CN108977750B - Non-stick coating, preparation method thereof, cooker and cooking equipment - Google Patents
Non-stick coating, preparation method thereof, cooker and cooking equipment Download PDFInfo
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- CN108977750B CN108977750B CN201710405471.4A CN201710405471A CN108977750B CN 108977750 B CN108977750 B CN 108977750B CN 201710405471 A CN201710405471 A CN 201710405471A CN 108977750 B CN108977750 B CN 108977750B
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- fluorine
- containing resin
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- 238000000576 coating method Methods 0.000 title claims abstract description 147
- 239000011248 coating agent Substances 0.000 title claims abstract description 144
- 238000010411 cooking Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 108
- 239000002245 particle Substances 0.000 claims abstract description 87
- 238000005507 spraying Methods 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 66
- 239000011347 resin Substances 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 64
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 63
- 239000011737 fluorine Substances 0.000 claims abstract description 63
- 239000000919 ceramic Substances 0.000 claims abstract description 62
- 239000007921 spray Substances 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 238000009826 distribution Methods 0.000 claims abstract description 31
- 238000007750 plasma spraying Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 35
- 239000011247 coating layer Substances 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000013618 particulate matter Substances 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000008429 bread Nutrition 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 235000013322 soy milk Nutrition 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 abstract description 2
- 238000005187 foaming Methods 0.000 description 27
- 230000002087 whitening effect Effects 0.000 description 26
- 239000007789 gas Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000000889 atomisation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000005422 blasting Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 240000000249 Morus alba Species 0.000 description 3
- 235000008708 Morus alba Nutrition 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000007590 electrostatic spraying Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000009991 scouring Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
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- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
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- 239000010959 steel Substances 0.000 description 2
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- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000467686 Eschscholzia lobbii Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- -1 Polytetrafluoroethylene Polymers 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
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- 235000013339 cereals Nutrition 0.000 description 1
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- 239000010431 corundum Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
- A47J36/00—Parts, details or accessories of cooking-vessels
- A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
- A47J36/025—Vessels with non-stick features, e.g. coatings
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
- A47J36/00—Parts, details or accessories of cooking-vessels
- A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
- A47J36/04—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay the materials being non-metallic
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Food Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cookers (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention relates to the technical field of electric heating appliances, and discloses a non-stick coating, a preparation method thereof, a cooker and cooking equipment. The method comprises the following steps: ceramic powder and fluorine-containing resin powder are used as raw materials, and a non-stick coating is formed on the surface of a substrate through plasma spraying treatment; wherein the particle size distribution of the ceramic powder is in the range of 35-65 mu m; the conditions of the plasma spraying treatment include: the spraying power of the plasma spray gun is 30-50kW, the spraying current is 500-650A, the main air flow in the working gas is 35-55L/min, the auxiliary air flow is 2-6L/min, and the spraying distance is 80-120mm; and ceramic powder is fed into the flame flow formed by the plasma spray gun at a distance D1 from the spray gun outlet, and fluorine-containing resin powder is fed into the flame flow formed by the plasma spray gun at a distance D2 from the spray gun outlet, wherein D2 is larger than D1. The non-stick coating has the advantage of high coating binding force.
Description
Technical Field
The invention relates to the technical field of electric heating appliances, in particular to a non-stick coating, a preparation method thereof, a cooker and cooking equipment.
Background
The conventional forming mode of the existing non-stick coating is mainly to adopt an air pressure spraying and electrostatic spraying mode and then sintering and solidifying at high temperature, the service life of the coating is generally only half a year to one year, the hardness of the coating is low (the Vickers hardness of the PTFE non-stick coating is 100-200HV, the Vickers hardness of the ceramic non-stick coating is 200-350 HV), the adhesive force of the coating is small (the bonding force of the PTFE non-stick coating is 2-10MPa, the bonding force of the ceramic non-stick coating is 2-5 MPa), the thickness of the coating is small (the thickness of the PTFE non-stick coating is 20-50 mu m, the thickness of the ceramic non-stick coating is 20-40 mu m), the acid-alkali resistance and the salt resistance are also generally, the coating can not be scraped, worn and corroded in the long-term use process, the coating can not fall off and fail, and the non-stick coating is not provided after the surface coating fails, so that the service life and application of the coating are limited to a great extent.
The existing cooking appliances, including frying pans, electric cookers, pressure cooker liners and the like, have widely used non-stick coatings, so that the coatings which are durable and non-stick and have excellent performance become key problems in the cooker industry.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a non-stick coating, a preparation method thereof, a pot and cooking equipment, wherein the non-stick coating has the advantage of high coating binding force.
The inventors of the present invention conducted a great deal of studies on the raw materials and the forming method of the non-stick coating layer in order to improve the performance of the non-stick coating layer, found that there are various advantages to each of the two materials, namely, the ceramic powder and the fluorine-containing resin powder, if the two materials can be combined together to prepare the non-stick coating layer, it would be expected to improve the comprehensive effect of the non-stick coating layer, based on this, the inventors conducted a great deal of studies again, found that the fluorine-containing resin material has a low melting point and is easily atomized under heating, and when the fluorine-containing resin material is atomized, the molten droplets of the ceramic particles pass through the atomized matter of the fluorine-containing resin material and strike the surface of the substrate, the coated particles of the ceramic particles coated with the fluorine-containing resin material can be formed. The thickness and the transverse area of the ceramic particle core in the formed coated particles can be controlled by controlling the spraying power, the flow rate and the spraying distance of working gas and the preheating temperature of the matrix in the step of plasma spraying treatment, so that the bonding strength and the wettability of a particle stacking layer (non-stick coating) formed by the coated particles are improved.
Accordingly, in order to achieve the above object, the present invention provides, in one aspect, a method of preparing a non-stick coating, the method comprising:
(1) Pretreating a matrix;
(2) Preheating the surface of the substrate obtained in the step (1);
(3) Ceramic powder and fluorine-containing resin powder are used as raw materials, and a non-stick coating is formed on the surface of a substrate through plasma spraying treatment;
wherein the particle size distribution of the ceramic powder is in the range of 35-65 μm; the conditions of the plasma spraying treatment include: the spraying power of the plasma spray gun is 30-50kW, the spraying current is 500-650A, the main air flow in the working gas is 35-55L/min, the auxiliary air flow is 2-6L/min, and the spraying distance is 80-120mm; and ceramic powder is fed into the flame flow formed by the plasma spray gun at a distance D1 from the spray gun outlet, and fluorine-containing resin powder is fed into the flame flow formed by the plasma spray gun at a distance D2 from the spray gun outlet, wherein D2 is larger than D1.
