CN1493874A - Integrated type dissolved oxygen, PH and salinity sensor and its manufacturing method and use method - Google Patents
Integrated type dissolved oxygen, PH and salinity sensor and its manufacturing method and use method Download PDFInfo
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- CN1493874A CN1493874A CNA031506682A CN03150668A CN1493874A CN 1493874 A CN1493874 A CN 1493874A CN A031506682 A CNA031506682 A CN A031506682A CN 03150668 A CN03150668 A CN 03150668A CN 1493874 A CN1493874 A CN 1493874A
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- electrode
- dissolved oxygen
- solution
- agcl
- salinity sensor
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- 239000001301 oxygen Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title 1
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 31
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000010944 silver (metal) Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 239000010946 fine silver Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000005684 electric field Effects 0.000 abstract description 6
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WFLRGOXPLOZUMC-UHFFFAOYSA-N [Li].O=C=O Chemical compound [Li].O=C=O WFLRGOXPLOZUMC-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
An integrated dissolved oxygen, pH and salinity sensor is composed of working Ir/IrO2 electrode, reference Ag/AgCl electrode, metallic anode and metallic cathode. Its application method features that when external electric field is cut off, the potential difference V1 between said working electrode and reference electrode is relative to the pH value of the solution to be measured, and when an external electric field is applied, the electric resistance of the solution between said anode and cathode is relative to the salinity of said solution while said potential difference is changed from V1 to V2. The V2-V1 is relative to the content of oxygen dissolved in solution.
Description
Technical field
The present invention relates to a kind of integrated form dissolved oxygen DO, pH and salinity sensor and making and using method.
Background technology
Acidity of Aikalinity, salinity and dissolved oxygen content are the important parameters of reacting solution character.In Environmental Studies, and fields such as chemistry, chemical industry need measure dissolved oxygen DO, pH value and salinity in the water body usually simultaneously, need to use different instruments measure these parameters at present, i.e. dissolved oxygen instrument, pH meter and conductivity meter.Not only equipment investment is big to use three instruments, and manipulation strength and maintenance cost are also high.Because what traditional dissolved oxygen instrument used is the Clarke type electrode, be that the activity of component to be measured is reflected on the strength of current between the electrode, what pH meter used is this special type electrode of energy, the activity of component to be measured is embodied on the potential difference (PD) between the electrode, salinity then and between the electrode resistivity of solution relevant.Difficulty is very big technically with the integrated use of this three classes electrode.
Summary of the invention
The purpose of this invention is to provide a kind of integrated form dissolved oxygen DO, pH and salinity sensor and making and using method.
Integrated form dissolved oxygen DO, pH and salinity sensor include Ir/IrO
2Electrode, Ag/AgCl contrast electrode, metal anode and metallic cathode.
The method for making of integrated form dissolved oxygen DO, pH and salinity sensor is that four electrode spread are in line Ir/IrO
2Electrode and Ag/AgCl contrast electrode are positioned at the inboard, metal anode and metallic cathode are positioned at the outside, at a distance of 1～10 millimeter, with epoxy resin or other cementing agent they are fixed on (5) on the insulativity sheet material between each electrode, the lead of electrode coats with the teflon heat-shrink tube.
The using method step of integrated form dissolved oxygen DO, pH and salinity sensor is as follows:
1) compound electrode is inserted solution to be measured, measure Ir/IrO with millivoltmeter (6)
2Potential difference (PD) between electrode and the Ag/AgCl contrast electrode position is designated as V
1, V
1The pH value that has reflected solution;
2) Closing Switch (7) records resistance R between metal anode (3) and the metallic cathode (4) by microhmmeter, and the size of R has reflected the salinity of solution;
3) energising was read potential difference (PD) V after 30～60 seconds on millivoltmeter (6)
2, V
2With V
1Difference be designated as Δ V, Δ V has reacted dissolved oxygen content in the solution;
4) cut-off switch (7), the potential difference (PD) on millivoltmeter this moment (6) is returned to V
1
Advantage of the present invention is, all exploring electrodes are the all-metal solid-state structure, and volume is tiny, has very high physical strength and toughness, has good working performance under the temperature of broadness, pressure condition.The shared four one metal wire electrodes of sensor can be measured dissolved oxygen DO, pH value and the salinity of solution simultaneously, help the miniaturization and the microminiaturization of detection instrument.The integrated sensor of this height is at the industrial sector that relates to the High Temperature High Pressure hydrothermal system, the above-critical state waste disposal, and there is irreplaceable using value in fields such as the online detection of extreme environment geologic function and physical environment and long term monitoring.
