CN111499911A - Extreme environment tolerance double-layer structure polyimide composite material and preparation method thereof - Google Patents
Extreme environment tolerance double-layer structure polyimide composite material and preparation method thereof Download PDFInfo
- Publication number
- CN111499911A CN111499911A CN202010489467.2A CN202010489467A CN111499911A CN 111499911 A CN111499911 A CN 111499911A CN 202010489467 A CN202010489467 A CN 202010489467A CN 111499911 A CN111499911 A CN 111499911A
- Authority
- CN
- China
- Prior art keywords
- mica
- polyamic acid
- nanosheet
- acid dispersion
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
- 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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a preparation method of a polyimide composite material with a double-layer structure, which comprises the following steps: s1) carrying out calcination, acid leaching and sodium treatment on mica powder, then carrying out intercalation on the mica powder by using small organic molecules, and carrying out ultrasonic crushing in a solvent to obtain a mica nanosheet suspension; s2) mixing the mica nanosheet suspension with the polyamic acid dissolving solution to obtain a mica nanosheet-polyamic acid dispersion solution; recording a mica nanosheet-polyamic acid dispersion solution with a concentration of 5 wt% -30 wt% as a low-concentration mica nanosheet-polyamic acid dispersion solution according to the content of the mica nanosheets; recording a 60-80 wt% mica nanosheet-polyamic acid dispersion as a high-concentration mica nanosheet-polyamic acid dispersion; s3) spraying the low-concentration mica nanosheet-polyamic acid dispersion liquid and the high-concentration mica nanosheet-polyamic acid dispersion liquid on the surface of the substrate in sequence by adopting a spraying assembly and thermal curing combined method to obtain the polyimide composite material with the double-layer structure.
Description
Technical Field
The invention relates to the technical field of material chemistry, in particular to a polyimide composite material with a double-layer structure and extreme environment tolerance and a preparation method thereof.
Background
Polyimide is a very practical engineering polymer material, has excellent mechanical properties, excellent thermal stability, inherent chemical resistance and outstanding dielectric properties, and is widely applied to the industries of microelectronics, aerospace and the like. In particular, polyimides have been used as outer layer materials for aerospace thermal blankets to protect spacecraft from low orbit hostile environments (atomic oxygen, ultraviolet light, extreme temperatures, space debris, etc.). Although polyimide has an excellent balance of properties, it is as sensitive as hydrocarbon polymers to attack by atomic oxygen. After atomic oxygen irradiation, elements such as carbon, hydrogen, nitrogen and the like in the polyimide react with atomic oxygen to form volatile gas molecules, so that the mechanical property and the service life of the polyimide are reduced.
Replicating the multi-scale structure of natural biomaterials has been shown to create artificial materials with unique combinations of properties. For example, the assembly of nanostructured elements into a seashell-like structure can significantly improve the mechanical properties and barrier properties (e.g., gas and current) of the polymer. In addition, the skin-like coating of the "brick and concrete" structure can effectively increase the hardness of the outer layer, protecting the inner layer from adverse environmental damage (e.g., chip impact and radiation). Mica nanosheets have been widely used as inorganic reinforcing materials and multifunctional materials due to their advantages over other nanostructure units in terms of mechanical properties, ultraviolet shielding, high temperature stability, chemical resistance, and the like. Therefore, the difficult problem of tolerance of the polyimide composite material to the low-orbit extreme environment is solved by means of the combined design of the novel shell-like structure and the skin-like structure based on the mica nanosheet as the structural unit, and the method has very important research and practical significance.
Advanced materials journal 2018, thirty volume 1803854, reports that a coating material based on a polyimide surface is prepared by taking polyhedral oligomeric silsesquioxane and 2-ureido-4 [1H ] -pyrimidinone as raw materials and adopting a fused deposition-hot pressing combined method, and the coating material realizes excellent mechanical property, high transparency, favorable thermal stability, excellent atomic oxygen corrosion resistance and self-repairing function. In journal of the american chemical society for applied materials and interfaces 2015, seventh volume 12047 reports that a high-performance composite film material is finally prepared by first preparing a carbon nanotube film through chemical vapor deposition, then pouring a dispersion of polyamic acid and polyhedral oligomeric silsesquioxane into the carbon nanotube film, and finally performing a series of steps such as heat treatment and the like, and achieves excellent mechanical properties, excellent atomic oxygen resistance and excellent conductivity. However, the existing polyimide composite membrane materials often have the defects of insufficient outstanding mechanical properties, inefficient atomic oxygen resistance, weak ultraviolet radiation resistance, insufficient high-temperature stability and the like.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polyimide composite material with a double-layer structure and extreme environmental tolerance and a preparation method thereof, wherein the prepared polyimide composite material has excellent mechanical properties, atomic oxygen corrosion resistance, ultraviolet radiation resistance and high temperature stability.
