Corrosion-resistant wear-resistant light cast stone plate and production process thereof

Abstract

The invention discloses a corrosion-resistant wear-resistant light cast stone plate and a production process thereof, and belongs to the field of inorganic non-metallic materials. In order to solve the problems that traditional cast stone is too heavy, and an existing light plate is poor in toughness and interface stability, the plate is composed of a crystallization type cast stone surface layer, an active glass-ceramic transition layer and a multi-scale pore ceramic core layer. The technical key points are as follows: core-shell structure toughened ceramic powder is introduced into a surface layer, surface mineralized grafted active basalt fibers are introduced into a core layer, and a chemically bonded gradient interface is formed by using a transition layer through an integrated hot-pressing co-firing process. While the weight is greatly reduced, the impact toughness and thermal shock resistance stability of the plate are remarkably improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of inorganic non-metallic materials, and particularly relates to a kind of corrosion and wear resistant lightweight cast stone plate and its production process. BACKGROUND

[0002] Cast stone material, especially crystalline basalt cast stone, has become a key material in the field of industrial corrosion and wear resistance due to its excellent chemical corrosion resistance and high hardness resulting in excellent wear resistance. However, the density of traditional solid cast stone plate is as high as 2.8-3.0 g / cm 3 , which leads to high self-weight, high transportation and installation cost, and high load requirements for supporting structures. Especially in high-altitude or complex working conditions, there are significant labor intensity and safety risk problems.

[0003] To solve the problem of weight reduction of cast stone, the existing technology mainly explores two paths: one is to prepare porous cast stone by introducing a foaming agent, but this method is difficult to accurately control the coordination of foaming and crystallization process, often leading to coarse and uneven pores, thinning or even missing of the surface dense layer, resulting in serious decline in wear resistance and corrosion resistance. The second is to composite thin cast stone plate with lightweight substrate by organic binder (such as epoxy resin). The fatal defect of this method is that the temperature resistance, chemical resistance and aging resistance of the organic bonding interface are far inferior to those of cast stone itself. In the industrial environment of acid, alkali, solvent or temperature cycle, the interface is easy to age, crack and delaminate, leading to premature failure of the composite structure.

[0004] Therefore, it is a technical bottleneck in the field to develop a lightweight plate that can greatly reduce the density while maintaining or even surpassing the core performance of traditional cast stone. The existing technology only focuses on simple "weight reduction" and "composite", ignoring the following deeper technical problems: (1) Inherent contradiction between hardness and toughness: traditional cast stone and existing ceramic-based composite materials generally have a "hardness-fragility paradox", that is, by introducing a high-hardness phase (such as Al2O3) to improve wear resistance, the toughness of the material is often sacrificed, leading to a decline in impact resistance and easy chipping and cracking under material impact. The existing technology lacks a synergistic enhancement mechanism for simultaneously achieving high hardness and high toughness within a single material system.

[0005] (2) Insufficient long-term stability of the interface bonding: even if inorganic bonding is used, the existing composite plate still faces a large difference in coefficient of thermal expansion (CTE) between the dense ceramic surface layer and the porous lightweight core layer. Under repeated temperature changes (thermal shock) or long-term thermal cycling conditions, a large alternating stress will be generated at the interface, causing micro-cracks to initiate and propagate, although not immediately leading to macro delamination, but gradually reducing the interface bonding strength, eventually leading to structural fatigue failure. The existing technology lacks effective solutions to the "interface fatigue" problem.

[0006] (3) The absence of synergistic effect between components: the existing design is a simple physical stacking of materials, which fails to build the interaction between raw materials from the perspective of component structure design and interface reaction to achieve 1+1>2 synergistic effect, leading to the difficulty in balancing weight reduction and comprehensive performance (especially impact resistance and thermal shock resistance).

