CN106009029A - Preparation method of porous conductive polymer material with pressure-sensitive property and application thereof - Google Patents
Preparation method of porous conductive polymer material with pressure-sensitive property and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of conductive polymer composites pressure-sensitive materials and particularly relates to a preparation method of a porous conductive polymer material with pressure-sensitive property and an application thereof. The preparation method of the porous conductive polymer material with pressure-sensitive property comprises the following steps: a) suspension preparation; b) unidirectional freezing; and c) low-temperature low-pressure drying. The porous conductive polymer composite with pressure-sensitive property prepared in the invention has excellent stability and resilience and can be used for preparing a light polymer-based strain sensor; and by combining the obtained conductive polymer composite with the circuit board and semiconductor technology, various pressure-sensitive sensors with good stability and long service life can be made.
Description
Technical field
The invention belongs to conductive polymer composite stress sensitive Material Field, be specifically related to the preparation method and applications of a kind of porous, electrically conductive macromolecular material with pressure-sensitive character.
Background technology
Strain transducer is the senser element that extraneous stress field can stimulate the output such as the signal that is converted into resistance, electric current and capacitance variations.The main organic and/or inorganic materials of traditional strain gauge transducer is made, such as metal strain chip sensor etc..Inorganic material flexibility is poor, and measurable range of strain is less, and this significantly limit the range of strain gauge transducer.
Porous, electrically conductive macromolecular material is electric conductivity and foamed materials light weight, the novel high polymer material of damping characteristics that a class has conducting polymer composite concurrently.It has the highest actual application value and theoretical research to be worth as a kind of functional high molecule material.Its potential using value in strain transducer field obtains the extensive concern of people in recent years, the article of entitled " the Manufacturable conducting rubber ambers and stretchable conductors from copper nanowire aerogel monoliths " that deliver on " ACS Nano " such as Tang Y etc. describes the conduction cellular material of a kind of polyvinyl alcohol/copper nano-wire, and its porosity characteristic makes composite can carry out performance detection in the range of large strain.But its for strain transducer time, existence and stability and recovery difference etc. shortcoming；And its random cellular material mechanical property prepared is poor, can meet with stresses less.Therefore, preparation can bear bigger stress, can detect large strain, and the strain transducer with good stability and recovery remains the research emphasis in this field at present.
Summary of the invention
The present invention is directed to drawbacks described above, provide the preparation method of a kind of new porous, electrically conductive macromolecular material with pressure-sensitive character (resistance is with pressure-sensitive characteristic), this method solve conductive polymer composite as pressure sensitive complicated process of preparation, flexible poor, the difficult problems such as compression strain is little can be born, prepared the porous, electrically conductive macromolecule pressure sensitive with good stability and recovery.
Technical scheme:
First technical problem that the invention solves the problems that is to provide the preparation method of a kind of porous, electrically conductive polymer composite with pressure-sensitive character, comprises the steps:
A) supending: conducting nanoparticles, soluble thermoplastic's polymer, polymer solvent are configured to uniform suspension；
B) unidirectional freezing:
The container that will be loaded with step a gained suspension is placed in cooler environment, loads the container only contact cooling environment bottom it of suspension, after carry out unidirectional freezing；Freezing when starting, the polymer solvent molecule of container bottom quickly forms a large amount of ice crystal, carries out ice crystal along thermograde direction oriented growth along with refrigerating process；Meanwhile, electrical-conductive nanometer filler and soluble thermoplastic's polymer are excluded outer at ice crystal and are gathered between the ice crystal grown；Wherein, the temperature of cooler environment is lower more than 10 DEG C than suspension freezing point temperature；In refrigerating process, suspension forms a stable thermograde from bottom to top；
C) low-temp low-pressure is dried: after polymer solvent crystal column has grown, the most freezing suspension and container are inserted rapidly in freezer dryer, treat that ice crystal distils under low-temp low-pressure completely, then take out sample to be dried, must have the porous, electrically conductive polymer composite of pressure-sensitive character.
