CN110924162A - Method for carrying out surface modification on reinforced fiber by using crystalline polyaryletherketone sizing agent - Google Patents
Method for carrying out surface modification on reinforced fiber by using crystalline polyaryletherketone sizing agent Download PDFInfo
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- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Abstract
A method for carrying out surface modification on reinforced fibers by using a crystalline polyaryletherketone sizing agent belongs to the technical field of surface treatment of reinforced fibers. Preparing a soluble polyaryletherketone precursor into a solution, adding an interface reinforcing filler under the ultrasonic oscillation condition to prepare a soluble polyaryletherketone sizing agent, and placing the sizing agent into a sizing tank; after sizing treatment is carried out on the reinforced fiber by using the sizing agent, the solvent is evaporated to dryness to ensure that a soluble polyarylether precursor is uniformly attached to the surface of the reinforced fiber, and then the precursor on the surface of the reinforced fiber is subjected to hydrolysis reaction under an acidic condition to be converted into polyarylether ketone which has crystallinity, is heat-resistant and is insoluble in an organic solvent; and finally, drying the water by distillation to obtain the reinforced fiber modified by the crystalline polyaryletherketone sizing agent. When the modified reinforcing fiber is used for reinforcing PEEK resin, the interfacial shear strength (IFSS) of the composite material is obviously improved (267%) compared with that of carbon fiber which is not sized, and the modified reinforcing fiber is solvent-resistant and can be used at high temperature.
Description
Technical Field
The invention belongs to the technical field of surface treatment of reinforced fibers, and particularly relates to a method for performing surface modification on reinforced fibers by using a crystalline polyaryletherketone sizing agent.
Background
Resin-based composite materials are widely used in various fields because of their light weight, excellent mechanical properties, designability, and the like. With the development of aerospace and defense industries, the traditional resin-based composite materials are difficult to meet the use requirements under high temperature, high strength and corrosive environments, so that the application of special engineering plastic-based composite materials represented by polyether ether ketone (PEEK) resin is more extensive. However, due to the molecular structure characteristics of the polyetheretherketone, strong interaction is difficult to generate between the polyetheretherketone and the reinforced fiber, so that the interface shear strength of the composite material is low, and the application of the polyetheretherketone is limited.
The reinforcing fiber sizing agent not only has the function of protecting fibers, but also can improve the interaction between the resin matrix and the reinforcing fibers, thereby improving the bonding capacity of the resin matrix and the reinforcing fibers and preventing micromolecules from permeating and initial microcracks from being generated, so the sizing agent has important significance on the composite material bearing shear load. The crystal structure of the PEEK enables the PEEK to have excellent thermal stability and solvent resistance, and no reports exist on the sizing agent which can enhance the interaction between a PEEK resin matrix and reinforcing fibers and can simultaneously exert the heat resistance and the solvent resistance of the PEEK.
Patent No. CN 102926204 a discloses an epoxy-based sizing agent with a polyarylether structure, aiming to improve the interaction of the sizing agent with PEEK by a similar chemical structure. But epoxy groups are remained due to no epoxy resin curing agent in the formula, the thermal decomposition temperature (less than or equal to 200 ℃) of the epoxy groups is lower than the processing temperature (400 ℃) of the PEEK composite material, and small molecules generated by the thermal decomposition of the sizing agent can cause interface defects, thereby affecting the product performance; the uncured epoxy resin is easy to dissolve in organic solvents such as acetone, so that the composite material is easy to generate defects at an interface in a complex chemical environment (such as the chemical field, crude oil extraction and the like); meanwhile, hydroquinone used in the formula of the sizing agent in the patent is easy to be oxidized in air, and the boiling point (304.5 ℃) of benzophenone is lower than the processing temperature of the PEEK composite material, so that the mechanical property of a PEEK composite material product can be influenced, and the sizing agent cannot be well matched with the processing condition and the use environment of the PEEK-based composite material.
Patent No. CN 102817241 a discloses a biphenyl naphthalene type polyaryletherketone (PPEK) sizing agent containing Carbon Nanotubes (CNTs), in which the compatibility between PPEK and PEEK is poor and strong interaction cannot be formed. The PPEK has no crystallinity, has lower mechanical strength than PEEK, is easy to dissolve in an organic solvent, and is not resistant to sodium hypochlorite (a common disinfectant) (Journal of Membrane Science,2012,389: 416-423, Table 5), so that the advantages of weather resistance and corrosion resistance of the PEEK-based composite material cannot be exerted, and the PPEK is not suitable for a PEEK-based composite material system. The PPEK sizing agent system developed by the subject group of professor Liuwenbo of Harbin Industrial university (doctor's paper: preparation and performance characterization of PPEK emulsion sizing agent, Lidaofei, Harbin Industrial university, 2012) is not suitable for PEEK composite material systems for the same reason.
The group of subjects hit by the university of Beijing aerospace developed a Polyetherimide (PEI) Graphene Oxide (GO) -carrying sizing agent system (Composites Science and Technology,2018,154: 175-186) for enhancing the interfacial interaction between PEEK and Carbon Fibers (CF), which has limited improvement in the interfacial properties of PEEK/CF Composites due to incomplete compatibility and inability of the PEI and PEEK to co-crystallize (44%, page 179, line 62); since PEI does not have crystallinity, has mechanical strength lower than that of PEEK, is easy to dissolve in an organic solvent, and imide groups are not resistant to an alkaline environment, the weather resistance and corrosion resistance advantages of PEEK-based composite materials cannot be exerted, and therefore PEI is not suitable for PEEK-based composite material systems. PEI sizing agents (Applied Surface Science,2013,266: 94-99) developed by Emile Perez, university of Tuluz, France, were not suitable for use in PEEK composite systems for the same reasons.
