CN110028789A - A kind of preparation method of high-strength wearable strain sensing fiber - Google Patents
A kind of preparation method of high-strength wearable strain sensing fiber Download PDFInfo
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- CN110028789A CN110028789A CN201910287423.9A CN201910287423A CN110028789A CN 110028789 A CN110028789 A CN 110028789A CN 201910287423 A CN201910287423 A CN 201910287423A CN 110028789 A CN110028789 A CN 110028789A
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- Prior art keywords
- sensing fiber
- strain sensing
- strength wearable
- preparation
- wearable strain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/04—Blended or other yarns or threads containing components made from different materials
- D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/10—Inorganic fibres based on non-oxides other than metals
- D10B2101/12—Carbon; Pitch
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/06—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Measurement Of Length, Angles, Or The Like Using Electric Or Magnetic Means (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention provides a kind of preparation methods of high-strength wearable strain sensing fiber, which comprises the following steps: step 1: carbon nano-tube film and fluoropolymer resin progress is compound, obtain the carbon nano-tube film compound with fluoropolymer resin；Step 2: the carbon nano-tube film compound with fluoropolymer resin that step 1 is obtained is twisted, and carbon nanotube complex yarn is obtained；Step 3: the obtained carbon nanotube complex yarn of step 2 is solidified to get high-strength wearable strain sensing fiber.The sensing fiber that the present invention uses has a good mechanics, electricity, sensing capabilities, and polymer coating assigns that yarn is good wear-resisting and insulation performance, suitable for being woven into rope, net and other fabric constructions, for monitoring the mechanical state of textile structural.Method of the invention is simple, is suitable for industrialized production, is with a wide range of applications in dual-use equal fields.
Description
Technical field
The invention belongs to the fields of new material, are related to a kind of preparation method of high-strength wearable strain sensing fiber.
Background technique
Traditional strain sensing material is mostly metal or ceramic material, has heavy and harder quality defect.It will be traditional
Strain sensing material is processed into fibre structure, it is also difficult to obtain flexible performance, can not apply braiding field.
Carbon nanotube has excellent mechanics electric property and special piezoresistive effect, it may be assumed that in stretching and compression
Resistance can change.Therefore, there is scholar by coating after carbon nanotube powder and mixed with polymers on yarn or fabric, from
And obtain the effect of strain sensing.But the size of carbon nanotube be in nanometer scale, when with mixed with polymers, carbon nanotube
It cannot uniformly scatter and cannot largely add.So the strain sensing effect of carbon nanotube coating yarn is limited, linearly
It spends poor；And stretching in friction process, functional coating is easy to fall off.The carbon nanotube obtained by floating catalyst system is fine
Dimension material is the aggregate of pure nano-carbon tube, has excellent mechanics and sensing capabilities.But the carbon nanotube that this method obtains
For fibre diameter usually at 5-50 microns, ultimate strength and wearability are all poor, cannot be used directly for weaving.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of high-strength wearable strain sensing fiber, are original with carbon nano-tube film
Material is prepared by resin compounded and twisting process, and the strain sensing fiber of excellent combination property is obtained after hot setting.
In order to achieve the above object, the present invention provides a kind of preparation methods of high-strength wearable strain sensing fiber, special
Sign is, comprising the following steps:
Step 1: carbon nano-tube film and fluoropolymer resin progress is compound, obtain the carbon nanotube compound with fluoropolymer resin
Film；
Step 2: the carbon nano-tube film compound with fluoropolymer resin that step 1 is obtained is twisted, and carbon nanotube is obtained
Complex yarn；
Step 3: the obtained carbon nanotube complex yarn of step 2 being solidified fine to get high-strength wearable strain sensing
Dimension.
Preferably, in the step 1 carbon nano-tube film with a thickness of 5~50 μm, width is 0.5~5cm, passes through regulation carbon
The thickness and width of nanotube films adjusts the diameter dimension of carbon nanotube yarn.
