CN103360836A - Metal protective paint and application thereof, and hot-dip metal material - Google Patents
Metal protective paint and application thereof, and hot-dip metal material Download PDFInfo
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- CN103360836A CN103360836A CN2012100918758A CN201210091875A CN103360836A CN 103360836 A CN103360836 A CN 103360836A CN 2012100918758 A CN2012100918758 A CN 2012100918758A CN 201210091875 A CN201210091875 A CN 201210091875A CN 103360836 A CN103360836 A CN 103360836A
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Abstract
The invention provides a metal protective paint which is prepared by uniformly mixing a raw material mixture, wherein the raw material mixture contains water-soluble silicate, silicon oxide filler, accelerator, water-soluble film-forming resin, C6H11NHCH2CH2CH2Si(OCH3)3 and water; and the accelerator is thiocarbamide and/or urea. The invention also discloses application of the metal protective paint in preparation of metal materials. The invention also provides a hot-dip metal material which comprises a hot-dip metal substrate and a coating attached to the hot-dip metal substrate, wherein the coating is the cured product of the metal protective paint. The protective film formed by the metal protective paint provided by the invention has very excellent corrosion resistance, water resistance, heat resistance and fingerprint resistance.
Description
Technical field
The present invention relates to the metal protection field, particularly, relate to a kind of metal protection coating, the purposes of this metal protection coating and a kind of hot-dip metal plated material.
Background technology
Hot-dip metal plated material comprises hot-dip galvanized metal material and hot-dip aluminizing zinc metallic substance, in order to prevent corrosion, and all can be at the surface of hot-dip metal plated material coating layer of metal protective coating to form protective film.Thereby the performance of metal protection coating is very important for the rust protection of hot-dip metal plated material.
For example, CN101608306A discloses a kind of passivating solution, also belongs to a kind of metal protection coating, it is characterized in that, this passivating solution is the aqueous solution that contains water-soluble molybdenum compound, boric acid, water soluble organic substance and silicon sol, and wherein, described water soluble organic substance is the mixture of pure and mild organic carboxyl acid.
But the solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing that experiment showed, the protective film that this metal protection coating forms are still relatively poor.
Summary of the invention
The objective of the invention is to overcome the relatively poor defective of solidity to corrosion, water tolerance, thermotolerance and anti-finger printing of the protective film that existing metal protection coating forms, provide a kind of and can form the preferably metal protection coating of protective film of solidity to corrosion, water tolerance, thermotolerance and anti-finger printing.
To achieve these goals, the invention provides a kind of metal protection coating, this metal protection coating obtains after being mixed by a kind of raw mix, and described raw mix contains water-soluble silicate, cilicon oxide filler, promotor, water-soluble film-forming resin, C
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3And water; Described promotor is thiocarbamide and/or urea.
The present invention also provides the purposes of above-mentioned metal protection coating in the preparation metallic substance.
The present invention also provides a kind of hot-dip metal plated material, this hot-dip metal plated material comprises hot-dip metal plated base material and the coating that is attached on this hot-dip metal plated base material, described hot-dip metal plated base material is pot galvanize metal base and/or hot-dip aluminizing zinc metal base, it is characterized in that described coating is the cured product of aforesaid metal protection coating.
By technique scheme, solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing of the protective film that metal protection coating provided by the invention forms are all very good.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
According to metal protection coating provided by the invention, wherein, this metal protection coating obtains after being mixed by a kind of raw mix, and described raw mix contains water-soluble silicate, cilicon oxide filler, promotor, water-soluble film-forming resin, C
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3And water; Described promotor is thiocarbamide and/or urea.
Wherein, C
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3Be called 3-hexahydroaniline propyl trimethoxy silicane, structural formula can be used as silane coupling agent suc as formula shown in (1), the commercially available various C that can be used as silane coupling agent
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3Commodity may be used to the present invention.
Formula (1)
Wherein, this metal protection coating is to obtain after described raw mix mixes, and is the liquid of comparatively stable and homogeneous.Under the preferable case, each component in the described raw mix mixed before use at this metal protection coating in 1-180 days.Wherein, the order by merging of each composition is not had special requirement, can directly each component in the described raw mix be carried out simultaneously, in batches or substep mix, as long as can obtain uniform stable phase, preferably make mixing more even by stirring.