The second aspect of the invention provides a non-stick coating prepared by the method of the invention.
The third aspect of the invention provides a pot comprising a substrate and a non-stick coating formed on the substrate, the non-stick coating being a stacked layer of particles having a flat structure, the particles comprising a ceramic particle core and a fluorine-containing resin material coating; the ceramic particle core has a thickness D distribution in the range of 1-10 μm, a transverse diameter R distribution in the range of 50-400 μm, and 1/4R 2 D is distributed at 8000-40000 μm 3 Within the range.
According to a fourth aspect of the present invention, there is provided a cooking apparatus comprising a pan according to the present invention.
According to the method for preparing the non-stick coating, the ceramic powder and the fluorine-containing resin powder are fed at different positions of flame flow formed by a plasma spray gun, so that molten drops of ceramic particles pass through atomized matters of the fluorine-containing resin material and then strike the surface of a substrate, and then particles of the fluorine-containing resin material coated with the ceramic particles are formed, and the non-stick coating is formed based on accumulation of the particles; the non-stick coating formed by the method has the following beneficial effects:
1) By controlling the spraying power, the flow rate of the working gas and the spraying distance in the non-stick coating forming process, the thickness D is distributed in the range of 1-10 mu m, the transverse diameter R is distributed in the range of 50-400 mu m, and 1/4R can be formed 2 D is distributed at 8000-40000 μm 3 A ceramic particle core within the range; further, the binding force, the porosity and the wettability of the coating are comprehensively improved while the hardness of the coating is maintained;
2) By further controlling the feeding position and the feeding amount of the fluorine-containing resin material in the non-stick coating forming process, the thickness of the fluorine-containing resin material in the non-stick coating can be further controlled, and the wettability of the corresponding non-stick coating can be optimized.
3) In the formed non-stick coating, the particles have a structure that the fluorine-containing resin material coats the ceramic particles, so that the non-stick coating has better scratch resistance and corrosion resistance, and the service life of the non-stick coating is prolonged;
4) The formed non-stick coating is formed by stacking flat particles with a coating structure, so that the formed non-stick coating is uniform and stable in structure from inside to outside, and even if the surface is locally worn in the use process, the inner layer structure is consistent with the surface layer structure, the hardness, the hydrophobicity, the non-stick property, the binding force, the scratch resistance and the corrosion resistance of the non-stick coating can be still kept, and the service life of the non-stick coating is prolonged.
Drawings
FIG. 1 is a schematic view of a pan of the present invention;
FIG. 2 is a side cross-sectional view of a non-stick coating of the present invention;
FIG. 3 is a top cross-sectional view of the non-stick coating of the present invention;
fig. 4 is a schematic view of the structure of particles constituting the non-stick coating of the present invention.
Description of the reference numerals
1 is a non-stick coating, 2 is a matrix, 10 is particulate matter, 11 is a ceramic particle core, and 12 is a fluorine-containing resin material coating layer.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In order to improve the surface hardness, coating binding force, and hydrophobic non-tackiness of the non-stick coating, there is provided in the present invention a method of preparing a non-stick coating, the method comprising: (1) pretreating a substrate; (2) Preheating the surface of the substrate obtained in the step (1) to 80-150 ℃; (3) Ceramic powder and fluorine-containing resin powder are used as raw materials, and a non-stick coating is formed on the surface of a substrate through plasma spraying treatment; wherein the particle size distribution of the ceramic powder is in the range of 35-65 μm (preferably 40-60 μm) (the fluidity of the ceramic powder is 10-30s/50 g); the conditions of the plasma spraying treatment include: the spraying power of the plasma spray gun is 30-50kW, the spraying current is 500-650A, the flow of main gas (such as argon) in working gas is 35-55L/min, the flow of auxiliary gas (such as hydrogen) is 2-6L/min, and the spraying distance is 80-120mm; and ceramic powder is fed into the flame flow formed by the plasma spray gun at a distance D1 from the spray gun outlet, and fluorine-containing resin powder is fed into the flame flow formed by the plasma spray gun at a distance D2 from the spray gun outlet, wherein D2 is larger than D1.
According to the method of the present invention, the fluorine-containing resin powder preferably has a particle size distribution in the range of 20 to 100. Mu.m, preferably in the range of 40 to 100. Mu.m, more preferably in the range of 45 to 60. Mu.m; the fluidity of the fluorine-containing resin powder is less than 30s/50g, preferably 10 to 25s/50g, more preferably 10 to 20s/50g.
According to the method of the present invention, when a fluorine-containing resin powder is selected, if the fluidity of a commercially available fluorine-containing resin powder cannot meet the requirement, the fluorine-containing resin powder may be modified to obtain a fluorine-containing resin powder having the fluidity meeting the requirement, and in a preferred case, the modified fluorine-containing resin powder is produced by a method comprising the steps of: (a) Mixing fluorine-containing resin powder, a binder, a lubricant and water to prepare a slurry; (b) subjecting the slurry to spray drying treatment.
Preferably, in step (a), the fluorine-containing resin powder is contained in an amount of 30 to 60% by weight, more preferably 38 to 55% by weight, based on the weight of the slurry; the content of the binder is 0.2 to 2 wt%, more preferably 0.2 to 0.5 wt%; the content of the lubricant is 0.5 to 3 wt%, further preferably 1 to 3 wt%; the water content is 35 to 68% by weight, more preferably 42 to 60% by weight.
Preferably, in step (a), the binder is at least one of polyvinyl alcohol, polyvinyl chloride and polyacrylate.
Preferably, in step (a), the lubricant is at least one of glycerin, paraffin wax and graphite.
Preferably, in step (b), the spray drying treatment is air-flow atomization drying, and the conditions of the air-flow atomization drying include: the atomization pressure is 0.3-0.6MPa, more preferably 0.3-0.5MPa; the flow rate of the atomized air flow is 1-4m 3 Preferably 1 to 3m 3 /h; the inlet temperature is 200-400 ℃, and more preferably 300-350 ℃; the temperature of the air outlet is 50-200 ℃, and more preferably 50-150 ℃.
