CN109374159B - Multi-walled carbon nanotube piezoresistive sensor and preparation method thereof - Google Patents
Multi-walled carbon nanotube piezoresistive sensor and preparation method thereof Download PDFInfo
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- CN109374159B CN109374159B CN201811144841.4A CN201811144841A CN109374159B CN 109374159 B CN109374159 B CN 109374159B CN 201811144841 A CN201811144841 A CN 201811144841A CN 109374159 B CN109374159 B CN 109374159B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/20—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress
- G01L1/22—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress using resistance strain gauges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
- G01B7/18—Measuring 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
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Abstract
A multi-walled carbon nanotube piezoresistive sensor and a preparation method thereof are provided, wherein the preparation method of the multi-walled carbon nanotube piezoresistive sensor comprises the following steps: preparing a conductive nanocomposite material in a molten state, and filling the conductive nanocomposite material into an injector; extruding the pre-made uncured silicone resin onto a printing substrate of a 3D printer, and standing to form a partially cured insulating matrix; printing a conductive nanocomposite material into a partially cured insulating matrix by a 3D printer to form a conductive trace; the multi-walled carbon nanotube piezoresistive sensor prepared by the preparation method of the multi-walled carbon nanotube piezoresistive sensor and the multi-walled carbon nanotube piezoresistive sensor not only solves the adhesion problem between the conductive layer and the substrate, but also has good stretchability and abrasion resistance, simplifies the design of internal complex circuit patterns through printing and preparation, and is simple to manufacture.
Description
Technical Field
The invention relates to the technical field of sensors, in particular to a multi-walled carbon nanotube piezoresistive sensor and a preparation method thereof.
Background
At present, flexible strain sensors have the problem that mainly the adhesion structure between the conductive layer and the substrate is not reasonable, and cracks and peeling can be caused, so that the application of the sensors is limited. In order to solve this problem, sensor manufacturers embed conductive liquid in the substrate, however, this approach can avoid the technical problems of coating film cracking and sensor lifetime, but since the liquid encapsulated in the stretchable substrate structure has no mechanical strength, the conductive liquid flows inside the component, resulting in the disadvantages of difficult embedding and difficult manufacturing.
Disclosure of Invention
The invention provides a multi-walled carbon nanotube piezoresistive sensor and a preparation method thereof in order to solve the problems in the prior art, and aims to solve the technical problems that a flexible strain sensor adopts conductive liquid packaged inside to increase the adhesion between a conductive layer and a substrate, but the conductive liquid flows inside the substrate, so that the conductive liquid is difficult to embed and the manufacturing difficulty is high.
In order to achieve the purpose, the invention provides a multi-walled carbon nanotube piezoresistive sensor which comprises an insulating substrate and a conductive trace, wherein the conductive trace is embedded in the insulating substrate, the insulating substrate is made of silicone, and the conductive trace is a conductive circuit formed by mixing a multi-walled carbon nanotube and siloxane.
In a further preferred embodiment of the present invention, the insulating substrate is in the form of a sheet, a tape, or a curved line.
In another aspect of the present invention, the present invention further provides a method for preparing a multi-walled carbon nanotube piezoresistive sensor, the method comprising the steps of:
s1, preparing a conductive nanocomposite material in a molten state, and filling the conductive nanocomposite material into an injector;
s2, extruding the pre-made uncured silicone resin onto a printing substrate of a 3D printer, and standing to form a partially cured insulating matrix;
s3, printing the conductive nanocomposite material into the partially cured insulating matrix by a 3D printer to form a conductive trace;
and S4, solidifying the insulating matrix printed with the conductive traces, and adhering the conductive traces and the insulating matrix to each other to obtain the multi-walled carbon nanotube piezoresistive sensor.
As a further preferable technical scheme of the invention, the 3D printer is formed by adopting a fused deposition mode.
As a further preferable technical solution of the present invention, the step S1 of preparing the conductive nanocomposite material in a molten state and loading the conductive nanocomposite material into an injector specifically includes:
adding the nanoparticles into uncured siloxane according to the required mass ratio, and centrifugally mixing to achieve uniform dispersion to obtain a conductive nanocomposite material formed by mixing a multiwalled carbon nanotube and siloxane in a molten state;
the conductive nanocomposite material in a molten state was loaded into a syringe in vacuum to avoid air bubbles.
