High-shock-resistance low-precipitation phosphate ceramic structure adhesive and preparation method thereof

Abstract

The invention provides a high-shock-resistance low-precipitation phosphate ceramic structure adhesive which comprises the following components in parts by weight: 100 parts of aluminum dihydrogen phosphate, 8-15 parts of zinc oxide powder, 35-45 parts of flaky aluminum oxide powder, 5-10 parts of nano zirconium oxide powder and 0.5-2 parts of layered zirconium phosphate powder. The ceramic further comprises 0.5-2 parts of titanium oxide powder and 5-10 parts of spherical aluminum oxide powder. The invention also discloses a preparation method and application of the adhesive. The adhesive disclosed by the invention can work for a long time at 500 DEG C or below, has high strength retention rate at high temperature, and solves the problem of easy failure at high temperature; through the toughening design, the impact resistance and thermal shock resistance are remarkably improved, and cracking in use is effectively prevented; the paint has good stability to acid, alkali, solvents and other chemical media, and is suitable for partial corrosive environments; the ion precipitation rate is extremely low, and the strict requirements of the fields of biological medicine, food and the like on the material purity are met; and the curing temperature is moderate, a precise matrix is not easy to damage, and on-site construction and complex structure bonding are facilitated.

Description

Technical Field

[0001] This invention relates to the field of adhesive technology, and in particular to a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive and its preparation method. Background Technology

[0002] In core fields such as high-end manufacturing, environmental protection and chemical engineering, biopharmaceuticals, and new energy, high-performance ceramic components are increasingly widely used due to their excellent high-temperature resistance, corrosion resistance, wear resistance, and chemical stability. These ceramic components (such as ceramic membranes, ceramic tubes, structural ceramic parts, and ceramic reactor linings) typically need to be connected to form complete functional units or equipment systems. The reliability of these connections directly determines the operational stability, service life, and safety of the entire equipment, making it one of the core technologies for ensuring long-term stable operation.

[0003] Currently, the main connection methods for ceramic components include mechanical connection, welding connection, and adhesive connection. Mechanical connection suffers from drawbacks such as complex assembly, stress concentration at the joint, and poor sealing performance, making it unsuitable for high-precision and high-sealing applications. Welding connection, on the other hand, is limited by the high brittleness and low plasticity of ceramic materials, easily resulting in defects such as cracks and porosity during welding, and requires extremely sophisticated welding equipment and processes, thus limiting its applicability. Therefore, adhesive connection, with its advantages of convenient construction, minimal damage to components, ability to achieve complex interface connections, and good sealing performance, has become the mainstream technical solution for connecting ceramic components.

[0004] However, the bonding materials used in existing ceramic component bonding technologies all have significant performance shortcomings and are difficult to meet the complex and demanding working conditions in the aforementioned fields.

[0005] Currently, widely used organic adhesives (typically represented by epoxy resins, acrylates, and silicone adhesives) can achieve rapid bonding of ceramic components at room temperature and pressure, and have good initial bonding strength and sealing performance. However, due to their core component being organic polymers, they have inherent structural defects, resulting in extremely poor durability under complex working conditions. The organic polymer skeleton is prone to thermal decomposition, oxidative cross-linking, and embrittlement under sustained high-temperature environments (typically exceeding 200°C), leading to a sharp decline in the mechanical properties of the adhesive layer, or even complete failure. This makes them unsuitable for high-temperature applications such as high-temperature ceramic membrane filtration systems and high-temperature chemical reactors. Furthermore, they are susceptible to long-term corrosion from strong acids, strong alkalis, organic solvents, and corrosive gases commonly found in environmental protection, chemical, and biopharmaceutical industries. Organic adhesives are prone to swelling, degradation, dissolution, or aging, which can lead to loss of bonding strength and even media leakage due to adhesive layer damage, causing equipment failure or material contamination. The thermal expansion coefficients of organic adhesives and ceramic matrices differ greatly. When drastic temperature fluctuations occur during equipment operation, significant thermal stress is generated at the bonding joint. This thermal stress cannot be released through the deformation of the adhesive layer itself, easily leading to cracking, detachment, or interface peeling, severely compromising the sealing reliability of the connection. Some organic adhesives release volatile organic compounds (VOCs) during use, and trace amounts may be released during long-term service, failing to meet the stringent requirements for material purity and hygiene safety in fields such as biopharmaceuticals and food processing.

