CN1128353C - Nitrogen oxide sensor made of doped polyaniline and its making process - Google Patents
Nitrogen oxide sensor made of doped polyaniline and its making process Download PDFInfo
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- CN1128353C CN1128353C CN 99114792 CN99114792A CN1128353C CN 1128353 C CN1128353 C CN 1128353C CN 99114792 CN99114792 CN 99114792 CN 99114792 A CN99114792 A CN 99114792A CN 1128353 C CN1128353 C CN 1128353C
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Abstract
The present invention discloses a nitric oxide gas sensor of doped polyaniline and a preparation method thereof. The nitric oxide gas sensor comprises a base sheet, electrodes, a polyaniline sensitive membrane and a conductive leading out terminal, wherein the base sheet is a rectangular, square or circular microcrystalline glass sheet, a ceramic sheet, a polymer having high insulation performance, or a high-resistance silicon chip; a pair of interdigital electrodes are burned or evaporated at the surface of one side of the base sheet after the base sheet is cleaned, and the electrodes are made of gold or a silver palladium alloy. The preparation method of the nitric oxide gas sensor comprises: the polyaniline sensitive membrane having high conductivity grows on the base sheet containing the interdigital electrodes with a doping and induced deposition self-assembly method or an in-situ polymerization deposition method; conductive wires are led out from the two electrode terminals. The present invention has the advantages of high anti-interference capability, high long-term stability of parts of the apparatus, convenient use, etc. The nitric oxide gas sensor can be widely applied to automobile tail gas detection, atmospherical environment detection, monitoring of nitric oxide leakage alarming devices in factories and warehouses, monitoring of nitric oxide concentration in military war environments and satellite launch sites, etc.
Description
The invention belongs to the gas sensor field.
Nitrogen oxide (NO
x) gas is to environment and the very serious pollutant of human health risk in the atmosphere.Therefore, the development nitrogen oxide gas sensor is so that know in the environment NO with relevant pollution source timely and accurately
xGas and concentration thereof are significant to environmental monitoring and environmental protection.The NO that present document is reported
xGas sensor adopts inorganic oxide such as SnO more
2, WO
3Sensitive material, working temperature generally all higher (200～500 ℃), the practical application of inconvenient sensor.
In recent years, can obtain day by day paying attention to as gas sensitive material at the organic material of working and room temperature especially conducting polymer materials.In conducting polymer, therefore polyaniline adopts polyaniline to make NO because its preparation is relatively simple, cost is low, electric conductivity is more stable
xGas sensitive material has more advantage.July in 1996 people such as disclosed Monkman on the 16th United States Patent (USP) " Polyaniline Gas Sensor " (" polyaniline gas sensor ", the patent No.: first polyaniline is used for nitrogen oxide gas sensor US05536473).But the sensitive membrane that people such as Monkman adopt is a polyaniline in eigenstate, and the conductivity of polyaniline in eigenstate is very low, is approximately 10
-11S/cm, the resistance of the sensor of making of its be greater than 1 begohm, handles for the detection of sensitive signal and back end signal and bring very big difficulty, poor anti jamming capability.In addition, their film-forming method is by technologies such as spin-coating method and vacuum evaporation, and the film that makes and the adhesion of substrate are relatively poor, makes the stability of sensor reduce.
The object of the present invention is to provide a kind of new polyaniline nitrogen oxide gas sensor and preparation method thereof.
The principle of work of nitrogen oxide sensor made of doped polyaniline of the present invention is that the conductivity of doped polyaniline is relevant with the degree of oxidation of himself, and degree of oxidation is higher, and conductivity is lower.Nitrogen oxide is a kind of oxidizing gas, after doped polyaniline contacts, the degree of oxidation of polyaniline is raise, so the resistance of sensitive element increases.The concentration of nitrogen oxide gas is bigger, and the degree of oxidation of polyaniline is just higher, and resistance raises just bigger.Therefore by the resistance of detecting element, just can detect the concentration of nitrogen oxide gas in the environment.
