CN104502420A - Humidity-sensitive composite membrane, preparation method of humidity-sensitive composite membrane and humidity sensor - Google Patents
Humidity-sensitive composite membrane, preparation method of humidity-sensitive composite membrane and humidity sensor Download PDFInfo
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- CN104502420A CN104502420A CN201410522330.7A CN201410522330A CN104502420A CN 104502420 A CN104502420 A CN 104502420A CN 201410522330 A CN201410522330 A CN 201410522330A CN 104502420 A CN104502420 A CN 104502420A
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- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 66
- 239000002184 metal Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000011259 mixed solution Substances 0.000 claims abstract description 55
- 238000004132 cross linking Methods 0.000 claims abstract description 36
- 238000011065 in-situ storage Methods 0.000 claims abstract description 29
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 28
- 230000008859 change Effects 0.000 claims abstract description 25
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 40
- 239000002105 nanoparticle Substances 0.000 claims description 39
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- 238000000034 method Methods 0.000 claims description 20
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000003252 repetitive effect Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 43
- 230000004044 response Effects 0.000 abstract description 23
- 238000001514 detection method Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011896 sensitive detection Methods 0.000 abstract description 4
- 238000012271 agricultural production Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 238000005956 quaternization reaction Methods 0.000 abstract 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 46
- 229920002451 polyvinyl alcohol Polymers 0.000 description 46
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 description 32
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 26
- 239000000463 material Substances 0.000 description 22
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 15
- 229920006037 cross link polymer Polymers 0.000 description 13
- 229910001961 silver nitrate Inorganic materials 0.000 description 13
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 12
- 230000032683 aging Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 229920000885 poly(2-vinylpyridine) Polymers 0.000 description 9
- 229920000747 poly(lactic acid) Polymers 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 230000026041 response to humidity Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 230000005641 tunneling Effects 0.000 description 5
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 4
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 4
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 4
- 229910018503 SF6 Inorganic materials 0.000 description 4
- 229940015043 glyoxal Drugs 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 4
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 229960000909 sulfur hexafluoride Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 2
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- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- -1 quaternary ammonium salt ion Chemical class 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a humidity-sensitive composite membrane. The humidity-sensitive composite membrane comprises a polyelectrolyte membrane and a conductive metal nanoparticle membrane. The polyelectrolyte membrane is obtained by a crosslinked quaternization reaction of a synthetic pyridine ring-containing polymer and dihaloalkane. The metal nanoparticle membrane is obtained by in-situ reduction crosslinking after metal salt-polymer mixed solution film forming. The humidity-sensitive composite membrane has low impedance (less than or equal to 10 megohms and even less than or equal to 1 megohm so that equipment detection is convenient) at low humidity (less than or equal to 30% RH), has high response sensitivity (wherein, preferably, 1-30% RH impedance change rate is 2000%), has good stability and water resistance, can be widely used for environment humidity detection and control in industrial and agricultural production, storage, meteorology, power supply security and protection, and daily life, and is especially suitable for sensitive detection of humidity in low-humidity environments such as insulating gas SF6 in a transformer box.
Description
Technical field
The present invention relates to sensitive material field, be specifically related to a kind of wet sensitive composite membrane, its preparation method and humidity sensor.
Background technology
The investigation and application of chemical-sensitive material is the key areas of society development in science and technology, and it plays a very important role for the detection and regulation and control etc. of modern chemical industry agricultural production and people's living environment.
Humidity is the physical quantity representing water vapor in air content, and relative humidity represents actual steam-laden dividing potential drop (P in air
w) and the dividing potential drop (P of synthermal lower saturated steam
n) number percent, namely
Usually, relative humidity (Relative Humidity) is represented with symbol %RH.When temperature and pressure changes, because of saturated steam change, even if so the air pressure of water vapor in gas is identical, its relative humidity also can change.Generally speaking, the multiplex relative humidity index of air humidity (see " sensitive material and sensor " 129-130 page of Chen Ai chief editor, Chemical Industry Press).
Humidity sensor is as the important chemical sensor of a class, and the humidity sensing film that adopts obtains more, and also day by day receive publicity and pay attention to, its development is very rapid at present.In many humidity materials, high molecule sensitivity investigation of materials is very active, and multiple high molecule humidity sensor achieves commercialization.But there is also that response sensitivity is lower, the response time be comparatively slow, humidity hysteresis is comparatively large, response reappearance is not good enough, under low humidity impedance too high causing cannot measure deficiencies such as (testing ranges namely exceeding conventional instrument), hinder its research and widespread use.
Nano structural material has the specific surface area much bigger compared with conventional bulk material, this can provide more reactivity site on the one hand, contribute to the sensitivity improving response, also can be conducive to the diffusion detecting hydrone simultaneously, thus add fast-response and improve reversibility.
The ratio (see " Fundamentals of Sensors & Application " 7 pages that Wang Huaxiang, Zhang Shuying write, publishing house of University Of Tianjin) of exporting change amount and the input variable quantity causing this to change when sensitivity of sensor refers to and arrives steady-working state.Impedance type humidity sensor is the sensor that the principle utilizing the resistance value of humidity-sensitive element to change with the change of humidity carries out moisture measurement, impedance type humidity sensor is under low humidity (≤30%RH) condition, often there is very high impedance, especially when lower than 10%RH, its impedance (is generally hundreds of individual to a few begohm, even higher) often far beyond the range (being generally tens megaohms) of conventional sense circuit (equipment), conventional sense circuit (equipment) cannot measure the output quantity (impedance) of impedance type humidity sensor.When inputting variable quantity scope and being certain (≤30%RH), impedance rate of change can be adopted to characterize the sensitivity of impedance type humidity sensor, and for impedance type humidity sensor, its exporting change amount is exactly the variable quantity R of resistance value
1-R
0(wherein, R
1for changing rear resistance value, R
0for initial impedance value), its sensitivity S and impedance rate of change are exporting change amount and the ratio exporting initial amount, namely
, when the impedance of impedance type humidity sensor cannot be measured, more its impedance rate of change and sensitivity cannot be measured.
