CN107384148A - Graphene-based heat radiation coating and preparation method thereof - Google Patents
Graphene-based heat radiation coating and preparation method thereof Download PDFInfo
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- CN107384148A CN107384148A CN201710608106.3A CN201710608106A CN107384148A CN 107384148 A CN107384148 A CN 107384148A CN 201710608106 A CN201710608106 A CN 201710608106A CN 107384148 A CN107384148 A CN 107384148A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention provides a kind of graphene-based heat radiation coating, and it includes the component of following parts by weight：30~50 parts of aqueous polyester resin, 5~10 parts of water-compatible amino resin, 5~30 parts of graphene composite powder, 5~10 parts of nanoscale hexagonal boron nitride, 3~10 parts of aerosil, 1~5 part of coupling agent, 0.1~2 part of levelling agent, 0.1~3 part of defoamer, 0.1~3 part of catalyst, 10~50 parts of water.The present invention also provides the preparation method of graphene-based heat radiation coating.
Description
Technical field
The present invention relates to heat radiation coating technical field, more particularly to a kind of weather resistance is excellent and excellent thermal conductivity
Graphene-based heat radiation coating and preparation method thereof.
Background technology
As rapid photo detector tends to integrated, miniaturization, caused heat is fast in electronic component operation
Speed distributes particularly important.The existing thermal dispersant coatings applied to electronic component have that radiating effect is bad, cohesive force is not strong, resistance to
The problems such as time property difference.
Graphene is a kind of individual layer laminated structure being made up of carbon atom, and it has, and intensity is high, specific surface area is big, high IR
The characteristic of emissivity.It is heat conduction system in the material being found at present meanwhile the thermal conductivity factor of graphene is up to 5300w/mK
Number highest material, therefore it has broad application prospects in field of radiating.But due to reunion caused by its high-specific surface area
Make its radiating effect in general heat radiation coating bad with highly conductive characteristic, and application is also restrained.
Nanoscale hexagonal boron nitride (h-BN) is a kind of layer structure feature and lattice parameter having similar to graphene
Material, due to its presentation white, also known as " white graphite alkene ".In the structure of boron nitride, hexatomic ring is being just between layers
Right, the B of last layer corresponds to next layer of N, and B positively chargeds N is negatively charged, and the conjugated pi electron in layer delocalization can not form big π completely
Key, therefore h-BN has good insulating properties.H-BN also has many excellent performances, such as high-mechanical property, high fever simultaneously
Conductance, high-fire resistance, low thermal coefficient of expansion, resistant to chemical etching, low-friction coefficient etc., therefore can have extensively in calorifics and electricity direction
Wealthy application.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of graphene-based heat radiation coating and preparation method thereof, with
Solve the problems of the prior art.
The present invention provides a kind of graphene-based heat radiation coating, and it includes the component of following parts by weight：Aqueous polyester resin 30
~50 parts, 5~10 parts of water-compatible amino resin, 5~30 parts of graphene composite powder, 5~10 parts of nanoscale hexagonal boron nitride, gas phase
3~10 parts of silica, 1~5 part of coupling agent, 0.1~2 part of levelling agent, 0.1~3 part of defoamer, 0.1~3 part of catalyst, water
10~50 parts.
The present invention also provides a kind of preparation method of above-mentioned graphene-based heat radiation coating, and it comprises the following steps：
(a) graphene composite powder, nanoscale hexagonal boron nitride, aerosil, appropriate water are mixed with auxiliary agent,
It is scattered 40 minutes~60 minutes with 3000 revs/min~5000 revs/min of rotating speed, graphene premix is obtained, wherein auxiliary agent includes
Coupling agent, levelling agent, defoamer；
(b) water of aqueous polyester resin, water-compatible amino resin, catalyst and step (a) equivalent is mixed, with 300 revs/min
~500 revs/min of rotating speed is scattered 20 minutes~30 minutes, obtains resin prefabricated solution；And
(c) graphene premix is added in resin prefabricated solution, with 300 revs/min~500 revs/min of rotating speed scattered 10
Minute~20 minutes, obtain the graphene-based heat radiation coating.