Description of drawings
Accompanying drawing is the structural representation of integrated form dissolved oxygen DO, pH and salinity sensor, among the figure: 1.Ir/IrO
2Electrode; 2.Ag/AgCl electrode; 3. metal anode; 4. metallic cathode; 5. insulcrete; 6. millivoltmeter; 7. switch; 8. microhmmeter; 9.2.4～9V direct supply.
Embodiment
Integrated form dissolved oxygen DO, pH and salinity sensor and making thereof and using method Ir/IrO
2Electrode is one section iridium wire, and the surface has coated active IrO
2Film, it can be the commercial goods, also can make by the following method:
1) cut-off directly is 0.1～0.5 millimeter a iridium wire, is cut into 1-3 centimetre length, places the crucible that fills the lithium carbonate powder, crucible is put into muffle furnace be heated to 750～850 ℃, and constant temperature 3～6 hours;
2) take out be chilled to room temperature after, with the lithium carbonate solid in the diluted hydrochloric acid dissolution crucible, then with washed with de-ionized water to remove soluble component, insert drying in 80～120 ℃ of baking ovens, its surface coverage uniform black oxide layer;
3) scrape off one section oxide layer at an end wiry.The plain conductor of burn-oning on this end is as circuit and physical connection.
The Ag/AgCl contrast electrode is one section filamentary silver, or scribbles the spun gold that contains super fine silver powder epoxy resin, and the surface is coated with active A gCl film, and it can be the commercial goods, one of also can be by the following method makes:
The AgCl powder is placed platinum crucible, heat on spirit lamp, until its fusion, will take out after the several seconds in the end immersion melt of filamentary silver, cooling is put room temperature and is got final product;
Perhaps: get two filamentary silvers, be connected on respectively on the both positive and negative polarity of 1.5～3.0V direct supply, immerse concentration and be in the hydrochloric acid solution of 0.1～0.5M and turn-on current, after 15～30 minutes, the filamentary silver surface that is connected on the positive pole has plated uniform AgCl film.
Perhaps: get a spun gold, length at 1～2 centimetre at one end is coated the epoxy resin that contains super fine silver powder, the oven dry back is not connected on the positive pole of 1.5～3.0V direct supply there being one of epoxy resin to terminate at, other gets a filamentary silver and is connected on the negative pole of same power supply, immerse in the hydrochloric acid solution that concentration is 0.1～0.5M simultaneously them and turn-on current, after 15～30 minutes, the epoxy resin surface that is connected on the positive pole has plated uniform AgCl film.
Metal anode and metallic cathode are a kind of of inert metal silks such as Au, Pt, Ir, Ru, Zr, Ti, and the DC potential difference between them is between 2.4～9.0V.
The serviceability of exploring electrode of the present invention, as signal intensity, signal to noise ratio (S/N ratio) and sensitivity etc., all irrelevant with the size of electrode.Therefore, under the prerequisite that ensures required physical strength, should select for use thinner tinsel to make electrode as far as possible, help reducing cost, and dwindle the size of electrode.Diameter wiry generally should be between 0.1～0.3 millimeter.
Ir/IrO
2Electrode is the working electrode surveyed of double as pH and dissolved oxygen DO in the present invention, and the key of making this electrode is will coat one deck in wire surface can see through H
+The active IrO of ion
2Film.It is the heating of medium that the present invention has adopted with the lithium carbonate.Heating-up temperature preferably should be controlled at 760～800 ℃.In operations such as cleaning, oven dry, welding, preferably use the instrument of band rubber sheath, in order to avoid the oxide film wearing and tearing.
The making of Ag/AgCl contrast electrode can be by the direct plating AgCl film on filamentary silver of fusion method or electrochemical process, makes simplyr, but that the AgCl film combines with metal base is firm inadequately, especially contains S in solution
2-, Br
-, I
-Electrode easily lost efficacy during Deng toxic component.Adopt spun gold to make base material, containing super fine silver powder epoxy resin is the middle layer, and the adhesion of AgCl film and electrode is obviously strengthened.The present invention recommends to use this scheme, and cost slightly increases, but electrode stability and serviceable life are doubled and redoubled.
