CN104502420B - 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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- CN104502420B CN104502420B CN201410522330.7A CN201410522330A CN104502420B CN 104502420 B CN104502420 B CN 104502420B CN 201410522330 A CN201410522330 A CN 201410522330A CN 104502420 B CN104502420 B CN 104502420B
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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 is and in particular to a kind of wet sensitive composite membrane, its preparation method and humidity sensor
Device.
Background technology
The research of chemical-sensitive material and application be today's society development in science and technology key areas, it for modernization workers and peasants
The detection of industry production and people's living environment and regulation and control etc. play a very important role.
Humidity is the physical quantity representing water vapor in air content, and relative humidity is to represent in the air actual institute containing water vapor
Partial pressure (pw) and synthermal lower saturated steam partial pressure (pn) percentage ratio, that is,
Generally, represent relative humidity (relative humidity) with symbol %rh.When temperature and pressure changes, because
Saturated steam changes, even if so the air pressure of vapor in gas is identical, its relative humidity also can change.General and
Speech, air humidity multiplex relative humidity index is (referring to 129-130 page of " sensitive material and the sensor " of Chen Ai chief editor, chemical work
Industry publishing house).
How humidity sensor, as the important chemical sensor of a class, is obtained using humidity sensing film, is also increasingly subject to close
Note and attention, its development is very rapid at present.In many humidity materials, high molecule sensitivity investigation of materials is very active, many
Plant high molecule humidity sensor and have been achieved with commercialization.But there is also that response sensitivity is relatively low, response time is slower, wet
Stagnant larger, repeatability is not good enough for response, impedance is too high under low humidity leads to not measure (testing range exceeding conventional instrument) etc.
Deficiency, hinders its research and extensive application.
Nano structural material has the much bigger specific surface area of more conventional bulk material, and on the one hand this can provide more
Reactivity site, is favorably improved the sensitivity of response, also can be conducive to detecting the diffusion of hydrone simultaneously, thus accelerating to ring
Should with improve reversibility.
Exporting change amount and the input change causing this change when the sensitivity of sensor refers to reach steady-working state
The ratio (" Fundamentals of Sensors ＆ Application " write referring to Wang Huaxiang, Zhang Shuying page 7, publishing house of University Of Tianjin) of amount.Impedance type is wet
Degree sensor is the sensor carrying out moisture measurement with the change of humidity using the principle that the resistance value of dew cell changes, resistance
Anti- type humidity sensor, under the conditions of low humidity (≤30%rh), often has very high impedance, especially less than 10%rh
When, its impedance (usually hundreds of individual extremely several begohms, even more high) is often far beyond the amount of conventional sense circuit (equipment)
Journey (usually tens megaohms), conventional sense circuit (equipment) cannot measure the output (resistance of impedance type humidity sensor
Anti-).In the case that input variable quantity scope is certain (≤30%rh), impedance type humidity can be characterized using impedance rate of change
The sensitivity of sensor, for impedance type humidity sensor, its exporting change amount is exactly the variable quantity r of resistance value1-r0(wherein,
r1For resistance value after change, r0For initial impedance value), its sensitivity s is impedance rate of change is exporting change amount and output initial amount
Ratio, that is,In the case of cannot measuring impedance type humidity sensor impedance, more cannot measure it
Impedance rate of change and sensitivity.
The response time of humidity sensor refers to when ambient humidity changes, humidity sensor complete moisture absorption or dehumidification and
Dynamic equilibrium (feel wet characteristic quantity and reach equilibrium valve, for impedance type humidity sensor, it feels wet characteristic quantity is exactly resistance value) mistake
Time required for journey.The change feeling wet characteristic quantity lags behind the change of ambient humidity, and this phenomenon is referred to as hysteresis.Actual
Adopt 63.2% or 90% response time, that is, the knots modification feeling wet characteristic quantity reaches needed for the 63.2% or 90% of total knots modification more
The time (referring to 166-167 page of " sensitive material and the sensor " of Chen Ai chief editor, Chemical Industry Press) wanted.The present invention is adopted
Response time standard is 90% response time.
For existing impedance type humidity sensor, reduce with humidity, its impedance raises, at low humidity (≤30%rh)
Under the conditions of, impedance type humidity sensor often has very high impedance, its impedance (usually hundreds of megaohm even more high)
Often far beyond the range (usually tens megaohms) of conventional sense circuit (equipment), conventional sense circuit (equipment) cannot
Measure the output (impedance) of impedance type humidity sensor, more cannot measure its rate of change, sensitivity, therefore existing impedance type
Humidity sensor is dfficult to apply to the Sensitive Detection of low moisture environments (≤30%rh).Especially in the environment of below 10%rh, resistance
Anti- type humidity sensor is too high because of impedance, and it often cannot detect to humidity response.Daily life is produced, generally requires essence
Really detect the humidity of low moisture environments, the especially safe handling of electrical equipment and protection.Transformation facility (the example of such as power system
As power transformation box) dielectric often be insulating gas (such as sulfur hexafluoride), in insulating gas the content of moisture to it in height
The insulating properties of pressure play very crucial effect, need to control its moisture in very low level, because when moisture contains
When amount increases, its insulating properties reduces, easily breakdown, leads to electricity consumption dangerous.The insulating gas of transformation facility adopts six mostly at present
Sulfur fluoride, itself can be reacted with water and produce the harmful gass such as Fluohydric acid., more need strictly to control hexafluoro in power transformation box
Change the humidity of sulfur.And, the measuring apparatus such as required dew point hygrometer week loaded down with trivial details to the accurate detection difficult of low moisture environments (≤30%rh)
Phase length (typically wants more than one week), equipment price costliness (typically wanting more than 100,000 yuan).Therefore it is badly in need of one kind to have in low humidity ring
Relatively low impedance (less than tens megaohms) can be shown under border (1%-30%rh), be easy to conventional sense circuit (equipment) inspection
Survey, response sensitivity high (impedance rate of change is high), low moisture environments accurately can be detected, stability and water-tolerant etc. are excellent
Point is it is possible to realize the sensor of the real-time detection to humidity, and the core of sensor is sensitive material.