Graphene-based heat radiation coating of the present invention has advantages below：
First, the graphene-based heat radiation coating include graphene composite powder, nanoscale hexagonal boron nitride microplate and
Aerosil, the graphene composite powder, nanoscale hexagonal boron nitride microplate and aerosil have good
Heat conductivility, the heat conduction network that point-line-face mutually overlaps, the thermal conductive network can be formed in the graphene-based heat radiation coating
The presence of network causes the graphene-based heat radiation coating to have excellent thermal conduction characteristic；
Second, the structure of the hexagonal boron nitride is similar to graphene, therefore, when being mixed with graphene composite powder, two
Person has good compatibility, and this is also more conducive to the formation of the heat conduction network, is formed when by the graphene-based heat radiation coating
For coating in use, the heat radiation emissivity of coating reaches more than 0.95, the coating possesses superpower heat dispersion；
3rd, by adding nanoscale hexagonal boron nitride and aerosil, nanoscale hexagonal boron nitride and gas
Aerosil has good insulating properties, thus can block the conductive path of graphene, reduces electric conductivity, also,
Aqueous polyester resin and water-compatible amino resin, which also further assign the graphene-based heat radiation coating, has good insulating properties；
4th, therefore, obtained as decentralized medium using waterborne polyester and water-compatible amino resin, and using deionized water
The graphene-based heat radiation coating arrived discharges in subsequent applications non-volatility gas, environment friendly and pollution-free.
The coating that the graphene-based heat radiation coating subsequent applications obtain has high rigidity, the characteristic of high-weatherability.It is described
Graphene-based heat radiation coating can be applied not only to interior, can also be applied to outdoor, widen the graphene-based heat radiation coating
Application field and the scope of application.
The preparation method of the graphene-based heat radiation coating has that technique is simple, requires the advantages of low to operator, is easy to
Industrialization.
Embodiment
The technical scheme in embodiment of the present invention will be clearly and completely described below, it is clear that described reality
Apply mode only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention,
All other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, belong to this
Invent the scope of protection.
The present invention provides a kind of graphene-based heat radiation coating.The graphene-based heat radiation coating includes the group of following parts by weight
Point：30~50 parts of aqueous polyester resin, 5~10 parts of water-compatible amino resin, 5~30 parts of graphene composite powder, the side of nanoscale six
5~10 parts of boron nitride, 3~10 parts of aerosil, 1~5 part of coupling agent, 0.1~2 part of levelling agent, 0.1~3 part of defoamer,
0.1~3 part of catalyst, 10~50 parts of water.
In view of being obtained during practical application, weather resistance is more preferable, heat conductivility is more excellent, the more preferable graphene of insulating properties
Base heat radiation coating, it is preferred that 33~45 parts of the aqueous polyester resin, 5~10 parts of water-compatible amino resin, graphene composite powder
5~10 parts, 5~10 parts of nanoscale hexagonal boron nitride, 3~5 parts of aerosil, 1~5 part of coupling agent, levelling agent 0.1~1
Part, 0.1~1 part of defoamer, 0.1~1 part of catalyst, 25~50 parts of water.
The graphene composite powder includes grapheme material and additive.The additive is nano carbon black, nanometer stone
At least one of black microplate, CNT, Nano diamond, nano carbon microsphere.The purpose of the additive is graphene
Disperseed in advance, obstructed equivalent to being formed between graphene, and avoid serious reunion.
The graphene composite powder can be prepared via a method which：First, grapheme material, additive are added to one
Solvent simultaneously mixes, and obtains a mixture；Again by the mixture ultrasonic disperse, the graphene composite powder is obtained after drying.
Wherein, the solvent is preferably the relatively low organic solvent of boiling point, specifically, can be 1-METHYLPYRROLIDONE, DPG, isopropyl
At least one of alcohol, N, N- dimethylethanolamines, propandiol butyl ether, dimethylbenzene, dichloromethane.The graphene and additive
Mass ratio be 1:0.1~1:0.5, be preferably, 1:0.1~1:0.3.The ratio of the graphene and the solvent for (1g~
2g):100mL, it is preferably, (1g~1.5g):100mL.The mode of the drying may include fluidized bed drying, spray drying or
Toast drying.
The grapheme material is the graphene of individual layer or the number of plies at 2 layers -50 layers.The grapheme material is graphite oxide
Alkene or the graphene with functional group, the functional group are at least one of hydroxyl, carboxyl, carbonyl, amino, sulfydryl.
