阅读说明：本技术 一种导电生物纤维及其制备方法及应用 (Conductive biological fiber and preparation method and application thereof ) 是由 靳世东 詹世治 彭礼明 于 2021-08-05 设计创作，主要内容包括：本发明涉及材料技术领域,具体涉及一种导电生物纤维及其制备方法及应用。本发明由以下各组分组成,并按下述重量份混合：丝素蛋白纤维10-20份；金属纳米线5-20份；聚苯乙烯微球1-3份；双蒸水20-70份；沙林树脂5-15份；紫外吸收剂1-3份；以及抗氧剂1-3份。本发明利用丝素蛋白纤维既柔韧、强度又高的结构特点,结合纳米银线可柔性且导电性高,制备的生物导电纤维具有较好的拉伸强度和断裂伸长率,纳米银线的加入可以改善纤维的耐弯折性能和导电性能,同时添加沙林树脂、紫外吸收剂以及抗氧剂用以保护金属纳米线与丝素蛋白的复合纺丝,具有较好的市场前景。(The invention relates to the technical field of materials, in particular to a conductive biological fiber and a preparation method and application thereof. The invention consists of the following components which are mixed according to the following parts by weight: 10-20 parts of silk fibroin fibers; 5-20 parts of metal nanowires; 1-3 parts of polystyrene microspheres; 20-70 parts of double distilled water; 5-15 parts of sarin resin; 1-3 parts of an ultraviolet absorbent; and 1-3 parts of antioxidant. The invention utilizes the structural characteristics of flexibility, strength and high conductivity of the silk fibroin fiber, combines the flexibility and high conductivity of the nano silver wire, and the prepared biological conductive fiber has better tensile strength and elongation at break, the addition of the nano silver wire can improve the bending resistance and conductivity of the fiber, and meanwhile, the sarin resin, the ultraviolet absorbent and the antioxidant are added to protect the composite spinning of the metal nanowire and the silk fibroin, thereby having better market prospect.)

1. A conductive biofiber, characterized in that: the composition consists of the following components in part by weight:

10-20 parts of silk fibroin fibers;

5-20 parts of metal nanowires;

1-3 parts of polystyrene microspheres;

20-70 parts of double distilled water;

5-15 parts of sarin resin;

1-3 parts of an ultraviolet absorbent;

1-3 parts of an antioxidant.

2. The conductive biofiber of claim 1, wherein: the composition consists of the following components in part by weight:

15 parts of silk fibroin fibers;

10 parts of metal nanowires;

2 parts of polystyrene microspheres;

60 parts of double distilled water;

15 parts of sarin resin;

2 parts of an ultraviolet absorbent;

1.5 parts of antioxidant.

3. The conductive biofiber of claim 1, wherein: the metal nanowire comprises at least one of a gold nanowire, a copper nanowire and a silver nanowire.

4. The conductive biofiber of claim 3, wherein: the diameter of the metal nanowire is 10-80nm, the length of the metal nanowire is 10-80 mu m, and the length-diameter ratio of the metal nanowire is more than 1000.

5. The conductive biofiber of claim 1, wherein: the ultraviolet absorbent comprises at least one of benzophenones, benzotriazoles, hindered amines and triazines.

6. The conductive biofiber of claim 1, wherein: the antioxidant comprises at least one of a phosphite antioxidant and a phenolic antioxidant.

7. The conductive biofiber of claim 6, wherein:

the phosphite ester antioxidant comprises antioxidant 168, triphenyl phosphite, diphenyl phosphite, triisooctyl phosphite, triisodecyl phosphite and trilauryl phosphite;

the phenolic antioxidant comprises antioxidant 1790, tert-butylhydroquinone, 2, 6-di-tert-butylphenol and hydroxytyrosol.

8. The conductive biofiber of claim 6, wherein: the antioxidant is prepared by mixing phosphite antioxidant and phenolic antioxidant according to the mass ratio of 1: 3.

9. A preparation method of conductive biological fiber is characterized in that: the method comprises the following steps:

the method comprises the following steps: preparing silk fibroin fibers;

step two: preparing a spinning solution: adding double distilled water into a three-neck flask, heating to a slightly boiling state, adding sarin resin while stirring, adding an ultraviolet absorbent, an antioxidant, polystyrene microspheres, silk fibroin fibers and metal nanowires in sequence after the sarin resin is dissolved, and stirring and mixing uniformly;

step three: pretreatment of spinning solution: filtering the spinning solution obtained in the step two through a filter, and defoaming;

step four: spinning and forming: and (4) feeding the spinning solution obtained in the step three into spinning machine equipment, controlling a spinning pump to measure, spinning the spinning solution through a spinning nozzle, and drying and curing the spun and formed biological fiber through gradient heating and cooling to obtain the conductive biological fiber.