[0006] In existing technologies, inorganic adhesives are used to replace organic adhesives, but their application scenarios remain limited. To improve the insufficient high-temperature resistance of organic adhesives, researchers have gradually adopted traditional inorganic adhesives, such as silicates, silica sols, and phosphates, for bonding ceramic components. These adhesives, with inorganic materials as their core components, exhibit significantly improved temperature resistance compared to organic adhesives. However, they still have many insurmountable shortcomings, resulting in poor overall performance and limited application scope. Traditional inorganic adhesives, after curing, form extremely brittle adhesive layers with very low impact strength, peel strength, and fracture toughness. When ceramic components are subjected to slight vibrations or external impacts during transportation, installation, or service, the bonded joints are prone to brittle fracture, making them unsuitable for equipment operating under vibration conditions. They also exhibit poor water and acid resistance, especially silicate-based inorganic adhesives. Their cured products contain unstable siloxane bonds, which are prone to hydrolysis in humid or acidic environments, leading to a significant decrease in bond strength and ion precipitation. This can contaminate materials in biopharmaceutical and food processing industries and may cause equipment and pipeline blockage due to the accumulation of hydrolysis products. Furthermore, traditional inorganic adhesives have high curing shrinkage rates. During curing, solvent evaporation and component condensation reactions result in significant volume shrinkage, which can easily occur within the adhesive layer or at the interface between the adhesive layer and the ceramic matrix. Microcracks can form at the bonding surface. These microcracks are difficult to detect with the naked eye, but they can severely reduce the mechanical strength of the bonded joint and may even become channels for corrosive media to penetrate, making it impossible to guarantee long-term sealing reliability. Some high-performance traditional inorganic adhesives require high-temperature curing conditions (usually exceeding 800℃, and some even exceeding 1200℃). The high-temperature curing process not only consumes a lot of energy and increases production costs, but may also cause thermal deformation, grain growth, or performance degradation of the ceramic matrix due to high temperatures, causing irreversible damage to ceramic components. At the same time, the high-temperature curing process has extremely high requirements for construction equipment and operating environment, making it difficult to achieve on-site construction and bonding of complex components. The interfacial bonding between traditional inorganic adhesives and ceramic matrices mainly relies on physical adsorption, with weak chemical bonding. When subjected to temperature fluctuations or external forces, interfacial delamination is prone to occur, leading to bonding failure.

[0007] In summary, existing ceramic component bonding technologies all suffer from a fundamental problem of "paying one thing while losing another," failing to achieve a synergistic balance between high seismic resistance, high temperature resistance, high corrosion resistance, low ion precipitation, high sealing reliability, and ease of processing. While organic adhesives offer convenient room-temperature application and good room-temperature bonding performance, they suffer from fatal flaws in key properties such as high-temperature resistance, corrosion resistance, and thermal shock resistance. Traditional inorganic adhesives, although improving temperature resistance, still have significant shortcomings in mechanical properties, water and acid resistance, ease of application, and interfacial bonding reliability.

[0008] The performance defects of existing bonding materials have become a core technical bottleneck restricting the efficient integration and stable operation of high-performance ceramic components in the aforementioned complex systems, severely limiting the application expansion of ceramic materials in high-end fields.

[0009] Therefore, developing a high-performance adhesive material specifically for ceramic components that can meet the above-mentioned performance requirements is of great practical significance and has an urgent market demand. Summary of the Invention

[0010] The first objective of this invention is to disclose a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive. It employs a ternary composite filler system of spherical alumina, lamellar alumina, and phase-change toughened nano-zirconia. In particular, the synergistic toughening effect of lamellar alumina and nano-zirconia increases the adhesive's vibration resistance and fatigue resistance. Layered zirconium phosphate is introduced as a functional additive, utilizing its ion exchange properties to fix free metal ions. Combined with nano-titanium oxide, it inhibits ion dissolution. This adhesive achieves a synergistic balance of high shock resistance, high temperature resistance, high corrosion resistance, low ion precipitation, high sealing reliability, and ease of processing, making it a dedicated adhesive material for ceramic components.

[0011] To achieve the above objectives, this invention discloses a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, which, by weight, comprises the following components: 100 parts of aluminum dihydrogen phosphate, 8-15 parts of zinc oxide powder, 35-45 parts of flake alumina powder, 5-10 parts of nano-zirconia powder, and 0.5-2 parts of layered zirconium phosphate powder.

[0012] In some embodiments, 0.5-2 parts of titanium dioxide powder are also included.

[0013] In some embodiments, 5-10 parts of spherical alumina powder are also included.

[0014] In some embodiments, the sheet-like alumina powder has a sheet diameter of 30-50 μm, and the nano-zirconia powder has a particle size of 30-50 nm.

[0015] In some embodiments, the titanium dioxide powder has a particle size of 0.2-0.5 μm.

[0016] In some embodiments, the particle size of the spherical alumina powder is 1-5 μm.

[0017] The second objective of this invention is to disclose a method for preparing a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive. The method employs a graded dispersion process to effectively prevent the agglomeration of nanoparticles and ensure uniform dispersion. Then, a gradient sintering process is used, which involves a three-stage heating procedure of low-temperature dehydration, medium-temperature polymerization, and high-temperature ceramicization.

[0018] To achieve the above objectives, this invention discloses a method for preparing a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0019] Step 1: Prepare an aqueous solution of aluminum dihydrogen phosphate (50-70 wt%) to obtain the base solution;

[0020] Step 2: Add appropriate amounts of zinc oxide powder, nano-zirconia powder and layered zirconium phosphate powder to the base solution in sequence, and stir and disperse at high speed to obtain a dispersion.

