A non-stick pan metal-ceramic composite coating material and preparation method thereof

Abstract

The present invention discloses a non-stick metal-ceramic composite coating material, comprising a thermally conductive base layer and a metal-ceramic surface layer sequentially deposited on the surface of a non-stick pan substrate; the thermally conductive base layer and the metal-ceramic surface layer are obtained by a single co-sintering process; the thermally conductive base layer is made of inorganic thermally conductive particles coated with an epoxy-based COF organic framework material. The non-stick metal-ceramic composite coating material of the present invention not only exhibits excellent bonding strength with the non-stick pan substrate but also exhibits excellent thermal conductivity, wear resistance, high temperature resistance, and chemical stability. The present invention also discloses a method for preparing the non-stick metal-ceramic composite coating material.

Description

Technical Field

[0001] The present invention relates to the technical field of non-stick pans, and in particular to a non-stick pan metal-ceramic composite coating material and a preparation method thereof. Background Art

[0002] Non-stick pans have entered thousands of households and are widely loved. Traditional iron-based non-stick pans are heavy and inconvenient to use; for this reason, people began to develop aluminum-based non-stick pans. There are many methods for preparing the non-stick coating of aluminum-based non-stick pans. The more traditional method is to coat a layer of polytetrafluoroethylene on the surface of the pre-treated aluminum-based non-stick pan substrate. Although this method satisfies the problem of non-sticking, the coating strength is not high and is prone to peeling and damage. For this reason, people have also begun to pay attention to the use of ceramic materials as non-stick coatings. However, the polymer adhesives of existing ceramic materials have poor high-temperature resistance and are potentially harmful to people's health after long-term use. At the same time, compared with iron-based non-stick pans, aluminum-based non-stick pans also have the problem of poor thermal conductivity. Summary of the Invention

[0003] In view of the above shortcomings of the prior art, the purpose of the present invention is to provide a non-stick pan metal-ceramic composite coating material to solve the comprehensive problems that the existing aluminum-based non-stick pan surface coating has low bonding strength with the non-stick pan embryo, and the coating material cannot take into account the comprehensive properties of thermal conductivity, wear resistance, high temperature resistance and chemical stability.

[0004] In order to achieve the above purpose, the technical solution adopted by the present invention is:

[0005] A non-stick pan metal-ceramic composite coating material, the composite coating material comprising a heat-conducting base layer and a metal-ceramic surface layer sequentially deposited on the surface of a non-stick pan substrate; the heat-conducting base layer and the metal-ceramic surface layer are obtained by a single co-sintering; wherein the raw material of the heat-conducting base layer comprises inorganic heat-conducting particles coated with an epoxy-based COF organic framework material.

[0006] The aluminum-based non-stick pan of the present invention is added with inorganic thermally conductive particles coated with epoxy-based COF organic framework materials. On the one hand, the unique porous network structure of COF is utilized to make the inorganic thermally conductive particles more evenly dispersed, thereby maximizing their thermal conductivity. In addition, combined with the certain thermal conductivity of the COF organic framework material, the high thermal conductivity of the bottom layer of the aluminum-based non-stick pan is further synergistically guaranteed. On the other hand, since the COF organic framework material carries epoxy groups, it can not only be firmly bonded to the aluminum-based non-stick pan substrate, but can also be chemically bonded to the inorganic thermally conductive particles.

[0007] Preferably, the raw materials of the thermal conductive bottom layer further include a wetting agent, a leveling agent and nano-silica sol.

[0008] Preferably, the epoxy COF organic framework material is obtained by firstly carrying out a molecular self-assembly reaction of a first COF organic monomer and a second COF organic monomer through covalent bonding, and then adding epoxy acrylate for grafting reaction.

[0009] Preferably, the first COF organic monomer is obtained by an aldehyde-amine condensation reaction of 1,3,5,7-tetrakis(4-benzaldehyde)-adamantane and vinylamine in a molar ratio of 1:2. The two benzaldehyde groups grafted onto the adamantane of the present invention undergo an aldehyde-amine condensation reaction with vinylamine to obtain an adamantane derivative that not only has two benzaldehyde groups but can also be covalently bonded to a second COF organic monomer with an active amine group through an aldehyde-amine condensation reaction, thereby forming a three-dimensional network structure on the surface of the inorganic thermally conductive particles through a molecular self-assembly reaction. Furthermore, the vinyl groups present in the adamantane allow for a grafting reaction with the added epoxy acrylate, resulting in the COF organic framework material having epoxy functional groups.

