CN100507543C - High-temperature high-pressure pH chemical sensor and making method - Google Patents
High-temperature high-pressure pH chemical sensor and making method Download PDFInfo
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- CN100507543C CN100507543C CNB2005100113176A CN200510011317A CN100507543C CN 100507543 C CN100507543 C CN 100507543C CN B2005100113176 A CNB2005100113176 A CN B2005100113176A CN 200510011317 A CN200510011317 A CN 200510011317A CN 100507543 C CN100507543 C CN 100507543C
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Abstract
A pH chemical transducer of high temperature and high pressure consists of measuring electrode being YSZ/HgO/Hg and / or Zr/ZrO2 electrode and reference electrode being Ag/AgCl electrode. YSZ/HgO/Hg electrode is used when measuring temperature is greater than 200 deg.C and Zr/ZrO2 electrode is used when measuring temperature is at 0-400deg.c . The pH chemical transducer can be used at temperature of 0-400 deg.c . under pressure of 40 Mpa to accuretely measure pH value in liquid and its preparing method is also disclosed .
Description
Technical field
The present invention relates to a kind of chemical sensor of tracer liquid pH value, relate in particular to a kind of pH value sensor that is used for liquid under the in situ detection high-temperature high-pressure state; The invention still further relates to the method for making of described pH value sensor.
Background technology
At present, the used chemical sensor of pH value that detects liquid under the High Temperature High Pressure is a solid state sensor, this class sensor that can not work more than 100 ℃ in the product of existing market.Solid-state Chemistry sensor in the existing report research is in the difficulty of working more than 200 ℃, particularly 0-400 ℃, be difficult to use in simultaneously the big High Temperature High Pressure scope of 40Mpa (about 400 atmospheric pressure) in.
The defective that the chemical sensor of existing research exists mainly contains the following aspects, and at first, the material of its electrode of pH chemical sensor of the prior art is stable inadequately, for example normal potential electrode Cu/CuO electrode or the Ni/NiO that uses
2Electrode, especially very unstable under High Temperature High Pressure because wherein Cu and Ni have multiple electricity price, can cause measurement result inaccurate thus.In addition, the hermetically-sealed construction of the chemical sensor of existing report is easy to lose efficacy under High Temperature High Pressure, causes the impaired of electrode thus or causes measuring the loop short circuit, causes the quick inefficacy of sensor.
At present, for deep-sea (containing the ore deposit hydrothermal solution) resource is developed and is studied, to carry out the real-time detection of multiple parameter to abyssalbenthic seawater, in order to adapt to this demand, and other similar High Temperature High Pressure hydrothermal solution application needs, require development a kind of can be normal under high temperature and high pressure environment, accurate, durable, the pH chemical sensor of corrosion-resistant use.
This chemical sensor can be installed in the actual deep-sea High Temperature High Pressure detector, also can use in the laboratory to be installed in demarcation and the detection of carrying out the various chemical parameters of High Temperature High Pressure in the autoclave.
Summary of the invention:
The objective of the invention is to improve the deficiencies in the prior art, provide a kind of and can to 40Mpa, can use, under High Temperature High Pressure, can accurately measure liquid pH value and long pH chemical sensor of working stability life-span at 0 ℃ to 400 ℃, high pressure;
Further aim of the present invention is to provide the method for making of above-mentioned chemical sensor;
The objective of the invention is to reach by the following technical programs:
A kind of High Temperature High Pressure pH chemical sensor, it comprises potential electrode and contrast electrode, described potential electrode is YSZ/HgO/Hg and or Zr/ZrO
2Potential electrode; When measuring temperature, use the YSZ/HgO/Hg potential electrode greater than 200 ℃; When measuring temperature, use Zr/ZrO at 0-400 ℃
2Potential electrode; Described contrast electrode is the Ag/AgCl electrode;
Described all electrodes can be divided into three parts, and the first one end is immersed in probe segment in the fluid to be measured as probe, and it two is the joining conductor part that connect of the other end and physical conductors, and it three is that part and the disconnected conductor part of not doing probe is center section.
Described contrast electrode Ag/AgCl has two kinds of structures:
First kind of structure is: be provided with the AgCl rete outside the Ag silk of the probe segment of electrode, at center section, its outer insulation course that is provided with, described insulation course can be the insulation heat-resistant coating, and/or outside the Ag silk, be with the polyfluortetraethylene pipe of insulation or the polyfluortetraethylene pipe of pyrocondensation; Be provided with hermetically-sealed construction in described insulation course outside and be used for sealing between sensor electrode and the autoclave jack.
Described hermetically-sealed construction is: be coated with described insulation heat-resistant coating layer sheathed graphite in outside and teflon mixture gasket circle at described center section, polyfluortetraethylene pipe in the sheathed insulation in the bottom of sealing packing ring, set firmly metal o-ring on this polyfluortetraethylene pipe, polyfluortetraethylene pipe and stainless steel sleeve pipe in the sheathed pyrocondensation in top of this graphite and teflon mixture gasket circle, on described center section, also be provided with a metal ferrule, be provided with upper coarse and lower fine through hole in the middle of it, the lower end abutment of described metal ferrule is on described metal o-ring, described graphite and teflon mixture gasket circle are resisted against on the through hole convex shoulder of described metal ferrule and seal, sealing shroud casting die is set in the stainless steel sleeve tube outside of described metal ferrule top, its be plugged in described metal ferrule top than being spirally connected in the coarse pore section.Constitute two-stage relay baton hermetically-sealed construction thus.
Second kind of structure is: the Ag silk places in the ceramic pipe (zirconia ceramics pipe or alundum (Al ceramic pipe or conventional ceramic pipe), is the AgCl layer that the AgCl pressed powder is melt into outside the Ag silk, the porous layer that is formed by the cement sintering in the shutoff of the two ends of this ceramic pipe; The AgCl/Ag wire electrode is being the back that is enclosed in cement sinter layer in the ceramic pipe at the end as probe, and the Ag silk that is connected with physical conductors of the other end of ceramic pipe be from the cement sinter layer, pass and in use in order to the connection circuit plate.This electrode is the three-decker of cement-AgCl/Ag-cement.
Further, the outside of the disconnected conductor part of the Ag silk that passes from described cement sinter layer is provided with insulation course, and described insulation course can be the insulation heat-resistant coating, and/or is with the polyfluortetraethylene pipe of insulation outside the Ag silk, or the polyfluortetraethylene pipe of pyrocondensation; Being provided with hermetically-sealed construction in described insulation course outside is used between sensor electrode and the autoclave jack or the sealing between detection sensor and the containment vessel on the spot.