[0007] In summary, the market urgently needs a new type of composite plate that can effectively solve the contradiction between hardness and toughness and fundamentally improve the long-term thermal stability of the interface bonding through the synergistic innovation design of the material system, while achieving lightweight, thereby comprehensively improving the wear resistance, corrosion resistance, impact resistance and thermal shock resistance. SUMMARY

[0008] The purpose of the present application is to overcome the above-mentioned defects of the prior art and provide an anti-corrosion and wear-resistant lightweight cast stone plate and a production process thereof. The present application improves the structure of the toughening phase in the crystalline cast stone surface layer and the reinforcing fibers in the multi-scale porous ceramic core layer, and uses an active transition layer to induce the formation of a chemically bonded gradient interface, achieving the synergistic effect of "dispersion strengthening and phase transformation toughening" of the surface layer and "physical reinforcement and chemical bonding" of the core layer, thereby significantly improving the impact resistance and thermal shock stability of the plate while greatly reducing the weight.

[0009] The purpose of the present application can be achieved by the following technical solutions: An anti-corrosion and wear-resistant lightweight cast stone plate, which is composed of a crystalline cast stone surface layer, an active glass-ceramic transition layer and a multi-scale porous ceramic core layer which are sequentially and solidly combined from top to bottom: 1. The crystalline cast stone surface layer has a thickness of 5-8 mm. The raw materials include, by mass fraction: Basalt powder: 65-80 parts; Soda-lime-silica glass fragments: 5-10 parts; Composite crystallization agent: 5-10 parts; Core-shell structure composite toughening ceramic powder: 2-8 parts; 2. The active glass-ceramic transition layer has a thickness of 120-200 μm. The raw materials include, by mass fraction: SiO2: 50-60 parts; Al2O3: 10-15 parts; B2O3: 8-14 parts; Na2O: 3-5 parts; K2O: 3-5 parts; CaO: 2-4 parts; MgO: 2-4 parts; P2O5: 0.5-2 parts; Li2O: 0.5-3 parts; 3. Multiscale porous ceramic core layer: thickness of 15-20 mm. Its raw materials include, by mass fraction: Composite lightweight aggregate: 60-75 parts; Low softening point borosilicate glass powder: 15-25 parts; Kaolin: 2-6 parts; Surface mineralized grafted active basalt fiber: 0.8-3 parts; Aluminum dihydrogen phosphate solution (mass fraction 50%): 0.5-1.5 parts.

[0010] Further, the composite crystallizing agent is composed of the following components by mass fraction: ZrSiO4 40-60 parts; Rutile TiO2 20-30 parts; Cr2O3 10-20 parts.

[0011] Further, the core-shell structure composite toughening ceramic powder is a composite powder composed of α-Al2O3 micropowder as the core and a cerium stabilized zirconium oxide coating (Ce-TZP coating) on the surface.

[0012] Further, the core-shell structure composite toughening ceramic powder is prepared by the following steps: Anhydrous ethanol is added to the α-Al2O3 micropowder and ultrasonically dispersed for 30 min, and an aqueous solution containing zirconium oxychloride, cerium nitrate and citric acid is added dropwise under stirring to form a sol, and ammonia water is continuously added dropwise to adjust the pH value to 9-10, and then aged for 12 h, and then filtered, washed, dried, pre-fired at 600-800°C, and calcined at 1200-1400°C and crushed to obtain the core-shell structure composite toughening ceramic powder.

[0013] Further, the amount ratio of α-Al2O3, anhydrous ethanol, zirconium oxychloride, cerium nitrate and citric acid is 150 g:500 mL:81.8 g:21.7 g:10 g.

[0014] Further, the average particle size of the α-Al2O3 micropowder is 0.5-2 μm.

[0015] Further, the composite lightweight aggregate is composed of fly ash hollow microbeads 60-80 parts by mass and expanded perlite 20-40 parts by mass.

[0016] Further, the surface mineralized grafted active basalt fiber is a chopped basalt fiber with a length of 3-6 mm, and a hydroxyapatite (HAP) nanowhisker coating is grown on the surface of the basalt fiber by in-situ liquid phase deposition.

[0017] Further, the surface mineralized grafted active basalt fiber is prepared by the following steps: The chopped basalt fibers are sequentially subjected to acid washing and alkali activation treatment, the activated fibers are immersed in a 1.5 times concentrated simulated body fluid, and are reacted in a 30-50 DEG C water bath constant temperature reaction for 24-48 hours; the fibers are taken out, washed with deionized water until neutral, and then dried at 80-100 DEG C to obtain surface mineralized grafted active basalt fibers.

