CN1629356A - Metallic plate coated with enamel layer and containing fluorine polymer, and method for making same - Google Patents

Metallic plate coated with enamel layer and containing fluorine polymer, and method for making same Download PDF

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CN1629356A
CN1629356A CNA2004100069107A CN200410006910A CN1629356A CN 1629356 A CN1629356 A CN 1629356A CN A2004100069107 A CNA2004100069107 A CN A2004100069107A CN 200410006910 A CN200410006910 A CN 200410006910A CN 1629356 A CN1629356 A CN 1629356A
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layer
enamel
fluoropolymer
enamel layer
frit
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CN1313645C (en
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许相熙
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    • 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
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D7/00—Treating the coatings, e.g. drying before burning
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates

Abstract

The invention relates to a metal substrate coated with a first porcelain enamel layer and a second porcelain enamel layer, and containing a fluoride polymer layer on the second porcelain enamel layer, which uses a high hardness porcelain enamel to provide an improved corrosion resistance of the metal substrate and a high coating hardness containing a fluoride polymerization layer. The invention futher provides the fluorine-containing polymer layer with the improved adhesion and wear resistance of the metal substrate by forming a porous bumpy area on the surface of the second porcelain enamel layer.

Description

Scribble metal sheet of enamel layer and fluoropolymer and preparation method thereof
Invention field
The invention provides a kind of metal sheet that scribbles fluoropolymer and a kind of with enamel layer and the fluoropolymer-coated method to the metal sheet.More particularly, the invention provides a kind of method that forms first enamel layer and second enamel layer on metal sheet, wherein second enamel layer contains crystal form aluminum oxide (aluminum oxide, the Al of specified amount 2O 3).(tetrafluoroethylene for example: PTFE etc.) layer is coated on the surface of second enamel layer with fluoropolymer then.The present invention further provides the metal sheet that scribbles enamel layer and fluoropolymer of preparation thus.
Background of invention
In general, acid or sandblast machine are often used in applying fluoropolymer (for example PTFE) process metal surfaces before.If use acid, then use acid treatment aluminium (Al) metal etc., the metallic surface fluoropolymer-coated after handling then.If the use sandblast machine, then the coated surface of steel or aluminum metal base carries out sanded with sandblast machine, thereby removes spot or impurity and make the surface-area expansion simultaneously, applies fluoropolymer then thereon.
But, by the ordinary method that the coated surface roughen is enlarged with the contact area of fluoropolymer (for example PTFE) shortcoming is arranged, promptly owing to the poor adhesion of fluoropolymer and metal base causes coming off or wearing and tearing of fluoropolymer may be taken place, cause the corrosion-resistant of metal base.
Another shortcoming is that the hardness of steel or aluminum metal base is low, thereby fluoropolymer is easy to peel off under physical strength and oscillating action, metal base the surface in addition may be scraped.
Summary of the invention
The purpose of this invention is to provide a kind of by between metal base and fluoropolymer layer, introducing the high enamel layer of hardness ratio metal base and by on enamel layer, applying the method that fluoropolymer improves the coating hardness of fluoropolymer.
The present invention further provides a kind of method that on metal sheet, forms the fluoropolymer layer that wear resistance and binding property be improved, wherein place the bonding force of improving on the second enamel layer surface between enamel layer and the fluoropolymer layer by the aluminum oxide and/or the silicon-dioxide that will have stronger porousness and unevenness.
The present invention further provides a kind of metal sheet that scribbles fluoropolymer, this plate has enamel layer between metal base and fluoropolymer, thereby improves erosion resistance and the binding property between metal sheet and fluoropolymer and the wear resistance of metal base.