Wherein, described polymer solvent is the suitable solvent that can dissolve selected soluble thermoplastic's polymer, including one or more in dioxane, water, acetone, toluene, dimethylbenzene, oxolane, dimethylformamide, methanol, ethanol, formic acid, dichloromethane, solvent load is: add 5～100ml solvents in every weight portion soluble thermoplastic's polymer.
Preferably, described solvent is dioxane.
Preferably, described soluble thermoplastic's polymer is the thermoplastic elastic material that can be completely dissolved or be formed stable emulsion in polymer solvent, including at least one in thermoplastic polyurethane, styrene butadiene styrene block copolymer (SBS), polyolefin elastomer, styrene isoprene styrene block copolymer (SIS) or polyester elastomer.
Described conducting nanoparticles is at least one in CNT, carbon fiber, white carbon black, metal nanoparticle, metal dust, metal nanometer line, metal oxide powder or Graphene；It is preferably multi-walled carbon nano-tubes (WMCNTs)；Wherein, soluble thermoplastic's polymer conductive nanometer particle=1 (mass parts) 0.001～0.2 (mass parts).
Further, in the preparation method of the above-mentioned porous, electrically conductive polymer composite with pressure-sensitive character, the preparation method of step a suspension is: first join in polymer solvent by conducting nanoparticles, mixed liquor is obtained after ultrasonic disperse is uniform, then described soluble thermoplastic's polymer is added in mixed liquor, heat while stirring to uniformly i.e. obtaining the suspension in step a with the speed of 10～1000rpm at 25～80 DEG C.
Further, in the preparation method of the above-mentioned porous, electrically conductive polymer composite with pressure-sensitive character, in the preparation of step a suspension, ultrasonic disperse is carried out in 15～25 DEG C of room temperature water-baths, and ultrasonic time is 5～120min, and ultrasonic power is 95W～1.5kW.Preferably, ultrasonic time is 30min, and ultrasonic power is 285W.
Further, in the preparation method of the above-mentioned porous, electrically conductive polymer composite with pressure-sensitive character, in step b, unidirectional freezing method uses following manner: the container loading step a gained suspension is removed bottom section and all uses insulated heat foamed materials to be closely coated with, then container is positioned on the metal iron block that smooth surface is smooth, after metal iron block, container are placed in liquid nitrogen bath together with heat barrier foam, and when being positioned over liquid nitrogen bath, liquid nitrogen liquid level is not higher than iron block height.
Further, in step c, cryodesiccated process conditions are: cryogenic temperature-80～-100 DEG C, freezing pressure 0.1～30Pa, drying time 12～120h.Preferably, freezing pressure 0.1～1Pa, drying time 12～72h.
Second technical problem that the invention solves the problems that is to provide a kind of conductive polymer composite with pressure-sensitive character, and it uses above-mentioned preparation method to prepare.
The 3rd technical problem that the invention solves the problems that is to provide a kind of pressure transducer, and including pressure sensitive, its pressure sensitive contains the conducing composite material using above-mentioned method to prepare.
In the present invention, voltage sensitive sensor uses existing method to prepare, and as being placed in by pressure sensitive between double layer of metal electrode, it is packaged by recycling insulation film.
Beneficial effects of the present invention:
1, the inventive method makes conducting nanoparticles be evenly dispersed in the abscess rib in porous, electrically conductive polymer composite and form good conductive network, prepares gained porous, electrically conductive porous material electric property and improves and stable, and excess effusion value is extremely low.
2, the inventive method uses orientation Freeze Drying Technique, and device is simple, efficiency is high, environmental friendliness.
3, the prices of raw materials that the inventive method is selected are cheap, and wide material sources effectively reduce preparation cost.
What 4, prepared by the inventive method has the porous, electrically conductive polymer composite of pressure-sensitive character, has the highest compression strain, good stability and recovery along orientation direction.
The porous, electrically conductive polymer composite of what 5, prepared by the present invention have pressure-sensitive character has stability and the recovery of excellence, can be used for preparing light-weight high-polymer base strain transducer.By gained conductive polymer composite combined circuit board of the present invention and semiconductor technology, can generate various voltage sensitive sensor, its good stability, service life are long.
