High-strength high-temperature-resistant ceramic material and preparation method thereof

Abstract

The application relates to the technical field of ceramics, and discloses a high-strength high-temperature-resistant ceramic material and a preparation method, wherein graphene oxide and polyamide naphthalene sulfonate dispersant are reacted, then mixed with clay, quartz powder, talc powder, fly ash and the like through ball milling, calcined, and finally a high-strength high-temperature-resistant ceramic material is obtained. The polyamide naphthalene sulfonate is grafted to the surface of graphene, the dispersibility of the graphene is improved, and the mechanical strength of the ceramic material is improved. The main chain of the polyamide naphthalene sulfonate dispersant contains an amide bond, and the side chain contains a naphthalene sulfonate structure, so that the quartz, fly ash and the like can be dispersed, the apparent porosity of the ceramic is significantly reduced, and the bending strength and other mechanical properties are improved.

Description

A high-strength, high-temperature resistant ceramic material and its preparation method Technical Field

[0001] This invention relates to the field of ceramic technology, specifically to a high-strength, high-temperature resistant ceramic material and its preparation method. Background Technology

[0002] Quartz ceramics are mainly composed of quartz, clay, dispersants, and additives. Their raw materials are inexpensive and readily available, and they exhibit good water resistance and corrosion resistance, making them important in fields such as bathroom fixtures, metallurgy, chemical engineering, and aerospace. However, the low strength of quartz ceramics limits their practical applications.

[0003] Dispersants used in ceramics mainly include polyacrylamide, naphthalene sulfonate dispersants, and carboxymethyl cellulose, which have a significant impact on the mechanical strength properties of ceramics. Therefore, the development of high-performance dispersants is a research hotspot. Graphene oxide, as a high-performance nanomaterial, is widely used in ceramic materials and other fields. The surface of graphene oxide contains active groups such as epoxy and carboxyl groups, which can participate in various chemical reactions. Modifying the surface of graphene can improve its dispersibility and enhance the strength and other properties of the material. This invention aims to improve the mechanical strength and high-temperature resistance of ceramic materials using graphene oxide and polyamide naphthalene sulfonate dispersants. Summary of the Invention

[0004] (I) Technical problem solved: This invention solves the problem of low strength and other properties of quartz ceramics, and improves mechanical strength and high temperature resistance.

[0005] (II) Technical Solution: A method for preparing a high-strength and high-temperature resistant ceramic material: Water, graphene oxide, and polyamide naphthalene sulfonate dispersant are added to a reaction vessel and stirred to obtain a graphene solution; then the graphene solution, clay, quartz powder, talc powder, and fly ash are added to a ball mill for ball milling and mixing. After ball milling, the material is pressed and shaped, dried, and then calcined to obtain a high-strength and high-temperature resistant ceramic material.

[0006] Preferably, the mass ratio of clay, quartz powder, talc powder, fly ash, graphene oxide, and polyamide naphthalene sulfonate dispersant is (23-40):(30-45):(12-20):(8-20):(0.05-0.2):(0.4-0.8).

[0007] Preferably, the temperature during the stirring reaction is 80-90℃, and the reaction time is 18-24h.

[0008] Preferably, the ball milling speed is 100-200 r / min and the time is 1-1.5 h.

[0009] Preferably, the pressure for pressure holding molding is 25-40 MPa, and the time is 40-60 seconds.

[0010] Preferably, calcination is carried out in a tube furnace, with the temperature raised to 1100-1300℃ and held for 1-1.5 hours.

[0011] Preferably, the preparation method of the polyamide naphthalene sulfonate dispersant includes:

[0012] (1) In an ice bath, add N,N-dimethylformamide, 1,4-diaminenaphthalene, diacyl chloride compound and triethylamine in a molar ratio of (1.08-1.14):1:(2-2.2) to a flask, stir and react at 20-40℃ for 12-18h, pour the solution into water, filter, wash with ethanol, and dry to obtain polyamide naphthalene precursor.

[0013] (2) Add 98.3% concentrated sulfuric acid and polyamide naphthalene precursor to the reactor, heat to 60-80℃, react for 1-3 hours, pour the solution into ice water, add sodium hydroxide to neutralize the pH to 7-8, add saturated sodium chloride solution, precipitate out the precipitate, filter and dry the precipitate to obtain polyamide naphthalene sulfonate dispersant. The preparation reaction formula is as follows:

[0014]

[0015] Preferably, the diacyl chloride compound is a short-chain diacyl chloride substance with low hydrophobicity, including malonyl chloride or succinyl chloride.

