CN102680387A - Real-time monitoring sensor for durability of concrete structures and fabricating method thereof - Google Patents
Real-time monitoring sensor for durability of concrete structures and fabricating method thereof Download PDFInfo
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Abstract
The invention discloses a real-time monitoring sensor for durability of concrete structures. The real-time monitoring sensor comprises a sensor shell, and further comprises a reference electrode, a rebar electrode, an auxiliary electrode, a chlorion probe, a pH probe and a concrete resistivity probe. The auxiliary electrode is laid on the upper surface of the shell, at least parts of the reference electrode, the rebar electrode, the chlorion probe, the pH probe and the concrete resistivity monitoring probe are exposed out of the upper surface of the sensor shell to serve as detecting ends, and the other ends are connected with copper cables which penetrate through the sensor shell from top to bottom and stretch out of the shell. According to the real-time monitoring sensor, not only corrosion rate, chlorion concentration and pH of rebar, but also concrete resistivity can be monitored in real time; further, system resistance can be compensated during the monitoring of rebar corrosion current density, and corrosion rate of rebar can be monitored more accurately by the monitoring of concrete resistance.
Description
Technical field
The present invention relates to reinforced concrete structures corrosion and guard technology field, particularly a kind of long-acting, harmless, the Multifunction Sensor that can monitor in real time concrete structure durability.
Technical background
Chlorion is invaded and concrete carbonization causes that the corrosion of reinforcing bar is the main reason that concrete structure durability descends, the military service security of serious threat xoncrete structure.Therefore, understand the residing chemical environment of reinforcing bar and etch state and corrosion rate closely, have great practical significance for the security and the durability evaluation of the science maintenance that guarantees reinforced concrete structure, military service residual life evaluation, structure.
Traditional concrete structure durability evaluation method mainly is to adopt the mode of getting the drillings sampling; Thereby grasp the permanance situation of xoncrete structure through powder appearance being carried out chemical analysis; This method is time-consuming, expensive, and xoncrete structure is had destructiveness, and can't realize real-time monitoring.Chloride of Concrete Structure is invaded and concrete carbonization causes that the corrosion of reinforcing bar mainly is galvanic corrosion, and the electrochemical monitoring method has original position, characteristics such as harmless, quick.Therefore development adopts the multifunction electric chemical sensor that thereby the chemical environment on etch state, corrosion rate and the surface thereof of reinforcing bar is monitored the inexorable trend that the permanance situation of comprehensively grasping xoncrete structure has become the development of permanance monitoring technology in real time.
" ladder type anode " monitoring system and the CorroWatch orificed anode permanance monitoring system processed based on macroscopical battery principle just appearred as far back as the eighties in last century.Can only judge qualitatively based on the permanance monitoring technology of this principle whether reinforcing bar corrodes, can't monitor its corrosion rate and each permanance parameter.Developed the ECI type flush type permanance monitor of directly measuring reinforcement corrosion speed based on linear polarization technique because of its U.S. VTI company, the built-in chlorion probe of ECI can be realized the real-time monitoring to reinforcement corrosion speed, chlorine ion concentration and concrete resistivity.Along with the continuous development of concrete durability technology, concrete pH also is the key factor that influences concrete durability, and it and each failure procedure all are closely related, but the ECI sensor does not possess the pH value is carried out real time monitoring function.
Domesticly also doing some researchs aspect the concrete structure durability monitoring in real time; Publication number is CN101334353A; Open day is on Dec 31st, 2008, and denomination of invention discloses a kind of corrosion rate, Cl that realizes reinforcing bar for the Chinese invention patent application of " a kind of Multifunction Sensor that is used for monitoring reinforced concrete structure erosion "
-The Multifunction Sensor that concentration and pH value are monitored in real time.Concrete is a kind of high resistant system, the corrosion rate of concrete resistance appreciable impact reinforcing bar.This patent of invention does not compensate system resistance with linear polarization method monitoring reinforcement corrosion speed the time, the corrosion rate that monitoring result can not true and accurate reaction reinforcing bar.In addition, contrast electrode is the core of monitoring system, adopts MnO in this invention
2Contrast electrode, reference electrolyte are liquid, adopt liquid electrolyte, and ion is prone to transmission in liquid, can not effectively reduce electrolytical loss, influences the stability and the serviceable life of contrast electrode.
