CN112848337B - Synergistic surface treatment method capable of improving adhesive property of polyether-ether-ketone and composite material thereof - Google Patents
Synergistic surface treatment method capable of improving adhesive property of polyether-ether-ketone and composite material thereof Download PDFInfo
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- CN112848337B CN112848337B CN202011554132.0A CN202011554132A CN112848337B CN 112848337 B CN112848337 B CN 112848337B CN 202011554132 A CN202011554132 A CN 202011554132A CN 112848337 B CN112848337 B CN 112848337B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
- B29C66/022—Mechanical pre-treatments, e.g. reshaping
- B29C66/0224—Mechanical pre-treatments, e.g. reshaping with removal of material
- B29C66/02245—Abrading, e.g. grinding, sanding, sandblasting or scraping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
- B29C66/026—Chemical pre-treatments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
- B29C66/028—Non-mechanical surface pre-treatments, i.e. by flame treatment, electric discharge treatment, plasma treatment, wave energy or particle radiation
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Abstract
The invention discloses a synergistic surface treatment method capable of improving the adhesive property of polyether-ether-ketone and a composite material thereof, relates to the field of chemical materials, and solves the problems of poor surface treatment effect, low adhesive strength and poor adhesive durability of the polyether-ether-ketone and the composite material thereof in the prior art. Including the machinery polish, acidizing sculpture and corona treatment's multiscale synergism, the machinery is polished and is polished for using abrasive paper and handle, the acidizing sculpture uses the concentrated sulfuric acid solution of dichromate, corona treatment is ordinary pressure low temperature plasma corona treatment. The multi-scale cooperative treatment method for the surfaces of the polyether-ether-ketone and the composite material thereof, which is disclosed by the invention, has the characteristics of simplicity in operation, strong operability and excellent treatment effect, and can greatly improve the surface wettability, bonding strength and bonding durability of the polyether-ether-ketone and the composite material thereof. The invention is applied to the field of material processing.
Description
Technical Field
The invention belongs to the field of chemical materials, and particularly relates to a synergistic surface treatment method capable of improving the adhesive property of polyether-ether-ketone and a composite material thereof.
Background
The high-performance thermoplastic resin-based composite material not only has the characteristics of light weight, high specific strength and specific stiffness, strong designability and the like of the thermosetting resin-based composite material, but also has the characteristics of high shock damage resistance potential, short forming period, weldability, convenience in repair and storage and the like. The field of the aeronautical industry has long received attention and the use in particular in aircraft has highlighted great advantages. The basic and application research of high-performance thermoplastic composite materials has been carried out by the aviation enterprises, including air passengers and boeing, in the European and American first-class research institute and colleges and universities. Polyether ether ketone (PEEK) is taken as a representative of advanced thermoplastic resin, has excellent toughness, mechanical properties, chemical stability and dimensional stability, and is the first advanced thermoplastic composite material with practical value in the field of aerospace. The welding technology can complete the connection of a simple reinforced structure, but the bonding technology cannot be separated for a large-area lap joint structure, a wallboard butt joint structure, a complex bidirectional reinforced structure, a honeycomb/foam sandwich structure, a metal mosaic structure, a thermoplastic composite material and thermosetting composite material connecting structure and the like. The PEEK has low surface energy and stable molecular structure, so that the PEEK and the composite material thereof are difficult to bond, low in bonding strength and poor in bonding durability. The bonding performance of PEEK and composite materials thereof depends heavily on surface treatment technology, and common single treatment methods such as mechanical grinding, solvent cleaning, flame treatment and corona treatment have poor effects and also face the problems of surface treatment timeliness and the like.
Disclosure of Invention
The invention provides a synergistic surface treatment method capable of improving the bonding performance of polyether-ether-ketone and a composite material thereof, and aims to solve the problems of poor surface treatment effect, low bonding strength and poor bonding durability of the polyether-ether-ketone and the composite material thereof in the prior art. The synergistic surface treatment method provided by the invention can improve the surface wettability of the polyether-ether-ketone and the composite material thereof, and improve the bonding strength and the bonding durability of the polyether-ether-ketone and the composite material thereof.
The invention relates to a synergistic surface treatment method capable of improving the bonding performance of polyether-ether-ketone and composite materials thereof, which comprises the synergistic action of mechanical polishing, solvent cleaning, acidification etching, drying and corona treatment, wherein the mechanical polishing is performed by using sand paper, the acidification etching is performed by using a concentrated sulfuric acid solution of dichromate, and the corona treatment is normal-pressure low-temperature plasma corona treatment; the sequence of the synergistic treatment method comprises mechanical grinding, solvent cleaning, acidification etching, drying and corona treatment.
