CN120350439B - Silk fibroin fiber and preparation method thereof - Google Patents
Silk fibroin fiber and preparation method thereofInfo
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- CN120350439B CN120350439B CN202510859000.5A CN202510859000A CN120350439B CN 120350439 B CN120350439 B CN 120350439B CN 202510859000 A CN202510859000 A CN 202510859000A CN 120350439 B CN120350439 B CN 120350439B
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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
- D01D5/06—Wet spinning methods
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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
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
- D01F4/02—Monocomponent artificial filaments or the like of proteins; Manufacture thereof from fibroin
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Abstract
本发明属于纤维加工技术领域，涉及一种丝素蛋白纤维及其制备方法，制备方法为：将纯丝素蛋白溶于甲酸中，得到丝素蛋白的甲酸溶液，再将丝素蛋白的甲酸溶液进行湿法纺丝，即得丝素蛋白纤维；丝素蛋白的甲酸溶液的浓度为18‑25wt%；湿法纺丝的工艺流程为：喷丝头挤出→凝固浴凝固→卷绕；凝固浴为水，凝固浴的温度为30‑35℃。本发明在湿法纺丝过程中，通过调节凝固浴的温度和丝素蛋白的甲酸溶液的浓度，提高了丝素蛋白分子链沿纤维轴向排列的有序性，省略了复杂的后处理工序，降低了生产成本和工艺复杂性，制备的丝素蛋白纤维具有优异的断裂强度和断裂伸长率，力学性能与天然蚕丝相接近，具有广阔的应用前景。The present invention belongs to the field of fiber processing technology and relates to a kind of silk fibroin fiber and preparation method thereof, preparation method comprises the following steps: dissolving pure silk fibroin in formic acid to obtain a formic acid solution of silk fibroin, and then wet-spinning the formic acid solution of silk fibroin to obtain silk fibroin fiber; the concentration of the formic acid solution of silk fibroin is 18-25wt%; the process flow of wet spinning comprises the following steps: extrusion from a spinneret → coagulation in a coagulation bath → winding; the coagulation bath is water, and the temperature of the coagulation bath is 30-35℃. In the wet spinning process, the present invention improves the orderliness of the arrangement of silk fibroin molecular chains along the fiber axis by adjusting the temperature of the coagulation bath and the concentration of the formic acid solution of silk fibroin, omits complicated post-processing steps, reduces production cost and process complexity, and the prepared silk fibroin fiber has excellent breaking strength and elongation at break, and mechanical properties are close to those of natural silk, and has broad application prospects.
Description
Technical Field
The invention belongs to the technical field of fiber processing, and relates to a silk fibroin fiber and a preparation method thereof.
Background
The silk fibroin fiber is regenerated silk fibroin fiber obtained by firstly preparing silk fibroin solution from degummed natural silk and then spinning the silk fibroin solution, has unique molecular structure, excellent mechanical property and good biocompatibility, and is widely applied to the new material fields of medical care, biological medicine and the like at present, so that the research on the preparation method of the silk fibroin fiber has important significance.
However, silk fibroin is weak in mechanical properties in a nascent state, and is easily soluble in water, limiting its practical application. Currently, researchers generally improve the mechanical properties of fibers by adjusting their condensed structure (β -sheet and crystallinity), the increase of β -sheet being able to enhance the stiffness and water solubility resistance of the fibers.
To facilitate the formation and orientation of the β -sheet structure of silk fibroin, there are currently two main approaches:
the first method is to introduce external additives, for example, patent application with the publication number of CN115947945A discloses a silk fibroin modified material, a preparation method and application thereof, wherein the interaction between a flexible chain segment of a flexible high polymer substance (polyethylene glycol, polyvinyl alcohol, polylactic acid and the like) and silk fibroin is adopted as a specific hydrogen bond synergistic effect to form a beta-sheet structure. However, the maximum breaking strength of the supermolecular acting cross-linked silk fibroin is 19.8MPa, and the mechanical properties of the supermolecular acting cross-linked silk fibroin are still greatly different from those of natural silk.
