CN112126358B - Method for repairing Glare laminate by using modified adhesive in adhesive bonding manner - Google Patents
Method for repairing Glare laminate by using modified adhesive in adhesive bonding manner Download PDFInfo
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- CN112126358B CN112126358B CN202010992914.6A CN202010992914A CN112126358B CN 112126358 B CN112126358 B CN 112126358B CN 202010992914 A CN202010992914 A CN 202010992914A CN 112126358 B CN112126358 B CN 112126358B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C09J179/085—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/14—Glass
- C09J2400/146—Glass in the pretreated surface to be joined
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
- C09J2400/166—Metal in the pretreated surface to be joined
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the field of repairing of fiber metal laminated plates (Glare laminates), and particularly relates to a method for repairing a Glare laminate by gluing a modified adhesive. The invention adopts a low-cost and low-consumption flame method to grow a carbon nanotube layer on the surface of the carbon fiber in situ to prepare the carbon nanotube-coated composite carbon fiber; the chopped composite carbon fibers are mixed into the adhesive in proportion, so that the bonding strength of an interface between the adhesive layer and the light material and the strength of a body of the adhesive layer are enhanced, the bonding strength between the motherboard and the patch in the repair of the Glare laminate is improved, and a better repair effect is achieved; the materials of the patch and the motherboard are the same, so that the stiffness of the patch and the motherboard is the same, and the patch and the motherboard have better compatibility. The method is simple and quick, has extremely low cost, and has wide application prospect in the field of bonding of light materials such as aerospace, transportation and the like.
Description
Technical Field
The invention belongs to the field of repairing of a fiber metal laminated plate (Glare laminate), and particularly relates to a method for repairing the Glare laminate by bonding short-cut composite carbon fiber modified adhesive wrapped by a carbon nano tube layer.
Background
Glare laminates are a fiber reinforced metal material made of alternate laminates of glass fibers and aluminum alloys. It is widely used because of its advantages such as high specific strength, good fatigue properties, high damage tolerance, and good environmental resistance. Generally, the light weight structure is widely used in the manufacture of aircraft. Repairing damaged Glare laminates is therefore one of the indispensable technologies in the aerospace industry. The most widely used Glare ply repair techniques in the aerospace field are mechanical repair and adhesive repair. The disadvantages of mechanical repairs include stress concentration caused by drilling, deterioration of repair performance due to excessive rivet strength, and the like. The adhesive bonding repair has no stress concentration, good fatigue resistance, less abrasion and less structural weight increase. Meanwhile, the existence of the glue layer isolates the repaired motherboard from being contacted with a corrosive medium, and the development of corrosion damage is prevented. The glue-bonding repair technology can relatively well realize the repair of the Glare laminate.
The adhesive bonding repair refers to the process of adhering a high-strength load patch to a defect by means of the adhesive action of an adhesive, so that the mechanical property of the damaged Glare laminate is enhanced, the load transfer characteristic is recovered to the greatest extent, and the service life of the material is prolonged. The adhesive strength of the adhesive is a key factor affecting the structural strength after repair. The traditional adhesives such as epoxy resin (EP) used in the process of repairing the airplane have limited adhesive strength, so that the modified adhesive has a very wide application prospect in the maintenance of the airplane. The mechanical strength of the adhesive layer can be effectively improved by adding chopped fibers, carbon nanotubes, graphene and other rigid carbon materials into the adhesive; however, since the chopped fibers have smooth surfaces, attachment points cannot be provided for the adhesive, so that micro-interface cracks are caused, and the improvement of the interface bonding performance is not obvious; in addition, the agglomeration benefit of the nano material causes that the nano material is difficult to be uniformly dispersed in the adhesive, and the construction process performance of the adhesive is influenced.
The invention adopts a low-cost and low-consumption flame method to grow a carbon nanotube layer on the surface of the carbon fiber in situ to prepare the carbon nanotube-coated composite carbon fiber; and the chopped composite carbon fibers are mixed into the adhesive in proportion, so that the bonding strength of the interface between the adhesive layer and the light material and the strength of the body of the adhesive layer are enhanced, the bonding strength between the motherboard and the patch in the repair of the Glare laminate is improved, and a better repair effect is achieved. The invention is expected to have wide application prospect in the fields of aerospace, transportation and transportation.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a Glare laminate repairing method by using a modified adhesive, which mainly adopts the way that a carbon nanotube layer grows on the surface of carbon fiber in situ by a flame process, and then the chopped composite fiber modified adhesive is used for realizing the high-strength bonding of a Glare laminate and a bonding repairing patch thereof and increasing the repairing effect of the Glare laminate. The method is simple and quick, has extremely low cost, and has wide application prospect in the field of bonding of light materials such as aerospace, transportation and the like.