Further, the polyetheretherketone and the composite material thereof are specifically as follows: polyether-ether-ketone thermoplastic plastics and one or more reinforced polyether-ether-ketone composite materials selected from chopped carbon fibers, glass fibers, quartz fibers, aramid fibers, unidirectional long fibers, fiber fabrics and inorganic fillers.
Furthermore, the polyether-ether-ketone thermoplastic, chopped fiber reinforced and inorganic filler reinforced polyether-ether-ketone composite material is ground in a direction which is 45 degrees to the length direction of the test piece by taking the horizontal direction as a reference, and the unidirectional long fiber and fiber fabric reinforced polyether-ether-ketone composite material is ground in the horizontal shearing stress direction.
Furthermore, the mechanical grinding adopts emery of sand paper with the size of 60-500 meshes, and the emery is firstly ground by 300-500 meshes of sand paper and then ground by 60-200 meshes of sand paper.
Further, the concentrated sulfuric acid solution of the dichromate is formed by mixing dichromate, concentrated sulfuric acid and deionized water, wherein the mass ratio of the dichromate to the concentrated sulfuric acid to the deionized water is 1: 6-20: 0.5 to 2; the dichromate is one or a mixture of sodium dichromate and potassium dichromate in any proportion; the chemical etching treatment temperature is 15-60 ℃, and the treatment time is 15-60 s.
Further, the corona treatment adopts normal-pressure low-temperature plasma corona treatment, the treatment voltage is 80-200V, the distance between a discharge device of the corona equipment and a treated sample is 1-3mm, and the treatment time is 5-40 s.
Further, the processing method comprises the following steps:
firstly, polishing the polyether-ether-ketone and the composite material thereof by using 300-sand 500-mesh sand paper, and then polishing by using 60-200-mesh sand paper, wherein the polyether-ether-ketone thermoplastic and chopped fiber reinforced polyether-ether-ketone composite material is polished in a direction which forms a 45-degree angle with the length direction of a test piece by taking the horizontal direction as a reference, and the unidirectional long fiber and fiber fabric reinforced composite material is polished in the horizontal shearing stress direction;
step two, cleaning the surface of the test piece polished in the step one by using one or more of acetone, butanone, ethyl acetate and ethanol, and drying for 30-60min at the temperature of 60-90 ℃;
step three, adding concentrated sulfuric acid with the mass fraction of 98% into deionized water, stirring while adding to form a concentrated sulfuric acid solution A, adding dichromate into the concentrated sulfuric acid solution A, stirring at room temperature for 2-3h to form a solution B, placing the sample dried in the step two into the solution B for acidification treatment, washing the treated sample with running water for 2-5min, and drying the washed sample at 60-90 ℃ for 30-60min, wherein the mass ratio of dichromate, concentrated sulfuric acid to deionized water is 1: 6-20: 0.5 to 2; the temperature of the solution B in the acidification treatment is 15-60 ℃, and the treatment time is 15-60 s;
and step four, carrying out corona treatment on the sample dried in the step three by using normal-pressure low-temperature plasma equipment, wherein the treatment voltage is 80-200V, the distance from the sample to be treated is 1-3mm, and the treatment time is 5-40s, so that the multi-scale collaborative surface treatment method for improving the adhesive property of the polyether-ether-ketone and the composite material thereof is completed.
The invention relates to a synergistic surface treatment method capable of improving the adhesive property of polyether-ether-ketone and composite materials thereof, which comprises the following steps of firstly, improving the roughness and the adhesive area of an adhered substrate by using a mechanical polishing method; then changing the molecular packing structure of the surface of the bonded substrate by using an acidification etching method, and introducing a polar functional group; and secondly, an energy treatment method, namely a normal-pressure low-temperature plasma corona treatment method is used for further improving the wettability of the bonded surface, so that the bonding strength and the bonding durability are guaranteed. Mechanical polishing promotes roughness and bonding area, can promote bonding strength at the physical aspect, and the acidizing sculpture introduces the functional group and can makes glue bonding and form the chemical bonding effect by the face of bonding, further effectively promotes bonding performance, and corona treatment can improve the durability of gluing in the time of effectively improving by the infiltration nature of bonding surface. Wherein, the mechanical polishing is a physical scale combining different roughness, the acidification etching is a chemical scale changing the molecular chain accumulation mode, and the corona treatment is an energy scale further improving the surface wettability.
