CN113215815B - Preparation method of graphene functionalized silk fiber - Google Patents

Preparation method of graphene functionalized silk fiber Download PDF

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CN113215815B
CN113215815B CN202110076786.5A CN202110076786A CN113215815B CN 113215815 B CN113215815 B CN 113215815B CN 202110076786 A CN202110076786 A CN 202110076786A CN 113215815 B CN113215815 B CN 113215815B
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graphene oxide
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chitosan
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CN113215815A (en
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程群峰
曹璨
林宗恺
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Beihang University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres

Abstract

The invention relates to a preparation method of graphene functionalized silk fibers, which comprises the following steps: (1) uniformly dispersing chitosan powder in an acetic acid aqueous solution to obtain a chitosan dispersion liquid; (2) preparing graphene oxide powder into a uniform graphene oxide aqueous solution; (3) mixing the chitosan dispersion liquid with a graphene oxide aqueous solution to obtain a graphene oxide/chitosan dispersion liquid; (4) mixing a reducing agent with the graphene oxide/chitosan dispersion liquid, and reacting to obtain a reduced graphene oxide/chitosan dispersion liquid; (5) preparing silk cocoons into silk fibers; (6) and (4) soaking the silk fiber in the reduced graphene oxide chitosan dispersion liquid obtained in the step (4), and drying to obtain the graphene functionalized silk fiber. The fiber prepared by the method has high tensile strength, high toughness, excellent conductivity, excellent temperature response and deformation response functions.

Description

Preparation method of graphene functionalized silk fiber
Technical Field
The invention relates to a preparation method of graphene functionalized silk fibers, and belongs to the field of preparation of nano composite materials.
Background
Because natural silk fibers are widely applied in the textile field (Nature 2002,418,714.), the conversion of silk with rich yield into functional fibers with high mechanical properties at room temperature has important significance for replacing chemical fibers with high pollution and high energy consumption. Researches show that the graphene material has excellent mechanical properties, electric conductivity, heat conduction and other functions, so that the method for improving the performance function of the silk fiber by functionalizing the silk fiber with the graphene nanosheets is a feasible idea. Currently, although there are many advanced technologies that can realize the preparation of graphene functionalized silk fiber, such as feeding graphene nanoplatelets to silkworms (Nano lett.2016,16,6695.), physicochemical modification of silk fiber (Matter 2019,1,1411.), composite material prepared from regenerated silk protein (adv.funct.matter.2018, 28,1705291), etc., how to optimize graphene nanoplatelet functionalized silk fiber from the perspective of interface design still remains a significant challenge.
In the research of the graphene composite film, the interface design plays an important role in improving the material performance. Graphene oxide was produced in Dikin et al (Nature 2007,448,457.) in 2007After the (GO) nanosheets are assembled into the self-supporting thin film, a great deal of research work is devoted to improving the mechanical properties of the graphene thin film by enhancing the crosslinking among the nanosheet layers. The surface of GO nano-sheet is composed of oxidized regions and sp2The conjugated regions are composed alternately, which readily form hydrogen bonds, ionic bonds, covalent bonds, and conjugated pi bonds. For example, Putz et al (adv.funct.mater.2010,20,3322.) use synthetic polyvinyl alcohol to build hydrogen bonding networks between GO layers, producing high strength GO composite films; yeh et al (nat. chem.2014,7,166.) have demonstrated that metal ion crosslinking can effectively improve the mechanical properties of GO films; an et al (adv.mater.2011, 23,3842.) introduce borate between adjacent GO nano-sheets to realize covalent crosslinking, so as to prepare a high-strength and high-modulus GO thin film; ni et al (ACS appl. mater. interfaces 2017,9,24987.) produced highly tough, electrically conductive graphene films via conjugated pi-bonds.
Generally, the mechanical properties of the graphene composite material can be effectively improved through different interfacial crosslinking strategies and interfacial synergistic effects. Therefore, the method for designing the graphene functionalized fiber combined interface is a feasible idea for preparing the functionalized silk fiber with high strength, high toughness and high conductivity. At present, no literature and patent reports for preparing graphene functionalized silk fibers by utilizing hydrogen bond network crosslinking exist.
Disclosure of Invention
The technical problem of the invention is solved: the defects of the prior art are overcome, and the preparation method of the graphene functionalized silk fiber is provided, so that the prepared fiber not only has ultrahigh tensile strength, toughness and conductivity, but also has excellent temperature and deformation response functions.