[0021] Step 3: Add an appropriate amount of flake alumina powder to the dispersion and continue stirring until the mixture is uniform to obtain a paste-like slurry;

[0022] Step 4: Transfer the paste to a ball mill jar and ball mill for a certain period of time;

[0023] Step 5: Transfer the ball-milled slurry to a vacuum mixer for vacuum degassing to prepare a fine finished slurry, obtaining a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, and seal it for later use.

[0024] In some embodiments, an appropriate amount of titanium dioxide powder is added to step two.

[0025] In some embodiments, an appropriate amount of spherical alumina powder is added to step three.

[0026] In some embodiments, in step two, the stirring is carried out at a high speed of 800-1200 rpm for 15-25 minutes.

[0027] In some embodiments, in step four, zirconia balls are used as the milling medium, and milling is performed at 200-300 rpm for 2-4 hours.

[0028] In some embodiments, in step five, degassing is performed for 15-25 minutes under a vacuum of -0.1 MPa or higher.

[0029] The third objective of this invention is to disclose a relatively simple process with a suitable curing temperature, which avoids thermal damage to the precision ceramic substrate and facilitates on-site construction and bonding of complex components.

[0030] To achieve the above objectives, this invention discloses the application of a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0031] Step 1: Substrate surface treatment: Clean the surface of the substrate to be bonded with anhydrous ethanol and dry it;

[0032] Step 2: Apply adhesive: Apply the high shock-resistant, low-precipitation phosphate ceramic structural adhesive evenly to the surface of the substrate;

[0033] Step 3: Gradient temperature curing: Heat the coated substrate to 80-120℃ and hold for a certain time, then heat to 350-450℃ and hold for a certain time, then continue to heat to 800-900℃ and hold for a certain time, and finally cool down to room temperature to obtain the coated substrate.

[0034] In some embodiments, in step two, the thickness of the adhesive layer is 0.1-0.3 mm.

[0035] In some embodiments, in step three, the temperature is first increased to 80-120°C at a rate of 1-2°C / min and held for 1-1.5 hours; then increased to 350-450°C at a rate of 3-5°C / min and held for 0.5-1 hours; then increased to 800-900°C at a rate of 5-8°C / min and held for 2-3 hours; and finally decreased to 300°C at a rate of 3-5°C / min and cooled to room temperature with the furnace.

[0036] In some embodiments, the cooling rate of the furnace cooling is ≤2℃ / min

[0037] Compared with the prior art, the beneficial effects of the present invention are: (1) The present invention introduces a nano-zirconia phase transformation toughening phase, combined with a sheet-like alumina skeleton support, which significantly improves the impact resistance and thermal shock resistance performance, effectively prevents cracking during use, and solves the problem of inorganic adhesives being prone to failure under vibration conditions; (2) The total amount of ion precipitation of the adhesive made by adding a layered zirconium phosphate ion trapping phase is much lower than the level of the prior art, which meets the stringent requirements for material purity in the fields of biomedicine and food; (3) The adhesive can work for a long time below 500℃, has a high strength retention rate at high temperature, solves the problem of easy failure at high temperature, has good stability to chemical media such as acids, alkalis, and solvents, and is suitable for some corrosive environments; (4) The curing temperature is moderate, which does not easily damage the precision substrate, and is convenient for on-site construction and bonding of complex structures; (5) The present invention achieves high shock resistance, low precipitation, high temperature resistance, and corrosion resistance through component synergy, namely toughening phase + low precipitation phase + skeleton phase + functional additives and process optimization. Attached Figure Description

[0038] Figure 1 This is an experimental diagram showing the water flux test of a dynamic ceramic membrane filter element made using the high shock resistance and low precipitation phosphate ceramic structural adhesive disclosed in Example 1. Detailed Implementation

[0039] The present invention will now be described in detail with reference to the embodiments shown in the accompanying drawings. However, it should be noted that these embodiments are not intended to limit the present invention. Any equivalent substitutions or replacements in function, method, or structure made by those skilled in the art based on these embodiments are within the scope of protection of the present invention.

[0040] Example 1

[0041] A high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, by weight, comprises the following components: 100 parts aluminum dihydrogen phosphate, 8-15 parts zinc oxide powder, 35-45 parts flake alumina powder, 5-10 parts nano-zirconia powder, and 0.5-2 parts layered zirconium phosphate powder.

[0042] In this embodiment, the preferred composition is 12 parts zinc oxide powder, 40 parts flake alumina powder, 8 parts nano zirconium oxide powder, and 1 part layered zirconium phosphate powder.

[0043] The alumina powder has a sheet diameter of 30-50 μm, and the zirconium oxide nanoparticles have a particle size of 30-50 nm.

[0044] The present invention discloses a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, which uses aluminum dihydrogen phosphate as a binder phase and as a matrix. The matrix is ​​dehydrated and polycondensed at high temperature to form a three-dimensional network structure, providing the skeleton of the adhesive.

[0045] Zinc oxide powder, as a curing accelerator and network modifier, can optimize the thermal expansion coefficient of adhesives, improve high-temperature stability, enhance the adaptability of curing processes, and strengthen the dimensional stability and creep resistance of adhesive layers at high temperatures.

