CN111057346B - Carbon fiber reinforced PEEK unidirectional tape and preparation method thereof - Google Patents
Carbon fiber reinforced PEEK unidirectional tape and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a carbon fiber reinforced PEEK unidirectional tape and a preparation method thereof, wherein the thickness of the carbon fiber reinforced PEEK unidirectional tape is 0.10-0.20 mm, and the width is 100-800 mm; comprises PEEK resin and carbon fiber, wherein the weight percentage of the PEEK resin is 32-36%; the carbon fiber is in a bundle shape, and the volume fraction of the carbon fiber is 55-65%; the PEEK resin is contained in a solidified suspension glue solution, the suspension glue solution is a water suspension system, the turbidity weight fraction of the suspension glue solution is 8-13%, and the suspension glue solution comprises the PEEK resin, a dispersing agent, a coupling agent, a self-defoaming emulsifying agent, a wetting agent, a penetrating agent, a surfactant, a thickening agent and deionized water. The preparation method comprises the steps of preparing suspension glue solution, drawing and spreading yarns, removing burrs, rolling and impregnating, heating, curing, melting and impregnating, preheating a die, pressing at high temperature and rolling by a roller. The invention has the advantages of excellent mechanical property, good environmental tolerance, excellent radiation resistance, high use temperature, flame retardance, wear resistance and short forming period.
Description
Technical Field
The invention belongs to the field of composite material manufacturing, and particularly relates to a carbon fiber reinforced PEEK unidirectional tape and a preparation method thereof.
Background
The unidirectional tape is one kind of prepreg, and is a composition prepared by impregnating continuous fibers with a resin matrix under strictly controlled conditions to prepare the resin matrix and a reinforcement, is an intermediate material for preparing a composite material, and is a basis of the composite material. The prepreg is a term in the industry of composite materials, and means fibers pre-impregnated with resin, which can ensure that the resin and the fibers are uniformly distributed in the composite material, and the fibers can be unidirectional carbon fibers, glass fiber cloth or aramid fibers. The resin may be a thermosetting plastic such as an epoxy resin, a polyester resin, or a phenol resin, or a thermoplastic plastic such as PEEK, PEKK, PEI, or PPS. Certain properties of the composite material are continuously improved, the process technology is gradually developed, and the application range is continuously expanded. However, the preparation of high performance thermoplastic resin based prepregs also presents some problems. The high-performance engineering thermoplastic resin such as polyether ether ketone (PEEK), polyimide Ether (PEI), polyphenylene sulfide (PPS) and the like has a melting point of more than 300 ℃, the melt viscosity is generally more than 100 Pa.s, and the viscosity changes little with the temperature.
Therefore, the key technology for preparing the thermoplastic resin prepreg is to solve the problem of impregnation of the reinforcing fibers by the thermoplastic resin. Xu Yan, the preparation method of prepreg at home and abroad, mentions that the common methods for preparing thermoplastic prepreg include solution method, hot melt method, powder method impregnation method, suspension impregnation method, fiber mixing method, in-situ polymerization method, etc.
The suspension impregnation method is a new method for preparing continuous fiber reinforced thermoplastic resin-based prepreg. The preparation method comprises the steps of preparing resin powder and other additives into suspension, enabling fiber filaments to pass through a glue dipping tank, fully dipping the fiber filaments in the suspension, then enabling the fiber filaments to enter a heating furnace to dry the suspension, and enabling the resin to be melted and dipped into the fibers to obtain the prepreg. The suspension is usually an aqueous solution containing a thickener such as polyethylene oxide or methyl ethyl cellulose. The resin powder should be as fine as possible, preferably having a diameter of less than 10 μm and less than the fiber diameter, in order to be uniformly distributed and to allow the fibers to be impregnated. The sheet produced by the method has the advantages of uniform fiber distribution, good fluidity of the prepreg during molding and processing, and suitability for manufacturing products with complex geometric shapes and thin-wall structures.
