CN109385684A - A kind of composite conducting fiber and preparation method thereof - Google Patents

A kind of composite conducting fiber and preparation method thereof Download PDF

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Publication number
CN109385684A
CN109385684A CN201811162534.9A CN201811162534A CN109385684A CN 109385684 A CN109385684 A CN 109385684A CN 201811162534 A CN201811162534 A CN 201811162534A CN 109385684 A CN109385684 A CN 109385684A
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solution
composite conducting
conducting fiber
preparation
fiber
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刘向阳
刘强
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Xiamen University
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Xiamen University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F4/00Monocomponent artificial filaments or the like of proteins; Manufacture thereof
    • D01F4/02Monocomponent artificial filaments or the like of proteins; Manufacture thereof from fibroin
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/09Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention provides a kind of composite conducting fiber and preparation method thereof, is related to conductive fiber technical field.Its step includes: S1, prepares silk fibroin protein solution.Silk fibroin protein solution is mixed with multi-walled carbon nanotube solution, obtains spinning solution by S2;Wherein, the mass ratio of fibroin albumen and multi-walled carbon nanotube is 1:0.1~0.35 in spinning solution.Spinning solution is injected into coagulating bath solidification using wet spinning technology and obtains as-spun fibre by S3, and the as-spun fibre is via stretching, obtain composite conducting fiber after steam treatment.Fibroin albumen and multi-walled carbon nanotube are combined by this composite conducting fiber on a molecular scale, guarantee that multi-walled carbon nanotube is not easy to fall off, have good flexibility and electric conductivity.And its preparation process is simple and is easy to produce in batches.

Description

A kind of composite conducting fiber and preparation method thereof
Technical field
The present invention relates to conductive fiber technical fields, and in particular to a kind of composite conducting fiber and preparation method thereof.
Background technique
Silk fiber is unique one kind in the extensive natural polymer subbundle of modern Application, there is the laudatory title of " fiber queen ", It can be applied to the fields such as textile garment, biomedicine, photoelectric material, composite material, be prepare composite conducting fiber main One of ingredient.Its main component of silk fiber is fibroin albumen and sericin, and wherein fibroin albumen accounts for about silk total weight 70-80%, sericin account for the 20-30% of total weight.
Currently, the preparation method of composite conducting fiber is main are as follows: conductive material is attached to fiber using different methods Surface, to assign filamentary conductive, such as: (1) using adhesive by conductive material coating be attached on non-conductive fibre surface; (2) conductive material is deposited on by fiber surface by chemistry or electrochemical method;(3) make conduction using airless spraying or plating Material is deposited on fiber surface.Wherein method (1) is most commonly seen adherence method, and still, this adherence method exists conductive Coating is thicker when material is coated on fiber, causes the conductive fiber being prepared excessively sturdy, and the conductive material of coating For particle because the reason of adhering to is easy to fall off, conductive material meets the disadvantages of water is easy dissolution.
Therefore, prepare that a kind of electric conductivity is strong, and conductive material composite conducting fiber not easily to fall off is art technology The research emphasis of personnel.
Summary of the invention
The purpose of the present invention is to provide a kind of composite conducting fiber, this composite conducting fiber is by fibroin albumen and multi wall carbon Nanotube is combined on a molecular scale, guarantees that multi-walled carbon nanotube is not easy to fall off, and composite conducting provided by the invention Fiber have both silk fiber it is flexible simultaneously, and include the multi-walled carbon nanotube of high concentration, it is ensured that composite conducting fiber With good flexibility and electric conductivity.
Another object of the present invention is to provide a kind of preparation method of composite conducting fiber, preparation process it is simple and It is easy to produce in batches.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of preparation method of composite conducting fiber, comprising the following steps:
S1 prepares silk fibroin protein solution.
The silk fibroin protein solution is mixed with multi-walled carbon nanotube solution, obtains spinning solution by S2;Wherein, the spinning The mass ratio of fibroin albumen and multi-walled carbon nanotube is 1:0.1~0.35 in liquid.