According to the method of the invention, the spraying power of the ion spray gun is preferably 40-50kW, and preferably 40-45kW; the spraying current is 500-600A, preferably 560-600A; the main air flow in the working gas is 40-50L/min, and the auxiliary air flow is 3-5L/min; the spraying distance is 90-110mm. Preferably, in the step of the plasma spraying treatment, the spraying angle is 70-90 °.
According to the method of the present invention, preferably, 1/6.ltoreq.D2-D1.ltoreq.D2 of the flame flow length, more preferably, 1/4.ltoreq.D2-D1.ltoreq.D3 of the flame flow length, even more preferably, the D1 is 1/4-1/3 of the flame flow length, and the D2 is 1/2-2/3 of the flame flow length; wherein the flame flow length is preferably 14-18cm.
According to the method of the present invention, preferably, in the step of the plasma spraying treatment, the moving speed of the spray gun is 60 to 100mm/s, preferably 75 to 85mm/s; the thickness of the non-stick coating is 50-2000 μm, preferably 100-300 μm.
According to the method of the present invention, preferably, the ceramic powder is fed in an amount of 3.5 to 5g/min; the powder feeding amount of the fluorine-containing resin powder is 2.5-3.5g/min. In the plasma spraying process, in the process of atomizing and attaching the fluorine-containing resin particles on the surface of the ceramic particle core, part of the fluorine-containing resin raw material is lost, and as can be seen from the measurement of the prepared non-stick coating by a chemical analysis method, the prepared non-stick coating comprises, based on the total weight thereof, by controlling the powder feeding amount in the above range: 55-90 wt% of ceramic particles and 10-45 wt% of fluorine-containing resin material.
According to the method of the present invention, preferably, the ceramic powder is alumina and/or titania, the fluorine-containing resin powder is Polytetrafluoroethylene (PTFE) and/or tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA), and preferably, the fluorine-containing resin powder has a melting point of 350 to 420 ℃, and more preferably, 400 to 420 ℃.
According to the method of the invention, the substrate can be a metal substrate such as a stainless steel substrate, an aluminum alloy substrate, a titanium alloy substrate and the like or a multi-layer (including double layers and more than three layers) metal composite substrate. Wherein, the multilayer metal composite matrix can be a stainless steel/aluminum matrix, a stainless steel/copper matrix, a stainless steel/aluminum/copper matrix, etc. Preferably, the thickness of the substrate is 0.5-6mm.
According to the method of the present invention, the pretreatment method of step (1) may preferably include a blasting treatment and a degreasing treatment, and the method of the blasting treatment and the degreasing treatment is not particularly limited, and may be various methods commonly used in the art, respectively. For example, the method of blasting includes: the air jet pressure is controlled to be 0.2-0.9MPa by adopting 60-150 mesh sand grains (such as glass sand, brown steel sand, black brown jade, white corundum, carborundum and the like), and the obtained roughness is about Ra2-8 mu m. After the blasting treatment, the fine powder particles and the like remaining on the inner surface of the substrate are removed, and the method of removal is not particularly limited, and may be either cleaned by high-pressure air flow or removed by water washing, which are well known to those skilled in the art and will not be described in detail herein. For example, the degreasing treatment may include alkali washing, acid washing, water washing and high-temperature drying (e.g., drying at 200-450 ℃ C. For 10-15 min) in this order.
According to the process of the present invention, the substrate surface obtained in step (1) is preferably preheated in step (2) to a temperature of 80-150 ℃, preferably 100-120 ℃.
In a second aspect, the invention provides a non-stick coating prepared by the method described above.
In a third aspect, as shown in fig. 1 to 4, the present invention provides a pot comprising a base 2 and a non-stick coating 1 formed on the base 2, the non-stick coating being a stacked layer of particles 10 having a flat structure, the particles 10 comprising a ceramic particle core 11 and a fluorine-containing resin material coating layer 12 coated on the outer periphery of the ceramic particle core 11; the ceramic particle core 11 has a thickness D distribution in the range of 1-10 μm, a transverse diameter R distribution in the range of 50-400 μm, and 1/4R 2 D is distributed at 8000-40000 μm 3 Within the range.
The particle size of the particles in the non-stick coating provided by the invention can be measured by a scanning electron microscope, when the size of each particle is measured, the maximum value of the thickness of the ceramic particle core in the particle is recorded as thickness D, and the maximum value of the transverse diameter (the diameter of the cross section perpendicular to the thickness direction) is used as transverse diameter R; in addition, when the distribution ranges of the thickness D and the transverse diameter R of the ceramic particle cores in the non-stick coating are measured, 5-10 areas are randomly selected in the non-stick coating, 10-20 particles are measured in each area, the thickness and the transverse diameter of the particles are counted, and when the ranges of the thickness and the transverse diameter of the particles meet the requirements, the non-stick coating is considered to meet the requirements of the ranges.
Preferably, the ceramic particle cores 11 have an average thickness D distribution in the range of 2-5 μm and an average transverse diameter R distribution in the range of 80-280 μm.
Preferably, the single-sided thickness of the fluororesin material coating layer 12 of the particulate matter 10 is in the range of 0.2 to 2 μm. Wherein the thickness of the single side of the fluorine-containing resin material coating layer is also measured by a scanning electron microscope, and the maximum thickness of the single side of the fluorine-containing resin material coating layer in each particulate matter is recorded as the thickness of the single side thereof, and the thickness distribution of the fluorine-containing resin material coating layer in each particulate matter in the non-stick coating layer is measured according to the foregoing measurement method.
Preferably, the non-stick coating 1 comprises, based on the total weight thereof: 55-90 wt% of ceramic particles and 10-45 wt% of fluorine-containing resin material.
Preferably, the ceramic material in the ceramic particle core 11 is alumina and/or titania.
Preferably, the fluororesin material in the fluororesin coating layer 12 is PTFE and/or PFA.
Preferably, the thickness of the substrate 2 is 0.5-6mm;
preferably, the thickness of the non-stick coating 1 is 50-2000 μm, more preferably 100-300 μm.
Preferably, the non-stick coating 1 is a non-stick coating according to the present invention.
In a fourth aspect, the present invention provides a cooking apparatus comprising a pan according to the present invention. Preferably, the cooking device is a frying pan, air frying pan, frying and baking machine, bread machine, electric rice cooker, electric pressure cooker or soymilk machine.