The invention is realized by the following technical scheme:
a preparation method of graphene functionalized silk fibers is characterized by comprising the following steps:
(1) uniformly dispersing chitosan powder in an acetic acid aqueous solution to obtain a chitosan dispersion liquid; preferably, the dispersion is carried out by stirring;
(2) dispersing Graphene Oxide (GO) powder in water to prepare a uniform GO aqueous solution; preferably, the dispersion is carried out by stirring and ultrasound;
(3) mixing the chitosan dispersion liquid with a GO aqueous solution to obtain a GO/chitosan (GO/CS) dispersion liquid; preferably, the mixing is performed by adding the aqueous GO solution to the chitosan dispersion while stirring;
(4) mixing a reducing agent with the GO/CS dispersion liquid, and reacting to obtain a reduced graphene oxide/chitosan (rGO/CS) dispersion liquid; preferably, the reducing agent is ascorbic acid; preferably the reaction is carried out with stirring;
(5) preparing silk cocoons into silk fibers; preferably, the silk cocoons are put into a heated alkaline solution to remove sericin, and are washed and dried to prepare silk fibers; preferably, the sericin is removed from the silkworm cocoons in a heated alkaline solution, and the process is repeated for one or more times; preferably, the alkaline solution is Na2CO3A solution;
(6) and (4) soaking the silk fiber in the rGO/CS dispersion liquid obtained in the step (4), and drying to obtain the graphene functionalized silk fiber.
In the step (1), the concentration of the acetic acid aqueous solution is 1-2 wt%, and the concentration of chitosan in the dispersion liquid is 5-20 mg/mL; preferably, the concentration of chitosan in the dispersion is 10 mg/mL; preferably, the stirring reaction time is 24-48 h.
In the step (2), the concentration of the GO aqueous solution is 1-2 mg/mL; preferably, the stirring time is 1-3 h, the ultrasonic time is 2-3 min, and the ultrasonic power is 20-80W.
In the step (3), the mass ratio of GO to chitosan is 1: 10-2: 5, and the stirring time is 1-2 h.
In the step (4), the mass ratio of ascorbic acid to GO is 20: 1-5: 1, and the stirring time is 24-36 h; preferably, the mass ratio of ascorbic acid to GO is 10: 1.
In the step (5), Na2CO3The concentration of the solution is 0.1-1 wt%, the temperature is 90-100 ℃, the reaction time of placing the solution into the silkworm cocoons is 15-45 minutes, and the process is repeated after the reaction to obtain single silk fibers; preferably, the washing method is in deionized waterSoaking for 5-30 minutes, and repeating for several times; preferably, the drying process is drying for 12-24 hours in a natural environment.
In the step (6), the soaking time of the silk fibers in the rGO/CS dispersion liquid is 1-10 seconds; preferably, the soaking time is 2-5 seconds; preferably, the soaking times are 1-40 times, and each time interval is 5-60 seconds; more preferably, the soaking times are 25-35 times, and the interval of each time is 5-60 seconds.
In the step (6), the drying process is carried out for 12-24 hours in a natural environment.
In particular, the present invention is realized by:
a preparation method of graphene functionalized silk fibers comprises the steps of firstly, respectively preparing Chitosan (CS) and Graphene Oxide (GO) into aqueous solutions; then adding the GO solution into a chitosan solution; adding an ascorbic acid reduction solution into the GO/CS mixed solution to obtain a reduced graphene oxide/chitosan (rGO/CS) dispersion solution; and soaking the silk fiber without sericin in the rGO/CS dispersion liquid, and drying to obtain the hydrogen bond network crosslinked graphene functionalized silk fiber.
The method comprises the following concrete steps:
a preparation method of graphene functionalized silk fibers comprises the following steps:
(1) uniformly dissolving chitosan powder in an acetic acid aqueous solution by using a stirring method to obtain a chitosan dispersion liquid;
(2) preparing GO powder into a uniform GO aqueous solution by using a stirring and ultrasonic method;
(3) adding the GO aqueous solution into the CS dispersion liquid while stirring to obtain a GO/CS dispersion liquid;
(4) adding ascorbic acid into the GO/CS dispersion liquid, and stirring for reaction to obtain an rGO/CS dispersion liquid;
(5) placing silkworm cocoon into heated Na2CO3Removing sericin from the solution, repeating the steps once, and washing and drying to obtain silk fiber;
(6) and (4) soaking the silk fiber in the rGO/CS dispersion liquid obtained in the step (4), and washing and drying to obtain the graphene functionalized silk fiber (GS).
In the step (1), the concentration of the acetic acid aqueous solution is 1-2 wt%, and the concentration of chitosan in the dispersion liquid is 5-20 mg/mL; preferably, the concentration of chitosan in the dispersion is 10 mg/mL; stirring and reacting for 24-48 h. Stirring to make the chitosan fully hydrolyzed.
In the step (2), the concentration of the GO aqueous solution is 1-2 mg/mL, the stirring time is 1-3 h, the ultrasonic time is 2-3 min, and the ultrasonic power is 20-80W. GO nanosheet dispersion is uniform through stirring and ultrasound, and meanwhile, GO nanosheet breakage is avoided.
In the step (3), the mass ratio of GO to chitosan is 1: 10-2: 5, and the stirring time is 1-2 h. The chitosan was allowed to fully disperse the GO nanosheets by stirring.
In the step (4), the mass ratio of ascorbic acid to GO is 20: 1-5: 1, and the stirring time is 24-36 h; preferably, the mass ratio of ascorbic acid to GO is 10: 1. GO nanosheets are fully reduced by stirring and are in full dispersion with chitosan.
