CN100383517C - Process for making puncture composite sensor for measuring pH and sensor therefor - Google Patents
Process for making puncture composite sensor for measuring pH and sensor therefor Download PDFInfo
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- CN100383517C CN100383517C CNB2004100262833A CN200410026283A CN100383517C CN 100383517 C CN100383517 C CN 100383517C CN B2004100262833 A CNB2004100262833 A CN B2004100262833A CN 200410026283 A CN200410026283 A CN 200410026283A CN 100383517 C CN100383517 C CN 100383517C
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Abstract
The present invention discloses a method for preparing a puncture compound sensor used for measuring pH value and a senor thereof. The preparing method comprises the following steps: 1) antimony 3 of which the purity is greater than or equal to 99.99% is filled in a glass tube 2 stretched into a pH indicating electrode 1; 2) a silver wire of which the purity is greater than or equal to 99.9% is selected, agar powder and silver chloride (AgCl) powder are added to a saturated potassium chloride (KCl) solution so as to be made into gel 9 of internal filled liquid; the silver (Ag) wire is inserted into the gel of internal filled liquid and is made into a solid state bare silver-silver chloride reference electrode 8; 3) sensor assembly: the pH indicating electrode 1 of the sensor is stuck to the external wall of a sensor body 4, and is integrated into a whole along with the external wall, and the upper end of the indicating electrode 1 is connected with a conducting wire and is led to an indication joint 6 through the shielding wire 5 of the sensor main body 4; the reference electrode 8 and the gel 9 of internal filled liquid are arranged in the sensor body 4, and the reference electrode 8 is arranged in the gel 9 of internal filled liquid; the upper end of the reference electrode 8 is connected with the conducting wire and is led to a reference joint 7 through the shielding wire 5, and an inclined plane of which the inclination degree is less than or equal to 75 DEG is designed in the position of the tube opening at the lower end of the sensor.
Description
Technical field
The present invention relates to galvanochemistry pH value field tests, particularly a kind of preparation method and sensor thereof of measuring the pH value with the puncture compound sensor.
Background technology
The mensuration of pH value is fields such as chemistry, chemical industry, biology, environment, food, leather, papermaking and soil monitoring projects the most widely.At present, the method for measuring the pH value both at home and abroad all adopts glass electrode, and is confined to the mensuration of pH value of water solution fully.And all can't not have damaged mensuration by direct in-situ for object surfaces such as solid common in the above-mentioned field, semisolid, soil, pastel, macromolecule and colloid and inner pH value, and need to destroy behind the sample with a certain proportion of water-soluble pH value that extract is measured in the back of separating, leave standstill, filter, length consuming time, error is big.Therefore, the original position technology of directly measuring solid, semisolid, pastel, soil, fruits and vegetables, plant, fiber and organism surface and internal pH-values has become the research direction that pH in recent years measures.
The present research of calling both at home and abroad is existing pH glass electrode is made tapered all-solid-state pH glass electrode, but still the shortcoming of unresolved glass-film cracky and the high internal resistance of vitreous electricity, and because the cone-shaped glass film makes internal resistance higher, thereby causes degree of accuracy lower.And common antimony electrode is also because of the preparation technology and the purity of electrode are limited at present, because employed antimony is for smelting antimony during preparation, the purity of antimony≤99%, and adopt direct wire drawing to form, and there is not a support of glass tube, fragile, cause measuring accuracy low, cause it only can be used for the pH Potential Titration Analysis.
In addition, in the contrast electrode of prior art, mercurous chloride electrode is arranged, its shortcoming is to use the temperature can only be being lower than below 75 ℃, and when temperature was higher than 75 ℃, disproportionation reaction can take place mercurous chloride electrode, caused current potential to change, and was difficult to work; Shortcomings such as electrodeposition-type silver-silver chloride contrast electrode then exists coating easily to peel off, and serviceable life is short, and same batch of prepared electrode also there is some difference, thereby influence its usable range.
Summary of the invention
Shortcoming such as the objective of the invention is to overcome existing cracky in the above-mentioned prior art, internal resistance height, precision is low, serviceable life is short, preparation method and a kind of mensuration pH value puncture compound sensor of a kind of pH of mensuration value with the puncture compound sensor is provided, finish in the prior art the field that can't realize, but original position is directly measured the pH value of objects such as solid or semi-solid surface and inside, pastel, colloid, soil.