[0016] (III) Beneficial Technical Effects: This invention reacts graphene oxide with the active-terminal amino groups of an excess of polyamide naphthalene sulfonate dispersant, grafting a portion of the polyamide naphthalene sulfonate onto the graphene surface. This improves the dispersibility of the graphene and enhances the mechanical strength of the ceramic material. The grafted graphene surface introduces a large number of sulfonic acid groups, forming strong interactions with the surfaces of clay, quartz, talc, etc., strengthening the interfacial strength between the graphene and the ceramic matrix. This helps reduce the apparent porosity of the ceramic and further improves the mechanical strength of the ceramic material.

[0017] The polyamide naphthalene sulfonate dispersant of this invention has amide bonds in its main chain and naphthalene sulfonate structures in its side chains. It can disperse quartz, fly ash, etc., significantly reducing the apparent porosity of ceramics and improving mechanical properties such as flexural strength and modulus of rupture. The prepared quartz ceramics, after calcination at 1100-1300℃, maintain excellent mechanical properties and exhibit superior high-temperature resistance. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described below through specific embodiments. However, it should be understood that these descriptions are merely exemplary and not intended to limit the scope of the invention.

[0019] Example 1

[0020] (1) In an ice bath, add 50 mL of N,N-dimethylformamide, 22 mmol of 1,4-diaminenaphthalene, 20 mmol of malonyl chloride and 44 mmol of triethylamine to a flask, stir and react at 20 °C for 18 h, pour the solution into water, filter, wash with ethanol, and dry to obtain polyamide naphthalene precursor.

[0021] (2) Add 1L of concentrated sulfuric acid with a mass fraction of 98.3% and 30g of polyamide naphthalene precursor to the reaction vessel, heat to 70℃, react for 1h, pour the solution into ice water, add sodium hydroxide to neutralize the pH to 8, add saturated sodium chloride solution, precipitate out, filter and dry the precipitate to obtain polyamide naphthalene sulfonate dispersant.

[0022] (3) Add 0.8L of water, 5g of graphene oxide (thickness between 1-3nm, diameter 4-7μm, the same below), and 60g of polyamide naphthalene sulfonate dispersant to the reaction vessel, heat to 80℃, and stir for 24h to obtain a graphene solution; then add the graphene solution and 4kg of clay (bulk density about 2100kg / m³) to the reaction vessel. 3 3.5 kg of quartz powder (average particle size 1300 mesh, the same below), 1.7 kg of talc powder (average particle size 600 mesh, the same below), and 0.8 kg of fly ash (average particle size 200 mesh, the same below) were added to a ball mill and ball-milled for 1.5 h at a speed of 100 r / min. After ball milling, the material was pressed and molded in a molding press for 40 s at a pressure of 30 MPa. After drying, it was placed in a tube furnace and heated to 1200 °C at a heating rate of 5 °C / min. It was then calcined for 1 h to obtain a high-strength, high-temperature resistant ceramic material.

[0023] Example 2

[0024] (1) In an ice bath, add 50 mL of N,N-dimethylformamide, 21.6 mmol of 1,4-diaminenaphthalene, 20 mmol of succinyl chloride and 40 mmol of triethylamine to a flask, stir and react at 40 °C for 12 h, pour the solution into water, filter, wash with ethanol, and dry to obtain polyamide naphthalene precursor.

[0025] (2) Add 1.2L of concentrated sulfuric acid with a mass fraction of 98.3% and 30g of polyamide naphthalene precursor to the reaction vessel, heat to 60℃, react for 3h, pour the solution into ice water, add sodium hydroxide to neutralize the pH to 7, add saturated sodium chloride solution, precipitate out, filter and dry the precipitate to obtain polyamide naphthalene sulfonate dispersant.

[0026] (3) Add 1L of water, 20g of graphene oxide, and 40g of polyamide naphthalene sulfonate dispersant to the reactor, heat to 90℃, stir and react for 18h to obtain graphene solution; then add graphene solution, 3.5kg of clay, 3kg of quartz powder, 2kg of talc powder, and 1.5kg of fly ash to a ball mill and ball mill for 1h at a speed of 200r / min; after ball milling, press the material in a molding press for 60s at a pressure of 40MPa, dry it, and place it in a tube furnace. Heat it to 1300℃ at a heating rate of 5℃ / min and calcine it for 1.5h to obtain high-strength high-temperature resistant ceramic material.

