A method for manufacturing a ceramic tube for a fuse

Abstract

This invention relates to the field of alumina ceramic technology and discloses a method for preparing a ceramic tube for fuses. Compared to ceramic tubes made from traditional alumina ceramic materials, the ceramic tube of this invention exhibits superior toughness and is less brittle. The preparation method includes the following five steps: 1) synthesizing functional monomers containing phosphate esters; 2) synthesizing organosilicon-coated HNTs; 3) synthesizing HNTs@organosilicon / COF with hydroxyl groups on the surface; 4) surface-modifying the HNTs@organosilicon / COF and then reacting it with polysilazane to synthesize reinforcing fillers; 5) using the reinforcing fillers, alumina, glass fiber, and silane coupling agent as raw materials, and then ball-milling, pre-sintering, and sintering to obtain the ceramic tube.

Description

Technical Field

[0001] This invention relates to the field of alumina ceramic technology, and more specifically to a method for preparing a ceramic tube for a fuse. Background Technology

[0002] A fuse is a component used for circuit protection and is widely used in various electronic devices such as televisions, refrigerators, air conditioners, and washing machines. A common fuse consists of a tubular shell, a fuse wire inside the tube, a copper cap, lead wires, and an external epoxy resin encapsulation. The tubular shell is mostly made of glass or ceramic materials. However, glass tubes have disadvantages such as poor thermal conductivity, poor heat dissipation, and fragility, which limits their practical application.

[0003] Analysis of alumina ceramic materials reveals that their use in fabricating outer shells can compensate for the poor thermal conductivity and heat dissipation of glass tubes. However, alumina ceramics are prone to breakage under impact due to their relatively poor toughness. The toughening mechanisms of alumina ceramics mainly include three aspects: bridging mechanism, pull-out mechanism, and crack deflection. Therefore, researchers can utilize the synergistic effect of these three mechanisms to further improve the material's toughness, giving it excellent toughness and preventing breakage due to poor toughness. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a method for preparing a ceramic tube for a fuse.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A method for preparing a ceramic tube for a fuse, comprising the following steps:

[0007] Step A1: Mix chloroplatinic acid in isopropanol until homogeneous, and record this as the catalyst solution. Stir allyl phosphate diethyl ester, toluene, and the catalyst solution at 45-55℃ for 1 hour, then raise the temperature to 70℃. Under nitrogen atmosphere, slowly add tetramethyltetrahydrocyclotetrasiloxane. After the addition is complete, continue the reaction at 80℃ for 5-8 hours. After the reaction is complete, add activated carbon and stir at room temperature for 5 hours. Filter and rotary evaporate to obtain the functional monomer.

[0008] Step A2: Disperse halloysite nanotubes (HNTs) evenly in ethanol, add tetraethyl orthosilicate, γ-aminopropyltriethoxysilane and functional monomers and stir for 20 min, then add deionized water and stir at 30-40℃ for 3-5 h, then raise the temperature to 115-125℃ and continue the reaction for 3-5 h. After the reaction is completed, filter and dry to obtain HNTs@organosilicon.

[0009] Step A3: Add 2,5-diamino-1,4-dihydroxyphenyl dihydrochloride and triethylamine to N,N-dimethylformamide and disperse evenly. Then add cyanuric chloride and HNTs@organosilicon and sonicate for 30 min. Transfer to an autoclave and react at 120℃ for 12 h. After the reaction is completed, wash and dry to obtain HNTs@organosilicon / COF.

[0010] Step A4: Disperse HNTs@organosilicon / COF and triethylamine evenly in N,N-dimethylformamide. Add acryloyl chloride under ice-water bath conditions and raise the temperature to 30-40℃ and stir for 2-3 hours. After the reaction is completed, filter and collect the product. Then disperse the product, polysilazane and caster platinum catalyst in toluene and stir evenly. Stir and react at 60-70℃ and pH 1-2 for 3-5 hours. Filter and dry to obtain the reinforcing filler.

[0011] Step A5: Mix the reinforcing filler, alumina, glass fiber, silane coupling agent and ethanol, and ball mill at 200-400 rpm for 5 hours. Raise the system temperature to 90-100℃, maintain the temperature and dry for 12 hours, then transfer it to a mold and sinter at 40-45 MPa and 1000-1100℃ for 1-2 hours, and then sinter at 1450-1550℃ for 2 hours. After cooling to room temperature, the fuse ceramic tube is obtained.

