CN110747551A - Hydrogel fiber of artificial spider silk and preparation method thereof - Google Patents
Hydrogel fiber of artificial spider silk and preparation method thereof Download PDFInfo
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- CN110747551A CN110747551A CN201911060113.XA CN201911060113A CN110747551A CN 110747551 A CN110747551 A CN 110747551A CN 201911060113 A CN201911060113 A CN 201911060113A CN 110747551 A CN110747551 A CN 110747551A
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/26—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre with characteristics dependent on the amount or direction of twist
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
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Abstract
A hydrogel fiber of artificial spider silk and its preparation method are provided. The artificial spider silk is generated by polymerizing acrylic acid and silica nanoparticles to form hydrogel fibers and then inducing fiber self-assembly through water evaporation. The artificial spider silk is composed of hydrogel fibers with a core-shell structure, and the mechanical property of the artificial spider silk can be enhanced through ion doping and twisting. The tensile strength of the fiber is 895MPa, the stretchability is 44.3%, and the mechanical properties equivalent to those of spider silk can be realized.The material also has 370MJ m‑3High toughness and 95% damping capacity. When used for cushioning, the hydrogel fibers showed only 1/9 for the cotton yarn impact force, and the rebound was negligible. The work opens up a way for the preparation of the artificial spider silk, and the artificial spider silk can be applied to the fields of kinetic energy buffering and shock absorption.
Description
Technical Field
The invention belongs to the field of bionics, and particularly relates to a hydrogel fiber of artificial spider silk and a preparation method thereof.
Background
Spider silk is a natural hydrogel fiber with a specific combination of properties, namely high strength, high elongation and high damping capacity, with higher toughness compared to other fiber materials. Previous studies have shown that spider silks have a core-shell structure, the core being an elastic core surrounded by a plastic outer layer, which is the key component providing mechanical properties to the silk thread, while the outer layer provides some protection against the effects of the external environment. The novel fiber material is designed by simulating the structural characteristics of spider silks, is applied to the fields of shock absorption, energy absorption and the like, such as high-rise escape ropes, life saving nets and the like, and has important significance in actual life.
Currently, some work has been done in reproducing the superior mechanical properties of spider silk using artificial fibers. The CNT composite fiber made of CNT and silk protein shows a breaking strength of 600MPa, a breaking strain of 73% and a toughness of 290MJ m-3. The supermolecule hydrogel fiber shows 193MPa of breaking strength, 18 percent of breaking strain and 22.8MJ m of toughness-3. Rayon fibers based on regenerated silk protein are the most widely studied, achieving excellent mechanical properties (breaking strength 1.34GPa, breaking strain 36% and tenacity 334MJ m-3). Although these regenerated silk protein-based fibers have the mechanical properties of natural spider silk, the use of non-protein methods to make artificial spider silk remains very difficult, which greatly limits the large-scale use of artificial spider silk in real-life production applications. Therefore, there is a need for a method for producing an artificial spider silk having excellent mechanical properties by a non-protein method, in which the structure of a natural spider silk is accurately known and different structural models (amorphous regions crosslinked with crystallites, helical nanofibers, and core-shell structures) are combined.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a hydrogel fiber of artificial spider silk and a preparation method thereof aiming at the limitations in the prior art and the use requirements in special application scenes.
The technical scheme of the invention is as follows:
the hydrogel fiber of the artificial spider silk is hydrogel fiber formed by polymerization of acrylic acid and silica nano particles, and is prepared into the artificial spider silk fiber with a core-shell structure by self-assembly of polypropylene acrylic acid hydrogel controlled by water evaporation based on the core-shell structure of natural spider silk. The method comprises the characteristics of ion doping, twisting and core-shell structure; the core-shell structure consists of a transparent core and an opaque shell, the core and the shell of the fiber both consist of the same polymer (acrylic and silica nanoparticles) from a materials point of view, the shell has a lower water content than the core, the core decreases gradually as the time the fiber is exposed to air increases, and the shell increases gradually.