In one embodiment, the invention provides a kind of method that on the metallic surface, applies enamel layer and fluoropolymer layer, may further comprise the steps: all apply first frit for porcelain enamel on the two sides on the pretreated metal base 10, wherein first frit for porcelain enamel comprises glaze, clay that contains cobalt (Co) and nickel (Ni) and the interground addition that contains Sodium Nitrite; By dryly in advance scribbling the metal base of first frit for porcelain enamel and, form first enamel layer 20 then in 400-950 ℃ of baking in 90-110 ℃; Apply second frit for porcelain enamel on the one side of first enamel layer of above-mentioned formation, wherein second frit for porcelain enamel forms by glaze and interground addition are mixed, and wherein glaze comprises the SiO of 40-60 weight % 2, 14-20 weight % Al 2O 3, 24-30 weight % B 2O 3, all alkalimetal oxides of CaO, 15-25 weight % of 2-5 weight % and the F of 0.5-6 weight %, wherein interground addition comprises the 5-15 weight part clay in 100 weight part glaze, the Al of 20-30 weight part 2O 3, the 0.1-1.0 weight part borax, 0.1 weight part or NaNO still less 2And 0.1 weight part or quartz still less; By dryly in advance scribbling the metal base of second frit for porcelain enamel and, form second enamel layer 30 then in 400-950 ℃ of baking in 90-110 ℃; To second enamel layer and in 200-430 ℃ of baking, form fluoropolymer layer 40 with passing through with fluoropolymer-coated.
The present invention further provides and a kind of enamel layer and fluoropolymer layer are coated to method on the metallic surface, wherein the thickness of first enamel layer 20 is 80-150 microns, and the thickness of second enamel layer 30 is 15-20 microns.
The present invention further provides and a kind of enamel layer and fluoropolymer layer are coated to method on the metallic surface, wherein contained aluminum oxide (Al in second frit for porcelain enamel 2O 3) granularity be the 0.1-55 micron, preferred 10-20 micron.
The present invention further provides and a kind of enamel layer and fluoropolymer layer are coated to method on the metallic surface, wherein contained interground addition further comprises the silicon-dioxide (SiO of 20-30 weight part in second frit for porcelain enamel 2), in 100 weight part glaze.
The present invention further provides and a kind of enamel layer and fluoropolymer layer are coated to method on the metallic surface, wherein the granularity of contained silicon-dioxide is the 0.1-55 micron in interground addition, preferred 10-20 micron.
The present invention further provides and a kind of enamel layer and fluoropolymer layer are coated to method on the metallic surface, wherein fluoropolymer is PTFE.
The present invention further provides a kind of metal product that scribbles enamel layer and fluoropolymer layer by method for preparing.
The present invention further provides a kind of metal product that scribbles enamel layer and fluoropolymer layer, wherein fluoropolymer layer is the black that has white point.
The present invention further provides a kind of metal product that scribbles enamel layer and fluoropolymer layer, wherein fluoropolymer layer comprises antiseptic-germicide.
The accompanying drawing summary
In order to understand essence of the present invention and purpose better, describe in more detail with reference to the following drawings, wherein:
Fig. 1 a has shown metal base 10, and it will be applied by enamel layer and fluoropolymer layer according to embodiment of the present invention;
Fig. 1 b shows first enamel layer 20 that forms according to embodiment of the present invention on the two sides of metal base;
Fig. 1 c has shown second enamel layer 30 with the uneven place 31 of porous, and it is to form on the one side of first enamel layer 20 according to embodiment of the present invention;
Fig. 1 d has shown according to embodiment of the present invention and has been coated in fluoropolymer layer 40 on second enamel layer 30;
Fig. 2 a is the electron microscope picture that shows with the metallic substrate surface of commercial blast machine sanded;
Fig. 2 b is the electron microscope picture that shows the uneven place 31 of porous that forms according to an embodiment of the present invention on second enamel layer, 30 surfaces;
Fig. 3 shows the electron microscope picture (amplifying 60 times) of the cross section of the metal product that scribbles enamel layer and fluoropolymer layer of preparation according to an embodiment of the present invention; With
Fig. 4 shows the electron microscope picture (amplifying 700 times) of the cross section of the metal product that scribbles enamel layer and fluoropolymer layer of preparation according to an embodiment of the present invention.
