Ceramic nozzle material and preparation method

Abstract

The present invention relates to the field of ceramic technology, and discloses a ceramic nozzle material and a preparation method. The ceramic nozzle material of the present invention includes 100 parts by weight of aluminum oxide, 2-6 parts by weight of a betaine dispersant, and 0.3-2 parts by weight of graphene oxide. The side chain of the betaine dispersant contains a sulfonic acid quaternary ammonium salt zwitterionic group, and the sulfonate can interact with the surface of the aluminum oxide, thereby reducing the agglomeration of the aluminum oxide. The hydroxyl group contained in the dispersant forms a hydrogen bond force with the surface of the graphene oxide, thereby improving the interface bonding performance of graphene and aluminum oxide, and reducing the phase separation defect between graphene and aluminum oxide. Thus, the relative density of the ceramic material is increased, the ceramic material has higher flexural strength, and the wear rate is significantly reduced, and the wear resistance is better.

Description

Technical Field

[0001] The present invention relates to the field of ceramic technology, in particular to a ceramic nozzle material and a preparation method. Background Art

[0002] Textile machine nozzles primarily serve the fiber transport, forming, lubrication, and cooling functions of yarn spinning. They are primarily made of alloys and ceramics. Alumina ceramics are inexpensive, readily available, and offer excellent thermal conductivity and electrical insulation. They are used in textile machine nozzles, ceramic bearings, high-temperature furnace tubes, and other components. However, alumina ceramics exhibit poor dispersion during the slurrying and sintering processes, which can affect the mechanical strength and wear resistance of the ceramic, necessitating the addition of a dispersant.

[0003] Graphene has high mechanical strength, strong wear resistance, and excellent thermal and electrical conductivity, making it widely used in materials such as ceramics, plastics, and alloys. However, graphene easily agglomerates and forms phase separation when sintered with alumina, resulting in defects and micropores that affect the mechanical strength and wear resistance of the ceramic material. Patent Publication No. CN119161172B discloses a high-strength alumina ceramic and its processing technology. Using ammonium polyacrylate and branched polyamide as dispersants, alumina, graphene, aluminum nitride, yttrium oxide, and lanthanum oxide are blended and sintered to produce a high-strength alumina ceramic. However, this patent does not improve the ceramic's wear resistance, hindering its practical application in textile machine ceramic nozzles and other applications. Summary of the Invention

[0004] The present invention solves the problem of poor dispersibility of aluminum oxide and graphene in ceramics, while improving the mechanical strength and wear resistance of the ceramic material.

[0005] The technical solution provided by the present invention is: a ceramic nozzle material and a preparation method, wherein the ceramic nozzle material comprises 100 parts by weight of aluminum oxide, 2-6 parts by weight of a betaine dispersant, and 0.3-2 parts by weight of graphene oxide.

[0006] (1) Add N,N-dimethylformamide, N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer, and 2-haloethanesulfonic acid sodium compound to a reaction vessel, introduce nitrogen, heat to the reaction temperature, add saturated sodium chloride solution after the reaction, extract with dichloromethane, add n-hexane to the dichloromethane organic layer, filter and dry to obtain a betaine dispersant. The reaction formula is:

[0007] .

[0008] (2) Water, aluminum oxide, graphene oxide, and betaine dispersant are added to a ball mill. After ball milling, the slurry is filtered, placed in a mold, and dried to form a nozzle blank, which is then sintered in a sintering furnace to obtain a ceramic nozzle material.

[0009] Preferably, the reaction temperature in (1) is 90-120°C, and the reaction time is 18-36 hours.

[0010] Preferably, the mass of the sodium 2-haloethanesulfonate compound in (1) is 42-70% of the mass of the butanediol diglycidyl ether-N,N-dimethylethylenediamine copolymer.

[0011] Preferably, the sodium 2-haloethanesulfonate compound in (1) is sodium 2-bromoethanesulfonate or sodium 2-chloroethanesulfonate monohydrate.

[0012] Preferably, the preparation method of the N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer in (1) comprises: adding ethanol and 100 parts by weight of N,N-dimethylethylenediamine to a reaction vessel, dripping an ethanol solution containing 184-206 parts by weight of butanediol diglycidyl ether in an ice-water bath, introducing nitrogen, then heating to 40-45°C, reacting for 18-24 hours, performing vacuum distillation, adding the product to n-hexane, filtering and drying the product to obtain the N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer. The reaction formula is:

[0013] .

[0014] Preferably, the ratio of water to alumina in (2) is (300-500) g / L.

[0015] Preferably, the rotation speed during ball milling in (2) is 300-600 r / min, and the time is 4-8 h.

[0016] Preferably, the pressure of the sintering furnace in (2) is 25-40 MPa, the sintering temperature is 1300-1600°C, and the sintering time is 1-1.5 h.

