CN104774510B - Antistatic thermal control coating composition, preparation method and applications thereof - Google Patents
Antistatic thermal control coating composition, preparation method and applications thereof Download PDFInfo
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- CN104774510B CN104774510B CN201510125862.1A CN201510125862A CN104774510B CN 104774510 B CN104774510 B CN 104774510B CN 201510125862 A CN201510125862 A CN 201510125862A CN 104774510 B CN104774510 B CN 104774510B
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- 239000008199 coating composition Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 74
- 239000011248 coating agent Substances 0.000 claims abstract description 73
- 239000003973 paint Substances 0.000 claims abstract description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical class [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 29
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 239000011737 fluorine Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920002050 silicone resin Polymers 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 230000037452 priming Effects 0.000 claims abstract 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000945 filler Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 claims description 12
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 6
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- -1 cyanate modified methyl silicon Chemical class 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000005587 bubbling Effects 0.000 abstract 1
- 238000005562 fading Methods 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 21
- 239000010410 layer Substances 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000523 sample Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000005382 thermal cycling Methods 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 201000009310 astigmatism Diseases 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
- C09D5/24—Electrically-conducting paints
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses an antistatic thermal control coating composition, a preparation method and applications thereof. The coating composition comprises priming paint and finish paint. The priming paint is composed of a matrix namely organic fluorine resin and a filling material namely modified zinc oxide powder; wherein the zinc oxide is capable of forming vertical channels in the priming paint layer. The finish paint is composed of a matrix namely methyl silicone resin with multiple functional groups and a filling material namely modified zinc oxide powder; wherein part of the filling material penetrates the interface between the priming paint layer and the finish paint layer. The prepared antistatic thermal control coating has a white color, a thickness of 130 to 200 [mu]m, a solar absorption ratio of 0.20 to 0.25, a hemispherical emissivity of 0.85 to 0.91, a total mass loss (TML) not more than 1%, collectable volatile condensed mass (CVCM) not more than 0.1%, and a volume resistivity ([rho]v) not more than 107 [omega].m. The coating does not have the phenomenon of cracking, peeling, bubbling, and fading after 100 times of high-low temperature thermal cycle experiments in a temperature range of -100 to 100 DEG C, the optical properties of the coating is stable, and the adhesive force of the coating is high.
Description
Technical field
The present invention relates to heat control material technical field, and in particular to a kind of antistatic thermal control coating composition and its preparation side
Method, purposes.
Background technology
As the heat control system of one of the overall important leverage system of spacecraft, equally weigh just as the body temperature control system of people
Will, the premise for ensureing that new internal each several part instrument and structure can normally be run is not only, and even more ensure spacecraft energy
The necessary condition of the enough stable operation in space.The normal operation of each several part device inside spacecraft is all regulation in a constant temperature
In the range of degree, so needing by the temperature control of spacecraft inside and surface environment in the range of requiring, temperature to be reduced as far as possible
The amplitude size of degree change.Accordingly, it would be desirable to for the thermal control of spacecraft carries out more careful and in-depth study, come at present real
Most basic, the most effective way of existing spacecraft thermal control is exactly to use special heat management material.Nowadays spacecraft is made
In heat control material, the range of application most best class heat control material of wide, using effect is exactly thermal control coating, on spacecraft
It plays the effect as human body skin, protects spacecraft.
Charging can be divided into surface and charge and two kinds of bulk charging：Charge and refer to because the injection of a large amount of electric charges causes material in surface
Surface potential is significantly higher than the phenomenon of surrounding enviroment current potential；Bulk charging is referred to because xenogenesis electric charge injection depth is different in material
It is internally formed the phenomenon of internal electric field.
Because electronics heat movement speed is far above ion, thus spacecraft surface will have a substantial amounts of electronic deposition and band is negative
Electricity.Because spacecraft different surfaces part can be at the difference of different environmental condition (if any no light) and direction of relative movement
Under orientation (such as punching press-wake flow), in addition surfacing can be different (difference such as photoemission, secondary emissionratio) so as to can band
There are different potentials, so as to form uneven charging, appearance potential is poor.It is higher than tens electronics that bulk charging (deep layer charging) is energy
To on spacecraft, its energy penetrable surface, its penetration depth increases and increases the electron impact of volt with incident electron energy,
Assemble the charging phenomenon that the incident electron ion co-energy with surface is formed under surface at some tens of pm.When spacecraft surfacing
During insulation, they will be charged to different potentials in space plasma, consequently, it is possible to causing electric discharge, cause Spacecraft anomaly
Failure.Charge and discharge phenomena of the spacecraft under space environment is a kind of group effect.According to plate condenser charge model, fill
Discharge effect depends on material behavior in the present context.