The spinning solution is injected into solidification in coagulating bath using wet spinning technology and obtains as-spun fibre by S3, described first Raw fiber is via stretching, obtain composite conducting fiber after steam treatment.
The present invention also proposes a kind of composite conducting fiber, is prepared according to the method described above.
A kind of beneficial effect of composite conducting fiber provided by the invention and preparation method thereof is:
(1) composite conducting fiber provided by the invention has been given up compared with prior art and has coated conduction directly on fiber The method of material guarantees multi-walled carbon nanotube by the way that fibroin albumen and multi-walled carbon nanotube to be combined on a molecular scale Particle is not easily to fall off to fall off from composite conducting fiber, it is ensured that the maintenance of composite conducting fiber electric conductivity.
(2) composite conducting fiber provided by the invention has both the flexible of silk fiber because of the fibroin albumen with high concentration Property and while biocompatibility, and include the multi-walled carbon nanotube of high concentration, it is ensured that composite conducting fiber has good Flexibility and electric conductivity.The present invention has widened the application range of silk fiber, is conducive to push following intelligent textile garment, intelligence The development of flexible wearable electronic device.
(3) preparation method of the invention is simple, easy to operate, no pollution to the environment, and is easy to produce in batches.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this A little attached drawings obtain other relevant attached drawings.
Fig. 1 is composite conducting fiber preparation flow figure provided by the invention;
Fig. 2 is the production composite conducting fiber SEM scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 provides.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase Product.
A kind of composite conducting fiber of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of preparation method of composite conducting fiber provided in an embodiment of the present invention, comprising the following steps:
S1 prepares silk fibroin protein solution.
Further, the preparation method of the silk fibroin protein solution includes the following steps:
S11 puts into the sodium bicarbonate solution that mass fraction is 0.5%~1% after silk cleans and carries out degumming, floats Wash, dry after obtain fibroin fiber.Further, the silk after removal of impurities is placed in the bicarbonate that mass fraction is 0.5%~1% In sodium solution, 60~90min of degumming under the conditions of 60~100 DEG C then obtains fibroin fiber by rinsing, baking step.
S12: the fibroin fiber is placed in lysate and dissolves, obtain initial silk fibroin protein solution after filtering.
Further, the lysate is selected from one of lithium-bromide solution, calcium chloride solution, formic acid, and the fibroin Solution temperature of the fiber in the lysate is 40~60 DEG C, and dissolution time is 4~6h.Preferably, of the invention preferably real It applies in example, the LiBr solution of 9.0~9.5mol/L is selected to dissolve fibroin fiber.
S13 dialyses in ultrapure water after the initial silk fibroin protein solution is placed in bag filter, obtains pure silk Fibroin solution.Further, the molecular cut off of the bag filter is 3500~8000kDa, and initial silk fibroin protein solution exists It dialyses 2~3 days in ultrapure water.
S14, the pure silk fibroin protein solution is counter in anti-dialyzate to be dialysed after centrifugation and filtering, obtains matter Amount score is 20%~40% silk fibroin protein solution.Further, the anti-dialyzate is mass fraction 10%~20% PEG20000 solution.
By being dialysed to silk fibroin protein solution is counter, the silk fibroin protein solution that mass fraction is 20~40% is obtained, really Possessing sufficient concentrations of fibroin albumen can be combined with multi-walled carbon nanotube, guarantee during subsequent wet spinning, spin Silk liquid can be rapidly solidificated into fiber.
The silk fibroin protein solution is mixed with multi-walled carbon nanotube solution, obtains spinning solution by S2;Wherein, the spinning The mass ratio of fibroin albumen and multi-walled carbon nanotube is 1:0.1~0.35 in liquid.It is further preferable that fibroin albumen is received with multi wall carbon Mitron mass ratio is 1:0.2~0.35.Under this ratio, composite conducting fiber prepared by the present invention not only has good stretching Ability, and have good electric conductivity, and inventor also found when multi-walled carbon nanotube content is lower than the content of fibroin albumen 10%, then be unable to get the composite fibre for having electric conductivity.And when multi-walled carbon nanotube content is higher than the content of fibroin albumen 35%, the multi wall carbon mitron of too high levels is easy to reunite in the silk fibroin protein solution of high concentration, leads to fibroin albumen With multi-walled carbon nanotube incomplete mixing, and post-stretching step can not be carried out.