The response time of humidity sensor refers to when ambient humidity changes, humidity sensor completes moisture absorption or dehumidification and mobile equilibrium and (feels wet characteristic quantity and reach equilibrium value, for impedance type humidity sensor, the wet characteristic quantity of its sense is exactly resistance value) time required for process.The change of the wet characteristic quantity of sense lags behind the change of ambient humidity, and this phenomenon is called hysteresis phenomenon.63.2% or 90% response time of actual many employings, namely the knots modification of the wet characteristic quantity of sense reaches the time (see " sensitive material and sensor " 166-167 page of Chen Ai chief editor, Chemical Industry Press) required for 63.2% or 90% of total knots modification.Response time standard of the present invention was for 90% response time.
For existing impedance type humidity sensor, reduce with humidity, its impedance raises, under low humidity (≤30%RH) condition, impedance type humidity sensor often has very high impedance, its impedance (being generally a hundreds of megaohm even higher) is often far beyond the range (being generally tens megaohms) of conventional sense circuit (equipment), conventional sense circuit (equipment) cannot measure the output quantity (impedance) of impedance type humidity sensor, more cannot measure its rate of change, sensitivity, therefore existing impedance type humidity sensor is difficult to the Sensitive Detection being applied to low moisture environments (≤30%RH).In the environment of especially below 10%RH, impedance type humidity sensor because of impedance too high, it often cannot detect humidity response.Daily life is produced, often needs the humidity accurately detecting low moisture environments, especially the safe handling of consumer and protection.The insulating medium of the transformation facility (such as power transformation box) of such as electric system is often insulating gas (such as sulfur hexafluoride), in insulating gas, the content of moisture plays very crucial effect to its insulating property under high pressure, need to control its moisture in very low level, because when moisture increases, its insulativity reduces, easily breakdown, cause electricity consumption dangerous.The insulating gas of current transformation facility adopts sulfur hexafluoride mostly, and itself to react harmful gases such as producing hydrofluorite with water, more needs the humidity strictly controlling sulfur hexafluoride in power transformation box.And loaded down with trivial details to the accurate detection difficult of low moisture environments (≤30%RH), the measuring apparatus cycles such as required dew point hygrometer long (generally wanting more than one week), equipment price costliness (generally wanting more than 100,000 yuan).Therefore be badly in need of one to have can show lower impedance (below tens megaohms) under low moisture environments (1%-30%RH), be convenient to conventional sense circuit (equipment) detect, response sensitivity high (impedance rate of change is high), accurately can detect low moisture environments, the advantage such as stability and water-tolerant, and the sensor of the real-time detection to humidity can be realized, and the core of sensor is sensitive material.
Summary of the invention
For the deficiencies in the prior art, technical matters to be solved by this invention can realize under low moisture environments (≤30%RH), show lower impedance (≤10 megaohms while of being to provide a kind of, be very easy to realize equipment Inspection), and response sensitivity is high, and (impedance rate of change is high, there is very high sensitivity), accurately can detect low moisture environments, stability and water-tolerant, and can realize detecting and preparing the wet sensitive composite membrane of easy, low cost and other advantages in real time and comprise the moisture sensor of this wet sensitive composite membrane to humidity.
Preferably, impedance≤1 megaohm of wet sensitive composite membrane provided by the invention, and impedance rate of change >=1000% in the low humidity interval of 1%RH-30%RH.
The present invention adopts following technical scheme:
A kind of wet sensitive composite membrane, described wet sensitive composite membrane is made up of the polyelectrolyte film with cross-linked structure and the conducting metal film of nanoparticles be deposited thereon, described conducting metal film of nanoparticles is that crosslinked polymer network structure and the conducting metal nano particle be dispersed in described crosslinked polymer network structure are formed jointly, described conducting metal film of nanoparticles plays and falls low-impedance effect, can improve the electric conductivity of material.Crosslinked polymer network in described conducting metal film of nanoparticles and dispersed metal nanoparticle acting in conjunction wherein, for the electronic conduction of described conducting metal film of nanoparticles provides good conductive channel; Produce between described polyelectrolyte film and the conducting metal film of nanoparticles be deposited thereon and act synergistically, jointly form conductive network; Described conductive network acts on the electronic conduction of the ionic conduction of described polyelectrolyte film and described conducting metal film of nanoparticles simultaneously, and with tunneling effect, described polyelectrolyte film and conducting metal film of nanoparticles form conductive channel respectively, this makes described humidity sensing film under low moisture environments (≤30%RH), have lower impedance (≤10 megaohms, even can reach≤1 megaohm), and higher response sensitivity (impedance rate of change is high).The cross-linked structure of described polyelectrolyte film and the cross-linked structure acting in conjunction of described conducting metal film of nanoparticles, for described humidity sensing film provides good stability and water tolerance.
As preferably, described conducting metal film of nanoparticles is obtained by in-situ reducing cross-linking method, described in-situ reducing cross-linking method is while reducing to metal salt solution, generating conducting metal nano particle, cross-linking reaction is carried out to polymkeric substance, obtained conducting metal film of nanoparticles, described conducting metal film of nanoparticles is that crosslinked polymer network structure and the conducting metal nano particle be dispersed in described crosslinked polymer network structure are formed jointly.The crosslinking chemical of described cross-linking reaction should have reducing power metal salt solution being reduced to conducting metal nano particle, has again and makes described polymkeric substance that crosslinked, to generate crosslinked polymer network structure ability occur.