In the step (5), Na2CO3The concentration of the solution is 0.1-1 wt%, the temperature is 90-100 ℃, the reaction time of placing the solution into the silkworm cocoons is 15-45 minutes, and the process is repeated after the reaction to obtain single silk fibers; the washing method comprises the steps of soaking in deionized water for 5-30 minutes, and repeating for a plurality of times; the drying process is drying for 12-24 hours in a natural environment. By repeating the above procedure, Na is added2CO3The reaction in the solution is mainly to dissolve and remove sericin in the silkworm cocoons in an alkaline environment. The washing is repeated for a plurality of times, so that the salt on the fiber is fully washed. The water was removed by drying.
In the step (6), the soaking time of the silk fibers in the rGO/CS dispersion liquid is 1-10 seconds, wherein the preferable soaking time range is 2-5 seconds. Too long soaking time will make the excessive adsorbed rGO/CS composite molecule of fibre, be unfavorable for forming even rGO/CS parcel layer to be unfavorable for promoting the mechanical properties of graphite alkene functionalization silk fibre. The content of the rGO/CS coating layer on the functional fiber can be controlled according to the repeated soaking times. In order to better optimize the performance of the graphene functionalized silk fibers, the repeated soaking times are respectively 10,20, 30 and 40, the correspondingly prepared 4 graphene functionalized silk fibers are respectively marked as GS-1, GS-2, GS-3 and GS-4, and the volume fraction content of the rGO/CS coating layers is 0.5-25%.
In the step (6), the drying process is carried out for 12-24 hours in a natural environment. The water was removed by drying.
The Graphene Oxide (GO) is an oxygen-containing derivative of graphene, contains active groups such as hydroxyl, carboxyl, epoxy groups and the like on the surface, is easily soluble in water, and can be reduced into reduced graphene oxide (rGO) with a conjugated structure partially recovered after being reduced by ascorbic acid; the cross-linking molecule is chitosan, is natural polysaccharide, has good solubility under acidic conditions, has a large amount of hydroxyl and amino groups on a molecular chain, and can generate hydrogen bond network cross-linking with the rGO nano-sheet, so that a hydrogen bond cross-linking network structure can be formed between the graphene functionalized wrapping layer and the silk fiber.
The graphene functionalized silk fiber is a fiber material, and the diameter of the graphene functionalized silk fiber is 6-10 mu m.
The principle of the invention is as follows: through the evolution of hundreds of millions of years, the natural core-sheath structural material has excellent mechanical properties (including high strength and high toughness) and functional characteristics (including protection, hydrophobic function and the like), which are mainly due to the synergistic effect of the core-sheath structure. Based on the inspiration, the silk fiber is functionally modified by utilizing a graphene composite material hydrogen bond network crosslinking strategy, so that the interface strength between a functional layer and the fiber is greatly improved, and the electrical function of the natural silk fiber is endowed, thereby preparing the graphene functional silk fiber with super-strong toughness and high conductivity. Compared with the prior art of graphene functionalized silk fiber, the invention has the characteristics and advantages that:
(1) the graphene derivative graphene oxide has high mechanical properties (such as tensile strength) and can provide high-density hydrogen bond crosslinking functional groups, so that the graphene functionalized layer is beneficial to introducing rich hydrogen bond crosslinking, and the mechanical properties of the fiber are greatly functionalized;
(2) the chitosan molecules not only have rich oxygen-containing functional groups and generate hydrogen bond crosslinking with GO nano sheets to improve the bonding strength of a functionalized layer, but also can be crosslinked with a fiber matrix to form a hydrogen bond network crosslinking structure to endow the rGO nano sheets with a larger sliding space, so that the toughness of graphene functionalized fibers can be improved;
(3) the hydrogen bond network crosslinking strategy is not only to sp of the surface of the rGO nano sheet2The conjugated structure is not influenced, and the reduced rGO nanosheets can be effectively dispersed to form a stable rGO dispersion liquid, so that a uniform graphene functionalized wrapping layer can be formed, and the conductivity can be improved;
(4) the graphene functionalized silk fiber has excellent temperature response and deformation response functions due to excellent conductivity.
Therefore, the hydrogen bond network crosslinked graphene functional silk fiber (GS) prepared by the method not only has ultrahigh tensile strength (564-836 MPa) but also has high toughness (93-187 MJ/m)3) And high conductivity (0.2-0.4S/m), and has excellent temperature-resistance response, tensile-resistance response, and bending-resistance response functions, for example, the resistance of the fiber is reduced along with the temperature rise at 30-100 ℃, and the current temperature value can be detected according to the change of the resistance; circularly stretching the fiber under the strain of 0-3%, wherein the resistance of the fiber is increased along with the increase of the strain, and the current fiber stretching deformation can be detected according to the change of the resistance; the fiber is bent under 0-50% strain, the resistance of the fiber is increased along with the increase of the strain, and the current fiber bending deformation can be detected according to the change of the resistance.
