CN118029129A - Aramid fiber/polyether-ether-ketone composite material prepared based on plasma grafting modification and preparation method thereof - Google Patents
Aramid fiber/polyether-ether-ketone composite material prepared based on plasma grafting modification and preparation method thereof Download PDFInfo
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 73
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 230000004048 modification Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000002715 modification method Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000012986 modification Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 80
- 238000004513 sizing Methods 0.000 claims description 78
- 238000001035 drying Methods 0.000 claims description 55
- 239000000843 powder Substances 0.000 claims description 49
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000748 compression moulding Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004381 surface treatment Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004760 aramid Substances 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- 229920003235 aromatic polyamide Polymers 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 description 13
- 238000009832 plasma treatment Methods 0.000 description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 5
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- 239000013543 active substance Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- -1 isocyanate radical Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses an aramid fiber/polyether-ether-ketone composite material prepared based on plasma grafting modification and a preparation method thereof. The high-temperature resistant aramid fiber/polyether-ether-ketone composite material prepared by the method has excellent interfacial bonding strength.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a method for preparing an aramid fiber/polyether-ether-ketone composite material based on plasma grafting modification.
Background
The Aramid Fiber (AF) is used as a high-performance advanced composite reinforcing material and is widely applied to the fields of national defense and aerospace. AF surface in the aramid fiber reinforced polymer matrix composite is smooth, interface performance is poor, the aramid fiber reinforced polymer matrix composite has the characteristic of chemical inertia, strength of the aramid fiber reinforced resin matrix composite is obviously affected, and use of the aramid fiber reinforced resin matrix composite is greatly limited. In order to promote the interaction between AF and polymer matrix, and to change the characteristics of AF surface chemical inertness, various strategies have been proposed, including electrochemical oxidation, plasma treatment, chemical grafting, sizing, etc.
Polyetheretherketone (PEEK) is a high performance resin. Because the PEEK molecular chain has no functional group capable of being crosslinked, no chemical reaction occurs in the material curing process, so that the interface combination of AF and PEEK resin matrix is weaker, and the construction of a good interface layer is the key for improving AF/PEEK composite materials. However, PEEK is difficult to use as a film and coating because of its low solubility in almost all known solvents except concentrated sulfuric acid. Much research on PEEK has focused on introducing groups to improve solubility, processability, and other desirable properties. The introduction of the groups does not change the molecular structure of the main chain, but the strength of the polarity of the groups influences the interaction and combination ability of the modified PEEK with AF when the modified PEEK is used as a sizing agent.
Disclosure of Invention
In view of the above, the invention discloses a preparation method of an aramid fiber/polyether-ether-ketone composite material based on plasma grafting modification, so as to prepare a high-temperature-resistant aramid fiber/polyether-ether-ketone composite material with excellent interface bonding strength.
The technical scheme provided by the invention is that the method for preparing the aramid fiber/polyether-ether-ketone composite material based on plasma grafting modification comprises the following steps:
And (3) grafting sizing agent on the surface of the aramid fiber by adopting a plasma surface treatment method to obtain grafted modified aramid fiber, and using a compression molding process to enable the grafted modified aramid fiber to fully infiltrate PEEK glue solution to finally obtain the aramid/polyether ether ketone composite material, wherein the sizing agent has compatibility with PEEK.
The preparation method of the sizing agent comprises the following steps:
PEEK powder was mixed with NaBH 4 according to 10:3 mixing and adding the mixture into 125-130 mL of DMSO solvent, reacting for 20-30 h at 120 ℃, and washing and drying to obtain HPEEK powder;
HPEEK powder and diisocyanate reactants are added into butanone according to the ratio of 1:1-1:1.8 for reaction for 2-3 hours, and PEEK-NCO powder is obtained after washing and drying;
PEEK-NCO formula is:
wherein R is
A structure or a mixture of several of the above;
PEEK-NCO powder is dissolved in an organic solvent DMF to prepare sizing agent solutions with different concentrations.
