa.

[0073] S5. Curing and maintenance: After the molded material is covered with a film, it is transported to a high-temperature room for curing at 80℃ for 3 days.

[0074] S6. Cutting: Cut the cured raw blocks to a fixed thickness.

[0075] S7. Polishing: Polish the cut material with a polishing machine to obtain the secondary-excitation process non-sintering vitrified inorganic artificial stone.

[0076] Example 3

[0077] The first aspect of this embodiment provides a secondary activation process for non-sintering vitrified inorganic artificial stone, the raw materials for which are prepared by mass parts are: 60 parts inorganic gel material, 20 parts adjusting auxiliary material, 9 parts activator 1, 6 parts activator 2, 70 parts aggregate, 2 parts auxiliary agent, and 2 parts additive.

[0078] The inorganic gel material is slag powder.

[0079] The regulating additive is aluminum oxide.

[0080] The activator 1 is sodium silicate and sodium hydroxide, with a mass ratio of 3:2.

[0081] The activator 2 is aluminum dihydrogen phosphate.

[0082] The aggregate is silica powder.

[0083] The additives are high-performance water-reducing agent calcium lignosulfonate, dispersant hydroxypropyl methylcellulose, setting regulator trisodium citrate, and water-repellent sodium methylsilicate; the mass ratio of high-performance water-reducing agent calcium lignosulfonate, dispersant hydroxypropyl methylcellulose, setting regulator trisodium citrate, and water-repellent sodium methylsilicate is 1:1:1:1.

[0084] The additives are alkali glass fiber as a toughening agent and iron oxide as a colorant, with a mass ratio of 3:2.

[0085] The second aspect of this embodiment provides a method for preparing non-sintering vitrified inorganic artificial stone using a secondary activation process, specifically comprising the following steps:

[0086] S1. Initial activation: Mix the inorganic cementitious materials, auxiliary materials and aggregates, and add the additives, auxiliaries, activator 1 and water. Mix evenly and stir at room temperature (25°C) for 8 minutes. Then, perform thorough mixing and initial activation treatment in a mixer.

[0087] S2, Secondary Activation: After the initial activation, activator 2 is added to the reaction system, and the reaction is stirred for another 5 minutes.

[0088] S3. Fabric: The material obtained after secondary excitation is evenly distributed on the working surface using a scraper.

[0089] S4. Block Forming: The material after the cloth is laid is formed using a vacuum pressing method with a vacuum degree of 0.1MPa.

[0090] S5. Curing and maintenance: After the molded material is covered with a film, it is transported to a high-temperature room for curing at 80℃ for 3 days.

[0091] S6. Cutting: Cut the cured raw blocks to a fixed thickness.

[0092] S7. Polishing: Polish the cut material with a polishing machine to obtain the secondary-excitation process non-sintering vitrified inorganic artificial stone.

[0093] Comparative Example 1

[0094] The specific implementation method of this comparative example is the same as that of Example 2, except that the mass fraction of activator 1 is 2 parts.

[0095] Comparative Example 2

[0096] The specific implementation method of this comparative example is the same as that of Example 3, except that the raw materials do not include activator 2, and the preparation steps do not include the secondary activation step.

[0097] Comparative Example 3

[0098] The specific implementation method of this comparative example is the same as that of Example 1, except that in the curing and maintenance step, the curing temperature is 40°C and the curing time is 1 day.

[0099] Comparative Example 4

[0100] A cement-based product disclosed in prior art CN111574143A.

[0101] Performance Evaluation

[0102] I. Physical Properties

[0103] Test subjects: Artificial stones obtained in Examples 1-3 and Comparative Examples 1-4

[0104] The test method was based on GB / T 41919-2022, "Artificial Stone Building Slabs", and the results were recorded in Table 1.

[0105] Table 1

[0106]

[0107] II. Durability

[0108] Test subjects: Artificial stone obtained in Examples 1-3 and Comparative Examples 1-4. The test method was based on GB / T 50082-2009, and the results were recorded in Table 2.

[0109] Table 2

[0110]

Claims

1. A non-sintering vitrified inorganic artificial stone using a secondary activation process, characterized in that: The raw materials for preparation include, by mass, 25-60 parts of inorganic gel material, 3-20 parts of conditioning excipients, 2-10 parts of activator 1, 2-10 parts of activator 2, 30-70 parts of aggregate, 0.1-2 parts of auxiliary agent, and 0.5-2 parts of additive. The mass ratio of activator 1 to activator 2 is (1.5-2.5):1; The activator 1 is an alkaline activator, including one or more of potassium silicate, sodium silicate, sodium sulfate, calcium sulfate, sodium hydroxide, and potassium hydroxide; The activator 2 is a phosphate activator, including one or more of ammonium phosphate, potassium dihydrogen phosphate, potassium trihydrogen phosphate, aluminum dihydrogen phosphate, trisodium phosphate, sodium dihydrogen phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, magnesium phosphate, and copper phosphate. The additives include one or more of toughening materials and colorants; The preparation method of the non-sintering vitrified inorganic artificial stone by the secondary activation process includes at least the following steps: S1. Initial activation: Mix the inorganic cementitious materials, auxiliary materials and aggregates, and add the additives, auxiliaries, activator 1 and water. Mix evenly and stir at room temperature for 3-10 minutes. Then, carry out thorough mixing and initial activation treatment in a mixer. S2, Secondary Activation: After the initial activation, activator 2 is added to the reaction system, and the reaction is stirred for 3-5 minutes. S3, Fabric: The material obtained after secondary excitation is evenly distributed on the working surface for uniform fabrication; S4. Block Forming: The material after the cloth is laid is formed. Vacuum forming method can be used, with a vacuum degree of 0.1MPa. S5. Curing and maintenance: After the molded material is covered with a film, it is transported to a high-temperature room for curing. The curing temperature is 60-100℃ and the curing time is 2-3 days. S6. Cutting: Cut the cured raw blocks to a fixed thickness. S7. Polishing: Polish the cut material with a polishing machine to obtain the secondary activation process non-sintering vitrified inorganic artificial stone. The inorganic gel material is an active mineral, including one or more of slag powder, fly ash, metakaolin, silica fume, and active coal gangue powder; The conditioning additives include one or more of silica fume, nano-silica, and aluminum oxide.

2. The non-sintering vitrified inorganic artificial stone produced by the secondary activation process according to claim 1, characterized in that: The phosphate activator includes one or more of ammonium phosphate, aluminum dihydrogen phosphate, and trisodium phosphate.

3. The non-sintering vitrified inorganic artificial stone produced by the secondary activation process according to claim 1, characterized in that: The additives include one or more of the following: high-performance water-reducing agents, dispersants, setting regulators, and water-repellent agents.

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