Preferably, polymer resin is epoxy resin, polyvinyl alcohol resin, polyurethane resin and polyamide in the step 1
Any one in resin.
Preferably, carbon nano-tube film and fluoropolymer resin progress are compound in the step 1 specifically: soak carbon nano-tube film
Stain 1~500s into polymer resin solution, dip time are selected according to polymer resin solution viscosity and type.
It is highly preferred that acrylic glycidol ether, phenyl glycidyl ether and second can be used in the polymer resin solution
Glycol bisglycidyl ether isoreactivity diluent any one or a few or use water, benzene, ethyl alcohol, acetone, butanol and two
Any one or a few of the non-activated thinners such as butyl ester is diluted to obtain to fluoropolymer resin；The polymer resin solution
Viscosity should control between 100~300mPa.s.
Preferably, the twist number range twisted in the step 2 is at 0.1~100/ centimetre, and turn angular range is 10~70
Degree.
Preferably, the diameter range of carbon nanotube complex yarn is 30~500 μm in the step 2.
Preferably, in the step 3 in carbon nanotube complex yarn fluoropolymer resin curing time, temperature, pressure etc.
Condition is determined by selected adhesive and resin.
The sensing fiber that the present invention uses has good mechanics, electricity, sensing capabilities and flexibility, and polymer coating assigns
Yarn is good wear-resisting and insulation performance, suitable for being woven into rope, net and other fabric constructions, for monitoring textile structural
Mechanical state.
Compared with prior art, the beneficial effects of the present invention are:
1. the preparation of carbon nanotube film roll yarn of the present invention solves, carbon nano-tube fibre diameter is thin, weavability difference
Disadvantage, while the film roll yarn prepared can also arbitrarily control the diameter of yarn, to meet the needs of different condition.
2. of the invention handled using resinous coat or other matter coatings, it can make yarn that there is high temperature resistant, height to insulate, is resistance to
The features such as radiation, the performance for capableing of effective protection carbon nanotube yarn are stablized.
3. strain sensing fiber of the present invention can be used for weaving the textile of different structure, it is made to obtain power induction energy
Power.
4. method proposed by the present invention is simple, it is suitable for industrialized production.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of high-strength wearable strain sensing fiber is present embodiments provided, specific preparation process is as follows::
Step 1: by 10 μm of thickness, the carbon nano-tube film (Suzhou Jie Di nano material Co., Ltd) of purity > 90% is cut
For long 50cm, width 2cm strip after be impregnated into polyimide resin solution (Changhu Jiafa chemistry Co., Ltd., model:
PI-84 10s in) makes resin uniformly be coated in the surface of carbon nanotube, obtains the carbon nanotube compound with fluoropolymer resin
Film；
Step 2: the carbon nano-tube film compound with fluoropolymer resin that step 1 is obtained is twisted, yarn twist 10/
Centimetre, turn angle is 30 degree, and film roll yarn is scraped off the extra tree on carbon nanotube composite yarn surface by sley point after twisting
Rouge obtains carbon nanotube complex yarn；
Step 3: after the obtained carbon nanotube complex yarn both ends of step 2 are fixed, baking and curing in an oven is placed,
80 DEG C of solidification temperature, natural cooling is to get high-strength wearable strain sensing fiber after curing time 2h.
The diameter for being prepared into high-strength wearable strain sensing fiber is 210 μm, and ultimate strength is 5.5 newton, and transduction factor is
3.3。
Embodiment 2
A kind of high-strength wearable strain sensing fiber is present embodiments provided, specific preparation process is as follows::
Step 1: by 10 μm of thickness, the carbon nano-tube film (Suzhou Jie Di nano material Co., Ltd) of purity > 90% is cut
For long 50cm, wide 3cm strip after be impregnated into 5~10s in polyvinyl alcohol resin solution, so that resin is uniformly coated in carbon nanometer
The surface of pipe obtains the carbon nano-tube film compound with fluoropolymer resin；
Wherein, 5g granule of polyvinyl alcohol (Kuraray Co., Ltd., board the preparation of polyvinyl alcohol resin solution: are weighed
Number PVA205), solvent chooses water and ethyl alcohol, and wherein the ratio of water and ethyl alcohol is 4:1, the water of 80mL and the ethyl alcohol of 20mL are measured,
With 95 DEG C, revolving speed 400r/min on blender, continue 8~10h, until granule of polyvinyl alcohol is completely dissolved, obtains 5wt%'s
Polyvinyl alcohol resin solution.