[0012] Further, in step A1, the ratio of allyl phosphate diethyl ester, toluene, catalyst solution, tetramethyltetrahydrocyclotetrasiloxane and activated carbon is 0.041-0.1 mol: 20-40 mL: 5-8 g: 1 mol: 1-2 g, and the mass ratio of chloroplatinic acid and isopropanol in the catalyst solution is 0.1: 100.

[0013] Furthermore, in step A2, the ratio of halloysite nanotubes, ethanol, tetraethyl orthosilicate, γ-aminopropyltriethoxysilane, functional monomer, and deionized water is 2-4 g: 50 mL: 2-3 g: 0.5-1.5 g: 0.3-0.6 g: 10 mL;

[0014] Further, in step A3, the ratio of 2,5-diamino-1,4-dihydroxyphenyl dihydrochloride, triethylamine, N,N-dimethylformamide, cyanuric chloride, and HNTs@organosilicon is 0.1-0.2 mol: 15 mL: 200 mL: 0.05-0.1 mol: 0.5-1.2 g;

[0015] Further, in step A4, the ratio of HNTs@organosilicon / COF, triethylamine, N,N-dimethylformamide, and acryloyl chloride is 1-3g:1-2mL:100mL:5-10mL, and the ratio of product, polysilazane, caster platinum catalyst, and toluene is 0.5-1.5g:10-30g:0.01-0.03g:200mL.

[0016] Furthermore, in step A5, the mass ratio of reinforcing filler, alumina, glass fiber, silane coupling agent, and ethanol is 3-6:25:1-2:0.05-0.15:25.

[0017] The beneficial effects of this invention are:

[0018] The ceramic tube prepared by this invention first utilizes the C=C bond in diethyl allyl phosphate and the Si-H bond in tetramethyltetrahydrocyclotetrasiloxane to synthesize a functional monomer containing a phosphate ester structure. Then, tetraethyl orthosilicate, γ-aminopropyltriethoxysilane, and the functional monomer are used as raw materials to synthesize polysiloxane. The hydrolysis and condensation reaction of the siloxane is used to synthesize HNTs@organosilicon containing amino groups. Next, the amino groups on the surface of HNTs@organosilicon react with the -Cl groups in COF (covalent organic framework) to form -NH- chemical bonds, thereby loading COF onto HNTs@organosilicon to form HNTs@organosilicon / COF containing hydroxyl groups. Then, the hydroxyl groups in HNTs@organosilicon / COF react with the acyl chloride groups in acryloyl chloride to generate a product containing a double bond structure. The double bond then reacts with the Si-H bonds in the polysilazane to generate a reinforcing filler. Finally, the reinforcing filler, alumina, glass fiber, and silane coupling agent are used as raw materials, and the ceramic tube is obtained through ball milling, pre-sintering, and sintering. This ceramic tube exhibits excellent toughness. When subjected to external impact, HNTs@organosilicon / COF acts as a cohesive force, generating a force that closes cracks in the matrix and consuming the work done by the applied load, thereby increasing the toughness and strength of the matrix. Simultaneously, it can also utilize the energy consumed during the pull-out process to further enhance the toughness of the matrix. HNTs themselves possess excellent toughness, thermal conductivity, and insulation properties. Combining them with organosilicon and COF enhances the synergistic effect among the three, improving the toughness of the matrix. The ceramic tube material has a multi-layered coating structure, with COF introduced between the layers forming a three-dimensional network structure. This effectively disperses the energy generated during crack formation, reduces stress concentration at the crack tip, and prevents crack propagation, thus improving the toughness of the matrix. Furthermore, the phosphorus element introduced into HNTs@organosilicon / COF also improves the thermal stability of the matrix. Detailed Implementation

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0020] Example 1

[0021] A method for preparing a ceramic tube for a fuse, comprising the following steps:

[0022] Step A1: Mix 0.1g of chloroplatinic acid with 100g of isopropanol and stir until homogeneous. This mixture is called the catalyst solution. Stir 0.041mol of allyl phosphate diethyl ester, 20mL of toluene and 5g of catalyst solution at 45℃ for 1h, then raise the temperature to 70℃. Under nitrogen atmosphere, slowly add 1mol of tetramethyltetrahydrocyclotetrasiloxane. After the addition is complete, continue the reaction at 80℃ for 5h. After the reaction is complete, add 1g of activated carbon and stir at room temperature for 5h. Filter and rotary evaporate to obtain the functional monomer.