Specifically, the method for grafting sizing agent on the surface of the aramid fiber by adopting a plasma surface treatment method to obtain the grafted modified aramid fiber comprises the following steps:
pretreating aramid fibers;
and etching and grafting the surface of the pretreated aramid fiber with the sizing agent by adopting an oxygen plasma surface treatment method, and then heating and drying the obtained product to finally obtain the grafted and modified aramid fiber.
Specifically, the washing involved in the preparation of HPEEK powder is specifically: after cooling to room temperature, filtering, and sequentially passing through: washing with absolute ethyl alcohol for multiple times, washing with one solution of 0.1mol/L hydrochloric acid, acetic acid and nitric acid, and washing with deionized water;
the drying conditions involved in the preparation of HPEEK powder are specifically as follows: heating and drying, wherein the heating temperature is 80 ℃ and the drying time is 24 hours;
the HPEEK powder reacts with diisocyanate for 2 to 3 hours at room temperature;
the drying conditions involved in the preparation of the PEEK-NCO powder are specifically as follows: heating and drying, wherein the heating temperature is 150 ℃ and the drying time is 5 hours;
The diisocyanate reactant is one or a mixture of more of toluene diisocyanate/diphenylmethane diisocyanate/hexamethylene diisocyanate/isophorone diisocyanate/dicyclohexylmethane-4, 4' -diisocyanate;
the ratio of the mass of PEEK-NCO powder to the volume of DMF is 1g: (2-10) L.
Specifically, the pretreatment of the aramid fiber comprises:
Sizing agent and dust on the surface of the aramid fiber are removed: cleaning and soaking the aramid fiber by adopting one or a mixture of methanol, ethanol, acetone and ethyl acetate for 24 hours; cleaning the surface of the soaked aramid fiber by adopting deionized water, and soaking the aramid fiber in the deionized water for 24 hours at normal temperature;
And heating and drying the aramid fiber soaked by deionized water to obtain the pretreated aramid fiber, wherein the drying temperature is 100 ℃ and the drying time is 3 hours.
Specifically, the method for etching and grafting the pretreated aramid fiber surface with the sizing agent by adopting an oxygen plasma surface treatment method comprises the following steps:
Oxygen plasma is adopted to treat the surface of the aramid fiber, wherein the discharge power is 100W-300W, and the treatment time is 0-30 min;
Immediately immersing the obtained aramid fiber into a sizing agent solution after treatment, and carrying out a plasma grafting reaction on the aramid fiber;
and after grafting the sizing agent, heating and drying the obtained product, and evaporating the solvent in the sizing agent, wherein the heating temperature is not higher than 120 ℃.
Specifically, the grafting modified aramid fiber is fully soaked in PEEK glue solution by using a compression molding process, the molding pressure is 0.6MPa, the temperature is increased to 370 ℃ from room temperature, the temperature is kept for 30min, the temperature is reduced to 300 ℃ and the temperature is kept for 2h, and finally, the temperature is naturally cooled to the room temperature;
after the PEEK glue solution is fully soaked by the grafted and modified aramid fiber, the aramid fiber is required to be dried and then is paved according to (0 degree/90 degree) s.
The invention also provides the aramid fiber/polyether-ether-ketone composite material prepared by the method, and the interfacial bonding strength of the material is 60-70 Mpa.
According to the aramid fiber/polyether-ether-ketone composite material prepared based on the plasma grafting modification and the preparation method thereof, the interface of the aramid fiber is reinforced by the plasma grafting modification of the aramid fiber, and particularly the uniform full coverage of the aramid fiber by the plasma grafting modification PEEK sizing agent is realized, so that the interface bonding strength between the fiber and a matrix is remarkably improved, the mechanical property of the monofilament aramid fiber is well maintained, and the monofilament aramid fiber has good wettability.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure of the invention as claimed.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic view of the surface energy of a fiber after plasma treatment of aramid fibers according to an embodiment of the present disclosure.
Detailed Description
Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numbers in different drawings refer to the same or similar elements, unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the invention. Rather, they are merely examples of systems consistent with aspects of the invention as detailed in the accompanying claims.
