CN111118905B - Surface modification method of aramid fiber - Google Patents
Surface modification method of aramid fiber Download PDFInfo
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- CN111118905B CN111118905B CN202010055750.4A CN202010055750A CN111118905B CN 111118905 B CN111118905 B CN 111118905B CN 202010055750 A CN202010055750 A CN 202010055750A CN 111118905 B CN111118905 B CN 111118905B
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Abstract
A surface modification method of aramid fibers comprises the following steps: cleaning and drying the surface of the aramid fiber; step 2: pretreating the surface of aramid fiber; and step 3: functionalized treatment of graphene oxide GO; and 4, step 4: synergistic modification of hyperbranched polysiloxane and graphene oxide GO. Due to the addition reaction between the sulfydryl and the double bonds of the rubber and the improvement of the surface energy after modification, and the graphene oxide grafted on the surface of the aramid fiber can convert the self fracture energy into the interface energy, the invention can obviously improve the bonding strength between the aramid fiber and the rubber matrix; in addition, due to the wrapping effect of the functionalized graphene oxide nanosheets and the mercapto hyperbranched polysiloxane on the surface of the fiber, the fiber can be effectively assisted to bear tensile stress, so that the strength of the monofilament is also obviously improved. The invention has larger industrial application potential, and the aramid fiber/rubber composite material has more application prospect due to the universality of the polydopamine initial layer.
Description
Technical Field
The invention relates to the technical field of aramid fiber modification, in particular to a surface modification method of aramid fiber, and particularly relates to a method for synergistically modifying the surface of aramid fiber through hyperbranched polysiloxane and graphene oxide.
Background
The composite material is a new material formed by optimizing and combining material components with different properties by applying an advanced material preparation technology. And the high-performance long fiber reinforced composite material (such as aramid fiber, carbon fiber, ultra-high molecular weight polyethylene fiber and the like) is widely applied to the fields of aerospace engineering, weapon engineering, protection engineering and the like due to the unique excellent performance. Among them, aramid fibers are often used as a framework material of rubber-based composite materials such as tires and conveyor belts because of their excellent toughness, modulus, and strength, good flame retardancy, and high melting point. The mechanical property of the rubber-based composite material is often closely related to the interface property, and when the interface property is poor, the interface layer is easy to break or delaminate firstly under the action of stretching, bending, impact and the like, and the overall failure of the composite material is gradually caused. The regular molecular chain structure of aramid fiber ensures the excellent performance of the aramid fiber and simultaneously generates the defects of strong surface chemical inertness and difficult tight combination with a matrix, so that the effective modification of the fiber surface is very important.
Besides the surface coating modification method commonly used in industry, the nanomaterial grafting method is a commonly used surface modification method for aramid fibers. The functionalized carbon nano tube, graphene, nano silicon dioxide and other materials are grafted on the surface of the aramid fiber, so that the functional groups on the surface of the aramid fiber have diversity, selectivity and directivity, the application range of the fiber is expanded while the interface performance of the aramid fiber and a matrix is improved, various excellent performances of the nano material are fully utilized, the transmission of stress is promoted, and the excessive stress diffusion of the surface defects of the aramid fiber is prevented.
Among a plurality of nanomaterials, graphene, as a typical carbon nanomaterial with a two-dimensional structure, has extremely excellent properties, such as extremely high young modulus (about 1TPa), breaking strength (130GPa) and specific area (736.6m2/g), and due to the unique wrinkle morphology, the interface performance of the composite material can be better improved. However, the graphene surface lacks effective functional groups, and is relatively insoluble in polar and nonpolar solvents, which is not favorable for the modification reaction.
Disclosure of Invention
In order to solve the problems, the invention provides a surface modification method of aramid fibers, which is used for further improving the monofilament strength of the fibers while improving the interfacial strength of the aramid fibers/rubber, and effectively avoiding the defect that graphene used for surface modification of the aramid fibers in the prior art is not beneficial to the implementation of modification reaction.
In order to overcome the defects in the prior art, the invention provides a solution of a surface modification method of aramid fibers, which comprises the following steps:
a surface modification method of aramid fiber comprises the following steps:
step 1: cleaning and drying the surface of the aramid fiber;
step 2: pretreating the surface of aramid fiber;
and step 3: functionalized treatment of graphene oxide GO;
and 4, step 4: synergistic modification of hyperbranched polysiloxane and graphene oxide GO.