The suspension impregnation method is highly demanding of the suspension, which needs to have a suitable concentration, and the resin powder is to be uniformly dispersed in the liquid. In addition, the carrier liquid needs to be removed later on, otherwise the performance of the unidirectional tape is affected. The mechanical properties, especially the impact resistance and damage resistance of the PEEK unidirectional tape prepared by the preparation method adopted by the prior art can not meet the engineering requirements.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a carbon fiber reinforced PEEK unidirectional tape and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: a carbon fiber reinforced PEEK unidirectional tape is a sheet or a coiled material, the thickness of the PEEK unidirectional tape is 0.10-0.20 mm, and the breadth of the PEEK unidirectional tape is 100-800 mm; comprises PEEK resin and carbon fiber,
the weight fraction of the PEEK resin is 32-36%;
the carbon fiber is in a bundle shape, and the volume fraction of the carbon fiber is 55-65%;
the PEEK resin is contained in a solidified suspension glue solution, the suspension glue solution is an aqueous suspension system, the turbidity weight fraction of the suspension glue solution is 8-13%, and the suspension glue solution comprises the PEEK resin, a dispersing agent, a coupling agent, a self-defoaming emulsifying agent, a wetting agent, a penetrating agent, a surfactant, a thickening agent and deionized water;
further, the mass ratio of PEEK resin in the suspension glue solution is (70-120)% thousandths, the mass ratio of dispersing agent is (1-10)% thousandths, the mass ratio of coupling agent is (1-9)% thousandths, the mass ratio of self-defoaming emulsifier is (1-10),% the mass ratio of wetting agent is (1-8)% thousandths, the mass ratio of penetrating agent is (1-10)% thousandths, the mass ratio of surface active agent is (1-7)% thousandths, the mass ratio of thickening agent is (10-30)% thousandths, and the mass ratio of deionized water is (800-900)% thousandths.
Correspondingly, the preparation method of the carbon fiber reinforced PEEK unidirectional tape comprises the steps of glue solution preparation, traction yarn spreading, burr removal, rolling impregnation, heating solidification and melting impregnation, mold preheating and high-temperature pressing, and roller winding,
preparing a suspension glue solution: mixing PEEK resin powder with a dispersing agent, a coupling agent, a self-defoaming emulsifier, a wetting agent, a penetrating agent and a surfactant, and then putting the mixture into a high-speed stirrer for stirring to obtain a premix, wherein the rotating speed is 500-1000 r/min, and the stirring time is 0.2-0.6 hour, so that the components are uniformly dispersed;
adding a thickening agent and deionized water, stirring at a rotating speed of 300-500 r/min for 3-5 hours to uniformly disperse PEEK powder to obtain a suspended glue solution, and conveying the suspended glue solution into a stirring barrel; the suspension glue solution is circularly stirred in a stirring barrel, the rotating speed is 50-100 r/min, and precipitates are avoided;
the invention should reasonably control the preparation ratio of the premix and the deionized water in the suspension glue solution. When the content of the deionized water is too low, the suspension is too viscous to be well impregnated and combined with the continuous fibers; when the deionized water content is too high, the PEEK content in the suspension is low, so that the PEEK content of the final product is low, and the mechanical properties of the product are reduced.
Drawing and yarn spreading: the carbon fiber tows finish traction yarn spreading through a zigzag yarn spreading device under the traction action of a traction roller, so that carbon fiber yarns are uniformly arranged; the number of the drawing rolls is between 5 and 30, and the drawing speed is between 0.1 m/min and 3 m/min;
removing burrs: the burrs of the carbon fiber tows are removed by adopting infrared heating, the furnace temperature is 300-500 ℃, and the distance between an infrared heating head and the carbon fiber tows is 50-200 mm.
Rolling and dipping: circularly conveying the suspended glue solution from the stirring barrel to an ultrasonic impregnation tank by using a circulating pump, filling the impregnation tank with the glue solution, carrying out multi-roller turning rolling impregnation on continuous carbon fiber tows through the impregnation tank, and extruding redundant suspension liquid; the ultrasonic vibration frequency is between 20 kHz and 68 kHz, the ultrasonic power is between 300W and 400W, the number of ultrasonic vibration heads is between 10 and 30, and the ultrasonic vibration heads are orderly arranged at the bottom of the impregnation tank; the number of the steering rolling dipping rollers is 3 to 7.
The concentration control of the suspending liquid cement is preferably carried out by an on-line monitoring system or manual sampling detection. The sampling frequency is 1 to 12 times/hour, and when the solid (non-volatile matter) content rate of the glue solution is lower than the lower limit value, the suspension liquid needs to be supplemented into the stirring barrel.
