阅读说明：本技术 一种胶接固化吸波复合材料及其制备方法 (Adhesive curing wave-absorbing composite material and preparation method thereof ) 是由 李阳 刘甲 朱伟杰 闫丽生 宫元勋 于 2021-08-24 设计创作，主要内容包括：本发明提供了一种胶接固化吸波复合材料及其制备方法,该制备方法包括如下步骤：(1)将已固化的复合材料置于成型模具上,然后铺覆胶粘剂,得到铺覆有胶粘层的复合材料基体；(2)在所述铺覆有胶粘层的复合材料基体上铺覆至少一层吸波胶膜,得到吸波复合材料基体；其中,所述吸波胶膜包含：吸波剂和吸波树脂；(3)在所述吸波复合材料基体上铺覆至少一层用作阻抗匹配层的第一预浸料,得到包含阻抗匹配层的吸波复合材料基体,然后进行固化处理,得到所述胶接固化吸波复合材料。本方案提供的胶接固化吸波复合材料制备方法能够降低复合材料报废率。(The invention provides a glue-bonded cured wave-absorbing composite material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) placing the cured composite material on a forming die, and then paving an adhesive to obtain a composite material matrix paved with an adhesive layer; (2) paving at least one wave-absorbing adhesive film on the composite material matrix paved with the adhesive layer to obtain a wave-absorbing composite material matrix; wherein, the ripples glued membrane that absorbs water contains: wave absorbing agent and wave absorbing resin; (3) and paving at least one layer of first prepreg used as an impedance matching layer on the wave-absorbing composite material matrix to obtain the wave-absorbing composite material matrix containing the impedance matching layer, and then carrying out curing treatment to obtain the adhesive bonding cured wave-absorbing composite material. The preparation method of the adhesive bonding curing wave-absorbing composite material can reduce the rejection rate of the composite material.)

1. A preparation method of a glue-bonded cured wave-absorbing composite material is characterized by comprising the following steps:

(1) placing the cured composite material on a forming die, and then paving an adhesive to obtain a composite material matrix paved with an adhesive layer;

(2) paving at least one wave-absorbing adhesive film on the composite material matrix paved with the adhesive layer to obtain a wave-absorbing composite material matrix; wherein, the ripples glued membrane that absorbs water contains: wave absorbing agent and wave absorbing resin;

(3) and paving at least one layer of first prepreg used as an impedance matching layer on the wave-absorbing composite material matrix to obtain the wave-absorbing composite material matrix containing the impedance matching layer, and then carrying out curing treatment to obtain the adhesive bonding cured wave-absorbing composite material.

2. The production method according to claim 1, wherein in step (1):

the cured composite is a laminate composite, a honeycomb sandwich composite, or a foam sandwich composite; wherein the shape of the forming die matches the shape of the cured composite material; and/or

Before the solidified composite material is placed on the forming mould, the method further comprises the following steps: and (3) polishing the surface of the cured composite material by using 200-600-mesh sand paper.

3. The method of claim 1, wherein:

in the step (1), the adhesive is at least one selected from the group consisting of an epoxy resin film, a urethane resin film, a cyanate resin film, a polyimide resin film, a bismaleimide resin film and a phenol resin film.

4. The method of claim 1, wherein:

after the step (1) and before the step (2), further comprising:

paving at least one layer of second prepreg used as a reflecting layer on the composite material matrix paved with the adhesive layer, and then performing pre-compaction to obtain the composite material matrix containing the reflecting layer;

the second prepreg is a carbon fiber prepreg formed by compounding carbon fiber cloth and prepreg resin; wherein the prepreg resin is at least one selected from cyanate ester resin, epoxy resin, polyurethane resin, phenolic resin, polyimide resin and bismaleimide resin;

the thickness of the reflecting layer is more than or equal to 0.2 mm.

5. The method of claim 4, wherein:

pre-compacting after each layer or two layers of the second prepreg are laid; and/or

The pre-compaction temperature is 25-40 ℃, the pressure is 0.8-3MPa, and the pre-compaction time is 10-15 min.

6. The production method according to claim 1, wherein in step (2):

the wave absorbing agent is at least one selected from ferrite powder, carbonyl iron powder, conductive carbon black, carbon fiber, silicon carbide fiber, carbon nano tube and graphene;

the wave-absorbing resin is at least one selected from epoxy resin, polyurethane resin, cyanate resin and polyimide resin.

7. The production method according to claim 1, wherein in step (2):

the thickness of the wave-absorbing adhesive film is 0.1-5 mm;

the mass ratio of the wave absorbing agent to the wave absorbing resin in the wave absorbing adhesive film is 1-17: 20.