The above-mentioned two kinds of structures of contrast electrode Ag/AgCl can be selected a use.The sheathed described hermetically-sealed construction in described insulation course outside in second kind of structure can be the packing washer of graphite and teflon mixture, preferably the structure that is provided with at intervals of the packing washer of graphite and teflon mixture and metal washer and by pressing solidly with the metal threaded cutting ferrule that autoclave or corresponding protection shell are spirally connected.By the sealing structure to electrode and detect on the standardization experimental apparatus between the plug-in opening or the sealing between sensor and the containment vessel in surveying on the spot.
The structure of potential electrode YSZ/HgO/Hg:
Described YSZ/HgO/Hg electrode (be also referred to as YSZ/HgO/Hg pottery probe) comprise an end closure one end uncovered contain Y
2O
3Ceramic pipe, bottom in this ceramic pipe is filled with the Hg/HgO potpourri, described Hg/HgO mixture weight is (1-1.5) than scope: 1, in described ceramic pipe, be inserted with a platinum silk, its lower end is embedded in the described Hg/HgO potpourri, its upper end passes described ceramic pipe connection physical conductors or directly uses as physical conductors, in ceramic pipe, be filled with filling material above the Hg/HgO potpourri, this filling material is not for participating in electrochemical reaction, can adding fixed silicates material behind the water, with described Hg/HgO mixture compacted; Pass at platinum filament and be provided with this ceramic pipe outlet of washer sealing teflon or graphite and teflon mixture system in the outlet at ceramic pipe top; Outside in the disconnected conductor part of Pt tinsel that passes described ceramic pipe is provided with insulation course, and described insulation course can be insulation heat-resistant coating and/or the polyfluortetraethylene pipe that is with insulation outside platinum filament, or the teflon heat-shrink tube; Being provided with hermetically-sealed construction in described insulation course outside is used between sensor electrode and the autoclave jack or the sealing between detection sensor and the detector containment vessel on the spot.
The packed height of the Hg/HgO potpourri of filling in described ceramic pipe can be decided according to the required electrode length of environment for use, is preferably 2～3cm.
This ceramic pipe is with ZrO
2Composition is main 9% Y that contains
2O
3The ceramic pipe of stabilizing agent.This ceramic pipe is commonly called the zirconia ceramic (YSZ) with yttria stabilizing agent.
The filling material of filling the silicates material on the Hg/HgO potpourri can be grout, wherein cement: the ratio of water for example can be 1:1.The better scheme of this filling material is φ 2-4mmAl
2O
3The 3-5mm length short tube of pottery or conventional ceramic and the potpourri of grout, the volume ratio of described ceramic short tube and grout is preferably 1:1, and scale can be adjusted.In cement, add intensity and the solidity that ceramic short tube can improve filling material.
As described in the junction of described pottery probe (YSZ/HgO/Hg electrode) and metal sensor and detector containment vessel as the insertion oral pore wall of autoclave or in surveying on the spot hermetically-sealed construction be set in as described in graphite or graphite and teflon mixture gasket circle on the ceramic pipe, the preferably structure that is provided with at intervals of graphite grazing packing ring and metal washer and the extruded sealing structure that presses solidly by the metal threaded cutting ferrule that can be spirally connected with autoclave or corresponding protection shell and pressure cap.
Potential electrode Zr/ZrO
2Structure:
Described Zr/ZrO
2Electrode comprises the metal oxide film of the same race on this metal and this metal, is provided with insulation course and hermetically-sealed construction on the non-probe segment of described electrode and disconnected conductor part:
Described Zr/ZrO
2The ZrO that electrode is formed by Zr silk and Zr silk surface
2The top layer constitutes.One end of electrode has ZrO outside the Zr silk
2The top layer is as probe; The other end of electrode is the Zr silk, and it is connected with circuit, and described Zr silk outside is coated with coatings layer and cover teflon heat-shrink tube.Zr/ZrO
2Electrode is sheathed packing washer at the packoff that above-mentioned insulation course outside is provided with, be used for to electrode with detect on the standardization experimental apparatus between the plug-in opening or the sealing between detection sensor and the detector containment vessel on the spot.
The sealing structure is to be set in the graphite on the described electrode and the packing washer of teflon mixture, preferably the structure that is provided with at intervals of the packing washer of graphite and teflon mixture and metal washer and by pressing solidly with metal threaded cutting ferrule and the pressure cap that autoclave or corresponding protection shell are spirally connected.
ZrO
2The syndeton of/Zr electrode and plain conductor is: at the sheathed conducting metal pipe box that is easy to weld that is fixed with in the power connection end head outside of this electrode, when forming the electrode measurement circuit, lead and described conducting metal pipe box are welded to connect.
The described hermetically-sealed construction of second kind of electrode and two kinds of reference electrodes is the packing washer groups that are located in the external insulation layer outside of described ceramic pipe or electrode in the above-mentioned potential electrode, the sealing washer sets is a plurality of graphite gasket and/or graphite and teflon mixture gasket circle, or is a plurality of graphite gasket and/or the packing washer of graphite and teflon mixture and the bonded washer structure that metal washer wears at intervals; The sealing structure also comprises the metal threaded cutting ferrule and/or the pressure cap that can be spirally connected with autoclave or corresponding protection shell, and it presses solidly on described packing ring and/or is fastened in this packing ring outside.
This chemical sensor comprises that also one links together described potential electrode and contrast electrode and makes their mutual group become a chemical sensor and described electrode is put into High Temperature High Pressure hydrothermal solution environment detect or demarcate or the metal parts of the usefulness of detection, this metal parts can be detect and standardization experimental apparatus in autoclave on parts, it also can be the associated components of the fixing described electrode on the detector, these parts are provided with jack, be provided with in this jack with described electrode on the syndeton that is complementary of described hermetically-sealed construction.
Described jack is upper coarse and lower fine shoulder hole, syndeton be located at described than the screw thread on the hole wall of coarse pore section, described metal threaded cutting ferrule and/or pressure cap in itself and the described potential electrode on second kind of electrode and the two kinds of reference electrodes are spirally connected fixing, in the jack of described metal parts and the annular space between the described electrode, also be provided with O-ring seal, make between jack and described metal threaded cutting ferrule or pressure cap and/or the O-ring seal group to seal.For first kind of electrode in the described potential electrode, described metal o-ring is resisted against the jack enclosed electrode of described metal parts and the annular space between described jack.