The invention relates to a method for repairing a Glare laminate by gluing modified adhesive, which specifically comprises the following steps:
and designing the size and thickness of the patch according to the size of the damage area of the Glare laminate, and preparing the patch with the same material as the Glare layer mother board to be repaired.
ultrasonically cleaning the carbon fiber bundle in acetone for 30 min; taking out and putting into an oven for drying, uniformly spraying the prepared catalyst solution on the surface of the carbon fiber bundle through a spray gun, and putting into the oven for drying again; and placing the treated carbon fiber bundle in combustion flame, and staying for a certain time to grow a carbon nano tube layer on the surface of the carbon fiber bundle. Cutting the prepared carbon nanotube-wrapped composite carbon fiber bundle into short composite carbon fibers with the length of 1-5 mm; heating the adhesive to 30-80 ℃ to reduce the viscosity of the adhesive, adding a certain mass fraction of chopped composite carbon fibers, then adding a proper amount of curing agent matched with the adhesive, and mechanically stirring for 2-10min by using a stirrer.
And 3, carrying out mechanical treatment and electrochemical treatment on the damaged part of the mother board of the Glare layer to be repaired and the surface of the patch to form a rough surface which is favorable for bonding and is convenient for being combined with the modified adhesive.
And 4, coating modified adhesives on the surfaces of the Glare laminate to be repaired and the patch, then placing the patch on the damaged part of the Glare laminate to be repaired, finally placing the Glare laminate into an autoclave, and curing according to the curing process corresponding to the adhesives and curing agents, wherein the specific placing mode is shown in FIG. 3.
The method for repairing the Glare laminate by gluing the modified adhesive comprises the following steps:
in the step 2, the temperature of the oven for drying the carbon fiber bundles is preferably 70 ℃, the first drying time is 40-60min, and the second drying time is 10-30 min.
The adhesive in the step 2 comprises but is not limited to one or more of epoxy resin, bismaleimide resin, cyanate resin and phenolic resin.
The catalyst solution of step 2 includes, but is not limited to, one or a mixture of iron chloride solution, nickel nitrate solution and cobalt nitrate solution, and is preferably nickel nitrate solution.
The amount of the substance of the catalyst solution in the step 2 is 0.5-2 mol/L, and preferably 1 mol/L.
The curing agent in the step 2 is one of ethylenediamine, diethylenetriamine, tetraethylenepentamine, dimethylaminopropylamine, trimethylhexamethylenediamine and m-phenylenediamine.
The combustion flame of step 2 includes, but is not limited to, an ethanol flame, a methanol flame, a methane flame, a butane flame, a heptane flame, an acetone flame, an acetylene flame, an ethylene flame, etc., preferably an ethanol flame.
The carbon fiber bundle of the step 2 is treated in the flame for 10 to 60s, preferably 30 s.
The temperature of the combustion flame in the step 2 is 800-1100 ℃, preferably 800 ℃, because the temperature range is suitable for the growth of the carbon nano tube.
The mass of the chopped composite carbon fibers added in the step 2 is 0.2-2% of that of the adhesive, and the mass is preferably 0.8%.
In the step 3, the surface treatment method of the damaged part and the patch of the Glare layer mother board to be repaired is preferably to perform mechanical polishing and then perform anodic oxidation treatment to form a high-energy surface favorable for bonding.
In the step 4, the curing molding preferably adopts a two-stage curing mode; the curing time of the first stage is 2-4 h; the second stage curing time is 2 hours; the curing temperature of the first stage and the curing temperature of the second stage are both in a curing temperature range suitable for the adhesive and the curing agent, and the curing temperature of the second stage is 20-60 ℃ higher than that of the first stage. The first stage is a stage of gentle curing of the adhesive, and the second stage is used for increasing the curing temperature, so that the repair quality is improved. The curing method is simple to operate and can obtain better curing results.
The invention has the beneficial effects that:
1. the materials of the patch and the motherboard adopted in the invention are the same, so that the two materials have the same rigidity and better compatibility; meanwhile, the surface treatment modes of the two layers are the same, a microstructure beneficial to bonding is formed, and the adhesive strength of the adhesive is improved.