Summary of the invention
The present invention provides a kind of long-acting, harmless, Multifunction Sensor that permanance parameters such as reinforcement corrosion speed, Cl concentration, pH value and concrete resistivity are monitored in real time realized; And can carry out real-Time Compensation to system resistance according to the monitoring result of concrete resistivity; Make the monitoring result of reinforcement corrosion speed more accurate, for durability evaluating provides data more accurately.
In order to realize the foregoing invention purpose; The present invention has adopted following technical scheme: a kind of real-time monitoring sensor of concrete structure durability that is used for; It comprises a sensor outer housing; Also comprise contrast electrode, reinforcing bar electrode, auxiliary electrode, Cl probe, pH value probe and concrete resistivity monitoring probe, said auxiliary electrode is tiled in the upper surface of said shell, said contrast electrode, reinforcing bar electrode, Cl
-Probe, pH value probe and concrete resistivity monitoring probe have at least part to be exposed to the sensor outer housing upper surface as end of probe, and the other end connects copper cable, and said copper cable penetrates said sensor outer housing from top to bottom and stretches out in housing exterior.
As a kind of embodiment, said contrast electrode and reinforcing bar electrode are vertically installed and are fixed in shell inner cavity, and its upper surface is exposed to the sensor outer housing upper surface, maintain an equal level with said auxiliary electrode upper surface.
As a kind of embodiment, the sensor outer housing upper surface is provided with the horizontal groove that can hold said Cl probe, pH value probe and concrete resistivity monitoring probe, said Cl
-Probe, pH value probe and concrete resistivity probe are placed in the said groove, and fix with epoxy resin.
Said contrast electrode is an Ag/AgCl gel electrolyte contrast electrode; Has the overcoat that a teflon is processed; Interior reference liquid adopts 0.5mol/L KCl methyl cellulose gel electrolyte; One end of overcoat is provided with micropore ceramics, can keep electrolytical circulation inside and outside the contrast electrode, can effectively control the bleed rate of electrolyte inside again.
Said concrete resistivity monitoring probe is that 4 parallel equidistant are from the stainless steel wire of arranging.
Said reinforcing bar electrodes use and monitored reinforcing bar are with the bar reinforcement of material.
Said auxiliary electrode is for having chemically inert MMO titanium base Mixed Metal Oxide Coated Titanium Anodes net, and anode network is tiled in the sensor outer housing upper surface, and is connected and sealed with epoxy resin.
Said Cl
-Probe is for adopting the Ag/AgCl electrode of anode chloridising preparation; Said pH value probe is the pure Ti metal probe of surface coverage oxide that Ir is arranged.
The present invention can not only realize that corrosion rate, Cl-concentration and the pH value to reinforcing bar monitor in real time; And can also realize concrete resistivity is monitored in real time; Through monitoring to concrete resistivity; Can when the reinforcement corrosion current density is monitored, compensate, obtain more accurately to monitor the corrosion rate of reinforcing bar system resistance.On the other hand, the present invention adopts the Ag/AgCl contrast electrode, and the Ag/AgCl contrast electrode compares MnO
2Contrast electrode has better stability and economy.The electrolyte of contrast electrode is a gel electrolyte, and gel electrolyte can effectively reduce the loss of contrast electrode electrolytic solution, improves the stability and the serviceable life of contrast electrode, thereby makes sensor have longer serviceable life.
Description of drawings
Fig. 1 is a Multifunction Sensor transversary principle schematic of the present invention.
Fig. 2 is a Multifunction Sensor vertical structure principle schematic of the present invention.
