CN1651912A - Composite scanning chlorion sensitive micro-probe and preparing process thereof - Google Patents
Composite scanning chlorion sensitive micro-probe and preparing process thereof Download PDFInfo
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- CN1651912A CN1651912A CN 200510060012 CN200510060012A CN1651912A CN 1651912 A CN1651912 A CN 1651912A CN 200510060012 CN200510060012 CN 200510060012 CN 200510060012 A CN200510060012 A CN 200510060012A CN 1651912 A CN1651912 A CN 1651912A
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Abstract
The present invention relates to a new composite scanning chlorine ion sensing microprobe and its preparation method. A metal potential sensing microprobe and a chlorine ion selectivity microprobe are fixedly connected, their exterior is covered withan encapsulation layer, and the point portions of two microprobes are bared, and the point diameter of every microprobe is respectively 10-100 micrometers. Said invention also provides the concrete steps for preparing said composite scanning chlorine in sensing microprobe by utilizing siler wire and Pt-Ir alloy.
Description
Technical field
The present invention relates to a kind of probe, especially relate to a kind of composite scanning chlorion sensitive micro-probe.
Background technology
In physical environment, chlorion is a kind of extensive existence and the species with strong depassivation effect, and the inhomogeneity that chlorion distributes at metal/solution interface becomes the main reason that the metal local corrosion takes place, develops.(LinCJ such as Lin in 2000, Du RG, Nguyen T.In-situ imaging of chloride ions at the metal/solution interface by scanningcombination microelectrodes, Corrosion 56 (1): 41-47 2000) succeed in developing the combination electrode of forming by Ag/AgCl electrode and liquid chlorion selective membrane electrode, wherein as contrast electrode, chlorion selectivity liquid membrane electrode is as the chlorion probe by the microscopic capillary salt bridge for the Ag/AgCl electrode.System has detected migration of chlorion anode and enrichment in conjunction with the scanning microelectrode, forms on ' chlorine island '.Other technology that can realize metal/solution interface chlorion micro Distribution in site measurement is not appeared in the newspapers as yet.Yet above-mentioned composite micro-electrode remains in liquid membrane electrode weak point in serviceable life, response speed and reaches technical matterss such as the microelectrode manufacture difficulty is big slowly.
Summary of the invention
The present invention is intended to solve the problems of the technologies described above, and a kind of commercial new composite scanning chlorion sensitive micro-probe and preparation method thereof that is suitable for is provided.
The said composite scanning chlorion sensitive micro-probe of the present invention is provided with responsive microprobe of metal current potential and chlorion selectivity microprobe, responsive microprobe of metal current potential and chlorion selectivity microprobe are affixed, responsive microprobe of metal current potential and chlorion selectivity microprobe peripheral hardware encapsulated layer, the tip portion of two probes is exposed, and the tip diameter of two probes respectively is 10-100 μ m.The preferred Pt-Ir alloy of the responsive microprobe of said metal current potential microelectrode is as the reference probe of composite scanning chlorion sensitive micro-probe.The preferred Ag/AgCl electrode of said chlorion selectivity microprobe, establish coating at the Ag/AgCl electrode surface, said coating is selected from nail oil reservoir, paraffin layer or polymer coating film material layer, as the chlorion responsive probe of composite scanning chlorion sensitive micro-probe.Responsive microprobe of metal current potential and chlorion selectivity microprobe preferably are arranged side by side the preferred parallel setting.Said encapsulating material can adopt polymethylstyrene, paraffin or epoxy resin etc., preferred polymethylstyrene.The distance between two tips L of responsive microprobe of metal current potential and chlorion selectivity microprobe is preferably: 0＜L≤20 μ m.