Content of the invention
For the deficiencies in the prior art, the technical problem to be solved is to provide one kind to be capable of low simultaneously
Show relatively low impedance (≤10 megaohms, be very easy to realize equipment detection) under wet environment (≤30%rh), and respond spirit
Low moisture environments can accurately be detected by sensitivity high (impedance rate of change is high, has very high sensitivity), stability and water-fast
Property good, and humidity can be realized with real-time detection and preparation is easy, the wet sensitive composite membrane of low cost and other advantages and comprise this wet sensitive
The moisture sensor of composite membrane.
Preferably, impedance≤1 megaohm of the wet sensitive composite membrane that the present invention provides, and the low humidity area in 1%rh-30%rh
Interior impedance rate of change >=1000%.
The present invention adopts the following technical scheme that:
A kind of wet sensitive composite membrane, described wet sensitive composite membrane by the polyelectrolyte film with cross-linked structure and is deposited thereon
Conducting metal film of nanoparticles composition, described conducting metal film of nanoparticles is crosslinked polymer network structure and uniformly point
The conducting metal nanoparticle being dispersed in described crosslinked polymer network structure collectively forms, described conducting metal nanoparticle
Film plays the low-impedance effect of fall, can improve the electric conductivity of material.Polymer in described conducting metal film of nanoparticles is handed over
Networking network and the metal nanoparticle collective effect being uniformly distributed therein, are the electronics of described conducting metal film of nanoparticles
The good conductive channel of conductive offer；Produce between described polyelectrolyte film and the conducting metal film of nanoparticles being deposited thereon
Raw synergism, collectively forms conductive network；Described conductive network is with the ionic conduction of described polyelectrolyte film and described leading
The electronic conduction of electric metal film of nanoparticles acts on simultaneously, and with tunneling effect, described polyelectrolyte film and conducting metal are received
Rice corpuscles film forms conductive channel respectively, and it is relatively low that this makes described humidity sensing film have under low moisture environments (≤30%rh)
Impedance (≤10 megaohms, even up to arrive≤1 megaohm), and higher response sensitivity (impedance rate of change is high).Described poly- electricity
The solution cross-linked structure of plasma membrane and the cross-linked structure collective effect of described conducting metal film of nanoparticles, are described humidity sensing film
Good stability and resistance to water are provided.
Preferably, described conducting metal film of nanoparticles is obtained by in-situ reducing cross-linking method, described in-situ reducing is handed over
Connection method, while metal salt solution being carried out reduce, generate conducting metal nanoparticle, carries out cross-linking reaction to polymer, system
Obtain conducting metal film of nanoparticles, described conducting metal film of nanoparticles is crosslinked polymer network structure and is dispersed in
Conducting metal nanoparticle in described crosslinked polymer network structure collectively forms.The cross-linking agent of described cross-linking reaction should have
Have the reducing power that metal salt solution is reduced to conducting metal nanoparticle, have again so that described polymer is crosslinked,
Generate the ability of crosslinked polymer network structure.
Preferably, described in-situ reducing cross-linking method comprises the steps of: the mixing of preparing metal salt and polymer is molten
Liquid, after film forming, reducing metal ions is become conducting metal nanoparticle, and makes polymer crosslink reaction, generates conductive gold
Belong to film of nanoparticles.The optional dip-coating of film build method, spin coating, the method such as drop coating.
Preferably, described polymer is the polymer of hydroxyl in repetitives, it is selected from polyvinyl alcohol (pva), gathers
Ethylene glycol (peg), polylactide and its copolymer, polypropylene glycol etc..The cross-linking agent optional two of described in-situ reducing cross-linking reaction
Aldehyde material, the optional glutaraldehyde of twain-aldehyde compound material, hexandial, Biformyl, malonaldehyde etc..
Preferably, described conducting metal electrical conductivity need meet some requirements, could with there is cross-linked structure
Tunneling effect, preferably electrical conductivity >=5 × 10 of conducting metal are produced between polyelectrolyte film6s·m-1, preferred conducting metal
Electrical conductivity >=40 × 106s·m-1.
Preferably, described wet sensitive composite membrane 1%rh-30%rh low humidity interval in impedance rate of change >=
1000%, and its impedance≤10 megaohm；Preferred impedance≤1 megaohm.
Preferably, described conducting metal is selected from au, ag, cu.Preferred ag in the present invention, that is, metal salt solution used is excellent
Select silver nitrate solution, the now described wet sensitive composite membrane impedance rate of change in the low humidity interval of 1%rh-30%rh can reach
2000%, and its impedance≤10 megaohm；Preferred impedance≤1 megaohm.