The invention provides a preparation method of a polyimide composite material with a double-layer structure and extreme environment tolerance, which comprises the following steps:
s1) carrying out calcination, acid leaching and sodium treatment on mica powder, then carrying out intercalation on the mica powder by using small organic molecules, and then dispersing the intercalated mica powder in a solvent for ultrasonic crushing to obtain a mica nanosheet suspension;
s2) mixing the mica nanosheet suspension with the polyamic acid dissolving solution to obtain a mica nanosheet-polyamic acid dispersion solution; recording a mica nanosheet-polyamic acid dispersion solution with a concentration of 5 wt% -30 wt% as a low-concentration mica nanosheet-polyamic acid dispersion solution according to the content of the mica nanosheets; recording a 60-80 wt% mica nanosheet-polyamic acid dispersion as a high-concentration mica nanosheet-polyamic acid dispersion;
s3) spraying the low-concentration mica nanosheet-polyamic acid dispersion liquid and the high-concentration mica nanosheet-polyamic acid dispersion liquid on the surface of the substrate in sequence by adopting a spraying assembly and thermal curing combined method to obtain the polyimide composite material with the double-layer structure.
Preferably, in the step S1), the calcining includes heating the mica powder to 800 ℃ in a heating device at a heating rate of 4-12 ℃/min, and keeping the temperature for 0.5-2 hours to obtain calcined mica powder;
the acid leaching comprises the steps of reacting calcined mica powder in a nitric acid solution at 80-95 ℃ for 4-6 hours to obtain acid-leached mica powder;
the sodium treatment comprises the step of reacting acid-dipped mica powder in a sodium chloride solution at 80-95 ℃ for 3-6 hours to obtain sodium-treated mica powder.
Preferably, the organic small molecule is hexadecyl trimethyl ammonium chloride.
Preferably, the intercalation specifically includes:
mixing and reacting calcined, acid-dipped and sodium-treated mica powder with an organic small molecular compound, wherein the reaction temperature is 80-90 ℃, and the reaction time is 20-30 h;
the ultrasonication specifically comprises:
dispersing the intercalated mica powder in an ethanol solvent, carrying out ultrasonic crushing under the condition of magnetic stirring, and centrifugally collecting the upper-layer turbid liquid to obtain a mica nanosheet turbid liquid.
Preferably, the mica nanosheet suspension is an N, N-dimethylformamide suspension of mica nanosheets;
in the N, N-dimethylformamide suspension of the mica nanosheets, the content of the mica nanosheets is 8-10mg/m L;
the polyamic acid solution is prepared by mixing polyamic acid and N, N-dimethylformamide according to the weight ratio of 1: (1-4) the polyamic acid solution obtained by redissolving the polyamic acid solution by weight.
In some embodiments of the invention, the low concentration mica nanoplate-polyamic acid dispersion has a mica nanoplate content of 20 wt%.
In some embodiments of the invention, the high concentration mica nanoplate-polyamic acid dispersion has a mica nanoplate content of 70 wt%.
The invention provides a polyimide composite material with a double-layer structure, which comprises a bottom-layer shell-like structure and a top-layer surface-like coating; the bottom layer shell-like structure is formed by spraying and thermally curing 5-30 wt% of mica nanosheet-polyamic acid dispersion liquid; the top-layer skin-like coating is formed by spraying and thermally curing 60-80 wt% of mica nanosheet-polyamic acid dispersion liquid.
In some embodiments of the invention, the bottom layer shell-like structure is formed by spraying and thermally curing a 20 wt% mica nanosheet-polyamic acid dispersion; the top-layer skin-like coating is formed by spraying and thermally curing 70 wt% of mica nanosheet-polyamic acid dispersion liquid.
Preferably, the thickness of the bottom layer shell-like structure is 20-40 μm; the thickness of the top-layer skin-imitated coating is 1-4 mu m.
