CN103063722B - Solid calcium ion electrode based on conductive polyaniline and preparing method thereof - Google Patents
Solid calcium ion electrode based on conductive polyaniline and preparing method thereof Download PDFInfo
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- CN103063722B CN103063722B CN201210537962.1A CN201210537962A CN103063722B CN 103063722 B CN103063722 B CN 103063722B CN 201210537962 A CN201210537962 A CN 201210537962A CN 103063722 B CN103063722 B CN 103063722B
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Abstract
The invention discloses a solid calcium ion electrode based on conductive polyaniline and a preparing method thereof. The solid calcium ion electrode comprises a metal wire, the conductive polyaniline, soluble conductive polyaniline, calcium ion sensitive film and a heat shrink tube, wherein a layer of the conductive polyaniline is electroplated on the surface of the lower portion of the metal wire, a layer of the soluble conductive polyaniline is wrapped on the outer surface of the conductive polyaniline, the calcium ion sensitive film is wrapped on the outer surface of the soluble conductive polyaniline, and the heat shrink tube is wrapped on a portion located in the middle of the metal wire and with a distance greater than 0.5-1cm from the end portion of the calcium ion sensitive film. The solid calcium ion electrode based on the conductive polyaniline has the advantages of being high in mechanical strength, large in toughness, high in sensitivity, small in size, quick in detection response, low in detection limit, long in service life and the like. When matched with a solid reference electrode for use, the solid calcium ion electrode based on the conductive polyaniline is applicable to on line detection and long-term in situ monitoring of calcium ion content in seawater, aquaculture water and chemistry or chemical industry water mediums.
Description
Technical field
The present invention relates to electrochemical detection technology, relate in particular to a kind of solid calcium ion electrode based on electrically conductive polyaniline and preparation method thereof.
Background technology
In water body, calcium ion content is the important parameter that carries out water quality assessment, and for the activity of understanding organism in water, microorganism, and Water Pollution Monitoring is significant.Business calcium ion electrode for this type of object all belongs to liquid membrane electrode at present, and electrode interior need to fill electrolyte solution, i.e. and so-called " salt bridge ", its effect is the response signal that conduction detects between ion sensitive membrane and plain conductor.The major defect of liquid film type electrode comprises: volume more greatly, more fragile, easily there is signal drift, serviceable life is short.
Compare with traditional liquid film type electrode, solid electrode has that volume is little, intensity is high, and the comprehensive advantages such as long service life, are suitable for natural water body, especially the long term monitoring of marine environment and online observation.The present invention is directed to this demand and proposed a kind of solid calcium ion electrode based on electrically conductive polyaniline and preparation method thereof.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of solid calcium ion electrode based on electrically conductive polyaniline and preparation method thereof is provided.
The object of the invention is to be achieved through the following technical solutions:
Solid calcium ion electrode based on electrically conductive polyaniline comprises tinsel, electrically conductive polyaniline, fusible conductive polyaniline, calcium ion sensitive membrane, heat-shrink tube, tinsel lower surface is electroplated one deck electrically conductive polyaniline, the coated one deck fusible conductive polyaniline of outside surface at electrically conductive polyaniline, outside surface at fusible conductive polyaniline is coated with again calcium ion sensitive membrane, and in the middle part of tinsel and be, 0.5～1 centimetre away from calcium ion sensitive membrane end above part outside is coated with heat-shrink tube.
Described tinsel is Ag, Au, Pt, or surface is coated with copper wire or the nickel wire of Ag, Au, Pt metal film.Described fusible conductive polyaniline be tinsel in the hydrochloric acid solution of aniline monomer, electroplate to form.Described fusible conductive polyaniline is that mol ratio is the aniline of 1:5～5:1 and the doped hydrochloride multipolymer of 2.5-dimethoxyaniline.
The preparation method's of the solid calcium ion electrode based on electrically conductive polyaniline step is as follows:
1) by length, be the tinsel of 5～15 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1～2M watery hydrochloric acid, removes oxide, then with dry after deionized water ultrasonic cleaning;
2) aniline and hydrochloric acid are mixed with to the aniline hydrochloride solution of 0.5～1M by the mol ratio of 1:1, or by aniline hydrochloride chip solid, are dissolved in deionized water, make the aniline hydrochloride solution of 0.5～1M; By CHI760D electrochemical workstation, by cyclic voltammetry, on top layer wiry, electroplate one deck electrically conductive polyaniline; Wherein, scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel is done anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 0.5～1M, continuous sweep 10 ~ 20 circulations, have electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) get 5 to 50 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline, with N, dinethylformamide is that solvent is mixed with saturated solution, with the electrode that is coated with electrically conductive polyaniline, dip rapidly the N of soluble polyaniline, dinethylformamide saturated solution, is inserted in the crucible that fills sand, in 80～150 ℃ of baking ovens, dries 4～6 hours.
