High mechanical performance regenerated filament and method of making same
By introducing chromium carbide (Cr3C2) into regenerated silk fibroin fibers and preparing Cr3C2/RSF fiber composites using wet spinning, the problems of aging and mechanical property decline of regenerated silk fibroin fibers under ultraviolet light irradiation were solved, and their resistance to ultraviolet aging and breaking strength were significantly improved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JIANGSU UNIV OF SCI & TECH
- Filing Date
- 2025-03-28
- Publication Date
- 2026-07-07
AI Technical Summary
Regenerated silk fibroin fibers are prone to aging and mechanical property degradation under ultraviolet light irradiation, which limits their application in the field of fiber materials.
The mechanical properties of Cr3C2/RSF fiber composites were enhanced by mixing chromium carbide (Cr3C2) with silk fibroin solution and preparing the composites by wet spinning.
It significantly improves the UV aging resistance and breaking strength of recycled yarn, with the breaking strength increased to 1.54-2.08 times that of the original.
Smart Images
Figure CN120060993B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of silk modification, and more specifically, relates to a regenerated silk with high mechanical properties and its preparation method. Background Technology
[0002] Regenerated silk fibroin (RSF) fiber is a natural, high-performance biomaterial with excellent biocompatibility, mechanical properties, environmental friendliness, and biodegradability, showing broad application potential in functional textiles, biomedical dressings, and flexible electronics. However, natural RSF and its counterparts face many challenges in practical applications. For example, they are prone to aging and mechanical property degradation under ultraviolet light, high temperatures, and sweat, which seriously affects their expanded applications in the fiber material field. Therefore, improving the UV adaptability and functionality of RSF without damaging its structure has become crucial for RSF material functionalization research. Summary of the Invention
[0003] Purpose of the invention: The purpose of this invention is to provide a method for preparing regenerated yarn with high mechanical properties that significantly improves UV resistance; another purpose of this invention is to provide regenerated yarn with high mechanical properties.
[0004] Technical solution: The present invention provides a method for preparing regenerated yarn with high mechanical properties, comprising the following steps:
[0005] (1) Preparation of chromium carbide (Cr3C2) suspension;
[0006] (2) Preparation of functional regenerated silk (RSF) fiber: Cr3C2 suspension is mixed with silk fibroin solution to obtain Cr3C2 / RSF mixed solution. The Cr3C2 / RSF mixed solution is then prepared into a functional Cr3C2 / RSF fiber composite, i.e. regenerated silk with high mechanical properties, by wet spinning.
[0007] Furthermore, in step (1), the size of the Cr3C2 used is 480nm-520nm.
[0008] Further, in step (2), the silk fibroin solution is prepared by dissolving degummed silk in a calcium chloride formic acid solution, stirring, and dispersing evenly to obtain the silk fibroin solution.
[0009] Furthermore, the mass concentration of calcium chloride is 5%-10%, and the mass concentration of the prepared silk fibroin solution is 10%-15%.
[0010] Preferably, the mass concentration of calcium chloride is 5%, and the mass concentration of the prepared silk fibroin solution is 15%.
[0011] Furthermore, in step (2), the mass ratio of Cr3C2 to RSF in the Cr3C2 / RSF mixed solution is 1-5:100.
[0012] Preferably, in the preparation of the Cr3C2 / RSF fiber composite, the mass ratio of Cr3C2 to regenerated yarn (RSF) is 1:100, 2:100, 3:100, 4:100, or 5:100.
[0013] Further, in step (2), the wet spinning method is as follows: the Cr3C2 / RSF mixed solution is injected into the coagulation tank, and ethanol is used as the coagulation liquid; the Cr3C2 / RSF mixed solution enters the coagulation bath through the spinning needle, and then quickly coagulates into uniform filamentous Cr3C2 / RSF fibers in the coagulation bath, which are then wound onto the rotating shaft and collected after stretching treatment.
[0014] Furthermore, in the wet spinning method, 75% ethanol is used as the coagulation solution.
[0015] Furthermore, in the wet spinning method, the Cr3C2 / RSF mixed solution enters the coagulation bath through the spinning needle at a rate of 33.33 μL / min.
[0016] Further, the collected Cr3C2 / RSF fibers were placed in a 75% ethanol solution to remove residual solvent and set, and then air-dried naturally.
