1. A preparation method of natural rubber modified bucky paper is characterized by comprising the following steps:

dispersing carbon nanotubes into water containing a surfactant to obtain a dispersion liquid of the carbon nanotubes;

mixing the dispersion liquid of the carbon nano tube with natural latex to obtain a mixed liquid, and performing vacuum filtration on the mixed liquid by adopting a filter membrane to obtain a deposited film;

and cleaning the deposited film, and then removing the filter membrane in the deposited film to obtain the natural rubber modified bucky paper.

2. The method of claim 1, wherein the surfactant is triton x-100, sodium dodecyl sulfate, carbon nanotube water dispersant TNWDIS, sodium dodecyl benzene sulfonate or dodecyl trimethyl ammonium chloride; in the surfactant-containing water, the mass of the surfactant accounts for 0.4-2% of the mass of the water.

3. The method according to claim 1, wherein the concentration of the carbon nanotubes in the dispersion of carbon nanotubes is 0.1 to 1.5 mg/mL.

4. The method according to claim 1, wherein the mass ratio of the carbon nanotubes to the natural rubber latex in the dispersion of the carbon nanotubes is (1-6): 1.

5. the method according to claim 1, wherein the pore size of the filter membrane is 0.2 to 0.6 μm; the filter membrane is made of mixed fibers, PTFE, PVDF, PA, PP or polyether sulfone.

6. The natural rubber modified bucky paper prepared by the preparation method of any one of claims 1 to 5.

7. Use of the natural rubber modified buckypaper of claim 6 in electromagnetic shielding, deicing, hydrophobic, joule heating, heat dissipating or strain sensing materials.

8. A sandwich structure strain sensor comprises a first natural rubber layer, a natural rubber modified basepaper layer and a second natural rubber layer which are sequentially stacked; the natural rubber modified basepaper layer consisting of the natural rubber modified basepaper of claim 6.

9. The sandwich structure strain sensor of claim 8, wherein the first and second natural rubber layers independently have a thickness of 200-1000 μm; the thickness of the natural rubber modified basepaper layer is 10-300 mu m.

10. Use of the sandwich structured strain sensor of claim 9 in a wearable electronic device.

Background

The vigorous development of electronic devices and wireless communication has improved the living standard of people, and at the same time, it has generated serious electromagnetic interference (EMI) and radiation, which seriously affects the data precision and communication quality, even threatens human health.

Buckypaper (BP) is a lightweight, self-supporting and conductive film composed of tangled carbon nanotubes, which has great potential in electromagnetic shielding materials due to its high electrical conductivity. Compared with Chemical Vapor Deposition (CVD) and spin-coating methods, the vacuum filtration method has the advantages of simple process, convenient operation, short period and low cost, thereby being widely applied. However, BP prepared by vacuum filtration (strain at break: about 2%) has poor flexibility, which limits its further applications. To address this problem, many researchers have introduced polymers into BP to improve its flexibility by ultrasonic impregnation or crosslinking. Zhang et al prepared a multifunctional thin nanocomposite of Carbon Nanotube (CNT) Nanopaper (NP) reinforced Thermoplastic Polyurethane (TPU) by ultrasonic infiltration and impregnation (Zhang D, Yang H, Pan J, et al, Multi-functional CNT nanopaper nanocomposite reinforced by inorganic filler and di cushioning processes [ J ]. Composites Part B: Engineering,2019,182: 107646), the procedure was complex, involving special conditions, procedures and equipment. In addition, in the prior art, although the flexibility of BP is improved to a certain extent by introducing a polymer into BP, the conductivity of BP is greatly reduced, and good flexibility and conductivity cannot be achieved, so that the electromagnetic shielding performance of the material is influenced. Therefore, a simple, large-scale, efficient process for preparing high-performance flexible BPs remains a great challenge.

Disclosure of Invention

The invention aims to provide natural rubber modified bucky paper (N-BP) and a preparation method and application thereof, and a sandwich structure strain sensor and application thereof. The N-BP is used for preparing the sandwich structure strain sensor, has very high sensitivity, ultrashort response time, larger detection range and excellent cycle stability, and has wide application prospect in next generation wearable electronic equipment.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of natural rubber modified bucky paper, which comprises the following steps:

dispersing carbon nanotubes into water containing a surfactant to obtain a dispersion liquid of the carbon nanotubes;

mixing the dispersion liquid of the carbon nano tube with natural latex to obtain a mixed liquid, and performing vacuum filtration on the mixed liquid by adopting a filter membrane to obtain a deposited film;

and cleaning the deposited film, and then removing the filter membrane in the deposited film to obtain the natural rubber modified bucky paper.

Preferably, the surfactant is triton x-100, sodium dodecyl sulfate, carbon nano tube water dispersant TNWDIS, sodium dodecyl benzene sulfonate or dodecyl trimethyl ammonium chloride; in the surfactant-containing water, the mass of the surfactant accounts for 0.4-2% of the mass of the water.

Preferably, the concentration of the carbon nanotubes in the dispersion liquid of the carbon nanotubes is 0.1-1.5 mg/mL.

Preferably, the mass ratio of the carbon nanotubes to the natural latex in the dispersion of the carbon nanotubes is (1-6): 1.

preferably, the aperture of the filter membrane is 0.2-0.6 μm; the filter membrane is made of mixed fibers, PTFE, PVDF, PA, PP or polyether sulfone.

The invention provides the natural rubber modified bucky paper prepared by the preparation method in the scheme.

The invention provides application of the natural rubber modified bucky paper in the scheme in electromagnetic shielding materials, deicing materials, hydrophobic materials, Joule heating materials, heat dissipation materials or strain sensing materials.

The invention provides a sandwich structure strain sensor which comprises a first natural rubber layer, a natural rubber modified basepaper layer and a second natural rubber layer which are sequentially stacked; the natural rubber modified basepaper layer is composed of the natural rubber modified basepaper in the scheme.

Preferably, the thicknesses of the first natural rubber layer and the second natural rubber layer are 200-1000 μm independently; the thickness of the natural rubber modified basepaper layer is 10-300 mu m.

The invention provides application of the sandwich structure strain sensor in wearable electronic equipment.

