CN108106748B - Flexible ablation resistance film and preparation method thereof - Google Patents
Flexible ablation resistance film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flexible ablation resistance film and a preparation method thereof, the flexible ablation resistance film comprises a flexible substrate and an ablation resistance film, a composite transition layer is arranged between the flexible substrate and the ablation resistance film, wherein the composite transition layer comprises an alternative deposition Si3N4Layer, AlN layer and Al2O3Periodic composite films of layers. The preparation method comprises the steps of preparing the composite transition layer and preparing the ablation resistance film. The flexible ablation resistance film has the advantages of strong environmental interference resistance, high reliability level and the like, and the preparation method has the advantages of simple preparation process, strong environmental adaptability, good reliability and the like. The flexible ablation resistance film can be applied to heat-proof protective layers of spacecrafts such as hypersonic aircrafts, solid rocket engines and the like, can realize ablation amount measurement in severe environments such as high temperature and high heat flow scouring and the like, and has important significance for improving application reliability of the spacecrafts such as hypersonic aircrafts, solid rocket engines and the like.
Description
Technical Field
The invention belongs to the technical field of special film preparation, relates to an ablation resistance film and a preparation method thereof, and particularly relates to a flexible ablation resistance film and a preparation method thereof.
Background
The heat insulation layer is mainly applied to the heat protection of spacecrafts such as solid rocket engines and reentry air vehicles, and the performance of the heat insulation layer directly influences the reliability of the engine operation and even influences the success or failure of rocket launching. The working environment of the heat insulating layer is quite severe, the heat insulating layer is subjected to ablation of high-temperature and high-pressure gas and scouring of condensed phase particles, and the protection failure of the inner heat insulating layer can be caused in severe cases, and an engine shell is burnt through to cause the failure of an engine. Therefore, the thickness of the heat insulation layer, the geometry thereof and the like directly influence the structural reliability of the solid rocket motor, the design of the heat insulation layer is determined by the ablation condition of the heat insulation layer, and the ablation characteristic of the heat insulation layer material is one of important references for designing the heat insulation layer.
In order to adapt to and propel hypersonic aircrafts and solid rocket engines, the development of the hypersonic aircrafts and solid rocket engines is advanced, and an inner heat insulation layer material with higher performance (such as poorer heat conductivity and more favorable adaptation to the severe environment of high temperature and high heat flow scouring) is required. For example, chinese patent publication No. CN102353469A describes an online measurement device for high temperature on the outer surface of a high-speed aircraft, and a preparation and measurement method thereof, wherein a plurality of thin-film thermocouples are prepared by forming and depositing through a micro-processing process, and ablation measurement is achieved by the thin-film thermocouples, but the thin-film thermocouples in the patent technology are prepared on rigid substrate alumina ceramics, which cannot completely simulate the ablation condition of the material of the thermal insulation layer, and thus have no superiority; meanwhile, the sensor has the defects of complex structure, poor reliability level of working in severe environment, complex production process, high production cost, long production period and the like. For another example, chinese patent publication No. 102879434a describes a thin film ablation sensor and a method for manufacturing the same, wherein the thin film ablation sensor is made of a silicon wafer and Al2O3At least one of ceramic and borosilicate glass is a rigid substrate material, so that the prepared thin film ablation sensor has no performance of low thermal conductivity, and cannot ensure the reliability under severe environments such as high temperature, high heat flow scouring and the like, and thus cannot be used as a heat insulating material for hypersonic aircrafts and solid rocket engines. Obviously, the existing rigid substrate ablative film as the inner heat insulation layer material cannot meet the requirements of the hypersonic aircraft and the solid rocket engine under severe environments of high temperature, high heat flow scouring and the likeThe actual requirements.