Accompanying drawing illustrates:
The scanning electron microscope diagram sheet of the TPU/MWCNTs composite of Fig. 1 a embodiment of the present invention 6 preparation；From Fig. 1 a: embodiment 6 gained conductive polymer composite, there is typical orienting stephanoporate structure；Fig. 1 b is the enlarged drawing of Fig. 1 a；Fig. 1 c is the electron scanning micrograph of the random cellular material of comparative example 2 preparation.
Fig. 2 is the electric property curve of the TPU/MWCNTs composite of the embodiment of the present invention 1～7 preparation.
Fig. 3 a is that the TPU/MWCNTs composite of the embodiment of the present invention 2 preparation carries out time m-resistance curve when 15% Cyclic Strain compresses, and Fig. 3 b is that the TPU/MWCNTs composite of comparative example 3 of the present invention preparation carries out time m-resistance curve when 15% Cyclic Strain compresses.
Five, detailed description of the invention
The unidirectional freezing mode of the present invention: the container surrounding that first will be equipped with suspension uses insulated heat foamed materials to be positioned on the metal iron block that smooth surface is smooth after being closely coated with, then metal iron block, the container that is contained in suspension are placed in liquid nitrogen bath together with heat barrier foam, and when being positioned over liquid nitrogen bath, liquid nitrogen liquid level is not higher than iron block height；Placing iron block in liquid nitrogen bath as supporter, be placed on metal iron block by the container liquid being loaded with suspension, the container being loaded with suspension directly contacts with metal iron block and not sum liquid nitrogen directly contacts, and whole process does not exist motion.
The orientation freezing mechanism of the present invention: will be equipped with the container of suspension and after metal iron block puts into liquid nitrogen bath, owing to the heat conductivity that metal iron block is good is rapidly cooled to extremely low temperature, hence in so that suspension forms a stable thermograde from bottom to top；Container bottom contacts iron block and temperature reduces, thus quickly forms a large amount of ice crystal, and according to principle of dynamics, ice crystal tends to along thermograde direction oriented growth；Meanwhile, conducting nanoparticles and soluble thermoplastic's polymer are excluded outer at ice crystal and are gathered between the ice crystal grown；To be frozen complete after use Freeze Drying Technique remove oriented growth ice crystal, obtain the orienting stephanoporate structural material prepared by the present invention.
Example given below is the specific descriptions to the present invention; it is important to point out that following example are served only for that the invention will be further described; the present invention not makees any pro forma restriction, and nonessential improvement and adjustment that this art skilled person makes according to the invention described above content still fall within protection scope of the present invention.
In the present invention, multi-walled carbon nano-tubes used in embodiment 1: diameter 8～15nm, length 30～50 μm, purity > 95%, Chinese Academy of Sciences's Chengdu organic chemistry is produced；Thermoplastic polyurethane (TPU): model 1185A, BASF AG of Germany produces.
Embodiment 1 has the preparation of the porous, electrically conductive polymer composite of pressure-sensitive character
Concrete preparation process is:
(1) raw material drying: under the conditions of 80 DEG C, is dried 8h in vacuum drying oven by TPU and MWCNTs；
(2) preparation of suspension: 0.0513g MWCNTs powder is mixed in the beaker of 100ml with 40ml dioxane, under 15～25 DEG C of water-baths, ultrasonic disperse 30min obtains the mixed liquor of uniform MWCNTs/ dioxane, then 2g TPU it is added thereto to, stir about 1 hour at 40 DEG C, it is cooled to room temperature, obtains TPU/MWCNTs/ dioxane suspension；
(3) unidirectional freezing: suspension is poured in the height flat-bottomed glass test tube for a diameter of 2cm of 10cm, and seal with filter paper；Then test tube region in addition to bottom is all closely coated with heat barrier foam and is placed on ganoid length, width and height and is on the iron block of 10cm, then iron block, test tube and heat barrier foam are placed in together in the liquid nitrogen bath that the degree of depth is 8cm, till mixed solution completely freezing；
(4) low-temp low-pressure is dried: put into rapidly in freezer dryer by the test tube after freezing, lyophilization 72h, and temperature is-85 DEG C, and vacuum is 0.8Pa；Solvent ice crystal distils i.e. obtain the porous, electrically conductive polymer composite with pressure-sensitive character completely.