Metal anode and metallic cathode recommend to use spun gold to make, and spun gold obtains easily, and is difficult for and solution generation electrochemical reaction.Extra electric field between metal anode and the metallic cathode preferably uses 3～5V DC voltage.
In use, when switch 7 is in open position, Ir/IrO
2Exist following pH detection reaction right on the electrode:
According to energy Si Tedinglv, metal in (1) formula (Ir °) and oxidation film (IrO
2) between potential difference (PD) be:
Δ E in the formula
Ir(V) be the actual electrical potential difference, E °
T, PBe standard electric potential difference, a
wBe the activity of water.All these data can be found from the thermodynamic data under specifying T, P-condition.R and F are respectively gaseous state constant and Faraday constant.Arrangement (2) formula can obtain fluid pH value (pH
T, P) and (1) formula reaction potential difference between funtcional relationship (seeing (3) formula).
This moment Ir/IrO
2Potential difference (PD) V between electrode and the Ag/AgCl contrast electrode position
1Linear with the pH value of solution, can try to achieve the pH value of solution according to working curve.
When switch 7 closures, there is electric current to pass through between metal anode 3 and the metallic cathode 4.The size of the resistance R between two electrodes is relevant with the salinity of solution, can draw the salinity of solution by working curve.Notice that Closing Switch 7 initial resistance between metal anode and metallic cathode is directly relevant with the solution salinity, along with prolong conduction time, the electrochemical reaction in the solution can make its resistance value change.Therefore the resistance that should record according to Closing Switch moment is as the foundation of calculating the solution salinity.
After switch 7 closures, dissolved oxygen DO and water have following reaction:
Be that dissolved oxygen DO is under the effect of applying direct current electric field, with water reaction generation OH
-Thereby, changing the pH value of metal anode and negative electrode periphery solution, this variation makes Ir/IrO
2Potential difference (PD) between electrode and the Ag/AgCl contrast electrode is from changing:
ΔV＝V
2-V
1 (5)
V wherein
1And V
2Be respectively to connect extra electric field front and back Ir/IrO
2Potential difference (PD) between electrode and the Ag/AgCl contrast electrode.Δ V is relevant with the content of dissolved oxygen DO in the solution, can draw the concentration of dissolved oxygen DO in the solution by working curve.Before and after the cancellation external electric field, Ir/IrO
2Potential difference (PD) between electrode and the Ag/AgCl contrast electrode is returned to V
1
Below in conjunction with embodiment the present invention is elaborated.
Example 1:Ir/IrO
2The making of pH electrode
1) cut-off directly is 0.15 millimeter an Ir silk, after mechanical grinding is removed oxidation film, places corundum crucible, and covers with the Carbon Dioxide lithium powder; Crucible is placed muffle furnace, be heated to 780 ℃, and constant temperature 5 hours;
2) be chilled to room temperature after, with the lithium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, removing soluble component, it is a dry night in 80 ℃ the baking oven that the Ir silk is moved into temperature, its surface coverage the IrO of black densification
2Layer;
3) scrape off the oxide layer of about 1 millimeters long at an end of Ir silk.The diameter of burn-oning on this end is 0.1 millimeter a spun gold, as circuit and physical connection.
The making of example 2:Ag/AgCl contrast electrode
Get the filamentary silver of suitable length, 3 gram AgCl powder are placed the platinum crucible of 5mL, heat on spirit lamp, until its fusion, a end that will filamentary silver immerses in the melt and takes out after the several seconds, and cooling is put room temperature and got final product.
The making of example 3:Ag/AgCl contrast electrode
1) adding 100mL concentration in the beaker of 200mL is the HCl of 0.1M;
2) getting two filamentary silvers, be connected on respectively on the both positive and negative polarity of 2.4V direct supply, is in the 0.1M hydrochloric acid solution and turn-on current with the about 1 centimetre of immersion concentration of one end, take out after 20 minutes, the filamentary silver surface that is connected on the positive pole has plated uniform AgCl film, uses distilled water flushing, and oven dry gets final product.
The making of example 4:Ag/AgCl contrast electrode
1) adding 100mL concentration in the beaker of 200mL is the HCl of 0.1M;
2) get a spun gold, coat the epoxy resin that contains super fine silver powder in the length of 1～2 centimetre at one end, the oven dry back is not connected on the positive pole of 2.4V direct supply there being one of epoxy resin to terminate at, and other gets a filamentary silver and is connected on the negative pole of same power supply;
3) immerse in the concentration hydrochloric acid solution and turn-on current two one metal wires, one end for about 1 centimetre, take out after 20 minutes, the argentiferous epoxy resin surface that is connected on the positive pole has plated uniform AgCl film, uses distilled water flushing, and oven dry gets final product.
