CN106291015A - A kind of deep-sea long-life electric-field sensor and interior electrode cores preparation - Google Patents
A kind of deep-sea long-life electric-field sensor and interior electrode cores preparation Download PDFInfo
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- CN106291015A CN106291015A CN201610601088.1A CN201610601088A CN106291015A CN 106291015 A CN106291015 A CN 106291015A CN 201610601088 A CN201610601088 A CN 201610601088A CN 106291015 A CN106291015 A CN 106291015A
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- core body
- interior electrode
- electrode core
- silver
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- 230000005684 electric field Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 14
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 239000007943 implant Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 4
- -1 graphite alkene Chemical class 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 3
- 239000010439 graphite Substances 0.000 claims abstract description 3
- 229910000679 solder Inorganic materials 0.000 claims abstract 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000010946 fine silver Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 238000012163 sequencing technique Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims 4
- 239000004411 aluminium Substances 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- 238000005660 chlorination reaction Methods 0.000 claims 2
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 7
- 238000004891 communication Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 3
- 238000009931 pascalization Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 208000002193 Pain Diseases 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- ZYDVNTYVDVZMKF-UHFFFAOYSA-N [Cl].[Ag] Chemical compound [Cl].[Ag] ZYDVNTYVDVZMKF-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R3/00—Apparatus or processes specially adapted for the manufacture or maintenance of measuring instruments, e.g. of probe tips
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
- Measuring Fluid Pressure (AREA)
Abstract
The present invention is to provide a kind of electric-field sensor being applicable to abyssal environment, including protection shell, the interior electrode core body being arranged in from top to bottom in shell and filter element, it is characterized in that: described filter element is diatom ceramic cylinder, described interior electrode core body is suppressed calcining by nanometer silver and nano silver/silver chloride powder body admixed graphite alkene slurry and is formed, the upper end of interior electrode core body is filled with epoxy sealing, electrode cable is drawn shell by solder joint by the upper end of interior electrode core body after epoxy sealing implant, interior electrode core body is fixed on the fixing seal of protection shell upper end and puts, it is diatom ceramic cylinder and protection shell the most successively, the opposite side of protection shell is connected with external environment, pressure cap is fixed bottom it.Can be applicable to the electric field signal prison detection in deep-sea oil pipeline, deep sea communication cable, deep-sea detection equipment and automatic controlling device probe.The present invention has the advantages such as simple in construction, stable performance, highly sensitive, length in service life, and application prospect is preferable.
Description
Technical field
The present invention relates to a kind of electric-field sensor, a kind of long-life electricity that can stablize use in abyssal environment
Field sensor, and the preparation method of interior electrode core body.
Background technology
Along with oceanologic development, the detection of ocean electric field has become as the important high-new skill of in scientific research of seas
Art, is widely used at aspects such as deep-sea oil pipeline, deep sea communication cable, deep-sea detectings.Due to the electric field signal in ocean
The faintest, high sensitivity, the development of ocean electric transducer of low noise become one of important research content of marine electromagnetic detection.
The sensor probe being currently used for ocean electric field detecting is mainly all solid state Ag/AgCl electrode, for other electrode, entirely
Solid-state Ag/Ag Cl electrode due to pressure, anticorrosive, high stability and high sensitivity, de-grain husk in terms of the electric field detecting of ocean and
Go out, and be widely used in preparing electric field sensor for marine environments.
Nano silver particles is except having the general noble metal nano particles such as quantum size effect, small-size effect, skin effect
Characteristic outside, also present the electric property being better than common material so that it is application more and more extensively (Analytical
Chemistry, 2009,81:6496-6502).The distinctive lattice structure of Graphene, makes it have the electric conductivity having excellence with big
Specific surface area, be widely used in prepared by electrode and battery.Nano silver/silver chloride and nanometer silver and the mixing of Graphene slurry are made
Standby interior electrode core body, process conditions are simple, and electrode performance is stable, easy to use, has a extensive future.