[0018] Further, the production process of the corrosion-resistant and wear-resistant lightweight cast stone plate comprises the following steps: S1: basalt powder, sodium-calcium-silicon glass fragments, composite crystallization agent and core-shell structure composite toughening ceramic powder are weighed according to mass fraction, mixed and ball milled to a particle size of less than 75 mu m, granulated, melted at 1300-1350 DEG C for 1-2 hours, cast into a plate, annealed at 580-620 DEG C for 4 hours, and then subjected to crystallization heat treatment at 850-920 DEG C for 4-6 hours to obtain a crystalline cast stone surface layer.

[0019] S2: the composite lightweight aggregate, low-softening-point borosilicate glass powder, kaolin and surface mineralized grafted active basalt fiber are mixed uniformly in a dry method, then aluminum dihydrogen phosphate solution is sprayed into the mixture and continuously mixed to prepare a wet material, the wet material is molded under a pressure of 4-8 MPa, and then dried at 100-120 DEG C for 2-4 hours to obtain a multi-scale porous ceramic core layer green body.

[0020] S3: the active glass-ceramic transition layer raw materials are weighed according to mass fraction, mixed with polyvinyl alcohol (PVA) solution with a mass fraction of 6-10% to prepare a slurry with a solid content of 50%; the slurry is uniformly coated on the back of the crystalline cast stone surface layer and the surface of the multi-scale porous ceramic core layer green body, the dry weight of single-side coating is 120-200 g / m 2 , and the coated green body is dried at 110-150 DEG C; the dried crystalline cast stone surface layer and the multi-scale porous ceramic core layer green body are aligned and laminated to obtain a composite green body; the composite green body is put into a hot press furnace, a contact pressure of 0.2-0.4 MPa is applied, the temperature is raised to 760-820 DEG C at a rate of 3-5 DEG C / min, and the temperature is kept for 20-40 min; in this process, the borosilicate glass phase in the multi-scale porous ceramic core layer softens and flows, the lightweight aggregate and the active basalt fiber are sintered, the transition layer glass melt penetrates to the surface layer and the core layer in two directions, and interface reactions occur between the Ce-TZP at the bottom of the surface layer and the HAP coating on the surface of the core layer, so that the three-layer integrated chemical bonding composite is realized; finally, the temperature is lowered to 500 DEG C at a rate of 2-4 DEG C / min, and then the furnace is cooled to room temperature, the edges are trimmed, and the finished corrosion-resistant and wear-resistant lightweight cast stone plate is obtained.

[0021] The beneficial effects of the present application are as follows: (1) Breakthrough hard and tough contradiction, excellent impact resistance: the present application introduces core-shell structure composite toughening ceramic powder in the surface layer, coupling the dispersion strengthening of α-Al2O3 (providing high hardness and high wear resistance) and the phase change toughening of Ce-TZP (absorbing impact energy) on the microscale, effectively solving the problem of "hard and brittle" of traditional cast stone. Compared with the prior art, the plate of the present application has high wear resistance while the impact toughness is greatly improved.

[0022] (2) Build a reaction interface, excellent thermal shock resistance: the present application introduces surface mineralized active basalt fiber in the core layer, and in the process of hot pressing and co-firing, the active transition layer induces the interface reaction between the glass matrix and the bottom of the surface layer to form a chemically bonded gradient transition zone. The gradient zone can effectively buffer the thermal expansion mismatch stress between the surface layer and the core layer, and inhibit the initiation and expansion of interface microcracks during thermal cycling. Therefore, the plate of the present application has excellent thermal shock stability and long-term service reliability.

[0023] (3) Synergistic effect, comprehensive performance improvement: the present application realizes the "1+1>2" superposition enhancement effect of material performance through the innovative design of "hard and tough synergy" of the surface layer and "physical and chemical synergy" of the core layer. The final lightweight plate not only has a density reduced by more than 45% compared with traditional solid cast stone, but also has key indicators such as bending strength, impact toughness, and thermal shock stability that are significantly better than existing lightweight solutions, even surpassing traditional solid cast stone.