The boron nitride microplate that the nanoscale hexagonal boron nitride is individual layer or the number of plies is 2 layers~50 layers.
The coupling agent is silane coupler, titanate coupling agent, at least one of aluminate coupling agent, described stream
Flat agent is water soluble acrylic acid ester type levelling agent or waterborne organic silicon levelling agent, and the defoamer is water-based organic silicon modified by polyether class
Defoamer and higher alcohols non-silicon class defoamer, the catalyst are dinonylnaphthalene disulfonic acid salt, dinonylnaphthalene sulfonic acid salt, dodecane
At least one of base benzene sulfonate and toluenesulfonate.
The present invention also provides a kind of preparation method of graphene-based heat radiation coating.The preparation of the graphene-based heat radiation coating
Method comprises the following steps：
(a) graphene composite powder, nanoscale hexagonal boron nitride, aerosil, appropriate water are mixed with auxiliary agent,
It is scattered 40 minutes~60 minutes with 3000 revs/min~5000 revs/min of rotating speed, graphene premix is obtained, wherein auxiliary agent includes
Coupling agent, levelling agent, defoamer；
(b) water of aqueous polyester resin, water-compatible amino resin, catalyst and step (a) equivalent is mixed, with 300 revs/min
~500 revs/min of rotating speed is scattered 20 minutes~30 minutes, obtains resin prefabricated solution；And
(c) graphene premix is added in resin prefabricated solution, with 300 revs/min~500 revs/min of rotating speed scattered 10
Minute~20 minutes, obtain the graphene-based heat radiation coating.
In above-mentioned preparation method the ratio of each raw material referring to each component in above-mentioned graphene-based heat radiation coating proportioning.
This is not repeated.
Further it will be illustrated below by multiple embodiments.
Embodiment 1：
A kind of graphene-based heat radiation coating, it includes the component of following parts by weight：33 parts of aqueous polyester resin, water-based amino
5 parts of resin, 7 parts of graphene composite powder, 5 parts of nanoscale hexagonal boron nitride, 3 parts of aerosil, 2 parts of coupling agent, levelling
0.3 part of agent, 0.5 part of defoamer, 0.2 part of catalyst, 44 parts of deionized water.Wherein, graphene composite powder is graphene and received
Rice carbon black, CNT are according to 8:1:Composite powder formed by spray drying after 1 mixing.Coupling agent is vinyl triethoxyl silicon
Alkane coupling agent, levelling agent are the polyether-modified acrylate levelling agent of macromolecular, and defoamer defoams for water-based organic silicon modified by polyether
Agent, catalyst are toluene sulfonic acide ammonium salt.
The preparation method of the graphene-based heat radiation coating is as follows：
(1) by the graphene composite powder of above-mentioned parts by weight, nanoscale hexagonal boron nitride, aerosil, appropriate
Deionized water mixes with auxiliary agent, scattered 40 minutes~60 minutes with 3000 revs/min~5000 revs/min of rotating speed, obtains graphene
Premix, wherein auxiliary agent include coupling agent, levelling agent, defoamer.
(2) water of the aqueous polyester resin of above-mentioned parts by weight, water-compatible amino resin, catalyst and step (a) equivalent is mixed
Close, it is scattered 20 minutes~30 minutes with 300 revs/min~500 revs/min of rotating speed, obtain resin prefabricated solution.
(3) graphene premix is added in resin prefabricated solution, with 300 revs/min~500 revs/min of rotating speed scattered 10
Minute~20 minutes, obtain the graphene-based heat radiation coating.
Thermal dispersant coatings are made in the graphene-based heat radiation coating, are accelerated under the conditions of 50 DEG C and 300W ultraviolet light irradiations old
Change test period 6000 hours, aberration Δ E≤1.2,0~1 grade of cohesive force (3M adhesive tapes), lead radiating efficiency and reach 33%.