It shows good biocompatibility, anti-microbial property, non-linear optical property etc. so that it is in catalyst, dielectric
The aspects such as material, anti-biotic material and surface enhanced raman spectroscopy technology have a wide range of applications.Therefore, nanometer silver is as one
New material becomes the focus of electrochemical field research in recent years.
Patent 201210239174.4 describes a kind of reference electrode for deep-sea high hydrostatic pressure.The salt bridge of this electrode by
The potassium chloride shot-like particle that saturated potassium chloride collosol and gel and even dispersion are distributed in saturated potassium chloride collosol and gel is constituted, permissible
Reduce oozing out or running off of salt bridge filling liquid, improve service life, reduce maintenance times.But electrode interior yet suffers from liquid to be connect
, there is the pollution of inner electrode in electromotive force, in high hydrostatic pressure environment, its stability and sensitivity are easily reduced, thus causes by mistake
Survey.
Silver prepared by Li Jiao powder pressing method/silver halide reference electrode short-term stability is preferable, and extreme difference is at 0.4-0.8mV
Between, but to place for a long time in sea water and need about one week electrode just to reach stable, extreme difference is between 0.7-0.8mV.This electrode
It is limited that long-time stability make it apply.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of deep-sea long-life electric-field sensor and prepared by interior electrode cores body
Method.
For sufficiently achieving object above, the technical solution used in the present invention is:
Including protection shell, the interior electrode core body being arranged in from top to bottom in shell and filter element, it is characterized in that: described filter
Core is diatom ceramic cylinder, and described interior electrode core body is suppressed calcining by nanometer silver and nano silver/silver chloride powder body admixed graphite alkene slurry
Forming, the upper end of interior electrode core body is filled with epoxy sealing, and electrode cable is passed through bump by the upper end of interior electrode core body
Drawing shell after epoxy sealing implant, interior electrode core body is fixed on the fixing seal of protection shell upper end and puts,
Being diatom ceramic cylinder and protection shell the most successively, the opposite side of protection shell is connected with external environment, has one to fix bottom it
Pressure cap.
By analytical pure AgNO under room temperature3It is placed in ball mill according to weight ratio 1:1.2 with NaCl powder body and carries out sequencing powder
Broken ball milling 50min, obtains nano silver/silver chloride powder body.Nanometer silver and nano silver/silver chloride powder body according to the ratio of weight ratio 1:1.72,
With the binding agent mixing granulation of 2% mass parts, pressing pressure is 10MPa, sinters after molding at a temperature of 210 DEG C.Compacting uses
Binding agent be Graphene slurry.
Present invention additionally comprises:
1) described shell is made up of fixing seal sleeve pipe, sleeve pipe and fixing pressure cap, and the two ends up and down of sleeve pipe are divided by screw thread
Do not overlap with fixing seal sleeve pipe and fixing pressure cap and be connected.
2) fixing seal sleeve pipe material is nylon, and sleeve pipe material can be the one in AB, PE, PVC.
3) fine silver cylinder is inlayed in the upper end of interior electrode core body, and one end of electrode cable is by scolding tin node with fine silver cylinder even
It is connected together.
Advantage for present invention:
Technical scheme solves three big technical barriers: one, fixing seal sleeve pipe, sleeve pipe employ pressure,
One in nylon that corrosion resistance is excellent or AB, PE, PVC, shell one end can make sea water free in and out, it is to avoid at deep-sea
Pressure differential huge inside and outside electric transducer enclosure cavity under the conditions of high hydrostatic pressure causes electricity shell deformation or pressure break.Its two, make
It is mixed with interior electrode core body with nano level argentum powder and silver chloride powder body with Graphene, specific surface area can be greatly increased, and
Lower than the fusing point of conventional argentum powder and silver chloride powder body, it is achieved that the electrode compacting under lower temperature, technique is the most simple,
And highly sensitive, good stability.Its three, diatom ceramic cylinder both can be with the insoluble organic and inorganic matter in filtering sea as filter element
The silver ion on electrode core body and silver chlorine complex ion can be prevented first as the second liquid junction boundary of reference electrode again
The silver nitride precipitation that formed on interface and block electrode, significantly lower and pollute the drift of electrode potential caused.
