Enamel material and method for its production

Abstract

The application discloses a kind of enamel materials and preparation method thereof, belong to the technical field of enamel materials, including the following weight fraction components: base glaze 100 parts, lithium-based bentonite 5-7 parts, carbon nanotube composite material 1.2-2.2 parts, auxiliary agent 0.1-0.5 parts, deionized water 55-65 parts.Carbon nanotube is added concentrated nitric acid and polyvinylpyrrolidone, and non-covalent modified carbon nanotube is obtained, then nanometer titanium dioxide and nanometer silicon dioxide are coated in turn by sol-gel method, and carbon nanotube composite material is obtained.The method for preparing the enamel material of the application is to first pretreat the steel plate, then put the base glaze, lithium-based bentonite, auxiliary agent, carbon nanotube composite material and deionized water into an ultrasonic cleaning machine for ultrasonic dispersion, for 40-60 min, grind for 3-5 h, sieve, and obtain enamel glaze slurry.The obtained enamel glaze slurry is uniformly coated on the pretreated steel plate, dried, sintered in a vacuum high-temperature sintering furnace at a temperature rising rate of 3-3.4 DEG C / min, kept warm, cooled, and the enamel material is obtained.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of enamel materials, and particularly relates to an enamel material and a preparation method thereof. BACKGROUND

[0002] Traditional enamel materials are formed by coating glaze on the surface of a metal base and sintering at high temperature. The unique glass properties not only make the surface look smooth and solid, but also have the characteristics of high hardness, high temperature resistance, corrosion resistance, easy processing, etc., and are widely used in daily household furniture, building decoration, medical machinery, high temperature corrosion resistant equipment and electronic components, etc. When the enamel material also has the characteristics of sterilization, photocatalytic degradation, electrical properties, etc., it also shows application potential in building exterior decoration, sanitary wares and artificial intelligence, etc. Building multi-component micro-nano composite materials on the surface of the enamel surface can endow it with unique optical, electrical, toughness and chemical properties, and realize multi-functionalization and expansion. For example, Chinese patent CN114180839 discloses a particle toughening enamel glaze paste, enamel plate and preparation method. The nano-aluminum oxide used only relies on the single-point action of crack deflection and particle pinning for toughening, and relies on the physical suspension of clay, and the adhesion is not strong.

[0003] Composite materials are new materials composed of two or more different types of materials. Through their mutual combination, the advantages of various materials can be fully utilized. Composite materials usually include a main matrix material and one or more reinforcing materials. Carbon nanotubes as reinforcing materials can significantly improve the performance of the matrix material, such as strength, hardness, electrical conductivity and other mechanical properties and electrochemical properties. Carbon nanotube composite materials with carbon nanotubes as reinforcing materials have many excellent performance characteristics, including excellent mechanical properties, electrical conductivity, thermal properties, etc. and have shown wide application prospects in many fields. For example, Chinese patent CN118459092A discloses a carbon nanotube composite material, a preparation method and application thereof. In the invention, the common action of a specific content of acidized and carboxylated carbon nanotubes and enamel powder is used. Since the carboxyl group forms a hydrogen bond with the metal oxide in the enamel, which is much weaker than a covalent bond, and the adhesion to the steel plate substrate is not strong.

[0004] Therefore, the present application develops an enamel material and a preparation method thereof to solve the problems of poor toughening effect and weak adhesion to the steel plate substrate in the prior art. SUMMARY

[0005] The purpose of the present application is to provide an enamel material and a preparation method thereof to solve the problems of poor toughening effect and weak adhesion to the steel plate substrate in the prior art.

[0006] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] A kind of enamel material, including the following weight parts of components: base glaze 100 parts, lithium-based bentonite 5-7 parts, carbon nanotube composite material 1.2-2.2 parts, auxiliary agent 0.1-0.5 parts, deionized water 55-65 parts.