The preparation method of the said composite scanning chlorion sensitive micro-probe of the present invention the steps include:
1), preparation chlorion selectivity microprobe: at long 20～100mm, the tip portion of one end processing, 10～100 μ m of the filamentary silver of diameter 0.1～0.5mm, be that constant current anode oxidation is handled to the filamentary silver surface and generated one deck AgCl film in the HCl solution of 0.001～1mol/L in concentration then, the Ag/AgCl electrode surface that forms is established coating, coating thickness is 1～10 μ m, said coating is selected from nail oil reservoir, paraffin layer or polymer coating film material layer etc., expose the Ag/AgCl tip portion, form chlorion selectivity microprobe;
2), the responsive microprobe of preparation metal current potential: at long 20～100mm, the tip portion of Pt-Ir alloy silk one end processing 10～100 μ m of diameter 0.1～0.5mm forms the responsive microprobe of metal current potential;
3), responsive microprobe of metal current potential and chlorion selectivity microprobe is affixed, form combined probe;
4), at combined probe peripheral hardware encapsulated layer, only tip portion exposes, and promptly forms composite scanning chlorion sensitive micro-probe.
In step 1), it is 1～10h that said constant current anode oxidation is handled its time, and Control current is 0.001～1mA/cm2.In step 2) in, the preferred Pt70%-Ir30% alloy of said Pt-Ir alloy.In step 3), the said affixed bonding agent that adopts is bonding; Two probes are arranged side by side, the preferred parallel setting; The distance between two tips L of responsive microprobe of metal current potential and chlorion selectivity microprobe is preferably: 0＜L≤20 μ m.In step 4=, said encapsulated layer can adopt polymethylstyrene layer, paraffin layer or epoxy resin layer etc., preferred polymethylstyrene layer.
The said composite scanning chlorion sensitive micro-probe of the present invention approaches sample surfaces and carries out scanning survey under the driving of two-dimensional stage and control program, has detected the potential difference (PD) between the compound microprobe, thereby can obtain the microdistribution of surperficial chlorine ion concentration.Chlorion selectivity microprobe adopts the Ag/AgCl electrode, and its principle of work can be used formula (1) and (2) expression:
Formula (1) is the half-cell reaction formula of Ag/AgCl electrode, and formula (2) shows between the logarithm of chlorine ion concentration in the electrode potential of Ag/AgCl and the solution and has linear relationship.By the current potential of measuring probe, just can calculate the chlorine ion concentration in the solution easily.
Employing is the key that realizes the microdistribution of original position, high-space resolution degree and accurate surface measurements chlorine ion concentration by responsive microprobe of metal current potential and chlorion selectivity microprobe closely compound (rather than single chlorion probe scanning is measured).Two kinds of probe tip sizes and the distance between the two of forming combined probe are the deciding factors of spatial resolving power of the present invention, and the present invention has developed the good probe combination process of a kind of operability, the distance between the needle point can be controlled within the 20 μ m.
Advantage of the present invention is: with the Ag/AgCl electrode be chlorion probe and the compound formation of Pt-Ir potential probes combination electrode quickly and accurately in site measurement metal surface chlorine ion concentration distribute at micro-meter scale, similar techniques yet there are no report.Compare with original combined probe, the present invention adopts the Pt-Ir electrode to replace the glass capillary microelectrode as micro reference electrode, and this improvement has two advantages, and at first electrode production process is simpler, and tip size is littler, improves the spatial resolving power of probe; The second, can utilize the tunnel current of metal needle point accurately to control distance between combined probe and the sample surfaces, measure sensitivity and spatial resolution thereby improve greatly.It is as described below that combined probe approaches the process of sample surfaces: at first make combined probe and sample surfaces close under stn mode, enter the tunnel current district, the step motor control probe by the Z direction retreats suitable distance subsequently.
Description of drawings
Fig. 1 is the structural representation of composite scanning chlorion sensitive micro-probe embodiment.
Fig. 2 is a chlorine ion concentration relation curve in Ag/AgCl electrode potential and the solution.In Fig. 2, horizontal ordinate is chlorine ion concentration lg[cl-]/md.L-1, ordinate is current potential E/mVvs.SCE.Slope (slope) is-56.9mV.
Fig. 3 is time-potential curve (a) and the corresponding dE/dt curve (b) that adds saturated NaCl solution A g/AgCl electrode in 0.001mol.L-1NaCl solution.In Fig. 3 (a), horizontal ordinate is time t/s, and ordinate is identical with Fig. 2; In Fig. 3 (b), horizontal ordinate is time t/s, and ordinate is dE/dt, and E is a current potential.