Heating for solidification and melting for impregnation: the suspension glue solution is put into a heating and curing furnace, the heating and curing furnace is divided into a drying section, a pre-melting section and a melting section, and the drying section, the pre-melting section and the melting section have the length proportion of 2:1:1; the temperature of the drying section of the heating curing furnace is 260-440 ℃, the temperature of the premelting section is 350-620 ℃, and the temperature of the melting section is 450-730 ℃; fully melting and impregnating the PEEK resin in a furnace with continuous carbon fiber bundles, and bonding the carbon fiber bundles together;
preheating a mould and pressing at high temperature: the preheating temperature of the die is 380-450 ℃, and the pressing temperature of the die is 360-430 ℃.
The structure of the carbon fiber reinforced PEEK unidirectional tape product can be uniform and compact by preheating and high-temperature pressing the die.
And (3) rolling the roller: and (3) rolling and winding the continuous carbon fiber reinforced PEEK unidirectional tape obtained after the die pressing through a coiling machine, and then shearing to obtain a finished product of the continuous carbon fiber reinforced PEEK unidirectional tape.
Furthermore, the specification of the carbon fiber tows is 3 k-24 k.
Furthermore, the PEEK resin is ultrafine powder with the particle size of 6.5-38 microns.
The invention uniformly disperses the PEEK superfine powder in deionized water, then the continuous fiber is dipped in the suspension, and the PEEK powder can be uniformly distributed among tows of the carbon fiber. If the PEEK powder particle size is too big, the PEEK powder can not enter between the tows of the carbon fiber completely in the production process, but floats on the surface of the carbon fiber tows, so that the PEEK powder and the carbon fiber tows are completely combined, and the mechanical strength of the product is not enough. If the PEEK powder is too fine, the production of the PEEK powder is difficult and high in cost, so that the particle size of the PEEK ultrafine powder is reasonably selected according to the product performance requirements.
Further, the dispersant is ethanol, acetone and styrene-maleic acid copolymer hyperdispersant.
The dispersant of the invention has the functions of fully infiltrating PEEK, reducing the surface tension of water and well dispersing the PEEK in deionized water.
Further, the coupling agent is an epoxy-based or methylacetyl-based silane coupling agent.
When the silane coupling agent is interposed between the inorganic (carbon fiber) and the organic interface (PEEK resin), a bonding layer of an organic matrix-the silane coupling agent-the inorganic matrix is formed, thereby improving the bonding force between the carbon fiber and the PEEK resin.
Further, the self-defoaming emulsifier is alkylphenol ethoxylates, polydimethylsiloxane or other aqueous system defoaming agents.
The defoaming agent can reduce the surface tension of the suspension and prevent the formation of foam.
Further, the wetting agent is alkylphenol polyoxyethylene, polyoxyethylene octyl phenyl ether, silicon alcohol or other nonionic surfactants.
The main function of the wetting agent is to reduce the surface tension of water, enabling the PEEK resin powder surface to be wetted by water, while enabling the suspension to wet and spread out on the carbon fiber tow surface during impregnation.
Further, the penetrating agent is alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether or other nonionic surfactants.
The penetrating agent mainly has the function of reducing the contact angle between the glue solution and the carbon fiber, so that the wettability of the glue solution to the carbon fiber tows is enhanced.
Further, the surfactant is dimethylformamide, polyethylene glycol octyl phenyl ether or ester non-silicon surfactant.
The primary function of the surfactant is to reduce the surface tension of water.
Further, the thickening agent is hydroxymethyl cellulose polyethylene glycol, polyvinyl alcohol pyrrolidone and hydroxyethyl cellulose.
The thickening agent of the invention has the function of keeping PEEK powder in a suspended state in water for a long time and stabilizing the content of PEEK in the production process.
Furthermore, the conductivity of the deionized water is less than 10 mu S/cm.
Preferably meets the requirement of analyzing the tertiary water of the laboratory water in GB/T6682-2008 'specification and test method for analyzing the laboratory water'.