Embodiment 2-7 has the preparation of the porous, electrically conductive polymer composite of pressure-sensitive character
Each proportioning raw materials of embodiment 2-7 is as shown in table 1.Concrete preparation method is the most same as in Example 1.
The preparation of the random porous material of comparative example 1 conducting polymer
Concrete preparation process is:
(1) raw material drying: under the conditions of 80 DEG C, is dried 8h in vacuum drying oven by TPU and MWCNTs；
(2) preparation of suspension: 0.0408g MWCNTs powder is mixed in the beaker of 100ml with 40ml dioxane, under 15～25 DEG C of water-baths, ultrasonic disperse 30min obtains the mixed liquor of uniform MWCNTs/ dioxane, then 2g TPU it is added thereto to, stir about 1 hour at 40 DEG C, it is cooled to room temperature, obtains TPU/MWCNTs/ dioxane suspension；
(3) freezing: suspension to be poured in the height flat-bottomed glass test tube for a diameter of 2cm of 10cm, and seal with filter paper；Then test tube is put in mixture of ice and water, take out after 1 hour and be positioned in the refrigerator of-20 DEG C freezing 12h；
(4) low-temp low-pressure is dried: put into rapidly in freezer dryer by the test tube after freezing, lyophilization 72h, and temperature is-85 DEG C, and vacuum is 0.8Pa；Solvent ice crystal distils i.e. obtain control sample completely.
Comparative example 2
This comparative example is essentially identical with comparative example 1 step, without MWCNTs when difference is in step (2) preparation of altogether suspension, is directly dissolved in 40ml solvent by 2g TPU.
Comparative example 3
This comparative example is substantially the same manner as Example 2, simply freezing mode is different, particularly as follows: in refrigerating process, the suspension that step (2) prepares is placed in special container, being slowly immersed in liquid nitrogen with the speed of 1mm/s by container by constant speed or speed change mobile device, container places 15min after being completely immersed in liquid nitrogen.
Performance test:
1) microscopic appearance is observed: obtained conductive polymer composite is placed in liquid nitrogen brittle failure along the longitudinal direction rapidly after freezing 1h, after section metal spraying processes, utilize scanning electron microscope (Zeiss Carl of Germany, model EVO18) its brittle failure face microscopic appearance is observed, Fig. 1 a, b is the scanning electron microscopic picture of embodiment 6, and Fig. 1 c is the scanning electron microscopic picture of comparative example 2；From Fig. 1 a and Fig. 1 b it can be seen that material prepared by embodiment 6 appears similar to the orienting stephanoporate structure of ladder；Fig. 1 b is the enlarged drawing of Fig. 1 a, Fig. 1 b: pore size be 10-20 μm, and micropore is through hole, and Fig. 1 c is random abscess picture.
2) electrical performance testing: in order to investigate specific insulation and the excess effusion value of porous, electrically conductive macromolecular material prepared by the present invention, use DMM4050 digital multimeter (Tyke Science and Technology Ltd. of the U.S.), height is carried out electric performance test for the cylindrical sample that 10mm, basal diameter are 15mm；Specific insulation is less than 106The sample of Ω cm uses DMM4050 digital multimeter, and specific insulation is more than 106Ω cm tests with ZC-36 type ultra-high resistance tester (Town in Shanghai mark Electronics Co., Ltd.), first coats appropriate elargol at sample two ends and reduce the impact of contact resistance as far as possible before test；The specific insulation of the orientation conducting polymer porous material of preparation is shown in Table 2 in detail, and Fig. 2 show the exceeding of porous, electrically conductive polymer composite of preparation and oozes curve.