The sulfonated polyether sulfone sizing agent (scientific research paper: composite material science 2015,32 (2): 420-426) developed by the subject group of the professor Liujie of Beijing chemical university cannot form strong interaction because sulfonated polyether sulfone and PEEK are not completely compatible and cannot be co-crystallized. The sulfonated polyether sulfone has no crystallinity, has mechanical strength lower than that of PEEK, is easy to dissolve in an organic solvent, and has sulfonic acid groups easy to absorb water, so that the advantages of weather resistance and corrosion resistance of the PEEK-based composite material cannot be exerted, and the sulfonated polyether sulfone is not suitable for a PEEK-based composite material system.
Patent No. CN108004779a discloses a method for surface modification of fibers with PEEK powder suspension emulsion. The PEEK powder does not have two functions of sizing the fiber bundle and protecting the sizing agent of the fibers, the powder and the fiber bundle do not have adhesive force, the powder is easy to fall off to pollute the environment and lose efficacy, and the wetting capacity of the powder to the fibers in the processing process is limited due to the large viscosity of PEEK melt. In addition, the alkylphenol polyvinyl ether used is not suitable for PEEK composite material systems because the thermal decomposition temperature is lower than the processing temperature of PEEK composite materials. The PEEK oligomer suspension sizing agent developed by Emile Perez project group, third university of Turutz, France (SCI article: Journal of applied polyamide science,2015,132:42550) is not suitable for PEEK composite systems for the same reason.
Disclosure of Invention
In order to solve the problems, the invention achieves the purposes of enabling a sizing agent to be uniformly infiltrated, enabling an interface layer to be crystallized, resistant to solvent and resistant to heat, and enabling the interface layer to generate strong interaction with PEEK.
The invention is realized by the following method: preparing a soluble polyaryletherketone precursor into a solution, adding an interface reinforcing filler under the ultrasonic oscillation condition to prepare a soluble polyaryletherketone sizing agent, and placing the sizing agent in a sizing tank; after sizing treatment is carried out on the reinforced fiber by using the sizing agent, the solvent is evaporated to dryness to ensure that a soluble polyarylether precursor is uniformly attached to the surface of the reinforced fiber, and then the precursor on the surface of the reinforced fiber is subjected to hydrolysis reaction (taking ketimine polyetheretherketone as an example, the hydrolysis reaction formula is shown in (I)) under an acidic condition to be converted into polyarylether ketone which has crystallinity, is heat-resistant and is insoluble in an organic solvent; and finally, drying the water by distillation and rolling to obtain the reinforcing fiber modified by the crystalline polyaryletherketone sizing agent. When the modified reinforcing fiber is used for reinforcing PEEK resin, the interfacial shear strength (IFSS) of the composite material is obviously improved (267%) compared with that of carbon fiber which is not sized, and the modified reinforcing fiber is solvent-resistant and can be used at high temperature.
n is a positive integer;
the invention provides a sizing agent which can uniformly modify crystalline polyaryletherketone which is insoluble in an organic solvent at room temperature on the surface of a reinforced fiber, improves IFSS (internal stability and tensile strength) by 267 percent compared with carbon fiber which is not sized, resists the solvent and can be used at high temperature and a fiber surface treatment method, and the method comprises the following specific steps:
(1) dissolving a soluble polyaryletherketone precursor which can be converted into crystalline polyaryletherketone in a good solvent to prepare a solution with the mass fraction of 0.25-3 wt%, and adding an interface reinforcing filler with the mass fraction of 0-0.8 wt% (wherein the total mass is the sum of a polymer, the interface reinforcing filler and the solvent, and the mass fractions are the same as those described below) under an ultrasonic oscillation condition to obtain a soluble polyaryletherketone precursor sizing agent; for example, ketimine polyether ether ketone is dissolved in Tetrahydrofuran (THF) to prepare a solution with a mass fraction of 0.25 wt% as a sizing agent; or dissolving polyether-ether-ketone-1, 3-dioxolane in NMP, and adding acidified carbon nano tubes with the mass fraction of 0.1 wt% as a sizing agent under the ultrasonic oscillation state after the polyether-ether-ketone-1, 3-dioxolane is fully dissolved;
(2) carrying out primary sizing treatment on the reinforced fibers by using the sizing agent in the step (1), wherein the fiber pulling rate is 1-100 mm/min, and obtaining the reinforced fibers with the surface modified with the sizing agent; for example, when the effective stroke of the carbon fiber which is not sized in the sizing tank is 1m, the pulling rate is 100 mm/min;
(3) evaporating the solvent of the reinforced fiber of the surface modification sizing agent obtained in the step (2) to dryness; for example, when THF is used as a solvent, resistance wires can be used for heating, and the evaporation temperature is 100 ℃;
(4) introducing the reinforcing fiber of the surface modification sizing agent of which the solvent is evaporated in the step (3) into a hydrolysis tank, and carrying out acidification hydrolysis treatment to convert a soluble polyaryletherketone precursor into insoluble crystalline polyaryletherketone; for example, a sizing agent containing no interfacial reinforcing filler and having a ketimine polyether ether ketone mass fraction of 0.25 wt% is used to treat carbon fibers that have not been sized and the solvent is evaporated to dryness, and then the carbon fibers are introduced into a hydrolysis tank containing a 10 wt% sulfuric acid solution to cause a chemical reaction as shown in fig. 1, thereby uniformly modifying crystalline polyether ether ketone on the surfaces of the reinforcing fibers;
(5) and (4) drying the reinforced fiber after the acidification and hydrolysis treatment in the step (4) to obtain the reinforced fiber modified by the crystalline polyaryletherketone. For example, a carbon fiber which has not been subjected to sizing treatment with a sizing agent containing no interfacial reinforcing filler in an amount of 0.25 wt% based on the mass fraction of ketimine polyetheretherketone is subjected to solvent evaporation, then introduced into a 10 wt% sulfuric acid solution hydrolysis tank to be hydrolyzed, and then dried at 150 ℃ to obtain a crystalline polyetheretherketone surface-modified carbon fiber.