The aramid fiber surface cleaning and drying method comprises the following steps: and (2) washing the aramid fiber by using ethyl acetate and acetone in turn to obtain clean aramid fiber, and then drying the clean aramid fiber in a vacuum oven at the temperature of 100 ℃ until the dry aramid fiber is obtained.
The aramid fiber is washed by ethyl acetate and acetone for 5-10 times in turn.
The pretreatment of the surface of the aramid fiber comprises the following steps: soaking the dried aramid fiber into 2g/L of dopamine hydrochloride solution, adjusting the pH value of the dopamine hydrochloride solution to 8.5 by using an alkaline substance, and stirring the dopamine hydrochloride solution at a set rotating speed for a set time at the temperature of 25 ℃, so as to graft polydopamine on the surface of the aramid fiber to form a polydopamine layer serving as an initial layer; and then, washing the aramid fiber subjected to the grafting reaction for several times by using deionized water, and drying the washed aramid fiber in a vacuum oven at the temperature of 100 ℃ to obtain the pretreated aramid fiber.
The set rotating speed in the pretreatment of the aramid fiber surface is 18-20 r/min;
the set time in the pretreatment of the aramid fiber surface is 10-12 h;
the number of times of pretreatment of the aramid fiber surface is 5-10 times.
The functionalized treatment of the graphene oxide GO comprises the following steps: weighing 100mg of unpurified graphene oxide GO and 10mL of (3-mercaptopropyl) trimethoxysilane KH-590, adding the unpurified graphene oxide GO and the 10mL of (3-mercaptopropyl) trimethoxysilane KH-590 into a solution formed by mixing 90mL of methanol and water together to form a mixture, adjusting the pH value of the mixture to 8.5 by using an alkaline substance, stirring the mixture for 15-30 min, carrying out ultrasonic treatment on the mixture for a set time to react, filtering to obtain reacted functionalized graphene oxide GO, washing the functionalized graphene oxide GO with methanol for several times to remove redundant (3-mercaptopropyl) trimethoxysilane KH-590, and then putting the functionalized graphene oxide GO into a vacuum oven and drying the GO at the temperature of 100 ℃.
In the functionalized treatment of graphene oxide GO, the weight ratio of methanol to water in a solution formed by mixing methanol and water is 7: 2, namely methanol: water 7: 2;
the set time of ultrasonic treatment in the functionalized treatment of the graphene oxide GO is 3-4 h;
the ultrasonic frequency and the ultrasonic power of ultrasonic treatment in the functionalized treatment of the graphene oxide GO are respectively 40KHz and 250W;
the number of times of the functionalized graphene oxide GO is 8-10 times.
The synergistic modification of the hyperbranched polysiloxane and graphene oxide GO comprises the following steps: adding functionalized graphene oxide GO100mg into 90mL of a solution formed by mixing methanol and water to form a mixture, and adjusting the pH value of the mixture to 8.5 by using an alkaline substance; then, carrying out ultrasonic treatment on the mixture for 2 hours to prepare a functionalized graphene oxide GO suspension;
soaking pretreated aramid fiber into functionalized graphene oxide GO suspension, adding 10mL of (3-mercaptopropyl) trimethoxysilane KH-590 to form a mixture, stirring the mixture at a set rotating speed for a set time to react to obtain the reacted aramid fiber, taking the reacted aramid fiber out of the mixture, washing the reacted aramid fiber for several times by using methanol to remove the redundant (3-mercaptopropyl) trimethoxysilane KH-590, and drying the reacted aramid fiber in a vacuum oven at the temperature of 100 ℃.
In the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO, the weight ratio of methanol to water in a solution formed by mixing methanol and water is 7: 2, namely methanol: water 7: 2;
the reaction setting time in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO is 10-12 h;
the rotation speed set in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO is 18-20 r/min.
