High-strength thin ceramic integrated plate as well as preparation method and application thereof

Abstract

The invention provides a high-strength thin ceramic integrated plate and a preparation method and application thereof. The high-strength thin ceramic integrated plate comprises a backing layer, a heat preservation layer and a ceramic layer which are arranged in a stacked mode. Wherein the ceramic layer comprises a fiber material and a crack self-repairing material. According to the invention, the fiber material and the crack self-repairing material are introduced into the ceramic layer of the ceramic integrated plate to cooperate with each other, so that not only are the problems of breaking and falling of the thin ceramic integrated plate solved, but also the crack self-repairing is realized, the crack propagation is effectively delayed, the stable performance of the plate is maintained, and the strength recovery rate after repairing is high. Therefore, the impact resistance and durability of the thin ceramic integrated plate are greatly improved, the service life of the thin ceramic integrated plate is greatly prolonged, the green and environment-friendly advantages are outstanding, the development trend of green building materials is met, and application of green and high-performance building materials in the building field is promoted.

Description

Technical Field

[0001] The present invention belongs to the field of building materials, and in particular relates to a high-strength thin ceramic integrated plate and a preparation method and application thereof. Background Art

[0002] With the continuous development of the construction industry, the performance requirements for building materials are becoming increasingly stringent. Thermal insulation and decorative integrated panels are new building materials that integrate functions such as decoration, energy saving, and fire prevention. Among them, ceramic thin plate integrated panels are widely used in the field of building decoration due to their excellent finish and convenient installation. Traditional ceramic thin plate integrated panels are composed of ceramic thin plates, insulation layers, and back plates. They have defects such as being fragile after impact and easy to fall off fragments, posing a safety hazard. The existing technology has made improvements to this. For example, patent CN214302643U discloses a thin ceramic facing thermal insulation and decorative integrated panel, which includes a cement-based backing layer, a ceramic fiber insulation core layer, and a thin ceramic finishing layer stacked in sequence; the ceramic fiber insulation core layer and the thin ceramic finishing layer are bonded by a second PIR polyurethane bonding layer; the thickness of the second PIR polyurethane bonding layer is 0.5-0.7mm. Patent CN206957114U discloses a fireproof, thermally insulated, and decorative integrated panel, comprising a main panel and a decorative layer applied to the surface of the main panel. The decorative layer is provided with flame-retardant particles. The main panel comprises a base plate, on which a thermal insulation layer, a fireproof layer, and a panel are sequentially stacked. The side of the main panel is provided with fireproof needle-punched felt. Several anchors are provided between the main panel and the fireproof needle-punched felt. One end of the anchor is provided with a first fixing rod inserted between the decorative layer and the panel, and the other end is provided with a fixing piece extending from the fireproof needle-punched felt. The first fixing rod is provided with several claws that are embedded in the panel. However, the above-mentioned prior art still has a certain degree of breakage and shedding problems, and cracks caused by long-term use in complex environments are inevitable, affecting performance.

[0003] Therefore, how to solve the problem of breakage and falling off of ceramic integrated panels and reduce cracks, thereby effectively improving the impact resistance, durability and service life of ceramic integrated panels, is a technical difficulty that needs to be solved urgently. Summary of the Invention

[0004] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a high-strength thin ceramic integrated board and its preparation method and application. The present invention not only solves the problem of breakage and falling off of the thin ceramic integrated board by introducing fiber materials and crack self-repairing materials into the ceramic layer of the ceramic integrated board, but also realizes self-repair of cracks, effectively delays the expansion of cracks, maintains the stability of the board performance, and has a high strength recovery rate after repair. Therefore, the present invention greatly improves the impact resistance, durability and service life of the thin ceramic integrated board, and has outstanding green and environmental protection advantages, conforms to the development trend of green building materials, and helps promote the application of green and high-performance building materials in the construction field.

[0005] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a high-strength thin ceramic integrated board, comprising a backing layer, a thermal insulation layer, and a ceramic layer that are stacked.

[0007] Wherein, the ceramic layer includes fiber materials and crack self-repairing materials.

[0008] By introducing fiber materials and crack self-repairing materials into the ceramic layer of the ceramic integrated board, the present invention not only solves the problem of breakage and shedding of thin ceramic integrated boards, but also achieves self-repair of cracks, effectively delaying crack expansion, maintaining stable board performance, and achieving a high strength recovery rate after repair. Therefore, the present invention greatly improves the impact resistance, durability, and service life of thin ceramic integrated boards, and has outstanding green and environmental advantages, which is in line with the development trend of green building materials and helps promote the application of green, high-performance building materials in the construction field.

[0009] It should be noted that the present invention does not limit the material of the insulation layer. For example, it can be polystyrene, polyurethane or rock wool board. The present invention does not limit the material of the backing layer. For example, it can be fiber cement board, plywood or aluminum honeycomb board.

[0010] Preferably, the fiber material includes any one of basalt fiber, oxide fiber, glass fiber or carbon fiber, or a combination of at least two of them.

[0011] In the present invention, basalt fiber helps to enhance the performance of ceramic thin plates and improve crack resistance and durability; in scenarios where there are requirements for plate strength, the use of oxide fiber can make the density of the ceramic layer reach more than 90%, obtaining a high-strength, thin ceramic integrated plate with low porosity; in scenarios that are cost-sensitive and have relatively low strength requirements, the use of glass fiber can improve the flexural strength of the ceramic plate by 20-30%; in high-end applications of ultra-high strength and lightweight, the use of carbon fiber can significantly improve tensile and bending strength, and the tensile strength can be increased by more than 50%.