10. Use of the conductive biofiber of any one of claims 1-8 in the field of smart skin, sensors, wearable electronics.

Technical Field

The invention relates to the technical field of materials, in particular to a conductive biological fiber and a preparation method and application thereof.

Background

In recent years, with the rapid development of electronic information, flexible, light and thin conductive products have become objects of wide attention; the flexible transparent conductive film is a flexible film material with high light transmittance and excellent conductive performance in a visible light range, and is an important component of flexible photoelectric devices such as intelligent skin, sensors, wearable electronic devices and the like. At present, the most used conductive polymer materials, such as poly (3, 4-ethylenedioxythiophene) (PEDOT) and its derivatives, polypyrrole (PPy), Polyaniline (PANi), have good biocompatibility and excellent conductivity, but are brittle and difficult to process, which limits their applications in the field of tissue engineering or flexible deformation.

In an invention patent (CN110230113A) of a silver nanowire/silk fibroin composite fiber and a preparation method thereof, a spinning fiber directly compounding silk fibroin and silver nanowires is disclosed, but silk fibroin is easily oxidized to deteriorate and yellow, and simultaneously, silver nanowires are easily oxidized to generate silver oxide under the action of illumination, when a substance containing chlorine element exists in the environment, chloride ions with strong corrosivity can be generated in a humid environment, so that the chloride ions chemically react with the silver oxide to generate silver chloride powder, and the color of the silver chloride gradually becomes dark under the action of illumination, so that the original gray silver wires are changed into gray or gray black. Therefore, it is important to develop a conductive bio-fiber with stable performance.

Disclosure of Invention

In order to solve the technical problems, the invention provides a conductive biological fiber, which can improve the stability of a metal nanowire in practical application, so that when the metal nanowire is matched with silk fibroin fibers for use, the conductivity of a product can be increased, and the toughness of the product can be enhanced.

In a first aspect, the invention provides a conductive biological fiber, which consists of the following components in parts by weight:

10-20 parts of silk fibroin fibers;

5-20 parts of metal nanowires;

1-3 parts of polystyrene microspheres;

20-70 parts of double distilled water;

5-15 parts of sarin resin;

1-3 parts of an ultraviolet absorbent;

1-3 parts of an antioxidant.

Preferably, the conductive biological fiber consists of the following components in parts by weight:

15 parts of silk fibroin fibers;

10 parts of metal nanowires;

2 parts of polystyrene microspheres;

60 parts of double distilled water;

15 parts of sarin resin;

2 parts of an ultraviolet absorbent;

1.5 parts of antioxidant.

The inventor of the invention finds out through a large number of experiments that the silk fibroin fiber is a natural material with a multilevel structure, and the excellent comprehensive mechanical property of the silk fibroin fiber has a close and inseparable relationship with the multilevel structure. The silk fibroin fiber surface which looks smooth is actually composed of a plurality of oriented nanofiber bundles, the nanofibers are composed of a fishing net-shaped structure formed by mutually connecting beta-crystals and amorphous protein, the beta-crystals serve as nodes for bearing stress in the fishing net-shaped structure, and the amorphous structure connects the beta-crystals of the nodes like ropes to form a structure which is flexible and high in strength;

the metal nanowire is used as an inorganic metal material, the high length-diameter ratio effect of the metal nanowire enables the metal nanowire to have outstanding advantages in electric conductivity, in addition, the nano-scale size effect of the metal nanowire enables the metal nanowire to have excellent light transmission and bending resistance flexibility, and the bending resistance and the electric conductivity of the fiber can be improved by adding the metal nanowire into the silk fibroin fiber.

In some embodiments of the present invention, the metal nanowires include at least one of gold nanowires, copper nanowires, and silver nanowires.

Preferably, the diameter of the metal nanowire is 10-80nm, the length is 10-80 μm, and the aspect ratio is more than 1000.

In certain embodiments of the present invention, the ultraviolet absorber comprises at least one of benzophenones, benzotriazoles, hindered amines, triazines.

Preferably, the ultraviolet absorbent is an ultraviolet absorbent capable of absorbing UVA (wavelength 320-420nm) and UVB (wavelength 280-320nm) bands.

In certain embodiments of the present invention, the antioxidant comprises at least one of a phosphite antioxidant and a phenolic antioxidant.

Preferably, the phosphite antioxidant comprises antioxidant 168, triphenyl phosphite, diphenyl phosphite, triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite;

the phenolic antioxidant comprises antioxidant 1790, tert-butylhydroquinone, 2, 6-di-tert-butylphenol and hydroxytyrosol.

More preferably, the antioxidant is prepared by mixing a phosphite antioxidant and a phenolic antioxidant according to a mass ratio of 1: 3.