Further, the mass fraction of the multi-walled carbon nanotube solution is 5%-10%.With the multi wall carbon under this concentration Nanotube solution is mixed, and is avoided in mixed process, solution because generating aggregation, deposition containing excessive multi-walled carbon nanotube, The spinning solution multi-walled carbon nanotube prepared and fibroin albumen is caused to disperse uneven, to influence subsequent step.
Further, the silk fibroin protein solution and multi-walled carbon nanotube solution mixing step are as follows: be by mass fraction The multi-walled carbon nanotube solution of 5%-10% be directly added into mass fraction be 20~40% silk fibroin protein solutions in, then slowly into Row turns upside down after mixing, obtains spinning solution after carrying out centrifugation bubble removing to mixed liquor with the revolving speed of 1000rpm.In this mixing step In rapid, ultrasonic mixing and fierce concussion mixing not can be carried out, the fibroin albumen property of high concentration is unstable, in mixed process easily Plastic is solidified, silk fibroin protein solution is eventually led to multi-walled carbon nanotube solution and mixes unevenness, influence the system of composite conducting fiber It is standby.
The spinning solution is injected into solidification in coagulating bath using wet spinning technology and obtains as-spun fibre by S3, described first Raw fiber is via stretching, obtain composite conducting fiber after steam treatment.
Wet spinning technology is that spinning solution is dissolved in solvent, sprays thread by spinneret orifice, forms fibre into coagulating bath The chemical fibre spinning method of dimension.In an embodiment of the present invention, coagulating bath is in methanol, ethyl alcohol, saturated ammonium sulfate solution One kind, coagulating bath can be such that the fibroin albumen in spinning solution solidifies.
Further, the coagulating bath is placed in the container that a length is 1.5~2m, it is ensured that when having enough solidifications Between solidify spinning solution.
Further, the composite conducting fiber is via 2~6 that the length after stretching step is the as-spun fibre length Times.Because of the design feature of multi-walled carbon nanotube, as-spun fibre is stretched to suitable length, peomotes multi-walled carbon nanotube Orientation is neat, facilitates the electric conductivity of product.And to as-spun fibre stretching transition, it is fine to will lead to the composite conducting being prepared Tie up easy fracture;Conversely, stretching is insufficient, then it will affect electric conductivity.
Further, the as-spun fibre after stretching needs to carry out steam treatment, the steaming step are as follows: 40~60 2~6h of steam treatment under the conditions of DEG C, wherein the steam is water vapour or alcohol vapour.Steam treatment can composite conducting fiber mention High-crystallinity keeps the composite conducting fiber after stretching not easy to break to enhance the intensity of composite conducting fiber.
Further, the diameter of the composite conducting fiber is 10~40 μm, is conducive to composite conducting fiber to weave Mode be woven into fabric, the development for following intelligent textile garment, intelligent flexible wearable electronic device lays the foundation.
The present invention also provides a kind of composite conducting fibers, are made according to above-mentioned preparation method.Composite conducting obtained is fine Dimension has given up the method that conductive material is coated directly on fiber, by by fibroin albumen and multi wall carbon compared with prior art Nanotube is combined on a molecular scale, is guaranteed that multi-wall carbon nano-tube tube particle is not easily to fall off and is fallen off from composite conducting fiber, Ensure the maintenance of composite conducting fiber electric conductivity.And composite conducting fiber has both silk because of the fibroin albumen with high-content It while the flexibility and biocompatibility of fiber, and include the multi-walled carbon nanotube of high concentration, it is ensured that composite conducting fiber With good flexibility and electric conductivity.The present invention has widened the application range of silk fiber, is conducive to that the following intelligence is pushed to spin The development of woven garment, intelligent flexible wearable electronic device.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of composite conducting fiber is provided in the present embodiment, is prepared according to the following steps:
(1) 2.5L distilled water is poured into heating in heating kettle to boil, the silk and 25g sodium bicarbonate after 20g is cleaned are consolidated Body pours into carry out degumming in pot together, and control degumming temperature is maintained at 80 DEG C or so, usually time 90min.After degumming Rinsed, dry after obtain fibroin fiber.