It can be seen that just have good electric conductivity when conducting nanoparticles content is the lowest by the porous, electrically conductive polymer composite that the preparation method of the present invention is prepared from table 2 and Fig. 2, its Chongqing is oozed value and is only 0.0023vol%.
3) mechanical property and voltage-dependent characteristic test
Sample is cut into the cylindrical sample of diameter 15mm length 10mm, two ends elargol is positioned over after being stained with aluminium flake on electronics general-purpose sample for testing machine platform, the aluminium flake at upper and lower for sample two ends is connected with DMM4050 digital multimeter simultaneously, then pressure head loads with the speed of 5mm/min, it is compressed to after necessarily straining again with the speed uncompression of 5mm/min, carry out 50 circulations, synchronous recording load-deformation curve and time m-resistance curve.The pressure-sensitive curve of circulation of the porous, electrically conductive polymer composite of preparation is as shown in Fig. 3 a, b, Fig. 3 a is that the TPU/MWCNTs composite of the embodiment of the present invention 2 preparation carries out time m-resistance curve when 15% Cyclic Strain compresses, and Fig. 3 b is that the TPU/MWCNTs composite of comparative example 3 of the present invention preparation carries out time m-resistance curve when 15% Cyclic Strain compresses.
Can be seen that material prepared by the present invention has good stability and recovery from Fig. 3 a, remain to reach 99.53% (only declining 0.47%) of initial value after 50 circulations, still keeping stable, illustrative material is applicable to life-time service.Can be seen that from Fig. 3 b, after the composite that comparative example 3 prepares carries out 50 circulations, resistance is only 94.37% (have dropped 5.63%) of preliminary examination value, the degree declined exceeds an order of magnitude than the present invention, and stability and recovery are substantially not as the material prepared by the present invention, absolutely prove that the conducting polymer orienting stephanoporate material prepared by the present invention is more suitable for pressure sensitive.In actual application, if the good stability of material, then the degree of accuracy detecting strain is higher, is more suitable for life-time service；If stability is bad, can cause its in use resistance decline always, then test result can be produced deviation, and along with the deviation that increases of access times is gradually increased；Visible, the porous, electrically conductive polymer composite utilizing side of the present invention to prepare is more suitable for the making requiring higher strain transducer service life.
Additionally, the compressive strength result that stress is its compressive strength, embodiment and comparative example when definition material is compressed to 50% is as shown in table 3.As can be seen from Table 3, orient cellular material (embodiment resulting materials) under the same terms to be significantly improved than random cellular material (comparative example resulting materials) mechanical property, the compressive strength of pure TPU cellular material is risen to the 15.07kPa of orientation cellular material by the 10.01kPa of random cellular material, improves 50.54%；The compressive strength of the composite containing 0.04857vol%CNTs has risen to 20.27kPa from the 11.89kPa of random cellular material, improves 70.42%；And the mechanical property of orientation cellular material promotes further with the increase of MWCNTs content.
For comparative example 3, immerse in coolant owing to being the container that will be equipped with suspension with certain speed orientation, during container is entered freezing liquid, container bottom and sidewall all inevitably contact refrigeration liquid, owing to there is the problem of container side wall heat transfer, therefore can inevitably form a horizontal thermograde (be different from the present invention and only form a thermograde from bottom to top) while forming a longitudinal temperature gradient；Ice crystal also can grow while growth along the longitudinal direction in transverse direction.Therefore, the structure of the material that this comparative example is prepared is actually marginal area horizontal orientation and the machine-direction oriented structure in central area, i.e. cannot obtain having good one-dimension oriented material；This defect can affect its use making pressure sensitive (from the figure 3, it may be seen that the stability of material using this freezing mode to obtain and recovery are the most bad, it is impossible to be applicable to higher to voltage-dependent characteristic requirement and service life is required higher field)；Because the orientation concordance that good pressure sensitive has needed use with the mechanical property and circulation compression improving material required for good stability and recovery.