The invention provides a preparation method of natural rubber modified bucky paper, which comprises the following steps: dispersing carbon nanotubes into water containing a surfactant to obtain a dispersion liquid of the carbon nanotubes; mixing the dispersion liquid of the carbon nano tube with natural latex to obtain a mixed liquid, and performing vacuum filtration on the mixed liquid by adopting a filter membrane to obtain a deposited film; and cleaning the deposited film, and then removing the filter membrane in the deposited film to obtain the natural rubber modified bucky paper.

The invention adopts latex blending and vacuum filtration to prepare N-BP, and the preparation method is simple and convenient and is easy for large-scale manufacture.

The N-BP prepared by the invention comprises natural rubber and carbon nano tubes; the natural rubber is used as an adhesive among the carbon nanotubes, enhances the interaction among the carbon nanotubes, promotes the stress transfer, and enables the stress to be uniformly dispersed in the N-BP. Meanwhile, natural rubber particles are diffused into adjacent carbon nanotubes, the entanglement of the carbon nanotubes is not influenced, and only interface resistance is slightly caused, so that the N-BP provided by the invention has good mechanical property and high conductivity, and the high conductivity enables the N-BP to have Joule heating property and electromagnetic shielding property. In addition, the carbon nano tube has hydrophobicity, and the surface of the N-BP is rough, so that the hydrophobicity of the N-BP is further improved. N-BP has high conductivity and hydrophobicity, so that the N-BP has quick deicing performance, and can deice in 10s under the condition of 6V voltage. In addition, the N-BP also has higher thermal conductivity and can play a good role in heat dissipation in products which generate heat by microelectronics or electrons.

The results of the examples show that the N-BP prepared by the invention has the ultra-high elongation at break of 190% and the electrical conductivity of more than 21.74 s/cm. Total electromagnetic shielding effectiveness of N-BP at a thickness of 50 μm (EMI SE)_T) Greater than 28.3dB, and specific shielding effectiveness value (SSE/t) of 6232dB cm²More than g. Due to good mechanical flexibility, the EMI SE of N-BP can be folded for 5000 times at 180 degrees and after 5000 times of folding at 180 degrees_TRemain substantially unchanged. In addition, N-BP also has joule heating performance and quick deicing performance at low drive voltage.

The invention provides a sandwich structure strain sensor which comprises a first natural rubber layer, a natural rubber modified basepaper layer and a second natural rubber layer which are sequentially stacked; the natural rubber modified basepaper layer is composed of the natural rubber modified basepaper in the scheme.

The sandwich structure strain sensor takes the middle N-BP as a sensing layer, and the deformation of the sandwich structure strain sensor under the action of external force causes the damage of a conductive network so as to cause the resistance change, so that the sandwich structure strain sensor has good sensing performance, and has large detection range and cycle stability due to the excellent fatigue resistance of rubber. The results of the examples show that the strain sensor of the invention has a very high sensitivity, with a sensitivity factor of 2280; the response time is ultra-short and is 21 ms; the detection range is wide, the detection range is 500%, the cycling stability is excellent, and 2000 cycles can be performed under 100% strain.

The sandwich structure strain sensor can accurately capture larger or delicate human body motions including limb joint motions and facial motions, even can distinguish pronunciations of different English words, and has wide application prospect in next generation wearable electronic equipment.

Drawings

FIG. 1 is a flow chart of the preparation of N-BP;

FIG. 2 is a graph of standing images, UV-VIS absorption spectra and conductivity changes of CW and CWT; wherein a is standing images of CW and CWT at different times, b is a graph of variation of ultraviolet-visible absorption spectra of CW and CWT with standing time, and c is a graph of variation of conductivity of CWT with standing time;

FIG. 3, a is a macro photograph of CNR4 prepared in example 1, b is a photograph of CNR4 folded into a paper crane and a paper boat placed on the flower, c is a thermogravimetric plot of BP and N-BP, d is a typical stress-strain curve of N-BP at different addition amounts of NR, e is tensile strength and elongation at break of N-BP at different addition amounts of NR, and f is electrical conductivity of N-BP at different addition amounts of NR;

FIG. 4 is an SEM image of the top surface and cross-section of BP, CNR4 and CNR 1; wherein, a and d are SEM images of the upper surface and the cross section of BP, respectively, b and e are SEM images of the upper surface and the cross section of CNR4, respectively, and c and f are SEM images of the upper surface and the cross section of CNR1, respectively;

FIG. 5 is a graph of Joule heating performance of CNR4 at different voltages; wherein, a is a temperature curve and an infrared camera image of the CNR4 under different working voltages, b is a temperature evolution of the CNR4 when the voltage is gradually increased from 2V to 6V, c is a heating cycle curve of the CNR4 when the voltage is 2V, 4V and 6V, and d is a temperature stability curve of the CNR4 when the voltage is 4V and the voltage is constant for 2 hours;

fig. 6 is water contact angle and SEM images and deicing performance images of BP, CNR4, and CNR1, wherein a is the SEM image of the upper surface of BP with the corresponding water contact angle image inserted in the upper right corner; b is an SEM image of the top surface of CNR4 with the corresponding water contact angle image inserted in the upper right corner; c is the SEM image of the top surface of CNR1 with the corresponding water contact angle image inserted in the upper right corner; d is a photograph of the milk, water and coffee droplets remaining nearly spherical on the surface of CNR 4; e is a photograph of the state of the upper ice when no voltage is applied to CNR 4; f is a photograph of the state of ice after the voltage is not applied to the CNR4 for 200 s; g is a photograph of the state of the ice on the CNR4 just after the application of 6V voltage; h is a photograph of the state of the ice after the CNR4 applies the voltage of 6V for 10 s;

FIG. 7 is a graph of the electromagnetic shielding performance of the N-BP; wherein, a is the electromagnetic shielding performance of BP and N-BP in the frequency range of 5.85-8.2GHz, and b is the total shielding effectiveness SE of BP and N-BP_TAbsorption shielding effectiveness SE_AAnd reflective shielding effectiveness SE_RC is EMI SE of N-BP with different thickness_TAnd d is EMI SE before and after the CNR4 and CNR2 are folded 180 degrees and 5000 times_TAnd e is an electromagnetic shielding mechanism diagram of N-BP;

FIG. 8 is the thermal conductivity of N-BP and BP;

