CN113956592A - Perfluoro polymer film, preparation method and application thereof, and aerospace equipment - Google Patents

Perfluoro polymer film, preparation method and application thereof, and aerospace equipment Download PDF

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CN113956592A
CN113956592A CN202111425632.9A CN202111425632A CN113956592A CN 113956592 A CN113956592 A CN 113956592A CN 202111425632 A CN202111425632 A CN 202111425632A CN 113956592 A CN113956592 A CN 113956592A
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perfluoropolymer
filler
membrane
slurry
film
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CN113956592B (en
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赵其斌
曹康丽
刘刚
宋效坤
王惠芬
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Shanghai Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

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Abstract

The invention discloses a perfluorinated polymer membrane, a preparation method and application thereof, and aerospace equipment, relates to the field of material modification, and aims to solve the technical problem that a radiation refrigeration membrane in the prior art cannot realize high reflectivity and high radiation resistance at the same time. The perfluoropolymer membrane of the embodiment of the invention is prepared by adopting the following formula: the formula at least comprises perfluoropolymer and filler which is non-absorbent in ultraviolet band, wherein the filler comprises Al2O3、Y2O3、ZrO2One or more of (a). The invention also discloses a preparation method of the perfluorinated polymer membrane and application of the perfluorinated polymer membrane in electrical products and aerospace equipment. The perfluoropolymer film provided by the invention has high reflectivity and radiation resistance, and can be used for equipment in a space environment.

Description

Perfluoro polymer film, preparation method and application thereof, and aerospace equipment
Technical Field
The disclosure relates to the technical field of material modification, in particular to a perfluoropolymer membrane, a preparation method and application thereof, and aerospace equipment.
Background
In the electronic equipment in the cosmos space, the heat generated by the operation of the electronic equipment per se is absorbed, and the cosmos space is a high-vacuum environment, so that the heat of the electronic equipment per se can be radiated only by depending on the radiation of a middle infrared band, and the temperature of the electronic equipment is reduced. The radiation refrigeration film is cooled by high reflectivity of a solar spectrum wave band and high emissivity of an infrared wave band, wherein the high reflectivity can prevent electronic equipment from absorbing solar energy, and the high emissivity can improve the capability of the electronic equipment for emitting energy to the space.
The existing radiation refrigeration film mainly has a secondary surface mirror and a porous polymer structure, the reflection property of a metal reflecting film in the secondary surface mirror reaches the limit, and the reflectivity of a common metal reflecting film is obviously reduced after the metal reflecting film is combined with an emitting layer; most of matrix materials of the porous polymer structure are low-radiation-resistance materials, can be instantaneously broken down in a space environment, and reduce reflectivity due to the fact that the appearance of the porous polymer structure is changed due to different atmospheric pressure and space pressure. The radiation refrigeration film in the prior art cannot realize high reflectivity and high radiation resistance at the same time.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a perfluoropolymer film, a preparation method and an application thereof, so that the prepared perfluoropolymer film has both high reflection performance in the solar spectrum band and high infrared emission performance, and has high radiation resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a perfluoropolymer membrane, wherein said perfluoropolymer membrane is made using the following formulation: the formula at least comprises perfluoropolymer and filler which is non-absorbent in ultraviolet band, wherein the filler comprises Al2O3、Y2O3、ZrO2One or more of (a).
According to at least one embodiment of the present disclosure, the filler volume fraction comprises 30% to 50% of the perfluoropolymer membrane.
According to at least one embodiment of the present disclosure, the perfluoropolymer comprises one or more of polytetrafluoroethylene, perfluoroalkoxy resin, and perfluoroethylene propylene copolymer in any ratio combination.
According to at least one embodiment of the present disclosure, the formulation comprises at least perfluoropolymer and ultraviolet band non-absorbing filler both in powder form;
the particle size of the filler is 0.5-1.5 mu m; and/or
The particle size of the perfluoropolymer is 0.5-1.5 μm.
According to at least one embodiment of the present disclosure, the thickness of the perfluoropolymer membrane is 200-400 μm.