Preferably, described polyelectrolyte film is the polymeric film containing pyridine ring with crosslinked quaternized structure, can
Select P4VP, poly- (2- vinylpyridine) etc., the preferred alkylene dihalide of crosslinked quaternizing agent, optional Isosorbide-5-Nitrae-two
N-butyl bromide, pentamethylene bromide, 1,6- dibromo-hexane, Isosorbide-5-Nitrae-dichloroetane etc., preferred Isosorbide-5-Nitrae-dibromobutane, preferably poly- herein
Dielectric film is crosslinked quaternized P4VP film.
Second purpose of the present invention is the preparation method providing described wet sensitive composite membrane, comprises the steps:
1) prepare polyelectrolyte precursor solution, be subsequently adding crosslinked quaternizing agent and obtain mixed solution, described mixing
Carried out heat treatment after solution film forming, the polyelectrolyte film with crosslinked quaternary ammoniated structure is obtained；Described has crosslinked knot
The polyelectrolyte film of structure has sensitive response to humidity, can improve the sensitivity to humidity for the composite membrane；
2) mixed solution of preparing metal salt and polymer, in step 1) obtained by polyelectrolyte film on film forming, then
In-situ reducing is crosslinked, obtains conducting metal film of nanoparticles, with step 1) described in the poly- electrolysis with crosslinked quaternary ammoniated structure
Plasma membrane collectively forms wet sensitive composite membrane.Described conducting metal film of nanoparticles is crosslinked polymer network structure and dispersed
Conducting metal nanoparticle in described crosslinked polymer network structure collectively forms, described conducting metal film of nanoparticles
Play the low-impedance effect of fall, the electric conductivity of material can be improved.Crosslinked polymer in described conducting metal film of nanoparticles
Network and the metal nanoparticle collective effect being uniformly distributed therein, are that the electronics of described conducting metal film of nanoparticles is led
Electricity provides good conductive channel；Produce between described polyelectrolyte film and the conducting metal film of nanoparticles being deposited thereon
Synergism, collectively forms conductive network；Described conductive network is with the ionic conduction of described polyelectrolyte film and described conduction
The electronic conduction of metal nanoparticle film acts on simultaneously, and with tunneling effect, described polyelectrolyte film and conducting metal nanometer
Particle membrane forms conductive channel respectively, this make described humidity sensing film have under low humidity relatively low impedance (≤10 megaohms, very
To can≤1 megaohm).The cross-linked structure of the cross-linked structure of described polyelectrolyte film and described conducting metal film of nanoparticles is altogether
Same-action, provides good stability and resistance to water for described humidity sensing film.
Preferably, described in-situ reducing cross-linking method comprises the steps of: the mixing of preparing metal salt and polymer is molten
Liquid, after film forming, reducing metal ions is become conducting metal nanoparticle, and makes polymer crosslink reaction, generates conductive gold
Belong to film of nanoparticles.The optional dip-coating of film build method, spin coating, the method such as drop coating.
Preferably, described step 1) in polyelectrolyte film be the polymerization containing pyridine ring with crosslinked quaternized structure
Thing film, optional P4VP, poly- (2- vinylpyridine) etc.；The concentration of described polyelectrolyte presoma is preferably 5
～400mg/ml.
Preferably, described step 1) in the preferred alkylene dihalide of crosslinked quaternizing agent, optional Isosorbide-5-Nitrae-dibromobutane,
Pentamethylene bromide, 1,6- dibromo-hexane, Isosorbide-5-Nitrae-dichloroetane etc., more preferably Isosorbide-5-Nitrae-dibromobutane；Described crosslinked quaternized examination
The amount of agent is preferably 0.2～15 times with the mol ratio of polyelectrolyte presoma.
Preferably, described step 1) in heat treatment preferably 40～200 DEG C of temperature, time preferably 0.2～48h.
Preferably, described step 1) in can add film former, for assisting described mixed solution film forming, described film former
Selected from polyvinyl alcohol, polyvinyl butyral resin, polyvinyl pyrrolidone etc., more preferably polyvinyl butyral resin；Described one-tenth
Membrane concentration is preferably 0.5～100mg/ml.
Preferably, described step 2) described in the concentration of polymer be preferably 3～300mg/ml.
Preferably, described step 2) in polymer be hydroxyl in repetitives polymer, be selected from polyethylene
Alcohol (pva), Polyethylene Glycol (peg), polylactide and its copolymer, polypropylene glycol etc.；The friendship of described in-situ reducing cross-linking reaction
Connection agent optional twain-aldehyde compound material, the optional glutaraldehyde of twain-aldehyde compound material, hexandial, Biformyl, malonaldehyde etc.；Preferably in-situ reducing
Crosslinking temperature is 10～200 DEG C, and the time is 0.1～48h.
Preferably, described wet sensitive composite membrane 1%rh-30%rh low humidity interval in impedance rate of change >=
1000%, and its impedance≤10 megaohm；Preferred impedance≤1 megaohm.
Preferably, described step 2) in slaine be selected from and contain au+、au3+、ag+、cu2+Soluble-salt；Preferably
h[aucl4]、agno3、cuso4Deng；The concentration of described slaine is preferably 0.005～1mol/l.
