CN113604083B - Solar spectrum total reflection type antistatic thermal control coating and preparation method thereof - Google Patents
Solar spectrum total reflection type antistatic thermal control coating and preparation method thereof Download PDFInfo
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- CN113604083B CN113604083B CN202110765802.1A CN202110765802A CN113604083B CN 113604083 B CN113604083 B CN 113604083B CN 202110765802 A CN202110765802 A CN 202110765802A CN 113604083 B CN113604083 B CN 113604083B
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
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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
- C09D5/004—Reflecting paints; Signal paints
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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
- C09D5/24—Electrically-conducting paints
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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
- 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
Abstract
The invention discloses a solar spectrum total reflection type antistatic thermal control coating and a preparation method thereof, belonging to the field of new materials; the thermal control coating material mainly comprises the ultra-wide forbidden band oxide pigment, the inorganic water glass binder and the functional auxiliary agent, the coating of the ultra-wide forbidden band oxide pigment has excellent radiation stability of protective particles, and the prepared coating is water-based environment-friendly paint, can be sprayed, brushed or scraped in air and has the characteristic of room temperature curing. The solar absorption ratio of the coating is as low as 0.08 to 0.09, the emissivity is 0.88 to 0.92, and the surface resistivity is 10 5 ~10 7 Omega m, can be applied to thermal control systems of various spacecrafts which are in service under the synergistic effect of complex and harsh environments such as space high solar heat flow, strong particle radiation, ionized layer charge and discharge, atomic oxygen environment and the like.
Description
Technical Field
The invention relates to a solar spectrum total reflection type antistatic thermal control coating and a preparation method thereof, belonging to the field of new materials.
Background
The thermal control coating is an important component of a thermal control subsystem of the spacecraft, is coated on the outer surface of the spacecraft and has the solar absorption ratio (a) through the self thermophysical characteristic s ) And hemispherical emissivity (e) H ) To regulate the surface heat balance temperature (T) of the spacecraft s ) I.e. T s ∝(a s /e H ) 1/4 Thereby achieving the purpose of heat control. The ZnO-based thermal control coating is widely applied to thermal control systems of various types of spacecrafts at home and abroad due to the low absorption and high emission performance and good process characteristics of the ZnO-based thermal control coating. Such as domestic S781 white paint, KSZ white paint, ACR white paint, and AZ Technology Z-93 white paint in the united states, all pigmented with ZnO, correspond to solar absorptance of about 0.20, 0.15, 0.23 and 0.15, respectively. However, the solar spectrum reflectivity of the ZnO coating is low, only about 85%, and there is almost no reflection effect on high-energy ultraviolet portions (200 to 380 nm) occupying about 6.6% of the total solar radiation energy in the solar radiation spectrum. On the one hand, the thermal protection task of the near-day detector which is in service under high-strength solar irradiation environments such as Venus, mercury and sun and the like which are developed rapidly is difficult to meet; on the other hand, the active photocatalytic activity and strong absorption of ultraviolet rays of semiconductor pigments such as ZnO in the coating layer can cause particle irradiation and ultraviolet raysUnder the action of comprehensive environments such as air cooling heat exchange circulation and the like, the color center absorption of the coating in a visible light area and the near infrared absorption of free electrons are induced, so that the solar heat flow reflection capability of the coating is rapidly reduced, and the aging degradation of a coating binder and the optical pollution effect are caused. In addition, the common ZnO thermal control coating does not have antistatic capability, and the surface resistivity of the coating can reach 10 12 Omega m. This will result in the deposition of high energy incident electrons on the surface and even inside the coating, resulting in charge and discharge effects due to the potential difference.