The second method is that the spun fiber is subjected to post-treatments such as drafting, steam treatment, organic solvent soaking and the like, for example, a CaCl 2/HCOOH binary solution system is used as a solvent to dissolve degummed natural mulberry silk to prepare regenerated silk protein solution in literature (dry and wet spinning of regenerated silk protein filaments and performance research [ D ]. Suzhou: 2014:31-34 ]), the wet spinning process is adopted to prepare regenerated silk primary fiber, finally the prepared regenerated silk primary fiber is subjected to post-treatments such as drafting and the like by adopting an ethanol aqueous solution with the volume fraction of 75 percent to obtain regenerated silk protein filaments, in the wet spinning process, the concentration of the regenerated silk protein solution is 12-18wt%, deionized water is adopted as a coagulation bath, the temperature of the coagulation bath is 25 ℃, the dry state breaking strength of the prepared regenerated silk protein fiber is 428.42 +/-43.07 MPa, and the dry state breaking elongation is 26.50 +/-2.43%. Although the mechanical property of the silk is similar to that of natural silk, the energy consumption of drafting is high, the cost is high, the efficiency is low, and the ethanol volatilizes when the organic solvent is soaked, so that the potential problem in the aspect of environmental safety can be caused. Experiments show that if the post-treatment process is omitted, the dry breaking strength of the prepared regenerated silk fibroin fiber is 260-280MPa, the dry breaking elongation is 30-40%, and the mechanical property can be obviously reduced.
Therefore, it is necessary to develop a method for preparing silk fibroin fibers with excellent fiber mechanical properties and without post-treatment.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of silk fibroin fibers.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A preparation method of silk fibroin fiber comprises dissolving pure silk fibroin in formic acid to obtain formic acid solution of silk fibroin, and wet spinning the formic acid solution of silk fibroin to obtain silk fibroin fiber;
The concentration of the formic acid solution of the silk fibroin is 18-25wt%;
The wet spinning process includes extrusion in spinneret, coagulation in coagulating bath and winding;
the coagulating bath is water, and the temperature of the coagulating bath is 30-35 ℃.
Compared with the dry and wet spinning of regenerated silk fibroin filaments and the performance research thereof [ D ]. Suzhou: suzhou university, 2014:31-34 ], the invention can prepare silk fibroin fibers with excellent mechanical performance on the premise of omitting post-treatment procedures, mainly because the invention improves the concentration of formic acid solution of silk fibroin and the temperature of coagulation bath.
After the formic acid solution of the silk fibroin enters water, the silk fibroin molecular chain migrates and diffuses at the interface of formic acid and water, and the migration and diffusion behavior shows certain asymmetry, namely, the migration and diffusion behavior of the silk fibroin molecular chain on the formic acid side and the water side are different, namely, the diffusion rates are inconsistent. This asymmetry is more pronounced when the concentration of the formic acid solution of the silk fibroin and the temperature of the coagulation bath are higher, because higher concentrations of silk fibroin allow for longer residence times of the silk fibroin molecules on the formic acid side, further exacerbating migration and diffusion differences on the formic acid side and the water side. When the temperature of the coagulating bath is higher, the molecular movement of water is more intense, the impact on the silk fibroin molecules is stronger, so that the migration and diffusion speed of the silk fibroin molecules on one side of water is faster, and the asymmetry is further enhanced. The more obvious the asymmetry is, the more favorable the drive of the silk fibroin molecular chains to be orderly arranged along the fiber axis, because the asymmetric migration and diffusion actions make the silk fibroin molecules more easily guided and arranged by water molecules on the water side. The polarity of the water molecules will cause the silk fibroin molecules to align axially along the fiber, forming a more ordered structure. Due to the different diffusion rates at the formic acid side and the water side, the silk fibroin molecules are subjected to a stretching or guiding action at the interface, so that the silk fibroin molecules are more easily migrated along the axial direction of the fiber, and the order of molecular chains is enhanced. The higher the ordering of the silk fibroin molecular chains along the axial direction of the fiber, the more favorable the improvement of the orientation degree of the fiber, the more favorable the reduction of defects such as pores, cracks and the like, the more favorable the improvement of the crystallinity of the fiber and the enhancement of the stability of a microstructure, so that the overall mechanical property of the fiber is better.