[0017] The present invention has the beneficial technical effect of ball-milling aluminum oxide, graphene, and a betaine dispersant to form a nozzle blank, which is then sintered at high temperature to obtain a ceramic nozzle material. The betaine dispersant has a side chain containing a zwitterionic group of a quaternary ammonium sulfonate. The sulfonate can interact with the aluminum oxide surface, forming a modified surface and improving the dispersibility of the aluminum oxide. The quaternary ammonium salt cations form a double layer, generating electrostatic repulsion between aluminum oxide particles, reducing agglomeration, and improving the mechanical strength of the ceramic.

[0018] The betaine dispersant of the present invention contains a large number of hydroxyl groups, which form hydrogen bonding forces with hydroxyl groups, carboxyl groups, etc. on the surface of graphene oxide, thereby improving the interfacial bonding performance between graphene and aluminum oxide, reducing the phase separation defects between graphene and aluminum oxide, thereby increasing the relative density of the ceramic material, making the ceramic material have higher bending strength, significantly reducing the wear rate, and improving the wear resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the infrared spectrum of betaine dispersant. DETAILED DESCRIPTION

[0020] The present invention is further described below with reference to examples. It should be noted that the following examples are intended only to illustrate the present invention in more detail and are not intended to narrow the scope of protection of the present invention. Improvements and modifications made without departing from the spirit of the present invention are within the scope of protection claimed in the present invention.

[0021] The nano-aluminum oxide of the present invention has an average particle size of 400 nm; the graphene oxide has a diameter of 0.5-2 μm and a thickness of 0.6-1.4 nm.

[0022] Example 1

[0023] (1) Add 60 mL of ethanol and 20 g of N,N-dimethylethylenediamine to a reaction vessel. In an ice-water bath, add dropwise 90 mL of an ethanol solution containing 41.2 g of butanediol diglycidyl ether. Pass nitrogen through the reaction vessel, then heat to 45°C and react for 18 h. Distill under reduced pressure. Add the product to n-hexane, filter, and dry the product to obtain an N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer.

[0024] (2) Add 600 mL of N,N-dimethylformamide, 40 g of N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer, and 21.2 g of sodium 2-bromoethane sulfonate to a reaction vessel, introduce nitrogen, heat to 90°C, stir and react for 36 hours, cool, add saturated sodium chloride solution, extract with dichloromethane, add n-hexane to the dichloromethane organic layer, filter and dry to obtain a betaine dispersant. Figure 1 In the infrared spectrum, 3404cm -1 is the stretching vibration peak of hydroxyl group, 2973cm -1 、2926cm -1 It is the absorption peak of methyl -CH3 and methylene -CH2-, 1448cm -1 It is quaternary ammonium salt-CN + - characteristic peak, 1087cm -1 It is the absorption peak of ether bond COC, 1149cm -1 、1027cm -1 It is sulfonate SO3 -1 The stretching vibration peak of -S=O- and the asymmetric stretching vibration peak.

[0025] (3) Add 2 L of water, 1 kg of aluminum oxide, 3 g of graphene oxide, and 20 g of betaine dispersant into a ball mill and mill for 6 h at a speed of 300 r / min. Filter the slurry, place it in a mold, and make it into a nozzle blank after drying. Then, place it in a sintering furnace at a sintering pressure of 30 MPa, raise the temperature to 1500 °C, and sinter for 1 h to obtain a ceramic nozzle material.

[0026] Example 2

[0027] (1) Add 60 mL of ethanol and 20 g of N,N-dimethylethylenediamine to a reaction vessel. In an ice-water bath, add dropwise 100 mL of an ethanol solution containing 36.8 g of butanediol diglycidyl ether. Pass nitrogen through the mixture, then heat to 40 °C and react for 24 h. Distill under reduced pressure. Add the product to n-hexane, filter, and dry the product to obtain an N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer.

[0028] (2) Add 700 mL of N,N-dimethylformamide, 40 g of N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer, and 28 g of sodium 2-bromoethanesulfonate to a reaction vessel, introduce nitrogen, heat to 120°C, stir and react for 24 hours, cool, add saturated sodium chloride solution, extract with dichloromethane, add n-hexane to the dichloromethane organic layer, filter and dry to obtain a betaine dispersant.

[0029] (3) Add 2.6 L of water, 1 kg of aluminum oxide, 12 g of graphene oxide, and 42 g of betaine dispersant into a ball mill and mill for 4 h at a speed of 600 r / min. Filter the slurry, place it in a mold, and make it into a nozzle blank after drying. Then, place it in a sintering furnace at a sintering pressure of 40 MPa, raise the temperature to 1300 °C, and sinter for 1.5 h to obtain a ceramic nozzle material.