Nitrogen oxide sensor made of doped polyaniline of the present invention is made up of substrate, electrode, polyaniline sensitive membrane and conduction exit.Substrate is the polymkeric substance or the high resistant silicon chip of rectangle, square or circular microcrystalline glass, potsherd, good insulation preformance, fires or evaporates a pair of interdigital electrode at the one side surface after cleaning, and electrode material is gold or silver palladium alloy.Containing employing doping induction and deposition self-assembly method or in-situ polymerization sedimentation grow doping attitude polyaniline sensitive membrane on the substrate sections of interdigital electrode, draw lead at two electrode tips.Wherein doped polyaniline is meant the polyaniline of half oxidation semi-reduction state of protonic acid doping.
The film-forming process of doping induction and deposition self-assembly method is in the solution and polymkeric substance aqueous acid of the N-Methyl pyrrolidone that alternately immerses polyaniline in eigenstate of the substrate with surface acidityization, take out behind the certain hour, use organic solvent and deionized water rinsing respectively, dry up.Detailed process is seen Chinese patent (" the doping induction and deposition prepares the preparation method of polyaniline ultrathin membrane ", application number: 98121862.8,1998 years).Similar document (the Li Yongming of the film-forming process of in-situ polymerization sedimentation, Wan Meixiang, the research that the dipping polymerization prepares transparent polyaniline film, the macromolecule journal, 2 (1998), 177-183) Bao Dao process: dispose earlier pH value respectively and be about 0 the 0.05M aniline acid solution and the aqueous solution of 0.025M ammonium persulfate, subsequently these two kinds of solution equal-volumes are mixed the insertion substrate, stir, reacted about 3～5 hours, and proposed substrate, wash with acid solution, soaked 20 minutes, with behind the deionized water rinsing, dry up again, obtain the polyaniline film of protonic acid doping.Used acid can be hydrochloric acid, sulfuric acid or p-toluenesulfonic acid.The film that different with document is so makes will be 1～10% ammoniacal liquor immersion treatment dedoping with concentration, polyaniline film is immersed in the polymkeric substance aqueous acid 1～5 hour again, makes polyaniline be aggregated thing acid and mixes.Polymeric acid can be organic polymer acid such as polystyrolsulfon acid, polyacrylic acid, also can be inorganic polymer acid such as the isopolyacid of transition metal such as molybdenum, tungsten or heteropoly acid.Experiment shows that the stability of the polyaniline film that polymeric acid mixes better.
In order further to improve the adhesion of polyaniline film and substrate, substrate surface can be handled with polymer dielectric earlier.Disposal route is after earlier substrate being cleaned up, to soak 5～30 minutes in the aqueous solution of the poly-diallyl alkyl dimethyl ammonium chloride of polycation, takes out the back and rinses the surface that obtains the polycation processing with deionized water well; The substrate of cationization can also immerse in the solution of polystyrolsulfon acid, polyacrylic acid or other polymeric acid and soak 5～30 minutes, spends Gao Zishui after the taking-up and rinses well and obtain the surface that polyanion is handled.Substrate can strengthen the adhesion of polyaniline sensitive membrane through processing like this.
Accompanying drawing and description of drawings:
Fig. 1: the floor map of nitrogen oxide sensor made of doped polyaniline substrate: the 1st, substrate; The 2nd, interdigital electrode; The 4th, contact conductor;
Fig. 2: the side schematic view of nitrogen oxide sensor made of doped polyaniline: the 1st, substrate; The 2nd, interdigital electrode; The 3rd, the doped polyaniline sensitive membrane; The 4th, contact conductor;
Fig. 3: the sensitivity characteristic curve of the polyaniline nitrogen oxide gas sensor that polystyrolsulfon acid mixes: sensitive membrane is prepared by doping induction and deposition method;
Fig. 4: the sensitivity characteristic curve of the polyaniline nitrogen oxide gas sensor that polystyrolsulfon acid mixes: sensitive membrane is prepared by the in-situ polymerization sedimentation;
Fig. 5: the sensitivity characteristic curve of the polyaniline nitrogen oxide gas sensor that wolframic acid mixes: sensitive membrane is prepared by doping induction and deposition method;
Fig. 6: the sensitivity characteristic curve of the polyaniline nitrogen oxide gas sensor that wolframic acid mixes: sensitive membrane is prepared by the in-situ polymerization sedimentation.