The content of the invention
It is an object of the invention to provide a kind of antistatic thermal control coating composition of new white and preparation method thereof, use
On the way；Because white thermal control coating prepared by common zinc oxide powder does not possess antistatic effect, its surface resistivity can reach 1012
Ω m, it is difficult to meet the demand of spacecraft surface anti-static.The present invention is modified for Zinc oxide powder, by for tool
The zinc oxide for having space particular configuration carries out surface modification treatment, so as to strengthen the blending of modified zinc oxide powder and resin system
Ability, while improving the electric conductivity of coating system.Antistatic thermal control coating made by the coating composition of the present invention, can eliminate
Product Electrostatic Hidden Troubles in particular circumstances, ensure spacecraft reliability of operation, meet product and antistatic white hot control is applied
The demand of layer.
The purpose of the present invention is achieved through the following technical solutions：
In a first aspect, the present invention relates to a kind of antistatic thermal control coating composition of bi-component, the coating composition includes
Primer base and topcoat paint；The primer base includes organic solvent a and mass ratio to be had for 60～75: 25～40 modified
Machine fluororesin and modified oxidized zinc powder；The topcoat paint includes that organic solvent b and mass ratio are 65～75: 25～35
Polyfunctional group methyl silicon resin and modified oxidized zinc powder.
Preferably, in order to the three-dimensional channel for improving coating system internal oxidation zinc filler is set up, resistivity is reduced,
The modified oxidized zinc powder is to be obtained with space particular configuration Zinc oxide powder is modified；The space particular configuration is selected from
One or more in four needle-likes, bar-shaped, wire, tubulose.
Preferably, it is that raising modified zinc oxide is optical with the blending ability of resin system and coating itself
Can, the modified oxidized zinc powder first passes around the process of silane coupler surface impregnation, 400 DEG C～700 DEG C of Jing after 50 DEG C of drying
High-temperature heat treatment is obtained；The modified zinc oxide mealy structure size distribution ranges are 3～100 μm.
Preferably, the consumption of the organic solvent a is modified oxidized zinc powder and modified organic fluorine gross weight
0.1～0.2 times of amount；The modified oxidized zinc powder accounts for 50～70wt% of primer base solid content.
Preferably, the consumption of the organic solvent b is modified oxidized zinc powder and polyfunctional group methyl silicon resin
0.5～0.7 times of gross weight；The modified oxidized zinc powder accounts for 65～75wt% of topcoat paint solid content.
Preferably, it is the different use environments of reply and base material, described organic solvent a, b are respectively selected from third
One or more in ketone, butyl acetate, dimethylbenzene；Described organic solvent a, b may be the same or different.
Preferably, it is to adapt to different solidifying requirements and coating self performance demand, the polyfunctional group methyl
Silicones can be methyl phenyl silicone resin, polyurethane-modified methyl silicon resin, cyanate ester modified methyl silicones, epoxide modified first
One kind in base silicones.
Second aspect, the invention further relates to a kind of preparation side of the antistatic thermal control coating composition of bi-component of the present invention
Method, methods described comprises the steps：
A, primer base are prepared：In modified organic fluorine, modified oxidized zinc powder is added, mixed, addition has
Machine solvent a, mixing, ultrasonic agitation is uniform；
B, topcoat paint are prepared：In polyfunctional group methyl silicon resin, modified oxidized zinc powder is added, mixed, plus
Enter organic solvent b, mix, ultrasonic agitation is uniform.
The third aspect, the invention further relates to a kind of antistatic thermal control coating composition of bi-component of the present invention is anti-quiet in preparation
Purposes in electric thermal control coating, the coating includes upwards prime coat and top coat layer from base material；The prime coat is with modified
Based on organic fluorine, modified oxidized zinc powder is filler, and the modified zinc oxide in prime coat can form vertical in prime coat
To passage；The top coat layer based on polyfunctional group methyl silicon resin, modified oxidized zinc powder be filler, partially modified oxidation
Zinc is through prime coat and the interface of top coat layer.
