CN102830139B - Preparation method for zinc oxide thick-film gas sensitivity sensor with acetone selectivity characteristic - Google Patents

Preparation method for zinc oxide thick-film gas sensitivity sensor with acetone selectivity characteristic Download PDF

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CN102830139B
CN102830139B CN201210309003.4A CN201210309003A CN102830139B CN 102830139 B CN102830139 B CN 102830139B CN 201210309003 A CN201210309003 A CN 201210309003A CN 102830139 B CN102830139 B CN 102830139B
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powder
colloid
preparation
gel
coo
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CN102830139A (en
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何平
周亚同
杨帆
曹冠龙
潘国峰
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Hebei University of Technology
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Hebei University of Technology
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Abstract

The invention discloses a preparation method for a zinc oxide thick-film gas sensitivity sensor with an acetone selectivity characteristic. The preparation method comprises following steps of firstly preparing colloid of zinc hydroxide (Zn(OH)2): preparing by utilizing zinc acetate (Zn(CH3COO)2.2H2O) and sodium hydroxide (NaOH) as raw materials; then aging, concentrating and baking the obtained Zn(OH)2 colloid to obtain Zn(OH)2 gel, adequately grinding the gel, mixing cerium oxide with the gel powder according to 7 percent by weight, finally placing the mixed powder into a muffle furnace to be annealed at the temperature of 700 DEG C for 3 hours, mixing the annealed mixed powder with methylcellulose, and then placing the mixture onto a ceramic pipe to be annealed and sintered. The preparation way is simple, and the cost is low. A film is prepared by adopting the sol-gel method, and the preparation condition can be met under the room temperature. By selecting technical parameters of the preparation method, gas sensitivity elements can have high selectivity, sensitivity and stability for the acetone.