As preferably, described in-situ reducing cross-linking method comprises following steps: the mixed solution of preparing metal salt and polymkeric substance, after film forming, reducing metal ions is become conducting metal nano particle, and makes polymkeric substance generation cross-linking reaction, generates conducting metal film of nanoparticles.The optional dip-coating of film build method, spin coating, drip the methods such as painting.
As preferably, described polymkeric substance is the polymkeric substance of hydroxyl in repetitive, optional from polyvinyl alcohol (PVA) (PVA), polyglycol (PEG), PLA, polylactide and its copolymer, polypropylene glycol etc.The optional twain-aldehyde compound material of crosslinking chemical of described in-situ reducing cross-linking reaction, the optional glutaraldehyde of twain-aldehyde compound material, hexandial, glyoxal, MDA etc.
As preferably, the condition that the conductivity demand fulfillment of described conducting metal is certain, produces tunneling effect, conductivity>=5 × 10 of preferred conducting metal between the polyelectrolyte film could and with cross-linked structure
6sm
-1, conductivity>=40 × 10 of preferred conducting metal
6sm
-1.
As preferably, impedance rate of change >=1000% of described wet sensitive composite membrane in the low humidity interval of 1%RH-30%RH, and its impedance≤10 megaohm; Preferred impedance≤1 megaohm.
As preferably, described conducting metal is selected from Au, Ag, Cu.Preferred Ag, the i.e. preferred liquor argenti nitratis ophthalmicus of metal salt solution used in the present invention, the now described impedance rate of change of wet sensitive composite membrane in the low humidity interval of 1%RH-30%RH can reach 2000%, and its impedance≤10 megaohm; Preferred impedance≤1 megaohm.
As preferably, described polyelectrolyte film is the polymer film containing pyridine ring with crosslinked quaternized structure, optional P4VP, poly-(2-vinylpyridine) etc., the crosslinked preferred alkylene dihalide of quaternizing agent, optional 1,4-dibromobutane, 1, pentamethylene bromide, 1,6-dibromo-hexane, 1,4-dichloroetane etc., preferred Isosorbide-5-Nitrae-dibromobutane herein, preferred polyelectrolyte film is crosslinked quaternized P4VP film.
The present invention's second object is to provide the preparation method of described wet sensitive composite membrane, comprises the steps:
1) prepare polyelectrolyte precursor solution, then add crosslinked quaternizing agent and obtain mixed solution, heat-treated after described mixed solution film forming, the obtained polyelectrolyte film with crosslinked quaternary ammoniated structure; The described polyelectrolyte film with cross-linked structure has sensitive response to humidity, can improve the sensitivity of composite membrane to humidity;
2) mixed solution of preparing metal salt and polymkeric substance, in step 1) obtained by polyelectrolyte film on film forming, then in-situ reducing is cross-linked, obtain conducting metal film of nanoparticles, with step 1) described in the polyelectrolyte film with crosslinked quaternary ammoniated structure jointly form wet sensitive composite membrane.Described conducting metal film of nanoparticles is that crosslinked polymer network structure and the conducting metal nano particle be dispersed in described crosslinked polymer network structure are formed jointly, described conducting metal film of nanoparticles plays and falls low-impedance effect, can improve the electric conductivity of material.Crosslinked polymer network in described conducting metal film of nanoparticles and dispersed metal nanoparticle acting in conjunction wherein, for the electronic conduction of described conducting metal film of nanoparticles provides good conductive channel; Produce between described polyelectrolyte film and the conducting metal film of nanoparticles be deposited thereon and act synergistically, jointly form conductive network; Described conductive network acts on the electronic conduction of the ionic conduction of described polyelectrolyte film and described conducting metal film of nanoparticles simultaneously, and with tunneling effect, described polyelectrolyte film and conducting metal film of nanoparticles form conductive channel respectively, this make described humidity sensing film have under low humidity lower impedance (≤10 megaohms, even can≤1 megaohm).The cross-linked structure of described polyelectrolyte film and the cross-linked structure acting in conjunction of described conducting metal film of nanoparticles, for described humidity sensing film provides good stability and water tolerance.
As preferably, described in-situ reducing cross-linking method comprises following steps: the mixed solution of preparing metal salt and polymkeric substance, after film forming, reducing metal ions is become conducting metal nano particle, and makes polymkeric substance generation cross-linking reaction, generates conducting metal film of nanoparticles.The optional dip-coating of film build method, spin coating, drip the methods such as painting.
As preferably, the polyelectrolyte film in described step 1) is the polymer film containing pyridine ring with crosslinked quaternized structure, optional P4VP, poly-(2-vinylpyridine) etc.; The concentration of described polyelectrolyte presoma is preferably 5 ~ 400 mg/mL.
As preferably, the preferred alkylene dihalide of crosslinked quaternizing agent in described step 1), optional Isosorbide-5-Nitrae-dibromobutane, 1, pentamethylene bromide, 1,6-dibromo-hexane, Isosorbide-5-Nitrae-dichloroetane etc., more preferably Isosorbide-5-Nitrae-dibromobutane; It is 0.2 ~ 15 times that the amount of described crosslinked quaternizing agent is preferably with the mol ratio of polyelectrolyte presoma.
As preferably, heat treated temperature preferably 40 ~ 200 DEG C in described step 1), the time is 0.2 ~ 48 h preferably.
As preferably, can add film forming agent in described step 1), for auxiliary described mixed solution film forming, described film forming agent is selected from polyvinyl alcohol (PVA), polyvinyl butyral, polyvinyl pyrrolidone etc., more preferably polyvinyl butyral; Described film forming agent concentration is preferably 0.5 ~ 100 mg/mL.