[0012] Preferably, the oxide fiber includes any one of aluminum oxide fiber, zirconium oxide fiber or silicon oxide fiber, or a combination of at least two of them.

[0013] Preferably, the diameters of the basalt fibers, oxide fibers, glass fibers and carbon fibers are independently 4-28 μm, for example, 4 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm or 28 μm.

[0014] In the present invention, the appropriate fiber diameter helps to combine with other materials in the ceramic layer, be evenly dispersed in the ceramic layer, and effectively transfer stress, thereby improving the crack resistance and durability of the ceramic integrated board. In addition, the appropriate fiber diameter is easy to process and shape, and can take into account the needs of different application scenarios and meet different architectural scenarios and performance requirements.

[0015] Preferably, the diameter of the basalt fiber is 6-13 μm, for example, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm or 13 μm.

[0016] Preferably, the lengths of the basalt fiber, oxide fiber, glass fiber and carbon fiber are independently 5-28 mm, for example, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm or 28 mm.

[0017] In the present invention, the appropriate fiber length helps to form a more effective skeleton structure in the ceramic layer, withstand a larger load, thereby significantly improving the strength and toughness of the ceramic integrated board, and the fibers are evenly dispersed, thereby ensuring the consistency of the performance of the ceramic layer.

[0018] Preferably, the length of the basalt fiber is 6-24 mm, for example, 6 mm, 10 mm, 15 mm, 20 mm or 24 mm.

[0019] Preferably, the length of the glass fiber is 8-20 mm, for example, 8 mm, 10 mm, 15 mm or 20 mm.

[0020] Preferably, the length of the carbon fiber is 5-15 mm, for example, 5 mm, 8 mm, 10 mm, 12 mm or 15 mm.

[0021] Preferably, based on the mass of the ceramic layer, the mass fraction of the fiber material is 3-15%, for example, 3%, 5%, 8%, 10%, 12% or 15%, etc. Exemplarily, if the fiber material is basalt fiber, the mass fraction of basalt fiber is 5-10% (for example, 5%, 6%, 7%, 8%, 9% or 10%, etc.), if the fiber material is glass fiber, the mass fraction of glass fiber is 10-15% (for example, 10%, 11%, 12%, 13%, 14% or 15%, etc.), and if the fiber material is carbon fiber, the mass fraction of carbon fiber is 3-8% (for example, 3%, 4%, 5%, 6%, 7% or 8%, etc.).

[0022] In the present invention, the appropriate mass fraction of the fiber material in the ceramic layer can fully improve the mechanical properties of the ceramic layer and avoid the problems of breakage and falling off.

[0023] Preferably, the crack self-repairing material includes any one of a conductive agent, a self-repairing microcapsule or a shape memory material, or a combination of at least two of them.

[0024] In the present invention, the conductive agent can be used in conjunction with the electric field when the crack first appears, so that the ions migrate and an electrochemical reaction occurs to generate new substances to fill the crack, which speeds up the repair process. The self-repairing microcapsules rupture when the crack expands, and the repair agent inside the capsule is exposed to repair the crack. The shape memory material can restore its shape at a certain temperature to close the crack when the crack appears.

[0025] Preferably, based on the mass of the ceramic layer, the mass fraction of the crack self-repairing material is 1-10%, for example, it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0026] In the present invention, with an appropriate mass fraction, the crack self-repairing material can effectively repair the cracks and maintain the ceramic performance, thereby further improving the service life and reliability of the ceramic layer.

[0027] Preferably, the conductive agent comprises carbon nanotubes and / or metal nanoparticles. For example, the metal nanoparticles may be gold nanoparticles, silver nanoparticles, or aluminum nanoparticles.

[0028] Preferably, the self-repairing microcapsules contain a repairing agent.

[0029] Preferably, the repair agent includes epoxy resin or microorganisms. It should be noted that when epoxy resin is used as a repair agent, it must be used in conjunction with a curing agent to achieve curing when the epoxy resin is used to repair cracks. In addition, microorganisms include, for example, Bacillus and its nutrients (such as calcium and carbon sources). When cracks appear, Bacillus is activated to grow, and the calcium and carbon sources are used to produce calcium carbonate precipitation to fill the cracks. The strength recovery rate after repair can reach 80-90%.

[0030] Preferably, the shape memory material comprises any one of shape memory alloys, shape memory polymers, or shape memory ceramics, or a combination of at least two. For example, the shape memory alloy may be, for example, nickel-titanium alloy, which exhibits a filamentous morphology and restores its shape upon reaching the phase transition temperature, thereby closing the crack. The shape memory polymer may be, for example, polynorbornene, which restores its shape upon exposure to temperature to repair the crack. The shape memory ceramic may be, for example, zirconia ceramic, which utilizes the volume expansion generated by its martensitic phase transition at 800-1000°C to fill the crack, and has higher high-temperature resistance and chemical stability than shape memory alloys and shape memory polymers.

[0031] Preferably, the ceramic layer includes ceramic components, and the ceramic components include, by mass percentage:

[0032] Kaolin 40-60%, for example, 40%, 50% or 60%, feldspar 15-30%, for example, 15%, 20%, 25% or 30%, quartz 10-25%, for example, 10%, 15%, 20% or 25%, clay 5-15%, for example, 5%, 10% or 15%, calcium carbonate 3-8%, for example, 3%, 4%, 5%, 6%, 7% or 8%, aluminum oxide 2-5%, for example, 2%, 3%, 4% or 5%, etc.; or, the ceramic components include, by mass percentage:

[0033] Kaolin 40-60%, for example, it can be 40%, 50% or 60%, spodumene 10-20%, for example, it can be 10%, 15% or 20%, quartz stone 10-25%, for example, it can be 10%, 15%, 20% or 25%, diatomaceous earth 10-15%, for example, it can be 10%, 11%, 12%, 13%, 14% or 15%, calcium carbonate 3-8%, for example, it can be 3%, 4%, 5%, 6%, 7% or 8%, aluminum oxide 2-5%, for example, it can be 2%, 3%, 4% or 5%, etc.