2. According to the method, the carbon nano tube layer is grown on the surface of the carbon fiber bundle in situ by adopting a flame method, and the short-cut composite carbon fiber reinforced patch, the surface of the Glare laminate to be repaired and the body strength of the adhesive joint adhesive layer of the adhesive are utilized, so that the mechanical strength of the light material adhesive joint is improved.
3. According to the invention, the adhesive is modified by adopting the short-cut composite carbon fibers wrapped by the carbon nanotube layer, and when the adhesive is broken, a large amount of energy is consumed by stretching and pulling out the short-cut composite carbon fibers, so that the cohesive force of the adhesive is increased. In addition, the carbon nano tube can also increase the adhesive force between the resin and the carbon fiber interface layer, thereby further enhancing the adhesive bonding performance.
4. The chopped composite carbon fibers adopted in the invention can not only increase the mechanical property of adhesives such as epoxy resin and the like, but also increase the conductivity of adhesives such as epoxy resin and the like due to excellent conductivity, and the chopped composite carbon fibers can be used for self-detection after repair.
5. The method for repairing the Glare laminate by gluing the modified adhesive is also suitable for the bonding forming of the fiber reinforced metal laminate and metal materials and the repairing of other fiber metal laminates.
Drawings
FIG. 1 is a carbon nanotube-wrapped chopped fiber of example 1.
FIG. 2 shows the micro-morphology of the chopped carbon composite fiber modified epoxy resin adhesive in example 1.
FIG. 3 is a schematic view of a modified adhesive repaired Glare laminate.
Reference numerals: 1-patches of the same material as the master; 2-modified epoxy resin adhesive; and 3, preparing a Glare laminate to be repaired.
Detailed Description
In order to make the technical means, innovative features and attainment effects of the present invention easier to understand, the present invention will be further described with reference to the following detailed description, but not limited thereto.
Example 1
A method for performing adhesive bonding and repairing on a Glare laminate containing impact damage by using an epoxy resin adhesive modified by carbon nanotube-coated chopped carbon fibers comprises the following implementation steps:
to perform this example, damaged Glare laminates were fabricated by first preparing a complete Glare laminate and then simulating Glare laminate damage. The specific operation mode is that firstly, an anodizing method is adopted to carry out surface treatment on the aluminum plate, then adhesive is sprayed to lay glass fiber pre-impregnated material, and the glass fiber pre-impregnated material is hot-pressed and cured to be processed into a required shape. And then carrying out ultrasonic scanning nondestructive testing on the processed test piece, and detecting whether the defects which can not be observed by naked eyes are generated in the preparation and processing processes. Drop hammer impact experiments were used to simulate impact damage to Glare laminates. The simulated damage is at a level that repairs the damage; and determining the area of the damaged area according to the ultrasonic scanning image, and removing the damaged area.
The concrete repairing steps are as follows:
designing the size and thickness of the patch according to the size of the damaged area, and preparing the patch which is made of the same material as the Glare layer mother board to be repaired;
cleaning the carbon fiber bundle with acetone for 10min, uniformly spraying a ferric chloride solution with the amount concentration of the prepared substance being 1mol/L on the surface of the carbon fiber bundle subjected to polishing pretreatment through a spray gun, placing the surface of the carbon fiber bundle loaded with the catalyst at the position of the flame temperature of the ethanol being 850 ℃, and staying for 30s to prepare the carbon nanotube layer. Cutting the carbon nanotube-wrapped composite carbon fiber bundle into short-cut composite carbon fibers with the length of 1-5mm, heating epoxy resin to 50 ℃, preparing epoxy resin added with the short-cut composite carbon fibers, wherein the addition amount of the short-cut carbon fibers is 0.8 wt% of the epoxy resin, and simultaneously adding ethylenediamine curing agent accounting for 3 wt% of the epoxy resin;
step 4, coating a modified epoxy resin adhesive on the processed Glare layer mother board to be repaired and the patch, and then putting the Glare layer mother board to be repaired into an autoclave for curing at a preset temperature, wherein the specific placement modes of the patch and the Glare layer mother board to be repaired are shown in FIG. 3; a two-stage curing mode is adopted, namely a mode of curing for 4 hours at 80 ℃ is adopted in the first stage; then curing for 2 hours at 120 ℃ in the second stage; the adhesive is cured smoothly in the first stage, and the curing temperature is increased in the second stage, so that the repair quality can be improved.