8. The production method according to claim 1, wherein in step (2):

when the mass fraction of the wave absorbing agent in the wave absorbing adhesive film is more than or equal to 75 percent, the method also comprises the step of laying a layer of resin film after laying each layer of the wave absorbing adhesive film; wherein the resin film is at least one selected from the group consisting of a cyanate resin film, a urethane resin film, an epoxy resin film, a phenol resin film, a polyimide resin film, and a bismaleimide resin; and/or;

and pre-compacting after one or two layers of the wave-absorbing adhesive films are paved.

9. The production method according to any one of claims 1 to 8, characterized in that, in step (3):

the first prepreg is formed by compounding prepreg resin and glass fiber cloth or quartz fiber cloth; wherein the prepreg resin is at least one selected from cyanate ester resin, epoxy resin, polyurethane resin, phenolic resin, polyimide resin and bismaleimide resin; and/or

The curing temperature of the curing treatment is 90-350 ℃, the curing time is 100-.

10. A glue-bonded cured wave-absorbing composite material, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of wave-absorbing materials, in particular to a glue-bonded cured wave-absorbing composite material and a preparation method thereof.

Background

The wave-absorbing material is a functional material which can be used for attenuating incident radar waves so as to reduce the radar scattering cross section, and is widely applied to the fields of airplane stealth, ship stealth, flying missile stealth, tank stealth and the like. The wave-absorbing adhesive film is a special wave-absorbing material prepared from a resin matrix and an absorbent, has the characteristics of good paving and following property, convenient construction and capability of being integrally glued, cured and molded with a composite material product compared with a wave-absorbing coating material and a wave-absorbing patch material, and is commonly used for preparing the wave-absorbing composite material.

At present, for the existing cured composite material, when the higher requirement on the wave absorption performance of the composite material is provided, the composite material meeting the requirement on the wave absorption performance is often adopted to be directly replaced, but the rejection rate of the composite material is inevitably higher. Therefore, for the cured composite material, a method for improving the wave absorption performance of the composite material on the basis of not changing the original composite material structure is urgently needed.

Disclosure of Invention

The invention provides a glue curing wave-absorbing composite material and a preparation method thereof, and the provided preparation method of the glue curing wave-absorbing composite material can reduce the rejection rate of the composite material and improve the wave-absorbing performance of the existing composite material.

In a first aspect, the invention provides a preparation method of a glue curing wave-absorbing composite material, which comprises the following steps:

(1) placing the cured composite material on a forming die, and then paving an adhesive to obtain a composite material matrix paved with an adhesive layer;

(2) paving at least one wave-absorbing adhesive film on the composite material matrix paved with the adhesive layer to obtain a wave-absorbing composite material matrix; wherein, the ripples glued membrane that absorbs water contains: wave absorbing agent and wave absorbing resin;

(3) and paving at least one layer of first prepreg used as an impedance matching layer on the wave-absorbing composite material matrix to obtain the wave-absorbing composite material matrix containing the impedance matching layer, and then carrying out curing treatment to obtain the adhesive bonding cured wave-absorbing composite material.

Preferably, in step (1), the cured composite is a laminate composite, a honeycomb sandwich composite or a foam sandwich composite; wherein the shape of the forming die matches the shape of the cured composite material.

Preferably, in step (1), before placing the cured composite material on the forming mold, the method further comprises: and (3) polishing the surface of the cured composite material by using 200-600-mesh sand paper.

Preferably, in the step (1), the adhesive is at least one selected from the group consisting of an epoxy resin film, a urethane resin film, a cyanate resin film, a polyimide resin film, a bismaleimide resin film and a phenol resin film.

Preferably, after the step (1) and before the step (2), further comprising:

paving at least one layer of second prepreg used as a reflecting layer on the composite material matrix paved with the adhesive layer, and then performing pre-compaction to obtain the composite material matrix containing the reflecting layer;

the second prepreg is a carbon fiber prepreg formed by compounding carbon fiber cloth and prepreg resin; wherein the prepreg resin is at least one selected from cyanate ester resin, epoxy resin, polyurethane resin, phenolic resin, polyimide resin and bismaleimide resin;

the thickness of the reflecting layer is more than or equal to 0.2 mm.

Preferably, pre-compaction is performed after each application of one or two layers of the second prepreg.

Preferably, the pre-compaction temperature is 25-40 ℃, the pressure is 0.8-3MPa, and the pre-compaction time is 10-15 min.

Preferably, in the step (2), the wave absorbing agent is at least one selected from ferrite powder, carbonyl iron powder, conductive carbon black, carbon fiber, silicon carbide fiber, carbon nanotube and graphene;

the wave-absorbing resin is at least one selected from epoxy resin, polyurethane resin, cyanate resin and polyimide resin.

Preferably, in the step (2), the thickness of the wave-absorbing glue film is 0.1-5 mm;

the mass ratio of the wave absorbing agent to the wave absorbing resin in the wave absorbing adhesive film is 1-17: 20.