Fig. 3 is an Ag/AgCl contrast electrode electrode structure synoptic diagram.
Fig. 4 is Cl of the present invention
-The probe electrode current potential is with Cl
-The change curve of change in concentration.
Fig. 5 is the change curve that the electrode potential of pH value probe of the present invention changes with the pH value.
Embodiment
Fig. 1 and Fig. 2 are the vertical and horizontal structural representations of the Multifunction Sensor developed of the present invention, for the structure to Multifunction Sensor has understanding more clearly, among Fig. 1 with reinforcing bar electrode, contrast electrode, Cl
-Probe, pH value probe and concrete resistivity probe are arranged in order, and the arrangement of electrode and probe is as shown in Figure 2 among the embodiment.
It mainly comprises the sensor that is used for concrete structure durability monitoring in real time as illustrated in fig. 1 and 2: Ag/AgCl gel electrolyte contrast electrode 1, reinforcing bar electrode 2, auxiliary electrode 3, Cl probe 4, pH value probe 5, concrete resistivity monitoring probe 6, sensor outer housing 7, copper cable 11,21,31,41,51 and 61, the epoxy resin articulamentum 8 between auxiliary electrode 3 and the shell 7.
The multifunctional sensing implement body manufacturing approach that is used for concrete structure durability monitoring in real time of the present invention is following:
1. prepare contrast electrode 1, reinforcing bar electrode 2, auxiliary electrode 3, Cl respectively
- Probe 4, pH value probe 5 and concrete resistivity probe 6.
The preparation of contrast electrode 3: the KCl solution of preparation 0.5mol/L, will join solution be heated to more than 70 ℃, add methylcellulose (amount of adding adds the 1g methylcellulose by every 10mL solution) again in the solution of thermotropism.Be injected into teflon sleeve after slowly stirring, be cooled to room temperature and can make gel electrolyte.The Ag/AgCl electrode that is welded with copper cable is inserted along the center line of teflon sleeve, with epoxy resin the openend of teflon sleeve is carried out encapsulation process again and just can form Ag/AgCl contrast electrode of the present invention.As shown in Figure 3; The agent structure of contrast electrode 1 comprises copper cable 11, epoxy sealing cover 12, teflon sleeve 13, methylcellulose base gel electrolyte 14, Ag/AgCl electrode 15, micropore ceramics piece 16, epoxy resin fit sealing spare 17 teflon protective sleeves 18.
The preparation of reinforcing bar electrode 2: select for use and the bar reinforcement of actual monitored reinforcing bar with material; Be processed into the bar reinforcement of Φ 20 * 50mm; One end and the copper cable 21 of bar reinforcement weld; And with epoxy resin welding end surface and reinforcing bar side are sealed, unencapsulated other end is as workplace.
The preparation of auxiliary electrical anode 3: MMO titanium base Mixed Metal Oxide Coated Titanium Anodes net is processed into the rectangular-shaped of 70 * 80mm, and two circular holes of processing Φ 22 and Φ 24 on anode network are used to assemble contrast electrode and reinforcing bar electrode again.
The preparation of Cl probe 4: will be of a size of the bar-shaped pure Ag (99.99%) of Φ 2 * 25mm and the copper wire welding back of copper cable 41 and weld sealed, to prevent the generation of bimetallic corrosion with the suitable heat-shrink tube of diameter.The Ag rod is put into the greasy dirt that acetone soln is removed the surface behind 600# sand paper uniform grinding, put into 5% salpeter solution 1min after water cleans to remove the oxide on surface, more silver-colored rod is put into alcohol and cleans with ultrasound wave.Silver-colored rod after cleaning is put into electrolytic cell, and the silver rod is as anode, and MMO titanium base mixed-metal oxides is as negative electrode, with 1mA/cm
2Current density anode polarization in the HCl of 0.1mol/L solution made the Ag/AgCl probe in 0.5 hour, the KCl solution of the electrode for preparing being put into 0.1mol/L is for use.