The carbon nanotube-coated chopped carbon fiber prepared in the step 2 is shown in fig. 1, and it can be seen that a large number of vertically grown carbon nanotubes are coated on the surface of the chopped composite carbon fiber. This macroscopic "forest-tree" structure occurs when a large number of individual carbon nanotubes are aligned together and grown in situ on the surface of the carbon fiber. The microstructure of the adhesive is shown in fig. 2, and it can be seen that the short-cut composite carbon fibers do not agglomerate in the adhesive, because the short fibers wrapping the carbon nanotubes can more easily adsorb the resin matrix on the surface of the short fibers by using the capillary action, the agglomeration of the short fibers in the adhesive is avoided.
In this embodiment, the Glare laminate containing impact damage is repaired by using an epoxy resin adhesive modified by carbon nanotube-coated chopped carbon composite fibers. And respectively carrying out impact experiments with the same energy on the undamaged standard test piece, the unmodified repair test piece and the short-cut composite carbon fiber modified adhesive repair test piece, and comparing the dynamic responses under the same drop hammer impact energy. The permanent displacement of the undamaged standard test piece is 3.72mm, the permanent displacement of the unmodified repair test piece is 4.51mm, and the permanent displacement of the chopped composite carbon fiber modified adhesive repair test piece is 4.05 mm. The test result shows that the performance of the repair test piece of the chopped composite carbon fiber modified adhesive is closer to the impact resistance of an undamaged standard test piece.
Example 2
A method for performing adhesive bonding and repairing on a Glare laminate containing impact damage by using a bismaleimide resin adhesive modified by carbon nanotube-coated chopped composite carbon fibers comprises the following implementation steps:
to perform this example, damaged Glare laminates were fabricated by first preparing a complete Glare laminate and then simulating Glare laminate damage. The specific operation mode is that firstly, an anodizing method is adopted to carry out surface treatment on the aluminum plate, then adhesive is sprayed to lay the glass fiber pre-impregnated material, and the glass fiber pre-impregnated material is hot-pressed and cured to be processed into a required shape. And then, carrying out ultrasonic scanning nondestructive testing on the processed test piece, and detecting whether the defects which can not be observed by naked eyes are generated in the preparation and processing processes. And simulating the damage of the Glare laminate under the action of cyclic load through fatigue crack simulation, wherein the simulated damage is in the extent of repairing the damage.
The concrete repairing steps are as follows:
designing the size and thickness of the patch according to the size of the damaged area, and preparing the patch which is made of the same material as the Glare mother board to be repaired;
cleaning the carbon fiber bundle with acetone for 30min, uniformly spraying a nickel nitrate solution with the quantity concentration of a prepared substance of 1.1mol/L on the surface of the carbon fiber bundle subjected to polishing pretreatment through a spray gun, placing the surface of the carbon fiber bundle loaded with the catalyst at the position of 800 ℃ of alcohol flame, and staying for 20s to prepare the carbon nanotube layer. Cutting the carbon nanotube-coated composite carbon fiber bundle into short-cut composite carbon fibers with the length of 1-5mm, heating bismaleimide resin to 50 ℃, preparing bismaleimide resin added with the short-cut composite carbon fibers, wherein the addition amount of the short-cut carbon fibers is 0.6 wt% of the bismaleimide resin, and simultaneously adding 2 wt% of tetraethylenepentamine curing agent into the bismaleimide resin;
step 4, coating the processed Glare layer mother board and the patch to be repaired with a modified bismaleimide resin adhesive, and then putting the Glare layer mother board and the patch into equipment for curing at a preset temperature, wherein the specific placement mode is shown in FIG. 2; a two-stage curing mode is adopted, namely a mode of curing for 4 hours at 180 ℃ is adopted in the first stage, and then curing for 2 hours at 200 ℃ is adopted in the second stage; the adhesive is cured smoothly in the first stage, and the curing temperature is increased in the second stage, so that the repair quality can be improved.
In this embodiment, a carbon nanotube-coated chopped composite carbon fiber modified bismaleimide resin adhesive is used to repair a Glare @ laminate containing impact damage. And respectively carrying out impact experiments with the same energy on the undamaged standard test piece, the unmodified repair test piece and the short-cut composite carbon fiber modified adhesive repair test piece, and comparing the dynamic responses under the same drop hammer impact energy. The permanent displacement of the undamaged standard test piece is 3.32mm, the permanent displacement of the unmodified repair test piece is 4.31mm, and the permanent displacement of the chopped composite carbon fiber modified adhesive repair test piece is 3.75 mm. The test result shows that the performance of the repair test piece of the chopped composite carbon fiber modified adhesive is closer to the impact resistance of an undamaged standard test piece.