Preferably, in the step (2), when the mass fraction of the wave absorbing agent in the wave absorbing adhesive film is more than or equal to 75%, the method further comprises the step of paving a resin film after paving one layer of the wave absorbing adhesive film; wherein the resin film is at least one selected from the group consisting of a cyanate resin film, a urethane resin film, an epoxy resin film, a phenol resin film, a polyimide resin film, and a bismaleimide resin.

Preferably, in the step (2), pre-compaction is performed after one or two layers of the wave-absorbing adhesive film are laid.

Preferably, in the step (3), the first prepreg is formed by compounding prepreg resin and glass fiber cloth or quartz fiber cloth; wherein the prepreg resin is at least one selected from cyanate ester resin, epoxy resin, polyurethane resin, phenolic resin, polyimide resin and bismaleimide resin.

Preferably, in the step (3), the curing temperature of the curing treatment is 90-350 ℃, the curing time is 100-240min, and the curing pressure is 0.075-0.7 MPa.

In a second aspect, the invention provides a glue curing wave-absorbing composite material prepared by the preparation method of the first aspect of the invention.

Compared with the prior art, the invention at least has the following beneficial effects:

(1) the prepared adhesive bonding curing wave-absorbing composite material comprises a reflecting layer, a wave-absorbing layer and an impedance matching layer, can carry out secondary processing on the existing cured composite material which does not have wave-absorbing performance or does not meet the requirement of the current wave-absorbing performance, and has more excellent wave-absorbing performance on the basis of not changing the structure of the original composite material, thereby reducing the rejection rate of the composite material and improving the resource utilization rate of the existing composite material; meanwhile, the service life of the composite material is prolonged, and the production and maintenance cost is reduced.

(2) According to the preparation method of the glue-bonding curing wave-absorbing composite material, the wave-absorbing adhesive film with good paving and following properties is used as the wave-absorbing layer, so that the wave-absorbing performance and the mechanical property of the glue-bonding curing wave-absorbing composite material can be controllably improved, and the construction of operators is more convenient.

Drawings

FIG. 1 is a schematic structural diagram of a glue-cured wave-absorbing composite material prepared in example 1 of the present invention;

FIG. 2 is a reflectivity curve diagram of the adhesive cured wave-absorbing composite material prepared in example 1 of the present invention;

FIG. 3 is a reflectivity curve diagram of the adhesive cured wave-absorbing composite material prepared in example 2 of the present invention;

FIG. 4 is a graph comparing the reflectivity curves of the adhesive cured wave-absorbing composite material prepared in example 3 before damage and after repair.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.

The invention provides a preparation method of a glue-bonded cured wave-absorbing composite material, which comprises the following steps:

(1) placing the cured composite material on a forming die, and then paving an adhesive to obtain a composite material matrix paved with an adhesive layer;

(2) paving at least one wave-absorbing adhesive film on the composite material matrix paved with the adhesive layer to obtain a wave-absorbing composite material matrix; wherein, the ripples glued membrane that absorbs water contains: wave absorbing agent and wave absorbing resin;

(3) and paving at least one layer of first prepreg used as an impedance matching layer on the wave-absorbing composite material matrix to obtain the wave-absorbing composite material matrix containing the impedance matching layer, and then carrying out curing treatment to obtain the adhesive bonding cured wave-absorbing composite material.

According to some preferred embodiments, in step (1), the cured composite is a laminate composite, a honeycomb sandwich composite or a foam sandwich composite; wherein the shape of the forming die matches the shape of the cured composite material.

For example, if the cured composite material is in a flat plate shape, the forming mold is a flat plate tooling (i.e. the profile of the tooling is consistent with the profile of the cured composite material); if the cured composite material is arc-shaped, the forming die is an arc-shaped tool (the molded surface of the tool is consistent with the molded surface of the cured composite material).

According to some preferred embodiments, in step (1), before placing the cured composite material on the forming mold, further comprising: the surface of the cured composite material is sanded with 200-600 mesh (e.g., 200, 300, 400, 500, or 600 mesh) sandpaper.

In the invention, in order to ensure that the adhesive can be stably adhered to the cured composite material, the surface of the cured composite material needs to be polished to form a rough surface, so that the wave-absorbing adhesive film can be stably paved on the adhesive of the composite material, and debonding or layering is avoided.

According to some preferred embodiments, in the step (1), the adhesive is at least one selected from the group consisting of an epoxy resin film, a urethane resin film, a cyanate resin film, a polyimide resin film, a bismaleimide resin film and a phenol resin film.

It should be noted that the adhesive may also be a structural adhesive, including a normal temperature cured structural adhesive or a medium temperature cured structural adhesive, and commonly used structural adhesive brands include but are not limited to 914 normal temperature cured structural adhesive (purchased from Yanhai chemical Co., Ltd., Tianjin), J133C, and J-47A medium temperature cured structural adhesive (all purchased from petrochemical research institute of academy of sciences of Heilongjiang province).

At least one of them is a mixture of any one or any several of them mixed in any ratio.