FIG. 9 is a flowchart of the preparation of a sandwich-structured strain sensor according to application example 1;

in fig. 10, a is tensile property of pure NR and the sandwich structure strain sensor of application example 1, and b is a schematic structural diagram of the sandwich structure strain sensor;

FIG. 11 is an SEM image of a cross section of a sandwich-structured strain sensor prepared in application example 1;

fig. 12 is an SEM image of the surface and cross-section of CNR4 and a sandwich structured strain sensor prepared in application example 1; wherein a is a top surface SEM image of CNR 4; b is a partial enlarged view of a, and c is a sectional SEM image of CNR 4; d is a partial enlarged view of c; e is a cross-sectional SEM image of the sandwich structure strain sensor; f is a partial enlarged view of e; g is a cross-sectional SEM image of the infiltration layer; h is a partial enlarged view of g;

FIG. 13 is a graph of the sensing performance of a sandwich structured strain sensor prepared in application example 1; wherein a is a current-voltage characteristic curve of the sandwich structure strain sensor in a large deformation range of 0-500%, b is a relation curve of resistance change and strain, c is a relation graph of strain and GF of the sandwich structure strain sensor in a strain range of 0-520%, and d is a change graph of the structure of the sandwich structure strain sensor in a stretching process;

FIG. 14 is a digital image of LED brightness in different states;

FIG. 15 is an evolution mechanism diagram of a sandwich structure strain sensor conductive network;

in fig. 16, a is a real-time resistance response diagram of the sandwich structure strain sensor, b is a resistance change diagram of the sandwich structure strain sensor after 2000 cycles, c is an SEM image of the N-BP layer before cyclic stretching, and d is an SEM image of the N-BP layer after cyclic stretching;

in fig. 17, a is a graph of the change in resistance of the sandwich structure strain sensor prepared in application example 1 under different strains during the stepwise stretching and releasing process, b is the response of the sandwich structure strain sensor to the strain caused by tapping, c is a graph of the feedback of the electrical signals of the sandwich structure strain sensor to the weak air pressure during the monitoring, d is a graph of the feedback of the electrical signals of the sandwich structure strain sensor to the joint movement during the detection, (1) finger movement, (2) wrist joint movement, (3) elbow joint movement, and e is a graph of the feedback of the electrical signals of the sandwich structure strain sensor to the fine movement during the monitoring, (1) frown, (2) and (3) speaking.

Detailed Description

The invention provides a preparation method of natural rubber modified bucky paper, which comprises the following steps:

dispersing carbon nanotubes into water containing a surfactant to obtain a dispersion liquid of the carbon nanotubes;

mixing the dispersion liquid of the carbon nano tube with natural latex to obtain a mixed liquid, and performing vacuum filtration on the mixed liquid by adopting a filter membrane to obtain a deposited film;

and cleaning the deposited film, and then removing the filter membrane in the deposited film to obtain the natural rubber modified bucky paper.

In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.

The invention disperses the carbon nano tube into the water containing the surfactant to obtain the dispersion liquid of the carbon nano tube.

In the invention, the diameter of the carbon nano tube is preferably 10-20 nm, and the length of the carbon nano tube is preferably 10-30 μm; the surfactant is preferably triton x-100, sodium dodecyl sulfate, carbon nano tube water dispersant TNWDIS, sodium dodecyl benzene sulfonate or dodecyl trimethyl ammonium chloride, and more preferably triton x-100; the water is preferably distilled water. Compared with the carbon nanotubes with other sizes, the carbon nanotube with the size has better film forming property.

In the present invention, in the surfactant-containing water, the mass of the surfactant is preferably 0.4 to 2%, more preferably 0.8 to 1.5%, and most preferably 1% of the mass of the water.

The present invention preferably grinds the carbon nanotubes before dispersing them into water containing a surfactant; the rotation speed of the grinding is preferably 400r/min, and the grinding time is preferably 30 min. The present invention utilizes grinding to initially disentangle the carbon nanotubes.

The present invention preferably disperses the carbon nanotubes into water containing a surfactant under conditions of agitation and an ultrasonic bath. The present invention does not require any particular speed of agitation, and can employ agitation speeds well known in the art. In the invention, the power adopted by the ultrasonic bath is preferably 325W, and the time of the ultrasonic bath is preferably 30-120 min, and more preferably 60-90 min.

In the present invention, the concentration of the carbon nanotubes in the dispersion of carbon nanotubes is preferably 0.1 to 1.5mg/mL, more preferably 0.3 to 1.2mg/mL, and still more preferably 0.6 to 0.9 mg/mL.

In the invention, the presence of the surfactant is beneficial to the uniform dispersion of the carbon nano tube in water, and provides guarantee for the subsequent preparation of N-BP with good performance.

After the dispersion liquid of the carbon nano tube is obtained, the dispersion liquid of the carbon nano tube is mixed with natural latex to obtain a mixed liquid.

In the invention, the mass ratio of the carbon nanotubes to the natural rubber latex in the dispersion of the carbon nanotubes is preferably (1-6): 1, in embodiments of the invention, specifically 1:1, 2:1, 4:1 or 6: 1.

The present invention preferably adds the natural latex to the dispersion of the carbon nanotubes dropwise so that the natural latex and the carbon nanotubes are dispersed more uniformly. Preferably, the natural latex is dripped under the stirring condition, and the stirring is continued for 5-30 min after the dripping is finished; in the process, the stirring speed is preferably 60-300 r/min. In the present invention, it is preferable that the natural rubber latex is diluted with water and then added dropwise to the dispersion of the carbon nanotubes. The dilution ratio is not particularly required in the present invention, and in the examples of the present invention, the natural rubber latex is specifically diluted to an aqueous natural rubber latex solution having a solid content of 60 wt%.

After the mixed solution is obtained, the mixed solution is subjected to vacuum filtration by using a filter membrane to obtain a deposited film.

In the present invention, the pore diameter of the filter membrane is preferably 0.2 to 0.6. mu.m, more preferably 0.3 to 0.5. mu.m, and still more preferably 0.45. mu.m. The filter membrane with the pore size is beneficial to obtaining the N-BP with optimal performance. In the present invention, the material of the filter membrane is preferably mixed fiber, PTFE, PVDF, PA, PP, or polyethersulfone, and more preferably a mixed fiber filter membrane.