The each proportioning raw materials of table 1 embodiment 1-7
| Embodiment | TPU(g) | MWCNTs(g) | Dioxane (ml) |
| 1 | 2 | 0.0513 | 40 |
| 2 | 2 | 0.0408 | 40 |
| 3 | 2 | 0.0305 | 40 |
| 4 | 2 | 0.0202 | 40 |
| 5 | 2 | 0.0101 | 40 |
| 6 | 2 | 0.0020 | 40 |
| 7 | 2 | 0 | 40 |
Table 2 embodiment 1-7 content of carbon nanotubes and the volume conductance of gained composite
| Embodiment | Ratio (vol%) shared by MWCNTs | Volume conductance (S/m) |
| 1 | 0.06107 | 2.29×10-3 |
| 2 | 0.04857 | 1.10×10-3 |
| 3 | 0.03631 | 3.21×10-4 |
| 4 | 0.02405 | 6.01×10-5 |
| 5 | 0.01202 | 3.46×10-6 |
| 6 | 0.00238 | 1.13×10-14 |
| 7 | 0 | 5.76×10-15 |
The compressive strength of table 3 conductive polymer composite
| MWCNTs addition (vol%) | Compressive strength (kPa) | |
| Embodiment 2 | 0.04857 | 20.27 |
| Embodiment 4 | 0.02405 | 18.14 |
| Embodiment 7 | 0 | 15.07 |
| Comparative example 1 | 0.04857 | 11.89 |
| Comparative example 2 | 0 | 10.01 |
| Comparative example 3 | 0.04857 | 19.7 |
Claims (10)
1. there is the preparation method of the porous, electrically conductive polymer composite of pressure-sensitive character, it is characterised in that comprise the steps:
A) supending: be configured to suspend uniformly by conducting nanoparticles, soluble thermoplastic's polymer, polymer solvent
Liquid；
B) unidirectional freezing: the container that will be loaded with step a gained suspension is placed in cooler environment, only loads the container of suspension
Contact cooling environment bottom it, after carry out unidirectional freezing；During freezing beginning, the polymer solvent molecule of container bottom quickly forms
A large amount of ice crystals, carry out ice crystal along thermograde direction oriented growth along with refrigerating process；Meanwhile, electrical-conductive nanometer filler and solvable
Property thermoplastic polymer be excluded outer at ice crystal and be gathered between the ice crystal grown；Wherein, the temperature of cooler environment is than outstanding
Supernatant liquid freezing point temperature is low more than 10 DEG C；In refrigerating process, suspension forms a stable thermograde from bottom to top；
C) low-temp low-pressure is dried: after polymer solvent crystal column has grown, and the most freezing suspension and container is inserted rapidly
In freezer dryer, treat that ice crystal distils under low-temp low-pressure completely, then take out sample and be dried, must have pressure-sensitive character
Porous, electrically conductive polymer composite.
The most according to claim 1, have the preparation method of the porous, electrically conductive polymer composite of pressure-sensitive character, its feature exists
In, described polymer solvent is the suitable solvent that can dissolve selected soluble thermoplastic's polymer, including dioxane,
In water, acetone, toluene, dimethylbenzene, oxolane, dimethylformamide, methanol, ethanol, formic acid, dichloromethane one
Planting or several, solvent load is: add 5～100ml solvents in every weight portion soluble thermoplastic's polymer.
The preparation method of the porous, electrically conductive polymer composite with pressure-sensitive character the most according to claim 1 or claim 2, it is special
Levying and be, described soluble thermoplastic's polymer is the thermoplastic that can be completely dissolved or be formed stable emulsion in polymer solvent
Property elastomeric material, including thermoplastic polyurethane, styrene butadiene styrene block copolymer (SBS), polyolefin elastomer, benzene
At least one in ethylene-isoprene-styrene block copolymer or polyester elastomer.
4. there is according to any one of claims 1 to 3 the preparation method of the porous, electrically conductive polymer composite of pressure-sensitive character,
It is characterized in that, described conducting nanoparticles is CNT, carbon fiber, white carbon black, metal nanoparticle, metal dust, gold
Belong at least one in nano wire, metal oxide powder or Graphene；Wherein, soluble thermoplastic's polymer and electrical-conductive nanometer
The mass ratio of particle is: soluble thermoplastic polymer conductive nanometer particle=1 0.001～0.2.
