KR20130110803A - Ph microelectrode and manufacturing method thereof - Google Patents

Abstract

PURPOSE: A pH measuring microelectrode and a manufacturing method thereof are provided to effectively perform a study on a primary production effect of a benthic microalgae inhabiting on the sea bottom. CONSTITUTION: A pH measuring microelectrode includes a liquid-ion exchanging penetrating film (40), an inner glass tube (10), an outer case (20), a pH electrolyte (32), a shielding electrolyte, 3M KCl (34), an Ag/AgCl signal detecting electrode, and an Ag/AgCl reference electrode (52). The inner glass tube is composed of a green glass tube (12) and an Ar glass (14) and includes the pH electrolyte inside. The shielding electrolyte and the Ag/AgCl reference electrode are arranged inside a space between the inner glass tube and the outer case. The Ag/AgCl signal detecting electrode is arranged inside the inner glass tube.

Description

PH measurement microelectrode and its manufacturing method {pH microelectrode and manufacturing method

The present invention relates to a microelectrode for measuring pH used in the study of the benthic environment, and to a method for manufacturing the same, more specifically, a microelectrode for measuring the pH more suitable for the primary production effect of the benthic microalgae inhabiting the seabed and its It is about a manufacturing method.

As is well known to those skilled in the art, microelectrodes used in microbial ecology and low microalgae are in the form of needles with a tip size of 1-100 micrometers and are instruments for measuring the concentration of specific compounds.

The benthic microalgae are benthic microalgae that inhabit the seabed, and the contents of the microalgae are disclosed in Korean Patent Laid-Open No. 10-2007-0056619.

The narrow reaction range at the tip of the microelectrode enables local measurements in biofilm, floc, aggregates, microbial mats and sediments. Although microelectrodes are introduced into the sample, their small tip diameters have little effect on structure or biological activity.

There are four types of microelectrodes: amperometric, voltammetric, potentiometric, and optical.

The potentiometric measurement of the microelectrode is based on the measurement of the electrical potential difference at the tip of the microelectrode generated by charge separation at the interface (interface). Typically, the interface is formed by an ion selective permeable membrane.

The potentiometric microelectrode as described above includes a pH microelectrode, and the microelectrode for pH measurement is manufactured based on a liquid ion-exchanging membrane (LIX) microelectrode.

Liquid ion exchange membrane microelectrode techniques have been developed by cell physiologists for the measurement of various ion concentrations in cells. Liquid ion-exchange membrane microelectrodes can also have tip diameters of less than 1 micron. Many media in the environment are measured by liquid ion exchange membrane electrodes (eg NH ₄ ⁺ , NO ₃ ⁻ , NO ₂ ⁻ , H ⁺ , Ca ^{2 +} , CO ₂ , CO ₃ ^{2 −,} etc.).

_{^{NH 4 +, NO 2 -,}} NO 3 - microelectrode used in the nitrogen cycle studies in biofilms and deposits on the fresh water and the inter-tidal environment, H ^+, Ca ^{2 +,} CO ₂ electrode has recently reef on, foraminifera, sediment, It is used for the study of photosynthesis, calcification, respiration, etc. of a microorganism mat. The disadvantage is that it lasts only a few days.

SUMMARY OF THE INVENTION An object of the present invention is to provide a microelectrode for measuring PH and a method of manufacturing the same, which are more suitable for the study of the primary production effect of benthic microalgae inhabiting the seabed.

In order to achieve the above object, the pH measurement microelectrode according to the present invention includes a liquid ion exchange membrane permeable membrane and an internal glass tube, in the pH measurement microelectrode for measuring a pH concentration change accompanying a carbon dioxide concentration change. An outer case, a PH electrolyte, a protective electrolyte, an Ag / AgCl signal detection electrode, an Ag / AgCl reference electrode; The inner glass tube includes a green glass tube and a white glass tube (AR glass), and includes a PH electrolyte therein; A space between the inner glass tube and the outer case includes the shielding electrolyte (3M KCl) and the Ag / AgCl reference electrode; Ag / AgCl signal detection electrode is disposed in the inner glass tube.