Embodiment 2：
A kind of graphene-based heat radiation coating, it includes the component of following parts by weight：38 parts of aqueous polyester resin, water-based amino
8 parts of resin, 8 parts of graphene composite powder, 5 parts of nanoscale hexagonal boron nitride, 4 parts of aerosil, 3 parts of coupling agent, levelling
0.3 part of agent, 0.5 part of defoamer, 0.2 part of catalyst, 33 parts of deionized water.Wherein composite graphite alkene powder is graphene and nanometer
Carbon black, CNT, carbon nano-fiber are according to 7:1:1:Composite powder formed by spray drying after 1 mixing.Coupling agent is ammonia third
Ethyl triethoxy silicane alkane coupling agent, levelling agent are water-based polyether modified siloxane levelling agent, and defoamer is ether modified polyorganosiloxane
Defoamer, catalyst are toluene sulfonic acide ammonium salt.
The preparation method of the graphene-based heat radiation coating will not be described here with embodiment 1.
Thermal dispersant coatings are made in the graphene-based heat radiation coating, are accelerated under the conditions of 50 DEG C and 300W ultraviolet light irradiations old
Change test period 6500 hours, aberration Δ E≤1.5,0~1 grade of cohesive force (3M adhesive tapes), lead radiating efficiency and reach 37%.
Embodiment 3
A kind of graphene-based heat radiation coating, it includes the component of following parts by weight：45 parts of aqueous polyester resin, water-based amino
10 parts of resin, 5 parts of graphene composite powder, 8 parts of nanoscale hexagonal boron nitride, 4 parts of aerosil, 3 parts of coupling agent, levelling
0.2 part of agent, 0.6 part of defoamer, 0.4 part of catalyst, 24 parts of deionized water.Wherein composite graphite alkene powder is graphene and nanometer
Carbon black is according to 7:Composite powder formed by spray drying after 3 mixing.Coupling agent is pyrophosphate titanate coupling agent, and levelling agent is
Water-based polyether modified siloxane levelling agent, defoamer are high-carbon alkoxide polymer defoamer, and catalyst is dinonylnaphthalene disulfonic acid ammonium
Salt.
The preparation method of the graphene-based heat radiation coating will not be described here with embodiment 1.
Thermal dispersant coatings are made in the graphene-based heat radiation coating, are accelerated under the conditions of 50 DEG C and 300W ultraviolet light irradiations old
Change test period 6300 hours, aberration Δ E≤1.3,0~1 grade of cohesive force (3M adhesive tapes), lead radiating efficiency and reach 38%.
Embodiment 4
A kind of graphene-based heat radiation coating, it includes the component of following parts by weight：40 parts of aqueous polyester resin, water-based amino
10 parts of resin, 8 parts of graphene composite powder, 8 parts of nanoscale hexagonal boron nitride, 3 parts of aerosil, 3 parts of coupling agent, levelling
0.2 part of agent, 0.6 part of defoamer, 0.4 part of catalyst, 27 parts of deionized water.Wherein composite graphite alkene powder is graphene and nanometer
Carbon black, nano carbon microsphere are according to 6:3:Composite powder formed by spray drying after 1 mixing.Coupling agent is glycydoxy
Trimethoxysilane coupling agent and phenyltrimethoxysila,e, levelling agent are water-based fluorin modified crylic acid ester levelling agent, defoamer
For water-based PPG defoamer, catalyst is dodecyl benzene sulfonate.
The preparation method of the graphene-based heat radiation coating will not be described here with embodiment 1.
Thermal dispersant coatings are made in the graphene-based heat radiation coating, are accelerated under the conditions of 50 DEG C and 300W ultraviolet light irradiations old
Change test period 6700 hours, aberration Δ E≤1.5,0~1 grade of cohesive force (3M adhesive tapes), lead radiating efficiency and reach 35%.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, professional and technical personnel in the field are enable to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (9)
1. a kind of graphene-based heat radiation coating, it is characterised in that it includes the component of following parts by weight：Aqueous polyester resin 30~
50 parts, 5~10 parts of water-compatible amino resin, 5~30 parts of graphene composite powder, 5~10 parts of nanoscale hexagonal boron nitride, gas phase two
3~10 parts of silica, 1~5 part of coupling agent, 0.1~2 part of levelling agent, 0.1~3 part of defoamer, 0.1~3 part of catalyst, water 10
~50 parts.
2. a kind of graphene-based heat radiation coating as claimed in claim 1, it is characterised in that it includes the group of following parts by weight
Point：33~45 parts of the aqueous polyester resin, 5~10 parts of water-compatible amino resin, 5~10 parts of graphene composite powder, nanoscale
5~10 parts of hexagonal boron nitride, 3~5 parts of aerosil, 1~5 part of coupling agent, 0.1~1 part of levelling agent, defoamer 0.1~1
Part, 0.1~1 part of catalyst, 25~50 parts of water.
