CN103572395A - Strengthened toughened regenerated silk fibers and preparation method thereof - Google Patents
Strengthened toughened regenerated silk fibers and preparation method thereof Download PDFInfo
- Publication number
- CN103572395A CN103572395A CN201310566935.1A CN201310566935A CN103572395A CN 103572395 A CN103572395 A CN 103572395A CN 201310566935 A CN201310566935 A CN 201310566935A CN 103572395 A CN103572395 A CN 103572395A
- Authority
- CN
- China
- Prior art keywords
- solution
- regenerated silk
- aqueous solution
- graphene oxide
- fibroin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to strengthened toughened regenerated silk fibers and a preparation method thereof. The preparation method comprises the following steps of 1, degumming silkworm cocoons, and dissolving the degummed silkworm cocoons to obtain a regenerated silk fibroin aqueous solution, 2, blending a graphene oxide aqueous solution subjected to ultrasonic treatment and the regenerated silk fibroin aqueous solution according to a certain ratio, 3, adding metal-oxide hydrosol into the mixture according to a certain ratio, 4, adding a CaCl2 solution into the mixture obtained by the step 3 to adjust a calcium ion molar concentration to 0.15-0.3mol/L, and sequentially carrying out concentration, 5, carrying out dry spinning on the concentrated solution as a spinning liquid at a room temperature, and 6, after-treating the composite fibers by an ethanol-water solution. The preparation method has simple processes and utilizes the raw materials having wide sources. The treated composite fibers have good strength and good toughness and have breaking strength of 70-380MPa, breaking elongation of 20-150% and breaking energy of 30-100J/g.
Description
Technical field
The invention belongs to silk fiber field, relate to toughness reinforcing regenerated silk fiber of a kind of enhancing and preparation method thereof, particularly relate to and a kind ofly based on graphene oxide/fibroin albumen compound system, add the 3rd component to strengthen the preparation method of toughness reinforcing regenerated silk fiber, wherein the 3rd component is mainly metal oxide nanoparticles.
Background technology
Spider silk and silk are watched by the world because of the performance of its many excellence, and especially the traction fiber in spider silk is one of the most tough fiber of occurring in nature up to now.But because spider has cannibalistic nature, and make spider silk not obtain commercial applications widely.And silk is very far-reaching in the application of weaving, clothes, medicine, cosmetics, biotechnology field.
As everyone knows, spider silk is the fiber of a kind of high strength, high tenacity, and its fracture strength can reach 1GPa; Its elongation at break (35%) surpasses nylon and mild steel (approximately 25%), is one of the most tough material known to the mankind up to now.And animal silk how manually to prepare mechanical property excellence has become the study hotspot in new material, organizational project, biology, the field such as bionical at present.There are some researches show, by forcing spinning to improve the spinning speed of silk, can make the natural silk that mechanical property and spider silk match in excellence or beauty.Therefore, a kind of thinking of preparing artificial animal silk is exactly that employing source is abundant, fibroin albumen with low cost carries out bionical spinning at present.By take the fibroin albumen of silkworm, be model, imitate the spinning mode of spider and silkworm, and condensed state structure in spinning process is controlled, can prepare the regenerated silk fibroin fiber of mechanical property excellence.
In the last few years, many researchers were devoted to research and prepared artificial silk in the mode of electrostatic spinning or wet spinning, but with regard to spinning technique, the spinning mode of these spinning modes and spider and silkworm still makes a big difference.So in order to reach the object of bionical spinning, in succession there is again dry spinning and the microfluid dry spinning of regenerated silk fibroin.By the improvement to spinning process, and the post processing of fiber, the intensity of artificial silk and elongation at break have approached or have surpassed natural silk, but this still cannot compare with spider silk.So in order further to improve the mechanical property of fiber, also must consider other its strengthen toughness reinforcing means.
How on earth further improving intensity and the toughness of artificial animal silk, make it considerably beyond every mechanical property of natural silk, and compare favourably with spider silk, is the emphasis that numerous researchers are concerned about.Some attempt by add nano particle in regenerated silk solution, as the nano particle of Graphene, metal oxide etc., to prepare, strengthen toughness reinforcing regenerated fibroin fiber.Application number is that 201310125764.9 Chinese patents pass through silk fibroin protein solution, graphene solution and formic acid solution three blend, adopt the mode of electrostatic spinning to carry out spinning, prepare Graphene/silk Combined Electrostatic and spun fibrofelt, the fracture strength of this fibrofelt is 24.7MPa, and elongation at break is 3.6%.Application number is that 201210402478.8 Chinese patent has reported that they are by regenerated silk fibroin solution and the blend by a certain percentage of the metal oxide nanoparticles hydrosol, then in dry spinning mode, prepared and strengthened toughness reinforcing regenerated silk, its fracture strength is 50～250MPa, and elongation at break is 50%～150%.In 2013, the people such as Kesong Hu publish thesis at Advanced Materials, reported that they take graphene oxide as reinforcing material, adopt spin coating technique that finely dispersed graphene oxide solution and silk fibroin protein solution are alternately spin-coated in polystyrene substrate, prepared nano level fibroin albumen film, this film is through ethanol post processing, and its fracture strength can reach 300MPa, elongation at break is 1.0 ± 0.4%, and energy to failure is 2.2～2.4MJ/m
3.We know, graphene oxide is important a kind of in the derivative of Graphene, and its structure is similar to Graphene, just in two-dimentional basal plane Shang He edge, are connected with some oxygen-containing functional groups.These functional groups are mainly hydroxyl, epoxy radicals, carbonyl and carboxyl.Exist just these polar functional groups can make some polar molecules and polymer form nano composite material with graphene oxide.
The structure of fibroin is more more complicated than synthetic polymer, interaction between it and graphene oxide or metal nanoparticle is complicated more than the interaction of synthetic polymer and nano particle, so the mechanism of nano particle reinforced tenacity increased regenerated silk fiber can not be considered according to the theory of traditional nano particle reinforced tenacity increased synthesized polymer material completely.For example: between graphene oxide and silk fibroin molecular, exist complicated interaction, as hydrogen bond, covalent bond, affinity interaction etc., and these effects are cross-linked with each other into network, are conducive to form a kind of middle phase, and jointly fiber are played the effect of enhancing with graphene oxide in the middle of this.
When preparing the compound system of fibroin albumen/graphene oxide, the difficult problem conventionally running into is how to allow the dispersion that graphene oxide can be good in silk fibroin protein solution.In this system, in order to maintain the rock-steady structure of fibroin albumen in solution, need to add Ca
2+ion, but add Ca
2+after the aqueous solution blend of the silk fibroin protein solution of ion and graphene oxide, can there is serious reunion in graphene oxide, so this is cannot effectively prepare the main cause of fibroin albumen/graphene oxide compound system at present.Therefore in silk fibroin water solution, when add Ca
2+ion, graphene oxide and metal nanoparticle are one of keys of successfully preparing by the compound dry-spinning fiber of fibroin albumen/graphene oxide/metal nanoparticle.