Preferred slaine is agno3, now described wet sensitive composite membrane is in the low humidity interval of 1%rh-30%rh
Impedance rate of change can reach 2000%, and its impedance≤10 megaohm；Preferred impedance≤1 megaohm.
Preferably, the preparation method of described wet sensitive composite membrane specifically includes following steps:
1. prepare the mixed solution of polyelectrolyte presoma and film former, the concentration of described polyelectrolyte presoma is preferably
5～400mg/ml, film forming agent concentration is preferably 0.5～100mg/ml；
2. add the saturated dihalide being 0.2～15 times with polyelectrolyte presoma mol ratio, ageing 0.5～48h forms mixed
Close solution；
3. by step 2. in mixed solution film forming, heat 0.2～48h at 40～200 DEG C after drying, poly- electrolysis be obtained
Plasma membrane；
4. the mixed solution of preparing metal salt and polymer, the concentration of slaine is preferably 0.005～1mol/l, described poly-
The concentration of compound is preferably 3～300mg/ml；
5. by step 4. described in mixed solution on polyelectrolyte film film forming；
6. under cross-linking agent environment, under the conditions of 10～200 DEG C of temperature, carry out in-situ reducing cross-linking reaction 0.1～48h, system
Obtain wet sensitive composite membrane.
Preferably, described step 1. in polyelectrolyte presoma be polymer containing pyridine ring, optional poly- (4- ethylene
Yl pyridines), poly- (2- vinylpyridine) etc.；
Preferably, described step 1. in can add film former, for assisting described mixed solution film forming, described film former
Selected from polyvinyl alcohol, polyvinyl butyral resin, polyvinyl pyrrolidone etc., more preferably polyvinyl butyral resin；
Preferably, described step 2. in the preferred alkylene dihalide of crosslinked quaternizing agent, optional Isosorbide-5-Nitrae-dibromobutane,
Pentamethylene bromide, 1,6- dibromo-hexane, Isosorbide-5-Nitrae-dichloroetane etc., more preferably Isosorbide-5-Nitrae-dibromobutane；
Preferably, preferably 40～200 DEG C of the temperature of described step 3. middle heat treatment, time preferably 0.2～48h；
Preferably, described step 4. in polymer be repetitives in hydroxyl polymer, be selected from polyethylene
Alcohol (pva), Polyethylene Glycol (peg), polylactide and its copolymer, polypropylene glycol etc.；
Preferably, described step 4. in slaine be selected from contain au+、au3+、ag+、cu2+Soluble salt solutions；Can
Select h [aucl4]、agno3、cuso4Deng more preferably agno3Solution；
Preferably, described step 6. described in cross-linking agent optional twain-aldehyde compound material, the optional glutaraldehyde of twain-aldehyde compound material, oneself
Dialdehyde, Biformyl, malonaldehyde etc.；
Third object of the present invention is the humidity sensor providing by the use of described wet sensitive composite membrane as sensitive material,
Described humidity sensor has matrix, and described matrix can be ceramic matrix, glass basis, ito substrate, silicon chip substrate；
There is multipair interdigital gold electrode in described matrix photomask surface and evaporation, described interdigital gold electrode connects leaded, using leaching
Painting, spin coating, drop coating etc. become membrane meanses matrix and interdigital gold electrode surfaces deposition have have cross-linked structure polyelectrolyte film and
The conducting metal film of nanoparticles being deposited thereon, the polyelectrolyte film with cross-linked structure is that polymer containing pyridine ring passes through
Crosslink quaterisation with crosslinked quaternizing agent to obtain, conducting metal film of nanoparticles is by in-situ reducing crosslinking legal system
, occur in-situ reducing cross-linking reaction to be obtained by the mixed solution of slaine and polymer and cross-linking agent.The wet sensitive of the present invention
Sensor can be widely applied to the inspection of ambient humidity in industrial and agricultural production, storage, meteorology, Electrical Safety and protection and daily life
Survey and control, be particularly suited 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 new double-decker wet sensitive composite membrane, and wherein polyelectrolyte film has spirit to humidity
Quick response, can improve the sensitivity to humidity for the composite membrane；Conducting metal film of nanoparticles plays the low-impedance effect of fall, can
To improve the electric conductivity of material, the especially electric conductivity under low moisture environments；The wet sensitive that described two membranes obtain after combining is multiple
Close film and can decline Low ESR (1 megaohm of ＜) in low moisture environments, it is to avoid the problem leading to not because impedance is too high measure, simultaneously
There is good sensitivity (under 1-30%rh environment, its impedance rate of change can reach 2000%), and can smoothly realize
Low moisture environments humidity sensitive is detected.
2., in double-decker, by reduction, cross-linked structure is simultaneously introduced for conducting metal nanoparticle layers, can be effectively
Avoid the reunion of metal nanoparticle it is ensured that good conductive path can be formed in conducting metal nanoparticle layers and unlikely
In making conducting metal nanoparticle reunite, lead to short circuit cannot embody wet sensitive response.Polyelectrolyte film and conducting metal
Nanoparticle is intermembranous to produce mutual synergism, collectively forms conductive network, described conductive network is with described polyelectrolyte film
The electronic conduction of ionic conduction and described conducting metal film of nanoparticles acts on 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 is realized to containing using crosslinked quaternizing agent as cross-linking agent
There is the crosslinking of the polymer of pyridine ring quaternized, necessary quaternary ammonium salt ion, conducting metal nanometer can be provided for conducting process
Particle membrane forms cross-linked structure using the method for cross-linking agents polymer and can effectively improve conducting metal nanoparticle
The homogeneity of son distribution in conducting metal film of nanoparticles.Described two membranes all have cross-linked structure, can effectively improve
The stability of wet sensitive composite membrane.