[0010] Preferably, the second COF organic monomer is at least one of 1,4-naphthalenediamine, 2,6-naphthalenediamine, and 2,6-diaminoanthracene.

[0011] Preferably, the epoxy acrylate is at least one of 2,3-epoxypropyl acrylate, 4-(2-oxiranylmethoxy)butyl acrylate, and 2,3-epoxypropyl methacrylate.

[0012] Preferably, the inorganic thermally conductive particles are aluminum oxide and / or aluminum nitride.

[0013] Preferably, the metal ceramic surface layer is formed by compounding at least one metal ceramic material of titanium carbide and / or titanium boride with perfluorinated modified nano-silica sol.

[0014] Preferably, the perfluorinated nano-silica sol is prepared using acetonitrile-dispersed nano-silica sol as a raw material, and then co-condensed with the hydrolyzed perfluorinated chlorosilane and the silica sol. The perfluorinated nano-silica sol of the present invention not only allows the metal ceramic surface layer and the thermally conductive base layer to be simultaneously co-sintered to produce a strong, dense, hard, and wear-resistant composite coating, but also provides the non-stick pan surface coating with excellent anti-stick properties, thermal stability, and chemical stability.

[0015] Another aspect of the present invention is to provide a method for preparing the non-stick pan metal-ceramic composite coating material as described above, the preparation method comprising the following steps:

[0016] S1: Shot blasting and roughening the aluminum non-stick pan substrate to form an uneven convex structure on the inner surface of the pan;

[0017] S2: Compounding the epoxy-based COF organic framework material-coated inorganic thermal conductive particles, a wetting agent, a leveling agent, and nano-silica sol, stirring and mixing them evenly, and then coating the mixture on the aluminum-based non-stick pan substrate obtained in step S1;

[0018] S3: mixing the metal ceramic material and the perfluorinated nano-silica sol uniformly by high-speed ball milling, and coating the mixture on the aluminum-based non-stick pan substrate obtained in step S2;

[0019] S4: placing the aluminum-based non-stick pan substrate obtained in step S3 in a high-temperature sintering furnace for a co-sintering reaction to obtain the composite coating material.

[0020] Beneficial effects of the present invention:

[0021] The non-stick pan metal-ceramic composite coating material of the present invention is prepared using a thermally conductive base layer comprised of inorganic thermally conductive particles coated with an epoxy-based COF organic framework material, along with a wetting agent, leveling agent, and nano-silica sol. This material not only exhibits excellent thermal conductivity but also bonds well with the aluminum cookware base, while maintaining sintering properties that match those of the metal-ceramic surface layer. After co-sintering, the two create an integrated structure, resulting in a strong bond and excellent compactness. Furthermore, the metal-ceramic surface layer, prepared using the metal-ceramic material and perfluorinated nano-silica sol as raw materials, exhibits excellent anti-sticking properties, wear resistance, and thermal and chemical stability.

[0022] In general, the non-stick pan metal-ceramic composite coating material of the present invention solves the comprehensive problems of low bonding strength between the existing aluminum-based non-stick pan surface coating and the non-stick pan embryo, and the coating material's inability to take into account the properties of thermal conductivity, wear resistance, high temperature resistance and chemical stability, and has good use effect. DETAILED DESCRIPTION

[0023] The following description is intended to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are merely examples, and those skilled in the art may conceive of other obvious variations.

[0024] Example 1

[0025] The non-stick pan metal-ceramic composite coating material of this embodiment comprises a thermally conductive base layer and a metal-ceramic surface layer sequentially deposited on the surface of a non-stick pan substrate. The thermally conductive base layer and the metal-ceramic surface layer are obtained by a single co-sintering process. The thermally conductive base layer is made of inorganic thermally conductive particles coated with an epoxy-based COF organic framework material. The base layer also includes a wetting agent, a leveling agent, and nano-silica sol. The metal-ceramic surface layer is a compound of titanium carbide and perfluorinated nano-silica sol.

