CN102087202A - Preparation method of all solid state reference electrode for monitoring reinforcement corrosion - Google Patents
Preparation method of all solid state reference electrode for monitoring reinforcement corrosion Download PDFInfo
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Abstract
The invention provides a preparation method of an all solid state reference electrode for monitoring reinforcement corrosion, which is realized as follows: firstly, preparing a mixed metallic oxide function core of binary alloy by the EB-PVD (Electron Beam Physical Vapor Deposition) process; then, preparing an alkalinity conductive function layer by a montmorillonite composite material with excellent spatial structure; and finally, integrating the products to construct the solid state reference electrode with five-layer structure. The preparation method comprises the following specific steps of: preparing the function core of the reference electrode; preparing the function layer of the reference electrode; and preparing a cement transition layer. In the method, the binary alloy film is prepared on batch by the double-resource EB-PVD sputtering of a vacuum cavity with the diameter of 1m, the consistency of the microstructure of the film is guaranteed, and the consistency of the electrochemistry performance of the film is guaranteed. The EB-PVD deposition rate is high, and hundreds of micrometers of the function layer film can be deposited within 10-30min, and preparation time is greatly shortened.
Description
(1) technical field
The present invention relates to chemistry subject, is exactly the preparation method of a kind of monitoring corrosion of steel with all-solid-state reference electrode specifically.
(2) background technology
The reinforcement corrosion that studies show that in past is to cause one of steel and concrete structure damage and failure reasons, the whole world has dropped into great amount of manpower and material resources and financial resources to the maintenance and repair and the replacing member of corrosion structure, and the monitoring of reinforcement corrosion is the important component part of structural safety evaluation, maintenance and reinforcement and life-cycle design in civil engineering work.Under the concrete environment, because concrete poriness, moisture and oxygen can be along hole and crackle migrations, and this is the necessary condition of corrosions of steel such as mild carbon steel and high strength alloy steel just.It is in these holes because the hydration process of cement has formed the oxyhydroxide of calcium, sodium and the potassium of high concentration that reason for corrosion does not take place under most of situations, thereby kept pH value between 12～13, this high basicity environment is the steel passivation, forms the quick corrosion that fine and close γ type iron oxide has prevented steel.Yet, work as Cl
-(from deicer salts or seawater) assembled or because CO at rebar surface through concrete surface
2The effect of (from atmosphere, also being one of key factor that causes global warming) makes under the situation of hole solution pH value reduction, and passivating film is destroyed, and concrete lost efficacy to the protective effect of reinforcing bar, at O
2And H
2Under the situation of O abundance reinforcing steel area reduce or occur the erosion point.
The corrosion process of most in the civil engineering work (except the reaction of part high-temperature oxydation) steel all is an electrochemical process, so electrochemical method becomes the most essential method of corrosion of steel in the monitoring of structures.Researcher both domestic and external in the last few years adopts electrochemical method that the corrosion science problem has been carried out a large amount of research, research by stable state and transient state electrochemical method, not only can obtain such as corrosion electric current density, the such basic parameter of corrosion rate, can also learn the more detailed information that discloses the corrosion electrochemistry process, as generating process of polarization resistance, electric double layer capacitance, diffusion process, spot corrosion or the like.The measurement of these parameters can provide foundation more reliably for corrosion monitoring.
Foundation can in real time, accurately be grasped the etch state of reinforcing bar based on the corrosion monitoring system of electrochemical techniques, for the man-rate and the life-cycle design of extensive steel and concrete structure provides scientific basis.The Electrochemical Measurement Technology of corrosion sensor horn of plenty provides hardware supported, is to guarantee that various corrosion monitoring process can be able to application carrier and platform in actual engineering.(Reference Electrode is the core component that constitutes corrosion sensor RE) to contrast electrode, is " scale " of corrosion electrochemistry test process vacuum metrics electrode potential.Contrast electrode is the core parts that make up the monitoring corrosion of steel sensor.Research at present and the all-solid-state reference electrode of using are gone back ubiquity electrode potential instability, are subject to problems such as such environmental effects and service life weak point.
(3) summary of the invention
The object of the present invention is to provide the preparation method of a kind of monitoring corrosion of steel with all-solid-state reference electrode.