The invention has the beneficial effects that:
the invention utilizes the bionic modification principle of dopamine on the surface of the material, grafts the polydopamine layer as the initial layer on the surface of the aramid fiber, and provides reaction points with better activity for the surface of the aramid fiber on the basis of not damaging the structure of the aramid fiber. Secondly, according to the preparation method, the dehydration condensation reaction between silanol of (3-mercaptopropyl) trimethoxysilane KH-590 and hydroxyl of graphene oxide GO is utilized, the mercapto hyperbranched polysiloxane grows on the surface of the graphene oxide GO, and the mercapto functionalization of the graphene oxide GO is realized. Then, the invention also utilizes the Michael addition reaction between sulfydryl and polydopamine and the cohydrolysis reaction of (3-mercaptopropyl) trimethoxy silane KH-590 and sulfydryl graphene oxide GO to realize the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO on the surface of the aramid fiber, and forms a sulfydryl functionalized hyperbranched polysiloxane/graphene oxide GO mixed film on the surface. Due to the addition reaction between sulfydryl and a rubber double bond and the improvement of the surface energy after modification, and the graphene oxide GO grafted on the surface of the aramid fiber can effectively bear the fracture stress, the self fracture energy is converted into the interface energy, and the bonding strength between the aramid fiber and a rubber matrix can be obviously improved; in addition, due to the wrapping effect of the functionalized graphene oxide GO nano-sheets and the mercapto-polysiloxane on the surface of the aramid fiber, the aramid fiber can be effectively assisted to bear tensile stress and absorb fracture energy, and the monofilament tensile strength of the aramid fiber is also obviously improved. The invention has larger industrial application potential, and the aramid fiber/rubber composite material has more application prospect due to the universality of the poly-dopamine layer as the initial layer.
Drawings
Fig. 1 is a schematic diagram showing an aramid fiber surface modification method provided by the invention.
FIG. 2 is a surface topography of aramid fibers before and after modification; wherein, fig. 2(a) is a surface topography of the aramid fiber, and fig. 2(b) is a surface topography of the aramid fiber before modification.
Fig. 3 shows FTIR spectra of the aramid fibers before and after modification.
FIG. 4 shows XPS spectra of aramid fibers before and after modification; wherein, fig. 4(a) is an XPS broad spectrum of the aramid fiber, fig. 4(b) is a C1S fine spectrum of the aramid fiber before modification, and fig. 4(C), fig. 4(d) and fig. 4(e) are a C1S, S2p and Si2p fine spectrums of the aramid fiber after modification, respectively.
Detailed Description
Graphene oxide GO is a very important derivative of graphene, and contains a great number of excellent mechanical properties of graphene, and meanwhile, a great number of oxygen-containing functional groups (including hydroxyl and carboxyl at ports and epoxy in sheets) exist on the surface, so that the graphene oxide GO has good dispersibility and solubility in solvents such as water. On one hand, the graphene oxide GO has the potential of being directionally modified into other types of functional groups due to the high chemical reaction activity of oxygen-containing functional groups on the surface of the graphene oxide GO; on the other hand, the hydrophilic property of the modified composite material can enhance the surface energy of the modified composite material to a certain extent, so the modified composite material is an ideal interface modified material in the current research. In addition, as the ingredients of the rubber are complex, and the conventional amino and fluorinated functionalized graphene oxide GO is difficult to realize covalent bonding with the rubber, in the invention, the graphene oxide GO is firstly subjected to sulfydryl functional modification, and then the surface of the aramid fiber is subjected to synergistic modification through the cohydrolysis action between the modified graphene oxide GO and a silane coupling agent, so that the bonding performance between the aramid fiber and the rubber matrix is improved.
The invention will be further described with reference to the following figures and examples.
Example 1:
as shown in fig. 1, the surface modification method of aramid fiber includes:
step 1: cleaning and drying the surface of the aramid fiber;
step 2: pretreating the surface of aramid fiber;
and step 3: functionalized treatment of graphene oxide GO;
and 4, step 4: synergistic modification of hyperbranched polysiloxane and graphene oxide GO.
The aramid fiber surface cleaning and drying method comprises the following steps: and (2) washing the aramid fiber by using ethyl acetate and acetone in turn to obtain clean aramid fiber, and then drying the clean aramid fiber in a vacuum oven at the temperature of 100 ℃ until the dry aramid fiber is obtained.
The number of times of washing the aramid fiber by ethyl acetate and acetone in turn is 5.
