A uhp c glazed panel and a method of manufacturing the same

Abstract

The application discloses a UHPC glazed panel and a preparation method thereof. The structure of the UHPC glazed panel comprises a UHPC base body, a reaction bonding layer and a glaze layer which are sequentially stacked, and the reaction bonding layer is formed by a precursor film through a firing process, and the precursor film is diffused and reacted with raw materials of the UHPC base body and the glaze layer in the firing process. By adopting a unique UHPC base body and glaze formula, the application reduces the firing temperature, and avoids thermal damage to the base body and the risk of "thermal explosion" in the firing process. By setting the precursor film, the application initiates in-situ reaction at the interface through the firing process, generates a dense transition layer, i.e. the reaction bonding layer, which is continuously and gradually changed in composition and structure, perfectly matched in thermal expansion coefficient, and has extremely high bonding strength. The UHPC glazed panel has the advantages of high strength, high durability of the UHPC, and the advantages of wear resistance, corrosion resistance, easy cleaning and strong decoration of the glaze layer.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, and in particular to a UHPC glazed panel and its preparation method. Background Technology

[0002] Ultra-high performance concrete (UHPC) panels have shown great potential in building curtain walls and decoration due to their superior mechanical strength and durability. However, their application still has significant drawbacks: their surface hardness is relatively insufficient compared to ceramics, making them prone to scratches, and they are susceptible to surface staining under certain environments, affecting their aesthetic appearance. To improve appearance and durability, conventional methods often involve applying organic protective coatings. However, this method suffers from problems such as easy aging and yellowing of the coating, poor adhesion to the UHPC substrate, short maintenance cycles, and short-lasting effects. Applying a glaze layer has proven to be an ideal solution that can greatly improve surface performance, solving many problems such as wear resistance, stain resistance, aesthetics, and durability in one go. However, this process faces serious challenges when applied to UHPC substrates. The core issues are that the glazing process must undergo a high-temperature sintering process (the conventional glazing sintering temperature is above 1100℃) and the material properties of the glaze layer and the UHPC substrate are different. First, continuous high-temperature heating causes thermal damage to the UHPC matrix itself. Hydration products in the matrix, such as Ca(OH)2, decompose at 500-600℃. Quartz aggregate expands rapidly due to phase transformation above 573℃. The added reinforcing fibers deteriorate at high temperatures; for example, steel fibers continuously exposed to temperatures above 800℃ will severely deteriorate. At 800℃, significant temperature differences will occur between different parts of the UHPC, creating a temperature gradient and leading to thermal stress, causing cracks in the UHPC. These factors collectively result in a significant decrease in UHPC performance. Second, the internal structure of UHPC is extremely dense. If the heating rate is too rapid, the rapid vaporization and escape of residual moisture is hindered, easily generating enormous vapor pressure and triggering a "temperature explosion," leading to destructive cracks inside or on the surface of the substrate. Finally, the mismatch between the coefficient of thermal expansion (CTE) of the glaze and the UHPC matrix is ​​a key factor leading to failure. Conventional glazes have a CTE of 5-10 × 10⁻⁶. -6 The temperature (°C) is typically lower than that of the UHPC matrix (10⁻¹³ × 10⁻¹⁰). -6 During the cooling process, the shrinkage of the UHPC matrix is ​​greater than that of the glaze layer, and the glaze layer will be subjected to compressive stress. Although the compressive strength of the glaze layer is usually much higher than its tensile strength (about 50 times), if the compressive stress is too great or the interface bonding is poor, it may also cause the glaze layer to peel off as a whole or develop circular cracks, which will seriously affect the product qualification rate.

[0003] Currently, there are various glaze decoration methods available for ordinary concrete or specific cement-based materials. However, these methods have significant limitations and technical challenges when applied to ultra-high performance concrete (UHPC). For example, existing technologies employ a low-temperature rapid firing process (firing temperature 830-850℃, high-temperature section 4-6 minutes) and a glaze formulation primarily composed of flux (95% flux content) to reduce the impact on the properties of the concrete matrix. However, this method is mainly designed for ordinary concrete products, whose firing temperature, although relatively low, is still higher than the tolerance limit of traditional UHPC. Furthermore, it does not consider the internal decomposition and thermal stress problems that may result from the dense structure of UHPC. Existing technologies also propose methods for producing hydraulic cement concrete products, with a firing temperature range of 650-1000℃. The mechanical strength after firing is restored through specific aggregate ratios and post-firing curing. Although this method takes into account the issue of matching thermal expansion coefficients (such as using aggregates with low thermal expansion coefficients and aggregates with high thermal expansion coefficients in proportion to adjust the thermal expansion coefficient of the concrete blank), it does not fundamentally solve the problems of ordinary cement hydration products such as the thermal decomposition of Ca(OH)2 (500-600℃) and the phase transformation expansion of quartz in aggregates (573℃). These will significantly reduce the strength of UHPC and easily cause cracking of the UHPC matrix.

[0004] Therefore, developing a UHPC glaze panel and its preparation method to avoid the risk of heat damage and achieve a strong bond between the glaze layer and the substrate has become an urgent need in the current technology field. Summary of the Invention

[0005] The purpose of this invention is to overcome the above-mentioned technical deficiencies and propose a UHPC glaze panel and its preparation method, which solves the technical problems of high firing temperature, large thermal damage to the substrate, risk of "temperature explosion" and poor coordination of thermal expansion coefficient between the glaze layer and the UHPC substrate in the existing concrete glazing technology.

[0006] In a first aspect, the present invention provides a UHPC glaze panel, the structure of which includes a UHPC substrate, a reaction bonding layer, and a glaze layer stacked sequentially, wherein the reaction bonding layer is formed by firing a precursor film, and the precursor film undergoes interfacial diffusion and reaction with the raw materials of the UHPC substrate and the glaze layer during firing; wherein... By weight, the raw materials of the UHPC matrix include: 80-90 parts of refractory hydraulic cementitious material, 10-15 parts of first lithium slag, 2-3 parts of first nano SiO2, 10-15 parts of first waste ceramic powder, 85-100 parts of high-temperature resistant sand, 1-2 parts of high-temperature resistant fiber, 0.5-1 part of low-melting-point organic fiber, 1-1.5 parts of water-reducing agent, and 15-18 parts of first water; By weight, the raw materials for the precursor membrane include: 15-25 parts silicon source, 5-10 parts aluminum source, 4-8 parts calcium source + lithium source, 1-3 parts stabilizer, 40-60 parts ethanol, 10-20 parts second water and 0.1-1 parts catalyst. The raw materials for the glaze layer include basic components and external admixtures: by weight percentage, the raw materials for the basic components include: 42%-48% of the second waste ceramic powder, 18%-22% of the second lithium slag, 5%-7% of the second nano SiO2, 16%-20% of borax, 3%-7% of zinc oxide, 2%-4% of sodium carbonate decahydrate, 2%-4% of calcium carbonate, and 0.8%-1.2% of sodium bentonite; the external admixture is a silane coupling agent.

[0007] Secondly, the present invention provides a method for preparing a UHPC glaze panel, comprising the following steps: S1. Mix the raw materials for the UHPC matrix, and then mold, cure, and first dry to produce the UHPC matrix; S2. The raw materials of the precursor membrane are mixed and reacted to obtain a sol, which is then coated onto the surface of the UHPC substrate. After gelation and second drying, a precursor membrane is formed. S3. The raw materials for the glaze layer are made into glaze slurry, which is then coated onto the surface of the precursor film. After a third drying and firing process, the UHPC glaze panel is obtained.