Summary of the invention
The object of this invention is to provide toughness reinforcing regenerated silk fiber of a kind of enhancing and preparation method thereof, it is based on graphene oxide/fibroin albumen compound system, to add the method for the 3rd component modification regenerated silk fiber.In the present invention, on the basis at graphene oxide and regenerated silk fibroin solution blending, the preparation method of the toughness reinforcing regenerated silk fiber of preparation enhancing has further been proposed, in original graphene oxide/fibroin albumen compound system, add the 3rd component, be mainly metal oxide nanoparticles, improve the mechanical property of regenerated fibroin fiber, and can give composite fibre certain function, as antibiotic property, uviolresistance.What is more important, in this compound system, the dispersiveness of graphene oxide is also significantly improved, concrete is exactly by the graphene oxide aqueous dispersions preparing and regenerated silk fibroin solution blending, then add the metal oxide hydrosol, after mixing, add calcium chloride solution, regulate calcium ion concentration in blend solution, finally the spinning solution after concentrated is carried out to spinning in the mode of dry spinning, the spun filament obtaining is carried out post processing stretching in ethanol water, and its mechanical property is further improved.On the whole, the method is simple, and cost is low; Gained fiber has good mechanical property, and can have necessarily functional.
Toughness reinforcing regenerated silk fiber of a kind of enhancing of the present invention and preparation method thereof, step comprises:
(1) use Na
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution, after centrifugal, suction filtration, dialysis, obtains regenerated silk fibroin water solution, and then the mass percent that is concentrated into fibroin albumen is 10%～30%;
(2) graphite oxide aqueous solution is done to ultrasonic dispersion treatment, process 2～5min, then the ratio that is 1:500～10000 according to the mass ratio of graphene oxide and fibroin albumen, is joined in the aqueous solution of the regenerated silk fibroin obtaining after previous step concentrates, and is shaken up;
(3) ratio that is 1:1:500～10000 according to three's mass ratio of graphene oxide, metal oxide nanoparticles and fibroin albumen adds the metal oxide hydrosol again, and shakes up;
(4) add calcium chloride water, in regulator solution, calcium ion molar concentration is 0.15～0.3mol/L;
(5) continue to concentrate fibroin albumen/graphene oxide/metal oxide nanoparticles high concentration blend aqueous solution that the mass percent that obtains fibroin albumen is 48%～58%;
(6) described spinning solution is at room temperature carried out to dry spinning, after extruding from spinning nozzle, draw to take up roll, by the solvent in air evaporation fiber, finally obtain the as-spun fibre of composite fibre;
(7), for artificial animal silk, post processing is the effective way that further improves fibrous mechanical property.In the method, regenerated silk fiber is carried out to post processing, not only can promote the secondary structure of silk fibroin molecular to change, and nano particle is wherein disperseed can play a role again.By more different treatment systems, find to using that the aqueous solution of ethanol is better as post-treatment agent effect, and environmentally friendly, so composite fibre is immersed, drawn, fixed length were soaked after a period of time, took out, and had obtained the described toughness reinforcing regenerated silk fiber of a kind of enhancing.
As preferred technical scheme:
Toughness reinforcing regenerated silk fiber of a kind of enhancing as above and preparation method thereof, in step (1), described Na
2cO
3the mass percent of the aqueous solution is 0.5%～1%; The molar concentration of the described LiBr aqueous solution is 9.0 ± 0.5mol/L.
A kind of preparation method who strengthens toughness reinforcing regenerated silk fiber as above, in step (1), described centrifugal referring to 1.5 times of the silk fibroin protein solution dilutions after dissolving, utilize supercentrifuge to carry out centrifugal, rotating speed is made as to 3500r/min, and the time is 10min, and temperature is 18 ℃; Described dialysis is that the silk fibroin solution after suction filtration is placed in to cellulose bag filter, after sealing, is immersed in deionized water and dialyses, and temperature is at 6～12 ℃, and dialysis time is 72h, and exchange water cycle is 3～4 hours.After dialysis, the salt ion in silk fibroin protein solution can and be removed; Described concentrating is at 6～12 ℃, utilizes wind speed method to concentrate silk fibroin water solution, until its mass percent is 10%～30%.Silk fibroin protein solution is carried out before blend to pre-concentration, mainly because add graphene oxide and metal oxide nanoparticles when fibroin albumen quality mark is too low or too high, mixing between the hydrosol that can be unfavorable for graphite oxide aqueous solution, metal oxide nanoparticles and silk fibroin protein solution, thus cause between solution mixed effect bad.By great many of experiments, we find, when the mass percent of fibroin albumen is 10%～30%, to add graphene oxide and metal oxide nanoparticles, and the effect of mixing is better.
A kind of preparation method who strengthens toughness reinforcing regenerated silk fiber as above, in step (2), described graphene oxide concentration of aqueous solution is 0.5～3mg/mL; In step (3), in the described metal oxide nano hydrosol, the mass percent of metal oxide nanoparticles is 10%～50%.
A kind of preparation method who strengthens toughness reinforcing regenerated silk fiber as above, the metal oxide in the described metal oxide hydrosol is TiO
2, Fe
3o
4, ZnO, Al
2o
3or ZrO
2one or more, and the nano particle diameter in the described metal oxide hydrosol is 10～100nm.
A kind of preparation method who strengthens toughness reinforcing regenerated silk fiber as above, in step (4), in described calcium chloride water, the molar concentration of calcium chloride is 1.5～3.0mol/L, metal Ca wherein
2+the effect of ion is to maintain the rock-steady structure of fibroin albumen in solution, and regulates and controls Ca
2+in mixing, concentration is within the scope of 0.15～0.3mol/L; In step (5), described concentrated referring at 6～12 ℃ of temperature, utilizes wind speed method to concentrate mixed solution, until the mass percent of fibroin albumen is 48%～58% in mixed solution.Mixed solution is in concentration process, continuous rising along with fibroin albumen concentration, the stability of solution can decline, easily there is gelation or rotten, so in order to make spinning solution that gelation or rotten does not occur as far as possible, have good spinnability, we are controlled at 48%～58% by the concentration of fibroin albumen in spinning solution simultaneously.
A kind of preparation method who strengthens toughness reinforcing regenerated silk fiber as above, the winding speed of described curing coiling is 0.02～0.1m/s.
A kind of preparation method who strengthens toughness reinforcing regenerated silk fiber as above, described ethanol water, the volume fraction of ethanol is 70%～85%; The multiple of described stretching is 2～5 times, and the time that described fixed length is soaked is 1～8 hour.