The preparation of pH value probe 5: the bar-shaped pure titanium (99.99%) that will be of a size of Φ 2 * 25mm is put into 10% NaOH solution through 600# sand paper uniform grinding and is boiled and keep about 5 minutes; And then put into dense HCl and boil and keep about 10 minutes, take out after to put into absolute ethyl alcohol after cleaning with redistilled water subsequent use.
The chlordene iridium acid ammonium solution of preparation 1g/L immersed in the chamber type electric resistance furnace that dipping in the chlordene iridium acid ammonium solution evenly is placed on 75 ± 1 ℃ baking 0.5 hour with subsequent use titanium rod, repeated 3～5 times.The titanium rod that will dip in six ammonium chloroiridates again places chamber type electric resistance furnace to be heated to 720 ± 5 ℃ with the programming rate of 10 ℃/min, and constant temperature 0.5 hour, cools to room temperature then with the furnace, makes Ti/IrO
x(x=1～3) probe, an end of probe and copper cable welding back seal weld with the suitable heat-shrink tube of diameter, with the Ti/IrO that makes
xProbe is put into saturated Ca (OH)
2Can make pH value probe in aging 28 days in the solution.
Concrete resistivity monitoring probe 6: 4 stainless steel wires that will be of a size of Φ 2 * 35mm seal with the suitable heat-shrink tube of diameter one of which end and copper cable welding back behind the sand paper uniform grinding to weld, make the concrete resistivity probe.
2. assembling
Make sensor outer housing, can adopt the polytetrafluoroethylmaterial material manufacturing, sensor outer housing 7 is rectangle housings, the inner chamber with hollow, and the housing upper surface is provided with horizontal groove.Auxiliary electrode 3 is tiled in the upper surface of sensor outer housing 7, and is fixedly connected with epoxy resin.Contrast electrode 1, reinforcing bar electrode 2 adopt the mode that is threaded vertically to be installed on respectively in the sensor outer housing, and its workplace is exposed to case surface, and makes workplace and auxiliary electrode 3 upper surfaces maintain same surface level.Cl
-Probe 4, pH value probe 5 and 4 concrete resistivity monitoring probes 6 are placed in the horizontal groove of housing upper surface and with epoxy resin and fix.Copper cable 11,21,31,41,51,61 connects contrast electrode 1, reinforcing bar electrode 2, auxiliary electrode 3, Cl probe 4, pH value probe 5 and 4 concrete resistivity probes respectively; And stretch out shell, thereby process Multifunction Sensor of the present invention through the circular hole of shell bottom surface.
Utilize the above-mentioned sensor that makes that concrete reinforcement erosion is monitored in real time:
1, through contrast electrode 1, reinforcing bar electrode 2, auxiliary electrode 3, Cl
-Probe 4, pH value probe 5 and 6 pairs of reinforcing bar corrosion potentials of 4 concrete resistivity monitoring probes, reinforcement corrosion speed, concrete resistivity and rebar surface Cl
-Concentration and pH value are monitored.
2, when reinforcement corrosion speed is monitored, for making the data that record more accurate, utilize the monitoring result of concrete resistivity 6, use corresponding monitoring of software that system resistance is compensated, thereby obtain more accurate monitoring result in real time.
System resnstance transformer principle of work is following:
The corrosion rate of reinforcing bar can characterize with corrosion electric current density, utilizes linear polarization to measure the polarization resistance R that match obtains reflecting reinforcement corrosion speed
p, calculate acquisition corrosion electric current density i by following formula
Corr:
Wherein, β
aBe meant the Tafel slope of anode reaction, β
cBe meant the Tafel slope of cathode reaction, B is β
a, β
cRelevant constant.
