CN104264263A - Fibroin/carbon nano tube hybridization fiber and preparation method thereof - Google Patents
Fibroin/carbon nano tube hybridization fiber and preparation method thereof Download PDFInfo
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- CN104264263A CN104264263A CN201410456694.XA CN201410456694A CN104264263A CN 104264263 A CN104264263 A CN 104264263A CN 201410456694 A CN201410456694 A CN 201410456694A CN 104264263 A CN104264263 A CN 104264263A
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Abstract
The invention belongs to the technical field of natural polymer materials, organic/inorganic hybridization materials and textile fibers, and particularly discloses a fibroin/carbon nano tube hybridization fiber and a preparation method thereof. A fibroin and carbon nano tube mixed aqueous solution is adopted as a spinning solution; an ammonium sulfate aqueous solution is coagulating bath, and the fibroin/carbon nano tube hybridization fiber is prepared by adopting a wet spinning method. The preparation technology is simple, is environmentally friendly, saves energy, and is efficient; the obtained fibroin/carbon nano tube hybridization fiber is good in mechanical performance, is adjustable, is comparable with natural spider silk in comprehensive mechanical performance under an appropriate technological condition, and has very high application potential in the field of biological materials and the textile industry.
Description
Technical field
The invention belongs to natural macromolecular material, organic/inorganic hybridization material and textile fabric field, be specifically related to a kind of silk-fibroin/carbon nano-tube hybridization fiber and preparation method thereof.
Background technology
Spider silk attracts the research interest of many scientists with the mechanical property of its excellence always, and its comprehensive mechanical property exceedes current any one artificial fibre.But up to the present, natural spider silk still cannot obtain in a large number, have broad application prospects due to it in high performance material field, the fibrous material that therefore artificial preparation has spider silk excellent mechanical performance is the target that scientists is explored always simultaneously.Applicant is (publication number is respectively CN 1664183A and CN 1664184A) in the first two patent of invention, the high concentration regeneration Bombyx-mori Silk Proteins aqueous solution is adopted to be spinning solution, salting liquid or alcohols are coagulating bath, obtain by wet spinning the regenerated silk azelon that comprehensive mechanical property exceedes natural silk cocoon silk, but the performance of itself and spider silk still has a certain distance.
In recent years, people attempt the mechanical property improving regenerated silk azelon by adding inorganic matter in silk protein solution, and as Zhang Yaopeng etc. passes through to add titania nanoparticles, obtaining energy to failure is 93.1 ± 27.1 MJ/m
3hybridized fiber (J. Mater. Chem. B, 2014,2:1408).CNT is owing to having extremely excellent mechanical property (stretch modulus of Single Walled Carbon Nanotube and tensile strength can reach 1 TPa and 200 GPa) and electrical and thermal conductivity performance simultaneously, and therefore it shows great potential in the enhancing of macromolecular material.Existing some employing silk-fibroins and CNT carry out the report of electrostatic spinning, but cannot be compared with natural silk fibers by its mechanical property of these nanofibers that electrostatic spinning obtains, and they exist larger difference with traditional fibrous material.
Based on above situation, the present invention uses the regenerated silk azelon wet spinning process of inventor's prior disclosure, adopts regenerated silk albumen/CNT mixed aqueous solution to be spinning solution, obtains high performance silk-fibroin/carbon nano-tube hybridization fiber.Preparation technology of the present invention is simple, and environmental friendliness, efficient energy-saving, the silk-fibroin obtained/carbon nano-tube hybridization fiber, its comprehensive mechanical property can compare favourably with natural spider silk.
Summary of the invention
The object of the present invention is to provide a kind of preparation process simple, environmental friendliness, high-performance silk-fibroin/carbon nano-tube hybridization fiber of efficient energy-saving and preparation method thereof.
The preparation method of high-performance silk-fibroin/carbon nano-tube hybridization fiber that the present invention proposes, with regenerated silk albumen/CNT mixed aqueous solution for spinning solution, ammonium sulfate is that wet spinning is carried out in coagulating bath, and concrete steps are as follows:
(1) under agitation added in regenerated silk protein aqueous solution by carbon nano-tube aqueous solutions, making in the mass concentration of mixed aqueous solution intermediate filment is 13 ~ 20%, and the mass ratio of CNT and silk-fibroin is 1:1000 ~ 1:100;
(2) using regenerated silk albumen/CNT mixed solution as spinning solution, adopt common spinning equipment to carry out wet spinning.Wherein adopt mass concentration be the ammonium sulfate solution of 30 ~ 40% as coagulating bath, spinning temperature is 50 ~ 70 DEG C, and spinning speed is 7 ~ 15 m/min, and after-drawing multiplying power is 6 ~ 9 times.