The thermal insulation materials such as ethylene propylene diene monomer, polyimide and the like have the characteristics of low density, ablation resistance, scouring resistance, excellent process performance and the like, are used as flexible substrates of micro thin-film devices, and are widely applied to the thermal protection fields of ultrahigh-supersonic aircrafts, aerospace solid rocket engines and the like. However, ethylene propylene diene monomer and polyimide are flexible materials, and are prone to cracking, falling and the like in the preparation process of the flexible film, so that the reliability of the flexible film is affected. In order to overcome the above problems, researchers have optimized the preparation process of the thin film, for example, chinese patent publication No. CN102330067A introduces a method for rapidly and uniformly preparing a microcrystalline silicon thin film with a flexible substrate, and a hot-filament assisted very high frequency plasma enhanced chemical vapor deposition method is adopted to realize the preparation of a microcrystalline silicon thin film with a flexible substrate having high quality, high deposition rate and good uniformity at a low temperature. For another example, chinese patent publication No. CN104498883A describes a method for depositing a high c-axis oriented aluminum nitride film on a flexible substrate, in which a plasma is used to clean the flexible substrate, the cleaned flexible substrate is placed on a substrate stage of a magnetron sputtering coating machine, vacuum pumping is performed, working gas is filled, and reactive sputtering is performed to obtain the high c-axis oriented aluminum nitride film. Therefore, the flexible film prepared by the existing preparation method can only realize relative reliability under atmospheric environment conditions, and cannot be applied to heat protection of spacecrafts such as hypersonic aircrafts, solid rocket engines and the like.
Therefore, aiming at the defects and shortcomings of the existing flexible film in the aspects of complex preparation process, low reliability level and the like, the obtained flexible ablative resistance film with strong environmental interference resistance and high reliability level and the matched preparation method thereof have important significance for improving the application reliability of spacecrafts such as hypersonic aircrafts, solid rocket engines and the like in severe environments such as high temperature, high heat flow scouring and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a flexible ablation resistance film with strong environmental interference resistance and high reliability level and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a flexible ablative resistive film, the flexible ablative resistive film comprising a flexible substrate and an ablative resistive film; a composite transition layer is arranged between the flexible substrate and the ablation resistance thin film; the composite transition layer comprises an alternating deposit of Si3N4Layer, AlN layer and Al2O3Periodic composite films of layers.
In the flexible ablation resistance film, the periodic composite film is further improved in that the flexible substrate is taken as a basal plane to outwardly present' Si3N4Layer, AlN layer to Al2O3The tendency of the layers "to change periodically.
In the flexible ablation resistance film, the cycle number of the periodic composite film is less than or equal to 10; in the periodic composite film, the Si3N4The monolayer thickness of the layer is 50 nm-150 nm, the monolayer thickness of the AlN layer is 50 nm-150 nm, and the Al layer2O3The individual layer thickness of the layer is 50nm to 150 nm.
In the above flexible ablative resistance film, a further improvement is that the flexible ablative resistance film further comprises a first buffer layer and a second buffer layer; the first buffer layer is arranged between the flexible substrate and the composite transition layer; the second buffer layer is arranged between the composite transition layer and the ablation resistance thin film.
In the above flexible ablation resistance thin film, further improved, the first buffer layer is a C thin film; the thickness of the first buffer layer is 50 nm-100 nm.
In the above flexible ablation resistance thin film, further improved, the second buffer layer is an Al thin film; the thickness of the second buffer layer is 50 nm-100 nm.
In the flexible ablation resistance film, a protective film is arranged on the ablation resistance film; the protective film is made of dielectric material; the dielectric material is SiO2A film; the thickness of the protective film is 5 nm-20 nm.
In the flexible ablation resistance film, the flexible substrate is an ethylene propylene diene monomer film or a polyimide film; the thickness of the flexible substrate is 0.3 mm-0.5 mm;
and/or the ablation resistance thin film is a metal thin film with the resistivity less than or equal to 30n omega-m; the metal film is an Au film or a Cu film; the thickness of the ablation resistance film is 3.5-4 mu m.