[0027] Example 3

[0028] (1) In an ice bath, add 60 mL of N,N-dimethylformamide, 22.8 mmol of 1,4-diaminenaphthalene, 20 mmol of succinyl chloride and 44 mmol of triethylamine to a flask, stir and react at 30 °C for 18 h, pour the solution into water, filter, wash with ethanol, and dry to obtain polyamide naphthalene precursor.

[0029] (2) Add 1.2L of concentrated sulfuric acid with a mass fraction of 98.3% and 30g of polyamide naphthalene precursor to the reaction vessel, heat to 80℃, react for 1h, pour the solution into ice water, add sodium hydroxide to neutralize the pH to 7, add saturated sodium chloride solution, precipitate out, filter and dry the precipitate to obtain polyamide naphthalene sulfonate dispersant.

[0030] (3) Add 1L of water, 12g of graphene oxide, and 80g of polyamide naphthalene sulfonate dispersant to the reactor, heat to 80℃, stir and react for 24h to obtain graphene solution; then add graphene solution, 2.3kg of clay, 4.5kg of quartz powder, 1.2kg of talc powder, and 2kg of fly ash to a ball mill and ball mill for 1h at a speed of 200r / min; after ball milling, press the material in a molding press for 60s at a pressure of 25MPa, dry it, and place it in a tube furnace. Heat it to 1100℃ at a heating rate of 5℃ / min and calcine it for 1.5h to obtain high-strength, high-temperature resistant ceramic material.

[0031] Comparative Example 1

[0032] (1) Add 0.8L water, 5g graphene oxide, 4.1kg clay, 3.5kg quartz powder, 1.6kg talc powder and 0.8kg fly ash to a ball mill and mix for 1.5h at a ball mill speed of 100r / min. After ball milling, press the material in a molding press for 40s at a pressure of 30MPa. After drying, place it in a tube furnace and heat it to 1200℃ at a heating rate of 5℃ / min. Calcine it for 1h to obtain ceramics.

[0033] Comparative Example 2

[0034] (1) Add 0.8L of water, 5g of graphene oxide, and 60g of polyacrylamide dispersant to the reactor, heat to 80℃, and stir for 24h to obtain a graphene solution; then add the graphene solution, 4.1kg of clay, 3.5kg of quartz powder, 1.6kg of talc powder, and 0.8kg of fly ash to a ball mill and ball mill for 1.5h at a speed of 100r / min; after ball milling, press the material in a molding press for 40s at a pressure of 30MPa, dry it, and place it in a tube furnace. Heat it to 1200℃ at a heating rate of 5℃ / min and calcine it for 1h to obtain ceramics.

[0035] Comparative Example 3

[0036] (1) Add 0.8L of water, 5g of graphene oxide, and 60g of sodium polynaphthalene sulfonate dispersant to the reactor, heat to 80℃, and stir for 24h to obtain a graphene solution; then add the graphene solution, 4.1kg of clay, 3.5kg of quartz powder, 1.6kg of talc powder, and 0.8kg of fly ash to a ball mill and ball mill for 1.5h at a speed of 100r / min; after ball milling, press the material in a molding press for 40s at a pressure of 30MPa, dry it, and place it in a tube furnace. Heat it to 1200℃ at a heating rate of 5℃ / min and calcine it for 1h to obtain ceramics.

[0037] Comparative Example 4

[0038] (1) Add 0.8L water, 5g graphene oxide, 60g polyamide naphthalene sulfonate dispersant (prepared from Example 1), 4kg clay, 3.5kg quartz powder, 1.7kg talc powder, and 0.8kg fly ash to a ball mill and ball mill for 1.5h at a speed of 100r / min. After ball milling, press the material in a molding press for 40s at a pressure of 30MPa. After drying, place it in a tube furnace and heat it to 1200℃ at a heating rate of 5℃ / min. Calcine it at this temperature for 1h to obtain ceramics.