In the present invention, the mass concentration of step (1) described regenerated silk protein aqueous solution is 17 ~ 25%, can be passed through step acquisitions such as coming unstuck, lithium bromide dissolves, deionized water dialysis removing lithium bromide, Aqueous Solutions of Polyethylene Glycol retrodialysis are concentrated by natural silk;
The concrete operation step of said method is as follows:
According to the method that this area researcher knows, by natural silk through coming unstuck, lithium bromide dissolves, deionized water dialysis removing lithium bromide, Aqueous Solutions of Polyethylene Glycol retrodialysis are concentrated etc., and step obtains mass concentration is the regenerated silk protein aqueous solution of 17 ~ 25%; Be that the ratio of 1:2 joins in deionized water with mass ratio by functionalized multi-wall carbonnanotubes and lauryl sodium sulfate, after 30 min ultrasonic disperse, form the solution of stable uniform; Under agitation added in regenerated silk protein aqueous solution by carbon nano-tube aqueous solutions after stable, making in the mass concentration of mixed aqueous solution intermediate filment is 13 ~ 20%, and the mass ratio of CNT and silk-fibroin is 1:1000 ~ 1:100; Using regenerated silk albumen/CNT mixed aqueous solution as spinning solution, mass concentration is that the ammonium sulfate solution of 30 ~ 40% is as coagulating bath, common spinning equipment is adopted to carry out wet spinning, wherein spinning temperature is adopted to be 50 ~ 70 DEG C, spinning speed is 7 ~ 15 m/min, and after-drawing multiplying power is 6 ~ 9 times.
The present invention adopts regenerated silk albumen/CNT mixed aqueous solution as spinning solution, and ammonium sulfate solution is as coagulating bath, and whole wet spinning process does not relate to other poisonous and harmful organic solvents, environmental protection; The regenerated silk albumen obtained/its fracture strength of carbon nano-tube hybridization fiber is 0.1 ~ 0.5 GPa, and elongation at break is 30% ~ 120%, and energy to failure is 50 ~ 240 MJ/m
3, good mechanical performance, adjustable, its energy to failure of hybridized fiber that wherein performance is best has reached the level of natural spider silk.
Accompanying drawing explanation
Fig. 1 is the regenerated silk albumen/carbon nano-tube hybridization fiber prepared.
Detailed description of the invention
Below utilize embodiment to further describe the present invention, but can not think to limit scope of invention.
Embodiment 1: natural silk is passed through steps such as coming unstuck, lithium bromide dissolves, deionized water dialysis removing lithium bromide, Aqueous Solutions of Polyethylene Glycol retrodialysis are concentrated, acquisition mass concentration is the regenerated silk protein aqueous solution of 17 ~ 25%;
Under agitation added in regenerated silk protein aqueous solution by carbon nano-tube aqueous solutions after stable, making in the mass concentration of mixed aqueous solution intermediate filment is 15%, and the mass ratio of CNT and silk-fibroin is 1:1000, it can be used as spinning solution to carry out wet spinning.In wet spinning, the concentration of coagulating bath ammonium sulfate is 30%, and spinning temperature is 60 DEG C, and spinning speed is 9.5 m/min, and after-drawing multiplying power is 6 times.The fracture strength of the silk-fibroin obtained thus/carbon nano-tube hybridization fiber is 0.23 GPa, and elongation at break is 71%, and energy to failure is 130 MJ/m
3.
Embodiment 2: by natural silk through coming unstuck, lithium bromide dissolves, deionized water dialysis removing lithium bromide, Aqueous Solutions of Polyethylene Glycol retrodialysis are concentrated etc., and step obtains mass concentration is the regenerated silk protein aqueous solution of 17 ~ 25%; Under agitation added in regenerated silk protein aqueous solution by carbon nano-tube aqueous solutions after stable, making in the mass concentration of mixed aqueous solution intermediate filment is 15%, and the mass ratio of CNT and silk-fibroin is 1:500, it can be used as spinning solution to carry out wet spinning.In wet spinning, the concentration of coagulating bath ammonium sulfate is 30%, and spinning temperature is 60 DEG C, and spinning speed is 9.5 m/min, and after-drawing multiplying power is 9 times.The fracture strength of the silk-fibroin obtained thus/carbon nano-tube hybridization fiber is 0.42 GPa, and elongation at break is 59%, and energy to failure is 186 MJ/m
3.