Compared with the prior art, the invention provides a preparation method of a polyimide composite material with a double-layer structure and extreme environment tolerance, which comprises the following steps: s1) carrying out calcination, acid leaching and sodium treatment on mica powder, then carrying out intercalation on the mica powder by using small organic molecules, and then dispersing the intercalated mica powder in a solvent for ultrasonic crushing to obtain a mica nanosheet suspension; s2) mixing the mica nanosheet suspension with the polyamic acid dissolving solution to obtain a mica nanosheet-polyamic acid dispersion solution; recording a mica nanosheet-polyamic acid dispersion solution with a concentration of 5 wt% -30 wt% as a low-concentration mica nanosheet-polyamic acid dispersion solution according to the content of the mica nanosheets; recording a 60-80 wt% mica nanosheet-polyamic acid dispersion as a high-concentration mica nanosheet-polyamic acid dispersion; s3) spraying the low-concentration mica nanosheet-polyamic acid dispersion liquid and the high-concentration mica nanosheet-polyamic acid dispersion liquid on the surface of the substrate in sequence by adopting a spraying assembly and thermal curing combined method to obtain the polyimide composite material with the double-layer structure. According to the invention, by virtue of reasonable double-layer structure design (shell-like structure and skin-like structure), and by virtue of inherent advantages of mica nanosheets, the high-performance double-layer structure polyimide composite material is prepared by means of spraying, assembling and thermosetting technology, wherein the tensile stress, Young modulus and hardness of the high-performance double-layer structure polyimide composite material are respectively 125MPa, 5.5GPa and 0.37GPa, which are far higher than the mechanical properties of a pure polyimide film and a shell-like structure polyimide composite film. In addition, compared with the shell structure-imitated composite film and the traditional polyimide-based composite material reported in the past, the prepared double-layer structure film has better atomic oxygen resistance, ultraviolet aging resistance and high-temperature stability. The method provided by the invention is simple and economic to operate and can be prepared in a large scale; the prepared polyimide composite material with the extreme environment tolerance and the double-layer structure has wide application prospect as a protective material in a low-orbit environment.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a polyimide composite material having a two-layer structure according to the present invention;
FIG. 2 is an atomic force microscope photomicrograph of mica nanoplates of example 1 of the present invention;
FIG. 3 is a photograph showing a double-layer structure composite film in example 1 of the present invention;
FIG. 4 is an electron microscope photograph showing the microstructure of a two-layer structure composite film in example 1 of the present invention;
FIG. 5 shows the tensile strength and Young's modulus of the two-layer structure composite film of example 1;
FIG. 6 shows the modulus and hardness of the nanoindentation test for composite films of different structures in example 1 of the present invention;
FIG. 7 is a microstructure of the surface before and after atomic oxygen irradiation of a composite film of a different structure in example 1 of the present invention;
FIG. 8 shows the mass loss under atomic oxygen irradiation for composite films of different structures in example 1 of the present invention;
FIG. 9 shows the mechanical properties of the composite films of different structures in example 1 of the present invention under extreme environments;
FIG. 10 is a scanning electron micrograph of a single-layer shell-like mica-polyimide composite film according to example 1 of the present invention;
FIG. 11 is a graph of stress strain, tensile strength and tensile modulus of different single-layer seashell-like mica-polyimide composite films in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a polyimide composite material with a double-layer structure and extreme environment tolerance, which comprises the following steps:
s1) carrying out calcination, acid leaching and sodium treatment on mica powder, then carrying out intercalation on the mica powder by using small organic molecules, and then dispersing the intercalated mica powder in a solvent for ultrasonic crushing to obtain a mica nanosheet suspension;
s2) mixing the mica nanosheet suspension with the polyamic acid dissolving solution to obtain a mica nanosheet-polyamic acid dispersion solution; recording a mica nanosheet-polyamic acid dispersion solution with a concentration of 5 wt% -30 wt% as a low-concentration mica nanosheet-polyamic acid dispersion solution according to the content of the mica nanosheets; recording a 60-80 wt% mica nanosheet-polyamic acid dispersion as a high-concentration mica nanosheet-polyamic acid dispersion;
s3) spraying the low-concentration mica nanosheet-polyamic acid dispersion liquid and the high-concentration mica nanosheet-polyamic acid dispersion liquid on the surface of the substrate in sequence by adopting a spraying assembly and thermal curing combined method to obtain the polyimide composite material with the double-layer structure.
FIG. 1 is a schematic diagram of a preparation route of an extreme environment resistant polyimide composite material with a two-layer structure provided by the present invention.
The method comprises the steps of firstly calcining mica powder, carrying out acid leaching, carrying out sodium treatment and intercalation treatment, and then carrying out ultrasonic crushing to obtain a mica nanosheet suspension.
In some embodiments of the present invention, the calcining step comprises heating to 800 ℃ at a heating rate of 4-12 ℃/min in a heating device and maintaining the temperature for 0.5-2 h.
The acid treatment step comprises the step of placing 10-50 g of calcined mica powder in a nitric acid solution of 500m L3-6 mol/L mol for reaction for 4-6 hours at the temperature of 80-95 ℃.
The sodium treatment step comprises the step of adding 20-40 g of acid-dipped mica powder into a sodium chloride solution with the mass concentration of 30-50 wt% of 500m L to react for 3-6 h at the temperature of 80-95 ℃.
The organic micromolecule intercalation step comprises the step of adding 4-8 g of sodium mica powder and 10-20 g of hexadecyl trimethyl ammonium chloride into 500m L deionized water and reacting for 20-30 hours at the temperature of 80-90 ℃.