Fig. 4 is the 18-8 stainless steel surfaces chlorine ion concentration distribution plan that is soaked in 0.01mol.L-1NaCl.In Fig. 4, scanning process drips saturated NaCl to solution.
Embodiment
As shown in Figure 1, the said composite scanning chlorion sensitive micro-probe of the present invention is provided with responsive microprobe of metal current potential and chlorion selectivity microprobe, the responsive microprobe of metal current potential is elected Pt-Ir alloy microelectrode 1 as, as the reference probe of composite scanning chlorion sensitive micro-probe.Chlorion selectivity microprobe is elected Ag/AgCl electrode 2 as, applies one deck nail oil reservoir 4 at the Ag/AgCl electrode surface, as the chlorion responsive probe of composite scanning chlorion sensitive micro-probe.Responsive microprobe of metal current potential and chlorion selectivity microprobe 1,2 are affixed by bonding agent, and are sealed by polymethylstyrene 3, and the tip portion of two probes is exposed, and the tip diameter of two probes respectively is 10-100 μ m.Two probes 1,2 be arranged in parallel.The distance between two tips L of two probes is: 0＜L≤20 μ m.
Below provide the preparation technology of the said composite scanning chlorion sensitive micro-probe of the present invention.
Embodiment 1
It is pure that used medicine is analysis, and configuration solution adopts three deionized waters.Ag/AgCl electrode potential-concentration curve, current potential-time curve is measured and is finished by the Autolab electrochemical workstation device of Eco Chemi company.The 18-8 stainless steel with 400 to No. 1000 silicon carbide paper polishing, is polished to minute surface with 1 μ m aluminum oxide polishing powder, absolute ethyl alcohol, three water ultrasonic cleaning, drying successively.The scan-type electrochemical that the microcell scanning survey of metal surface chlorine ion concentration is developed voluntarily by Xiamen University/scanning tunnel microscope combined system is finished.
At first get long 20mm, the fine silver silk of diameter 0.2mm cuts the tip of 50 μ m with sharp scissors at one terminal tool, is that constant current anode oxidation is handled 3h in the HCl solution of 0.01mol/L in concentration then, and Control current is 0.5mA/cm2.The filamentary silver surface generated one deck sepia equably after anodic oxidation was finished, fine and close AgCl film.The Ag/AgCl electrode is after distilled water drip washing, drying, and the surface applies the nail polish of a layer thickness 5 μ m equably, notes exposing μ m level Ag/AgCl tip portion, forms the Ag/AgCl electrode.The same method of shearing that adopts, at long 20mm, the Pt-Ir alloy of diameter 0.2mm (Pt 70%-Ir30%) silk one end processes the tip (meeting common STM measurement requirement) of 70 μ m, forms reference probe.For making two kinds of needle points as close as possible (but can not contact), under microscopic, two probes (filamentary silver and Pt-Ir) are combined into combined probe by the mode of Fig. 1, fix with cementing agent.Combined probe must be through sealing, and only tip portion exposes.Encapsulating material adopts polymethylstyrene, is heated to proper temperature at special electric heater unit groove part, makes needle point pass the liquid of this layer thickness carefully, makes the microprobe surface apply one deck polymethylstyrene equably except that most advanced and sophisticated position.Fig. 1 is the structural representation of combined probe.
Fig. 2 is Ag/AgCl electrode current potential-concentration curve in sodium chloride solution that the present invention prepares, linear good between the logarithm of current potential and Cl-concentration as can be seen, and slope and theoretical value are very approaching, show that the response of Ag/AgCl electrode potential is good to the chlorion selectivity.