Description

The zinc paste thick film gas-sensitive sensor preparation method with acetone selectivity characteristic
Technical field
The present invention relates to gas sensing device field, relate in particular to a kind of preparation method acetone steam to the zinc paste thick film sensor of selectivity characteristic.
Technical background
Sensor technology is one of new and high technology developing rapidly, and it and computer technology, the communication technology have formed three large pillars of information industry jointly.Gas sensor, as the important branch of sensor, is also widely used in each field.Since the eighties, one of many countries gordian technique using gas sensor as focus development.Gas sensor is the core component of gas sensor, is used for detection inflammable and explosive, toxic and harmful.Nowadays increasing gas sensor has entered into the industries such as environmental monitoring, petrochemical complex, metallurgy, automobile, pharmacy, food, medical treatment, road traffic, municipal combustion gas, digital mine; In family, mainly for detection of coal gas, natural gas leakage, whether the formaldehyde of finishing, furniture exceeds standard etc.
At present, domestic gas sensor great majority are all wide spectrums, and its selectivity is poor, and sensitivity is lower, and the response-recovery time is longer, especially lack acetone steam is had to high selectivity, highly sensitive sensor.In addition, the preparation method that current sensor adopts mostly is sputtering method, and equipment is complicated, and preparation cost is high.
< < CDMD (master) engineering science and technology I is collected in " sign of Synthesis of ZnO Nanoparticles by Sol-Gel Method powder and nanometer Zinc oxide powder " paper of author in the > > first phase " Chen Huaijie " and has been introduced Synthesis of ZnO Nanoparticles by Sol-Gel Method powder, but for its specific aim should be used as to too much research.
Summary of the invention
Technical matters to be solved by this invention is, for the deficiencies in the prior art, to provide a kind of preparation method acetone steam to the zinc paste thick film sensor of selectivity characteristic.
The present invention has the zinc paste thick film gas-sensitive sensor preparation method of acetone selectivity characteristic, according to following step, carries out:
A. prepare Zn (OH) 2colloid: take respectively absolute ethyl alcohol and mix with deionized water, absolute ethyl alcohol and deionized water volume ratio are: 1:0.5-1:2 is stirred to evenly; With counter balance, take respectively Zn (CH 3cOO) 22H 2o and NaOH, Zn (CH 3cOO) 22H 2the mol ratio of O and NaOH is 1:1-1:3 and with the above-mentioned solvent 20ml preparing, dissolves respectively respectively; With stirring machine, stir Zn (CH 3cOO) 22H 2o solution, the about 80r/min-100r/min of rotating speed, splashes into Zn (CH by NaOH solution with the speed of dripping of 0.05ml/min-0.12ml/min 3cOO) 22H 2o solution; After PH=6.5-7.4, continue to stir 1-3h, close stirrer, 24 hours post-dryings of standing colloid also grind to form Zn (OH) 2colloid powder;
B. by the Zn obtaining (OH) 2colloid carries out ageing, condensing, baking obtains Zn (OH) 2gel;
C. by gel being cleaned, is dried fine grinding again with deionized water or ethanol after the abundant fine grinding heating of gel piece, be powder, and cerium oxide is mixed in gel powder according to percentage by weight 6 ω t%-8 ω t%, mixed-powder is put into muffle furnace, 500 ℃-900 ℃ of annealing temperatures, constant temperature 2.5-3h;
D. by the mixed-powder after above-mentioned mixing annealing and methylcellulose by weight the ratio of 1:3-1:5 mix, be then coated in the sintering of annealing on ceramic pipe, there is the zinc paste thick film gas-sensitive sensor of acetone selectivity characteristic
Use the present invention to test its gas-sensitive property, adopt the ceramic pipe that is built-in with electric furnace heating wire.Electric furnace heating wire connects heating circuit, is used for improving the working temperature of sensor, and the platinum electrode at ceramic pipe two ends connects and adds volt circuit, is used for detecting the variation of ceramic pipe resistance.Utilize CeO 2-ZnO thick film surface is with absorption during acetone steam, and the principle that resistance can change with its concentration change detects the content of the acetone in the middle of environment.
The present invention compared with prior art has the following advantages:
(1) antijamming capability is strong.The sensitive gas great majority of gas sensor be take acetone steam as basis in the market, and all the other organic gass can produce interference to a certain extent.Such as, the acetone leak detector that Weihai Jing Niu panalarm company limited develops also can detect H simultaneously 2s, CO, O 2, SO 2, CL 2, HCN, NO 2, NH 3, PH 3, ETO, CLO 2, O 3, NO, selectivity is poor.The CeO that adopts the present invention to prepare 2-ZnO is single for the selectivity of acetone steam, is not substantially subject to the interference of other organic gass.
(2) preparation method is simple, and cost is low.The present invention adopts sol-gal process to prepare thick film, and room temperature can meet preparation condition.Select technological parameter of the present invention, can make gas sensor there is very high selectivity, sensitivity and stability to acetone.
(3) novel smearing method.Traditional thick film normally forms after colloid and spreads upon on ceramic pipe and anneal, the mode that the present invention adopts be first by colloid doping, annealing, clean, then mixes and spreads upon on ceramic pipe with methylcellulose, thus the performance of raising gas sensor.
Traditional handicraft: methylcellulose and powder mix, spreads upon on ceramic pipe 700 ℃ of annealing 3 hours;
New technology: 700 ℃ of annealing of powder 3 hours, and spread upon on ceramic pipe after methylcellulose ground and mixed;
Following table is that the ceramic pipe that adopts traditional handicraft, new technology to smear is tested respectively the sensitivity with isocyatic each gas:
? Acetone Methyl alcohol Ethanol Toluene Ammoniacal liquor
Tradition 6.789 0.764 26.218 1.895 1.006
New technology 2602.18 8.956 41.801 1.551 1.014
By contrast, can find, the new application process that the present invention adopts has greatly improved the sensitivity to gas.
Main application of the present invention: detect acetone steam and concentration thereof.
Accompanying drawing explanation
Figure 1 shows that the structure of element;
Figure 2 shows that test circuit;
Figure 3 shows that gas sensor test typical consequence figure;
Fig. 4 is the infrared spectrum of unprocessed pure ZnO powder;
Fig. 5 is the infrared spectrum of the pure ZnO powder of cleaning treatment after first annealing.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1:
1. prepare colloid: preparation Zn (OH) 2colloid reaction principle is:
Zn 2++2OH -1→Zn(OH) 2
Zn(CH 3COO) 2·2H 2O→Zn(C 2H 3O 2) -→Zn(OH) 2→ZnO
1. with deionized water, repeatedly clean beaker, glass bar, and dry in baking box;
2. the solvent of colloid is prepared in configuration: take respectively absolute ethyl alcohol 30ml and mix with deionized water 30ml, be stirred to evenly;
3. with counter balance, take respectively the Zn (CH of 3.512g 3cOO) 22H 2the NaOH of O and 1.28g, and with the above-mentioned solvent 20ml preparing, dissolve respectively respectively; Wherein, due to Zn (CH 3cOO) 22H 2o is not soluble in water, need put it into 100 ℃ of baking 10min of baking box, and stir into solution;