Preferably, the pH electrolyte is a mixture of 300 mmol potassium chloride and 50 mmol sodium phosphate to make pH 7.0, and the protective electrolyte is made of potassium chloride (KCl).

Preferably, the material of the green glass tube is AR glass (Schott 8516), the material of the white glass tube is AR glass (Schott 8350).

In addition, in order to achieve the above object, the manufacturing method of the pH measurement microelectrode according to the present invention is a pH measurement microelectrode for measuring the pH change accompanying the carbon dioxide concentration change as a liquid ion exchange membrane permeation membrane and In the manufacturing method of the pH measurement microelectrode comprising an inner glass tube, an outer case, a PH electrolyte, a protective electrolyte, an Ag / AgCl signal detection electrode, Ag / AgCl reference electrode, the inner as a micro electrode for containing the PH electrolyte An inner glass tube manufacturing step of manufacturing a glass tube; Manufacturing an end of the microelectrode; Silanizing to seal the ends of the microelectrodes with a hydrophobic permeable membrane; Manufacturing an outer case for containing the protective electrolyte; Cutting and reinforcing the tip of the microelectrode; Preparing and inserting the PA electrolyte; Preparing and injecting the liquid ion exchange membrane permeable membrane; Detecting the Ag / AgCl signal and manufacturing a reference electrode; And inserting the protective electrolyte, wherein the inner glass tube manufacturing step includes preparing a green glass tube containing the liquid ion exchange membrane permeable membrane at an end thereof, and manufacturing a white glass tube for supporting the green glass tube. And combining the green glass tube and the white glass tube as heat.

Preferably, in the manufacturing step of the tip of the microelectrode, the tip of the green glass tube is 1-3 micrometers using a heating wire.

Preferably, the tip of the microelectrode is cut using a breaker made by melting the end of the thin portion of the pasture pipette with a torch.

Preferably, the tip of the microelectrode is heated to thicken to a predetermined thickness to reinforce the tip of the microelectrode.

Preferably, the pH electrolyte is mixed with 300 mmol potassium chloride and 50 mmol sodium phosphate to make pH 7.0.

Preferably, the liquid ion exchange membrane permeable membrane comprises an ionophore, an inert solvent, and an additive.

According to the microelectrode for measuring pH of the present invention and a method of manufacturing the same, it is possible to more effectively conduct the primary production impact study of benthic microalgae inhabiting the seabed.

1 is a block diagram of a microelectrode for measuring pH according to the present invention.
2 is a flowchart of a method for manufacturing a microelectrode for measuring pH according to the present invention.
3 to 15 are views for explaining a microelectrode for measuring the pH according to the present invention and a manufacturing method thereof.

Hereinafter, with reference to the accompanying drawings will be described in detail an embodiment of a microelectrode for measuring pH and a method of manufacturing the same according to the present invention. In describing the present invention, when it is determined that a detailed description of a known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted, and in the case of using the same structural member as the prior art member, Will use the same members. The following terms are defined in consideration of the functions of the present invention, and may be changed according to the intentions or customs of the user, the operator, and the like. Therefore, the definition should be based on the contents throughout this specification.

Referring to FIG. 1, the microelectrode 100 for measuring pH according to the present invention includes an inner glass tube 10, an outer case 20, a pH electrolyte 32, a protective electrolyte 34, and a liquid ion exchange membrane permeable membrane. 40, Ag / AgCl reference electrode 52, Ag / AgCl signal detection electrode 54, and epoxy resins 62 and 64 as sealing portions.

The inner glass tube 10 includes a green glass tube 12 and a white glass tube 14, and includes a PH electrolyte 32 therein.

The space between the inner glass tube 10 and the outer case 20 includes a shielding electrolyte (3M KCl) 34 and an Ag / AgCl reference electrode 52. The Ag / AgCl signal detection electrode 540 is disposed in the inner glass tube 10.

The manufacturing method of the microelectrode for measuring pH according to the present invention as described above, that is, the liquid ionic exchange membrane microelectrode is as follows.

1.Preparation (manufacturing) step (S100) of the green glass tube 12 of the inner glass tube 10:

As shown in FIG. 3, the green glass tube material (Scott 8516, Germany) is made into a capillary tube (green glass tube) 12 approximately 12 centimeters (cm) in length. The inner glass tube 10 is composed of a green glass tube 12 and a white glass tube 14 as a core part of the HS electrode, which is also referred to as a micro electrode in the present specification.