5. there is according to any one of Claims 1 to 4 the preparation method of the porous, electrically conductive polymer composite of pressure-sensitive character,
It is characterized in that, the preparation method of step a suspension is: first join in polymer solvent by conducting nanoparticles, ultrasonic point
After dissipating uniformly mixed liquor, then described soluble thermoplastic's polymer is added in mixed liquor, at 25～80 DEG C with 10～
The speed of 1000rpm heats while stirring to uniformly i.e. obtaining the suspension in step a.
6. there is according to any one of Claims 1 to 5 the preparation method of the porous, electrically conductive polymer composite of pressure-sensitive character,
It is characterized in that, in the preparation of step a suspension, ultrasonic disperse is carried out in 15～25 DEG C of room temperature water-baths, ultrasonic time be 5～
120min, ultrasonic power is 95W～1.5kW.
7. there is according to any one of claim 1～6 preparation method of the porous, electrically conductive polymer composite of pressure-sensitive character,
It is characterized in that, in step b, unidirectional freezing method uses following manner: will load the container of step a gained suspension the end of except
Region, portion all uses insulated heat foamed materials to be closely coated with, and is then positioned over by container on the metal iron block that smooth surface is smooth,
After metal iron block, container are placed in liquid nitrogen bath together with heat barrier foam, and when being positioned over liquid nitrogen bath, liquid nitrogen liquid level is not higher than iron block
Highly.
8. there is according to any one of claim 1～7 preparation method of the porous, electrically conductive polymer composite of pressure-sensitive character,
It is characterized in that, in step c, cryodesiccated process conditions are: cryogenic temperature-80～-100 DEG C, freezing pressure 0.1～30Pa,
Drying time 12～120h.
9. having a conductive polymer composite for pressure-sensitive character, it uses the method system described in any one of claim 1～8
?.
10. a pressure transducer, including pressure sensitive, it is characterised in that it is arbitrary that described pressure sensitive contains claim 1～8
The porous, electrically conductive polymer composite that method described in Xiang prepares.
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| CN106009029B CN106009029B (en) | 2018-10-09 |
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| CN106928487A (en) * | 2017-03-29 | 2017-07-07 | 同济大学 | A kind of graphene polymer pressure sensitive composite material and preparation method thereof |
| CN107236075A (en) * | 2017-05-31 | 2017-10-10 | 浙江理工大学 | Pressure-sensitive polymer composite foam with hierarchical porous structure and preparation method thereof |
| CN107629443A (en) * | 2017-08-04 | 2018-01-26 | 浙江新恒泰新材料有限公司 | Microporous foam conductive thermoplastic elastomer material and its production method with pressure-sensitive character |
| CN109400107A (en) * | 2018-11-14 | 2019-03-01 | 武汉纺织大学 | Has magnetic field and pressure with the magnetic graphite alkenyl aerogel material and preparation method thereof of sensing effect |
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| CN114455576A (en) * | 2022-01-24 | 2022-05-10 | 南方电网科学研究院有限责任公司 | Preparation method of graphene composite material for high-sensitivity detection of pressure change |
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| CN106928487B (en) * | 2017-03-29 | 2018-07-24 | 同济大学 | A kind of graphene polymer pressure sensitive composite material and preparation method thereof |
| CN106928487A (en) * | 2017-03-29 | 2017-07-07 | 同济大学 | A kind of graphene polymer pressure sensitive composite material and preparation method thereof |