Compared with the prior art, the perfluoropolymer film provided by the invention takes the perfluoropolymer and the filler which does not absorb in ultraviolet wave band as raw materials, and the prepared perfluoropolymer film can realize the performances of high reflectivity, high emissivity and high radiation resistance. The perfluoropolymer can be applied to space environment, and the perfluoropolymer can be used as a matrix to enable the perfluoropolymer film to become a high-radiation-resistance material. Meanwhile, the refractive index of the perfluoropolymer in the solar spectrum band (250-3000nm) is low, no absorption exists, and the perfluoropolymer film with high reflectivity can be obtained by adding the filler with high refractive index into the perfluoropolymer matrix. The embodiment of the invention uses Al2O3、Y2O3、ZrO2As fillers, these fillers are not only relatively high in refractive index but also low in cost, and since they are non-absorbing in the ultraviolet range (< 400nm), fillers such as TiO found in the prior art can be avoided2The filled film has the disadvantage of absorbing light in the ultraviolet band. When the perfluoropolymer film is illuminated, incident light is scattered when meeting filler particles in the matrix, but the embodiment of the invention can disperse enough particles in the matrix disorderly, so that the incident light is difficult to penetrate through the perfluoropolymer matrix under the action of multiple scattering to obtain high reflectivity.
Using Al of a given particle size2O3、Y2O3、ZrO2As fillers, illustratively, ofThe grain diameter is 0.5-1.5 μm. Illustratively, in embodiments of the present invention, the filler volume fraction comprises 30% to 50% of the perfluoropolymer membrane. The filler may be Al2O3、Y2O3、ZrO2May be Al2O3、Y2O3、ZrO2Various combinations of particles.
The types of perfluoropolymers described above are given below by way of example only and are not intended to be limiting.
The perfluorinated polymer is one or a combination of more of polytetrafluoroethylene, perfluoroalkoxy resin and a perfluorinated ethylene-propylene copolymer in any proportion. Wherein, polytetrafluoroethylene is known as polytetrafluoroethylene in English chemistry, abbreviated as PTFE and has the trade name of Teflon; perfluoroalkoxy resins (Perfluoroakoxy alkane, abbreviated as PFA), manufactured by Daikin Industries; perfluoroethylene propylene copolymer (abbreviated as FEP) was manufactured by Daikin Industries. The perfluoropolymer may be one of PTFE, PFA and FEP, or a mixture of several of PTFE, PFA and FEP, and the perfluoropolymer is in the form of powder and is more easily mixed with filler powder uniformly. In order to improve the volume fraction of the filler in the perfluoropolymer film and obtain good dispersion performance, the particle size range of the perfluoropolymer is controlled to be similar to or consistent with the particle size range of the filler particles, illustratively, the particle size range of the filler is 0.5-1.5 μm, and then the particle size range of the perfluoropolymer is controlled to be 0.5-1.5 μm, so that the filler and the perfluoropolymer powder in the same particle size range can be mixed uniformly more easily, and the volume fraction of the filler in the perfluoropolymer film can be increased more easily, so that more filler particles can be contained in the matrix, and good scattering effect can be obtained.
The function of the perfluoropolymer membrane of the present invention is shown in figure 1. The scattering efficiency is a key factor influencing the reflectivity of the radiation refrigeration film, and according to the Mie scattering theory, the scattering efficiency is higher when the refractive index contrast of the matrix and the filler is larger, while the refractive index of different perfluoropolymer matrixes is generally 1.35, so that the reflectivity is higher when the refractive index of the filler is higherThe higher the Al content, the higher the refractive index2O3、Y2O3、ZrO2As a filler, the perfluorinated polymer film can be ensured to have high reflectivity in the solar wave band (300-2Filled films have the disadvantage of absorbing light in the ultraviolet range.
According to kirchhoff's law of radiation (the refractive index is equal to the absorptivity in a steady state), when the extinction coefficient of a material in a certain waveband is 0, the material cannot absorb light in the waveband, and then the material cannot emit light in the waveband, so that the material with the extinction coefficient larger than 0 in an infrared waveband larger than 6 microns is selected as a perfluoropolymer matrix, and high emissivity in the infrared waveband can be realized, and the refractive index and the extinction coefficient of the perfluoropolymer FEP and zirconia are shown in FIG. 2.