As a general technical concept, the present invention also provides a method for preparing the flexible ablation resistance thin film, comprising the following steps:
s1, cleaning the flexible substrate;
s2, depositing a first buffer layer on the surface of the flexible substrate cleaned in the step S1 by adopting a magnetron sputtering technology;
s3, carrying out vacuum heat treatment on the first buffer layer in the step S2;
s4, depositing a composite transition layer on the first buffer layer subjected to the vacuum heat treatment in the step S3 by adopting an ion beam sputtering technology;
s5, depositing a second buffer layer on the composite transition layer in the step S4 by adopting an ion beam sputtering technology;
s6, carrying out vacuum heat treatment on the second buffer layer in the step S5;
s7, depositing an ablation resistance film on the second buffer layer subjected to the vacuum heat treatment in the step S6 by adopting an ion beam sputtering technology;
s8, depositing a protective film on the ablation resistance film in the step S4 by adopting an atomic layer deposition technology to obtain the flexible ablation resistance film.
In the above preparation method, a further improvement is that step S4 specifically includes: sequentially depositing Si on the first buffer layer3N4Layer, AlN layer, Al2O3Formation of Si layer3N4/AlN/Al2O3Composite film, periodic preparation of Si3N4/AlN/Al2O3And (5) compounding the film to obtain a composite transition layer.
In the above preparation method, further improved, in step S1, the flexible substrate is sequentially subjected to chemical cleaning and ion beam cleaning; the time for cleaning the ion beam is 15-20 min.
In the above preparation method, it is further improved that, in step S3, the vacuum heat treatment is sequentially performed at 110 to 130 ℃ for 40 to 60min and at 140 to 160 ℃ for 2 to 3h under a vacuum condition; the heating rate in the vacuum heat treatment process is 0.2-0.4 ℃/s.
In the above preparation method, it is further improved that, in step S6, the vacuum heat treatment is performed at 100 to 120 ℃ for 30 to 50min and at 140 to 150 ℃ for 1.5 to 2h in sequence under a vacuum condition; the heating rate in the vacuum heat treatment process is 0.2-0.4 ℃/s.
Compared with the prior art, the invention has the advantages that:
1. the invention provides a flexible ablation resistance film, which comprises a flexible substrate and an ablation resistance film, wherein a composite transition layer is arranged between the flexible substrate and the ablation resistance film, and the composite transition layer comprises an alternatively deposited Si3N4Layer, AlN layer, Al2O3Periodic composite films of layers. In the present invention, Si is alternately deposited according to the thermal matching coefficient of each material3N4Layer, AlN layer to Al2O3Layer of Si3N4/AlN/Al2O3Composite film of Si prepared periodically3N4/AlN/Al2O3The composite film is obtained by Si3N4、AlN、Al2O3The periodic composite film made of the material is used as a composite transition layer and arranged between the flexible substrate and the ablation resistance film, so that the defects of single material and insufficient buffer performance of the traditional transition layer can be overcome, the purposes of gradual transition and reduction of thermal stress between different film layers are achieved, and the reliable growth of the flexible film is ensured. The flexible ablation resistance film has the advantages of strong environmental interference resistance, high reliability level and the like.
2. The flexible ablation resistance film also comprises a first buffer layer arranged between the flexible substrate and the composite transition layer and a second buffer layer arranged between the composite transition layer and the ablation resistance film. In the invention, the first buffer layer is arranged between the flexible substrate and the composite transition layer to further enhance the bonding force between the flexible substrate and the composite transition layer, the second buffer layer is arranged between the composite transition layer and the ablation resistance film to further enhance the bonding force between the composite transition layer and the ablation resistance film, namely, the two buffer layers and the composite transition layer are arranged between the flexible substrate and the ablation resistance film to better realize the step-by-step buffer transition of each film layer, thereby further improving the thermal stress matching degree between the flexible substrate and the ablation resistance film, enabling the thermal stress matching of the flexible substrate and the ablation resistance film to be more perfect, further improving the environmental interference resistance and the reliability level of the flexible ablation resistance film, and enabling the flexible ablation resistance film to be applied to the heat-proof protective layers of spacecrafts such as hypersonic aircrafts, solid rocket engines and the like, can meet the ablation measurement requirements in severe environments such as high temperature, high heat flow scouring and the like.
3. The flexible ablation resistance film also comprises a protective film arranged on the ablation resistance film, and a layer of transparent ultrathin protective film is formed on the surface of the ablation resistance film, so that the ablation resistance film is prevented from being oxidized and broken under the severe environment and mechanical scratches caused in the transportation and installation processes, and the environment interference resistance and reliability level of the flexible ablation resistance film are further improved.
