CN110358415B - Aviation transparent part conducting film free of bottom coating and protective coating and preparation method - Google Patents

Aviation transparent part conducting film free of bottom coating and protective coating and preparation method Download PDF

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CN110358415B
CN110358415B CN201910717571.XA CN201910717571A CN110358415B CN 110358415 B CN110358415 B CN 110358415B CN 201910717571 A CN201910717571 A CN 201910717571A CN 110358415 B CN110358415 B CN 110358415B
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肖慧萍
曹家庆
周建萍
王云英
钟卫
王刚
翁闻升
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Nanchang Hangkong University
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Abstract

The aviation transparent part conducting film free of the base coat and the protective coat is an organic/inorganic nano composite film with a three-dimensional network structure, wherein graphene quantum dots GQDs are uniformly dispersed in a crosslinked conjugated polymer cPOOH containing hydroxyl side chains. The preparation method specifically comprises the following steps: synthesizing a transparent conjugated polymer cPFH (perfluoroethylene-perfluoroethylene) containing hydroxyl side chains and capable of being crosslinked by ultraviolet light; blending the graphene quantum dots and the polymer cPFH to form a composite solution; and (3) spin-coating the composite solution on the surface of the organic glass, and curing by ultraviolet irradiation to form the three-dimensional mesh transparent conductive film. The conductive film has the synergistic functions of good adhesive force with cabin organic glass, wear resistance, transparent conductivity and the like, and can realize transparent stealth without arranging a base coat and a protective coat when being applied to an aviation transparent piece. The preparation method is simple, easy to implement and convenient to apply.

Description

Aviation transparent part conducting film free of bottom coating and protective coating and preparation method
Technical Field
The invention relates to an aviation transparent part conducting film free of a bottom coating and a protective coating and a preparation method thereof.
Background
The aircraft cabin serving as one of three large scattering sources seriously influences the stealth performance of the aircraft, and the cabin stealth is a remarkable characteristic of modern aircraft, particularly fighters, and is an important development direction of aircraft stealth design. At present, the most common and effective method for realizing the stealth of the glass of the cabin is to plate a transparent conductive film on the inner surface of the glass under the condition that the light transmittance is allowed. The transparent conductive film has high transmittance in a visible light region, and the resistivity is close to the numerical value of metal; the device has a certain reflection effect on radar waves, and can reflect most of the detection radar waves incident to the surface of the device to an unimportant direction so as to prevent the detection radar waves from entering the interior of a cockpit to form cavity scattering; on the other hand, the electromagnetic wave entering the cabin can be prevented from radiating outwards, so that an enemy radar can not receive or can only receive a small amount of echo, the radar cross section of the whole aircraft is reduced, the electromagnetic shielding effect is achieved, and the stealth performance of the aircraft is improved. At present, the technology has been widely applied in active service at home and abroad and in the research of airplanes. Among them, the most widely used transparent conductive film for transparent members of airplanes is an Indium Tin Oxide (ITO) film.
The glass substrate of the cabin is organic glass (polymethyl methacrylate, abbreviated as PMMA) and belongs to a high molecular organic material, and the ITO film is indium tin oxide and belongs to an inorganic substance. The chemical bond formed between the organic material and the metal oxide is weak, and the interface bonding capability is poor; in addition, the difference between the two thermal expansion coefficients can cause additional stress when the temperature changes, thereby causing the film to fail and fall off. The cross section of organic glass of the cabin is usually designed into a circular arc, but an ITO film is made of oxidized ceramic and is not easy to bend and stretch, the bending deformation level is only 0.7%, and the continuity of the conductive film layer can be influenced. Moreover, the thermal deformation temperature of the organic glass is low (generally less than 120 ℃), when the ITO thin film is plated by adopting the magnetron sputtering method, only a low-temperature mode can be adopted, the activity of film-forming atoms is limited, the nucleation density is low, and therefore, pores are easy to generate at the interface to form an incompletely compact thin film. Therefore, due to the coating process, the inherent physical properties of the organic glass and the ITO film, the harsh environment of the airplane and the like, the ITO film has low adhesion on cabin glass and is easy to chap and peel off, so that the overall stealth effect of the airplane is reduced, and meanwhile, the problem of maintenance guarantee is brought. For this reason, at present, an undercoat layer (transition layer) is usually required to be disposed between the organic glass in the cabin and the ITO conductive film, so as to reduce abrupt change of physical properties of the interface, improve lattice matching and thermodynamic matching between the film and the substrate, alleviate stress concentration, and enhance adhesion between the film and the substrate.