Potential response speed is an important indicator of the present invention, therefore need test response speed, experimental technique is: add 100ml 0.001mol/L sodium chloride solution in the 200ml beaker earlier, measure the current potential-time curve of Ag/AgCl relative saturation mercurous chloride electrode with the 1000s-1 sample frequency, measurement begins to add the 20ml saturated nacl aqueous solution rapidly behind about 20s, other condition is constant, continues to measure to reach stable once more until current potential.Continue agitating solution with magnetic stirring apparatus in the measuring process, evenly mix to accelerate solution.Measurement result as shown in Figure 3.Can see that from Fig. 3 a adding saturated NaCl solution front and back, it is stable that the Ag/AgCl electrode potential keeps, amplitude of variation is in 1mV.In the moment that saturated solution adds, current potential sharply reduces, and reaches stable in 1s rapidly.Fig. 3 b is the result of Fig. 3 a to the time differentiate, and equally as can be seen, before adding saturated solution and after the solution mixing fully, Ag/AgCl electrode dE/dt approaches 0V.s-1, shows the current potential quite stable.When in the solution during Cl-concentration change, potential response is rapid, surpasses 400mV.s-1.The presentation of results of two figure, the Ag/AgCl electrode potential is stable, and it is fast that chlorine ion concentration is changed response, helps as the chlorion probe, follows the tracks of the dynamic change of electrode surface chlorine ion concentration.
Fig. 4 is that the 18-8 stainless steel is immersed in the 0.001mol/L-1NaCl solution, utilizes its surperficial chlorine ion concentration distribution plan of combined probe scanning survey, drips saturated NaCl solution to solution in the scanning process.Can see,, in the chlorine ion concentration distribution plan, follow the tangible groove in appearance 8 roads with the adding of 8 saturated NaCl solution, parallel with the electrode direction of scanning, and other regional Potential distribution is even.Generally speaking, add behind the saturated NaCl solution chlorine ion concentration slightly rise (current potential slightly reduces).The above results shows that the potential response of combined probe is quick, can reflect the instantaneous variation of the distribution of electrode surface chlorine ion concentration exactly.And, impel chlorion in the solution to accelerate in the diffusion of mixing direction because the mechanical scanning process of scanning microprobe has unidirectional beating action, from the chlorine ion concentration distribution plan, also can reflect the dynamic process of chlorine ion concentration space distribution truly.
Embodiment 2
Similar to Example 1, when its difference is to prepare the Ag/AgCl electrode, get long 50mm, the fine silver silk of diameter 0.3mm, cut the tip of 70 μ m at one terminal tool with sharp scissors, be that constant current anode oxidation is handled 5h in the HCl solution of 0.001mol/L in concentration then, Control current is 0.001mA/cm2.The filamentary silver surface generated one deck sepia equably after anodic oxidation was finished, fine and close AgCl film.The Ag/AgCl electrode is after distilled water drip washing, drying, and the surface applies the nail oil reservoir of a layer thickness 1 μ m equably.When the preparation reference probe, at long 50mm, the Pt-Ir alloy (Pt70%-Ir30%) of diameter 0.3mm silk one end processes the tip of 50 μ m.
Embodiment 3
Similar to Example 1, when its difference is to prepare the Ag/AgCl electrode, get long 70mm, the fine silver silk of diameter 0.1mm, cut the tip of 20 μ m at one terminal tool with sharp scissors, be that constant current anode oxidation is handled 10h in the HCl solution of 0.05mol/L in concentration then, Control current is 0.01mA/cm2.The filamentary silver surface generated one deck sepia equably after anodic oxidation was finished, fine and close AgCl film.The Ag/AgCl electrode is after distilled water drip washing, drying, and the surface applies the nail oil reservoir of a layer thickness 7 μ m equably.When the preparation reference probe, at long 70mm, the Pt-Ir alloy (Pt70%-Ir30%) of diameter 0.5mm silk one end processes the tip of 20 μ m.
Embodiment 4
Similar to Example 1, when its difference is to prepare the Ag/AgCl electrode, get long 100mm, the fine silver silk of diameter 0.5mm, cutting the tip of 100 μ m with sharp scissors at one terminal tool, is that constant current anode oxidation is handled 1h in the HCl solution of 1mol/L in concentration then, and Control current is 1mA/cm2.The filamentary silver surface generated one deck sepia equably after anodic oxidation was finished, fine and close AgCl film.The Ag/AgCl electrode is after distilled water drip washing, drying, and the surface applies the nail oil reservoir of a layer thickness 10 μ m equably.When the preparation reference probe, at long 100mm, the Pt-Ir alloy of diameter 0.1mm (Pt 70%-Ir30%) silk one end processes the tip of 100 μ m.
