CN1035735C - Metal/polymer composite material interface electric potential distribution measuring device - Google Patents
Metal/polymer composite material interface electric potential distribution measuring device Download PDFInfo
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- CN1035735C CN1035735C CN95107524A CN95107524A CN1035735C CN 1035735 C CN1035735 C CN 1035735C CN 95107524 A CN95107524 A CN 95107524A CN 95107524 A CN95107524 A CN 95107524A CN 1035735 C CN1035735 C CN 1035735C
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Abstract
The present invention relates to a device for testing or analyzing materials by using an electrochemical method. An M*N array electrode and a reference electrode are put in an electrolytic bath, the lead-out end of the array electrode is connected to a multi-channel analog switch, and the output passes through an A/D converter and then is sent to a microcomputer. The control signal output by the microcomputer passes through a digital I/O and a level converter to be connected to the multi-channel analog switch. The device can directly implement the in-situ measurement of the potential distribution of a metal/polymer interface so as to research the transmission process of a corrosive material in a polymer coating layer, the non-homogeneity and the defect distribution of the polymer coating layer and the corrosion electrochemical mechanism of the metal/polymer interface and evaluate the corrosion resistance of the polymer coating layer.
Description
The present invention relates to a kind of device with electrochemical method test or analysis of material.
Various compound substances such as metal/polymer or metal/inorganic material have more and more important effect in modern project.The damage inactivation of these compound substances at first occurs in the interface of metal/polymer or metal/inorganic material usually.The essential overwhelming majority of the corrosion failure of metal/coating interface is an electrochemical process, therefore, multiple electrochemical techniques comprise that direct current steady state techniques and ac impedance technology etc. are widely used in studying the corrosion failure mechanism at metal/polymer interface, and the corrosion resisting property of evaluation and test coating.Yet because the polymkeric substance high-insulativity of metal surface, the traditional electrical chemistry is difficult to detect the corrosion behavior at metal/polymer interface.The measurement of metal/polymer interfacial corrosion current potential is understood the corrosion failure mechanism of metal/polymer composite material for research metal/polymer interface inhomogeneity, and the corrosion resisting property of evaluation and test organic polymer coat is very important.
Develop multiple technologies at present both at home and abroad and attempted to measure metal/polymer interface inhomogeneity, comprised scanning ac impedance technology, synnema electrode and scanning Kelvin probe technique etc.J.V.Standish and H.Leidheiser Jr. (Corrosion, 1980,36:390) the scanning ac impedance technology of Ti Chuing is to utilize miniature probe to scan at organic coating layer surface, and apply the ac-excited signal of single-frequency, the current-responsive of surface measurements diverse location is to obtain the AC impedance distribution plan.T.Y.Jun (Progressin Organic Coatings, 1991,19:95) the synnema electrode of Ti Chuing is to be enclosed in admittedly together with epoxy resin behind a branch of tinsel mutually insulated, tinsel is stochastic distribution, the cross section is coated with organic coating, thereafter place solution manual measurement resistance wiry one by one, thereby obtain the inhomogeneity of organic coating.(Phys.Chen., 1991,95:1365 such as M.Stratmann; Electrocjimica Acta, 1994,39:1207) Yan Jiu scanning Kelvin probe technique is to utilize a chromium/nickel needle point with the fixed frequency concussion (being the Kelvin probe) to scan at coating surface, by measuring voltaic (Volta) current potential between coating surface and the probe, can obtain the corrosion potential of metal/coating interface.Above-mentioned these technology have bigger limitation, scanning ac impedance technology and synnema electrode method all can not directly obtain the three-dimensional corrosion potential in metal/polymer interface and distribute, scanning Kelvin probe technique surveying instrument complexity, and when coating is thicker, be difficult to record the corrosion potential distribution of metal/coating interface.
The object of the present invention is to provide a kind of employing array electrode to cooperate multiple-channel electronic switches and micro-computer technology, but direct in-situ is measured the device that metal/polymer composite material interface electric potential distributes.