The soluble polyaryletherketone precursor in the step (1) is as follows: one or more of ketimine polyether ether ketone, ketimine polyether ether ketone, ketimine polyether ketone, ketimine biphenyl polyether ether ketone, ketimine polybiphenyl ether ketone, polyether ether ketone-1, 3-dioxolane, polyether ether ketone-1, 3-dioxolane, polyether ketone-1, 3-dioxolane, biphenyl polyether ether ketone-1, 3-dioxolane and biphenyl ether ketone-1, 3-dioxolane. The polymer has good solubility, can generate crystalline polyaryletherketone after hydrolysis, and can be prepared into a solution type sizing agent by utilizing the solubility of the polymer, thereby overcoming the defect that the surface treatment is carried out on fibers by utilizing powder in the patent number CN 108004779A; meanwhile, the crystalline polyaryletherketone generated after hydrolysis has good solvent resistance and high-temperature service performance, and can be cocrystallized with special engineering plastics such as PEEK and the like to provide good interface interaction, so that the IFSS is improved by 267% to the maximum extent compared with carbon fibers which are not subjected to sizing. The soluble polymer is used as the main component of the sizing agent, and simultaneously satisfies the improvement of sizing effect, solvent resistance, high-temperature usability and interface bonding strength, and is the most important innovation point of the invention.
The number average molecular weight of the soluble polyaryletherketone precursor in the step (1) is 2000-60000 g/mol. The molecular weight and the mass fraction of the soluble polyaryletherketone precursor, the type of the interface reinforcing filler and the mass fraction of the interface reinforcing filler influence the interface performance between the sized reinforcing fiber and the resin matrix, such as IFSS. The number average molecular weight of 2000-60000 g/mol is an optimal value screened by a large number of experiments, when the polymer with the number average molecular weight of less than 2000g/mol is used as an effective component of the sizing agent, the molecular chain is short, so the improvement of the interface performance is limited, when the polymer with the number average molecular weight of more than 60000g/mol is used as the effective component of the sizing agent, the solubility is poor, the melt viscosity is high, and the sizing is not uniform, so the number average molecular weight range is defined as a claim.
When the solution is prepared in the step (1), the organic solvent which can be used is one of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-Dimethylformamide (DMAC), Tetrahydrofuran (THF) and dichloromethane, wherein THF is preferably used as the solvent for the ketimine polymer, because the ketimine polymer has good solubility in THF, the boiling point of THF is low, and the energy consumption required by the evaporation process is low; for the same reason, the 1, 3-dioxolane polymer is selected from solvents according to the priority of dichloromethane > DMF > DMAC > NMP, depending on the molecular weight and chemical structure. The selection of the solvent is the result of matching and screening through a large number of experiments, and in addition, the solvent cannot simultaneously have the characteristics of dissolving the precursor and being easy to dry.
The interface reinforcing material in the step (1) is one or more of carbon nano tube, acidified carbon nano tube, graphene oxide, cage-type Polysilsesquioxane (POSS), gold nano particle, gold nano wire, copper nano particle, copper nano wire, silver nano particle, silver nano wire, nano silicon dioxide, silicon dioxide nano tube and hydroxyapatite nano tube (the filler can be purchased or synthesized by oneself) (. the addition of the interface reinforcing material can further improve IFSS (the IFSS can be enhanced by experiments).
The interface reinforcing material in the step (1) can also be prepared by adding the dispersion liquid into the polymer solution under the ultrasonic oscillation condition.
The sizing rate in the step (2) is a test result comprehensively considering fiber tension, frictional damage, fiber spreading effect, sizing time and sizing efficiency during sizing. The sizing rate is lower than 1mm/min, the sizing efficiency is too low, and the fiber spreading effect is poor; the fiber friction damage is serious when the sizing rate is higher than 100 mm/min. The specific sizing rate needs to be combined with the effective stroke of the fibers in the sizing tank, and the effective sizing time is guaranteed to be 10 min.