As a further preferable technical solution of the present invention, in the step S2, the step of extruding the pre-made uncured silicone resin onto the printing substrate of the 3D printer, and the step of forming the partially cured insulating matrix after standing specifically includes:
extruding the pre-prepared uncured silicone resin onto a printing substrate through a nozzle with the diameter of 0.6 mm, wherein the thickness of the silicone resin is uniform;
and standing for 20 minutes to cure the silicone resin at the bottom of the insulating matrix, and keeping the silicone resin at the surface in a fluid state.
As a further preferred embodiment of the present invention, the step S3 of printing the conductive nanocomposite material into the partially cured insulating matrix by a 3D printer to form the conductive trace specifically includes:
inserting an injection head of an injector into the partially cured insulating matrix, driving a printing substrate to move on an X-Y plane relative to the injector by a transmission mechanism of a 3D printer, and injecting the conductive nanocomposite material in a molten state into the partially cured insulating matrix to form a conductive trace;
the moving speed of the printing substrate relative to the injector is not more than 3 mm/s.
As a further preferable embodiment of the present invention, the shape of the conductive trace is a straight line, a curved line, or a meander line composed of a plurality of lines.
As a further preferred embodiment of the present invention, in step S4, the step of curing the insulating substrate printed with the conductive traces to bond the conductive traces and the insulating substrate to each other to obtain the multi-walled carbon nanotube piezoresistive sensor specifically includes:
and (3) standing the insulating substrate printed with the conductive traces at room temperature for curing, and bonding the conductive traces and the insulating substrate to each other to obtain the multi-walled carbon nanotube piezoresistive sensor.
The multi-walled carbon nanotube piezoresistive sensor and the preparation method thereof can achieve the following beneficial effects:
the multi-walled carbon nanotube piezoresistive sensor comprises an insulating substrate and a conductive trace, wherein the conductive trace is embedded in the insulating substrate, the insulating substrate is made of silicon resin, and the conductive trace is a conductive circuit formed by mixing a multi-walled carbon nanotube and siloxane, so that the multi-walled carbon nanotube piezoresistive sensor not only solves the problem of adhesion between the conductive layer and a substrate, but also has good stretchability and wear resistance, can be prepared by printing, and is simple to manufacture.
The preparation method of the multi-walled carbon nanotube piezoresistive sensor comprises the following steps: s1, preparing a conductive nanocomposite material in a molten state, and filling the conductive nanocomposite material into an injector; s2, extruding the pre-made uncured silicone resin onto a printing substrate of a 3D printer, and standing to form a partially cured insulating matrix; s3, printing the conductive nanocomposite material into the partially cured insulating matrix by a 3D printer to form a conductive trace; s4, solidifying the insulating matrix printed with the conductive traces, and bonding the conductive traces and the insulating matrix to obtain the multi-walled carbon nanotube piezoresistive sensor, so that the multi-walled carbon nanotube piezoresistive sensor prepared by the preparation method of the multi-walled carbon nanotube piezoresistive sensor not only solves the problem of adhesion between the conductive layer and the substrate, but also has good stretchability and wear resistance, and the design of internal complex circuit patterns is simplified through printing and preparation, and the manufacturing is simple.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a schematic diagram of a multi-walled carbon nanotube piezoresistive sensor according to an embodiment of the present invention;
FIG. 2 is a flow chart of a method for providing an example of a method for fabricating a multi-walled carbon nanotube piezoresistive sensor according to the present invention;
fig. 3 is a schematic diagram of a structure for printing embedded conductive traces in a partially cured insulating matrix.
In the figure: 100. conductive trace, 200, insulating matrix;
1. printing substrate, 2, conductive nanocomposite material in molten state, 3, syringe, 4, injection head, 5, partially cured insulating matrix.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for clarity of description only, and are not used to limit the scope of the invention, and the relative relationship between the terms and the terms is not changed or modified substantially without changing the technical content of the invention.
As shown in fig. 1, the multi-walled carbon nanotube piezoresistive sensor includes an insulating substrate 200 and a conductive trace 100, the conductive trace 100 is embedded inside the insulating substrate 200, the insulating substrate 200 is made of silicone, and the conductive trace 100 is a conductive circuit formed by mixing multi-walled carbon nanotubes and siloxane. The multi-walled carbon nanotube piezoresistive sensor not only solves the adhesion problem between the conductive layer and the substrate, but also has good stretchability and wear resistance.