(2) 6g fibroin fiber is put into the lithium bromide closed container of 9.3mol/L, constant temperature dissolves under the conditions of 60 DEG C, obtains To initial silk fibroin protein solution.
(3) initial silk fibroin protein solution is filtered and is filled in bag filter again, bag filter is placed in ultrapure water thoroughly 48h is analysed, pure silk fibroin protein solution is obtained.
(4) it is filtered after pure silk fibroin protein solution being centrifuged 20min under 5000rpm revolving speed, is then then transferred to dialysis The PEG20000 solution that 15% is placed in bag obtain after instead dialysing mass fraction as 20% silk fibroin protein solution.
(5) the multi-walled carbon nanotube solution that mass fraction is 8% is added to silk fibroin protein solution and carries out uniformly mixed, system Spinning solution is obtained, wherein the mass ratio of fibroin albumen and multi-walled carbon nanotube is 1:0.25 in the spinning solution.
(6) it takes suitable spinning solution to be transferred in 5ml syringe and be mounted on syringe pump, spinning solution is squeezed from injection needle Enter the coagulation forming into saturated ammonium sulfate solution coagulating bath, obtains as-spun fibre;As-spun fibre is stretched to the 4 of original length Times, steam treatment 4h under the conditions of 40 DEG C obtains composite conducting fiber.
As shown in Fig. 2, for the composite conducting fiber SEM scanning electron microscope (SEM) photograph that embodiment 1 provides, by calculating composite conducting The equivalent diameter of fiber is 20-30 μm.
Embodiment 2
A kind of composite conducting fiber is provided in the present embodiment, is prepared according to the following steps:
(1) 2.5L distilled water is poured into heating in heating kettle to boil, the silk and 12.5g sodium bicarbonate after 20g is cleaned Solid pours into carry out degumming in pot together, and control degumming temperature is maintained at 80 DEG C or so, usually time 80min.Degumming terminates After rinsed, dry after obtain fibroin fiber.
(2) 5g fibroin fiber is put into the lithium bromide closed container of 9.5mol/L, constant temperature dissolves under the conditions of 40 DEG C, obtains To initial silk fibroin protein solution.
(3) initial silk fibroin protein solution is filtered and is filled in bag filter again, bag filter is placed in ultrapure water thoroughly 36h is analysed, pure silk fibroin protein solution is obtained.
(4) it is filtered after pure silk fibroin protein solution being centrifuged 20min under 6000rpm revolving speed, is then then transferred to dialysis The PEG20000 solution that 15% is placed in bag obtain after instead dialysing mass fraction as 30% silk fibroin protein solution.
(5) by mass fraction be 10% multi-walled carbon nanotube solution be added to silk fibroin protein solution carry out it is uniformly mixed, Spinning solution is made, wherein the mass ratio of fibroin albumen and multi-walled carbon nanotube is 1:0.3 in the spinning solution.
(6) it takes suitable spinning solution to be transferred in 5ml syringe and be mounted on syringe pump, spinning solution is squeezed from injection needle Enter the coagulation forming into saturated ammonium sulfate solution coagulating bath, obtains as-spun fibre;As-spun fibre is stretched to the 3 of original length Times, steam treatment 4h under the conditions of 50 DEG C obtains composite conducting fiber.
Embodiment 3
A kind of composite conducting fiber is provided in the present embodiment, is prepared according to the following steps:
(1) 2.5L distilled water is poured into heating in heating kettle to boil, the silk and 12.5g sodium bicarbonate after 20g is cleaned Solid pours into carry out degumming in pot together, and control degumming temperature is maintained at 80 DEG C or so, usually time 90min.Degumming terminates After rinsed, dry after obtain fibroin fiber.