Compared with the prior art, the invention has the following beneficial effects:
the scheme of the invention aims at the characteristics of simple operation, strong operability and excellent treatment effect of the cooperative treatment method of the surface of the polyetheretherketone and the composite material thereof, and solves the technical problems of poor surface treatment effect, and poor surface bonding performance and durability of the treated surface of the polyetheretherketone and the composite material thereof in the existing surface treatment technology. The surface treatment method provided by the invention can ensure that the bonding strength of the material reaches more than 45MPa, and the bonding strength after the wet-heat aging is 1000 hours reaches more than 35 MPa.
The synergistic surface treatment method for improving the adhesive property of the polyetheretherketone and the composite material thereof has the following advantages:
1. the invention adopts a synergistic surface treatment method, wherein the mechanical method can increase the roughness of the adhesive surface and the total adhesive surface area, the chemical method and the energy treatment method can change the molecular structure characteristics of the surface of the adhered substrate, and polar functional groups are introduced, and the synergistic method can simultaneously and greatly improve the adhesive strength and the adhesive durability of the polyetheretherketone and the composite material thereof.
2. The synergistic surface method is simple and effective, and the effect of the synergistic surface method is greatly superior to that of a single treatment method.
3. The surface of the base material treated by the synergistic method has excellent stability, the bonding performance after the base material is placed for 1 week is not reduced, and the operation time is greatly prolonged.
Drawings
FIG. 1 is a photograph of a failure mode of a single lap joint specimen of polyetheretherketone thermoplastic;
FIG. 2 is a contact angle between water and a treated surface under different treatment methods of the unidirectional carbon fiber reinforced polyetheretherketone thermoplastic composite;
FIG. 3 shows the surface energy of the unidirectional carbon fiber reinforced polyetheretherketone thermoplastic composite after being treated by different treatment methods;
FIG. 4 is a photograph of a failure mode of a single lap joint specimen of unidirectional carbon fiber reinforced polyetheretherketone thermoplastic composite;
FIG. 5 shows the single lap shear strength of different surface treatment methods of the unidirectional carbon fiber reinforced polyetheretherketone thermoplastic composite;
FIG. 6 shows the bonding durability of the unidirectional carbon fiber reinforced polyetheretherketone thermoplastic composite material by different surface treatment methods.
Detailed Description
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples of practicing the invention, and that various changes in form and detail may be made therein without departing from the spirit and scope of the invention in practice.
To make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following detailed description clearly illustrates the spirit of the present disclosure, and any person skilled in the art who knows the embodiments of the present disclosure can make changes and modifications to the technology taught by the present disclosure without departing from the spirit and scope of the present disclosure.
The exemplary embodiments of the present invention and the description thereof are provided to explain the present invention and not to limit the present invention.
Detailed description of the preferred embodiment example 1
The synergistic surface treatment method capable of improving the bonding performance of the polyetheretherketone and the composite material thereof comprises mechanical polishing, solvent cleaning, acidification etching, drying and corona treatment, wherein the mechanical polishing is performed for using sand paper, the acidification etching uses a concentrated sulfuric acid solution of dichromate, and the corona treatment is normal-pressure low-temperature plasma corona treatment.
The sequence of the multi-scale synergetic surface treatment comprises mechanical polishing, solvent cleaning, drying, acidification etching, running water washing, drying and corona treatment.
The mechanical treatment method comprises the steps of firstly grinding with 300-mesh sand paper and then grinding with 60-mesh sand paper.
The cleaning solvent is acetone.
The drying condition is 60min at 60 ℃.
The concentrated sulfuric acid solution of the dichromate comprises sodium dichromate, concentrated sulfuric acid and deionized water, wherein the mass ratio of the sodium dichromate to the concentrated sulfuric acid to the deionized water is 1: 6: 0.5, the treatment temperature of the sample was 15 ℃ and the treatment time was 60 s.
The voltage of the normal-pressure low-temperature plasma corona treatment is 80V, the distance from the sample to be treated is 1mm, and the treatment time is 40 s.