[0008] Compared with the prior art, the beneficial effects of the present invention include: This invention employs a unique UHPC matrix and glaze formulation to lower the firing temperature and avoid thermal damage to the matrix and the risk of "temperature explosion" during firing. By placing a precursor film between the raw materials of the UHPC matrix and the glaze layer, an in-situ reaction is initiated at the interface during firing, generating a dense transition layer—a reaction bonding layer—with continuously varying composition and structure and perfectly matched coefficients of thermal expansion. This perfectly coordinates the significant difference in thermal expansion coefficients between the UHPC matrix and the glaze layer, achieving extremely high bonding strength. The UHPC glaze panel of this invention not only possesses the high strength of UHPC but also the wear resistance, easy cleaning, and strong decorative properties of the glaze layer. Attached Figure Description

[0009] Figure 1 This is a schematic diagram of one embodiment of the UHPC glaze panel provided by the present invention; Figure 1 In the middle, 1. UHPC matrix, 2. Reactive bonding layer, 3. Glaze layer. Detailed Implementation

[0010] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0011] In existing technologies, UHPC substrates are prone to decomposition of hydration products, quartz phase transformation, deterioration of fiber properties, and the risk of "temperature explosion" at high temperatures. Furthermore, the difference in the coefficient of thermal expansion between the glaze layer and the UHPC substrate (the CTE of conventional glazes is 5-10 × 10⁻⁶) further exacerbates the problem. -6 At / ℃, the CTE of a conventional UHPC matrix is ​​10-13×10 -6 The high temperature ( / ℃) causes excessive compressive stress on the glaze layer during cooling, leading to peeling or circular cracks. It is evident that traditional UHPC glazing techniques generally suffer from high firing temperatures, significant thermal damage to the substrate, the risk of "temperature explosion," and poor coordination of thermal expansion coefficients. Based on these issues, this invention is proposed.

[0012] Please see Figure 1 In a first aspect, the present invention provides a UHPC glaze panel, the structure of which includes a UHPC substrate 1, a reaction bonding layer 2, and a glaze layer 3 stacked sequentially, wherein the reaction bonding layer 2 is formed by firing a precursor film, and the precursor film undergoes interfacial diffusion and reaction with the raw materials of the UHPC substrate 1 and the glaze layer 3 during the firing process; wherein, By weight, the raw materials of the UHPC matrix include: 80-90 parts of refractory hydraulic cementitious material, 10-15 parts of first lithium slag, 2-3 parts of first nano SiO2, 10-15 parts of first waste ceramic powder, 85-100 parts of high-temperature resistant sand, 1-2 parts of high-temperature resistant fiber, 0.5-1 part of low-melting-point organic fiber, 1-1.5 parts of water-reducing agent, and 15-18 parts of first water; By weight, the raw materials for the precursor membrane (a composite sol membrane used to pre-place an active layer on the surface of a UHPC substrate) include: 15-25 parts silicon source, 5-10 parts aluminum source, 4-8 parts calcium source + lithium source, 1-3 parts stabilizer, 40-60 parts ethanol, 10-20 parts second water and 0.1-1 parts catalyst. The raw materials for the glaze layer include basic components and external admixtures: by weight percentage, the raw materials for the basic components include: 42%-48% of the second waste ceramic powder, 18%-22% of the second lithium slag, 5%-7% of the second nano SiO2, 16%-20% of borax, 3%-7% of zinc oxide, 2%-4% of sodium carbonate decahydrate, 2%-4% of calcium carbonate, and 0.8%-1.2% of sodium bentonite; the external admixture is a silane coupling agent.

[0013] In this invention, waste ceramic powder is used in the UHPC matrix and glaze layer, utilizing its highly active glassy phase (SiO2). 2、The system utilizes Al2O3 and residual fluxes (K2O, Na2O) to provide highly reactive SiO2 and Al2O3 in the matrix and glaze, and introduces K2O, Na2O, etc., to create a compatible chemical environment for interfacial reactions. By using lithium slag and nano-SiO2 in the UHPC matrix and glaze layer, an "active silicon-lithium network" is constructed throughout the system. Nano-SiO2 acts as a highly efficient filler, pozzolanic activator, and glaze sintering promoter, while lithium slag provides a strong flux Li2O, which significantly reduces the glaze melting temperature. Together, they ensure that the interfacial reaction can proceed fully at a low temperature of 780-820℃.

[0014] In this invention, a precursor film is pre-placed between the raw materials of the UHPC matrix and the glaze layer. The precursor film, with its chemical composition between the raw materials of the UHPC matrix and the glaze layer, acts as a "molecular bridge" to significantly reduce the interfacial reaction energy barrier. Its nanoporous structure provides channels for ion diffusion, and the uniformly distributed Ca, Al, Si, and Li elements in the precursor film become directional nucleation centers for the target crystal phase. During the firing process, the precursor film diffuses and reacts with the active components of the UHPC matrix and the surface of the molten glaze, ultimately forming a reaction bonding layer with a gradient distribution of composition. This reaction bonding layer is rich in anorthite, spodumene, cristobalite, and zircon microcrystals, and its coefficient of thermal expansion exhibits a continuous gradient change in the thickness direction, which is beneficial for achieving efficient stress buffering and dissipation.

[0015] Preferably, the refractory hydraulic cementitious material is selected from at least one of cement and cement clinker; the cement is made from cement clinker, and the firing temperature of the cement clinker is ≥1450℃. When the firing temperature of the cement clinker meets the above range, it can withstand high temperatures above 1000℃. At high temperatures, its hydration products will transform into a high-temperature resistant ceramic phase, forming a solid skeleton, while avoiding harmful reactions that would cause ordinary cement to collapse.

[0016] Preferably, the refractory hydraulic cementitious material is aluminate cement and / or aluminate cement clinker, specifically including but not limited to at least one selected from low-calcium aluminate cement, calcium-magnesium aluminate cement, low-calcium aluminate cement clinker, and calcium-magnesium aluminate cement clinker.

[0017] Preferably, the composition of the first lithium slag by weight percentage is: SiO2 20%-65%, Al2O3 15%-65%, CaO 4%-9%, Na2O+K2O 7%-12%, Li2O 0.5%-2.0%, and others 1.0%-1.5%.

[0018] Preferably, the particle size of the first lithium slag is >400 mesh.

[0019] Preferably, the particle size of the first nano-SiO2 is 1-15 nm.

[0020] Preferably, the original firing temperature of the first waste ceramic powder is ≤1180℃. Medium-low temperature ceramic powder with an original firing temperature ≤1180℃ is selected, which contains a highly active glassy phase (SiO₂). 2、 The use of Al2O3 and residual fluxes (K2O, Na2O) makes the chemical composition of the UHPC matrix and glaze more similar, creating a compatible chemical environment for interfacial reactions. It should be noted that the original firing temperature refers to the highest temperature reached when the aforementioned waste ceramic powder is first fired as a ceramic body. This invention does not limit the source of the first waste ceramic powder; those skilled in the art can select it according to actual conditions, as long as it meets the aforementioned original firing temperature and particle size requirements, including but not limited to construction or daily-use waste ceramic powder.

[0021] Preferably, the composition of the first waste ceramic powder by weight percentage is: SiO2 65%-75%, Al2O3 18%-24%, Na2O+K2O 3%-7%, CaO 1%-2%, and others 2%-3%.

[0022] Preferably, the particle size of the first waste ceramic powder is 1000-1500 mesh. When the particle size of the first ceramic powder meets the above range, its micro-aggregate filling effect can be fully utilized. At the same time, the ultrafine powder has a higher specific surface area and chemical reactivity, making it easier to undergo pozzolanic reaction and interfacial fusion with cement hydration products.

[0023] Preferably, the high-temperature resistant sand is selected from at least one of corundum sand, zirconium oxide sand, and mullite sand. Compared with conventional quartz sand, high-temperature resistant sand has better high-temperature stability and a lower coefficient of thermal expansion.