The fiber in the step (2) is one of unsized carbon fiber, carbon fiber washed with sizing agent, unsized basalt fiber, washed with sizing agent basalt fiber, unsized glass fiber, washed with sizing agent glass fiber, unsized Kevlar fiber, washed with sizing agent Kevlar fiber, unsized boron nitride fiber, washed with sizing agent boron nitride fiber, unsized carbon nanotube fiber, unsized graphene fiber and unsized carbon nanofiber. Experiments prove that the sizing agent and the fiber surface treatment method provided by the invention can achieve an interface enhancement effect on carbon fibers, basalt fibers, glass fibers, boron nitride fibers, carbon nanotube fibers, graphene fibers, Kevlar fibers and carbon nanofibers. Meanwhile, the existing commercial sizing agents have disadvantages as described in the background art, and the presence thereof is detrimental to the effect of the invention, so that the fibers used are limited to fibers which are not sized or washed with sizing agents.
And (4) evaporating the solvent in the step (3) by adopting infrared heating or resistance wire heating. Tests prove that other heating modes, such as hot air heating, can damage the fibers due to airflow. Infrared heating and resistance wire heating, while commonly used, are safe and effective heating means for the invention.
The evaporation temperature when the solvent is evaporated in the step (3) is as follows: NMP: 230 ℃, DMF: 200 ℃, DMAC: 210 ℃, THF: 100 ℃, dichloromethane: 80 ℃. Under vacuum, the temperature was reduced by 50 ℃. Experiments prove that in the continuous production process, when the temperature is too low and the solvent is evaporated to dryness, the solvent can not be completely evaporated, and the subsequent processing effect and the final product performance are influenced; since an excessively high temperature requires a high facility and leads to a high facility investment and high energy consumption, the above temperature is defined as a claim.
The reagent for acidification and hydrolysis treatment in the step (4) is a dilute sulfuric acid solution with the concentration of 0.1-9 mol/L or a hydrochloric acid solution with the concentration of 0.1-9 mol/L. The acidification treatment time is 2 h. The soluble polyaryletherketone precursor used in the step (1) can be hydrolyzed into crystalline polyaryletherketone in water, and the hydrolysis rate is accelerated under acidic conditions to ensure complete hydrolysis. The dilute sulfuric acid solution is preferably used from the viewpoint of environmental protection.
And (5) drying at a temperature of more than or equal to 145 ℃ for 2-5 h. The crystalline polyaryletherketone obtained by hydrolysis in the step (4) is in a low-crystallinity state and can be subjected to cold crystallization above the glass transition temperature, so that the crystalline polyaryletherketone is dried at a higher temperature under tension, and the crystalline polyaryletherketone is promoted to crystallize to eliminate internal stress while drying moisture.
The characteristics and advantages are as follows:
(1) the invention relates to a method for surface modification of reinforced fiber by using crystalline polyaryletherketone material, which has the characteristics of uniform sizing, solvent resistance, high temperature resistance and strong interaction with polyaryletherketone special engineering plastics;
(2) the invention greatly improves the interface shearing performance of PEEK and other polyaryletherketone special engineering plastics and fibers, and can improve the interface shearing performance by 267 percent compared with carbon fibers which are not sized, thereby solving the bonding problem between the resin matrix and the fibers;
(3) the raw materials are easy to obtain (the ketimine polymer can be obtained by polymerizing ketimine monomers, the energy consumption in the polymerization process is lower than that of commercial polyether sulfone; the 1, 3-dioxolane polymer can be obtained by post-treating commercial polyaryletherketone), the continuous production can be realized, the room-temperature sizing can be realized, the post-treatment means is mild, and the method is a reinforced fiber sizing scheme with commercial value;
(4) the selectable polyaryletherketone sizing agent has a large molecular weight range, and can meet the requirements of different composite materials.
Drawings
FIG. 1 is a scanning electron microscope image of the surface topography of carbon fibers before (a) and after (b) sizing in example 1;
FIG. 2 interfacial shear performance test curves for the products of examples 1 and 2.
Detailed Description
The method of the present invention is further described by the following specific examples, which are merely specific descriptions of the claims of the present invention, including but not limited to the contents of the examples. The range limitations of mass fraction, sizing rate, number average molecular weight and acid concentration are only selected as representative examples.
Example 1:
dissolving 2.5g of ketimine polyether ether ketone (the number average molecular weight is 2000g/mol) in 997.5mL of NMP, placing the mixture into a sizing tank with an effective stroke of 1m after the mixture is completely dissolved, and sizing the carbon fiber bundle which is not sized at the speed of 100 mm/min; drying the preliminarily sized carbon fibers in a resistance wire evaporator at 230 ℃ by using NMP; and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain a crystalline polyether-ether-ketone-sized carbon fiber bundle, drying the carbon fiber bundle at 150 ℃, and rolling to obtain the crystalline polyether-ether-ketone-sized carbon fiber. The surface topography of the carbon fibers before and after sizing is shown in FIG. 1, which is 60MPa compared to 60MPa for PEEK, which is 100% greater for the carbon fibers without sizing (30MPa) (IFSS test curves are shown in FIG. 2).
Example 2:
dissolving 10g of ketimine polyether ether ketone (with the number average molecular weight of 4000g/mol) in 1040mL of DMF, slowly adding 0.25g of carbon nano tubes under the ultrasonic oscillation condition after complete dissolution, placing the mixture into a sizing tank with the effective stroke of 10mm after full dispersion, and sizing the carbon fiber bundle washed with sizing agent (acetone ultrasonic washing for 48 hours is used as the method for removing the sizing agent) at the speed of 1 mm/min; drying the preliminarily sized carbon fibers in a resistance wire evaporator at 200 ℃ to obtain DMF (dimethyl formamide); and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.9mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain a carbon fiber bundle subjected to crystalline polyetheretherketon sizing, drying the carbon fiber bundle at 150 ℃, and rolling to obtain the carbon fiber subjected to crystalline polyetheretherketon sizing. Its IFSS compared to PEEK was 110MPa, which is increased by 267% compared to the IFSS of the carbon fiber reinforced PEEK composite material without sizing (IFSS test curve see fig. 2).