Fig. 5 shows the coating hardness of fluoropolymer layer and the situation that the coatingsurface slipperiness changes along with the granularity of aluminum oxide and silicon-dioxide.
Detailed description of the preferred embodiments
The preferred embodiments of the invention are described below with reference to the accompanying drawings.
1, forms first enamel layer
The metal base 10 (Fig. 1 a 10) that is used for enamel etc. carries out pre-treatment, and the two sides of this metal base all applies first glaze then, forms first enamel layer.
Metal base 10 is not limited to specific metal, but aluminium or steel are preferred.
First frit for porcelain enamel comprises glaze, clay that contains Co and Ni and the interground addition that contains Sodium Nitrite.
With the metal base that scribbles first frit for porcelain enamel in 100 ℃ dry 10 minutes in advance, then with it in the storing temperature baking that is fit to, form first enamel layer 20 (referring to Fig. 1 b).
Storing temperature is according to the enamelled kind and difference, but is preferably 400-950 ℃.
The thickness of first enamel layer 20 of Xing Chenging 80-150 micron preferably as stated above.If the thickness of first enamel layer 20 is less than 80 microns, then enamel layer can since too thin and in the process of experience baking in the stove internal combustion.On the other hand, if the thickness of first enamel layer 20 greater than 150 microns, then the enamel layer of Xing Chenging is easy to embrittlement.
Can be improved aspect the erosion resistance by forming first enamel layer 20 thereon according to metal base of the present invention, the coating hardness of fluoropolymer also can be improved by enamelled high rigidity characteristic.
2, form second enamel layer
Second frit for porcelain enamel is coated on first enamel layer that forms according to the method described above, forms second enamel layer.
Second frit for porcelain enamel is main by glaze and interground addition are mixed formation, and wherein glaze comprises the SiO of 40-60 weight % 2, 14-20 weight % Al 2O 3, 24-30 weight % B 2O 3, all alkalimetal oxides of CaO, 15-25 weight % of 2-5 weight % and the F of 0.5-6 weight %, wherein interground addition comprises the 5-15 weight part clay in 100 weight part glaze, the Al of 20-30 weight part 2O 3, the 0.1-1.0 weight part borax, 0.1 weight part or NaNO still less 2And 0.1 weight part or quartz still less.
The interground addition of second frit for porcelain enamel can further comprise the silicon-dioxide of 20-30 weight part, in 100 weight part glaze.
Second frit for porcelain enamel can be powder type or slip form.The frit for porcelain enamel of powder type applies by the electrostatic powder coating method, and the frit for porcelain enamel of slip form applies by spraying method.
By in 100 ℃ of dry in advance metal bases that scribble second frit for porcelain enamel 10 minutes, and, form second enamel layer 30 (referring to Fig. 1 c) then in the temperature baking that is fit to.
The storing temperature of second enamel layer is lower about 0-25 ℃ than the first enamel layer storing temperature, thereby by realize bonding fully between first and second enamel layers in baking in the scope between the fusing point of enamelled stagnation point to the second enamel layer that constitutes first enamel layer.
The storing temperature of second enamel layer also is preferably 400-950 ℃, and this storing temperature to first enamel layer is similar.
If second enamel layer toasts in above-mentioned specific range of temperatures, contained aluminum oxide (Al in the interground addition of second frit for porcelain enamel then 2O 3) and/or silicon-dioxide (SiO 2) can fusion, but remain, on the surface of second enamel layer 30, form 31 (referring to Fig. 1 c) of the uneven place of porous.The uneven place 31 of the porous that forms on second enamel layer given and fluoropolymer layer 40 between excellent adhesiveness.
The granularity of aluminum oxide and silicon-dioxide in the 0.1-55 micrometer range, preferred 10-20 micron.
If the granularity of aluminum oxide and silicon-dioxide, then can not form the uneven place of porous fully less than 0.1 micron, cause and fluoropolymer layer between poor adhesion.On the other hand, if this granularity surpasses 55 microns, then and the binding property between the fluoropolymer layer can keep well, but the coatingsurface of fluoropolymer layer because the macroparticle of aluminum oxide and silicon-dioxide becomes unevenness and coarse.
Fig. 5 shows the coating hardness of fluoropolymer layer and the situation that the coatingsurface slipperiness changes along with the granularity of above-mentioned aluminum oxide and silicon-dioxide.