The vacuum filtration process is not particularly required in the present invention, and a filtration process well known in the art may be used.

After the deposition film is obtained, the invention cleans the deposition film, and then removes the filter membrane in the deposition film to obtain the N-BP.

The present invention preferably cleans the deposited film with water or acetone. The invention has no special requirements on the process of cleaning the deposited film, and can be directly washed by water or acetone. The invention preferably employs deionized water for cleaning. The invention uses water or acetone to clean the deposition film so as to remove the surfactant in the deposition film, and the existence of the surfactant can reduce the conductivity of N-BP and influence the electromagnetic shielding performance of the N-BP.

The invention preferably selects the mode of removing the filter membrane according to the material of the filter membrane. In the invention, when the material of the filter membrane is mixed fiber, the deposited film is preferably soaked in acetone, and the mixed fiber filter membrane is dissolved and removed by using the acetone; when the material of the filter membrane is PTFE, PVDF, PA, PP or polyethersulfone, the filter membrane is preferably directly stripped.

The invention utilizes latex blending and vacuum filtration to prepare N-BP, and the preparation method is simple and convenient and is easy for large-scale manufacture.

The invention provides the natural latex modified bucky paper (N-BP) prepared by the preparation method in the scheme. In the present invention, the thickness of the N-BP is preferably not less than 25 μm. The thicker the thickness of the N-BP is, the better the electromagnetic shielding performance is. In embodiments of the invention, the thickness of the N-BP is specifically 25 μm, 50 μm, 75 μm, 100 μm, 150 μm or 200 μm. The N-BP of the invention comprises natural rubber and carbon nanotubes; the natural rubber is used as an adhesive among the carbon nanotubes, enhances the interaction among the carbon nanotubes, promotes the stress transfer, and enables the stress to be uniformly dispersed in the N-BP. Meanwhile, natural rubber particles are diffused into adjacent carbon nanotubes, the entanglement of the carbon nanotubes is not influenced, and only interface resistance is slightly caused, so that the N-BP provided by the invention has good mechanical property and high conductivity, and the high conductivity enables the N-BP to have Joule heating property and good electromagnetic shielding property. In addition, the carbon nano tube has hydrophobicity, and the surface of the N-BP is rough, so that the hydrophobicity of the N-BP is further improved. N-BP has high conductivity and hydrophobicity, so that the N-BP has quick deicing performance, and can deice in 10s under the condition of 6V voltage. In addition, the N-BP also has higher thermal conductivity and can play a good role in heat dissipation in products which generate heat by microelectronics or electrons.

These multifunctional properties of the N-BP, coupled with its ease of large-scale manufacturing, have broad application prospects in aerospace and next-generation flexible electronics.

The invention provides application of the natural latex modified bucky paper in the scheme in electromagnetic shielding materials, deicing materials, hydrophobic materials, Joule heating materials, heat dissipation materials or strain sensing materials.

The invention provides a sandwich structure strain sensor which comprises a first natural rubber layer, a natural rubber modified basepaper layer and a second natural rubber layer which are sequentially stacked; the natural rubber modified basepaper layer is composed of the natural rubber modified basepaper in the scheme.

The sandwich structure strain sensor provided by the invention comprises a first natural rubber layer and a second natural rubber layer. In the invention, the thicknesses of the first natural rubber layer and the second natural rubber layer are independent and preferably 200-1000 μm, more preferably 300-900 μm, and even more preferably 400-800 μm.

The sandwich structure strain sensor provided by the invention comprises a natural rubber modified basepaper layer positioned between a first natural rubber layer and a second natural rubber layer, wherein the natural rubber modified basepaper layer is composed of the natural rubber modified basepaper in the scheme.

In the invention, the thickness of the natural rubber modified basepaper layer is preferably 10-300 μm, more preferably 20-100 μm, and even more preferably 40-60 μm.

In the invention, the thickness of the sandwich structure strain sensor is preferably 500-1500 μm, more preferably 700-1200 μm, and further preferably 900-1100 μm. The thickness of the sandwich structure strain sensor is controlled within the range, so that the sandwich structure strain sensor is easier to deform under external force. In the embodiment of the invention, the thickness of the sandwich structure strain sensor is 1000 μm, the thickness of the natural rubber modified basepaper layer is 50 μm, and the thicknesses of the natural rubber layers on the two sides are equal.

In the invention, the first natural rubber layer and the second natural rubber layer are respectively infiltrated into the natural rubber modified basepaper layer to form two infiltration layers. In an embodiment of the invention, each infiltration layer has a thickness of 5 μm.

The preparation method of the sandwich structure strain sensor has no special requirements, and the structure can be obtained. The sandwich structure strain sensor is preferably prepared by adopting a casting curing method. The invention has no special requirements on the specific implementation process of the casting curing method, and the process which is well known in the field can be adopted. In the embodiment of the invention, in order to test the performance of the sandwich structure strain sensor conveniently, the sandwich structure strain sensor is provided with the electrode, and the specific preparation process comprises the following steps: cutting an N-BP into a rectangle with the size of 25mm multiplied by 4mm, coating silver paste on two tail ends of the rectangle, and sticking a copper adhesive tape as an electrode to obtain the N-BP with the electrode; fixing the N-BP with the electrode on a customized PMMA mould, filling natural latex in the mould, and drying at room temperature to obtain the N-BP with a Natural Rubber (NR) film on one side to form a first (or second) natural rubber layer and a natural rubber modified basepaper layer. By repeatedly casting the NR latex, the other side of the N-BP is also covered by the solid NR film, and finally the N-BP is clamped between two NR layers to form the sandwich structure strain sensor.

The sandwich structure strain sensor takes the middle N-BP as a sensing layer, and the deformation of the sandwich structure strain sensor under the action of external force causes the damage of a conductive network so as to cause the resistance change, so that the sandwich structure strain sensor has good sensing performance, and has large detection range and cycle stability due to the excellent fatigue resistance of rubber. The strain sensor has very high sensitivity, and the sensitivity factor is 2280; the response time is ultra-short and is 21 ms; the detection range is larger and 500%, the cycle stability is excellent, 2000 cycles can be performed under 100% strain, and the method has a wide application prospect in next-generation wearable electronic equipment.