According to the manufacturing method of the present invention, first, the green glass tube 12 is manufactured, and the white glass tube 14 is manufactured to bond the two glass tubes. Hereinafter, the manufacturing process of the green glass tube 12 will be described.

The green glass tube material (Schott 8516, outer diameter: 3.5 millimeters, thickness 0.45 millimeters) is cut to a length of about 15 centimeters. Schott 8516, a green glass tube material, is mainly used in the manufacture of microelectrodes because of its relatively low strain temperature and excellent stretching properties of about 440 ° C.

As shown in FIG. 3, the green glass tube is held by both hands and heated until it is red by using a Bunsen burner. About 1-2 seconds after starting to become red, pull both ends of the glass tube to form a capillary tube approximately 1 millimeter in diameter and 30 centimeters in length. When cooling, turn the glass tube round and straight so that the glass tube is not bent. Leave about 5-10 millimeters thick and cut with a glass cutter. The thin part is cut off about 15 centimeters.

As shown in FIG. 1, the green glass tube 12 includes a liquid ion exchange membrane permeable membrane 40 at an end thereof, a process for which will be described later.

2. Preparing the white glass tube (14) of the inner glass tube (10) and the green glass tube (12) and bonding step (S200):

The white glass tube 14 of the present invention serves to support the green glass tube 12.

As shown in FIG. 4A, the white glass tube material (AR glass, Schott 8350, outer diameter: 5.0 millimeters, thickness: 0.5 millimeters) is cut about 15 centimeters, and the glass tube is grasped with both hands, and the middle portion is heated using a torch.

AR glass (Schott 8350), a white glass tube material, is similar to Schott 8516, a green glass tube material, with similar properties such as expansion coefficient, density, and deformation temperature. If the properties of the glass tubes to be combined are different, one side may heat up quickly and break due to fast cooking.

After the white glass tube material has sufficiently reddened, pull the glass tube with both hands as it rotates to a diameter of 2 millimeters. The reason for the diameter of 2 millimeters is to facilitate the joining when combined with the thick portion of the green glass tube.

Once the white glass tube material is as described above, use a glass tube cutter to cut the thin portion (the portion made of 2 millimeters) leaving about 1 centimeter. One hand holds the green glass tube (12) produced in step S100, the other hand holds the white glass tube (14) produced above, and the two glass tubes using a torch while facing the thick portion of the green glass tube and the thin glass tube. Heat the thick portion of the green glass tube while rotating simultaneously. In this case, as shown in FIG. 4B, the green glass tube 12 melts and adheres to the white glass tube 14. If the thin portion of the white glass tube is too thin, the green glass tube needs to be heated a lot so that the thin portion of the white glass tube is about 2 millimeters.

After the two parts are combined in the red sweetened state as described above, the white glass tube and the green glass tube are aligned in a straight line by pulling both glass tubes while pulling them. The combined glass tube as shown in Figure 4c is placed in the beaker. If the heated part is placed on the floor before it is completely cooled, the glass tube may break, so care should be taken.

3. Micro electrode tip production (S300):

The manufacturing of the tip of the microelectrode for measuring PH is a step in which the tip of the green glass tube is 1-3 micrometers using a heating wire.

5 and 6a, 6b and 6c, the fine portion of the green glass tube 12 produced in step S200 to the micromanipulator is suspended above the hot wire produced by the 1 mm square line between them Position (FIGS. 5 and 6A). The area where the green glass tube and the hot wire cross each other is about 5 centimeters above the white glass pipe joint and is installed so that the hot wire can be observed with a stereo microscope (FIG. 6B).

The heating wire is connected to the AC power supply and the heating wire is slowly attached while raising the AC power supply voltage while observing with a stereo microscope. In this way, the hot wire becomes red and the green glass tube is melted and stretched (FIG. 6C). When the green glass tube starts to melt, the voltage of the AC power supply is lowered to lower the temperature of the heating wire. Raise and lower the temperature until the capillary section is about 50-100 micrometers.