Hereinafter, the non-stick coating according to the present invention and the method of preparing the same will be described in detail by way of examples. In the following examples, unless otherwise indicated, the materials used are all commercially available and the methods used are all conventional in the art.
In the following examples, the measurement methods involved are described below:
the flowability of the PFA powder was determined according to GB1482-84 using a Hall flowmeter.
The purity of the PFA powder was determined using an automatic polarimeter (available from Aituo China, model number AP-300).
The melting point of the PFA powder was determined using a micro-melting point tester (available from Jinan Heinai instruments Co., ltd., model MP-300).
The surface roughness Ra of the PFA powder was measured by a surface roughness meter (model TIME3201, available from peak technology limited in beijing age).
The contact angle measurement instrument (available from Shenzhen Xin Heng Sen trade Co., ltd., model XHSCZA-2) was used to measure the original contact angle and the post-friction contact angle, and the measurement range was 0-180 degrees.
In the following examples, the raw materials involved are described below:
alumina powder A1 was purchased from Beijing mulberry yao technology development Co., ltd, and had a particle size distribution of 38-46 μm and a flowability of 21s/50g.
Alumina powder A2 was purchased from Beijing mulberry yao technology development Co., ltd, and had a particle size distribution of 52-62 μm and a flowability of 23s/50g.
Titanium oxide powder is purchased from Beijing mulberry Yao technology development Co., ltd, has a particle size distribution of 42-54 μm and a flowability of 25s/50g.
The normal PFA powder was purchased from Dajinfu paint (Shanghai) Co., ltd, particle size D50 of 15 μm, sphericity of 95% powder of 18%, fluidity of 78s/50g, purity of 94%, melting point of 345℃and surface roughness of Ra0.6μm.
The preparation method of the modified PFA powder A1 comprises the following steps: (1) 47.6kg of ordinary PFA powder, 0.4kg of polyvinyl alcohol (model PVA1788 from Shanghai Fusi spring technology Co., ltd.), 2kg of glycerin and 50kg of water were mixed to prepare a slurry; (2) Carrying out airflow atomization drying treatment on the slurry, wherein the airflow atomization drying conditions comprise: the atomization pressure is 0.4MPa, and the flow rate of the atomization airflow is 2m 3 And/h, the inlet temperature is 320 ℃, the air outlet temperature is 100 ℃, and the modified PFA powder A1 is obtained. The particle diameter D50 of the modified PFA powder A1 was measured to be 52. Mu.m, the fluidity was 15s/50g, the purity was 99.9%, the melting point was 410℃and the surface roughness was Ra0.2. Mu.m.
The preparation method of the modified PFA powder A2 comprises the following steps: (1) 54.8kg of ordinary PFA powder, 0.2kg of polyvinyl chloride (available from Shanghai Ji Ning Co., ltd., model K55-59), 3kg of paraffin wax and 42kg of water were mixedMixing to prepare slurry; (2) Carrying out airflow atomization drying treatment on the slurry, wherein the airflow atomization drying conditions comprise: the atomization pressure is 0.3MPa, and the flow rate of the atomization airflow is 1m 3 And/h, the inlet temperature is 300 ℃, the air outlet temperature is 60 ℃, and the modified PFA powder A2 is obtained. The particle diameter D50 of the modified PFA powder was determined to be 46. Mu.m, the fluidity was determined to be 13s/50g, the purity was determined to be 99.5%, the melting point was determined to be 405℃and the surface roughness was determined to be Ra 0.15. Mu.m.
Example 1
This example illustrates a method for preparing a non-stick coating using a plasma spray process.
(1) Pretreating an aluminum pot substrate (with the thickness of 2.5 mm), wherein the pretreatment method comprises the following steps: a) Deoiling at 55deg.C for 8 min; b) Washing with deionized water; c) Drying at 100deg.C for 5min; d) Adopting 60-80 mesh brown steel sand, carrying out sand blasting treatment on the inner surface of the aluminum pot body under the air jet pressure of 0.6MPa to ensure that the surface roughness of the inner surface is Ra3 mu m, and then blowing out residual powder particles on the inner surface of the pot body by using air flow (air); e) Alkaline washing with 40 wt% NaOH solution at 80℃for 1 minute; f) Neutralizing with 20 wt% nitric acid solution for 3 min; g) Washing with deionized water, and drying at 300 ℃ for 12 minutes;
(2) Preheating the surface of the substrate obtained in the step (1) to 120 ℃;
(3) Taking aluminum oxide powder A1 and modified PFA powder A1 as raw materials, and forming a non-stick coating on the surface of a substrate through plasma spraying treatment; wherein, the conditions of the plasma spraying treatment include: the spraying power of the plasma spray gun is 45kW, the spraying current is 580A, the flow rate of hydrogen in the working gas is 4L/min, and the flow rate of argon is 45L/min; the spraying distance between the plasma spray gun and the substrate is 100mm, the spraying angle is 80 degrees+/-1 degrees, and the moving speed of the spray gun is 80mm/s; feeding aluminum oxide powder A1 at a position which is away from a spray gun outlet D1 (1/4 of the flame flow length) in flame flow formed by a plasma spray gun, wherein the powder feeding amount is 4.2g/min, and feeding modified PFA powder A1 at a position which is away from the spray gun outlet D2 (1/2 of the flame flow length), and the powder feeding amount is 2.8g/min; a non-stick coating having a thickness of 200 μm was formed and designated as S1.
Non-stick coatings prepared by scanning electron microscopy at different magnificationsThe transverse and longitudinal sections of the layer S1, it can be seen that the non-stick coating is formed by the accumulation of particles, each of which comprises a core and a coating; the transverse diameter and thickness of the particles in the non-stick coating are counted by a zonal measurement method (10 particles are counted in each zone, 5 different zones are randomly selected for counting), the transverse diameter R of the core (ceramic particles) in the particles in the non-stick coating S1 is counted to be distributed in the range of 98-142 mu m, the thickness D is distributed in the range of 3.2-3.8 mu m, and 1/4R 2 D is distributed in 0.9X10 4 -1.6×10 4 The single-sided thickness distribution of the fluorine-containing resin material coating layer is in the range of 0.48-0.52 μm.
Example 2
This example illustrates a method for preparing a non-stick coating using a plasma spray process.