The pretreatment of the surface of the aramid fiber comprises the following steps: soaking the dried aramid fiber into 2g/L of dopamine hydrochloride solution, adjusting the pH value of the dopamine hydrochloride solution to 8.5 by using an alkaline substance, and slowly stirring the dopamine hydrochloride solution at a set rotating speed for a set time at the temperature of 25 ℃, so that polydopamine is grafted on the surface of the aramid fiber to form a polydopamine layer serving as an initial layer on the surface of the aramid fiber; and then, washing the aramid fiber subjected to the grafting reaction for several times by using deionized water, and drying the washed aramid fiber in a vacuum oven at the temperature of 100 ℃ to obtain the pretreated aramid fiber.
The set rotating speed in the pretreatment of the aramid fiber surface is 18 r/min;
the set time in the pretreatment of the aramid fiber surface is 10 hours;
the number of times of pretreatment of the aramid fiber surface is 5 times.
The functionalized treatment of the graphene oxide GO comprises the following steps: weighing 100mg of unpurified graphene oxide GO and 10mL of (3-mercaptopropyl) trimethoxysilane KH-590, adding the unpurified graphene oxide GO and the 10mL of (3-mercaptopropyl) trimethoxysilane KH-590 into a solution formed by mixing 90mL of methanol and water together to form a mixture, adjusting the pH value of the mixture to 8.5 by using an alkaline substance, stirring the mixture for 15min, carrying out ultrasonic treatment on the mixture for a set time, filtering to obtain reacted functionalized graphene oxide GO, washing the functionalized graphene oxide GO with methanol for several times to remove redundant (3-mercaptopropyl) trimethoxysilane KH-590, and then putting the functionalized graphene oxide GO into a vacuum oven and drying at the temperature of 100 ℃.
In the functionalized treatment of graphene oxide GO, the weight ratio of methanol to water in a solution formed by mixing methanol and water is 7: 2, namely methanol: water 7: 2;
the set time of ultrasonic treatment in the functionalized treatment of the graphene oxide GO is 3 h;
the ultrasonic frequency and the ultrasonic power of ultrasonic treatment in the functionalized treatment of the graphene oxide GO are respectively 40KHz and 250W;
the number of times of the functionalized graphene oxide GO is 8.
The synergistic modification of the hyperbranched polysiloxane and graphene oxide GO comprises the following steps: adding functionalized graphene oxide GO100mg into 90mL of a solution formed by mixing methanol and water to form a mixture, and adjusting the pH value of the mixture to 8.5 by using an alkaline substance; then, carrying out ultrasonic treatment on the mixture for 2 hours to prepare a functionalized graphene oxide GO suspension;
soaking pretreated aramid fiber into functionalized graphene oxide GO suspension, adding 10mL of (3-mercaptopropyl) trimethoxysilane KH-590 into the mixture to form a mixture, slowly stirring the mixture at a set rotating speed for reacting for a set time to obtain the reacted aramid fiber, taking the reacted aramid fiber out of the mixture, washing the reacted aramid fiber for several times by using methanol to remove the redundant (3-mercaptopropyl) trimethoxysilane KH-590, and then placing the reacted aramid fiber into a vacuum oven to dry at the temperature of 100 ℃.
In the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO, the weight ratio of methanol to water in a solution formed by mixing methanol and water is 7: 2, namely methanol: water 7: 2;
the reaction setting time in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO is 10 h;
the rotation speed set in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO is 18 r/min.
As shown in fig. 2, in the SEM image of the unmodified aramid fiber, the surface was smooth and there was only a small amount of marking generated during the processing, and the diameter of the aramid fiber was about 14.67 μm. After the hyperbranched polysiloxane and the graphene oxide GO of the embodiment are synergistically modified, a composite membrane structure with the graphene oxide GO wrapped by polysiloxane appears on the surface of the aramid fiber, wherein the sheet structure of the graphene oxide GO is shown as an arrow mark position. At this time, the diameter of the aramid fiber increased to about 16.35 μm, which can be attributed to the attachment and accumulation of hyperbranched polysiloxane and graphene oxide GO on the surface of the aramid fiber.
As shown in fig. 3, comparing the FTIR spectra of the aramid fibers before and after modification in this example, the FTIR spectra of the aramid fibers treated by the method in this example were found to be 3412cm each-1、2928-2846cm-1、2558cm-1And 689cm-1This can be attributed to the stretching vibrations of hydroxyl, methylene, S-H bond and S-C bond, respectively; furthermore, S-CH2And Si-CH2The symmetric variable angle vibration of the two-dimensional vibration generating device respectively generates vibration at 1341cm-1And 1250cm-1New absorption peak of (a); absorption peak and 1108cm generated by antisymmetric telescopic vibration of Si-O-Si-1The absorption peak at (A) is associated to be located at 1096cm-1High intensity peak of (2). By FTIR spectrogram analysis, the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO on the surface of the aramid fiber can be further confirmed.