[0008] Preferably, the base glaze includes the following weight parts of components:

[0009] Boron trioxide 10.0-18.0 parts, sodium oxide 8.0-11.0 parts, magnesium oxide 2.0-3.0 parts, aluminum trioxide 2.0-3.0 parts, silicon dioxide 30.0-45.0 parts, lithium oxide 1-2 parts, potassium oxide 1-2.5 parts, diaphosphorus pentoxide 2.0-3.0 parts, zinc oxide 1.0-2.0 parts, titanium dioxide 15.0-20.0 parts and sodium fluorosilicate 5.0-10.0 parts.

[0010] Preferably, the preparation method of the carbon nanotube composite material includes the following steps:

[0011] Step one, carbon nanotubes are added to concentrated nitric acid at 115-125℃ for 1-2h, cooled, filtered to obtain filter cake, which is first washed with 4-6% sodium hydroxide for 1-3 times, then washed with deionized water for 1-3 times, dried at 75-85℃ for 8-12h, then ultrasonically dispersed with polyvinylpyrrolidone in deionized water for 12-24h, filtered through a 0.2μm porous filter membrane, washed and dried to obtain non-covalently modified carbon nanotubes;

[0012] Step two, the product of step one is ultrasonically dispersed in 8-12wt% isopropanol solution for 20-30min, the pH value is adjusted to 2-2.4, then tetrabutyl titanate is added, stirred at room temperature for 2-4h, filtered to obtain filter cake, which is washed alternately with anhydrous ethanol and deionized water for 2-4 times, dried at 95-105℃ for 2-3h, finally sintered to 440-480℃ at a temperature rising speed of 5-10℃ / min in vacuum for 2-6h to obtain titanium dioxide / non-covalently modified carbon nanotubes;

[0013] Step three, tetraethyl orthosilicate is stirred with anhydrous ethanol at 55-65℃ for 2-4h to obtain solution A, then the product of step two, polyvinylpyrrolidone and deionized water are stirred at room temperature for 10-30min, solution A is added, stirred at 38-42℃ for 1-3h, centrifuged, separated to obtain filter cake, which is washed alternately with anhydrous ethanol and deionized water for 2-4 times, dried at 50-55℃ for 1-3h, finally sintered at 360-385℃ in vacuum for 2-4h to obtain carbon nanotube composite material.

[0014] Preferably, the amount of carbon nanotubes, concentrated nitric acid and polyvinylpyrrolidone in step one is 1g: 100mL: 25-36mg.

[0015] Preferably, the amount of step one product and tetrabutyl titanate in step two is 1g: 80-90mL.

[0016] Preferably, the amount of tetraethyl orthosilicate, step two product and polyvinylpyrrolidone in step three is 72-80mL: 1g: 18-24mg.

[0017] Preferably, the auxiliary agent is one or more of potassium fluosilicate, potassium chloride and potassium carbonate.

[0018] A preparation method of an enamel material, comprising the following steps:

[0019] Firstly, the steel plate is sandblasted with white jade, and then the surface of the steel plate is cleaned with anhydrous ethanol and acetone, and dried to obtain a pretreated steel plate;

[0020] Secondly, the base glaze, lithium-based bentonite, auxiliary agent, carbon nanotube composite material and deionized water are placed in an ultrasonic cleaning machine for ultrasonic dispersion for 40-60min, grinding for 3-5h, and sieving through an 80-160mesh sieve to obtain an enamel slurry;

[0021] Thirdly, the enamel slurry is uniformly coated on the pretreated steel plate, dried, and sintered in a vacuum high-temperature sintering furnace at a temperature rising rate of 3-3.4℃ / min, and then cooled to obtain the enamel material.

[0022] Preferably, the drying temperature is 55-65℃, and the drying time is 30-50min.

[0023] Preferably, the holding temperature is 790-840℃, and the holding time is 5-6min.