The invention provides application of the sandwich structure strain sensor in wearable electronic equipment.

The following examples are provided to illustrate the natural rubber modified buckypaper (N-BP) and its preparation method and application, and the sandwich structure strain sensor and its application, but they should not be construed as limiting the scope of the present invention.

The carbon nanotubes used in the following examples and application examples have a diameter of 10 to 20nm and a length of 10 to 30 μm.

Example 1

The carbon nanotubes were milled for 30 minutes and then dispersed in distilled water containing 1 wt% triton x-100 with stirring and with the aid of an ultrasonic bath to form a uniform dispersion of carbon nanotubes at a concentration of 0.6mg/mL, denoted CWT. Then, the NR natural latex was dropped into the carbon nanotube CNTs dispersion and stirred for 30 minutes with the ratio of CNTs to NR being 4: 1. The NR/CNTs homogeneous mixture was vacuum filtered through a mixed fiber filter (pore size 0.45 μm) to obtain a deposited film. Finally, the deposited film was rinsed with a large amount of deionized water and then soaked several times in an acetone bath to dissolve the mixed fiber filter membrane to obtain an isolated N-BP having a thickness of 50 μm and named CNR 4. The complete preparation process is shown in fig. 1.

Examples 2 to 4

The only difference from example 1 is that the ratios of CNTs to NR were 6:1, 2:1 and 1:1 in this order, and the resulting N-BP were named CNR6, CNR2 and CNR1, respectively, and had a thickness of 50 μm.

Examples 5 to 9

The difference from example 1 is only that the thickness of N-BP is 25 μm, 75 μm, 100 μm, 150 μm and 200 μm in this order by adjusting the amount of the carbon nanotube CNTs dispersion (the mass ratio of CNTs to NR is kept constant).

Comparative example 1

Pure BP was also prepared under the same conditions, except that no natural latex NR was added as in example 1.

Comparative example 2

Only a dispersion of carbon nanotubes was prepared, which was different from example 1 in that triton-100 was not included, specifically: the carbon nanotubes were milled for 30 minutes and then dispersed in distilled water with the help of stirring and an ultrasonic bath to give an aqueous dispersion of CNTs, noted CW.

The dispersion of CNTs is the key for preparing excellent BP and N-BP, and the CNTs can be effectively dispersed in an aqueous solution under the action of a nonionic surfactant Triton X-100 to form a stable dispersion liquid.

The CW of comparative example 2 and the CWT of example 1 were left for different times, respectively, and the results are shown in a of fig. 2. As can be seen from a in FIG. 2, CNTs aqueous dispersion (i.e., CW) without TritonX-100 added exhibited significant CNTs sedimentation after 1 day. CNTs/water dispersion (i.e., CWT) added with Triton X-100 was stable after 30 days at the same CNTs concentration.

The long-term stability of the CNTs dispersion was evaluated using the UV-Vis absorption spectrum and the conductivity. As shown in b of FIG. 2, the UV-visible absorbance of the CW dispersion in the range of 240 to 400nm sharply decreases from 0.14 to 0.01 due to the precipitation. In contrast, CWT dispersions showed excellent stability within 7 days from the nearly constant uv-vis absorbance and conductivity in b and c of figure 2. Thus, the CNTs are dispersed optimally by the action of ball milling, sonication and surfactants.

N-BP Structure and Performance characterization

1. Fig. 3 a is a macro photograph of CNR4 prepared in example 1, and as can be seen from fig. 3 a, vacuum assisted filtration can be easily scaled up to provide CNR4 of a4 paper or larger size, with CNR4 of 27cm x 18cm in size in a. As can be seen from b of fig. 3, the manufactured CNR4 can be further folded into paper crane and paper boat to be placed on the flower, and has good flexibility, foldability and light weight. The content of NR in N-BP was estimated by thermogravimetric analysis (TGA) and the result is shown in c of FIG. 3. As can be seen from c in FIG. 3, although there is some loss of CNTs and NR during the vacuum filtration, the mass ratio of CNTs and NR is substantially the same as the theoretical mass ratio. In practical applications, the mechanical properties of the material are essential. The mechanical properties of N-BP were tested by tensile test and the results are shown in d-e of FIG. 3. FIG. 3d is a typical stress-strain curve of N-BP at different NR addition levels, and the detailed mechanical property data are shown in FIG. 3 e and Table 1. As can be seen from FIG. 3 and Table 1, all N-BPs are significantly superior to pure BP in tensile strength, toughness and ductility compared to pure BP. Due to the lack of strong interaction between carbon nanotubes, BP exhibits brittle fracture with a tensile strength of 5.38MPa and a strain at fracture of 1.85%. The tensile strength of CNR6, CNR4, CNR2 and CNR1 increased to 5.73, 5.94, 7.32 and 13.19MPa, respectively, after addition of NR. Elongation at break of CNR6, CNR4, CNR2 and CNR1 were increased to 15.80%, 27.80%, 72.33% and 191.23%, respectively.

The conductivity measurements of the N-BP of examples 1-4 and the pure BP of comparative example 1 are shown in f of FIG. 3, and the corresponding data are shown in Table 1.

TABLE 1 mechanical Properties and conductivity of N-BP and BP

Samples	Tensile Strength (MPa)	Elongation at Break (%)	Density (g/cm)3)	Conductivity (S/cm)
					BP	5.38	1.85	0.6563	40
CNR6	5.73	15.80	0.7253	34.48
					CNR4	5.94	27.80	0.7504	32.26
CNR2	7.32	72.33	0.8341	28.57
					CNR1	13.19	191.23	0.9091	21.74

2. SEM test

SEM observations of the upper surface and cross-section of BP, CNR4 and CNR1 are shown in FIG. 4. In fig. 4, a and d are SEM images of the upper surface and cross section of BP, respectively, b and e are SEM images of the upper surface and cross section of CNR4, respectively, and c and f are SEM images of the upper surface and cross section of CNR1, respectively. As can be seen from FIG. 4, CNTs are randomly stacked in BP, and some adjacent CNTs overlap each other (a and d in FIG. 4). NR can effectively fill the space between adjacent CNTs, forming NR accumulation regions (dotted circles) on the top surface and cross section of CNR4 (b and e in fig. 4). As NR increases, more NR accumulation occurs on the top surface and cross section of CNR1 (c and f in fig. 4). The excellent mechanical property and conductivity of N-BP can be attributed to the fact that NR can be used as a 'bonding agent' between carbon nanotubes, the interaction is enhanced, the stress transfer is promoted, and the stress is uniformly dispersed in the N-BP. At the same time, the diffusion of the NR particles into the adjacent CNTs does not affect the entanglement of the CNTs, and causes only slight interfacial resistance.