[0030] Example 3

[0031] (1) 600 mL of N,N-dimethylformamide, 40 g of N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer (prepared in the same manner as in Example 1), and 16.8 g of sodium 2-chloroethanesulfonate monohydrate were added to a reaction vessel, nitrogen was introduced, and the mixture was heated to 110°C and stirred for 18 h. After cooling, a saturated sodium chloride solution was added, and the mixture was extracted with dichloromethane. N-hexane was added to the dichloromethane organic layer, and the mixture was filtered and dried to obtain a betaine dispersant.

[0032] (2) Add 3.3 L of water, 1 kg of aluminum oxide, 20 g of graphene oxide, and 60 g of betaine dispersant into a ball mill and mill for 8 h at a speed of 400 r / min. Filter the slurry, place it in a mold, and make it into a nozzle blank after drying. Then, place it in a sintering furnace at a sintering pressure of 25 MPa, raise the temperature to 1600 °C, and sinter for 1 h to obtain a ceramic nozzle material.

[0033] Comparative Example 1

[0034] (1) Add 2 L of water, 1 kg of aluminum oxide, and 3 g of graphene oxide to a ball mill and mill for 6 h at a speed of 300 r / min. Filter the slurry, place it in a mold, and make a nozzle blank after drying. Then, place it in a sintering furnace at a sintering pressure of 30 MPa, raise the temperature to 1500 °C, and sinter for 1 h to obtain a ceramic nozzle material.

[0035] Comparative Example 2

[0036] (1) Add 2 L of water, 1 kg of aluminum oxide, 3 g of graphene oxide, and 20 g of N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer (prepared in the same manner as in Example 1) into a ball mill and mill for 6 h at a speed of 300 r / min. Filter the slurry, place it in a mold, and make a nozzle blank after drying. Then, place it in a sintering furnace at a sintering pressure of 30 MPa, raise the temperature to 1500 °C, and sinter for 1 h to obtain a ceramic nozzle material.

[0037] Comparative Example 3

[0038] (1) 600 mL of N,N-dimethylformamide, 40 g of N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer (prepared in the same manner as in Example 1), and 21.2 g of bromoethane were added to a reaction vessel, nitrogen was introduced, and the mixture was heated to 90°C and stirred for 36 hours. After cooling, a saturated sodium chloride solution was added, and the mixture was extracted with dichloromethane. N-hexane was added to the dichloromethane organic layer, and the mixture was filtered and dried to obtain a cationic dispersant.

[0039] (2) Add 2L of water, 1kg of aluminum oxide, 3g of graphene oxide, and 20g of cationic dispersant to a ball mill and mill for 6h at a ball mill speed of 300r / min. Filter the slurry, place it in a mold, and make it into a nozzle blank after drying. Then, place it in a sintering furnace at a sintering pressure of 30MPa, raise the temperature to 1500℃, and sinter for 1h to obtain a ceramic nozzle material.

[0040] Comparative Example 4

[0041] (1) Add 2 L of water, 1 kg of aluminum oxide, 3 g of graphene oxide, and 20 g of sodium polystyrene sulfonate to a ball mill and mill for 6 h at a speed of 300 r / min. Filter the slurry, place it in a mold, and make a nozzle blank after drying. Then, place it in a sintering furnace at a sintering pressure of 30 MPa, raise the temperature to 1500 °C, and sinter for 1 h to obtain a ceramic nozzle material.

[0042] Comparative Example 5

[0043] (1) Add 2L of water, 1kg of aluminum oxide, 3g of graphene oxide, and 20g of sodium dodecylbenzenesulfonate into a ball mill and mill for 6h at a ball mill speed of 300r / min. Filter the slurry, place it in a mold, and make it into a nozzle blank after drying. Then, place it in a sintering furnace at a sintering pressure of 30MPa, raise the temperature to 1500℃, and sinter for 1h to obtain a ceramic nozzle material.

[0044] Performance test of ceramic materials: Taking Example 1 as an example, 2L of water, 1kg of aluminum oxide, 3g of graphene oxide, and 20g of betaine dispersant were added to a ball mill, and the ball milling was carried out for 6 hours at a ball mill speed of 300r / min. The slurry was filtered, placed in a mold, and pressed into a green body after drying. Then, in a sintering furnace, the sintering pressure was controlled to 30MPa, the temperature was raised to 1500℃, and sintered for 1h to obtain a ceramic material.

[0045] The relative density of ceramic materials was tested according to the Archimedes method. Each sample was tested 5 times and the average value was taken.

[0046] The three-point bending method was used to test the flexural strength of the ceramic material. The sample size was 35 mm × 4 mm × 3 mm and the loading rate was 0.5 mm / min.

[0047] The wear rate of ceramic materials was tested according to the method specified in the standard JC / T 848.1-2010.