Drawings
Fig. 1 is a preparation process of graphene functionalized silk fiber (GS) according to the present invention;
FIG. 2 is a mechanical property representation of the graphene functionalized silk fiber of the present invention;
FIG. 3: the invention relates to a toughness mechanism of graphene functionalized silk fiber;
FIG. 4: the functional application of the graphene functionalized silk fiber is disclosed.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments. The following examples are only for explaining the present invention, the scope of the present invention shall include the full contents of the claims, and the full contents of the claims of the present invention can be fully realized by those skilled in the art through the following examples.
The method of the invention is realized as follows:
fig. 1 shows a preparation process of graphene functionalized silk fiber (GS): firstly, mixing a graphene oxide solution and a chitosan solution to form a graphene oxide/chitosan uniformly-mixed dispersion liquid; then adding ascorbic acid into the dispersion liquid, and reducing the graphene oxide; reuse of Na2CO3Removing sericin on the silkworm cocoons by using the solution to obtain single silk fiber; and finally, soaking the fiber in a reduced graphene oxide/chitosan solution, and drying to obtain the graphene functionalized silk fiber. By changing the soaking times of the fibers in the reduced graphene oxide/chitosan solution, the content of the graphene functional wrapping layer on the graphene functional silk fibers can be regulated and controlled, so that the performance of the fibers is optimized.
When the volume fraction content of the graphene functional wrapping layer is 23%, the performance of the functional silk fiber is optimal and is marked as GS-3, the tensile strength of the functional silk fiber is up to 836MPa, and the corresponding toughness is 187MJ/m3The conductivity was 0.23S/m. In addition, the composite film also has excellent resistance-temperature response and resistance-deformation response functions, for example, the resistance of the fiber tends to change in a nearly linear manner along with the temperature increase at 30-100 ℃, which shows that the resistance of the graphene functionalized layer can realize temperature responsiveness; at a 3% strain draw cycle of 10000 seconds, the resistance of the fiber increases with the elongation of the fiber, and the resistance returns to the original value when the fiber recovers; the fiber resistance also has excellent responsiveness to 50% bending deformation, the resistance of the fiber increases with the degree of bending of the fiber, and the resistance decreases back to the original value when the fiber recovers.
The Graphene Oxide (GO) is an oxygen-containing derivative of graphene, contains active groups such as hydroxyl, carboxyl, epoxy groups and the like on the surface, is easily soluble in water, and can be reduced into reduced graphene oxide (rGO) with a conjugated structure partially recovered after being reduced by ascorbic acid; the cross-linking molecule is chitosan, is natural polysaccharide, has good solubility under acidic conditions, has a large amount of hydroxyl and amino groups on a molecular chain, and can generate hydrogen bond network cross-linking with the rGO nano-sheet, so that a hydrogen bond cross-linking network structure can be formed between the graphene functionalized wrapping layer and the silk fiber;
the graphene functionalized silk fiber is a fiber material, and the diameter of the graphene functionalized silk fiber is 6-10 mu m.
Sample fibers of graphene functionalized silk fibers prepared as described in examples 1-4 below were tested using the following test method:
embedding the prepared sample fiber with epoxy resin (Spurr, SPI company, usa), brittle-breaking the obtained fiber resin embedded sample under liquid nitrogen to obtain an exposed fiber resin embedded section, measuring the sectional area of the fiber resin embedded section under a scanning electron microscope (SU8010, HITACHI company, japan), and calculating the volume fraction of the graphene functionalized layer according to the ratio of the sectional area of the graphene functionalized layer to the sectional area of the graphene functionalized fiber in the section; fixing both ends of the prepared sample fiber by conductive silver adhesive (SPI company in America), and carrying out conductivity test on the sample fiber by using a two-end method (2400Source Meter, Agilent company in America); fixing the two ends of the fiber with the length of 10mm on a universal mechanical testing machine (SUNS UTM4103, Shenzhen Sansi longitudinal and transverse technologies Co., Ltd.), performing tensile test on the fiber by using a 10N sensor, wherein the tensile rate is 0.3mm/min, and performing calculation processing (a known calculation method) on a force-displacement curve obtained by the test to obtain the maximum load force value, the tensile strength and the toughness of the sample fiber. The tested pure silk samples are designated ss.