[0046] Flaky alumina powder, acting as a skeletal reinforcing phase, overlaps and crosses within the adhesive layer to form a robust skeleton, greatly improving mechanical strength, stiffness, and wear resistance. It effectively inhibits curing shrinkage and crack propagation, providing a highly earthquake-resistant skeletal support.

[0047] Using nano-zirconia powder as the core toughening phase, the stress-induced phase transformation toughening mechanism significantly improves fracture toughness and thermal shock resistance.

[0048] Layered zirconium phosphate powder, as a particle adsorption phase, can efficiently capture free Al³⁺, Zn²⁺, etc. in the colloidal layer and fix them in the layered structure, greatly reducing the amount of metal ion precipitation.

[0049] This embodiment also discloses a method for preparing a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0050] Step 1: Prepare a 50-70 wt% aqueous solution from 100 parts of aluminum dihydrogen phosphate to obtain the base solution; in this embodiment, 60 wt% is preferred.

[0051] Step 2: Add 12 parts of zinc oxide powder, 8 parts of nano-zirconia powder and 1 part of layered zirconium phosphate powder to the base liquid in Step 1 in sequence, and stir at high speed at 800-1200 rpm for 15-25 min to obtain a dispersion. In this embodiment, the preferred speed is 1000 rpm and the stirring time is 20 min.

[0052] Step 3: Add 40 parts of flake alumina powder to the dispersion, adjust the speed to 500 rpm and continue stirring for 30 minutes until the mixture is uniform, and obtain a paste-like slurry without obvious particle agglomeration;

[0053] Step 4: Transfer the paste to a ball mill jar, add zirconia balls with a particle size of 5nm as the grinding medium, and grind at a ball mill speed of 200-300rpm for 2-4 hours. The temperature during the ball milling process should be controlled at ≤40℃. In this embodiment, the preferred speed is 250rpm and the grinding time is 3 hours.

[0054] Step 5: Transfer the ball-milled slurry to a vacuum mixer for vacuum degassing treatment. The mixing speed is 150 rpm, the vacuum degree is set to -0.1 MPa, and the degassing time is 15-25 min. In this embodiment, 20 min is preferred to obtain a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive. Seal it for later use.

[0055] The preparation method first adds zinc oxide, nano-zirconia, and layered zirconium phosphate fine powder components and disperses them at high speed, and then adds flaky alumina. This can prevent the fine powder from being wrapped by the flaky particles and ensure that each component can be evenly dispersed.

[0056] This invention discloses the application of a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0057] Step 1: Substrate surface treatment: Clean the surface of the substrate to be bonded with anhydrous ethanol and dry it. In this embodiment, a self-made disc ceramic membrane filter element support layer is selected as the substrate.

[0058] Step 2: Apply adhesive using a scraper to evenly coat the high-shock-resistant, low-precipitation phosphate ceramic structural adhesive onto the substrate surface. The adhesive layer thickness should be controlled between 0.1-0.3 mm, with 0.2 mm being preferred in this embodiment. Allow the adhesive to stand for 30 minutes after application.

[0059] Step 3: Place the coated substrate in a box oven for gradient temperature curing. First, raise the temperature to 80-120℃ at 1-2℃ / min and hold for 1-1.5h; then raise the temperature to 350-450℃ at 3-5℃ / min and hold for 0.5-1h; then raise the temperature to 800-900℃ at 5-8℃ / min and hold for 2-3h; finally, lower the temperature to 300℃ at 3-5℃ / min and then cool it to room temperature with the oven at a cooling rate of ≤2℃ / min to obtain the coated substrate.

[0060] The preferred process conditions in this embodiment are as follows: heating to 100℃ at 1.5℃ / min and holding for 1.2h; then heating to 400℃ at 4℃ / min and holding for 0.8h; then heating to 850℃ at 6℃ / min and holding for 2h; finally cooling to 300℃ at 4℃ / min and then cooling to room temperature at a cooling rate of ≤2℃ / min.

[0061] Example 2

[0062] A high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, by weight, comprises the following components: 100 parts aluminum dihydrogen phosphate, 12 parts zinc oxide powder, 40 parts flake alumina powder, 8 parts nano-zirconia powder, and 1 part layered zirconium phosphate powder.

[0063] The difference from Example 1 is that 0.5-2 parts of titanium dioxide powder with a particle size of 0.2-0.5 μm are added to the above materials. In this example, 1.2 parts of titanium dioxide powder with a particle size of 0.3 μm are preferred.

[0064] This embodiment describes a method for preparing a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0065] Step 1: Prepare a 50-70 wt% aqueous solution from 100 parts of aluminum dihydrogen phosphate to obtain the base solution; in this embodiment, 60 wt% is preferred.

[0066] Step 2: Add 12 parts of zinc oxide powder, 8 parts of nano-zirconia powder, 1.2 parts of titanium oxide powder and 1 part of layered zirconium phosphate powder to the base solution in Step 1 in sequence, and stir at high speed at 1000 rpm for 20 min to obtain a dispersion.