Polyether ether ketone and its composite material treated by the examples:
the polyether-ether-ketone composite material is a polyether-ether-ketone composite material (comprising unidirectional carbon fibers, unidirectional glass fibers, unidirectional quartz fibers and unidirectional aramid fibers) reinforced by unidirectional long fibers and fiber fabrics, the tensile strength of the polyether-ether-ketone composite material along the direction of the unidirectional fibers is high, the material cannot break in a single lap joint experiment, and the single lap joint shear strength and the bonding durability can be tested, so that the data can be used for embodying the multi-scale surface treatment method provided by the invention, and the high strength and high durability bonding of the polyether-ether-ketone composite material can be realized.
The second type is polyetheretherketone thermoplastic, chopped fiber reinforced polyetheretherketone composite materials (including chopped carbon fibers, chopped glass fibers, chopped quartz fibers and chopped aramid fibers) and inorganic filler reinforced polyetheretherketone composite materials, which have low tensile strength, and in a single lap joint experimental test, a bonded joint shows the fracture of a bonded material in the test process through the treatment of a multi-scale surface treatment method, which can also show that reliable bonding of the materials (on the premise that the materials are not damaged) can be realized through the treatment of the multi-scale surface treatment method.
Therefore, the processing object in the embodiment is to take the unidirectional long carbon fiber reinforced polyetheretherketone composite material as an example, and the excellent bonding performance of the unidirectional long fiber and fiber fabric reinforced polyetheretherketone composite material is highlighted; and secondly, the adhesive bonding reliability of the material is embodied by the polyether-ether-ketone thermoplastic, the chopped fiber and the inorganic filler reinforced polyether-ether-ketone composite material.
The specific operation comprises the following steps:
step one, mechanical treatment method for surface of polyether-ether-ketone composite material
Firstly, mechanical polishing is carried out on the polyether-ether-ketone and the composite material thereof by using 300-mesh abrasive paper, a weak boundary layer is removed, the specific surface area of the base material is improved, and then 60-mesh abrasive paper is used for polishing to further improve the roughness of the surface of the base material. Wherein, the PEEK thermoplastic plastics and the chopped fiber reinforced composite materials are polished along the direction of 45 degrees, and the unidirectional long fiber and fiber fabric reinforced composite materials are polished along the horizontal direction of shearing stress;
step two, solvent deoiling treatment of the coarse surface of the polyether-ether-ketone and the composite material thereof
Deoiling the surface of the test piece polished in the step one, cleaning the surface by using acetone, and drying for 60min at the temperature of 60 ℃ after cleaning;
step three, chemical treatment of the crude and clean surface of the polyetheretherketone and the composite material thereof
(1) Slowly adding concentrated sulfuric acid with the mass fraction of 98% into deionized water, and stirring while adding to form a concentrated sulfuric acid solution A, wherein the mass ratio of the deionized water to the concentrated sulfuric acid is 1: 3; (2) adding sodium dichromate into the solution A, wherein the mass ratio of the sodium dichromate to the solution A is 1:6.5, and stirring for 2 hours at room temperature to form a solution B; (3) treating the sample dried in the step two in the solution B at 15 ℃ for 60s, washing the treated sample for 2min by using running water, and drying the washed sample for 60min at 60 ℃;
step four, energy treatment of the surface of the polyether-ether-ketone and the composite material thereof
And (3) performing corona treatment on the surface of the sample dried in the step three by using an atmospheric pressure low-temperature plasma device, wherein the treatment voltage is 80V, the distance from the sample to be treated is 1mm, and the treatment time is 40 s.
After the treatment, aiming at the unidirectional continuous carbon fiber reinforced polyether-ether-ketone composite material, the single lap joint shear strength of a cementing test piece is 46.73MPa at room temperature, and the cementing strength after the wet-heat aging is 36.46MPa after 1000 hours; for the polyether-ether-ketone thermoplastic, the chopped fiber and the inorganic filler reinforced polyether-ether-ketone composite material, the test piece is broken as a result of a single lap shear test at room temperature, and the test piece is still broken as a result of the single lap shear test after the thermal aging is carried out for 1000 hours.
Detailed description of the preferred embodiment example 2
The multiscale collaborative surface treatment method capable of greatly improving the bonding performance of the polyetheretherketone and the composite material thereof comprises mechanical polishing, solvent cleaning, acidification etching, drying and corona treatment, wherein the mechanical polishing is performed by using abrasive paper, the acidification etching is performed by using a bichromate concentrated sulfuric acid solution, and the corona treatment is normal-pressure low-temperature plasma corona treatment.