The ultrasonic crushing step comprises the steps of dispersing 5-20 g of intercalated mica powder in 500m L ethanol, carrying out ultrasonic crushing by adopting 665W power, and centrifuging at 3000r/min for 10min every 0.5h to collect upper-layer suspension, namely mica nanosheet suspension.
And then mixing the mica nanosheet suspension with the polyamic acid solution to obtain a mica nanosheet-polyamic acid dispersion liquid.
According to the invention, the preparation of the mica nanosheet suspension comprises the steps of dispersing the mica nanosheet in ethanol, centrifuging for 10-20 min at 8000-10000 r/min to collect a sample, washing for multiple times by using N, N-dimethylformamide, and dispersing in the N, N-dimethylformamide to prepare the mica nanosheet N, N-dimethylformamide suspension with the concentration of 8-10mg/m L.
The preparation of the polyamic acid solution comprises the steps of mixing polyamic acid and N, N-dimethylformamide according to the weight ratio of 1: and (1) stirring again and dissolving the mixture according to the proportion of (1) to (4) to obtain an amic acid solution.
The present invention is not limited to the specific arrangement, and the raw materials may be commercially available without being limited to the sources thereof.
According to the invention, the mixing process further comprises stirring, centrifuging and washing; the stirring temperature is 20-35 ℃; the stirring time is 0.5-1 h; the rotating speed of the centrifugation is 8000-10000 r/min; the centrifugation time is 10-15 min.
The washing times are preferably 2-3 times, and finally mica nanosheet suspension of 8-10mg/m L is obtained, and then the mica nanosheet-polyamic acid dispersion liquid with the concentration of 5-50 wt.% is obtained through stirring and dissolving.
The invention preferably comprises the following components: and (3) centrifugally dispersing the mica nanosheet suspension in a solvent (such as N, N-dimethylformamide) again, adding the solvent into the polyamic acid solution under the stirring condition, and continuously oscillating to obtain a uniform mica nanosheet-polyamic acid dispersion solution.
In the mica nanosheet-polyamic acid dispersion liquid, the mass content of the mica nanosheet is preferably 5 wt.% to 30 wt.%, and the mass content is recorded as a low-concentration mica nanosheet-polyamic acid dispersion liquid.
Specifically, the content may be 5 wt.%, 10 wt.%, 20 wt.% or 30 wt.%, respectively.
The stirring and the continuous shaking are not limited in the present invention, and those skilled in the art can easily understand the stirring and the continuous shaking.
Centrifuging and washing 20 wt.% mica nanosheet-polyamide acid dispersion liquid, and then re-dispersing in a solvent to prepare the mica nanosheet-polyamide acid dispersion liquid with high mica nanosheet content, wherein the mass content of the mica nanosheets is preferably 60-80 wt%.
Specifically, the content may be 60 wt%, 70 wt%, or 80 wt%, respectively.
The preparation comprises centrifugation, washing and oscillation; the rotating speed of the centrifugation is preferably 8000-10000 r/min; the centrifugation time is preferably 10-20 min, the washing frequency is preferably 2 times, and the suspension is dispersed by continuous oscillation in a proper amount.
And after mica nanosheet-polyamide acid dispersion liquid with different concentrations is obtained, preparing the mica nanosheet-polyamide acid dispersion liquid into the double-structure polyimide composite film by adopting a spraying assembly method and a thermosetting combination method.
The method for spray assembly is not limited in the present invention, and may be well known to those skilled in the art.
Compared with other methods, the method for preparing the double-structure composite membrane by combining spraying, assembling and thermosetting has higher speed; time can be saved considerably.
According to the invention, the distance between the spray gun used for spraying and the substrate is preferably 10-20 cm; more preferably 12-18 cm; most preferably 15 cm.
The spraying speed is preferably 3m L/min, and the spraying time is 2 min.
The thickness of the bottom layer of the double-layer structure composite film obtained by spraying is preferably 20-40 mu m; the thickness of the top coating is 1-4 μm.
The thermosetting treatment specifically comprises the following steps: sequentially molding at four temperatures of 120 ℃,160 ℃,180 ℃ and 250 ℃ for 0.5h, 1h and 0.5 h.
The invention provides a polyimide composite material with a double-layer structure, which is obtained according to the preparation method and comprises a bottom-layer shell-like structure and a top-layer surface-like coating; the bottom layer shell-like structure is formed by spraying and thermally curing 5-30 wt% of mica nanosheet-polyamic acid dispersion liquid; the top-layer skin-like coating is formed by spraying and thermally curing 60-80 wt% of mica nanosheet-polyamic acid dispersion liquid.
Preferably, the thickness of the bottom layer shell-like structure is 20-40 μm; the thickness of the top-layer skin-imitated coating is 1-4 mu m.