Example 3
A method for performing adhesive bonding and repairing on a Glare laminate containing impact damage by using a phenolic resin adhesive modified by carbon nanotube-coated chopped composite carbon fibers comprises the following implementation steps:
to perform this example, damaged Glare laminates were fabricated by first preparing a complete Glare laminate and then simulating Glare laminate damage. The specific operation mode is that firstly, an anodizing method is adopted to carry out surface treatment on the aluminum plate, then adhesive is sprayed to lay glass fiber pre-impregnated material, and the glass fiber pre-impregnated material is hot-pressed and cured to be processed into a required shape. And then, carrying out ultrasonic scanning nondestructive testing on the processed test piece, and detecting whether the defects which can not be observed by naked eyes are generated in the preparation and processing processes. Drop hammer impact experiments were used to simulate impact damage to Glare laminates. The simulated damage is at a level that repairs the damage; and determining the area of the damaged area according to the ultrasonic scanning image, and removing the damaged area.
The concrete repairing steps are as follows:
designing the size and thickness of the patch according to the size of the damaged area, and preparing the patch which is made of the same material as the Glare layer mother board to be repaired;
cleaning the carbon fiber bundle with acetone for 10min, uniformly spraying a cobalt nitrate solution with the amount concentration of a prepared substance of 1mol/L on the surface of the carbon fiber bundle subjected to polishing pretreatment through a spray gun, placing the surface of the carbon fiber bundle loaded with the catalyst at the position of 900 ℃ of acetone flame temperature, and staying for 45s to prepare the carbon nanotube layer. Cutting the carbon nanotube-coated composite carbon fiber bundle into short-cut composite carbon fibers with the length of 1-5mm, heating phenolic resin to 50 ℃, preparing phenolic resin added with the short-cut composite carbon fibers, wherein the addition amount of the short-cut carbon fibers is 0.8 wt% of the phenolic resin, and simultaneously adding trimethyl hexamethylene diamine curing agent in an amount of 7 wt% of the phenolic resin;
step 4, coating modified phenolic resin adhesive on the processed Glare layer mother board and the processed patch to be repaired, and then putting the Glare layer mother board and the patch into an autoclave for curing at a preset temperature, wherein the specific placement mode is shown in FIG. 2; a two-stage curing mode is adopted, namely a mode of curing for 2 hours at 120 ℃ is adopted in the first stage, and then curing for 2 hours at 160 ℃ is adopted in the second stage; the adhesive is cured smoothly in the first stage, and the curing temperature is increased in the second stage, so that the repair quality can be improved.
In this embodiment, the Glare laminate containing impact damage is repaired by using a phenolic resin adhesive modified by carbon nanotube-coated chopped composite carbon fibers. And respectively carrying out impact experiments with the same energy on the undamaged standard test piece, the unmodified repair test piece and the short-cut composite carbon fiber modified adhesive repair test piece, and comparing the dynamic responses under the same drop hammer impact energy. The permanent displacement of the undamaged standard test piece is 3.92mm, the permanent displacement of the unmodified repair test piece is 4.73mm, and the permanent displacement of the chopped composite carbon fiber modified adhesive repair test piece is 4.25 mm. The test result shows that the performance of the repair test piece of the chopped composite carbon fiber modified adhesive is closer to the impact resistance of an undamaged standard test piece.
Claims (6)
1. A method for repairing a Glare laminate by using modified adhesive through adhesive bonding is characterized by comprising the following steps:
step 1, preparing a patch:
designing the size and thickness of a patch according to the size of the damaged area of the mother board of the Glare layer to be repaired, and preparing the patch with the same material as the mother board of the Glare layer to be repaired;
step 2, preparing a modified adhesive:
ultrasonically cleaning the carbon fiber bundle in acetone for 30 min; taking out and putting into an oven for drying, uniformly spraying the prepared catalyst solution on the surface of the carbon fiber bundle through a spray gun, and putting into the oven again for drying; placing the treated carbon fiber bundle in combustion flame, and staying for a certain time to grow a carbon nanotube layer on the surface of the carbon fiber bundle; cutting the prepared carbon nanotube-coated composite carbon fiber bundle into short-cut composite carbon fibers with the length of 1-5 mm; heating an adhesive to 30-80 ℃ to reduce the viscosity of the adhesive, adding a certain mass fraction of chopped composite carbon fibers, then adding a proper proportion of curing agent capable of being matched with the adhesive according to the type of the adhesive, and mechanically stirring for 2-10min by using a stirrer to obtain a modified adhesive;
step 3, carrying out mechanical treatment and electrochemical treatment on the damaged part of the mother board of the Glare layer to be repaired and the surface of the patch to form a rough surface which is favorable for bonding and is convenient for being combined with the modified adhesive;
and 4, coating modified adhesives on the surfaces of the processed Glare layer mother board to be repaired and the patch, placing the patch on the damaged part of the Glare layer mother board to be repaired, then placing the patch into an autoclave, and curing by adopting a proper process according to the types of the adhesives and the curing agents.