In the invention, the adhesive can enhance the connection strength of the magnetic wave-absorbing adhesive film and the composite material.

According to some preferred embodiments, after step (1) and before step (2), further comprising:

paving at least one layer of second prepreg used as a reflecting layer on the composite material matrix paved with the adhesive layer, and then performing pre-compaction to obtain the composite material matrix containing the reflecting layer;

the second prepreg is a carbon fiber prepreg formed by compounding carbon fiber cloth and prepreg resin; wherein the prepreg resin is at least one selected from cyanate ester resin, epoxy resin, polyurethane resin, phenolic resin, polyimide resin and bismaleimide resin;

the thickness of the reflective layer is 0.2mm or more (for example, 0.2mm, 0.4mm, 1mm, 1.5mm or 2 mm).

In the invention, the carbon fiber has good dielectric and conductive capacities and is a dielectric loss type wave-absorbing material. When electromagnetic waves propagate among the carbon fibers, in addition to electromagnetic energy loss caused by the skin effect, part of the electromagnetic waves are scattered among the carbon fiber bundles to generate a phase cancellation-like phenomenon, so that the reflection of the electromagnetic waves can be reduced, and part of the energy of the electromagnetic waves can be consumed. Meanwhile, the continuous carbon fiber cloth has good conductivity and can generate strong reflection effect on electromagnetic waves, so that the continuous carbon fiber cloth can be used as a reflection layer to reflect the electromagnetic waves and be secondarily lost, and the wave absorbing performance of the adhesive bonding curing wave absorbing composite material is further improved.

According to some preferred embodiments, pre-compaction is performed after each application of one or two layers of the second prepreg.

According to some preferred embodiments, the pre-compaction temperature is 25-40 ℃ (e.g., 25 ℃, 30 ℃, 35 ℃ or 40 ℃) and the pressure is 0.8-3MPa (e.g., 0.8, 1, 1.5, 2, 2.5 or 3MPa), and the pre-compaction time is 10-15min (e.g., 10min, 11min, 12min, 13min, 14min or 15 min).

According to some preferred embodiments, in the step (2), the wave absorbing agent is at least one selected from ferrite powder, carbonyl iron powder, conductive carbon black, carbon fiber, silicon carbide fiber, carbon nanotube and graphene;

the wave-absorbing resin is at least one selected from epoxy resin, polyurethane resin, cyanate resin and polyimide resin.

According to some preferred embodiments, in the step (2), the thickness of the wave-absorbing adhesive film is 0.1-5mm (for example, 0.1mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm or 5mm may be possible);

the mass ratio of the wave absorbing agent to the wave absorbing resin in the wave absorbing adhesive film is 1-17:20 (for example, 1:20, 2:20, 5:20, 10:20, 15:20 or 17: 20).

In the invention, the wave-absorbing adhesive film can be obtained according to the wave-absorbing adhesive film material with the application number of CN202010950674.3 and the preparation method disclosed by the preparation method, the wave-absorbing adhesive film material produced by the mixing and calendering method has no problem of wave-absorbing agent sedimentation, the interior of the adhesive film is compact and uniform, the stability of batch production is improved, an organic solvent is not used in the whole production process, and the production cost is effectively reduced while the problem of environmental protection is solved.

According to some preferred embodiments, in the step (2), when the mass fraction of the wave-absorbing agent in the wave-absorbing adhesive film is greater than or equal to 75% (for example, it may be 75%, 80%, 85%, or 90%), the method further comprises the step of laying a resin film after each layer of the wave-absorbing adhesive film is laid; wherein the resin film is at least one selected from the group consisting of a cyanate resin film, a urethane resin film, an epoxy resin film, a phenol resin film, a polyimide resin film, and a bismaleimide resin.

In the invention, when the content of the wave absorbing agent in the wave absorbing adhesive films is more than or equal to 75 percent, a layer of resin film is required to be laid between each layer of wave absorbing adhesive film to increase the bonding strength between the wave absorbing adhesive films and avoid layering and debonding between the wave absorbing adhesive films, thereby ensuring the mechanical property of the adhesive cured wave absorbing composite material.

According to some preferred embodiments, in the step (2), pre-compaction is performed after each one or two layers of the wave-absorbing adhesive film are laid. And when the mass fraction of the wave absorbing agent in the wave absorbing adhesive film is more than or equal to 75%, pre-compacting after the wave absorbing adhesive film and the resin film are sequentially paved. Wherein the pre-compacting temperature is 25-40 deg.C (for example, 25 deg.C, 30 deg.C, 35 deg.C or 40 deg.C), the pressure is 0.8-3MPa (for example, 0.8MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa or 3MPa), and the pre-compacting time is 10-15min (for example, 10min, 11min, 12min, 13min, 14min or 15 min).