Researchers at home and abroad have proposed a series of modification technologies in recent years to improve the solar heat flow reflection capability and antistatic performance of the thermal control coating, however, both of the technologies have a dilemma, and the thermal control coating with both solar spectrum high reflection and low resistivity cannot be obtained at the same time. For example, the patent (application No. CN109439186A is an illumination fully-adaptive spacecraft thermal control coating) adopts SiO 2 Hollow microspheres, baSO 4 The low-absorption thermal control white paint is prepared for the pigment, but the surface resistivity of the coating is far larger than that of the antistatic thermal control coating in GJB 2502 spacecraft thermal control coating test method<10 9 And omega m. In the patent (with the authorization number CN103666248B, novel antistatic white thermal control coating and a preparation method thereof), volume resistivity is prepared by adding metal micro-sheets into a ZnO coating<10 7 Omega m, but the solar absorption ratio of the coating is as high as 0.24 to 0.29.
Therefore, the thermal control coating with solar spectrum total reflection and antistatic property is researched and prepared, and the thermophysical property and the application range of the rail environment of the conventional thermal control coating are greatly improved, so that the thermal control precision and the service reliability of the spacecraft are improved.
Disclosure of Invention
The invention aims to overcome the defects of low solar heat flow reflectivity, large surface potential difference, poor radiation stability of a space environment and the like of the current active thermal control white paint, and provides a solar spectrum total reflection type antistatic thermal control white paint and a preparation method thereof based on spectrum design and an energy band regulation principle so as to obtain a thermal control coating with high solar heat flow reflectivity and antistatic property at the same time, and the solar spectrum total reflection type antistatic thermal control white paint can be applied to the fields of surface thermal protection, industrial passive radiation refrigeration and the like of various spacecrafts in service in an extreme space environment.
The invention is realized by the following steps:
the solar spectrum total reflection type antistatic thermal control coating is characterized by being prepared from the following raw materials in percentage by mass: 30% -60% of ultra-wide forbidden band oxide pigment; 30% -50% of water glass liquid binder; 2% -10% of a functional additive; the balance of distilled water. The coating of the ultra-wide forbidden band oxide pigment is suitable for having excellent radiation stability of protective particles, and the prepared coating is water-based environment-friendly paint which can be sprayed, brushed or scraped in air and has the characteristic of curing at room temperature.
Furthermore, the super wide forbidden band oxide pigment is MgO and Ga 2 O 3 One or a mixture of both.
Further, the liquid sodium silicate binder is an inorganic liquid sodium silicate binder, and the inorganic liquid sodium silicate binder is potassium sodium silicate or lithium sodium silicate.
Further, the functional auxiliary agent comprises one or a mixture of more of aluminum phosphate, calcium fluoride and KH560 silane coupling agent.
The invention discloses a preparation method of a solar spectrum total reflection type antistatic thermal control coating, which is characterized by comprising the following steps:
step one, taking 30% -60% of ultra-wide forbidden band oxide powder pigment, and carrying out ball milling treatment on the pigment; the ultra-wide bandgap oxide powder pigment is MgO and Ga 2 O 3 One or a mixture of two of them;
weighing 30-50% of a water glass liquid binder, wherein the water glass liquid binder is potassium water glass or lithium water glass, adding a proper amount of distilled water into the potassium water glass or the lithium water glass for dilution, and forming a silica network structure through hydrolysis so as to form a coating;
step three, uniformly pouring the oxide powder in the step one into the water glass liquid binder solution in the step two, adding a proper amount of distilled water, stirring and dispersing, controlling the rotating speed at 500-2000 r/min, and stirring for 4 hours;
step four, weighing 2-10% of functional auxiliary agent, adding the functional auxiliary agent into the solution obtained in the step three, and fully dispersing and mixing the functional auxiliary agent; the auxiliary agent is one or a mixture of more of aluminum phosphate, calcium fluoride and KH560 silane coupling agent;
and step five, sieving the obtained coating solution by a 200-mesh sieve, preparing a thermal control coating by air spraying, manual brush coating or blade coating, and drying and curing at 80 ℃ for 4 hours or standing for drying and curing at room temperature.