[0024] In summary, due to the adoption of the above technical solutions, the present application has the following advantages:

[0025] The present application is through the synergistic effect of lithium bentonite, carbon nanotube composite material, auxiliary agent and base glaze with specific composition, wherein the lithium bentonite can improve the stability and rheological property of the glaze, prevent the solid particles from settling, ensure uniform coating, and enhance the adhesion between the glaze layer and the steel plate substrate in the initial stage of drying and sintering, and reduce the risk of cracking; the carbon nanotube composite material serves as the core toughening and interface reinforcing phase, in the enamel glaze layer, the carbon nanotube forms a three-dimensional network in the glaze layer, which can effectively bridge the micro-cracks and hinder the propagation of the cracks, and the toughness network formed by the phosphorus pentoxide in the base glaze cooperates to significantly improve the toughness and impact resistance of the glaze layer; the outermost layer of nano-silica particles uniformly disperse and adhere to the grain boundaries of the base glaze grains during the sintering process, inhibiting the abnormal growth of the grains, not only improving the hardness, but also when the hard nano-silica particles adhere to the grain boundaries, local compressive stress field is generated around the substrate grains, and tensile stress is also generated inside the substrate grains, which makes the substrate grains form a large number of sub-grain boundaries with different directions, forces the cracks to propagate along a more tortuous path, and increases the possibility of the cracks directly penetrating through the interior of the grains rather than only propagating along the grain boundaries, effectively absorbing and dissipating the fracture energy, and realizing the toughening of the material in multiple scales; the flexible carbon nanotube of the nano-titanium dioxide provides rigid support to prevent it from bending, breaking or agglomerating due to melt flow or grain extrusion during the sintering process of the glaze, and the surface of the nano-titanium dioxide is rich in hydroxyl groups, which can be tightly combined with the nano-silica layer through chemical bonds (Ti-O-Si bonds), and when the crack propagates to the vicinity of the carbon nanotube, it can also promote the deflection of the crack. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0027] The carbon nanotube is produced by Zhongke Nanometer Era, the model is IM299CP, the purity is >99%, the outer diameter is 5-15nm, the length is 10-20um, and the specific surface area is 260-330m 2 / g.

[0028] Embodiment 1: The present embodiment provides a preparation method of a carbon nanotube composite material, comprising the following steps:

[0029] Step one, 2g carbon nanotubes are added to 200mL concentrated nitric acid, 1h at 115℃, cooling, filtering, obtaining filter cake, the filter cake is first washed with 50mL of 4% concentration of sodium hydroxide 1 times, and then washed with 50mL of deionized water 1 times, drying at 75℃ for 8h, then with 50mg polyvinylpyrrolidone in 4L deionized water ultrasonic dispersion 12h, filtering through 0.2μm porous filter membrane, washing, drying, obtaining non-covalent modification carbon nanotubes;

[0030] Step two, 2g of step one product is ultrasonic dispersed in 100mL of 8wt% isopropanol solution for 20min, adjusting the pH value to 2, then adding 160mL of tetrabutyl titanate, stirring at 25℃ for 2h, filtering, obtaining filter cake, the filter cake is washed with 50mL of anhydrous ethanol and 50mL of deionized water alternately for 2 times, drying at 95℃ for 2h, finally sintering in vacuum with the temperature rising speed of 5℃ / min to 440℃, keeping for 2h, obtaining titanium dioxide / non-covalent modification carbon nanotubes;

[0031] Step three, 72mL of tetraethyl orthosilicate is stirred with 300mL of anhydrous ethanol at 55℃ for 2h, obtaining solution A, then 1g of step two product, 18mg of polyvinylpyrrolidone and 3.5L of deionized water are stirred at 25℃ for 10min, then solution A is added, stirring at 38℃ for 1h, centrifuging, separating, obtaining filter cake, the filter cake is washed with 50mL of anhydrous ethanol and 50mL of deionized water alternately for 2 times, drying at 50℃ for 1h, finally sintering in vacuum at 360℃ for 2h, obtaining carbon nanotube composite material.

[0032] The embodiment provides a preparation method of the enamel material, which comprises the following steps:

[0033] First step, the BTC1 cold-rolled steel plate is sandblasted with white jade, and then the surface of the steel plate is cleaned with anhydrous ethanol and acetone, and dried, to obtain a pretreated steel plate;

[0034] Second step, 100 parts of base glaze, 5 parts of lithium-based bentonite, 1.2 parts of carbon nanotube composite material, 0.1 part of potassium carbonate and 55 parts of deionized water are prepared.