Preferably, the thickness of the prime coat is 50 μm～100 μm, the thickness of the top coat layer is 50 μm～
100μm。
Preferably, prepare antistatic thermal control coating to specifically include：The primer base is sprayed in matrix surface,
Solidify 5～10h at 22～55 DEG C, spray the topcoat paint, 24～48h is solidified at 30～65 DEG C, obtain final product described antistatic
Thermal control coating.
The novel antistatic white thermal control coating that the present invention is provided, with following characteristic：
A) outward appearance：White, coating surface is uniform, bubble-free, flawless, without peeling, without coming off；
B) thickness：130 μm～200 μm；
C) hemispherical emissivity：0.85～0.91；
D) solar absorptance：0.20～0.25；
E) electric conductivity：ρv≤107Ω·m。
F) vacuum deflation performance：It is satisfied by TML ＜ 1%, CVCM ＜ 0.1%；
G) thermal cycling test：Coating meet -100～+100 DEG C of 100 high/low temperature thermal cycling tests after, without cracking, peel off,
Foaming and metachromatism, stable optical performance, adhesive force are good；
Compared with prior art, the present invention has the advantages that：The novel antistatic white thermal control coating of the present invention
On the basis of ensureing that coating has good thermal control performance (solar absorptance, hemispherical emissivity), with preferable coated conductive
Performance, while coating construction is simple, easy to learn, with stronger exploitativeness, and undergoes -100～+100 DEG C of 100 temperature punchings
Adhesive force after test is hit good, with relatively low vacuum deflation amount.
Description of the drawings
The detailed description by reading non-limiting example made with reference to the following drawings, the further feature of the present invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the structural representation of novel antistatic white thermal control coating；
Fig. 2 is the electrical conduction mechanism schematic diagram with space particular configuration (four needle-like) zinc oxide fillers；
Fig. 3 is scanning electron microscopy (SEM) figure with space particular configuration (four needle-like) zinc oxide fillers；
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, some deformations and improvement can also be made.These belong to the present invention
Protection domain.
Embodiment 1
The present embodiment is related to a kind of antistatic thermal control coating composition and preparation method thereof, and antistatic thermal control coating group
Application of the compound in novel antistatic white thermal control coating is prepared.
The present embodiment novel antistatic white thermal control coating as shown in figure 1, the coating from base material 3 upwards, point
It is not made up of two-layer heterogeneity coating；It is referred to as prime coat 2 positioned at subbing, it is by modified organic fluorine and special with space
Different configuration zinc oxide composition；Being coated on the coating on surface becomes top coat layer 1, by polyfunctional group methyl silicon resin and modified zinc oxide
Composition.
The novel antistatic white thermal control coating of the present embodiment adopts the antistatic thermal control coating composition of bi-component, the coating
Composition includes primer base and topcoat paint；The primer base includes organic solvent a (dimethylbenzene), modified organic fluorine
With modified oxidized zinc powder；The topcoat paint includes organic solvent b (dimethylbenzene), polyfunctional group methyl silicon resin and modified oxygen
Change zinc powder.
The modified oxidized zinc powder of this example is that the Zinc oxide powder for having steric configuration was entered into modification, by sky
Between particular configuration Zinc oxide powder carry out surface modification treatment, first pass around surface modification liquid dipping, after 50 DEG C of drying, pass through
400 DEG C～700 DEG C of high-temperature heat treatment；Described surface modification solution is the mixed solution of silane coupler and deionized water,
Mass ratio is 1: 9.Fig. 3 is scanning electron microscopy (SEM) figure with space particular configuration (four needle-like) zinc oxide fillers, by scheming
3 understand that the space between the Zinc oxide powder with space particular configuration is larger, it is difficult to resin system blending, it is therefore desirable to right
In space, special construction zinc oxide carries out surface modification treatment.