In consideration of the influence of the thickness of the perfluoropolymer film on the reflectivity of the sunlight wave band, the thickness of the perfluoropolymer film of the embodiment of the invention is controlled to be 200-400 μm, and the perfluoropolymer film can be ensured to have higher reflectivity and lower areal density in the solar spectrum wave band in the thickness range, so that the perfluoropolymer film cannot cause larger weight gain to the coated device.
The invention also provides a preparation method of the perfluoropolymer membrane, which is used for preparing the perfluoropolymer membrane.
Uniformly mixing the perfluoropolymer at least included in the perfluoropolymer formula, filler powder without absorption in an ultraviolet band and water to obtain slurry;
and coating the slurry in a mold, drying and sintering to obtain the perfluoropolymer membrane.
Compared with the prior art, the preparation method of the perfluoropolymer membrane has the following advantages:
the preparation method of the perfluoropolymer membrane has the same advantages as those of the perfluoropolymer membrane, and is not described again.
According to at least one embodiment of the present disclosure, the perfluoropolymer included in the perfluoropolymer formulation and the filler powder having no absorption in the ultraviolet band are uniformly mixed with water to obtain a slurry, wherein the solid content of the slurry is 40% to 70%.
According to at least one embodiment of the present disclosure, the method of sintering includes air sintering after pressurizing the dried slurry.
The invention also provides the aerospace equipment, wherein the surface of the aerospace equipment is coated with the perfluorinated polymer membrane, or the surface of the aerospace equipment is coated with the perfluorinated polymer membrane prepared by the preparation method of the perfluorinated polymer membrane.
Compared with the prior art, the aerospace device has the following advantages:
the aerospace device has the same advantages as the perfluoropolymer membrane or the perfluoropolymer membrane prepared by the preparation method of the perfluoropolymer membrane, and the details are not repeated herein.
The invention also provides application of the perfluoropolymer film in electrical products, or application of the perfluoropolymer film prepared by the preparation method of the perfluoropolymer film in electrical products.
Compared with the prior art, the application of the perfluoropolymer film in the electrical product has the following advantages:
the advantages of the perfluoropolymer film in the electrical product are the same as those of the perfluoropolymer film or the perfluoropolymer film prepared by the preparation method of the perfluoropolymer film, and the advantages are not repeated herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.
Fig. 1 is a schematic diagram of a radiation refrigeration principle of a perfluoropolymer membrane provided in an embodiment of the present invention.
FIG. 2 shows the refractive index and extinction coefficient of the zirconia and FEP matrices provided by the examples of the present invention.
FIG. 3 is a graph of the reflectance and particle size of perfluoropolymer membranes containing different volume fractions of filler according to examples of the present invention.
FIG. 4 is a graph of the reflectivity of perfluoropolymer films of different thicknesses according to an embodiment of the present invention.
FIG. 5 is a comparison of the reflectance of inventive examples 1 and 2 and comparative examples 1 and 2.
Fig. 6 is a flow chart of a method for preparing a perfluoropolymer membrane according to an embodiment of the present invention.
Reference numerals: 1-a perfluoropolymer; 2-filler particles; 3-scattered light; 4-high infrared emission.
Detailed Description
The present disclosure will be described in further detail with reference to the drawings and embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present disclosure. It should be further noted that, for the convenience of description, only the portions relevant to the present disclosure are shown in the drawings.
It should be noted that the embodiments and features of the embodiments in the present disclosure may be combined with each other without conflict. The present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
The cosmic space is a high-vacuum and extremely-low-temperature environment, heat of electronic equipment can only be radiated by radiation, and radiation refrigeration is a typical passive thermal control mode and can be applied to electronic equipment running in the cosmic space to cool, such as artificial satellites and the like. Meanwhile, with the miniaturization and integration degree of commercial artificial satellites being higher and higher, the heat generated by electronic devices is higher and higher, and thus the performance requirements on the radiation refrigeration film are higher and higher.