Example 3:
dissolving 10g of ketimine polyether ketone (the number average molecular weight is 6000g/mol) in 1060mL of DMF, slowly adding 0.5g of acidified carbon nano tube under the ultrasonic condition after complete dissolution, placing the acidified carbon nano tube in a sizing tank with an effective stroke of 1m after full dispersion, and sizing the unglued basalt fiber at the speed of 100 mm/min; drying the primarily sized basalt fiber in an infrared heating evaporator at 210 ℃ to obtain DMAC; and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.9mol/L dilute hydrochloric acid for acidification treatment for 2h, hydrolyzing to obtain a crystalline polyetherketone-sized basalt fiber bundle, drying the basalt fiber bundle at 150 ℃, and rolling to obtain the crystalline polyetherketone-sized basalt fiber. It has an IFSS of 78MPa compared to PEEK, which is 160% greater than that of unbleached basalt fibers (31 MPa).
Example 4:
dissolving 10g of ketiminated biphenyl type polyether-ether-ketone (the number average molecular weight is 8000g/mol) in 1100mL of THF, slowly adding 0.75g of graphene under the ultrasonic condition after complete dissolution, placing the graphene in a sizing tank with an effective stroke of 1m after full dispersion, and sizing the basalt fiber washed with sizing agent at the speed of 100 mm/min; drying the primarily sized basalt fiber in an infrared heating evaporator at 100 ℃ to obtain THF; and (2) introducing the fiber bundle of the dried solvent into a hydrolysis tank filled with 0.1mol/L dilute hydrochloric acid for acidification treatment for 2h, hydrolyzing to obtain a crystalline biphenyl type polyether-ether-ketone-sized basalt fiber bundle, drying the basalt fiber bundle at 150 ℃, and rolling to obtain the crystalline polyether-ketone-sized basalt fiber. The IFSS of the composite material and PEEK is 83MPa, and the composite material is 177% higher than that of unsized basalt fiber.
Example 5:
dissolving 10g of ketimine poly-biphenyl type polyether ether ketone (with the number average molecular weight of 10000g/mol) in 750mL of dichloromethane, slowly adding 1g of graphene oxide under the ultrasonic condition after complete dissolution, placing the mixture into a sizing tank with the effective stroke of 1m after full dispersion, and sizing the unsized glass fiber at the speed of 100 mm/min; drying the primarily sized glass fiber in an infrared heating evaporator at 80 ℃ to obtain dichloromethane; and (3) introducing the fiber bundle with the dried solvent into a hydrolysis tank filled with 0.1mol/L diluted hydrochloric acid for acidification treatment for 2h, hydrolyzing to obtain a glass fiber bundle with the crystallized biphenyl polyetheretherketon sizing, drying the glass fiber bundle at 150 ℃, and rolling to obtain the crystallized biphenyl polyetheretherketon sizing glass rock fiber material. It has an IFSS of 104MPa compared to PEEK, which is increased by 197% compared to the unsized glass fibers (35 MPa).
Example 6:
dissolving 10g of polyether-ether-ketone-1, 3-dioxolane (with the number average molecular weight of 20000g/mol) in 990mL of NMP, slowly adding 1g of POSS under the ultrasonic condition after completely dissolving, placing the mixture into a sizing tank with an effective stroke of 1m after fully dispersing, and sizing the glass fiber washed with sizing agent at the rate of 100 mm/min; drying the preliminarily sized glass fiber in an infrared heating evaporator at 230 ℃ by NMP; and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain a glass fiber bundle subjected to crystalline polyether-ether-ketone sizing, drying the glass fiber bundle at 150 ℃, and rolling to obtain the glass fiber subjected to crystalline polyether-ether-ketone sizing. It has an IFSS of 91MPa compared to PEEK, which is 160% greater than that of the unsized glass fibers.
Example 7:
dissolving 10g of polyetheretherketon-1, 3-dioxolane (the number average molecular weight is 30000g/mol) in 990mL of NMP, slowly adding 1g of gold nanoparticles under the ultrasonic condition after completely dissolving, placing in a sizing tank with an effective stroke of 1m after fully dispersing, and sizing the unsized boron nitride fibers at the speed of 100 mm/min; drying the preliminarily sized boron nitride fibers in an infrared heating evaporator at 230 ℃ by NMP; and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain a boron nitride fiber bundle subjected to crystalline polyetheretherketon sizing, drying the boron nitride fiber bundle at 150 ℃, and rolling to obtain the boron nitride fiber subjected to crystalline polyetheretherketon sizing. It has an IFSS of 87 compared to PEEK, an increase of 156% compared to unsized boron nitride (34MPa) fibers.