The sequence of the multi-scale synergetic surface treatment comprises mechanical polishing, solvent cleaning, drying, acidification etching, running water washing, drying and corona treatment.
The mechanical treatment method comprises the steps of firstly grinding with 500-mesh sand paper and then grinding with 100-mesh sand paper.
The cleaning solvent is ethyl acetate.
The drying condition is drying at 90 ℃ for 30min.
The concentrated sulfuric acid solution of the dichromate comprises potassium dichromate, concentrated sulfuric acid and deionized water, wherein the mass ratio of the potassium dichromate to the concentrated sulfuric acid to the deionized water is 1: 20: 2, the treatment temperature of the sample is 60 ℃ and the treatment time is 15 s.
The voltage of the normal-pressure low-temperature plasma corona treatment is 200V, the distance from the sample to be treated is 3mm, and the treatment time is 5 s.
The specific operation comprises the following steps:
step one, mechanical treatment method for surface of polyether-ether-ketone and composite material thereof
Firstly, mechanically polishing the polyether-ether-ketone and the composite material thereof by using 500-mesh abrasive paper, removing a weak boundary layer and improving the specific surface area of the base material, and then polishing by using 100-mesh abrasive paper to further improve the roughness of the surface of the base material. Wherein, the PEEK thermoplastic plastics and the chopped fiber reinforced composite materials are polished along the direction of 45 degrees, and the unidirectional long fiber and fiber fabric reinforced composite materials are polished along the horizontal direction of shearing stress;
step two, solvent deoiling treatment of the coarse surface of the polyether-ether-ketone and the composite material thereof
Deoiling the surface of the test piece polished in the step one, cleaning the surface by using acetone, and drying for 30min at 90 ℃;
step three, chemical treatment of the crude and clean surface of the polyether-ether-ketone and the composite material thereof
(1) Slowly adding concentrated sulfuric acid with the mass fraction of 98% into deionized water, and stirring while adding to form a concentrated sulfuric acid solution A, wherein the mass ratio of the deionized water to the concentrated sulfuric acid is 1: 40; (2) adding sodium dichromate into the solution A, wherein the mass ratio of the sodium dichromate to the solution A is 1:22, and stirring for 3 hours at room temperature to form a solution B; (3) treating the sample dried in the step two in the solution B at the treatment temperature of 60 ℃ for 15s, washing the treated sample for 5min by using running water, and drying the washed sample for 30min at the temperature of 90 ℃;
step four, energy treatment of the surface of the polyether-ether-ketone and the composite material thereof
And (3) performing corona treatment on the surface of the sample dried in the third step by using normal-pressure low-temperature plasma equipment, wherein the treatment voltage is 200V, the distance from the sample to be treated is 3mm, and the treatment time is 5 s.
After the treatment, aiming at the unidirectional continuous carbon fiber reinforced polyether-ether-ketone composite material, the single lap joint shear strength of a cementing test piece is 47.42MPa at room temperature, and the cementing strength after the damp-heat aging is 37.55MPa after 1000 hours; aiming at the polyether-ether-ketone thermoplastic, the chopped fiber and the inorganic filler reinforced polyether-ether-ketone composite material, the test piece fracture is the result of a single lap shear test at room temperature, and the test piece fracture is still the result of the single lap shear test after 1000 hours of thermal aging.
Detailed description of the preferred embodiment example 3
The multiscale collaborative surface treatment method capable of greatly improving the bonding performance of the polyetheretherketone and the composite material thereof comprises mechanical polishing, solvent cleaning, acidification etching, drying and corona treatment, wherein the mechanical polishing is performed by using abrasive paper, the acidification etching is performed by using a bichromate concentrated sulfuric acid solution, and the corona treatment is normal-pressure low-temperature plasma corona treatment.
The sequence of the multi-scale synergetic surface treatment comprises mechanical polishing, solvent cleaning, drying, acidification etching, running water washing, drying and corona treatment.
The mechanical treatment method comprises the steps of firstly grinding with 400-mesh sand paper and then grinding with 200-mesh sand paper.
The cleaning solvent is ethanol.
The drying condition is drying at 80 ℃ for 40min.
The concentrated sulfuric acid solution of the dichromate comprises potassium dichromate, concentrated sulfuric acid and deionized water, wherein the mass ratio of the potassium dichromate to the concentrated sulfuric acid to the deionized water is 1: 13: 1.25, the treatment temperature of the sample was 40 ℃ and the treatment time was 20 s.