The concrete preparation method of novel antistatic white thermal control coating of the present embodiment comprises the steps：
1) primer base is prepared：In organic fluorine containing P Modification, modified oxidized zinc powder is added, mixed, plus
Enter dimethylbenzene, mix, ultrasonic agitation is uniform；By mass percentage：In primers modified oxidized zinc powder accounts for coating solids
70wt%, modified organic fluorine accounts for the mass ratio of the 30wt% of coating total amount, modified fluorin resin and modified oxidized zinc powder and is
30: 70, diformazan benzene diluter by 0.2 that its consumption is modified oxidized zinc powder filler and modified organic fluorine gross weight extraordinarily
Enter.
2) topcoat paint is prepared：In methyl phenyl silicone resin, modified oxidized zinc powder is added, mixed, add two
Toluene, mixing, ultrasonic agitation is uniform；By mass percentage：Modified oxidized zinc powder is (through silane coupler surface in finish paint
Processing) filler accounts for the 70wt% of coating solids, and methyl phenyl silicone resin accounts for the 30wt% of coating total amount, methyl phenyl silicone resin
It is 30: 70 with the mass ratio of Zinc oxide powder, diformazan benzene diluter is modified oxidized zinc powder and polyfunctional group first by its consumption
0.6 times of addition of base silicones gross weight.
3) during prepares coating, spray-applied primer → at 55 DEG C is sprayed first and solidifies 5h → spray paint → at 30 DEG C
Solidification 24h, you can.Wherein, the thickness of prime coat is 50 μm, and the thickness of the top coat layer is 50 μm.
As shown in Figure 2, steric configuration zinc oxide fillers form vertical passage in coating system.
Embodiment 2
The present embodiment is related to a kind of antistatic thermal control coating composition and preparation method thereof, and antistatic thermal control coating group
Application of the compound in novel antistatic white thermal control coating is prepared.
Substantially with embodiment 1, institute's difference is the present embodiment：
1) primer base is prepared：In organic fluorine containing P Modification, modified oxidized zinc powder is added, mixed, plus
Enter butyl acetate, mix, ultrasonic agitation is uniform；By mass percentage：In primers modified oxidized zinc powder accounts for coating solids
60wt%, modified organic fluorine accounts for the 40wt% of coating total amount, the matter of be modified organic fluorine and modified oxidized zinc powder
Than being 60: 40, butyl acetate diluent is modified oxidized zinc powder filler and modified organic fluorine gross weight by its consumption to amount
0.1 times of addition.
2) topcoat paint is prepared：In methyl phenyl silicone resin, modified oxidized zinc powder is added, mixed, add third
Ketone, mixing, ultrasonic agitation is uniform；By mass percentage：Modified zinc oxide powder filler accounts for coating solids in finish paint
75wt%, polyfunctional group methyl silicon resin accounts for the 25wt% of coating total amount, methyl phenyl silicone resin and modified oxidized zinc powder
Mass ratio is 25: 75, and acetone diluent is by 0.7 times that its consumption is modified oxidized zinc powder and methyl phenyl silicone resin gross weight
Add.
3) during prepares coating, spray-applied primer → at 22 DEG C is sprayed first and solidifies 10h → spray paint → at 30 DEG C
Lower solidification 48h, you can.Wherein, the thickness of prime coat is 100 μm, and the thickness of the top coat layer is 100 μm.
Embodiment 3
The present embodiment is related to a kind of antistatic thermal control coating composition and preparation method thereof, and antistatic thermal control coating group
Application of the compound in novel antistatic white thermal control coating is prepared.
Substantially with embodiment 1, institute's difference is the present embodiment：
1) primer base is prepared：In organic fluorine containing P Modification, modified oxidized zinc powder is added, mixed, plus
Enter dimethylbenzene, mix, ultrasonic agitation is uniform；By mass percentage：In primers modified oxidized zinc powder accounts for coating solids
50wt%, modified organic fluorine accounts for the 50wt% of coating total amount, the quality of be modified organic fluorine and modified oxidized zinc powder
Than for 50: 50, diformazan benzene diluter is by 0.15 that its consumption is modified oxidized zinc powder filler and modified organic fluorine gross weight
Add again.
2) topcoat paint is prepared：In methyl phenyl silicone resin, modified oxidized zinc powder is added, mixed, add second
Acid butyl ester, mixing, ultrasonic agitation is uniform；By mass percentage：Modified zinc oxide powder filler accounts for coating solids in finish paint
65wt%, methyl phenyl silicone resin accounts for the matter of the 35wt% of coating total amount, methyl phenyl silicone resin and modified oxidized zinc powder
, than being 35: 65, butyl acetate diluent is by 0.5 that its consumption is modified oxidized zinc powder and methyl phenyl silicone resin gross weight for amount
Add again.