As preferably, described step 2) described in the concentration of polymkeric substance be preferably 3 ~ 300 mg/mL.
As preferably, described step 2) in polymkeric substance be the polymkeric substance of hydroxyl in repetitive, optional from polyvinyl alcohol (PVA) (PVA), polyglycol (PEG), PLA, polylactide and its copolymer, polypropylene glycol etc.; The optional twain-aldehyde compound material of crosslinking chemical of described in-situ reducing cross-linking reaction, the optional glutaraldehyde of twain-aldehyde compound material, hexandial, glyoxal, MDA etc.; Preferred in-situ reducing crosslinking temperature is 10 ~ 200 DEG C, and the time is 0.1 ~ 48 h.
As preferably, impedance rate of change >=1000% of described wet sensitive composite membrane in the low humidity interval of 1%RH-30%RH, and its impedance≤10 megaohm; Preferred impedance≤1 megaohm.
As preferably, described step 2) in slaine be selected from containing Au
+, Au
3+, Ag
+, Cu
2+soluble-salt; Can preferred H [AuCl
4], AgNO
3, CuSO
4deng; The concentration of described slaine is preferably 0.005 ~ 1 mol/L.
Preferred slaine is AgNO
3, the now described impedance rate of change of wet sensitive composite membrane in the low humidity interval of 1%RH-30%RH can reach 2000%, and its impedance≤10 megaohm; Preferred impedance≤1 megaohm.
As preferably, the preparation method of described wet sensitive composite membrane specifically comprises the steps:
1. prepare the mixed solution of polyelectrolyte presoma and film forming agent, the concentration of described polyelectrolyte presoma is preferably 5 ~ 400 mg/mL, and film forming agent concentration is preferably 0.5 ~ 100 mg/mL;
2. adding with polyelectrolyte presoma mol ratio is the saturated dihalide of 0.2 ~ 15 times, and ageing 0.5 ~ 48 H-shaped becomes mixed solution;
3. by step 2. in mixed solution film forming, at 40 ~ 200 DEG C, heat 0.2 ~ 48 h after drying, obtained polyelectrolyte film;
4. the mixed solution of preparing metal salt and polymkeric substance, the concentration of slaine is preferably 0.005 ~ 1 mol/L, and the concentration of described polymkeric substance is preferably 3 ~ 300 mg/mL;
5. by step 4. described in mixed solution film forming on polyelectrolyte film;
6. under crosslinking chemical environment, under temperature 10 ~ 200 DEG C of conditions, in-situ reducing cross-linking reaction 0.1 ~ 48 h is carried out, obtained wet sensitive composite membrane.
As preferably, described step 1. in polyelectrolyte presoma be polymkeric substance containing pyridine ring, optional P4VP, poly-(2-vinylpyridine) etc.;
As preferably, described step 1. in can add film forming agent, for auxiliary described mixed solution film forming, described film forming agent is selected from polyvinyl alcohol (PVA), polyvinyl butyral, tygon and pyrrolidone etc., more preferably polyvinyl butyral;
As preferably, described step 2. in the preferred alkylene dihalide of crosslinked quaternizing agent, optional Isosorbide-5-Nitrae-dibromobutane, 1, pentamethylene bromide, 1,6-dibromo-hexane, Isosorbide-5-Nitrae-dichloroetane etc., more preferably Isosorbide-5-Nitrae-dibromobutane;
As preferably, described step 3. in heat treated temperature preferably 40 ~ 200 DEG C, the time is 0.2 ~ 48 h preferably;
As preferably, described step 4. in polymkeric substance be the polymkeric substance of hydroxyl in repetitive, optional from polyvinyl alcohol (PVA) (PVA), polyglycol (PEG), polylactide and its copolymer, polypropylene glycol etc.;
As preferably, described step 4. in slaine be selected from containing Au
+, Au
3+, Ag
+, Cu
2+soluble salt solutions; Optional H [AuCl
4], AgNO
3, CuSO
4deng, more preferably AgNO
3solution;
As preferably, described step 6. described in the optional twain-aldehyde compound material of crosslinking chemical, the optional glutaraldehyde of twain-aldehyde compound material, hexandial, glyoxal, MDA etc.;
3rd object of the present invention is to provide the humidity sensor of the wet sensitive composite membrane described in utilization as sensitive material, and described humidity sensor has matrix, and described matrix can be at the bottom of ceramic matrix, glass basis, ITO substrate, silicon wafer-based, multipair interdigital gold electrode is had in described matrix surface photoetching and evaporation, described interdigital gold electrode is connected with lead-in wire, adopt dip-coating, spin coating, dripping painting etc. becomes membrane means to deposit the polyelectrolyte film with cross-linked structure and the conducting metal film of nanoparticles be deposited thereon at matrix and interdigital gold electrode surfaces, the polyelectrolyte film with cross-linked structure is that the polymkeric substance containing pyridine ring obtains by there is crosslinked quaterisation with crosslinked quaternizing agent, conducting metal film of nanoparticles is obtained by in-situ reducing cross-linking method, obtained by the mixed solution of slaine and polymkeric substance and crosslinking chemical generation in-situ reducing cross-linking reaction.Moisture sensor of the present invention can be widely used in the detection and control of ambient humidity in industrial and agricultural production, storage, meteorology, Electrical Safety and protection and daily life, is particularly useful for the Sensitive Detection of humidity under the low moisture environments such as insulating gas SF6 in power transformation box.