The present embodiment uses plasma technology for modification of aramid composites. Due to the selection of the configuration and the processing parameters of the plasma system, active substances such as positive ions, negative ions, neutral ions, atoms, free radicals and the like collide with the molecules on the surface of the fiber, so that the plasma and the surface of the fiber have wide chemical and physical interactions, the surface roughness of the fiber is increased, and active free radicals or functional groups are generated, thereby improving the surface activity of the fiber.
The embodiment provides a method for preparing an aramid fiber/polyether-ether-ketone composite material based on plasma grafting modification, which adopts a plasma surface treatment method to graft a high-temperature-resistant high-molecular sizing agent with good compatibility with PEEK on the surface of an aramid fiber. And then preparing the high-temperature resistant aramid fiber/polyether-ether-ketone composite material by using a compression molding process. The high-temperature resistant aramid fiber/polyether-ether-ketone composite material prepared by the method has excellent interfacial bonding strength.
Specifically, the method comprises the following steps:
Step 1: synthetic sizing agent
PEEK powder was mixed with NaBH 4 according to 10:3 are mixed and added into 125-130 mL of DMSO solvent to react for 20-30 h at 120 ℃, and HPEEK powder is obtained after washing and drying. Further preferably, 5g of dry PEEK powder and NaBH 4 1.5.5 g are slowly poured into a round bottom flask containing 125-130 ml of DMSO solution at a constant speed, and NaBH 4 is dissolved in DMSO by magnetic stirring;
HPEEK powder and diisocyanate reactant are added into butanone according to the ratio of 1:1-1:1.8 for reaction for 2-3 h, and PEEK-NCO powder is obtained after washing and drying.
The structural formula is as follows:
wherein R is
A structure or a mixture of several of the above.
PEEK-NCO powder is dissolved in an organic solvent DMF to prepare sizing agent solutions with different concentrations.
Aiming at the molecular characteristics of aramid fiber and PEEK, a plasma surface treatment method is adopted to modify the surface of the aramid fiber, and the roughness of the aramid fiber is improved by the impact of active particles in plasma; meanwhile, the active free radical in the plasma is utilized to initiate the grafting reaction of the PEEK-NCO sizing agent with the-NCO group, so that the chemical characteristics of the surface of the aramid fiber are changed; both mechanisms are beneficial to improving the infiltration performance of the surface of the aramid fiber, so that the interfacial bonding performance between the aramid fiber and the PEEK resin is improved.
Preferably, in step 1, the washing method is: after cooling to room temperature, filtering, washing with absolute ethyl alcohol for multiple times, washing with one solution of hydrochloric acid, acetic acid and nitric acid with 0.1mol/L, and washing with deionized water. Heating and drying, wherein the heating temperature is 80 ℃ and the drying time is 24 hours.
HPEEK reacting powder with diisocyanate reactant at room temperature for 2-3 h. And washing and drying to obtain PEEK-NCO powder, wherein the heating temperature is 150 ℃ and the drying time is 5 hours. The diisocyanate reactant is one or a mixture of more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate. The ratio of the mass of PEEK-NCO to the volume of DMF was 1g: (2-10) L; further preferably, the PEEK-NCO powder is dissolved in DMF solvent to prepare sizing agent solutions of 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L and 0.5g/L
The diisocyanate reactant can be used as a bridging agent, the first isocyanate group reacts with hydroxyl in HPEEK molecular chains, the reaction activity is high, the reaction can be fast, and the reaction can be carried out at a low temperature; the second isocyanate group reacts again with the surface of the aramid fiber after plasma treatment, the reactivity is reduced, and the temperature is raised or the reaction time is prolonged to make the aramid fiber fully react.
Step 2: etching and grafting treatment by an oxygen plasma surface treatment method:
And removing sizing agent and dust on the surface of the aramid fiber and drying to obtain the pretreated aramid fiber.
And (3) carrying out etching grafting treatment on the surface of the pretreated aramid fiber by adopting an oxygen plasma surface treatment method, and heating and drying after grafting the sizing agent to obtain the grafted modified aramid fiber.
The grafting agent in the embodiment is PEEK-NCO sizing agent, isocyanate groups and hydroxyl groups on the surface of the activated fibers undergo addition polymerization reaction, cyanate esters can be formed at high temperature, the polarity of the surface of the fibers is improved, and the grafting agent has good compatibility with PEEK resin. The high-temperature mechanical property of the aramid fiber/polyether-ether-ketone composite material is kept.