[0024] Preferably, the particle size of the high-temperature resistant sand is 80-120 mesh.

[0025] Preferably, the high-temperature resistant fiber is selected from at least one of basalt fiber, carbon fiber, and silicon carbide fiber. Compared with steel fiber, high-temperature resistant fiber can maintain better mechanical and chemical stability under high temperature conditions above 800℃, enhance the temperature explosion resistance of UHPC, and has a lower coefficient of thermal expansion.

[0026] Preferably, the high-temperature resistant fiber has an average diameter of 10-20 μm and an average aspect ratio of 50-80.

[0027] Preferably, the low-melting-point organic fiber is selected from at least one of polypropylene fiber, polyethylene fiber, polyoxymethylene fiber, and polyvinyl alcohol fiber. The low-melting-point organic fiber has a low melting point and can melt in the range of 150-300℃ to form pores, which facilitates the release of internal moisture and internal pressure during heating.

[0028] Preferably, the low-melting-point organic fiber has an average diameter of 20-30 μm and an average aspect ratio of 40-70.

[0029] Preferably, the water-reducing agent is a superplasticizer with a water reduction rate of ≥40%, which can achieve high fluidity at a low water-cement ratio and delay setting time.

[0030] Preferably, the water-reducing agent is a polycarboxylate water-reducing agent.

[0031] Preferably, the solid content of the water-reducing agent is 40%-50%.

[0032] Preferably, the silicon source is selected from at least one of tetraethyl orthosilicate (TEOS) or nano silica sol.

[0033] Preferably, the aluminum source is selected from at least one of aluminum isopropoxide, aluminum nitrate, aluminum chloride, and aluminum sulfate.

[0034] Preferably, the calcium source is selected from at least one of calcium nitrate, calcium chloride, and calcium sulfate.

[0035] Preferably, the lithium source is selected from at least one of lithium nitrate, lithium chloride, and lithium sulfate.

[0036] Preferably, in the calcium source and lithium source, the molar ratio of Ca to Li is (2-5):1.

[0037] Preferably, the stabilizer is selected from at least one of acetylacetone or glacial acetic acid.

[0038] Preferably, the catalyst is selected from at least one of nitric acid or hydrochloric acid, and is used to adjust the pH of the sol to 2-4.

[0039] Preferably, the original firing temperature of the second waste ceramic powder is ≤1180℃. Medium-low temperature ceramic powder with an original firing temperature ≤1180℃ is selected, which contains a highly active glassy phase (SiO₂). 2、 The use of Al2O3 and residual fluxes (K2O, Na2O) makes the chemical composition of the UHPC matrix and glaze more similar, creating a compatible chemical environment for interfacial reactions. It should be noted that the original firing temperature refers to the highest temperature reached when the aforementioned waste ceramic powder is first fired as a ceramic body. This invention does not limit the source of the second waste ceramic powder; those skilled in the art can select it according to actual conditions, as long as it meets the aforementioned original firing temperature and particle size requirements, including but not limited to construction or daily-use waste ceramic powder.

[0040] Preferably, the composition of the second waste ceramic powder by weight percentage is: SiO2 65%-75%, Al2O3 18%-24%, Na2O+K2O 3%-7%, CaO 1%-2%, and others 2%-3%.

[0041] Preferably, the particle size of the second waste ceramic powder is 200-400 mesh. When the particle size of the second waste ceramic powder meets the above range, it can form a reasonable skeleton structure and melt viscosity during the glaze melting process, which not only ensures the suspension stability and coating uniformity of the glaze slurry, but also moderately melts and releases active SiO2 and Al2O3 during firing, and introduces K2O and Na2O, which synergistically promote low-temperature eutectic melting with Li2O introduced by lithium slag and nano-SiO2.

[0042] Preferably, the composition of the second lithium slag by weight percentage is: SiO2 20%-65%, Al2O3 15%-65%, CaO 4%-9%, Na2O+K2O 7%-12%, Li2O 0.5%-2.0%, and others 1.0%-1.5%.

[0043] Preferably, the particle size of the second lithium slag is >400 mesh.

[0044] Preferably, the particle size of the second nano-SiO2 is 1-15 nm.

[0045] Preferably, the sodium-based bentonite contains 60%-88% montmorillonite and ≥1.28% Na2O by weight percentage; according to GB / T 20973-2020 standard, its colloidal value is ≥99ml / 15g, its expansion volume is 25-50ml / g, its blue absorption capacity is ≥80mmol / 100g, and its pH value is 8.9-10.

[0046] Preferably, the silane coupling agent is selected from at least one of KH550 and KH560.

[0047] Preferably, the amount of silane coupling agent added is 0.05%-0.3% of the mass of the matrix component.

[0048] Preferably, the thickness of the UHPC substrate is 10-20 mm.

[0049] Preferably, the thickness of the precursor film is 0.5-2.0 μm. In this invention, the thickness of the precursor film can be controlled to be 0.5-2.0 μm by one coating or multiple coatings.

[0050] Preferably, the thickness of the reactive bonding layer is 10-40 μm.

[0051] Preferably, the thickness of the glaze layer is 0.3-0.8 mm.

[0052] Secondly, the present invention provides a method for preparing a UHPC glaze panel, comprising the following steps: S1. Mix the raw materials for the UHPC matrix, and then mold, cure, and first dry to produce the UHPC matrix; S2. The raw materials of the precursor membrane are mixed and reacted to obtain a sol, which is then coated onto the surface of the UHPC substrate. After gelation and second drying, a precursor membrane is formed. S3. The raw materials for the glaze layer are made into glaze slurry, which is then coated onto the surface of the precursor film. After a third drying and firing process, the UHPC glaze panel is obtained.

[0053] In this invention, a precursor film is pre-placed on the surface of a UHPC substrate using sol-gel technology, followed by coating with glaze and then firing in an integrated manner. This allows the precursor film to react synchronously with the raw materials of the UHPC substrate and the glaze layer, generating a reaction bonding layer with continuously varying composition and structure and perfectly matched thermal expansion coefficients, thus achieving extremely high bonding strength.

[0054] Preferably, in step S1, mixing the raw materials for the UHPC matrix includes: S11. The refractory hydraulic cementitious material, the first lithium slag, the first nano-SiO2, the first waste ceramic powder and the high-temperature resistant sand are mixed to obtain the first intermediate material. S12. The first intermediate material and the premix of water-reducing agent and first water are mixed for the second time to obtain the second intermediate material; S13. The second intermediate material, high-temperature resistant fiber and low-melting-point organic fiber are mixed in a third step to obtain a mixture.

[0055] During the first mixing process, the rotation speed is 20-30 r / min and the mixing time is 2-4 min.

[0056] During the second mixing process, the rotation speed is 40-60 r / min and the mixing time is 4-6 min.

[0057] During the third mixing process, the rotation speed is 40-60 r / min and the mixing time is 4-6 min.

[0058] Preferably, in step S1, molding includes, but is not limited to, casting molding or pressing molding.

[0059] Preferably, in step S1, the curing includes: pre-curing and steam curing.

[0060] Pre-curing includes: covering to retain moisture, curing at 15-25℃ for 24-48 hours to achieve early strength.

[0061] Steam curing includes: heating to 60-70℃ at a rate of ≤10℃ / h, maintaining the temperature at a constant temperature for 48-72 h, and then cooling to room temperature at a rate of ≤15℃ / h.

[0062] Preferably, in step S1, the temperature of the first drying is 200-250°C, and the drying time is 24-48 h, to remove free water.