[0024] (4) Process simplification and high efficiency, economic: the present application adopts "integrated hot pressing and co-firing process", which combines the sintering and curing of the core layer with the compounding process of the three-layer structure, eliminating the steps of independent sintering and secondary bonding of each layer in the traditional compounding process, significantly shortening the production cycle, reducing the comprehensive energy consumption by about 30%, improving the production efficiency, and having good industrial application prospect. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application. Meanwhile, the raw materials, reagents or devices used in the following embodiments are commercially available or can be obtained by known methods if not otherwise specified.

[0026] Example 1: producing a corrosion and wear resistant lightweight cast stone plate, the plate is composed of a crystalline cast stone surface layer, an active glass-ceramic transition layer and a multi-scale porous ceramic core layer which are sequentially compounded and solidified from top to bottom: (1) Preparation of core-shell structure composite toughened ceramic powder: 150 g of α-Al2O3micropowder with an average particle size of 1 μm was weighed and added to 500 mL of anhydrous ethanol, and ultrasonic dispersion was performed for 30 min to obtain an Al2O3suspension. Separately, 81.8 g of zirconium oxychloride (ZrOCl2·8H2O) and 21.7 g of cerium nitrate (Ce(NO3)3·6H2O) were dissolved in 300 mL of deionized water, and 10 g of citric acid was added as a stabilizer. The solution was slowly added dropwise to the Al2O3suspension under stirring to form a sol. Then, ammonia water was added dropwise to the sol to adjust the pH to 9.5, and aging was performed for 12 h. After filtration, washing, and drying at 100°C, pre-sintering was performed at 700°C for 2 h, and calcination was performed at 1300°C for 2 h, and the core-shell structure composite toughened ceramic powder was obtained by air flow pulverization.

[0027] (2) Preparation of surface mineralized grafted active basalt fiber: 100 g of chopped basalt fiber with a length of 4 mm was taken, soaked in 1 mol / L HCl solution for 2 h, washed, and then activated in 0.5 mol / L NaOH solution for 1 h, and washed to obtain the active basalt fiber. A 1.5-fold concentration of simulated body fluid (1.5 SBF) was prepared and placed in a 40°C water bath. The activated fiber was immersed in the 1.5 SBF solution, and constant temperature reaction was performed for 36 h. The fiber was taken out, repeatedly washed with deionized water until neutral, and dried at 80°C to obtain the active basalt fiber with a uniform HAP nanowhisker coating on the surface.

[0028] (3) Preparation of corrosion-resistant and wear-resistant lightweight cast stone plate: A. Surface layer: 72 kg of basalt powder, 8 kg of sodium calcium silicon glass fragments, 7 kg of composite crystallization agent (3.5 kg of ZrSiO4, 2.1 kg of rutile TiO2, and 1.4 kg of Cr2O3), and 4 kg of the core-shell structure composite toughened ceramic powder prepared in step 1 were weighed by mass, ball milled for 4 h to a particle size of less than 50 μm, and granulated. Melting was performed at 1320°C for 1.5 h, and the plate with a thickness of 6 mm was cast, annealed at 600°C for 4 h, and then crystallized at 900°C for 5 h to obtain the crystalline cast stone surface layer.

[0029] B. Core layer: 52.5 kg of composite lightweight aggregate (36.75 kg of fly ash hollow microbeads and 15.75 kg of expanded perlite), 20 kg of low softening point borosilicate glass powder (softening point 650-700°C), 4 kg of kaolin, and 1.5 kg of the surface mineralized grafted active basalt fiber prepared in step 2 were weighed by mass, and dry mixing was performed for 15 min. 1 kg of 50% mass fraction aluminum dihydrogen phosphate solution was slowly sprayed, and wet mixing was performed for 10 min. Molding was performed under a pressure of 6 MPa, and the green body of the multi-scale porous ceramic core layer with a thickness of 18 mm was dried at 110°C for 3 h.