(1) Pretreatment of an aluminum pan substrate (thickness of 2.5 mm) was performed according to the method of example 1;
(2) Preheating the surface of the substrate obtained in the step (1) to 100 ℃;
(3) Titanium oxide powder and modified PFA powder A2 are used as raw materials, and a non-stick coating is formed on the surface of a substrate through plasma spraying treatment; wherein, the conditions of the plasma spraying treatment include: the spraying power of the plasma spray gun is 40kW, the spraying current is 560A, the flow rate of hydrogen in the working gas is 3L/min, and the flow rate of argon is 40L/min; the spraying distance between the plasma spray gun and the substrate is 110mm, the spraying angle is 80 degrees+/-1 degrees, and the moving speed of the spray gun is 85mm/s; feeding titanium oxide powder into a flame flow formed by a plasma spray gun at a position which is away from a spray gun outlet D1 (1/3 of the flame flow length), wherein the feeding amount is 5g/min, and feeding modified PFA powder A2 at a position which is away from a spray gun outlet D2 (2/3 of the flame flow length), and the feeding amount is 2.5g/min; a non-stick coating with a thickness of 200 μm was formed, designated S2.
The transverse diameter R of the core part (ceramic particles) in the particles in the non-stick coating S2 is measured and counted to be distributed in the range of 100-154 mu m, the thickness D is distributed in the range of 4.5-4.8 mu m, and the ratio of 1/4R 2 D is distributed in 1.2X10 4 -2.6×10 4 The single-sided thickness distribution of the fluorine-containing resin material coating layer is in the range of 0.45-0.52 μm.
Example 3
This example illustrates a method for preparing a non-stick coating using a plasma spray process.
(1) Pretreatment of an aluminum pan substrate (thickness of 2.5 mm) was performed according to the method of example 1;
(2) Preheating the surface of the substrate obtained in the step (1) to 150 ℃;
(3) Taking aluminum oxide powder A1 and modified PFA powder A1 as raw materials, and forming a non-stick coating on the surface of a substrate through plasma spraying treatment; wherein, the conditions of the plasma spraying treatment include: the spraying power of the plasma spray gun is 50kW, the spraying current is 600A, the flow rate of hydrogen in the working gas is 5L/min, and the flow rate of argon is 50L/min; the spraying distance of the plasma spray gun from the substrate is 90mm, the spraying angle is 80 degrees+/-1 degrees, and the moving speed of the spray gun is 75mm/s; feeding aluminum oxide powder A1 at a position which is away from a spray gun outlet D1 (1/4 of the flame flow length) in flame flow formed by a plasma spray gun, wherein the powder feeding amount is 3.5g/min, and feeding modified PFA powder A2 at a position which is away from a spray gun outlet D2 (1/2 of the flame flow length), and the powder feeding amount is 3.5g/min; a non-stick coating having a thickness of 200 μm was formed and designated S3.
The transverse diameter of the core (ceramic particles) in the particles in the non-stick coating S3 is measured and counted to be in the range of 134-162 mu m, the thickness is distributed in the range of 2.0-2.5 mu m, and 1/4R 2 D is distributed in 0.9X10 4 -1.6×10 4 The single-sided thickness distribution of the fluorine-containing resin material coating layer is in the range of 0.45-0.48 μm.
Example 4
The procedure of example 1 was followed except that in step (3), the same amount of alumina powder A2 was used instead of alumina powder A1; a non-stick coating with a thickness of 200 μm was formed, designated S4.
The transverse diameter of the core (ceramic particles) in the particles in the non-stick coating S4 is measured and counted to be distributed in the range of 130-185 mu m, the thickness is distributed in the range of 4.6-5.2 mu m, and 1/4R 2 D is distributed in 2.3X10 4 -3.9×10 4 The single-sided thickness distribution of the fluorine-containing resin material coating layer is in the range of 0.54-0.58 μm.
Example 5
According to the method of example 1, except that in step (3), alumina powder was fed at a distance D1 (1/4 of the flame flow length) from the gun outlet D1 and modified PFA powder A1 was fed at a distance D2 (2/3 of the flame flow length) from the gun outlet D1 in the flame flow formed by the plasma gun; a non-stick coating having a thickness of 200 μm was formed and designated as S5.
The transverse diameter R of the core (ceramic particles) in the particles in the non-stick coating S5 is measured and counted to be distributed in the range of 98-142 mu m, the thickness D is distributed in the range of 3.2-3.8 mu m, and the diameter is 1/4R 2 D is distributed in 0.9X10 4 -1.6×10 4 The single-sided thickness distribution of the fluorine-containing resin material coating layer is in the range of 0.42 to 0.48 μm.
Example 6
According to the method of example 1, except that in step (3), alumina powder was fed at a distance of 1/3 of the flame flow length from the torch outlet D1 (1/2 of the flame flow length) from the torch outlet D2 in the flame flow formed by the plasma torch, modified PFA powder A1 was fed to form a non-tacky coating having a thickness of 200 μm, denoted as S6.
The transverse diameter R of the core part (ceramic particles) in the particles in the non-stick coating S6 is distributed in the range of 108-150 mu m, the thickness D is distributed in the range of 2.8-3.2 mu m, and 1/4R 2 D is distributed in 0.9X10 4 -1.6×10 4 The single-sided thickness distribution of the fluorine-containing resin material coating layer is in the range of 0.42 to 0.46 μm.
Example 7
According to the method of example 1, except that in step (3), alumina powder was fed at a distance D1 (1/4 of the flame flow length) from the gun outlet in the flame flow formed by the plasma gun, and modified PFA powder A1 was fed at a distance D2 (5/6 of the flame flow length) from the gun outlet; a non-stick coating having a thickness of 200 μm was formed and designated as S7.
The measured transverse diameter R of the core part (ceramic particles) in the particles in the non-stick coating S7 is distributed in the range of 98-142 mu m, the thickness D is distributed in the range of 3.2-3.8 mu m, and the ratio of 1/4R 2 D is distributed in 0.9X10 4 -1.6×10 4 The single-sided thickness distribution of the fluorine-containing resin material coating layer is in the range of 0.38 to 0.42 μm.
Example 8
The procedure of example 1 was followed except that in step (3), the spraying power of the plasma spray gun was 30kW, the spraying current was 500A, the flow rate of hydrogen in the working gas was 2L/min, the flow rate of argon was 35L/min, the spraying distance was 80mm, and a non-stick coating layer having a thickness of 200 μm was formed, which was designated as S8.