According to metal protection coating provided by the invention, wherein, with respect to the described water-soluble silicate of 1 weight part, C
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3Consumption can be the 0.5-4.5 weight part, be preferably the 1.4-1.8 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the content of described promotor can be the 0.2-1.8 weight part, is preferably the 0.5-0.7 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of described cilicon oxide filler can be the 0.25-2.2 weight part, is preferably the 0.6-0.85 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, in solid, the consumption of described water-soluble film-forming resin can be the 0.8-6.8 weight part, is preferably the 2.1-2.7 weight part.Herein solid be used for to calculate or the solid implication of expression solid content identical, be remaining composition after the water-soluble film-forming resin desolventizing.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of water is the 10-100 weight part, is preferably the 25-40 weight part.Need to prove that the consumption of said water refers to the amount of the water that adds in addition among the present invention, do not comprise in above-mentioned other component of adding with solution or emulsion mode with the amount of water.
According to metal protection coating provided by the invention, wherein, described water-soluble silicate can be water glass and/or potassium silicate.
According to metal protection coating provided by the invention, wherein, described cilicon oxide filler does not have special requirement, can be the various fillers take silicon oxide as main body, and for example, described cilicon oxide filler can be nano-silica powder and/or silicon sol; Under the preferable case, described cilicon oxide filler is nano-silica powder, and the particle diameter of described nano-silica powder can be 10-90nm.
According to metal protection coating provided by the invention, wherein, described water-soluble film-forming resin can be for various water miscible and can be used in modification or the unmodified resin of film forming, described resin can use with suitable goods form, water-soluble emulsion for example, at least a in water-soluble solution and the water-soluble solid, the present invention does not have special requirement, as long as the film forming of can be used in, for example, described water-soluble film-forming resin can be the water-soluble polyester film-forming resin (water-soluble film-forming resin that is namely got by polyalcohols monomer and polynary acids monomer polymerization, for example available from Guangzhou Lapo Fine Chemicals Co., Ltd., the vibrin of trade mark CB2200), water-soluble phenylpropyl alcohol film-forming resin (namely by styrene monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, for example available from the super imperial Chemical Industry Science Co., Ltd in Guangzhou, the trade mark is the benzene emulsion of xy-108b), soluble epoxide film-forming resin (the water-soluble film-forming resin that is namely got by the monomer polymerization that contains epoxy group(ing), for example available from Dongguan City Heima Chemical Co., Ltd., the trade mark is the Resins, epoxy of BH620), the aqurous ployurethane film-forming resin (namely by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer polymerization and water-soluble film-forming resin, for example build Hua company available from Jinjiang, Fujian Province, the urethane resin of the trade mark 812), water-soluble silicon the third film-forming resin (namely by silicone based monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, the Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous for example, solid content is 48 % by weight), water-soluble acrylic film-forming resin (the water-soluble film-forming resin that is namely got by vinylformic acid (ester) class monomer polymerization, for example the trade mark available from Guangzhou Ou Peng chemical industry is the acrylic resin of A-3418) and the water-soluble fluorine carbon film-forming resin (water-soluble film-forming resin that is namely got by the fluorinated monomer polymerization, for example available from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I) at least a; Under the preferable case, described water-soluble film-forming resin is at least a in water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin, aqurous ployurethane film-forming resin and the water-soluble polyester film-forming resin.
Except containing mentioned component, metal protection coating of the present invention can also contain other various components that do not affect the metal protection coating property, such as in dyestuff, pigment, dispersion agent and the defoamer one or more.Take the gross weight of this metal protection coating as benchmark, the content of other component is no more than 20 % by weight, preferably is no more than 10 % by weight.Described defoamer can be various defoamer well known in the art, such as in polyethers defoamer, higher alcohols defoamer and the silicon defoamer etc. one or more.More particularly, described defoamer can be for being purchased in the SD-401 of limited liability company of the large Creative Science and Technology Co. Ltd of Dongying dan for example series defoamer one or more.Under the preferable case, take the total amount of described metal protection coating as benchmark, the content of described defoamer is the 0.01-0.05 % by weight.
Metal protection coating of the present invention need not dilution and can directly use.
The present invention also provides the purposes of above-mentioned metal protection coating in the preparation metallic substance.Above-mentioned metal protection coating can be in the mode of this area routine for the preparation of various metallic substance.
According to hot-dip metal plated material provided by the invention, this hot-dip metal plated material comprises pot galvanize metal base and the coating that is attached on this hot-dip metal plated base material, described hot-dip metal plated base material is pot galvanize metal base and/or hot-dip aluminizing zinc metal base, it is characterized in that described coating is the cured product of aforesaid metal protection coating.