Further, in the step one, the particle size distribution of the pigment is controlled to be 100 to 800nm through ball milling.
Further, the sodium silicate binder is prepared by adding analytically pure alkali metal hydroxide and silicon micropowder powder into distilled water according to the molar ratio of 2.5 to 5, mixing and dispersing, and placing into a hydrothermal reaction kettle to stand for 100 hours at 180 ℃.
Further, the alkali metal hydroxide is lithium hydroxide or sodium hydroxide.
The beneficial effects of the invention and the prior art are as follows:
the invention not only realizes the total reflection of solar radiation heat flow occupying more than 99 percent of solar radiation energy through spectral design and energy band regulation, but also obtains the antistatic performance of the coating based on the semiconductor state characteristics of the inorganic oxide semiconductor and the ionic compound binder.
The coating has extremely high solar spectrum total spectrum reflection capability, low surface resistivity and excellent irradiation stability in space environment, the solar absorption ratio of the coating is as low as 0.08 to 0.09, the emissivity is 0.88 to 0.92, and the surface resistivity is 10 5 ~10 7 Omega m. The device can be widely applied to the fields of spacecraft outer surface heat balance control with harsh temperature control precision and energy conservation and emission reduction such as buildings, large oil gas tanks, industrial pipelines, weapon and war chariot radiation refrigeration and the like, and is particularly suitable for service requirements of stratospheric detectors and near-earth orbit spacecrafts which are in service in environments such as space strong illumination, radiation, atomic oxygen and the like. The coating has the advantages of simple preparation process, water-based environmental protection, short period, low cost and easy large-scale production.
Drawings
FIG. 1 is an SEM photograph of the surface morphology of a thermal control coating prepared in example 1 of a solar spectrum total reflection type antistatic thermal control coating and a preparation method thereof according to the present invention;
FIG. 2 is a spectral reflection curve of a coating sample prepared in example 1 of a solar spectrum total reflection type antistatic thermal control coating and a preparation method thereof in a range of 200nm to 2500 nm.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention more clear, the present invention is further described in detail by referring to examples below. It should be noted that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) Weighing 40% of ultra-wide forbidden band Ga according to mass percentage 2 O 3 Powder pigment, wherein the particle size distribution of the pigment is controlled to be 100 to 800nm through ball milling; the Ga is 2 O 3 The powder pigment is analytically pure and has the purity above.
(2) 40% of potassium water glass binder is weighed and diluted by adding 10% of distilled water. The preparation method of the potassium water glass binder comprises the following steps: adding 5 percent distilled water into analytically pure potassium hydroxide and silicon micropowder powder according to the molar ratio of 3, mixing and dispersing, and placing the mixture into a hydrothermal reaction kettle to stand for 100 hours at 180 ℃.
(3) Uniformly pouring the gallium oxide powder pigment ground and dried in the step (1) into a potassium silicate binder solution, adding 5% of distilled water, stirring and dispersing, controlling the rotating speed at 1000r/min, and stirring for 4 hours;
(4) And (3) weighing 5% of functional auxiliary agent, adding the functional auxiliary agent into the solution in the step (3), and fully dispersing and mixing. The auxiliary agent is aluminum phosphate.
(5) The obtained coating solution is sieved by a 200-mesh sieve, and a thermal control coating is prepared by air spraying and is dried and cured for 4 hours at 80 degrees. The coating prepared in this example was examined, and fig. 1 is a photograph of the surface topography of the thermal control coating, it can be seen that the pigment was completely coated with the binder, and the surface topography of the coating was uniform and flat. FIG. 2 is a diagram of solar spectrum total reflection antistatic thermal controlThe spectral reflectance of the coating, the lower curve in the figure, is the standard solar irradiance spectrum outside the earth's atmosphere. It can be seen that the coating has a solar spectral reflectivity as high as 95% within a wave band of 200 to 1200nm, in which solar radiation energy is concentrated, and the coating prepared by the method has excellent solar heat flow reflection performance. The thickness of the prepared coating is 200 mu m, the solar absorption ratio of the coating is 0.088, the emissivity is 0.086, and the surface resistivity of the coating is 10 7 Omega m, after electron irradiation fluence of 10 years of simulated GEO orbit, a s About a degradation amount of less than 0.09.