4. conducting metal nanoparticle electrostatic spraying or directly compound with polyelectrolyte and material conductivity can be made anti-
And decline, and the present invention is evenly distributed by the conducting metal nanoparticle that the method for in-situ reducing is formed, and is in discontinuous
The sensitive membrane of state, applicants have unexpectedly found that be consequently formed this layer smooth but the conductive network of un-densified structure being capable of pole
The earth improves the electric conductivity of wet sensitive composite membrane, thus ensure that under low humidity, material has enough electric conductivity, is low moisture environments
Humidity Detection is laid a good foundation.And because preparation method is in-situ reducing, it is good that the method has a controllability, reaction condition is gentle,
Uniformly, dosage of crosslinking agent is less for reducing degree, many advantages, such as can reduce environmental pollution.
5. its moisture absorption response time of moisture sensor comprising wet sensitive composite membrane of the present invention can substantially shorten, during its moisture absorption
Between only need 20～30s.
6. conducting metal film of nanoparticles and the UV surface plasma resonance spectrum of polyelectrolyte film show, conducting metal
There is strong interaction, it is possible to use this synergism improves leading under low humidity between nanoparticle and polyelectrolyte
Charge migration electrically and under promotion different humidity, there is very close synergism in the two, simultaneously with tunneling effect, this
Be work before the present invention unexistent.
Brief description
Fig. 1 is the profile scanning electricity by the sensor with wet sensitive composite membrane as functional layer obtained by the method for the present invention
Mirror photo；
Fig. 2 is to be shone by the scanning electron microscope of the conducting metal nanoparticle environmental microbes obtained by the method for the present invention
Piece；
Fig. 3 is the wet sensitive response curve of the wet sensitive composite membrane using the inventive method preparation；
Fig. 4 is the response cycle test result figure for different humidity for the wet sensitive composite membrane of the present invention；
Fig. 5 is the response test result figure to low moisture environments for the wet sensitive composite membrane of the present invention.
Specific embodiment
Further illustrate the present invention below in conjunction with drawings and Examples.
Embodiment 1
The manufacture method of the wet sensitive composite membrane of the present invention, comprises the following steps:
1. the mixed solution of P4VP and polyvinyl butyral resin, P4VP concentration are prepared
For 36mg/ml, polyvinyl butyral resin concentration is 5mg/ml；
2. add the Isosorbide-5-Nitrae-dibromobutane of 2 times of P4VP mol ratio, ageing 10h forms mixed liquor；
3. by step 2. in mixed liquor film forming dry after, under the conditions of 110 DEG C heat 10h, be obtained first strata electrolysis
Plasma membrane；
4. prepare the mixed solution of silver nitrate and polyvinyl alcohol, the concentration of silver nitrate is 0.05mol/l, polyvinyl alcohol dense
Spend for 30mg/ml；
5. by step 4. in mixed solution on described polyelectrolyte film film forming dry；
6. under glutaraldehyde environment, under the conditions of 100 DEG C of temperature, carry out in-situ reducing cross-linking reaction 6h, prepared wet sensitive is combined
Film.
Using described 1.～step 6. can film forming on a ceramic substrate, be obtained using described wet sensitive composite membrane as function
The sensor of layer；Described sensor sectional drawing is as shown in figure 1, the wet sensitive composite membrane of the present invention is by having crosslinked quaternized structure
Polyelectrolyte film and conducting metal film of nanoparticles collectively constitute, have crosslinked quaternized structure polyelectrolyte film be synthesis
P4VP by obtaining with Isosorbide-5-Nitrae-dibromobutane crosslinking quaterisation, conducting metal film of nanoparticles is nitre
By occurring in-situ reducing cross-linking reaction to be obtained with glutaraldehyde after the mixed solution film forming of acid silver and polyvinyl alcohol.
, as shown in Fig. 2 metal nanoparticle is evenly distributed, size is homogeneous, institute for obtained wet sensitive composite film surface pattern
Prepared wet sensitive composite membrane has excellent Unordered system, and it is to the response diagram of humidity as shown in figure 3, to low humidity (1%-30%
Rh) response diagram of condition is as shown in Figure 5 it can be seen that the humidity under described wet sensitive composite membrane energy Sensitive Detection low moisture environments is believed
Breath, in the range of 1%-30%rh, using formulaSensitivity s=2000% can be calculated.In addition, it is described
The response cycle figure of wet sensitive composite membrane is as shown in Figure 4 it can be seen that it has good stability and recovery, by calculating it
Moisture absorption response time only needs 20～30s.