Example 8:
dissolving 10g of polyether ketone-1, 3-dioxolane (the number average molecular weight is 40000g/mol) in 990mL of NMP, slowly adding 1g of gold nanowire under the ultrasonic condition after completely dissolving, placing the gold nanowire in a sizing tank with an effective stroke of 1m after fully dispersing, and sizing the boron nitride fiber with the sizing agent removed at the speed of 100 mm/min; drying the preliminarily sized boron nitride fibers in an infrared heating evaporator at 230 ℃ by NMP; and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain a boron nitride fiber bundle subjected to crystalline polyether ketone sizing, drying the boron nitride fiber bundle at 150 ℃, and rolling to obtain the boron nitride fiber subjected to crystalline polyether ketone sizing. It had an IFSS of 84 compared to PEEK, an increase of 147% compared to unsized boron nitride fiber.
Example 9:
dissolving 10g of biphenyl polyether ether ketone-1, 3-dioxolane (the number average molecular weight is 50000g/mol) in 990mL of NMP, slowly adding 1g of copper nanoparticles under the ultrasonic condition after complete dissolution, placing the mixture in a sizing tank with an effective stroke of 1m after full dispersion, and sizing carbon nanotube fibers which are not sized at the speed of 100 mm/min; drying the carbon nano tube fiber subjected to preliminary sizing in an infrared heating evaporator at 230 ℃ by NMP; and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain a carbon nanotube fiber bundle subjected to crystallization biphenyl type polyether ether ketone sizing, drying the carbon nanotube fiber bundle at 150 ℃, and rolling to obtain the carbon nanotube fiber subjected to crystallization biphenyl type polyether ether ketone sizing. It has an IFSS of 108 compared to PEEK, which is 170% greater than that of the carbon nanotube fiber (40MPa) without sizing.
Example 10:
dissolving 10g of biphenyl ether ketone-1, 3-dioxolane (with the number average molecular weight of 60000g/mol) in 990mL of NMP, slowly adding 1g of copper nanowires under the ultrasonic condition after complete dissolution, placing the mixture into a sizing tank with an effective stroke of 1m after full dispersion, and sizing the ungelled graphene fibers at the rate of 100 mm/min; drying the preliminarily sized graphene fibers in an infrared heating evaporator at 230 ℃ by NMP; and (2) putting the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain a graphene fiber bundle subjected to crystalline biphenyl type polyetheretherketon sizing, drying the graphene fiber bundle at 150 ℃, and rolling to obtain the graphene fiber subjected to crystalline biphenyl type polyetheretherketon sizing. It had an IFSS of 113 compared to PEEK, which was increased by 190% compared to the unsized graphene fibers (39).
Example 11:
dissolving 10g of ketimine polyether ether ketone (the number average molecular weight is 60000g/mol) in 990mL of NMP, slowly adding 1g of silver nanoparticles under an ultrasonic condition after complete dissolution, fully dispersing, placing in a sizing tank with an effective stroke of 1m, and sizing the unsized Kevlar fiber at the speed of 100 mm/min; drying the primarily sized Kevlar fiber in an infrared heating evaporator at 230 ℃ by NMP; and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2h, hydrolyzing to obtain a Kevlar fiber bundle subjected to crystallization polyether ether ketone sizing, drying the Kevlar fiber bundle at 150 ℃, and rolling to obtain Kevlar fibers subjected to crystallization polyether ether ketone sizing. The IFSS of the composite material and PEEK is 82MPa, and the composite material is 173MPa higher than that of unbleached Kevlar fiber (30 MPa).
Example 12:
dissolving 10g of ketimine polyether ether ketone (the number average molecular weight is 60000g/mol) in 990mL of NMP, slowly adding 1g of silver nano-particle wire under the ultrasonic condition after completely dissolving, fully dispersing, placing in a sizing tank with an effective stroke of 1m, and sizing the Kevlar fiber washed with the sizing agent at the rate of 100 mm/min; drying the primarily sized Kevlar fiber in an infrared heating evaporator at 230 ℃ by NMP; and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2h, hydrolyzing to obtain a Kevlar fiber bundle subjected to crystallization polyether ether ketone sizing, drying the Kevlar fiber bundle at 150 ℃, and rolling to obtain Kevlar fibers subjected to crystallization polyether ether ketone sizing. It has an IFSS of 91 compared to PEEK, which is 203% greater than the unsized kevlar fiber.
Example 13:
dissolving 10g of ketimine polyether ether ketone (the number average molecular weight is 60000g/mol) in 990mL of NMP, slowly adding 1g of nano silicon dioxide under the ultrasonic condition after completely dissolving, fully dispersing, placing in a sizing tank with an effective stroke of 1m, and sizing the unsized nano carbon fiber at the speed of 100 mm/min; drying NMP in an infrared heating evaporator at 230 ℃; and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain the crystallized polyetheretherketone-sized carbon nanofibers, drying the carbon nanofibers at 150 ℃, and rolling to obtain the crystallized polyetheretherketone-sized carbon nanofibers. Compared with PEEK, the IFSS of the carbon nanofiber is 73MPa, and the growth of the carbon nanofiber is 118% compared with that of carbon nanofiber without sizing (32 MPa).
Example 14:
dissolving 10g of ketimine polyether ether ketone (the number average molecular weight is 60000g/mol) in 990mL of NMP, slowly adding 1g of silicon dioxide nanotubes under an ultrasonic condition after completely dissolving, fully dispersing, placing in a sizing tank with an effective stroke of 1m, and sizing carbon fibers which are not sized at the speed of 100 mm/min; drying the preliminarily sized carbon fibers in an infrared heating evaporator at 230 ℃ by NMP; and (3) putting the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain the crystalline polyetheretherketone-sized carbon fiber, drying the carbon fiber at 150 ℃, and rolling to obtain the crystalline polyetheretherketone-sized carbon fiber. It has an IFSS of 96MPa compared to PEEK, which is 220% greater than that of the carbon fiber without sizing.