3. Joule heating Property

The CNR4 was tested for joule heating performance at different voltages and the results are shown in fig. 5. In fig. 5, a is a temperature curve and an infrared camera image of the CNR4 at different operating voltages, b is a temperature evolution of the CNR4 when the voltage is gradually increased from 2V to 6V, c is a heating cycle curve of the CNR4 at voltages of 2V, 4V and 6V, and d is a temperature stability curve of the CNR4 at a constant voltage of 4V for 2 hours.

As can be seen from a of FIG. 5, the equilibrium temperature of CNR4 was 45.6 ℃ at a voltage of 2V, and increased to 104.9 ℃ and 155.5 ℃ at 4V and 6V, respectively; the infrared image corresponding to CNR4 shows a uniform temperature distribution, which is an important property of an electric heater. At the same voltage, the equilibrium temperatures of CNR1 were 39.9 deg.C, 85.9 deg.C, and 155.2 deg.C, respectively. It can be seen from b of fig. 5 that the temperature of the CNR4 is linearly increased and then reaches a balance by increasing the voltage by 1V every 1min, which indicates that the CNR4 heater has a fast temperature-increasing speed and a stable temperature-increasing performance. Therefore, the equilibrium temperature of CNR4 can be easily adjusted by adjusting the voltage. More importantly, the driving voltage of CNR4 is much lower compared to the recently reported materials. The lower drive voltage is both energy efficient and safe to the human body (well below 36V) and allows the heater to be powered by a portable battery or super capacitor. On the other hand, long-term heating stability is one of the keys to ensuring the operating life of the heater. As shown in fig. 5 c, the voltage loading and unloading correspond to stable and regular temperature rise and fall cycles, indicating that CNR4 has sufficient cycling stability. In addition, as can be seen from d of fig. 5, the long-term heating stability is also demonstrated by the small temperature fluctuation when a voltage of 4V exceeding 2h is applied to CNR 4.

4. Hydrophobicity and deicing Properties

The results of the water contact angle test and SEM observation of BP, CNR4 and CNR1 are shown in a-c of FIG. 6. In fig. 6, a is an SEM image of the upper surface of BP, with the corresponding water contact angle image inserted in the upper right corner; b is an SEM image of the top surface of CNR4 with the corresponding water contact angle image inserted in the upper right corner; c is an SEM image of the top surface of CNR1 with the corresponding water contact angle image inserted in the upper right corner.

As can be seen from a to c of fig. 6, unlike the relatively smooth morphology of the upper surface of BP, a large number of micro-scale protrusions corresponding to the pores of the mixed fiber filtration membrane appear on the lower surface, and the roughness is significantly increased. The Water Contact Angle (WCA) of pure BP reaches 87 degrees, which is mainly caused by the inherent hydrophobicity of CNTs and the micro-nano structure formed by the aggregation of the CNTs in the vacuum filtration process. With the incorporation of NR, the hydrophobicity of CNR4 and CNR1 was further increased and WCA was significantly increased, reaching 127 ° and 128 °, respectively, mainly due to the increase in surface roughness caused by the heterostructure of CNTs and NR.

Due to the excellent hydrophobicity of N-BP, various liquids such as milk, water and coffee droplets can remain nearly spherical on the CNR4 surface, as shown in d of fig. 6.

CNR4 was used as a conductive element to connect a dc power supply to a Light Emitting Diode (LED) bulb. Due to the hydrophobic nature of the film, there is no change in the brightness of the bulb when water drops onto the film. It is expected that the combination of hydrophobicity and joule heating performance will be very beneficial for rapid deicing in extremely cold conditions.

An ice layer with a thickness of 7mm was coated on the CNR4 and pure BP, and then a voltage was applied. The results are shown in FIG. 6 as e to h. As is evident from e-f in FIG. 6, the ice layer with a thickness of 7mm covered on CNR4 hardly changed within 200s at 15 ℃. In contrast, when a voltage of 6V was applied across CNR4, the entire ice layer completely slipped out of CNR4 (g and h in fig. 6) in 10 seconds, which is significantly lower than 120 seconds for the PDMS @ MWCNTs film. This is not only related to the joule heating characteristic of CNR4, but also to the hydrophobicity of CNR 4.

5. Electromagnetic shielding performance

The excellent conductivity of N-BP makes it have excellent electromagnetic shielding performance. FIG. 7, a, shows the electromagnetic shielding performance of BP and N-BP (50 μm thick) in the frequency range of 5.85-8.2GHz (c-band) using the waveguide method. Since BP has the highest conductivity, BP has excellent electromagnetic shielding property, EMI SE_T(total shielding effectiveness) was 33.5 dB. The electromagnetic shielding performance of N-BP is slightly reduced due to the reduction of conductivity caused by adding NR. However, the electromagnetic shielding of all N-BPs can still be kept at a high level. EMI SE of CNR4_T31.9dB, which is only 4.7% lower than BP. CNR1 containing 50 wt% NR also had an EMI SE of 28.3dB, CNR6_TEMI SE of CNR2 of 32.4dB_T30.0dB, both exceeding the requirements for commercial shielding applications (20 dB). Compared with the traditional carbon nano tube and graphene-based polymer composite material with much larger thickness, the N-BP prepared by the research has excellent electromagnetic shielding performance.

To understand the mechanism of electromagnetic shielding, the total shielding effectiveness SE_TAbsorption shielding effectiveness SE_AAnd reflective shielding effectiveness SE_RAs shown in b of fig. 7. B of fig. 7 shows that SEA is higher than SER for all samples, indicating that absorption shielding is the dominant shielding mechanism for N-BP.