4) Calcium ionophore of Sigma company and film forming agent, plastifier, negative ion impedance agent are dissolved in DMF, are mixed with mixed solution, its composition is respectively by percentage to the quality:
Form A:
Calcium ionophore II 1.0%;
Four (4-chlorphenyl) potassium borate 0.6%;
2-nitrobenzene octyl ether 65.6%;
PVC 32.8% ；
Form B:
Calcium ionophore IV 1.0%;
Four (4-chlorphenyl) potassium borate 0.28%;
2-nitrobenzene octyl ether 65.82%;
PVC 32.9% ；
Form C:
Calcium ionophore V 1.0%;
Four (4-chlorphenyl) potassium borate 0.9%;
2-nitrobenzene octyl ether 66.0%;
PVC 31.1% ；
5) with the surperficial electrode that is coated with soluble polyaniline, dip mixed solution 1～3 time, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains calcium ion sensitive membrane after volatilizing completely;
6) heat-shrink tube is coated on to tinsel middle part and more than 0.5～1 centimetre away from the calcium ion sensitive membrane end part be.
Exploring electrode volume of the present invention is little, highly sensitive, and probe response is fast, has very high physical strength and toughness, has good serviceability under condition of high voltage.Therefore be applicable to the calcium ion content in seawater, breeding water and chemistry, chemical industry aqueous medium to survey online and long-term in-situ monitoring, compare with traditional sampling analysis, both alleviated working strength, avoided the secondary pollution in sampling process, improved again the real-time of data, reliability.
accompanying drawing explanation:
Fig. 1 is the structural representation of the solid calcium ion electrode based on electrically conductive polyaniline;
In figure: tinsel 1, electrically conductive polyaniline 2, fusible conductive polyaniline 3, calcium ion sensitive membrane 4, heat-shrink tube 5.
Embodiment
Solid calcium ion electrode based on electrically conductive polyaniline comprises tinsel 1, electrically conductive polyaniline 2, fusible conductive polyaniline 3, calcium ion sensitive membrane 4, heat-shrink tube 5, tinsel 1 lower surface is electroplated one deck electrically conductive polyaniline 2, the coated one deck fusible conductive polyaniline 3 of outside surface at electrically conductive polyaniline 2, outside surface at fusible conductive polyaniline 3 is coated with again calcium ion sensitive membrane 4, tinsel 1 middle part and 0.5～1 centimetre away from calcium ion sensitive membrane 4 end above part outside is coated with heat-shrink tube 5 be.
Described tinsel 1 is Ag, Au, Pt, and its effect is that the response signal that electrode surface is formed by Calcium ionophore passes to detection circuit.Recommendation noble metal, the undesired signal that can avoid the dissolved constituent in tinsel self and water body to form because of electrochemical reaction.For reducing costs, can use copper wire, nickel wire that surface is coated with Ag, Au, Pt as electrode base material.
Described electrically conductive polyaniline 2 be tinsel 1 in the hydrochloric acid solution of aniline monomer, electroplate to form.Conductive polyaniline film 2 has good electric conductivity, and the electric current conduction between the two does not exist obvious interlayer barrier; In addition, conductive polyaniline film has changed surface nature wiry, has increased the affinity between the organic coating layer of it and follow-up formation.
Described fusible conductive polyaniline 3 is that mol ratio is the aniline of 1:5～5:1 and the doped hydrochloride multipolymer of 2.5-dimethoxyaniline.The doped hydrochloride multipolymer of aniline and 2,5-dimethoxyaniline can be used commercial product, also can oneself be synthetic, and its chemical synthesis process is consistent with polyaniline, is aniline and 2,5-dimethoxyaniline to be pressed to the mixture replacing aniline of 5:1 to 1:5.