The fibers contain hydrogen bonds and covalent networks, the key mechanism of which is the difference between the water evaporation rates of the fiber core and the fiber shell. The hydrogel is composed of polyacrylic acid crosslinked with vinyl functionalized silica nanoparticles (VSNPs). Fibers were made from the above hydrogels by a drawing process using a wooden stick and were reinforced by adding ions to the hydrogel (called ion doping) and inserting twists into the fibers.
The fiber had a tensile strength of 895MPa, a stretchability of 44.3%, a modulus of 28.7GPa, 370MJm-3High toughness and 95% damping capacity, showing mechanical properties comparable to natural spider silk.
A hydrogel fiber of artificial spider silk and a preparation method thereof comprise the following steps:
step 1: 20mM vinyltriethoxysilane is added into 30g water and stirred for 12h until the oily droplets disappear and become a transparent vinylsilane solution;
step 2: diluting the vinylsilane solution prepared in the step 1 to obtain a solution with the mass concentration of 0.1-0.5%;
and step 3: 0.16M acrylic acid and 18ml diluted vinyl silane solution are taken to be evenly stirred, and metal ions (Zn) are added2+，Mg2+，Na+，K+The concentration of metal ions is 0.02M; ) AddingInitiator ammonium persulfate 0.01mM is added, and N is added2Removing dissolved oxygen, and performing oil bath at 40 ℃ for 30h to obtain transparent hydrogel;
and 4, step 4: dipping a wooden stick with the diameter of about 0.2mm into the hydrogel prepared in the step 3, and drawing at the drawing speed of 4cm s-1(ii) a According to the depth of the wood stick inserted into the gel, the fiber with the diameter of 10-500 microns can be obtained;
and 5: fixing two ends of the silk pulled out in the step 4 on an iron frame, exposing the silk in the air, and shaping by water evaporation, wherein the shaping time is 20-350s, and when the inelastic shell and the elastic core reach mechanical balance, the length of the fiber is not changed, so that the hydrogel fiber of the artificial spider silk is obtained;
step 6: twisting the fiber, and enhancing the mechanical property due to the flattening of the fiber and the increase of shell layers;
and 7: the fiber is dried for different time, the core layer part is gradually reduced due to the evaporation of water, the shell layer thickness is increased, and the mechanical property is enhanced.
Specifically, the twisting density is 1-7 turn/mm.
Specifically, the drying time of the fiber is 0-2 h.
The invention has the advantages and beneficial effects that:
1. the artificial spider silk prepared by the invention is a novel artificial spider silk with a core-shell structure, and is also an artificial spider silk suitable for special application scenes.
2. The invention utilizes the difference between the water evaporation rates of the hydrogel fiber core and the fiber shell to form a core-shell structure, and the mechanical property is enhanced along with the prolonging of the time of the fiber exposed in the air.
3. According to the invention, metal ions are introduced into hydrogel fibers, and the mechanical property is enhanced by increasing the crosslinking among polymer chains.
4. The hydrogel fiber is twisted, and in the twisting process, the fiber is flattened, the shell is increased, and the mechanical property is increased.
Drawings
FIG. 1 is a laser confocal picture of the artificial spider silk fiber of the invention at different drying times.
FIG. 2 is a graph of the mechanical properties of the artificial spider silk fiber of the present invention at different vinylsilane contents.
FIG. 3 is a diagram of the mechanical properties of the artificial spider silk fiber of the present invention at 0.1% vinylsilane content and different metal ions (0.02M).
FIG. 4 is a metallographic microscope image of different twisting densities of the artificial spider silk fiber of the present invention.
FIG. 5 is an element map of a cross section of an artificial spider silk fiber of the present invention.
FIG. 6 is a graph showing the results of mechanical property tests of the artificial spider silk fiber according to the present invention, wherein a is a stress-strain graph and b is a graph showing Young's modulus and toughness.
FIG. 7 is a graph of the results of an energy dissipation test of an artificial spider silk fiber according to the present invention.
FIG. 8 is a graph showing the results of the shock absorbing ability test of the artificial spider silk fiber according to the present invention.
FIG. 9 is a schematic diagram showing the recovery of the artificial spider silk fiber from deformation under a humidity of 60% according to the present invention.