[0035] Put into the ultrasonic cleaning machine for ultrasonic dispersion, the time is 40min, and grind for 3h, and then pass through an 80-mesh screen to obtain the enamel slip;

[0036] Third step, the enamel slip is uniformly coated on the pretreated steel plate, dried at 55℃ for 30min, sintered in a vacuum high-temperature sintering furnace at the temperature rising speed of 3℃ / min, the holding temperature is 790℃, the holding time is 5min, and then cooled, to obtain the enamel material.

[0037] The base enamel is 10.0 parts of boron trioxide, 8.0 parts of sodium oxide, 2.0 parts of magnesium oxide, 2.0 parts of aluminum trioxide, 30.0 parts of silicon dioxide, 1 part of lithium oxide, 1 part of potassium oxide, 2.0 parts of phosphorus pentoxide, 1.0 part of zinc oxide, 15.0 parts of titanium dioxide, and 5.0 parts of sodium fluorosilicate.

[0038] Embodiment 2: The present embodiment provides a preparation method of carbon nanotube composite material, comprising the following steps:

[0039] Step one, 2g of carbon nanotubes is added to 200mL of concentrated nitric acid, and is treated at 125℃ for 2h, and is cooled, filtered to obtain a filter cake, which is first washed with 50mL of 6% sodium hydroxide solution for 3 times, and then washed with 50mL of deionized water for 3 times, and is dried at 85℃ for 12h, and then is ultrasonically dispersed with 72mg of polyvinylpyrrolidone in 4L of deionized water for 24h, and is filtered through a 0.2μm porous filter membrane, washed, and dried to obtain non-covalently modified carbon nanotubes;

[0040] Step two, 2g of the product of step one is ultrasonically dispersed in 100mL of 12wt% isopropyl alcohol solution for 30min, the pH value is adjusted to 2.4, and then 180mL of tetrabutyl titanate is added, and is stirred at 25℃ for 4h, and is filtered to obtain a filter cake, which is washed with 50mL of anhydrous ethanol and 50mL of deionized water alternately for 4 times, and is baked at 105℃ for 3h, and finally is sintered in vacuum at a temperature rising speed of 10℃ / min to 480℃, and is kept for 6h to obtain titanium dioxide / non-covalently modified carbon nanotubes;

[0041] Step three, 80mL of tetraethyl orthosilicate is stirred with 300mL of anhydrous ethanol at 65℃ for 4h to obtain solution A, and then 1g of the product of step two, 24mg of polyvinylpyrrolidone and 3.5L of deionized water are stirred at 25℃ for 30min, and then solution A is added, and is stirred at 42℃ for 3h, and is centrifuged, and is separated to obtain a filter cake, which is washed with 50mL of anhydrous ethanol and 50mL of deionized water alternately for 4 times, and is dried at 55℃ for 3h, and finally is sintered in vacuum at 385℃ for 4h to obtain carbon nanotube composite material.

[0042] The present embodiment provides a preparation method of enamel material, comprising the following steps:

[0043] First step, the BTC1 cold-rolled steel plate is sandblasted with white jade, and then the surface of the steel plate is cleaned with anhydrous ethanol and acetone, and is dried to obtain a pretreated steel plate;

[0044] Second step, 100 parts of base enamel, 7 parts of lithium-based bentonite, 2.2 parts of carbon nanotube composite material, 0.5 parts of potassium carbonate, and 65 parts of deionized water.

[0045] Put into ultrasonic cleaning machine for ultrasonic dispersion, time is 60 min, grinds 5h, passes 160 mesh sieve, obtains enamel slip;

[0046] Third step, evenly coat the enamel slip on the pretreated steel plate, dry at 65 DEG C for 50 min, sinter in vacuum high temperature sintering furnace with the temperature rising speed of 3.4 DEG C / min, the holding temperature is 840 DEG C, the holding time is 6 min, cool, obtain the enamel material.