[0026] The method for preparing the non-stick pan metal-ceramic composite coating material of this embodiment comprises the following steps:

[0027] S1: Shot blasting and roughening the aluminum non-stick pan substrate to form an uneven convex structure on the inner surface of the pan;

[0028] S2: Inorganic thermal conductive particles coated with epoxy COF organic framework material, a wetting agent (diisopropyl diacryloyl titanate), a leveling agent (polydimethylsiloxane) and nano-silica sol in a mass ratio of 50:3:5:42 are compounded, stirred and mixed evenly, and then coated on the aluminum-based non-stick pan substrate obtained in step S1, and the temperature is raised to 85°C and dried for 30 minutes;

[0029] S3: mixing titanium carbide, a metal ceramic material, and perfluorinated nano-silica sol in a mass ratio of 3:2 by high-speed ball milling to uniformly mix the mixture, and coating the mixture on the aluminum-based non-stick pan substrate obtained in step S2;

[0030] S4: placing the aluminum-based non-stick pan substrate obtained in step S3 in a high-temperature sintering furnace for a co-sintering reaction at a reaction temperature of 550° C. to obtain the non-stick pan metal-ceramic composite coating material.

[0031] The preparation method of the epoxy COF organic framework material coated inorganic thermal conductive particles is as follows: first, 1,3,5,7-tetrakis (4-benzaldehyde) -adamantane (20mmol) and ethyleneamine (40mmol) are added to a sodium hydroxide solution (250mL) with a mass concentration of 20%, and heated to 60°C to obtain vinylbenzaldehyde-adamantane (i.e., the first COF organic monomer) through an aldehyde-amine condensation reaction; secondly, 25g of inorganic thermal conductive particles aluminum nitride are ultrasonically uniformly dispersed in a reaction container containing 250mL of a mixed solvent of dimethyl sulfoxide and water (mass ratio of 2:3), the pH value of the mixed solvent is adjusted to 10, and then the first C OF organic monomer vinylbenzaldehyde adamantane (20mmol) and the second COF organic monomer 1,4-diaminenaphthalene (20mmol), set the reaction temperature to 80°C, the reaction pressure to 0.01MPa, the first COF organic monomer and the second COF organic monomer undergo molecular self-assembly reaction by covalent bond bonding for 72 hours to obtain vinyl COF organic skeleton material-coated inorganic thermal conductive particles, and finally add 2,3-epoxypropyl acrylate (25mmol), and carry out surface grafting modification reaction for 6 hours under the action of initiator ammonium persulfate to obtain the epoxy COF organic skeleton material-coated inorganic thermal conductive particles.

[0032] The perfluorinated nano-silica sol is prepared by weighing a certain amount of nano-silica and dispersing it in an acetonitrile solvent at a pH of 3.5 to form a silica sol (8.5% nano-silica by mass). (2-(perfluorohexyl)ethyl)trichlorosilane is then added to carry out a hydrolysis and polycondensation reaction for 25 minutes to obtain the perfluorinated nano-silica sol. The mass ratio of (2-(perfluorohexyl)ethyl)trichlorosilane to nano-silica is 3:10.

[0033] Example 2

[0034] The non-stick pan metal-ceramic composite coating material of this embodiment comprises a thermally conductive base layer and a metal-ceramic surface layer sequentially deposited on the surface of a non-stick pan substrate. The thermally conductive base layer and the metal-ceramic surface layer are obtained by a single co-sintering process. The thermally conductive base layer is made of inorganic thermally conductive particles coated with an epoxy-based COF organic framework material. The base layer also includes a wetting agent, a leveling agent, and nano-silica sol. The metal-ceramic surface layer is a compound of titanium boride and perfluorinated nano-silica sol.

[0035] The method for preparing the non-stick pan metal-ceramic composite coating material of this embodiment comprises the following steps:

[0036] S1: Shot blasting and roughening the aluminum non-stick pan substrate to form an uneven convex structure on the inner surface of the pan;

[0037] S2: Inorganic thermal conductive particles coated with epoxy COF organic framework material, a wetting agent (diisopropyl diacryloyl titanate), a leveling agent (polydimethylsiloxane) and nano-silica sol in a mass ratio of 55:2:5:38 are compounded, stirred and mixed evenly, and then coated on the aluminum-based non-stick pan substrate obtained in step S1, and the mixture is heated to 85°C and dried for 30 minutes;

[0038] S3: mixing titanium boride, a metal ceramic material, and perfluorinated nano-silica sol in a mass ratio of 3:2 by high-speed ball milling to uniformly mix the mixture, and coating the mixture on the aluminum-based non-stick pan substrate obtained in step S2;

[0039] S4: placing the aluminum-based non-stick pan substrate obtained in step S3 in a high-temperature sintering furnace for a co-sintering reaction at a reaction temperature of 600° C. to obtain the non-stick pan metal-ceramic composite coating material.