The invention has the beneficial effects as follows:
1. the present invention constructs a kind of novel double-decker wet sensitive composite membrane, and wherein polyelectrolyte film has sensitive response to humidity, can improve the sensitivity of composite membrane to humidity; Conducting metal film of nanoparticles plays and falls low-impedance effect, can improve the electric conductivity of material, the electric conductivity especially under low moisture environments; The wet sensitive composite membrane that described two membranes obtains after combining can to decline Low ESR (< 1 megaohm) at low moisture environments, avoid causing unmeasured problem because impedance is too high, there is good sensitivity (under 1-30%RH environment, its impedance rate of change can reach 2000%) simultaneously.This be at present in the world under low moisture conditions sensitivity the highest one of, and can realize smoothly detecting low moisture environments humidity sensitive.
2. in double-decker, cross-linked structure is introduced by reduction for conducting metal nanoparticle layers simultaneously, effectively can avoid the reunion of metal nanoparticle, ensure can form good conductive path at conducting metal nanoparticle layers, be unlikely to again conducting metal nano particle is reunited, cause short circuit cannot embody wet sensitive response.Polyelectrolyte film and the intermembranous generation of conducting metal nano particle act synergistically mutually, common formation conductive network, described conductive network acts on the electronic conduction of the ionic conduction of described polyelectrolyte film and described conducting metal film of nanoparticles simultaneously, and with tunneling effect, polyelectrolyte film and conducting metal film of nanoparticles form conductive channel respectively.
3. double-decker wet sensitive composite membrane, polyelectrolyte film adopts crosslinked quaternizing agent as crosslinking chemical, realize crosslinked quaternized to the polymkeric substance containing pyridine ring, can provide necessary quaternary ammonium salt ion for conducting process, conducting metal film of nanoparticles adopts the method for cross-linking agents polymkeric substance to form cross-linked structure can improve the homogeneity that conducting metal nano particle distributes in conducting metal film of nanoparticles effectively.Described two membranes all has cross-linked structure, effectively can improve the stability of wet sensitive composite membrane.
4. conducting metal nano particle electrostatic spraying or directly and polyelectrolyte compound and material conductivity can be made to decline on the contrary, and the conducting metal nano particle that the present invention is formed by the method for in-situ reducing is evenly distributed, it is the sensitive membrane being in discontinuous state, applicant be surprised to find that this layer of being formed thus smooth but the conductive network of non-compact texture greatly can improve the electric conductivity of wet sensitive composite membrane, thus material has enough electric conductivity under ensure that low humidity, for the Humidity Detection of low moisture environments is laid a good foundation.And due to preparation method be in-situ reducing, it is good that the method has controllability, and reaction conditions is gentle, and reducing degree is even, and dosage of crosslinking agent is less, can reduce the plurality of advantages such as environmental pollution.
5. its moisture absorption response time of moisture sensor comprising wet sensitive composite membrane of the present invention can obviously shorten, and its humidity exposure time only needs 20 ~ 30s.
6. the UV surface plasma resonance spectrum of conducting metal film of nanoparticles and polyelectrolyte film shows, strong interaction is there is between conducting metal nano particle and polyelectrolyte, this synergy can be utilized to improve the electric conductivity under low humidity and the charge migration under promoting different humidity, there is very close synergy in the two, simultaneously with tunneling effect, this works unexistent before being the present invention.
Accompanying drawing explanation
Fig. 1 be by obtained by method of the present invention with the profile scanning electromicroscopic photograph of the wet sensitive composite membrane sensor that is functional layer;
Fig. 2 is the stereoscan photograph by the conducting metal nano particle environmental microbes obtained by method of the present invention;
Fig. 3 is the wet sensitive response curve of the wet sensitive composite membrane adopting the inventive method to prepare;
Fig. 4 is the response cycle test result figure of wet sensitive composite membrane of the present invention for different humidity;
Fig. 5 is the response test result figure of wet sensitive composite membrane of the present invention to low moisture environments.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples.
Embodiment 1
The method for making of wet sensitive composite membrane of the present invention, comprises the following steps:
1. prepare the mixed solution of P4VP and polyvinyl butyral, P4VP concentration is 36 mg/mL, and polyvinyl butyral concentration is 5 mg/mL;
2. add the Isosorbide-5-Nitrae-dibromobutane of P4VP mol ratio 2 times, ageing 10 H-shaped becomes mixed liquor;
3. by step 2. in mixed liquor film forming dry after, under 110 DEG C of conditions, heat 10 h, obtained ground floor polyelectrolyte film;
4. prepare the mixed solution of silver nitrate and polyvinyl alcohol (PVA), the concentration of silver nitrate is 0.05mol/L, and the concentration of polyvinyl alcohol (PVA) is 30mg/mL;
5. by step 4. in mixed solution film forming on described polyelectrolyte film dry;
6. under glutaraldehyde environment, under temperature 100 DEG C of conditions, in-situ reducing cross-linking reaction 6 h is carried out, obtained wet sensitive composite membrane.
1. ~ step 6. described in employing can film forming on a ceramic substrate, the obtained sensor using described wet sensitive composite membrane as functional layer; Described sensor sectional drawing as shown in Figure 1, wet sensitive composite membrane of the present invention is made up of jointly the polyelectrolyte film and conducting metal film of nanoparticles with crosslinked quaternized structure, the polyelectrolyte film with crosslinked quaternized structure is that the P4VP of synthesis is by with 1,4-dibromobutane is cross-linked quaterisation and obtains, and conducting metal film of nanoparticles is by obtaining with glutaraldehyde generation in-situ reducing cross-linking reaction after the mixed solution film forming of silver nitrate and polyvinyl alcohol (PVA).