Wherein, described pot galvanize metal base can be for containing the metal base of zinc coating, and in the described zinc coating, the content of zinc can be the 92.5-95.5 % by weight.Described zinc coating also can contain other conventional ingredient, such as silicon.
Wherein, described hot-dip aluminizing zinc metallic substance can be for containing the metal base of zinc-aluminium coating, and in the described zinc-aluminium coating, the content of zinc can be the 41.5-43.5 % by weight, and the content of aluminium can be the 51.5-55.0 % by weight.Described zinc-aluminium coating also can contain other conventional ingredient, such as silicon.
According to hot-dip metal plated material provided by the invention, wherein, the thickness of described coating can be the conventional thickness of the erosion shield on the hot-dip metal plated base material, in order to improve the performance of described coating, under the preferable case, the thickness of described coating is the 0.05-2 micron, preferably can be the 0.1-1 micron.
According to hot-dip metal plated material provided by the invention, wherein, the method of adhering to described coating at hot-dip metal plated base material can comprise described metal protection coating is attached on the surface of hot-dip metal plated base material, then dry, dry temperature can be 60-120 ℃, be preferably 90-110 ℃, the time can be 0.5-3 second.The consumption of described metal protection coating can be determined according to the thickness of coating.
Wherein, the method for described drying can be in warm air drying, induction heating and the infrared radiation heating one or more.
Among the present invention, do not do in the situation of opposite explanation, the volume of all liquid and solid all refers to 20 ℃, the volume that 1 standard atmosphere is depressed.
Below will be explained in further detail the present invention by embodiment.
Embodiment 1
With the water-soluble silicate (water glass moistens rich Industrial Co., Ltd. available from Baoding) of 1 weight part, the promotor (urea) of 0.6 weight part, the C of 1.6 weight parts
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3(available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-58), the cilicon oxide filler (nano-silica powder of 0.72 weight part, available from U.S. GE company, RNS-E, mean particle size 20nm), the water-soluble film-forming resin of 2.4 weight parts (in solid) (water-soluble silicon the third film-forming resin (Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous, solid content is 48 % by weight)) and the water of 28 weight parts, under 1500 rev/mins stirring velocity, be mixed to evenly, obtain the metal protection coating of present embodiment.
Comparative Examples 1
Method according to embodiment 1 prepares metal protection coating, and different is to replace C with aminopropyl triethoxysilane (available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-1100)
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3
Comparative Examples 2
Method according to embodiment 1 prepares metal protection coating, and different is not add promotor.
Comparative Examples 3
Method according to embodiment 1 prepares metal protection coating, and different is not add water-soluble silicate.
Comparative Examples 4
Method according to embodiment 1 prepares metal protection coating, and different is not add cilicon oxide filler.
Embodiment 2
With the water-soluble silicate (potassium silicate moistens rich Industrial Co., Ltd. available from Baoding) of 1 weight part, the promotor (urea) of 0.5 weight part, the C of 1.4 weight parts
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3(available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-58), the cilicon oxide filler (nano silicon of 0.6 weight part, available from U.S. GE company, RNS-E, mean particle size 20nm), the water of the water-soluble film-forming resin of 2.1 weight parts (take solid) (water-soluble acrylic film-forming resin (available from the trade mark of the Guangzhou Ou Peng chemical industry acrylic resin as A-3418)) and 25 weight parts, under 1500 rev/mins stirring velocity, be mixed to evenly, obtain the metal protection coating of present embodiment.
Embodiment 3
With the water-soluble silicate (water glass moistens rich Industrial Co., Ltd. available from Baoding) of 1 weight part, the promotor (urea) of 0.7 weight part, the C of 1.8 weight parts
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3(available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-58), the cilicon oxide filler of the 0.85 weight part (silicon sol of 30 % by weight, usage quantity is in solid), (the aqurous ployurethane film-forming resin (is built Hua company available from Jinjiang, Fujian Province for the water-soluble film-forming resin of 2.7 weight parts (in solid), and the water of 40 weight parts the urethane resin of the trade mark 812)), under 1500 rev/mins stirring velocity, be mixed to evenly, obtain the metal protection coating of present embodiment.
Embodiment 4
With the water-soluble silicate (water glass moistens rich Industrial Co., Ltd. available from Baoding) of 1 weight part, the promotor (urea) of 0.3 weight part, the C of 0.6 weight part
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3(available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-58), the cilicon oxide filler (nano-silica powder of 2.1 weight parts, available from U.S. GE company, RNS-E, mean particle size 20nm), the water-soluble film-forming resin of 6.5 weight parts (in solid) (water-soluble silicon the third film-forming resin (Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous, solid content is 48 % by weight)) and the water of 90 weight parts, under 1500 rev/mins stirring velocity, be mixed to evenly, obtain the metal protection coating of present embodiment.