[0034] Preferably, the thickness ratio of the ceramic layer, the thermal insulation layer and the backing layer is (0.1-1): (100-300): (20-50), wherein the selection range of the ceramic layer "0.1-1" can be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc., the selection range of the thermal insulation layer "100-300" can be, for example, 100, 150, 200, 250 or 300, etc., and the selection range of the backing layer "20-50" can be, for example, 20, 30, 40 or 50, etc.

[0035] Preferably, the thickness of the ceramic layer is 0.1-1 mm, for example, it can be 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm or 1 mm.

[0036] Preferably, an adhesive layer is independently provided between the ceramic layer and the thermal insulation layer, and / or between the thermal insulation layer and the backing layer. It should be noted that the present invention does not limit the raw materials for preparing the adhesive layer. Exemplarily, the raw materials for preparing the adhesive layer include, in parts by weight:

[0037] 10-20 parts of polyether polyol (for example, it can be 10 parts, 15 parts or 20 parts, etc.), 10-20 parts of castor oil (for example, it can be 10 parts, 15 parts or 20 parts, etc.), 10-20 parts of modified polyether (for example, it can be 10 parts, 15 parts or 20 parts, etc.), 15-30 parts of calcium carbonate (for example, it can be 10 parts, 15 parts, 20 parts, 25 parts or 30 parts, etc.), 40-100 parts of isocyanate (for example, it can be 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts or 100 parts, etc.).

[0038] Preferably, the thickness of the adhesive layer is 0.2-0.5 mm, for example, 0.2 mm, 0.3 mm, 0.4 mm or 0.5 mm.

[0039] In a second aspect, the present invention provides a method for preparing the high-strength thin ceramic integrated plate as described in the first aspect, the preparation method comprising the following steps:

[0040] Ceramic raw materials, fiber materials and crack self-repairing materials are mixed, and then formed and fired to obtain a ceramic layer.

[0041] The ceramic layer, the thermal insulation layer and the backing layer are stacked and then hot-pressed to obtain the high-strength thin ceramic integrated board.

[0042] Preferably, the mesh number of the ceramic raw material is ≤300 mesh, for example, it can be 300 mesh, 250 mesh, 200 mesh, 150 mesh or 100 mesh.

[0043] Preferably, the mixing process is accompanied by stirring.

[0044] Preferably, the stirring rate is 120-150 rpm, for example, 120 rpm, 130 rpm, 140 rpm or 150 rpm.

[0045] Preferably, the molding process includes any one of isostatic pressing, injection molding or tape casting, or a combination of at least two of them.

[0046] In the present invention, the production efficiency of injection molding is several times higher than that of isostatic pressing, the production cycle can be shortened by more than 50%, and the dimensional accuracy can be controlled within ±0.1mm; the tape casting method can control the deviation of thickness uniformity within ±5μm.

[0047] Preferably, the isostatic pressing pressure is 300-600 MPa, for example, 300 MPa, 400 MPa, 500 MPa or 600 MPa.

[0048] Preferably, before the molding process is carried out, the mixed material is first subjected to vacuum mud kneading and aging treatment.

[0049] In the present invention, vacuum clay kneading involves mechanical stirring and extrusion in a vacuum environment, subjecting the clay to intense kneading and extrusion. This vacuum extracts the air from the clay, reducing air bubbles and pores. This not only improves the density and uniformity of the clay, but also enhances its plasticity and toughness, making it more suitable for subsequent molding processes.

[0050] In the present invention, aging treatment is a process in which the clay material that has undergone vacuum kneading is placed under certain environmental conditions and stored in a natural or specific environment for a period of time, so that the clay material undergoes a series of changes in physical and chemical properties, thereby improving the performance of the clay material.

[0051] Preferably, during the vacuum mud kneading process, the vacuum degree is ≥0.09 MPa, for example, it can be 0.09 MPa, 0.1 MPa, 0.12 MPa, 0.15 MPa, 0.2 MPa or 0.25 MPa.

[0052] Preferably, the firing method includes a pressure-variable coordinated sintering method or a microwave firing method.

[0053] In the present invention, the use of the variable pressure coordinated sintering method helps to make the sintered ceramic structure uniform and high-density, and can also inhibit the growth of grains to a certain extent, thereby obtaining a ceramic layer with a fine-grained structure and a more uniform microstructure of the ceramic layer.

[0054] In the present invention, the microwave firing method utilizes the microwave thermal effect and non-thermal effect to heat the inside and outside of the ceramic body simultaneously, with a short firing time and low energy consumption, and the obtained ceramic layer has high bending strength.

[0055] Preferably, the variable pressure co-sintering method is a high pressure-low pressure co-sintering method or a high pressure-normal pressure co-sintering method.

[0056] Preferably, in the high-pressure-low-pressure coordinated sintering method, the high pressure is 300-600 MPa, for example, 300 MPa, 400 MPa, 500 MPa or 600 MPa, etc., the low pressure is 50-100 MPa, for example, 50 MPa, 60 MPa, 70 MPa, 80 MPa, 90 MPa or 100 MPa, etc., the high-pressure sintering temperature is 180-200 ° C, for example, 180 ° C, 190 ° C or 200 ° C, etc., the low-pressure sintering temperature is 900-1000 ° C, for example, 900 ° C, 920 ° C, 940 ° C, 960 ° C, 980 ° C or 1000 ° C, etc.