3. a kind of graphene-based heat radiation coating as claimed in claim 1, it is characterised in that the graphene composite powder includes
Grapheme material and additive, the additive are nano carbon black, graphite nanosheets, CNT, Nano diamond, nanometer
At least one of carbon ball.
4. a kind of graphene-based heat radiation coating as claimed in claim 3, it is characterised in that the graphene composite powder passes through
It is prepared by following method：First, grapheme material, additive are added to a solvent and mixed, obtain a mixture；Again by described in
Mixture ultrasonic disperse, the graphene composite powder is obtained after drying, wherein, the solvent is 1-METHYLPYRROLIDONE, two
At least one of propane diols, isopropanol, N, N- dimethylethanolamines, propandiol butyl ether, dimethylbenzene, dichloromethane, the stone
The mass ratio of black alkene and additive is 1:0.1~1:0.5, the ratio of the graphene and the solvent is (1g~2g):
100mL。
A kind of 5. graphene-based heat radiation coating as claimed in claim 3, it is characterised in that the grapheme material be individual layer or
Graphene of the number of plies at 2 layers~50 layers.
6. a kind of graphene-based heat radiation coating as claimed in claim 3, it is characterised in that the grapheme material is oxidation stone
Black alkene or the graphene with functional group, the functional group are at least one of hydroxyl, carboxyl, carbonyl, amino, sulfydryl.
7. a kind of graphene-based heat radiation coating as claimed in claim 1, it is characterised in that the nanoscale hexagonal boron nitride is
Individual layer or the boron nitride microplate that the number of plies is 2 layers~50 layers.
8. a kind of graphene-based heat radiation coating as claimed in claim 1, it is characterised in that the coupling agent is silane coupled
At least one of agent, titanate coupling agent, aluminate coupling agent, described levelling agent are water-and acrylate levelling agent or water
Property organosilicon levelling agent, the defoamer are water-based organic silicon modified by polyether class defoamer and higher alcohols non-silicon class defoamer, institute
Catalyst is stated as in dinonylnaphthalene disulfonic acid salt, dinonylnaphthalene sulfonic acid salt, dodecyl benzene sulfonate and toluenesulfonate
At least one.
9. a kind of preparation method of heat radiation coating graphene-based as described in any one of claim 1~8, it is characterised in that it is wrapped
Include following steps：
(a) graphene composite powder, nanoscale hexagonal boron nitride, aerosil, appropriate water are mixed with auxiliary agent, with
3000 revs/min~5000 revs/min of rotating speed is scattered 40 minutes~60 minutes, obtains graphene premix, and wherein auxiliary agent includes even
Join agent, levelling agent, defoamer；
(b) water of aqueous polyester resin, water-compatible amino resin, catalyst and step (a) equivalent is mixed, with 300 revs/min~
500 revs/min of rotating speed is scattered 20 minutes~30 minutes, obtains resin prefabricated solution；And
(c) graphene premix is added in resin prefabricated solution, it is scattered 10 minutes with 300 revs/min~500 revs/min of rotating speed
~20 minutes, obtain the graphene-based heat radiation coating.
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| CN110776819A (en) * | 2019-11-26 | 2020-02-11 | 西安戴森电子技术有限公司 | Graphene heat dissipation coating for electronic and electric appliances |
| CN111534177A (en) * | 2020-06-04 | 2020-08-14 | 安徽宇航派蒙健康科技股份有限公司 | Graphene heat dissipation coating and preparation method thereof |
| CN111925652A (en) * | 2019-05-13 | 2020-11-13 | 江苏凯德圣达智能科技有限公司 | Preparation method of thermal interface material for packaging high-power LED lamp |
| CN112552754A (en) * | 2020-12-10 | 2021-03-26 | 哈工大机器人(中山)无人装备与人工智能研究院 | Preparation method of graphene heat dissipation coating |
| CN112899669A (en) * | 2021-01-20 | 2021-06-04 | 昆山富维金属制品有限公司 | Nano passivation coating galvanized sheet and production process thereof |
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