4. The invention also provides a preparation method of the flexible ablation resistance film, which adopts a process technology combining a magnetron sputtering technology, an ion beam sputtering technology and an atomic layer deposition technology, selects the most appropriate film preparation means and process technology according to the physical characteristics of different materials, has the advantages of simple preparation process, strong environmental adaptability, good reliability and the like, and can prepare the high-performance (such as high density, good thermal stress matching degree, strong environmental interference resistance, high reliability level and the like) flexible ablation resistance film meeting the use requirements of severe environments.
5. In the preparation method, the deposition and the vacuum heat treatment of the first buffer layer, the deposition of the composite transition layer, the deposition and the vacuum heat treatment of the second buffer layer and the deposition of the ablation resistance film are all carried out in the same processing chamber, so that the pollution caused by the traditional processing mode can be avoided, the activity of a film material is enhanced, the tight combination of different atoms is promoted, and the density and the bonding force of the film are improved.
6. In the preparation method, the first buffer layer and the second buffer layer are subjected to vacuum heat treatment, so that the crystal grains of the film can be refined, the density of the film is improved, the bonding strength among atoms of the film is further improved, and the bonding force of the film is increased.
7. In the preparation method, the atomic layer deposition technology (ALD) is adopted to deposit the protective film on the ablation resistance film, compared with the traditional deposition method, the bonding strength between the protective film and the ablation resistance film can be further improved, so that the bonding force of the film is further increased, the prepared protective film is more suitable for preventing the oxidation and the mechanical scratch of the ablation resistance film, and the method is an important guarantee for further improving the reliability of the flexible ablation resistance film.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a schematic structural diagram of a flexible ablation resistive thin film in embodiment 1 of the present invention.
FIG. 2 is a flow chart of a process for preparing a flexible ablative resistive film of example 1 of the present invention.
The reference numerals in the figures denote:
1. a flexible substrate; 2. a rigid substrate; 3. a first buffer layer; 4. si3N4A layer; 5. an AlN layer; 6. al (Al)2O3A layer; 7. a second buffer layer; 8. ablating the resistive film; 9. and (5) protecting the film.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
Example 1
A flexible ablation resistance film, as shown in figure 1, comprises a flexible substrate 1 and an ablation resistance film 8, wherein a composite transition layer is arranged between the flexible substrate 1 and the ablation resistance film 8, wherein the composite transition layer comprises Si deposited in sequence3N4Layer 4, AlN layer 5 to Al2O3Periodic composite film of layer 6.
In this embodiment, the periodic composite film takes the flexible substrate 1 as a basal plane to outwardly present "Si3N4Layer 4, AlN layer 5 to Al2O3The periodically changing tendency of the layer 6 ". The method specifically comprises the following steps: si is deposited outwards in sequence by taking the flexible substrate 1 as a basal plane3N4Layer 4, AlN layer 5, Al2O3Layer 6 forming Si3N4/AlN/Al2O3Composite film, periodic preparation of Si3N4/AlN/Al2O3And (5) compounding the film to obtain a periodic composite film, namely the composite transition layer.
In this example, the number of cycles of the periodic composite film was 7, where Si was3N4The monolayer thickness of the layer 4 is 65nm, the monolayer thickness of the AlN layer 5 is 85nm, and Al2O3The monolayer thickness of layer 6 is 93 nm.
In this embodiment, the flexible ablation resistive thin film further includes a first buffer layer 3 and a second buffer layer 7, the first buffer layer 3 is disposed between the flexible substrate 1 and the composite transition layer, and the second buffer layer 7 is disposed between the composite transition layer and the ablation resistive thin film 8; wherein, the first buffer layer 3 is a C film with the thickness of 70 nm; the second buffer layer 7 is an Al thin film with a thickness of 50 nm.
In this embodiment, a protective film 9 is disposed on the ablation resistance thin film 8, wherein the protective film 9 is a dielectric material, specifically, SiO2And the thickness of the film is 10 nm.