Example 5: the integrated and encapsulation of exploring electrode
1) the teflon heat-shrink tube is enclosed within Ir/IrO respectively
2On the connection lead of electrode, Ag/AgCl contrast electrode and two spun golds, heating makes its contraction, forms insulating protective layer;
2) cut-off directly is 1.5 centimetres a teflon plate, bores four apertures, 1 millimeter of diameter, 3 millimeters of spacings along diametric(al);
3) electrode and spun gold are passed aperture, wherein electrode is positioned at the inboard, and spun gold is positioned at outer the survey, and the length of passing aperture should be consistent, is about 0.8 centimetre, and is with epoxy resin that they are fixing one by one, and oven dry;
4) electrode and spun gold are fixed on the detecting head of sensor, and lead are connected on the response position of integrated circuit and get final product.
Claims (6)
1. an integrated form dissolved oxygen DO, pH and salinity sensor is characterized in that it includes Ir/IrO
2Electrode (1), Ag/AgCl contrast electrode (2), metal anode (3) and metallic cathode (4).
2. a kind of integrated form dissolved oxygen DO according to claim 1, pH and salinity sensor is characterized in that said Ir/IrO
2The method for making step of electrode is as follows:
1) cut-off directly is 0.1～0.5 millimeter a iridium wire, is cut into 1-3 centimetre length, places the crucible that fills the lithium carbonate powder, crucible is put into muffle furnace be heated to 750～850 ℃, and constant temperature 3～6 hours;
2) take out be chilled to room temperature after, with the lithium carbonate solid in the diluted hydrochloric acid dissolution crucible, then with washed with de-ionized water to remove soluble component, insert drying in 80～120 ℃ of baking ovens, its surface coverage uniform black oxide layer;
3) scrape off one section oxide layer at an end wiry.The plain conductor of burn-oning on this end is as circuit and physical connection.
3. a kind of integrated form dissolved oxygen DO according to claim 1, pH and salinity sensor, the method for making that it is characterized in that said Ag/AgCl contrast electrode is: the AgCl powder is placed platinum crucible, on spirit lamp, heat, until its fusion, to take out after the several seconds in the end immersion melt of filamentary silver, cooling is put room temperature and is got final product; Perhaps get two filamentary silvers, be connected on respectively on the both positive and negative polarity of 1.5～3.0V direct supply, immerse concentration and be in the hydrochloric acid solution of 0.1～0.5M and turn-on current, after 15～30 minutes, the filamentary silver surface that is connected on the positive pole has plated uniform AgCl film; Perhaps get a spun gold, length at 1～2 centimetre at one end is coated the epoxy resin that contains super fine silver powder, the oven dry back is not connected on the positive pole of 1.5～3.0V direct supply there being one of epoxy resin to terminate at, other gets a filamentary silver and is connected on the negative pole of same power supply, immerse in the hydrochloric acid solution that concentration is 0.1～0.5M simultaneously them and turn-on current, after 15～30 minutes, the epoxy resin surface that is connected on the positive pole has plated uniform AgCl film.
4. a kind of integrated form dissolved oxygen DO according to claim 1, pH and salinity sensor, it is characterized in that said metal anode and metallic cathode are a kind of of Au, Pt, Ir, Ru, Zr, Ti inert metal silk, the DC potential difference between them is between 2.4～9.0V.
5. the method for making of an integrated form dissolved oxygen DO, pH and salinity sensor is characterized in that, four electrode spread are in line Ir/IrO
2Electrode and Ag/AgCl contrast electrode are positioned at the inboard, metal anode and metallic cathode are positioned at the outside, at a distance of 1～10 millimeter, with epoxy resin or other cementing agent they are fixed on (5) on the insulativity sheet material between each electrode, the lead of electrode coats with the teflon heat-shrink tube.