[0039] Table 1 Properties of ceramics

[0040]

[0041] Compared to Comparative Example 1, each embodiment utilizes the reaction of the active-terminal amino groups of the polyamide naphthalene sulfonate dispersant with the epoxy groups on the surface of graphene oxide to graft polyamide naphthalene sulfonate onto the graphene surface. This improves the dispersibility of graphene and is beneficial for enhancing the mechanical strength of ceramic materials. The grafted graphene surface introduces a large number of sulfonic acid groups, forming strong interactions with the surfaces of clay, quartz, talc, etc., enhancing the interfacial strength between graphene and the ceramic matrix, which helps reduce the apparent porosity of ceramics and further improves the mechanical strength of ceramic materials. The main chain of the polyamide naphthalene sulfonate dispersant contains amide bonds, and the side chains contain naphthalene sulfonate structures, which can disperse quartz, fly ash, etc., significantly reducing the apparent porosity of ceramics and improving mechanical properties such as flexural strength and modulus of rupture.

[0042] Compared to Example 1, Comparative Example 2 used conventional polyacrylamide as a dispersant, which does not contain active amino groups and cannot react with graphene oxide, making it difficult to effectively improve the dispersibility of graphene. Furthermore, polyacrylamide does not contain naphthalene sulfonate groups, resulting in low dispersibility with quartz, fly ash, etc., which is detrimental to reducing the apparent porosity of ceramic materials, leading to lower flexural strength and modulus of rupture. Comparative Example 3 used sodium polynaphthalene sulfonate as a dispersant, which also does not contain active amino groups and cannot react with graphene oxide, making it difficult to effectively improve the dispersibility of graphene. Furthermore, sodium polynaphthalene sulfonate does not contain amide bonds, resulting in low dispersibility with quartz, fly ash, etc., which is detrimental to reducing the apparent porosity of ceramic materials, leading to lower flexural strength and modulus of rupture. Comparative Example 4 did not react the polyamide naphthalene sulfonate dispersant with graphene oxide, making it difficult to graft polyamide naphthalene sulfonate onto the graphene surface, thus failing to improve the dispersibility of graphene, resulting in lower flexural strength and modulus of rupture for the ceramic material compared to Example 1.

[0043] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a high-strength, high-temperature resistant ceramic material, characterized in that, The preparation method includes: adding water, graphene oxide, and polyamide naphthalene sulfonate dispersant to a reaction vessel, stirring and reacting to obtain a graphene solution; then adding the graphene solution, clay, quartz powder, talc powder, and fly ash to a ball mill for ball milling and mixing, pressing the material into a mold after ball milling, drying it, and calcining it to obtain a high-strength, high-temperature resistant ceramic material; the preparation method of the polyamide naphthalene sulfonate dispersant includes: (1) adding N,N-dimethylformamide, 1,4-diamine naphthalene, diacyl chloride compound, and triethylamine to a flask in an ice bath, stirring and reacting at 20-40℃ for 12-18h. Pour the solution into water, filter it, wash it with ethanol, and dry it to obtain the polyamide naphthalene precursor; (2) Add concentrated sulfuric acid and polyamide naphthalene precursor to the reaction vessel, heat it to 60-80℃, react for 1-3h, pour the solution into ice water, add sodium hydroxide to neutralize the pH to 7-8, add saturated sodium chloride solution, precipitate the precipitate, filter it and dry the precipitate to obtain polyamide naphthalene sulfonate dispersant; the molar ratio of 1,4-diamine naphthalene, diacyl chloride compound and triethylamine is (1.08-1.14):1:(2-2.2); the diacyl chloride compound is malonyl chloride or succinyl chloride.

2. The method for preparing high-strength, high-temperature resistant ceramic materials according to claim 1, characterized in that, The mass ratio of clay, quartz powder, talc powder, fly ash, graphene oxide, and polyamide naphthalene sulfonate dispersant is (23-40):(30-45):(12-20):(8-20):(0.05-0.2):(0.4-0.8).

3. The method for preparing high-strength, high-temperature resistant ceramic material according to claim 1, characterized in that, The temperature during the stirring reaction is 80-90℃, and the reaction time is 18-24h.

4. The method for preparing high-strength, high-temperature resistant ceramic material according to claim 1, characterized in that, The ball milling speed is 100-200 r / min, and the time is 1-1.5 h.

5. The method for preparing high-strength, high-temperature resistant ceramic material according to claim 1, characterized in that, The pressure for the pressure holding molding is 25-40 MPa, and the time is 40-60 seconds.

6. The method for preparing high-strength, high-temperature resistant ceramic material according to claim 1, characterized in that, The calcination is carried out in a tube furnace, with the temperature raised to 1100-1300℃ and held for 1-1.5 hours.

7. A high-strength, high-temperature resistant ceramic material obtained by the preparation method according to any one of claims 1-6.

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