Step 2: the carbon nano-tube film compound with fluoropolymer resin that step 1 is obtained is twisted, yarn twist 10/
Centimetre, turn angle is 20 degree, and film roll yarn is scraped off the extra tree on carbon nanotube composite yarn surface by sley point after twisting
Rouge obtains carbon nanotube complex yarn；
Step 3: after the obtained carbon nanotube complex yarn both ends of step 2 are fixed, baking and curing in an oven is placed,
60 DEG C of solidification temperature, natural cooling is to get high-strength wearable strain sensing fiber after curing time 6h.
The diameter for being prepared into high-strength wearable strain sensing fiber is 330 μm, and ultimate strength is 8.7 newton, and transduction factor is
4.5。
Claims (8)
1. a kind of preparation method of high-strength wearable strain sensing fiber, which comprises the following steps:
Step 1: carbon nano-tube film and fluoropolymer resin progress is compound, obtain the carbon nano-tube film compound with fluoropolymer resin；
Step 2: the carbon nano-tube film compound with fluoropolymer resin that step 1 is obtained is twisted, and it is compound to obtain carbon nanotube
Yarn；
Step 3: the obtained carbon nanotube complex yarn of step 2 is solidified to get high-strength wearable strain sensing fiber.
2. the preparation method of high-strength wearable strain sensing fiber as described in claim 1, which is characterized in that carbon in the step 1
Nanotube films with a thickness of 5~50 μm, width is 0.5~5cm.
3. the preparation method of high-strength wearable strain sensing fiber as described in claim 1, which is characterized in that gather in the step 1
Resin is epoxy resin, polyvinyl alcohol resin, any one in polyurethane resin and polyamide.
4. the preparation method of high-strength wearable strain sensing fiber as described in claim 1, which is characterized in that carbon in the step 1
Nanotube films carry out compound with fluoropolymer resin specifically: carbon nano-tube film is impregnated into 1~500s in polymer resin solution.
5. the preparation method of high-strength wearable strain sensing fiber as claimed in claim 4, which is characterized in that the fluoropolymer resin
Any of acrylic glycidol ether, phenyl glycidyl ether and ethylene glycol bisglycidyl ether reactive diluent can be used in solution
It is one or more of or right using any one or a few of water, benzene, ethyl alcohol, acetone, butanol and dibutyl ester non-activated thinner
Fluoropolymer resin is diluted to obtain.
6. the preparation method of high-strength wearable strain sensing fiber as claimed in claim 4, which is characterized in that the fluoropolymer resin
The viscosity of solution should control between 100~300mPa.s.
7. the preparation method of high-strength wearable strain sensing fiber as described in claim 1, which is characterized in that add in the step 2
The twist number range of twirl is at 0.1~100/ centimetre, and turn angular range is at 10~70 degree.
8. the preparation method of high-strength wearable strain sensing fiber as described in claim 1, which is characterized in that carbon in the step 2
The diameter range of nanotube complex yarn is 30~500 μm.