Purpose of the present invention is finished by the following technical solutions: mensuration pH value comprises the steps: with the preparation method of puncture compound sensor
1) preparation pH indicator electrode (1):
Containing≤1% boron or contain≤glass tube (2) of 1% lead in, this glass tube is used for the blowing bulb, fill the antimony grain (3) of purity 〉=99.99%, to the antimony grain be housed and contain boron or plumbous glass tube heating, be stretched to diameter of phi=1～2mm with glass tube, when it cooled off, it was antimony-glass bar that antimony and glass tube are combined as a whole, and became pH indicator electrode (1); Its wall thickness of glass tube≤1mm, internal diameter 3～4mm;
2) preparation of bareing silver-silver chloride contrast electrode (8):
A, select the filamentary silver of diameter 1～2mm purity 〉=99.9% for use, remove oxide layer and greasy dirt, and successively through the NaOH NaOH of 1mol/L solution, 99% acetone soln, 99% ethanolic solution and deionized water, it is stand-by that cleaning processing is carried out on its surface;
B, at room temperature adds the 4g agar powder and adds silver chloride AgCl powder 1g in the saturated potassium chloride (KCl) solution of 100mL, make it reach precipitation, and stirs and promptly make internal-filling liquid gel (9);
C, internal-filling liquid gel (9) is heated to boiling, under this temperature, be injected in the sensor main body glass tube (4), insert and add the 4g agar powder in the saturated potassium chloride (KCl) solution of 100mL in the main body glass tube (4) and add in the internal-filling liquid gel (9) that silver chloride AgCl powder 1g makes handling clean stand-by silver-colored Ag silk then, internal-filling liquid gel (9) is gel when it is cooled to room temperature, filamentary silver is coated by it, makes solid-state bareing silver-silver chloride contrast electrode (8);
3) assembling sensor:
Intercept a segment length and be the pH indicator electrode (1) about 10cm, front end is processed into the inclined-plane kerf, and make the inclined-plane towards contrast electrode (8), pH indicator electrode (1) sticks on the straight outer wall of sensor main body glass tube (4), it is become one, with the same inclined-plane of two mouth of pipe place polishings, make it possess the puncture function into about 75 °.
Measure pH value puncture compound sensor, pH indicator electrode (1) sticks on the straight outer wall of sensor body (4) and with it and becomes one, the upper end of pH indicator electrode (1) connects lead and the shielding line (5) through sensor main body glass tube (4) causes indicator sub (6), it is characterized in that in sensor main body glass tube (4), also being provided with contrast electrode (8) and internal-filling liquid gel (9), contrast electrode (8) is arranged in the internal-filling liquid gel (9), its upper end connects lead and causes reference joint (7) through shielding line (5), at the mouth of pipe place of sensor lower end one about 75 ° inclined-plane is arranged.
PH sensor with preparation method's manufacturing of the present invention is compared with the pH glass electrode of prior art, and internal resistance is extremely low, and response is fast, and electrode performance is stable, long service life, and have the puncture function, when measuring the pH value, do not destroy the original.
Description of drawings
Fig. 1 is antimony-glass bar synoptic diagram;
Fig. 2 is an one-piece construction synoptic diagram of the present invention;
Fig. 3 is that the A of Fig. 2 is to enlarged drawing.
Embodiment
The present invention is based on the metal/metal oxide sensor and has advantages such as good rigidly, internal resistance is low, volume is little, response is fast, and expansion research is made.This principle of sensors is to use metal-metallic oxide as indicator electrode, by high pure metal antimony to the meeting of Nernst response relation, to H
+Ion produces response, and its Response Mechanism is:
Electrode potential can be expressed as:
Following formula can be rewritten in the time of 25 ℃:
Measure the theoretical foundation of pH value for antimony electrode.
And created the preparation technology of bareing silver-silver chloride contrast electrode.Be applicable to the pH pH-value determination pH under the high temperature, and avoided the coating of electrodeposition-type silver-silver chloride contrast electrode shortcoming such as easily to peel off.Improve the stability of electrode, widened the scope of application.