The preparation method of above-mentioned High Temperature High Pressure pH chemical sensor is:
A. make the Ag/AgCl electrode, select a ground and adopt following steps:
A1. 470 ℃～550 ℃ with the AgCl fusion, the Ag silk is immersed the AgCl melt, make the Ag silk form the AgCl coating outward, take out then;
A2. the Ag silk is inserted (or Al in the zirconia ceramics pipe that fills the AgCl pressed powder in its internal cavity
2O
3Pottery, or conventional ceramic), shutoff cement in ceramic pipe two ends then, 500-550 ℃ of heating 1-3 hour, makes the fusing of AgCl solid powder with above-mentioned parts, forms the AgCl coating outside the Ag silk, and makes the cement that is equipped with at the two ends of this ceramic pipe form porous sintered layer; At this, filamentary silver is being the back that is enclosed in cement sinter layer in the ceramic pipe at the end as probe, and the other end filamentary silver of ceramic pipe passes from the cement sinter layer and in use in order to connect.
B. make the YSZ/HgO/Hg electrode
Filling Hg/HgO potpourri in the bottom of ceramic pipe 2～3cm height cavity; Platinum filament connects from top to bottom; The Hg/HgO potpourri is soft, uses the Al of φ 2-4mm diameter on it
2O
3Above the potpourri of the short tube of pottery or conventional ceramic (length 3-5mm) and white cement slurry is pressed in, does solid stuff and use, guarantee that inner Hg/HgO ten minutes is solid; The diameter of ceramic pipe and length also can be other numerical value.
C. make ZrO
2/ Zr electrode:
Select φ 1～1.2mm diameter Zr tinsel for use.
If select for use the surface to scribble the Zr tinsel of organic carbon, then need not clean, be placed directly in the alumina crucible of gold lining, at fusion NaCO
3Middle oxidation 890-900 ℃ of reaction 1-2 hours, forms ZrO thereon
2Film.
If select common zirconium silk for use, then before abovementioned steps, increase following cleaning step, its cleaning method is: earlier Zr silk surface grinding, soak with watery hydrochloric acid then, remove surperficial solvend, clean surface is removed the surface and is gone up organic contaminant and dust again.Dry then;
ZrO
2The method of mechanical crimping is taked in the connection of the plain conductor that/Zr electrode is connected with wiring board, that is:
At ZrO
2/ Zr electrode polish processing with link plain conductor, then the conductive metal pipe cover is pressed solidly on the electrode tip of described polishing, conductive metal pipe is connected with lead.
Zirconium in the zirconium dioxide has single electricity price under 400 ℃ of high temperature 40MPa high pressure, highly stable, is the preferred material of making the pyrostat electrode.But of no use in the prior art it do the record of electrode, its reason just is this material melting point height, extremely difficult welding the invention provides above-mentioned " mechanical crimping " method for making, and is simple and easy to use.
Use the sealing of graphite gasket, copper washer or stainless steel packing ring or graphite and teflon mixing packing ring or metal o-ring between described chemical sensor provided by the invention and the described autoclave compared with prior art, sealing effectiveness is better; By changing the size of cutting ferrule and copper washer or stainless steel packing ring, graphite gasket, graphite and teflon mixture packing ring or metal o-ring, and selecting for use to packing ring of different nature, can make this chemical sensor have different physical dimension, to adapt in the autoclave that is installed in heterogeneity and different size, (temperature can reach 400 ℃ at stable high temperature and high pressure environment, pressure can reach 40Mpa) under, sensor is detected and demarcates.Also can be installed on the detector of heterogeneity and different size simultaneously.
High Temperature High Pressure pH chemical sensor provided by the invention can use, can accurately measure the pH value of liquid at 0 ℃ to 400 ℃, high pressure to the 40MPa, and working stability, life-span are long.This chemical sensor can be placed in the laboratory and detect demarcation in the autoclave, also can be installed in to carry out the mensuration of the pH value of high-temperature, high pressure fluid on the spot on the detector in the high temperature and high pressure environment of reality.
Description of drawings
The present invention is described in detail below in conjunction with accompanying drawing.
Fig. 1 is the structural representation of the contrast electrode Ag/AgCl (first kind of structure) in the pH chemical sensor of the present invention;
Fig. 2 is the structural representation of the contrast electrode Ag/AgCl (second kind of structure) in the pH chemical sensor of the present invention;
The structural representation of YSZ/HgO/Hg first potential electrode in Fig. 3 pH chemical sensor of the present invention;
Fig. 4 is the Zr/ZrO in the pH chemical sensor of the present invention
2The structural representation of second potential electrode;
Fig. 5 is the structural representation of pH chemical sensor of the present invention.
Embodiment
Embodiment:
A kind of pH chemical sensor that is used under the High Temperature High Pressure, it comprises potential electrode and contrast electrode two parts, potential electrode is YSZ/HgO/Hg and Zr/ZrO
2Two potential electrode; When measuring temperature, use the YSZ/HgO/Hg potential electrode greater than 200 ℃; When measuring temperature, use Zr/ZrO at 0-400 ℃
2Potential electrode; Contrast electrode is the Ag/AgCl electrode;
Described contrast electrode Ag/AgCl has two kinds of structures:
First kind of structure: as shown in Figure 1, the Ag/AgCl electrode is formed jointly by being provided with AgCl rete 6 outside Ag silk 11 and the lower end Ag silk 11, use as probe its lower end, in the part of not doing probe and disconnected conductor part, its outer insulation course that is provided with, described insulation course in the present embodiment is a sealed insulation shellac varnish 12, be provided with teflon heat-shrink tube 13 in these shellac varnish 12 outsides, O-ring seal 14 in sheathed teflon in the outside of this heat-shrink tube and graphite mixture system, sheathed stainless-steel tube 5 outside the heat-shrink tube on O-ring seal 14 tops ', at the sheathed polyfluortetraethylene pipe 5 in the heat-shrink tube outside of O-ring seal 14 bottoms.Outside whole heat-shrink tube, be provided with two-stage relay baton type hermetically-sealed construction, it is for setting firmly a metal o-ring 17 on polyfluortetraethylene pipe 5, stainless-steel tube 5 on metal o-ring 17 ' on sheathed one the sealing swivel nut 16, establish external thread on the sealing swivel nut 16, be spirally connected with the internal thread of insertion mouth 70 on the autoclave 7, when this electrode was inserted in the patchhole 70 of autoclave 7, O-ring seal 17 was pressed on the convex shoulder on the patchhole and is extruded, and constitutes first seal structures in the relay baton type hermetically-sealed construction.On sealing swivel nut 16, be provided with a center ladder axis hole, the aperture, top of this axis hole is bigger, its hole inwall is provided with screw thread, the bottom is a unthreaded hole, has a convex shoulder between screw and the unthreaded hole, in the center ladder axis hole of sealing swivel nut 16, accommodate the O-ring seal 14 that is set in outside the electrode sheathed teflon and graphite mixture system on the heat-shrink tube, it is pressed on this convex shoulder, the stainless-steel tube 5 of sealing on the swivel nut 16 ' on sheathed packing follower 15, have the aperture of center ladder axis hole that male thread portion is plugged in sealing swivel nut 16 on the packing follower 15 than in the macropore section, be complementary with internal thread on the sealing swivel nut 16.Screwing hermetic cover casting die 15, its compresses seal 14 can form relay baton type hermetically-sealed construction second seal structures.