The present invention is made up of array electrode, reference electrode, electrolytic cell, multichannel analog switch, A/D converter, microcomputer, level translator.Wherein, array electrode is pressed M * N arrayed by one group of tinsel, and an end wiry is encapsulated in the insulating material lasso, end section brushing organic polymer coating, mutually insulated between every one metal wire.Array electrode and reference electrode place in the electrolytic cell, and the exit of array electrode connects multichannel analog switch and multichannel A/D converter respectively, and a public I/O end of multichannel analog switch links to each other with reference electrode.The output of multichannel A/D converter connects microcomputer, and the digital I/O port output of microcomputer connects level translator, and the ON/OFF control signal of level translator connects the multichannel analog switch.
Array electrode can adopt M * M array to be arranged in parallel.The multichannel analog switch can adopt CMOS-4 road bidirectional analog switch.
Utilize measuring system of the present invention, the control signal of sending when microcomputer makes the exit of array electrode all connect, and promptly is equivalent to a slice base metal surfaces and is covered with coating; And work as computer control the array electrode exit is disconnected mutually, and 64 electrodes are carried out corrosion potential scanning survey (array electrode exit disconnect mutually and time of potential measurement about the millisecond order of magnitude) one by one by Controlled by Microcomputer, by plotting program metals plotted/polymer interface corrosion potential (three dimensions) figure that distributes.Obviously, but the present invention's direct in-situ is measured metal/coating interface corrosion potential and is distributed, and can obtain the transmission course in the relevant coating thus, the inhomogeneity of coating and defect distribution, important research information such as metal erosion failure mechanism also can be used for evaluating and testing corrosion resistance of coating under the coating; The present invention not only can be used for studying the behavior of metal/polymer interfacial corrosion, but also can measure metal/inorganic material interfacial corrosion current potential and other composite material interface electric potential.Utilize the visual visual and clear of gained of the present invention, be convenient to data analysis, and method is simple, applicability is wide.Measuring method of the present invention and effect will be further described in following practical measuring examples.
Fig. 1 is a theory diagram of the present invention.
Fig. 2 is an array electrode structural drawing of the present invention.
Fig. 3 is the upward view of Fig. 3.
Fig. 4 is circuit theory diagrams of the present invention.
Fig. 5 is computer controlled measurement metal/coating interface corrosion potential distribution process flow diagram.
Fig. 6 is for to flood 4h in the 0.1M sodium chloride solution, the about 50 μ m thickness nitrate paints of array electrode surface-coated, the corrosion potential distribution plan of metal/coating interface when coating slightly scratches.
Fig. 7 is the X-Y distribution plan of Fig. 6.
Fig. 8 is for to flood 24h in the 0.1M sodium chloride solution, the about 50 μ m thickness nitrate paints of array electrode surface-coated, the corrosion potential distribution plan of metal/coating interface when coating slightly scratches.
Fig. 9 is the X-Y distribution plan of Fig. 8.
Figure 10 is for to flood 4h in the 0.1M sodium chloride solution, the about 50 μ m thickness nitrate paints of array electrode surface-coated, the corrosion potential distribution plan of metal/coating interface when coating has air blister defect.
Figure 11 is the X-Y distribution plan of Figure 10.
Figure 12 is for to flood 120h in the 0.1M sodium chloride solution, the about 50 μ m thickness nitrate paints of array electrode surface-coated, the corrosion potential distribution plan of metal/coating interface when coating has air blister defect.
Figure 13 is the X-Y distribution plan of Figure 12.
Figure 14 is for to flood 72h in the 0.1M sodium chloride solution, the about 50 μ m thickness nitrate paints of array electrode surface-coated, the corrosion potential distribution plan of metal/coating interface when substrate surface is polluted by corrosion.
Figure 15 is the X-Y distribution plan of Figure 14.
Figure 16 is for to flood 136h in the 0.1M sodium chloride solution, the about 50 μ m thickness nitrate paints of array electrode surface-coated, the corrosion potential distribution plan of metal/coating interface when substrate surface is polluted by corrosion.
Figure 17 is the X-Y distribution plan of Figure 16.