[0057] Preferably, in the high-pressure-normal-pressure co-sintering method, the high-pressure pressure is 300-600 MPa, for example, 300 MPa, 400 MPa, 500 MPa or 600 MPa, etc., the high-pressure sintering temperature is 180-200°C, for example, 180°C, 190°C or 200°C, etc., and the normal-pressure sintering temperature is 1000-1200°C, for example, 1000°C, 1100°C or 1200°C, etc.

[0058] Preferably, in the microwave firing method, the microwave power is 50-500W, for example, it can be 50W, 100W, 200W, 300W, 400W or 500W.

[0059] Preferably, the preparation method comprises the following steps:

[0060] (1) A ceramic raw material with a mesh size of ≤300 mesh, a fiber material and a crack self-repairing material are stirred and mixed at a rate of 120-150 rpm to obtain a mixture.

[0061] The ceramic raw materials include the following components in terms of mass percentage:

[0062] Kaolin 40-60%, feldspar 15-30%, quartz 10-25%, clay 5-15%, calcium carbonate 3-8%, aluminum oxide 2-5%; or, the ceramic raw materials include the following components in percentage by mass:

[0063] Kaolin 40-60%, spodumene 10-20%, quartz stone 10-25%, diatomaceous earth 10-15%, calcium carbonate 3-8%, alumina 2-5%.

[0064] (2) Under the condition of a vacuum degree of ≥0.09 MPa, the mixture is vacuum-kneaded and then aged, and then isostatically pressed at a pressure of 300-600 MPa for 10-20 minutes to obtain a formed body.

[0065] (3) The formed body is subjected to high-pressure sintering in an inert atmosphere (e.g., argon, nitrogen, or vacuum), dried, and then subjected to normal pressure sintering or low pressure sintering in an inert atmosphere (e.g., argon, nitrogen, or vacuum) to obtain a ceramic layer.

[0066] Among them, the pressure of high-pressure sintering is 300-600MPa, the heating rate is 5-10℃ / min, the temperature of high-pressure sintering is 180-200℃, and the holding time is 2-4h (for example, it can be 2h, 3h or 4h, etc.); the sintering temperature of normal pressure sintering is 1000-1200℃, the heating rate is 5-10℃ / min, and the holding time is 3-5h (for example, it can be 3h, 4h or 5h, etc.); the pressure of low-pressure sintering is 50-100MPa, the temperature is 900-1000℃, and the holding time is 1-3h (for example, it can be 1h, 2h or 3h, etc.).

[0067] (4) Coating an adhesive on one side surface of the ceramic layer, then laminating the thermal insulation layer at a temperature of 48-65°C (for example, 48°C, 50°C, 55°C, 60°C or 65°C, etc.) and pressing for 5-8 minutes (for example, 5 minutes, 6 minutes, 7 minutes or 8 minutes, etc.), then coating an adhesive on the outer surface of the thermal insulation layer, then laminating the backing layer at 48-65°C (for example, 48°C, 50°C, 55°C, 60°C or 65°C, etc.) and pressing for 5-8 minutes (for example, 5 minutes, 6 minutes, 7 minutes or 8 minutes, etc.) to obtain a high-strength thin ceramic integrated board.

[0068] In a third aspect, the present invention provides an application of the high-strength thin ceramic integrated board as described in the first aspect in the field of building materials.

[0069] The numerical range described in the present invention includes not only the point values listed above, but also any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.

[0070] Compared with the prior art, the present invention has the following beneficial effects:

[0071] By introducing fiber materials and crack self-repairing materials into the ceramic layer of the ceramic integrated board, the present invention not only solves the problem of breakage and shedding of thin ceramic integrated boards, but also achieves self-repair of cracks, effectively delaying crack expansion, maintaining stable board performance, and achieving a high strength recovery rate after repair. Therefore, the present invention greatly improves the impact resistance, durability, and service life of thin ceramic integrated boards, and has outstanding green and environmental advantages, which is in line with the development trend of green building materials and helps promote the application of green, high-performance building materials in the construction field. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] Figure 1 This is a schematic structural diagram of a high-strength thin ceramic integrated plate prepared in Example 1 of the present invention.

[0073] Among them, 1-backing layer; 2-insulation layer; 3-ceramic layer; 4-bonding layer. DETAILED DESCRIPTION

[0074] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0075] Example 1

[0076] This embodiment provides a high-strength thin ceramic integrated plate, the structural diagram of which is shown in FIG. Figure 1 As shown, the high-strength thin ceramic integrated plate includes a backing layer 1, a bonding layer 4, a thermal insulation layer 2, a bonding layer 4 and a ceramic layer 3 which are stacked.

[0077] The ceramic layer 3 includes ceramic components, basalt fibers and self-healing microcapsules, wherein the basalt fibers account for 7% of the mass of the ceramic layer and the self-healing microcapsules account for 5% of the mass of the ceramic layer; the ceramic components include, by mass percentage, 50% kaolin, 20% feldspar, 15% quartz stone, 7% clay, 5% calcium carbonate and 3% alumina; wherein the basalt fibers have a diameter of 10 μm and a length of 15 mm; the self-healing microcapsules contain epoxy resin, and the ceramic layer 3 also contains a polyamide curing agent, and the amount of the polyamide curing agent added is 50% of the mass of the epoxy resin.