| CN107236075A (en) * | 2017-05-31 | 2017-10-10 | 浙江理工大学 | Pressure-sensitive polymer composite foam with hierarchical porous structure and preparation method thereof |
| CN107629443A (en) * | 2017-08-04 | 2018-01-26 | 浙江新恒泰新材料有限公司 | Microporous foam conductive thermoplastic elastomer material and its production method with pressure-sensitive character |
| CN107629443B (en) * | 2017-08-04 | 2020-09-01 | 浙江新恒泰新材料有限公司 | Microcellular foamed conductive thermoplastic elastomer material with pressure-sensitive characteristic and production method thereof |
| CN110546193A (en) * | 2017-09-06 | 2019-12-06 | 新智德株式会社 | Pressure-sensitive elastomer porous body |
| CN110546193B (en) * | 2017-09-06 | 2021-04-16 | 新智德株式会社 | Pressure-sensitive elastomer porous body |
| CN111295403A (en) * | 2017-11-03 | 2020-06-16 | 麦格纳座椅公司 | Electrically conductive urethane foam |
| WO2019116955A1 (en) * | 2017-12-12 | 2019-06-20 | ナミックス株式会社 | Resin composition for forming varistor, and varistor |
| US11339269B2 (en) | 2017-12-12 | 2022-05-24 | Namics Corporation | Resin composition for forming varistor and varistor |
| JP2019104816A (en) * | 2017-12-12 | 2019-06-27 | ナミックス株式会社 | Resin composition for varistor formation and varistor |
| JP7112704B2 (en) | 2017-12-12 | 2022-08-04 | ナミックス株式会社 | Varistor-forming resin composition and varistor |
| CN110153403A (en) * | 2018-02-13 | 2019-08-23 | 中国石油化工股份有限公司 | Copper@polypyrrole nano line and preparation method thereof and pressure drag material and its application |
| CN109400107A (en) * | 2018-11-14 | 2019-03-01 | 武汉纺织大学 | Has magnetic field and pressure with the magnetic graphite alkenyl aerogel material and preparation method thereof of sensing effect |
| CN109400107B (en) * | 2018-11-14 | 2021-05-07 | 武汉纺织大学 | Magnetic graphene-based aerogel material with magnetic field and pressure sensing effects and preparation method thereof |
| CN109485910A (en) * | 2018-11-30 | 2019-03-19 | 四川大学 | Flexible high-resistance combustion property biology base aerogel material and preparation method thereof |
| CN110396215A (en) * | 2019-07-22 | 2019-11-01 | 北京航空航天大学 | A kind of orienting stephanoporate structure and preparation method thereof |
| CN110396215B (en) * | 2019-07-22 | 2021-02-09 | 北京航空航天大学 | Directional porous structure and preparation method thereof |
| CN111138835B (en) * | 2020-01-07 | 2020-11-10 | 中南大学 | Porous impact-resistant TPU composite pressure sensing material, preparation method and application |
| CN111138835A (en) * | 2020-01-07 | 2020-05-12 | 中南大学 | Porous impact-resistant TPU composite pressure sensing material, preparation method and application |
| CN111253598B (en) * | 2020-01-17 | 2022-03-11 | 清华大学 | Thin film piezoresistive material, preparation method thereof and electronic device |
| CN111253598A (en) * | 2020-01-17 | 2020-06-09 | 清华大学 | Thin film piezoresistive material, preparation method thereof and electronic device |
| WO2022041518A1 (en) * | 2020-08-28 | 2022-03-03 | 苏州烯时代材料科技有限公司 | Electrically conductive carbon paste for flexible pressure sensor and preparation method therefor, and pressure sensor |
| CN112525392A (en) * | 2020-11-05 | 2021-03-19 | 青岛大学 | Pressure sensing intelligent fabric and preparation method and application thereof |
| CN113337000A (en) * | 2021-05-24 | 2021-09-03 | 西安交通大学 | Anisotropic heat conduction flexible piezoelectric sensor and preparation method thereof |
| CN113337000B (en) * | 2021-05-24 | 2022-07-26 | 西安交通大学 | Anisotropic heat conduction flexible piezoelectric sensor and preparation method thereof |
| CN114455576A (en) * | 2022-01-24 | 2022-05-10 | 南方电网科学研究院有限责任公司 | Preparation method of graphene composite material for high-sensitivity detection of pressure change |
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