[0067] Step 3: Add 40 parts of flake alumina powder to the dispersion, adjust the speed to 500 rpm and continue stirring for 30 minutes until the mixture is uniform, and obtain a paste-like slurry without obvious particle agglomeration;

[0068] Step 4: Transfer the paste to a ball mill jar, add zirconia balls with a particle size of 5nm as the grinding medium, and grind at a ball mill speed of 200-300rpm for 2-4 hours. The temperature during the ball milling process should be controlled at ≤40℃. In this embodiment, the preferred speed is 250rpm and the grinding time is 3 hours.

[0069] Step 5: Transfer the ball-milled slurry to a vacuum mixer for vacuum degassing treatment. The mixing speed is 150 rpm, the vacuum degree is set to -0.1 MPa, and the degassing time is 15-25 min. In this embodiment, 20 min is preferred to obtain a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive. Seal it for later use.

[0070] The application process of a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive is the same as that in Example 1.

[0071] Example 3

[0072] A high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, by weight, comprises the following components: 100 parts aluminum dihydrogen phosphate, 12 parts zinc oxide powder, 40 parts flake alumina powder, 8 parts nano-zirconia powder, and 1 part layered zirconium phosphate powder.

[0073] The difference from Example 1 is that 5-10 parts of spherical alumina powder with a particle size of 1-5 μm are added to the above materials. In this example, 7 parts of spherical alumina powder with a particle size of 3 μm are preferred.

[0074] This embodiment describes a method for preparing a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0075] Step 1: Prepare a 50-70 wt% aqueous solution from 100 parts of aluminum dihydrogen phosphate to obtain the base solution; in this embodiment, 60 wt% is preferred.

[0076] Step 2: Add 12 parts of zinc oxide powder, 8 parts of nano-zirconia powder and 1 part of layered zirconium phosphate powder to the base solution in Step 1 in sequence, and stir at high speed at 1000 rpm for 20 min to obtain a dispersion.

[0077] Step 3: Add 7 parts of spherical alumina powder to the dispersion, adjust the speed to 500 rpm and stir for 15 minutes, then add 40 parts of flake alumina powder and continue stirring for 30 minutes until the mixture is uniform, so that the spherical alumina fills the gaps between the flake alumina, and a paste-like slurry without obvious particle agglomeration is obtained.

[0078] Step 4: Transfer the paste to a ball mill jar, add zirconia balls with a particle size of 5nm as the grinding medium, and grind at a ball mill speed of 200-300rpm for 2-4 hours. The temperature during the ball milling process should be controlled at ≤40℃. In this embodiment, the preferred speed is 250rpm and the grinding time is 3 hours.

[0079] Step 5: Transfer the ball-milled slurry to a vacuum mixer for vacuum degassing treatment. The mixing speed is 150 rpm, the vacuum degree is set to -0.1 MPa, and the degassing time is 15-25 min. In this embodiment, 20 min is preferred to obtain a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive. Seal it for later use.

[0080] The application process of a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive is the same as that in Example 1.

[0081] Example 4

[0082] A high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, by weight, comprises the following components: 100 parts aluminum dihydrogen phosphate, 12 parts zinc oxide powder, 40 parts flake alumina powder, 8 parts nano-zirconia powder, and 1 part layered zirconium phosphate powder.

[0083] This embodiment also includes 1.2 parts of titanium dioxide powder and 7 parts of spherical alumina powder.

[0084] This embodiment also discloses a method for preparing a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0085] Step 1: Prepare a 50-70 wt% aqueous solution from 100 parts of aluminum dihydrogen phosphate to obtain the base solution; in this embodiment, 60 wt% is preferred.

[0086] Step 2: Add 12 parts of zinc oxide powder, 8 parts of nano zirconium oxide powder, 1.2 parts of titanium oxide powder and 1 part of layered zirconium phosphate powder to the base liquid in Step 1 in sequence, and stir at high speed at 1000 rpm for 20 min to obtain a dispersion.

[0087] Step 3: First, add 7 parts of spherical alumina powder to the dispersion and stir for 15 minutes. Then, add 40 parts of flake alumina powder and continue stirring for 30 minutes until the mixture is uniform, resulting in a paste-like slurry without obvious particle agglomeration.

[0088] Step 4: Transfer the paste to a ball mill jar, add zirconia balls with a particle size of 5nm as the grinding medium, and grind at a ball mill speed of 250rpm for 3 hours. The temperature during the ball milling process should be controlled at ≤40℃.

[0089] Step 5: Transfer the ball-milled slurry to a vacuum mixer for vacuum degassing treatment. The mixing speed is 150 rpm, the vacuum degree is set to -0.1 MPa, and the degassing time is 20 min to obtain a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive. Seal it for later use.

[0090] The preparation method first adds zinc oxide, nano-zirconia, and layered zirconium phosphate fine powder components and disperses them at high speed, then adds flaky alumina. This avoids the fine powder being coated by the flaky particles and ensures that each component can be uniformly dispersed. In step three, spherical alumina powder is added first, followed by flaky alumina powder, so that the spherical alumina evenly fills the gaps between the flaky alumina.

[0091] This invention discloses the application of a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0092] Step 1: Substrate surface treatment: Clean the surface of the substrate to be bonded with anhydrous ethanol and dry it at 60°C. In this embodiment, a self-made disc ceramic membrane filter element support layer is selected as the substrate.