6. the using method of an integrated form dissolved oxygen DO, pH and salinity sensor is characterized in that its method step is as follows:
1) compound electrode is inserted solution to be measured, measure Ir/IrO with millivoltmeter (6)
2Potential difference (PD) between electrode and the Ag/AgCl contrast electrode position is designated as V
1, V
1The pH value that has reflected solution;
2) Closing Switch (7) records resistance R between metal anode (3) and the metallic cathode (4) by microhmmeter, and the size of R has reflected the salinity of solution;
3) energising was read potential difference (PD) V after 30～60 seconds on millivoltmeter (6)
2, V
2With V
1Difference be designated as Δ V, Δ V has reacted dissolved oxygen content in the solution;
4) cut-off switch (7), the potential difference (PD) on millivoltmeter this moment (6) is returned to V
1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031506682A CN1493874A (en) | 2003-08-27 | 2003-08-27 | Integrated type dissolved oxygen, PH and salinity sensor and its manufacturing method and use method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031506682A CN1493874A (en) | 2003-08-27 | 2003-08-27 | Integrated type dissolved oxygen, PH and salinity sensor and its manufacturing method and use method |
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| Publication Number | Publication Date |
|---|---|
| CN1493874A true CN1493874A (en) | 2004-05-05 |
Family
ID=34240592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031506682A Pending CN1493874A (en) | 2003-08-27 | 2003-08-27 | Integrated type dissolved oxygen, PH and salinity sensor and its manufacturing method and use method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210902B (en) * | 2007-12-25 | 2012-05-23 | 福州大学 | Metal-metallic oxide pH electrode and method for making same |
| CN101533031B (en) * | 2009-04-15 | 2012-05-23 | 中国农业大学 | Dissolved oxygen intelligent transducer |
| CN102841080A (en) * | 2012-08-06 | 2012-12-26 | 上海交通大学 | Two-parameter optical fiber sensor used for measurement of pH value and dissolved oxygen |
| CN103959053A (en) * | 2011-12-02 | 2014-07-30 | 皇家飞利浦有限公司 | Method and device for detecting PH value of a solution |
| CN104731120A (en) * | 2014-10-22 | 2015-06-24 | 中山欧麦克仪器设备有限公司 | Novel dissolved oxygen control device |
| CN105021663A (en) * | 2015-07-30 | 2015-11-04 | 东南大学 | Salinity measurement method |
| RU2606190C2 (en) * | 2011-12-02 | 2017-01-10 | Конинклейке Филипс Н.В. | METHOD AND DEVICE TO DETERMINE pH VALUE OF SOLUTION |
| CN110082409A (en) * | 2019-05-06 | 2019-08-02 | 李桂梅 | A kind of marine red tide on-line monitoring system |
| CN111108374A (en) * | 2017-09-13 | 2020-05-05 | 南安普敦大学 | PH sensor and calibration method for a PH sensor |
-
2003
- 2003-08-27 CN CNA031506682A patent/CN1493874A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210902B (en) * | 2007-12-25 | 2012-05-23 | 福州大学 | Metal-metallic oxide pH electrode and method for making same |
| CN101533031B (en) * | 2009-04-15 | 2012-05-23 | 中国农业大学 | Dissolved oxygen intelligent transducer |
| CN103959053A (en) * | 2011-12-02 | 2014-07-30 | 皇家飞利浦有限公司 | Method and device for detecting PH value of a solution |
| RU2606190C2 (en) * | 2011-12-02 | 2017-01-10 | Конинклейке Филипс Н.В. | METHOD AND DEVICE TO DETERMINE pH VALUE OF SOLUTION |
| CN103959053B (en) * | 2011-12-02 | 2017-05-24 | 皇家飞利浦有限公司 | Method and device for detecting PH value of a solution |
| US10024815B2 (en) | 2011-12-02 | 2018-07-17 | Koninklijke Philips N.V. | Method and device for detecting PH value of a solution |
| CN102841080A (en) * | 2012-08-06 | 2012-12-26 | 上海交通大学 | Two-parameter optical fiber sensor used for measurement of pH value and dissolved oxygen |
| CN104731120A (en) * | 2014-10-22 | 2015-06-24 | 中山欧麦克仪器设备有限公司 | Novel dissolved oxygen control device |
| CN105021663A (en) * | 2015-07-30 | 2015-11-04 | 东南大学 | Salinity measurement method |
| CN105021663B (en) * | 2015-07-30 | 2017-07-28 | 东南大学 | A kind of salimity measurement method |
| CN111108374A (en) * | 2017-09-13 | 2020-05-05 | 南安普敦大学 | PH sensor and calibration method for a PH sensor |
| CN110082409A (en) * | 2019-05-06 | 2019-08-02 | 李桂梅 | A kind of marine red tide on-line monitoring system |
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