By the enforcement of above-mentioned three kinds of technical measures, significantly reduce the pollution to electrode on liquid junction boundary, effectively
Prevent the drift of electrode potential, it is thus achieved that stable electrode potential；Good conductive material is prepared for matter by rational technique
Ground uniformly, specific surface area big, highly sensitive, good stability and electric transducer simple for process, it is achieved high pressure resistant, exempt from dimension
Protect, long-life using effect.Can be applicable to the electric field letter in deep-sea oil pipeline, deep sea communication cable, deep-sea detection equipment
Number prison detection and automatic controlling device pop one's head in.The present invention has simple in construction, stable performance, highly sensitive, length in service life etc.
Advantage, application prospect is preferable.
Accompanying drawing explanation
Fig. 1 is the structural representation of this invention.
Fig. 2 is the extreme difference potential diagram of this invention.
Detailed description of the invention
For illustrating the understanding to this invention feature, below in conjunction with the embodiment of some indefinitenesses the present invention done into
One step illustrates.
Embodiment 1: the invention will be further described in citing below in conjunction with the accompanying drawings:
In conjunction with Fig. 1.Contact conductor 1 one end is by scolding tin node 5 and the cylinder being embedded in silver/silver chloride pressed by powder sintering
Fine silver cylinder 6 in interior electrode core body 7 upper surface of shape links together, and interior electrode core body 7 is placed in the middle part of electrode sleeve pipe 9,
Epoxy sealing implant 4 is utilized to fix, it is desirable to interior electrode core body 7 exposes lower surface, and remaining surface uses epoxy sealing implant 4
Seal；Contact conductor 1 other end passes electrode sleeve pipe 9 upper shed and fixes close through electrode after epoxy sealing implant 4
Big envelope 3 through hole extend to outside reference electrode main body as connect the signaling interface such as prison, detection equipment and electrochemical workstation it
With；Being machined with external screw thread in electrode sleeve pipe 9 upper end, electrode fixing seal overlaps 3 inwall processing screw threads, electrode sleeve pipe 9 upper end outer wall
Female thread and the electrode fixing seal set 3 of processing to threaded, between add pressure-resistant seal pad 2 and realize fixing of electrode upper end
And sealing；Electrode sleeve pipe 9 lower end outer wall processing screw thread, realizes stinging with the female thread of electrode lower end electrode locking cap 10 inwall processing
Close；Electrode locking cap 10 be engaged in space with electrode sleeve pipe 9 utilize pressure-resistant seal pad 2 to realize the fixing of diatom ceramic cylinder 8 and
Seal.
Embodiment 2: the preparation of nano silver/silver chloride powder body.
By analytical pure AgNO under room temperature3It is placed in ball mill according to weight ratio 1:1.2 with NaCl powder body and carries out sequencing powder
Broken ball milling 50min, obtains nano silver/silver chloride powder body.
Embodiment 3: interior electrode core body compacting calcining.
Nanometer silver and nano silver/silver chloride powder body, according to the ratio of weight ratio 1:1.72, mix with the binding agent of 2% mass parts
Pelletize, pressing pressure is 10MPa, sinters after molding at a temperature of 210 DEG C.
Claims (9)
1. it is applicable to an electric transducer for abyssal environment, including protection shell, the interior electrode being arranged in from top to bottom in shell
Core body and filter element, is characterized in that: described filter element is diatom ceramic cylinder, and described interior electrode core body is by nanometer silver and nanometer chlorination
The compacting calcining of aluminium powder admixed graphite alkene slurry forms, and the upper end of interior electrode core body is filled with epoxy sealing, electrode cable
Being drawn shell by solder joint by the upper end of interior electrode core body after epoxy sealing implant, interior electrode core body is fixed on guarantor
The fixing seal protecting shell upper end puts, and is diatom ceramic cylinder and protection shell the most successively, and the opposite side of protection shell is with outer
Boundary's environment is connected, and fixes pressure cap bottom it.