[0078] The thickness of the ceramic layer 3 is 0.5 mm, and the thickness ratio of the ceramic layer 3, the thermal insulation layer 2 and the backing layer 1 is 0.5:200:35; the thickness of the bonding layer 4 between the ceramic layer 3 and the thermal insulation layer 2, and between the thermal insulation layer 2 and the backing layer 1 is 0.35 mm.

[0079] The material of the thermal insulation layer 2 is polystyrene, and the material of the backing layer 1 is aluminum.

[0080] This embodiment also provides a method for preparing the above-mentioned high-strength thin ceramic integrated plate, the preparation method comprising the following steps:

[0081] (1) A ceramic raw material with a mesh size of 300 mesh, basalt fiber and self-repairing microcapsules were stirred and mixed in a high-speed mixer at a speed of 140 rpm to obtain a mixture.

[0082] The ceramic raw materials include the following components in terms of mass percentage:

[0083] Kaolin 50%, feldspar 20%, quartz 15%, clay 7%, calcium carbonate 5%, alumina 3%.

[0084] (2) The mixture was subjected to vacuum slurry kneading under a vacuum degree of 0.1 MPa, and then aged for 15 days, and then isostatically pressed under a pressure of 450 MPa for 15 minutes to obtain a molded body.

[0085] (3) High-pressure-normal-pressure co-sintering method: The molded body is subjected to high-pressure sintering in an argon atmosphere while maintaining the pressure constant. After sintering, the body is transferred to a blast drying oven and dried at 200°C for 15 hours. The body is then subjected to normal-pressure sintering in an argon atmosphere to obtain a ceramic layer.

[0086] Among them, the pressure of high-pressure sintering is 450MPa, the heating rate is 8℃ / min, the temperature of high-pressure sintering is 190℃, and the holding time is 3h; the sintering temperature of normal pressure sintering is 1100℃, the heating rate is 8℃ / min, and the holding time is 4h.

[0087] (4) A binder is coated on one surface of the ceramic layer, and then a thermal insulation layer is laminated at a temperature of 52° C. and pressed for 6 minutes. Subsequently, a binder is coated on the outer surface of the thermal insulation layer, and then a backing layer is laminated at 52° C. and pressed for 6 minutes to obtain a high-strength thin ceramic integrated plate.

[0088] The binder includes the following components in parts by weight: 14 parts of polyether polyol (TYHR-1050), 15 parts of castor oil, 15 parts of modified polyether (commercially available polyurethane-modified polyether polyol), 21 parts of calcium carbonate, and 75 parts of isocyanate (MDI).

[0089] Example 2

[0090] This embodiment provides a high-strength thin ceramic integrated board, which includes a backing layer, an adhesive layer, a thermal insulation layer, an adhesive layer, and a ceramic layer that are stacked.

[0091] The ceramic layer includes ceramic components, basalt fibers and self-healing microcapsules, wherein the basalt fibers account for 5% of the mass of the ceramic layer and the self-healing microcapsules account for 10% of the mass of the ceramic layer; the ceramic components include, by mass percentage, 50% kaolin, 20% feldspar, 15% quartz stone, 7% clay, 5% calcium carbonate, and 3% alumina; wherein the basalt fibers have a diameter of 6 μm and a length of 24 mm; the self-healing microcapsules contain epoxy resin, and the ceramic layer also contains only polyamide curing agent, and the added amount of polyamide curing agent is 50% of the mass of the epoxy resin.

[0092] The thickness of the ceramic layer is 0.1 mm, and the thickness ratio of the ceramic layer, the thermal insulation layer and the backing layer is 0.1:100:20; the thickness of the bonding layer between the ceramic layer and the thermal insulation layer, and between the thermal insulation layer and the backing layer are both 0.2 mm.

[0093] The material of the heat-insulating layer is polystyrene, and the material of the backing layer is aluminum.

[0094] This embodiment also provides a method for preparing the above-mentioned high-strength thin ceramic integrated plate, the preparation method comprising the following steps:

[0095] (1) A ceramic raw material with a mesh size of 200 mesh, basalt fiber and self-repairing microcapsules were stirred and mixed in a high-speed mixer at a speed of 120 rpm to obtain a mixture.

[0096] The ceramic raw materials include the following components in terms of mass percentage:

[0097] Kaolin 50%, feldspar 20%, quartz 15%, clay 7%, calcium carbonate 5%, alumina 3%.

[0098] (2) The mixture was subjected to vacuum slurry kneading under a vacuum degree of 0.1 MPa, and then aged for 15 days, and then isostatically pressed at a pressure of 300 MPa for 20 minutes to obtain a molded body.

[0099] (3) High-pressure-normal-pressure co-sintering method: The molded body is sintered under high pressure in an argon atmosphere while maintaining the pressure constant. After sintering, it is transferred to a blast drying oven and dried at 200°C for 12 hours. It is then sintered under normal pressure in an argon atmosphere to obtain a ceramic layer.

[0100] Among them, the pressure of high-pressure sintering is 300MPa, the heating rate is 5℃ / min, the temperature of high-pressure sintering is 180℃, and the holding time is 4h; the sintering temperature of normal pressure sintering is 1000℃, the heating rate is 5℃ / min, and the holding time is 5h.

[0101] (4) A binder is coated on one surface of the ceramic layer, and then a thermal insulation layer is laminated at a temperature of 48° C. and pressed for 8 minutes. Subsequently, a binder is coated on the outer surface of the thermal insulation layer, and then a backing layer is laminated at 48° C. and pressed for 8 minutes to obtain a high-strength thin ceramic integrated board.

[0102] The binder includes the following components in parts by weight: 14 parts of polyether polyol (TYHR-1050), 15 parts of castor oil, 15 parts of modified polyether (commercially available polyurethane-modified polyether polyol), 21 parts of calcium carbonate, and 75 parts of isocyanate (MDI).