[0030] C. Compounding: SiO255 parts, Al2O312 parts, B2O311 parts, Na2O 4 parts, K2O 4 parts, CaO 3 parts, MgO 3 parts, P2O51 part, Li2O 2 parts are weighed by mass fraction, mixed with a polyvinyl alcohol (PVA) solution with a mass fraction of 6-10% to prepare a slurry with a solid content of 50%; the slurry is uniformly coated on the back of the surface layer and the surface of the green body of the core layer, with a single-sided coating dry weight of 160 g / m2, and is dried at 120°C respectively. The two are aligned and stacked after drying, placed in a hot press furnace, a contact pressure of 0.3 MPa is applied, the temperature is raised to 800°C at a rate of 4°C / min, and the temperature is maintained for 30 min, then the temperature is lowered to 500°C at a rate of 3°C / min, and the furnace is cooled. Trim the edges to obtain finished corrosion-resistant and wear-resistant lightweight cast stone panels with a total thickness of about 24 mm.

[0031] Example 2: The remaining raw materials, raw material amounts and production processes are the same as those of Example 1, except for the following conditions, and finally the finished corrosion-resistant and wear-resistant lightweight cast stone panels are obtained: (1) The amount of core-shell structure composite toughening ceramic powder in the crystalline cast stone surface layer raw material is 2 kg; (2) The amount of surface mineralized grafted active basalt fiber in the multi-scale porous ceramic core layer raw material is 3 kg; (3) In step S3, the holding temperature is 760°C.

[0032] Example 3: The remaining raw materials, raw material amounts and production processes are the same as those of Example 1, except for the following conditions, and finally the finished corrosion-resistant and wear-resistant lightweight cast stone panels are obtained: (1) The amount of core-shell structure composite toughening ceramic powder in the crystalline cast stone surface layer raw material is 8 kg; (2) The amount of surface mineralized grafted active basalt fiber in the multi-scale porous ceramic core layer raw material is 0.8 kg; (3) In step S3, the holding temperature is 820°C.

[0033] Comparative Example 1: Comparative Example 1 is a control group of Example 1. Comparative Example 1 has the same formula and process as Example 1, except that 4 kg of "core-shell structure composite toughening ceramic powder" prepared in step 1 is not added to the surface layer raw material. To maintain the total mass unchanged, it is replaced with 4 kg of basalt powder. All other raw materials, amounts and process parameters remain the same as in Example 1.

[0034] Comparative Example 2: Comparative Example 2 is a control group of Example 1. Comparative Example 2 has the same formula and process as Example 1, except that 4 kg of "core-shell structure composite toughening ceramic powder" prepared in step 1 is replaced with an equal amount (4 kg) of pure α-Al2O3 micro powder with an average particle size of 1 μm (i.e. only "core", no "shell") in the surface layer. All other raw materials, amounts and process parameters remain the same as in Example 1.

[0035] Comparative Example 3: Comparative Example 3 is a control group of Example 1. The formulation and process of Comparative Example 3 are exactly the same as Example 1, except that 1.5 kg of the "surface-mineralized grafted active basalt fibers" prepared in Step 2 are replaced by equal mass (1.5 kg) and equal length (4 mm) but not any surface-treated ordinary chopped basalt fibers (raw material). All other raw materials, amounts and process parameters remain the same as Example 1.

[0036] Comparative Example 4: Comparative Example 4 is a control group of Example 1. Comparative Example 4 uses a traditional step-by-step composite process.

[0037] Face layer: prepared separately and sintered into crystalline-type cast stone face layer according to the formulation of Example 1.

[0038] Core layer: dry-mixed and wet-mixed according to the formulation of Example 1, then directly sintered into porous ceramic core layer plate in a hot-pressing furnace (contact pressure of 0.3 MPa, temperature rising to 800°C at 4°C / min, holding for 30 min, then temperature decreasing to 500°C at 3°C / min, and furnace cooling).

[0039] Composite: after the two plates are cooled, the face layer and the core layer are bonded together using a commercially available high-performance inorganic ceramic adhesive (phosphate adhesive), and cured at the curing temperature required by the adhesive (200°C in this comparative example). The "active glass-ceramic transition layer" of the present application is not used.