The thickness plays a crucial role in shielding electromagnetic waves, and the electromagnetic shielding performance of the N-BP prepared in example 1 and examples 5-9 with different thicknesses was tested, and the result is shown in c of FIG. 7. As can be seen from c in fig. 7, increasing the thickness of the shielding material can improve the electromagnetic shielding performance. As the thickness increases from 25 μm to 200 μm, the total electromagnetic shielding effectiveness of CNR4 increases from 24.9dB to 44.8dB due to the enhanced interaction of the electromagnetic waves with the conductive network. It is noted that CNR4 can meet commercial electromagnetic shielding application requirements (20dB) at a thickness of no more than 25 μm.

In addition, the durability of the electromagnetic shielding performance is of great significance in practical application. The stability of electromagnetic shielding performance under continuous mechanical deformation is discussed herein. In FIG. 7 d is EMI SE before and after CNR4 and CNR2 were folded 180 ° repeatedly 5000 times_T. Due to stable normalized resistance (R/R)₀) EMI SE of CNR4 and CNR2_TRemains substantially unchanged (d insert in fig. 7).

Based on the microstructure characteristics of N-BP, the electromagnetic shielding mechanism of N-BP is proposed as shown in e in FIG. 7. When an incident electromagnetic wave contacts CNR4, part of the electromagnetic wave is reflected back due to impedance mismatch. The remaining electromagnetic waves pass through and interact with the high density of electrons in CNR4, resulting in loss of electrons and polarization. Meanwhile, due to the porous structure of the CNR4 and the interface between the conductive CNT and the insulating NR, after the electromagnetic wave is internally reflected and scattered for many times, the transmission path is increased, thereby enhancing the absorption and attenuation of the electromagnetic wave.

In view of the necessity for light weight and ultra-thinness in smart electronics and aerospace applications, specific shielding effectiveness (SSE/t, defined as EMI SE/density/thickness) is used to measure electromagnetic shielding performance. At high SSE/t, the N-BP of the invention still exhibits high strain, in particular: the SSE/t value of CNR4 is 8504dB cm²(iv)/g, elongation at break 27.80%; the SSE/t value of CNR1 was 6232dB cm²(iv)/g, elongation at break 191.23%. They are much higher than shielding materials including metals, carbon nanotubes, graphene and MXene-based materials and composites thereof.

6. Thermal conductivity

The thermal conductivity of N-BP and BP was tested and the results are shown in FIG. 8. As can be seen from FIG. 8, the thermal conductivities in the vertical and horizontal directions of BP are respectively 0.358 and 9.046W/mK, the thermal conductivities in the vertical and horizontal directions of CNR4 are respectively 0.346 and 6.977W/mK, and the thermal conductivities in the vertical and horizontal directions of CNR1 are respectively 0.403 and 4.457W/mK. The N-BP has excellent thermal conductivity, high thermal conductivity and quick heat dissipation, can play a role in heat dissipation in products generating heat in microelectronics or electrons, and avoids the damage of electronic products due to heat.

Application example 1

As shown in fig. 9, the CNR4 prepared in example 1 was cut into a 25mm × 4mm rectangle, and both ends were coated with silver paste and applied with copper tape as an electrode. And then fixing the rectangular N-BP on a customized PMMA mould, filling 1.5mLNR latex in the mould, and drying at room temperature for 72h to obtain the N-BP with the NR film on one surface. By repeated casting of the NR latex, the other side of the N-BP is also covered by a solid NR film, eventually sandwiching the N-BP between two NR layers, forming a sandwich structure strain sensor.

And (3) testing the performance of the strain sensor:

1. basic Performance of N-BP and Sandwich-structured Strain Sensors

The cross section of the sandwich structure strain sensor is observed by a scanning electron microscope, and the result is shown in figure 11. As can be seen from FIG. 11, the overall thickness of the sandwich structure strain sensor is about 1000 μm, the thicknesses of the upper and lower NR layers are substantially the same, and the thickness of the N-BP layer is 50 μm. The thickness of the sandwich structure strain sensor makes the strain sensor more easily deformed by external force, which is very beneficial to the sensing capability of the sensor.

The mechanical properties of the sandwich structure strain sensor were tested, and the results are shown as a and b in fig. 10. As can be seen from a in fig. 10, the elongation at break of the sandwich structure strain sensor can reach a surprising 600% compared to pure NR, and we speculate that the NR layer and the N-BP layer do not exist independently. In N-BP there may be a transition layer formed by penetration of rubber, called the penetration layer. The infiltrated layer can be viewed as a NR and CNTs composite (b in fig. 10) containing internal defects. When the sandwich structure strain sensor deforms under the action of external force, the infiltration layer is firstly damaged to generate fine cracks, so that the NR layer is easy to break, and the breaking elongation of the sandwich structure strain sensor is reduced. It is worth noting that the modulus of the sandwich structure strain sensor is far higher than that of pure NR, and reaches 3.0 MPa. This is mainly due to the fact that in the initial stage of the stretching process, the BP layer with higher strength and lower elongation at break is destroyed first, resulting in a large increase in the modulus of NR/N-BP/NR.

2. SEM characterization of CNR4 and Sandwich Structure Strain Sensors

Scanning electron microscope observation of the surface and cross section of the CNR4 and sandwich structure strain sensor is shown in fig. 12. Wherein a is a top surface SEM image of CNR 4; b is a partial enlarged view of a, and c is a sectional SEM image of CNR 4; d is a partial enlarged view of c; e is a cross-sectional SEM image of the sandwich structure strain sensor; f is a partial enlarged view of e; g is a cross-sectional SEM image of the infiltration layer; h is a partial enlargement of g.

As can be seen from fig. 12 a and b, the CNR4 surface is not very flat, with some irregular protrusions. It can also be seen that the overlap between the CNTs is very tight, which ensures that the N-BP has good conductivity. The thickness of the CNR4 is approximately 50 μm as seen in the sem cross-sectional image shown in fig. 12 c. The magnified sem image further showed the structure of CNR4, from which it was found that there was no bulk NR in CNR 4. That is, the distribution of the rubber in CNR4 was very uniform (d in fig. 12). As can be seen from e and f in FIG. 12, NR is distributed on both sides of the N-BP layer, and adheres tightly to the N-BP layer. In addition, part of the NR has penetrated into the N-BP layer, forming a penetrated layer. In order to observe the morphology of the permeated layer between NR and N-BP more intuitively, the NR layer on the N-BP surface was carefully peeled off to observe the morphology of the permeated layer. The thickness of the infiltrated layer was about 5 μm, as shown in fig. 12, g and h. In addition, the permeation layer is more dense in internal structure due to the presence of a large amount of NR as compared with the N-BP layer.