The object of the present invention is achieved like this: at first adopt the EB-PVD technology to prepare the mixed-metal oxides function core of bianry alloy, use smectite Composite Preparation alkalescence conducting function layer then with excellent space structure, last integrated above-mentioned achievement, framework has the all-solid-state reference electrode of 5 layers of structure; Step is as follows:
Step 1: preparation contrast electrode function core
The preparation of contrast electrode function core comprises EB-PVD attitude and two processes of oxidation state, by optimizing the EB-PVD deposition process parameters, obtains preparing attitude bianry alloy film on the Ti rod; And then, by the control partial pressure of oxygen alloy film for preparing attitude is carried out oxidation processes.Adopt dual-source evaporation EB-PVD to prepare alloy film, by adjusting substrate temperature, rate of sedimentation, target-substrate distance, steam incident angle optimal preparation technology.In the ratio change procedure from low to high of the fusing point Tm of substrate temperature Ts and evaporating materials, the rete of formation is changed to axialite through column crystal by amorphous state, selected 0.3＜Ts/Tm＜0.5 and a substrate temperature district, 0.5＜Ts/Tm＜1 two; Selected EB-PVD controlled variable sees Table 1
The controlled variable of table 1EB-PVD deposition functional film layer
Bianry alloy film after EB-PVD preparation finished carries out oxidation processes in high temperature furnace, oxidizing temperature is 760 ℃, and holding the time of carrying is 20min, and heating rate is 5 ℃/min.
Step 2: preparation contrast electrode conducting function layer
With the carrier material of smectite as solid state reference electrode conducting function layer, carry out interlayer ion and be mingled with, form contrast electrode conductive layer, exchange cation and H with satisfactory electrical conductivity
2O is connected with faint hydrogen bond, forms hydration status, thereby reduces H
2The flowability of O molecule, and then in interlayer structure, make kation exist with stable solution state, adopt smectite: conducting particles: water is 1: 0.6: 0.3, adopt smectite and the conducting particles of diameter≤100 μ m to carry out dry mash premix 30min in the preparation process, add distilled water then and stir 30min once more, the conduction slurries that finally prepare are injected in the housing of contrast electrode.
Step 3: the preparation of cement transition bed
Inject P.O.42.5 cement in the sensor housing bottom: the cement grout of water=1: 0.4, adopt the compacting of 1MPa pressure, forming highly is the grout cylinder of 0.5cm, is maintenance 7 days under 80 ℃, appropriate 90% state in temperature;
Step 4: the encapsulation of contrast electrode
Welding Cu lead in the hole that Ti rod axle center is reserved injects epoxy sealing then in the PVC of contrast electrode housing, the epoxy resin layer thickness is 0.5cm.Behind epoxy resin cure, the end of PVC housing emitted tighten;
Step 5: the preservation of contrast electrode
The contrast electrode of preparation attitude adopts the medicinal alcohol wiping, puts into then and adopts medical cotton-wool environmental sealing at vacuum box, and vacuum box is once opening, and contrast electrode need be installed in the locations of structures of required monitoring immediately, enters the military service phase.
Ultimate principle of the present invention is to have stable electrochemical potential E development according to MMO under stable conducting function layer environment to come.Because the needs of large-scale industrial production adopt the double source EB-PVD sputter mass with diameter 1m vacuum chamber to prepare the bianry alloy film, guarantee the consistance of the micromechanism of film, and then guarantee the consistance of thin film electrochemistry performance.In addition, the rate of sedimentation of EB-PVD is very fast, can deposit hundreds of microns functional layer film in 10min～30min, greatly reduces preparation time.The film of preparation attitude adopts the rear oxidation PROCESS FOR TREATMENT, makes film the gradient state of complete oxidation occur never being oxidized to, guarantees the validity of chemical property.Employing has the montmorillonite material of excellent space structure as carrier, for contrast electrode function core provides the conducting function of stablizing Service Environment layer.Finally, adopt to have cement slurry, to reduce liquid junction potential (Liquid Junction Potentials, influence LJP), and the all-solid-state reference electrode of structure five-layer structure as transition bed.
(4) description of drawings
Fig. 1 is the MMO all-solid-state reference electrode synoptic diagram with five-layer structure;
Fig. 2 is an EB-PVD equipment synoptic diagram;
Fig. 3 is a smectite space structure synoptic diagram.
(5) specific embodiments
The invention will be further described for example below in conjunction with accompanying drawing.