Detailed Description
Example 1:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to the accompanying drawings.
The preparation method of the artificial spider silk hydrogel fiber comprises the following steps:
step 1: 20mM vinyl triethoxysilane is added into 30g water and stirred for 12h until the oily droplets disappear and become a transparent vinyl silane solution;
step 2: diluting the vinylsilane solution prepared in the step 1 to different concentrations; specifically, 101.2, 202.4, 253, 303.6, 404.8. mu.l of the extract was taken in 100ml of H2Stirring in O for 30 min; obtaining 0.1%, 0.2%, 0.25%, 0.3%, 0.4% vinyl silane solution;
and step 3: respectively stirring 0.16M acrylic acid and 18ml of the vinyl silane solution obtained in the step 2 for 30min, and adding an initiator ammonium persulfate of 0.1mMIntroduction of N2Removing dissolved oxygen, and performing oil bath at 40 ℃ for 30h to obtain transparent hydrogel;
and 4, step 4: dipping a wooden stick with a diameter of about 0.2mm into the hydrogel prepared in step 3 for 0.5mm in 4cm s-1Drawing at a rate of (2) to obtain fibers having a diameter of 20 microns;
and 5: fixing two ends of the wire drawn out in the step 4 on an iron frame, exposing the wire in the air, and shaping the wire for 20s through water evaporation, wherein when the inelastic shell and the elastic core reach mechanical balance, the length of the fiber is unchanged;
the artificial spider silk fiber formed by self-assembly of polyacrylic acid hydrogel controlled by water evaporation has an obvious core-shell structure, wherein the core of the fiber is elastic, stretchable and transparent; the fibrous shell is inelastic, non-stretchable, and opaque. The structure is caused by the difference of water evaporation rate between the core and the shell of the fiber, as the drying time of the fiber in the air is increased, part of water molecules are desorbed, the core is converted into the shell, and the mechanical property of the shell is higher than that of the core, so that the mechanical property of the whole fiber is improved. As shown in fig. 1, the time of exposure of the fiber to air was 0, 0.5, 1.0, 2.0 hours, respectively, and the thickness of the core was gradually decreased and the thickness of the shell was gradually increased.
The artificial spider silk fiber obtained in this example was tested as follows:
mechanical Properties testing hydrogel fibers 20 μm in diameter containing 0.1% -0.4% VSNP were subjected to a tensile test at an air humidity of 40% (tensile rate of 27.8% s)-1) As shown in FIG. 2, the artificial spider silk fiber obtained in this example had a tensile strength of 127MPa and a stretchability of 73% in a content of 0.1% VSNP.
Example 2:
the preparation method of the artificial spider silk hydrogel fiber comprises the following steps:
step 1: 20mM vinyl triethoxysilane is added into 30g water and stirred for 12h until the oily droplets disappear and become a transparent vinyl silane solution;
step 2: mixing the vinylsilane solution prepared in the step 1Diluting to different concentrations; specifically, take 101.2 microliters in 100ml H2Stirring in O for 30 min; obtaining 0.1 percent vinyl silane solution;
and step 3: respectively stirring 0.16M acrylic acid and 18ml of the 0.1% vinylsilane solution obtained in the step 2 for 30min, and respectively adding metal ions Zn2+，Mg2+，Na+，K+0.02M, initiator ammonium persulfate 0.1mM was added and N was added2Removing dissolved oxygen, and performing oil bath at 40 ℃ for 30h to obtain transparent hydrogel;
and 4, step 4: dipping a wooden stick with a diameter of about 0.2mm into the hydrogel prepared in step 3 for 0.5mm in 4cm s-1Drawing at a rate of (2) to obtain fibers having a diameter of 20 microns;
and 5: fixing two ends of the wire drawn out in the step 4 on an iron frame, exposing the wire in the air, and shaping the wire for 20s through water evaporation, wherein when the inelastic shell and the elastic core reach mechanical balance, the length of the fiber is unchanged;
will contain 0.1% VSNP, Zn2+Elemental mapping analysis of the cross section of a hydrogel fiber with a concentration of 0.02M and a diameter of 20 microns revealed Zn2+Uniformly distributed in the fiber, as shown in fig. 3, the metal ions introduced into the hydrogel fiber can increase the degree of crosslinking of the polymer chains, thereby enhancing the mechanical properties.