The voltage of the normal-pressure low-temperature plasma corona treatment is 100V, the distance from the sample to be treated is 2mm, and the treatment time is 30 s.
The specific operation comprises the following steps:
step one, mechanical treatment method for surface of polyether-ether-ketone and composite material thereof
Firstly, mechanically polishing the polyether-ether-ketone and the composite material thereof by using 400-mesh sand paper, removing a weak boundary layer and improving the specific surface area of the base material, and then polishing by using 200-mesh sand paper to further improve the roughness of the surface of the base material. Wherein, the PEEK thermoplastic plastics and the chopped fiber reinforced composite material are polished in the direction of 45 degrees, and the unidirectional long fiber and fiber fabric reinforced composite material is polished in the horizontal direction of shearing stress;
step two, solvent deoiling treatment of the coarse surface of the polyether-ether-ketone and the composite material thereof
Deoiling the surface of the test piece polished in the step one, cleaning the surface by using acetone, and drying for 40min at 80 ℃;
step three, chemical treatment of the crude and clean surface of the polyetheretherketone and the composite material thereof
(1) Slowly adding concentrated sulfuric acid with the mass fraction of 98% into deionized water, and stirring while adding to form a concentrated sulfuric acid solution A, wherein the mass ratio of the deionized water to the concentrated sulfuric acid is 1: 21.5; (2) adding a mixture of sodium dichromate and potassium dichromate in any proportion into the solution A, wherein the mass ratio of the sodium dichromate to the solution A is 1:14, and stirring at room temperature for 2.5 hours to form a solution B; (3) treating the sample dried in the step two in the solution B at the treatment temperature of 40 ℃ for 20s, washing the treated sample for 3min by using running water, and drying the washed sample for 40min at the temperature of 80 ℃;
step four, energy treatment of the surface of the polyether-ether-ketone and the composite material thereof
And (3) performing corona treatment on the surface of the sample dried in the third step by using normal-pressure low-temperature plasma equipment, wherein the treatment voltage is 100V, the distance from the sample to be treated is 2mm, and the treatment time is 30 s.
After the treatment, aiming at the unidirectional continuous carbon fiber reinforced polyetheretherketone composite material, the single lap joint shear strength of a cementing test piece is 45.83MPa at room temperature, and the cementing strength after the humid heat aging is 1000 hours is 36.84 MPa; aiming at the polyether-ether-ketone thermoplastic, the chopped fiber and the inorganic filler reinforced polyether-ether-ketone composite material, the test piece fracture is the result of a single lap shear test at room temperature, and the test piece fracture is still the result of the single lap shear test after 1000 hours of thermal aging.
Detailed description of the preferred embodiment example 4
The treatment method of the invention was examined separately below for mechanical grinding, solvent cleaning, acid etching, drying and corona treatment to demonstrate the significant advantages of the solution of the invention.
1. Mechanical treatment method for surface of polyether-ether-ketone and composite material thereof
Firstly, mechanically polishing the polyether-ether-ketone and the composite material thereof by using 400-mesh sand paper, removing a weak boundary layer and improving the specific surface area of the base material, and then polishing by using 200-mesh sand paper to further improve the roughness of the surface of the base material. Wherein, the PEEK thermoplastic plastics and the chopped fiber reinforced composite material are polished along the direction of 45 degrees, and the unidirectional long fiber and fiber fabric reinforced composite material is polished along the horizontal direction of shearing stress.
After the treatment, the single lap joint shear strength of the cementing test piece of the unidirectional continuous fiber reinforced polyether-ether-ketone composite material at room temperature is 17.54MPa, and the cementing strength after the humid heat aging is 1000 hours is 13.27 MPa.
2. Energy treatment of surface of polyether-ether-ketone and composite material thereof
The surface of the sample to be bonded was subjected to corona treatment using a normal pressure low temperature plasma apparatus at a treatment voltage of 100V and a distance of 2mm from the sample to be treated for 30 s.
After the treatment, the single lap joint shear strength of the cementing test piece of the unidirectional continuous fiber reinforced polyether-ether-ketone composite material at room temperature is 26.43MPa, and the cementing strength after the humid heat aging is 1000 hours is 20.31 MPa.