3) during prepares coating, spray-applied primer → at 35 DEG C is sprayed first and solidifies 7h → spray paint → at 45 DEG C
Solidification 36h, you can.Wherein, the thickness of prime coat is 80 μm, and the thickness of the top coat layer is 70 μm.
Embodiment 4
Performance test is carried out to the novel antistatic white thermal control coating of above example 1,2,3, method of testing is as follows：
Coating layer thickness is tested
The thickness of the calibrator testing coatings of MiniTest 600 produced using German EPK companies.Measurement range be 0～
300 μm, error ± 2 μm；Minimum profile curvature radius 5mm (convex), 25mm (recessed)；Minimum measurement area φ 20mm；Instrument size 64 ×
15×25mm；14 × 62mm of probe size φ.The coating layer thickness tested meets technical indicator 130 between 130～180 μm
～200 μm of requirement.
Adhesive force is tested
By GJB 2704A-2006 spacecraft thermal control coating general specification test requirements documents.It is 2N/cm～4N/ with peel strength
The adhesive tape of cm, is close to coating zone line, and isolated edge is not less than 3mm.With having pulled adhesive tape one end, and make adhesive tape and surface into
90 °, slow (about 5mm/s) is pulled away from adhesive tape behind surface, without coming off in all line and stroke lattice, meets technical requirement.
Solar absorptance is tested
The LAMBDA950 type ultraviolet-visibles that this test is produced using U.S.'s PerkinElmer (Perkin-Elmer) company-
Near infrared spectrometer (UV/VIS/NIR Spectrophotometer) is measuring the sun of antistatic white thermal control coating
Absorptance.Its measurable wave-length coverage is 200nm to 2500nm, and the resolution ratio of instrument is 0.1nm, and bandwidth≤0.05nm is miscellaneous
Astigmatism≤0.00008%T, noise ＜ 0.0008A, photometer repeatability ＜ 0.0001A, baseline drift ＜ 0.0002A/h, baseline
It is straight：± 0.001A, good stability, baseline straightening degree are high, veiling glare is extremely low.Step-length is set to 5nm in experiment, and slit width is set to
4nm。
The coating solar absorptance of table 1 and emissivity
| Sample number into spectrum | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Solar absorptance | 0.197 | 0.211 | 0.225 |
| Hemispherical emissivity | 0.868 | 0.864 | 0.90 |
Hemispherical emissivity is tested
The TEMP 2000A emissivity measurements instrument developed using AZ TECHNOLOGY companies of the U.S. measures sample at room temperature
The hemispherical emissivity of 3～35 mu m wavebands, its certainty of measurement is ± 3%, and all band repeatability is ± 0.5%.
Specific insulation is tested
Using volumetric surface resistance determinator (Instrument Ltd. is tested in model GEST-121, Beijing hat test), by GB/
T1410-2006 solid insulating materials specific insulation and surface resistivity test method and QJ2220.2-92 coating electrical insulating properties
Can method of testing insulaion resistance, surface resistivity, the method for testing of specific insulation require, coating is carried out volume resistance and
Sheet resistance is tested, and calculates the specific insulation and surface resistivity of sample according to formula.
Thermal cycle test
Using temperature shock case (model ZTS010, Shanghai increases up to environmental test equipment Co., Ltd), by Q/RJ133.1-
The requirement of 2002S781 white paint thermal control coating specifications thermal cycling test, in normal atmospheric conditions it, -100 DEG C～+100 DEG C of Jing temperature
100 thermal cycles, experimental condition is as follows：
1) test temperature：High-end temperature is 100 DEG C, and low side temperature is set to -100 DEG C；
2) cycle-index：100 times；
3) temperature control error：High temperature ± 5 DEG C, low temperature ± 10 DEG C；
4) thermocirculator should have in the constant temperature zone of two different temperatures, sample 10s and is transferred to separately from a flat-temperature zone
One flat-temperature zone；
5) in high temperature, low-temperature end insulation 5min, it is ensured that test piece temperature is identical with environment temperature；
6) dehumidifying measure should be taken when testing, strip frosting is prevented；
Result of the test：The height warm-up cycle well-tended appearance of modified coating Jing -100～+100 DEG C 100 times, optical property is steady
Fixed, adhesive force well meets technical requirement.