[0047] The base glaze is 18.0 parts of boron trioxide, 11.0 parts of sodium oxide, 3.0 parts of magnesium oxide, 3.0 parts of aluminum trioxide, 45.0 parts of silicon dioxide, 2 parts of lithium oxide, 2.5 parts of potassium oxide, 3.0 parts of phosphorus pentoxide, 2.0 parts of zinc oxide, 20.0 parts of titanium dioxide and 10.0 parts of sodium fluorosilicate.

[0048] Example 3: The present embodiment provides a preparation method of carbon nanotube composite material, comprising the following steps:

[0049] Step one, 2g carbon nanotube is added into 200mL concentrated nitric acid, 1.5h at 120 DEG C, cool, filter, obtain filter cake, the filter cake is washed with 50mL 5% concentration sodium hydroxide for 2 times, then washed with 50mL deionized water for 2 times, dry at 80 DEG C for 10h, then ultrasonic dispersion with 60mg polyvinylpyrrolidone in 4L deionized water for 15h, filter through 0.2μm porous filter membrane, wash, dry, obtain non-covalent modification carbon nanotube;

[0050] Step two, 2g step one product is ultrasonic dispersed in 100mL 10wt% isopropyl alcohol solution for 25min, adjust the pH value to 2.2, then add 170mL tetrabutyl titanate, stir at 25 DEG C for 3h, filter, obtain filter cake, the filter cake is washed with 50mL anhydrous ethanol and 50mL deionized water alternately for 3 times, dry at 100 DEG C for 2.5h, finally sinter in vacuum with the temperature rising speed of 8 DEG C / min, to 460 DEG C, keep for 4h, obtain titanium dioxide / non-covalent modification carbon nanotube;

[0051] Step three, 76mL tetraethyl orthosilicate is stirred with 300mL anhydrous ethanol at 55 DEG C for 3h, obtain solution A, then 1g step two product, 20mg polyvinylpyrrolidone and 3.5L deionized water are stirred at 25 DEG C, the stirring time is 20min, then add solution A, stir at 40 DEG C for 2h, centrifugal, separate, obtain filter cake, the filter cake is washed with 50mL anhydrous ethanol and 50mL deionized water alternately for 3 times, dry at 52 DEG C for 2h, finally sinter in vacuum at 380 DEG C for 3h, obtain carbon nanotube composite material.

[0052] The present embodiment provides a preparation method of enamel material, comprising the following steps:

[0053] Firstly, the BTC1 cold-rolled steel plate is sandblasted with white corundum, and then the surface of the steel plate is cleaned with anhydrous ethanol and acetone, and dried to obtain a pretreated steel plate;

[0054] Secondly, 100 parts of base glaze, 6 parts of lithium-based bentonite, 1.6 parts of carbon nanotube composite material, 0.4 parts of potassium carbonate and 60 parts of deionized water are mixed.

[0055] The mixture is placed in an ultrasonic cleaning machine for ultrasonic dispersion for 50 min, and then ground for 4 h, and then sieved through a 120-mesh sieve to obtain a porcelain enamel slurry.

[0056] Thirdly, the porcelain enamel slurry is uniformly coated on the pretreated steel plate, dried at 60℃ for 40 min, and then sintered in a vacuum high-temperature sintering furnace at a temperature increasing rate of 3.2℃ / min, with a holding temperature of 820℃ and a holding time of 5.5 min, and then cooled to obtain a porcelain material.

[0057] The base glaze comprises 12 parts of boron trioxide, 10 parts of sodium oxide, 2.5 parts of magnesium oxide, 2.8 parts of aluminum trioxide, 40 parts of silicon dioxide, 1.5 parts of lithium oxide, 2 parts of potassium oxide, 2.5 parts of phosphorus pentoxide, 1.5 parts of zinc oxide, 18 parts of titanium dioxide and 8 parts of sodium fluorosilicate.