With reference to figure 5, along with the granularity increase of aluminum oxide and/or silicon-dioxide, the coating hardness of fluoropolymer layer increases, but the coatingsurface slipperiness of fluoropolymer layer reduces.
Particularly, for obtain and fluoropolymer layer 40 between excellent adhesiveness, contained aluminum oxide (Al in the interground addition of second frit for porcelain enamel 2O 3) and/or silicon-dioxide (SiO 2) content 20-30 weight part preferably, in 100 weight part glaze.If this content, then can not form the uneven place of competent porous less than 20 weight parts, and if this content surpasses 30 weight parts, then because uneven the locating of too much porous forms uneven coatingsurface, production cost also increases.
The thickness of second enamel layer 30 is the 15-20 micron preferably.If the thickness of second enamel layer is less than or equal to 15 microns, then and the binding property between the fluoropolymer layer strong inadequately, and if this thickness is 20 microns or higher, then can not successfully form fluoropolymer layer.
3, form fluoropolymer layer
By spraying fluoropolymer-coated to second enamel layer 30, heat-treat then, form fluoropolymer layer 40 (referring to Fig. 1 d).
Fluoropolymer can be selected from PTFE, polymonochlorotrifluoroethylene, poly(vinylidene fluoride) (PVDF) and fluorinated ethylene propylene (PVF), but preferred PTFE.
The thermal treatment temp of fluoropolymer layer and time is according to the type of polymkeric substance and different, but carries out 5 minutes in 200-430 ℃ of scope usually.
By the uneven place 31 of the porous of the aluminum oxide that forms on second enamel layer, 30 surfaces, the fluoropolymer layer 40 and second enamel layer are bonded together securely.Therefore, the binding property of fluoropolymer coating and wear resistance are improved.
Fluoropolymer layer can further comprise antiseptic-germicide, is used for antibiotic.
In addition, can wait the color of regulating fluoropolymer by adding ink pigment, thereby can obtain to have the black of white point.This color of fluoropolymer can provide the marble outward appearance.
As shown in the viewgraph of cross-section of Fig. 1 d, first enamel layer 20 and second enamel layer 30 are to form on the surface of the metal base 10 of steel, aluminium etc., and second enamel layer 30 is to have aluminum oxide (Al therein 2O 3) the top at the uneven place 31 of porous on form.The fluoropolymer layer 40 of PTFE (Teflon ) is to form on the surface of second enamel layer 30.
An embodiment:
1, forms first enamel layer
After the steel plate of metal base carries out pre-treatment, the glaze that contains Co and Ni, the clay of slip form and first frit for porcelain enamel that contains the interground addition of Sodium Nitrite are coated on the two sides of steel plate by spraying.
With this metal base in 100 ℃ dry in advance 10 minutes, then with it in 400-950 ℃ of baking, form first enamel layer.The thickness of first enamel layer that forms is 120 microns.
2, form second enamel layer
To be coated on first enamel layer by second frit for porcelain enamel that glaze and interground addition form, wherein glaze comprises the SiO of 43 weight % 2, 15.5 weight % Al 2O 3, 24 weight % B 2O 3, all alkalimetal oxides of CaO, 15 weight % of 2 weight % and the F of 0.5 weight %, wherein interground addition comprises in 13 parts by weight of clay of 100 weight part glaze, the Al of 25 weight parts 2O 3, 20 weight parts SiO 2, the borax of 0.5 weight part, the NaNO of 0.05 weight part 2And the quartz of 0.05 weight part.
Contained Al in above-mentioned interground addition 2O 3And SiO 2Granularity be the 0.1-55 micron.Second frit for porcelain enamel uses with the slip form, and applies by spraying method.
The metal base that scribbles second frit for porcelain enamel in 100 ℃ dry 10 minutes in advance, then in 400-950 ℃ of baking.
The thickness of second enamel layer that forms is 17 microns.
Fig. 2 a is the electron microscope picture that shows with the metallic substrate surface of commercial blast machine sanded.Fig. 2 b is the electron microscope picture that shows the uneven place 31 of porous that forms according to an embodiment of the present invention on second enamel layer, 30 surfaces.
3, form fluoropolymer layer
By spraying fluoropolymer PTFE is coated on the surface of second enamel layer 30, in 200-430 ℃ of baking 5 minutes, forms fluoropolymer layer 40 then.
Added antiseptic-germicide in the fluoropolymer layer, be used for antibiotic.