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| CN201910287423.9A CN110028789A (en) | 2019-04-11 | 2019-04-11 | A kind of preparation method of high-strength wearable strain sensing fiber |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242533A (en) * | 2019-09-03 | 2021-01-19 | 北京新能源汽车技术创新中心有限公司 | Fuel cell bipolar plate based on carbon nanotube membrane composite material and preparation method and application thereof |
| CN113564767A (en) * | 2021-07-14 | 2021-10-29 | 北京航空航天大学 | Conductive spiral yarn self-powered sensor with surface spacing structure and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090268561A1 (en) * | 2008-04-28 | 2009-10-29 | Tsinghua University | Thermoacoustic device |
| CN101967699A (en) * | 2010-10-13 | 2011-02-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of high-performance carbon nanotube fiber |
| CN102953171A (en) * | 2011-08-30 | 2013-03-06 | 苏州捷迪纳米科技有限公司 | Carbon nanotube spinning machine and method for preparing carbon nanotube yarns by use of same |
| CN103474630A (en) * | 2013-09-23 | 2013-12-25 | 复旦大学 | Silicon/oriented carbon nanotube yarn as well as preparation method and application thereof |
| CN103904357A (en) * | 2014-03-09 | 2014-07-02 | 复旦大学 | Stretchable linear lithium ion battery and preparation method thereof |
| CN104392845A (en) * | 2014-10-17 | 2015-03-04 | 复旦大学 | Stretchable linear supercapacitor and lithium ion battery preparation method |
| CN106044739A (en) * | 2015-04-09 | 2016-10-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Highly-oriented carbon nanotube film or fiber, and micro-comb-process preparation apparatus and method thereof |
| CN106337215A (en) * | 2016-06-06 | 2017-01-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube composite fiber and production method thereof |
| CN109295550A (en) * | 2018-09-21 | 2019-02-01 | 武汉大学苏州研究院 | A kind of high intensity, high elastic modulus, the carbon fiber material of good malleability and preparation method |
-
2019
- 2019-04-11 CN CN201910287423.9A patent/CN110028789A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090268561A1 (en) * | 2008-04-28 | 2009-10-29 | Tsinghua University | Thermoacoustic device |
| CN101967699A (en) * | 2010-10-13 | 2011-02-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of high-performance carbon nanotube fiber |
| CN102953171A (en) * | 2011-08-30 | 2013-03-06 | 苏州捷迪纳米科技有限公司 | Carbon nanotube spinning machine and method for preparing carbon nanotube yarns by use of same |
| CN103474630A (en) * | 2013-09-23 | 2013-12-25 | 复旦大学 | Silicon/oriented carbon nanotube yarn as well as preparation method and application thereof |
| CN103904357A (en) * | 2014-03-09 | 2014-07-02 | 复旦大学 | Stretchable linear lithium ion battery and preparation method thereof |
| CN104392845A (en) * | 2014-10-17 | 2015-03-04 | 复旦大学 | Stretchable linear supercapacitor and lithium ion battery preparation method |
| CN106044739A (en) * | 2015-04-09 | 2016-10-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Highly-oriented carbon nanotube film or fiber, and micro-comb-process preparation apparatus and method thereof |
| CN106337215A (en) * | 2016-06-06 | 2017-01-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube composite fiber and production method thereof |
| CN109295550A (en) * | 2018-09-21 | 2019-02-01 | 武汉大学苏州研究院 | A kind of high intensity, high elastic modulus, the carbon fiber material of good malleability and preparation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242533A (en) * | 2019-09-03 | 2021-01-19 | 北京新能源汽车技术创新中心有限公司 | Fuel cell bipolar plate based on carbon nanotube membrane composite material and preparation method and application thereof |
| CN112242533B (en) * | 2019-09-03 | 2021-08-03 | 北京新能源汽车技术创新中心有限公司 | Fuel cell bipolar plate based on carbon nanotube membrane composite material and preparation method and application thereof |
| CN113564767A (en) * | 2021-07-14 | 2021-10-29 | 北京航空航天大学 | Conductive spiral yarn self-powered sensor with surface spacing structure and preparation method thereof |
| CN113564767B (en) * | 2021-07-14 | 2022-10-28 | 北京航空航天大学 | Conductive spiral yarn self-powered sensor with surface spacing structure and preparation method thereof |
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