The commonly used radiation refrigeration film mainly comprises a secondary surface mirror and a porous polymer structure, wherein the secondary surface mirror is a thermal control film obtained by combining a metal reflective bottom layer and a transparent film surface emitting layer with a certain thickness, but the reflection performance of the metal reflective film of the thermal control film can not be improved after reaching the limit, and the reflectivity of the commonly used metal reflective film can be obviously reduced after the metal reflective film is combined with the emitting layer. The complex hole structure in the porous polymer can form multiple scattering effect, and the average transmission free path of light is reduced, so that high reflectivity is obtained, but the porous structure is easy to pollute and the surface is easy to damage, and the matrix materials of the porous polymer are low-radiation-resistant materials and can be instantaneously punctured when being applied to a space environment; meanwhile, due to the porous structure of the porous polymer, the pressures in the atmosphere and in the space are different, so that the surface of the porous polymer is easily deformed, and the reflectivity is reduced.
In view of the above problems, an embodiment of the present invention provides a perfluoropolymer membrane, which is prepared according to the following formula: the formula at least comprises perfluoropolymer and filler which is non-absorbent in ultraviolet band, wherein the filler comprises Al2O3、Y2O3、ZrO2One or more of (a).
In the embodiment of the invention, in order to improve the reflectivity of the perfluoropolymer film, simultaneously not reduce the strength of the film and keep certain flexibility, the volume fraction of the filler is controlled to be about 30-50%. As shown in the schematic diagram of fig. 1, the radiation refrigeration of the perfluoropolymer film is that a large amount of filler is randomly dispersed in the perfluoropolymer matrix, which causes a large amount of continuous scattering of incident solar light, so that the incident light cannot penetrate through the perfluoropolymer film, and the perfluoropolymer film has high reflectivity. The perfluoropolymer and the filler in the embodiment of the invention are in the form of powder, so that the perfluoropolymer and the filler can be mixed more uniformly, and the volume fraction of the filler in the perfluoropolymer film can be improved.
For the perfluoropolymer, whether one or more of PTFE, PFA, and FEP, the refractive index is generally 1.35, and in order to make the perfluoropolymer film more efficient in scattering and further improve the reflectivity, a larger difference in refractive index between the filler and the matrix is required. Therefore, under the condition that the refractive index of the perfluoropolymer is basically determined, the filler with the highest refractive index is used as far as possible, and the filler is ensured to have no absorption in the ultraviolet band of sunlight, and the filler used in the embodiment of the invention is Al2O3、Y2O3、ZrO2As can be seen in FIG. 2The refractive index difference between the zirconium oxide and the FEP matrix is obvious, and the reflectivity of the perfluoropolymer film formed by the zirconium oxide and the FEP matrix is correspondingly improved in a wider wavelength range of sunlight.
Different filler particle sizes have different scattering coefficients for different bands of light, taking into account the effect of filler particle size on scattering efficiency. In order to obtain high reflectivity in the whole solar wave band (250-2500nm), the particle size of the filler is controlled to be 0.5-1.5 μm, and optionally 1.3 μm. As shown in FIG. 3, the reflectivity between the zirconia filler and the FEP matrix increases with the increase of the volume fraction of the filler, and the optimal filler particle size corresponding to the maximum reflectivity also increases with the volume fraction, and the optimal particle size increases from about 500nm to 1.3 μm at the volume fraction of 5% to 60%, illustratively, the filler particle size of the invention is controlled to be 0.5-1.5 μm, and the reflectivity of the final prepared perfluoropolymer film is obviously reduced beyond or below the particle size range.