[0063] Preferably, in step S2, the process of mixing and reacting the raw materials of the precursor membrane to obtain a sol includes: S21. The silicon source, aluminum source, ethanol and stabilizer are mixed in a fourth step to obtain a silicon-aluminum-ethanol mixture. S22. Dissolve the calcium source and lithium source in part of the second water to obtain a calcium-lithium aqueous solution; S23. The calcium-lithium aqueous solution and the silicon-aluminum-ethanol mixture are mixed for the fifth time, and then the remaining second water and catalyst are added. After stirring and standing aging, a sol is obtained.

[0064] During the fourth mixing process, the rotation speed is 200-400 r / min and the mixing time is 30-60 min.

[0065] Of these, the second water accounts for 30%-50% of the total second water volume.

[0066] The fifth mixing of the calcium-lithium aqueous solution and the silicon-aluminum ethanol mixture includes adding the calcium-lithium aqueous solution dropwise to the silicon-aluminum ethanol mixture.

[0067] Specifically, the dropping temperature is 5-10℃, the dropping time is 60-90 minutes, and the dropping process is carried out under stirring.

[0068] More specifically, the stirring speed is 350-450 r / min.

[0069] The stirring reaction was carried out at room temperature for 2-4 hours and at a stirring speed of 400-550 r / min.

[0070] The temperature for the static aging reaction is 25-35℃, and the time for the static aging reaction is 12-24 h.

[0071] The present invention does not limit the coating method in step S2, and those skilled in the art can choose according to the actual situation. For example, spraying, spin coating, dip coating, etc. can be used. In some specific embodiments of the present invention, dip coating is used and the lifting speed is 2-6 mm / s, or precision spraying is used and the pressure is 0.2-0.4 MPa.

[0072] Preferably, in step S2, before coating, the process further includes: pre-treating the UHPC substrate, and the pre-treatment includes: sandblasting the UHPC substrate and then cleaning the surface.

[0073] During the sandblasting process, 80-120 mesh diamond abrasive is used at a pressure of 0.4-0.6 MPa.

[0074] The UHPC matrix is ​​pretreated to give it a uniform matte finish with a surface roughness Ra of 3-6 μm, and the surface laitance and oil are completely removed to expose the interface between fresh aggregate and cementitious material.

[0075] Preferably, in step S2, during the gelation process, the temperature is 20-30℃, the relative humidity is 40%-60%, and the standing time is 10-30 minutes.

[0076] Preferably, in step S2, the temperature of the second drying is 60-80℃, and the drying time is 2-4 h.

[0077] Preferably, in step S3, the process of preparing the raw material of the glaze layer into a glaze slurry includes: melting the basic component of the raw material of the glaze layer, quenching it in water to form particles, and then mixing and ball milling it with the external admixture and the third water to obtain the glaze slurry.

[0078] Preferably, in step S3, the fineness of the glaze slurry is ≥300 mesh, and the Baume degree of the glaze slurry is 40-60°Bé.

[0079] The present invention does not limit the coating method in step S3, and those skilled in the art can choose according to the actual situation. For example, spraying, spin coating, dip coating, etc. can be used. In some specific embodiments of the present invention, spraying is used, and the pressure is 0.4-0.6 MPa, and the spraying distance is 200-300 mm.

[0080] Preferably, the third drying method is natural drying, and the third drying time is 12-24 hours.

[0081] Preferably, the firing process includes a heating stage and a cooling stage.

[0082] The heating phase includes: The temperature is increased from room temperature to a first temperature (preferably 380-420°C) at a first heating rate (preferably 1-2°C / min); a lower heating rate is used in this stage to ensure the decomposition of organic fibers and the gradual release of moisture. The temperature is increased from the first temperature (preferably 380-420℃) to the second temperature (preferably 480-520℃) at a second heating rate (preferably 3-4℃ / min). During this stage, a moderate heating rate is used to ensure that the residual organic matter and nitrate in the precursor film are fully decomposed and released, while avoiding excessive gas release due to excessive heating, which could cause film bubbling or microcracks. The precursor film begins to form a nanoporous active structure rich in amorphous SiO2-Al2O3-CaO-Li2O. The membrane is kept at a second temperature (preferably 480-520℃) for a first time (preferably 30-60 minutes). This stage is the key window for the transformation of the precursor membrane. Organic matter and nitrates in the precursor membrane are completely decomposed to form a nanoporous active layer rich in amorphous SiO2-Al2O3-CaO-Li2O, which is initially combined with the substrate surface. The temperature is increased from the second temperature (preferably 480-520°C) to the third temperature (preferably 580-620°C) at a third heating rate (preferably 3-4°C / min). During this stage, the active layer continues to densify, and the moderate heating rate promotes uniform relaxation and contraction of the amorphous network structure in the active layer, allowing the nanopores to close smoothly to form a dense framework. In addition, this rate can gently pass through the quartz phase transition temperature region (about 573°C), effectively mitigating the volume effect caused by crystal transformation and ensuring the structural integrity of the interface between the active layer and the UHPC matrix. The temperature is increased from the third temperature (preferably 580-620°C) to the fourth temperature (preferably 740-760°C) at a fourth heating rate (preferably 5-6°C / min). The faster heating rate in this stage is intended to quickly pass through the temperature range before the initial melting of the glaze, avoid the excessive agglomeration of low-melting-point components in the low-temperature range, and promote the uniform spread of the melt by utilizing the thermal inertia generated by the faster heating, and accumulate energy for the subsequent interfacial reaction. The temperature is increased from the fourth temperature (preferably 740-760°C) to the firing temperature (preferably 780-820°C) at a fifth heating rate (preferably 2-3°C / min). This stage employs a slow heating rate of 2-3°C / min, designed to address the high-temperature sensitive stage where the glaze is fully melted, preventing bubble retention and glaze flow defects caused by excessively low melt viscosity, and providing a suitable environment for Ca... 2+ Al 3+ Si 4+ Li + The interdiffusion of plasmas provides ample time; Hold at the firing temperature (preferably 780-820℃) for 30-50 minutes; during this stage, the glaze is fully melted, and the precursor film guides Ca... 2+ Al 3+ Si 4+ Li + Plasma interdiffusion acts as a nucleation site, inducing the epitaxial growth of crystals such as anorthite and spodumene, forming a dense gradient transition layer.

[0083] Stepped cooling is employed.

[0084] The cooling stage includes: First, the temperature is lowered from the firing temperature to the fifth temperature (preferably 580-620℃) at a first cooling rate (preferably 4-6℃ / min). The faster cooling rate at this stage is intended to quickly pass through the softening temperature range of the glaze melt and avoid excessive growth of the transition layer crystals due to excessive high-temperature residence time, which would cause the transition layer crystals to become brittle. Hold at the fifth temperature for 10-15 minutes to release stress; perform heat treatment near the glass transition temperature of the glaze layer so that the thermal stress generated by the difference in thermal shrinkage between the glaze layer, the reaction bonding layer and the UHPC matrix can be uniformly released through viscoelastic flow, preventing glaze cracking or interface peeling caused by stress concentration during subsequent cooling. Then, at a second cooling rate (preferably 2-4℃ / min), the temperature is lowered from the fifth temperature to the sixth temperature (preferably 280-320℃). This stage uses a slow cooling rate to ensure that the shrinkage rate of the glaze layer during complete curing is synchronized with that of the UHPC substrate, so that the gradient structure in the reaction bonding layer can fully play its stress buffering role, while avoiding thermal shock cracks caused by excessively rapid cooling. Finally, the furnace is cooled to room temperature; residual thermal stress is then eliminated by a gentle cooling method to ensure the dimensional stability and interfacial integrity of the UHPC glaze panel.