3. Sensing performance of sandwich structure strain sensor

The sensing performance of the sandwich structure strain sensor is tested, and the result is shown in fig. 13.

In fig. 13, a is a current-voltage characteristic curve (I-V curve) of the sandwich structure strain sensor in a large deformation range of 0% to 500%. As can be seen from a in fig. 13, the strain sensor exhibits good ohmic behavior regardless of the applied strain, and the slope of the I-V curve changes sharply with an increase in the amount of deformation, and finally becomes small. In FIG. 13, b is a relationship curve between the resistance change and the strain, and it can be seen from b in FIG. 13 that the relative resistance change (R-R) of the sandwich structure strain sensor is within the strain range of 0-500%₀)/R₀) Can achieve the purpose of1200000%, shows a surprising strain sensitivity.

In addition, we use a small blue LED bulb to connect the strain sensor into a complete circuit to more visually observe the change in resistance of the sensor, with an operating voltage of 3V. When the sandwich structure strain sensor is deformed by external force, the brightness of the small bulb is reduced by the sudden increase of the resistance, and when the external force is removed and the sensor is restored to the original state, the small bulb is lightened again, and the result is shown in fig. 14.

In order to more accurately evaluate the strain sensing sensitivity of the strain sensor, the relationship between the sensitivity factor (GF) and the strain of the sensor is further studied, and in fig. 13 c, the relationship between the strain of the sandwich-structure strain sensor and GF in the strain range of 0 to 520% is shown. Overall, when the strain reaches 500%, the GF value has a good positive correlation with the tensile deformation of the sensor, and then the GF value suddenly increases. The sandwich-type strain sensor of the invention has an excellent large sensing range of 520% and an ultra-high GF value of 2280, which is far superior to the strain sensors reported in the literature (see Table 2). However, as can be seen from the partial enlargement of c in FIG. 13, the entire increase process of the GF value is roughly divided into 3 stages, (1) strain ranges from 0% to 50%, (2) from 50% to 250%, and (3) from 250% to 500%. In the strain range of 0-50%, the GF value of the sandwich structure strain sensor is rapidly increased to about 108, and then a relatively stable state is maintained until the strain reaches 250%. Subsequently, when the strain exceeds 250%, the GF value shows a significant tendency to increase again. As can be seen from the analysis in g of FIG. 12 and h of FIG. 12, the NR layer and the N-BP layer of the sandwich strain sensor are not present alone, and an NR permeation layer having a thickness of about 5 μm is present between the NR layer and the N-BP layer. The N-BP layer was destroyed during the initial stretching phase (< 50% deformation) resulting in a rapid increase of the GF value. As the amount of deformation increases, the destruction of the infiltrated conductive layer gradually becomes a factor causing the change in the GF value. However, due to the slow failure rate of the conductive network, the GF value of the strain sensor keeps a relatively stable value in the second stage of stretching (the strain range is 50-250%). When the tensile deformation of the sensor exceeded 250%, the conductive network of the infiltrated layer began to fail extensively, resulting in a rapid increase in GF values again (fig. 15). From the optical micrograph of the sandwich sensor, it can be seen that the N-BP layer breaks significantly when the sensor is deformed by 50%, but there is still a good overlap between the CNTs. However, when the amount of deformation is further increased to 500%, there is almost no overlap between the carbon layers, indicating that the conductive network is almost completely destroyed (d in fig. 13).

TABLE 2 Primary Properties of the Sandwich construction Strain Sensors prepared according to the present invention and recently reported Flexible stretchable Strain Sensors

Furthermore, the corresponding electrical signal can be fed back in an ultra short time of 21ms, which means that the sensor can give a response immediately after sensing an external force (a in fig. 16). It is noteworthy that our sandwich sensor maintains a fairly stable output signal (b in fig. 16) even after 2000 cycles at 100% of large strain, showing good sensing stability and repeatability. Carefully peeling off the NR layer of the sandwich type strain sensor after the cyclic test, and observing the structural change of the N-BP layer by using a scanning electron microscope. As shown in fig. 16 c and d, the N-BP layer was uniformly and densely broken after 2000 stretching cycles, but good contact between the carbon layers was still maintained, thereby ensuring good cycling performance of the sensor.

As shown in a of fig. 17, the sandwich structure strain sensor applies a programmed step-wise strain with a predetermined stretching range of 100% to 250%, and the resistance also generates a significant step-wise change. It has been shown that the change in resistance during stretching and release depends only on the deformation of the strain sensor. The sensor can also quickly capture the deformation caused by the tap and accurately give a regular response signal (b in fig. 17). Even more surprising is that the strain sensor is able to sense small deformations caused by weak air flows and generate regular electrical signal feedback, as shown in fig. 17 c. As shown in (1) to (3) of d in fig. 17, the sandwich-structured strain sensor was attached to the finger, wrist, and elbow joint, and the monitoring performance on the body limb movement was evaluated. As can be seen from d in fig. 17, different joint movements will produce corresponding changes in the electrical signal, and when the joint returns to its original state again, the resistance of the sensor will immediately return to its original value. In addition, when the joint bending angle is changed from 30 to 90 °, the relative resistance change values of the strain sensors are different, and the larger the bending angle is, the larger the resistance change is. The sandwich strain sensor is also sensitive to slight body movements. As can be seen from (1) of e in fig. 17, the sensor attached to the forehead can easily capture the minute movement of the face caused by the frown. Meanwhile, different generated sound signals can be well detected and distinguished through the sandwich structure strain sensor adhered to the throat. It can be seen that the electrical signal generated by the pronunciation of "DUT" has two peaks, while "World" has only one peak (e (2) and (3) in FIG. 17).

According to the embodiments, the invention provides the natural rubber modified bucky paper (N-BP) and the preparation method and application thereof, and the sandwich structure strain sensor and the application thereof. The N-BP is used for preparing the sandwich structure strain sensor, has very high sensitivity, ultrashort response time, larger detection range and excellent cycle stability, and has wide application prospect in next generation wearable electronic equipment.

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the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.