As shown in fig. 4, comparing the XPS broad spectrum of the aramid fiber before and after modification of this example, after the synergistic modification, the content of the O1S peak on the surface of the aramid fiber sharply increases, while the contents of the N1S peak and the C1S peak are significantly reduced, and in addition, new peaks at both S2p and Si2p appear. In the C1s fine pattern of the aramid fiber before modification, 4 peaks can be fit, which are C-C/C ═ C at 284.79eV, C-N at 286.05eV, C ═ O at 287.74eV, and O ═ C-O at 288.70eV, respectively, corresponding to the chemical structure of the aramid fiber. After the modification, as shown in fig. 4(C), the fitting peaks of the C1S peak include C — Si at 284.00eV, C — O at 286.66eV, and C — S at 287.08, and it can be known that sulfur and silicon elements appear on the surface of the aramid fiber. In the fine map of S2p in FIG. 4(d), the two fitted peaks at 163.24eV and 164.40eV are attributed to the S2p3/2 peak and the S2p1/2 peak, respectively. In FIG. 4(e), Si2p can be fit to Si-C at 102.03eV and Si-O-Si at 102.81eV, consistent with the chemical structure of hyperbranched polysiloxanes.
Table 1 shows the contact angles of the aramid fibers before and after modification in this example. After modification, the surface energy of the fiber is obviously enhanced, which shows that the synergistic modification provided by the invention can greatly improve the surface wetting property of the aramid fiber and enhance the interface strength with a rubber matrix.
TABLE 1
The bonding performance between aramid fiber and rubber is generally characterized and evaluated by the result of the pull-out force test of the fiber bundle and the rubber matrix. Under the test conditions of the same gauge length and the same matrix mold, the extraction forces between the fiber and the rubber before and after modification in the embodiment are respectively 28.3 +/-1.8N and 56.4 +/-3.4N, which indicates that the interface performance of the aramid fiber/rubber composite material is obviously enhanced.
The monofilament strength test results of the aramid fibers show that the monofilament average strength of the fibers before and after modification of the embodiment is 3.86 +/-0.47 GPa and 4.51 +/-0.30 GPa respectively at a gauge length of 20 mm. The result can be obtained, after the synergistic modification of the hyperbranched polymer and the graphene oxide, the strength of the aramid fiber monofilament is improved by about 16.8%, and the strength distribution of the fiber in the test sample is more concentrated.
Example 2:
the surface modification method of the aramid fiber comprises the following steps:
step 1: cleaning and drying the surface of the aramid fiber;
step 2: pretreating the surface of aramid fiber;
and step 3: functionalized treatment of graphene oxide GO;
and 4, step 4: synergistic modification of hyperbranched polysiloxane and graphene oxide GO.
The aramid fiber surface cleaning and drying method comprises the following steps: and (2) washing the aramid fiber by using ethyl acetate and acetone in turn to obtain clean aramid fiber, and then drying the clean aramid fiber in a vacuum oven at the temperature of 100 ℃ until the dry aramid fiber is obtained.
The number of times of washing the aramid fiber by ethyl acetate and acetone in turn is 8.
The pretreatment of the surface of the aramid fiber comprises the following steps: soaking the dried aramid fiber into 2g/L of dopamine hydrochloride solution, adjusting the pH value of the dopamine hydrochloride solution to 8.5 by using an alkaline substance, and slowly stirring the dopamine hydrochloride solution at a set rotating speed for a set time at the temperature of 25 ℃, so that polydopamine is grafted on the surface of the aramid fiber to form a polydopamine layer serving as an initial layer on the surface of the aramid fiber; and then, washing the aramid fiber subjected to the grafting reaction for several times by using deionized water, and drying the washed aramid fiber in a vacuum oven at the temperature of 100 ℃ to obtain the pretreated aramid fiber.
The set rotating speed in the pretreatment of the aramid fiber surface is 19 r/min;
the set time in the pretreatment of the aramid fiber surface is 11 h;
the number of times of pretreatment of the aramid fiber surface is 8 times.