Antimony-glass bar synoptic diagram referring to Fig. 1, in the clean glass tube (2) of surface treated boracic≤1% or lead≤1%, wall thickness of glass tube≤1mm, internal diameter 3～4mm, put into the high-purity antimony (3) of purity 99.99%, the heating back is stretched to diameter of phi=1～2mm with glass tube (2), when it cools off, microdilatancy of antimony material and glass tube are combined into antimony-glass bar, also are pH indicator electrode (1).
Sensor construction synoptic diagram referring to Fig. 2, the present invention measures the pH value: pH indicator electrode (1) sticks on the straight outer wall of sensor main body glass tube (4) and with it and becomes one, the upper end of pH indicator electrode (1) connects lead and the shielding line (5) through sensor main body glass tube (4) causes indicator sub (6), bareing silver-silver chloride contrast electrode (8) is inserted in the internal-filling liquid gel (9), the upper end of contrast electrode (8) connects lead and leads to reference joint (7) through shielding line (5), and there is about 75 a ° inclined-plane at the mouth of pipe place that becomes one in the pH of sensor lower end indicator electrode (1) and sensor body (4).
The contrast electrode of this sensor (2) is a bareing Ag-AgCl electrode, can replace existing electrolysis-type Ag-AgCl electrode.The preparation of bareing silver-silver chloride Ag-AgCl contrast electrode (8) is a filamentary silver of selecting diameter 1～2mm for use, with abrasive paper for metallograph polishing filamentary silver surface, removes oxide layer; The filamentary silver that polishing is good after the NaOH NaOH of 0.1～1mol/L solution, 99% acetone soln, 99% ethanolic solution and deionized water surface cleaning are handled, is dried the surface with lens wiping paper and is got final product successively.
The preparation of internal-filling liquid gel (9) is under 25 ℃ of temperature, the 4g agar powder is joined in the saturated potassium chloride (KCl) solution of 100mL, and add 1g silver chloride AgCl powder, makes it reach precipitation, and stirs and make internal-filling liquid gel (9); Wherein saturated potassium chloride (KCl) and silver chloride AgCl and silver-colored Ag constitute reversible equilibrium system, and agar is for forming the medium of gel.
The internal-filling liquid gel (9) of above preparation is heated to 90 ℃, under this temperature, inject the glass tube of sensor main body (4), insert in the internal-filling liquid gel (9) of glass tube handling clean silver-colored Ag silk then, when it is cooled to room temperature when being gel, promptly make solid-state bareing silver-silver chloride contrast electrode (8); The above-mentioned pH indicator electrode of making (1), bareing silver-silver chloride contrast electrode (8) and internal-filling liquid gel (9) are assembled into mensuration pH value puncture compound sensor together.
At first intercept a segment length and be the pH indicator electrode (1) about 10cm, front end is processed into the inclined-plane kerf, with the inclined-plane towards bareing silver-silver chloride contrast electrode (8), pH indicator electrode (1) sticks on the straight outer wall of sensor main body glass tube (4), it is become one, with the same inclined-plane of two mouth of pipe place polishings, make it have the puncture function into about 75 °; Then, the shielding line (5) of lead through sensor body (4) that pH indicator electrode (1) upper end is connected causes indicator sub (6), and the lead that bareing silver-silver chloride contrast electrode (8) upper end is connected leads to reference joint (7) through shielding line (5).
The compound pH sensor of puncturing uses high-purity antimony (purity 〉=99.99%), makes the outer rigidity material that coats of antimony, as glass tube etc., and becomes the all-solid-state pH sensor with puncture function; Bareing silver-silver chloride Ag-AgCl contrast electrode, use purity is 99.9% filamentary silver, can replace existing plating type silver-silver chloride Ag-AgCl contrast electrode.Therefore, the present invention considers from the aspects such as structure, pre-service, preparation technology and aftertreatment of antimony and oxide thereof, the compound pH sensor physical strength height of preparation, response are soon, internal resistance is low, measuring accuracy is high, both having can be used for aqueous solution pH measures, can be used for Polymer Solution and colloidal solution pH again measures, more meaningfully can be used for directly measuring thing surface and inner pH such as solid and semisolid, also can be used for the pH potentiometric titration, solved the fields of measurement that the pH glass electrode can't be finished up hill and dale.