The working principle of the invention is as follows:
the technological process of the carbon fiber reinforced PEEK unidirectional tape comprises glue solution preparation, traction yarn spreading, burr removal, rolling impregnation, drying, solidification, melting impregnation, mold preheating, high-temperature pressing and roller winding. Firstly, preparing a suspension glue solution, conveying the glue solution into an ultrasonic impregnation tank, and filling the impregnation tank with the glue solution; then, uniformly arranging the carbon fiber yarns by a traction yarn spreading device, and removing burrs on the surface of the carbon fiber yarns in an infrared oven; secondly, rolling and impregnating the continuous carbon fiber tows in an ultrasonic impregnation tank, and extruding redundant suspension liquid; then, drying the carbon fiber tows by a heating and curing furnace, and simultaneously melting and impregnating PEEK resin into the carbon fiber tows to obtain carbon fiber reinforced PEEK unidirectional tape prepreg; thirdly, preheating the carbon fiber reinforced PEEK unidirectional tape through a mold and pressing the carbon fiber reinforced PEEK unidirectional tape at high temperature; and finally, winding the unidirectional tape by a winding machine to obtain the continuous carbon fiber reinforced PEEK unidirectional tape composite material product.
The invention has the beneficial effects that:
1. the continuous carbon fiber reinforced PEEK unidirectional tape disclosed by the invention belongs to a thermoplastic carbon fiber composite material, can be continuously produced, has excellent mechanical properties, particularly impact resistance and damage resistance, and has the advantages of good environmental tolerance, excellent irradiation resistance, high use temperature, flame retardance, wear resistance and short forming period. Can be applied to the advanced industrial fields of aerospace, automobiles, consumer electronics and the like;
2. the continuous carbon fiber reinforced PEEK unidirectional tape disclosed by the invention has the advantages that the volume content of carbon fibers is more than or equal to 55%, the mass fraction of the PEEK resin is more than or equal to 32%, the structural void content is less than or equal to 1%, the minimum thickness can reach 0.1 mm, and the maximum width can reach 800 mm. Can be formed and processed for many times, is suitable for manufacturing thin plates and hot press forming or autoclave processes, and can be recycled.
Drawings
FIG. 1 is a schematic perspective view of the structure of a carbon fiber reinforced PEEK unidirectional tape of the present invention;
fig. 2 is a schematic step view of a carbon fiber reinforced PEEK unidirectional tape preparation method according to the present invention.
Detailed Description
The details of the present invention are described below in conjunction with the accompanying drawings and specific embodiments.
As shown in FIG. 1, a carbon fiber reinforced PEEK unidirectional tape is a sheet or a coiled material, the thickness of the PEEK unidirectional tape is 0.10-0.20 mm, and the width of the PEEK unidirectional tape is 100-800 mm; comprises PEEK resin and carbon fiber,
the weight fraction of the PEEK resin is 32-36%;
the carbon fiber is in a bundle shape, and the volume fraction of the carbon fiber is 55-65%;
the PEEK resin is contained in a solidified suspension glue solution, the suspension glue solution is a water suspension system, the turbidity weight fraction of the suspension glue solution is 8% -13%, and the suspension glue solution comprises the PEEK resin, a dispersing agent, a coupling agent, a self-defoaming emulsifier, a wetting agent, a penetrating agent, a surfactant, a thickening agent and deionized water.
The product performance parameters of the carbon fiber reinforced PEEK unidirectional tape are shown in table 1:
TABLE 1 Performance parameters of carbon fiber reinforced PEEK unidirectional tapes with a carbon fiber volume content of 60%
| Properties of | Test standards | Data of |
| Density of | ISO1183 | 1.32g/cm 3 |
| Water absorption | DIN53495 | 0.5% |
| Continuous use temperature | -40～260℃ | |
| Tensile strength at yield | ISO527 | 97MPa |
| Strain at yield | ISO527 | 4.9% |
| Ultimate tensile strain | ISO527 | >60% |
| Toughness of impact resistance | ISO179 | 0.B.kJ/m 2 |
| Notched impact toughness | ISO179 | 8.2kJ/m 2 |
| Rockwell ball hardness | ISO2039-1 | M99MPa |
| Shore D hardness | DIN53505 | 90 |
| Bending strength | ISO178 | 170MPa |
| Modulus of elasticity | ISO527 | 3660Mpa |
| Vicat softening temperature | ISO306 | 250℃ |
| Temperature of heat distortion | ISO75 | 240℃ |
| Coefficient of thermal linear expansion | DIN53752 | 0.47K-1*104 |
| Thermal conductivity 20 DEG C | DIN52612 | 0.25w/(mxk) |
Correspondingly, a preparation method of the continuous carbon fiber reinforced PEEK unidirectional tape takes the carbon fiber reinforced PEEK unidirectional tape with the carbon fiber volume content of 60 percent as an example.