4. with stirring machine, stir Zn (CH 3cOO) 22H 2o solution, the about 100r/min of rotating speed, splashes into Zn (CH by NaOH solution with the speed of dripping of 0.1ml/min 3cOO) 22H 2o solution;
5. form colloid: after PH=7, continue to stir 1h, close stirrer, 24 hours post-dryings of standing colloid grind into powder A, the infrared spectrum that Fig. 4 is powders A.
2. clean colloid
1. repeatedly use washed with de-ionized water beaker, glass bar, and dry in baking box;
2. by muffle furnace 300 ℃ of annealing for powders A, and pour in deionized water and fully stir, the impurity in powder is dissolved completely.With filter paper sieve, stay the residue of comparatively pure powders A;
3. repeatedly clean 3 times, with baking box, dry, grind into powder B, Fig. 5 is the infrared spectrum of powder B;
From the contrast of Fig. 4 and Fig. 5, show through technique of the present invention, the powder purity of cleaning gained after first 300 ℃ of annealing in process is high, substantially at more than 700 peak values, obviously weakens, and that is to say that the interference of impurity obviously reduces, and the purity of ZnO improves.
3. doping
1. powder B and CeO 2powder mixes: by CeO 2(cerium oxide) is mixed in powder B according to percentage by weight 7 ω t%, and in mortar, potpourri fully ground;
2. the powder after mixed grinding is put into muffle furnace, 700 ℃ of annealing temperatures, constant temperature 3h, takes out and is required sample after cooling 10h;
3. with methylcellulose, mix in the ratio of 1:5 with sample, dropwise splash into deionized water and stir, becoming the sticking colloid of tool is coated in sample on ceramic pipe, and be welded on special-purpose pedestal, as shown in Figure 1, in ceramic pipe, place heating nickel filament, in order to heating ceramic pipe, nickel filament is connected with test circuit with heater circuit respectively with the platinum wire extraction electrode on ZnO film, in figure: ceramic pipe 1; Platinum wire 2 around pipe two ends; The ZnO thick film 3 that coating method is made; Be placed in the nickel chromium triangle heater strip 4 in ceramic pipe;
4. with HW-30A type air-sensitive tester, measure its gas-sensitive property, heating voltage is elected 6V as.(Rz is sensitive element resistance, and R is pull-up resistor, and R selects according to Rz size, and Vc is test loop service voltage to use circuit test shown in Fig. 2; Vout is the test voltage of output, and the service voltage that Vh is heating circuit, selects according to the heating-up temperature needing), result is shown in Fig. 3: to isocyatic acetone, ethanol, methyl alcohol, toluene, the sensitivity of formaldehyde ammonia is respectively: S=9634.23,554,1388,26,57,6.While measuring acetone, the response time of gas sensor of the present invention is 4 seconds, and be 2 seconds release time.This shows that gas sensor of the present invention has very strong selectivity to acetone, can get rid of the interference of measuring other common organic steams in atmosphere.
Embodiment 2:
1. prepare colloid:
1) with deionized water, repeatedly clean beaker, glass bar, and dry in baking box;
2) solvent of colloid is prepared in configuration: take respectively absolute ethyl alcohol 30ml and mix with deionized water 60ml, be stirred to evenly;
3) with counter balance, take respectively the Zn (CH of 3.512g 3cOO) 22H 2the NaOH of O and 2.46g, and with the above-mentioned solvent 20ml preparing, dissolve respectively respectively; Wherein, due to Zn (CH 3cOO) 22H 2o is not soluble in water, need put it into 100 ℃ of baking 10min of baking box, and stir into solution;
4) with stirring machine, stir Zn (CH 3cOO) 22H 2o solution, the about 100r/min of rotating speed, splashes into Zn (CH by NaOH solution with the speed of dripping of 0.08ml/min 3cOO) 22H 2o solution;
5) form colloid: after PH=6.5, continue to stir 2h, close stirrer, 24 hours post-dryings of standing colloid grind into powder A.
2. clean colloid
1. repeatedly use washed with de-ionized water beaker, glass bar, and dry in baking box;
2. by muffle furnace 300 ℃ of annealing for powders A, and pour in deionized water and fully stir, the impurity in powder is dissolved completely.With filter paper sieve, stay the residue of comparatively pure powders A;
3. repeatedly clean 3 times, with baking box, dry grind into powder B;
3. doping
1. powder B and CeO 2powder mixes: by CeO 2(cerium oxide) is mixed in powder B according to percentage by weight 7 ω t%, and in mortar, potpourri fully ground;
2. the powder after mixed grinding is put into muffle furnace, 500 ℃ of annealing temperatures, constant temperature 2.5h, takes out and is required sample after cooling 10h;
3. with methylcellulose, mix in the ratio of 1:5 with sample, dropwise splash into deionized water and stir, become the sticking colloid of tool sample is coated on ceramic pipe, and be welded on special-purpose pedestal, as shown in Figure 1;
4. with HW-30A type air-sensitive tester, measure its gas-sensitive property, heating voltage is elected 6V as.Gas sensor of the present invention has very strong selectivity to acetone, can get rid of the interference of measuring other common organic steams in atmosphere.
Embodiment 3:
1. prepare colloid:
1) with deionized water, repeatedly clean beaker, glass bar, and dry in baking box;
2) solvent of colloid is prepared in configuration: take respectively absolute ethyl alcohol 30ml and mix with deionized water 40ml, be stirred to evenly;
3) with counter balance, take respectively the Zn (CH of 3.512g 3cOO) 22H 2the NaOH of O and 3.08g, and with the above-mentioned solvent 20ml preparing, dissolve respectively respectively; Wherein, due to Zn (CH 3cOO) 22H 2o is not soluble in water, need put it into 100 ℃ of baking 10min of baking box, and stir into solution;
4) with stirring machine, stir Zn (CH 3cOO) 22H 2o solution, the about 100r/min of rotating speed, splashes into Zn (CH by NaOH solution with the speed of dripping of 0.12ml/min 3cOO) 22H 2o solution;
5) form colloid: after PH=7.4, continue to stir 1h, close stirrer, 24 hours post-dryings of standing colloid grind into powder A.
2. clean colloid
1. repeatedly use washed with de-ionized water beaker, glass bar, and dry in baking box;
2. by muffle furnace 300 ℃ of annealing for powders A, and pour in deionized water and fully stir, the impurity in powder is dissolved completely.With filter paper sieve, stay the residue of comparatively pure powders A;
3. repeatedly clean 3 times, with baking box, dry grind into powder B;
3. doping
1. powder B and CeO 2powder mixes: by CeO 2(cerium oxide) is mixed in powder B according to percentage by weight 7 ω t%, and in mortar, potpourri fully ground;
2. the powder after mixed grinding is put into muffle furnace, 900 ℃ of annealing temperatures, constant temperature 2.5h, takes out and is required sample after cooling 10h;
3. with methylcellulose, mix in the ratio of 1:4 with sample, dropwise splash into deionized water and stir, become the sticking colloid of tool sample is coated on ceramic pipe, and be welded on special-purpose pedestal, as shown in Figure 1;
4. with HW-30A type air-sensitive tester, measure its gas-sensitive property, heating voltage is elected 6V as.Gas sensor of the present invention has very strong selectivity to acetone, can get rid of the interference of measuring other common organic steams in atmosphere.
The present invention adopts sol-gal process to prepare gas sensor, and method is convenient, stable performance.The prepared gas sensor of the present invention only has sensitivity characteristic to acetone steam, for other common are machine steam (as ethanol, toluene, formaldehyde, gasoline etc.) substantially insensitive, can be in numerous mixing organic vapors, whether and concentration the existence that detects acetone steam.