Comparative example 1
1. the mixed solution of P4VP and polyvinyl butyral resin, P4VP concentration are prepared
For 36mg/ml, polyvinyl butyral resin concentration is 5mg/ml；
2. add the Isosorbide-5-Nitrae-dibromobutane of 2 times of P4VP mol ratio, ageing 10h forms mixed liquor；
3. by step 2. in mixed liquor film forming dry after, under the conditions of 110 DEG C heat 10h, be obtained first strata electrolysis
Plasma membrane；
4. prepare silver nitrate solution, the concentration of silver nitrate is 0.05mol/l；
5. by step 4. in solution on described polyelectrolyte film film forming dry；
6. under glutaraldehyde environment, under the conditions of 100 DEG C of temperature, carry out in-situ reducing cross-linking reaction 6h, prepared wet sensitive is combined
Film.
Detection comparative example 1 is obtained impedance and the sensitivity of wet sensitive composite membrane: obtained wet sensitive composite membrane is in low humidity
Impedance under the conditions of (≤30%rh) is very low, and only less than 1 kilo-ohm, but described wet sensitive composite membrane does not almost ring to humidity
Should, in the range 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, do not form the crosslinked polymer network in conducting metal film of nanoparticles, result system
The sensitivity of the wet sensitive composite membrane obtaining is extremely low, illustrates that crosslinked polymer network has to the sensitivity of described wet sensitive composite membrane very big
Contribution.
Comparative example 2
1. the mixed solution of P4VP and polyvinyl butyral resin, P4VP concentration are prepared
For 36mg/ml, polyvinyl butyral resin concentration is 5mg/ml；
2. add the Isosorbide-5-Nitrae-dibromobutane of 2 times of P4VP mol ratio, ageing 10h forms mixed liquor；
3. by step 2. in mixed liquor film forming dry after, under the conditions of 110 DEG C heat 10h, be obtained first strata electrolysis
Plasma membrane；
4. prepare the mixed solution of Graphene and polyvinyl alcohol, the concentration of Graphene is 3mg/ml, the concentration of polyvinyl alcohol
For 30mg/ml；
5. by step 4. in mixed solution on described polyelectrolyte film film forming dry；
6. under glutaraldehyde environment, under the conditions of 100 DEG C of temperature, carry out in-situ reducing cross-linking reaction 6h, prepared wet sensitive is combined
Film.
Detection comparative example 2 is obtained impedance and the sensitivity of wet sensitive composite membrane: obtained wet sensitive composite membrane is in low humidity
Impedance under the conditions of (≤30%rh) is relatively low, and only less than 10 megaohms, but described wet sensitive composite membrane does not almost ring to humidity
Should, in the range 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, there is no shape
Become conducting metal nanoparticle, the prepared wet sensitive composite membrane sensitivity of result is very low, illustrates conducting metal nanoparticle to described wet
The sensitivity tool of quick composite membrane has contributed much.
Comparative example 3
1. the mixed solution of P4VP and polyvinyl butyral resin, P4VP concentration are prepared
For 36mg/ml, polyvinyl butyral resin concentration is 5mg/ml；
2. add the Isosorbide-5-Nitrae-dibromobutane of 2 times of P4VP mol ratio, ageing 10h forms mixed liquor；
3. by step 2. in mixed liquor film forming dry after, under the conditions of 110 DEG C heat 10h, be obtained first strata electrolysis
Plasma membrane；
4. prepare the mixed solution of CNT and polyvinyl alcohol, the concentration of CNT is 5mg/ml, polyvinyl alcohol
Concentration is 30mg/ml；
5. by step 4. in mixed solution on described polyelectrolyte film film forming dry；
6. under glutaraldehyde environment, carry out in-situ reducing exchange reaction 6h under the conditions of 100 DEG C of temperature, prepared wet sensitive is combined
Film.
Detection comparative example 3 is obtained impedance and the sensitivity of wet sensitive composite membrane: obtained wet sensitive composite membrane is in low humidity
Impedance under the conditions of (≤30%rh) is relatively low, and less than 10 megaohms, but described wet sensitive composite membrane does not almost respond to humidity,
In the range of 1%-30%rh, its sensitivity only has 130%.This comparative example is exactly in step with the difference of embodiment 1
4. do not add the soluble-salt of conducting metal in, but add the preferable CNT of electric conductivity in material with carbon element, do not formed
Conducting metal nanoparticle, the prepared wet sensitive composite membrane sensitivity of result is very low, illustrates conducting metal nanoparticle to described wet sensitive
The sensitivity tool of composite membrane has contributed much.
Comparative example 4
1. the mixed solution of P4VP and polyvinyl butyral resin, P4VP concentration are prepared
For 36mg/ml, polyvinyl butyral resin concentration is 5mg/ml；
2. add the Isosorbide-5-Nitrae-dibromobutane of 2 times of P4VP mol ratio, ageing 10h forms mixed liquor；
3. by step 2. in mixed liquor film forming dry after, under the conditions of 110 DEG C heat 10h, be obtained first strata electrolysis
Plasma membrane；
4. prepare the mixed solution of silver nitrate and polyvinyl alcohol, the concentration of silver nitrate is 0.05mol/l, polyvinyl alcohol dense
Spend for 350mg/ml；
5. by step 4. in mixed solution on described polyelectrolyte film film forming dry；
6. under glutaraldehyde environment, under the conditions of 100 DEG C of temperature, carry out in-situ reducing cross-linking reaction 6h, prepared wet sensitive is combined
Film.