Use the doped hydrochloride multipolymer of aniline and 2,5-dimethoxyaniline to there are triple effects:
it has electric conductivity as electrically conductive polyaniline;
the plated conductive polyaniline composition of it and internal layer approaches, and chemical affinity is strong;
it and outermost layer Calcium ionophore can be dissolved in DMF, thereby can be partly dissolved in the process of coated Calcium ionophore, make calcium ion sensitive membrane and soluble polyaniline close contact, conductive impairment between eliminating layer.
The preparation method's of the solid calcium ion electrode based on electrically conductive polyaniline step is as follows:
1) by length, be the tinsel 1 of 5～15 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1～2M watery hydrochloric acid, removes oxide, then with dry after deionized water ultrasonic cleaning;
2) aniline and hydrochloric acid are mixed with to the aniline hydrochloride solution of 0.5～1M by the mol ratio of 1:1, or by aniline hydrochloride chip solid, are dissolved in deionized water, make the aniline hydrochloride solution of 0.5～1M; By CHI760D electrochemical workstation, by cyclic voltammetry, on the top layer of tinsel 1, electroplate one deck electrically conductive polyaniline 2; Wherein, scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel 1 is done anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 0.5～1M, continuous sweep 10 ~ 20 circulations, have electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) get 5 to 50 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline, with N, dinethylformamide is that solvent is mixed with saturated solution, with the electrode that is coated with electrically conductive polyaniline 2, dip rapidly the N of soluble polyaniline, dinethylformamide saturated solution, is inserted in the crucible that fills sand, in 80～150 ℃ of baking ovens, dries 4～6 hours;
4) Calcium ionophore of Sigma company and film forming agent, plastifier, negative ion impedance agent are dissolved in DMF, are mixed with mixed solution, its composition is respectively by percentage to the quality:
Form A:
Calcium ionophore II 1.0%;
Four (4-chlorphenyl) potassium borate 0.6%;
2-nitrobenzene octyl ether 65.6%;
PVC 32.8% ；
Form B:
Calcium ionophore IV 1.0%;
Four (4-chlorphenyl) potassium borate 0.28%;
2-nitrobenzene octyl ether 65.82%;
PVC 32.9% ；
Form C:
Calcium ionophore V 1.0%;
Four (4-chlorphenyl) potassium borate 0.9%;
2-nitrobenzene octyl ether 66.0%;
PVC 31.1% ；
5) with the surperficial electrode that is coated with soluble polyaniline 3, dip mixed solution 1～3 time, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains calcium ion sensitive membrane 4 after volatilizing completely; Vacuum drying under recommendation normal temperature, avoids using hyperthermia drying, is in order better to protect the activity of calcium ion sensitive membrane.
6) heat-shrink tube 5 is coated on to tinsel 1 middle part and more than 0.5～1 centimetre away from the calcium ion sensitive membrane 4 ends part be.
Embodiment 1
1) by length, be the tinsel 1 of 10 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1M watery hydrochloric acid, removes oxide, then with dry after deionized water ultrasonic cleaning;
2) take 1.9439g commodity aniline hydrochloride chip solid, be dissolved in 15ml deionized water, make the aniline hydrochloride solution of 1M; By CHI760D electrochemical workstation, by cyclic voltammetry, on the top layer of tinsel 1, electroplate one deck electrically conductive polyaniline 2.
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel 1 is done anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulations, have electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) take 35 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline (mol ratio of the two is 5:1), be dissolved in and in 10mlDMF, be mixed with saturated solution, with the electrode that surface is coated with electrically conductive polyaniline 2, dip rapidly the N of soluble polyaniline, dinethylformamide (DMF) saturated solution, be inserted in the crucible that fills sand, in 80 ℃ of baking ovens, dry 6 hours.
4) Calcium ionophore and attached component thereof are dissolved in DMF according to forming A, are mixed with mixed solution, its composition A is by percentage to the quality:
Calcium ionophore (Calcium ionophore II) 1.0%,
Four (4-chlorphenyl) potassium borate (Potassium tetrakis (4-chlorophenyl) borate) 0.6%,
2-nitrobenzene octyl ether (2-Nitrophenyl octyl ether) 65.6%,
PVC(Poly(vinyl chloride) high molecular weight)32.8% ；
5) with the surperficial electrode that is coated with soluble polyaniline 3, dip fast mixed solution, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains calcium ion sensitive membrane 4 after volatilizing completely;
6) heat-shrink tube 5 is coated on to tinsel 1 middle part and more than 0.5 centimetre away from the calcium ion sensitive membrane 4 ends part be.