Theory diagram of the present invention as shown in Figure 1, by the surface apply cated 8 * 8 array electrodes (1), Electrolytic cell (2), multichannel analog switch (3), reference electrode (4), A/D converter (5), little calculating Machine (6) and level translator (8) form. Referring to Fig. 2,3, the array electrode is by a branch of 64 diameters For the wire (for example iron wire) of 0.3mm is arranged in parallel by 8 * 8 arrays, the one end seals with epoxy resin Be contained in the lucite lasso (11), the organic polymer coating (12) that the end section brushing will be studied, Mutually insulated between every wire. The research of array electrode fit on is inserted with reference to electricity with electrolytic cell (2) The utmost point (4) is filled with the various solution mediums of required research. All electrode leads to client of array electrode are direct Be connected with measuring system by multichannel analog switch (3), from the experiment parameter of computer installation necessity (as measure number of times, measure blanking time, total experimental period etc.), working procedure can automatically measure and Draw metal/polymer interface corrosion potential distribution image.
Fig. 4 provides circuit theory diagrams of the present invention, and 8 * 8 array electrodes are imported by JP1, receives the input of No. 64 multiplexers of ADC by JP2, and receives simultaneously U1～U
1616 CMOS-4 roads An I/O end of two-way analog switch (MC4066), another I/O end of 16 MC4066 is connected Link to each other together, and with reference electrode (4). When PC from JP3 output TTL high level (＞3.6V) time, warp U17(LF351) level conversion output+5V, the MC4066 switch conduction, all electrodes are shorted together. And when the high level of PC output TIL (＜0.35V) time, through U17Level conversion output-5V, the MC4066 switch Cut-off, at this moment each electrode independently separately can be selected respectively to measure by the ADC multiplexer. Thus can See, control so that the exit of array electrode all connects when microcomputer (PC), namely be equivalent to a slice The base metal surface is covered with coating, and work as microcomputer control the array electrode leads to client is disconnected mutually, and by Microcomputer control is carried out one by one scanning survey of corrosion potential to 64 electrodes, and measurement data is changed through A/D, Send microcomputer to process, be depicted as the three dimensions potential image by plotting program, the multichannel analog switch Action is sent signal by microcomputer, is controlled by digital I/O port (7) level translator. Usually exist Under the immersion condition, 64 whole short circuits of line end of array electrode together, namely variable connector is in " opening " State, and only when measuring metal/coating interfacial corrosion current potential, 64 line ends of array electrode are All mutually disconnect, at this moment, variable connector is in " breaking " state. Computer-controlled measurement flow process Figure as shown in Figure 5. Below provide 3 and measure example.
Fig. 6～9 for array electrode applies the thick zapon of about 50 μ m, there is together slight artificial cut on the surface, the interfacial corrosion Potential distribution image of dipping 4 hours and 24 hours in 0.1M NaCl solution.The Potential distribution image clearly indicates defective (scuffing) position of polymer coating.Corrosion preferentially takes place at defective locations, and there is the cathodic area in the anodic site of center for corroding in defective on every side in the anodic site, and corrosion process develops with soak time.Can responsively detect the holiday position thus, investigate the influence of defective coating or compound substance corrosion failure.
2. Figure 10～13 are the thick zapons of the about 50 μ m of array electrode surface-coated, the interfacial corrosion Potential distribution image of dipping 4 hours and 120 hours in 0.1MNaCl solution.The most negative position of corrosion potential is just in time corresponding to the bubble position in the coating (bubble is introduced naturally by coating procedure) among the figure.Bubble is a defective important and common in the polymer coating, and obviously corrosion at first occurs in the position of air blister defect, and develops along with soak time.
3. Figure 14～17th, the about 50 μ m left and right sides zapons of array electrode surface-coated, the interfacial corrosion Potential distribution image of dipping 72 hours and 136 hours in 0.1MNaCl solution.Find that organic coating is uneven, corrosion failure preferentially occurs in weak position, and develops in time.Pay particular attention to, be attended by the existence of cathodic area (position of current potential paddy) in the anodic site (current potential peak position) of corrosion on every side.Dissolving, the corrosion of metal take place in the anodic site, and in the cathodic area coating foaming, delamination destruction are taken place.The cathodic area is constantly expansion also, and the anodic site is development thereupon also, the basic process of Here it is metal/polymer corrosion failure.