Vacuum deflation performance test
Normative reference QJ1558 carries out vacuum deflation test, and experimental condition is as follows：
1) 125 DEG C ± 1 DEG C or 150 DEG C ± 1 DEG C of sample heating temperature；
2) collected volatile condensable materials temperature：25℃；
3) test pressure：Better than 7 × 10-3Pa；
4) temperature retention time：24h；
5) sample early stage is processed：23 DEG C ± 1 DEG C, humidity 45%RH ± 10%RH keeps 24h；
6) balance measurement sensitivity：1μg.
Material total mass loss (TML) in measuring and calculation vacuum, volatile matter (CVCM) can be coagulated；As shown in table 2.
Table 2
| Sample number into spectrum | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Total matter damages TML | 0.3603% | 0.3807% | 0.2505% |
| Volatilization CVCM can be coagulated | 0.0311% | 0.0433% | 0.0270% |
With reference to table 1,2 and experimental test result, the performance of the novel antistatic white thermal control coating of the present invention is as follows：
A) outward appearance：White, coating surface is uniform, bubble-free, flawless, without peeling, without coming off；
B) thickness：130 μm～200 μm；
C) solar absorptance：0.20～0.25；
D) hemispherical emissivity：0.85～0.91；
E) thermal cycling test：Coating meet -100～+100 DEG C of 100 high/low temperature thermal cycling tests after, without cracking, peel off,
Foaming and metachromatism, stable optical performance, adhesive force are good；
F) vacuum deflation performance：It is satisfied by TML ＜ 1%, CVCM ＜ 0.1%；
G) electric conductivity：ρv≤107Ω·m。
In sum, novel antistatic of the invention white thermal control coating has good thermal control performance (too ensureing coating
Positive absorptance, hemispherical emissivity) on the basis of, with preferable conductive coating performance, and coating can be with cold curing, it is to avoid
Impact during coating baking-curing to spacecraft product, while coating construction is simple, easy to learn, implements with stronger
Property, and it is good to undergo adhesive force after -100～+100 DEG C of 100 temperature shock tests.Above to the specific embodiment of the present invention
It is described.It is to be appreciated that the invention is not limited in above-mentioned particular implementation, those skilled in the art can be
Various modifications or modification are made in the range of claim, this has no effect on the flesh and blood of the present invention.
Claims (8)
1. the antistatic thermal control coating composition of a kind of double-component, it is characterised in that the coating composition include primer base and
Topcoat paint；The primer base includes that organic solvent a and mass ratio are 60～75:25～40 modified organic fluorine and
Modified oxidized zinc powder；The topcoat paint includes that organic solvent b and mass ratio are 65～75:25～35 polyfunctional group first
Base silicones and modified oxidized zinc powder；
The modified oxidized zinc powder is to be obtained with space particular configuration Zinc oxide powder is modified；The space particular configuration
One or more in four needle-likes, bar-shaped, wire, tubulose；
The modified oxidized zinc powder first passes around the process of silane coupler surface impregnation, 400 DEG C～700 DEG C of Jing after 50 DEG C of drying
High-temperature heat treatment is obtained.
2. the antistatic thermal control coating composition of double-component as claimed in claim 1, it is characterised in that the organic solvent a's
Consumption is 0.1～0.2 times of modified oxidized zinc powder and modified organic fluorine gross weight；The modified oxidized zinc powder accounts for bottom
50～70wt% of paint coating solids；The consumption of the organic solvent b is modified oxidized zinc powder and polyfunctional group methyl silicon
0.5～0.7 times of total resin weight；The modified oxidized zinc powder accounts for 65～75wt% of topcoat paint solid content.
3. the antistatic thermal control coating composition of double-component as claimed in claim 1, it is characterised in that described organic solvent a, b
It is respectively selected from one or more in acetone, butyl acetate, dimethylbenzene；Described organic solvent a, b may be the same or different.
4. the antistatic thermal control coating composition of double-component as claimed in claim 1, it is characterised in that the polyfunctional group methyl
Silicones is selected from methyl phenyl silicone resin, polyurethane-modified methyl silicon resin, cyanate modified methyl silicon resin, epoxide modified first
One kind in base silicones.