3. Mechanical polishing and energy treatment of surface of polyether-ether-ketone and composite material thereof
Firstly, mechanically polishing the polyether-ether-ketone and the composite material thereof by using 400-mesh sand paper, removing a weak boundary layer and improving the specific surface area of the base material, and then polishing by using 200-mesh sand paper to further improve the roughness of the surface of the base material. Wherein, the PEEK thermoplastic plastics and the chopped fiber reinforced composite material are polished in the direction of 45 degrees, and the unidirectional long fiber and fiber fabric reinforced composite material is polished in the horizontal direction of shearing stress;
4. the surface of the sample to be bonded was subjected to corona treatment using a normal pressure low temperature plasma apparatus at a treatment voltage of 100V and a distance of 2mm from the sample to be treated for 30 s.
After the treatment, the single lap joint shear strength of the cementing test piece of the unidirectional continuous fiber reinforced polyether-ether-ketone composite material at room temperature is 28.26MPa, and the cementing strength after the humid heat aging is 1000 hours is 22.15 MPa.
5. Chemical treatment of surface of polyether-ether-ketone and its composite material
(1) Slowly adding 98% by mass of concentrated sulfuric acid into deionized water, and stirring while adding to form a concentrated sulfuric acid solution A, wherein the mass ratio of the deionized water to the concentrated sulfuric acid is 1: 21.5; (2) adding a mixture of sodium dichromate and potassium dichromate in any proportion into the solution A, wherein the mass ratio of the sodium dichromate to the solution A is 1:14, and stirring at room temperature for 2.5 hours to form a solution B; (3) and (3) treating the bonded sample in the solution B at 40 ℃ for 20s, washing the treated sample for 3min by using running water, and drying the washed sample for 40min at 80 ℃.
After the treatment, the single lap joint shear strength of the cementing test piece of the unidirectional continuous fiber reinforced polyether-ether-ketone composite material at room temperature is 33.54MPa, and the cementing strength after the humid heat aging is 1000 hours is 22.76 MPa.
6. Chemical treatment and corona treatment of surface of polyether-ether-ketone and composite material thereof
(1) Slowly adding concentrated sulfuric acid with the mass fraction of 98% into deionized water, and stirring while adding to form a concentrated sulfuric acid solution A, wherein the mass ratio of the deionized water to the concentrated sulfuric acid is 1: 21.5; (2) adding a mixture of sodium dichromate and potassium dichromate in any proportion into the solution A, wherein the mass ratio of the sodium dichromate to the solution A is 1:14, and stirring at room temperature for 2.5 hours to form a solution B; (3) and (3) treating the bonded sample in the solution B at 40 ℃ for 20s, washing the treated sample for 3min by using flowing water, and drying the washed sample at 80 ℃ for 40min. (4) The surface of the dried sample to be bonded was subjected to corona treatment using an atmospheric pressure low temperature plasma apparatus at a treatment voltage of 100V and a distance of 2mm from the sample to be treated for 30 s.
After the treatment, the single lap shear strength of the unidirectional continuous fiber reinforced polyetheretherketone composite material at room temperature of a bonding test piece is 40.28MPa, and the bonding strength after the wet-heat aging is 1000 hours is 28.57 MPa.
The contact angle between water and the treated surface of the treated unidirectional carbon fiber reinforced polyether ether ketone thermoplastic composite material in different treatment methods is shown in fig. 2, the surface energy of the unidirectional carbon fiber reinforced polyether ether ketone thermoplastic composite material treated by different treatment methods is shown in fig. 3, the single lap shear strength of the unidirectional carbon fiber reinforced polyether ether ketone thermoplastic composite material in different surface treatment methods is shown in fig. 5, and the bonding durability (the performance is measured under the conditions of humid heat aging: 71 ℃, 95-100% humidity and 1000 hours) of the unidirectional carbon fiber reinforced polyether ether ketone thermoplastic composite material in different surface treatment methods is shown in fig. 6. As can be seen from fig. 2, 3, 5 and 6, after the multi-scale surface is treated by the method of the above embodiment, the wettability and the surface energy of the fiber reinforced polyetheretherketone composite material are greatly improved, the bonding strength and the bonding durability of the bonded joint after the material treatment are significantly improved, the bonding strength of the polyetheretherketone and the composite material thereof can reach more than 45MPa at most, and the bonding strength after the wet-heat aging for 1000 hours can reach more than 35MPa at most.