In specific implementation, the insulating substrate 200 is in a sheet shape, a belt shape or a curve shape, and the conductive traces 100 are arranged on the insulating substrate by printing, so that the design of an internal complex circuit pattern is simplified, and the manufacturing is simple.
As shown in fig. 2, a method for manufacturing a multi-walled carbon nanotube piezoresistive sensor comprises the following steps:
step S1, preparing a conductive nanocomposite material in a molten state, and filling the conductive nanocomposite material into an injector;
step S2, extruding the pre-made uncured silicone resin onto a printing substrate of a 3D printer, standing to form a partially cured insulating matrix;
step S3, printing the conductive nanocomposite material into the partially cured insulating matrix by a 3D printer to form a conductive trace;
and step S4, solidifying the insulating matrix printed with the conductive traces, and adhering the conductive traces and the insulating matrix to each other to obtain the multi-walled carbon nanotube piezoresistive sensor.
In specific implementation, in step S1, the preparing the conductive nanocomposite material in a molten state and loading the conductive nanocomposite material into an injector specifically includes:
adding the nanoparticles into uncured siloxane according to the required mass ratio, and centrifugally mixing to achieve uniform dispersion to obtain a conductive nanocomposite material formed by mixing a multiwalled carbon nanotube and siloxane in a molten state;
the conductive nanocomposite material in a molten state was loaded into a syringe in vacuum to avoid air bubbles.
In a specific implementation, in step S2, extruding a pre-made uncured silicone resin onto a printing substrate of a 3D printer, and standing to form a partially cured insulating matrix specifically includes:
extruding the pre-prepared uncured silicone resin onto a printing substrate through a nozzle with the diameter of 0.6 mm, wherein the thickness of the silicone resin is uniform;
and standing for 20 minutes to cure the silicone resin at the bottom of the insulating matrix, and keeping the silicone resin at the surface in a fluid state.
In a specific implementation, the step S3 of printing the conductive nanocomposite material into the partially cured insulating matrix by a 3D printer to form the conductive trace specifically includes:
as shown in fig. 3, the injection head 4 of the injector 3 is inserted into the partially solidified insulating matrix 5, and the driving mechanism of the 3D printer drives the printing substrate 1 to move in the X-Y plane relative to the injector 3, so that the conductive nanocomposite material 2 in a molten state is injected into the partially solidified insulating matrix 5 to form a conductive trace;
the moving speed of the printing substrate 1 relative to the injector 4 does not exceed 3 mm/s, and during the printing process, the relative moving direction is as shown by an arrow in fig. 3, so that different shapes of conductive traces can be obtained by changing different relative moving tracks.
Preferably, the conductive traces are in the shape of straight lines, curved lines or meander lines composed of multiple segments of lines.
As a further preferred embodiment of the present invention, in step S4, the step of curing the insulating substrate printed with the conductive traces to bond the conductive traces and the insulating substrate to each other to obtain the multi-walled carbon nanotube piezoresistive sensor specifically includes:
and (3) standing the insulating substrate printed with the conductive traces at room temperature for curing, and bonding the conductive traces and the insulating substrate to each other to obtain the multi-walled carbon nanotube piezoresistive sensor.
It should be noted that, although the above preferred solutions of each step of step S1, step S2, and step S3 are given, but the scope of the present invention is not limited thereby, that is, step S1 to step S4 of the present invention, each step can be implemented by other specific technical solutions, which only satisfies the technical problems actually solved by the present application, that is, the multi-walled carbon nanotube piezoresistive sensor and the manufacturing method thereof according to the present invention solve the adhesion problem between the conductive layer and the substrate, have good stretchability and wear resistance, and simplify the design of the internal complex circuit pattern by printing and manufacturing, and are simple to manufacture.
By testing the multi-walled carbon nanotube piezoresistive sensor prepared by the method in the embodiment of the application in the aspects of large strain stretching, temperature dependence of electrical conductivity and the like, the following test results are obtained:
(1) large strain elongation
The measurements were performed by clamping samples of the multi-walled carbon nanotube piezoresistive sensors on a precision motion stage, which samples were stretched at a controlled speed while measuring the resistance with a source measurement unit. The relationship between strain and resistance remains linear when the sensor is stretched 4 times its original length, where R2 is 0.996 at 300% tension.