Embodiment 3: by natural silk through coming unstuck, lithium bromide dissolves, deionized water dialysis removing lithium bromide, Aqueous Solutions of Polyethylene Glycol retrodialysis are concentrated etc., and step obtains mass concentration is the regenerated silk protein aqueous solution of 17 ~ 25%; Under agitation added in regenerated silk protein aqueous solution by carbon nano-tube aqueous solutions after stable, making in the mass concentration of mixed aqueous solution intermediate filment is 13%, and the mass ratio of CNT and silk-fibroin is 1:100, it can be used as spinning solution to carry out wet spinning.In wet spinning, the concentration of coagulating bath ammonium sulfate is 30%, and spinning temperature is 60 DEG C, and spinning speed is 9.5 m/min, and after-drawing multiplying power is 9 times.The fracture strength of the silk-fibroin obtained thus/carbon nano-tube hybridization fiber is 0.34 GPa, and elongation at break is 56%, and energy to failure is 150 MJ/m
3.
Embodiment 4: by natural silk through coming unstuck, lithium bromide dissolves, deionized water dialysis removing lithium bromide, Aqueous Solutions of Polyethylene Glycol retrodialysis are concentrated etc., and step obtains mass concentration is the regenerated silk protein aqueous solution of 17 ~ 25%; Under agitation added in regenerated silk protein aqueous solution by carbon nano-tube aqueous solutions after stable, making in the mass concentration of mixed aqueous solution intermediate filment is 17%, and the mass ratio of CNT and silk-fibroin is 1:500, it can be used as spinning solution to carry out wet spinning.In wet spinning, the concentration of coagulating bath ammonium sulfate is 30%, and spinning temperature is 50 DEG C, and spinning speed is 9.5 m/min, and after-drawing multiplying power is 6 times.The fracture strength of the silk-fibroin obtained thus/carbon nano-tube hybridization fiber is 0.11 GPa, and elongation at break is 81%, and energy to failure is 84 MJ/m
3.
Embodiment 5: the carbon nano-tube aqueous solutions after stable is under agitation added in regenerated silk protein aqueous solution, making in the mass concentration of mixed aqueous solution intermediate filment is 15%, the mass ratio of CNT and silk-fibroin is 1:500, it can be used as spinning solution to carry out wet spinning.In wet spinning, the concentration of coagulating bath ammonium sulfate is 40%, and spinning temperature is 60 DEG C, and spinning speed is 14 m/min, and after-drawing multiplying power is 6 times.The fracture strength of the silk-fibroin obtained thus/carbon nano-tube hybridization fiber is 0.16 GPa, and elongation at break is 49%, and energy to failure is 63 MJ/m
3.
Embodiment 6: the carbon nano-tube aqueous solutions after stable is under agitation added in regenerated silk protein aqueous solution, making in the mass concentration of mixed aqueous solution intermediate filment is 15%, the mass ratio of CNT and silk-fibroin is 1:200, it can be used as spinning solution to carry out wet spinning.In wet spinning, the concentration of coagulating bath ammonium sulfate is 30%, and spinning temperature is 70 DEG C, and spinning speed is 12 m/min, and after-drawing multiplying power is 6 times.The fracture strength of the silk-fibroin obtained thus/carbon nano-tube hybridization fiber is 0.21 GPa, and elongation at break is 94%, and energy to failure is 163 MJ/m
3.
Embodiment 7: by natural silk through coming unstuck, lithium bromide dissolves, deionized water dialysis removing lithium bromide, Aqueous Solutions of Polyethylene Glycol retrodialysis are concentrated etc., and step obtains mass concentration is the regenerated silk protein aqueous solution of 17 ~ 25%; Under agitation added in regenerated silk protein aqueous solution by carbon nano-tube aqueous solutions after stable, making in the mass concentration of mixed aqueous solution intermediate filment is 15%, and the mass ratio of CNT and silk-fibroin is 1:500, it can be used as spinning solution to carry out wet spinning.In wet spinning, the concentration of coagulating bath ammonium sulfate is 30%, and spinning temperature is 60 DEG C, and spinning speed is 7 m/min, and after-drawing multiplying power is 9 times.The fracture strength of the silk-fibroin obtained thus/carbon nano-tube hybridization fiber is 0.33 GPa, and elongation at break is 90%, and energy to failure is 240 MJ/m
3.