The artificial spider silk fiber obtained in this example was tested as follows:
mechanical property test, 20 microns in diameter, 0.1 wt% of VSNP and different metal ions Zn2+，Mg2+，Na+，K+0.02M hydrogel fiber was subjected to a tensile test at 40% air humidity (tensile rate of 1.1% s)-1) When Zn, as shown in FIG. 42+At a concentration of 0.02M, it had a tensile strength of 261MPa and a stretchability of 49.2%.
Example 3:
the preparation method of the artificial spider silk hydrogel fiber comprises the following steps:
step 1: 20mM vinyl triethoxysilane is added into 30g water and stirred for 12h until the oily droplets disappear and become a transparent vinyl silane solution;
step 2: diluting the vinylsilane solution prepared in the step 1 to different concentrations; specifically, take 101.2 microliters in 100ml H2Stirring in O for 30 min; obtaining 0.1 percent vinyl silane solution;
and step 3: respectively stirring 0.16M acrylic acid and 18ml of the 0.1% vinylsilane solution obtained in step 2 for 30min, and adding metal ions Zn2+0.02M, 0.1mM ammonium persulfate as initiator was added, and N was added2Removing dissolved oxygen, and performing oil bath at 40 ℃ for 30h to obtain transparent hydrogel;
and 4, step 4: dipping a wooden stick with a diameter of about 0.2mm into the hydrogel prepared in step 3 for 0.5mm in 4cm s-1Drawing at a rate of (2) to obtain fibers having a diameter of 20 microns;
and 5: fixing two ends of the wire drawn out in the step 4 on an iron frame, exposing the wire in the air, and shaping the wire for 30s through water evaporation, wherein when the inelastic shell and the elastic core reach mechanical balance, the length of the fiber is unchanged;
step 6: fixing one end of the hydrogel fiber obtained in the step (5) on a motor, hanging a small weight on the other end of the hydrogel fiber, and twisting;
as shown in FIG. 5, hydrogel fibers having a diameter of 20 μm were twisted at a twist density of 1, 3, 5, and 7turn/mm in this order, the fibers were flattened, and the inner core became opaque, the fibers became more shell-like, and the mechanical properties were improved.
The artificial spider silk fiber obtained in this example was tested as follows:
1. mechanical property test, 20 microns in diameter, 0.1 wt% VSNP, 0.02M Zn2+Hydrogel fibers having a twist density of 7turn/mm were subjected to a tensile test at an air humidity of 40% -100% (tensile rate of 27.8% s)-1) As shown in FIG. 6, a and b, the artificial spider silk fiber obtained in the present example had a tensile strength of 895MPa, a stretchability of 44.3%, and a modulus of 28.7GPa, and exhibited mechanical properties comparable to those of natural spider silk.
2. Energy dissipation Performance test 20 micron diameter, 0.1 wt% VSNP, 0.02M Zn2+Hydrogel fibers with a twisting density of 3turn/mm were subjected to a progressive stretch-release cycle at an air humidity of 40%, as shown in FIG. 7, and the artificial spider silk fibers obtained in this example had a damping capacity of 95% and 245MJ m-3Energy dissipation of.
3. The shock absorption performance test is carried out by attaching a 20g weight to the bottom end of 100 hydrogel fibers with the diameter of 20 micrometers, allowing the weight to fall freely for 15 centimeters under the humidity of 60%, and as shown in FIG. 8, the artificial spider silk fibers obtained in the example have the elongation of 150%, have negligible rebound, have the impact force of 0.36N, and are 8 times smaller than cotton threads at the same falling height. The hydrogel fibers used in this test contained 0.1 wt% VSNP, 0.02M Zn2+And the twisting density was 3 turn/mm.
4. Deformation recovery test, namely weaving hydrogel fibers with the diameter of 20 micrometers into a net, fixing the net on an iron ring, placing the net in an environment with the humidity of 60%, placing a 200g weight on the hydrogel net, deforming the net, taking off the weight, and recovering the deformation of the gel network, as shown in fig. 9. The hydrogel fibers used in this test contained 0.1 wt% VSNP, 0.02M Zn2+And the twisting density was 3 turn/mm.
In addition, other changes, such as modifications, equivalents and improvements, which may occur to persons skilled in the art according to the technical solutions of the present invention, are also included in the scope of the present invention.
Claims (9)
1. The hydrogel fiber of the artificial spider silk is characterized in that the fiber is a hydrogel fiber formed by polymerizing acrylic acid and silicon dioxide nano particles, and then the fiber is prepared into the artificial spider silk fiber with a core-shell structure through self-assembly of polyacrylic acid hydrogel controlled by water evaporation, and the fiber has the characteristics of ion doping, twisting and core-shell structure; the core-shell structure consists of a transparent core and an opaque shell, from the material point of view, the core and the shell of the fiber both consist of the same polymer acrylic acid and silica nanoparticles, the shell has less water content compared with the core, the core gradually decreases and the shell gradually increases in thickness as the fiber is exposed to air for a longer time.
2. The hydrogel fiber of claim 1, wherein the core on the core-shell structure is elastic, stretchable; the shell is non-elastic.
3. The hydrogel fiber of claim 1, wherein the twisting is a process of fixing one end of the fiber on a motor and hanging a small weight on the other end to twist the fiber, and the fiber is flattened by twisting, and the inner core becomes opaque; the twisting density is 1-7 turn/mm.
4. A method of making hydrogel fibres of an artificial spider silk according to claim 1, comprising the steps of:
step 1: 20mM vinyl triethoxysilane is added into 30g water and stirred for 12h until the oily droplets disappear and become a transparent vinyl silane solution;
step 2: diluting the vinyl silane solution prepared in the step 1 to a mass concentration of 0.1-0.5%;
and step 3: taking 0.16M acrylic acid and 18ml of vinyl silane solution diluted in the step 2, stirring uniformly, adding metal ions, adding an initiator ammonium persulfate of 0.1mM, and introducing N2Removing dissolved oxygen, and performing oil bath at 40 ℃ for 30h to obtain transparent hydrogel;
and 4, step 4: dipping a wooden stick with the diameter of 0.2mm into the hydrogel prepared in the step 3, and drawing wires;
and 5: and (4) fixing the two ends of the silk pulled out in the step (4), exposing the silk in the air, and shaping by water evaporation, wherein when the inelastic shell and the elastic core reach mechanical balance, the length of the fiber is unchanged, and the hydrogel fiber of the artificial spider silk is obtained.
5. The method for producing a hydrogel fiber according to claim 4, wherein the metal ion is Zn2+、Mg2+、Na+Or K+The concentration used was 0.02M.
6. The method for preparing hydrogel fiber according to claim 4, wherein the 0.2mm stick drawing rate is 4cm s-1。
7. The method for preparing hydrogel fibers according to claim 4, wherein the wood stick is inserted into the hydrogel to be drawn, and fibers having a diameter of 10 to 500 μm can be obtained according to the depth of insertion into the gel.
8. The method of claim 4, wherein the setting time of the fiber is 20 to 350 seconds.
9. The method for producing a hydrogel fiber according to any one of claims 4 to 8, further comprising:
step 6: twisting the fiber with twisting density of 1-7turn/mm to enhance mechanical performance due to fiber flattening and shell increase;
and 7: drying the fiber for 0-2h, wherein the core layer is gradually reduced due to the evaporation of water, the shell layer is increased in thickness, and the mechanical property is enhanced.
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| CN113089131A (en) * | 2021-04-07 | 2021-07-09 | 大连工业大学 | Preparation method of inorganic nanoparticle dynamic cross-linking double-network modified natural polymer material |
| CN113089324A (en) * | 2021-04-15 | 2021-07-09 | 南开大学 | Preparation method of artificial spider silk based on double-network hydrogel |
| CN115354409A (en) * | 2022-08-30 | 2022-11-18 | 南开大学 | Preparation method of super-strong artificial spider silk based on nanogel |
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