In the sensitivity characteristic curve in Fig. 3, Fig. 4, Fig. 5, Fig. 6, its horizontal ordinate is NO
2Concentration, unit is ppm (1,000,000/), ordinate is the resistance of polyaniline nitrogen oxide gas sensor, unit be K Ω (kilohm).
Nitrogen oxide sensor made of doped polyaniline resistance of the present invention is in hundreds of ohm～tens kilohm scope, the resistance of the gas sensor of making than polyaniline in eigenstate is low 6 more than the order of magnitude, therefore the signal of its output is easy to gather and further handle, antijamming capability is strong, the strong adhesion of sensitive membrane and substrate, the long term device good stability; Have easy to usely in addition, do not need advantages such as well heater, volume be little.Can be widely used in vehicle exhaust and detect the prosecution of the nitrogen oxide gas concentration at the nitrogen oxide gas leakage warning device in atmospheric environment detection, factory and warehouse and military battlefield environment, satellites transmits scene etc.
Embodiment one:
The substrate that as shown in Figure 1 steaming is had an interdigital gold electrode (sees the patent in early stage for details: 98121862.8) after the surface acidity processing, substrate electrod partly alternately immersed in the aqueous solution of the N-Methyl pyrrolidone solution of 0.2% polyaniline and 1% polystyrolsulfon acid 60 minutes, use dimethyl formamide and deionized water rinsing respectively, dry up, so circulation is 8 times, handled 2 hours at 50～80 ℃ at last, promptly get the polyaniline nitrogen oxide gas sensor of the polystyrolsulfon acid doping of adopting doping induction and deposition manufactured.Fig. 3 is its sensitivity characteristic curve.
Embodiment two:
The substrate that the steaming as shown in Figure 1 that cleans up is had an interdigital gold electrode soaked 30 minutes in the aqueous solution of 1% poly-diallyl alkyl dimethyl ammonium chloride, took out the back and rinsed well with deionized water.Dispose the ammonium persulfate aqueous solution of 20ml aniline acid solution and 0.025M respectively, the concentration of aniline is 0.05M in the aniline solution, and the concentration of p-toluenesulfonic acid is 0.5M.Subsequently these two kinds of solution are mixed, insert substrate, stir, reacted about 5 hours, substrate is proposed, p-toluenesulfonic acid solution flushing with 0.05M, soaked 20 minutes, and after the flushing, put into 5% ammonia spirit and handled 1 hour again, taking out the back rinses well with deionized water, in the aqueous solution of 1% polystyrolsulfon acid, handled 2 hours, take out, rinse well with deionized water, handled 2 hours at 50～80 ℃ at last, promptly get the polyaniline nitrogen oxide gas sensor of the polystyrolsulfon acid doping of adopting the manufacturing of in-situ polymerization sedimentation.Fig. 4 is its sensitivity characteristic curve.
Embodiment three:
Wolframic acid substituted polystyrene sulfonic acid with 1% with the method for embodiment one, promptly gets the polyaniline nitrogen oxide gas sensor of the wolframic acid doping of adopting doping induction and deposition manufactured.Fig. 5 is its sensitivity characteristic curve.
Embodiment four:
Wolframic acid substituted polystyrene sulfonic acid with 1% with the method for embodiment two, promptly gets the polyaniline nitrogen oxide gas sensor of the wolframic acid doping of adopting the manufacturing of in-situ polymerization sedimentation.Fig. 6 is its sensitivity characteristic curve.