In order to ensure that the ITO film stably exists in the environments of high temperature, high humidity, temperature difference change, chemical media and the like and has higher wear resistance and scratch resistance, a protective coating needs to be coated after the ITO film is coated on the organic glass transparent part. The protective coating needs to be combined with the base coating and the conductive film to meet the functional requirements of the whole film system.
While current research into conductive films based on aerospace transparencies has developed many processes for performance improvement, such work does not involve the preparation of conductive films free of undercoats and protective coatings and related information.
Therefore, the research and development of the transparent conductive film free of the base coat and the protective coat are needed to be carried out aiming at the problem that the existing aviation transparent part conductive film needs to be provided with the base coat and the protective coat, and the transparent conductive film has important significance for improving the stealth performance of the airplane.
Disclosure of Invention
The aviation transparent part conducting film free of the bottom coating and the protective coating is composed of graphene quantum dots and a crosslinkable conjugated polymer containing hydroxyl side chains, is a three-dimensional reticular thin film structure with strong adhesive force, wear resistance and a synergistic transparent stealth function, is deposited on organic glass in a cabin, can be firmly adhered to an organic glass substrate, has good wear resistance, and can obtain a good transparent stealth effect.
The technical scheme of the invention is as follows:
the aviation transparent part conducting film free of the base coat and the protective coat is a three-dimensional reticular organic/inorganic nano composite film with graphene quantum dots GQDs uniformly dispersed in a crosslinked conjugated polymer cPFH (conjugated polymer) containing hydroxyl side chains;
the chemical structure of the conjugated polymer cPFOH is as follows:
Figure BDA0002155979060000021
wherein n is a natural number of 1-10000;
the preparation method of the conductive film comprises the following steps:
the preparation method comprises the following steps of taking graphene quantum dots GQDs and a cross-linkable conjugated polymer cPFH containing hydroxyl side chains as raw materials, blending the raw materials to form a compound solution, and curing the compound solution by ultraviolet light to form a film so as to obtain the conductive film, wherein the specific steps are as follows:
step 1: preparation of Polymer cPFH
Dissolving 2, 7-bis (4,4,5, 5-dimethyl-1, 3, 2-dioxaborane-2-yl) -9,9 ' -bis (6- (3-hexyloxymethyl-3-ethyl-oxetanyl)) fluorene (monomer 1) and 2, 7-dibromo-bis [9,9 ' -bis (6,6 ' -bromohexyl) ] fluorene (monomer 2) in toluene according to a molar ratio of 1: 1, respectively adding palladium acetate, tricyclohexylphosphine and tetraethylammonium hydroxide aqueous solution under the protection of argon, stirring under reflux for 48h under an argon atmosphere, adding phenylboronic acid, reacting for 6h, and adding bromobenzene to react for 6 h; wherein the molar ratio of the phenylboronic acid to the bromobenzene is 1: 1; after the reaction is finished, cooling the product to room temperature, then pouring the product into methanol for precipitation, filtering and then carrying out vacuum drying on the precipitate, re-dissolving the obtained polymer in tetrahydrofuran, wherein the volume ratio of the polymer to the tetrahydrofuran is 1: 10, filtering the product through a Polytetrafluoroethylene (PTFE) filter tip with the aperture of 0.45 mu m, carrying out reduced pressure distillation and concentration, dropwise adding the product into the methanol, and then carrying out precipitation, filtration and vacuum drying to obtain a solid polymer P1; dissolving a solid polymer P1 in a mixed solvent of tetrahydrofuran and N, N-dimethylformamide, adding diethanolamine, wherein the molar ratio of the polymer P1 to the diethanolamine is 1: 2, reacting for 72 hours at room temperature under the protection of argon, then pouring a reaction system into water for precipitation, filtering, drying in the air overnight, and then drying in vacuum for 24 hours to obtain a green solid polymer cPOOH;