Also can obtain fluoropolymer with the black form that has white point, thereby the marble outward appearance is provided by adding ink pigment etc.
4, the electron microscope picture that shows the cross section of the metal product that scribbles enamel layer and fluoropolymer prepared in accordance with the present invention
Fig. 3 and 4 is the electron microscope pictures that show the cross section of the metal product that scribbles enamel layer and fluoropolymer layer prepared in accordance with the present invention.Fig. 3 amplifies 60 times, and Fig. 4 amplifies 700 times.Fig. 4 has shown the unevenness place that forms on the second enamel layer surface.
5, detection is according to the physicals of fluoropolymer layer of the present invention
Following contrast experiment is presented at the coating physicals between metal product that scribbles fluoropolymer layer according to the present invention and the metal product (Comparative Examples 1-5) of the handling and scribble fluoropolymer by the commercial blast machine.
(a) pencil hardness experiment
Experimentize according to conventional pencil hardness, and the record result.
(b) SBAR experiment
The power of 4.5kg vertically is applied on the surface of scotch tape (for example 3M Scotch ), then stripping tape.Repeat this step, and the record cycle index.
(c) binding property experiment
On fluoropolymer coating, carry out the X-shaped cutting, then metal sheet was placed in boiling water 15 minutes.Then, scotch tape (for example 3M Scotch ) attached on the metal sheet surface, is peeled off then.
(d) erosion resistance experiment
On fluoropolymer coating, carry out the X-shaped cutting, then metal sheet is immersed in 5% salt solution.After making metal sheet be in 72-73 ℃, (for example 3M Scotch ) peels off experiment on metal sheet surface with scotch tape.
(e) clingtest not
Milk, soy sauce, sugar+soy sauce+water (ratio of mixture is 1: 1: 1) and vinegar are dropped on the fluoropolymer layer for 10 times, then metal sheet was placed 1 hour in 150 ℃ and 200 ℃ in baking oven.Behind cool to room temperature, with the sponge wiping fluoropolymer layer that has kitchen detergent.Above-mentioned result of experiment is listed in the following table 1.
Table 1
Experiment Comparative Examples 1 Embodiment of the present invention Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Comparative Examples 5
Pencil hardness 3H 4H H H 4H 3H
SBAR 220 times 690 times Do not have, because out-of-shape Do not have, because out-of-shape 9 times 18 times
Binding property By By By Failure By By
Erosion resistance 84hrs/OK 168hrs/ is still, does not have and peels off and rusty stain 24hrs/ bubbles, no rusty stain with peel off Some foaming of 132hrs/, no rusty stain and peeling off The many foamings of 48hrs/, no rusty stain and peel off at the X cutting zone 24hrs/ seriously bubbles and gets rusty, and seriously peels off at the X cutting zone
Viscosity not 150℃ By By By By By Failure
200℃ By By Failure By Failure
*The explanation of Comparative Examples *
(a) Comparative Examples 1: through after the sandblasting, scribble the metal sheet of C company's T eflon  2 coating systems.
(b) Comparative Examples 2: the electroplating steel plate (459-567/455-290) that scribbles the PTFE of DuPont company 2 coating systems.
(c) Comparative Examples 3: the calorize steel plate (459-104/455-283) that scribbles the PTFE of DuPont company 2 coating systems.
(d) Comparative Examples 4: the electroplating steel plate (Okisumo 2 coatings on electroplating steel plate) that scribbles the PTFE of Okisumo company 2 coating systems.
(e) Comparative Examples 5: the electroplating steel plate (the silica-based coating of Nobel single coating on electroplating steel plate) that scribbles silicon.
From last table as seen, compare with the fluoropolymer coating that does not have enamel layer, the metal sheet that scribbles fluoropolymer according to the present invention has excellent pencil hardness, SBAR, binding property, erosion resistance and non-viscosity.
From the above description as seen, the advantage that has the metal sheet of first and second enamel layers according to the present invention is that the erosion resistance of metal sheet is improved by using the enamel of high rigidity, and the coating hardness of fluoropolymer increases.
Another advantage is to make and can combine securely with fluoropolymer layer in the uneven structure of the lip-deep porous of second enamel layer, thereby favourable binding property and wear resistance is provided.
Therefore, can obtain the fluoropolymer coating that binding property, erosion resistance and wear resistance are improved by coating method of the present invention.