The transverse diameter R of the core part (ceramic particles) in the particles in the non-stick coating S8 is distributed in the range of 81-115 mu m, the thickness D is distributed in the range of 5.0-5.6 mu m, and 1/4R 2 D is distributed in 0.9X10 4 -1.6×10 4 The single-sided thickness distribution of the fluorine-containing resin material coating layer is in the range of 0.48-0.52 μm.
Example 9
The procedure of example 1 was followed except that in step (3), the spraying power of the plasma spray gun was 50kW, the spraying current was 650A, the flow rate of hydrogen in the working gas was 6L/min, the flow rate of argon was 55L/min, the spraying distance was 80mm, and a non-stick coating layer having a thickness of 200 μm was formed, which was designated as S9.
The measured transverse diameter R of the core part (ceramic particles) in the particles in the non-stick coating S9 is distributed in the range of 126-166 μm, the thickness D is distributed in the range of 1.6-2.0 μm, and the ratio of 1/4R 2 D is distributed in 0.9X10 4 -1.6×10 4 The single-sided thickness distribution of the fluorine-containing resin material coating layer is in the range of 0.35-0.4 μm.
Comparative example 1
The procedure of example 1 was followed, except that the modified PFA powder A1 was not added in step (3), to form a non-tacky coating having a thickness of 200. Mu.m.
Comparative example 2
The procedure of example 1 was followed except that the non-stick coating was formed in steps (3) - (4) as follows: an electrostatic spraying treatment was performed with a general PFA powder (ACX-33 powder commercially available from large gold PFA) to form a PFA non-stick coating D1 on the substrate surface, wherein the conditions of the electrostatic spraying treatment include: powder spraying is carried out by adopting an electrostatic spray gun, the voltage is 35kV, the electrostatic current is 15 mu A, the flow speed pressure is 0.45MPa, the atomization pressure is 0.4MPa, the thickness of a sprayed coating is 40 mu m, the powder is dried in an infrared furnace after the spraying is finished, the powder is dried for 10min at a low temperature section of 120 ℃, and the powder is insulated for 20min at a high temperature section of 400 ℃.
Comparative example 3
Spraying a PTFE non-stick coating by adopting an air pressure spraying mode, wherein the coating comprises a bottom layer and a surface layer; the base oil comprises fluororesin, binder, pigment and auxiliary agent, and the surface oil comprises fluororesin, wear-resistant particles and film-forming auxiliary agent. The method comprises the following specific steps:
(1) Pretreating an aluminum pot substrate according to the step (1) of the embodiment 1;
(2) Preheating the surface of the substrate obtained in the step (1) to 85 ℃;
(3) And (3) spraying base oil: the spraying pressure is 0.3MPa, the spraying angle is 70 degrees, the spraying distance is 30cm, the thickness of the film layer is 20 mu m, the drying temperature is 130 ℃, and the heat preservation is carried out for 12min;
(4) Spraying surface oil: the spraying pressure is 0.4MPa, the spraying angle is 70 degrees, the spraying distance is 35 mu m, the film thickness is 30 mu m, the drying and curing temperature is 420 ℃, and the heat preservation is carried out for 15min.
Comparative example 4
Spraying a ceramic non-stick coating by adopting an air pressure spraying mode, wherein the coating comprises a bottom layer and a surface layer; the primer includes a binder, a pigment, and an auxiliary agent, and the topcoat includes silica and alumina. The method comprises the following specific steps:
(1) Pretreating an aluminum pot substrate according to the step (1) of the embodiment 1;
(2) Preheating the surface of the substrate obtained in the step (1) to 60 ℃;
(3) And (3) spraying base oil: the spraying pressure is 0.3MPa, the spraying angle is 70 degrees, the spraying distance is 25cm, the thickness of a film layer is 25 mu m, the pre-drying temperature is 70 ℃, and the heat preservation is carried out for 10min;
(4) Spraying surface oil: the spraying pressure is 0.3MPa, the spraying distance is 25cm, the spraying angle is 70 degrees, the thickness of the film layer is 10 mu m, and the film layer is sintered at 280 ℃ after the spraying is finished and is kept for 15min.
Test examples
1. Coating surface hardness: the Vickers hardness of each coating was determined according to GB/T9790-1988 using a Vickers hardness tester (available from Shanghai rectangular optics, inc., model HX-1000). The results are shown in Table 1.
2. Coating binding force: coating binding force was measured according to G98642-88. The results are shown in Table 1.
3. Coating porosity: the porosity of the coating was determined according to the mechanical industry standard JB/T7509-94 of the people's republic of China. The results are shown in Table 1.
4. Coating spraying efficiency: according to the formula: spraying efficiency= (weight of workpiece after spraying-weight of workpiece before spraying)/(powder feeding amount, deposition rate), wherein the deposition rate was fixed at 70%. The calculation results are shown in Table 1.
5. Scratch resistance of the coating: the cleaning liquid is used for preparing the cleaning water with the concentration of 5 weight percent, the 3M (7447C) scouring pad bears a load of 2.5kgf, the scouring pad is swung left and right for 1 time once, the scouring pad is replaced for 250 times each time, whether the coating falls off or a substrate is exposed after each scraping or not is checked (the exposure of more than 10 lines is taken as a termination test), and the wear-resisting times are recorded. The results are shown in Table 1.
6. Acid, alkali, salt:
acid resistance: adding acetic acid solution with the concentration of 5 wt% into the inner pot until reaching the maximum scale water level of the inner wall of the inner pot, putting the inner pot into a corresponding pot, electrifying the inner pot, closing the cover, continuously heating and boiling (keeping the boiling state) for 10 minutes, then preserving heat at 100 ℃ and soaking for 24 hours, cleaning the inner pot after the test is finished, visually checking the surface change condition of the coating, and the result is shown in table 2.
Alkali resistance: adding 0.5 wt% sodium hydroxide solution into the inner pot until reaching the maximum scale water level of the inner wall of the inner pot, putting the inner pot into a corresponding pot, electrifying the cover, continuously heating and boiling (keeping boiling state) for 10 minutes, then preserving heat at 100 ℃ and soaking for 24 hours, cleaning the inner pot after the test is finished, and visually checking the surface change condition of the coating, wherein the result is shown in Table 2.