[0048] Table 1 Properties of ceramics

[0049]

[0050] As shown in Table 1, aluminum oxide and graphene oxide are carried out ball milling blending by comparative example 1, and due to the poor dispersibility of aluminum oxide and graphene oxide, it is shown that graphene oxide is easily reunited, and phase separation defect is formed in alumina ceramics, causing the relative density and the flexural strength of ceramic material to be lower, and wear rate is larger, and wear resistance is poor. Embodiment 1-embodiment 3 has added betaine dispersant, and its side chain contains a large amount of sulfonic acid quaternary ammonium salt zwitterionic groups, and sulfonate can form interaction with aluminum oxide surface, be modified on aluminum oxide surface, improve dispersibility, quaternary ammonium salt cation forms double electric layer characteristic, produces electrostatic repulsion, reduces the reunion of aluminum oxide, is conducive to improving the mechanical strength of ceramic, and betaine dispersant contains a large amount of hydroxyl, forms hydrogen bond force with the hydroxyl, carboxyl etc. on graphene oxide surface, improves the interface bonding performance of graphene and aluminum oxide, is conducive to reducing the phase separation defect between graphene and aluminum oxide, improves the relative density of ceramic material, makes ceramic material have higher flexural strength, and wear rate is obviously reduced, and wear resistance improves.

[0051] Compared with Example 1, the N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer of Comparative Example 2 does not contain sulfonate quaternary ammonium salt zwitterionic groups, which makes it difficult to improve the dispersibility of alumina, resulting in a lower relative density and flexural strength of the ceramic, a higher wear rate, and poor wear resistance.

[0052] Comparative Example 3 uses bromoethane as a raw material, and the cationic dispersant prepared does not contain a sulfonate group, which has a poor dispersion effect on alumina, resulting in a low relative density and flexural strength of the ceramic, a high wear rate, and poor wear resistance.

[0053] Comparative Examples 4 and 5 use conventional sodium polystyrene sulfonate and sodium dodecylbenzene sulfonate as dispersants, which do not contain quaternary ammonium salt cations or hydroxyl groups, have poor dispersion effects on alumina, and are difficult to improve the interfacial bonding performance between graphene and alumina, resulting in low relative density and flexural strength of the ceramics, a high wear rate, and poor wear resistance.

[0054] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A ceramic nozzle material, characterized in that: The ceramic nozzle material includes 100 parts by weight of aluminum oxide, 2-6 parts by weight of betaine dispersant, and 0.3-2 parts by weight of graphene oxide; The preparation method of the betaine dispersant comprises: adding N,N-dimethylformamide, N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer, and 2-haloethanesulfonic acid sodium compound into a reaction container, introducing nitrogen, heating to a reaction temperature, adding a saturated sodium chloride solution after the reaction, extracting with dichloromethane, adding n-hexane to the dichloromethane organic layer, filtering, and drying to obtain the betaine dispersant.

2. The ceramic nozzle material according to claim 1, characterized in that The reaction temperature is 90-120° C., and the reaction time is 18-36 hours.

3. The ceramic nozzle material according to claim 1, characterized in that The mass of the sodium 2-haloethane sulfonate compound is 42-70% of the mass of the N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer.

4. The ceramic nozzle material according to claim 1, characterized in that The sodium 2-halogenoethanesulfonate compound is sodium 2-bromoethanesulfonate or sodium 2-chloroethanesulfonate monohydrate.

5. The ceramic nozzle material according to claim 3, characterized in that The preparation method of the N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer comprises: adding ethanol and 100 parts by weight of N,N-dimethylethylenediamine into a reaction container, dropwise adding an ethanol solution containing 184-206 parts by weight of butanediol diglycidyl ether in an ice-water bath, introducing nitrogen, heating to 40-45° C., reacting for 18-24 hours, performing reduced pressure distillation, adding the product to n-hexane, filtering the product, and drying the product to obtain the N,N-dimethylethylenediamine-butanediol diglycidyl ether polymer.

6. A method for preparing the ceramic nozzle material according to any one of claims 1 to 5, characterized in that: The preparation method comprises: adding water, aluminum oxide, graphene oxide, and betaine dispersant into a ball mill, filtering the slurry after ball milling, placing it in a mold, drying it to form a nozzle blank, and then sintering it in a sintering furnace to obtain a ceramic nozzle material.

7. The method for preparing a ceramic nozzle material according to claim 6, characterized in that: The ratio of water to aluminum oxide is (300-500) g / L.

8. The method for preparing a ceramic nozzle material according to claim 6, wherein: The rotation speed during ball milling is 300-600 r / min and the time is 4-8 hours.

9. The method for preparing a ceramic nozzle material according to claim 6, wherein: The pressure of the sintering furnace is 25-40 MPa, the sintering temperature is 1300-1600° C., and the sintering time is 1-1.5 hours.

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