Second kind of structure: as shown in Figure 2, the latter half as the Ag silk 21 of Ag/AgCl electrode is set in zirconia (YSZ) ceramic pipe 27, be the AgCl rete 28 that AgCl pressed powder fusing forms in ceramic pipe 27, the shutoff of the two ends of this ceramic pipe have honeycombed cement agglomerate 29 and 29 '; On the first half of the filamentary silver of the part of not doing probe and disconnected conductor part, its outer insulation course teflon heat-shrink tube 22 that is provided with, outside at insulation course is provided with hermetically-sealed construction, it is the packing washer 26 that is set on the heat-shrink tube 22, two stainless steel packing rings 24 and be clipped in packing washer 25 between the stainless steel packing ring 24, sheathed fastening swivel nut 20 on stainless steel packing ring 24, its lower end is the concave shape end face, form annular seal space, packing washer 23 places the sealing chamber, the bottom is resisted against on the stainless steel packing ring 24, this sensor probe is plugged in the grafting screw 70 of autoclave 7, screw fastening swivel nut 20, by above-mentioned packing washer 23,25, the hermetically-sealed construction of 26 3 road relay baton types has sealed the gap between electrode and the autoclave well.The cement agglomerate 29 that the lower end of ceramic pipe 27 sets firmly gets up the lower end closed of ceramic pipe, and electrode 21 lower end probe segments 28 are enclosed in the ceramic pipe 27.Cement agglomerate 29 is a porous medium, and it can make fluid to be measured penetrate in the ceramic pipe 27 and contact with the electrode of sensor, makes this chemical sensor operate as normal, and it can play a very good protection to electrode again, slows down the consumption of electrode, prolongs its life-span.The upper end of the inboard corresponding probe segment 28 of the upper port of ceramic pipe 27 also be installed with a cement agglomerate 29 ', this cement agglomerate 29 ' upper end closed of ceramic pipe 27 is got up, it is effectively kept apart electrode and autoclave still wall, can prevent the short circuit that the electrode corrosion may cause, further improve the serviceable life of this sensor.
In the present embodiment, by cement agglomerate 29 ' on the hermetically-sealed construction of three road relay baton types of packing washer 26, packing washer 25 between two stainless steel packing rings 24 and the packing washer 23 between stainless steel packing ring 24 and the fastening swivel nut 20, gap between Ag/AgCl and the patchhole is sealed reliably, wherein be provided with the cement agglomerate in the ceramic pipe upper end, on agglomerate, establish packing washer 26, like this, better than the sealing effectiveness of on ceramic pipe, directly placing packing washer.And the ferrule sealing structure of packing washer is set between two stainless steel packing rings, and can avoid the problems such as displacement of packing washer, guarantee positiver sealing.And limited in the annular seal space of uppermost packing washer 23 on fastening swivel nut 20, as the afterbody sealing, its sealing property also is very reliable.Therefore, this packoff can be in the solution environmental of high-temperature high-pressure chemical medium excellent sealing.
The filamentary silver part of the upper end of the contrast electrode Ag/AgCl of above-mentioned two kinds of structures is connected then connecting circuit plate more in use with physical conductors.Make contrast electrode and select the thickness of filamentary silver for use, do not influence electrode measurement.Select 0.5～1mm diameter filamentary silver comparatively firm.
The method for making of above-mentioned contrast electrode Ag/AgCl is as follows:
The contrast electrode Ag/AgCl of above-mentioned first kind of structure makes of following step: at 470 ℃～550 ℃ (as 470 ℃ or 550 ℃ or 500 ℃) with the AgCl fusion, the bottom probe segment of Ag silk is immersed in the AgCl melt, make and on the Ag silk, form the AgCl coating, the required time of this operating process, to be that the temperature according to concrete operating environment temperature and melt is different decided, usually can be in 3-15 second, till its surface forms argentine chloride coating.By conventional method described insulation course is fixed on the first half of electrode, the upper end of filamentary silver stretches out insulation course and is used to connect lead and forms the loop.
Detailed process is:
1, the processing of filamentary silver:
The Ag silk is polished by ultra-fine quartzy crocus cloth.Remove surface contamination or oxide, clean, use distilled water flushing again with watery hydrochloric acid.Be immersed in then in the acetone liquid and clean more than half an hour, wash down the dust and the organism of surface adsorption with supersonic wave cleaning machine.Clean more than half an hour with supersonic wave cleaning machine with normal hexane liquid again.At last, take out air-dry automatically, or 80 ℃ of oven dry.
2, system AgCl layer on filamentary silver:
Get chemical pure AgCl powder, heating is 470 ℃～550 ℃ in ceramic crucible, makes its fusing under basic anoxic, will immerse in the AgCl melt through the Ag silk that step 1 is handled then, takes out after treating to form the AgCl shell on it.