Example 15:
dissolving 10g of ketimine polyether ether ketone (the number average molecular weight is 60000g/mol) in 990mL of NMP, slowly adding 1g of hydroxyapatite nanotube under an ultrasonic condition after complete dissolution, fully dispersing, placing in a sizing tank with an effective stroke of 1m, and sizing carbon fibers which are not sized at the speed of 100 mm/min; drying the preliminarily sized carbon fibers in an infrared heating evaporator at 230 ℃ by NMP; and (3) introducing the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain crystalline polyetheretherketone-sized carbon fibers, drying the carbon fibers at 150 ℃, and rolling to obtain the crystalline polyetheretherketone-sized carbon fibers. It has an IFSS of 89MPa compared to PEEK, which is increased by 197% compared to unsized carbon fibers.
Example 16:
dissolving 10g of ketimine polyether ether ketone (the number average molecular weight is 60000g/mol) in 990mL of NMP, slowly adding 0.5g of acidified carbon nanotube and 0.5g of graphene oxide under an ultrasonic condition after completely dissolving, placing the mixture in a sizing tank with an effective stroke of 1m after fully dispersing, and sizing the carbon fiber which is not sized at the speed of 100 mm/min; drying the preliminarily sized carbon fibers in an infrared heating evaporator at 230 ℃ by NMP; and (3) putting the fiber bundle subjected to solvent removal into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2 hours, hydrolyzing to obtain the crystalline polyetheretherketone-sized carbon fiber, drying the carbon fiber at 150 ℃, and rolling to obtain the crystalline polyetheretherketone-sized carbon fiber. It has an IFSS of 108MPa compared to PEEK, which is 260% greater than that of the carbon fiber without sizing.
Example 17:
dissolving 30g of ketimine polyether ether ketone (the number average molecular weight is 60000g/mol) in 970mL of NMP, slowly adding 8g of acidified carbon nanotubes under an ultrasonic condition after complete dissolution, fully dispersing, placing in a sizing tank with an effective stroke of 1m, and sizing the non-sized Kevlar fiber at the rate of 100 mm/min; drying the primarily sized Kevlar fiber in an infrared heating evaporator at 230 ℃ by NMP; and (3) putting the fiber bundle with the solvent removed into a hydrolysis tank filled with 0.1mol/L dilute sulfuric acid for acidification treatment for 2h, hydrolyzing to obtain Kevlar fiber subjected to crystallization polyether-ether-ketone sizing, drying the Kevlar fiber at 150 ℃, and rolling to obtain Kevlar fiber subjected to crystallization polyether-ether-ketone sizing. The IFSS compared with PEEK is 107MPa, which is 259 percent higher than that of unsized Kevlar fiber.
Claims (9)
1. A method for carrying out surface modification on reinforced fibers by using a crystalline polyaryletherketone sizing agent comprises the following steps:
(1) dissolving a soluble polyaryletherketone precursor capable of being converted into crystalline polyaryletherketone in a good solvent to prepare a solution with the mass fraction of 0.25-3 wt%, and adding an interface reinforcing filler with the mass fraction of 0-0.8 wt% under the ultrasonic oscillation condition to obtain a soluble polyaryletherketone precursor sizing agent;
(2) carrying out primary sizing treatment on the reinforced fibers by using the sizing agent in the step (1), wherein the fiber pulling rate is 1-100 mm/min, and obtaining the reinforced fibers with the surface modified with the sizing agent;
(3) evaporating the solvent of the reinforced fiber of the surface modification sizing agent obtained in the step (2) to dryness;
(4) introducing the reinforcing fiber of the surface modification sizing agent of which the solvent is evaporated in the step (3) into a hydrolysis tank, and carrying out acidification hydrolysis treatment to uniformly modify the crystalline polyether-ether-ketone on the surface of the reinforcing fiber;
(5) and (4) drying the reinforced fiber after the acidification and hydrolysis treatment in the step (4) to obtain the reinforced fiber modified by the crystalline polyaryletherketone.
2. The method of claim 1, wherein the reinforcing fiber is surface-modified with a crystalline polyaryletherketone sizing agent, wherein: the soluble polyaryletherketone precursor in the step (1) is one or more of ketimine polyetheretherketone, ketimine polyetherketone, ketimine biphenyl polyetheretherketone, ketimine polydiphenyl polyetheretherketone, polyetheretherketone-1, 3-dioxolane, polyetherketone-1, 3-dioxolane, biphenyl polyetheretherketone-1, 3-dioxolane, and biphenyl polyetheretherketone-1, 3-dioxolane.
3. The method of claim 1, wherein the reinforcing fiber is surface-modified with a crystalline polyaryletherketone sizing agent, wherein: the number average molecular weight of the soluble polyaryletherketone precursor in the step (1) is 2000-60000 g/mol.
4. The method of claim 1, wherein the reinforcing fiber is surface-modified with a crystalline polyaryletherketone sizing agent, wherein: the solvent in the step (1) is one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylformamide, tetrahydrofuran or dichloromethane.