Detection comparative example 4 is obtained impedance and the sensitivity of wet sensitive composite membrane: obtained wet sensitive composite membrane is in low humidity
Impedance under the conditions of (≤30%rh) is very high, reaches tens megaohms, and in the range of 1%-30%rh, its sensitivity only has 470%.
This comparative example is exactly in the step 4. middle polyvinyl alcohol adding excessive (350mg/ml), shape with the difference of embodiment 1
Become excessive crosslinked polymer network, resultant impedance is very high, but sensitivity is relatively low, and the amount that crosslinked polymer network is described is to institute
State the impedance of wet sensitive composite membrane and sensitivity all has a significant impact.
Comparative example 5
1. the mixed solution of P4VP and polyvinyl butyral resin, P4VP concentration are prepared
For 36mg/ml, polyvinyl butyral resin concentration is 5mg/ml；
2. add the Isosorbide-5-Nitrae-dibromobutane of 2 times of P4VP mol ratio, obtain mixed solution a；
3. prepare the mixed solution of silver nitrate and polyvinyl alcohol, the concentration of silver nitrate is 0.05mol/l, polyvinyl alcohol dense
Spend for 350mg/ml, obtain mixed solution b；
4. described mixed solution a and described mixed solution b is mixed to get mixed solution c, is aged 5h；
5. by step 4. in mixed solution c film forming dry；
6. under glutaraldehyde environment, under the conditions of 100 DEG C of temperature, carry out in-situ reducing cross-linking reaction 6h, prepared wet sensitive is combined
Film.
Detection comparative example 5 is obtained impedance and the sensitivity of wet sensitive composite membrane: obtained wet sensitive composite membrane is in low humidity
Impedance under the conditions of (≤30%rh) is very high, reaches tens megaohms, and in the range of 1%-30%rh, its sensitivity only has 340%.
Polyelectrolyte film and conducting metal film of nanoparticles have exactly been made one layer with the difference of embodiment 1 by this comparative example
Membrane structure, rather than double-decker, result sensitivity is very low, illustrates synergism between two-layer compound membrane structure to described wet
The impedance of quick composite membrane and sensitivity all have a significant impact.
Embodiment 2
1. prepare the mixed solution of poly- (2- vinylpyridine) and polyvinyl alcohol, poly- (2- vinylpyridine) concentration is 5mg/
Ml, polyvinyl alcohol concentration is 100mg/ml；
2. add the pentamethylene bromide of 0.2 times of poly- (2- vinylpyridine) mol ratio, ageing 48h forms mixed liquor；
3. by step 2. in mixed liquor film forming dry after, under the conditions of 40 DEG C heat 48h, prepared ground floor polyelectrolyte
Film；
4. prepare the mixed solution of copper sulfate and Polyethylene Glycol, the concentration of copper sulfate is 0.005mol/l, Polyethylene Glycol
Concentration is 300mg/ml；
5. by step 4. in mixed solution on described polyelectrolyte film film forming dry；
6. under hexandial environment, under the conditions of 10 DEG C of temperature, carry out in-situ reducing cross-linking reaction 48h, prepared wet sensitive is combined
Film.
Impedance under the conditions of low humidity (≤30%rh) for the obtained wet sensitive composite membrane is relatively low, less than 10 megaohms, to humidity
There is preferable response, in the range of 1%-30%rh, its sensitivity reaches 1160%.
Embodiment 3
1. prepare the mixed solution of P4VP and polyvinyl pyrrolidone, P4VP is dense
Spend for 400mg/ml, polyvinyl pyrrolidone concentration is 0.5mg/ml；
2. add 1, the 6- dibromo-hexane of 15 times of P4VP mol ratio, ageing 0.5h forms mixed liquor；
3. by step 2. in mixed liquor film forming dry after, under the conditions of 200 DEG C heat 0.2h, be obtained first strata electrolysis
Plasma membrane；
4. prepare gold chloride (h [aucl4]) with the mixed solution of polypropylene glycol, the concentration of gold chloride is 1mol/l, poly- third
The concentration of glycol is 3mg/ml；
5. by step 4. in mixed solution on described polyelectrolyte film film forming dry；
6. under malonaldehyde environment, under the conditions of 200 DEG C of temperature, carry out in-situ reducing cross-linking reaction 0.1h, prepared wet sensitive is multiple
Close film.
Impedance under the conditions of low humidity (≤30%rh) for the obtained wet sensitive composite membrane is relatively low, less than 10 megaohms, to wet
Degree has preferable response, and in the range of 1%-30%rh, its sensitivity reaches 1350%.
Embodiment 4
1. the mixed solution of poly- (2- vinylpyridine) and polyvinyl butyral resin, poly- (2- vinylpyridine) concentration are prepared
For 72mg/ml, polyvinyl butyral resin concentration is 75mg/ml；
2. add the Isosorbide-5-Nitrae-dichloroetane of 4 times of poly- (2- vinylpyridine) mol ratio, ageing 5h forms mixed liquor；
3. by step 2. in mixed liquor film forming dry after, under the conditions of 50 DEG C heat 20h, prepared 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, gathers breast
The concentration of acid and its copolymer is 100mg/ml；
5. by step 4. in mixed solution on described polyelectrolyte film film forming dry；
6. under Biformyl environment, under the conditions of 120 DEG C of temperature, carry out in-situ reducing cross-linking reaction 8h, prepared wet sensitive is combined
Film.