As shown in fig. 4, when the volume fraction of the filler is 30% and the particle size is 1 μm, the reflectance of the perfluoropolymer films with different thicknesses increases continuously with the increase of the thickness of the perfluoropolymer film, but the increasing trend gradually slows down, and for example, the thickness of the perfluoropolymer film of the embodiment of the present invention is 200-400 μm, within this thickness range, the reflectance of the perfluoropolymer film can be ensured to be high, and the areal density cannot be too large, which leads to an excessive weight increase of the coated device, and especially in the space environment, the cost can be greatly increased. Meanwhile, the higher thickness of the perfluoropolymer film may cause the flexibility of the perfluoropolymer film to be reduced, so that cracks are generated, and the temperature reduction effect of the perfluoropolymer film is failed. Optionally, the perfluoropolymer membrane is 300 μm thick, and further optionally, 350 μm thick.
The embodiment of the invention provides a preparation method of a perfluoropolymer membrane, which is prepared by the following steps: as shown in figure 6 of the drawings,
step S100: the perfluoropolymer and filler powder which is not absorbed in ultraviolet wave band and is at least contained in the perfluoropolymer formula are uniformly mixed with water to obtain slurry;
step S200: coating the slurry in a mold, drying and sintering to obtain a perfluoropolymer membrane;
specifically, in step S100, the filler powder and the matrix powder are weighed according to the proportion of the filler accounting for 30% -50% of the total volume, and the filler powder and the matrix powder are mixed with water to prepare the slurry with the solid content of 40-70%. The filler powder is Al2O3、Y2O3、ZrO2The matrix powder is one of PFA, PTFE and FEP; uniformly mixing the slurry by using a ball mill or a high-speed stirrer at the rotation speed of 1000-2000 rpm;
in the step S200, the uniformly mixed coating is coated in a mold, the thickness is controlled to be 200-400 μm, and drying is carried out at 70-90 ℃; and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture for 0.5 to 1 hour in air at the temperature of 280-320 ℃, and obtaining the perfluoropolymer radiation refrigeration film after sintering and cooling.
Illustratively, embodiments of the present invention utilize pressurized post-air sintering to produce perfluoropolymer films that have a higher volume fraction of filler by using thermal energy and stress to promote the bonding of perfluoropolymer powder particles and filler powder particles and densification of the material. The perfluoropolymer membrane prepared by air sintering after pressurization has high flatness and high overall mechanical property, and is not easy to damage when being scratched. Compared with the porous polymer structure in the prior art, the shape of the porous polymer film is not easy to change due to air pressure change, and the high reflectivity of the perfluoropolymer film is not influenced.
The invention also provides the aerospace equipment, wherein the surface of the aerospace equipment is coated with the perfluorinated polymer membrane, or the surface of the aerospace equipment is coated with the perfluorinated polymer membrane prepared by the preparation method of the perfluorinated polymer membrane.
Compared with the prior art, the aerospace device has the following advantages:
the aerospace device has the same advantages as the perfluoropolymer membrane or the perfluoropolymer membrane prepared by the preparation method of the perfluoropolymer membrane, and the details are not repeated herein.
The invention also provides application of the perfluoropolymer film in electrical products, or application of the perfluoropolymer film prepared by the preparation method of the perfluoropolymer film in electrical products. For example, the electrical product can be an electrical casing or a digital product casing used outdoors, and can also be a casing part of various devices or various electronic devices exposed in a space environment on the aerospace equipment.
Compared with the prior art, the application of the perfluoropolymer film in the electrical product has the following advantages:
the application of the perfluoropolymer membrane in the electrical product has the same advantages as the perfluoropolymer membrane or the perfluoropolymer membrane prepared by the preparation method of the perfluoropolymer membrane, and the advantages are not repeated herein.
Illustratively, the formulations used in the examples of the present invention are all commercially available products.
In the following examples, the reflectance was measured by an ultraviolet-visible-near infrared spectrophotometer Lambda950 using a PTFE integrating sphere;
the infrared emissivity is measured by an infrared spectrometer Nicolet6700 by using a gold integrating sphere;
several examples of perfluoropolymer membranes are given below and representative perfluoropolymer membranes are selected for material property analysis.