Claims (1)

1. a zinc paste thick film gas-sensitive sensor preparation method with acetone selectivity characteristic, is characterized in that, according to following step, carries out:
A. prepare Zn (OH) 2colloid: take respectively absolute ethyl alcohol and mix with deionized water, absolute ethyl alcohol and deionized water volume ratio are: 1:0.5-1:2 is stirred to evenly; With counter balance, take respectively Zn (CH 3cOO) 22H 2o and NaOH, Zn (CH 3cOO) 22H 2the mol ratio of O and NaOH is 1:1-1:3 and with the above-mentioned solvent 20ml preparing, dissolves respectively respectively; With stirring machine, stir Zn (CH 3cOO) 22H 2o solution, the about 80r/min-100r/min of rotating speed, splashes into Zn (CH by NaOH solution with the speed of dripping of 0.05ml/min-0.12ml/min 3cOO) 22H 2o solution; After PH=6.5-7.4, continue to stir 1-3h, close stirrer, 24 hours post-dryings of standing colloid also grind to form Zn (OH) 2colloid powder;
B. by the Zn obtaining (OH) 2colloid carries out ageing, condensing, baking obtains Zn (OH) 2gel;
C. by gel being cleaned, is dried fine grinding again with deionized water or ethanol after the abundant fine grinding heating of gel piece, be powder, and cerium oxide is mixed in gel powder according to percentage by weight 6 ω t%-8 ω t%, mixed-powder is put into muffle furnace, 500 ℃-900 ℃ of annealing temperatures, constant temperature 2.5-3h;
D. by the mixed-powder after above-mentioned mixing annealing and methylcellulose by weight the ratio of 1:3-1:5 mix, be then coated in the sintering of annealing on ceramic pipe, there is the zinc paste thick film gas-sensitive sensor of acetone selectivity characteristic.
CN201210309003.4A 2012-08-28 2012-08-28 Preparation method for zinc oxide thick-film gas sensitivity sensor with acetone selectivity characteristic Expired - Fee Related CN102830139B (en)

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