Embodiment 1: in conjunction with Fig. 1, a kind of monitoring corrosion of steel of the present invention is with the preparation method of all-solid-state reference electrode: at first adopt the EB-PVD technology to prepare the mixed-metal oxides function core of bianry alloy, use smectite Composite Preparation alkalescence conducting function layer then with excellent space structure, last integrated above-mentioned achievement, framework has the all-solid-state reference electrode of 5 layers of structure; Step is as follows:
Step 1: preparation contrast electrode function core
The preparation of contrast electrode function core comprises EB-PVD attitude and two processes of oxidation state, by optimizing the EB-PVD deposition process parameters, obtains preparing attitude bianry alloy film on the Ti rod; And then, by the control partial pressure of oxygen alloy film for preparing attitude is carried out oxidation processes.Adopt dual-source evaporation EB-PVD to prepare alloy film, by adjusting substrate temperature, rate of sedimentation, target-substrate distance, steam incident angle optimal preparation technology.In the ratio change procedure from low to high of the fusing point Tm of substrate temperature Ts and evaporating materials, the rete of formation is changed to axialite through column crystal by amorphous state, selected 0.3＜Ts/Tm＜0.5 and a substrate temperature district, 0.5＜Ts/Tm＜1 two; Selected EB-PVD controlled variable sees Table 1
The controlled variable of table 1EB-PVD deposition functional film layer
Bianry alloy film after EB-PVD preparation finished carries out oxidation processes in high temperature furnace, oxidizing temperature is 760 ℃, and holding the time of carrying is 20min, and heating rate is 5 ℃/min.
Step 2: preparation contrast electrode conducting function layer
With the carrier material of smectite as solid state reference electrode conducting function layer, carry out interlayer ion and be mingled with, form contrast electrode conductive layer, exchange cation and H with satisfactory electrical conductivity
2O is connected with faint hydrogen bond, forms hydration status, thereby reduces H
2The flowability of O molecule, and then in interlayer structure, make kation exist with stable solution state, adopt smectite: conducting particles: water is 1: 0.6: 0.3, adopt smectite and the conducting particles of diameter≤100 μ m to carry out dry mash premix 30min in the preparation process, add distilled water then and stir 30min once more, the conduction slurries that finally prepare are injected in the housing of contrast electrode.
Step 3: the preparation of cement transition bed
Inject P.O.42.5 cement in the sensor housing bottom: the cement grout of water=1: 0.4, adopt the compacting of 1MPa pressure, forming highly is the grout cylinder of 0.5cm, is maintenance 7 days under 80 ℃, appropriate 90% state in temperature;
Step 4: the encapsulation of contrast electrode
Welding Cu lead in the hole that Ti rod axle center is reserved injects epoxy sealing then in the PVC of contrast electrode housing, the epoxy resin layer thickness is 0.5cm.Behind epoxy resin cure, the end of PVC housing emitted tighten;
Step 5: the preservation of contrast electrode
The contrast electrode of preparation attitude adopts the medicinal alcohol wiping, puts into then and adopts medical cotton-wool environmental sealing at vacuum box, and vacuum box is once opening, and contrast electrode need be installed in the locations of structures of required monitoring immediately, enters the military service phase.
Embodiment 2: as follows in conjunction with Fig. 1, Fig. 2, Fig. 3 principle of the present invention and preparation technology:
1.MMO the preparation of contrast electrode function core
The preparation of MMO comprises EB-PVD attitude and two processes of oxidation state, by optimizing the EB-PVD deposition process parameters, obtains preparing attitude bianry alloy film on the Ti rod; And then, by the control partial pressure of oxygen alloy film for preparing attitude is carried out oxidation processes.Adopt dual-source evaporation EB-PVD shown in Figure 2 to prepare alloy film, by adjusting parameter optimization preparation technologies such as substrate temperature, rate of sedimentation, target-substrate distance, steam incident angle.In the ratio change procedure from low to high of the fusing point Tm of substrate temperature Ts and evaporating materials, the rete that forms is changed to equiax crystal through column crystal by amorphous state, consider the military service performance of all-solid-state reference electrode, selected 0.3＜Ts/Tm＜0.5 and a substrate temperature district, 0.5＜Ts/Tm＜1 two; The rate of sedimentation of EB-PVD a large amount of holes and defective can occur in the rete when very fast relatively, yet after reducing rate of sedimentation, hole reduces gradually, and the compactness of rete also improves; Along with the raising of target-substrate distance, the alloy film laminar surface roughness of EB-PVD preparation presents downtrending, but target-substrate distance is excessive, and deposition efficiency significantly reduces, thus need be under the prerequisite that guarantees rete military service performance, balance rate of sedimentation and surfaceness; Along with the variation of steam incident angle, marked change can take place in the direction of growth of rete columnar grain and since as the Ti rod of matrix (height 2cm) in deposition process around its axis rotation, so incident angle is less to the influence of functional film layer homogeneity.Take all factors into consideration the influence of above-mentioned factor, selected EB-PVD controlled variable sees Table 1.Bianry alloy film after EB-PVD preparation finished carries out oxidation processes in high temperature furnace, oxidizing temperature is 760 ℃, and holding the time of carrying is 20min, and heating rate is 5 ℃/min.