As a preferable technical scheme:
The preparation process of the pure silk fibroin comprises the steps of dissolving degummed silk in a formic acid solution of calcium chloride to prepare a film, and removing the calcium chloride in the film to obtain the pure silk fibroin.
According to the preparation method of the silk fibroin fiber, when the spinneret is used for extrusion, the extrusion speed is 1-1.5mL/min, the ambient temperature is 20+/-5 ℃, and the ambient relative humidity is 30+/-5%.
A method for preparing silk fibroin fiber as described above, the coagulation bath length is 25-30cm.
The preparation method of the silk fibroin fiber has the winding speed of 3-3.5m/min.
The invention also provides a silk fibroin fiber which is prepared by adopting the preparation method of the silk fibroin fiber.
As a preferable technical scheme:
The dry breaking strength of the silk fibroin fiber is 400-420MPa, the dry breaking elongation is 1.5-1.7%, the wet breaking strength is 410-425MPa, and the wet breaking elongation is 23-26%.
The beneficial effects are that:
(1) In the wet spinning process, the ordering of the silk fibroin molecular chains along the axial direction of the fiber is improved by adjusting the temperature of the coagulating bath and the concentration of the formic acid solution of the silk fibroin, any post-treatment is not needed, the beta-sheet content in the fiber is directly improved in the spinning process, the complex post-treatment procedure is omitted, and the production cost and the process complexity are reduced.
(2) The invention does not need volatile organic solvents such as ethanol, and the like, and the volatilization degree of formic acid in the wet spinning process is low, so that the potential problem in the aspect of environmental safety is avoided.
(3) The silk fibroin fiber prepared by the invention has excellent breaking strength and breaking elongation, has mechanical properties similar to those of natural silk, and has wide application prospect.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The following are the relevant performance detection methods for each example and comparative example:
(1) The dry state breaking strength is tested by a universal material testing machine, wherein the testing parameters are that the distance between chucks is 5cm, the stretching rate is 1.5mm/min, the ambient temperature is 23+/-5 ℃, and the ambient relative humidity is 40+/-5%.
(2) The dry state elongation at break is tested by a universal material testing machine, wherein the testing parameters are that the distance between chucks is 5cm, the stretching rate is 1.5mm/min, the ambient temperature is 23+/-5 ℃, and the ambient relative humidity is 40+/-5%.
(3) Wet breaking strength, namely immersing a sample to be tested in water for 48 hours, taking out, and testing by a universal material tester, wherein the testing parameters are that the distance between chucks is 5cm, the stretching rate is 1.5mm/min, the ambient temperature is 23+/-5 ℃, and the ambient relative humidity is 40+/-5%.
(4) Wet elongation at break, which is to soak a sample to be tested in water for 48 hours, take out, test the sample by a universal material tester, wherein the test parameters are that the distance between chucks is 5cm, the stretching rate is 1.5mm/min, the ambient temperature is 23+/-5 ℃, and the ambient relative humidity is 40+/-5%.
Example 1
A preparation method of silk fibroin fibers comprises the following specific steps:
(1) Preparing raw materials;
degummed silk, degummed silk;
Formic acid;
The concentration of the formic acid solution of the calcium chloride is 4wt%;
PDMS film with thickness of 200 μm;
deionized water;
(2) Preparing pure silk fibroin;
placing degummed silk in formic acid solution of calcium chloride, wherein the weight ratio of degummed silk to the formic acid solution of calcium chloride is 1:25, continuously stirring by a magnetic stirrer at 25 ℃ to completely dissolve degummed silk, stirring at 400r/min,
Uniformly spreading the silk fibroin-calcium chloride-formic acid solution on a PDMS film, drying the PDMS film on a hot table at 60 ℃ for 4 hours to obtain a silk fibroin film, removing the silk fibroin film from the PDMS film, soaking the silk fibroin film in water for 24 hours to remove calcium chloride, taking out the soaked silk fibroin film, and drying the silk fibroin film at room temperature to obtain pure silk fibroin;
(3) Preparing silk fibroin fibers;
dissolving pure silk fibroin in formic acid to obtain a formic acid solution of the silk fibroin, and carrying out wet spinning on the formic acid solution of the silk fibroin to obtain silk fibroin fibers;
the concentration of the formic acid solution of silk fibroin was 23wt%;
The wet spinning process includes extrusion in spinneret, coagulation in coagulating bath and winding;
when the spinneret is used for extrusion, the extrusion speed is 1mL/min, the ambient temperature is 20 ℃, and the ambient relative humidity is 35%;
the coagulating bath is water, the temperature of the coagulating bath is 30 ℃, and the length of the coagulating bath is 25cm;
the winding speed was 3m/min.