[0017] In a preferred embodiment, the wet spinning method is as follows: a Cr3C2CDs / RSF mixed solution is injected into a coagulation tank with a length of 1 m, using 75% ethanol as the coagulation liquid, and introduced into the coagulation bath through a spinning needle at a speed of 33.33 μL / min. The mixed solution rapidly coagulates into uniform filamentous fibers in the coagulation bath, which are then stretched and wound onto a rotating shaft for collection.
[0018] On the other hand, the present invention provides a regenerated yarn with high mechanical properties prepared by the above method.
[0019] Beneficial Effects: This invention has the following significant advantages: Without Cr3C2 doping, the tensile strength of RSF fibers is 203.32±5.22 MPa; after doping, the tensile strength increases to 313.23±3.68 MPa, which is 1.54 times the original. After UV aging treatment, the tensile strength of RSF fibers decreases to 126.54±4.88 MPa, while that of Cr3C2 / RSF is 263.42±4.30 MPa, which is 2.08 times the original. Attached Figure Description
[0020] Figure 1 Tensile test diagrams of Cr3C2 / RSF silk fibers obtained in Examples 1-5;
[0021] Figure 2 The image shows the tensile test results of the Cr3C2 / RSF silk fiber obtained in Example 6 after UV aging.
[0022] Figure 3 The images show the tensile test results of the silk fibers obtained in Comparative Examples 1 and 2 before and after UV aging. Detailed Implementation
[0023] The technical solution of the present invention will be further described below with reference to the accompanying drawings.
[0024] The chromium carbide used in the embodiments of this invention was purchased from Hebei Yuanying New Materials Co., Ltd., with a specification of 500nm.
[0025] Example 1
[0026] This embodiment provides a method for preparing regenerated yarn with high mechanical properties, including the following steps:
[0027] Accurately weigh 1.0 g of anhydrous calcium chloride (CaCl2) and 19.0 g of formic acid (FA) solution, mix and stir until dissolved to prepare a 5 wt% FA-CaCl2 solution, which is then refrigerated at 4°C for later use. Weigh 0.5 g of degummed silk and dissolve it in 2.835 g of FA-CaCl2 solution, stirring at room temperature for 4 h to prepare a 15 wt% RSF solution.
[0028] Functional Cr3C2 / RSF fiber composites were prepared by mixing Cr3C2 with a silk fibroin solution and then spinning using a wet spinning method. First, Cr3C2 was added to a 5 wt% calcium chloride formic acid solution and stirred for 0.5 h to ensure uniform dispersion of Cr3C2, resulting in a Cr3C2 suspension. Then, 0.5 g of degummed silk was added and stirred for 4 h to prepare a 1% (w / w) Cr3C2 / RSF solution (Cr3C2 to RSF mass ratio 1:100).
[0029] Using a self-made wet spinning apparatus, the spinning solution was injected into a coagulation tank via a syringe. The coagulation tank was 1 m long, and 75% ethanol was used as the coagulation solution. The spinning solution entered the coagulation bath through the spinning needle at a rate of 33.33 μL / min. The spinning solution rapidly coagulated into uniform filaments in the coagulation bath. The nascent fibers were stretched and then wound onto a rotating shaft for collection. The collected RSF fibers were placed in a 75% ethanol solution for 2 hours to remove residual solvent and set the fibers. Finally, the RSF fibers were removed and air-dried for 24 hours.
[0030] The tensile strength of the Cr3C2 / RSF fiber obtained in Example 1 is concentrated at 261.54 ± 3.61 MPa. Figure 1 ).
[0031] Example 2
[0032] The specific implementation method is basically the same as that in Example 1, except that the mass ratio of Cr3C2 to RSF is 2:100.
[0033] The breaking strength of the CDs / RSF fibers obtained in Example 2 is concentrated at 266.88 ± 4.64 MPa. Figure 1 ).
[0034] Example 3
[0035] The specific implementation method is basically the same as that in Example 1, except that the mass ratio of Cr3C2 to RSF is 3:100.
[0036] The tensile strength of the Cr3C2 / RSF fiber obtained in Example 3 is concentrated at 313.23 ± 3.68 MPa. Figure 1 ).