Embodiment 5
With the water-soluble silicate (water glass moistens rich Industrial Co., Ltd. available from Baoding) of 1 weight part, the promotor (urea) of 1.7 weight parts, the C of 4.5 weight parts
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3(available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-58), the cilicon oxide filler (nano-silica powder of 0.3 weight part, available from U.S. GE company, RNS-E, mean particle size 20nm), the water-soluble film-forming resin of 1.0 weight parts (in solid) (water-soluble silicon the third film-forming resin (Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous, solid content is 48 % by weight)) and the water of 15 weight parts, under 1500 rev/mins stirring velocity, be mixed to evenly, obtain the metal protection coating of present embodiment.
Embodiment 6
Method according to embodiment 1 prepares metal protection coating, and different is to use thiocarbamide as promotor.
Embodiment 7
Method according to embodiment 1 prepares metal protection coating, and different is, uses mixture that thiocarbamide and urea is mixed to get by 1: 1 weight ratio as promotor.
Embodiment 8
Method according to embodiment 1 prepares metal protection coating, and different is to use water-soluble phenylpropyl alcohol film-forming resin (available from the super imperial Chemical Industry Science Co., Ltd in Guangzhou, the trade mark is the benzene emulsion of xy-108b) as water-soluble film-forming resin.
Embodiment 9
Method according to embodiment 1 prepares metal protection coating, and different is to use soluble epoxide film-forming resin (available from Dongguan City Heima Chemical Co., Ltd., the trade mark is the aqueous epoxy resin emulsion of BH620) as water-soluble film-forming resin.
Embodiment 10
Method according to embodiment 1 prepares metal protection coating, and different is to use water-soluble polyester film-forming resin (available from chemical industry company limited of the poly-section of Yancheng, Jiangsu Province, the trade mark is the waterborne polyester of PE-10030-P) as water-soluble film-forming resin.
Preparation Example 1
Get the metal protection coating that embodiment 1-10 and Comparative Examples 1-4 obtain and be coated on respectively steel plate galvanized (available from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX54D, contain zinc 95 % by weight in the zinc coating) the surface, 90-110 ℃ of lower warm air drying 2 seconds, the steel plate galvanized 1-14 after obtaining processing.Wherein, coating amount is so that the thickness of the coating on the steel plate galvanized 1-14 is 0.8 micron.The thickness of coating is the numerical value of measuring with XRF (fluorescence spectrophotometer) survey meter.
Preparation Example 2
Get the metal protection coating that embodiment 1-10 and Comparative Examples 1-4 obtain and be coated on respectively Al-Zn coated steel (available from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX51D+AZ, contain zinc 42.5 % by weight in the aluminum-zinc alloy layer, contain aluminium 52.3 % by weight) the surface, 90-110 ℃ of lower warm air drying 2 seconds, the Al-Zn coated steel 1-14 after obtaining processing.Wherein, coating amount is so that the thickness of the coating on the Al-Zn coated steel 1-14 is 0.8 micron.The thickness of coating is the numerical value of measuring with XRF (fluorescence spectrophotometer) survey meter.
Test implementation example 1
By the requirement of regulation among the GB/T 10,125 1997, carry out neutral salt spray test, measure the corrosion resistance nature of steel plate galvanized 1-14 and Al-Zn coated steel 1-14.It is qualified to be considered as by " salt-fog test 96h, corrosion area<20% ".
As follows, measure the water resistance of steel plate galvanized 1-14 and Al-Zn coated steel 1-14.
Surface at steel plate galvanized 1-14 and the Al-Zn coated steel 1-14 of horizontal positioned, drip about 2 milliliters boiling water, after seasoning in 24 hours, adhere to the 3M adhesive tape place of will dripping, to the counting of the spot under being stained with on the adhesive tape, according to the counting of sticking lower spot on every square centimeter of adhesive tape, judge the quality of rete water tolerance, spot under sticking is more, and water tolerance is poorer.
As follows, measure the thermotolerance of steel plate galvanized 1-14 and Al-Zn coated steel 1-14.
Steel plate galvanized 1-14 and Al-Zn coated steel 1-14 are placed in the hotblast stove, 300 ℃ of lower bakings 20 minutes, then take out and observe the coatingsurface morphology change, and adopt Δ L (brightness variable), Δ a (red green variable), the Δ b (champac variable) of color difference meter test baking front and back specimen surface to be worth, and calculate Δ E (aberration)=(Δ L
2+ Δ a
2+ Δ b
2)
1/2The less coating of Δ E namely has better thermotolerance.