Embodiment 2
1) by length, be the tinsel 1 of 8 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 2M watery hydrochloric acid, removes oxide, then with dry after deionized water ultrasonic cleaning;
2) take respectively 10.1388g hydrochloric acid, 9.313g aniline, in 100ml volumetric flask, add water to the solution that scale obtains hydrochloric acid: aniline=1M:1M; By CHI760D electrochemical workstation, by cyclic voltammetry, on the top layer of tinsel 1, electroplate one deck electrically conductive polyaniline 2;
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel 1 is done anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulations, have electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) take 35 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline (mol ratio of the two is 1:1), be dissolved in and in 10mlDMF, be mixed with saturated solution, with the electrode that surface is coated with electrically conductive polyaniline 2, dip rapidly the DMF saturated solution of soluble polyaniline, be inserted in the crucible that fills sand, in 100 ℃ of baking ovens, dry 5 hours.
4) Calcium ionophore and attached component thereof are dissolved in DMF according to forming A, are mixed with mixed solution, its composition A is by percentage to the quality:
Calcium ionophore (Calcium ionophore II) 1.0%,
Four (4-chlorphenyl) potassium borate (Potassium tetrakis (4-chlorophenyl) borate) 0.6%,
2-nitrobenzene octyl ether (2-Nitrophenyl octyl ether) 65.6%,
PVC(Poly(vinyl chloride) high molecular weight)32.8% ；
5) with the surperficial electrode that is coated with soluble polyaniline 3, dip fast mixed solution, repeat once, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains calcium ion sensitive membrane 4 after volatilizing completely;
6) heat-shrink tube 5 is coated on to tinsel 1 middle part and more than 0.8 centimetre away from the calcium ion sensitive membrane 4 ends part be.
Embodiment 3
1) by length, be the tinsel 1 of 10 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1M watery hydrochloric acid, removes oxide, then with dry after deionized water ultrasonic cleaning;
2) take 0.9720g commodity aniline hydrochloride chip solid, be dissolved in 15ml deionized water, make the aniline hydrochloride solution of 0.5M; By CHI760D electrochemical workstation, by cyclic voltammetry, on the top layer of tinsel 1, electroplate one deck electrically conductive polyaniline 2;
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel 1 is done anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulations, have electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) take 35 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline (mol ratio of the two is 5:1), be dissolved in and in 10mlDMF, be mixed with saturated solution, with the electrode that surface is coated with electrically conductive polyaniline 2, dip rapidly the DMF saturated solution of soluble polyaniline, be inserted in the crucible that fills sand, in 150 ℃ of baking ovens, dry 4 hours;
4) Calcium ionophore and attached component thereof are dissolved in DMF according to forming B, are mixed with mixed solution, its composition B is by percentage to the quality:
Calcium ionophore (Calcium ionophore IV) 1.0%,
Four (4-chlorphenyl) potassium borate (Potassium tetrakis (4-chlorophenyl) borate) 0.28%,
2-nitrobenzene octyl ether (2-Nitrophenyl octyl ether) 65.82%,
PVC(Poly(vinyl chloride) high molecular weight)32.9% ；
5) with the surperficial electrode that is coated with soluble polyaniline 3, dip fast mixed solution, repeat twice, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains calcium ion sensitive membrane 4 after volatilizing completely;
6) heat-shrink tube 5 is coated on to tinsel 1 middle part and more than 1 centimetre away from the calcium ion sensitive membrane 4 ends part be.
Embodiment 4
1) by length, be the tinsel 1 of 15 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1M watery hydrochloric acid, removes oxide, then with dry after deionized water ultrasonic cleaning;
2) take 1.9439g commodity aniline hydrochloride chip solid, be dissolved in 15ml deionized water, make the aniline hydrochloride solution of 1M; By CHI760D electrochemical workstation, by cyclic voltammetry, on the top layer of tinsel 1, electroplate one deck electrically conductive polyaniline 2;
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel 1 is done anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulations, have electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) take 35 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline (mol ratio of the two is 1:5), be dissolved in and in 10mlDMF, be mixed with saturated solution, with the electrode that surface is coated with electrically conductive polyaniline 2, dip rapidly the DMF saturated solution of soluble polyaniline, be inserted in the crucible that fills sand, in 150 ℃ of baking ovens, dry 4 hours;
4) Calcium ionophore and attached component thereof are dissolved in DMF according to forming C, are mixed with mixed solution, its composition C is by percentage to the quality:
Calcium ionophore (Calcium ionophore V) 1.0%,
Four (4-chlorphenyl) potassium borate (Potassium tetrakis (4-chlorophenyl) borate) 0.9%,
2-nitrobenzene octyl ether (2-Nitrophenyl octyl ether) 66.0%,
PVC(Poly(vinyl chloride) high molecular weight)31.1% ；
5) with the surperficial electrode that is coated with soluble polyaniline 3, dip fast mixed solution, repeat once, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains calcium ion sensitive membrane 4 after volatilizing completely;
6) heat-shrink tube 5 is coated on to tinsel 1 middle part and more than 0.5 centimetre away from the calcium ion sensitive membrane 4 ends part be.