Claims (3)
1. a preparation method for silk-fibroin/carbon nano-tube hybridization fiber, is characterized in that: with regenerated silk albumen/CNT mixed aqueous solution for spinning solution, and ammonium sulfate is that wet spinning is carried out in coagulating bath, and concrete steps are as follows:
(1) under agitation added in regenerated silk protein aqueous solution by carbon nano-tube aqueous solutions, making in the mass concentration of mixed aqueous solution intermediate filment is 13 ~ 20%, and the mass ratio of CNT and silk-fibroin is 1:1000 ~ 1:100;
(2) using regenerated silk albumen/CNT mixed solution as spinning solution, carry out wet spinning; Wherein adopt mass concentration be the ammonium sulfate solution of 30 ~ 40% as coagulating bath, spinning temperature is 50 ~ 70 DEG C, and spinning speed is 7 ~ 15 m/min, and after-drawing multiplying power is 6 ~ 9 times.
2. preparation method according to claim 1, it is characterized in that: the mass concentration of step (1) described regenerated silk protein aqueous solution is 17 ~ 25%, by natural silk through coming unstuck, lithium bromide dissolves, deionized water dialyses removing lithium bromide, Aqueous Solutions of Polyethylene Glycol retrodialysis is concentrated obtains.
3. the silk-fibroin obtained by preparation method according to claim 1/carbon nano-tube hybridization fiber, is characterized in that: fracture strength is 0.1 ~ 0.5 GPa, and elongation at break is 30% ~ 120%, and energy to failure is 50 ~ 240 MJ/m
3.
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Cited By (8)
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| CN104894681A (en) * | 2015-06-08 | 2015-09-09 | 苏州威尔德工贸有限公司 | Spider silk protein/carbon nanotube conductive composite fiber and preparation method thereof |
| CN104975368A (en) * | 2015-07-27 | 2015-10-14 | 天津工业大学 | Multiwalled carbon nanotube and graphene reinforced modified regenerated protein fiber and preparation method thereof |
| 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 |
| CN107475807A (en) * | 2017-08-30 | 2017-12-15 | 常州豫春化工有限公司 | A kind of preparation method of the fiber of modification of nylon 6 |
| 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 |
| CN109385684A (en) * | 2018-09-30 | 2019-02-26 | 厦门大学 | A kind of composite conducting fiber and preparation method thereof |
| CN109401337A (en) * | 2018-09-30 | 2019-03-01 | 厦门大学 | A kind of flexible compound conductive film and preparation method thereof |
| CN109505029A (en) * | 2018-12-25 | 2019-03-22 | 徐敏 | A kind of preparation method of modified silk fiber |
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| CN1664183A (en) * | 2005-03-17 | 2005-09-07 | 复旦大学 | Regenerated silk fiber with salt solution as coagulating bath and method for preparing same |
| CN101748504A (en) * | 2009-12-23 | 2010-06-23 | 东华大学 | Preparation method of regenerative silk protein fiber with skin-core structure |
| 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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| WO2005045122A1 (en) * | 2003-11-04 | 2005-05-19 | Drexel University | Electrospun carbon nanotube reinforced silk fibers |
| CN1664183A (en) * | 2005-03-17 | 2005-09-07 | 复旦大学 | Regenerated silk fiber with salt solution as coagulating bath and method for preparing same |
| CN101748504A (en) * | 2009-12-23 | 2010-06-23 | 东华大学 | Preparation method of regenerative silk protein fiber with skin-core structure |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104894681A (en) * | 2015-06-08 | 2015-09-09 | 苏州威尔德工贸有限公司 | Spider silk protein/carbon nanotube conductive composite fiber and preparation method thereof |
| CN104975368A (en) * | 2015-07-27 | 2015-10-14 | 天津工业大学 | Multiwalled carbon nanotube and graphene reinforced modified regenerated protein fiber and preparation method thereof |
| CN104975368B (en) * | 2015-07-27 | 2017-04-12 | 天津工业大学 | Multiwalled carbon nanotube and graphene reinforced modified regenerated protein fiber and preparation method thereof |
| 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 |
| CN107475807A (en) * | 2017-08-30 | 2017-12-15 | 常州豫春化工有限公司 | A kind of preparation method of the fiber of modification of nylon 6 |
| 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 |
| CN109385684A (en) * | 2018-09-30 | 2019-02-26 | 厦门大学 | A kind of composite conducting fiber and preparation method thereof |
| CN109401337A (en) * | 2018-09-30 | 2019-03-01 | 厦门大学 | A kind of flexible compound conductive film and preparation method thereof |
| CN109505029A (en) * | 2018-12-25 | 2019-03-22 | 徐敏 | A kind of preparation method of modified silk fiber |
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