Obtained wet sensitive composite film surface pattern as shown in Figure 2, metal nanoparticle is evenly distributed, size is homogeneous, obtained wet sensitive composite membrane has excellent Unordered system, it to the response diagram of low humidity (1%-30%RH) condition as shown in Figure 5, can find out the humidity information under described wet sensitive composite membrane energy Sensitive Detection low moisture environments to the response diagram of humidity as shown in Figure 3, within the scope of 1%-30%RH, utilize formula
sensitivity S=2000% can be calculated.In addition, the response cycle figure of described wet sensitive composite membrane as shown in Figure 4, can find out that it has good stability and recovery, only needs 20 ~ 30s by calculating its moisture absorption response time.
Comparative example 1
1. prepare the mixed solution of P4VP and polyvinyl butyral, P4VP concentration is 36 mg/mL, and polyvinyl butyral concentration is 5 mg/mL;
2. add the Isosorbide-5-Nitrae-dibromobutane of P4VP mol ratio 2 times, ageing 10 H-shaped becomes mixed liquor;
3. by step 2. in mixed liquor film forming dry after, under 110 DEG C of conditions, heat 10 h, obtained ground floor polyelectrolyte film;
4. prepare liquor argenti nitratis ophthalmicus, the concentration of silver nitrate is 0.05mol/L;
5. by step 4. in solution film forming on described polyelectrolyte film dry;
6. under glutaraldehyde environment, under temperature 100 DEG C of conditions, in-situ reducing cross-linking reaction 6 h is carried out, obtained wet sensitive composite membrane.
Detect impedance and sensitivity that comparative example 1 obtains wet sensitive composite membrane: the impedance of the wet sensitive composite membrane obtained under low humidity (≤30%RH) condition is very low, only less than 1 kilo-ohm, but described wet sensitive composite membrane does not almost respond humidity, within the scope of 1%-90%RH, its sensitivity only has 10%; The difference of this comparative example and embodiment 1 be exactly step 4. in do not add polyvinyl alcohol (PVA), do not form the crosslinked polymer network in conducting metal film of nanoparticles, the sensitivity of the wet sensitive composite membrane that result obtains is extremely low, illustrates that the sensitivity of crosslinked polymer network to described wet sensitive composite membrane has very large contribution.
Comparative example 2
1. prepare the mixed solution of P4VP and polyvinyl butyral, P4VP concentration is 36 mg/mL, and polyvinyl butyral concentration is 5 mg/mL;
2. add the Isosorbide-5-Nitrae-dibromobutane of P4VP mol ratio 2 times, ageing 10 H-shaped becomes mixed liquor;
3. by step 2. in mixed liquor film forming dry after, under 110 DEG C of conditions, heat 10 h, obtained ground floor polyelectrolyte film;
4. prepare the mixed solution of Graphene and polyvinyl alcohol (PVA), the concentration of Graphene is 3mg/mL, and the concentration of polyvinyl alcohol (PVA) is 30mg/mL;
5. by step 4. in mixed solution film forming on described polyelectrolyte film dry;
6. under glutaraldehyde environment, under temperature 100 DEG C of conditions, in-situ reducing cross-linking reaction 6 h is carried out, obtained wet sensitive composite membrane.
Detect impedance and sensitivity that comparative example 2 obtains wet sensitive composite membrane: the impedance of the wet sensitive composite membrane obtained under low humidity (≤30%RH) condition is lower, only less than 10 megaohms, but described wet sensitive composite membrane does not almost respond humidity, within the scope of 1%-30%RH, its sensitivity only has 175%.The difference of this comparative example and embodiment 1 be exactly step 4. in do not add the soluble-salt of conducting metal, but add the best Graphene of electric conductivity in material with carbon element, do not form conducting metal nano particle, it is very low that result obtains the sensitivity of wet sensitive composite membrane, illustrates that the sensitivity of conducting metal nano particle to described wet sensitive composite membrane has very large contribution.
Comparative example 3
1. prepare the mixed solution of P4VP and polyvinyl butyral, P4VP concentration is 36 mg/mL, and polyvinyl butyral concentration is 5 mg/mL;
2. add the Isosorbide-5-Nitrae-dibromobutane of P4VP mol ratio 2 times, ageing 10 H-shaped becomes mixed liquor;
3. by step 2. in mixed liquor film forming dry after, under 110 DEG C of conditions, heat 10 h, obtained ground floor polyelectrolyte film;
4. prepare the mixed solution of carbon nano-tube and polyvinyl alcohol (PVA), the concentration of carbon nano-tube is 5mg/mL, and the concentration of polyvinyl alcohol (PVA) is 30mg/mL;
5. by step 4. in mixed solution film forming on described polyelectrolyte film dry;
6. under glutaraldehyde environment, under temperature 100 DEG C of conditions, carry out in-situ reducing exchange reaction 6 h, obtained wet sensitive composite membrane.
Detect impedance and sensitivity that comparative example 3 obtains wet sensitive composite membrane: the impedance of the wet sensitive composite membrane obtained under low humidity (≤30%RH) condition is lower, less than 10 megaohms, but described wet sensitive composite membrane does not almost respond humidity, within the scope of 1%-30%RH, its sensitivity only has 130%.The difference of this comparative example and embodiment 1 be exactly step 4. in do not add the soluble-salt of conducting metal, but add the good carbon nano-tube of electric conductivity in material with carbon element, do not form conducting metal nano particle, it is very low that result obtains the sensitivity of wet sensitive composite membrane, illustrates that the sensitivity of conducting metal nano particle to described wet sensitive composite membrane has very large contribution.