Example 1
Firstly, preparing a 10mg/mL chitosan solution: measuring 4mL of glacial acetic acid, adding the glacial acetic acid into 196mL of deionized water, mechanically stirring for 30min, weighing 2g of chitosan, adding the chitosan into the solution, and mechanically stirring for 24h to obtain a light yellow transparent solution; preparing 1mg/mL GO aqueous solution: weighing 20mg of graphene oxide, adding the graphene oxide into 20mL of deionized water, carrying out ultrasonic treatment at 20W for 2min, and mechanically stirring for 2h to obtain a brown transparent solution; then slowly adding 20mL of the prepared GO aqueous solution into 20mL of chitosan solution, and continuously stirring for 2h to obtain a tan solution; then weighing 200mg of ascorbic acid, adding the ascorbic acid into the graphene oxide/chitosan mixtureIn the dispersion liquid, carrying out reduction reaction for 24 hours under the condition of stirring at room temperature to obtain a reduced graphene oxide/chitosan solution, and preparing the reduced graphene oxide/chitosan solution on site; 0.5 wt% Na is prepared2CO3Solution: weighing 1g of Na2CO3Adding into 200mL deionized water; subsequently soaking silkworm cocoon in boiling Na prepared as above2CO3Soaking in deionized water for 0.5 hr, taking out, washing for 0.5 hr, and soaking in boiling Na2CO3Soaking and washing the solution for 0.5h by using deionized water after taking out the solution, and drying the solution for 24h in a natural environment to obtain single silk fibers; and finally, soaking the single silk fiber in the prepared reduced graphene oxide/chitosan solution for 2 seconds at intervals of 20 seconds every time, repeating the soaking process for 10 times, and drying for 12 hours in a natural environment to obtain the graphene functionalized silk fiber with the diameter of 6-8 microns. The obtained graphene functionalized silk fiber is marked as GS-1.
The volume fraction content of the graphene functional layer in the graphene functional silk fiber is 0.5%, and the mechanical property and electrical property tests of 3 sample fibers with the length of 10mm show that the tensile strength of the graphene functional silk fiber is 654.6 +/-7.8 MPa, and the toughness of the graphene functional silk fiber is 103.7 +/-0.9 MJ/m3The conductivity was 0.
Example 2
Firstly, preparing a 10mg/mL chitosan solution: measuring 4mL of glacial acetic acid, adding the glacial acetic acid into 196mL of deionized water, mechanically stirring for 30min, weighing 2g of chitosan, adding the chitosan into the solution, and mechanically stirring for 24h to obtain a light yellow transparent solution; preparing 1mg/mL GO aqueous solution: weighing 20mg of graphene oxide, adding the graphene oxide into 20mL of deionized water, carrying out ultrasonic treatment at 20W for 2min, and mechanically stirring for 2h to obtain a brown transparent solution; then slowly adding 20mL of the prepared GO aqueous solution into 20mL of chitosan solution, and continuously stirring for 2h to obtain a tan solution; then weighing 200mg of ascorbic acid, adding the ascorbic acid into the graphene oxide/chitosan mixed dispersion liquid, stirring at room temperature, carrying out reduction reaction for 24 hours to obtain a reduced graphene oxide/chitosan solution, and preparing the reduced graphene oxide/chitosan solution on site; 0.5 wt% Na is prepared2CO3Solution: weighing 1g of Na2CO3Adding into 200mL deionized water; subsequently soaking silkworm cocoon in boiling Na prepared as above2CO3Soaking in deionized water for 0.5 hr, taking out, washing for 0.5 hr, and soaking in boiling Na2CO3Soaking and washing the solution for 0.5h by using deionized water after taking out the solution, and drying the solution for 24h in a natural environment to obtain single silk fibers; and finally, soaking the single silk fiber in the prepared reduced graphene oxide/chitosan solution for 2 seconds at intervals of 20 seconds every time, repeating the soaking process for 20 times, and drying for 12 hours in a natural environment to obtain the graphene functionalized silk fiber with the diameter of 6-8.5 microns. The obtained graphene functionalized silk fiber is marked as GS-2.
The volume fraction content of the graphene functional layer in the graphene functional silk fiber is 13%, and the mechanical property and the electrical property of 3 sample fibers with the length of 10mm are tested, and the result shows that the tensile strength of the graphene functional silk fiber is 603.7 +/-3.4 MPa, and the toughness of the graphene functional silk fiber is 107.3 +/-0.6 MJ/m3The conductivity was 0.
Example 3
Firstly, preparing a 10mg/mL chitosan solution: measuring 4mL of glacial acetic acid, adding the glacial acetic acid into 196mL of deionized water, mechanically stirring for 30min, weighing 2g of chitosan, adding the chitosan into the solution, and mechanically stirring for 24h to obtain a light yellow transparent solution; preparing 1mg/mL GO aqueous solution: weighing 20mg of graphene oxide, adding the graphene oxide into 20mL of deionized water, carrying out ultrasonic treatment at 20W for 2min, and mechanically stirring for 2h to obtain a brown transparent solution; then slowly adding 20mL of the prepared GO aqueous solution into 20mL of chitosan solution, and continuously stirring for 2h to obtain a tan solution; then weighing 200mg of ascorbic acid, adding the ascorbic acid into the graphene oxide/chitosan mixed dispersion liquid, stirring at room temperature, carrying out reduction reaction for 24 hours to obtain a reduced graphene oxide/chitosan solution, and preparing the reduced graphene oxide/chitosan solution on site; 0.5 wt% Na is prepared2CO3Solution: weighing 1g of Na2CO3Adding into 200mL deionized water; subsequently soaking silkworm cocoon in boiling Na prepared as above2CO3Soaking in deionized water for 0.5 hr, taking out, washing for 0.5 hr, and soaking in boiling Na2CO3Soaking and washing the solution for 0.5h by using deionized water after taking out the solution, and drying the solution for 24h in a natural environment to obtain single silk fibers; finally, soaking single silk fiber in the preparationThe reduced graphene oxide/chitosan solution is soaked for 30 times at intervals of 20 seconds for 2 seconds, and the soaking process is repeated for 12 hours in a natural environment to obtain the graphene functionalized silk fiber with the diameter of 6.5-9.5 microns. The obtained graphene functionalized silk fiber is marked as GS-3.