The inventor also finds that the composite spinning of the silver nanowires and the silk fibroin can be protected by adding the sarin resin, the ultraviolet absorbent and the antioxidant to obtain a good effect, wherein the sarin resin mainly forms a layer of thin film to play a role in blocking water and oxygen, and the ultraviolet absorbent and the antioxidant are added to mainly absorb ultraviolet rays with the wavelength of 290-400nm, so that the silk fibroin-based composite spinning is anti-aging.

In a second aspect, the present invention provides a method for preparing a conductive bio-fiber, comprising the following steps:

the method comprises the following steps: preparing silk fibroin fibers;

step two: preparing a spinning solution: adding double distilled water into a three-neck flask, heating to a slightly boiling state, adding sarin resin while stirring, adding an ultraviolet absorbent, an antioxidant, polystyrene microspheres, silk fibroin fibers and metal nanowires in sequence after the sarin resin is dissolved, and stirring and mixing uniformly;

step three: pretreatment of spinning solution: filtering the spinning solution obtained in the step two through a filter, and defoaming;

step four: spinning and forming: and (4) feeding the spinning solution obtained in the step three into spinning machine equipment, controlling a spinning pump to measure, spinning the spinning solution through a spinning nozzle, and drying and curing the spun and formed biological fiber through gradient heating and cooling to obtain the conductive biological fiber.

In a third aspect, the invention provides an application of the conductive biological fiber in the fields of intelligent skin, sensors, wearable electronic devices and the like.

Compared with the prior art, the invention has the following advantages:

the silk fibroin fiber is characterized by flexibility, strength and high structure, the nano silver wires are combined to be flexible and have high conductivity, the prepared biological conductive fiber has good tensile strength and elongation at break, the bending resistance and conductivity of the fiber can be improved by adding the nano silver wires, and the composite spinning of the metal nanowires and the silk fibroin is protected by adding the sarin resin, the ultraviolet absorbent and the antioxidant, so that the silk fibroin fiber has good use effect and is expected to have wide application prospects in the fields of sensors, wearable electronic devices, intelligent skin and the like.

Detailed Description

The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

1) The conductive biological fiber comprises the following components in parts by weight:

20 parts of silk fibroin fibers;

20 parts of nano silver wires;

2 parts of polystyrene microspheres;

60 parts of double distilled water;

15 parts of sarin resin;

2 parts of an ultraviolet absorbent;

1.5 parts of antioxidant.

2) The preparation method of the conductive biological fiber specifically comprises the following steps:

the method comprises the following steps: preparing silk fibroin fibers; first 10g of sodium bicarbonate (NaHCO)₃) Adding into deionized water at 90 deg.C, stirring, dispersing and dissolving; then adding 10g of cut silkworm cocoons, and stirring for 30min at the rotating speed of 800 rpm; finally obtaining the degummed silk fibroin fiber. Soaking the prepared silk fibroin fiber with double distilled water, stirring for 30min, repeating for 3 times to remove NaHCO residual on the surface of the silk fibroin fiber₃；

Step two: preparing a spinning solution: adding double distilled water into a three-neck flask, heating to a slightly boiling state, adding the parts by weight of the surlyn resin while stirring at the stirring speed of 100-200rpm, sequentially adding the parts by weight of the ultraviolet absorbent, the antioxidant, the polystyrene microspheres, the silk fibroin fibers and the metal nanowires after the surlyn resin is dissolved, stirring for 2-2.5 hours, uniformly mixing to obtain a spinning solution, and standing for later use;

step three: pretreatment of spinning solution: sequentially passing the spinning solution obtained in the step two through 50um and 30um distributed filters, filtering and then carrying out defoaming treatment for 30 min;

step four: spinning and forming: and (4) feeding the defoamed spinning solution obtained in the step three into spinning machine equipment, controlling the metering of a spinning pump, spinning the spinning solution through a spinning nozzle, and drying and curing the spun and formed biological fiber at a gradient temperature of 80-120-60 ℃ to obtain the conductive biological fiber.

3) Mechanical properties, resistivity and light transmission test:

and (3) testing mechanical properties: the sample size was: the length is 100mm, the diameter is 5mm, the stretching speed is 1mm/min, each sample is tested for 3-5 times on average, and the average value is taken.

And (3) resistivity testing: the sample size was: the length is 100mm, each sample is tested 3-5 times on average, and the average value is taken.

Xenon weather resistance test: λ: 340nm, irradiance: 0.51W/m2, blackboard temperature: 63 ℃, in-box temperature: 38 ℃, humidity: the light transmission of the conductive fiber was measured at 50% for 500 hours (corresponding to 365 days in the natural environment) (instrument: BYK: ASTM D1003).

Comparative examples 1 to 2

As shown in Table 1, the components shown in comparative examples 1 to 2 in Table 1 were added in the same amounts by weight as in example 1, and the test results obtained were filled in Table 4.