[0085] In the following embodiments and comparative examples of the present invention, some of the raw materials are summarized as follows: Aluminate cement: Jianai® CA50-A600 is used, conforming to GB 201-2000 standard; Lithium slag: by weight percentage, its composition is: SiO2 23%, Al2O3 58%, CaO 6%, Na2O+K2O 10%, Li2O 1.5%, and others 1.5%; Waste ceramic powder: The main phases are quartz phase and mullite phase. By weight percentage, its composition is: SiO2 70%, Al2O3 21%, Na2O+K2O 5%, CaO 1.5%, and the remainder is 2.5% impurities. Sodium-based bentonite: by weight percentage, montmorillonite content 75%, Na2O content 1.5%, colloidal value 105mL / 15g, swelling capacity 35ml / g, blue absorption capacity 90mmol / 100g, pH value 9.5.

[0086] Example 1 This embodiment provides a UHPC glazed panel and its preparation method. The structure of the UHPC glazed panel includes a UHPC substrate, a reaction bonding layer, and a glaze layer stacked sequentially. The reaction bonding layer is formed by firing a precursor film. During the firing process, the precursor film undergoes interfacial diffusion and reaction with the raw materials of the UHPC substrate and the glaze layer. The thickness of the UHPC substrate is approximately 15 mm; the thickness of the precursor film is approximately 1 μm; the thickness of the reaction bonding layer is approximately 25 μm; and the thickness of the glaze layer is approximately 0.5 mm.

[0087] By weight, the raw materials of the UHPC matrix include: 85 parts aluminate cement, 13 parts lithium slag (>400 mesh), 2.5 parts nano SiO2 (particle size 1-15nm), 12 parts waste ceramic powder (particle size 1000-1500 mesh, original firing temperature 1150℃), 90 parts corundum sand (80-120 mesh), 1.5 parts basalt fiber (average diameter 15μm, average aspect ratio 60), 0.8 parts polyethylene fiber (average diameter 25μm, average aspect ratio 50), 1.3 parts polycarboxylate superplasticizer (Jiangsu Subote PCA®-I type liquid superplasticizer, solid content 40%), and 16.5 parts water.

[0088] By weight, the raw materials for the precursor membrane include: 20 parts tetraethyl orthosilicate (TEOS), 8 parts aluminum isopropoxide, 5.26 parts calcium nitrate, 0.74 parts lithium nitrate (Ca:Li molar ratio = 3:1), 2 parts acetylacetone, 50 parts ethanol, 13.5 parts dihydrate, and 0.5 parts nitric acid (mass fraction 68%).

[0089] The glaze layer consists of a base component and an external admixture. By weight percentage, the raw materials of the base component include: 45% waste ceramic powder (200-400 mesh, original firing temperature 1150℃), 20% lithium slag (>400 mesh), 26% nano-SiO (particle size 1-15nm), 18% borax, 5% ZnO, 3% sodium carbonate decahydrate, 32% CaCO3, and 1% sodium bentonite. The external admixture is KH550, which is added at 0.2% of the mass of the base component.

[0090] Preparation methods include: (1) Weigh aluminate cement, lithium slag, nano-SiO2, waste ceramic powder, and corundum sand according to the proportion, put them into a mixer and dry mix at 25 r / min for 3 min to obtain the first intermediate material; add polycarboxylate superplasticizer and water premixed into the first intermediate material and stir at 50 r / min for 5 min to obtain the second intermediate material; add high-temperature resistant fiber and low-melting-point organic fiber to the second intermediate material and continue stirring at 50 r / min for 5 min to obtain the mixture; pour the mixture into a mold, cover it to retain water, and cure it at 20±5℃ for 36 hours; then steam curing is carried out, and the steam curing regime is: raise the temperature to 65℃ at 8℃ / h, keep it at a constant temperature for 60h, and then lower it to room temperature at 12℃ / h; finally, place it in an oven and dry it at 250℃ for 24h to obtain the UHPC matrix; use diamond abrasive (80-120 mesh) to sandblast the glazed surface of the UHPC matrix at a pressure of 0.5 The surface is treated with a pressure of MPa to achieve a uniform matte finish with a surface roughness Ra of 3-6 μm. This process completely removes surface laitance and oil, exposing the interface between fresh aggregate and cementitious material. The surface is then cleaned after sandblasting.

[0091] (2) Tetraethyl orthosilicate, aluminum isopropoxide, ethanol and acetylacetone were mixed and stirred at 300 r / min for 45 min to obtain a silica-alumina-ethanol mixture; calcium nitrate and lithium nitrate were dissolved in deionized water accounting for 40% of the total second water to obtain a calcium-lithium aqueous solution; the calcium-lithium aqueous solution was added dropwise to the silica-alumina-ethanol mixture at a stirring rate of 400 r / min, the dropping temperature was controlled at 5-10℃ by an ice-water bath, the dropping time was 75 min, the remaining deionized water was added, and the pH was adjusted to about 3 with nitric acid. The mixture was stirred at 500 r / min for 3 hours at room temperature and aged at 30℃ for 18 hours to obtain a sol; the sol was uniformly coated on the upper glaze surface of the UHPC substrate by dip-coating method (coating speed of 4 mm / s); then it was allowed to stand for 20 minutes at 25℃ and 50% relative humidity to complete gelation, and finally dried at 70℃ for 3 hours to form a precursor film.

[0092] (3) The basic component raw materials of the glaze layer are melted and quenched into granules in a tank kiln, and then mixed with KH550 and water and ball-milled to control the fineness of the milling to ≥300 mesh and the glaze slurry Baume degree to 55°Bé. The glaze is then sprayed (pressure 0.5MPa, spraying distance 250mm) onto the surface of the precursor film; then naturally dried for 18h, and finally fired in an integrated manner to obtain the UHPC glaze panel. The firing process is as follows: the temperature is increased from room temperature to 400℃ at a heating rate of 1.5℃ / min, then increased from 400℃ to 500℃ at a heating rate of 3.5℃ / min, and held at 500℃ for 45 minutes; the temperature is increased from 500℃ to 600℃ at a heating rate of 3.5℃ / min; the temperature is increased from 600℃ to 750℃ at a heating rate of 5.5℃ / min, then increased from 750℃ to 800℃ at a heating rate of 2.5℃ / min, and held at 800℃ for 40 minutes; then the temperature is decreased to 600℃ at a heating rate of 5℃ / min, held for 10 minutes, then decreased to 300℃ at a heating rate of 3℃ / min, and then naturally cooled to room temperature in the furnace (the cooling rate during this stage is <1℃ / min).

[0093] Example 2 Compared with Example 1, the only difference is that the raw materials of the basic components of the glaze layer include: 42% waste ceramic powder, 22% lithium slag, 26% nano SiO, 20% borax, 3% ZnO, 3% sodium carbonate decahydrate, 3% CaCO3, and 1% sodium bentonite.

[0094] Example 3 Compared with Example 1, the only difference is that in the raw materials of the UHPC matrix, there are 15 parts of lithium slag and 10 parts of waste ceramic powder, and the types and amounts of the remaining components are the same as in Example 1; by weight percentage, the raw materials of the basic components of the glaze layer include: 48% waste ceramic powder, 18% lithium slag, 7% nano SiO2, 16% borax, 5% ZnO, 3% sodium carbonate decahydrate, 2% CaCO3, and 1% sodium bentonite.

[0095] Comparative Example 1 Compared with Example 1, the only difference is that, by weight, the raw materials of the UHPC matrix include: 90 parts of ordinary Portland cement (P·O 52.5) ​​and silica fume (average particle size of 0.15 μm, specific surface area of ​​18000 m²). 2 15 parts ( / kg) of silica sand (80-120 mesh), 110 parts of ordinary silica powder (200-400 mesh), 20 parts of steel fiber (average diameter 0.3 mm, average aspect ratio 60), 2 parts of polycarboxylate superplasticizer (Jiangsu Subote PCA®-I type liquid superplasticizer, solid content 40%), and 18 parts of water.