(2) 5g fibroin fiber is put into the lithium bromide closed container of 9mol/L, constant temperature dissolves under the conditions of 50 DEG C, obtains Initial silk fibroin protein solution.
(3) initial silk fibroin protein solution is filtered and is filled in bag filter again, bag filter is placed in ultrapure water thoroughly 72h is analysed, pure silk fibroin protein solution is obtained.
(4) it is filtered after pure silk fibroin protein solution being centrifuged 20min under 8000rpm revolving speed, is then then transferred to dialysis The PEG20000 solution that 20% is placed in bag obtain after instead dialysing mass fraction as 30% silk fibroin protein solution.
(5) by mass fraction be 10% multi-walled carbon nanotube solution be added to silk fibroin protein solution carry out it is uniformly mixed, Spinning solution is made, wherein the mass ratio of fibroin albumen and multi-walled carbon nanotube is 1:0.35 in the spinning solution.
(6) it takes suitable spinning solution to be transferred in 5ml syringe and be mounted on syringe pump, spinning solution is squeezed from injection needle Enter the coagulation forming into ethanol solution coagulating bath, obtains as-spun fibre;As-spun fibre is stretched to 2 times of original length, 50 Steam treatment 4h under the conditions of DEG C, obtains composite conducting fiber.
Comparative example 1
This comparative example provides a kind of composite conducting fiber, and difference from Example 3 is:
The redox graphene solution that mass fraction is 1% is added to silk fibroin protein solution and mixed by step (5) Uniformly, spinning solution is made, wherein the mass ratio of fibroin albumen and graphene is 1:0.2 in the spinning solution.
Step (6) takes suitable spinning solution to be transferred in 5ml syringe and on the syringe pump, by spinning solution from injection needle Head is squeezed into coagulation forming in saturated ammonium sulfate solution coagulating bath, and obtaining as-spun fibre is composite conducting fiber.
Comparative example 2
This comparative example provides a kind of pure fibroin fiber, and difference from Example 3 is:
It omits step (5).
Step (6) takes suitable silk fibroin protein solution to be transferred in 5ml syringe and on the syringe pump, by spinning solution from Injection needle is squeezed into coagulation forming in saturated ammonium sulfate solution coagulating bath, obtains as-spun fibre;As-spun fibre is stretched to original 2 times for carrying out length, steam treatment 4h under the conditions of 50 DEG C, obtain pure fibroin fiber.
Test example
Conductance is obtained after Examples 1 to 3 and comparative example 1~2 are tested its resistance with four probe semiconductor parametric testers Rate, the results are shown in Table 1.
1~2 conducting performance test table of 1. Examples 1 to 3 of table and comparative example
Conductivity (S/cm)
Embodiment 1 0.771
Embodiment 2 1.225
Embodiment 3 6.389
Comparative example 1 0
Comparative example 2 0
As can be seen from Table 1, Examples 1 to 3 is conductive, and multi-walled carbon nanotube content in composite fibre More, electric conductivity is stronger.But it is corresponding, multi-walled carbon nanotube content is more, and fibroin albumen content tails off, level of stretch Weaken therewith.Thus good level of stretch can be guaranteed by taking median both, can also have good electric conductivity.
Comparative example 1 finds that it can not be stretched during the experiment, and comparative example 1 and comparative example 2 as can be seen from Table 1 Do not have electric conductivity, thus demonstrate not any conductive material can in conjunction with fibroin albumen after have Standby electric conductivity.This is because the group contained by the material of electric conductivity is different, can destroy fibroin albumen structure to a certain extent makes It does not have stretch capability, and in destructive process, and conductive material can also change the structure of oneself, it is caused not have conduction Property.But by inventor it has been investigated that the combination of multi-walled carbon nanotube and fibroin albumen, it can prepare and obtain and have both high-flexibility With the composite conducting fiber of high conduction performance.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts Every other embodiment, shall fall within the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of composite conducting fiber, which comprises the following steps:
S1 prepares silk fibroin protein solution;
The silk fibroin protein solution is mixed with multi-walled carbon nanotube solution, obtains spinning solution by S2;Wherein, in the spinning solution The mass ratio of fibroin albumen and multi-walled carbon nanotube is 1:0.1~0.35;
The spinning solution is injected into solidification in coagulating bath using wet spinning technology and obtains as-spun fibre, the nascent fibre by S3 It ties up and obtains composite conducting fiber via after stretching, steam treatment.