According to the invention, by virtue of reasonable double-layer structure design (shell-like structure and skin-like structure) and by virtue of inherent advantages of mica nanosheets, the high-performance double-layer structure polyimide composite material is prepared by combining a spraying assembly technology and a thermosetting technology, wherein the tensile stress, Young modulus and hardness of the high-performance double-layer structure polyimide composite material are respectively 125MPa, 5.5GPa and 0.37GPa, which are far higher than the mechanical properties of a pure polyimide film and a shell-like structure polyimide composite film. In addition, compared with the shell structure-imitated composite film and the traditional polyimide-based composite material reported in the past, the prepared double-layer structure film has better atomic oxygen resistance, ultraviolet aging resistance and high-temperature stability. The method provided by the invention is simple and economic to operate and can be prepared in a large scale; the prepared polyimide composite material with the extreme environment tolerance and the double-layer structure has wide application prospect as a protective material in a low-orbit environment.
In order to further illustrate the present invention, the following examples are given to describe the extreme environment resistant polyimide composite material and the preparation method thereof in detail.
Example 1
Preparing a polyimide composite material with a double-layer structure:
a. firstly, putting mica powder into an electric furnace, raising the temperature to 800 ℃ at a heating rate of 5 ℃/min, then keeping the temperature for 1h, then adding 15g of calcined mica powder into 500m L of 5 mol/L nitric acid solution, reacting for 5h at 95 ℃, filtering, washing and drying, then adding 15g of acid-dipped mica powder into 500m L of 40 wt.% of sodium chloride solution, reacting for 3h at 95 ℃, filtering, washing and drying, then adding 5g of sodium-treated mica powder and 15g of hexadecyl trimethyl ammonium chloride into 500m L of deionized water, reacting for 24h at 80 ℃, filtering, washing and drying, finally adding 20g of intercalated mica powder into 500m L of ethanol, and collecting the upper layer by adopting 3000r/min for 10min at intervals of 0.5h through ultrasonic crushing with a power of 665W under the condition of magnetic stirring to obtain the mica suspension, wherein figure 2 is an atomic force microscope photo of the mica suspension of the nanoplate suspension in embodiment 1 of the invention.
b. Weighing 10g of polyamide acid (with the concentration of 20 wt.%), adding the polyamide acid into 30m L N, N-dimethylformamide, stirring for a certain time at normal temperature, completely dissolving the polyamide acid to obtain 5 wt.% of polyamide acid solution, centrifuging a mica sheet suspension, re-dispersing the mica sheet suspension in the N, N-dimethylformamide, adding the polyamide acid solution into a uniform mica nanosheet-polyamide acid dispersion solution, regulating and controlling the content of mica sheets, centrifuging the 20 wt.% mica nanosheet-polyamide acid dispersion solution for 10min at the rotating speed of 8000r/min, washing for 2 times, and continuously oscillating and dispersing the suspension in a proper amount to obtain 70 wt.% mica nanosheet-polyamide acid dispersion solution.
c. Preparing a polyimide composite material with a double-layer structure: pouring 20 wt.% mica nanosheet-polyamide acid suspension into a spray gun, spraying the suspension on the surface of a glass substrate at 80 ℃ to form a film, pouring 70 wt.% mica nanosheet-polyamide acid suspension into the spray gun, and finally spraying the suspension on the surface of the film, wherein the thicknesses of different structures are controlled by the volume of the suspension, and then sequentially carrying out heat treatment on the suspension at 120 ℃ (0.5h), at 160 ℃ (0.5h), at 180 ℃ (1h) and at 250 ℃ (0.5h) to obtain the polyimide composite material with the double-layer structure.
Fig. 3 is a photograph showing a microstructure of the polyimide composite material having a two-layer structure according to example 1 of the present invention, as shown in fig. 4, and fig. 4 is an electron microscope view showing a microstructure of the polyimide composite material having a two-layer structure according to example 1 of the present invention.
Through the tensile and nano-indentation tests of the polyimide composite material with the double-layer structure, as shown in fig. 5 and 6, fig. 5 is a graph showing tensile stress and young modulus curves of the polyimide composite material with the double-layer structure with different surface layer thicknesses in example 1 of the present invention; FIG. 6 is a bar graph of modulus and hardness of a polyimide composite material having a two-layer structure with different skin thicknesses in example 1 of the present invention. The results showed that the tensile stress, modulus and hardness of the polyimide composite material having a two-layer structure with a surface layer thickness of 2 μm were-125 MPa, -5.5 GPa and-0.37 GPa, respectively.