3, the making of Ag/AgCl electrode sealing construction:
Coat coatings (poly-acetyl diamines), the heat-shrink tube of overcoat teflon then at the Ag of 1mm diameter silk.The described packoff of peripheral hardware again.Use teflon sleeve, use " relay baton type " twice sealing.As shown in Figure 1.Be installed on the poly-four fluorine tube 13 with copper (or stainless steel) cutting ferrule 17 and seal as the first order.Second level sealing be the top of this polyfluortetraethylene pipe 13 be stainless-steel tube 5 ', between two kinds of different materials φ 3mm pipes " relay baton type " sealing joint parts 14, the heat-shrink tube 13 outer stainless-steel tubes that overlap again of its top peripheral hardware, the poly-four fluorine tube 5 of heat-shrink tube 13 outer covers again of its underpart peripheral hardware.Add 15,16 sealings of stainless steel cutting ferrule.This hermetically-sealed construction can guarantee anti-250 ℃ and 40MPa high pressure.
The contrast electrode Ag/AgCl of above-mentioned second kind of structure makes of following step:
The processing of 1 filamentary silver: the Ag/AgCl electrode filamentary silver disposal route of the same a kind of structure of its disposal route is identical.
2, system AgCl layer on filamentary silver:
The latter half of Ag silk is inserted (or the Al in zirconia ceramics pipe (YSZ) that wherein fills the AgCI pressed powder
2O
3Pottery, or conventional ceramic), at the two ends of ceramic pipe shutoff cement, heating is melted in AgCI solid powder to form coating outside the Ag silk and cement sinters the honeycombed cement piece under anoxic.
The AgCl/Ag electrode that this method is made forms the cement-AgCI/Ag-cement three-decker that contains the opening ceramic pipe, can durablely use.
3, the making of Ag/AgCl electrode sealing construction:
Coat coatings (poly-acetyl diamines), the heat-shrink tube of overcoat teflon then at the Ag of 1mm diameter silk.The described packoff of peripheral hardware again.Adopt teflon and graphite to mix the packing washer 15,16 of system.
Add teflon and graphite in the outside of the insulation course of the upper end of the Ag/AgCl electrode of the cement of making-AgCl/Ag-cement three-decker successively and mix that gasket circle 26, stainless steel packing ring 24, teflon and graphite mix gasket circle 25, stainless steel packing ring 24 and teflon and graphite mixes gasket circle 23 with ceramic pipe, on packing washer 23, sheathed stainless-steel tube outside the heat-shrink tube of electrode; Sheathed its lower end is the fastening swivel nut 20 that the concave shape end face forms annular seal space on stainless steel packing ring 24, teflon and graphite mix gasket circle 23 and place the sealing chamber, the bottom is resisted against on the stainless steel packing ring 24, the AgCl/Ag sensor probe of making like this is plugged in the grafting screw of autoclave 7, screw fastening swivel nut 20, form the hermetically-sealed construction of three road relay baton types by above-mentioned packing washer 23,25,26.The hermetically-sealed construction that this method is made can anti-400 ℃ of 40MPa High Temperature High Pressure.
Use the material packing ring mode of anti-400 ℃ of coating and Delanium to seal at 400 ℃/40MPa.Connection is to seal with the composite material packing ring of graphite gasket or graphitiferous teflon and the combination of stainless steel packing ring.Be placed on M20 * 1.5, M10 * 1 is in the metal interface of M8 * 1.
The material that described teflon and graphite mix the gasket circle is to be the common material that can buy on market.
First potential electrode as shown in Figure 3, described YSZ/HgO/Hg electrode (be also referred to as YSZ/HgO/Hg pottery probe) comprise an end closure one end uncovered contain Y
2O
3Ceramic pipe, ceramic pipe 39, be filled with Hg/HgO potpourri 38 in the bottom of ceramic pipe 39, the Hg/HgO mixture weight is 1.2:1 than scope, be inserted with a platinum silk 31 in ceramic pipe 39, its lower end is embedded in the Hg/HgO potpourri 38, and its upper end passes ceramic pipe 39 connection physical conductors (not shown)s or directly uses as physical conductors, be filled with filling material 30 in ceramic pipe 39 above the Hg/HgO potpourri 38, this filling material 30 is φ 3mmAl
2O
3The potpourri of the short tube of pottery or conventional ceramic and white cement slurry is with 38 compactings of Hg/HgO potpourri; Pass packing ring 33 sealings that are provided with teflon or graphite and teflon mixture system in the outlet at ceramic pipe 39 tops at platinum filament 31; Outside in the Pt silk 31 disconnected conductor part that pass ceramic pipe 39 is provided with insulation course, and it is the teflon heat-shrink tube of insulation heat-resistant coating layer and sheathed insulation outside it; Be provided with hermetically-sealed construction in insulation course outside and be used for sealing between sensor electrode and the autoclave jack.The extruded sealing structure that the sealing structure is made of the graphite gasket of insulated enclosure or graphite and teflon mixture system packing ring, stainless steel packing ring and stainless steel cutting ferrule is formed.Particularly, the sealing structure comprises the stainless steel packing ring 34 that is set in successively on the ceramic pipe 39, graphite gasket 35 and stainless steel packing ring 34, also comprise a stainless steel cutting ferrule 36 and a STAINLESS STEEL NUTS 36 ', has a upper coarse and lower fine through hole in the middle of the cutting ferrule 36, below ceramic pipe 39 is plugged in the thinner through hole, be enclosed within the seal element stainless steel packing ring 34 on the ceramic pipe, graphite gasket 35 and stainless steel packing ring 34 are against on the convex shoulder of upper coarse and lower fine through hole in the cutting ferrule 36, be provided with an inner cavity in the middle of the bottom of nut 36 ', mate than the screw thread on the gross porosity inwall on the lower thread of nut 36 ' and cutting ferrule 36 tops, nut lower end evagination end face extruded sleeve is located at the graphite gasket on the ceramic pipe 39, and the extruding of indent end face is located at the packing ring 33 of the teflon in the ceramic pipe outlet in the middle of the nut.This ceramic pipe that has above-mentioned packoff is plugged in the ladder perforation of autoclave, on the perforation convex shoulder, establish annular groove, establish graphite gasket 37 in it, the lower surface shape of cutting ferrule and the ladder hole form fit of autoclave, this lower surface compresses this graphite gasket 37, and the packing ring 33 by graphite gasket 37, stainless steel packing ring 34, graphite gasket 35 and stainless steel packing ring 34 and teflon has constituted three grades of extruded sealing structures.
This ceramic pipe is ZrO preferably
2Composition is main 9% Y that contains
2O
3The ceramic pipe of stabilizing agent.The zirconia ceramic (YSZ) that is called as three stabilized with yttrium oxide agent.