The toughness reinforcing regenerated silk fiber of a kind of enhancing making by above-mentioned preparation method, its fracture strength is 0.05～0.38GPa, and elongation at break is 20%～150%, and energy to failure is 30～100J/g; The described toughness reinforcing regenerated silk fiber of a kind of enhancing is in regenerated silk fiber, to be dispersed with graphene oxide and metal oxide nanoparticles, the mass percent of graphene oxide in fiber is 0.05%～0.1%, and the mass percent of metal oxide nanoparticles in fiber is 0.05%～0.5%.
In the present invention, it should be noted that especially graphene oxide solution, the metal oxide nanoparticles hydrosol and calcium chloride water three's addition sequence, cannot put upside down, because found through experiments, if first add calcium chloride water, can make graphene oxide in mixed solution reunite in concentration process, thereby make the dispersion effect variation of graphene oxide in mixed solution.Primary Study reason wherein may be Ca
2+between ion and silk fibroin molecular, chelation has occurred, and this effect is more eager to excel in whatever one does than the interaction between graphene oxide and silk fibroin molecular, thereby has hindered the interaction between graphene oxide and silk fibroin molecular.In addition, Ca
2+after ion is combined with silk fibroin molecular, can make the binding site of graphene oxide and silk fibroin molecular reduce, in conjunction with above two kinds of reasons, make graphene oxide in the dispersed variation of mixed solution.If but before silk fibroin water solution adds calcium chloride water, first add graphite oxide aqueous solution, so in mixed solution the dispersiveness of graphene oxide be just significantly improved.This is perhaps because carboxyl, hydroxyl Deng Han oxygen group and the silk fibroin molecular of graphene oxide surface and edge are had an effect and form hydrogen bond, and occupied the most binding site of silk fibroin molecular, thereby graphene oxide dispersiveness is improved.
Abundant oxy radical is contained on the surface of graphene oxide, can form and interact with amphiphatic silk fibroin molecular, this interaction is very complicated, may comprise hydrogen bond, polar bond, coordination etc., and these interactions are intertwined to form network, be conducive to form boundary layer between fibroin albumen and graphene oxide, i.e. third phase, thus can play the effect of enhancing.On the other hand, silk fibroin molecular also can and metal oxide nanoparticles between have an effect, this effect is equally also very complicated, we think silk fibroin molecular can with metal oxide nanoparticles surface non-matching atom generation chelation, produce the firm bonding interface that obtains, this interface has been played and has been strengthened toughness reinforcing effect.But the final performance of nano composite material not only with want the interfacial structure of particulate and matrix relevant, also relevant with factors such as structure, aggregated structure and its synergisticing performance of nanoparticle, the structure of matrix, processing technologys.
The present invention adds the nano particle of two kinds in silk fibroin protein solution to simultaneously, to regenerated silk fiber, carries out composite modified.Can utilize variety classes nano particle in the synergy of fiber on the one hand, to reach, strengthen toughness reinforcing object, on the other hand, due to some nano particles, as nano-TiO
2, ZnO both had antibiotic characteristic, had again the function to ultraviolet screener, therefore can give composite fibre certain function.
Research shows, from the spinning mechanism of spider and silkworm, metallic element has very important effect to the performance of the moulding of animal silk and fiber.Therefore the people such as Lee is penetrated into Ti, Al metallic element in natural spider silk with the form of oxide by multiple-pulse vapor infiltration method (MPI), and is connected with spider silk fibroin molecule with covalent bond, and result can make the mechanical property of spider silk significantly improve.In addition, post processing is the effective way of the fiber reinforced enhancing modification of RSF, so in order further to improve the mechanical property of nanometer particle-modified rear regenerated silk fiber, the as-spun fibre of the present invention after to modification stretches, fixed length, the post processing of soaking in ethanol water, finally prepared a kind of regenerated silk fiber of mechanical property excellence.
The present invention adopts the dry spinning method that bionical degree is higher, take water as solvent, normal temperature, and normal pressure directly becomes silk in air, and very similar with the spinning technique of spider and silkworm, environmental protection, has a extensive future.
Beneficial effect:
The toughness reinforcing regenerated silk fiber of a kind of enhancing that the present invention is prepared, is the performance such as utilized the intensity of graphene oxide and metal oxide nanoparticles large, modulus is high, and regenerated silk fiber is strengthened toughness reinforcing by the synergy between two constituent elements.Strengthen the regenerated silk fiber after toughness reinforcing, all regenerated silk fibers before its fracture strength, elongation at break superorder far away.This method preparation technology is simple, is easy to promotion and application.The fiber of preparing according to the present invention, its fracture strength is 70～380MPa, and elongation at break is 20%～150%, and energy to failure is 30～100J/g, to preparing high-performance animal silk, provides a kind of new method.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
The Na that is 0.5% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.0mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 6 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 6 ℃ of temperature, utilize wind speed method, it is 10% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 3mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:500 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add TiO
2mass fraction is 30%, the nano-TiO that particle diameter is 20nm
2the hydrosol also shakes up, and makes graphene oxide in mixed solution, TiO
2three's mass ratio of nano particle and fibroin albumen is 1:1:500.The calcium chloride water that interpolation molar concentration is 1.5mol/L, in regulator solution, calcium ion molar concentration is 0.15mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 48%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.02m/s, obtains graphene oxide/titanium dioxide fibroin albumen composite fibre.
It is in 80% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 2 times, and fixed length is soaked 8 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 82MPa, and elongation at break is 120%, and energy to failure is 60J/g.
Embodiment 2
The Na that is 1.0% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.0mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 8 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 8 ℃ of temperature, utilize wind speed method, it is 20% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 3mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:1000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add TiO
2mass fraction is 10%, the nano-TiO that particle diameter is 100nm
2the hydrosol also shakes up, and makes graphene oxide in mixed solution, TiO
2three's mass ratio of nano particle and fibroin albumen is 1:1:1000.The calcium chloride water that interpolation molar concentration is 3.0mol/L, in regulator solution, calcium ion molar concentration is 0.3mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 53%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.1m/s, obtains graphene oxide/titanium dioxide/fibroin albumen composite fibre.
It is in 85% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 3 times, and fixed length is soaked 3 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 250MPa, and elongation at break is 65%, and energy to failure is 51J/g.
Embodiment 3
The Na that is 1.0% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.5mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 12 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 12 ℃ of temperature, utilize wind speed method, it is 20% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 3mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:10000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add TiO
2mass fraction is 50%, the nano-TiO that particle diameter is 10nm
2the hydrosol also shakes up, and makes graphene oxide in mixed solution, TiO
2three's mass ratio of nano particle and fibroin albumen is 1:1:10000.The calcium chloride water that interpolation molar concentration is 3.0mol/L, in regulator solution, calcium ion molar concentration is 0.3mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 58%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.08m/s, obtains graphene oxide/titanium dioxide/fibroin albumen composite fibre.
It is in 75% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 4 times, and fixed length is soaked 3 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 320MPa, and elongation at break is 70%, and energy to failure is 68J/g.