Embodiment
Getting one section 10cm contains≤1% boron glass pipe, this glass tube is used for the blowing bulb, 5 in the antimony of filling purity 〉=99.99%, to the antimony grain be housed and contain the glass tube heating of boron, be stretched to diameter of phi=2mm with glass tube, when it cooled off, it was antimony-glass bar that antimony and glass tube are combined as a whole, and becomes the pH indicator electrode; Its wall thickness of glass tube=0.5mm, internal diameter 3mm;
Select the filamentary silver of diameter 1mm purity 〉=99.9% for use, remove oxide layer and greasy dirt, and, cleaning is carried out on its surface handled stand-by successively through the NaOH NaOH of 1mol/L solution, 99% acetone soln, 99% ethanolic solution and deionized water;
Under 25 ℃, in the saturated potassium chloride (KCl) solution of 100mL, add the 4g agar powder and add silver chloride AgCl powder 1g, make it reach precipitation, and stir and promptly make the internal-filling liquid gel;
C, the internal-filling liquid gel is heated to boiling, 90 ℃ of temperature, under this temperature, be injected in the sensor main body glass tube, then in the internal-filling liquid gel of handling in the clean stand-by silver-colored Ag silk insertion glass tube, the internal-filling liquid gel is gel when it is cooled to room temperature, filamentary silver is coated by it, makes solid-state bareing silver-silver chloride contrast electrode;
Getting a segment length is the pH indicator electrode of 10cm, front end is processed into the inclined-plane kerf, and make the inclined-plane towards bareing silver-silver chloride contrast electrode, the pH indicator electrode sticks on the straight outer wall of sensor main body glass tube, it is become one, with the same inclined-plane of two mouth of pipe place polishings, make it possess the puncture function into about 75 °.
This compound pH sensor preparation of puncturing is finished.
The invention effect
Test by to the compound pH sensor that punctures has obtained good measurement effect.The following table data are test result:
The accuracy of the compound pH sensor of table 1 puncture
This table as can be seen, the compound pH sensor that punctures is differing in the 0.05pH value in relatively with theoretical value and glass electrode, degree of accuracy is higher.
The compound pH sensor response slope of table 2 puncture
As can be seen from the table, the response slope of the compound pH sensor that punctures and stripped deviation meet the electrode requirement in 5mV
The compound pH sensor stability test of table 3 puncture (mV)
In the table as can be seen, the stability of the compound pH sensor that punctures better, as the drift of spending the night is in the 3mV, and it is good to reappear row, the deviation of each electrode is little.
Comparing result with prior art:
The present invention is widely used, and except that alternative pH glass electrode is used for the mensuration of pH value of water solution, also can finish its unmeasured field, and the results of comparison that the present invention and pH glass electrode are measured actual samples is listed in the table below.
The contrast test result of table 4 compound pH sensor of puncture and pH glass electrode
In the last table, the compound pH sensor that punctures can be finished the test event that many glass electrodes can't be finished, and as toothpaste, glass electrode can't be measured, and the compound pH sensor that punctures then can be finished.
Claims (2)
1. a preparation method who measures the pH value with the puncture compound sensor is characterized in that: comprise the steps:
1) preparation pH indicator electrode (1):
At boracic or leaded wall thickness≤1mm, in internal diameter=3～4mm glass tube (2), fill the antimony grain (3) of purity 〉=99.99%, to the antimony grain be housed and contain boron or plumbous glass tube heating, be stretched to diameter of phi=1～2mm with glass tube, when its cooling, it is antimony-glass bar that antimony and glass tube are combined as a whole, and becomes pH indicator electrode (1);
2) preparation of bareing silver-silver chloride contrast electrode (8):
A, select the filamentary silver of diameter 1～2mm purity 〉=99.9% for use, remove oxide layer and greasy dirt, and successively through the NaOH NaOH of 1mol/L solution, 99% acetone soln, 99% ethanolic solution and deionized water, it is stand-by that cleaning processing is carried out on its surface;
B, at room temperature adds the 4g agar powder and adds silver chloride AgCl powder 1g in the saturated potassium chloride (KCl) solution of 100mL, make it reach precipitation, and stirs and promptly make internal-filling liquid gel (9);
C, internal-filling liquid gel (9) is heated to boiling, under this temperature, be injected in the sensor main body glass tube (4), then in the internal-filling liquid gel of handling in the clean stand-by silver-colored Ag silk insertion sensor main body glass tube (4) (9), internal-filling liquid gel (9) is gel when it is cooled to room temperature, filamentary silver is coated by it, makes solid-state bareing silver-silver chloride contrast electrode (8);
3) assembling sensor:
Intercept a segment length and be the pH indicator electrode (1) about 10cm, front end is processed into the inclined-plane kerf, and make the inclined-plane towards contrast electrode (8), pH indicator electrode (1) sticks on the straight outer wall of sensor main body glass tube (4), it is become one, with the same inclined-plane of two mouth of pipe place polishings, make it possess the puncture function into about 75 °.