[0023] Step A2: Disperse 2g halloysite nanotubes evenly in 50mL ethanol, add 2g tetraethyl orthosilicate, 0.5g γ-aminopropyltriethoxysilane and 0.3g functional monomer and stir for 20min, then add 10mL deionized water and stir at 30℃ for 3h, then raise the temperature to 115℃ and continue the reaction for 3h. After the reaction is completed, filter and dry to obtain HNTs@organosilicon;

[0024] Step A3: Add 0.1 mol of 2,5-diamino-1,4-dihydroxyphenyl dihydrochloride and 15 mL of triethylamine to 200 mL of N,N-dimethylformamide and disperse evenly. Then add 0.05 mol of cyanuric chloride and 0.5 g of HNTs@organosilicon and sonicate for 30 min. Transfer to an autoclave and react at 120 °C for 12 h. After the reaction is complete, wash and dry to obtain HNTs@organosilicon / COF.

[0025] Step A4: Disperse 1g of HNTs@organosilicon / COF and 1mL of triethylamine in 100mL of N,N-dimethylformamide. Add 5mL of acryloyl chloride in an ice-water bath and raise the temperature to 30℃ and stir for 2h. After the reaction is complete, filter and collect the product. Then disperse 0.5g of the product, 10g of polysilazane and 0.01g of caster platinum catalyst in 200mL of toluene and stir until homogeneous. Stir and react at 60℃ and pH 1 for 3h. Filter and dry to obtain the reinforcing filler.

[0026] Step A5: Mix 3g of reinforcing filler, 25g of alumina, 1g of glass fiber, 0.05g of KH550 and 25g of ethanol, and ball mill at 200rpm for 5h. Raise the system temperature to 90℃, maintain the temperature and dry for 12h, then transfer to a mold and sinter at 40MPa and 1000℃ for 1h, and then sinter at 1450℃ for 2h. After cooling to room temperature, the fuse ceramic tube is obtained.

[0027] Example 2

[0028] A method for preparing a ceramic tube for a fuse, comprising the following steps:

[0029] Step A1: Mix 0.1g of chloroplatinic acid with 100g of isopropanol and stir until homogeneous. This mixture is designated as the catalyst solution. Stir 0.075mol of allyl phosphate diethyl ester, 30mL of toluene, and 6g of the catalyst solution at 50℃ for 1h. Then, raise the temperature to 70℃ and slowly add 1mol of tetramethyltetrahydrocyclotetrasiloxane under nitrogen atmosphere. After the addition is complete, continue the reaction at 80℃ for 7h. After the reaction is complete, add 1.5g of activated carbon and stir at room temperature for 5h. Filter and rotary evaporate to obtain the functional monomer.

[0030] Step A2: Disperse 3g halloysite nanotubes evenly in 50mL of ethanol, add 2.5g tetraethyl orthosilicate, 1g γ-aminopropyltriethoxysilane and 0.5g functional monomer and stir for 20min, then add 10mL of deionized water and stir at 35℃ for 4h, then raise the temperature to 120℃ and continue the reaction for 4h. After the reaction is completed, filter and dry to obtain HNTs@organosilicon.

[0031] Step A3: Add 0.15 mol of 2,5-diamino-1,4-dihydroxyphenyl dihydrochloride and 15 mL of triethylamine to 200 mL of N,N-dimethylformamide and disperse evenly. Then add 0.075 mol of cyanuric chloride and 0.8 g of HNTs@organosilicon and sonicate for 30 min. Transfer to an autoclave and react at 120 °C for 12 h. After the reaction is complete, wash and dry to obtain HNTs@organosilicon / COF.

[0032] Step A4: Disperse 2g of HNTs@organosilicon / COF and 1.5mL of triethylamine in 100mL of N,N-dimethylformamide. Add 7mL of acryloyl chloride in an ice-water bath and raise the temperature to 35℃ and stir for 2.5h. After the reaction is complete, filter and collect the product. Then disperse 1g of the product, 20g of polysilazane and 0.02g of caster platinum catalyst in 200mL of toluene and stir until homogeneous. Stir and react at 65℃ and pH 2 for 4h. Filter and dry to obtain the reinforcing filler.

[0033] Step A5: Mix 4.5g reinforcing filler, 25g alumina, 1.5g glass fiber, 0.1g KH550 and 25g ethanol, and ball mill at 300rpm for 5h. Raise the system temperature to 95℃, maintain the temperature and dry for 12h, then transfer to a mold and sinter at 45MPa and 1050℃ for 1-2h, then sinter at 1500℃ for 2h. After cooling to room temperature, the fuse ceramic tube is obtained.