[0037] Example 4
[0038] The specific implementation method is basically the same as in Example 1, except that the mass ratio of Cr3C2 to RSF is 4:100.
[0039] The tensile strength of the Cr3C2 / RSF fiber obtained in Example 4 is concentrated at 296.83 ± 6.81 MPa. Figure 1 ).
[0040] Example 5
[0041] The specific implementation method is basically the same as in Example 1, except that the mass ratio of Cr3C2 to RSF is 5:100.
[0042] The breaking strength of the CDs / RSF fibers obtained in Example 5 is concentrated at 286.50 ± 3.50 MPa. Figure 1 ).
[0043] Example 6
[0044] After obtaining the Cr3C2 / RSF fiber from Example 3, it was aged outdoors under natural light for 30 days (RH: 70%, 26℃). After aging, the sample was removed and placed in a disposable plastic bag, stored at room temperature away from light, pending tensile property testing. The results are as follows: Figure 2 As shown, the breaking strength of Cr3C2 / RSF fiber is concentrated at 263.42±4.30MPa.
[0045] Comparative Example 1
[0046] The specific implementation method is basically the same as in Example 1, except that the amount of Cr3C2 added in step (1) is 0g. This comparative example is a blank control group. The fracture strength of the obtained RSF was tested according to the method in Example 1, and the results are as follows. Figure 3 As shown, the breaking strength of silk fibers is concentrated at 203.32±5.22MPa.
[0047] Comparative Example 2
[0048] The specific implementation method is basically the same as in Example 6, except that the tested fiber is not Cr3C2 / RSF, but rather blank control RSF fiber. The results are as follows: Figure 3 As shown, the breaking strength of RSF fibers is concentrated at 126.54±4.88MPa.
Claims
1. A method for preparing regenerated yarn with high mechanical properties, characterized in that, Includes the following steps: (1) Preparation of Cr3C2 suspension: 480 nm - 520 nm Cr3C2 is added to calcium chloride formic acid solution and stirred to make Cr3C2 uniformly dispersed in solution to obtain Cr3C2 suspension; (2) Preparation of functional regenerated silk fibers: Cr3C2 suspension is mixed with silk fibroin solution to obtain Cr3C2 / RSF mixed solution. The Cr3C2 / RSF mixed solution is then used to prepare a functional Cr3C2 / RSF fiber composite, i.e. regenerated silk with high mechanical properties, by wet spinning. The RSF is regenerated silk. The mass ratio of Cr3C2 to RSF in the Cr3C2 / RSF mixed solution is 1-5:
100.
2. The method for preparing high-mechanical-performance regenerated yarn according to claim 1, characterized in that, In step (2), the silk fibroin solution is prepared by dissolving degummed silk in a calcium chloride formic acid solution, stirring, and dispersing evenly to obtain the silk fibroin solution.
3. The method for preparing high-mechanical-performance regenerated yarn according to claim 2, characterized in that, The mass concentration of calcium chloride is 5%-10%, and the mass concentration of the prepared silk fibroin solution is 10%-15%.
4. The method for preparing high-mechanical-performance regenerated yarn according to claim 1, characterized in that, In step (2), the wet spinning method is as follows: the Cr3C2 / RSF mixed solution is injected into the coagulation tank and ethanol is used as the coagulation liquid; the Cr3C2 / RSF mixed solution enters the coagulation bath through the spinning needle and then quickly solidifies into uniform filamentous Cr3C2 / RSF fibers in the coagulation bath, which are then wound onto the rotating shaft and collected after stretching treatment.
5. The method for preparing high-mechanical-performance regenerated yarn according to claim 4, characterized in that, In the wet spinning process, 75% ethanol is used as the coagulation solution.
6. The method for preparing high-mechanical-performance regenerated yarn according to claim 4, characterized in that, In the wet spinning process, the Cr3C2 / RSF mixed solution enters the coagulation bath through the spinning needle at a rate of 33.33 μL / min.
7. The method for preparing high-mechanical-performance regenerated yarn according to claim 4, characterized in that, The collected Cr3C2 / RSF fibers were placed in a 75% ethanol solution to remove residual solvent and set, and then air-dried naturally.
8. A regenerated yarn with high mechanical properties prepared by the method according to any one of claims 1-4.