Comparative example 4
1. prepare the mixed solution of P4VP and polyvinyl butyral, P4VP concentration is 36 mg/mL, and polyvinyl butyral concentration is 5 mg/mL;
2. add the Isosorbide-5-Nitrae-dibromobutane of P4VP mol ratio 2 times, ageing 10 H-shaped becomes mixed liquor;
3. by step 2. in mixed liquor film forming dry after, under 110 DEG C of conditions, heat 10 h, obtained ground floor polyelectrolyte film;
4. prepare the mixed solution of silver nitrate and polyvinyl alcohol (PVA), the concentration of silver nitrate is 0.05mol/L, and the concentration of polyvinyl alcohol (PVA) is 350mg/mL;
5. by step 4. in mixed solution film forming on described polyelectrolyte film dry;
6. under glutaraldehyde environment, under temperature 100 DEG C of conditions, in-situ reducing cross-linking reaction 6 h is carried out, obtained wet sensitive composite membrane.
Detect impedance and sensitivity that comparative example 4 obtains wet sensitive composite membrane: the impedance of the wet sensitive composite membrane obtained under low humidity (≤30%RH) condition is very high, reaches tens megaohms, and within the scope of 1%-30%RH, its sensitivity only has 470%.The difference of this comparative example and embodiment 1 be exactly step 4. in add the polyvinyl alcohol (PVA) of excessive (350mg/mL), define excessive crosslinked polymer network, resultant impedance is very high, but sensitivity is lower, illustrate that the amount of crosslinked polymer network all has a significant impact the impedance of described wet sensitive composite membrane and sensitivity.
Comparative example 5
1. prepare the mixed solution of P4VP and polyvinyl butyral, P4VP concentration is 36 mg/mL, and polyvinyl butyral concentration is 5 mg/mL;
2. add the Isosorbide-5-Nitrae-dibromobutane of P4VP mol ratio 2 times, obtain mixed solution A;
3. prepare the mixed solution of silver nitrate and polyvinyl alcohol (PVA), the concentration of silver nitrate is 0.05mol/L, and the concentration of polyvinyl alcohol (PVA) is 350mg/mL, obtains mixed solution B;
4. described mixed solution A and described mixed solution B are mixed to get mixed solution C, ageing 5h;
5. by step 4. in mixed solution C film forming dry;
6. under glutaraldehyde environment, under temperature 100 DEG C of conditions, in-situ reducing cross-linking reaction 6 h is carried out, obtained wet sensitive composite membrane.
Detect impedance and sensitivity that comparative example 5 obtains wet sensitive composite membrane: the impedance of the wet sensitive composite membrane obtained under low humidity (≤30%RH) condition is very high, reaches tens megaohms, and within the scope of 1%-30%RH, its sensitivity only has 340%.Polyelectrolyte film and conducting metal film of nanoparticles have been made skim structure with the difference of embodiment 1 by this comparative example exactly, instead of double-decker, result sensitivity is very low, illustrates that the synergy between two-layer compound membrane structure all has a significant impact the impedance of described wet sensitive composite membrane and sensitivity.
Embodiment 2
1. the mixed solution of preparation poly-(2-vinylpyridine) and polyvinyl alcohol (PVA), poly-(2-vinylpyridine) concentration is 5 mg/mL, and polyvinyl alcohol concentration is 100 mg/mL;
2. add 1 of poly-(2-vinylpyridine) mol ratio 0.2 times, pentamethylene bromide, ageing 48 H-shaped becomes mixed liquor;
3. by step 2. in mixed liquor film forming dry after, under 40 DEG C of conditions, heat 48 h, obtained ground floor polyelectrolyte film;
4. prepare the mixed solution of copper sulphate and polyglycol, the concentration of copper sulphate is 0.005mol/L, and the concentration of polyglycol is 300mg/mL;
5. by step 4. in mixed solution film forming on described polyelectrolyte film dry;
6. under hexandial environment, under temperature 10 DEG C of conditions, in-situ reducing cross-linking reaction 48h is carried out, obtained wet sensitive composite membrane.
The impedance of the wet sensitive composite membrane obtained under low humidity (≤30%RH) condition is lower, less than 10 megaohms, has good response to humidity, and within the scope of 1%-30%RH, its sensitivity reaches 1160%.
Embodiment 3
1. prepare the mixed solution of P4VP and polyvinyl pyrrolidone, P4VP concentration is 400 mg/mL, and polyvinyl pyrrolidone concentration is 0.5 mg/mL;
2. add 1,6-dibromo-hexane of P4VP mol ratio 15 times, ageing 0.5 H-shaped becomes mixed liquor;
3. by step 2. in mixed liquor film forming dry after, under 200 DEG C of conditions, heat 0.2 h, obtained ground floor polyelectrolyte film;
4. gold chloride (H [AuCl is prepared
4]) with the mixed solution of polypropylene glycol, the concentration of gold chloride is 1mol/L, and the concentration of polypropylene glycol is 3mg/mL;
5. by step 4. in mixed solution film forming on described polyelectrolyte film dry;
6. under MDA environment, under temperature 200 DEG C of conditions, in-situ reducing cross-linking reaction 0.1 h is carried out, obtained wet sensitive composite membrane.
The impedance of the wet sensitive composite membrane obtained under low humidity (≤30%RH) condition is lower, is no more than 10 megaohms, has good response to humidity, and within the scope of 1%-30%RH, its sensitivity reaches 1350%.
Embodiment 4
1. the mixed solution of preparation poly-(2-vinylpyridine) and polyvinyl butyral, poly-(2-vinylpyridine) concentration is 72mg/mL, and polyvinyl butyral concentration is 75mg/mL;
2. add the Isosorbide-5-Nitrae-dichloroetane of poly-(2-vinylpyridine) mol ratio 4 times, ageing 5 H-shaped becomes mixed liquor;
3. by step 2. in mixed liquor film forming dry after, under 50 DEG C of conditions, heat 20 h, obtained ground floor polyelectrolyte film;
4. prepare the mixed solution of silver nitrate and polylactide and its copolymer, the concentration of silver nitrate is 0.1mol/L, and the concentration of polylactide and its copolymer is 100mg/mL;
5. by step 4. in mixed solution film forming on described polyelectrolyte film dry;
6. under glyoxal environment, under temperature 120 DEG C of conditions, in-situ reducing cross-linking reaction 8h is carried out, obtained wet sensitive composite membrane.