In this example, a Japan Dongli carbon fiber T700-12K was used as a reinforcing fiber, and 10 μm PEEK micropowder of Wedges, UK was used as a matrix resin. The drawing speed of the production line is 1.2 m/min, the thickness of the carbon fiber reinforced PEEK unidirectional tape prepreg is 0.14mm, and the breadth is 300 mm. The method comprises the following steps:
1. preparing glue solution: 10 parts of Polyetheretherketone (PEEK) ultrafine powder, 0.5 part of acetone (dispersing agent), 0.5 part of silane coupling agent KH-560 (coupling agent), 0.1 part of NXZ defoaming agent (self-defoaming emulsifier), 0.3 part of Triton X-100 (wetting agent), 0.3 part of polyoxyethylene octylphenol ether OP-10 (penetrating agent) and 0.3 part of QX-202 (surfactant) are mixed, and then the mixture is put into a high-speed stirrer to be stirred at the rotating speed of 800 r/min for 0.5 hour to uniformly disperse the components to obtain a premix. And then putting the obtained premix and 1 part of polyvinylpyrrolidone PVP K-30 (thickening agent) into a high-speed stirrer, adding 98 parts of deionized water, stirring at the rotating speed of 400 r/min for more than 4 hours to uniformly disperse PEEK powder to obtain a suspended glue solution with the solid (non-volatile matter) content of 12 percent, and conveying the suspended glue solution into a stirring barrel for later use. The suspension glue solution is circularly stirred in the stirring barrel at the rotating speed of 100 r/min, so that the occurrence of precipitates is avoided.
2. Drawing and yarn spreading: the carbon fiber tows finish traction yarn spreading through the zigzag yarn spreading device under the traction action of 10 traction rollers, so that the carbon fiber yarns are uniformly arranged. The drawing speed was 1.2 m/min.
3. Removing burrs: the carbon fiber tows are subjected to an infrared heating furnace to remove surface burrs, the temperature of the deburring furnace is 400 ℃, and the distance between an infrared heater and the carbon fiber tows is 120 mm.
4. Rolling and dipping: and (3) circularly conveying the suspended glue solution obtained in the step (1) from the stirring barrel to an ultrasonic impregnation tank by using a circulating pump, filling the impregnation tank with the glue solution, carrying out 3-roller turning, rolling and impregnating on the continuous carbon fiber tows through the impregnation tank, and extruding redundant suspension. The sampling frequency of the suspension glue solution is 2 times/hour, and when the solid (non-volatile matter) content of the glue solution is lower than 10 wt%, the suspension liquid needs to be supplemented into the stirring barrel. The ultrasonic vibration frequency is 40kHz, and the total power is 350W. The number of ultrasonic horns was 15 (3*5 arrangement).
5. Heating, solidifying and melting and dipping: the temperature of the drying section of the heating curing furnace is set to be 380 ℃, the temperature of the pre-melting section is set to be 390 ℃, and the temperature of the melting section is set to be 400 ℃. The length ratio of the three sections is 2:1:1
6. Preheating a mould and pressing at high temperature: the temperature of the mold preheating section was set to 410 ℃ and the temperature of the high temperature pressing section was set to 400 ℃.
7. And (3) rolling the roller: and (4) rolling and winding the PEEK continuous carbon fiber unidirectional tape obtained after the die pressing through a coiler, and shearing the PEEK continuous carbon fiber unidirectional tape to obtain a carbon fiber reinforced PEEK unidirectional tape product.
In practical application, the carbon fiber tows have the specification of 3 k-24 k.
In practical application, the PEEK resin is preferably superfine powder with the particle size of 6.5-38 microns. The invention uniformly disperses the PEEK superfine powder in deionized water, then the continuous fiber is dipped in the suspension, and the PEEK powder can be uniformly distributed among tows of the carbon fiber. If the PEEK powder particle size is too big, the PEEK powder can not enter between the tows of the carbon fiber completely in the production process, but floats on the surface of the carbon fiber tows, so that the PEEK powder and the carbon fiber tows are completely combined, and the mechanical strength of the product is not enough. If the PEEK powder is too fine, the PEEK powder is difficult to produce and high in cost, so that the particle size of the PEEK ultrafine powder is reasonably selected according to the product performance requirements.
In practical application, the dispersant is preferably ethanol, acetone or styrene-maleic acid copolymer hyperdispersant. The dispersant of the invention has the functions of fully infiltrating PEEK, reducing the surface tension of water and well dispersing the PEEK in deionized water.