The functionalized treatment of the graphene oxide GO comprises the following steps: weighing 100mg of unpurified graphene oxide GO and 10mL of (3-mercaptopropyl) trimethoxysilane KH-590, adding the unpurified graphene oxide GO and the 10mL of (3-mercaptopropyl) trimethoxysilane KH-590 into a solution formed by mixing 90mL of methanol and water together to form a mixture, adjusting the pH value of the mixture to 8.5 by using an alkaline substance, stirring the mixture for 22min, carrying out ultrasonic treatment on the mixture for a set time, filtering to obtain reacted functionalized graphene oxide GO, washing the functionalized graphene oxide GO with methanol for several times to remove redundant (3-mercaptopropyl) trimethoxysilane KH-590, and then putting the functionalized graphene oxide GO into a vacuum oven and drying at the temperature of 100 ℃.
In the functionalized treatment of graphene oxide GO, the weight ratio of methanol to water in a solution formed by mixing methanol and water is 7: 2, namely methanol: water 7: 2;
the set time of ultrasonic treatment in the functionalized treatment of the graphene oxide GO is 3.5 h;
the ultrasonic frequency and the ultrasonic power of ultrasonic treatment in the functionalized treatment of the graphene oxide GO are respectively 40KHz and 250W;
the number of times of the functionalized graphene oxide GO is 9.
The synergistic modification of the hyperbranched polysiloxane and graphene oxide GO comprises the following steps: adding functionalized graphene oxide GO100mg into 90mL of a solution formed by mixing methanol and water to form a mixture, and adjusting the pH value of the mixture to 8.5 by using an alkaline substance; then, carrying out ultrasonic treatment on the mixture for 2 hours to prepare a functionalized graphene oxide GO suspension;
soaking pretreated aramid fiber into functionalized graphene oxide GO suspension, adding 10mL of (3-mercaptopropyl) trimethoxysilane KH-590 into the mixture to form a mixture, slowly stirring the mixture at a set rotating speed for reacting for a set time to obtain the reacted aramid fiber, taking the reacted aramid fiber out of the mixture, washing the reacted aramid fiber for several times by using methanol to remove the redundant (3-mercaptopropyl) trimethoxysilane KH-590, and then placing the reacted aramid fiber into a vacuum oven to dry at the temperature of 100 ℃.
In the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO, the weight ratio of methanol to water in a solution formed by mixing methanol and water is 7: 2, namely methanol: water 7: 2;
the reaction setting time in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO is 11 h;
the rotation speed set in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO is 19 r/min.
Under the test conditions of the same gauge length and the same matrix mold, the extraction forces between the fiber and the rubber before and after modification in the embodiment are respectively 28.3 +/-1.8N and 55.8 +/-2.7N, which indicates that the interface performance of the aramid fiber/rubber composite material is remarkably enhanced and is improved by about 97.2%.
The monofilament strength test results of the aramid fibers show that the monofilament average strength of the fibers before and after modification of the embodiment is 3.86 +/-0.47 GPa and 4.49 +/-0.34 GPa respectively at the gauge length of 20 mm. The result can be obtained, after the synergistic modification of the hyperbranched polymer and the graphene oxide, the strength of the aramid fiber monofilament is improved by about 16.3%, and the strength distribution of the fiber in the test sample is more concentrated.
Example 3:
the surface modification method of the aramid fiber comprises the following steps:
step 1: cleaning and drying the surface of the aramid fiber;
step 2: pretreating the surface of aramid fiber;
and step 3: functionalized treatment of graphene oxide GO;
and 4, step 4: synergistic modification of hyperbranched polysiloxane and graphene oxide GO.
The aramid fiber surface cleaning and drying method comprises the following steps: and (2) washing the aramid fiber by using ethyl acetate and acetone in turn to obtain clean aramid fiber, and then drying the clean aramid fiber in a vacuum oven at the temperature of 100 ℃ until the dry aramid fiber is obtained.
The number of times of washing the aramid fiber by ethyl acetate and acetone in turn is 10.