Impedance under the conditions of low humidity (≤30%rh) for the obtained wet sensitive composite membrane is relatively low, less than 10 megaohms, to wet
Degree has preferable response, and in the range of 1%-30%rh, its sensitivity reaches 1660%.
Embodiment 5
1. the mixed solution of P4VP and polyvinyl butyral resin, P4VP concentration are prepared
For 144mg/ml, polyvinyl butyral resin concentration is 200mg/ml；
2. add the Isosorbide-5-Nitrae-dibromobutane of 3 times of P4VP mol ratio, ageing 3h forms mixed liquor；
3. by step 2. in mixed liquor film forming dry after, under the conditions of 180 DEG C heat 5h, prepared ground floor polyelectrolyte
Film；
4. prepare the mixed solution of silver nitrate and polyvinyl alcohol, the concentration of silver nitrate is 0.01mol/l, polyvinyl alcohol dense
Spend for 150mg/ml；
5. by step 4. in mixed solution on described polyelectrolyte film film forming dry；
6. under glutaraldehyde environment, under the conditions of 150 DEG C of temperature, carry out in-situ reducing cross-linking reaction 4h, prepared wet sensitive is combined
Film.
Impedance under the conditions of low humidity (≤30%rh) for the obtained wet sensitive composite membrane is relatively low, less than 10 megaohms, to wet
Degree has preferable response, and in the range of 1%-30%rh, its sensitivity reaches 1100%.
Embodiment 6
1. the mixed solution of P4VP and polyvinyl butyral resin, P4VP concentration are prepared
For 288mg/ml, polyvinyl butyral resin concentration is 50mg/ml；
2. add the Isosorbide-5-Nitrae-dibromobutane of 12 times of P4VP mol ratio, ageing 1h forms mixed liquor；
3. by step 2. in mixed liquor film forming dry after, under the conditions of 180 DEG C heat 24h, be obtained first strata electrolysis
Plasma membrane；
4. prepare the mixed solution of copper sulfate and polylactic acid, the concentration of silver nitrate is 0.8mol/l, and the concentration of polylactic acid is
200mg/ml；
5. by step 4. in mixed solution on described polyelectrolyte film film forming dry；
6. under glutaraldehyde environment, under the conditions of 130 DEG C of temperature, carry out in-situ reducing cross-linking reaction 8h, prepared wet sensitive is combined
Film.
Impedance under the conditions of low humidity (≤30%rh) for the obtained wet sensitive composite membrane is relatively low, less than 10 megaohms, to wet
Degree has preferable response, and in the range of 1%-30%rh, its sensitivity reaches 1850%.
Above example is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that reading
After the content that the present invention lectures, those skilled in the art can make various changes or modifications to the present invention, these shapes of equal value
Formula equally falls within the application appended claims limited range.
Claims (10)
1. a kind of wet sensitive composite membrane it is characterised in that: described wet sensitive composite membrane by have cross-linked structure polyelectrolyte film and
The conducting metal film of nanoparticles composition being deposited thereon, described conducting metal film of nanoparticles is cross-linked network structure polymer
Collectively form with the conducting metal nanoparticle being dispersed in described cross-linked network structure polymer.
2. wet sensitive composite membrane according to claim 1 it is characterised in that: described conducting metal film of nanoparticles is by original position also
Former cross-linking method is obtained.
3. wet sensitive composite membrane according to claim 2 it is characterised in that: described in-situ reducing cross-linking method includes walking as follows
Rapid: the mixed solution of preparing metal salt and polymer, after film forming, reducing metal ions are become conducting metal nanoparticle, and makes
Polymer crosslinks reaction, obtains conducting metal film of nanoparticles.
4. wet sensitive composite membrane according to claim 1 it is characterised in that: described wet sensitive composite membrane is 1%rh-30%rh's
Impedance rate of change >=1000% in low humidity interval.
5. wet sensitive composite membrane according to claim 1 is it is characterised in that electrical conductivity >=5 × 10 of described conducting metal6s·
m-1.
6. wet sensitive composite membrane according to claim 1 it is characterised in that: described conducting metal be selected from au, ag, cu.
7. wet sensitive composite membrane according to claim 1 it is characterised in that: described polymer is hydroxyl in repetitives
Polymer.
8. the wet sensitive composite membrane according to any one of claim 1-7 it is characterised in that: described polyelectrolyte film be have
The polymeric film containing pyridine ring of crosslinked quaternized structure.
9. the preparation method of wet sensitive composite membrane described in claim 2 is it is characterised in that comprise the steps:
1) prepare polyelectrolyte precursor solution, be subsequently adding crosslinked quaternizing agent and obtain mixed solution, described mixed solution
Carried out heat treatment after film forming, the polyelectrolyte film with crosslinked quaternary ammoniated structure is obtained；
2) mixed solution of preparing metal salt and polymer, in step 1) obtained by polyelectrolyte film on film forming, then in situ
Reduction is crosslinked, obtains wet sensitive composite membrane.
10. a kind of humidity sensor it is characterised in that: described sensor comprises the wet sensitive described in any one of claim 1-8
Composite membrane.
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| CN108195888A (en) * | 2017-12-27 | 2018-06-22 | 长春理工大学 | Impedance type dew cell using the compound wet sensory material of cross-linked polymer and preparation method thereof |
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