Polarization resistance R
pBe to utilize the match of linear polarization measuring method to obtain, still, the LPR (R that adopts the match of linear polarization measuring method to obtain
p') be the polarization resistance R of reflection reinforcement corrosion speed in fact
pResistance R with test system
sSum, that is:
R′
p＝R
p+R
s
Work as R
sWhen very little, R
sCan ignore.At this moment, R
pWith R
p' approximately equal, that is:
R
p≈R′
p
Concrete system is the high resistant system, the system resistance R
sVery big, can not ignore polarization resistance R
pShould be:
R
p＝R′
p-R
s
At this moment, if simply measure the LPR R that match obtains with linear polarization
p' represent polarization resistance R
p, the reinforcement corrosion speed that monitoring obtains is wrong, must be from R
p' middle deduction system resistance R
s, could obtain the polarization resistance R of real reflection reinforcement corrosion speed
p
Therefore, utilize 4 sonde methods to obtain concrete electricalresistivity among the present invention, through formula
R
s=ρ/2 π a (a is the distance between contrast electrode and the working electrode)
Calculate the system resistance R
s, through formula
R
p＝R′
p-R
s
The LPR R that system resistance R s is measured from linear polarization
p' middle deduction obtains the polarization resistance R of real reflection reinforcement corrosion speed
pThereby, obtain the correct monitoring result of reinforcement corrosion speed.
Fig. 4 is the prepared Cl of the present invention
-Probe is at different Cl
-The corresponding relation of current potential that records in the concentration solution (with respect to SCE) and Cl concentration, as can be seen from the figure: current potential presents good linear relationship with the Cl change in concentration.
Fig. 5 is the current potential (with respect to SCE) that in different pH value, records of the prepared pH value probe of the present invention and the corresponding relation of pH value, and as can be seen from the figure: current potential presents good linear relationship with the variation of pH value.
Claims (9)
1. one kind is used for the real-time monitoring sensor of concrete structure durability, it is characterized in that: comprise a sensor outer housing, also comprise contrast electrode, reinforcing bar electrode, auxiliary electrode, Cl
-Probe, pH value probe and concrete resistivity monitoring probe, said auxiliary electrode is tiled in the upper surface of said shell, said contrast electrode, reinforcing bar electrode, Cl
-Probe, pH value probe and concrete resistivity monitoring probe have at least part to be exposed to the sensor outer housing upper surface as end of probe, and the other end connects copper cable, and said copper cable penetrates said sensor outer housing from top to bottom and stretches out in housing exterior.
2. the real-time monitoring sensor of concrete structure durability that is used for according to claim 1; It is characterized in that: said contrast electrode and reinforcing bar electrode are vertically installed and are fixed in shell inner cavity; Its upper surface is exposed to the sensor outer housing upper surface, maintains an equal level with said auxiliary electrode upper surface.
3. the real-time monitoring sensor of concrete structure durability that is used for according to claim 1, it is characterized in that: the sensor outer housing upper surface is provided with the horizontal groove that can hold said Cl probe, pH value probe and concrete resistivity monitoring probe, said Cl
-Probe, pH value probe and concrete resistivity probe are placed in the said groove, and fix with epoxy resin.
4. the real-time monitoring sensor of concrete structure durability that is used for according to claim 1; It is characterized in that: said contrast electrode is an Ag/AgCl gel electrolyte contrast electrode; Has the overcoat that a teflon is processed; Interior reference liquid adopts 0.5mol/L KCl methyl cellulose gel electrolyte, and an end of overcoat is provided with micropore ceramics.
5. the real-time monitoring sensor of concrete structure durability that is used for according to claim 1 is characterized in that: said concrete resistivity monitoring probe is 4 and is arranged in parallel in the stainless steel wire of sensor outer housing upper surface.
6. the real-time monitoring sensor of concrete structure durability that is used for according to claim 1 is characterized in that: said reinforcing bar electrodes use and monitored reinforcing bar are with the pole reinforcing bar of material, and diameter is 20mm.
7. the real-time monitoring sensor of concrete structure durability that is used for according to claim 1; It is characterized in that: said auxiliary electrode is for having chemically inert MMO titanium base Mixed Metal Oxide Coated Titanium Anodes net; Anode network is tiled in the sensor outer housing upper surface, and is connected and sealed with epoxy resin.