[0093] Step 2: Apply the high shock-resistant, low-precipitation phosphate ceramic structural adhesive evenly to the substrate surface using a scraper. The adhesive layer thickness should be controlled at 0.2 mm. After application, allow the adhesive to stand for 30 minutes.

[0094] Step 3: Place the coated substrate in a box oven and cure it by gradient heating. Increase the temperature to 100℃ at 1.5℃ / min and hold for 1.2h; then increase the temperature to 400℃ at 4℃ / min and hold for 0.8h; then increase the temperature to 850℃ at 6℃ / min and hold for 2h; finally, decrease the temperature to 300℃ at 4℃ / min and then decrease it to room temperature at a rate of ≤2℃ / min to obtain the coated substrate.

[0095] Example 5

[0096] A high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, by weight, comprises the following components: 100 parts aluminum dihydrogen phosphate, 8 parts zinc oxide powder, 35 parts flake alumina powder, 5 parts nano-zirconia powder, and 0.5 parts layered zirconium phosphate powder.

[0097] This embodiment also includes 0.5 parts of titanium dioxide powder and 5 parts of spherical alumina powder.

[0098] This embodiment also discloses a method for preparing a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0099] Step 1: Prepare a 50wt% aqueous solution from 100 parts of aluminum dihydrogen phosphate to obtain the base solution;

[0100] Step 2: Add 8 parts of zinc oxide powder, 5 parts of nano-zirconia powder, 0.5 parts of titanium oxide powder and 0.5 parts of layered zirconium phosphate powder to the base solution in Step 1 in sequence, and stir at high speed at 800 rpm for 15 min to obtain a dispersion.

[0101] Step 3: First, add 5 parts of spherical alumina powder to the dispersion and stir for 15 minutes. Then add 35 parts of flake alumina powder and continue stirring for 30 minutes until the mixture is uniform, resulting in a paste-like slurry without obvious particle agglomeration.

[0102] Step 4: Transfer the paste to a ball mill jar, add zirconia balls with a particle size of 5nm as the grinding medium, and grind at a ball mill speed of 200rpm for 2 hours. The temperature during the ball milling process should be controlled at ≤40℃.

[0103] Step 5: Transfer the ball-milled slurry to a vacuum mixer for vacuum degassing treatment. The mixing speed is 150 rpm, the vacuum degree is set to -0.1 MPa, and the degassing time is 15 min to obtain a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive. Seal it for later use.

[0104] The preparation method first adds zinc oxide, nano-zirconia, and layered zirconium phosphate fine powder components and disperses them at high speed, then adds flaky alumina. This avoids the fine powder being coated by the flaky particles and ensures that each component can be uniformly dispersed. In step three, spherical alumina powder is added first, followed by flaky alumina powder, so that the spherical alumina evenly fills the gaps between the flaky alumina.

[0105] This invention discloses the application of a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0106] Step 1: Substrate surface treatment: Clean the surface of the substrate to be bonded with anhydrous ethanol and dry it at 60°C. In this embodiment, a self-made disc ceramic membrane filter element support layer is selected as the substrate.

[0107] Step 2: Apply the high-shock-resistant, low-precipitation phosphate ceramic structural adhesive evenly to the substrate surface using a scraper. The adhesive layer thickness should be controlled at 0.1 mm. After application, allow the adhesive to stand for 30 minutes.

[0108] Step 3: Place the coated substrate in a box oven and cure it by gradient heating. Increase the temperature to 80℃ at 1℃ / min and hold for 1 hour; then increase the temperature to 350℃ at 3℃ / min and hold for 0.5 hours; then increase the temperature to 800℃ at 5℃ / min and hold for 2 hours; finally, decrease the temperature to 300℃ at 3℃ / min and then decrease it to room temperature at a rate of ≤2℃ / min to obtain the coated substrate.

[0109] Example 6

[0110] A high-shock-resistant, low-precipitation phosphate ceramic structural adhesive comprises, by weight, the following components: 100 parts aluminum dihydrogen phosphate, 15 parts zinc oxide powder, 45 parts flake alumina powder, 10 parts nano-zirconia powder, and 2 parts layered zirconium phosphate powder.

[0111] This embodiment also includes 2 parts of titanium dioxide powder and 10 parts of spherical alumina powder.

[0112] This embodiment also discloses a method for preparing a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0113] Step 1: Prepare a 70wt% aqueous solution from 100 parts of aluminum dihydrogen phosphate to obtain the base solution;

[0114] Step 2: Add 15 parts of zinc oxide powder, 10 parts of nano-zirconia powder, 2 parts of titanium oxide powder and 2 parts of layered zirconium phosphate powder to the base liquid in Step 1 in sequence, and stir at high speed at 800 rpm for 15 min to obtain a dispersion.

[0115] Step 3: First, add 10 parts of spherical alumina powder to the dispersion and stir for 15 minutes. Then, add 45 parts of flake alumina powder and continue stirring for 30 minutes until the mixture is uniform, resulting in a paste-like slurry without obvious particle agglomeration.