Salt resistance: adding sodium chloride solution with the concentration of 5 wt% into an inner pot until the maximum scale water level of the inner wall of the inner pot, putting the inner pot into a corresponding pot, electrifying a sealing cover, continuously heating and boiling for 8 hours (supplementing water 1 time every 2 hours, keeping the liquid level at the position at the beginning of the test), keeping the temperature at 80 ℃ for 16 hours as a period, visually checking the surface change condition of the coating after each period test, and recording the period number of the bad phenomena such as foaming, protruding points and the like of the coating, wherein the result is shown in Table 2.
7. Abrasion resistance and wettability: the frictional wear test was performed according to GB/T1768-79 (89), the contact angle (the original contact angle and the post-frictional contact angle, respectively) and the weight before and after the frictional wear test were measured and weighed, and the weight loss ratio was calculated according to the formula, wherein the weight loss ratio= (weight before friction-weight after friction)/weight before friction, and the results are shown in table 3. Wherein, the test result shows that: the non-stick coating of the invention has good wettability inside after surface abrasion, and the wettability is kept good as long as the substrate is not exposed, and the friction abrasion test is carried out on three samples, namely the PTFE non-stick coating, the ceramic non-stick coating and the non-stick coating of the invention, so that the following can be found: the non-stick coating of the invention only has partial powder falling off in the friction and abrasion process, the usability is not affected, and the PTFE non-stick coating and the ceramic non-stick coating are both flaky falling off between layers, and the difference is larger.
TABLE 1
TABLE 2
| Acid-resistant | Alkali-proof | Salt tolerance | |
| Example 1 | No whitening and foaming phenomena | No whitening and foaming phenomena | 20 cycles of |
| Example 2 | No whitening and foaming phenomena | No whitening and foaming phenomena | 20 cycles of |
| Example 3 | No whitening and foaming phenomena | No whitening and foaming phenomena | 20 cycles of |
| Example 4 | No whitening and foaming phenomena | No whitening and foaming phenomena | 18 cycles |
| Example 5 | No whitening and foaming phenomena | No whitening and foaming phenomena | 18 cycles |
| Example 6 | No whitening and foaming phenomena | No whitening and foaming phenomena | 20 cycles of |
| Example 7 | No whitening and foaming phenomena | No whitening and foaming phenomena | 16 cycles |
| Example 8 | No whitening and foaming phenomena | No whitening and foaming phenomena | 12 cycles |
| Example 9 | No whitening and foaming phenomena | No whitening and foaming phenomena | 20 cycles of |
| Comparative example 1 | No whitening and foaming phenomena | No whitening and foaming phenomena | 10 cycles of |
| Comparative example 2 | No whitening and foaming phenomena | No whitening and foaming phenomena | 6 cycles of |
| Comparative example 3 | No whitening and foaming phenomena | No whitening and foaming phenomena | 4 cycles of |
| Comparative example 4 | No whitening and foaming phenomena | No whitening and foaming phenomena | 2 periods of |
TABLE 3 Table 3
| Number of rubs | Loss ratio (%) | Original contact angle (°) | Contact angle after rubbing (°) | |
| Example 1 | 1000 | 1.2 | 116 | 112 |
| Example 1 | 2000 | 2.0 | 116 | 109 |
| Example 1 | 3000 | 2.9 | 116 | 106 |
| Example 2 | 1000 | 1.2 | 119 | 112 |
| Example 3 | 1000 | 1.1 | 112 | 105 |
| Example 4 | 1000 | 1.2 | 108 | 103 |
| Example 5 | 1000 | 1.5 | 120 | 112 |
| Example 6 | 1000 | 1.3 | 110 | 99 |
| Example 7 | 1000 | 1.8 | 123 | 115 |
| Example 8 | 1000 | 2.2 | 113 | 107 |
| Example 9 | 1000 | 0.9 | 102 | 92 |
| Comparative example 1 | 1000 | 0.8 | 20 | 20 |
| Comparative example 2 | 1000 | 6.0 | 125 | 90 |
| Comparative example 3 | 1000 | 8.9 | 121 | 87 |
| Comparative example 4 | 1000 | 4.8 | 110 | 78 |
As can be seen from the results in tables 1 to 3, in the method for preparing the non-stick coating by adopting the plasma spraying technology, the mixture of the PFA powder and the ceramic powder can be sprayed with a layer of non-stick coating on the surface of the substrate, the non-stick coating with excellent performance can be obtained, and the obtained non-stick coating has the advantages of high surface hardness, high coating binding force, good scratch resistance, good corrosion resistance, good wettability, long service life and the like.
Wherein, comparing the results of example 1 with those of examples 4-6, it is found that the addition of ceramic powder and fluorine-containing resin powder within a specific interval (i.e., 1/6.ltoreq.D2-D1.ltoreq.flame flow length 1/2, preferably 1/4.ltoreq.D2-D1.ltoreq.flame flow length 1/3) is advantageous for further achieving comprehensive optimization of the surface hardness and wettability of the non-stick coating.
Comparing the results of the examples 1 and 7-8, it is known that under the specific plasma spraying treatment condition (namely, the spraying power is 40-40kW, the spraying current is 560-600A, the main air flow in the working gas is 40-50L/min, the auxiliary air flow in the working gas is 3-5L/min, and the spraying distance is 90-110 mm), the surface hardness, the coating binding force, the scratch resistance, the corrosion resistance, the wettability and the service life of the non-adhesive coating can be further improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (21)
1. A method of preparing a non-stick coating, the method comprising:
(1) Pretreating a matrix;
(2) Preheating the surface of the substrate obtained in the step (1) to 80-150 ℃;
(3) Ceramic powder and fluorine-containing resin powder are used as raw materials, and a non-stick coating is formed on the surface of a substrate through plasma spraying treatment;
wherein the particle size distribution of the ceramic powder is in the range of 35-65 μm; the conditions of the plasma spraying treatment include: the spraying power of the plasma spray gun is 30-50kW, the spraying current is 500-650A, the main air flow in the working gas is 35-55L/min, the auxiliary air flow is 2-6L/min, and the spraying distance is 80-120mm; and ceramic powder is fed into flame flow formed by the plasma spray gun at a position which is far from a spray gun outlet D1, fluorine-containing resin powder is fed into the plasma spray gun at a position which is far from a spray gun outlet D2, wherein D2 is larger than D1, and the flame flow length is not smaller than 1/4 and not larger than D2-D1 and not larger than 1/3 of the flame flow length.