The final silk fibroin fiber has a dry breaking strength of 420MPa, a dry breaking elongation of 1.6%, a wet breaking strength of 425MPa and a wet breaking elongation of 25%.
Comparative example 1
A process for preparing silk fibroin fibers, substantially the same as in example 1, except that in step (3), the concentration of formic acid solution of silk fibroin was 15wt%.
The final silk fibroin fiber has a dry breaking strength of 300MPa, a dry breaking elongation of 1%, a wet breaking strength of 310MPa and a wet breaking elongation of 10%.
Compared with example 1, the dry state breaking elongation of comparative example 1 is not obviously changed, the dry state breaking strength is reduced by 28.6%, the wet state breaking strength is reduced by 27.1%, and the wet state breaking elongation is reduced by 60%, because when the concentration of the formic acid solution of the silk fibroin is 15wt%, the concentration of the silk fibroin is too low, the viscosity of the spinning solution is lower, defects or loose structures are easy to occur in the fiber forming process, and the mechanical property is reduced.
Comparative example 2
A process for preparing silk fibroin fibers, substantially the same as in example 1, except that in step (3), the concentration of formic acid solution of silk fibroin was 28wt%.
The final silk fibroin fiber has a dry breaking strength of 350MPa, a dry breaking elongation of 1.2%, a wet breaking strength of 365MPa and a wet breaking elongation of 20%.
In comparison with example 1, the change in the dry breaking elongation and the wet breaking elongation of comparative example 2 was not obvious, the dry breaking strength was reduced by 16.7%, and the wet breaking strength was reduced by 14.1%, because the concentration of silk fibroin was too high when the concentration of formic acid solution of silk fibroin was 28wt%, crystalline lumps or agglomerates inside the fiber were easily generated during spinning, resulting in non-uniformity of the fiber structure, and lowering of the overall strength.
Comparative example 3
A process for the preparation of silk fibroin fibers substantially as described in example 1, except that in step (3), the coagulation bath temperature was 25 ℃.
The final silk fibroin fiber has a dry breaking strength of 303MPa, a dry breaking elongation of 1%, a wet breaking strength of 314MPa and a wet breaking elongation of 18%.
The change in the dry breaking elongation and the wet breaking elongation of comparative example 3 was not obvious compared with example 1, and the dry breaking strength was reduced by 27.9% and the wet breaking strength was reduced by 26.1%, because at a temperature of 25 ℃ in the coagulation bath, too low a temperature of the coagulation bath would slow down the curing speed of the fiber in the coagulation bath, resulting in insufficient crystallization or poor molecular orientation of the fiber, affecting mechanical properties.
Comparative example 4
A process for the preparation of silk fibroin fibers substantially as described in example 1, except that in step (3), the coagulation bath temperature was 40 ℃.
The final silk fibroin fiber has a dry breaking strength of 320MPa, a dry breaking elongation of 1.5%, a wet breaking strength of 335MPa and a wet breaking elongation of 20%.
The change in the dry breaking elongation and the wet breaking elongation of comparative example 4 was not obvious, and the dry breaking strength was reduced by 23.8% and the wet breaking strength was reduced by 21.2% as compared with example 1, because an excessively high coagulation bath temperature may cause excessive softening or deformation of the fiber portion to form micro cracks or defects at a coagulation bath temperature of 40 ℃.