In this embodiment, the flexible substrate 1 is an ethylene propylene diene monomer film, the length and width dimensions of which are 40mm × 28mm, and the thickness of which is 0.3 mm.
In this embodiment, the ablation resistance thin film 8 is a metal thin film having a resistivity of not more than 30n Ω · m, specifically, an Au thin film, and the thickness of the ablation resistance thin film 8 is 4 μm.
The preparation method of the flexible ablation resistance thin film of the embodiment has the preparation process flow shown in fig. 2, and includes the following steps:
(1) an ethylene propylene diene monomer film with the length and width of 40mm multiplied by 28mm and the thickness of 0.3mm is taken as a flexible substrate 1, the flexible substrate 1 is chemically cleaned, and oil stains, impurity stains and the like on the polished surface of the substrate are removed.
(2) And (2) uniformly adhering the back surface of the chemically cleaned flexible substrate 1 in the step (1) to a rigid substrate 2 (the rigid substrate 2 is a stainless steel sheet with the same size as the flexible substrate 1) by using high-temperature glue, and curing at a constant temperature of 80 ℃ for 2 hours to obtain a cured substrate. The flexible substrate 1 is fixed on the stainless steel sheet through high-temperature glue, so that the surface of the flexible substrate is kept flush in the installation and film deposition processes, and reliable preparation of the film is facilitated.
(3) And (3) fixing the cured substrate in the step (2) on a substrate table of a magnetic control-ion beam all-in-one machine, performing ion beam cleaning on the polished surface of the flexible substrate 1 for 18min by using an ion beam, removing pits and residual microparticles on the surface of the substrate, and activating the activity of the flexible substrate.
(4) And (3) depositing a first buffer layer 3 (specifically, a C film) on the surface of the flexible substrate 1 subjected to the cleaning and micro-polishing treatment in the step (3) by adopting a magnetron sputtering technology, so as to enhance the bonding force between the composite transition film layer and the flexible substrate. By magnetron sputteringThe specific parameters for depositing the C film are that the air pressure is 1.0 multiplied by 10-2Pa, 800V of screen electrode and 160mA of beam current.
(5) Vacuum-pumping to 5.0 × 10-4Pa, introducing N2Setting the flow rate to be 12 sccm-15 sccm, performing vacuum heat treatment on the first buffer layer 3 (specifically, the C film) obtained in the step (4) under the vacuum condition, refining C film crystal grains through the vacuum heat treatment, and improving the interatomic bonding strength of the film; meanwhile, the problems that dust particles are easy to generate in the traditional preparation process and the like can be avoided. The vacuum heat treatment is specifically that the temperature is raised to 120 ℃ for heat treatment for 50min at the temperature raising rate of 0.4 ℃/s, and then the temperature is raised to 150 ℃ for heat treatment for 2h at the temperature raising rate of 0.4 ℃/s.
(6) Respectively introducing N2、O2Depositing a composite transition layer on the first buffer layer 3 (specifically, the C film) subjected to the vacuum heat treatment in the step (5) by adopting an ion beam sputtering technology, specifically, sequentially depositing Si on the first buffer layer 3 (specifically, the C film)3N4Layer 4, AlN layer 5, Al2O3Layer 6 forming Si3N4/AlN/Al2O3Composite film, periodic preparation of Si3N4/AlN/Al2O3And (3) compounding the film, wherein the periodicity n is 7, so that a periodic compounding film, namely a compounding transition layer, is obtained.
Deposition of Si by ion beam sputtering3N4The specific parameter of the layer 4 is the gas pressure 4.1X 10-2Pa，N222.5sccm, aligning the vent hole to the surface of the substrate, heating the substrate at 235 ℃, shielding the electrode at 630V and performing beam current at 180 mA.
The specific parameters for depositing the AlN layer 5 by the ion beam sputtering technique are that the gas pressure is 3.5 multiplied by 10-2Pa，N219.5sccm, aligning the vent hole to the surface of the substrate, heating the substrate at 160 ℃, shielding 450V and beam current of 100 mA.