Claims (10)

1, a kind of method that applies enamel layer and fluoropolymer layer on the metallic surface may further comprise the steps:
All apply first frit for porcelain enamel on the two sides on the pretreated metal base, wherein said first frit for porcelain enamel comprises glaze, clay that contains cobalt (Co) and nickel (Ni) and the interground addition that contains Sodium Nitrite;
By in the 90-110 ℃ of dry in advance described metal base that scribbles described first frit for porcelain enamel, then with described metal base in 400-950 ℃ of baking, form first enamel layer;
Apply second frit for porcelain enamel on the one side of described first enamel layer, wherein said second frit for porcelain enamel is by mixing formation with glaze and interground addition, and wherein glaze comprises the SiO of 40-60 weight % 2, 14-20 weight % Al 2O 3, 24-30 weight % B 2O 3, all alkalimetal oxides of CaO, 15-25 weight % of 2-5 weight % and the F of 0.5-6 weight %, wherein interground addition comprises the 5-15 weight part clay in 100 weight part glaze, the Al of 20-30 weight part 2O 3, the 0.1-1.0 weight part borax, 0.1 weight part or NaNO still less 2And 0.1 weight part or quartz still less;
By in the 90-110 ℃ of dry in advance described metal base that scribbles described second frit for porcelain enamel, then with described metal base in 400-950 ℃ of baking, form second enamel layer; With
By with fluoropolymer-coated to described second enamel layer, and with described metal base in 200-430 ℃ of baking, form fluoropolymer layer.
2, according to the process of claim 1 wherein that the thickness of described first enamel layer is the 80-150 micron, the thickness of described second enamel layer is the 15-20 micron.
3, according to the process of claim 1 wherein contained Al in the described interground addition of described second frit for porcelain enamel 2O 3Granularity be the 0.1-55 micron.
4, according to the method for claim 3, Al wherein 2O 3Granularity be the 10-20 micron.
5, according to the process of claim 1 wherein that the granularity with the 20-30 weight part is the silicon-dioxide (SiO of 0.1-55 micron 2) further be added in the described interground addition contained in described second frit for porcelain enamel, in 100 weight part glaze.
6, according to the method for claim 5, wherein the granularity of silicon-dioxide is the 10-20 micron.
7, be used for the antimicrobial antiseptic-germicide according to the process of claim 1 wherein that described fluoropolymer layer comprises.
8, according to the process of claim 1 wherein that fluoropolymer is a tetrafluoroethylene.
9, a kind of metal product that scribbles enamel layer and fluoropolymer layer, wherein said metal product are to prepare by each method among the claim 1-8.
10, according to the metal product of claim 9, wherein said fluoropolymer layer is the black that has white.
CNB2004100069107A 2003-12-15 2004-02-26 Metallic plate coated with enamel layer and containing fluorine polymer, and method for making same Expired - Fee Related CN1313645C (en)

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KR1020030091168A KR100551748B1 (en) 2003-12-15 2003-12-15 Metal plate coated with porcelain layer and fluoric resin layer and the preparation method thereof

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CN102355805B (en) * 2011-09-30 2013-05-01 沪华五金电子(吴江)有限公司 Surface glazing technology for aluminium shell of electronic product
CN105419409A (en) * 2015-11-23 2016-03-23 沈阳黎明航空发动机(集团)有限责任公司 High-temperature-fuel-gas-washing-resistant coating and preparation method and application thereof
CN108483917A (en) * 2018-06-06 2018-09-04 无锡大塘复合材料有限公司 A kind of improved enamel not adhering process method
CN108483917B (en) * 2018-06-06 2021-03-23 无锡大塘复合材料有限公司 Improved enamel non-stick process
WO2021000924A1 (en) * 2019-07-03 2021-01-07 Program Contractors Limited Self-cleaning antibacterial vitreous enamel panels
CN112570239A (en) * 2019-09-29 2021-03-30 浙江绍兴苏泊尔生活电器有限公司 Preparation method of inner pot and inner pot

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