Embodiment 4
The Na that is 1.0% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.0mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 8 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 8 ℃ of temperature, utilize wind speed method, it is 10% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 0.5mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:10000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add Al
2o
3mass fraction is 10%, the nanometer Al that particle diameter is 100nm
2o
3the hydrosol also shakes up, and makes graphene oxide in mixed solution, Al
2o
3three's mass ratio of nano particle and fibroin albumen is 1:1:10000.The calcium chloride water that interpolation molar concentration is 1.5mol/L, in regulator solution, calcium ion molar concentration is 0.15mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 55%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.02m/s, obtains graphene oxide/Al
2o
3/ fibroin albumen composite fibre.
It is in 80% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 2 times, and fixed length is soaked 4 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 110MPa, and elongation at break is 70%, and energy to failure is 25J/g.
Embodiment 5
The Na that is 0.5% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 8.5mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 9 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 9 ℃ of temperature, utilize wind speed method, it is 20% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 0.5mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:1000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add Al
2o
3mass fraction is 20%, the nanometer Al that particle diameter is 30nm
2o
3the hydrosol also shakes up, and makes graphene oxide in mixed solution, Al
2o
3three's mass ratio of nano particle and fibroin albumen is 1:1:1000.The calcium chloride water that interpolation molar concentration is 2.0mol/L, in regulator solution, calcium ion molar concentration is 0.2mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 55%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.05m/s, obtains graphene oxide/Al
2o
3/ fibroin albumen composite fibre.
It is in 80% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 5 times, and fixed length is soaked 8 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 240MPa, and elongation at break is 60%, and energy to failure is 55J/g.
Embodiment 6
The Na that is 1.0% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.0mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 9 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 9 ℃ of temperature, utilize wind speed method, it is 30% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 0.5mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:500 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add Al
2o
3mass fraction is 50%, the nanometer Al that particle diameter is 10nm
2o
3the hydrosol also shakes up, and makes graphene oxide in mixed solution, Al
2o
3three's mass ratio of nano particle and fibroin albumen is 1:1:500.The calcium chloride water that interpolation molar concentration is 3.0mol/L, in regulator solution, calcium ion molar concentration is 0.3mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 54%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.05m/s, obtains graphene oxide/Al
2o
3fibroin albumen composite fibre.
It is in 85% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 2.5 times, and fixed length is soaked 8 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 81MPa, and elongation at break is 100%, and energy to failure is 37J/g.
Embodiment 7
The Na that is 1.0% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.5mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 10 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 10 ℃ of temperature, utilize wind speed method, it is 30% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 0.5mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:500 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add Fe
3o
4mass fraction is 50%, the nanometer Fe that particle diameter is 10nm
3o
4the hydrosol also shakes up, and makes graphene oxide in mixed solution, Fe
3o
4three's mass ratio of nano particle and fibroin albumen is 1:1:500.The calcium chloride water that interpolation molar concentration is 1.5mol/L, in regulator solution, calcium ion molar concentration is 0.15mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 52%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.08m/s, obtains graphene oxide/Fe
3o
4/ fibroin albumen composite fibre.
It is in 85% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 4 times, and fixed length is soaked 1 hour, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 200MPa, and elongation at break is 95%, and energy to failure is 51J/g.
Embodiment 8
The Na that is 1.0% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.5mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 12 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 12 ℃ of temperature, utilize wind speed method, it is 20% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 0.5mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:2000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add Fe
3o
4mass fraction is 20%, the nanometer Fe that particle diameter is 20nm
3o
4the hydrosol also shakes up, and makes graphene oxide in mixed solution, Fe
3o
4three's mass ratio of nano particle and fibroin albumen is 1:1:2000.The calcium chloride water that interpolation molar concentration is 2.0mol/L, in regulator solution, calcium ion molar concentration is 0.2mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 52%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.08m/s, obtains graphene oxide/Fe3O4/ fibroin albumen composite fibre.
It is in 80% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 2 times, and fixed length is soaked 8 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 102MPa, and elongation at break is 120%, and energy to failure is 40J/g.
Embodiment 9
The Na that is 1.0% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.5mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 12 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 12 ℃ of temperature, utilize wind speed method, it is 10% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 0.5mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:10000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add Fe
3o
4mass fraction is 10%, the nanometer Fe that particle diameter is 100nm
3o
4the hydrosol also shakes up, and makes graphene oxide in mixed solution, Fe
3o
4three's mass ratio of nano particle and fibroin albumen is 1:1:10000.The calcium chloride water that interpolation molar concentration is 3.0mol/L, in regulator solution, calcium ion molar concentration is 0.3mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 49%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.02m/s, obtains graphene oxide/Fe3O4/ fibroin albumen composite fibre.
It is in 80% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 5 times, and fixed length is soaked 4 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 185MPa, and elongation at break is 52%, and energy to failure is 50J/g.
Embodiment 10
The Na that is 0.5% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.0mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 10 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 10 ℃ of temperature, utilize wind speed method, it is 10% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 3mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:10000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then adding ZnO mass fraction is 10%, and the nano-ZnO hydrosol that particle diameter is 100nm also shakes up, and the three's mass ratio that makes graphene oxide in mixed solution, ZnO nano particle and fibroin albumen is 1:1:10000.The calcium chloride water that interpolation molar concentration is 3.0mol/L, in regulator solution, calcium ion molar concentration is 0.3mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 49.8%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.02m/s, obtains graphene oxide/ZnO/ fibroin albumen composite fibre.
It is in 75% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 5 times, and fixed length is soaked 4 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 195MPa, and elongation at break is 49%, and energy to failure is 43J/g.
Embodiment 11
The Na that is 0.5% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.0mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 10 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 10 ℃ of temperature, utilize wind speed method, it is 20% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 3mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:500 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then adding ZnO mass fraction is 20%, and the nano-ZnO hydrosol that particle diameter is 20nm also shakes up, and the three's mass ratio that makes graphene oxide in mixed solution, ZnO nano particle and fibroin albumen is 1:1:500.The calcium chloride water that interpolation molar concentration is 1.5mol/L, in regulator solution, calcium ion molar concentration is 0.15mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 56.5%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.02m/s, obtains graphene oxide/ZnO/ fibroin albumen composite fibre.
It is in 80% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 2 times, and fixed length is soaked 1 hour, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 62MPa, and elongation at break is 100%, and energy to failure is 33J/g.
Embodiment 12
The Na that is 0.5% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.0mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 10 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 10 ℃ of temperature, utilize wind speed method, it is 30% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 3mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:1000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then adding ZnO mass fraction is 30%, and the nano-ZnO hydrosol that particle diameter is 50nm also shakes up, and the three's mass ratio that makes graphene oxide in mixed solution, ZnO nano particle and fibroin albumen is 1:1:1000.The calcium chloride water that interpolation molar concentration is 2.0mol/L, in regulator solution, calcium ion molar concentration is 0.2mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 50.2%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.05m/s, obtains graphene oxide/ZnO/ fibroin albumen composite fibre.