Example 2
A preparation method of silk fibroin fibers comprises the following specific steps:
(1) Preparing raw materials;
degummed silk, degummed silk;
Formic acid;
The concentration of the formic acid solution of the calcium chloride is 3.5wt percent;
PDMS film with thickness of 200 μm;
deionized water;
(2) Preparing pure silk fibroin;
Placing degummed silk in a formic acid solution of calcium chloride, wherein the weight ratio of degummed silk to the formic acid solution of calcium chloride is 1:20, continuously stirring by a magnetic stirrer at 20 ℃ to ensure that degummed silk is completely dissolved, wherein the stirring speed is 100r/min, and the stirring time is 40min to obtain a silk fibroin-calcium chloride-formic acid solution;
(3) Preparing silk fibroin fibers;
dissolving pure silk fibroin in formic acid to obtain a formic acid solution of the silk fibroin, and carrying out wet spinning on the formic acid solution of the silk fibroin to obtain silk fibroin fibers;
the concentration of the formic acid solution of silk fibroin was 25wt%;
The wet spinning process includes extrusion in spinneret, coagulation in coagulating bath and winding;
When the spinneret is used for extrusion, the extrusion speed is 1.5mL/min, the ambient temperature is 25 ℃, and the ambient relative humidity is 32%;
The coagulating bath is water, the temperature of the coagulating bath is 35 ℃, and the length of the coagulating bath is 28cm;
the winding speed was 3.2m/min.
The final silk fibroin fiber has a dry breaking strength of 400MPa, a dry breaking elongation of 1.5%, a wet breaking strength of 410MPa and a wet breaking elongation of 23%.
Example 3
A preparation method of silk fibroin fibers comprises the following specific steps:
(1) Preparing raw materials;
degummed silk, degummed silk;
Formic acid;
the concentration of the formic acid solution of the calcium chloride is 5wt%;
PDMS film with thickness of 200 μm;
deionized water;
(2) Preparing pure silk fibroin;
placing degummed silk in a formic acid solution of calcium chloride, wherein the weight ratio of degummed silk to the formic acid solution of calcium chloride is 1:22, continuously stirring by a magnetic stirrer at 40 ℃ to ensure that degummed silk is completely dissolved, wherein the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain a silk fibroin-calcium chloride-formic acid solution;
(3) Preparing silk fibroin fibers;
dissolving pure silk fibroin in formic acid to obtain a formic acid solution of the silk fibroin, and carrying out wet spinning on the formic acid solution of the silk fibroin to obtain silk fibroin fibers;
The concentration of the formic acid solution of silk fibroin was 20wt%;
The wet spinning process includes extrusion in spinneret, coagulation in coagulating bath and winding;
When the spinneret is used for extrusion, the extrusion speed is 1.4mL/min, the ambient temperature is 23 ℃, and the ambient relative humidity is 30%;
the coagulating bath is water, the temperature of the coagulating bath is 31 ℃, and the length of the coagulating bath is 30cm;
the winding speed was 3.5m/min.
The final silk fibroin fiber has a dry breaking strength of 416MPa, a dry breaking elongation of 1.7%, a wet breaking strength of 415MPa and a wet breaking elongation of 24%.
Example 4
A preparation method of silk fibroin fibers comprises the following specific steps:
(1) Preparing raw materials;
degummed silk, degummed silk;
Formic acid;
the concentration of the formic acid solution of the calcium chloride is 2.5wt percent;
PDMS film with thickness of 200 μm;
deionized water;
(2) Preparing pure silk fibroin;
placing degummed silk in a formic acid solution of calcium chloride, wherein the weight ratio of degummed silk to the formic acid solution of calcium chloride is 1:30, continuously stirring by a magnetic stirrer at the temperature of 30 ℃ to ensure that degummed silk is completely dissolved, wherein the stirring speed is 300r/min, and the stirring time is 18min to obtain a silk fibroin-calcium chloride-formic acid solution;
(3) Preparing silk fibroin fibers;
dissolving pure silk fibroin in formic acid to obtain a formic acid solution of the silk fibroin, and carrying out wet spinning on the formic acid solution of the silk fibroin to obtain silk fibroin fibers;
the concentration of the formic acid solution of silk fibroin was 18wt%;
The wet spinning process includes extrusion in spinneret, coagulation in coagulating bath and winding;
When the spinneret is used for extrusion, the extrusion speed is 1.3mL/min, the ambient temperature is 15 ℃, and the ambient relative humidity is 25%;
the coagulating bath is water, the temperature of the coagulating bath is 33 ℃, and the length of the coagulating bath is 27cm;
The winding speed was 3.1m/min.