By performing an atomic oxygen test on a polyimide composite material having a double-layer structure, as shown in FIG. 7, FIG. 7 is a scanning electron micrograph before and after atomic oxygen irradiation of a polyimide composite material having a double-layer structure and a surface layer thickness of 2 μm in example 1 of the present invention, wherein FIG. a is a scanning electron micrograph before atomic oxygen irradiation of a pure polyimide film, FIG. b is a scanning electron micrograph after atomic oxygen irradiation of a pure polyimide film, FIG. c is a scanning electron micrograph before atomic oxygen irradiation of a seashell-like composite film, FIG. d is a scanning electron micrograph after atomic oxygen irradiation of a seashell-like composite film, FIG. e is a scanning electron micrograph before atomic oxygen irradiation of a double-layer structure composite film, and FIG. f is a scanning electron micrograph after atomic oxygen irradiation of a double-layer structure composite film, it is found that the surface structure of the polyimide composite material having a double-layer structure and a surface layer thickness of 2 μm in example 1 of the present invention hardly changes, and FIG. 8 is a scanning electron micrograph before atomic oxygen irradiation of the polyimide composite material having a double-layer structure and a20atoms cm-2) Mass loss after this is 0.075mg cm-2。
The mechanical properties of the polyimide composite material with the double-layer structure after being respectively subjected to atomic oxygen radiation, ultraviolet irradiation and high-temperature treatment are shown in fig. 9, and fig. 9 shows the tolerance of the polyimide composite material with the double-layer structure in example 1 of the present invention in an extreme environment.
Comparative example 1
Preparation of single-layer shell-like mica-polyimide composite membrane
A mica nanoplate suspension was prepared according to example 1, step a.
b. Weighing 10g of polyamide acid (with the concentration of 20 wt.%), adding the polyamide acid into 30m L N, N-dimethylformamide, stirring for a certain time at normal temperature, completely dissolving the polyamide acid to obtain 5 wt.% of polyamide acid solution, centrifuging the mica sheet suspension, re-dispersing the mica sheet suspension in the N, N-dimethylformamide, adding the mica sheet suspension into the polyamide acid solution, continuously oscillating to obtain uniform mica nanosheet-polyamide acid dispersion liquid, and regulating and controlling the content of mica sheets;
c. pouring the mica nanosheet-polyamic acid suspension with uniform low concentration (0 wt.%, 5 wt.%, 10 wt.%, 20 wt.%, 30 wt.%) into a spray gun, spraying onto the surface of a glass substrate at 80 ℃, and sequentially treating at 120, 160, 180, and 250 ℃ for 0.5h, 1h, and 0.5h, respectively, to obtain mica-polyimide composite films with different ratios.
Fig. 10 is a scanning electron micrograph of a cross section of a pure polyimide film, fig. b is a cross section of a 5 wt.% mica-polyimide composite film, fig. c is a cross section of a 10 wt.% mica-polyimide composite film, fig. d is a cross section of a 20 wt.% mica-polyimide composite film, and fig. e is a cross section of a 30 wt.% mica-polyimide composite film, respectively, in comparative example 1 of the present invention. Due to different proportions of mica nanosheets, the ordering degree of the composite membrane brick mud structure is different. Mechanical tensile test is carried out on the prepared different composite membrane materials, and the result shows that when the addition amount of the mica nanosheet is 20 wt%, the mechanical property is optimal. Fig. 11 is a graph showing the comparison of mechanical tensile properties of different composite films, where fig. 11 is a graph showing the comparison of stress-strain of different composite films in comparative example 1 of the present invention, where a is a stress-strain curve of different mica-polyimide composite films, and b is an average value of tensile strength and modulus of different mica-polyimide composite films.
Comparative example 2
Preparing a pure polyimide film material:
a. the polyamic acid solution was prepared as in example 1.
b. A pure polyimide film was prepared as in example 1.
By subjecting the polyimide film to tensile and nanoindentation tests, it was found that the tensile stress, modulus and hardness of the pure polyimide film were-86 MPa, -3 GPa, and-0.22 GPa, respectively, as shown in FIGS. 6 and 11.
Atomic oxygen irradiation of the polyimide film revealed that the pure polyimide film was severely damaged and had many corrosion sites as shown in FIGS. 7 and 8, atomic oxygen irradiation was performed for 6h (3.09 × 10)20atoms cm-2) The mass loss after this is 1.25mg cm-2。
The mechanical properties of the pure polyimide film after being respectively subjected to atomic oxygen radiation, ultraviolet irradiation and high-temperature treatment are shown in fig. 9, and the mechanical properties of the pure polyimide film in an extreme environment are greatly damaged.
Comparative example 3
Preparing a single-layer shell-like polyimide composite material:
a. mica nanoplatelets and polyamic acid solution were prepared as in example 1.
b. The preparation of the 20% mica nanosheet-polyimide composite membrane was the same as in example 1.