As follows, measure the anti-finger printing of steel plate galvanized 1-14 and Al-Zn coated steel 1-14.
Adopt Δ L (brightness variable), Δ a (red green variable), Δ b (champac variable) value of color difference meter test steel plate galvanized 1-14 and 0.5 g/m of Vaseline front and back of Al-Zn coated steel 1-14 coating, and calculate Δ E (aberration)=(Δ L
2+ Δ a
2+ Δ b
2)
1/2, the less coating of Δ E namely has better anti-finger printing energy.
Aforesaid test result is as shown in table 1.
Table 1
According to the data of table 1 as seen, solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing of the protective film that forms of metal protection coating provided by the invention are all very good.And according to the data of table 1 as seen, with respect to the described water-soluble silicate of 1 weight part, the content of described promotor is the 0.5-0.7 weight part, C preferably
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3Consumption be the 1.4-1.8 weight part, the consumption of described cilicon oxide filler is the 0.6-0.85 weight part, in solid, the consumption of described water-soluble film-forming resin is the 2.1-2.7 weight part, the consumption of water is in the situation of 25-40 weight part, can further improve solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing of the protective film of described metal protection coating formation.
More than describe preferred implementation of the present invention in detail; but the present invention is not limited to the detail in the above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in above-mentioned embodiment in reconcilable situation, can make up by any suitable mode, for fear of unnecessary repetition, the present invention is to the no longer separately explanation of various possible array modes.
Claims (9)
1. metal protection coating, this metal protection coating obtains after being mixed by a kind of raw mix, and described raw mix contains water-soluble silicate, cilicon oxide filler, promotor, water-soluble film-forming resin, C
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3And water; Described promotor is thiocarbamide and/or urea.
2. metal protection coating according to claim 1, wherein, with respect to the described water-soluble silicate of 1 weight part, C
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3Consumption be the 0.5-4.5 weight part, the consumption of described cilicon oxide filler is the 0.25-2.2 weight part, and the content of described promotor is the 0.2-1.8 weight part, in solid, the consumption of described water-soluble film-forming resin is the 0.8-6.8 weight part, and the consumption of water is the 10-100 weight part.
3. metal protection coating according to claim 2, wherein, with respect to the described water-soluble silicate of 1 weight part, the content of described promotor is the 0.5-0.7 weight part, C
6H
11NHCH
2CH
2CH
2Si (OCH
3)
3Consumption be the 1.4-1.8 weight part, the consumption of described cilicon oxide filler is the 0.6-0.85 weight part, in solid, the consumption of described water-soluble film-forming resin is the 2.1-2.7 weight part, the consumption of water is the 25-40 weight part.
4. the described metal protection coating of any one according to claim 1-3, wherein, described cilicon oxide filler is nano-silica powder and/or silicon sol.
5. the described metal protection coating of any one according to claim 1-3, wherein, described water-soluble film-forming resin is at least a in water-soluble polyester film-forming resin, water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, aqurous ployurethane film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin and the water-soluble fluorine carbon film-forming resin.
6. the described metal protection coating of any one according to claim 1-3, wherein, described raw mix also contains one or more in dispersion agent, defoamer and the stablizer.
Among the claim 1-6 the described metal protection coating of any one in the purposes of preparation in the metallic substance.
8. hot-dip metal plated material, this hot-dip metal plated material comprises hot-dip metal plated base material and the coating that is attached on this hot-dip metal plated base material, described hot-dip metal plated base material is pot galvanize metal base and/or hot-dip aluminizing zinc metal base, it is characterized in that described coating is the cured product of the described metal protection coating of any one among the claim 1-6.
9. hot-dip metal plated material according to claim 8, wherein, the thickness of described coating is the 0.1-1 micron.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1730570A (en) * | 2005-08-02 | 2006-02-08 | 陈国军 | High temperature energy-saving corrosion-resisting paint , preparation and usage |
CN101058696A (en) * | 2007-05-16 | 2007-10-24 | 曾庆衿 | High temperature environment-friendly type energy-saving coating for metal |
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CN1730570A (en) * | 2005-08-02 | 2006-02-08 | 陈国军 | High temperature energy-saving corrosion-resisting paint , preparation and usage |
CN101058696A (en) * | 2007-05-16 | 2007-10-24 | 曾庆衿 | High temperature environment-friendly type energy-saving coating for metal |
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