Specifically, when the size of the wave-absorbing adhesive film is less than or equal to 500mm multiplied by 500mm, pre-compaction can be performed after 2 layers of wave-absorbing adhesive films are laid; when the size of the wave-absorbing adhesive film is more than 500mm multiplied by 500mm, 1 layer of wave-absorbing adhesive film needs to be paved and pre-compacted once so as to completely discharge gas between layers during paving and avoid bubbles, bulges and the like from influencing the mechanical properties of the adhesive bonding curing wave-absorbing composite material. More specifically, the thickness of the paved wave-absorbing adhesive film can be calculated according to the requirement on the wave-absorbing performance of the composite material.

In the invention, the paving manufacturability of the wave-absorbing adhesive film is not influenced by the thickness of the wave-absorbing adhesive film and the paving curved surface, is suitable for paving various curved surfaces, and has higher technological operability, better mechanical property and more convenient operation compared with the wave-absorbing paster. And the wave-absorbing adhesive film with the same thickness have better wave-absorbing performance than the wave-absorbing adhesive film, so that when the wave-absorbing adhesive film is paved on a composite material with specific wave-absorbing performance requirements, multiple layers of the wave-absorbing adhesive film need to be paved, the composite material is too thick, the paving manufacturability is further influenced, and the mechanical property of the obtained composite material is also influenced due to the lower adhesive force.

According to some preferred embodiments, in the step (3), the first prepreg is formed by compounding prepreg resin and glass fiber cloth or quartz fiber cloth; wherein the prepreg resin is at least one selected from cyanate ester resin, epoxy resin, polyurethane resin, phenolic resin, polyimide resin and bismaleimide resin.

According to some more preferred embodiments, in step (3), pre-compaction is performed after each layer or two layers of the second prepreg are laid, wherein the pre-compaction temperature is 25 to 40 ℃ (for example, 25 ℃, 30 ℃, 35 ℃ or 40 ℃), the pressure is 0.8 to 3MPa (for example, 0.8MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa or 3MPa), and the pre-compaction time is 10 to 15min (for example, 10min, 11min, 12min, 13min, 14min or 15 min).

In the invention, the impedance matching layer is added on the surface of the wave-absorbing adhesive film and is used for impedance matching between the wave-absorbing adhesive film and air so as to improve the absorption efficiency of the wave-absorbing layer on electromagnetic waves and provide good impedance matching performance for the adhesive bonding curing wave-absorbing composite material.

According to some preferred embodiments, in the step (3), the curing temperature of the curing treatment is 90 to 350 ℃ (for example, may be 90 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃ or 350 ℃), the curing time is 100-.

In the curing treatment, the temperature rise rate is 0.15 to 3 ℃/min (for example, 0.15 ℃/min, 0.2 ℃/min, 0.5 ℃/min, 0.75 ℃/min, 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min, or 3 ℃/min), and the temperature fall rate is not more than 3 ℃/min (for example, 0.15 ℃/min, 0.2 ℃/min, 0.5 ℃/min, 0.75 ℃/min, 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min, or 3 ℃/min).

In the invention, fig. 1 shows a schematic structural diagram of a glue-bonding cured wave-absorbing composite material, wherein 1 is used for representing the surface of the cured composite material after polishing treatment; 2 is for an adhesive layer; 3 is used to denote a reflective layer; 4, the wave-absorbing layer obtained after the wave-absorbing adhesive film is laid in the step (2) is used for representing, and the wave-absorbing composite material matrix is obtained by the components 1, 2, 3 and 4 in the figure 1; and 5 is used to denote an impedance matching layer.

It should be noted that the thicknesses of the reflecting layer, the wave-absorbing layer and the impedance matching layer can be designed according to the mechanical property and the wave-absorbing property of the required composite material. The structural schematic of the cured composite material containing the reflective layer includes only 1, 2, 4, and 5.

The invention also provides an adhesive curing wave-absorbing composite material, which is prepared by the preparation method of the adhesive curing wave-absorbing composite material.

According to the invention, the wave-absorbing adhesive film can be subjected to secondary curing molding with the cured and molded composite material, so that the wave-absorbing adhesive film has stealth performance on the basis of not changing the appearance of the original composite material member, and becomes a structural/stealth integrated composite material; meanwhile, the wave absorbing layer on the surface of the structure/stealth integrated composite material can be repaired, and the rejection rate of the structure/stealth integrated composite material is reduced.

In order to more clearly illustrate the technical scheme and advantages of the present invention, the following will describe in detail a method for preparing a glue-cured wave-absorbing composite material by using several embodiments.