[0103] Example 3

[0104] This embodiment provides a high-strength thin ceramic integrated board, which includes a backing layer, an adhesive layer, a thermal insulation layer, an adhesive layer, and a ceramic layer that are stacked.

[0105] The ceramic layer includes ceramic components, basalt fibers and self-healing microcapsules, wherein the basalt fibers account for 10% of the mass of the ceramic layer and the self-healing microcapsules account for 1% of the mass of the ceramic layer; the ceramic components include, by mass percentage, 50% kaolin, 20% feldspar, 15% quartz stone, 7% clay, 5% calcium carbonate, and 3% alumina; wherein the basalt fibers have a diameter of 13 μm and a length of 6 mm; the self-healing microcapsules contain epoxy resin, and the ceramic layer also contains only polyamide curing agent, and the added amount of polyamide curing agent is 50% of the mass of the epoxy resin.

[0106] The thickness of the ceramic layer is 1 mm, and the thickness ratio of the ceramic layer, the thermal insulation layer and the backing layer is 1:300:50; the thickness of the bonding layer between the ceramic layer and the thermal insulation layer, and between the thermal insulation layer and the backing layer are both 0.5 mm.

[0107] The material of the heat-insulating layer is polystyrene, and the material of the backing layer is aluminum.

[0108] This embodiment also provides a method for preparing the above-mentioned high-strength thin ceramic integrated plate, the preparation method comprising the following steps:

[0109] (1) A ceramic raw material with a mesh size of 200 mesh, basalt fiber and self-repairing microcapsules were stirred and mixed in a high-speed mixer at a speed of 150 rpm to obtain a mixture.

[0110] The ceramic raw materials include the following components in terms of mass percentage:

[0111] Kaolin 50%, feldspar 20%, quartz 15%, clay 7%, calcium carbonate 5%, alumina 3%.

[0112] (2) The mixture was subjected to vacuum slurry kneading under a vacuum degree of 0.1 MPa, and then subjected to aging treatment for 15 days, and then isostatically pressed under a pressure of 600 MPa for 10 minutes to obtain a molded body.

[0113] (3) High-pressure-low-pressure co-sintering method: The molded body is subjected to high-pressure sintering in an argon atmosphere while maintaining the pressure constant. After sintering, it is transferred to a blast drying oven and dried at 200°C for 18 hours. It is then subjected to low-pressure sintering in an argon atmosphere to obtain a ceramic layer.

[0114] Among them, the pressure of high-pressure sintering is 600MPa, the heating rate is 10℃ / min, the temperature of high-pressure sintering is 200℃, and the holding time is 2h; the pressure of low-pressure sintering is 75MPa, the sintering temperature is 950℃, and the holding time is 2h.

[0115] (4) A binder is coated on one surface of the ceramic layer, and then a thermal insulation layer is laminated at a temperature of 65°C and pressed for 5 minutes. Subsequently, a binder is coated on the outer surface of the thermal insulation layer, and then a backing layer is laminated at 65°C and pressed for 5 minutes to obtain a high-strength thin ceramic integrated board.

[0116] The binder includes the following components in parts by weight: 14 parts of polyether polyol (TYHR-1050), 15 parts of castor oil, 15 parts of modified polyether (commercially available polyurethane-modified polyether polyol), 21 parts of calcium carbonate, and 75 parts of isocyanate (MDI).

[0117] Example 4

[0118] The difference between this embodiment and embodiment 1 is that the basalt fiber is replaced by glass fiber with a diameter of 10 μm and a length of 14 mm, and the mass fraction is adjusted to 12%.

[0119] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0120] The high-strength thin ceramic integrated plate prepared in this embodiment was subjected to a flexural strength test using the test method according to GB / T3810.4-2016. The test results showed that the plate had excellent flexural strength.

[0121] Example 5

[0122] The difference between this embodiment and embodiment 1 is that the basalt fiber is replaced by carbon fiber with a diameter of 10 μm and a length of 10 mm, and the mass fraction is adjusted to 5%.

[0123] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0124] The high-strength thin ceramic integrated plate prepared in this embodiment was subjected to a tensile strength test using the test method GB / T23805-2009. The test results showed that the plate had excellent tensile strength.

[0125] Example 6

[0126] The difference between this embodiment and embodiment 1 is that the feldspar is replaced by spodumene, and the mass fraction is adjusted to 15%.

[0127] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0128] The high-strength thin ceramic integrated panels prepared in Example 1 and Example 6 were tested for thermal expansion coefficient using the test method according to GB / T 16535-2008. The test results showed that the thermal expansion coefficient of the high-strength thin ceramic integrated panel in Example 6 was reduced by 15%.

[0129] Example 7

[0130] The difference between this embodiment and embodiment 1 is that the clay is replaced by diatomaceous earth, and the mass fraction is adjusted to 12%.

[0131] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0132] The density and thermal conductivity of the high-strength thin ceramic integrated panels prepared in Example 1 and Example 7 were tested. The test results showed that the density of the high-strength thin ceramic integrated panel in Example 7 was reduced by 12% and the thermal conductivity was reduced by 20%, indicating that its weight was reduced, the cost was reduced, and the thermal insulation performance was enhanced.

[0133] Example 8

[0134] The difference between this embodiment and embodiment 1 is that the isostatic pressing process in step (2) is replaced by an injection molding process.

[0135] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0136] Compared with Example 1, the preparation method provided in this embodiment shortens the production cycle by 60%, and the dimensional accuracy reaches ±0.08 mm.