The volume fraction content of the graphene functional layer in the graphene functional silk fiber is 23%, and the mechanical property and electrical property tests of 3 sample fibers with the length of 10mm show that the tensile strength of the graphene functional silk fiber is 836.0 +/-25.0 MPa, and the toughness of the graphene functional silk fiber is 186.6 +/-2.2 MJ/m3The conductivity was 0.23. + -. 0.10S/m. The tensile strength and the toughness are the highest values (633MPa,54 MJ/m) of the modified silk fiber reported by the prior literature3,Matter 2019,1,1411.；697MPa,48MJ/m3,Mater. Lett.2017,194,224.；590MPa,39MJ/m3Nano lett.2016,16,6695.). By measuring the resistance of the fibers at different temperatures, the result of GS fiber resistance and temperature response is obtained, and the resistance of the fibers tends to change nearly linearly with the temperature increase at 30-100 ℃, as shown in FIG. 4A, which indicates that the resistance of the graphene functionalized layer can realize the temperature response; at a 3% strain draw cycle of 10000 seconds, the resistance of the fiber increases with the elongation of the fiber, and upon recovery of the fiber, the resistance decreases back to the original value, as shown in FIG. 4B; the fiber resistance also has excellent responsiveness to 50% bending deformation, as shown in fig. 4C, the resistance of the fiber increases with the bending of the fiber, and the resistance decreases back to the original value when the fiber recovers.
Example 4
Firstly, preparing a 10mg/mL chitosan solution: measuring 4mL of glacial acetic acid, adding the glacial acetic acid into 196mL of deionized water, mechanically stirring for 30min, weighing 2g of chitosan, adding the chitosan into the solution, and mechanically stirring for 24h to obtain a light yellow transparent solution; preparing 1mg/mL GO aqueous solution: weighing 20mg of graphene oxide, adding the graphene oxide into 20mL of deionized water, carrying out ultrasonic treatment at 20W for 2min, and mechanically stirring for 2h to obtain a brown transparent solution; then slowly adding 20mL of the prepared GO aqueous solution into 20mL of chitosan solution, and continuously stirring for 2h to obtain a tan solution; then weighing 200mg of ascorbic acid, adding the ascorbic acid into the graphene oxide/chitosan mixed dispersion liquid, and carrying out reduction reaction for 24 hours under stirring at room temperature to obtain the ascorbic acidPreparing an original graphene oxide/chitosan solution in situ; 0.5 wt% Na is prepared2CO3Solution: weighing 1g of Na2CO3Adding into 200mL deionized water; subsequently soaking silkworm cocoon in boiling Na prepared as above2CO3Soaking in deionized water for 0.5 hr, taking out, washing for 0.5 hr, and soaking in boiling Na2CO3Soaking and washing the solution for 0.5h by using deionized water after taking out the solution, and drying the solution for 24h in a natural environment to obtain single silk fibers; and finally, soaking the single silk fiber in the prepared reduced graphene oxide/chitosan solution for 2 seconds at intervals of 20 seconds every time, and repeating the soaking process for 40 times to obtain the graphene functionalized silk fiber with the diameter of 7-10 microns. The obtained graphene functionalized silk fiber is marked as GS-4.
The volume fraction content of the graphene functional layer in the graphene functional silk fiber is 25%, and the mechanical property and the electrical property of 3 sample fibers with the length of 10mm are tested, and the result shows that the tensile strength of the graphene functional silk fiber is 564.1 +/-1.2 MPa, and the toughness of the graphene functional silk fiber is 92.7 +/-1.2 MJ/m3The conductivity is 0.37 +/-0.06S/m. As in fig. 4D, at a 3% strain draw cycle of 10000 seconds, the resistance of the fiber increases with the elongation of the fiber, and upon recovery of the fiber, the resistance returns to the original value; as shown in fig. 4E, the fiber resistance also had excellent responsiveness to 50% bending strain, the resistance of the fiber increased with the bending of the fiber, and the resistance decreased back to the original value when the fiber recovered.