[0040] Comparative Example 5: Comparative Example 5 is a control group of Example 1. Comparative Example 5 only uses the raw materials of the crystalline-type cast stone face layer in Example 1 to produce a cast stone plate (the core-shell structure composite toughening ceramic powder is replaced by basalt powder, i.e. in Comparative Example 5, the formulation is basalt powder: sodium calcium silicon glass fragments: composite crystallization agent = 80 kg: 8 kg: 7 kg), and after melting, directly cast into a solid cast stone plate with the same total thickness as the finished product of Example 1 (about 24 mm). The crystallization heat treatment process is the same as the face layer of Example 1.

[0041] Test Example 1: The cast stone plates produced in Examples 1-3 and Comparative Examples 1-5 are tested for performance, and the performance testing process is as follows, and the test results are shown in Table 1: (1) Apparent density: cut 3 pieces of 100 mm x 100 mm samples. According to GB / T 1966-1996, test by Archimedes drainage method.

[0042] (2) Bending strength: according to GB / T9966.2-2001, prepare 3 pieces of 200 mm x 50 mm samples, with a span of 160 mm, a loading rate of 0.5 mm / min, and test on a universal material testing machine.

[0043] (3) Wear resistance (volume abrasion): Refer to ASTM G65-A method, sample size 75mm x 25mm, taken from the surface of the slab. Load 130N, abrasive AFS 50 / 70 silica sand, rubber wheel 6000 rotations. Measure the mass loss before and after abrasion, and convert to volume abrasion according to the sample density. The smaller the volume abrasion, the better the wear resistance.

[0044] (4) Impact resistance: Use Charpy (unnotched) impact test, according to GB / T1043.1-2008, sample size 80mm x 10mm x 4mm, taken from the surface of the slab downward, including the crystalline cast stone surface layer. Span 60mm, test on a pendulum impact testing machine.

[0045] (5) Acid corrosion resistance (mass loss rate): According to GB / T3297-2007, sample 25mm x 25mm, seal the four sides and back with acid-resistant paraffin, only expose the crystalline cast stone surface layer. Dry and weigh before testing, then immerse in 80℃, 20wt% H2SO4 solution for 72h. After washing and drying, weigh again to calculate the mass loss rate.

[0046] (6) Thermal shock resistance (strength retention rate): Prepare 6 samples of 100mm x 25mm, 3 for testing initial flexural strength. The other 3 are placed in a 250℃ muffle furnace for 30min, quickly taken out and placed in 20℃ cold water for 5min, which is one cycle. After 50 cycles, test the residual flexural strength. Strength retention rate = (cycled flexural strength / initial flexural strength) x 100%.

[0047] Table 1 Test results

[0048] Result analysis and verification: (1) Density comparison (Example 1 vs. Comparative Example 5): The density of Example 1 (1.58g / cm 3 ) is significantly lower than that of traditional solid cast stone Comparative Example 5 (2.95g / cm 3 ), with a reduction of nearly 45%, achieving the lightweight goal. The densities of the remaining comparative examples are basically the same as Example 1 because the core structure has not changed.

[0049] 2. Impact resistance comparison (Example 1 vs. Comparative Examples 1, 2, 5): The impact resistance of Example 1 (8.5kJ / m 2 ) is higher than that of Comparative Example 1 (4.2kJ / m 2 , no toughening powder), Comparative Example 2 (5.0kJ / m 2 , only Al2O3) and Comparative Example 5 (3.5kJ / m2 , traditional solid cast stone).

[0050] Analysis: Impact toughness data comparison proves the effect of "core-shell structure composite toughening ceramic powder". Comparative example 1 and traditional cast stone comparative example 5 show typical brittleness. Comparative example 2, although adding hard phase Al2O3, has no obvious improvement in toughness, but has better wear resistance (lowest volume wear). This shows the existing problem of "hard and brittle". Example 1 realizes high wear resistance and high impact toughness through the synergistic effect of the core-shell structure, verifying the improvement and breakthrough of the present application to the "hard and tough contradiction".

