CN110407164A - A kind of preparation method and application of carbon nanotube polymer composite membrane - Google Patents

A kind of preparation method and application of carbon nanotube polymer composite membrane Download PDF

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Publication number
CN110407164A
CN110407164A CN201910547990.3A CN201910547990A CN110407164A CN 110407164 A CN110407164 A CN 110407164A CN 201910547990 A CN201910547990 A CN 201910547990A CN 110407164 A CN110407164 A CN 110407164A
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CN
China
Prior art keywords
carbon nanotube
composite membrane
polymer composite
preparation
nanotube polymer
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CN201910547990.3A
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Chinese (zh)
Inventor
刘天西
高继升
张超
刘志崇
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Donghua University
National Dong Hwa University
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Donghua University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82BNANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009Forming specific nanostructures
    • B82B3/0023Forming specific nanostructures comprising flexible or deformable elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01BMEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B7/00Measuring arrangements characterised by the use of electric or magnetic techniques
    • G01B7/16Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
    • G01B7/18Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in resistance

Abstract

The invention discloses a kind of preparation methods of carbon nanotube polymer composite membrane, which comprises the following steps: step 1: carbon nanotube being dissolved in organic solvent, ultrasonic disperse, then filters and carbon nano-tube film is made;Step 2: SEBS piece is made by hot-pressing processing in SEBS;Step 3: the carbon nano-tube film that step 1 is obtained is placed on the SEBS piece surface that step 2 obtains and carries out hot-pressing processing, then ultrasonic in a solvent, dry, obtains carbon nanotube polymer laminated film.Invention preparation method of the present invention is simple, high sensitivity, the linearity are good, cyclical stability is excellent, and the present invention utilizes pressure sintering, penetrates into polymer melt in carbon nanotube, finally obtains the good carbon nanotube polymer laminated film of stress sensing property.