[0116] Step 4: Transfer the paste to a ball mill jar, add zirconia balls with a particle size of 5nm as the grinding medium, and grind at 300rpm for 4 hours. The temperature during the ball milling process should be controlled to be ≤40℃.

[0117] Step 5: Transfer the ball-milled slurry to a vacuum mixer for vacuum degassing treatment. The mixing speed is 150 rpm, the vacuum degree is set to -0.1 MPa, and the degassing time is 25 min to obtain a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive. Seal it for later use.

[0118] The preparation method first adds zinc oxide, nano-zirconia, and layered zirconium phosphate fine powder components and disperses them at high speed, then adds flaky alumina. This avoids the fine powder being coated by the flaky particles and ensures that each component can be uniformly dispersed. In step three, spherical alumina powder is added first, followed by flaky alumina powder, so that the spherical alumina evenly fills the gaps between the flaky alumina.

[0119] This invention discloses the application of a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, comprising the following steps:

[0120] Step 1: Substrate surface treatment: Clean the surface of the substrate to be bonded with anhydrous ethanol and dry it at 60°C. In this embodiment, a self-made disc ceramic membrane filter element support layer is selected as the substrate.

[0121] Step 2: Apply the high-shock-resistant, low-precipitation phosphate ceramic structural adhesive evenly to the substrate surface using a scraper. The adhesive layer thickness should be controlled at 0.1 mm. After application, allow the adhesive to stand for 30 minutes.

[0122] Step 3: Place the coated substrate in a box oven and cure it by gradient heating. Increase the temperature to 120℃ at 2℃ / min and hold for 1.5h; then increase the temperature to 450℃ at 5℃ / min and hold for 1h; then increase the temperature to 900℃ at 8℃ / min and hold for 3h; finally, decrease the temperature to 300℃ at 5℃ / min and then decrease it to room temperature at a rate of ≤2℃ / min to obtain the coated substrate.

[0123] Comparative Example 1

[0124] Compared with Example 1, Comparative Example 1 did not add nano-zirconia powder.

[0125] Comparative Example 2

[0126] Compared with Example 1, Comparative Example 2 did not add layered zirconium phosphate powder.

[0127] Comparative Example 3

[0128] Compared with Example 1, the difference in the preparation method of Comparative Example 3 is that the preparation method of a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive includes the following steps:

[0129] Step 1: Prepare a 60wt% aqueous solution from 100 parts of aluminum dihydrogen phosphate to obtain the base solution;

[0130] Step 2: Add 12 parts of zinc oxide powder, 8 parts of nano-zirconia powder and 1 part of layered zirconium phosphate powder to the base solution in Step 1 in sequence, and stir at high speed at 600 rpm for 10 min to obtain a dispersion.

[0131] Step 3: Add 40 parts of flake alumina powder to the dispersion, adjust the speed to 500 rpm and continue stirring for 30 minutes until the mixture is uniform, and obtain a paste-like slurry without obvious particle agglomeration;

[0132] Step 4: Transfer the paste to a ball mill jar, add zirconia balls with a particle size of 5nm as the grinding medium, and grind at a ball mill speed of 150rpm for 1 hour. The temperature during the ball milling process should be controlled at ≤40℃.

[0133] Step 5: Transfer the ball-milled slurry to a vacuum mixer for vacuum degassing treatment. The mixing speed is 150 rpm, the vacuum degree is set to -0.1 MPa, and the degassing time is 10 min to obtain a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive. Seal it for later use.

[0134] Comparative Example 4

[0135] Commercially available aluminum phosphate adhesive was used to bond the substrate of the self-made disc ceramic membrane filter element support layer. Compared with Example 1, it does not contain nano-zirconia or layered zirconium phosphate components.

[0136] Comparative Example 5

[0137] Commercially available epoxy adhesives were used for bonding the substrate of the self-made disc ceramic membrane filter element support layer.

[0138] Performance testing

[0139] A self-made disc-shaped ceramic membrane filter element support layer was selected as the ceramic component.

[0140] 1. Seismic resistance test: The impact resistance of the adhesive layer is tested according to GB / T1834-2008 "Test of Impact Strength of Plastic Cantilever Beams".

[0141] 2. Ion precipitation test: The cured adhesive sample was immersed in deionized water at room temperature for 72 hours, and the concentration of Al³⁺ and Zn²⁺ ions in the immersion solution was tested;

[0142] 3. High temperature resistance test: The cured adhesive samples were kept at 25℃ and 800℃ for 2 hours respectively, and the adhesive strength was tested.

[0143] 4. Corrosion resistance test: The cured adhesive samples were immersed in 10wt% H2SO4 solution and 10wt% NaOH solution for 72h at room temperature, respectively, and the adhesive strength after immersion was tested.

[0144] 5. Water flux test of disc ceramic membrane filter element: Install the cured adhesive sample into the dynamic ceramic membrane filtration system, run it for 80 hours, and test the water flux of the system at regular intervals.

[0145]

[0146] As can be seen from Table 1 above, the addition of titanium dioxide powder as a functional additive to the adhesive disclosed in this invention can improve the interfacial adhesion between the adhesive and the substrate, and further enhance the heat resistance and corrosion resistance; the addition of spherical alumina powder as a filler phase improves the density of the adhesive layer, makes the adhesive layer structure more uniform, reduces stress concentration, and improves the overall strength.