It is in 80% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 4 times, and fixed length is soaked 8 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 390MPa, and elongation at break is 55%, and energy to failure is 68J/g.
Embodiment 13
The Na that is 1.0% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.0mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 7 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 7 ℃ of temperature, utilize wind speed method, it is 10% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 0.5mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:10000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add ZrO
2mass fraction is 10%, the nanometer ZrO that particle diameter is 100nm
2the hydrosol also shakes up, and makes graphene oxide in mixed solution, ZrO
2three's mass ratio of nano particle and fibroin albumen is 1:1:10000.The calcium chloride water that interpolation molar concentration is 3.0mol/L, in regulator solution, calcium ion molar concentration is 0.3mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 51%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.02m/s, obtains graphene oxide/ZrO2/ fibroin albumen composite fibre.
It is in 85% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 2 times, and fixed length is soaked 4 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 107MPa, and elongation at break is 115%, and energy to failure is 38J/g.
Embodiment 14
The Na that is 1.0% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.0mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 7 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 7 ℃ of temperature, utilize wind speed method, it is 20% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 0.5mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:2000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add ZrO
2mass fraction is 30%, the nanometer ZrO that particle diameter is 25nm
2the hydrosol also shakes up, and makes graphene oxide in mixed solution, ZrO
2three's mass ratio of nano particle and fibroin albumen is 1:1:2000.The calcium chloride water that interpolation molar concentration is 2.0mol/L, in regulator solution, calcium ion molar concentration is 0.2mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 53.2%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.02m/s, obtains graphene oxide/ZrO2/ fibroin albumen composite fibre.
It is in 80% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 4 times, and fixed length is soaked 1 hour, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 210MPa, and elongation at break is 90%, and energy to failure is 80J/g.
Embodiment 15
The Na that is 1.0% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.0mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 7 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 7 ℃ of temperature, utilize wind speed method, it is 30% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 0.5mg/ml graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:500 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add ZrO
2mass fraction is 50%, the nanometer ZrO that particle diameter is 10nm
2the hydrosol also shakes up, and makes graphene oxide in mixed solution, ZrO
2three's mass ratio of nano particle and fibroin albumen is 1:1:500.The calcium chloride water that interpolation molar concentration is 3.0mol/L, in regulator solution, calcium ion molar concentration is 0.3mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 50.8%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.1m/s, obtains graphene oxide/ZrO2/ fibroin albumen composite fibre.
It is in 80% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 5 times, and fixed length is soaked 8 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 170MPa, and elongation at break is 65%, and energy to failure is 49J/g.
Embodiment 16
The Na that is 0.5% with mass percent
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution of 9.5mol/L.After dilution, utilize supercentrifuge to carry out centrifugal.After suction filtration, silk fibroin protein solution is placed in to cellulose bag filter, after sealing, immerses in deionized water and dialyse, temperature is 7 ℃, and dialysis time is 72h, and exchange water cycle is 4 hours.Then at 7 ℃ of temperature, utilize wind speed method, it is 20% that regenerated silk fibroin water solution is concentrated into mass percent.By concentration, be that 3mg/mL graphite oxide aqueous solution is made ultrasonic dispersion treatment, the ratio that is then 1:10000 according to the mass ratio of graphene oxide and fibroin albumen, joins graphite oxide aqueous solution in regenerated silk fibroin water solution, shakes up.Then add respectively TiO
2mass fraction is 10%, the nano-TiO that particle diameter is 100nm
2the hydrosol and Al
2o
3mass fraction is 10%, the nanometer Al that particle diameter is 100nm
2o
3the hydrosol, after shaking up, makes graphene oxide in mixed solution, TiO
2nano particle, Al
2o
3the mass ratio of nano particle and fibroin albumen is 1:0.5:0.5:10000.The calcium chloride water that interpolation molar concentration is 3mol/L, in regulator solution, calcium ion molar concentration is 0.3mol/L.Continue to concentrate, finally obtain the spinning solution that fibroin albumen quality percentage is 58%.
Above-mentioned spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled, winding speed is 0.08m/s, obtains graphene oxide/titanium dioxide/Al
2o
3/ fibroin albumen composite fibre.
It is in 75% alcohol-water mixed solution that as-spun fibre is immersed in to volume fraction of ethanol, stretches 4 times, and fixed length is soaked 3 hours, takes out.Fiber is deposited balance 48 hours under 25 ℃, relative humidity 50% constant temperature and humidity condition, obtains the described toughness reinforcing regenerated silk fiber of a kind of enhancing, and its fracture strength is 300MPa, and elongation at break is 65%, and energy to failure is 60J/g.
Claims (9)
1. strengthen a preparation method for toughness reinforcing regenerated silk fiber, it is characterized in that step comprises:
(1) use Na
2cO
3the aqueous solution, to degumming silkworm cocoons, is then dissolved with the LiBr aqueous solution, and after centrifugal, suction filtration, dialysis, obtains regenerated silk fibroin water solution, and then the mass percent that is concentrated into fibroin albumen is 10%～30%;
(2) graphite oxide aqueous solution is done to ultrasonic dispersion treatment, process 2～5min, the regenerated silk fibroin water solution obtaining after then concentrating with previous step carries out blend for 1:500～10000 in mass ratio, obtains graphene oxide/fibroin albumen mixed solution;
(3) ratio that is 1:1:500～10000 according to graphene oxide, metal oxide nanoparticles and fibroin albumen three's mass ratio adds the metal oxide hydrosol, and shakes up;
(4) add calcium chloride water, in regulator solution, calcium ion molar concentration is 0.15～0.3mol/L;
(5) continuing to concentrate, is 48%～58% until fibroin albumen obtains the percentage of quality, has now obtained the spinning solution of fibroin albumen/graphene oxide/metal oxide nanoparticles;
(6) described spinning solution is at room temperature extruded from spinning nozzle, in air set, reeled;
(7) above-mentioned regenerated silk is immersed in the solution of alcohol-water, drawn, fixed length were soaked after a period of time, took out, and obtained a kind of toughness reinforcing regenerated silk fiber of enhancing that adds metal oxide nanoparticles based on graphene oxide/fibroin albumen compound system.
2. a kind of preparation method who strengthens toughness reinforcing regenerated silk fiber according to claim 1, is characterized in that, in step (1), and described Na
2cO
3the mass percent of the aqueous solution is 0.5%～1%; The molar concentration of the described LiBr aqueous solution is 9.0 ± 0.5mol/L.
3. a kind of preparation method who strengthens toughness reinforcing regenerated silk fiber according to claim 1, it is characterized in that, in step (1), described centrifugal referring to 1.5 times of the silk fibroin protein solution dilutions after dissolving, then utilize supercentrifuge to carry out centrifugal, rotating speed is made as 3500r/min, and the time is 10min, and temperature is 18 ℃; Described dialysis is that the silk fibroin protein solution after suction filtration is placed in to cellulose bag filter, after sealing, is immersed in deionized water and dialyses, and temperature is at 6～12 ℃, and dialysis time is 72h, and exchange water cycle is within 3～4 hours, to change deionized water one time; Described concentrated referring at 6～12 ℃ of temperature, utilizes wind speed method to concentrate silk fibroin water solution, until mass percent is 10%～30%.