Deposition of Al by ion beam sputtering2O3The specific parameter of the layer 6 is the gas pressure 4.5X 10-2Pa，N2And (5) 25sccm, aligning the vent hole to the surface of the substrate, heating the substrate at 260 ℃, shielding 800V and performing beam current 160 mA.
In the preparation process of the composite transition layer, Si is sputtered3N4Layer 4, AlN layer 5, Al2O3The target needs to be ion beam cleaned prior to layer 6 to remove surface oxides and impurities.
(7) And (3) depositing a second buffer layer 7 (specifically an Al film) on the composite transition layer obtained in the step (6) by adopting an ion beam sputtering technology to enhance the bonding force between the ablation resistance film and the composite transition layer. The specific parameters of the Al film deposited by the ion beam sputtering technology are that the air pressure is 3.0 multiplied by 10-2Pa, screen electrode 400V and beam current 130 mA.
(8) Vacuum-pumping to 5.0 × 10-4Pa, introducing N2And (3) setting the flow rate to be 12 sccm-15 sccm, performing vacuum heat treatment on the second buffer layer 7 (specifically the Al thin film) obtained in the step (7) under the vacuum condition, refining Al thin film grains through the vacuum heat treatment, and improving the interatomic bonding strength of the thin film. The vacuum heat treatment is specifically that the temperature is raised to 100 ℃ for heat treatment for 40min at the temperature raising rate of 0.2 ℃/s, and then the temperature is raised to 140 ℃ for heat treatment for 2h at the temperature raising rate of 0.2 ℃/s.
(9) And (3) depositing an ablation resistance thin film 8 (specifically, an Au thin film) on the second buffer layer 7 (specifically, an Al thin film) subjected to the vacuum heat treatment in the step (8) by using an ion beam sputtering technology. The specific parameters of the Au film deposited by the ion beam sputtering technology are as follows: air pressure of 3.0 x 10-2Pa, screen electrode 500V and beam current 120 mA.
The preparation processes in the steps (3) to (9) are all carried out on the magnetic control-ion beam integrated machine, wherein a vacuum valve is arranged between the magnetic control cavity and the ion beam cavity, the fixed substrate is transferred from the magnetic control cavity to the ion beam cavity through a vacuum transfer rod, a cavity does not need to be taken out, pollution outside the cavity is avoided, and the reliability of the film is ensured.
(10) Depositing a protective film 9 (specifically SiO) on the ablated resistive film 8 (specifically Au film) of step (6) by atomic deposition2Thin films) to prevent oxidation, cracking, and mechanical scratching of the ablative resistive thin films. Deposition of SiO by atomic deposition2The specific parameters of the film are 4.5X 10 of air pressure-2Pa，N225sccmThe vent hole is aligned to the surface of the substrate, the substrate is heated, the temperature is 260 ℃, the screen electrode is 800V, and the beam current is 160 mA.
(11) And (3) disassembling the rigid substrate (2) (specifically a stainless steel sheet), and removing the high-temperature glue on the back surface of the flexible substrate by adopting a chemical method to obtain the ablation resistance film.