The controlled variable of table 1EB-PVD deposition functional film layer
2. the preparation of contrast electrode conducting function layer
By the current potential of contrast electrode control or measurement Research electrode surface, in this process, need faint electric current and arrive contrast electrode function core, thereby make the function core can play the effect of contrast electrode.The conducting function layer provides path for this weak current on the one hand; In addition,, thereby guarantee the stability of the current potential of contrast electrode own, promptly fixedly keep the particle of electrode function core electrochemical properties, make it can not run off along with the variation of environment in the concrete also for contrast electrode function core provides stable Service Environment.
The three-D space structure pattern that smectite had has determined it to can be used as solid state reference electrode conducting function layer and has got the ideal carrier material.Use E
x(H
2O)
4{ (Al
2-x, Mg
x)
2[(Si, Al)
4O
10] (OH)
2The excellent stratiform space structure (as shown in Figure 3) of smectite, carry out interlayer ion and be mingled with, can form contrast electrode conductive layer with satisfactory electrical conductivity.In addition, exchange cation and H
2O is connected with faint hydrogen bond, forms hydration status, thereby reduces H
2The flowability of O molecule, and then in interlayer structure, make kation exist with stable solution state.Concrete is because hydrated reaction of cement forms the high alkalinity environment, the different meetings of kind, concentration, activity, rate of diffusion and the diffusing capacity of particle cause appearance (the Liquid Junction Potentials of liquid junction potential between conducting function layer and the concrete, LJP), the existence meeting of LJP further hinders the transmission of ion, influences the military service performance of electrode.Take all factors into consideration above-mentioned factor, adopt smectite: conducting particles: water is 1: 0.6: 0.3.Adopt smectite and the conducting particles of diameter≤100 μ m to carry out dry mash premix 30min in the preparation process, add distilled water then and stir 30min once more, the conduction slurries that finally prepare are injected in the housing of contrast electrode.
3. the preparation of cement transition bed
Inject P.O.42.5 cement in the sensor housing bottom: the cement grout of water=1: 0.4, adopt the compacting of 1MPa pressure, forming highly is the grout cylinder of 0.5cm, is that maintenance got final product in 7 days under 80 ℃, appropriate 90% state in temperature.
4. the encapsulation of contrast electrode
Welding Cu lead in the hole that Ti rod axle center is reserved injects epoxy sealing then in the PVC of contrast electrode housing, the epoxy resin layer thickness is 0.5cm.Behind epoxy resin cure, the end of PVC housing emitted tighten.
5. the preservation of contrast electrode
In order to guarantee the validity of contrast electrode before formal the military service, the contrast electrode of preparation attitude adopts the medicinal alcohol wiping, puts into then and adopts medical cotton-wool environmental sealing at vacuum box, and vacuum box is once opening, contrast electrode need be installed in the locations of structures of required monitoring immediately, enters the military service phase.