2. The method for repairing Glare laminates by utilizing modified adhesive in an adhesive bonding mode according to claim 1, wherein in the step 2, the adhesive is one or more of epoxy resin, bismaleimide resin, cyanate resin and phenolic resin; the catalyst solution in the step 2 is one or more of ferric chloride solution, nickel nitrate solution and cobalt nitrate solution; the amount of the substance of the catalyst solution in the step 2 is 0.5-2 mol/L; the curing agent in the step 2 is one or more of ethylenediamine, diethylenetriamine, tetraethylenepentamine, dimethylaminopropylamine and trimethylhexamethylenediamine; the combustion flame in the step 2 is one of an ethanol flame, a methanol flame, a methane flame, a butane flame, a heptane flame, an acetone flame, an acetylene flame and an ethylene flame; the residence time of the carbon fiber bundle in the flame in the step 2 is 10-60 s; the combustion flame temperature in the step 2, namely the growth temperature of the carbon nano tube is 800-1100 ℃; and the mass of the chopped composite carbon fibers added in the step 2 is 0.2-2% of the mass of the adhesive.
3. The method for repairing Glare laminates by using modified adhesive in an adhesive bonding mode according to claim 1 or 2, wherein in the step 2, the catalyst solution is a nickel nitrate solution, the amount of the substance is 1mol/L, the combustion flame is an ethanol flame, the residence time of the carbon fiber bundles in the flame is 30s, the temperature of the combustion flame, namely the growth temperature of the carbon nano tubes is 800 ℃, and the mass of the added chopped composite carbon fibers is 0.8% of the mass of the adhesive.
4. The method for repairing Glare laminates by gluing through the modified adhesive according to claim 1 or 2, wherein in the step 2, the heating temperature for drying through an oven is 70 ℃, the first drying time is 40-60min, and the second drying time is 10-30 min.
5. The method for repairing Glare laminate by modified adhesive bonding according to claim 1 or 2, wherein in the step 3, the damaged part and the patch of the Glare layer to be repaired are treated by mechanical grinding and then anodic oxidation treatment to form a high energy surface for bonding.
6. The method for repairing Glare laminate by modified adhesive bonding according to claim 1 or 2, wherein in the step 4, the curing is performed by a two-stage curing method: the curing time of the first stage is 2-4 h; the second stage curing time is 2 hours; the curing temperature of the first stage and the curing temperature of the second stage are both in a curing temperature range suitable for the adhesive and the curing agent, and the curing temperature of the second stage is 20-60 ℃ higher than that of the first stage.
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| CN1425730A (en) * | 2002-11-29 | 2003-06-25 | 国家工业建筑诊断与改造工程技术研究中心 | Method for reinforcing and repairing steel structure using fibre reinforced composite material |
| US20120289112A1 (en) * | 2006-03-31 | 2012-11-15 | Applied Nanotech Holdings, Inc. | Carbon nanotube reinforced adhesive |
| WO2008114669A1 (en) * | 2007-03-12 | 2008-09-25 | Taisei Plas Co., Ltd. | Aluminum alloy composite and method of bonding therefor |
| EP1990394A1 (en) * | 2007-05-08 | 2008-11-12 | Technische Universiteit Delft | Epoxy-resin adhesive and method for bonding using such an epoxy resin adhesive |
| CN104974697B (en) * | 2015-07-21 | 2017-06-16 | 中国科学院上海应用物理研究所 | Carbon/carbon composite binding agent, adhesive method and carbon/carbon composite component |
| CN107738497B (en) * | 2017-11-23 | 2020-04-28 | 河北工业大学 | Filling and repairing method for adhesive bonding and repairing |
| CN110877464A (en) * | 2019-09-25 | 2020-03-13 | 西北工业大学 | Standard hard patching method for rapid repair of aircraft composite materials |
| CN111334062B (en) * | 2020-04-19 | 2021-06-11 | 华中科技大学 | High-damping fiber reinforced resin matrix composite material and preparation method thereof |
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