[0096] Comparative Example 2 Compared with Example 1, the only difference is that high-temperature resistant corundum sand was not added to the raw materials of the UHPC matrix, but ordinary quartz sand (80-120 mesh) was used as an equal substitute.

[0097] Comparative Example 3 Compared with Example 1, the only difference is that lithium slag and waste ceramic powder were not added to the raw materials of the UHPC matrix, and an equal amount of aluminate cement was used to replace them.

[0098] Comparative Example 4 Compared with Example 1, the only difference is that the UHPC substrate surface is only cleaned with a wire brush and not sandblasted.

[0099] Comparative Example 5 Compared with Example 1, the only difference is that no precursor film was set, and glazing was applied directly after sandblasting and cleaning.

[0100] Comparative Example 6 Compared with Example 1, the only difference is that, by weight percentage, the raw materials of the basic components of the glaze layer include: 53% waste ceramic powder, 18% lithium slag, 25% nano-SiO, 16% borax, 3% ZnO, 2% sodium carbonate decahydrate, 2% CaCO3, and 1% sodium bentonite.

[0101] Comparative Example 7 Compared with Example 1, the only difference is that, by weight percentage, the raw materials of the basic components of the glaze layer include: 48% waste ceramic powder, 22% lithium slag, 20% nano SiO, 18% borax, 5% ZnO, 3% sodium carbonate decahydrate, 3% CaCO3, and 1% sodium bentonite.

[0102] Comparative Example 8 Compared with Example 1, the only difference is that, by weight percentage, the raw materials of the basic components of the glaze layer include: 48% waste ceramic powder, 15% lithium slag, 7% nano SiO2, 18% borax, 5% ZnO, 3% sodium carbonate decahydrate, 3% CaCO3, and 1% sodium bentonite.

[0103] Comparative Example 9 Compared with Example 1, the only difference is that, by weight percentage, the raw materials of the base components of the glaze layer include: 50% waste ceramic powder, 25% lithium slag, 25% nano SiO, 12% borax, 3% ZnO, 2% sodium carbonate decahydrate, 3% CaCO3, and 1% sodium bentonite.

[0104] Comparative Example 10 Compared to Example 1, the only difference is that, by weight percentage, the raw materials of the base components of the glaze layer include: 35% potassium feldspar, 25% quartz, 10% kaolin, 20% borax, 5% ZnO, 3% sodium carbonate decahydrate, and 32% CaCO3. That is, this comparative example uses a traditional glaze formula.

[0105] Comparative Example 11 Compared with Example 1, the only difference is that the firing process is unreasonable, the critical 500°C holding temperature is omitted, and a stepped slow cooling process is not adopted. Specifically, the temperature is increased from room temperature to 800°C at a rate of 5°C / min, and held at 800°C for 40 minutes, after which the kiln is directly shut off for natural cooling.

[0106] Performance testing The UHPC glaze panels prepared in the examples and comparative examples were subjected to performance tests, and the test results are shown in the table below. (1) Microhardness (HV) test of UHPC glaze panel: conducted according to GB / T 16534-2009 "Test method for room temperature hardness of fine ceramics".

[0107] (2) Adhesion performance test of UHPC glazed panel after freeze-thaw cycle: The adhesion test was conducted according to the rapid freeze-thaw method combined with the ASTM D3359 cross-cut adhesion test in GB / T 50082-2024 "Standard for Test Methods of Long-term Performance and Durability of Concrete".

[0108] (3) Average linear thermal expansion coefficient (CET, ×10) -6 / ℃, the test temperature range is from room temperature to the highest firing temperature) Test: conducted according to GB / T 4339-2008 "Determination of Thermal Expansion Characteristic Parameters of Metallic Materials"; among which, Preparation of individual glaze layer samples: Glazes were prepared according to the raw material ratios of the glaze layers in each embodiment and comparative example. After the glaze layer raw materials were mixed evenly, they were placed in a refractory mold and melted and cooled according to the same firing regime as the integrated firing of the UHPC glaze panel. The cooled glaze blocks were cut, ground and processed into specimens with dimensions of 10×10×50mm.

[0109] Preparation of individual UHPC matrix samples: Specimens were prepared according to the raw material ratios, molding, and curing methods of the UHPC matrix in each embodiment and comparative example. After curing, the specimens were cut and processed into specimens with dimensions of 10×10×50mm.

[0110] (4) Compressive strength and high-temperature residual compressive strength tests of UHPC matrix: UHPC matrix specimens were prepared according to the raw material ratio, molding, and curing methods of the UHPC matrix in each embodiment and comparative example. Among them, After curing, the UHPC matrix compressive strength specimens were cooled to room temperature before the compressive strength test was performed. After curing, the UHPC matrix high-temperature residual compressive strength specimens were cooled to room temperature and then dried in an oven (according to the drying temperature and drying time in each embodiment and comparative example). They were then placed in a high-temperature furnace for heat treatment (according to the heating rate, holding time and cooling method of the firing regime in each embodiment and comparative example) and compressive strength tests were performed.

[0111] (5) Appearance evaluation: The evaluation is based on the integrity and defects of the glaze surface after firing.

[0112] Table 1

[0113] Please refer to Table 1. As can be seen from Table 1, by controlling the formulation components and structural design in Examples 1-3 of the present invention, UHPC glaze panels with excellent comprehensive performance can be obtained, which confirms the effectiveness of the technical solution of the present invention.

[0114] Compared to Example 1, Comparative Example 1 uses a conventional UHPC formulation, and its matrix thermal expansion coefficient is as high as 11.5 × 10⁻⁶. -6 / ℃, with the glaze layer (6.5×10 -6 The difference in temperature (°C) is significant. During cooling, the matrix shrinks drastically while the glaze shrinks less, causing the glaze to bear enormous compressive stress exceeding its bonding strength, resulting in complete peeling. Simultaneously, the hydration products of ordinary silicate cement decompose severely at temperatures exceeding 500°C (with a large amount of calcium hydroxide, the core component, decomposing), causing the residual compressive strength to plummet to 65 MPa, indicating that the matrix has suffered thermal damage.

[0115] Compared to Example 1, Comparative Example 2 used quartz sand instead of corundum sand. During the firing process, the quartz underwent a phase transformation expansion at 573°C, which disrupted the originally dense microstructure inside the UHPC matrix, resulting in an increase in the matrix's thermal expansion coefficient to 8.9 × 10⁻⁶. -6 At ℃, this localized stress concentration not only reduced the residual strength of the matrix (98 MPa) but also destroyed the gradient transition layer induced by the precursor film, leading to stress cracks in the glaze surface.

[0116] Compared to Example 1, Comparative Example 3, lacking both lithium slag and waste ceramic powder, showed a significant deterioration in the interfacial bonding ability of the UHPC matrix. The absence of lithium slag prevented the formation of a low-expansion spodumene microcrystalline phase at high temperatures, while the lack of waste ceramic powder reduced the source of active SiO2 and Al2O3, resulting in a decrease in the densification degree of the matrix during high-temperature sintering, a weakening of its thermal stress buffering capacity, and an increase in the matrix's thermal expansion coefficient to 8.2 × 10⁻⁶. -6 / ℃. Meanwhile, the surface activity of the substrate, Ca... 2+ Al 3+ Si 4+ Insufficient plasma hinders the interfacial diffusion reaction with the precursor film. Furthermore, the increased coefficient of thermal expansion leads to poor thermal matching with the glaze layer, resulting in significant tensile stress at the interface during cooling. Ultimately, the interfacial bonding severely deteriorates (adhesion grade 1B, 35-65% peeling). Visually, the glaze layer exhibits glaze shrinkage, peeling pits, and microcracks due to insufficient matrix activity and thermal mismatch, indicating that the transition layer failed to form effectively and the bond between the glaze and the substrate is weak.