Example 2
(1) Weighing 30 percent of ultra-wide forbidden band Ga according to mass percentage 2 O 3 Powder pigment, wherein the particle size distribution of the pigment is controlled to be 100 to 800nm through ball milling; the Ga is 2 O 3 The powder pigment is analytically pure and has the purity above.
(2) 50% of lithium water glass binder is weighed and diluted by adding 8% of distilled water. The lithium water glass adhesive is prepared by adding analytically pure lithium hydroxide and silicon micropowder powder into 4 percent distilled water according to the molar ratio of 2.5, mixing and dispersing, and placing into a hydrothermal reaction kettle to stand for 100 hours at 180 ℃.
(3) Uniformly pouring the gallium oxide powder pigment ground and dried in the step (1) into a lithium silicate binder solution, adding 4% distilled water, stirring and dispersing, controlling the rotating speed at 1000r/min, and stirring for 4 hours;
(4) And (4) weighing 8% of functional auxiliary agent, adding the functional auxiliary agent into the solution in the step (3), and fully dispersing and mixing. The auxiliary agent is KH560.
(5) The obtained coating solution is sieved by a 200-mesh sieve, and a thermal control coating is prepared by air spraying and is dried and cured for 4 hours at 80 degrees. The thickness of the prepared coating is 180 mu m, the solar absorption ratio of the coating is 0.080, the emissivity is 0.088, and the surface resistivity of the coating is 10 5 Ωm。
Example 3
(1) Weighing 50% of ultra-wide forbidden band MgO powder pigment by mass percentage, and controlling the particle size distribution of the pigment within 100-800nm by ball milling; the MgO powder pigment has the purity of analytical grade and above.
(2) 40 percent of potassium silicate binder is weighed and diluted by adding 2 percent of distilled water. The potassium silicate binder is prepared by adding analytically pure potassium hydroxide and silicon micropowder powder into 2 percent of distilled water according to the molar ratio of 4, mixing and dispersing, and placing into a hydrothermal reaction kettle to stand for 100 hours at 180 ℃.
(3) Uniformly pouring the MgO powder pigment ground and dried in the step (1) into a potassium water glass binder solution, adding 3% of distilled water, stirring and dispersing, controlling the rotating speed at 800r/min, and stirring for 4 hours;
(4) And (3) weighing 5% of functional auxiliary agent, adding the functional auxiliary agent into the solution in the step (3), and fully dispersing and mixing. The auxiliary agent is 2% of aluminum phosphate and 3% of calcium fluoride.
(5) The resulting coating solution was sieved through a 200 mesh sieve, and a thermal control coating was prepared by manual brush coating, followed by room temperature standing and curing. The thickness of the prepared coating is 350 mu m, the solar absorption ratio of the coating is 0.088, the emissivity is 0.92, and the surface resistivity of the coating is 10 7 Ωm。
Example 4
(1) Weighing 60% of an ultra wide bandgap MgO powder pigment according to mass percentage, and controlling the particle size distribution of the pigment to be 100 to 800nm through ball milling; the MgO powder pigment has the purity of analytical grade and above.
(2) 30 percent of potassium silicate binder is weighed and diluted by adding 6 percent of distilled water. The potash water glass adhesive is prepared through adding analytically pure potassium hydroxide and silicon micropowder powder into 3% distilled water according to the molar ratio of 2.5, mixing and dispersing, and placing in a hydrothermal reaction kettle to stand for 100 hours at 180 ℃.