4. a kind of preparation method who strengthens toughness reinforcing regenerated silk fiber according to claim 1, is characterized in that, in step (2), described graphene oxide concentration of aqueous solution is 0.5～3mg/mL; In step (3), in the described metal oxide hydrosol, the mass percent of metal oxide nanoparticles is 10%～50%.
5. a kind of preparation method who strengthens toughness reinforcing regenerated silk fiber according to claim 1, is characterized in that, the metal oxide in the described metal oxide hydrosol is TiO
2, Fe
3o
4, ZnO, Al
2o
3or ZrO
2one or more of nano particle, and the nano particle diameter in the described metal oxide hydrosol is 10～100nm.
6. a kind of preparation method who strengthens toughness reinforcing regenerated silk fiber according to claim 1, is characterized in that, in step (4), in described calcium chloride water, the molar concentration of calcium chloride is 1.5～3.0mol/L; In step (5), described concentrated referring at 6～12 ℃ of temperature, utilizes the solution after the concentrated blend of wind speed method, until fibroin albumen quality percentage is 48%～58%.
7. a kind of preparation method who strengthens toughness reinforcing regenerated silk fiber according to claim 1, is characterized in that, the winding speed of described curing coiling is 0.02～0.1m/s.
8. a kind of preparation method who strengthens toughness reinforcing regenerated silk fiber according to claim 1, is characterized in that, in described ethanol-water solution, volume fraction of ethanol is 70%～85%; The multiple of described stretching is 2～5 times, and the time that described fixed length is soaked is 1～8 hour.
9. a kind of preparation method who strengthens toughness reinforcing regenerated silk fiber according to claim 1, it is characterized in that: the fracture strength of the toughness reinforcing regenerated silk fiber of described enhancing is 0.05～0.38GPa, elongation at break is 20%～150%, and energy to failure is 30～100J/g; The toughness reinforcing regenerated silk fiber of described enhancing is in regenerated silk fiber, to be dispersed with graphene oxide and metal oxide nanoparticles, the mass percent of graphene oxide in fiber is 0.05%～0.1%, and the mass percent of metal oxide nanoparticles in fiber is 0.05%～0.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310566935.1A CN103572395B (en) | 2013-11-14 | 2013-11-14 | A kind of activeness and quietness regenerated silk fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310566935.1A CN103572395B (en) | 2013-11-14 | 2013-11-14 | A kind of activeness and quietness regenerated silk fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103572395A true CN103572395A (en) | 2014-02-12 |
| CN103572395B CN103572395B (en) | 2015-08-12 |
Family
ID=50045078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310566935.1A Active CN103572395B (en) | 2013-11-14 | 2013-11-14 | A kind of activeness and quietness regenerated silk fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103572395B (en) |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562638A (en) * | 2014-12-29 | 2015-04-29 | 无锡蚕魅科技有限公司 | Preparation method of oxidation-resistant and flame-retardant toughened silk |
| CN104674362A (en) * | 2015-03-11 | 2015-06-03 | 湖州吉昌丝绸有限公司 | Preparation method of fibroin/graphene conductive fiber |
| CN104886008A (en) * | 2015-04-29 | 2015-09-09 | 东华大学 | Graphene oxide-feeding silkworm rearing method for preparing high-strength silk and product of silk |
| CN105040415A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Nano-antibacterial fabric |
| CN105696098A (en) * | 2016-02-25 | 2016-06-22 | 苏州三和开泰花线织造有限公司 | Strengthening-toughening modification type nano monofilament silk fiber and preparation method thereof |
| CN105908374A (en) * | 2016-06-23 | 2016-08-31 | 盐城工业职业技术学院 | Preparation method of porous nano fiber membrane |
| CN105926075A (en) * | 2016-05-13 | 2016-09-07 | 东莞市联洲知识产权运营管理有限公司 | Graphene modified silk fiber preparing method |
| CN106367831A (en) * | 2016-08-30 | 2017-02-01 | 江苏金太阳纺织科技股份有限公司 | Method for preparing antibacterial deodorization regenerated cellulose fiber |
| CN107189080A (en) * | 2017-05-23 | 2017-09-22 | 苏州市晨煊纺织科技有限公司 | A kind of preparation method of the regenerated silk fibroin hydrogel with graphene oxide |
| CN107338503A (en) * | 2017-07-16 | 2017-11-10 | 长沙善道新材料科技有限公司 | A kind of technique that strong mechanical performance silk fabric is prepared using silk cocoon |
| CN107348580A (en) * | 2017-06-23 | 2017-11-17 | 宁波高新区达康工业科技有限公司 | A kind of antiultraviolet farinfrared health-care material |
| CN107474304A (en) * | 2017-09-17 | 2017-12-15 | 钱景 | A kind of graphene oxide sodium alginate magnetic composite and preparation method |
| CN107556761A (en) * | 2017-09-17 | 2018-01-09 | 钱景 | A kind of graphene/silk/salix monogolica nano composite material and preparation method thereof |
| CN107556760A (en) * | 2017-09-17 | 2018-01-09 | 钱景 | Graphene oxide silk salix monogolica nano composite material and preparation method thereof |
| CN107619497A (en) * | 2017-09-17 | 2018-01-23 | 钱景 | A kind of graphene silk three-dimensional porous nano composite and preparation method |
| CN107641841A (en) * | 2017-09-15 | 2018-01-30 | 厦门大学 | Regenerated silk fiber of polystyrene induction mesoscopic structure enhancing and preparation method thereof |
| CN107858762A (en) * | 2017-11-15 | 2018-03-30 | 金剑梅 | A kind of preparation method of high intensity silk fiber |
| WO2018086150A1 (en) * | 2016-11-11 | 2018-05-17 | 海安县恒业制丝有限公司 | Collagen/nano-tio2/graphene composite fiber |
| CN108144116A (en) * | 2018-02-26 | 2018-06-12 | 丁文铃 | A kind of novel antibacterial artificial ligament |
| CN108261563A (en) * | 2018-02-26 | 2018-07-10 | 丁文铃 | A kind of bionical ligament of activeness and quietness |
| CN108441977A (en) * | 2018-02-07 | 2018-08-24 | 广西大学 | Nano-meter CaCO33Strengthen the preparation method of silk fiber |
| CN108754660A (en) * | 2018-06-01 | 2018-11-06 | 苏州先蚕丝绸有限公司 | A kind of preparation method for the natural silk fiber that graphene is modified |