The impedance of the wet sensitive composite membrane obtained under low humidity (≤30%RH) condition is lower, is no more than 10 megaohms, has good response to humidity, and within the scope of 1%-30%RH, its sensitivity reaches 1660%.
Embodiment 5
1. prepare the mixed solution of P4VP and polyvinyl butyral, P4VP concentration is 144 mg/mL, and polyvinyl butyral concentration is 200 mg/mL;
2. add the Isosorbide-5-Nitrae-dibromobutane of P4VP mol ratio 3 times, ageing 3 H-shaped becomes mixed liquor;
3. by step 2. in mixed liquor film forming dry after, under 180 DEG C of conditions, heat 5 h, obtained ground floor polyelectrolyte film;
4. prepare the mixed solution of silver nitrate and polyvinyl alcohol (PVA), the concentration of silver nitrate is 0.01mol/L, and the concentration of polyvinyl alcohol (PVA) is 150mg/mL;
5. by step 4. in mixed solution film forming on described polyelectrolyte film dry;
6. under glutaraldehyde environment, under temperature 150 DEG C of conditions, in-situ reducing cross-linking reaction 4 h is carried out, obtained wet sensitive composite membrane.
The impedance of the wet sensitive composite membrane obtained under low humidity (≤30%RH) condition is lower, is no more than 10 megaohms, has good response to humidity, and within the scope of 1%-30%RH, its sensitivity reaches 1100%.
Embodiment 6
1. prepare the mixed solution of P4VP and polyvinyl butyral, P4VP concentration is 288mg/mL, and polyvinyl butyral concentration is 50 mg/mL;
2. add the Isosorbide-5-Nitrae-dibromobutane of P4VP mol ratio 12 times, ageing 1 H-shaped becomes mixed liquor;
3. by step 2. in mixed liquor film forming dry after, under 180 DEG C of conditions, heat 24 h, obtained ground floor polyelectrolyte film;
4. prepare the mixed solution of copper sulphate and PLA, the concentration of silver nitrate is 0.8mol/L, and the concentration of PLA is 200mg/mL;
5. by step 4. in mixed solution film forming on described polyelectrolyte film dry;
6. under glutaraldehyde environment, under temperature 130 DEG C of conditions, in-situ reducing cross-linking reaction 8 h is carried out, obtained wet sensitive composite membrane.
The impedance of the wet sensitive composite membrane obtained under low humidity (≤30%RH) condition is lower, is no more than 10 megaohms, has good response to humidity, and within the scope of 1%-30%RH, its sensitivity reaches 1850%.
Above embodiment is only not used in for illustration of the present invention and limits the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Claims (10)
1. a wet sensitive composite membrane, it is characterized in that: described wet sensitive composite membrane is made up of the polyelectrolyte film with cross-linked structure and the conducting metal film of nanoparticles be deposited thereon, described conducting metal film of nanoparticles is that cross-linked network structure polymkeric substance and the conducting metal nano particle be dispersed in described cross-linked network structure polymkeric substance are formed jointly.
2. wet sensitive composite membrane according to claim 1, is characterized in that: described conducting metal film of nanoparticles is obtained by in-situ reducing cross-linking method.
3. wet sensitive composite membrane according to claim 2, it is characterized in that: described in-situ reducing cross-linking method comprises the steps: the mixed solution of preparing metal salt and polymkeric substance, after film forming, reducing metal ions is become conducting metal nano particle, and make polymkeric substance generation cross-linking reaction, obtain conducting metal film of nanoparticles.
4. wet sensitive composite membrane according to claim 1, is characterized in that: impedance rate of change >=1000% of described wet sensitive composite membrane in the low humidity interval of 1%RH-30%RH.
5. wet sensitive composite membrane according to claim 1, is characterized in that conductivity>=5 × 10 of described conducting metal
6sm
-1.
6. wet sensitive composite membrane according to claim 1, is characterized in that: described conducting metal is selected from Au, Ag, Cu.
7. wet sensitive composite membrane according to claim 1, is characterized in that: described polymkeric substance is the polymkeric substance of hydroxyl in repetitive.
8. the wet sensitive composite membrane according to any one of claim 1-7, is characterized in that: described polyelectrolyte film is the polymer film containing pyridine ring with crosslinked quaternized structure.
9. the preparation method of wet sensitive composite membrane described in claim 2, is characterized in that comprising the steps:
1) prepare polyelectrolyte precursor solution, then add crosslinked quaternizing agent and obtain mixed solution, heat-treated after described mixed solution film forming, the obtained polyelectrolyte film with crosslinked quaternary ammoniated structure;
2) mixed solution of preparing metal salt and polymkeric substance, in step 1) obtained by polyelectrolyte film on film forming, then in-situ reducing be cross-linked, obtain wet sensitive composite membrane.
10. a humidity sensor, is characterized in that: described sensor comprises the wet sensitive composite membrane described in any one of claim 1-8.
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| CN110746774B (en) * | 2018-07-24 | 2021-10-26 | 中国科学院宁波材料技术与工程研究所 | Renewable two-dimensional composite membrane, and preparation method and application thereof |
| CN112876835A (en) * | 2021-01-22 | 2021-06-01 | 南京邮电大学 | Multicolor fluorescent polymer film with environment humidity response and preparation method and application thereof |
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