the molar ratio of the palladium acetate to the tricyclohexylphosphine to the tetraethylammonium hydroxide is 1: 1;
step 2: preparation of polymer cPFOH-graphene quantum dot GQDs compound solution
In a glove box in a nitrogen atmosphere, blending a polymer cPFH (chlorinated polyethylene) and graphene quantum dots GQDs in a blending solvent, and adding a photoacid with the mass fraction of 1% of the polymer cPFH to obtain a compound solution of the polymer cPFH and the graphene quantum dots GQDs; wherein, in every 1mL of compound solution, the content of the polymer cPFOH is 0.5-2 g, and the content of the graphene quantum dots GQDs is 0.1-1 g;
and step 3: film formation
Spin-coating a compound solution of a polymer cPFOH and graphene quantum dots GQDs on the surface of organic glass, irradiating for 1min by an ultraviolet lamp with the wavelength of 365nm after coating, and carrying out heat treatment on a heating plate at the temperature of less than or equal to 70 ℃ for 15min to obtain a three-dimensional reticular structure film, namely a conductive film, wherein the graphene quantum dots GQDs are uniformly dispersed in the cross-linked polymer cPFOH, and the thickness of the conductive film is 50-500 nm.
The blending solvent is a mixed solution of methanol and acetic acid with the volume ratio of 10: 1.
The average particle size of the graphene quantum dots GQDs is 2-15 nm.
The synthetic route of the invention is as follows:
synthetic route of crosslinkable conductive conjugated polymer poly {2,7- [9,9 '-bis (3-ethyl-3- (6-hexyl) methyl ether-oxetane) fluorene ] -co-2, 7- [9, 9' -bis (6-N, N-diethanolamino) -hexyl ] fluorene ] } (polymer cpoh for short):
Figure BDA0002155979060000031
wherein SPC represents Suzuki polycondensation; monomer 1: 2, 7-bis (4,4,5, 5-dimethyl-1, 3, 2-dioxaborane-2-yl) -9, 9' -bis (6- (3-hexyloxymethyl-3-ethyl-oxetane)) fluorene, monomer 2: 2, 7-dibromo-bis [9,9 '-bis (6, 6' -bromohexyl) ] fluorene; polymer P1: poly {2,7- [9,9 ' -bis (3-ethyl-3- (6-hexyl) methylether-oxetane) fluorene ] -co-2, 7- [9,9 ' -bis (6,6 ' -bromohexyl) ] fluorene }.
The invention has the beneficial effects that:
(1) the conductive film material can be dissolved in methanol with a small amount of acetic acid, a thin layer can be coated on organic glass by solution processing modes such as rotation, printing and the like, and a thin film structure with a three-dimensional network structure and GQDs uniformly dispersed therein is formed by ultraviolet light curing, so that the preparation process is simple and easy.
(2) The conductive film material can form hydrogen bonds with organic glass and is firmly adhered to an organic glass substrate.
(3) The conductive film material has good wear resistance and scratch resistance, can resist the corrosion of common chemical solvents (including acid, alkali, water and the like), and has good environmental stability.
(4) The conductive film material of the invention can show good transmittance in the visible light range, has excellent conductivity and electromagnetic wave reflection capacity, and is suitable for being used as a stealth conductive film of an aviation transparent part.
(5) The conductive film has the synergistic functions of good adhesive force with cabin organic glass, wear resistance, transparent conductivity and the like, and can realize transparent stealth without arranging a base coat and a protective coat when being applied to an aviation transparent piece.
Drawings
FIG. 1 is a flow chart of the process for preparing the aviation transparent part conductive film without the primer and protective coating of the invention;
FIG. 2 is a schematic structural view of an aircraft transparency conductive film free of a primer and protective coating in accordance with the present invention;
in the figure: 1. organic glass; 2. the graphene quantum dots GQDs are uniformly dispersed in the cross-linked conductive conjugated polymer cPFH; 3. graphene quantum dots GQDs; 4. a conjugated polymer cpoh;
FIG. 3 is a transmitted light spectrum of a cPFOH, GQDs conductive film and an ITO conductive film of example 1 of the present invention;
in the figure: curves 1 and 2 show transmission spectrum curves of the cPFH, GQDs and ITO conductive films, respectively.