[0034] Example 3

[0035] A method for preparing a ceramic tube for a fuse, comprising the following steps:

[0036] Step A1: Mix 0.1g of chloroplatinic acid with 100g of isopropanol until homogeneous, and record this as the catalyst solution. Stir 0.1mol of allyl phosphate diethyl ester, 40mL of toluene and 8g of catalyst solution at 55℃ for 1h, then raise the temperature to 70℃. Under nitrogen atmosphere, slowly add 1mol of tetramethyltetrahydrocyclotetrasiloxane. After the addition is complete, continue the reaction at 80℃ for 5-8h. After the reaction is complete, add 2g of activated carbon and stir at room temperature for 5h. Filter and rotary evaporate to obtain the functional monomer.

[0037] Step A2: Disperse 4g halloysite nanotubes evenly in 50mL of ethanol, add 3g tetraethyl orthosilicate, 1.5g γ-aminopropyltriethoxysilane and 0.6g functional monomer and stir for 20min, then add 10mL of deionized water and stir at 40℃ for 3-5h, then raise the temperature to 125℃ and continue the reaction for 5h. After the reaction is completed, filter and dry to obtain HNTs@organosilicon.

[0038] Step A3: Add 0.2 mol of 2,5-diamino-1,4-dihydroxyphenyl dihydrochloride and 15 mL of triethylamine to 200 mL of N,N-dimethylformamide and disperse evenly. Then add 0.1 mol of cyanuric chloride and 1.2 g of HNTs@organosilicon and sonicate for 30 min. Transfer to an autoclave and react at 120 °C for 12 h. After the reaction is complete, wash and dry to obtain HNTs@organosilicon / COF.

[0039] Step A4: Disperse 3g of HNTs@organosilicon / COF and 2mL of triethylamine in 100mL of N,N-dimethylformamide. Add 10mL of acryloyl chloride in an ice-water bath and raise the temperature to 40℃ and stir for 3h. After the reaction is complete, filter and collect the product. Then disperse 1.5g of the product, 30g of polysilazane and 0.03g of caster platinum catalyst in 200mL of toluene and stir until homogeneous. Stir and react at 70℃ and pH 2 for 5h. Filter and dry to obtain the reinforcing filler.

[0040] Step A5: Mix 6g of reinforcing filler, 25g of alumina, 2g of glass fiber, 0.15g of KH550 and 25g of ethanol, and ball mill at 400rpm for 5h. Raise the system temperature to 100℃, maintain the temperature and dry for 12h, then transfer to a mold and sinter at 45MPa and 1100℃ for 2h, then sinter at 1550℃ for 2h. After cooling to room temperature, the fusible ceramic tube is obtained.

[0041] Comparative Example 1

[0042] This comparative example is a ceramic tube, which differs from Example 3 in that an equal amount of tetraethyl orthosilicate is used instead of the functional monomer, while all other aspects are the same.

[0043] Comparative Example 2

[0044] This comparative example is a ceramic tube, which differs from Example 3 in that it is prepared by the following steps:

[0045] 6g of HNTs@organosilicon / COF prepared in Example 3, 25g of alumina, 2g of glass fiber, 0.15g of KH550 and 25g of ethanol were mixed and ball-milled at 400rpm for 5h. The system temperature was raised to 100℃ and dried at the temperature for 12h. The mixture was then transferred to a mold and sintered at 45MPa and 1100℃ for 2h, and then sintered at 1550℃ for 2h. After cooling to room temperature, the ceramic tube was obtained.

[0046] Comparative Example 3

[0047] This comparative example is a ceramic tube, which differs from Example 3 in that it is prepared by the following steps:

[0048] 6g of polysilazane, 25g of alumina, 2g of glass fiber, 0.15g of KH550 and 25g of ethanol were mixed and ball-milled at 400rpm for 5h. The system temperature was raised to 100℃ and dried at that temperature for 12h. The mixture was then transferred to a mold and sintered at 45MPa and 1100℃ for 2h, and then sintered at 1550℃ for 2h. After cooling to room temperature, the ceramic tube was obtained.

[0049] The aluminum ceramic post insulator materials obtained in Examples 1-3 and Comparative Examples 1-3 were made into 34mm×5mm×5mm specimens. The bending strength of the specimens was tested using a universal testing machine with a spacing of 16mm and a head loading speed of 0.5mm / min. The bending strength was taken as the average of three measurements. The fracture toughness of the specimens was tested using the single-sided notched beam method with a head loading speed of 0.05mm / min. The test results are shown in the table below.

[0050] The test results are shown in the table below:

[0051]

[0052] As can be seen from the table above, after bending strength and fracture toughness tests, the ceramic tubes prepared in Examples 1-3 of this invention exhibit bending strength in the range of 638 MPa-653 MPa and fracture toughness in the range of 9.29 MPa·m. 1 / 2 -9.43 MPa·m 1 / 2 Within the specified range, this indicates that the ceramic tube possesses excellent toughness and has promising application prospects in fuses.