Preferably, in the step 2, the method for removing sizing agent and dust is to clean and soak the sizing agent and dust by adopting one or a mixture of methanol, ethanol, acetone and ethyl acetate for 24 hours. Cleaning with deionized water, and soaking in deionized water at normal temperature for 24h; heating and drying, wherein the drying temperature is 100 ℃ and the drying time is 3 hours, so as to obtain the pretreated aramid fiber; during oxygen plasma treatment, the discharge power is 100W-300W, and the treatment time is 0-30 min; immediately immersing the aramid fiber into a sizing agent solution after the plasma treatment is finished; and (3) heating and drying the aramid fiber at the temperature of not higher than 120 ℃ after plasma grafting, and evaporating the solvent in the sizing agent.
Step 3: the high temperature resistant aramid fiber/polyether-ether-ketone composite material is prepared, compression molding is adopted, and after the aramid fiber is fully soaked in PEEK glue solution, layering is carried out according to (0 DEG/90 DEG) s after drying. Preferably, in compression molding, the molding pressure is 0.6MPa, the temperature is raised to 370 ℃ from room temperature, the temperature is kept for 30min, the temperature is lowered to 300 ℃ and the temperature is kept for 2h, and finally, the natural cooling is carried out to the room temperature. The heating and drying process is helpful for the condensation reaction of the second isocyanate radical and the surface of the activated aramid fiber. The PEEK forming temperature is above 350 ℃, and the PEEK-NCO sizing agent does not change the PEEK main chain structure, so that the PEEK has higher heat resistance, and the original structure is kept not to be decomposed at the forming temperature of 370 ℃.
The following describes the embodiments of the present invention in further detail with reference to the drawings.
In the following examples, corresponding composite materials were prepared according to the PEEK-NCO type and different plasma grafting parameters, respectively, and the schematic structure thereof is shown in FIG. 1.
Example 1
(1) PEEK powder and NaBH 4 are adopted according to the following ratio of 10:3 are mixed and added into 125mL of DMSO solvent to react for 20h to prepare HPEEK. Subsequently, the high temperature dried HPEEK powder was mixed with toluene diisocyanate according to 1:1 for 2 hours, washing and drying to obtain PEEK-NCO powder. The PEEK-NCO powder was dissolved in DMF solvent to prepare a sizing agent solution of 0.5 g/L.
In the sizing agent solution adopted in the embodiment, the molecular structural formula of the sizing agent is as follows:
(2) And removing sizing agent and dust on the surface of the aramid fiber and drying. And (3) carrying out etching grafting treatment on the surface of the aramid fiber by adopting oxygen plasma, wherein in the oxygen plasma treatment process, the discharge power is 100W, and the treatment time is 10min, so as to obtain the plasma modified aramid fiber. Immersing the treated aramid fiber into a sizing agent filled with PEEK-NCO, removing the redundant sizing agent through a guide roller, enabling isocyanate groups in the sizing agent to react with hydroxyl groups on the surface of the plasma-treated aramid fiber, grafting the sizing agent onto the surface of the fiber, and drying to obtain the grafted modified aramid fiber.
(3) According to the layering mode of (0 degree/90 degree) s, paving 12 layers, in compression molding, the molding pressure is 0.6MPa, heating from room temperature to 370 ℃, preserving heat for 30min, cooling to 300 ℃, preserving heat for 2h, and finally naturally cooling to room temperature. Obtaining the aramid fiber/polyether-ether-ketone composite material, wherein the ILSS value of the aramid fiber/polyether-ether-ketone composite material is 61-62 MPa.
Example 2
(1) PEEK powder and NaBH 4 are adopted according to the following ratio of 10:3 are mixed and added into 125mL of DMSO solvent to react for 30h to prepare HPEEK. Subsequently, the high temperature dried HPEEK powder was mixed with diphenylmethane diisocyanate according to 1:1.2 for 2h, washing and drying to obtain PEEK-NCO powder. The PEEK-NCO powder was dissolved in DMF solvent to prepare a sizing agent solution of 0.4 g/L.
In the sizing agent solution adopted in the embodiment, the molecular structural formula of the sizing agent is as follows:
(2) And removing sizing agent and dust on the surface of the aramid fiber and drying. And (3) carrying out etching grafting treatment on the surface of the aramid fiber by adopting oxygen plasma, wherein in the oxygen plasma treatment process, the discharge power is 200W, and the treatment time is 20min, so as to obtain the plasma modified aramid fiber. Immersing the treated aramid fiber into a sizing agent filled with PEEK-NCO, removing the redundant sizing agent through a guide roller, enabling isocyanate groups in the sizing agent to react with hydroxyl groups on the surface of the plasma-treated aramid fiber, grafting the sizing agent onto the surface of the fiber, and drying to obtain the grafted modified aramid fiber.
(3) According to the layering mode of (0 degree/90 degree) s, paving 12 layers, in compression molding, the molding pressure is 0.6MPa, heating from room temperature to 370 ℃, preserving heat for 30min, cooling to 300 ℃, preserving heat for 2h, and finally naturally cooling to room temperature. Obtaining the aramid fiber/polyether-ether-ketone composite material, wherein the ILSS value of the aramid fiber/polyether-ether-ketone composite material is 64-65 MPa.
Example 3
(1) PEEK powder and NaBH 4 are adopted according to the following ratio of 10:3 are mixed and added into 130mL of DMSO solvent to react for 20h to prepare HPEEK. Subsequently, the high temperature dried HPEEK powder was mixed with hexamethylene diisocyanate according to 1:1.4 for 3 hours, washing and drying to obtain PEEK-NCO powder. The PEEK-NCO powder was dissolved in DMF solvent to prepare a sizing agent solution of 0.3 g/L.
In the sizing agent solution adopted in the embodiment, the molecular structural formula of the sizing agent is as follows:
(2) And removing sizing agent and dust on the surface of the aramid fiber and drying. And (3) carrying out etching grafting treatment on the surface of the aramid fiber by adopting oxygen plasma, wherein in the oxygen plasma treatment process, the discharge power is 300W, and the treatment time is 30min, so as to obtain the plasma modified aramid fiber. Immersing the treated aramid fiber into a sizing agent filled with PEEK-NCO, removing the redundant sizing agent through a guide roller, enabling isocyanate groups in the sizing agent to react with hydroxyl groups on the surface of the plasma-treated aramid fiber, grafting the sizing agent onto the surface of the fiber, and drying to obtain the grafted modified aramid fiber.
(3) According to the layering mode of (0 degree/90 degree) s, paving 12 layers, in compression molding, the molding pressure is 0.6MPa, heating from room temperature to 370 ℃, preserving heat for 30min, cooling to 300 ℃, preserving heat for 2h, and finally naturally cooling to room temperature. Obtaining the aramid fiber/polyether-ether-ketone composite material, wherein the ILSS value of the aramid fiber/polyether-ether-ketone composite material is 67-69 MPa.
Example 4
(1) PEEK powder and NaBH 4 are adopted according to the following ratio of 10:3 are mixed and added into 130mL of DMSO solvent to react for 30h to prepare HPEEK. Subsequently, the high temperature dried HPEEK powder was mixed with isophorone diisocyanate according to 1:1.6 for 3h, washing and drying to obtain PEEK-NCO powder. The PEEK-NCO powder was dissolved in DMF solvent to prepare a sizing agent solution of 0.2 g/L.
In the sizing agent solution adopted in the embodiment, the molecular structural formula of the sizing agent is as follows:
(2) And removing sizing agent and dust on the surface of the aramid fiber and drying. And (3) carrying out etching grafting treatment on the surface of the aramid fiber by adopting oxygen plasma, wherein in the oxygen plasma treatment process, the discharge power is 200W, and the treatment time is 10min, so as to obtain the plasma modified aramid fiber. Immersing the treated aramid fiber into a sizing agent filled with PEEK-NCO, removing the redundant sizing agent through a guide roller, enabling isocyanate groups in the sizing agent to react with hydroxyl groups on the surface of the plasma-treated aramid fiber, grafting the sizing agent onto the surface of the fiber, and drying to obtain the grafted modified aramid fiber.
(3) According to the layering mode of (0 degree/90 degree) s, paving 12 layers, in compression molding, the molding pressure is 0.6MPa, heating from room temperature to 370 ℃, preserving heat for 30min, cooling to 300 ℃, preserving heat for 2h, and finally naturally cooling to room temperature. Obtaining the aramid fiber/polyether-ether-ketone composite material, wherein the ILSS value of the aramid fiber/polyether-ether-ketone composite material is 65-67 MPa.
Example 5
(1) PEEK powder and NaBH 4 are adopted according to the following ratio of 10:3 were added to 125mL of DMSO solvent for 30h to prepare HPEEK. Subsequently, the high temperature dried HPEEK powder was mixed with dicyclohexylmethane-4, 4' -diisocyanate according to 1:1.8 for 3h, washing and drying to obtain PEEK-NCO powder. The PEEK-NCO powder was dissolved in DMF solvent to prepare a sizing agent solution of 0.1 g/L.
In the sizing agent solution adopted in the embodiment, the molecular structural formula of the sizing agent is as follows:
(2) And removing sizing agent and dust on the surface of the aramid fiber and drying. And (3) carrying out etching grafting treatment on the surface of the aramid fiber by adopting oxygen plasma, wherein in the oxygen plasma treatment process, the discharge power is 300W, and the treatment time is 10min, so as to obtain the plasma modified aramid fiber. Immersing the treated aramid fiber into a sizing agent filled with PEEK-NCO, removing the redundant sizing agent through a guide roller, enabling isocyanate groups in the sizing agent to react with hydroxyl groups on the surface of the plasma-treated aramid fiber, grafting the sizing agent onto the surface of the fiber, and drying to obtain the grafted modified aramid fiber.
(3) According to the layering mode of (0 degree/90 degree) s, paving 12 layers, in compression molding, the molding pressure is 0.6MPa, heating from room temperature to 370 ℃, preserving heat for 30min, cooling to 300 ℃, preserving heat for 2h, and finally naturally cooling to room temperature. Obtaining the aramid fiber/polyether-ether-ketone composite material, wherein the ILSS value of the aramid fiber/polyether-ether-ketone composite material is 64-65 MPa.
Comparative example 1
The overall preparation steps are the same as in example 1, except that steps (1) to (2) are not performed, and the aramid fiber is directly immersed into the PEEK resin slurry, dried and then subjected to compression molding. The molding pressure is 0.6MPa, the temperature is raised to 370 ℃ from room temperature for 30min, the temperature is lowered to 300 ℃ for 2h, and finally the molding pressure is naturally cooled to room temperature. Obtaining the aramid fiber/polyether-ether-ketone composite material.
Comparative example 2
The whole preparation step is the same as in example 1, except that step (1) is not adopted, plasma treatment is only carried out on the aramid fiber, and the obtained composite material PEEK melt is insufficient in spreading and low in interface bonding strength.
Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. This application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.
Claims (8)
1. The method for preparing the aramid fiber/polyether-ether-ketone composite material based on the plasma grafting modification is characterized by comprising the following steps of:
And (3) grafting sizing agent on the surface of the aramid fiber by adopting a plasma surface treatment method to obtain grafted modified aramid fiber, and using a compression molding process to enable the grafted modified aramid fiber to fully infiltrate PEEK glue solution to finally obtain the aramid/polyether ether ketone composite material, wherein the sizing agent has compatibility with PEEK.
2. The method for preparing the aramid fiber/polyether ether ketone composite material based on the plasma grafting modification according to claim 1, wherein the preparation method of the sizing agent is as follows:
PEEK powder was mixed with NaBH 4 according to 10:3 mixing and adding the mixture into 125-130 mL of DMSO solvent, reacting for 20-30 h at 120 ℃, and washing and drying to obtain HPEEK powder;
HPEEK powder and diisocyanate reactants are added into butanone according to the ratio of 1:1-1:1.8 for reaction for 2-3 hours, and PEEK-NCO powder is obtained after washing and drying;
PEEK-NCO formula is:
wherein R is
A structure or a mixture of several of the above;
PEEK-NCO powder is dissolved in an organic solvent DMF to prepare sizing agent solutions with different concentrations.
3. The method for preparing the aramid fiber/polyether ether ketone composite material based on the plasma grafting modification according to claim 1, wherein,
The method for grafting sizing agent on the surface of aramid fiber to obtain grafting modified aramid fiber by adopting a plasma surface treatment method comprises the following steps:
pretreating aramid fibers;
and etching and grafting the surface of the pretreated aramid fiber with the sizing agent by adopting an oxygen plasma surface treatment method, and then heating and drying the obtained product to finally obtain the grafted and modified aramid fiber.
4. The method for preparing an aramid/polyetheretherketone composite material based on plasma grafting modification according to claim 2, characterized in that the washing involved in the preparation of HPEEK powder is in particular: after cooling to room temperature, filtering, and sequentially passing through: washing with absolute ethyl alcohol for multiple times, washing with one solution of 0.1mol/L hydrochloric acid, acetic acid and nitric acid, and washing with deionized water;
the drying conditions involved in the preparation of HPEEK powder are specifically as follows: heating and drying, wherein the heating temperature is 80 ℃ and the drying time is 24 hours;
the HPEEK powder reacts with diisocyanate for 2 to 3 hours at room temperature;
the drying conditions involved in the preparation of the PEEK-NCO powder are specifically as follows: heating and drying, wherein the heating temperature is 150 ℃ and the drying time is 5 hours;
The diisocyanate reactant is one or a mixture of more of toluene diisocyanate/diphenylmethane diisocyanate/hexamethylene diisocyanate/isophorone diisocyanate/dicyclohexylmethane-4, 4' -diisocyanate;
the ratio of the mass of PEEK-NCO powder to the volume of DMF is 1g: (2-10) L.
5. A method of preparing an aramid/polyetheretherketone composite material based on plasma graft modification according to claim 3, wherein the pre-treating the aramid fiber comprises:
Sizing agent and dust on the surface of the aramid fiber are removed: cleaning and soaking the aramid fiber by adopting one or a mixture of methanol, ethanol, acetone and ethyl acetate for 24 hours; cleaning the surface of the soaked aramid fiber by adopting deionized water, and soaking the aramid fiber in the deionized water for 24 hours at normal temperature;
And heating and drying the aramid fiber soaked by deionized water to obtain the pretreated aramid fiber, wherein the drying temperature is 100 ℃ and the drying time is 3 hours.
6. A process for preparing an aramid/polyether-ether-ketone composite based on plasma graft modification according to claim 3, wherein,
The surface of the pretreated aramid fiber is etched and grafted with the sizing agent by adopting an oxygen plasma surface treatment method, and the method comprises the following steps:
Oxygen plasma is adopted to treat the surface of the aramid fiber, wherein the discharge power is 100W-300W, and the treatment time is 0-30 min;
Immediately immersing the obtained aramid fiber into a sizing agent solution after treatment, and carrying out a plasma grafting reaction on the aramid fiber;
and after grafting the sizing agent, heating and drying the obtained product, and evaporating the solvent in the sizing agent, wherein the heating temperature is not higher than 120 ℃.
7. The method for preparing the aramid fiber/polyether ether ketone composite material based on the plasma grafting modification according to claim 1, wherein,
The grafting modified aramid fiber is fully soaked in PEEK glue solution by using a compression molding process, the molding pressure is 0.6MPa, the temperature is increased to 370 ℃ from room temperature, the temperature is kept for 30min, the temperature is reduced to 300 ℃ and the temperature is kept for 2h, and finally, the temperature is naturally cooled to the room temperature;
after the PEEK glue solution is fully soaked by the grafted and modified aramid fiber, the aramid fiber is required to be dried and then is paved according to (0 degree/90 degree) s.
8. An aramid/polyetheretherketone composite material prepared by the method of claims 1 to 7, characterized in that the interfacial bond strength of the material is 60 to 70Mpa.
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