By performing tensile and nanoindentation tests on the 20% mica nanosheet-polyimide composite film, as shown in fig. 6 and 11, the tensile stress, modulus and hardness of the 20% mica nanosheet-polyimide composite film are respectively 125MPa, 4.4GPa and 0.32 GPa.
Atomic oxygen irradiation of 20% mica nanoplate-polyimide composite film was found to have a lower degree of destruction of 20% mica nanoplate-polyimide composite film as shown in fig. 7 and 8, atomic oxygen irradiation was performed for 6h (3.09 × 10)20atoms cm-2) The mass loss after the reaction is 0.11mg cm-2。
As can be seen from the above examples and comparative examples, the polyimide film with a double-layer structure provided by the invention has better mechanical properties, atomic oxygen resistance, ultraviolet aging resistance and high-temperature stability.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (7)
1. A preparation method of a polyimide composite material with a double-layer structure and extreme environment tolerance comprises the following steps:
s1) carrying out calcination, acid leaching and sodium treatment on mica powder, then carrying out intercalation on the mica powder by using small organic molecules, and then dispersing the intercalated mica powder in a solvent for ultrasonic crushing to obtain a mica nanosheet suspension;
s2) mixing the mica nanosheet suspension with the polyamic acid dissolving solution to obtain a mica nanosheet-polyamic acid dispersion solution; recording a mica nanosheet-polyamic acid dispersion solution with a concentration of 5 wt% -30 wt% as a low-concentration mica nanosheet-polyamic acid dispersion solution according to the content of the mica nanosheets; recording a 60-80 wt% mica nanosheet-polyamic acid dispersion as a high-concentration mica nanosheet-polyamic acid dispersion;
s3) spraying the low-concentration mica nanosheet-polyamic acid dispersion liquid and the high-concentration mica nanosheet-polyamic acid dispersion liquid on the surface of the substrate in sequence by adopting a spraying assembly and thermal curing combined method to obtain the polyimide composite material with the double-layer structure.
2. The preparation method according to claim 1, wherein in the step S1), the calcining comprises heating the mica powder to 800 ℃ in a heating device at a heating rate of 4-12 ℃/min and keeping the temperature for 0.5-2 h to obtain calcined mica powder;
the acid leaching comprises the steps of reacting calcined mica powder in a nitric acid solution at 80-95 ℃ for 4-6 hours to obtain acid-leached mica powder;
the sodium treatment comprises the step of reacting acid-dipped mica powder in a sodium chloride solution at 80-95 ℃ for 3-6 hours to obtain sodium-treated mica powder.
3. The method of claim 1, wherein the small organic molecule is cetyltrimethylammonium chloride.
4. The preparation method according to claim 1, wherein the intercalation specifically comprises:
mixing and reacting calcined, acid-dipped and sodium-treated mica powder with an organic micromolecular compound;
the reaction temperature is 80-90 ℃, and the reaction time is 20-30 h;
the ultrasonication specifically comprises:
dispersing the intercalated mica powder in an ethanol solvent, carrying out ultrasonic crushing under the condition of magnetic stirring, and centrifugally collecting the upper-layer turbid liquid to obtain a mica nanosheet turbid liquid.
5. The production method according to claim 1, wherein the mica nanosheet suspension is an N, N-dimethylformamide suspension of mica nanosheets;
in the N, N-dimethylformamide suspension of the mica nanosheets, the content of the mica nanosheets is 8-10mg/m L;
the polyamic acid solution is prepared by mixing polyamic acid and N, N-dimethylformamide according to the weight ratio of 1: (1-4) the polyamic acid solution obtained by redissolving the polyamic acid solution by weight.
6. A polyimide composite material with a double-layer structure comprises a bottom-layer shell-like structure and a top-layer skin-like coating; the bottom layer shell-like structure is formed by spraying and thermally curing 5-30 wt% of mica nanosheet-polyamic acid dispersion liquid; the top-layer skin-like coating is formed by spraying and thermally curing 60-80 wt% of mica nanosheet-polyamic acid dispersion liquid.