Example one
Firstly, ZrO is weighed according to the proportion of the volume fraction of the filler accounting for 30 percent of the total volume of the perfluoropolymer film2Filler powder, and FEP matrix powder, wherein ZrO2The average particle diameter of the filler powder was about 1 μm, the FEP matrix powder was about 1.5 μm, and the ZrO powder was weighed2Adding water into filler powder and FEP base powder to prepare slurry with solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
Example two
Firstly, weighing Y according to the volume fraction of the filler accounting for 30 percent of the total volume of the perfluoropolymer membrane2O3Filler powder, and FEP base powder, wherein Y2O3The average particle diameter of the filler powder was about 1 μm, the FEP base powder was about 1.5 μm, and Y was weighed2O3Adding water into filler powder and FEP base powder to prepare slurry with solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
EXAMPLE III
Firstly, weighing Al according to the volume fraction of the filler accounting for 30 percent of the total volume of the perfluoropolymer film2O3Filler powder, and FEP base powder, wherein Al2O3Filler powder having an average particle size of about 1 μm and FEP base powder of about 1.5 μm, A l powder to be weighed2O3Adding water into filler powder and FEP base powder to prepare slurry with solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
Example four
Firstly, ZrO is weighed according to the proportion that the volume fraction of the filler accounts for 40 percent of the total volume of the perfluorinated polymer membrane2Filler powderPowder, and PFA matrix powder, wherein ZrO2Filler powder having an average particle diameter of about 1 μm and PFA matrix powder of about 1.5 μm, and ZrO to be weighed2Adding water into filler powder and FEP base powder to prepare slurry with solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
EXAMPLE five
Firstly, ZrO is weighed according to the proportion that the volume fraction of the filler accounts for 40 percent of the total volume of the perfluorinated polymer membrane2Filler powder, and PTFE matrix powder, wherein ZrO2The average particle diameter of the filler powder was about 1 μm, the average particle diameter of the PTFE matrix powder was about 1.5. mu.m, and the ZrO powder was weighed2Adding water into filler powder and FEP base powder to prepare slurry with solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
EXAMPLE six
Firstly, weighing Y according to the volume fraction of the filler accounting for 50 percent of the total volume of the perfluoropolymer membrane2O3Filler powder, and PFA base powder, wherein Y2O3Filler powder having an average particle diameter of about 1 μm and PFA base powder of about 1.5 μm, and Y to be weighed2O3Adding water into filler powder and FEP base powder to prepare slurry with solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
EXAMPLE seven
Firstly, weighing Y according to the volume fraction of the filler accounting for 50 percent of the total volume of the perfluoropolymer membrane2O3Filler powder, and PTFE base powder, wherein Y2O3The average particle diameter of the filler powder was about 1 μm, the PTFE base powder was about 1.5. mu.m, and Y was weighed2O3Adding water into filler powder and FEP base powder to prepare slurry with solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
Example eight
Firstly, weighing Al according to the volume fraction of the filler accounting for 30 percent of the total volume of the perfluoropolymer film2O3Filler powder, and PFA base powder, wherein Al2O3Filler powder having an average particle diameter of about 1 μm and PFA base powder of about 1.5 μm, and Al to be weighed2O3Adding water into filler powder and FEP base powder to prepare slurry with solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
Example nine
Firstly, weighing Al according to the volume fraction of the filler accounting for 30 percent of the total volume of the perfluoropolymer film2O3Filler powder, and PTFE base powder, wherein Al2O3Filler powder having an average particle diameter of about 1 μm and PTFE matrix powder having an average particle diameter of about 1.5 μm, and Al to be weighed2O3Adding water into filler powder and FEP base powder to prepare slurry with solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
Comparative example 1
Firstly, ZrO is weighed according to the proportion of the volume fraction of the filler accounting for 30 percent of the total volume of the perfluoropolymer film2Filler powder, and FEP matrix powder, wherein ZrO2The average particle diameter of the filler powder was about 100nm, the FEP matrix powder was about 1.5 μm, and the ZrO was weighed2Adding water into filler powder and FEP base powder to prepare slurry with solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
Comparative example No. two
Firstly, SiO is weighed according to the volume fraction of the filler accounting for 30 percent of the total volume of the perfluoropolymer film2Filler powder, and FEP base powder, wherein SiO2The average particle diameter of the filler powder was about 1 μm, the FEP base powder was about 1.5 μm, and SiO was weighed2Filler materialAdding water into the powder and the FEP base powder to prepare slurry with the solid content of 60%;
mixing the slurry at 2000rpm by using a high-speed stirrer;
coating the uniformly mixed slurry in a mold, controlling the thickness of the slurry to be 300 mu m, and drying at 80 ℃;
and after the slurry is dried, placing the mold in a muffle furnace, pressurizing the mixture, sintering the mixture in air for 1 hour at the temperature of 300 ℃, and cooling the sintered mixture to obtain the perfluoropolymer film.