5. The method of claim 1, wherein the reinforcing fiber is surface-modified with a crystalline polyaryletherketone sizing agent, wherein: the interface reinforcing material in the step (1) is one or more of carbon nano tubes, acidified carbon nano tubes, graphene oxide, cage type polysilsesquioxane, gold nano particles, gold nano wires, copper nano particles, copper nano wires, silver nano particles, silver nano wires, nano silicon dioxide, silicon dioxide nano tubes and hydroxyapatite nano tubes.
6. The method of claim 1, wherein the reinforcing fiber is surface-modified with a crystalline polyaryletherketone sizing agent, wherein: the reinforcing fiber in the step (2) is one of unsized carbon fiber, sizing agent-washed carbon fiber, unsized basalt fiber, sizing agent-washed basalt fiber, unsized glass fiber, sizing agent-washed glass fiber, unsized Kevlar fiber, sizing agent-washed Kevlar fiber, unsized boron nitride fiber, sizing agent-washed boron nitride fiber, unsized carbon nanotube fiber, unsized graphene fiber or unsized carbon nanofiber.
7. The method of claim 1, wherein the reinforcing fiber is surface-modified with a crystalline polyaryletherketone sizing agent, wherein: and (4) heating the solvent evaporator in the step (3) by adopting infrared heating or resistance wire heating.
8. The method of claim 1, wherein the reinforcing fiber is surface-modified with a crystalline polyaryletherketone sizing agent, wherein: the reagent for acidification and hydrolysis treatment in the step (4) is a dilute sulfuric acid solution with the concentration of 0.1-9 mol/L or a hydrochloric acid solution with the concentration of 0.1-9 mol/L, and the acidification treatment time is 2 hours.
9. The method of claim 1, wherein the reinforcing fiber is surface-modified with a crystalline polyaryletherketone sizing agent, wherein: and (5) drying at a temperature of more than or equal to 145 ℃ for 2-5 h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111777776A (en) * | 2020-07-20 | 2020-10-16 | 吉林大学 | Fabric-reinforced heat-conducting filler-soluble polymer heat-conducting composite material and preparation method thereof |
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| CN111979775A (en) * | 2020-07-24 | 2020-11-24 | 福建创立佳科技有限公司 | Preparation method of surface sizing agent for aramid fiber composite material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102307920A (en) * | 2009-02-05 | 2012-01-04 | 阿科玛股份有限公司 | Fibers sized with polyetherketoneketones |
| CN103069063A (en) * | 2010-11-16 | 2013-04-24 | 东丽碳纤维美国公司 | Carbon fiber |
| US20160102180A1 (en) * | 2013-12-16 | 2016-04-14 | Ut-Battelle, Llc | Multifunctional curing agents and their use in improving strength of composites containing carbon fibers embedded in a polymeric matrix |
| CN109505135A (en) * | 2018-11-28 | 2019-03-22 | 中国科学院宁波材料技术与工程研究所 | A kind of method that polyether ketone ketone sizing agent and its starching prepare carbon fibre composite |
-
2019
- 2019-12-09 CN CN201911247570.XA patent/CN110924162B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102307920A (en) * | 2009-02-05 | 2012-01-04 | 阿科玛股份有限公司 | Fibers sized with polyetherketoneketones |
| CN103069063A (en) * | 2010-11-16 | 2013-04-24 | 东丽碳纤维美国公司 | Carbon fiber |
| US20160102180A1 (en) * | 2013-12-16 | 2016-04-14 | Ut-Battelle, Llc | Multifunctional curing agents and their use in improving strength of composites containing carbon fibers embedded in a polymeric matrix |
| CN109505135A (en) * | 2018-11-28 | 2019-03-22 | 中国科学院宁波材料技术与工程研究所 | A kind of method that polyether ketone ketone sizing agent and its starching prepare carbon fibre composite |
Cited By (15)
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|---|---|---|---|---|
| CN111777776A (en) * | 2020-07-20 | 2020-10-16 | 吉林大学 | Fabric-reinforced heat-conducting filler-soluble polymer heat-conducting composite material and preparation method thereof |
| CN111777776B (en) * | 2020-07-20 | 2021-06-25 | 吉林大学 | Fabric-reinforced heat-conducting filler-soluble polymer heat-conducting composite material and preparation method thereof |
| CN111979775A (en) * | 2020-07-24 | 2020-11-24 | 福建创立佳科技有限公司 | Preparation method of surface sizing agent for aramid fiber composite material |
| CN111979775B (en) * | 2020-07-24 | 2022-05-27 | 福建创立佳科技有限公司 | Preparation method of surface sizing agent for aramid fiber composite material |
| CN111952648B (en) * | 2020-08-25 | 2022-03-11 | 吉林大学 | Enhanced composite polymer electrolyte membrane and preparation method and application thereof |
| CN111952648A (en) * | 2020-08-25 | 2020-11-17 | 吉林大学 | Enhanced composite polymer electrolyte membrane and preparation method and application thereof |
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| CN112980024B (en) * | 2021-02-23 | 2022-06-21 | 吉林大学 | Fiber fabric reinforced polyaryletherketone resin-based prepreg, and preparation method and application thereof |
| CN113105620B (en) * | 2021-04-13 | 2021-12-28 | 吉林大学 | Amino-terminated soluble polyaryletherketone and preparation method and application thereof |
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| CN115321842A (en) * | 2022-09-16 | 2022-11-11 | 四川轻化工大学 | Corrosion-resistant basalt fiber and preparation method thereof |
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