TABLE 1

Serial number	Silk fibroin fiber	Nano silver wire	Polystyrene microsphere	Double distilled water	Sarin resin	Ultraviolet absorber	Antioxidant agent
								Example 1	20	20	2	60	15	2	1.5
Comparative example 1	20	--	2	60	15	2	1.5
								Comparative example 2	--	20	2	60	15	2	1.5

Examples 2 to 4

Examples 2-4 include most of the processing steps of example 1, with the following differences:

the components shown in examples 2 to 4 in Table 2 were added in the same weight parts as in example 1 during the preparation of the spinning dope, and the test results obtained were filled in Table 4.

TABLE 2

Serial number	Silk eggWhite fiber	Nano silver wire	Polystyrene microsphere	Double distilled water	Sarin resin	Ultraviolet absorber	Antioxidant agent
								Example 1	20	20	2	60	15	2	1.5
Example 2	15	20	2	60	15	2	1.5
								Example 3	15	10	2	60	15	2	1.5
Example 4	10	5	2	60	15	2	1.5

Examples 5 to 6

Examples 5-6 include most of the processing steps of example 1, with the following differences:

the components shown in examples 5 to 6 in Table 3 were added in the same manner as in example 1 in the preparation of the spinning dope, and the test results obtained were filled in Table 4.

Comparative example 3

As shown in Table 3, the components shown in comparative example 3 of Table 3 were added in the same amounts as in example 1, and the test results obtained were filled in Table 4.

TABLE 3

Serial number	Silk fibroin fiber	Nano silver wire	Polystyrene microsphere	Double distilled water	Sarin resin	Ultraviolet absorber	Antioxidant agent
								Example 5	15	10	2	60	10	2	1.5
Example 6	15	10	2	60	5	2	1.5
								Comparative example 3	15	10	2	60	--	--	--

The results of the mechanical properties, resistivity and light transmittance tests of inventive examples 1-6 and comparative examples 1-3 are shown in Table 4:

TABLE 4

The results were analyzed in conjunction with Table 4.

Compared with the comparative example 1 and the comparative example 2, the comparative analysis of the embodiment 1 and the comparative example 1 shows that the elasticity of the biological fiber material can be effectively improved by adding the nano silver wires into the silk fibroin fibers, and meanwhile, the silk fibroin fibers without adding the nano silver wires have no conductivity, so that the conductivity of the biological fiber material can be obviously improved by adding the nano silver wires into the silk fibroin fibers, and the biological fiber material has great application value.

Comparing and analyzing the examples 1 to 4, when the weight part ratio of the silk fibroin fibers to the nano silver wires is 1.5:1, a better use effect can be obtained, and when the concentration of the nano silver wires is higher, for example, the weight part ratio of the silk fibroin fibers to the nano silver wires is 3:4, although a more ideal conductive performance can be obtained, the mechanical performance of the silk fibroin fibers is obviously reduced, and when the concentration of the nano silver wires is lower, for example, the weight part ratio of the silk fibroin fibers to the nano silver wires is 2:1, the mechanical performance and the conductive performance of the silk fibroin fibers and the nano silver wires are obviously reduced, so that the concentration of the nano silver wires has a very obvious influence on the performance of the product, and the proper concentration of the nano silver wires can effectively improve the mechanical performance of the product, and can also improve the conductive performance of the product.

Comparing and analyzing the examples 1, 5-6 and the comparative example 3, when the weight ratio of the sarin resin and the silk fibroin fiber is at least 1:1, better protection effect can be obtained, and the test data of xenon weather resistance test shows that after the test is carried out for 500 hours (equivalent to 365 days under natural environment), the transmissivity of the conductive biological fiber prepared by adding the sarin resin which is at least the same as that of the silk fibroin fiber is all more than 80%, meanwhile, the larger the weight part of the sarin resin is, the larger the value of the transmissivity is, when the weight ratio of the sarin resin and the silk fibroin fiber is 1.5:1, the transmissivity can be up to 90%, because the sarin resin can form a layer of protective film to play a role of blocking water and oxygen, and simultaneously, the ultraviolet absorbent and the antioxidant which are mainly used for absorbing ultraviolet rays in the 400nm waveband of 290 nm are added, thereby realizing the effect of oxidation resistance. When the weight parts of the sarin resin are gradually reduced to be 1:3 of the weight parts of the sarin resin and the silk fibroin fibers, the transmittance of the prepared product is also obviously reduced by 73 percent, so that the light transmittance of the product after the product is used for a period of time is poor, but the transmittance is better than that of the product prepared without the sarin resin, the ultraviolet absorbent and the antioxidant.

The present invention has been further described with reference to specific embodiments, but it should be understood that the detailed description should not be construed as limiting the spirit and scope of the present invention, and various modifications made to the above-described embodiments by those of ordinary skill in the art after reading this specification are within the scope of the present invention.