In practical applications, the coupling agent is preferably an epoxy-based or methylacetyl-based silane coupling agent. When the silane coupling agent is interposed between the inorganic (carbon fiber) and the organic interface (PEEK resin), a bonding layer of an organic matrix-the silane coupling agent-the inorganic matrix is formed, thereby improving the bonding force between the carbon fiber and the PEEK resin.
In practical applications, the self-defoaming emulsifier is preferably alkylphenol ethoxylates, polydimethylsiloxane or other aqueous system defoaming agents. The defoaming agent can reduce the surface tension of the suspension and prevent the formation of foam.
In practical applications, the wetting agent is preferably alkylphenol ethoxylates, polyethylene glycol octyl phenyl ether, silanol or other nonionic surfactants. The main function of the wetting agent is to reduce the surface tension of water, enabling the PEEK resin powder surface to be wetted by water, while enabling the suspension to wet and spread out on the carbon fiber tow surface during impregnation.
In practical applications, preferably, the penetrating agent is alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ethers or other nonionic surfactants. The penetrating agent mainly has the function of reducing the contact angle between the glue solution and the carbon fiber, so that the wettability of the glue solution to the carbon fiber tows is enhanced.
In practical application, the surfactant is preferably dimethylformamide, polyethylene glycol octyl phenyl ether or ester non-silicon surfactant. The primary function of the surfactant is to reduce the surface tension of water.
In practical application, the thickener is preferably hydroxymethyl cellulose polyethylene glycol, polyvinyl alcohol pyrrolidone, or hydroxyethyl cellulose. The thickening agent of the invention has the function of keeping PEEK powder in a suspended state in water for a long time and stabilizing the content of PEEK in the production process.
In practical application, the conductivity of the deionized water is preferably less than 10 muS/cm. The requirement of analyzing the tertiary water of the laboratory water in GB/T6682-2008 'water specification and test method for analyzing the laboratory' needs to be met.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the foregoing embodiments are merely illustrative of the technical spirit and features of the present invention, and the present invention is not limited thereto but may be implemented by those skilled in the art.
Claims (5)
1. The utility model provides a PEEK unidirectional tape of carbon fiber reinforcement which characterized in that: is a sheet or a coiled material, the thickness is between 0.10 and 0.20 mm, and the breadth is between 100 and 800 mm; comprises PEEK resin and carbon fiber,
the weight fraction of the PEEK resin is 32-36%;
the carbon fiber is in a bundle shape, and the volume fraction of the carbon fiber is 55-65%;
the PEEK resin is contained in a solidified suspension glue solution, the suspension glue solution is a water suspension system, the turbidity weight fraction of the suspension glue solution is 8-13%, and the suspension glue solution comprises the PEEK resin, a dispersing agent, a coupling agent, a self-defoaming emulsifying agent, a wetting agent, a penetrating agent, a surfactant, a thickening agent and deionized water.
2. A carbon fiber reinforced PEEK unidirectional tape according to claim 1, wherein: the mass ratio of PEEK resin in the suspension glue solution is (70-120)% per thousand, the mass ratio of dispersing agent is (1-10)% per thousand, the mass ratio of coupling agent is (1-9)% per thousand, the mass ratio of self-defoaming emulsifier is (1-10), the mass ratio of wetting agent is (1-8)% per thousand, the mass ratio of penetrating agent is (1-10)% per thousand, the mass ratio of surfactant is (1-7)% per thousand, the mass ratio of thickening agent is (10-30)% per thousand, and the mass ratio of deionized water is (800-900)% per thousand.
3. A carbon fibre reinforced PEEK unidirectional tape according to claim 1 or 2, characterized in that: the specification of the carbon fiber is 3 k-24 k;
the dispersant is ethanol, acetone and styrene-maleic acid copolymer hyper-dispersant;
the coupling agent is epoxy group or methyl acetyl group silane coupling agent;
the self-defoaming emulsifier is alkylphenol ethoxylates, polydimethylsiloxane or other aqueous system defoaming agents;
the wetting agent is alkylphenol polyoxyethylene, polyethylene glycol octyl phenyl ether, silanol or other nonionic surfactants;
the penetrating agent is alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether or other nonionic surfactants;
the surfactant is dimethylformamide, polyethylene glycol octyl phenyl ether or ester non-silicon surfactant;
the thickening agent is hydroxymethyl cellulose polyethylene glycol, polyvinyl alcohol pyrrolidone and hydroxyethyl cellulose;
the conductivity of the deionized water is less than 10 muS/cm.