The electric-field sensor being applicable to abyssal environment the most according to claim 1, is characterized in that: described shell is close by fixing
Big envelope pipe, sleeve pipe and fixing pressure cap composition, the two ends up and down of sleeve pipe by screw thread respectively with fixing seal sleeve pipe and fixing pressure cap
Set connects.
The electric transducer being applicable to abyssal environment the most according to claim 2, is characterized in that: fixing seal sleeve pipe material is
One in nylon, ABS, PE, PVC.
The electric-field sensor being applicable to abyssal environment the most according to claim 1 and 2, is characterized in that: interior electrode core body
Upper end embedding fine silver cylinder, one end of electrode cable is linked together with fine silver cylinder by weldering node.
The electric-field sensor being applicable to abyssal environment the most according to claim 4, is characterized in that: interior electrode core body is by nanometer
Silver and nano silver/silver chloride pressed by powder sintering form.
The electric-field sensor being applicable to abyssal environment the most according to claim 4, is characterized in that: by analytical pure under room temperature
AgNO3It is placed in ball mill with powder body NaCl and carries out sequencing pulverizing ball milling 50min, nanometer chlorination needed for electrode core body in preparing
Aluminium powder.
The electric-field sensor being applicable to abyssal environment the most according to claim 4, is characterized in that: analytical pure AgNO3And powder body
NaCl mixes according to weight ratio 1:1.2.
8. according to the interior electrode core body described in claim 5 or 6, it is characterized in that: nanometer silver and nano silver/silver chloride powder body are according to weight
The amount ratio than 1:1.72, with the binding agent mixing granulation of 2% mass parts, pressing pressure is 10MPa, in 210 DEG C of temperature after molding
The lower sintering of degree.
Interior electrode core body the most according to claim 8, is characterized in that: the binding agent that compacting uses is Graphene slurry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610601088.1A CN106291015B (en) | 2016-07-28 | 2016-07-28 | A kind of deep-sea long-life electric-field sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610601088.1A CN106291015B (en) | 2016-07-28 | 2016-07-28 | A kind of deep-sea long-life electric-field sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106291015A true CN106291015A (en) | 2017-01-04 |
| CN106291015B CN106291015B (en) | 2019-08-30 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107271799A (en) * | 2017-06-02 | 2017-10-20 | 中国地质大学（武汉） | A kind of preparation method of the small solid electrode of extreme difference drift |
| CN110174704A (en) * | 2019-06-24 | 2019-08-27 | 青岛科技大学 | A kind of electric field sensor for marine environments based on TRIZ theory |
| EP4086617A1 (en) * | 2021-05-06 | 2022-11-09 | i-Sens, Inc. | Paste for reference electrode, reference electrode, and biosensor including the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107271799A (en) * | 2017-06-02 | 2017-10-20 | 中国地质大学（武汉） | A kind of preparation method of the small solid electrode of extreme difference drift |
| CN110174704A (en) * | 2019-06-24 | 2019-08-27 | 青岛科技大学 | A kind of electric field sensor for marine environments based on TRIZ theory |
| EP4086617A1 (en) * | 2021-05-06 | 2022-11-09 | i-Sens, Inc. | Paste for reference electrode, reference electrode, and biosensor including the same |
| AU2022202498B2 (en) * | 2021-05-06 | 2023-11-23 | I-Sens, Inc. | Paste for reference electrode, reference electrode, and biosensor including the same |
| US11967440B2 (en) | 2021-05-06 | 2024-04-23 | I-Sens, Inc. | Paste for reference electrode, reference electrode, and biosensor including the same |
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| CN106291015B (en) | 2019-08-30 |
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