Description

A kind of preparation method and application of carbon nanotube polymer composite membrane
Technical field
The invention belongs to technical field of electronic equipment, in particular to a kind of preparation method of carbon nanotube polymer composite membrane And its application.
Background technique
Flexible sensor, microelectronics and artificial skin increasingly cause the concern of researcher.Stretchable resistance-type Extensive exploitation has been obtained in strain sensing material, and is used for wearable device.Resistance strain problems faced It is to realize big strain and have the good linearity under strained condition.Traditional resistance-type metal strain sensor measurement range It is small, because they cannot restore under big deformation.Conduction usually by the way that conducting nanoparticles and elastomer are mixed The sensitivity and big deformation that composite materials have had, however there is no good linear relationships between its resistance and strain. Based on this, designing a kind of big deformation, high sensitivity and the strain transducer with good linear relationship just seems particularly important .
Carbon nanotube (CNT) is the one-dimensional amount with special construction being mainly made of the carbon atom of hexagonal arrangement Sub- material, diameter is between 0.3 nanometer to tens nanometers, and length is up to a few micrometers.Carbon nanotube is compared with steel, and density is only There is the 1/6 of steel, but theoretical strength is about 100 times of steel, it can be with tolerable temperature up to 3593 DEG C, and there is brilliant thermal conductivity And ductility.The carbon nanotube of single-layer or multi-layer is referred to as single-walled carbon nanotube (SWNT) and multi-walled carbon nanotube (MWNT), single Wall carbon nano tube is from the appearance hollow cylinder, is to be curled by graphite by the plane that two-dimensional approach rearranges, Due to different from the mode that graphite arranges, the single-walled carbon nanotube of different structure is formd, and cylindrical body two sides are then by carbon The curved surface of the curved arrangement of atom and formation.If by the ascending concentric intussusception of the single-walled carbon nanotube of different structure size, Its every adjacent layer distance between commutator segments is about 0.36 nanometer, then can form multi-walled carbon nanotube.Electronics in carbon nanotube be not with Meaning movement, but limited by quantum confinement factor, these electronics are typically only capable to be moved along axial resistivity, and It cannot the crisscross motion in different graphite flake layers.
SEBS is using polystyrene as end segment, and the ethylene-butene copolymer obtained with polybutadiene plus hydrogen is intermediate bullet The linear tri-block copolymer of property block.SEBS is free of unsaturated double-bond, therefore with good stability and resistance to ag(e)ing.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation method of carbon nanotube polymer composite membrane and its Using.
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation method of carbon nanotube polymer composite membrane, Characterized by comprising the following steps:
Step 1: carbon nanotube being dissolved in organic solvent, ultrasonic disperse, then filter and carbon nano-tube film is made;
Step 2: SEBS piece is made by hot-pressing processing in SEBS;
Step 3: the carbon nano-tube film that step 1 is obtained is placed on the SEBS piece surface that step 2 obtains and carries out hot-pressing processing, so It is cleaned by ultrasonic in a solvent afterwards, it is dry, obtain carbon nanotube polymer laminated film.
Preferably, organic solvent is ethyl alcohol, one of tetrahydrofuran or N-Methyl pyrrolidone in the step 1.
Preferably, carbon nanotube and the solid-to-liquid ratio of organic solvent are 2~10mg/mL in the step 1, and ultrasonic power is 300~500W, time are 30~60min.
Preferably, hot pressing time is 5~20min in the step 2, and temperature is 180~210 DEG C, and pressure is 5~15MPa.
Preferably, in the step 3 hot pressing time be 10~180min, temperature be 180~210 DEG C, pressure be 4~ 6MPa。
Preferably, the mass ratio of carbon nano-tube film and SEBS piece is (20~100): (3000~5000) in the step 3.
Solvent is one of water, ethyl alcohol or N-Methyl pyrrolidone in the step 3, and drying temperature is 50~80 DEG C, Drying time is 1~10h.
The present invention also provides application of the carbon nanotube polymer composite membrane of above method preparation in strain transducer.
Compared with prior art, the beneficial effects of the present invention are:
(1) preparation method of the present invention is simple, and operation is easy, and the method using simple hot pressing makes polymer melt in pressure It is penetrated into carbon nanotube under effect, carbon nanotube portion is embedded in inside film, and part inlay is formed similar in film surface The structure of " carpet " assigns film conductivity.
(2) experimental design of the present invention is ingenious, can regulate and control polymer melt by adjusting hot pressing time and penetrate into carbon nanometer Thickness in pipe.
(3) carbon nanotube polymer laminated film prepared by the present invention has superior electrical conductivity, can measure big deformation, and With highly sensitive, good linear relationship and excellent cyclical stability, it is suitble to stretchable strain sensing material.It strains reachable 80%, severity factor is 18.5 under small deformation, and severity factor is 12.5 under big deformation, also keeps excellent after circulation 1000 times Sensing capabilities.
Detailed description of the invention
Fig. 1 is the figure of carbon nanotube polymer composite film surface SEM made from embodiment 1;
Fig. 2 a is the figure of carbon nanotube polymer composite membrane T-10 section SEM made from embodiment 1;
Fig. 2 b is the figure of carbon nanotube polymer composite membrane T-30 section SEM made from embodiment 2;
Fig. 2 c is the figure of carbon nanotube polymer composite membrane T-60 section SEM made from embodiment 3;
Fig. 3 is the response curve of carbon nanotube polymer composite membrane T-10 relative resistance and strain made from embodiment 1;
Fig. 4 is the cyclical stability under 40% strained condition of carbon nanotube polymer composite membrane T-10 made from embodiment 1 Curve.
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.
Carbon nanotube polymer THIN COMPOSITE is characterized using scanning electron microscope (SEM), universal tensile machine, digital sourcemeter Film pattern and strain sensing performance.Use fixed composite membrane (50 × 5 × 1mm of the fixture with electro-insulating rubber layer3), between fixture Original gauge length be 20mm.During the test, the rate of extension and range of strain of electronic universal tester Control Assay, simultaneously The record of data is tested in deadline, stress, strain etc..When composite membrane strains, electrode is moved synchronously with fixture, same with this When, digital multimeter records the instantaneous resistance value of sample during stretching in situ.
Embodiment 1
Present embodiments provide a kind of preparation method of carbon nanotube polymer composite membrane, the specific steps are as follows:
Step 1: taking 20mg carbon nanotube to be dissolved in 10mL N-Methyl pyrrolidone, ultrasound 1h, ultrasonic function in ultrasonic machine Carbon nano tube dispersion liquid is made in rate 500W, dispersion liquid is filtered, carbon nano-tube film is made, carbon nano-tube film is put into baking oven Drying for standby;
Step 2: taking 4gSEBS, the hot pressing under the conditions of 200 DEG C, 10MPa, 10min obtains SEBS piece;
Step 3: carbon nano-tube film being placed on SEB on piece, carbon nanometer is made in the hot pressing under the conditions of 200 DEG C, 4MPa, 10min Carbon nanotube polymer laminated film ultrasound 2h in ethanol is then placed in 70 DEG C of baking ovens and is done by pipe polymer composite film Dry 1h, carbon nanotube polymer composite membrane obtained is denoted as T-10 eventually.
As shown in Figure 1, SEM test result shows: carbon nanotube is uniformly attached to the surface of laminated film.
As shown in figure 3, sensing capabilities test shows: T-10 test scope is big, can reach 80% of strain or so sensitivity Height, severity factor is 18.5, within the scope of Large strain, severity factor 12.5 within the scope of low strain dynamic.
As shown in figure 4, T-10 cyclical stability is excellent, sensing capabilities are also protected after recycling under 40% strained condition 1000 times It is fixed to keep steady.
Embodiment 2
The present embodiment the difference from embodiment 1 is that, hot pressing time is changed to 30min in step 3, remaining with embodiment 1, Final carbon nanotube polymer composite membrane obtained is denoted as T-30.
Embodiment 3
The present embodiment the difference from embodiment 1 is that, hot pressing time is changed to 60min in step 3, remaining with embodiment 1, Final carbon nanotube polymer composite membrane obtained is denoted as T-60.
Fig. 2 a is the figure of carbon nanotube polymer composite membrane T-10 section SEM made from embodiment 1;
Fig. 2 b is the figure of carbon nanotube polymer composite membrane T-30 section SEM made from embodiment 2;
Fig. 2 c is the figure of carbon nanotube polymer composite membrane T-60 section SEM made from embodiment 3;
Such as Fig. 2 a, shown in Fig. 2 b, Fig. 2 c, when hot pressing time increases 60min from 10min, composite coating thickness gradually increases Adding from 69 μm increases to 198 μm.