(3) Uniformly pouring the MgO powder pigment ground and dried in the step (1) into a potassium water glass binder solution, adding 2% of distilled water, stirring and dispersing, controlling the rotating speed at 800r/min, and stirring for 4 hours;
(4) And (4) weighing 2% of functional auxiliary agent, adding the functional auxiliary agent into the solution in the step (3), and fully dispersing and mixing. The auxiliary agent is 2% of aluminum phosphate and 3% of calcium fluoride.
(5) The resulting coating solution was sieved through a 200 mesh sieve, and a thermal control coating was prepared by manual brush coating and cured by standing at room temperature.
Example 5
(1) Weighing 40% of ultra-wide forbidden band Ga according to mass percentage 2 O 3 Powder pigment, wherein the particle size distribution of the pigment is controlled to be 100 to 800nm through ball milling; the Ga is 2 O 3 The powder pigment has analytical purity and above.
(2) 40% of potassium water glass binder is weighed and diluted by adding 8% of distilled water. The potassium silicate binder is prepared by adding analytically pure potassium hydroxide and silicon micropowder powder into 4 percent of distilled water according to the molar ratio of 5, mixing and dispersing, and placing into a hydrothermal reaction kettle to stand for 100 hours at 180 ℃.
(3) Uniformly pouring the gallium oxide powder pigment ground and dried in the step (1) into a potassium silicate binder solution, adding 2% distilled water, stirring and dispersing, controlling the rotating speed at 1000r/min, and stirring for 4 hours;
(4) And (3) weighing 10% of functional auxiliary agent, adding the functional auxiliary agent into the solution in the step (3), and fully dispersing and mixing. The auxiliary agent is aluminum phosphate.
(5) The obtained coating solution is sieved by a 200-mesh sieve, and a thermal control coating is prepared by air spraying and is dried and cured for 4 hours at 80 degrees.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications can be made without departing from the principle of the present invention, and these modifications should also be regarded as the protection scope of the present invention.
Claims (2)
1. The solar spectrum total reflection type antistatic thermal control coating is characterized by being prepared from the following raw materials in percentage by mass:
30% -60% of ultra-wide forbidden band oxide pigment;
30% -50% of water glass liquid binder;
2% -10% of functional auxiliary agent;
the balance of distilled water;
the ultra-wide forbidden band oxide pigment is MgO and Ga 2 O 3 One or two ofMixing; the sodium silicate liquid binder is an inorganic liquid sodium silicate binder which is potassium sodium silicate or lithium sodium silicate;
the preparation method of the thermal control coating specifically comprises the following steps:
step one, taking 30% -60% of ultra-wide forbidden band oxide pigment, and carrying out ball milling treatment on the pigment;
weighing 30-50% of a water glass liquid binder, wherein the water glass liquid binder is potassium water glass or lithium water glass, adding a proper amount of distilled water into the potassium water glass or the lithium water glass for dilution, and forming a silica network structure through hydrolysis so as to form a coating;
step three, uniformly pouring the oxide powder in the step one into the water glass liquid binder solution in the step two, adding a proper amount of distilled water, stirring and dispersing, controlling the rotating speed at 500-2000 r/min, and stirring for 4 hours;
step four, weighing 2-10% of functional auxiliary agent, adding the functional auxiliary agent into the solution obtained in the step three, and fully dispersing and mixing the functional auxiliary agent; the auxiliary agent is one or a mixture of more of aluminum phosphate, calcium fluoride and KH560 silane coupling agent;
and step five, sieving the obtained coating solution by a 200-mesh sieve, preparing a thermal control coating by air spraying, manual brush coating or blade coating, and drying and curing at 80 ℃ for 4 hours or standing and drying and curing at room temperature.
2. The solar spectrum total reflection type antistatic thermal control coating according to claim 1, wherein in the first step, the pigment particle size distribution is controlled to be between 100 and 800nm by ball milling.
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