Fig. 2 shows the mechanical property characterization of the graphene functionalized silk fiber. In fig. 2A): the comparison of the breaking strength of each sample is shown in fig. 2A), the maximum load force values in the force-displacement curves of the pure silkworms (ss), the GS-1 (example 1), the GS-2 (example 2) and the GS-4 (example 4) are respectively 0.043N, 0.042N and 0.048N, and the maximum load force value of the GS-3 (example 3) is 0.070N, which is a significant improvement, and shows that under the condition, the graphene functional wrapping layer effectively improves the mechanical properties of the fiber. In fig. 2B): further, the tensile strength and fracture toughness of each sample were calculated from the cross-sectional area of the sample, and the results are shown in FIG. 2B), where the tensile strength of each of the ss, GS-1, GS-2, GS-3, and GS-4 samples was 606.0 + -3.6 MPa, 654.6 + -7.8 MPa, 603.7 + -3.4 MPa, 836.0 + -25.0 MPa and 564.1 + -1.2 MPa, and the fracture toughness is 112.8 + -0.3 MJ/m3、103.7±0.9MJ/m3、107.3±0.6MJ/m3、186.6 ±2.2MJ/m3、92.7±1.2MJ/m3. The GS-3 sample has obviously improved mechanical properties, and compared with silk monofilaments, the strength of the GS-3 sample is improved by about 34%, and the toughness of the GS-3 sample is improved by about 66%. The result of the mechanical test shows that the strength and toughness of the fiber are effectively improved by functionalizing the silk by using a reduced graphene oxide/chitosan (rGO/CS) system. As shown in fig. 2C), as the number of times of pulling increases, the conductivity of the fibers increases with the content of the graphene layer, and the fibers are non-conductive starting from GS-1 and GS-2 to GS-3 and GS-4 respectively having conductivities of 0.23 ± 0.10 and 0.37 ± 0.06S/m. Compared with other modified silk fiber, such as modified silk obtained by feeding silkworm nanometer material, composite material reconstituted by dissolving fibroin, and surface modified silk fiber (633MPa,54 MJ/m)3,Matter 2019,1,1411.；697MPa,48MJ/m3, Mater.Lett.2017,194,224.；590MPa,39MJ/m3Nano Lett.2016,16,6695.), the graphene functionalized silk fiber prepared by the work has outstanding tensile strength and toughness. The interface enhancement strategy proves that the interface interaction between the functional wrapping layer and the fiber matrix is effectively improved, so that the mechanical property of the fiber is effectively improved;
fig. 3 shows the toughness mechanism of graphene functionalized silk fiber example 3 (GS-3). Fig. 3A) is a schematic view of the fiber change during stretching, which further illustrates the role of the functionalized coating during stretching. Tensile in-process fibre is the state that freely extends at first, after the loading stress, the fibre atress is stretched straightly, although adjacent rGO/CS parcel layer can take place to slide at the stress loading in-process that lasts, nevertheless because hydrogen bond network effect, the parcel layer of graphite alkene nanometer piece still closely adsorbs on silk fibre surface, at this in-process, the dissociation that the hydrogen bond lasts can dissipate partial fracture energy, and abundant hydrogen bond network between rGO/CS parcel layer and the fibre base member has played the effect of stress transfer, the excessive accumulation of stress has been avoided. Continuing to load stress until the fiber is finallyAnd (3) breaking, namely dissociating the direct covalent bond between the rGO and the CS to further absorb breaking energy. The wrapping layer plays a role in strengthening and toughening in the whole process. FIG. 3B) is an infrared spectrum of each sample, 3300cm of rGO/CS in the infrared spectrum characterization-1The intensity of the nearby O-H, N-H peak was reduced compared to that of GO, demonstrating efficient reduction of GO, while the 3272cm of GS was-1The peak at N-H is higher than that at pure ss (3274 cm)-1) A certain red shift is generated, which indicates the hydrogen bond effect between the rGO/CS wrapping layer and the ss fiber matrix; the close recombination between rGO and CS is determined by the CO-H peak (1380 cm) of GO in the infrared spectrum-1) And epoxy Peak (1072 cm)-1) Evidence of a clear red shift. The presence of rGO/CS wrapping on the fiber can be measured by GS sample vs. ss at 1377cm-1(C-H vibration peak) and the like. Fig. 3C) shows that the characteristic structures of the silk fiber ss, such as the amide I band (C ═ O stretching vibration in β -sheet and reverse β -sheet), and the amide III band, are 1226cm-1、1263cm-1、1661cm-1、1699cm-1Raman characteristic peaks are near the equal parts, and after graphene is functionalized, the Raman spectrum of a GS sample is similar to that of GO and rGO/CS samples, and graphene is 1350cm-1And 1620cm-1Near D peak and G peak Raman characteristic peak. Furthermore, I of GO sampleD/IG1.15, I of rGO/CS sampleD/IG1.36, I of GS sampleD/IGAt 1.30, the efficient reduction of GO is demonstrated.