2. The method according to claim 1, wherein the fluorine-containing resin powder has a particle size distribution in the range of 20-100 μm; the fluidity of the fluorine-containing resin powder is less than 30s/50g.
3. The method according to claim 2, wherein the fluorine-containing resin powder has a particle size distribution in the range of 40-100 μm; the fluidity of the fluorine-containing resin powder is 10-25s/50g.
4. A method according to claim 3, wherein said fluorine-containing resin powder has a particle size distribution in the range of 45-60 μm; the fluidity of the fluorine-containing resin powder is 10-20s/50g.
5. The method of claim 1, wherein the ion gun has a spray power of 40-50kW; the spraying current is 500-600A; the main air flow in the working gas is 40-50L/min, and the auxiliary air flow is 3-5L/min; the spraying distance is 90-110mm.
6. The method of claim 5, wherein the ion gun has a spray power of 40-45kW; the spraying current is 560-600A.
7. The method of claim 1, wherein D1 is 1/4-1/3 of the flame flow length and D2 is 1/2-2/3 of the flame flow length.
8. The method of claim 1, wherein in the step of plasma spraying treatment, a spray gun moving speed is 60-100mm/s.
9. The method of claim 8, wherein the plasma spray treatment is performed at a spray gun movement speed of 75-85mm/s.
10. The method according to claim 1, wherein the ceramic powder is fed in an amount of 3.5-5g/min; the powder feeding amount of the fluorine-containing resin powder is 2.5-3.5g/min.
11. The method according to any one of claims 1 to 10, wherein the ceramic powder is alumina and/or titania and the fluorine-containing resin powder is PTFE and/or PFA.
12. A non-stick coating prepared by the method of any one of claims 1-11.
13. The pan is characterized by comprising a base body (2) and a non-stick coating (1) formed on the base body (2), wherein the non-stick coating (1) is a stacked layer of particles (10) with a flat structure, and the particles (10) comprise ceramic particle cores (11) and fluorine-containing resin material coating layers (12) coated on the peripheries of the ceramic particle cores (11); the ceramic particle core (11) has a thickness D in the range of 1-10 μm, a transverse diameter R in the range of 50-400 μm, and a 1/4R D in the range of 8000-40000 μm;
the non-stick coating is the non-stick coating of claim 12.
14. Pan according to claim 13, wherein the ceramic particle cores (11) have a thickness D distribution in the range of 2-5 μm and a transverse diameter R distribution in the range of 80-280 μm.
15. Pan according to claim 13, wherein the single-sided thickness distribution of the coating layer (12) of fluorine-containing resin material of the particulate matter (10) is in the range of 0.2-2 μm.
16. Pan according to claim 13, wherein the non-stick coating (1) comprises, based on its total weight: 55-90 wt% of ceramic particles and 10-45 wt% of fluorine-containing resin material.
17. Pan according to claim 13, wherein the ceramic material in the ceramic particle core (11) is alumina and/or titania; the fluorine-containing resin material in the fluorine-containing resin coating layer (12) is PTFE and/or PFA.
18. Pan according to claim 13, wherein the thickness of the base body (2) is 0.5-6mm; the thickness of the non-stick coating (1) is 50-2000 mu m.
19. Pan according to claim 18, wherein the non-stick coating (1) has a thickness of 100-300 μm.
20. A cooking device, characterized in that it comprises a pan according to any one of claims 13-19.
21. The cooking apparatus of claim 20, wherein the cooking apparatus is a wok, a fryer, an air fryer, a roaster, a bread maker, an electric rice cooker, an electric pressure cooker, or a soymilk machine.
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| CN201710405471.4A CN108977750B (en) | 2017-06-01 | 2017-06-01 | Non-stick coating, preparation method thereof, cooker and cooking equipment |
| KR1020180046009A KR102090639B1 (en) | 2017-04-25 | 2018-04-20 | Cookware and cooking equipment |
| JP2018083976A JP6641411B2 (en) | 2017-04-25 | 2018-04-25 | Method of manufacturing pot utensil and method of manufacturing cookware |
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| CN201710405471.4A CN108977750B (en) | 2017-06-01 | 2017-06-01 | Non-stick coating, preparation method thereof, cooker and cooking equipment |
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| CN109136817B (en) * | 2017-06-15 | 2023-09-29 | 佛山市顺德区美的电热电器制造有限公司 | Non-stick coating, preparation method thereof, cooker and cooking equipment |
| CN110432786B (en) * | 2019-08-29 | 2021-04-09 | 武汉安在厨具有限公司 | Cooker with ceramic fluorite coating and production process thereof |
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| DE2401085A1 (en) * | 1974-01-10 | 1975-07-24 | Ritter Aluminium Gmbh | Aluminium cooking or baking utensil - has ceramics plasma-sprayed coating with PTFE or other anti-adhesive plastics |
| US5660934A (en) * | 1994-12-29 | 1997-08-26 | Spray-Tech, Inc. | Clad plastic particles suitable for thermal spraying |
| WO2016145731A1 (en) * | 2015-03-17 | 2016-09-22 | 方成 | Plasma non-stick pan and method for manufacturing same |
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| EP1387896B1 (en) * | 2001-05-05 | 2005-01-05 | Linde Aktiengesellschaft | Cooking utensils with thermally sprayed coating and method for the production of said coating |
| US7488515B2 (en) * | 2004-03-19 | 2009-02-10 | All-Clad Metalcrafters Llc | Method of making non-stick cookware |
| US20140178641A1 (en) * | 2012-12-21 | 2014-06-26 | General Electric Company | Methods of coating a surface and articles with coated surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2401085A1 (en) * | 1974-01-10 | 1975-07-24 | Ritter Aluminium Gmbh | Aluminium cooking or baking utensil - has ceramics plasma-sprayed coating with PTFE or other anti-adhesive plastics |
| US5660934A (en) * | 1994-12-29 | 1997-08-26 | Spray-Tech, Inc. | Clad plastic particles suitable for thermal spraying |
| WO2016145731A1 (en) * | 2015-03-17 | 2016-09-22 | 方成 | Plasma non-stick pan and method for manufacturing same |
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| 含氟不粘性涂料研究进展;贾正峰, 武超, 周静芳, 张治军;涂料工业(11);全文 * |
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