The final silk fibroin fiber has 415MPa dry breaking strength, 1.5% dry breaking elongation, 420MPa wet breaking strength and 26% wet breaking elongation.
Example 5
A preparation method of silk fibroin fibers comprises the following specific steps:
(1) Preparing raw materials;
degummed silk, degummed silk;
Formic acid;
a formic acid solution of calcium chloride, wherein the concentration of the calcium chloride is 2wt%;
PDMS film with thickness of 200 μm;
deionized water;
(2) Preparing pure silk fibroin;
Placing degummed silk in a formic acid solution of calcium chloride, wherein the weight ratio of degummed silk to the formic acid solution of calcium chloride is 1:27, continuously stirring by a magnetic stirrer at the temperature of 35 ℃ to ensure that degummed silk is completely dissolved, stirring the degummed silk at the speed of 350r/min for 25min to obtain a silk fibroin-calcium chloride-formic acid solution, uniformly spreading the silk fibroin-calcium chloride-formic acid solution on a PDMS film, drying the PDMS film on a hot table at 80 ℃ for 2h to obtain a silk fibroin film, removing the silk fibroin film from the PDMS film, soaking the silk fibroin film in water for 6h to remove the calcium chloride, taking out the soaked silk fibroin film, and drying the silk fibroin film at room temperature to obtain pure silk fibroin;
(3) Preparing silk fibroin fibers;
dissolving pure silk fibroin in formic acid to obtain a formic acid solution of the silk fibroin, and carrying out wet spinning on the formic acid solution of the silk fibroin to obtain silk fibroin fibers;
The concentration of the formic acid solution of silk fibroin was 22wt%;
The wet spinning process includes extrusion in spinneret, coagulation in coagulating bath and winding;
When the spinneret is used for extrusion, the extrusion speed is 1.2mL/min, the ambient temperature is 18 ℃, and the ambient relative humidity is 28%;
the coagulating bath is water, the temperature of the coagulating bath is 32 ℃, and the length of the coagulating bath is 29cm;
The winding speed was 3.3m/min.
The final silk fibroin fiber has a dry breaking strength of 409MPa, a dry breaking elongation of 1.6%, a wet breaking strength of 418MPa and a wet breaking elongation of 23%.
In the above examples and comparative examples, degummed silk is prepared by manually peeling clean silk cocoons into thin layers, boiling in aqueous sodium carbonate solution to remove sericin, taking out, washing with water, and repeating the above degumming-washing steps twice to obtain degummed silk.
Claims (6)
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| CN103320886A (en) * | 2013-07-15 | 2013-09-25 | 苏州大学 | Bionic regenerated silk fibroin filament fiber and preparation method thereof |
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| CN106048765B (en) * | 2016-07-14 | 2018-05-08 | 苏州经贸职业技术学院 | A kind of preparation method of artificial ligament material |
| CN108396425A (en) * | 2018-03-16 | 2018-08-14 | 青岛大学 | A kind of fibroin albumen/carbon nanotube serialization filament yarn and preparation method thereof |
| JP2022001669A (en) * | 2018-07-19 | 2022-01-06 | Ｓｐｉｂｅｒ株式会社 | Method of manufacturing protein fiber |
| CN117431695A (en) * | 2023-10-24 | 2024-01-23 | 杭州电子科技大学 | A high-strength silk fibroin fiber membrane and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103320886A (en) * | 2013-07-15 | 2013-09-25 | 苏州大学 | Bionic regenerated silk fibroin filament fiber and preparation method thereof |
| CN104436285A (en) * | 2014-12-12 | 2015-03-25 | 苏州大学 | A kind of regenerated silk fibroin gel film and its preparation method |
| CN108149387A (en) * | 2018-01-17 | 2018-06-12 | 青岛大学 | A kind of hydrogel filament mask substrate |
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