| CN109264709A (en) * | 2018-09-03 | 2019-01-25 | 浙江理工大学 | A kind of preparation method of the implantable biosensor of graphene oxide modification |
| CN109402773A (en) * | 2018-10-17 | 2019-03-01 | 李涛 | A kind of preparation method of protein composite fiber |
| CN109505029A (en) * | 2018-12-25 | 2019-03-22 | 徐敏 | A kind of preparation method of modified silk fiber |
| CN109529125A (en) * | 2018-12-28 | 2019-03-29 | 佛山科学技术学院 | A kind of molten spray Preparation Method of bioengineered tissue bracket |
| CN109667059A (en) * | 2018-12-28 | 2019-04-23 | 佛山科学技术学院 | A kind of molten spray Preparation Method of fibroin albumen bioengineered tissue bracket |
| CN110257943A (en) * | 2019-07-04 | 2019-09-20 | 金寨新丝路纺织有限公司 | A method of crease-resistant type regenerated silk being made using substandard products silk cocoon |
| CN110269955A (en) * | 2019-06-21 | 2019-09-24 | 淮阴工学院 | A kind of preparation method of tussah silk fibroin/Aloe Vera Gel combine dressing |
| CN110354315A (en) * | 2019-06-21 | 2019-10-22 | 淮阴工学院 | A kind of fibroin albumen/graphene/titanium dioxide bone tissue engineering scaffold preparation method of three-dimensional porous antibacterial |
| CN112195528A (en) * | 2020-09-28 | 2021-01-08 | 浙江理工大学 | Preparation method of temperature-sensitive conductive hydrogel fiber reinforced by nano-cellulose |
| CN113278294A (en) * | 2021-05-28 | 2021-08-20 | 西南大学 | Kevlar nanofiber/regenerated silk fibroin composite film and preparation method thereof |
| CN116288771A (en) * | 2023-04-27 | 2023-06-23 | 苏州市绿中缘纺织科技有限公司 | High-toughness silk fiber and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102543270A (en) * | 2012-01-31 | 2012-07-04 | 苏州大学 | Grapheme-based composite film and preparation method therefor, conductive electrode and preparation method therefor |
| CN102912470A (en) * | 2012-10-19 | 2013-02-06 | 东华大学 | Metal oxide nanoparticle-enhanced and toughened regenerated silk fiber and preparation method thereof |
| CN102940907A (en) * | 2012-11-09 | 2013-02-27 | 南京工业大学 | Graphene oxide and silk fibroin composite membrane and preparation method thereof |
| CN103173882A (en) * | 2013-04-11 | 2013-06-26 | 大连海事大学 | Method for preparing graphene/ silk composite fiber |
-
2013
- 2013-11-14 CN CN201310566935.1A patent/CN103572395B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102543270A (en) * | 2012-01-31 | 2012-07-04 | 苏州大学 | Grapheme-based composite film and preparation method therefor, conductive electrode and preparation method therefor |
| CN102912470A (en) * | 2012-10-19 | 2013-02-06 | 东华大学 | Metal oxide nanoparticle-enhanced and toughened regenerated silk fiber and preparation method thereof |
| CN102940907A (en) * | 2012-11-09 | 2013-02-27 | 南京工业大学 | Graphene oxide and silk fibroin composite membrane and preparation method thereof |
| CN103173882A (en) * | 2013-04-11 | 2013-06-26 | 大连海事大学 | Method for preparing graphene/ silk composite fiber |
Cited By (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562638A (en) * | 2014-12-29 | 2015-04-29 | 无锡蚕魅科技有限公司 | Preparation method of oxidation-resistant and flame-retardant toughened silk |
| CN104674362A (en) * | 2015-03-11 | 2015-06-03 | 湖州吉昌丝绸有限公司 | Preparation method of fibroin/graphene conductive fiber |
| CN104886008A (en) * | 2015-04-29 | 2015-09-09 | 东华大学 | Graphene oxide-feeding silkworm rearing method for preparing high-strength silk and product of silk |
| CN105040415A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Nano-antibacterial fabric |
| CN105696098A (en) * | 2016-02-25 | 2016-06-22 | 苏州三和开泰花线织造有限公司 | Strengthening-toughening modification type nano monofilament silk fiber and preparation method thereof |
| CN105696098B (en) * | 2016-02-25 | 2018-11-13 | 苏州三和开泰花线织造有限公司 | A kind of monofilament nanometer silk fiber and preparation method thereof that Strengthening and Toughening is modified |
| CN105926075A (en) * | 2016-05-13 | 2016-09-07 | 东莞市联洲知识产权运营管理有限公司 | Graphene modified silk fiber preparing method |
| CN105926075B (en) * | 2016-05-13 | 2018-01-30 | 肇庆涞馨美体内衣有限公司 | A kind of preparation method for the silk fiber that graphene is modified |
| CN105908374A (en) * | 2016-06-23 | 2016-08-31 | 盐城工业职业技术学院 | Preparation method of porous nano fiber membrane |
| CN105908374B (en) * | 2016-06-23 | 2018-03-13 | 盐城工业职业技术学院 | A kind of preparation method of porous nanofiber membrane |
| CN106367831A (en) * | 2016-08-30 | 2017-02-01 | 江苏金太阳纺织科技股份有限公司 | Method for preparing antibacterial deodorization regenerated cellulose fiber |
| WO2018086150A1 (en) * | 2016-11-11 | 2018-05-17 | 海安县恒业制丝有限公司 | Collagen/nano-tio2/graphene composite fiber |
| CN107189080A (en) * | 2017-05-23 | 2017-09-22 | 苏州市晨煊纺织科技有限公司 | A kind of preparation method of the regenerated silk fibroin hydrogel with graphene oxide |
| CN107348580A (en) * | 2017-06-23 | 2017-11-17 | 宁波高新区达康工业科技有限公司 | A kind of antiultraviolet farinfrared health-care material |
| CN107348580B (en) * | 2017-06-23 | 2019-01-29 | 宁波高新区达康工业科技有限公司 | A kind of antiultraviolet farinfrared health-care material |
| CN107338503A (en) * | 2017-07-16 | 2017-11-10 | 长沙善道新材料科技有限公司 | A kind of technique that strong mechanical performance silk fabric is prepared using silk cocoon |
| CN107641841A (en) * | 2017-09-15 | 2018-01-30 | 厦门大学 | Regenerated silk fiber of polystyrene induction mesoscopic structure enhancing and preparation method thereof |
| CN107641841B (en) * | 2017-09-15 | 2020-03-27 | 厦门大学 | Polystyrene-induced mesostructure-enhanced regenerated silk fiber and preparation method thereof |
| CN107619497A (en) * | 2017-09-17 | 2018-01-23 | 钱景 | A kind of graphene silk three-dimensional porous nano composite and preparation method |
| CN107556760A (en) * | 2017-09-17 | 2018-01-09 | 钱景 | Graphene oxide silk salix monogolica nano composite material and preparation method thereof |
| CN107556761A (en) * | 2017-09-17 | 2018-01-09 | 钱景 | A kind of graphene/silk/salix monogolica nano composite material and preparation method thereof |
| CN107474304A (en) * | 2017-09-17 | 2017-12-15 | 钱景 | A kind of graphene oxide sodium alginate magnetic composite and preparation method |