2. the preparation method of composite conducting fiber according to claim 1, which is characterized in that the steaming step Are as follows: water vapour or alcohol vapour handle 2~6h to the as-spun fibre after stretching under the conditions of 40~60 DEG C.
3. according to the preparation method of composite conducting fiber described in claim 1, which is characterized in that the as-spun fibre is via stretching Length after step is 2~6 times of initial length.
4. the preparation method of composite conducting fiber according to claim 1, which is characterized in that the coagulating bath is selected from first One of alcohol, ethyl alcohol, saturated ammonium sulfate solution.
5. the preparation method of composite conducting fiber according to claim 1, which is characterized in that the composite conducting fiber Diameter is 10~40 μm.
6. according to the preparation method of composite conducting fiber described in claim 1, which is characterized in that the system of the silk fibroin protein solution Preparation Method includes the following steps:
S11: putting into after silk is cleaned and carry out degumming in the sodium bicarbonate solution that mass fraction is 0.5%~1%, and rinsing is dried Fibroin fiber is obtained after dry;
S12: the fibroin fiber is placed in lysate and dissolves, obtain initial silk fibroin protein solution after filtering;
S13: dialysing in ultrapure water after the initial silk fibroin protein solution is placed in bag filter, obtains pure fibroin egg White solution;
S14: the pure silk fibroin protein solution is counter in anti-dialyzate to be dialysed after centrifugation and filtering, obtains quality point Number is 20%~40% silk fibroin protein solution.
7. according to the preparation method of composite conducting fiber as claimed in claim 6, which is characterized in that in step s 12, the dissolution Liquid is selected from one of lithium-bromide solution, calcium chloride solution, formic acid, and dissolution temperature of the fibroin fiber in the lysate Degree is 40~60 DEG C, and dissolution time is 4~6h.
8. according to the preparation method of composite conducting fiber as claimed in claim 6, which is characterized in that in step s 13, the dialysis The molecular cut off of bag is 3500~8000kDa.
9. according to the preparation method of composite conducting fiber as claimed in claim 6, which is characterized in that described anti-saturating in step S14 Analyse the PEG20000 solution that liquid is mass fraction 10%~20%.
10. a kind of composite conducting fiber, which is characterized in that the preparation method of any one is made according to claim 1~9.
CN201811162534.9A 2018-09-30 2018-09-30 A kind of composite conducting fiber and preparation method thereof Pending CN109385684A (en)

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CN110230113A (en) * 2019-06-14 2019-09-13 武汉纺织大学 A kind of silver nanowires/fibroin albumen composite fibre and preparation method thereof
CN112326743A (en) * 2020-11-05 2021-02-05 重庆医科大学 C-SF-FA flexible conductive film based on silk fibroin, wearable wound monitoring sensor and preparation method of wearable wound monitoring sensor

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CN104451933A (en) * 2014-12-09 2015-03-25 张丽明 Method for preparing nano-fiber material containing sericin/nano carbon
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110230113A (en) * 2019-06-14 2019-09-13 武汉纺织大学 A kind of silver nanowires/fibroin albumen composite fibre and preparation method thereof
CN110230113B (en) * 2019-06-14 2021-12-03 武汉纺织大学 Silver nanowire/silk fibroin composite fiber and preparation method thereof
CN112326743A (en) * 2020-11-05 2021-02-05 重庆医科大学 C-SF-FA flexible conductive film based on silk fibroin, wearable wound monitoring sensor and preparation method of wearable wound monitoring sensor
CN112326743B (en) * 2020-11-05 2024-01-16 重庆医科大学 C-SF-FA flexible conductive film based on silk fibroin, wearable wound monitoring sensor and preparation method thereof

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Application publication date: 20190226