Claims (5)
1, a kind of preparation method of nitrogen oxide gas sensor of doped polyaniline, it is characterized in that adopting the preparation of in-situ polymerization sedimentation, concrete preparation method is: the substrate that the steaming that will clean up has an interdigital gold electrode soaked 30 minutes in the aqueous solution of 1% poly-diallyl alkyl dimethyl ammonium chloride, took out the back and rinsed well with deionized water; Dispose the ammonium persulfate aqueous solution of 20ml aniline acid solution and 0.025M respectively, the concentration of aniline is 0.05M in the aniline solution, and the concentration of p-toluenesulfonic acid is 0.5M; Subsequently these two kinds of solution are mixed, insert substrate, stir, reacted about 5 hours, substrate is proposed, p-toluenesulfonic acid solution flushing with 0.05M, soaked 20 minutes, and after the flushing, put into 5% ammonia spirit and handled 1 hour again, taking out the back rinses well with deionized water, in the aqueous solution of 1% polystyrolsulfon acid, handled 2 hours, take out, rinse well with deionized water, handled 2 hours at 50～80 ℃ at last, promptly get the polyaniline nitrogen oxide gas sensor of the polystyrolsulfon acid doping of adopting the preparation of in-situ polymerization sedimentation.
2, a kind of preparation method of nitrogen oxide gas sensor of doped polyaniline, it is characterized in that adopting the preparation of doping induction and deposition method, concrete preparation method is: the substrate that steaming is had interdigital gold electrode is after the surface acidity processing, substrate electrod partly alternately immersed in the aqueous solution of the N-Methyl pyrrolidone solution of 0.2% polyaniline and 1% polystyrolsulfon acid 60 minutes, use dimethyl formamide and deionized water rinsing respectively, dry up, so circulation is 8 times, handled 2 hours at 50～80 ℃ at last, promptly get the polyaniline nitrogen oxide gas sensor of the polystyrolsulfon acid doping of adopting the preparation of doping induction and deposition method.
3, the preparation method of the nitrogen oxide gas sensor of a kind of doped polyaniline according to claim 1, it is characterized in that behind the polyaniline film that the polystyrolsulfon acid with the preparation of in-situ polymerization sedimentation mixes, to be 1～10% ammoniacal liquor immersion treatment dedoping with concentration, again polyaniline film was immersed in the polymkeric substance aqueous acid 1～5 hour, and made polyaniline be aggregated thing acid dedoping.
4, the preparation method of the nitrogen oxide gas sensor of a kind of doped polyaniline according to claim 1, before it is characterized in that adopting situ aggregation method dopant deposition attitude polyaniline film, substrate adopts the polymer dielectric pre-service, the polymer dielectric preprocess method is: after earlier substrate being cleaned up, in the aqueous solution of the poly-diallyl alkyl dimethyl ammonium chloride of polycation, soaked 5～30 minutes, take out the back and rinse the surface that obtains the polycation processing with deionized water well; The substrate of cationization can also immerse in the solution of polystyrolsulfon acid, polyacrylic acid or other polymeric acid and soak 5～30 minutes, takes out the back and rinses well with deionized water and obtain the surface that polyanion is handled.
5, the preparation method of the nitrogen oxide gas sensor of a kind of doped polyaniline according to claim 3, it is characterized in that described polymeric acid can be organic polymer acid such as polystyrolsulfon acid, polyacrylic acid, also can be inorganic polymer acid such as the isopolyacid of transition metal such as molybdenum, tungsten or heteropoly acid.
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| CN101692004B (en) * | 2009-07-23 | 2012-08-01 | 李海旋 | Novel differential force (capacitance) type flow transducer, processing technique and application thereof |
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| GB0509632D0 (en) * | 2005-05-11 | 2005-06-15 | Dart Sensors Ltd | Electrochemical sensors |
| CN101545885B (en) * | 2009-05-07 | 2012-05-23 | 重庆大学 | Method for testing electrochemical performance of polyaniline synthesized by chemical method |
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| CN104407035A (en) * | 2014-11-14 | 2015-03-11 | 无锡信大气象传感网科技有限公司 | Gas sensor chip |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101692004B (en) * | 2009-07-23 | 2012-08-01 | 李海旋 | Novel differential force (capacitance) type flow transducer, processing technique and application thereof |
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