The pretreatment of the surface of the aramid fiber comprises the following steps: soaking the dried aramid fiber into 2g/L of dopamine hydrochloride solution, adjusting the pH value of the dopamine hydrochloride solution to 8.5 by using an alkaline substance, and slowly stirring the dopamine hydrochloride solution at a set rotating speed for a set time at the temperature of 25 ℃, so that polydopamine is grafted on the surface of the aramid fiber to form a polydopamine layer serving as an initial layer on the surface of the aramid fiber; and then, washing the aramid fiber subjected to the grafting reaction for several times by using deionized water, and drying the washed aramid fiber in a vacuum oven at the temperature of 100 ℃ to obtain the pretreated aramid fiber.
The set rotating speed in the pretreatment of the aramid fiber surface is 20 r/min;
the set time in the pretreatment of the aramid fiber surface is 12 hours;
the number of times in the pretreatment of the aramid fiber surface is 10 times.
The functionalized treatment of the graphene oxide GO comprises the following steps: weighing 100mg of unpurified graphene oxide GO and 10mL of (3-mercaptopropyl) trimethoxysilane KH-590, adding the unpurified graphene oxide GO and the 10mL of (3-mercaptopropyl) trimethoxysilane KH-590 into a solution formed by mixing 90mL of methanol and water together to form a mixture, adjusting the pH value of the mixture to 8.5 by using an alkaline substance, stirring the mixture for 15-30 min, carrying out ultrasonic treatment on the mixture for a set time to react, filtering to obtain reacted functionalized graphene oxide GO, washing the functionalized graphene oxide GO with methanol for several times to remove redundant (3-mercaptopropyl) trimethoxysilane KH-590, and then putting the functionalized graphene oxide GO into a vacuum oven and drying the GO at the temperature of 100 ℃.
In the functionalized treatment of graphene oxide GO, the weight ratio of methanol to water in a solution formed by mixing methanol and water is 7: 2, namely methanol: water 7: 2;
the set time of ultrasonic treatment in the functionalized treatment of the graphene oxide GO is 4 h;
the ultrasonic frequency and the ultrasonic power of ultrasonic treatment in the functionalized treatment of the graphene oxide GO are respectively 40KHz and 250W;
the number of times of the functionalized graphene oxide GO is 10.
The synergistic modification of the hyperbranched polysiloxane and graphene oxide GO comprises the following steps: adding functionalized graphene oxide GO100mg into 90mL of a solution formed by mixing methanol and water to form a mixture, and adjusting the pH value of the mixture to 8.5 by using an alkaline substance; then, carrying out ultrasonic treatment on the mixture for 2 hours to prepare a functionalized graphene oxide GO suspension;
soaking pretreated aramid fiber into functionalized graphene oxide GO suspension, adding 10mL of (3-mercaptopropyl) trimethoxysilane KH-590 into the mixture to form a mixture, slowly stirring the mixture at a set rotating speed for reacting for a set time to obtain the reacted aramid fiber, taking the reacted aramid fiber out of the mixture, washing the reacted aramid fiber for several times by using methanol to remove the redundant (3-mercaptopropyl) trimethoxysilane KH-590, and then placing the reacted aramid fiber into a vacuum oven to dry at the temperature of 100 ℃.
In the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO, the weight ratio of methanol to water in a solution formed by mixing methanol and water is 7: 2, namely methanol: water 7: 2;
the reaction setting time in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO is 12 h;
the rotation speed set in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO is 20 r/min.
Under the test conditions of the same gauge length and the same matrix mold, the extraction forces between the fiber and the rubber before and after modification in the embodiment are respectively 28.3 +/-1.8N and 57.1 +/-2.5N, which indicates that the interface performance of the aramid fiber/rubber composite material is remarkably enhanced and is improved by about 101.8%.
The monofilament strength test results of the aramid fibers show that the monofilament average strength of the fibers before and after modification of the embodiment is 3.86 +/-0.47 GPa and 4.54 +/-0.29 GPa respectively at the gauge length of 20 mm. The result can be obtained, after the synergistic modification of the hyperbranched polymer and the graphene oxide, the strength of the aramid fiber monofilament is improved by about 17.6%, and the strength distribution of the fiber in the test sample is more concentrated.
The present invention has been described in an illustrative manner by the embodiments, and it should be understood by those skilled in the art that the present disclosure is not limited to the embodiments described above, but is capable of various changes, modifications and substitutions without departing from the scope of the present invention.