4. A preparation method of a carbon fiber reinforced PEEK unidirectional tape is characterized by comprising the following steps: comprises glue solution preparation, traction yarn spreading, burr removal, rolling impregnation, heating solidification and melting impregnation, mold preheating and high-temperature pressing, and roller winding,
preparing a suspension glue solution: mixing PEEK resin powder with a dispersing agent, a coupling agent, a self-defoaming emulsifier, a wetting agent, a penetrating agent and a surfactant, and then putting the mixture into a high-speed stirrer for stirring to obtain a premix, wherein the rotating speed is 500-1000 r/min, and the stirring time is 0.2-0.6 hour, so that the components are uniformly dispersed; adding a thickening agent and deionized water, stirring at a rotating speed of 300-500 r/min for 3-5 hours to uniformly disperse PEEK powder to obtain a suspended glue solution, and conveying the suspended glue solution into a stirring barrel; the suspension glue solution is circularly stirred in a stirring barrel, the rotating speed is 50-100 r/min, and precipitates are avoided;
drawing and yarn spreading: the carbon fiber tows finish traction yarn spreading through a zigzag yarn spreading device under the traction action of a traction roller, so that carbon fiber yarns are uniformly arranged; the number of the drawing rolls is between 5 and 30, and the drawing speed is between 0.1 m/min and 3 m/min;
removing burrs: removing burrs of the carbon fiber tows by adopting infrared heating, wherein the furnace temperature is 300-500 ℃, and the distance between an infrared heating head and the carbon fiber tows is 50-200 mm;
rolling and dipping: circularly conveying the suspended glue solution from the stirring barrel to an ultrasonic impregnation tank by using a circulating pump, filling the impregnation tank with the glue solution, carrying out multi-roller turning rolling impregnation on continuous carbon fiber tows through the impregnation tank, and extruding redundant suspension liquid; the ultrasonic vibration frequency is between 20 kHz and 68 kHz, the power of ultrasonic waves is between 300W and 400W, the number of ultrasonic vibration heads is between 10 and 30, and the ultrasonic vibration heads are orderly arranged at the bottom of the impregnation tank; the number of the steering rolling impregnation rollers is 3 to 7;
heating for solidification and melting for impregnation: the suspension glue solution is put into a heating and curing furnace, the heating and curing furnace is divided into a drying section, a pre-melting section and a melting section, and the drying section, the pre-melting section and the melting section have the length proportion of 2:1:1; the temperature of the drying section of the heating curing furnace is 260-440 ℃, the temperature of the premelting section is 350-620 ℃, and the temperature of the melting section is 450-730 ℃; fully melting and impregnating the PEEK resin into the continuous carbon fiber bundles in a furnace, and bonding the carbon fiber bundles together;
preheating a mould and pressing at high temperature: the preheating temperature of the die is 380-450 ℃, and the pressing temperature of the die is 360-430 ℃;
and (3) rolling the roller: and (3) rolling and winding the continuous carbon fiber reinforced PEEK unidirectional tape obtained after the die pressing through a coiling machine, and then shearing to obtain a finished product of the continuous carbon fiber reinforced PEEK unidirectional tape.
5. The method for preparing a carbon fiber reinforced PEEK unidirectional tape according to claim 4, characterized in that: the specification of the carbon fiber tows is 3 k-24 k;
the PEEK resin powder is ultrafine powder with the particle size of 6.5-38 micrometers;
the dispersant is ethanol, acetone and styrene-maleic acid copolymer hyper-dispersant;
the coupling agent is epoxy group or methyl acetyl group silane coupling agent;
the self-defoaming emulsifier is alkylphenol ethoxylates, polydimethylsiloxane or other aqueous system defoaming agents;
the wetting agent is alkylphenol polyoxyethylene, polyethylene glycol octyl phenyl ether, silanol or other nonionic surfactants;
the penetrating agent is alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether or other nonionic surfactants;
the surfactant is dimethylformamide, polyethylene glycol octyl phenyl ether or ester non-silicon surfactant;
the thickening agent is hydroxymethyl cellulose polyethylene glycol, polyvinyl alcohol pyrrolidone and hydroxyethyl cellulose;
the conductivity of the deionized water is less than 10 muS/cm.
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