Claims (5)
1. A synergistic surface treatment method capable of improving the adhesive property of polyetheretherketone and composite materials thereof is characterized in that: the method comprises the synergistic effects of mechanical polishing, solvent cleaning, acidification etching, drying and corona treatment, wherein the mechanical polishing is polishing treatment by using abrasive paper, the acidification etching uses a concentrated sulfuric acid solution of dichromate for chemical etching, and the corona treatment is normal-pressure low-temperature plasma corona treatment; the sequence of the cooperative treatment method comprises mechanical polishing, solvent cleaning, acidification etching, drying and corona treatment; the polyether-ether-ketone and the composite material thereof are specifically as follows: polyether-ether-ketone thermoplastic plastics and one or more reinforced polyether-ether-ketone composite materials selected from chopped carbon fibers, glass fibers, quartz fibers, aramid fibers, unidirectional long fibers, fiber fabrics and inorganic fillers; the polyether-ether-ketone thermoplastic, chopped fiber reinforced and inorganic filler reinforced polyether-ether-ketone composite material is ground in a direction which is 45 degrees to the length direction of a test piece by taking the horizontal direction as a reference, and the unidirectional long fiber and fiber fabric reinforced polyether-ether-ketone composite material is ground in the horizontal shearing stress direction.
2. The synergistic surface treatment method for improving the adhesive bonding performance of polyetheretherketone and composites thereof according to claim 1, wherein the surface treatment method comprises the following steps: the mechanical grinding adopts emery of sand paper with the size of 60-500 meshes, wherein the emery is firstly ground by using 300-500 meshes of sand paper and then ground by using 60-200 meshes of sand paper.
3. The cooperative surface treatment method for improving the adhesive bonding performance of polyetheretherketone and its composite material according to claim 1, wherein the surface treatment method comprises the following steps: the concentrated sulfuric acid solution of the dichromate is formed by mixing dichromate, concentrated sulfuric acid and deionized water, wherein the mass ratio of the dichromate to the concentrated sulfuric acid to the deionized water is 1: 6-20: 0.5 to 2; the dichromate is one or a mixture of sodium dichromate and potassium dichromate in any proportion; the chemical etching treatment temperature is 15-60 ℃, and the treatment time is 15-60 s.
4. The synergistic surface treatment method for improving the adhesive bonding performance of polyetheretherketone and composites thereof according to claim 1, wherein the surface treatment method comprises the following steps: the corona treatment adopts normal-pressure low-temperature plasma corona treatment, the treatment voltage is 80-200V, the distance between a discharge device of corona equipment and a treated sample is 1-3mm, and the treatment time is 5-40 s.
5. The synergistic surface treatment method for improving the cementing property of polyetheretherketone and composites thereof as claimed in any one of claims 1 to 4, wherein the treatment method comprises the following steps:
firstly, polishing the polyether-ether-ketone and the composite material thereof by using 300-sand 500-mesh sand paper, and then polishing by using 60-200-mesh sand paper, wherein the polyether-ether-ketone thermoplastic and chopped fiber reinforced polyether-ether-ketone composite material is polished in a direction which forms a 45-degree angle with the length direction of a test piece by taking the horizontal direction as a reference, and the unidirectional long fiber and fiber fabric reinforced composite material is polished in the horizontal shearing stress direction;
step two, cleaning the polished surface of the test piece in the step one by using one or more of acetone, butanone, ethyl acetate and ethanol, and drying for 30-60min at the temperature of 60-90 ℃;
step three, adding concentrated sulfuric acid with the mass fraction of 98% into deionized water, stirring while adding to form a concentrated sulfuric acid solution A, adding dichromate into the concentrated sulfuric acid solution A, stirring at room temperature for 2-3h to form a solution B, placing the sample dried in the step two into the solution B for acidification treatment, washing the treated sample with running water for 2-5min, and drying the washed sample at 60-90 ℃ for 30-60min, wherein the mass ratio of the dichromate, the concentrated sulfuric acid and the deionized water is 1: 6-20: 0.5 to 2; the temperature of the solution B in the acidification treatment is 15-60 ℃, and the treatment time is 15-60 s;
and step four, performing corona treatment on the sample dried in the step three by using normal-pressure low-temperature plasma equipment, wherein the treatment voltage is 80-200V, the distance from the sample to be treated is 1-3mm, and the treatment time is 5-40s, so that the synergistic surface treatment method for improving the adhesive bonding strength of the polyether-ether-ketone and the composite material thereof is completed.
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