[0137] Example 9

[0138] The difference between this embodiment and embodiment 1 is that the isostatic pressing process in step (2) is replaced by a tape casting process.

[0139] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0140] The thickness uniformity deviation of the formed body obtained by the tape casting process provided in this embodiment is ±3 μm.

[0141] Example 10

[0142] The difference between this embodiment and embodiment 1 is that the high pressure-normal pressure synergistic sintering method in step (3) is replaced by a microwave sintering method. The specific steps include:

[0143] The formed green body was transferred to a microwave sintering furnace and the microwave power was set to 200W.

[0144] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0145] Compared with Example 1, the firing time of this embodiment is shortened by 40%, the energy consumption is reduced by 20%, and the bending strength (test method: GB / T 4740-2024) of the obtained high-strength thin ceramic integrated plate is increased by 15% compared with Example 1.

[0146] Example 11

[0147] The difference between this embodiment and embodiment 1 is that the self-repairing microcapsules are replaced with nickel-titanium alloy.

[0148] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0149] Example 12

[0150] The difference between this embodiment and embodiment 1 is that the self-repairing microcapsules are replaced by polynorbornene.

[0151] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0152] Example 13

[0153] The difference between this embodiment and embodiment 1 is that the self-repairing microcapsules are replaced by zirconia ceramics.

[0154] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0155] Example 14

[0156] The difference between this embodiment and embodiment 1 is that the self-repairing microcapsules are replaced by carbon nanotubes.

[0157] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0158] A simulated crack repair was performed on Example 1 and Example 15, and it was found that the crack repair speed of Example 15 was 2.5 times faster than that of Example 1.

[0159] Example 15

[0160] The difference between this embodiment and embodiment 1 is that the epoxy resin in the self-repairing microcapsules is replaced by Bacillus and its nutrients.

[0161] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0162] Example 16

[0163] The difference between this embodiment and embodiment 1 is that the mass fraction of the basalt fiber is 1%.

[0164] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0165] Example 17

[0166] The difference between this embodiment and embodiment 1 is that the mass fraction of the basalt fiber is 20%.

[0167] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0168] Example 18

[0169] The difference between this embodiment and embodiment 1 is that the mass fraction of the self-repairing microcapsules is 0.5%.

[0170] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0171] Example 19

[0172] The difference between this embodiment and embodiment 1 is that the mass fraction of the self-repairing microcapsules is 15%.

[0173] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0174] Comparative Example 1

[0175] The difference between this comparative example and Example 1 is that no self-repairing microcapsules are added.

[0176] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0177] Comparative Example 2

[0178] The difference between this comparative example and Example 1 is that basalt fiber is not added.

[0179] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0180] Comparative Example 3

[0181] The difference between this comparative example and Example 1 is that basalt fiber and self-repairing microcapsules are not added.

[0182] The remaining preparation methods and parameters were the same as those in Example 1 and will not be described again here.

[0183] Performance Testing

[0184] The high-strength thin ceramic integrated plates prepared in the above examples and comparative examples were subjected to impact resistance test, service life test and self-repairing performance test.

[0185] Among them, the test method for impact resistance test is: GB / T 15227-2019; the self-healing performance test uses artificially created simulated cracks of specific width (such as 0.5mm) and depth (such as 0.5mm) to simulate crack repair and record the strength recovery rate.

[0186] The test results are shown in Table 1.

[0187] Table 1

[0188]

[0189]

[0190] analyze:

[0191] As shown in Table 1, the present invention not only solves the problem of breakage and shedding of thin ceramic integrated panels by introducing fiber materials and crack self-repairing materials into the ceramic layer of the ceramic integrated panel, but also achieves self-repair of cracks, effectively delaying crack propagation, maintaining stable panel performance, and achieving a high strength recovery rate after repair. Therefore, the present invention greatly improves the impact resistance, durability, and service life of thin ceramic integrated panels, and has outstanding green and environmental advantages, which is in line with the development trend of green building materials and helps promote the application of green, high-performance building materials in the construction field.

[0192] By comparing Example 1 with Examples 16-17, it can be seen that if the mass fraction of basalt fiber is too small, the reinforcing and toughening effect of the fiber cannot be fully exerted, and the performance improvement of the ceramic layer is not obvious; if the mass fraction of basalt fiber is too large, too many fibers will form more pores or defects in the ceramic layer, reducing the density of the ceramic layer and affecting the durability and hardness of the ceramic integrated board.

[0193] By comparing Example 1 with Examples 18-19, it can be seen that if the mass fraction of the self-repairing microcapsules is too small, the repair effect is not obvious, it is difficult to form a complete repair network, and the overall repair effect is affected; if the mass fraction of the self-repairing microcapsules is too large, it may cause the density of the ceramic layer to decrease, thereby affecting its strength and other mechanical properties, and the repair effect is deteriorated.

[0194] It should be noted that while the present invention illustrates the process method through the above-described embodiments, the present invention is not limited to the above-described process steps, and does not necessarily rely on the above-described process steps for implementation. Those skilled in the art will appreciate that any improvements to the present invention, equivalent replacements for the raw materials used, additions of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A high-strength thin ceramic integrated plate, characterized in that: The high-strength thin ceramic integrated plate comprises a backing layer, a thermal insulation layer and a ceramic layer which are stacked; Wherein, the ceramic layer includes fiber materials and crack self-repairing materials.