[0040] The preparation method of the epoxy COF organic framework material coated inorganic thermal conductive particles is as follows: first, 1,3,5,7-tetrakis (4-benzaldehyde) -adamantane (20mmol) and ethyleneamine (40mmol) are added to a sodium hydroxide solution (250mL) with a mass concentration of 20%, and heated to 65°C to obtain vinylbenzaldehyde-based adamantane (i.e., the first COF organic monomer) through an aldehyde-amine condensation reaction; secondly, 25g of inorganic thermal conductive particles aluminum nitride are ultrasonically uniformly dispersed in a reaction vessel containing 250mL of a mixed solvent of dimethyl sulfoxide and water (mass ratio of 2:3), the pH value of the mixed solvent is adjusted to 10, and then the first COF organic monomer is added. The monomer vinylbenzaldehyde adamantane (20mmol) and the second COF organic monomer 2,6-naphthalene diamine (20mmol) are prepared, the reaction temperature is set to 80°C, the reaction pressure is set to 0.02MPa, the first COF organic monomer and the second COF organic monomer undergo molecular self-assembly reaction by covalent bond bonding for 72 hours to obtain vinyl COF organic skeleton material-coated inorganic thermal conductive particles, and finally 4-(2-oxiranylmethoxy)butyl acrylate (25mmol) is added, and the surface grafting modification reaction is carried out under the action of initiator ammonium persulfate for 6 hours to obtain the epoxy COF organic skeleton material-coated inorganic thermal conductive particles.

[0041] The perfluorinated nano-silica sol is prepared by weighing a certain amount of nano-silica and dispersing it in an acetonitrile solvent at a pH of 3.5 to form a silica sol (9% nano-silica by mass). (2-(perfluorohexyl)ethyl)trichlorosilane is then added to carry out a hydrolysis and polycondensation reaction for 25 minutes to obtain the perfluorinated nano-silica sol. The mass ratio of (2-(perfluorohexyl)ethyl)trichlorosilane to nano-silica is 2.5:10.

[0042] Example 3

[0043] The non-stick pan metal-ceramic composite coating material of this embodiment comprises a thermally conductive base layer and a metal-ceramic surface layer sequentially deposited on the surface of a non-stick pan substrate; the thermally conductive base layer and the metal-ceramic surface layer are obtained by a single co-sintering process. The thermally conductive base layer is made from inorganic thermally conductive particles coated with an epoxy-based COF organic framework material. The base layer also includes a wetting agent, a leveling agent, and nano-silica sol. The metal-ceramic surface layer is formed from a metal-ceramic material composed of titanium carbide and titanium boride in a 1:1 mass ratio, compounded with perfluorinated nano-silica sol.

[0044] The method for preparing the non-stick pan metal-ceramic composite coating material of this embodiment comprises the following steps:

[0045] S1: Shot blasting and roughening the aluminum non-stick pan substrate to form an uneven convex structure on the inner surface of the pan;

[0046] S2: Inorganic thermal conductive particles coated with epoxy COF organic framework material, a wetting agent (diisopropyl diacryloyl titanate), a leveling agent (polydimethylsiloxane) and nano-silica sol in a mass ratio of 58:2:5:35 are compounded, stirred and mixed evenly, and then coated on the aluminum-based non-stick pan substrate obtained in step S1, and the mixture is heated to 85°C and dried for 30 minutes;

[0047] S3: uniformly mixing the metal ceramic material and the perfluorinated modified nano-silica sol in a mass ratio of 3:2 by high-speed ball milling, and coating the mixture on the aluminum-based non-stick pan substrate obtained in step S2;

[0048] S4: placing the aluminum-based non-stick pan substrate obtained in step S3 in a high-temperature sintering furnace for a co-sintering reaction at a reaction temperature of 600° C. to obtain the non-stick pan metal-ceramic composite coating material.