5. the preparation method of the antistatic thermal control coating composition of a kind of double-component as any one of Claims 1 to 4, its
It is characterised by, methods described comprises the steps：
A, primer base are prepared：In modified organic fluorine, modified oxidized zinc powder is added, mixed, added organic molten
Agent a, mixing, ultrasonic agitation is uniform；
B, topcoat paint are prepared：In polyfunctional group methyl silicon resin, modified oxidized zinc powder is added, mixed, addition has
Machine solvent b, mixing, ultrasonic agitation is uniform.
6. a kind of antistatic thermal control coating composition of double-component as any one of Claims 1 to 4 prepare it is antistatic
Purposes in thermal control coating, it is characterised in that the coating includes upwards prime coat and top coat layer from base material；The priming paint
Based on modified organic fluorine, modified oxidized zinc powder is filler to layer, and the modified zinc oxide in prime coat can be in prime coat
Middle formation vertical passage；The top coat layer based on polyfunctional group methyl silicon resin, modified oxidized zinc powder be filler, part
Modified zinc oxide is through prime coat and the interface of top coat layer.
7. purposes as claimed in claim 6, it is characterised in that the thickness of the prime coat is 50 μm～100 μm, the finish paint
The thickness of layer is 50 μm～100 μm.
8. purposes as claimed in claim 6, it is characterised in that prepare antistatic thermal control coating and specifically include：In matrix surface
Spray the primer base, 5～10h solidified at 22～55 DEG C, spray the topcoat paint, at 30～65 DEG C solidification 24～
48h, obtains final product the antistatic thermal control coating.
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| CN106590221A (en) * | 2016-12-07 | 2017-04-26 | 上海卫星装备研究所 | POSS-modified long life thermal control coating combination and preparation method thereof |
| CN114316440B (en) * | 2022-03-17 | 2022-07-12 | 宁波博利隆复合材料科技有限公司 | Antistatic polypropylene-based composite material, and preparation method and application thereof |
| CN115806752B (en) * | 2022-11-24 | 2024-03-22 | 北京星驰恒动科技发展有限公司 | Antistatic electric control coating and preparation method thereof |
| CN116851236A (en) * | 2023-07-26 | 2023-10-10 | 中国空气动力研究与发展中心高速空气动力研究所 | Preparation method of wide-temperature-range electrothermal-temperature-sensitive composite coating of high-temperature high-Reynolds number wind tunnel |
| CN117126560A (en) * | 2023-08-24 | 2023-11-28 | 上海卫星装备研究所 | Low-resistance inorganic thermal control coating and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4167602A (en) * | 1978-05-26 | 1979-09-11 | Monsanto Company | Electrographic recording material |
| CN1748877A (en) * | 2005-09-30 | 2006-03-22 | 大连理工大学 | A kind of preparation method of functional heat transfer surface |
| CN103666248A (en) * | 2013-12-03 | 2014-03-26 | 上海卫星装备研究所 | Novel antistatic white thermal control coating and preparation method thereof |
| CN103756379A (en) * | 2014-01-26 | 2014-04-30 | 黑龙江省科学院石油化学研究院 | White inorganic anti-static thermal control coating material |
-
2015
- 2015-03-20 CN CN201510125862.1A patent/CN104774510B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4167602A (en) * | 1978-05-26 | 1979-09-11 | Monsanto Company | Electrographic recording material |
| CN1748877A (en) * | 2005-09-30 | 2006-03-22 | 大连理工大学 | A kind of preparation method of functional heat transfer surface |
| CN103666248A (en) * | 2013-12-03 | 2014-03-26 | 上海卫星装备研究所 | Novel antistatic white thermal control coating and preparation method thereof |
| CN103756379A (en) * | 2014-01-26 | 2014-04-30 | 黑龙江省科学院石油化学研究院 | White inorganic anti-static thermal control coating material |
Non-Patent Citations (1)
| Title |
|---|
| "四针状氧化锌晶须在抗静电高分子材料中的应用"，;刑欣等;《安全与电磁兼容》;20080825(第4期);第40-43页，标题"2 四针状氧化锌晶须应用于制备抗静电高分子材料的特点"下的内容 * |
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