Claims (8)

1. a kind of preparation method of carbon nanotube polymer composite membrane, which comprises the following steps:
Step 1: carbon nanotube being dissolved in organic solvent, ultrasonic disperse, then filter and carbon nano-tube film is made;
Step 2: SEBS piece is made by hot-pressing processing in SEBS;
Step 3: the carbon nano-tube film that step 1 is obtained is placed on the SEBS piece surface that step 2 obtains and carries out hot-pressing processing, then exists It is ultrasonic in solvent, it is dry, obtain carbon nanotube polymer laminated film.
2. the preparation method of carbon nanotube polymer composite membrane as described in claim 1, which is characterized in that have in the step 1 Solvent is ethyl alcohol, one of tetrahydrofuran or N-Methyl pyrrolidone.
3. the preparation method of carbon nanotube polymer composite membrane as described in claim 1, which is characterized in that carbon in the step 1 The solid-to-liquid ratio of nanotube and organic solvent is 2~10mg/mL, and ultrasonic power is 300~500W, and the time is 30~60min.
4. the preparation method of carbon nanotube polymer composite membrane as described in claim 1, which is characterized in that hot in the step 2 The pressure time is 5~20min, and temperature is 180~210 DEG C, and pressure is 5~15MPa.
5. the preparation method of carbon nanotube polymer composite membrane as described in claim 1, which is characterized in that hot in the step 3 The pressure time is 10~180min, and temperature is 180~210 DEG C, and pressure is 4~6MPa.
6. the preparation method of carbon nanotube polymer composite membrane as described in claim 1, which is characterized in that carbon in the step 3 The mass ratio of nanotube films and SEBS piece is (20~100): (3000~5000).
7. the preparation method of carbon nanotube polymer composite membrane as described in claim 1, which is characterized in that molten in the step 3 Agent is one of water, ethyl alcohol or N-Methyl pyrrolidone, and drying temperature is 50~80 DEG C, and drying time is 1~10h.
8. carbon nanotube polymer composite membrane the answering in strain transducer of any one of claim 1~7 the method preparation With.
CN201910547990.3A 2019-06-24 2019-06-24 A kind of preparation method and application of carbon nanotube polymer composite membrane Pending CN110407164A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111336912A (en) * 2020-03-04 2020-06-26 东北大学 Preparation method of flexible strain sensor with adjustable sensing performance

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030133865A1 (en) * 2001-07-06 2003-07-17 William Marsh Rice University Single-wall carbon nanotube alewives, process for making, and compositions thereof
US20080206559A1 (en) * 2007-02-26 2008-08-28 Yunjun Li Lubricant enhanced nanocomposites
US20090118420A1 (en) * 2007-10-10 2009-05-07 University Of Central Florida Research Foundation, Inc. Dispersions of carbon nanotubes in copolymer solutions and functional composite materials and coatings therefrom
CN101462391A (en) * 2007-12-21 2009-06-24 清华大学 Method for preparing carbon nano-tube composite material
CN101691280A (en) * 2009-10-30 2010-04-07 上海交通大学 Method for preparing carbon nano tube film
CN109387307A (en) * 2018-12-12 2019-02-26 深圳大学 A kind of flexibility stress sensor and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030133865A1 (en) * 2001-07-06 2003-07-17 William Marsh Rice University Single-wall carbon nanotube alewives, process for making, and compositions thereof
US20080206559A1 (en) * 2007-02-26 2008-08-28 Yunjun Li Lubricant enhanced nanocomposites
US20090118420A1 (en) * 2007-10-10 2009-05-07 University Of Central Florida Research Foundation, Inc. Dispersions of carbon nanotubes in copolymer solutions and functional composite materials and coatings therefrom
CN101462391A (en) * 2007-12-21 2009-06-24 清华大学 Method for preparing carbon nano-tube composite material
CN101691280A (en) * 2009-10-30 2010-04-07 上海交通大学 Method for preparing carbon nano tube film
CN109387307A (en) * 2018-12-12 2019-02-26 深圳大学 A kind of flexibility stress sensor and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111336912A (en) * 2020-03-04 2020-06-26 东北大学 Preparation method of flexible strain sensor with adjustable sensing performance
CN111336912B (en) * 2020-03-04 2021-08-24 东北大学 Preparation method of flexible strain sensor with adjustable sensing performance

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Application publication date: 20191105