[0058] Comparative Example 1: The present comparative example provides a method for preparing a carbon nanotube composite material, comprising the following steps:

[0059] Step one: 2g of carbon nanotubes is added to 200mL of concentrated nitric acid and stirred at 120℃ for 1.5h, then cooled and filtered to obtain a filter cake, which is first washed with 50mL of 5% sodium hydroxide solution for 2 times, and then washed with 50mL of deionized water for 2 times, and then dried at 80℃ for 10h, and then ultrasonically dispersed with 60mg of polyvinylpyrrolidone in 4L of deionized water for 15h, filtered through a 0.2μm porous filter membrane, washed and dried to obtain non-covalently modified carbon nanotubes.

[0060] Step two: 76mL of tetraethyl orthosilicate is stirred with 300mL of anhydrous ethanol at 55℃ for 3h to obtain solution A, and then 1g of the product of step one, 20mg of polyvinylpyrrolidone and 3.5L of deionized water are stirred at 25℃ for 20min, and then solution A is added and stirred at 40℃ for 2h, and then centrifuged, separated and filtered to obtain a filter cake, which is washed with 50mL of anhydrous ethanol and 50mL of deionized water alternately for 3 times, dried at 52℃ for 2h, and finally sintered at 380℃ under vacuum for 3h to obtain a carbon nanotube composite material.

[0061] The present comparative example provides a method for preparing a porcelain material, comprising the following steps:

[0062] First step, the BTC1 cold-rolled steel plate is sandblasted with white jade, and then the surface of the steel plate is cleaned with anhydrous ethanol and acetone, and dried to obtain a pretreated steel plate;

[0063] Second step, 100 parts of base glaze, 6 parts of lithium bentonite, 1.6 parts of carbon nanotube composite material, 0.4 parts of potassium carbonate, and 60 parts of deionized water.

[0064] Put into the ultrasonic cleaning machine for ultrasonic dispersion, time is 50 min, grinds 4h, passes through 120 mesh sieve, obtains the enamel glaze;

[0065] Third step, the enamel glaze is evenly coated on the pretreated steel plate, dried at 60℃ for 40 min, sintered in a vacuum high-temperature sintering furnace at a temperature rising speed of 3.2℃ / min, the holding temperature is 820℃, the holding time is 5.5 min, and cooled to obtain the enamel material.

[0066] The base glaze is 12 parts of boron trioxide, 10 parts of sodium oxide, 2.5 parts of magnesium oxide, 2.8 parts of aluminum oxide, 40 parts of silicon dioxide, 1.5 parts of lithium oxide, 2 parts of potassium oxide, 2.5 parts of phosphorus pentoxide, 1.5 parts of zinc oxide, 18 parts of titanium dioxide and 8 parts of sodium fluorosilicate.

[0067] Comparative example 2: this comparative example provides a preparation method of a carbon nanotube composite material, comprising the following steps:

[0068] Step one, 2g of carbon nanotubes is added to 200mL of concentrated nitric acid, and is treated at 120℃ for 1.5h, cooled, filtered to obtain a filter cake, the filter cake is first washed with 50mL of 5% sodium hydroxide solution for 2 times, then washed with 50mL of deionized water for 2 times, dried at 80℃ for 10h, then ultrasonic dispersed with 60mg of polyvinylpyrrolidone in 4L of deionized water for 15h, filtered through a 0.2μm porous filter membrane, washed, dried to obtain non-covalent modified carbon nanotubes;

[0069] Step two, 2g of the product of step one is ultrasonic dispersed in 100mL of 10wt% isopropyl alcohol solution for 25min, the pH value is adjusted to 2.2, then 170mL of tetrabutyl titanate is added, stirred at 25℃ for 3h, filtered to obtain a filter cake, the filter cake is washed with 50mL of anhydrous ethanol and 50mL of deionized water alternately for 3 times, dried at 100℃ for 2.5h, finally sintered in vacuum at a temperature rising speed of 8℃ / min to 460℃, and kept for 4h to obtain titanium dioxide / non-covalent modified carbon nanotubes.

[0070] This comparative example provides a preparation method of an enamel material, comprising the following steps:

[0071] The first step, the BTC1 cold-rolled steel plate is sandblasted with white jade, and then the surface of the steel plate is cleaned with anhydrous ethanol and acetone, and dried to obtain a pretreated steel plate;

[0072] The second step, 100 parts of base glaze, 6 parts of lithium-based bentonite, 1.6 parts of carbon nanotube composite material, 0.4 parts of potassium carbonate, and 60 parts of deionized water.