[0051] 3. Thermal shock resistance comparison (Example 1 vs. Comparative Examples 3, 4, 5): The strength retention rate of Example 1 (92%). The strength retention rate of Comparative Example 3 (using ordinary fibers) decreases significantly (65%), and the strength retention rate of Comparative Example 4 (using adhesive) is low after cycling. The thermal shock resistance of traditional solid cast stone Comparative Example 5 is also poor (55%) due to its brittleness and large internal and external temperature difference.

[0052] Analysis: Example 1 vs. Comparative Example 3: The only difference between the two is whether the fiber is surface mineralized. The results show that the untreated fiber has weak interfacial adhesion, which is easy to debond and pull out under thermal stress, leading to structural failure. In Example 1, the fiber activated by HAP coating forms a stable interface through chemical bonding with the active transition layer, which can effectively resist thermal shock. This verifies the key role of "surface mineralization grafting" in improving the stability of the interface; Example 1 vs. Comparative Example 4: The gradient chemical bonding interface formed by integrated co-firing in Example 1 can effectively buffer and release stress. This verifies the excellent effect of the "chemical bonding gradient interface" formed by the "active transition layer + integrated co-firing" process of the present application.

[0053] 4. Comprehensive performance analysis: Bending strength: Comparative Example 3 has the lowest bending strength, indicating that weak interfacial adhesion seriously affects the load-carrying capacity of the material; wear resistance and corrosion resistance: These two performances are mainly determined by the crystalline cast stone surface layer. Therefore, as long as the surface layer formula and process remain unchanged, there is little difference between the groups. Comparative Example 5 and Comparative Example 2 may have the highest surface hardness, with slightly better wear resistance, but this sacrifices the key toughness. Example 1 significantly improves other key performance while maintaining excellent wear and corrosion resistance.

[0054] It should be noted that in this text, terms such as "include, contain" or any other variants thereof are intended to cover non-exclusive inclusion, so that the process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or includes elements inherent to such process, method, article or device.

[0055] While embodiments of the application have been shown and described, it is to be understood that the embodiments described are merely exemplary of the principles and application of the present application. Numerous modifications and changes can be made by those skilled in the art without departing from the spirit and scope of the application. The scope of the application is not to be limited by the embodiments shown and described, but only by the claims and their equivalents.

Claims

1. A corrosion and abrasion resistant lightweight cast stone panel, characterized by, The plate is composed of a crystalline cast stone surface layer, an active glass-ceramic transition layer and a multi-scale porous ceramic core layer which are sequentially and integrally combined from top to bottom. The raw material of the crystalline cast stone surface layer comprises, by mass fraction: basalt powder 65-80 parts; sodium calcium silicon glass fragments 5-10 parts; composite crystallization agent 5-10 parts; and core-shell structure composite toughening ceramic powder 2-8 parts. The raw material of the active glass-ceramic transition layer comprises, by mass fraction: SiO2 50-60 parts; Al2O3 10-15 parts; B2O3 8-14 parts; Na2O 3-5 parts; K2O 3-5 parts; CaO 2-4 parts; MgO 2-4 parts; P2O5 0.5-2 parts; and Li2O 0.5-3 parts. The raw material of the multi-scale porous ceramic core layer comprises, by mass fraction: composite lightweight aggregate 60-75 parts; low softening point borosilicate glass powder 15-25 parts; kaolin 2-6 parts; surface mineralized grafted active basalt fiber 0.8-3 parts; and aluminum dihydrogen phosphate solution 0.5-1.5 parts.

2. The corrosion and wear resistant lightweight agglomerated stone slab according to claim 1, characterized in that, The composite crystallization agent is composed of the following components by mass fraction: ZrSiO4 40-60 parts; rutile TiO2 20-30 parts; and Cr2O3 10-20 parts.

3. The corrosion and wear resistant lightweight agglomerated stone slab of claim 1, wherein, The core-shell structure composite toughening ceramic powder is a composite powder with α-Al2O3 micropowder as the core and a cerium stabilized zirconium oxide coating layer on the surface.