TABLE 1 perfluoropolymer membranes prepared in examples and comparative examples
Figure BDA0003378284400000122
As can be seen from table 1, in the above embodiments one to nine, the infrared emissivity in the weighted average reflectivity (solar band) and the atmospheric window band is high. The seventh and fourth effects are most preferred. Compared with the filler with the diameter of 100nm adopted in the first comparative example, the filler with the diameter of micron order adopted in the first to ninth examples has the advantages that although the infrared emissivity is similar, the weighted average reflectivity is only 78.0 percent, and therefore, when the particle size of the filler is high in volume fraction, the corresponding particle size is increased, otherwise, the reflectivity of the perfluoropolymer film is seriously influenced. Comparative example II Using SiO2The infrared emissivity of the filler is not reduced compared to the fillers used in examples one to nine, but the weighted average reflectivity is also significantly reduced, which is comparable to that of SiO2The refractive index of the particles is low, so that SiO2The refractive index contrast between the particulate filler and the perfluoropolymer is small, which in turn affects the reflectivity of the perfluoropolymer film.
In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present application, "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.

Claims (10)

1. A perfluoropolymer membrane, wherein said perfluoropolymer membrane is made using the following formulation: the formula at least comprises perfluoropolymer and filler which is non-absorbent in ultraviolet band, wherein the filler comprises Al2O3、Y2O3、ZrO2One or more of (a).
2. The perfluoropolymer membrane according to claim 1, wherein said filler volume fraction comprises 30% to 50% of said perfluoropolymer membrane.
3. The perfluoropolymer membrane according to claim 1, wherein said perfluoropolymer comprises one or more of polytetrafluoroethylene, perfluoroalkoxy resin, and perfluoroethylene propylene copolymer in any ratio combination.
4. The perfluoropolymer membrane according to claim 1,
the perfluoropolymer and the ultraviolet band non-absorption filler which are at least contained in the formula are both powder;
the particle size of the filler is 0.5-1.5 mu m; and/or
The particle size of the perfluoropolymer is 0.5-1.5 μm.
5. The perfluoropolymer membrane according to claim 1, wherein said perfluoropolymer membrane has a thickness of 200-400 μm.
6. A method for preparing the perfluoropolymer film according to any one of claims 1 to 5, wherein a slurry is obtained by uniformly mixing the perfluoropolymer contained in the formulation of the perfluoropolymer according to any one of claims 1 to 5, a filler powder having no absorption in the ultraviolet band, and water;
and coating the slurry in a mold, drying and sintering to obtain the perfluoropolymer membrane.
7. The method for preparing a perfluoropolymer film according to claim 6, wherein the slurry is obtained by uniformly mixing the perfluoropolymer contained in the perfluoropolymer formulation, the filler powder having no absorption in the ultraviolet band, and water, wherein the solid content of the slurry is 40% to 70%.
8. The method of making a perfluoropolymer membrane according to claim 7, wherein said sintering comprises air sintering after pressurizing said dried slurry.
9. Use of a perfluoropolymer membrane according to any one of claims 1 to 5 or of a process for the preparation of a perfluoropolymer membrane according to any one of claims 6 to 8 in an electrical product.
10. An aerospace device, wherein the surface of the aerospace device is coated with the perfluoropolymer film according to any one of claims 1 to 5, or wherein the surface of the aerospace device is coated with the perfluoropolymer film obtained by the method for producing a perfluoropolymer film according to any one of claims 6 to 8.
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