FIG. 4 shows functional applications of graphene functionalized silk fibers in example 3(GS-3) and example 4 (GS-4). By measuring the resistance of the GS fiber at different temperatures, the results of the resistance and the temperature response of the GS fiber are obtained, as shown in FIG. 4A, the resistance of the GS-3 fiber tends to change nearly linearly with the temperature increase at 30-100 ℃, which shows that the resistance of the graphene functionalized layer can realize the temperature response. As in fig. 4B, the resistance of GS-3 fibers increased with fiber elongation at a 3% strain draw cycle of 10000 seconds, and decreased back to the original value upon fiber recovery; as shown in fig. 4C, the GS-3 fiber resistance also had excellent responsiveness to 50% bending strain, the resistance of the fiber increased with the bending of the fiber, and the resistance decreased back to the original value upon recovery of the fiber. As in fig. 4D, at a 3% strain draw cycle of 10000 seconds, the resistance of GS-4 fibers increased with fiber elongation and decreased back to the original value upon fiber recovery; as shown in fig. 4E, GS-4 fiber resistance also had excellent response to 50% bend strain, and the resistance of the fiber increased with the bending of the fiber, and decreased back to the original value upon recovery of the fiber.
In a word, the hydrogen bond network crosslinked graphene functional silk fiber (GS) prepared by the method not only has ultrahigh tensile strength (564-836 MPa) but also has high toughness (93-187 MJ/m)3) And high conductivity (0.2-0.4S/m), and has excellent temperature-resistance response, tensile-resistance response, and bending-resistance response functions, for example, the resistance of the fiber is reduced along with the temperature rise at 30-100 ℃, and the current temperature value can be detected according to the change of the resistance; cyclically drawing the fiber under the strain of 3%, wherein the resistance of the fiber is increased along with the increase of the strain, and the current fiber drawing deformation can be detected according to the change of the resistance; the fiber is bent under 50% strain, the resistance of the fiber increases along with the increase of the strain, and the current fiber bending deformation can be detected according to the change of the resistance. The high-performance multifunctional graphene functionalized silk fiber has wide application in the fields of intelligent fabrics, flexible electronic devices and the like.
It should be noted that, according to the above embodiments of the present invention, those skilled in the art can fully implement the full scope of the present invention as defined by the independent claims and the dependent claims, and implement the processes and methods as the above embodiments; and the invention has not been described in detail so as not to obscure the present invention.
The above description is only a part of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (9)

1. A preparation method of graphene functionalized silk fibers is characterized by comprising the following steps:
(1) uniformly dispersing chitosan powder in an acetic acid aqueous solution to obtain a chitosan dispersion liquid;
(2) dispersing graphene oxide powder in water to prepare a uniform graphene oxide aqueous solution;
(3) mixing the chitosan dispersion liquid with a graphene oxide aqueous solution to obtain a graphene oxide/chitosan dispersion liquid; the mass ratio of the graphene oxide to the chitosan is 1: 10-2: 5;
(4) mixing ascorbic acid with the graphene oxide/chitosan dispersion liquid, and reacting to obtain a reduced graphene oxide/chitosan dispersion liquid;
(5) preparing silk cocoons into silk fibers; putting the silkworm cocoons into a heated alkaline solution to remove sericin, and washing and drying to prepare silk fibers; putting the silkworm cocoons into a heated alkaline solution to remove sericin, and repeating the process one or more times to prepare single silk fiber; the alkaline solution is Na2CO3A solution;
(6) soaking silk fibers in the reduced graphene oxide/chitosan dispersion liquid obtained in the step (4), and washing and drying to obtain graphene functionalized silk fibers; the soaking time of the silk fibers in the reduced graphene oxide/chitosan dispersion liquid is 1-10 seconds, the soaking times are 25-35 times, and the interval is 5-60 seconds every time.
2. The method of claim 1, wherein: in the step (1), the concentration of the acetic acid aqueous solution is 1-2 wt%, and the concentration of the chitosan in the dispersion liquid is 5-20 mg/mL.
3. The method of claim 1, wherein: in the step (2), the concentration of the graphene oxide aqueous solution is 1-2 mg/mL.
4. The method of claim 1, wherein: in the step (3), the mixing is performed by adding the graphene oxide aqueous solution to the chitosan dispersion solution while stirring.
5. The method of claim 4, wherein: in the step (3), the stirring time is 1-2 h.
6. The method of claim 1, wherein: in the step (4), the reaction is carried out with stirring; the mass ratio of the ascorbic acid to the graphene oxide is 20: 1-5: 1, and the stirring time is 24-36 h.
7. The method of claim 1, wherein: in the step (5), Na2CO3The concentration of the solution is 0.1-1 wt%, the temperature is 90-100 ℃, the reaction time of placing the solution into the silkworm cocoons is 15-45 minutes, and the reaction is repeated after the reaction to obtain single silk fibers; the washing method comprises the steps of soaking in deionized water for 5-30 minutes, and repeating for a plurality of times; the drying process is drying for 12-24 hours in a natural environment.
8. The method of claim 1, wherein: in the step (6), the silk fiber is soaked in the reduced graphene oxide/chitosan dispersion liquid for 2-5 seconds.
9. The method of claim 1, wherein: in the step (6), the drying process is carried out for 12-24 hours in a natural environment.
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