[0117] Compared with Example 1, Comparative Example 4, which was not sandblasted, had significantly lower freeze-thaw adhesion rating and glaze hardness than Example 1. This indicates that sandblasting can remove weak interface layers, increase mechanical anchoring, and expose active particles, thereby improving the performance of the UHPC glaze panel.

[0118] Compared with Example 1, Comparative Example 5 did not have a precursor film, and its freeze-thaw adhesion level and glaze hardness were significantly lower than those of Example 1. This indicates that the precursor film, as a "molecular bridge" and "reaction guiding layer", plays a decisive role in reducing the reaction energy barrier and promoting the formation of the gradient transition layer.

[0119] Compared with Example 1, the amount of waste ceramic powder in the basic component raw materials of the glaze layer in Comparative Example 6 was too high, which resulted in the CET of the glaze layer being significantly lower than that of the UHPC matrix. During the cooling process, the glaze layer was subjected to excessive compressive stress, while the UHPC matrix was subjected to tensile stress. This caused glaze cracks at stress concentration points and weakened the interfacial bonding.

[0120] Compared with Example 1, the basic component raw materials of the glaze layer in Comparative Example 7 did not contain nano-SiO2, and the hardness of the glaze layer also decreased significantly, indicating that nano-SiO2 plays a key role in promoting glaze sintering and improving the hardness and density of the glaze layer.

[0121] Compared with Example 1, the amount of lithium slag in the basic component raw materials of the glaze layer in Comparative Example 8 was too low, and the overall performance of the glaze layer also decreased significantly. This indicates that the amount of lithium slag was too low, and the strong fluxing agent Li2O introduced was insufficient, resulting in a decrease in the melting and spreading performance of the glaze (glaze shrinkage), which affected the fullness of the interfacial reaction and ultimately had an adverse effect on the overall performance of the glaze.

[0122] Compared with Example 1, the total amount of active skeleton components in Comparative Example 9 was too high, resulting in a relative deficiency of flux components (borax, ZnO, etc.), which led to excessively high high-temperature viscosity and poor homogenization of the glaze. After firing, the CET of the micro-regions inside the glaze layer was uneven, and local tensile stress concentration occurred during cooling, forming a network crack. In addition, the high viscosity also hindered its full interdiffusion with the pre-placed layer, resulting in poor development of the transition layer.

[0123] Compared with Example 1, Comparative Example 10 uses a traditional glaze formulation, whose CET is much higher than that of the UHPC matrix. The thermal expansion mismatch directly leads to glaze cracking and failure.

[0124] Compared to Example 1, Comparative Example 11 did not employ the stepped firing regime of this invention. On one hand, it could not precisely control the process through gradient heating in stages to achieve synergistic optimization of the entire process—dehydration and plastic removal, active layer conversion, phase change buffering, melt spreading, and interfacial reaction—ensuring the formation of a complete gradient structure in the reaction bonding layer and eliminating thermal stress. Furthermore, the lack of a crucial 500°C holding stage resulted in incomplete precursor film conversion. On the other hand, directly shutting down the kiln at 800°C and allowing it to cool naturally resulted in a cooling rate in the high-temperature section far exceeding the stepped slow cooling rate (5°C / min → holding → 3°C / min) used in Example 1. This led to significant thermal stress between the glaze layer, the reaction bonding layer, and the UHPC substrate due to differences in thermal shrinkage, and without the release of this stress through stepped holding, the final product performance suffered severe degradation. Therefore, the stepped firing regime used in this invention is indispensable for controlling the reaction process and releasing stress.

[0125] Compared with the prior art, the beneficial effects of the present invention include: (1) Revolutionary interface bonding: By pre-setting the precursor film through sol-gel technology, the molecular-level composition design and structural laying from the UHPC matrix to the glaze layer are realized, making the in-situ reaction controllable and sufficient, the transition layer dense and uniform, and the interface bonding strength extremely high (adhesion can reach the highest level after freeze-thaw cycle).

[0126] (2) Excellent comprehensive performance: UHPC glaze panel has the high compressive strength and high temperature residual strength of UHPC substrate, as well as the high hardness, high wear resistance, corrosion resistance and rich decorative properties of glaze layer.

[0127] (3) Green and environmentally friendly: It makes extensive use of industrial solid waste such as lithium slag and waste ceramic powder, which reduces costs and is in line with the concept of sustainable development.

[0128] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A UHPC glazed panel, characterized in that, The structure of the UHPC glaze panel includes a UHPC substrate, a reaction bonding layer, and a glaze layer stacked sequentially. The reaction bonding layer is formed by firing a precursor film. During firing, the precursor film undergoes interfacial diffusion and reaction with the raw materials of the UHPC substrate and the glaze layer. By weight, the raw materials of the UHPC matrix include: 80-90 parts of refractory hydraulic cementitious material, 10-15 parts of first lithium slag, 2-3 parts of first nano-SiO2, 10-15 parts of first waste ceramic powder, 85-100 parts of high-temperature resistant sand, 1-2 parts of high-temperature resistant fiber, 0.5-1 part of low-melting-point organic fiber, 1-1.5 parts of water-reducing agent, and 15-18 parts of first water; The precursor membrane, by weight, comprises: 15-25 parts silicon source, 5-10 parts aluminum source, 4-8 parts calcium source + lithium source, 1-3 parts stabilizer, 40-60 parts ethanol, 10-20 parts second water, and 0.1-1 parts catalyst. The raw materials for the glaze layer include a base component and an external admixture: by weight percentage, the base component includes: 42%-48% of second waste ceramic powder, 18%-22% of second lithium slag, 5%-7% of second nano-SiO2, 16%-20% of borax, 3%-7% of zinc oxide, 2%-4% of sodium carbonate decahydrate, 2%-4% of calcium carbonate, and 0.8%-1.2% of sodium bentonite; the external admixture is a silane coupling agent.