Embodiment 5
The demarcation of solid calcium ion-selective electrode:
Preparation calcium ion standard solution mother liquor used is the 0.1M calcium ion standard solution that Sigma company produces, and thinning agent used is deionized water;
Pipette 10ml10
-1the calcium ion standard solution of M, is diluted to 100ml with deionized water, makes 10
-2the ionic calcium soln of M, dilution preparation 10 successively
-3m, 10
-4m, 10
-5m, 10
-6the ionic calcium soln of M.
The self-control calcium ion-selective electrode of take is working electrode, commodity Ag/AgCl electrode is contrast electrode, respectively working electrode and contrast electrode are connected to CHI760D electrochemical workstation, the response electric signal from high concentration toward low concentration sequentially determining, according to response signal intensity and concentration relationship mapping, the two linear relationship slope is between 27.9 ~ 31.9, and meeting can Si Tedinglv.
Claims (1)
1. a preparation method for the solid calcium ion electrode based on electrically conductive polyaniline, is characterized in that its step is as follows:
1) by length, be the tinsel (1) of 5～15 centimetres, first ultrasonic cleaning in acetone soln, removes surface and oil contaminant, then ultrasonic cleaning in 1～2M watery hydrochloric acid, removes oxide, then with dry after deionized water ultrasonic cleaning;
2) aniline and hydrochloric acid are mixed with to the aniline hydrochloride solution of 0.5～1M by the mol ratio of 1:1, or by aniline hydrochloride chip solid, are dissolved in deionized water, make the aniline hydrochloride solution of 0.5～1M; By CHI760D electrochemical workstation, by cyclic voltammetry, on the top layer of tinsel (1), electroplate one deck electrically conductive polyaniline (2); Wherein, scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4a/V; Tinsel (1) is done anode, and auxiliary electrode is Pt electrode, and contrast electrode is business Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 0.5～1M, continuous sweep 10 ~ 20 circulations, have electroplated the rear anhydrous alcohol drip washing electrode of using, stand-by after alcohol volatilization;
3) get 5 to 50 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline, aniline and 2 wherein, the mol ratio of the doped hydrochloride multipolymer of 5-dimethoxyaniline is 1:5,1:1,5:1, and the DMF of take is mixed with saturated solution as solvent, with the electrode that is coated with electrically conductive polyaniline (2), dip rapidly the N of soluble polyaniline, dinethylformamide saturated solution, is inserted in the crucible that fills sand, in 80～150 ℃ of baking ovens, dries 4～6 hours;
4) Calcium ionophore of Sigma company and film forming agent, plastifier, negative ion impedance agent are dissolved in DMF by component A or B component, are mixed with mixed solution, component A, B component are respectively by percentage to the quality:
Form A:
Calcium ionophore II 1.0%;
Four (4-chlorphenyl) potassium borate 0.6%;
2-nitrobenzene octyl ether 65.6%;
PVC 32.8% ；
Form B:
Calcium ionophore IV 1.0%;
Four (4-chlorphenyl) potassium borate 0.28%;
2-nitrobenzene octyl ether 65.82%;
PVC 32.9% ；
5) with the electrode that surface is coated with soluble polyaniline (3), dip mixed solution 1～3 time, be inserted on polyfoam, be placed in vacuum dryer vacuum drying 24 hours, until solvent obtains calcium ion sensitive membrane (4) after volatilizing completely;
6) heat-shrink tube (5) is coated on to tinsel (1) middle part and more than 0.5～1 centimetre away from calcium ion sensitive membrane (4) end part be.
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