Claims (1)
1. a monitoring corrosion of steel is with the preparation method of all-solid-state reference electrode, it is characterized in that: at first adopt the EB-PVD technology to prepare the mixed-metal oxides function core of bianry alloy, use smectite Composite Preparation alkalescence conducting function layer then with excellent space structure, last integrated above-mentioned achievement, framework has the all-solid-state reference electrode of 5 layers of structure; Step is as follows:
Step 1: preparation contrast electrode function core
The preparation of contrast electrode function core comprises EB-PVD attitude and two processes of oxidation state, by optimizing the EB-PVD deposition process parameters, obtains preparing attitude bianry alloy film on the Ti rod; And then, by the control partial pressure of oxygen alloy film for preparing attitude is carried out oxidation processes; Adopt dual-source evaporation EB-PVD to prepare alloy film, by adjusting substrate temperature, rate of sedimentation, target-substrate distance, steam incident angle optimal preparation technology, in the ratio change procedure from low to high of the fusing point Tm of substrate temperature Ts and evaporating materials, the rete that forms is changed to axialite through column crystal by amorphous state, selected 0.3＜Ts/Tm＜0.5 and a substrate temperature district, 0.5＜Ts/Tm＜1 two; Selected EB-PVD controlled variable sees Table 1
The controlled variable of table 1EB-PVD deposition functional film layer
Bianry alloy film after EB-PVD preparation finished carries out oxidation processes in high temperature furnace, oxidizing temperature is 760 ℃, and holding the time of carrying is 20min, and heating rate is 5 ℃/min;
Step 2: preparation contrast electrode conducting function layer
With the carrier material of smectite as solid state reference electrode conducting function layer, carry out interlayer ion and be mingled with, form contrast electrode conductive layer, exchange cation and H with satisfactory electrical conductivity
2O is connected with faint hydrogen bond, forms hydration status, thereby reduces H
2The flowability of O molecule, and then in interlayer structure, make kation exist with stable solution state, adopt smectite: conducting particles: water is 1: 0.6: 0.3, adopt smectite and the conducting particles of diameter≤100 μ m to carry out dry mash premix 30min in the preparation process, add distilled water then and stir 30min once more, the conduction slurries that finally prepare are injected in the housing of contrast electrode;
Step 3: the preparation of cement transition bed
Inject P.O.42.5 cement in the sensor housing bottom: the cement grout of water=1: 0.4, adopt the compacting of 1MPa pressure, forming highly is the grout cylinder of 0.5cm, is maintenance 7 days under 80 ℃, appropriate 90% state in temperature;
Step 4: the encapsulation of contrast electrode
Welding Cu lead injects epoxy sealing then in the PVC of contrast electrode housing in the hole that Ti rod axle center is reserved, and the epoxy resin layer thickness is 0.5cm, behind epoxy resin cure, the end of PVC housing is emitted tighten;
Step 5: the preservation of contrast electrode
The contrast electrode of preparation attitude adopts the medicinal alcohol wiping, puts into then and adopts medical cotton-wool environmental sealing at vacuum box, and vacuum box is once opening, and contrast electrode need be installed in the locations of structures of required monitoring immediately, enters the military service phase.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102353705A (en) * | 2011-06-28 | 2012-02-15 | 哈尔滨工业大学 | Preparation method of comb-shaped sensing unit for monitoring corrosion of steel |
| CN104792692A (en) * | 2015-04-09 | 2015-07-22 | 中国民航大学 | Corrosive working electrode |
| CN110333588A (en) * | 2019-08-12 | 2019-10-15 | 程慧玲 | One kind communicating networked devices based on Internet of Things security key |
| CN112011758A (en) * | 2020-07-16 | 2020-12-01 | 西安怡速安智能科技有限公司 | Anode production process for improving anode activity by electrochemical electrode PVD method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102353705A (en) * | 2011-06-28 | 2012-02-15 | 哈尔滨工业大学 | Preparation method of comb-shaped sensing unit for monitoring corrosion of steel |
| CN102353705B (en) * | 2011-06-28 | 2013-04-17 | 哈尔滨工业大学 | Preparation method of comb-shaped sensing unit for monitoring corrosion of steel |
| CN104792692A (en) * | 2015-04-09 | 2015-07-22 | 中国民航大学 | Corrosive working electrode |
| CN110333588A (en) * | 2019-08-12 | 2019-10-15 | 程慧玲 | One kind communicating networked devices based on Internet of Things security key |
| CN110333588B (en) * | 2019-08-12 | 2020-09-29 | 深圳市承和润文化传播股份有限公司 | Internet of things-based security key communication networking equipment |
| CN112011758A (en) * | 2020-07-16 | 2020-12-01 | 西安怡速安智能科技有限公司 | Anode production process for improving anode activity by electrochemical electrode PVD method |
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