Detailed Description
Example 1
Cutting the organic glass sheet into square sheets of 20mm multiplied by 4mm, and then cleaning and drying the square sheets for later use. In a glove box under nitrogen atmosphere, 0.5g of polymer cPFH and 0.1g of GQDs (average particle size of 5nm) were dissolved in 1mL of methanol (with a small amount of acetic acid added) to form a cPFH: GQDs complex solution A, and 0.005g of photoacid [2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine ] was added to this solution. The composite solution was spin-coated on the surface of organic glass with a spin coater, and after coating, the coated film was irradiated with an ultraviolet lamp having a wavelength of 365nm for 1 minute and heat-treated on a hot plate at 70 ℃ for 15 minutes. Forming a film of the compound of the cPFH and GQDs with a three-dimensional network structure, wherein the polymer is crosslinked, and the GQDs are uniformly dispersed in the film. The thickness of the film is 120 nm. The light transmittance of the test sample is measured by a WGT-S type light transmittance haze meter and is measured with a substrate. The sheet resistance of the conductive film was tested using an SZ-82 digital four-probe tester. The adhesion of the conductive film was measured by the cross-hatch method in GB/T9286-1998. The pendulum hardness of the conductive film is measured according to GB/T6379.
In order to show the effect of the conducting film adopted by the invention, an ITO conducting film is plated on the organic glass as a reference. Specifically, an ITO film is prepared on an organic glass substrate by utilizing full-automatic magnetron sputtering coating equipment and a direct-current magnetron sputtering method. The ITO ceramic target material with the purity of 99.99 percent is adopted In the experiment, wherein In2O3With SnO2In a mass ratio of 9: 1, with a target surface diameter of 4 inches. When the vacuum degree of the sputtering vacuum chamber reaches 5 multiplied by 10-5After Pa, high-purity Ar and O with certain flow rate are introduced2The deposition pressure is adjusted to 0.5Pa by a molecular pump valve, and the sputtering power is 100W. The chassis rotation speed is 20 r/min. The sputtering time is 20min, the film thickness is 250nm, and the oxide on the surface of the target material is removed by pre-sputtering for 2min before each sputtering. The performance test method is the same as above.
TABLE 1 Performance of conductive films with a ratio of cPOOH to GQDs of 0.5 g: 0.1g
Figure BDA0002155979060000051
As can be seen from Table 1 and FIG. 3, compared with the optical properties of the ITO film prepared on the organic glass substrate, the transmission rate of the conductive film of cPFH and GQDs with the ratio of cPFH to GQDs of 0.5g to 0.1g in the visible light region is 89.4%, which is higher than that of the ITO film, and the conductive film has good visible light transmission. The square resistance of the conductive film of the cPFOH and the GQDs is slightly higher than that of the ITO film. The adhesion force of the cPFOH to GQDs conductive film on the organic glass is 1 grade, the hardness is 230s, and the film is far superior to the ITO film.
Example 2
The procedure is as in example 1, where the ratio of the polymers cPFH to GQDs is changed to 0.5 g: 0.2 g.
TABLE 2 Performance of conductive films with a ratio of cPOOH to GQDs of 0.5 g: 0.2g
Figure BDA0002155979060000052
As can be seen from Table 2, the transmission rates of the conductive films of cPFH and GQDs with the ratio of 0.5g to 0.2g are equivalent in the visible light region and both have good visible light transmittance, compared with the optical performance of the ITO thin film prepared on the organic glass substrate. The square resistance of the conductive film of the cPFOH and the GQDs is slightly higher than that of the ITO film. The adhesion force of the cPFOH to GQDs conductive film on the organic glass is 1 grade, the hardness is 280s, and the film is far superior to the ITO film.