[0147] The high-shock-resistant, low-precipitation phosphate ceramic structural adhesive disclosed in this invention features a synergistic effect among its components to achieve its superior properties: lamellar alumina forms the macroscopic framework, while spherical alumina provides dense filling, together constituting a robust matrix. When the adhesive is subjected to external force, nano-zirconia undergoes a phase transformation at the microcrack tip, consuming energy and preventing crack propagation.

[0148] Aluminum dihydrogen phosphate forms a stable inorganic network structure with low solubility. Layered zirconium phosphate acts as both an ion adsorption phase and a stationary phase, further fixing any small amount of metal ions that may be released from the network. This dual protection ensures low precipitation.

[0149] The addition of zinc oxide makes the curing reaction and network formation easier to control. The gradient curing process can ensure that each component can fully react, defoam, densify, and smoothly transition to the phase transition point.

[0150] The detailed descriptions listed above are merely specific descriptions of feasible embodiments of the present invention, and are not intended to limit the scope of protection of the present invention. All equivalent embodiments or modifications made without departing from the spirit of the present invention should be included within the scope of protection of the present invention.

[0151] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, characterized in that, By weight, it contains the following components: 100 parts aluminum dihydrogen phosphate, 8-15 parts zinc oxide powder, 35-45 parts flake alumina powder, 5-10 parts nano zirconium oxide powder, and 0.5-2 parts layered zirconium phosphate powder.

2. The high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 1, characterized in that, It also includes 0.5-2 parts of titanium dioxide powder.

3. The high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 1, characterized in that, It also includes 5-10 parts of spherical alumina powder.

4. The high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 1, characterized in that, The alumina powder has a sheet diameter of 30-50 μm, and the zirconium oxide nanoparticles have a particle size of 30-50 nm.

5. The high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 2, characterized in that, The titanium dioxide powder has a particle size of 0.2-0.5 μm.

6. The high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 3, characterized in that, The particle size of the spherical alumina powder is 1-5 μm.

7. A method for preparing the high seismic resistance and low precipitation phosphate ceramic structural adhesive as described in claim 1, characterized in that, Includes the following steps: Step 1: Prepare an aqueous solution of aluminum dihydrogen phosphate (50-70 wt%) to obtain the base solution; Step 2: Add appropriate amounts of zinc oxide powder, nano-zirconia powder and layered zirconium phosphate powder to the base solution in sequence, and stir and disperse at high speed to obtain a dispersion. Step 3: Add an appropriate amount of flake alumina powder to the dispersion and continue stirring until the mixture is uniform to obtain a paste-like slurry; Step 4: Transfer the paste to a ball mill jar and ball mill for a certain period of time; Step 5: Transfer the ball-milled slurry to a vacuum mixer for vacuum degassing to prepare a fine finished slurry, obtaining a high-shock-resistant, low-precipitation phosphate ceramic structural adhesive, and seal it for later use.

8. The preparation method of the high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 7, characterized in that, Add an appropriate amount of titanium dioxide powder to step two.

9. The preparation method of the high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 7 or 8, characterized in that, Add an appropriate amount of spherical alumina powder to step three.

10. The preparation method of the high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 7, characterized in that, In step two, the mixture is stirred at high speed at 800-1200 rpm for 15-25 minutes.

11. The preparation method of the high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 7, characterized in that, In step four, zirconia balls are used as the milling medium, and the balls are milled at 200-300 rpm for 2-4 hours.

12. The preparation method of the high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 7, characterized in that, In step five, degassing is performed for 15-25 minutes under a vacuum of -0.1 MPa or higher.

13. The application of the high seismic resistance and low precipitation phosphate ceramic structural adhesive as described in claim 7, characterized in that, Includes the following steps: Step 1: Substrate surface treatment: Clean the surface of the substrate to be bonded with anhydrous ethanol and dry it; Step 2: Apply adhesive: Apply the high shock-resistant, low-precipitation phosphate ceramic structural adhesive evenly to the surface of the substrate; Step 3: Gradient temperature curing: Heat the coated substrate to 80-120℃ and hold for a certain time, then heat to 350-450℃ and hold for a certain time, then continue to heat to 800-900℃ and hold for a certain time, and finally cool down to room temperature to obtain the coated substrate.

14. The application of the high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 13, characterized in that, In step two, the thickness of the adhesive layer is 0.1-0.3 mm.

15. The application of the high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 13, characterized in that, In step three, the temperature is first increased to 80-120℃ at 1-2℃ / min and held for 1-1.5h; then increased to 350-450℃ at 3-5℃ / min and held for 0.5-1h; then increased to 800-900℃ at 5-8℃ / min and held for 2-3h; finally, the temperature is decreased to 300℃ at 3-5℃ / min and then cooled to room temperature in the furnace.

16. The application of the high seismic resistance and low precipitation phosphate ceramic structural adhesive according to claim 15, characterized in that, The cooling rate of the furnace cooling is ≤2℃ / min.

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