The filling material of filling on the Hg/HgO potpourri can be grout, wherein cement: the ratio of the water for example better scheme of 1:1 is that the volume ratio of described ceramic pipe and grout is preferably 1:1.The filling material that adds ceramic short tube formation in cement can improve the intensity and the solidity of filling material.
The ceramic pipe external diameter 6.3mm of pottery probe (YSZ/HgO/Hg electrode).Forming the O-ring seal group by graphite circle or graphite and teflon mixture system packing ring and stainless steel coil is enclosed within outside the ceramic pipe.The teflon at the item place of ceramic pipe or soft circle packing ring internal orifice dimension φ 1 to the φ 3mm of graphite and teflon mixture system.
The method for making of the first potential electrode YSZ/HgO/Hg is:
Filling Hg/HgO potpourri in the bottom of ceramic pipe 2～3cm height cavity, platinum filament inserts in the ceramic pipe, and the Hg/HgO potpourri is imbedded in the lower end, and platinum filament connects from top to bottom, and the upper end is exposed at outside the ceramic pipe; The Hg/HgO potpourri is soft, fills the Al of φ 3mm diameter thereon
2O
3The short tube of pottery or conventional ceramic (5mm) and white cement pulp mixture, this potpourri solidifies coagulation above being pressed in the Hg/HgO potpourri, as solid stuff, guarantees that inner Hg/HgO ten minutes is solid;
Second potential electrode as shown in Figure 4, Zr/ZrO
2The ZrO that electrode is formed by Zr silk 47 and Zr silk surface
2Top layer 41 constitutes.The Zr silk has ZrO outward
2One end on top layer 41 is as probe; The other end of electrode Zr silk 47 is connected with circuit, and Zr silk 47 outsides are coated with coatings layer and cover teflon heat-shrink tube 44.Outside heat-shrink tube 44, add cover stainless-steel tube 49 again.Zr/ZrO
2The packoff that electrode is provided with outside above-mentioned insulation course or heat-shrink tube is sheathed packing washer, it is: at cover teflon the heat-shrink tube 44 outer sheathed graphite in interval and teflon mixture system packing ring 42 and stainless steel packing ring 43 successively from top to bottom, sheathed metal nut 46 on the stainless steel packing ring on upper strata, when in the upper coarse and lower fine ladder jack 451 that this electrode is plugged in autoclave 45, lower floor's stainless steel packing ring is resisted against on the jack convex shoulder, be provided with in the thin jack 451 of nethermost packing washer 42 ' below convex shoulder, screw thread coupling on screw thread on the nut 46 and the jack, the stainless steel packing ring 43 of lower end is supported on the convex shoulder of jack fixing, screw metal nut 46, be compressible gasket 43 and packing ring 42, make it the gap secure seal between electrode and the jack.ZrO
2The syndeton of/Zr electrode and plain conductor is: at the sheathed conducting metal shell 48 that is easy to weld that is fixed with in the power connection end head outside of this electrode, when forming the electrode measurement circuit, lead and described conducting metal shell are welded to connect.
The second potential electrode Zr/ZrO
2Method for making as follows:
1, handle the Zr tinsel:
Select φ 1～1.2mm diameter Zr tinsel for use.Zr silk surface grinding, use quartzy emery cloth with thickness sand paper (corundum powder) again, polishing Zr silk surface, soak with watery hydrochloric acid then, remove surperficial solvend, after cleaning with distilled water, place acetone with ultrasonic cleaner clean surface half an hour, remove the surface and go up organic contaminant and dust.Clean with normal hexane then, still in ultrasonic cleaner, clean half an hour, take out the back and use distilled water peace and quiet, air-dry again or 80 ℃ of oven dry.
If select the Zr tinsel of organic carbon coating for use, can not carry out above-mentioned surface treatment.
2, on the Zr tinsel, generate ZrO
2Film:
Zirconium tinsel after handling or that have the organic carbon coating is placed in the alumina crucible of gold lining, uses fusion NaCO
3Oxidation was 890-900 ℃ of reaction 1.5 hours.
At NaCO
3Form ZrO in the melt
2In the film operating process, the time of heating-up temperature and stable high temperature is crucial.
Zr/ZrO
2The other end Zr tinsel of electrode is coated with coatings, and the sealing of teflon heat-shrink tube is to adopt washer sealing, and does not adopt welding method.ZrO
2The plain conductor of/Zr electrode and circuit connect the method for taking mechanical crimping, that is:
At ZrO
2/ Zr electrode polish processing with link plain conductor, then conducting metal cover 48 is pressed solidly on the electrode tip of described polishing, conductive metal pipe is connected with lead.
Second potential electrode is used Zr/ZrO
2Can in big temperature range, use.
As shown in Figure 5, when this chemical sensor potential electrode A and contrast electrode B are provided with two jack C1 on the autoclave C in the in vitro detection standardization experimental apparatus and C2, realize ceramic pipe or the external insulation layer of electrode and the sealing between autoclave jack C1 and the C2 metallic walls on the electrode by being arranged on described graphite gasket on the electrode or copper washer or stainless steel packing ring or graphite and teflon mixture system packing ring or metal o-ring between described pH chemical sensor and the described autoclave.
In actual detector, above-mentioned hermetically-sealed construction be equally applicable to and detector on the metallic walls of jack between sealing.
Claims (13)
1, a kind of High Temperature High Pressure pH chemical sensor, it comprises potential electrode and contrast electrode, described potential electrode is YSZ/HgO/Hg and/or Zr/ZrO
2Potential electrode; When temperature during, use the YSZ/HgO/Hg potential electrode greater than 200 ℃; When temperature during, use Zr/ZrO at 0-400 ℃
2Potential electrode; Described contrast electrode is the Ag/AgCl electrode;
Described all electrodes are divided into three parts, the first one end is immersed in probe segment in the fluid to be measured as probe, it two is the joining conductor part that connect of the other end and physical conductors, it three is that part and the disconnected conductor part of not doing probe segment is center section, described center section is provided with insulation course, and its outside is provided with hermetically-sealed construction.
2, chemical sensor according to claim 1 is characterized in that:
First kind of structure of described contrast electrode Ag/AgCl is:
Outside the Ag silk of the probe segment of electrode, be provided with the AgCl rete, at center section, its outer insulation course that is provided with, described insulation course is the insulation heat-resistant coating, and/or is with the polyfluortetraethylene pipe of insulation outside the Ag silk; Being provided with hermetically-sealed construction in described insulation course outside is used between sensor electrode and the autoclave jack or the sealing between detection sensor and the containment vessel on the spot; Or
Second kind of structure places in the conventional ceramic pipe for the Ag silk, is the AgCl layer that the AgCl pressed powder is melt into outside the Ag silk, the porous layer that is formed by the cement sintering in the shutoff of the two ends of this ceramic pipe; The AgCl/Ag wire electrode is being the back that is enclosed in cement sinter layer in the ceramic pipe at the end as probe, and the Ag silk that is connected with physical conductors of the other end of ceramic pipe be from the cement sinter layer, pass and in use in order to the connection circuit plate; This electrode is the three-decker of cement-AgCl/Ag-cement; The disconnected conductor part of the Ag silk that passes from described cement sinter layer is that the outside of center section is provided with insulation course, is provided with hermetically-sealed construction in described insulation course outside and is used between sensor electrode and the autoclave jack or the sealing between detection sensor and the containment vessel on the spot; With
Described YSZ/HgO/Hg potential electrode comprises ceramic pipe, bottom in this ceramic pipe is filled with the Hg/HgO potpourri, described Hg/HgO mixture weight is 1--1.5:1 than scope, in described ceramic pipe, be inserted with a platinum Pt tinsel, its lower end is embedded in the described Hg/HgO potpourri, its upper end passes described ceramic pipe connection physical conductors or directly uses as physical conductors, in ceramic pipe, be filled with filling material above the Hg/HgO potpourri, this filling material is not for participating in electrochemical reaction, add can be fixed behind the water the silicates material, with described Hg/HgO mixture compacted; Pass at platinum filament and be provided with this ceramic pipe outlet of washer sealing teflon or graphite and teflon mixture system in the outlet at ceramic pipe top; In the disconnected conductor part of Pt tinsel that passes described ceramic pipe is that the outside of center section is provided with insulation course; Being provided with hermetically-sealed construction in described insulation course outside is used between sensor electrode and the autoclave jack or the sealing between detection sensor and the containment vessel on the spot; And/or,
Described Zr/ZrO
2Electrode comprises the metal oxide film of the same race on this metal and this metal, is to be provided with insulation course and hermetically-sealed construction on the center section in the non-probe segment and the disconnected conductor part of described electrode:
Described Zr/ZrO
2The ZrO that electrode is formed by Zr silk and Zr silk surface
2The top layer constitutes, and an end of electrode has ZrO outside the Zr silk
2The top layer is as probe; The other end of electrode is the Zr silk, and it is connected with circuit, and described Zr silk outside is coated with coatings layer and cover teflon heat-shrink tube, Zr/ZrO
2Electrode is sheathed packing washer at the packoff that above-mentioned insulation course outside is provided with, be used for to electrode with detect on the standardization experimental apparatus between the autoclave plug-in opening or the sealing between detection sensor and the detector containment vessel on the spot; ZrO
2The syndeton of/Zr electrode and plain conductor is: at the sheathed conducting metal pipe box that is easy to weld that is fixed with in the power connection end head outside of this electrode, when forming the electrode measurement circuit, lead and described conducting metal pipe box are welded to connect.
3, chemical sensor according to claim 2 is characterized in that: described conventional ceramic pipe is zirconia ceramics pipe or alundum (Al ceramic pipe.
4, chemical sensor according to claim 2, it is characterized in that: hermetically-sealed construction is described in first kind of structure of described contrast electrode Ag/AgCl: be coated with described insulation heat-resistant coating layer at described center section, sheathed graphite in outside and teflon mixture gasket circle, polyfluortetraethylene pipe in the sheathed insulation in the bottom of sealing packing ring, set firmly metal o-ring on this polyfluortetraethylene pipe, it is a primary seal; Polyfluortetraethylene pipe and stainless steel sleeve pipe in the sheathed pyrocondensation in top of this graphite and teflon mixture gasket circle, on described center section, also be provided with a metal ferrule, be provided with upper coarse and lower fine through hole in the middle of it, the lower end abutment of described metal ferrule is on described metal o-ring, described graphite and teflon mixture gasket circle are resisted against on the through hole convex shoulder of described metal ferrule and seal, a sealing shroud casting die is set in the stainless steel sleeve tube outside of described metal ferrule top, its be plugged in described metal ferrule top than being spirally connected in the coarse pore section, it is a secondary seal; Constitute two-stage relay baton hermetically-sealed construction thus.
5, chemical sensor according to claim 2, it is characterized in that: the second kind of structure of described contrast electrode Ag/AgCl and the described hermetically-sealed construction of described contrast electrode are the packing washer group that is located in the external insulation layer outside of described ceramic pipe or electrode, the sealing washer sets is a plurality of graphite gasket and/or graphite and teflon mixture gasket circle, or is a plurality of graphite gasket and/or the packing washer of graphite and teflon mixture and the bonded washer structure that metal washer wears at intervals; The sealing structure also comprises the metal threaded cutting ferrule and/or the pressure cap that can be spirally connected with autoclave or corresponding protection shell, and it presses solidly on described packing ring and/or is fastened in this packing ring outside; By the sealing structure to electrode and detect on the standardization experimental apparatus between the plug-in opening or the sealing between sensor and the containment vessel in surveying on the spot.
6, chemical sensor according to claim 2 is characterized in that: the packed height of the Hg/HgO potpourri of filling in described ceramic pipe at described potential electrode YSZ/HgO/Hg is 2～3cm; The filling material of filling the silicates material on the Hg/HgO potpourri is a grout, wherein cement: the ratio of water is 1:1; Or this filling material is φ 2-4mmAl
2O
3The length of pottery or conventional ceramic is the potpourri of 3-5mm short tube and white cement slurry.
7, chemical sensor according to claim 2 is characterized in that: described insulation course is the insulation heat-resistant coating, and/or the insulation polyfluortetraethylene pipe of overcoat.
8, according to claim 2 or 7 described chemical sensors, it is characterized in that: described polyfluortetraethylene pipe is the polyfluortetraethylene pipe of pyrocondensation.
9, a kind of preparation method of High Temperature High Pressure pH chemical sensor: it comprises:
A. make the Ag/AgCl electrode, select a ground and adopt following steps:
A1. 470 ℃～550 ℃ with the AgCl fusion, the Ag silk is immersed the AgCl melt, make the Ag silk form the AgCl coating outward, take out then;
At the center section of Ag silk, its peripheral hardware insulation course, described insulation course are the insulation heat-resistant coatings, and/or are with the polyfluortetraethylene pipe of insulation outside the Ag silk; Establishing hermetically-sealed construction in described insulation course outside is used between sensor electrode and the autoclave jack or the sealing between detection sensor and the containment vessel on the spot;
A2. the Ag silk is inserted in the zirconia ceramics pipe that fills the AgCl pressed powder in its internal cavity or Al
2O
3Pottery, or conventional ceramic, shutoff cement in ceramic pipe two ends then, 500-550 ℃ of heating 1-3 hour, makes the fusing of AgCl solid powder with above-mentioned parts, forms the AgCl coating outside the Ag silk, and makes the cement that is equipped with at the two ends of this ceramic pipe form porous sintered layer; At this, filamentary silver is being the back that is enclosed in cement sinter layer in the ceramic pipe at the end as probe, and the other end filamentary silver of ceramic pipe passes from the cement sinter layer and in use in order to connect;
The disconnected conductor part of the Ag silk that passes from described cement sinter layer is that insulation course is established in the outside of center section, establishes hermetically-sealed construction in described insulation course outside and is used between sensor electrode and the autoclave jack or the sealing between detection sensor and the containment vessel on the spot; With
The preparation method of B, potential electrode: it comprises:
Make potential electrode YSZ/HgO/Hg:
Filling Hg/HgO potpourri in the bottom of ceramic pipe 2～3cm height cavity; Platinum filament is connected from top to bottom; The Hg/HgO potpourri is soft, uses the Al of φ 2-4mm diameter on it
2O
3Pottery or conventional ceramic pipe, its length are 3-5mm, above being pressed in the potpourri of white cement slurry, do solid stuff and use, and guarantee that inner Hg/HgO ten minutes is solid;
In the disconnected conductor part of Pt tinsel that passes described ceramic pipe is that insulation course is established in the outside of center section; Establishing hermetically-sealed construction in described insulation course outside is used between sensor electrode and the autoclave jack or the sealing between detection sensor and the containment vessel on the spot; And/or
Make potential electrode ZrO
2/ Zr:
Select the Zr tinsel for use,, then need not clean, be placed directly in the alumina crucible of gold lining, at fusion NaCO if select for use the surface to scribble the Zr tinsel of organic carbon
3Middle oxidation 890-900 ℃ of reaction 1-2 hours, forms ZrO thereon
2Film;
If select common zirconium silk for use, then before abovementioned steps, increase following cleaning step, its cleaning method is: earlier Zr silk surface grinding, soak with watery hydrochloric acid then, remove surperficial solvend, again clean surface, remove the surface and go up organic contaminant and dust, dry then;
ZrO
2The method of mechanical crimping is taked in the connection of the plain conductor that/Zr electrode is connected with wiring board, that is: at ZrO
2/ Zr electrode polish processing with link plain conductor, then the conductive metal pipe cover is pressed solidly on the electrode tip of described polishing, conductive metal pipe is connected with lead;
Non-probe segment and disconnected conductor part at described electrode are that order is established insulation course and packing washer on the center section.
10, the preparation method of High Temperature High Pressure pH chemical sensor according to claim 9 is characterized in that: potential electrode ZrO
2Among the preparation method of/Zr, select the cleaning of common zirconium silk for use: select φ 1～1.2mm diameter Zr tinsel for use, Zr silk surface grinding, use quartzy emery cloth with corundum powder flint glass paper again, polishing Zr silk surface, soak with watery hydrochloric acid then, remove surperficial solvend, after cleaning with distilled water, place acetone ultrasonic cleaner clean surface, half an hour, remove the surface and go up organic contaminant and dust; Clean with normal hexane then, still clean half an hour in ultrasonic cleaner, takes out the back and use distilled water peace and quiet, air-dry again or 80 ℃ of oven dry.
11, according to claim 2 or 3 or 4 described chemical sensors, it is characterized in that: comprise that also one links together described potential electrode and contrast electrode and makes their mutual group become a chemical sensor and described electrode is put into High Temperature High Pressure hydrothermal solution environment detect or demarcate or the metal parts of the usefulness of detection, this metal parts be detect and standardization experimental apparatus in autoclave on parts, or the associated components of the fixing described electrode on the detector, these parts are provided with jack, be provided with in this jack with described electrode on the syndeton that is complementary of described hermetically-sealed construction.
12, chemical sensor according to claim 5, it is characterized in that: comprise that also one links together described potential electrode and contrast electrode and makes their mutual group become a chemical sensor and described electrode is put into High Temperature High Pressure hydrothermal solution environment detect or demarcate or the metal parts of the usefulness of detection, this metal parts be detect and standardization experimental apparatus in autoclave on parts, or the associated components of the fixing described electrode on the detector, these parts are provided with jack, be provided with in this jack with described electrode on the syndeton that is complementary of described hermetically-sealed construction.
13, chemical sensor according to claim 12, it is characterized in that: described jack is upper coarse and lower fine shoulder hole, syndeton be located at described than the screw thread on the hole wall of coarse pore section, described metal threaded cutting ferrule and/or pressure cap on itself and the described electrode are spirally connected fixing, also be provided with O-ring seal in the annular space between described jack and described electrode, make between jack and described metal threaded cutting ferrule or pressure cap and/or the O-ring seal group to seal.
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| US8828207B2 (en) * | 2012-06-13 | 2014-09-09 | Honeywell International Inc. | Deep sea pH sensor |
| CN105021678B (en) * | 2015-08-12 | 2018-04-06 | 中国科学院地球化学研究所 | A kind of pH chemical sensors for high pressure hydrothermal system and preparation method thereof |
| CN106369246B (en) * | 2016-10-18 | 2018-12-25 | 北京空间技术研制试验中心 | Pneumatic gauging sensor heat-sealing processes |
| CN112903774A (en) * | 2021-01-21 | 2021-06-04 | 北京科技大学 | All-solid-state pH sensor for deep sea and preparation method thereof |
| CN112986366B (en) * | 2021-02-24 | 2022-07-01 | 中国核动力研究设计院 | Sensor for in-situ measurement of pH of high-temperature and high-pressure water and measurement method |
| CN113030193B (en) * | 2021-02-24 | 2022-06-14 | 中国核动力研究设计院 | High-temperature and high-pressure resistant online conductivity sensor and measurement system |
| CN112772296B (en) * | 2021-03-09 | 2023-07-04 | 贵州贵旺生物科技有限公司 | Liquid strain culture device and culture method for pleurotus eryngii |
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