The ablated resistive film prepared in example 1 was examined. The 3M600 adhesive tape is adhered to the protective film of the ablation resistance film, is compressed and then is torn upwards, and as a result, the ablation resistance film is intact and has no phenomena of fracture, falling and the like. The product adopting the ablation resistance film is tested under severe environmental conditions of high temperature, high heat flow scouring and the like of simulating the running environment of hypersonic aircrafts and solid rocket engines, and the result is that the phenomena of engine burn-through and the like do not occur. The ablation resistance film has the advantages of strong environmental interference resistance, high reliability level and the like, can be applied to heat-proof protective layers of spacecrafts such as hypersonic aircrafts, solid rocket engines and the like, can realize ablation measurement of the spacecrafts such as the hypersonic aircrafts, the solid rocket engines and the like in severe environments such as high temperature and high heat flux scouring and the like, and has important significance for improving the application reliability of the spacecrafts such as the hypersonic aircrafts, the solid rocket engines and the like.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (6)
1. A flexible ablative resistive film, characterized in that it comprises a flexible substrate (1) and an ablative resistive film (8); a composite transition layer is arranged between the flexible substrate (1) and the ablation resistance thin film (8); the composite transition layer comprises an alternating deposit of Si3N4Layer (4), AlN layer (5) and Al2O3A periodic composite film of layer (6); the periodic composite film takes a flexible substrate (1) as a basal plane and outwards presents' Si3N4Layer (4), AlN layer (5) to Al2O3The tendency of the layer (6) "to change periodically; the periodicity of the periodic composite film is 7-10; in the periodic composite film, the Si3N4The monolayer thickness of the layer (4) is 50 nm-150 nm, the monolayer thickness of the AlN layer (5) is 50 nm-150 nm, and the Al is2O3The thickness of the single layer of the layer (6) is 50 nm-150 nm; the flexible ablative resistive thin film further comprises a first buffer layer (3) and a second buffer layer (7); the first buffer layer (3) is arranged between the flexible substrate (1) and the composite transition layer; the second buffer layer (7) is arranged between the composite transition layer and the ablation resistance thin film (8); the first buffer layer (3) is a C film; the thickness of the first buffer layer (3) is 50 nm-100 nm; the second buffer layer (7) is an Al film; the thickness of the second buffer layer (7) is 50 nm-100 nm; the flexible substrate (1) is an ethylene propylene diene monomer film; the thickness of the flexible substrate (1) is 0.3-0.5 mm; the ablation resistance film (8) is a metal film with the resistivity less than or equal to 30n omega-m; the metal film is an Au film or a Cu film; the thickness of the ablation resistance film (8) is 3.5-4 mu m.
2. The flexible ablative resistive film of claim 1, wherein a protective film (9) is provided on the ablative resistive film (8); the protective film (9) is made of a dielectric material; the dielectric material is SiO2A film; the thickness of the protective film (9) is 5 nm-20 nm.
3. A method of making a flexible ablative resistive film of claim 2, comprising the steps of:
s1, cleaning the flexible substrate (1);
s2, depositing a first buffer layer (3) on the surface of the flexible substrate (1) cleaned in the step S1 by adopting a magnetron sputtering technology;
s3, carrying out vacuum heat treatment on the first buffer layer (3) in the step S2;
s4, depositing a composite transition layer on the first buffer layer (3) subjected to the vacuum heat treatment in the step S3 by adopting an ion beam sputtering technology;
s5, depositing a second buffer layer (7) on the composite transition layer in the step S4 by adopting an ion beam sputtering technology;
s6, carrying out vacuum heat treatment on the second buffer layer (7) in the step S5;
s7, depositing an ablation resistance film (8) on the second buffer layer (7) subjected to the vacuum heat treatment in the step S6 by adopting an ion beam sputtering technology;
and S8, depositing a protective film (9) on the ablation resistance film (8) in the step S7 by adopting an atomic layer deposition technology to obtain the flexible ablation resistance film.
4. The preparation method according to claim 3, wherein the step S4 is specifically: depositing Si on the first buffer layer (3) in sequence3N4Layer (4), AlN layer (5), Al2O3Layer (6) forming Si3N4/AlN/Al2O3Composite film, periodic preparation of Si3N4/AlN/Al2O3And (5) compounding the film to obtain a composite transition layer.
5. The production method according to claim 3 or 4, wherein in step S1, the flexible substrate (1) is subjected to chemical cleaning, ion beam cleaning in sequence; the time for cleaning the ion beam is 15-20 min.
6. The preparation method according to claim 3 or 4, wherein in step S3, the vacuum heat treatment is performed under vacuum conditions of 110-130 ℃ for 40-60 min and 140-160 ℃ for 2-3 h; the heating rate in the vacuum heat treatment process is 0.2-0.4 ℃/s;
and/or in step S6, the vacuum heat treatment is carried out for 30 min to 50min at 100 ℃ to 120 ℃ and for 1.5 h to 2h at 140 ℃ to 150 ℃ in sequence under the vacuum condition; the heating rate in the vacuum heat treatment process is 0.2-0.4 ℃/s.
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