The results in tables 1 and 2 show that the visible light transmittance and the square resistance of the conductive film of the cPFH/GQDs are equivalent to those of an ITO film, the adhesion and the hardness on the machine glass are far superior to those of the ITO film, and the cPFH/GQDs film is not only a transparent conductive film, has a transparent and invisible function, has good adhesion and wear resistance with organic glass, and can be directly used as a conductive film of an aviation transparent part without using a bottom coating and a protective coating.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (3)

1. An aviation transparent part conducting film free of a base coating and a protective coating is characterized in that: the conducting film is a three-dimensional network structure organic/inorganic nano composite film formed by uniformly dispersing graphene quantum dots GQDs in a cross-linked conjugated polymer cPFH containing hydroxyl side chains;
the chemical structure of the conjugated polymer cPFOH is as follows:
Figure FDA0002746890930000011
wherein n is a natural number of 1-10000;
the preparation method of the conductive film comprises the following steps:
the preparation method comprises the following steps of taking graphene quantum dots GQDs and a cross-linkable conjugated polymer cPFH containing hydroxyl side chains as raw materials, blending the raw materials to form a compound solution, and curing the compound solution by ultraviolet light to form a film so as to obtain the conductive film, wherein the specific steps are as follows:
step 1: preparation of Polymer cPFH
Dissolving 2, 7-bis (4,4,5, 5-dimethyl-1, 3, 2-dioxaborane-2-yl) -9,9 ' -bis (6- (3-hexyloxymethyl-3-ethyl-oxetane)) fluorene and 2, 7-dibromo-bis [9,9 ' -bis (6,6 ' -bromohexyl) ] fluorene in a molar ratio of 1: 1 in toluene, respectively adding palladium acetate, tricyclohexylphosphine and tetraethylammonium hydroxide aqueous solution under the protection of argon, stirring under reflux for 48h under the protection of argon, adding phenylboronic acid, reacting for 6h, and then adding bromobenzene to react for 6 h; wherein the molar ratio of the phenylboronic acid to the bromobenzene is 1: 1; after the reaction is finished, cooling the product to room temperature, then pouring the product into methanol for precipitation, filtering and then carrying out vacuum drying on the precipitate, dissolving the obtained polymer into tetrahydrofuran again, wherein the volume ratio of the polymer to the tetrahydrofuran is 1: 10, filtering the product through a polytetrafluoroethylene filter tip with the aperture of 0.45 mu m, carrying out reduced pressure distillation and concentration, dropwise adding the product into the methanol, and then carrying out precipitation, filtration and vacuum drying to obtain a solid polymer P1; dissolving a solid polymer P1 in a mixed solvent of tetrahydrofuran and N, N-dimethylformamide, adding diethanolamine, wherein the molar ratio of the polymer P1 to the diethanolamine is 1: 2, reacting for 72 hours at room temperature under the protection of argon, then pouring a reaction system into water for precipitation, filtering, drying in the air overnight, and then drying in vacuum for 24 hours to obtain a green solid polymer cPOOH;
the molar ratio of the palladium acetate to the tricyclohexylphosphine to the tetraethylammonium hydroxide is 1: 1;
step 2: preparation of polymer cPFOH-graphene quantum dot GQDs compound solution
In a glove box in a nitrogen atmosphere, blending a polymer cPFH (chlorinated polyethylene) and graphene quantum dots GQDs in a blending solvent, and adding a photoacid with the mass fraction of 1% of the polymer cPFH to obtain a compound solution of the polymer cPFH and the graphene quantum dots GQDs; wherein, in every 1mL of compound solution, the content of the polymer cPFOH is 0.5-2 g, and the content of the graphene quantum dots GQDs is 0.1-1 g;
and step 3: film formation
Spin-coating a compound solution of a polymer cPFOH and graphene quantum dots GQDs on the surface of organic glass, irradiating for 1min by an ultraviolet lamp with the wavelength of 365nm after coating, and carrying out heat treatment on a heating plate at the temperature of less than or equal to 70 ℃ for 15min to obtain a three-dimensional reticular structure film, namely a conductive film, wherein the graphene quantum dots GQDs are uniformly dispersed in the cross-linked polymer cPFOH, and the thickness of the conductive film is 50-500 nm.
2. The primer-free and protective coating aircraft transparency conductive film of claim 1 wherein: the blending solvent is a mixed solution of methanol and acetic acid with the volume ratio of 10: 1.
3. The primer-free and protective coating aircraft transparency conductive film of claim 1 wherein: the average particle size of the graphene quantum dots GQDs is 2-15 nm.
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