In the following embodiments, the preparation method of the wave-absorbing adhesive film comprises the following steps: the preparation method disclosed by CN202010950674.3 (a wave-absorbing adhesive film material and a preparation method thereof) is adopted:

firstly, putting wave-absorbing resin and a wave-absorbing agent into an internal mixer for banburying and rough mixing to obtain rough-mixed wave-absorbing resin; the technological conditions of banburying and coarse mixing are as follows: the temperature of the banburying and rough mixing is 150 ℃, the time of the banburying and rough mixing is 45min, and the rotating speed of a rotor of the banburying and rough mixing is 200 r/min;

secondly, putting the rough mixed wave-absorbing resin obtained in the first step into a resin open mill for refining and fine mixing to obtain a wave-absorbing resin blank which is uniformly mixed; the technological conditions for refining and mixing are as follows: the temperature of the starting and refining mixture is 180 ℃, the time of the starting and refining mixture is 45min, and the roller speed of the starting and refining mixture is 12 m/min;

placing the wave-absorbing resin blank obtained in the step two into a precision calender for precision calendering of the wave-absorbing adhesive film, and obtaining the wave-absorbing resin adhesive film after calendering; the process conditions of calendering are as follows: the temperature of the rolling is 150 ℃, the pressure of the rolling is 1000N, and the speed of the rolling is 4 m/s;

and fourthly, pasting the base cloth and the release film on the wave-absorbing resin adhesive film obtained in the third step through a thermal pasting machine, cutting and then rolling to complete the preparation of the wave-absorbing adhesive film material.

Example 1

(1) Selecting a metal flat plate tool matched with a flat plate-shaped cured composite material as a forming die, cleaning the forming surface of the forming die by using acetone, and brushing a release agent for 3 times, wherein the time interval of brushing the release agent for each time is 10 min;

placing the cured composite material on a forming die, polishing the surface of the cured composite material by using 500-mesh abrasive paper, and then spreading 1 layer of adhesive (3068 epoxy resin film with the thickness of 0.1mm) on the surface of the polished cured composite material to obtain a composite material matrix spread with an adhesive layer; wherein, the resin matrix of the cured composite material is 3068 epoxy resin, has no wave-absorbing performance, has the thickness of 2mm and the size of 600mm multiplied by 600 mm;

(2) paving second prepreg (compounded by carbon fiber cloth and epoxy resin) on the composite material matrix paved with the adhesive layer obtained in the step (1), and pre-compacting for 15min by paving 2 layers of second prepreg every time to obtain a composite material matrix containing a reflecting layer with the thickness of 0.4 mm;

(3) paving wave-absorbing adhesive films (wherein the mass fraction of the wave-absorbing agent is 70%) on the composite material substrate containing the reflecting layer obtained in the step (2), and pre-compacting for 15min for 1 layer of wave-absorbing adhesive film to obtain a wave-absorbing composite material substrate containing a wave-absorbing layer with the thickness of 2.6 mm; wherein, inhale ripples glued membrane contains: carbonyl iron powder and epoxy resin;

(4) paving a first prepreg (formed by compounding glass fiber cloth and epoxy resin) on the wave-absorbing composite material substrate obtained in the step (3), pre-compacting for 15min by paving 2 layers of the first prepreg for each time to obtain a wave-absorbing composite material substrate containing an impedance matching layer with the thickness of 2mm, then carrying out bag-making packaging on the paved wave-absorbing composite material substrate, and placing the packaged wave-absorbing composite material substrate in an oven for curing treatment to obtain a glue-bonded cured wave-absorbing composite material; vacuumizing the whole curing process, wherein the forming pressure in a vacuum bag is more than or equal to 0.09MPa, the heating rate is 0.5 ℃/min, when the temperature is increased to 130 ℃, heat preservation is started for 120min, and after the heat preservation is finished, the temperature of a forming die is reduced to room temperature (25 ℃) at the cooling rate of 1 ℃/min, demoulding is carried out, so as to obtain the adhesive bonding curing wave-absorbing composite material;

wherein the prepressing temperature of the prepressing in the steps is 25 ℃, and the pressure is 1.5 MPa.

Example 2

(1) Selecting a forming die matched with the cured composite material of the missile wing without stealth performance, cleaning the forming surface of the forming die by acetone, and brushing a release agent for 3 times, wherein the time interval of brushing the release agent for each time is 10 min;

placing the cured composite material on a forming die, polishing the surface of the cured composite material by using 400-mesh abrasive paper, and then paving 1 layer of adhesive (J-47A structural adhesive with the thickness of 0.2mm) on the surface of the polished cured composite material to obtain a composite material matrix paved with an adhesive layer;

(2) paving second prepreg (compounded by carbon fiber cloth and cyanate resin) on the composite material matrix paved with the adhesive layer obtained in the step (1), and pre-compacting for 15min by paving 2 layers of second prepreg every time to obtain a composite material matrix containing a reflecting layer with the thickness of 0.4 mm;

(3) paving wave-absorbing glue films (wherein the mass fraction of the wave-absorbing agent is 50%) on the composite material substrate containing the reflecting layer obtained in the step (2), and pre-compacting for 15min by paving 1 layer of wave-absorbing glue film to obtain a wave-absorbing composite material substrate containing a wave-absorbing layer with the thickness of 3 mm; wherein, inhale ripples glued membrane contains: ferrite powder and cyanate resin;