| CN107858762A (en) * | 2017-11-15 | 2018-03-30 | 金剑梅 | A kind of preparation method of high intensity silk fiber |
| CN108441977A (en) * | 2018-02-07 | 2018-08-24 | 广西大学 | Nano-meter CaCO33Strengthen the preparation method of silk fiber |
| CN108144116A (en) * | 2018-02-26 | 2018-06-12 | 丁文铃 | A kind of novel antibacterial artificial ligament |
| CN108261563A (en) * | 2018-02-26 | 2018-07-10 | 丁文铃 | A kind of bionical ligament of activeness and quietness |
| CN108754660A (en) * | 2018-06-01 | 2018-11-06 | 苏州先蚕丝绸有限公司 | A kind of preparation method for the natural silk fiber that graphene is modified |
| CN109264709A (en) * | 2018-09-03 | 2019-01-25 | 浙江理工大学 | A kind of preparation method of the implantable biosensor of graphene oxide modification |
| CN109264709B (en) * | 2018-09-03 | 2021-08-31 | 浙江理工大学 | Preparation method of graphene oxide modified implantable biosensor |
| CN109402773A (en) * | 2018-10-17 | 2019-03-01 | 李涛 | A kind of preparation method of protein composite fiber |
| CN109505029A (en) * | 2018-12-25 | 2019-03-22 | 徐敏 | A kind of preparation method of modified silk fiber |
| CN109529125A (en) * | 2018-12-28 | 2019-03-29 | 佛山科学技术学院 | A kind of molten spray Preparation Method of bioengineered tissue bracket |
| CN109667059A (en) * | 2018-12-28 | 2019-04-23 | 佛山科学技术学院 | A kind of molten spray Preparation Method of fibroin albumen bioengineered tissue bracket |
| CN109667059B (en) * | 2018-12-28 | 2022-01-07 | 佛山科学技术学院 | Method for preparing silk fibroin biological tissue engineering scaffold by solvent spraying |
| CN110269955A (en) * | 2019-06-21 | 2019-09-24 | 淮阴工学院 | A kind of preparation method of tussah silk fibroin/Aloe Vera Gel combine dressing |
| CN110354315A (en) * | 2019-06-21 | 2019-10-22 | 淮阴工学院 | A kind of fibroin albumen/graphene/titanium dioxide bone tissue engineering scaffold preparation method of three-dimensional porous antibacterial |
| CN110354315B (en) * | 2019-06-21 | 2020-07-24 | 淮阴工学院 | Preparation method of three-dimensional porous antibacterial silk fibroin/graphene/titanium dioxide bone tissue engineering scaffold |
| CN110257943A (en) * | 2019-07-04 | 2019-09-20 | 金寨新丝路纺织有限公司 | A method of crease-resistant type regenerated silk being made using substandard products silk cocoon |
| CN112195528A (en) * | 2020-09-28 | 2021-01-08 | 浙江理工大学 | Preparation method of temperature-sensitive conductive hydrogel fiber reinforced by nano-cellulose |
| CN112195528B (en) * | 2020-09-28 | 2022-06-21 | 浙江理工大学 | Preparation method of temperature-sensitive conductive hydrogel fiber reinforced by nano-cellulose |
| CN113278294A (en) * | 2021-05-28 | 2021-08-20 | 西南大学 | Kevlar nanofiber/regenerated silk fibroin composite film and preparation method thereof |
| CN113278294B (en) * | 2021-05-28 | 2022-03-01 | 西南大学 | Kevlar nanofiber/regenerated silk fibroin composite film and preparation method thereof |
| CN116288771A (en) * | 2023-04-27 | 2023-06-23 | 苏州市绿中缘纺织科技有限公司 | High-toughness silk fiber and preparation method thereof |
| CN116288771B (en) * | 2023-04-27 | 2023-11-10 | 苏州市绿中缘纺织科技有限公司 | High-toughness silk fiber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103572395B (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103572395B (en) | A kind of activeness and quietness regenerated silk fiber and preparation method thereof | |
| CN102912470B (en) | Metal oxide nanoparticle-enhanced and toughened regenerated silk fiber and preparation method thereof | |
| CN103570951B (en) | Preparation method of silk fibroin/graphene oxide high-concentration blended aqueous solution | |
| CN103498210B (en) | A kind of bionics method for preparation of high intensity regenerated fibroin fiber | |
| CN102181957B (en) | Preparation method for regenerated fibroin fiber | |
| CN103173892B (en) | A kind of preparation method of nano bamboo fiber composite material | |
| CN106928729B (en) | A kind of nanometer silver antimicrobial regenerated silk fibroin material and preparation method thereof | |
| CN103320886B (en) | Bionic regenerated silk fibroin filament fiber and preparation method thereof | |
| CN106906531A (en) | The preparation method of Graphene fibroin protein functional fiber | |
| CN105926065B (en) | The nanofiber-based macroscopic fibres and preparation method thereof aligned of bacteria cellulose | |
| CN104178845A (en) | Multifunctional high-performance carbon-based nanoparticle/sodium alginate composite fibers and preparation method thereof | |
| CN1796444A (en) | Method for preparing functional material of regenerated cellulose | |
| CN105926075A (en) | Graphene modified silk fiber preparing method | |
| CN110230113B (en) | Silver nanowire/silk fibroin composite fiber and preparation method thereof | |
| CN104672495A (en) | Organic-inorganic composite heat conductive filler as well as preparation method and application thereof | |
| US20190032247A1 (en) | Method of spinning fibres or extrusion, and the products obtained | |
| CN105926050B (en) | The macroscopic fibres and preparation method thereof aligned based on bacteria cellulose nanofiber | |
| CN104448365B (en) | It is a kind of prepare epoxidized vegetable oil it is epoxy resin toughened/method of cellulose composite membrane | |
| CN106265129A (en) | A kind of fibroin albumen alginate composite membrane and its preparation method and application | |
| Zhang et al. | Biological fibers based on naturally sourced proteins: Mechanical investigation and applications | |
| CN1837435B (en) | Composite nano-grade silk fiber product and method for preparing the same | |
| CN110028685B (en) | Preparation method of fibroin/chitosan/porous graphene oxide composite three-dimensional scaffold | |
| CN102383213B (en) | Preparation method for ultrahigh molecular weight polyethylene/biomass nanocrystal composite fibers | |
| CN101575749B (en) | Keratin crystal whisker enhanced homogeneous composite fiber and preparation method thereof | |
| CN105040277A (en) | Nano-cellulose/cellulose triacetate composite nano-fiber membrane capable of adsorbing and desorbing proteins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |