CN101726525B - Embedded-type sensor for detecting concrete chloride ion content and preparation method thereof - Google Patents

Embedded-type sensor for detecting concrete chloride ion content and preparation method thereof Download PDF

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CN101726525B
CN101726525B CN200910073383A CN200910073383A CN101726525B CN 101726525 B CN101726525 B CN 101726525B CN 200910073383 A CN200910073383 A CN 200910073383A CN 200910073383 A CN200910073383 A CN 200910073383A CN 101726525 B CN101726525 B CN 101726525B
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sensor
layer
manganese dioxide
filamentary silver
plastic tube
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CN101726525A (en
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高小建
杨英姿
张剑
邓宏卫
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention discloses an embedded-type sensor for detecting concrete chloride ion content and a preparation method thereof, relating to a sensor and a preparation method. The invention solves the problems that the existing sensor can not detect concrete chloride ion content in real time and has larger voltage drop, poor sturdiness and poor stability, and the sensor manufactured with the existing method can not continuously detect changed chloride ion concentration and has inaccurate detection result. A micro-expansion fiber cement semipermeable membrane layer, an alkaline gel layer and a manganese dioxide layer are successively arranged in a sensor barrel from bottom to top. The method is as follows: successively arranging the manufactured micro-expansion fiber cement semipermeable membrane layer, the alkaline gel layer and the manganese dioxide layer from bottom to top in the sensor barrel; and dipping the lower part of the manufactured sensor into simulative concrete pore fluid. The sensor of the invention can detect concrete chloride ion content in real time, has favourable sturdiness and favourable long-term stability; the sensor manufactured by the invention can continuously detect changed chloride ion concentration and has accurate detection result.

Description

Detect embedded-type sensor of concrete chloride ion content and preparation method thereof
Technical field
The present invention relates to a kind of sensor that detects concrete chloride ion content and preparation method thereof.
Background technology
Under marine environment and deicer salts environment; It is the main cause of concrete structure durability destruction that the intrusion of villaumite causes steel bar corrosion, receives extent of corrosion and military service performance significant so can in time, accurately grasp in the concrete chlorion distribution for estimating and control actual xoncrete structure.
At present, the method that generally adopts mainly comprises two types:
One, to new construction, through a large amount of assay optimization concrete mixs and protective layer thickness, and according to laboratory concrete resistance of chloride ion penetration can test findings and the practical structures working environment predict; Yet; Because the performance of concrete material own is constantly development and change in time; Gap between on-site concrete fabricating quality and the laboratory is bigger; Many factors such as the time dependent uncertainty of actual environment for use, this prediction result is common and actual deviation is bigger, causes actual engineering the prior destruction of unanticipated to occur;
Two,, when it obvious destruction occurs and need repair, just carry out on-site sampling, or in the operational maintenance process, regularly structure is carried out core boring sampling to having built concrete works; Under condition of high voltage, concrete mesoporosity solution is squeezed out then; Or it is concrete sample is levigate; Carry out chemical analysis again and measure the distribution situation of chlorion in concrete; The method is comparatively ripe, detects but its workload is big, operating process is numerous and diverse, belong to damage type, in some Important Project, can't use.
Up-to-date both at home and abroad report employing is imbedded Fibre Optical Sensor chloride ion content in the concrete is detected in real time; In recent years through anodized filamentary silver as contrast electrode in the research in galvanochemistry and metal erosion field with use morely, also have a small amount of report that it is used for measuring the research of chlorine ion concentration in the concrete as working electrode.But existing embedded-type sensor contrast electrode is arranged on the concrete sample outside; Can't in actual concrete works, carry out the real-time detection concrete chloride ion content of long-term flush type; And in testing process, have bigger voltage drop to exist, and its soundness is not enough, and long-time stability are poor; The embedded-type sensor that the preparation method of existing embedded-type sensor makes can only detect predefined threshold values concentration value, the chlorine ion concentration that can not continuous detecting changes; And the chemical reaction the when embedded-type sensor of the embedded-type sensor that the preparation method of existing embedded-type sensor makes detects is irreversible, and testing result is inaccurate when recurrent fluctuations appears in chlorine ion concentration.
Summary of the invention
The purpose of this invention is to provide a kind of embedded-type sensor that detects concrete chloride ion content and preparation method thereof; Be arranged on the concrete sample outside to solve existing embedded-type sensor contrast electrode; Can't detect concrete chloride ion content in real time, have big voltage drop, less robust, chlorine ion concentration, irreversible, the inaccurate problem of testing result of chemical reaction when detecting that the embedded-type sensor that the preparation method of poor stability and existing embedded-type sensor makes can not continuous detecting changes.
The embedded-type sensor of detection concrete chloride ion content of the present invention comprises sensor cylindrical shell, annular filamentary silver, input copper conductor, output copper conductor, microdilatancy fiber cement semi-permeable diaphragm layer, base gel layer, manganese dioxide layer, metal staving and insulated enclosure glue-line; The bottom of said sensor cylinder body outer wall has annular groove along the circumferencial direction of sensor cylindrical shell; Said sensor cylinder body outer wall has axial notch along short transverse; And said annular groove is communicated with said axial notch; Said annular filamentary silver is sleeved in the annular groove of sensor cylindrical shell, and the bottom of said input copper conductor is positioned at axial notch, and the lower end of said input copper conductor and annular filamentary silver are affixed; Said microdilatancy fiber cement semi-permeable diaphragm layer, base gel layer and manganese dioxide layer are successively set in the sensor cylindrical shell from the bottom to top; Said metal staving is made up of metal cylinder and metal end, and said metal end is packed in the upper end of metal cylinder, and said metal cylinder is arranged between manganese dioxide layer and the sensor cylindrical shell; Said metal end is positioned on the upper surface of manganese dioxide layer; The lower end of said output copper conductor is packed in the middle part of the upper surface of metal end, scribbles the insulated enclosure glue-line on the upper surface of said metal end, and said sensor cylindrical shell is that insulating material is processed.
The preparation method of the embedded-type sensor of detection concrete chloride ion content of the present invention realizes according to following steps:
Step 1, choose the hard PVC plastic tube that length is 30～50mm, wherein external diameter is that 8～12mm, wall thickness are 1～1.5mm; Circumferencial direction in hard PVC plastic tube bottom along the hard PVC plastic tube is processed an annular groove; Wherein the center line of annular groove is 3～6mm to the distance of hard PVC plastic tube bottom face, and the degree of depth 0.5～0.8mm of annular groove, annular groove width are 0.8～1.2mm;
Step 2, polished with flint glass paper in the two ends up and down of hard PVC plastic tube inwall;
Step 3, choose the high-purity filamentary silver that diameter is 0.5～1.0mm; Filamentary silver purity is 99.999%, and the length of choosing filamentary silver is 30～40mm, and the lower end that will import copper conductor then is welded on the filamentary silver; Guarantee that filamentary silver is vertical with the input copper conductor, and carry out insulated enclosure with epoxy resin at weld;
Step 4, treat the epoxy resin adhesive curing after; Adopt flint glass paper to be polished in the filamentary silver surface earlier, adopt fine sandpaper to be polished in the filamentary silver surface then, remove the filamentary silver surface oxide layer; Filamentary silver is curved annular be fixed in the annular groove, the bottom of importing copper conductor is placed in the axial notch;
Step 5, the bottom of hard PVC plastic tube is immersed in concentration is in 10% the ammoniacal liquor, guarantees that filamentary silver all is immersed in the ammoniacal liquor, and soak time is six hours;
Step 6, the bottom of hard PVC plastic tube is immersed in concentration is in the 0.1mol/L hydrochloric acid solution, guarantees that filamentary silver all is immersed in the hydrochloric acid solution, with the hydrochloric acid solution energising, filamentary silver is carried out anodization, and wherein current density is 0.4～0.6mA/cm 2, 4～6 hours conduction time is through the AgCl coating of an even compact of anodized filamentary silver surface formation;
Step 7, the hard PVC plastic tube is taken out from hydrochloric acid solution; Do not form at the weld of input copper conductor and filamentary silver that coating and uneven coating are even locates to use the epoxide-resin glue encapsulation process; After treating epoxy resin cure; The filamentary silver of hard PVC plastic tube bottom is immersed in the sodium chloride solution that concentration is 0.5mol/L, kept in Dark Place three～seven days;
Step 8, the hard PVC plastic tube is taken out from said sodium chloride solution; Neat portland cement, swelling agent and water are mixed by mass ratio at 100: 4: 25; Wherein the water cement ratio of portland cement is processed microdilatancy fiber cement semi-permeable diaphragm layer after fully mixing between 0.3～0.35, and microdilatancy fiber cement semi-permeable diaphragm layer is filled in the bottom in the hard PVC plastic tube; Wherein the thickness of microdilatancy fiber cement semi-permeable diaphragm layer is 4～6mm, moisture-keeping maintaining two～three days;
Step 9, with the super water-absorbent macromolecular material, promptly fully stir and process the base gel body by the supersaturated aqueous solution of NaOH, potassium hydroxide, calcium oxide; Wherein concentration sodium hydroxide is that the concentration of 0.2mol/L, potassium hydroxide is 0.6mol/L; To manufacture the base gel body then and be placed on the upper surface of the microdilatancy fiber cement semi-permeable diaphragm layer in the hard PVC plastic tube, the thickness of base gel body is 8～10mm;
Step 10, the lower end that will export copper conductor are welded on the middle part of the upper surface of metal end; Suppress three～five layers of manganese dioxide cake body; Three～five layers of manganese dioxide cake body that suppress are set gradually by under last, with place mat layer of copper silk screen between every two layers of manganese dioxide cake body, process manganese dioxide layer then; Guarantee being connected with the inwall of metal staving of every layer of copper mesh all around; Again manganese dioxide layer is put into the metal staving, the metal staving that manganese dioxide layer is housed is placed on the upper surface of the base gel body in the hard PVC plastic tube, and guarantee that the base gel body closely contacts with undermost manganese dioxide cake body;
Step 11, the insulated enclosure glue-line is coated in the upper surface of metal end, promptly make the embedded-type sensor that detects concrete chloride ion content;
Step 12, the simulation concrete pore solution is immersed in the bottom of the above-mentioned embedded-type sensor that makes; Be to soak in the mixed solution of NaOH, potassium hydroxide, saturated calcium hydroxide; Concentration sodium hydroxide is that the concentration of 0.2mol/L, potassium hydroxide is 0.6mol/L in the mixed solution; Make the abundant aquation of microdilatancy fiber cement semi-permeable diaphragm layer; Make simultaneously between microdilatancy fiber cement semi-permeable diaphragm layer and the base gel layer to reach chemical equilibrium, behind the above-mentioned embedded-type sensor immersion fortnight that makes, the chlorion sensor just can normally use.
The invention has the beneficial effects as follows:
The present invention is buried micro-expansion sensor fiber cement semipermeable layer, the gel layer, and alkaline manganese dioxide layer is disposed on the cylinder body of the sensor, the sensor is embedded within three in the form a stable manganese dioxide solid reference electrode, can be carried out in the actual concrete term, real-time detection of buried concrete chloride ion content, the detection process to avoid the presence of a large voltage drop and ruggedness, long-term stability; present invention, the anode of silver Chan around the sensor ring to the outer wall of the annular groove of the cylinder, thereby effectively increasing the length of the work of the working electrode, the anode of silver in the same horizontal plane, the detection accuracy improves, while the Working electrodes provides effective protection against silver anodized damaged during the buried;
In the microdilatancy fiber cement semi-permeable diaphragm layer of the present invention through mixing swelling agent; Obviously improved the anti-shrinkage cracking performance of whole cement stone; Thereby avoided forming between cement stone and the sensor cylindrical shell slit and cement stone formation microfracture itself, thereby reduced the excessive and migration loss of the alkaline matter in the alkaline gel effectively; The embedded-type sensor that the preparation method of embedded-type sensor of the present invention makes can not only detect predefined threshold values concentration value, the chlorine ion concentration that can also continuous detecting changes; Chemical reaction when the embedded-type sensor of the embedded-type sensor that the preparation method of embedded-type sensor of the present invention makes detects is reversible, and testing result is accurate when recurrent fluctuations appears in chlorine ion concentration.
Description of drawings
The master of Fig. 1 embedded-type sensor of the present invention looks cut-open view, and Fig. 2 is the vertical view of Fig. 1.
Embodiment
Embodiment one: shown in Fig. 1～2; The embedded-type sensor of the detection concrete chloride ion content of this embodiment comprises sensor cylindrical shell 1, annular filamentary silver 2, input copper conductor 3, output copper conductor 4, microdilatancy fiber cement semi-permeable diaphragm layer 5, base gel layer 6, manganese dioxide layer 7, metal staving 8 and insulated enclosure glue-line 9; The bottom of said sensor cylindrical shell 1 outer wall has annular groove 1-1 along the circumferencial direction of sensor cylindrical shell 1; Said sensor cylindrical shell 1 outer wall has axial notch 1-2 along short transverse; And said annular groove 1-1 is communicated with said axial notch 1-2; Said annular filamentary silver 2 is sleeved in the annular groove 1-1 of sensor cylindrical shell 1, and the bottom of said input copper conductor 3 is positioned at axial notch 1-2, and the lower end of said input copper conductor 3 and annular filamentary silver 2 are affixed; Said microdilatancy fiber cement semi-permeable diaphragm layer 5, base gel layer 6 and manganese dioxide layer 7 are successively set in the sensor cylindrical shell 1 from the bottom to top; Said metal staving 8 is made up of metal cylinder 8-1 and metal end 8-2, and said metal end 8-2 is packed in the upper end of metal cylinder 8-1, and said metal cylinder 8-1 is arranged between manganese dioxide layer 7 and the sensor cylindrical shell 1; Said metal end 8-2 is positioned on the upper surface of manganese dioxide layer 7; The lower end of said output copper conductor 4 is packed in the middle part of the upper surface of metal end 8-2, scribbles insulated enclosure glue-line 9 on the upper surface of said metal end 8-2, and said sensor cylindrical shell 1 is processed for insulating material.
Said microdilatancy fiber cement semi-permeable diaphragm layer 5 is processed after fully being mixed in 100: 4: 25 by mass percentage by neat portland cement, swelling agent and water; Said base gel layer 6 is that the supersaturated aqueous solution by NaOH, potassium hydroxide, calcium oxide fully stirs and processes; Said manganese dioxide layer 7 is the manganese dioxide cake bodies that formed by the manganese dioxide powder compacting.
Embodiment two: as shown in Figure 1, the length of the said sensor cylindrical shell 1 of this embodiment is 30～50mm.So design, the size of sensor cylindrical shell 1 design is little, is convenient to sensor is imbedded in the concrete.Other composition and annexation are identical with embodiment one.
Embodiment three: shown in Fig. 1～2, the material of the said sensor cylindrical shell 1 of this embodiment is processed by the hard PVC plastics.So design, hard PVC plastics have good insulation performance property, are convenient to processing, and be waterproof and dampproof.Other composition and annexation are identical with embodiment one or two.
Embodiment four: as shown in Figure 1; The said sensor of this embodiment also comprises two～four layers of copper mesh 7-2; Said manganese dioxide layer 7 is made up of three～five layers of manganese dioxide cake body 7-1; Three～five layers of manganese dioxide cake body 7-1 from top to bottom set gradually, and are provided with layer of copper silk screen 7-2 between per two manganese dioxide cake body 7-1, contact with the inwall of metal staving 8 around every layer of copper mesh 7-2.So design, strengthened the monolithic conductive performance of manganese dioxide layer 7.So design, strengthened the monolithic conductive performance of manganese dioxide layer 7.Other composition and annexation are identical with embodiment three.
Embodiment five: shown in Fig. 1～2, preparation method's step of the embedded-type sensor of the detection concrete chloride ion content of this embodiment is following:
Step 1, choose the hard PVC plastic tube that length is 30～50mm, wherein external diameter is that 8～12mm, wall thickness are 1～1.5mm; Circumferencial direction in hard PVC plastic tube bottom along the hard PVC plastic tube is processed an annular groove 1-1; Wherein the center line of annular groove 1-1 is 3～6mm to the distance of hard PVC plastic tube bottom face, and the degree of depth 0.5～0.8mm of annular groove 1-1, annular groove 1-1 width are 0.8～1.2mm;
Step 2, polished with flint glass paper in the two ends up and down of hard PVC plastic tube inwall, make hard PVC plastic tube inner wall surface coarse, be beneficial to hard PVC plastic tube inwall two ends and fill sealing;
Step 3, choose the high-purity filamentary silver that diameter is 0.5～1.0mm; Filamentary silver purity is 99.999%; The length of choosing filamentary silver is 30～40mm; The lower end that to import copper conductor 3 then is welded on the filamentary silver, guarantees that filamentary silver is vertical with input copper conductor 3, and carries out insulated enclosure at weld with epoxy resin;
Step 4, treat the epoxy resin adhesive curing after; Adopt flint glass paper to be polished in the filamentary silver surface earlier; Adopt fine sandpaper to be polished in the filamentary silver surface then; Remove the filamentary silver surface oxide layer, filamentary silver is curved annular be fixed in the annular groove 1-1, the bottom of importing copper conductor 3 is placed in the axial notch 1-2;
Step 5, the bottom of hard PVC plastic tube is immersed in concentration is in 10% the ammoniacal liquor, guarantees that filamentary silver all is immersed in the ammoniacal liquor, and soak time is six hours, to remove filamentary silver surface grease dirt;
Step 6, the bottom of hard PVC plastic tube is immersed in concentration is in the 0.1mol/L hydrochloric acid solution, guarantees that filamentary silver all is immersed in the hydrochloric acid solution, with the hydrochloric acid solution energising, filamentary silver is carried out anodization, and wherein current density is 0.4～0.6mA/cm 2, 4～6 hours conduction time is through the AgCl coating of an even compact of anodized filamentary silver surface formation;
Step 7, the hard PVC plastic tube is taken out from hydrochloric acid solution; The weld of copper conductor 3 with filamentary silver do not form coating and the even place of uneven coating uses the epoxide-resin glue encapsulation process importing; After treating epoxy resin cure; The filamentary silver of hard PVC plastic tube bottom is immersed in the sodium chloride solution that concentration is 0.5mol/L, kept in Dark Place three～seven days;
Step 8, the hard PVC plastic tube is taken out from said sodium chloride solution; Neat portland cement, swelling agent and water are mixed by mass ratio at 100: 4: 25; Wherein the water cement ratio of portland cement is between 0.3～0.35, processes microdilatancy fiber cement semi-permeable diaphragm layer 4 after fully mixing, the bottom that microdilatancy fiber cement semi-permeable diaphragm layer 4 is filled in the hard PVC plastic tube; Wherein the thickness of microdilatancy fiber cement semi-permeable diaphragm layer 4 is 4～6mm, moisture-keeping maintaining two～three days;
Step 9, with the super water-absorbent macromolecular material, promptly fully stir and process base gel body 5 by the supersaturated aqueous solution of NaOH, potassium hydroxide, calcium oxide; Wherein concentration sodium hydroxide is that the concentration of 0.2mol/L, potassium hydroxide is 0.6mol/L; To manufacture base gel body 5 then and be placed on the upper surface of the microdilatancy fiber cement semi-permeable diaphragm layer 4 in the hard PVC plastic tube, the thickness of base gel body 5 is 8～10mm;
Step 10, the lower end that will export copper conductor 4 are welded on the middle part of the upper surface of metal end 8-2; Suppress three～five layers of manganese dioxide cake body 7-1; Three～five layers of manganese dioxide cake body 7-1 that suppress are set gradually by under last; Then with place mat layer of copper silk screen 7-2 between every two layers of manganese dioxide cake body 7-1; Process manganese dioxide layer 7, guarantee being connected with the inwall of metal staving 8 of every layer of copper mesh 7-2 all around, again manganese dioxide layer 7 is put into metal staving 8; The metal staving 8 that manganese dioxide layer 7 is housed is placed on the upper surface of the base gel body 5 in the hard PVC plastic tube, and guarantees that base gel body 5 closely contacts with undermost manganese dioxide cake body 7-1;
Step 11, insulated enclosure glue-line 9 is coated in the upper surface of metal end 8-2, promptly make the embedded-type sensor that detects concrete chloride ion content;
Step 12, the simulation concrete pore solution is immersed in the bottom of the above-mentioned embedded-type sensor that makes; Be to soak in the mixed solution of NaOH, potassium hydroxide, saturated calcium hydroxide; Concentration sodium hydroxide is that the concentration of 0.2mol/L, potassium hydroxide is 0.6mol/L in the mixed solution; Make microdilatancy fiber cement semi-permeable diaphragm layer 5 abundant aquation; Make simultaneously between microdilatancy fiber cement semi-permeable diaphragm layer 5 and the base gel layer 6 to reach chemical equilibrium, behind the above-mentioned embedded-type sensor immersion fortnight that makes, the chlorion sensor just can normally use.Can put into solution, also can imbed in the concrete chlorine ion concentration value in the testing environment medium.
Embodiment six: add the PVA fiber when neat portland cement, swelling agent and the water of this embodiment in step 8 mixes, the PVA fiber accounts for 1% of neat portland cement, swelling agent and water gross mass.The PVA fiber is a kind of soluble resin, generally as industries such as spinning sizing agent, bonding agent, buildings.Can make the sticking joint property of said mixture good, prevent cracking.Other is identical with embodiment five.
Principle of work:
Microdilatancy fiber cement semi-permeable diaphragm layer 5, base gel layer 6 and manganese dioxide layer 7 are set in the sensor cylindrical shell 1 have from the bottom to top constituted a stable manganese dioxide solid reference electrode; The anodization filamentary silver that twines on sensor cylindrical shell 1 outer wall has constituted a working electrode, between this electrode and surrounding medium, has following chemical equilibrium relation:
This special formula journey according to how, in any temperature T, when above-mentioned chemical reaction reached balance, electrode potential E can be expressed by following formula:
E = E Ag + / Ag 0 + RT F ( ln K s - ln α Cl - ) = ( E Ag + / Ag 0 + RT F ln K s ) - RT F ln α Cl -
In the formula:
Figure G2009100733834D00103
Be Ag +/ Ag normal potential, current potential value are 0.7991V; R is an ideal gas constant, and ideal gas constant is 8.3145Jmol -1K -1T is the environment temperature of electrode; F is a faraday constant, and faraday constant is 96485Cmol -1K sSolubility product for AgCl;
Figure G2009100733834D00104
Be Cl in the surrounding medium -Activity, get Cl usually -Concentration value.
In sum, under given temperature conditions,, can confirm the Cl in the working electrode surrounding medium through accurately measuring the relative potential value of working electrode with respect to the manganese dioxide solid reference electrode -Concentration value.

Claims (6)

1. embedded-type sensor that detects concrete chloride ion content; Said sensor comprises sensor cylindrical shell (1), annular filamentary silver (2), input copper conductor (3), output copper conductor (4), microdilatancy fiber cement semi-permeable diaphragm layer (5), base gel layer (6), manganese dioxide layer (7), metal staving (8) and insulated enclosure glue-line (9); It is characterized in that: the bottom of said sensor cylindrical shell (1) outer wall has annular groove (1-1) along the circumferencial direction of sensor cylindrical shell (1); Said sensor cylindrical shell (1) outer wall has axial notch (1-2) along short transverse; And said annular groove (1-1) is communicated with said axial notch (1-2); Said annular filamentary silver (2) is sleeved in the annular groove (1-1) of sensor cylindrical shell (1); The bottom of said input copper conductor (3) is positioned at axial notch (1-2); And the lower end of said input copper conductor (3) and annular filamentary silver (2) are affixed, and said microdilatancy fiber cement semi-permeable diaphragm layer (5), base gel layer (6) and manganese dioxide layer (7) are successively set in the sensor cylindrical shell (1) from the bottom to top, and said metal staving (8) is made up of metal cylinder (8-1) and metal end (8-2); Said metal end (8-2) is packed in the upper end of metal cylinder (8-1); Said metal cylinder (8-1) is arranged between manganese dioxide layer (7) and the sensor cylindrical shell (1), and said metal end (8-2) is positioned on the upper surface of manganese dioxide layer (7), and the lower end of said output copper conductor (4) is packed in the middle part of the upper surface of metal end (8-2); Scribble insulated enclosure glue-line (9) on the upper surface of said metal end (8-2), said sensor cylindrical shell (1) is processed for insulating material.
2. the embedded-type sensor of detection concrete chloride ion content according to claim 1 is characterized in that: the length of said sensor cylindrical shell (1) is 30～50mm.
3. the embedded-type sensor of detection concrete chloride ion content according to claim 1 and 2 is characterized in that: the material of said sensor cylindrical shell (1) is processed by the hard PVC plastics.
4. the embedded-type sensor of detection concrete chloride ion content according to claim 3; It is characterized in that: said sensor also comprises two～four layers of copper mesh (7-2); Said manganese dioxide layer (7) is made up of three～five layers of manganese dioxide cake body (7-1); Three～five layers of manganese dioxide cake body (7-1) from top to bottom set gradually, and are provided with layer of copper silk screen (7-2) between per two manganese dioxide cake bodies (7-1), contact with the inwall of metal staving (8) around every layer of copper mesh (7-2).
5. the preparation method of the embedded-type sensor of a claim 1,2 or 4 described detection concrete chloride ion contents, the preparation method's step of embedded-type sensor that it is characterized in that detecting concrete chloride ion content is following:
Step 1, choose the hard PVC plastic tube that length is 30～50mm, wherein external diameter is that 8～12mm, wall thickness are 1～1.5mm; Circumferencial direction in hard PVC plastic tube bottom along the hard PVC plastic tube is processed an annular groove (1-1); Wherein the center line of annular groove (1-1) is 3～6mm to the distance of hard PVC plastic tube bottom face, and the degree of depth 0.5～0.8mm of annular groove (1-1), annular groove (1-1) width are 0.8～1.2mm;
Step 2, polished with flint glass paper in the two ends up and down of hard PVC plastic tube inwall;
Step 3, choose the high-purity filamentary silver that diameter is 0.5～1.0mm; Filamentary silver purity is 99.999%; The length of choosing filamentary silver is 30～40mm; The lower end that to import copper conductor (3) then is welded on the filamentary silver, guarantees that filamentary silver is vertical with input copper conductor (3), and carries out insulated enclosure at weld with epoxy resin;
Step 4, treat the epoxy resin adhesive curing after; Adopt flint glass paper to be polished in the filamentary silver surface earlier; Adopt fine sandpaper to be polished in the filamentary silver surface then; Remove the filamentary silver surface oxide layer, filamentary silver is curved annular be fixed in the annular groove (1-1), the bottom that will import copper conductor (3) places in the axial notch (1-2);