[0073] Put into the ultrasonic cleaning machine for ultrasonic dispersion, time is 50 min, grind 4h, pass through 120 mesh screen, obtain the enamel glaze slurry;

[0074] The third step, the enamel glaze slurry is evenly coated on the pretreated steel plate, dried at 60℃ for 40 min, sintered in a vacuum high-temperature sintering furnace at a temperature rising speed of 3.2℃ / min, the holding temperature is 820℃, the holding time is 5.5 min, and cooled to obtain the enamel material.

[0075] The base glaze is 12 parts of boron trioxide, 10 parts of sodium oxide, 2.5 parts of magnesium oxide, 2.8 parts of aluminum oxide, 40 parts of silicon dioxide, 1.5 parts of lithium oxide, 2 parts of potassium oxide, 2.5 parts of phosphorus pentoxide, 1.5 parts of zinc oxide, 18 parts of titanium dioxide and 8 parts of sodium fluorosilicate.

[0076] Comparative Example 3: The present comparative example provides a preparation method of an enamel material, comprising the following steps:

[0077] The first step, the BTC1 cold-rolled steel plate is sandblasted with white jade, and then the surface of the steel plate is cleaned with anhydrous ethanol and acetone, and dried to obtain a pretreated steel plate;

[0078] The second step, 100 parts of base glaze, 6 parts of lithium-based bentonite, 1.6 parts of carbon nanotube composite material, 0.4 parts of potassium carbonate, and 60 parts of deionized water.

[0079] Put into the ultrasonic cleaning machine for ultrasonic dispersion, time is 50 min, grind 4h, pass through 120 mesh screen, obtain the enamel glaze slurry;

[0080] The third step, the enamel glaze slurry is evenly coated on the pretreated steel plate, dried at 60℃ for 40 min, sintered in a vacuum high-temperature sintering furnace at a temperature rising speed of 3.2℃ / min, the holding temperature is 820℃, the holding time is 5.5 min, and cooled to obtain the enamel material.

[0081] The base glaze is 12 parts of boron trioxide, 10 parts of sodium oxide, 2.5 parts of magnesium oxide, 2.8 parts of aluminum oxide, 40 parts of silicon dioxide, 1.5 parts of lithium oxide, 2 parts of potassium oxide, 2.5 parts of phosphorus pentoxide, 1.5 parts of zinc oxide, 18 parts of titanium dioxide and 8 parts of sodium fluorosilicate.

[0082] Comparative Example 4: Compared with Example 3, the "lithium-based bentonite" in Example 3 is replaced with "kaolin", and the remaining raw materials and preparation process are the same as those in Example 3.

[0083] The enamel materials obtained in Examples 1-3 and Comparative Examples 1-4 were tested, the adhesion test referred to GB / T 5210-2006 "Paint and Varnish Adhesion Test by Tearing Method", the hardness test referred to GB / T 9790-2021 "Vickers and Knoop Microhardness Test for Metals and Other Inorganic Coatings", and polishing and grinding were performed before testing; the fracture toughness was tested using the three-point bending method.

[0084] The test results are shown in Table 1:

[0085] Table 1

[0086] Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Adhesion (MPa) 7.4 7.8 7.9 6.4 6.2 5.8 6.0 Vickers Hardness (HV) 604.8 542.6 584.4 544.8 572.6 534.2 575.4 Fracture toughness (MPa / m 1 / 2 ]) at 20°C 19.84 20.68 20.46 19.22 19.04 18.16 19.68

[0087] As can be seen from Table 1, compared with Comparative Examples 1-4, the adhesion of the enamel materials prepared in Examples 1-3 is between 7.4-7.9 MPa, the Vickers hardness (HV) is between 542.6-604.8, and the fracture toughness is 19.84-20.68 MPa / m 1 / 2 It can be seen that the adhesion, Vickers hardness and fracture toughness of the enamel materials prepared in the present application are all good.