Claims (3)
1. measure the device that metal/polymer composite material interface electric potential distributes for one kind, this device comprises: array electrode, reference electrode, electrolytic cell, multichannel analog switch, A/D converter, microcomputer and level translator, therein, described array electrode is pressed M * N arrayed by a branch of tinsel, an end wiry is encapsulated in the insulating material lasso, end section brushing organic polymer coating, mutually insulated between every one metal wire; Array electrode and reference electrode place in the electrolytic cell, and another exit of array electrode connects multichannel analog switch and multichannel A/D converter respectively, and a public I/O end of multichannel analog switch links to each other with reference electrode; The output of multichannel A/D converter connects microcomputer, and the digital I/O port output of microcomputer connects level translator, and the ON/OFF control signal of level translator connects the multichannel analog switch.
2. device according to claim 1 is characterized in that described array electrode is that M * M array is arranged in parallel.
3. device according to claim 2 is characterized in that described array electrode is that 8 * 8 arrays are arranged in parallel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107524A CN1035735C (en) | 1995-07-04 | 1995-07-04 | Metal/polymer composite material interface electric potential distribution measuring device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107524A CN1035735C (en) | 1995-07-04 | 1995-07-04 | Metal/polymer composite material interface electric potential distribution measuring device |
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| Publication Number | Publication Date |
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| CN1119739A CN1119739A (en) | 1996-04-03 |
| CN1035735C true CN1035735C (en) | 1997-08-27 |
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| CN95107524A Expired - Fee Related CN1035735C (en) | 1995-07-04 | 1995-07-04 | Metal/polymer composite material interface electric potential distribution measuring device |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100338455C (en) * | 2005-03-18 | 2007-09-19 | 韶关学院 | On-line monitoring method for failure state of metal and protection layer inter face |
| CN115406945A (en) * | 2022-07-13 | 2022-11-29 | 武汉科思特仪器股份有限公司 | Sensor, system and method for online evaluation of coating life |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104120430B (en) * | 2013-04-27 | 2017-08-11 | 中国科学院金属研究所 | Inner potential Two dimensional Distribution measurement apparatus in gap under a kind of release coating |
| CN104122307B (en) * | 2013-04-27 | 2017-04-19 | 中国科学院金属研究所 | Multichannel potential measuring instrument |
| CN107389753A (en) * | 2015-02-25 | 2017-11-24 | 天津大学 | Cracks of metal surface detection method based on electrochemistry the cannot-harm-detection device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86103043A (en) * | 1986-04-28 | 1986-11-12 | 厦门大学 | The scanister that testing micro zone corrosion electric potential current density distributes |
| WO1993008460A1 (en) * | 1991-10-22 | 1993-04-29 | Isi Abt Services Limited | Surface sensing equipment |
-
1995
- 1995-07-04 CN CN95107524A patent/CN1035735C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86103043A (en) * | 1986-04-28 | 1986-11-12 | 厦门大学 | The scanister that testing micro zone corrosion electric potential current density distributes |
| WO1993008460A1 (en) * | 1991-10-22 | 1993-04-29 | Isi Abt Services Limited | Surface sensing equipment |
Non-Patent Citations (1)
| Title |
|---|
| PHYS CHEN,1991.95 1365 1991.1.1 M ST RATMAHH EF ALL PROGRESS ORGWHIC COATINGS,1991,1995 1991.1.1 T Y JUM ETAF * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100338455C (en) * | 2005-03-18 | 2007-09-19 | 韶关学院 | On-line monitoring method for failure state of metal and protection layer inter face |
| CN115406945A (en) * | 2022-07-13 | 2022-11-29 | 武汉科思特仪器股份有限公司 | Sensor, system and method for online evaluation of coating life |
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| CN1119739A (en) | 1996-04-03 |
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