Claims (12)
1, a kind of composite scanning chlorion sensitive micro-probe, it is characterized in that responsive microprobe of metal current potential and chlorion selectivity microprobe, responsive microprobe of metal current potential and chlorion selectivity microprobe are affixed, responsive microprobe of metal current potential and chlorion selectivity microprobe peripheral hardware encapsulated layer, the tip portion of two probes is exposed, and the tip diameter of two probes respectively is 10-100 μ m.
2, a kind of composite scanning chlorion sensitive micro-probe as claimed in claim 1 is characterized in that the preferred Pt-Ir alloy of the responsive microprobe of said metal current potential microelectrode.
3, a kind of composite scanning chlorion sensitive micro-probe as claimed in claim 1, it is characterized in that the preferred Ag/AgCl electrode of said chlorion selectivity microprobe, establish coating at the Ag/AgCl electrode surface, said coating is selected from nail oil reservoir, paraffin layer or polymer coating film material layer.
4, a kind of composite scanning chlorion sensitive micro-probe as claimed in claim 1 is characterized in that responsive microprobe of metal current potential and chlorion selectivity microprobe are arranged side by side the preferred parallel setting.
5, a kind of composite scanning chlorion sensitive micro-probe as claimed in claim 1 is characterized in that said encapsulated layer adopts polymethylstyrene layer, paraffin layer or epoxy resin layer, preferred polymethylstyrene layer.
6, a kind of composite scanning chlorion sensitive micro-probe as claimed in claim 1 is characterized in that the distance between two tips L of responsive microprobe of metal current potential and chlorion selectivity microprobe is 1＜L≤20 μ m.
7, composite scanning chlorion sensitive micro-probe preparation method is characterized in that the steps include:
1) at long 20～100mm, the tip portion of one end processing, 10～100 μ m of the filamentary silver of diameter 0.1～0.5mm, be that constant current anode oxidation is handled to the filamentary silver surface and generated one deck AgCl film in the HCl solution of 0.001～1mol/L in concentration then, the Ag/AgCl electrode surface that forms is established coating, coating thickness is 1～10 μ m, said coating is selected from nail oil reservoir, paraffin layer or polymer coating film material layer, exposes the Ag/AgCl tip portion, forms chlorion selectivity microprobe;
2), the responsive microprobe of preparation metal current potential: at long 20～100mm, the tip portion of Pt-Ir alloy silk one end processing 10～100 μ m of diameter 0.1～0.5mm forms the responsive microprobe of metal current potential;
3), responsive microprobe of metal current potential and chlorion selectivity microprobe is affixed, form combined probe;
4), at combined probe peripheral hardware encapsulated layer, only tip portion exposes, and promptly forms composite scanning chlorion sensitive micro-probe.
8, composite scanning chlorion sensitive micro-probe preparation method as claimed in claim 7 is characterized in that in step 1), and it is 1～10h that said constant current anode oxidation is handled its time, and Control current is 0.001～1mA/cm2.
9, composite scanning chlorion sensitive micro-probe preparation method as claimed in claim 7 is characterized in that in step 2) in, the preferred Pt70%-Ir30% alloy of said Pt-Ir alloy.
10, composite scanning chlorion sensitive micro-probe preparation method as claimed in claim 7 is characterized in that in step 3), and said affixed employing bonding agent is bonding, and two probes are arranged side by side, the preferred parallel setting.
11, composite scanning chlorion sensitive micro-probe preparation method as claimed in claim 7 is characterized in that in step 3), and the distance between two tips L of responsive microprobe of said metal current potential and chlorion selectivity microprobe is: 0＜L≤20 μ m.