2. a mensuration pH value of being made by claim 1 method is with the puncture compound sensor, pH indicator electrode (1) sticks on the straight outer wall of sensor main body glass tube (4) and with it and becomes one, the upper end of pH indicator electrode (1) connects lead and the shielding line (5) through sensor main body glass tube (4) causes indicator sub (6), it is characterized in that, bareing silver-silver chloride contrast electrode (8) is arranged in the internal-filling liquid gel (9), its upper end connects lead and causes reference joint (7) through shielding line (5), at the mouth of pipe place of sensor lower end one about 75 ° inclined-plane is arranged.
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| CNB2004100262833A CN100383517C (en) | 2004-06-29 | 2004-06-29 | Process for making puncture composite sensor for measuring pH and sensor therefor |
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| CNB2004100262833A CN100383517C (en) | 2004-06-29 | 2004-06-29 | Process for making puncture composite sensor for measuring pH and sensor therefor |
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| CN100383517C true CN100383517C (en) | 2008-04-23 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422728C (en) * | 2006-03-28 | 2008-10-01 | 浙江大学 | Metal antimony oxide electrode and method for tracking and detecting medium pH change |
| CN105628757A (en) * | 2015-12-30 | 2016-06-01 | 中国科学院电子学研究所 | ORP sensing chip based on MEMS and manufacturing method of ORP sensing chip |
| CN107084919A (en) * | 2017-04-10 | 2017-08-22 | 武汉理工大学 | A kind of preparation method of metallic bipolar plate materials decay resistance test reference electrode |
| US11815487B2 (en) * | 2020-11-11 | 2023-11-14 | Rosemount Inc. | Solid state reference gel |
| US20220205946A1 (en) * | 2020-12-28 | 2022-06-30 | Rosemount Inc. | Gamma-irradiation-compatible reference gel |
| CN114184654B (en) * | 2021-12-10 | 2024-01-05 | 中国科学院空天信息创新研究院 | Miniature all-solid-state pH sensor and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1418233A (en) * | 1973-04-23 | 1975-12-17 | Harco Electr Ltd | Antimony electrodes and method of manufacturing same |
| DE4220140A1 (en) * | 1992-06-19 | 1993-12-23 | Prominent Dosiertechnik Gmbh | Silver@-silver halide reference electrode prepn. for long life - by in-situ pptn. of silver halide, for amperometric and potentiometric two and three electrode probes with gel type or polymer electrolyte, monomer and/or prepolymer, etc. |
| CN1098503A (en) * | 1993-07-31 | 1995-02-08 | 福建星光造纸集团公司 | A kind of application of modified acidometer |
-
2004
- 2004-06-29 CN CNB2004100262833A patent/CN100383517C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1418233A (en) * | 1973-04-23 | 1975-12-17 | Harco Electr Ltd | Antimony electrodes and method of manufacturing same |
| DE4220140A1 (en) * | 1992-06-19 | 1993-12-23 | Prominent Dosiertechnik Gmbh | Silver@-silver halide reference electrode prepn. for long life - by in-situ pptn. of silver halide, for amperometric and potentiometric two and three electrode probes with gel type or polymer electrolyte, monomer and/or prepolymer, etc. |
| CN1098503A (en) * | 1993-07-31 | 1995-02-08 | 福建星光造纸集团公司 | A kind of application of modified acidometer |
Non-Patent Citations (2)
| Title |
|---|
| 溶胶-凝胶包埋法制备银离子选择电极的研究. 王大伟，黄西潮，刘亚强.理化检验-化学分册，第38卷第10期. 2002 * |
| 酶电极法测定肌苷注射液中肌苷含量. 孙士青，葛淑兰，王宁.中国药学杂志，第35卷第6期. 2000 * |
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