[0049] The preparation method of the epoxy COF organic framework material coated inorganic thermal conductive particles is as follows: first, 1,3,5,7-tetrakis(4-benzaldehyde)-adamantane (20 mmol) and ethyleneamine (40 mmol) are added to a sodium hydroxide solution (250 mL) with a mass concentration of 20%, and the mixture is heated to 70°C to obtain vinylbenzaldehyde-adamantane (i.e., the first COF organic monomer) through an aldehyde-amine condensation reaction; secondly, 25 g of inorganic thermal conductive particles of aluminum nitride are ultrasonically uniformly dispersed in a reaction vessel containing 250 mL of a mixed solvent of dimethyl sulfoxide and water (mass ratio of 2:3), the pH value of the mixed solvent is adjusted to 10, and then the first COF is added. F organic monomer vinylbenzaldehyde adamantane (20mmol) and the second COF organic monomer 2,6-diaminoanthracene (20mmol), set the reaction temperature to 85°C, the reaction pressure to 0.03MPa, the first COF organic monomer and the second COF organic monomer undergo molecular self-assembly reaction by covalent bond bonding for 72 hours to obtain vinyl COF organic skeleton material-coated inorganic thermal conductive particles, and finally add 2,3-epoxypropyl methacrylate (25mmol), and carry out surface grafting modification reaction for 6 hours under the action of initiator ammonium persulfate to obtain the epoxy COF organic skeleton material-coated inorganic thermal conductive particles.

[0050] The perfluorinated nano-silica sol is prepared by weighing a certain amount of nano-silica and dispersing it in an acetonitrile solvent at a pH of 3.5 to form a silica sol (9.5% nano-silica by mass). (2-(perfluorohexyl)ethyl)trichlorosilane is then added to carry out a hydrolysis and polycondensation reaction for 25 minutes to obtain the perfluorinated nano-silica sol. The mass ratio of (2-(perfluorohexyl)ethyl)trichlorosilane to nano-silica is 2:10.

[0051] The non-stick pan metal-ceramic composite coating materials prepared in Examples 1 to 3 were subjected to performance tests, and the performance results are shown in Table 1:

[0052] Table 1

[0053]

[0054]

[0055] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions only describe the principles of the present invention. Various changes and improvements are possible without departing from the spirit and scope of the present invention, and such changes and improvements fall within the scope of the invention as claimed.

Claims

1. A non-stick pan metal-ceramic composite coating material, characterized in that: The composite coating material includes a heat-conducting base layer and a metal-ceramic surface layer sequentially deposited on the surface of an aluminum-based non-stick pan substrate; the heat-conducting base layer and the metal-ceramic surface layer are obtained by co-sintering once; wherein, the raw materials of the heat-conducting base layer include inorganic heat-conducting particles coated with an epoxy-based COF organic framework material; the epoxy-based COF organic framework material is first obtained by molecular self-assembly reaction of a first COF organic monomer and a second COF organic monomer through covalent bonding, and then epoxy acrylate is added for grafting reaction; the first COF organic monomer is obtained by an aldehyde-amine condensation reaction of 1,3,5,7-tetrakis(4-benzaldehyde)-adamantane and ethyleneamine in a molar ratio of 1:2; the second COF organic monomer is at least one of 1,4-diaminonaphthalene, 2,6-naphthalenediamine, and 2,6-diaminoanthracene; the raw materials of the heat-conducting base layer also include a wetting agent, a leveling agent, and nano-silica sol; the metal-ceramic surface layer is compounded by at least one metal-ceramic material of titanium carbide and / or titanium boride and perfluorinated modified nano-silica sol.

2. The non-stick pan metal-ceramic composite coating material according to claim 1, characterized in that: The epoxy acrylate is at least one of 2,3-epoxypropyl acrylate, 4-(2-oxiranylmethoxy)butyl acrylate, and 2,3-epoxypropyl methacrylate.

3. The non-stick pan metal-ceramic composite coating material according to claim 1, characterized in that: The inorganic thermally conductive particles are aluminum oxide and / or aluminum nitride.

4. The non-stick pan metal-ceramic composite coating material according to claim 1, characterized in that: The perfluorinated modified nano-silica sol is prepared by using nano-scale silica sol dispersed in acetonitrile as a raw material, and then hydrolyzing perfluorinated chlorosilane and co-condensing it with the silica sol.

5. A method for preparing the non-stick pan metal-ceramic composite coating material according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: S1: Shot blasting and roughening the aluminum non-stick pan substrate to form an uneven convex structure on the inner surface of the pan; S2: Compounding the epoxy-based COF organic framework material-coated inorganic thermal conductive particles, a wetting agent, a leveling agent, and nano-silica sol, stirring and mixing them evenly, and then coating the mixture on the aluminum-based non-stick pan substrate obtained in step S1; S3: mixing the metal ceramic material and the perfluorinated nano-silica sol uniformly by high-speed ball milling, and coating the mixture on the aluminum-based non-stick pan substrate obtained in step S2; S4: placing the aluminum-based non-stick pan substrate obtained in step S3 in a high-temperature sintering furnace for a co-sintering reaction to obtain the composite coating material.

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