8. the real-time monitoring sensor of concrete structure durability that is used for according to claim 1 is characterized in that: said Cl
-Probe adopts the Ag/AgCl electrode of anode chloridising preparation; Said pH value probe is the pure Ti metal probe of surface coverage oxide that Ir is arranged.
9. one kind like the described manufacturing approach that is used for the real-time monitoring sensor of concrete structure durability of the arbitrary claim of claim 1～8, it is characterized in that may further comprise the steps:
(1) Ag/AgCl contrast electrode preparation:
Preparation 0.5mol/L KCl methyl cellulose gel electrolyte is as interior reference liquid; The Ag/AgCl electrode that is welded with copper cable is inserted along the center line of teflon sleeve, with epoxy resin the openend of teflon sleeve is carried out encapsulation process again and form the Ag/AgCl contrast electrode;
(2) preparation of reinforcing bar electrode:
Produce the bar reinforcement of Φ 20 * 50mm, an end and the copper cable of bar reinforcement weld, and with epoxy resin welding end surface and reinforcing bar side are sealed, and unencapsulated other end is as the detection operations face;
(3) preparation of impressed current anode:
MMO titanium base Mixed Metal Oxide Coated Titanium Anodes net is processed into rectangle, on anode network, processes two circular holes that are used to assemble said contrast electrode and reinforcing bar electrode again, impressed current anode is cemented in the sensor outer housing upper surface with epoxy resin;
(4) Cl
-The preparation of probe:
The copper wire welding back of bar-shaped pure Ag and copper cable is sealed weld; Preventing bimetallic corrosion, the Ag rod through polishing, oil removing, remove oxide on surface and clean after put into electrolytic cell, the silver rod is as anode; MMO titanium base mixed-metal oxides is as negative electrode, with 1mA/cm
2Current density anode polarization in the HCl of 0.1mol/L solution made the Ag/AgCl probe in 0.5 hour, the KCl solution of the electrode for preparing being put into 0.1mol/L is for use;
(5) preparation of pH probe:
The NaOH solution of putting into 10% after the bar-shaped pure titanium polishing is boiled and keeps 5 minutes, and then put into dense HCl and boil and kept 10 minutes, take out after to put into absolute ethyl alcohol after cleaning with redistilled water subsequent use;
The chlordene iridium acid ammonium solution of preparation 1g/L; Subsequent use titanium rod was immersed in the chamber type electric resistance furnace that dipping in the chlordene iridium acid ammonium solution evenly is placed on 75 ± 1 ℃ baking 0.5 hour; Repeat 3～5 times, the programming rate with 10 ℃/min is heated to 720 ± 5 ℃ again, and constant temperature 0.5 hour; Cool to room temperature then with the furnace, make Ti/IrO
xProbe, wherein x=1～3 seal weld after an end of probe and the copper cable welding, with the Ti/IrO that makes
xProbe is put into saturated Ca (OH)
2Wear out in the solution and promptly made pH value probe in 28 days;
(6) concrete resistivity probe:
After getting 4 stainless steel wire polishings one of which end and copper cable welding back are sealed weld, make the concrete resistivity probe;
(7) assembling:
Make a shell; Be tiled in the upper surface of sensor outer housing to auxiliary electrode, contrast electrode and reinforcing bar electrode are installed also along said housing axis and are fixed in shell inner cavity, and its upper surface is exposed to the sensor outer housing upper surface; And maintain same surface level with the auxiliary electrode upper surface, Cl
-Probe, pH value probe and concrete resistivity monitoring probe horizontal arrangement are at upper surface of outer cover; Penetrate shell with the copper cable that the concrete resistivity probe is connected, and stretch out housing exterior with contrast electrode, reinforcing bar electrode, Cl probe, pH value probe through the circular hole of shell bottom surface.
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