Step 5, the bottom of hard PVC plastic tube is immersed in concentration is in 10% the ammoniacal liquor, guarantees that filamentary silver all is immersed in the ammoniacal liquor, and soak time is six hours;
Step 6, the bottom of hard PVC plastic tube is immersed in concentration is in the 0.1mol/L hydrochloric acid solution, guarantees that filamentary silver all is immersed in the hydrochloric acid solution, with the hydrochloric acid solution energising, filamentary silver is carried out anodization, and wherein current density is 0.4～0.6mA/cm 2, 4～6 hours conduction time is through the AgCl coating of an even compact of anodized filamentary silver surface formation;
Step 7, the hard PVC plastic tube is taken out from hydrochloric acid solution; The weld of copper conductor (3) with filamentary silver do not form coating and the even place of uneven coating uses the epoxide-resin glue encapsulation process importing; After treating epoxy resin cure; The filamentary silver of hard PVC plastic tube bottom is immersed in the sodium chloride solution that concentration is 0.5mol/L, kept in Dark Place three～seven days;
Step 8, the hard PVC plastic tube is taken out from said sodium chloride solution; Neat portland cement, swelling agent and water are mixed by mass ratio at 100: 4: 25; Wherein the water cement ratio of portland cement is processed microdilatancy fiber cement semi-permeable diaphragm layer (4) after fully mixing between 0.3～0.35, and microdilatancy fiber cement semi-permeable diaphragm layer (4) is filled in the bottom in the hard PVC plastic tube; Wherein the thickness of microdilatancy fiber cement semi-permeable diaphragm layer (4) is 4～6mm, moisture-keeping maintaining two～three days;
Step 9, with the super water-absorbent macromolecular material, promptly fully stir and process base gel body (5) by the supersaturated aqueous solution of NaOH, potassium hydroxide, calcium oxide; Wherein concentration sodium hydroxide is that the concentration of 0.2mol/L, potassium hydroxide is 0.6mol/L; To manufacture base gel body (5) then and be placed on the upper surface of the microdilatancy fiber cement semi-permeable diaphragm layer (4) in the hard PVC plastic tube, the thickness of base gel body (5) is 8～10mm;
Step 10, the lower end that will export copper conductor (4) are welded on the middle part of the upper surface of metal end (8-2); Suppress three～five layers of manganese dioxide cake body (7-1); Three～five layers of manganese dioxide cake body (7-1) that suppress are set gradually by under last; Then with place mat layer of copper silk screen (7-2) between every two layers of manganese dioxide cake body (7-1); Process manganese dioxide layer (7), guarantee being connected with the inwall of metal staving (8) of every layer of copper mesh (7-2) all around, again manganese dioxide layer (7) is put into metal staving (8); The metal staving (8) that manganese dioxide layer (7) will be housed is placed on the upper surface of the base gel body (5) in the hard PVC plastic tube, and guarantees that base gel body (5) closely contacts with undermost manganese dioxide cake body (7-1); Step 11, insulated enclosure glue-line (9) is coated in the upper surface of metal end (8-2), promptly make the embedded-type sensor that detects concrete chloride ion content;
Step 12, the simulation concrete pore solution is immersed in the bottom of the above-mentioned embedded-type sensor that makes; Be to soak in the mixed solution of NaOH, potassium hydroxide, saturated calcium hydroxide; Concentration sodium hydroxide is that the concentration of 0.2mol/L, potassium hydroxide is 0.6mol/L in the mixed solution; Make fully aquation of microdilatancy fiber cement semi-permeable diaphragm layer (5); Make simultaneously between microdilatancy fiber cement semi-permeable diaphragm layer (5) and the base gel layer (6) to reach chemical equilibrium, behind the above-mentioned embedded-type sensor immersion fortnight that makes, the chlorion sensor just can normally use.
6. the preparation method of the embedded-type sensor of detection concrete chloride ion content according to claim 5; It is characterized in that: add the PVA fiber when neat portland cement in step 8, swelling agent and water mix, the PVA fiber accounts for 1% of neat portland cement, swelling agent and water gross mass.
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