[0088] It should be noted that, in this document, relational terms such as first and second and the like can be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0089] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. An enamel material, characterized in that, The composition includes the following components in parts by weight: 100 parts base glaze, 5-7 parts lithium-based bentonite, 1.2-2.2 parts carbon nanotube composite material, 0.1-0.5 parts additives, and 55-65 parts deionized water. The preparation method of carbon nanotube composite materials includes the following steps: Step 1: Add carbon nanotubes to concentrated nitric acid and heat at 115-125℃ for 1-2 hours. Cool and filter to obtain filter cake. Wash the filter cake with alkali, water and dry it. Then, ultrasonically disperse it with polyvinylpyrrolidone in deionized water for 12-24 hours. Filter, wash and dry to obtain non-covalently modified carbon nanotubes. Step 2: Disperse the product from Step 1 in an 8-12 wt% isopropanol solution using ultrasonication, adjust the pH to 2-2.4, add tetrabutyl titanate, stir at room temperature for 2-4 hours, filter to obtain a filter cake, wash and dry the filter cake, and finally sinter it in a vacuum at a heating rate of 5-10℃ / min to 440-480℃ and hold for 2-6 hours to obtain titanium dioxide / non-covalently modified carbon nanotubes. Step 3: Stir tetraethyl orthosilicate and anhydrous ethanol at 55-65℃ for 2-4 hours to obtain solution A. Then, stir the product from step 2, polyvinylpyrrolidone, and deionized water at room temperature for 10-30 minutes. Add solution A and stir at 38-42℃ for 1-3 hours. Centrifuge and separate the liquids to obtain a filter cake. Wash the filter cake alternately with anhydrous ethanol and deionized water, dry it at 50-55℃ for 1-3 hours, and finally sinter it under vacuum at 360-385℃ for 2-4 hours to obtain a carbon nanotube composite material. In step one, the ratio of carbon nanotubes, concentrated nitric acid, and polyvinylpyrrolidone is 1g:100mL:25-36mg. In step two, the ratio of the product from step one to tetrabutyl titanate is 1g:80-90mL. The ratio of tetraethyl orthosilicate, the product from step two, and polyvinylpyrrolidone in step three is 72-80 mL: 1 g: 18-24 mg.

2. The enamel material according to claim 1, characterized in that, The base glaze comprises the following components in parts by weight: Boron trioxide 10.0-18.0 parts, sodium oxide 8.0-11.0 parts, magnesium oxide 2.0-3.0 parts, aluminum oxide 2.0-3.0 parts, silicon dioxide 30.0-45.0 parts, lithium oxide 1-2 parts, potassium oxide 1-2.5 parts, phosphorus pentoxide 2.0-3.0 parts, zinc oxide 1.0-2.0 parts, titanium dioxide 15.0-20.0 parts, and sodium fluorosilicate 5.0-10.0 parts.

3. The enamel material according to claim 1, characterized in that, The additives are one or more of potassium fluorosilicate, potassium chloride, and potassium carbonate.

4. A method for preparing an enamel material according to any one of claims 1-3, characterized in that, Includes the following steps: The first step is to sandblast the steel plate with white alumina, then clean the surface of the steel plate with anhydrous ethanol and acetone, and dry it to obtain a pre-treated steel plate. The second step involves placing the base glaze, lithium-based bentonite, additives, carbon nanotube composite material, and deionized water into an ultrasonic cleaner for ultrasonic dispersion for 40-60 minutes, grinding for 3-5 hours, and then sieving to obtain enamel glaze slurry. The third step is to evenly coat the enamel slurry onto the pretreated steel plate, dry it, and then fire it in a vacuum high-temperature sintering furnace at a heating rate of 3-3.4℃ / min. After holding the temperature and cooling, the enamel material is obtained.

5. The method for preparing an enamel material according to claim 4, characterized in that, The drying temperature is 55-65℃, and the drying time is 30-50 minutes.

6. The method for preparing an enamel material according to claim 4, characterized in that, The heat preservation temperature is 790-840℃, and the heat preservation time is 4.6-5.5min.