7. The polyimide composite material with the double-layer structure as claimed in claim 6, wherein the thickness of the bottom layer shell-like structure is 20-40 μm; the thickness of the top-layer skin-imitated coating is 1-4 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010489467.2A CN111499911B (en) | 2020-06-02 | 2020-06-02 | Extreme environment tolerance double-layer structure polyimide composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010489467.2A CN111499911B (en) | 2020-06-02 | 2020-06-02 | Extreme environment tolerance double-layer structure polyimide composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111499911A true CN111499911A (en) | 2020-08-07 |
| CN111499911B CN111499911B (en) | 2021-03-09 |
Family
ID=71870422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010489467.2A Active CN111499911B (en) | 2020-06-02 | 2020-06-02 | Extreme environment tolerance double-layer structure polyimide composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111499911B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150553A (en) * | 2021-05-12 | 2021-07-23 | 武汉理工大学 | Preparation method of nano mica/silicone rubber composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214846A (en) * | 2013-03-21 | 2013-07-24 | 北京航空航天大学 | Hybrid material resistant to space environment atomic oxygen denudation and preparation method |
| CN105601919A (en) * | 2016-01-12 | 2016-05-25 | 湖南工业大学 | Polyimide nanocomposite of naphthalene-containing structure and preparation method and application of polyimide nanocomposite |
-
2020
- 2020-06-02 CN CN202010489467.2A patent/CN111499911B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214846A (en) * | 2013-03-21 | 2013-07-24 | 北京航空航天大学 | Hybrid material resistant to space environment atomic oxygen denudation and preparation method |
| CN105601919A (en) * | 2016-01-12 | 2016-05-25 | 湖南工业大学 | Polyimide nanocomposite of naphthalene-containing structure and preparation method and application of polyimide nanocomposite |
Non-Patent Citations (2)
| Title |
|---|
| CHAN JIANG: "Thermally Robust Bendable Silicon Dioxide/Polyimide Layered Composite Film Through Catalytic Fluorination", 《ACS APPL. POLYM. MATER.》 * |
| 潘晓锋: "利用喷涂组装的仿生层层复合结构的设计，构建与性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150553A (en) * | 2021-05-12 | 2021-07-23 | 武汉理工大学 | Preparation method of nano mica/silicone rubber composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111499911B (en) | 2021-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tong et al. | Graphene based materials and their composites as coatings | |
| Wang et al. | The effect of two‐dimensional d‐Ti3C2 on the mechanical and thermal conductivity properties of thermoplastic polyurethane composites | |
| Estaji et al. | Polycarbonate/poly (methyl methacrylate)/silica aerogel blend composites for advanced transparent thermal insulations: mechanical, thermal, and optical studies | |
| Wu et al. | Nondestructive strategy to effectively enhance the interfacial adhesion of PBO/epoxy composites | |
| CN111499911B (en) | Extreme environment tolerance double-layer structure polyimide composite material and preparation method thereof | |
| Li et al. | Synthesizing superior flexible oxide perovskite ceramic nanofibers by precisely controlling crystal nucleation and growth | |
| Tian et al. | Study on the construction of polyethyleneimine/nano-silica multilayer film on the carbon fiber surfaces to improve the interfacial properties of carbon fiber/epoxy composites | |
| CN112646489A (en) | Conductive coating and preparation method thereof | |
| CN115851199A (en) | Preparation method of novel flame retardant modified epoxy resin adhesive film | |
| Ma et al. | Preparation of PBO/ZnO fibers by hydrothermal synthesis method and its properties | |
| He et al. | Preparation of polyimide/siloxane‐functionalized graphene oxide composite films with high mechanical properties and thermal stability via in situ polymerization | |
| Ma et al. | Constructing “soft‐stiff” structure on the surface of carbon fiber to enhance the interfacial properties of its epoxy composites | |
| Zhou et al. | Targeted kinetic strategy for improving the thermal conductivity of epoxy composite containing percolating multi-layer graphene oxide chains. | |
| Lu et al. | Improving interfacial strength of epoxy composites by constructing “palm‐tree”‐like structure on carbon fiber | |
| Lv et al. | Interfacially enhancement of PBO/epoxy composites by grafting MWCNTs onto PBO surface through melamine as molecular bridge | |
| Wang et al. | Poly (amic acid)–clay nacrelike composites prepared by electrophoretic deposition | |
| CN112760972B (en) | PBO fiber sizing agent containing benzoxazole diamine compatilizer and application thereof | |
| KR102102594B1 (en) | Manufacturing method of carbon fiber-BN composite | |
| Song et al. | Poly (p-phenylene benzobisoxazole) fiber/epoxy composites reinforced with carbon nanotubes and graphene oxide for enhanced interfacial adhesion and mechanical strength | |
| Liu et al. | Fabrication of Si3N4 nanowire membranes: free standing disordered nanopapers and aligned nanowire assemblies | |
| Chen et al. | Storable silicon/shape memory polyurethane hybrid sols prepared by a facile synthesis process and their application to aramid fibers | |
| Huang et al. | Synthesis, mechanical property, and thermal stability of reduced graphene oxide–zinc oxide/cyanate ester/bismaleimide resin composites | |
| Zhu et al. | Epoxy resin composites reinforced with sheet stripping oxidized carbon nitride | |
| Lv et al. | Mechanical enhancement of amine‐functionalized TiO2 reinforced polyimine composites | |
| Yang et al. | Sequentially bridged MXene platelets for strong high‐temperature EM‐IR bi‐stealth sheets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |