Corrosion-resistant ceramic composite material and method for manufacturing the same

Abstract

The application discloses a kind of corrosion-resistant ceramic composite material and preparation method thereof, the preparation method includes, using corrosion-resistant ceramic slurry to be hung slurry to corrugated sub-board, then dry, obtain plate material;Multiple plate materials are bonded using corrosion-resistant ceramic slurry, obtain green body;After drying, sintering green body, obtain corrosion-resistant ceramic composite material;Wherein, the raw material of corrosion-resistant ceramic slurry includes, 70~80 parts kaolin, 20~30 parts potassium feldspar, 2~5 parts yttria stabilized zirconia, 0.5~2 parts nanometer cerium dioxide, 1~3 parts dispersing agent and 15~30 parts water by mass fraction.The application uses kaolin and potassium feldspar as main component, supplemented by yttria stabilized zirconia, nanometer cerium dioxide prepared by hydrothermal reaction is added spherical cluster, can effectively improve compactness, to obtain higher strength, corrosion-resistant and wear-resistant ceramic composite material.

Description

Technical Field

[0001] This invention relates to the field of ceramic materials technology, and in particular to a corrosion-resistant ceramic composite material and its preparation method. Background Technology

[0002] Ceramic corrugated packing is a new type of high-efficiency structured packing, composed of parallel stacked ceramic corrugated sheet units with the same geometry, typically in cylindrical form. Due to the unique structure of ceramics, it possesses excellent hydrophilic properties, and its surface can form extremely thin liquid films. The turbulence and inclined, tortuous channels of airflow promote airflow without obstructing it, allowing ceramic packing to rival metal packing. However, its corrosion resistance and high-temperature resistance are unmatched by metal packing, making it particularly suitable for harsh conditions such as highly corrosive, high-temperature, and high-purity separation. Currently, ceramic corrugated packing has become a key mass transfer element in industries such as chemical, environmental protection, energy, metallurgy, and pharmaceuticals.

[0003] With the continuous expansion of application fields, the performance requirements for ceramic corrugated packing have correspondingly increased. CN119075895A discloses a corrosion-resistant ceramic corrugated packing and its preparation method. The method involves covering the upper surface of a pre-formed ceramic corrugated plate with a sponge saturated with ceramic slurry. The ceramic slurry in the sponge covering the corrugated ridges tends to flow slowly down the slopes on both sides, converging into the sponge within the corrugated valleys. Subsequently, the high temperature of sintering melts and volatilizes the sponge, transforming the space originally occupied by the sponge into numerous pores. This creates porous sections at the contact points between the corrugated ridges and valleys of adjacent ceramic corrugated plates, effectively eliminating dead zones in the packing, reducing the retention and accumulation of adsorbates, and improving the corrosion resistance and service life of the packing. However, the actual corrosion resistance performance has not been tested, and the porous sections formed by decomposition may result in poor strength. CN115745657A discloses a method for preparing ceramic corrugated structured packing using chromium slag. The method includes: cutting a sponge precursor to obtain corrugated sub-plates; coating the corrugated sub-plates with a slurry containing chromium slag; drying the coated corrugated sub-plates; bonding several dried corrugated sub-plates together using the chromium slag-containing slurry to obtain a packing blank; and drying, degreasing, and sintering the packing blank. This method achieves comprehensive utilization of chromium slag and increases the reaction contact area of ​​the ceramic corrugated structured packing. However, this method mainly achieves comprehensive utilization of waste residue and does not evaluate corrosion resistance. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a method for preparing a corrosion-resistant ceramic composite material, comprising,

[0005] The corrugated sub-board is coated with a corrosion-resistant ceramic slurry and then dried to obtain the board material.

[0006] Multiple plates are bonded together using a corrosion-resistant ceramic slurry to obtain a green body;

[0007] The green body is dried and then sintered to obtain a corrosion-resistant ceramic composite material;

[0008] The raw materials of the corrosion-resistant ceramic slurry, by weight, include 70-80 parts kaolin, 20-30 parts potassium feldspar, 2-5 parts yttrium oxide-stabilized zirconium oxide, 0.5-2 parts nano-cerium dioxide, 1-3 parts dispersant, and 15-30 parts water.

[0009] The theoretical chemical formula of kaolin is Al₂O₃·2SiO₂·2H₂O, with its main components being Al₂O₃, SiO₂, and structural water. Kaolin imparts excellent plasticity and molding properties to clay, allowing ceramics to be shaped into various forms. Its rich Al₂O₃ content is the primary source of the ceramic's corrosion resistance and high-temperature resistance, forming the skeletal structure of the ceramic body after sintering and providing mechanical strength. Potassium feldspar's main component is KAlSi₃O₈, with the order of proportion being SiO₂, Al₂O₃, and K₂O. At high temperatures (starting at approximately 1130℃), it melts into a viscous glass, filling the intergranular gaps in the green body, significantly reducing the sintering temperature of the ceramic and decreasing energy consumption. Upon cooling, the molten feldspar forms a glassy phase, increasing the density and mechanical strength of the ceramic. Corrugated packings are subjected to mechanical stress during filling and use. The extremely high chemical stability of yttrium-stabilized zirconia (YSZ), combined with a high-alumina matrix, forms a more stable and denser microstructure, jointly resisting long-term corrosion from harsh chemical media. The toughening and reinforcing effect of YSZ prevents the corrugated sheets from breaking due to impact or vibration during installation and operation, improving their reliability. YSZ also possesses a certain degree of thermal shock resistance, helping to maintain the structural integrity of the packing. Adding nano-cerium dioxide to ceramic preparation can lower the sintering temperature, inhibit lattice growth, and improve the density of the ceramic, thereby obtaining ceramic products with higher strength and more stable performance. Furthermore, nano-cerium dioxide can form a protective film on friction surfaces, significantly reducing the coefficient of friction and wear rate, extending the service life of ceramics; however, this effect is usually achieved only when combined with carbon materials such as graphene and carbon nanotubes.

[0010] This invention uses kaolin and potassium feldspar as the main components, supplemented with yttrium oxide to stabilize zirconium oxide, and adds nano-cerium dioxide prepared into spherical clusters through hydrothermal reaction, which can effectively improve the density, thereby obtaining a ceramic composite material with higher strength, corrosion resistance and wear resistance.

[0011] The preparation method of the nano-cerium dioxide includes,

[0012] Soluble cerium salt, polyvinylpyrrolidone, and aqueous ethylene glycol were mixed in a mass ratio of 1~2:0.2~0.5:50~80, followed by a hydrothermal reaction, and the insoluble matter was collected.

[0013] Nano-cerium dioxide was obtained by calcining the insoluble material.

[0014] Furthermore, sodium polyaspartate, in an amount of 0.1 to 0.3 times the mass of the soluble cerium salt, is added during mixing.

[0015] Furthermore, the mass concentration of the ethylene glycol aqueous solution is 60%~80%;

[0016] The hydrothermal reaction was carried out at 150-180℃ for 5-10 hours.

[0017] The calcination is carried out at 450~700℃ for 1~3 hours.

[0018] Furthermore, the corrugated sub-plate is made of polyurethane foam with a porosity of 70% to 90% and an average pore size of 0.5 to 2 mm.

[0019] The arc center angle of the corrugated subplate is 90°~120°.

[0020] Furthermore, the kaolin and potassium feldspar have a particle size of 200-1500 mesh.

[0021] Furthermore, the sintering is carried out at 1250~1450℃.

[0022] Furthermore, the dispersant includes at least one of sodium phosphate, sodium silicate, hydroxypropyl methylcellulose, polyvinyl alcohol, and lignin sulfonate.

[0023] It should be noted that when using corrosion-resistant ceramic slurry to bond multiple plates, the amount of corrosion-resistant ceramic slurry used does not need to be strictly limited, as long as the green body can be formed after sintering.

[0024] The present invention also provides a corrosion-resistant ceramic composite material, which is obtained by the above-described preparation method.

[0025] The present invention also provides the application of the above-mentioned corrosion-resistant ceramic composite material in the fields of organic compound distillation, sulfuric acid absorption, and heat exchange.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] This invention uses kaolin and potassium feldspar as the main components, supplemented with yttrium oxide to stabilize zirconium oxide, and adds nano-cerium dioxide prepared into spherical clusters through hydrothermal reaction, which can effectively improve the density, thereby obtaining a ceramic composite material with higher strength, corrosion resistance and wear resistance. Attached Figure Description

[0028] Figure 1 A flowchart illustrating the preparation method of the corrosion-resistant ceramic composite material of the present invention is shown;

[0029] Figure 2 A schematic diagram of the structure of the blank of the present invention is shown;

[0030] Figure 3 A scanning electron microscope image of the nano-cerium dioxide prepared in Example 1 is shown;

[0031] Figure 4 A scanning electron microscope image of the nano-cerium dioxide prepared in Example 2 is shown. Detailed Implementation

[0032] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0033] Description of some of the raw materials used in the embodiments and comparative examples of this invention:

[0034] Kaolin with a mesh size of 1250 mesh contains approximately 45.55% Al2O3 and 51.48% SiO2 by mass, with Fe2O3 impurities accounting for less than 0.8% by mass.

[0035] Potassium feldspar, with a mesh size of 500, contains approximately 70.10% SiO2, 16.85% Al2O3, and 10.2% K2O by mass, with Fe2O3 impurity accounting for less than 0.2% by mass.

[0036] Yttrium-stabilized zirconia, grade Zirmil® GY3Z-R60, D50 particle size (μm) is 60, brand: Saint-Gobain.

[0037] The corrugated sub-board is made of polyurethane foam with a porosity of 85% and an average pore size of 0.8 mm through a hot melt cutting method. The thickness of the corrugated sub-board is 1 mm, the arc center angle is 110°, and the arc radius is 60 mm.

[0038] Polyvinylpyrrolidone, with an average molecular weight of 8000 and CAS number 9003-39-8, is sourced from Hunan Yunbang Biotechnology Co., Ltd.

[0039] Sodium polyaspartate, molecular weight 2000-11000, CAS number 181828-06-8.

[0040] All other unmentioned raw materials are common raw materials. The above content is only for illustrative purposes and should not be construed as a strict limitation of the present invention. Those skilled in the art can directly purchase commercially available raw materials or prepare the same / similar raw materials themselves. These contents will not be repeated in the embodiments.

[0041] The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] Example 1

[0043] like Figure 1 As shown, a method for preparing a corrosion-resistant ceramic composite material includes the following steps:

[0044] S1. Preparation of slurry: Add 70kg of kaolin, 25kg of potassium feldspar, 3kg of yttrium oxide-stabilized zirconium oxide, 1.2kg of nano-cerium dioxide, 1kg of sodium phosphate and 25kg of water into a ball mill and ball mill at 150rpm for 3h to obtain corrosion-resistant ceramic slurry;

[0045] S2. Slurry application: The corrosion-resistant ceramic slurry is poured onto the double rollers of the grouting machine using a dipping method. The corrugated sub-board is fed into the grouting machine, and the material is collected on the other side of the double rollers. The dipping is repeated 6 times. Then it is taken out and placed on a pallet to air dry naturally to obtain the board.

[0046] S3. Bonding: Bonding multiple sheets together using a corrosion-resistant ceramic mortar, such as... Figure 2 As shown, two adjacent corrugated sub-plates are mirror-symmetrical to obtain the billet;

[0047] S4. Sintering: The green body is dried at 90℃ for 5 hours, then placed in a sintering furnace and sintered at 1350℃ for 2 hours. Finally, it is naturally cooled to obtain a corrosion-resistant ceramic composite material.

[0048] The preparation method of nano-cerium dioxide is as follows: 1.5 kg of cerium nitrate hexahydrate, 0.3 kg of polyvinylpyrrolidone and 60 kg of 75% ethylene glycol aqueous solution are stirred at a stirring rate of 350 rpm for 30 min, and then transferred to a reaction vessel for hydrothermal reaction at 160℃ for 6 h. After the hydrothermal reaction is completed, the mixture is naturally cooled, filtered, and washed three times each with water and ethanol to obtain insoluble matter. The insoluble matter is placed in an oven at 120℃ and dried for 3 h. Finally, it is transferred to a muffle furnace in an air atmosphere at 500℃ and calcined for 2 h to obtain nano-cerium dioxide.

[0049] Example 2

[0050] A method for preparing a corrosion-resistant ceramic composite material, comprising the following steps:

[0051] S1. Preparation of slurry: Add 70kg kaolin, 25kg potassium feldspar, 3kg yttrium oxide stabilized zirconium oxide, 0.5kg nano cerium dioxide, 1kg sodium phosphate and 25kg water into a ball mill and ball mill at 150rpm for 3h to obtain corrosion-resistant ceramic slurry;

[0052] S2. Slurry application: The corrosion-resistant ceramic slurry is poured onto the double rollers of the grouting machine using a dipping method. The corrugated sub-board is fed into the grouting machine, and the material is collected on the other side of the double rollers. The dipping is repeated 6 times. Then it is taken out and placed on a pallet to air dry naturally to obtain the board.

[0053] S3. Bonding: Bonding multiple sheets together using a corrosion-resistant ceramic mortar, such as... Figure 2 As shown, two adjacent corrugated sub-plates are mirror-symmetrical to obtain the billet;

[0054] S4. Sintering: The green body is dried at 90℃ for 5 hours, then placed in a sintering furnace and sintered at 1350℃ for 2 hours. Finally, it is naturally cooled to obtain a corrosion-resistant ceramic composite material.

[0055] The preparation method of nano-cerium dioxide is as follows: 1.5 kg of cerium nitrate hexahydrate, 0.3 kg of polyvinylpyrrolidone, 0.2 kg of sodium polyaspartate and 60 kg of 75% ethylene glycol aqueous solution are stirred at a stirring rate of 350 rpm for 30 min, and then transferred to a reaction vessel for hydrothermal reaction at 160℃ for 6 h. After the hydrothermal reaction is completed, the mixture is naturally cooled, filtered, and washed three times each with water and ethanol to obtain insoluble matter. The insoluble matter is placed in an oven at 120℃ and dried for 3 h. Finally, it is transferred to a muffle furnace in an air atmosphere at 500℃ and calcined for 2 h to obtain nano-cerium dioxide.

[0056] Example 3

[0057] A method for preparing a corrosion-resistant ceramic composite material, comprising the following steps:

[0058] S1. Preparation of slurry: Add 70kg of kaolin, 25kg of potassium feldspar, 3kg of yttrium oxide-stabilized zirconium oxide, 1.2kg of nano-cerium dioxide, 1kg of sodium phosphate and 25kg of water into a ball mill and ball mill at 150rpm for 3h to obtain corrosion-resistant ceramic slurry;

[0059] S2. Slurry application: The corrosion-resistant ceramic slurry is poured onto the double rollers of the grouting machine using a dipping method. The corrugated sub-board is fed into the grouting machine, and the material is collected on the other side of the double rollers. The dipping is repeated 6 times. Then it is taken out and placed on a pallet to air dry naturally to obtain the board.

[0060] S3. Bonding: Bonding multiple sheets together using a corrosion-resistant ceramic mortar, such as... Figure 2 As shown, two adjacent corrugated sub-plates are mirror-symmetrical to obtain the billet;

[0061] S4. Sintering: The green body is dried at 90℃ for 5 hours, then placed in a sintering furnace and sintered at 1350℃ for 2 hours. Finally, it is naturally cooled to obtain a corrosion-resistant ceramic composite material.

[0062] The preparation method of nano-cerium dioxide is the same as in Example 2.

[0063] Example 4

[0064] A method for preparing a corrosion-resistant ceramic composite material, comprising the following steps:

[0065] S1. Preparation of slurry: Add 70kg kaolin, 25kg potassium feldspar, 3kg yttrium oxide stabilized zirconium oxide, 2kg nano cerium dioxide, 1kg sodium phosphate and 25kg water into a ball mill and ball mill at 150rpm for 3h to obtain corrosion-resistant ceramic slurry;

[0066] S2. Slurry application: The corrosion-resistant ceramic slurry is poured onto the double rollers of the grouting machine using a dipping method. The corrugated sub-board is fed into the grouting machine, and the material is collected on the other side of the double rollers. The dipping is repeated 6 times. Then it is taken out and placed on a pallet to air dry naturally to obtain the board.

[0067] S3. Bonding: Bonding multiple sheets together using a corrosion-resistant ceramic mortar, such as... Figure 2 As shown, two adjacent corrugated sub-plates are mirror-symmetrical to obtain the billet;

[0068] S4. Sintering: The green body is dried at 90℃ for 5 hours, then placed in a sintering furnace and sintered at 1350℃ for 2 hours. Finally, it is naturally cooled to obtain a corrosion-resistant ceramic composite material.

[0069] The preparation method of nano-cerium dioxide is the same as in Example 2.

[0070] Comparative Example 1

[0071] The difference from Example 1 is that the slurry does not contain nano-cerium dioxide.

[0072] Test case

[0073] The microstructure of the nano-cerium dioxide prepared in Examples 1 and 2 was observed using scanning electron microscopy, and the results are as follows: Figure 3 and Figure 4As shown, the prepared nano-cerium dioxide all exhibit a spherical structure. However, the nano-cerium dioxide prepared in Example 2 has a loose and porous structure, which is structurally similar to a cluster of small microspheres. This may be because the main chain peptide bonds of sodium polyaspartate degrade under hydrothermal conditions, producing ammonia, carbon dioxide, and water as products.

[0074] The prepared ceramic materials were tested in accordance with the national standard GB / T 4740-2024 "Test Methods for Strength of Ceramic Materials" and the results are shown in Table 1.

[0075] Table 1 Compressive strength results of ceramic materials

[0076]

[0077] As can be seen from the test results in Table 1, the compressive strength of Examples 1-4 with added nano-cerium dioxide is significantly better than that of Comparative Example 1. This is because nano-cerium dioxide lowers the sintering temperature, inhibits lattice growth, and improves the density of the ceramic to a certain extent, thereby enhancing the strength of the ceramic composite material. The strength of Example 3 is higher than that of Example 1, which may be because the porous nano-cerium dioxide has a stronger effect and can preferentially form a stable structure at the grain boundaries.

[0078] A 3 mol / L sulfuric acid aqueous solution was prepared as the corrosion solution. The test sample was subjected to corrosion testing in the solution at 90℃ for 168 hours. The mass change rate of the sample was calculated based on the effective area of ​​the sample and its mass before and after the test.

[0079] Table 2 Corrosion Test Results

[0080]

[0081] As can be seen from the test results in Table 2, the mass change rate of Examples 1-4 is significantly lower than that of Comparative Example 1. This is because nano-cerium dioxide improves the density of ceramics, thus enhancing the acid corrosion resistance of the material.

[0082] The tribological properties of the samples were tested using a functional tribological testing machine. The load was 20 N, the frequency was 1 Hz, and the running time was 30 min. Si3N4 ceramic balls with a diameter of 9 mm were used for grinding. The friction coefficient and wear rate of the samples were recorded. These results are shown in Table 3.

[0083] Table 3 Tribological Performance Results

[0084]

[0085] As can be seen from the test results in Table 3, the friction coefficient and wear rate of Examples 1-4 are significantly lower than those of Comparative Example 1. This is because nano-cerium dioxide can form a protective film on the friction surface, which significantly reduces the friction coefficient and wear rate.

[0086] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a corrosion-resistant ceramic composite material, characterized in that, include, The corrugated sub-board is coated with a corrosion-resistant ceramic slurry and then dried to obtain the board material. Multiple plates are bonded together using a corrosion-resistant ceramic slurry to obtain a green body; The green body is dried and then sintered to obtain a corrosion-resistant ceramic composite material; The raw materials of the corrosion-resistant ceramic slurry, by weight, include 70-80 parts kaolin, 20-30 parts potassium feldspar, 2-5 parts yttrium oxide stabilized zirconium oxide, 0.5-2 parts nano-cerium dioxide, 1-3 parts dispersant and 15-30 parts water; Soluble cerium salt, polyvinylpyrrolidone, and ethylene glycol aqueous solution are mixed in a mass ratio of 1~2:0.2~0.5:50~80, and sodium polyaspartate is added at a mass ratio of 0.1~0.3 times that of soluble cerium salt. Then, a hydrothermal reaction is carried out, and the insoluble matter is collected. Nano-cerium dioxide was obtained by calcining the insoluble material.

2. The method for preparing the corrosion-resistant ceramic composite material according to claim 1, characterized in that, The mass concentration of the ethylene glycol aqueous solution is 60%~80%; The hydrothermal reaction was carried out at 150-180℃ for 5-10 hours. The calcination is carried out at 450~700℃ for 1~3 hours.

3. The method for preparing the corrosion-resistant ceramic composite material according to claim 1, characterized in that, The corrugated sub-board is made of polyurethane foam with a porosity of 70% to 90% and an average pore size of 0.5 to 2 mm. The arc center angle of the corrugated subplate is 90°~120°.

4. The method for preparing the corrosion-resistant ceramic composite material according to claim 1, characterized in that, The kaolin and potassium feldspar have a particle size of 200-1500 mesh.

5. The method for preparing the corrosion-resistant ceramic composite material according to claim 1, characterized in that, The sintering is carried out at 1250~1450℃.

6. The method for preparing the corrosion-resistant ceramic composite material according to claim 1, characterized in that, The dispersant includes at least one of sodium phosphate, sodium silicate, hydroxypropyl methylcellulose, polyvinyl alcohol, and lignin sulfonate.

7. A corrosion-resistant ceramic composite material, characterized in that, It is obtained by the preparation method described in any one of claims 1 to 6.

8. The application of the corrosion-resistant ceramic composite material as described in claim 7 in the fields of organic compound distillation, sulfuric acid absorption, and heat exchange.

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