(2) Dependence of conductivity on temperature
To test the conduction mechanism of the fabricated multi-walled carbon nanotube piezoresistive sensors and find a model to allow strain readings to be temperature compensated, the resistance of the fixed composite samples was measured at different temperatures between 22 ℃ and 130 ℃, with the different effects varying more and more significantly over different temperature ranges, indicating that the resistance decreases with increasing temperature.
Therefore, according to the test results, the multi-walled carbon nanotube piezoresistive sensor prepared by the preparation method of the multi-walled carbon nanotube piezoresistive sensor has outstanding large strain elongation and electrical conductivity dependence, so that the multi-walled carbon nanotube piezoresistive sensor and the preparation method thereof not only solve the adhesion problem between the conductive layer and the substrate, but also have good stretchability and wear resistance, and through printing and preparation, the design of an internal complex circuit pattern is simplified, and the manufacturing is simple.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (7)
1. The preparation method of the multi-walled carbon nanotube piezoresistive sensor is characterized in that the multi-walled carbon nanotube piezoresistive sensor comprises an insulating substrate and a conductive trace, wherein the conductive trace is embedded in the insulating substrate, the insulating substrate is made of silicone, and the conductive trace is a conductive circuit formed by mixing a multi-walled carbon nanotube and siloxane; the preparation method comprises the following steps:
s1, preparing a conductive nanocomposite material in a molten state, and filling the conductive nanocomposite material into an injector;
s2, extruding the pre-made uncured silicone resin onto a printing substrate of a 3D printer, and standing to form a partially cured insulating matrix;
s3, printing the conductive nanocomposite material into the partially cured insulating matrix by a 3D printer to form a conductive trace;
and S4, solidifying the insulating matrix printed with the conductive traces, and adhering the conductive traces and the insulating matrix to each other to obtain the multi-walled carbon nanotube piezoresistive sensor.
2. The method of claim 1, wherein the 3D printer is configured by fused deposition.
3. The method of manufacturing a multi-walled carbon nanotube piezoresistive sensor according to claim 1 or 2, wherein in step S1, preparing the conductive nanocomposite material in a molten state and loading into an injector specifically comprises:
adding the nanoparticles into uncured siloxane according to the required mass ratio, and centrifugally mixing to achieve uniform dispersion to obtain a conductive nanocomposite material formed by mixing a multiwalled carbon nanotube and siloxane in a molten state;
the conductive nanocomposite material in a molten state was loaded into a syringe in vacuum to avoid air bubbles.
4. The method of claim 3, wherein the step S2 of extruding the pre-fabricated uncured silicone resin onto the printing substrate of the 3D printer to form the partially cured insulating matrix after standing comprises:
extruding the pre-prepared uncured silicone resin onto a printing substrate through a nozzle with the diameter of 0.6 mm, wherein the thickness of the silicone resin is uniform;
and standing for 20 minutes to cure the silicone resin at the bottom of the insulating matrix, and keeping the silicone resin at the surface in a fluid state.
5. The method of manufacturing a multi-walled carbon nanotube piezoresistive sensor according to claim 3, wherein in step S3, printing a conductive nanocomposite material into a partially cured insulating matrix by a 3D printer to form a conductive trace specifically comprises:
inserting an injection head of an injector into the partially cured insulating matrix, driving a printing substrate to move on an X-Y plane relative to the injector by a transmission mechanism of a 3D printer, and injecting the conductive nanocomposite material in a molten state into the partially cured insulating matrix to form a conductive trace;
the moving speed of the printing substrate relative to the injector is not more than 3 mm/s.
6. The method of claim 5, wherein the conductive trace is shaped as a straight line, a curved line, or a meander line composed of multiple segments of lines.
7. The method as claimed in claim 6, wherein the step S4, curing the dielectric substrate printed with the conductive traces, and adhering the conductive traces and the dielectric substrate to each other to obtain the multi-walled carbon nanotube piezoresistive sensor, comprises:
and (3) standing the insulating substrate printed with the conductive traces at room temperature for curing, and bonding the conductive traces and the insulating substrate to each other to obtain the multi-walled carbon nanotube piezoresistive sensor.
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| JP2005315819A (en) * | 2004-04-30 | 2005-11-10 | Kyowa Electron Instr Co Ltd | Moisture-proof structure for strain gage, and moisture-proofing method for strain gage |
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