12, composite scanning chlorion sensitive micro-probe preparation method as claimed in claim 7 is characterized in that in step 4), and said encapsulated layer adopts polymethylstyrene layer, paraffin layer or epoxy resin layer, preferred polymethylstyrene layer.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102121944A (en) * | 2010-01-08 | 2011-07-13 | 技鼎股份有限公司 | Microprobe structure and manufacturing method thereof |
| CN103076365A (en) * | 2013-01-08 | 2013-05-01 | 苏州热工研究院有限公司 | Pen-type potential-chloride ion sensor |
| CN104155476A (en) * | 2014-06-16 | 2014-11-19 | 厦门乐钢材料科技有限公司 | Compound microprobe for in-situ measurement of STM image and chloride ion concentration distribution and preparation method thereof |
| CN105021682A (en) * | 2015-07-02 | 2015-11-04 | 浙江大学 | Needle-like chlorine ion sensor and preparation method thereof |
| CN105067684A (en) * | 2015-07-02 | 2015-11-18 | 浙江大学 | Needle-shaped potassium ion sensor and preparation method thereof |
| CN105223252A (en) * | 2015-10-23 | 2016-01-06 | 吴国清 | A kind of sodium, potassium, chlorion biochemical analysis dry plate and preparation method thereof |
| CN105223245A (en) * | 2015-10-23 | 2016-01-06 | 吴国清 | A kind of chlorion biochemical analysis dry plate and preparation method thereof |
| CN106645809A (en) * | 2016-10-14 | 2017-05-10 | 厦门大学 | Preparation method for isolated needle point with housing layers wrapped in dual manner |
| CN109142490A (en) * | 2017-06-15 | 2019-01-04 | 无锡德医爱德医疗器材有限公司 | All-solid sodium ion selective sensor and its preparation and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2557323B2 (en) * | 1987-08-07 | 1996-11-27 | 理研計器株式会社 | Method for measuring chloride ion concentration of raw concrete |
| CN1351257A (en) * | 2001-11-27 | 2002-05-29 | 中国科学院广州化学研究所 | Method for measuring content of Cl element and its burner |
| JP2004069472A (en) * | 2002-08-06 | 2004-03-04 | Kurita Water Ind Ltd | Method for evaluating local corrosion and method for suppressing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102121944A (en) * | 2010-01-08 | 2011-07-13 | 技鼎股份有限公司 | Microprobe structure and manufacturing method thereof |
| CN103076365A (en) * | 2013-01-08 | 2013-05-01 | 苏州热工研究院有限公司 | Pen-type potential-chloride ion sensor |
| CN104155476A (en) * | 2014-06-16 | 2014-11-19 | 厦门乐钢材料科技有限公司 | Compound microprobe for in-situ measurement of STM image and chloride ion concentration distribution and preparation method thereof |
| CN105021682A (en) * | 2015-07-02 | 2015-11-04 | 浙江大学 | Needle-like chlorine ion sensor and preparation method thereof |
| CN105067684A (en) * | 2015-07-02 | 2015-11-18 | 浙江大学 | Needle-shaped potassium ion sensor and preparation method thereof |
| CN105067684B (en) * | 2015-07-02 | 2018-02-23 | 浙江大学 | A kind of needle-like potassium ion sensor and preparation method thereof |
| CN105223252A (en) * | 2015-10-23 | 2016-01-06 | 吴国清 | A kind of sodium, potassium, chlorion biochemical analysis dry plate and preparation method thereof |
| CN105223245A (en) * | 2015-10-23 | 2016-01-06 | 吴国清 | A kind of chlorion biochemical analysis dry plate and preparation method thereof |
| CN106645809A (en) * | 2016-10-14 | 2017-05-10 | 厦门大学 | Preparation method for isolated needle point with housing layers wrapped in dual manner |
| CN109142490A (en) * | 2017-06-15 | 2019-01-04 | 无锡德医爱德医疗器材有限公司 | All-solid sodium ion selective sensor and its preparation and application |
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Assignee: Ningbo Haike Constructional Corrosion Control Engineering Technology Co., Ltd. Assignor: Xiamen University Contract fulfillment period: 2008.10.20 to 2013.10.30 contract change Contract record no.: 2008351000003 Denomination of invention: Composite scanning chlorion sensitive micro-probe and preparing process thereof Granted publication date: 20080109 License type: Exclusive license Record date: 20081021 |
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