4. The corrosion and wear resistant lightweight agglomerated stone slab of claim 3, wherein, The core-shell structure composite toughening ceramic powder is prepared by the following steps: adding anhydrous ethanol to α-Al2O3 micropowder, ultrasonic dispersion for 30 min, adding a water solution containing zirconium oxychloride, cerium nitrate and citric acid dropwise under stirring to form a sol, continuing stirring and adding ammonia water to adjust the pH value to 9-10, aging for 12 h, and then filtering, washing, drying, pre-sintering at 600-800 ℃, and calcining at 1200-1400 ℃ and crushing to obtain the core-shell structure composite toughening ceramic powder.

5. The corrosion and wear resistant lightweight agglomerated stone slab of claim 4, wherein, The amount ratio of the α-Al2O3, anhydrous ethanol, zirconium oxychloride, cerium nitrate and citric acid is 150 g:500 mL:81.8 g:21.7 g:10 g.

6. The corrosion and wear resistant lightweight agglomerated stone slab of claim 5, wherein, The average particle size of the α-Al2O3 micropowder is 0.5-2 μm.

7. The corrosion and wear resistant lightweight agglomerated stone slab of claim 1, wherein, The composite lightweight aggregate is composed of fly ash hollow microbeads 60-80 parts by mass and expanded perlite 20-40 parts by mass.

8. The corrosion and wear resistant lightweight agglomerated stone slab of claim 1, wherein, The surface mineralized grafted active basalt fiber is a chopped basalt fiber with a length of 3-6 mm, and a hydroxyapatite nanowhisker coating layer is grown on the surface of the fiber by a liquid phase deposition method in situ.

9. A corrosion and wear resistant lightweight agglomerated stone slab according to claim 8, characterized in that, The surface mineralized grafted active basalt fiber is prepared by the following steps: The chopped basalt fiber is sequentially subjected to acid washing and alkali activation treatment, the activated fiber is immersed in a 1.5 times concentrated simulated body fluid, and the fiber is taken out after reacting at 30-50 ℃ in a water bath constant temperature for 24-48 hours, washed with deionized water until neutral, and then dried at 80-100 ℃ to obtain the surface mineralized grafted active basalt fiber.

10. The production process of a corrosion and wear resistant light weight agglomerated stone slab according to any one of claims 1 to 9, characterized in that, The method comprises the following steps: S1: basalt powder, soda-lime-silica glass powder, composite crystallization agent and core-shell structure composite toughening ceramic powder are weighed according to the quality parts, mixed and ball milled to a particle size of less than 75 μm, granulated, melted at 1300-1350 ℃ for 1-2 hours, cast into a plate, annealed at 580-620 ℃ for 4 hours, and then crystallized at 850-920 ℃ for 4-6 hours to obtain a crystalline stone surface layer; S2: the composite lightweight aggregate, low softening point borosilicate glass powder, kaolin and surface mineralized grafted active basalt fiber are mixed uniformly according to the quality parts, then the aluminum dihydrogen phosphate solution is sprayed into the mixture and continuously mixed to prepare a wet material, which is molded under a pressure of 4-8 MPa, and then dried at 100-120 ℃ for 2-4 hours to obtain a multi-scale porous ceramic core layer green body. S3: according to the quality part, the active glass-ceramic transition layer is mixed with the polyvinyl alcohol solution with a mass fraction of 6-10% to prepare a slurry with a solid content of 50%; the slurry is uniformly coated on the back of the crystalline cast stone surface layer and the surface of the green body of the multi-scale porous ceramic core layer, and the dry weight of single-sided coating is 120-200 g / m 2 The crystalline cast stone surface layer and the multi-scale porous ceramic core layer green body are aligned and laminated after drying at 110-150℃, to obtain a composite green body; the composite green body is sent into a hot press furnace, a contact pressure of 0.2-0.4 MPa is applied, the temperature is raised to 760-820℃ at a rate of 3-5℃ / min, and the temperature is maintained for 20-40 min; finally, the temperature is lowered to 500℃ at a rate of 2-4℃ / min, and then the furnace is cooled to room temperature; the finished product of the corrosion-resistant and wear-resistant lightweight cast stone plate is obtained after trimming.

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