(4) paving a first prepreg (compounded by glass fiber cloth and cyanate ester resin) on the wave-absorbing composite material substrate obtained in the step (3), pre-compacting for 15min by paving 2 layers of the first prepreg for each time to obtain a wave-absorbing composite material substrate containing an impedance matching layer with the thickness of 1.5mm, then carrying out bag-making packaging on the paved wave-absorbing composite material substrate, and placing the packaged wave-absorbing composite material substrate in a hot-pressing tank for curing treatment to obtain a glue-bonded cured wave-absorbing composite material; vacuumizing the whole curing process, wherein the forming pressure in the autoclave is 0.09MPa, the heating rate is 0.5 ℃/min, when the temperature is raised to 130 ℃, continuously pressurizing and preserving heat, the pressure of the autoclave is 0.25MPa, preserving heat for 150min, and after the heat preservation is finished; reducing the temperature of the forming die to 60 ℃ at a cooling rate of 1 ℃/min, then releasing the pressure and taking out of the tank, and opening the tank and demoulding when the forming die is recovered to room temperature (25 ℃) to obtain the adhesive bonding curing wave-absorbing composite material;

wherein the prepressing temperature of the prepressing in the steps is 30 ℃, and the pressure is 2 MPa.

Example 3

(1) Aiming at the cured composite material of the wing, because the front edge of the wing has the damaged wave-absorbing layer, a forming die matched with the front edge of the wing needs to be selected, the forming surface of the forming die is cleaned by acetone, and a release agent is brushed for 3 times, wherein the time interval of brushing the release agent every time is 10 min;

placing the cured composite material on a forming die, polishing the surface of the cured composite material by using 300-mesh abrasive paper, and then paving 1 layer of adhesive (J-47A structural adhesive with the thickness of 0.2mm) on the surface of the polished cured composite material to obtain a composite material matrix paved with an adhesive layer; wherein the cured composite material comprises a reflective layer;

(2) paving wave-absorbing adhesive films (wherein the mass fraction of the wave-absorbing agent is 60%) on the composite material substrate paved with the adhesive layer obtained in the step (1), and pre-compacting for 15min for 1 layer of wave-absorbing adhesive film to obtain a wave-absorbing composite material substrate with a wave-absorbing layer with the thickness of 1.8 mm; wherein, inhale ripples glued membrane contains: carbonyl iron powder and epoxy resin;

(3) paving 2 layers of first prepreg (compounded by glass fiber cloth and epoxy resin) on the wave-absorbing composite material substrate obtained in the step (2), pre-compacting for 15min to obtain a wave-absorbing composite material substrate containing an impedance matching layer with the thickness of 1.2mm, then carrying out bag-making packaging on the paved wave-absorbing composite material substrate, and placing the packaged wave-absorbing composite material substrate in a hot-pressing tank for curing to obtain a glue-bonded cured wave-absorbing composite material; vacuumizing the whole curing process, wherein the forming pressure in the autoclave is 0.09MPa, the heating rate is 1.5 ℃/min, when the temperature is raised to 130 ℃, continuously pressurizing and preserving heat, the pressure of the autoclave is 0.25MPa, preserving heat for 150min, and after the heat preservation is finished; reducing the temperature of the forming die to 60 ℃ at a cooling rate of 1 ℃/min, then releasing the pressure and taking out of the tank, and opening the tank and demoulding when the forming die is recovered to room temperature (25 ℃) to obtain the adhesive bonding curing wave-absorbing composite material;

wherein the prepressing temperature of the prepressing in the steps is 40 ℃, and the pressure is 2.5 MPa.

Example 4

Example 4 is essentially the same as example 1, except that: the adhesive is cyanate resin film, and the first prepreg is formed by compounding glass fiber cloth and polyimide resin; the second prepreg is formed by compounding carbon fiber cloth and bismaleimide resin;

in the step (3), wave-absorbing glue films are laid on the composite material matrix containing the reflecting layer obtained in the step (2) (wherein the mass fraction of the wave-absorbing agent is 80%), 1 layer of wave-absorbing glue film is laid for pre-compaction for 15min, and a resin film (epoxy film) needs to be laid between every two layers of wave-absorbing glue films, so that the wave-absorbing composite material matrix containing the wave-absorbing layer with the thickness of 3.8mm is obtained; wherein, inhale ripples glued membrane contains: carbonyl iron powder and epoxy resin.

Example 5

Example 5 is essentially the same as example 1, except that: the adhesive is 914 normal temperature curing structural adhesive, and the first prepreg is compounded by quartz fiber cloth and phenolic resin; the second prepreg is formed by compounding carbon fiber cloth and polyimide resin.