2. The UHPC glaze panel according to claim 1, characterized in that, The refractory hydraulic cementitious material is selected from at least one of cement and cement clinker; the cement is made from the cement clinker, and the firing temperature of the cement clinker is ≥1450℃; and / or, The refractory hydraulic cementitious material is at least one of aluminate cement and aluminate cement clinker; and / or, The first lithium slag, by weight percentage, comprises: SiO2 20%-65%, Al2O3 15%-65%, CaO 4%-9%, Na2O+K2O 7%-12%, Li2O 0.5%-2.0%, and other components 1.0%-1.5%; and / or, The particle size of the first lithium slag is >400 mesh; and / or, The particle size of the first nano-SiO2 is 1-15 nm; and / or, The original firing temperature of the first waste ceramic powder was ≤1180℃; and / or, By weight percentage, the composition of the first waste ceramic powder is: SiO2 65%-75%, Al2O3 18%-24%, Na2O+K2O 3%-7%, CaO 1%-2%, and other components 2%-3%; and / or, The particle size of the first waste ceramic powder is 1000-1500 mesh; and / or, The high-temperature resistant sand is selected from at least one of corundum sand, zirconium oxide sand, and mullite sand; and / or, The high-temperature resistant sand has a particle size of 80-120 mesh; and / or, The high-temperature resistant fiber is selected from at least one of basalt fiber, carbon fiber, and silicon carbide fiber; and / or, The low-melting-point organic fiber is selected from at least one of polypropylene fiber, polyethylene fiber, polyoxymethylene fiber, and polyvinyl alcohol fiber; and / or, The water-reducing agent is a superplasticizer with a water reduction rate ≥40%; and / or, The water-reducing agent is a polycarboxylate water-reducing agent; and / or, The water-reducing agent has a solid content of 40%-50%; and / or, The silicon source is selected from at least one of tetraethyl orthosilicate or nano silica sol; and / or The aluminum source is selected from at least one of aluminum isopropoxide, aluminum nitrate, aluminum chloride, and aluminum sulfate; and / or, The calcium source is selected from at least one of calcium nitrate, calcium chloride, and calcium sulfate; and / or, The lithium source is selected from at least one of lithium nitrate, lithium chloride, and lithium sulfate; and / or, In the calcium source and the lithium source, the molar ratio of Ca to Li is (2-5):1; and / or, The stabilizer is selected from at least one of acetylacetone or glacial acetic acid; and / or, The catalyst is selected from at least one of nitric acid or hydrochloric acid; and / or, The composition of the second lithium slag, by weight percentage, is: SiO2 20%-65%, Al2O3 15%-65%, CaO 4%-9%, Na2O+K2O 7%-12%, Li2O 0.5%-2.0%, and other components 1.0%-1.5%; and / or, The particle size of the second lithium slag is >400 mesh; and / or, The original firing temperature of the second waste ceramic powder was ≤1180℃; and / or, By weight percentage, the composition of the second waste ceramic powder is: SiO2 65%-75%, Al2O3 18%-24%, Na2O+K2O 3%-7%, CaO 1%-2%, and other components 2%-3%; and / or, The particle size of the second waste ceramic powder is 200-400 mesh; and / or, The particle size of the second nano-SiO2 is 1-15 nm; and / or, The sodium-based bentonite, by weight percentage, contains 60%-88% montmorillonite and ≥1.28% Na₂O; the sodium-based bentonite has a colloidal value ≥99 ml / 15g, an expansion volume of 25-50 ml / g, a blue absorption capacity ≥80 mmol / 100g, and a pH value of 8.9-10; and / or, The silane coupling agent is selected from at least one of KH550 and KH560; and / or, The amount of the silane coupling agent added is 0.05-0.3% of the mass of the matrix component.

3. The UHPC glaze panel according to claim 1, characterized in that, The thickness of the UHPC substrate is 10-20 mm; and / or, The thickness of the precursor film is 0.5-2.0 μm; and / or, The thickness of the reactive bonding layer is 10-40 μm; The thickness of the glaze layer is 0.3-0.8 mm.

4. A method for preparing a UHPC glaze panel as described in any one of claims 1-3, characterized in that, Includes the following steps: S1. The raw materials for the UHPC matrix are mixed, and then the mixture is formed, cured, and dried to produce the UHPC matrix. S2. The raw materials of the precursor membrane are mixed and reacted to obtain a sol, which is then coated onto the surface of the UHPC substrate, and gelled and dried to form a precursor membrane. S3. The raw materials of the glaze layer are made into glaze slurry, and then the glaze slurry is coated onto the surface of the precursor film. After a third drying and firing, a UHPC glaze panel is obtained.

5. The method for preparing the UHPC glaze panel according to claim 4, characterized in that, In step S1, mixing the raw materials for the UHPC matrix includes: S11. The refractory hydraulic cementitious material, the first lithium slag, the first nano-SiO2, the first waste ceramic powder and the high-temperature resistant sand are mixed to obtain the first intermediate material. S12. The first intermediate material and the premix of water-reducing agent and first water are mixed for the second time to obtain the second intermediate material; S13. The second intermediate material, high-temperature resistant fiber, and low-melting-point organic fiber are mixed in a third step to obtain a mixture; wherein... During the first mixing process, the rotation speed is 20-30 r / min, and the mixing time is 2-4 min; During the second mixing process, the rotation speed is 40-60 r / min, and the mixing time is 4-6 min; During the third mixing process, the rotation speed is 40-60 r / min and the mixing time is 4-6 min.

6. The method for preparing the UHPC glaze panel according to claim 4, characterized in that, In step S1, the curing includes: pre-curing and steam curing; wherein, The pre-curing includes: covering to retain moisture, and curing at 15-25℃ for 24-48 hours; The steam curing process includes: heating to 60-70℃ at a rate of ≤10℃ / h, maintaining the temperature at this rate for 48-72 h, and then cooling to room temperature at a rate of ≤15℃ / h; and / or, The first drying temperature is 200-250℃, and the first drying time is 24-48 h.

7. The method for preparing the UHPC glaze panel according to claim 4, characterized in that, In step S2, the process of mixing and reacting the precursor membrane raw materials to obtain a sol includes: S21. The silicon source, aluminum source, ethanol and stabilizer are mixed in a fourth step to obtain a silicon-aluminum-ethanol mixture. S22. Dissolve the calcium source and lithium source in part of the second water to obtain a calcium-lithium aqueous solution; S23. The calcium-lithium aqueous solution and the silica-alumina-ethanol mixture are mixed in the fifth step, followed by the addition of the remaining second water and the catalyst. After stirring and aging, a sol is obtained. During the fourth mixing process, the rotation speed is 200-400 r / min, and the mixing time is 30-60 min; and / or, The portion of the second water constitutes 30%-50% of the second water; and / or, The fifth mixing of the calcium lithium aqueous solution and the silica-alumina ethanol mixture includes: adding the calcium lithium aqueous solution dropwise to the silica-alumina ethanol mixture; the dropwise addition temperature is 5-10℃, the dropwise addition time is 60-90 min, and the dropwise addition process is carried out under stirring at a stirring speed of 350-450 r / min; and / or... During the stirring reaction, the temperature is room temperature, the reaction time is 2-4 hours, and the stirring speed is 400-550 r / min; and / or, During the static aging process, the temperature of the static aging reaction is 25-35℃, and the time of the static aging reaction is 12-24 h.

8. The method for preparing the UHPC glaze panel according to claim 4, characterized in that, In step S2, prior to coating, the process further includes: pre-treating the UHPC substrate, wherein the pre-treatment includes: sandblasting the UHPC substrate, followed by surface cleaning; and / or, During the gelation process, the temperature is 20-30℃, the relative humidity is 40%-60%, and the standing time is 10-30 minutes; and / or, The second drying temperature is 60-80℃, and the second drying time is 2-4 hours.

9. The method for preparing the UHPC glaze panel according to claim 4, characterized in that, In step S3, preparing the glaze slurry from the raw materials of the glaze layer includes: melting the basic components of the raw materials of the glaze layer, quenching them in water to form granules, and then mixing and ball-milling them with external admixtures and a third water to obtain the glaze slurry; and / or, The glaze slurry has a fineness ≥300 mesh and a Baume degree of 40-60°Bé; and / or, The third drying method is natural drying, and the third drying time is 16-20 hours.

10. The method for preparing the UHPC glaze panel according to claim 4, characterized in that, Firing includes: a heating stage and a cooling stage; wherein, The heating stage includes: heating from room temperature to 380-420℃ at a heating rate of 1-2℃ / min; heating from 380-420℃ to 480-520℃ at a heating rate of 3-4℃ / min; holding at 480-520℃ for 30-60 minutes; heating from 480-520℃ to 580-620℃ at a heating rate of 3-4℃ / min; heating from 580-620℃ to 740-760℃ at a heating rate of 5-6℃ / min; heating from 740-760℃ to 780-820℃ at a heating rate of 2-3℃ / min; and holding at 780-820℃ for 30-50 minutes. The cooling stage includes: first, cooling from 780-820℃ to 580-620℃ at a cooling rate of 4-6℃ / min; holding at 580-620℃ for 10-15 minutes; then cooling from 580-620℃ to 280-320℃ at a cooling rate of 2-4℃ / min; and finally cooling to room temperature with the furnace.

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