[0053] The above content is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the scope defined by the inventive concept, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a ceramic tube for a fuse, characterized in that, Prepared by the following steps: Step A1: Mix chloroplatinic acid in isopropanol until homogeneous, and record this as the catalyst solution. Stir allyl phosphate diethyl ester, toluene, and the catalyst solution at 45-55℃ for 1 hour, then raise the temperature to 70℃. Under nitrogen atmosphere, slowly add tetramethyltetrahydrocyclotetrasiloxane. After the addition is complete, continue the reaction at 80℃ for 5-8 hours. After the reaction is complete, add activated carbon and stir at room temperature for 5 hours. Filter and rotary evaporate to obtain the functional monomer. Step A2: Disperse halloysite nanotubes evenly in ethanol, add tetraethyl orthosilicate, γ-aminopropyltriethoxysilane and functional monomers and stir for 20 min, then add deionized water and stir at 30-40℃ for 3-5 h, then raise the temperature to 115-125℃ and continue the reaction for 3-5 h. After the reaction is completed, filter and dry to obtain HNTs@organosilicon. Step A3: Add 2,5-diamino-1,4-dihydroxyphenyl dihydrochloride and triethylamine to N,N-dimethylformamide and disperse evenly. Then add cyanuric chloride and HNTs@organosilicon and sonicate for 30 min. Transfer to an autoclave and react at 120℃ for 12 h. After the reaction is completed, wash and dry to obtain HNTs@organosilicon / COF. Step A4: Disperse HNTs@organosilicon / COF and triethylamine evenly in N,N-dimethylformamide. Add acryloyl chloride under ice-water bath conditions and raise the temperature to 30-40℃ and stir for 2-3 hours. After the reaction is completed, filter and collect the product. Then disperse the product, polysilazane and caster platinum catalyst in toluene and stir evenly. Stir and react at 60-70℃ and pH 1-2 for 3-5 hours. Filter and dry to obtain the reinforcing filler. Step A5: Mix the reinforcing filler, alumina, glass fiber, silane coupling agent and ethanol, and ball mill at 200-400 rpm for 5 hours. Raise the system temperature to 90-100℃, maintain the temperature and dry for 12 hours, then transfer it to a mold and sinter at 40-45 MPa and 1000-1100℃ for 1-2 hours, and then sinter at 1450-1550℃ for 2 hours. After cooling to room temperature, the fuse ceramic tube is obtained.

2. The method for preparing a ceramic tube for a fuse according to claim 1, characterized in that, In step A1, the ratio of allyl phosphate diethyl ester, toluene, catalyst solution, tetramethyltetrahydrocyclotetrasiloxane, and activated carbon is 0.041-0.1 mol: 20-40 mL: 5-8 g: 1 mol: 1-2 g.

3. The method for preparing a ceramic tube for a fuse according to claim 2, characterized in that, The mass ratio of chloroplatinic acid to isopropanol in the catalyst solution is 0.1:

100.

4. The method for preparing a ceramic tube for a fuse according to claim 1, characterized in that, In step A2, the ratio of halloysite nanotubes, ethanol, tetraethyl orthosilicate, γ-aminopropyltriethoxysilane, functional monomers, and deionized water is 2-4g:50mL:2-3g:0.5-1.5g:0.3-0.6g:10mL.

5. The method for preparing a ceramic tube for a fuse according to claim 1, characterized in that, In step A3, the ratio of 2,5-diamino-1,4-dihydroxyphenyl dihydrochloride, triethylamine, N,N-dimethylformamide, cyanuric chloride, and HNTs@organosilicon is 0.1-0.2 mol: 15 mL: 200 mL: 0.05-0.1 mol: 0.5-1.2 g.

6. The method for preparing a ceramic tube for a fuse according to claim 1, characterized in that, In step A4, the ratio of HNTs@organosilicon / COF, triethylamine, N,N-dimethylformamide and acryloyl chloride is 1-3g: 1-2mL: 100mL: 5-10mL, and the ratio of product, polysilazane, caster platinum catalyst and toluene is 0.5-1.5g: 10-30g: 0.01-0.03g: 200mL.

7. The method for preparing a ceramic tube for a fuse according to claim 1, characterized in that, In step A5, the mass ratio of reinforcing filler, alumina, glass fiber, silane coupling agent and ethanol is 3-6:25:1-2:0.05-0.15:25.

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