Comparative example 1

Comparative example 1 is substantially the same as example 1 except that: step (3) is to perform curing treatment in step (4) on the composite material matrix containing the reflecting layer obtained in step (2), then polish the cured composite material matrix containing the reflecting layer by using 500-mesh sand paper, and then lay and cover wave-absorbing patches (wherein the mass fraction of the wave-absorbing agent is 70%), pre-compact 1 layer of wave-absorbing patches for each time for 15min to obtain the wave-absorbing composite material matrix containing the wave-absorbing layer with the thickness of 2.6 mm; wherein, inhale ripples paster contains: carbonyl iron powder and nitrile rubber;

the curing treatment in the step (4) comprises the following steps: and (3) preserving the heat for 120min under the conditions that the forming pressure in the vacuum bag is more than or equal to 0.09MPa and the room temperature (25 ℃), and demoulding to obtain the adhesive bonding curing wave-absorbing composite material.

Comparative example 2

(1) Selecting a metal flat plate tool matched with a flat plate-shaped cured composite material as a forming die, cleaning the forming surface of the forming die by using acetone, and brushing a release agent for 3 times, wherein the time interval of brushing the release agent for each time is 10 min;

placing the cured composite material on a forming die, polishing the surface of the cured composite material by using 500-mesh sand paper, and then paving 1 layer of adhesive (J133C medium-temperature cured structural adhesive with the thickness of 0.1mm) on the surface of the polished cured composite material to obtain a composite material matrix paved with an adhesive layer; wherein, the resin matrix of the cured composite material is 3068 epoxy resin, has no wave-absorbing performance, has the thickness of 2mm and the size of 600mm multiplied by 600 mm;

(2) paving wave-absorbing patches on the composite material substrate paved with the adhesive layer obtained in the step (1) (wherein the mass fraction of the wave-absorbing agent is 70%), and pre-compacting for 15min for 1 layer of wave-absorbing patches to obtain a wave-absorbing composite material substrate containing a wave-absorbing layer with the thickness of 2.6 mm; wherein, inhale ripples paster contains: carbonyl iron powder and nitrile rubber.

(3) Making a bag and packaging the wave-absorbing composite material matrix, and placing the bag and the packaging in an oven for curing treatment to obtain a glue-bonded cured wave-absorbing composite material; wherein the whole curing process is vacuumized, the forming pressure in a vacuum bag is more than or equal to 0.09MPa, the temperature is kept at room temperature (25 ℃) for 120min, and demoulding is carried out to obtain the adhesive bonding curing wave-absorbing composite material;

wherein the prepressing temperature of the prepressing in the steps is 25 ℃, and the pressure is 1.5 MPa.

The adhesive bonding curing wave-absorbing composite materials obtained in examples 1 to 5 and comparative examples 1 and 2 were respectively subjected to adhesion and reflectance tests to obtain the mechanical property data as shown in table 1. Wherein, the reflection curves of the adhesive bonding curing wave-absorbing composite materials prepared in the embodiments 1, 2 and 3 under different testing frequencies are respectively shown in fig. 2, 3 and 4.

TABLE 1

As can be seen from Table 1, the adhesive bonding and curing wave-absorbing composite materials obtained in examples 1 to 5 have adhesion force obviously superior to that of the wave-absorbing composite materials obtained in comparative examples 1 to 2, and obviously, an obvious interface is easy to exist between the wave-absorbing layer of the wave-absorbing composite material prepared by adopting the wave-absorbing patch in comparative example 2 and the composite material, so the adhesion force is low.

As shown in FIG. 2, the cured composite material in example 1 has no stealth property (i.e., wave-absorbing property), but the wave-absorbing loss of the adhesive-bonded cured wave-absorbing composite material prepared by the above treatment is lower than-8.5 dB at 1-2 GHz. As can be seen from FIG. 3, the cured composite material in example 2 has no stealth performance, but the adhesive cured wave-absorbing composite material prepared by the above treatment has a wave-absorbing loss lower than-10 dB at 8-12 GHz. As can be seen from fig. 4, in example 3, after the wave-absorbing layer of the stealthy leading edge of the wing is damaged, the adhesive bonding curing wave-absorbing composite material prepared by the above treatment repairs the damaged wave-absorbing layer, so that the product rejection rate is reduced, and the difference between the wave-absorbing loss of the wing composite material before damage and that of the wing composite material after repair at 2-2.6 GHz is only 0.5dB, which can meet the use requirement of the wing. Experiments prove that the wave-absorbing loss of the adhesive bonding curing wave-absorbing composite material prepared in the embodiment 4 is lower than-8.7 dB at 1-2 GHz; the adhesive bonding curing wave-absorbing composite material prepared in the embodiment 5 has wave-absorbing loss lower than-8.4 dB at 1-2 GHz; the adhesive bonding curing wave-absorbing composite materials prepared in the comparative examples 1 and 2 have wave-absorbing loss lower than-4.0 dB at 1-2 GHz.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.