Claims (6)
1. A surface modification method of aramid fibers is characterized by comprising the following steps:
step 1: cleaning and drying the surface of the aramid fiber;
step 2: pretreating the surface of aramid fiber;
and step 3: functionalized treatment of graphene oxide GO;
and 4, step 4: synergistic modification of hyperbranched polysiloxane and graphene oxide GO;
the pretreatment of the surface of the aramid fiber comprises the following steps: soaking the dried aramid fiber into 2g/L of dopamine hydrochloride solution, adjusting the pH value of the dopamine hydrochloride solution to 8.5 by using an alkaline substance, and stirring the dopamine hydrochloride solution at a set rotating speed for a set time at the temperature of 25 ℃, so as to graft polydopamine on the surface of the aramid fiber to form a polydopamine layer serving as an initial layer; then, washing the aramid fiber subjected to the grafting reaction for several times by using deionized water, and drying the washed aramid fiber in a vacuum oven at the temperature of 100 ℃ to obtain the pretreated aramid fiber;
the functionalized treatment of the graphene oxide GO comprises the following steps: weighing 100mg of unpurified graphene oxide GO and 10mL of (3-mercaptopropyl) trimethoxysilane KH-590, adding the unpurified graphene oxide GO and the 10mL of (3-mercaptopropyl) trimethoxysilane KH-590 into a solution formed by mixing 90mL of methanol and water to form a mixture, adjusting the pH value of the mixture to 8.5 by using an alkaline substance, stirring the mixture for 15-30 min, reacting the mixture by using ultrasonic treatment for a set time, filtering to obtain a reacted functionalized graphene oxide GO, washing the functionalized graphene oxide GO with methanol for several times to remove redundant (3-mercaptopropyl) trimethoxysilane KH-590, and then putting the functionalized graphene oxide GO into a vacuum oven and drying the GO at the temperature of 100 ℃;
the synergistic modification of the hyperbranched polysiloxane and graphene oxide GO comprises the following steps: adding functionalized graphene oxide GO100mg into 90mL of a solution formed by mixing methanol and water to form a mixture, and adjusting the pH value of the mixture to 8.5 by using an alkaline substance; then, carrying out ultrasonic treatment on the mixture for 2 hours to prepare a functionalized graphene oxide GO suspension;
soaking pretreated aramid fiber into functionalized graphene oxide GO suspension, adding 10mL of (3-mercaptopropyl) trimethoxysilane KH-590 to form a mixture, stirring the mixture at a set rotating speed for a set time to react to obtain the reacted aramid fiber, taking the reacted aramid fiber out of the mixture, washing the reacted aramid fiber for several times by using methanol to remove the redundant (3-mercaptopropyl) trimethoxysilane KH-590, and drying the reacted aramid fiber in a vacuum oven at the temperature of 100 ℃.
2. The surface modification method of aramid fiber according to claim 1, wherein the washing and drying of the surface of the aramid fiber comprises: and (2) washing the aramid fiber by using ethyl acetate and acetone in turn to obtain clean aramid fiber, and then drying the clean aramid fiber in a vacuum oven at the temperature of 100 ℃ until the dry aramid fiber is obtained.
3. The surface modification method of the aramid fiber according to claim 2, wherein the number of times of washing the aramid fiber with ethyl acetate and acetone in turn is 5 to 10.
4. The surface modification method of aramid fibers according to claim 3, wherein the set rotation speed in the pretreatment of the surface of the aramid fibers is 18 to 20 r/min;
the set time in the pretreatment of the aramid fiber surface is 10-12 h;
the number of times of pretreatment of the aramid fiber surface is 5-10 times.
5. The surface modification method of aramid fibers as claimed in claim 4, wherein the weight ratio of methanol to water in a solution of methanol and water mixed in the functionalization treatment of graphene oxide GO is 7: 2, namely methanol: water 7: 2;
the set time of ultrasonic treatment in the functionalized treatment of the graphene oxide GO is 3-4 h;
the ultrasonic frequency and the ultrasonic power of ultrasonic treatment in the functionalized treatment of the graphene oxide GO are respectively 40KHz and 250W;
the number of times of the functionalized graphene oxide GO is 8-10 times.
6. The surface modification method of aramid fibers according to claim 5, wherein in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO, the weight ratio of methanol to water in a solution of mixed methanol and water is 7: 2, namely methanol: water 7: 2;
the reaction setting time in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO is 10-12 h;
the rotation speed set in the synergistic modification of the hyperbranched polysiloxane and the graphene oxide GO is 18-20 r/min.
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