2. The high-strength thin ceramic integrated plate according to claim 1, characterized in that: The fiber material includes any one of basalt fiber, oxide fiber, glass fiber or carbon fiber, or a combination of at least two thereof; Preferably, the oxide fiber comprises any one of aluminum oxide fiber, zirconium oxide fiber or silicon oxide fiber, or a combination of at least two thereof; Preferably, the diameters of the basalt fibers, oxide fibers, glass fibers and carbon fibers are each independently 4-28 μm; Preferably, the lengths of the basalt fiber, oxide fiber, glass fiber and carbon fiber are each independently 5-28 mm; Preferably, based on the mass of the ceramic layer, the mass fraction of the fiber material is 3-15%.

3. The high-strength thin ceramic integrated plate according to claim 1 or 2, characterized in that: The crack self-repairing material includes any one or a combination of at least two of a conductive agent, a self-repairing microcapsule or a shape memory material; Preferably, based on the mass of the ceramic layer, the mass fraction of the crack self-repairing material is 1-10%; Preferably, the conductive agent comprises carbon nanotubes and / or metal nanoparticles; Preferably, the self-repairing microcapsules contain a repairing agent; Preferably, the repair agent comprises epoxy resin or microorganisms; Preferably, the shape memory material includes any one of shape memory alloy, shape memory polymer or shape memory ceramic, or a combination of at least two of them.

4. The high-strength thin ceramic integrated plate according to any one of claims 1 to 3, characterized in that: The ceramic layer includes ceramic components, and the ceramic components include, by mass percentage: Kaolin 40-60%, feldspar 15-30%, quartz 10-25%, clay 5-15%, calcium carbonate 3-8%, alumina 2-5%; Alternatively, the ceramic component comprises, by mass percentage: Kaolin 40-60%, spodumene 10-20%, quartz stone 10-25%, diatomaceous earth 10-15%, calcium carbonate 3-8%, alumina 2-5%.

5. The high-strength thin ceramic integrated plate according to any one of claims 1 to 4, characterized in that: The thickness ratio of the ceramic layer, the thermal insulation layer and the backing layer is (0.1-1):(100-300):(20-50); Preferably, the thickness of the ceramic layer is 0.1-1 mm; Preferably, an adhesive layer is independently provided between the ceramic layer and the thermal insulation layer, and / or between the thermal insulation layer and the backing layer; Preferably, the thickness of the adhesive layer is 0.2-0.5 mm.

6. A method for preparing a high-strength thin ceramic integrated board according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: Mixing ceramic raw materials, fiber materials and crack self-repairing materials, and then forming and firing them to obtain a ceramic layer; The ceramic layer, the thermal insulation layer and the backing layer are stacked and hot pressed to obtain the high-strength thin ceramic integrated board.

7. The preparation method according to claim 6, characterized in that The mixing process is accompanied by stirring; Preferably, the stirring rate is 120-150 rpm; Preferably, the molding process includes any one or a combination of at least two of isostatic pressing, injection molding or tape casting; Preferably, the isostatic pressing pressure is 300-600 MPa; Preferably, before the molding process is carried out, the mixed material is first subjected to vacuum mud kneading and aging treatment.

8. The preparation method according to claim 6 or 7, characterized in that The firing method includes a pressure-variable coordinated sintering method or a microwave firing method; Preferably, the variable pressure synergistic sintering method is a high pressure-low pressure synergistic sintering method or a high pressure-normal pressure synergistic sintering method; Preferably, in the high-pressure-low-pressure coordinated sintering method, the high pressure is 300-600 MPa, the low pressure is 50-100 MPa, the high pressure sintering temperature is 180-200° C., and the low pressure sintering temperature is 900-1000° C.; Preferably, in the high pressure-normal pressure coordinated sintering method, the high pressure is 300-600 MPa, the high pressure sintering temperature is 180-200° C., and the normal pressure sintering temperature is 1000-1200° C.; Preferably, in the microwave firing method, the microwave power is 50-500W.

9. The preparation method according to any one of claims 6 to 8, characterized in that The preparation method comprises the following steps: (1) stirring and mixing a ceramic raw material with a mesh size of ≤300 mesh, a fiber material, and a crack self-repairing material at a rate of 120-150 rpm to obtain a mixture; The ceramic raw materials include the following components in terms of mass percentage: Kaolin 40-60%, feldspar 15-30%, quartz 10-25%, clay 5-15%, calcium carbonate 3-8%, aluminum oxide 2-5%; or, the ceramic raw materials include the following components in percentage by mass: Kaolin 40-60%, spodumene 10-20%, quartz 10-25%, diatomaceous earth 10-15%, calcium carbonate 3-8%, alumina 2-5%; (2) vacuum-kneading the mixture under a vacuum degree of ≥0.09 MPa, aging the mixture, and then isostatically pressing the mixture under a pressure of 300-600 MPa for 10-20 minutes to obtain a formed body; (3) sintering the formed body under high pressure in an inert atmosphere, drying the formed body, and then sintering the body under normal pressure or low pressure in an inert atmosphere to obtain a ceramic layer; Among them, the pressure of high-pressure sintering is 300-600MPa, the heating rate is 5-10℃ / min, the temperature of high-pressure sintering is 180-200℃, and the holding time is 2-4h; the sintering temperature of normal pressure sintering is 1000-1200℃, the heating rate is 5-10℃ / min, and the holding time is 3-5h; the pressure of low-pressure sintering is 50-100MPa, the temperature is 900-1000℃, and the holding time is 1-3h; (4) Coating an adhesive on one side of the ceramic layer, then laminating the thermal insulation layer at a temperature of 48-65°C and pressing for 5-8 minutes, then coating an adhesive on the outer surface of the thermal insulation layer, then laminating the backing layer at 48-65°C and pressing for 5-8 minutes to obtain a high-strength thin ceramic integrated board.

10. Use of the high-strength thin ceramic integrated board according to any one of claims 1 to 5 in the field of building materials.

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