The elongated glass tube is removed from the heating wire and slowly heated using a micro heating wire made of 50 micrometer platinum wire so that the end is 1-3 micrometers and separated from the upper part to fall down (FIG. 6D). At this time, the ends may be blocked while melting. Place a beaker with a cushion on the bottom of the glass tube to prevent the glass tube from being broken by the impact when it is dropped.

In FIG. 5, A, B, C, D, E, and F denote light sources, micro manipulators, hot wires, stereo microscopes, beakers, and AC power supplies, respectively.

After the production of the end of the micro-electrode as described above, as shown in FIG. 7, the holder is placed on a glass desiccator (3 L, Schott Duran, Germany), and the glass tube is inserted into the holder to prepare for the next process. The cradle is made of aluminum and can be manufactured in 10 centimeters in diameter and 5 centimeters in height.

4. Silane (S400):

In order to seal the tip of the microelectrode for measuring pH of the present invention with a hydrophobic permeable membrane, silanization is required.

As shown in FIG. 8, a desiccator containing the microelectrode prepared in the above step is placed in an oven installed in the fume hood, and dried at about 150 ° C. for 3 hours to completely remove moisture in the microelectrode. After removing water, 0.25 ml of silane solution, N, N-dimethyltrimethylsilamine (Fluka 41716) was added, and heated at 200 ° C. overnight. The next day, open the desiccator lid and heat it at 200 ° C. for about 1 hour to allow sufficient silane gas to flow. Silane gas is a toxic substance, so be careful not to inhale and carry out the whole process in the hood. After finishing the silanization process, keep the microelectrode in a dry, dust-free place.

5. Outer case production (S500):

In the microelectrode 100 for measuring pH according to the present invention, the concave portion of the pasture is cut out to leave only 2 centimeters and used as the outer case 20. After the inner glass tube 10 is finished until the step S400 is externally fixed to the bottom portion is fixed with epoxy resin 62 and the upper portion is not closed to the epoxy resin (64).

6. Cutting and reinforcing microelectrode tip (S600):

6-1. Microelectrode tip cutting (S610):

The tip of the microelectrode fabricated in step S300 is generally blocked, and must be broken in order to allow the blocked part to pass through and make the tip 1-3 micrometers in diameter. There are two ways to break the end, using forceps and breaking with a breaker. Both methods are performed under a microscope as shown in FIG. 9. On the left side, the micromanipulator (inner glass tube) is mounted on the left side of the microscope lens and the micromanipulator can be moved on the right side by a breaker.

1) Method using forceps: Carefully break while observing the tip under a microscope. If you are using forceps, it may be difficult to trim the tip to a suitable size because fine adjustment is difficult.

2) Method using a breaker: Melt the end of the thin part of the part pipette with a torch to make a round shape and use it as a breaker (Fig. 10). The breaker is fixed to the micromanipulator and the end is hit by the breaker while being moved back and forth through the stage of the microelectrode. Breaking the tip is easier than using forceps.

FIG. 10 shows an embodiment of microelectrode tip cutting, the left one being a breaker and the right one being the microelectrode tip.

6-2. Microelectrode tip reinforcement (S620):

In the above process, as the tip of the microelectrode is broken, the diameter may be larger than the desired size or a fine crack may be generated. Liquid ion exchange membrane microelectrodes according to the present invention can often break in deposits. That is, the liquid ion exchange membrane microelectrode, including the PH measurement microelectrode, is easily broken because it is made of a relatively weak green glass tube 12 having a tip of 1-5 micrometers.

Although the types of microelectrodes for measuring PH are different, most studies have focused on microbial mats or biofilms, and thus microelectrode mats or biofilms are softer than intertidal deposits. The green glass tube end of the glass tube is less likely to break. In other words, existing studies rarely target sediments.

However, the intertidal sediments are composed of particles of various sizes such as nizil, sani, and sand, which may be easily broken when the liquid ion exchange membrane microelectrode is used immediately. Therefore, in the present invention, the tip of the microelectrode is reinforced as follows in order not to be easily broken in the intertidal deposit.

That is, in the present invention, by slightly heating the tip of the microelectrode to make the tip slightly melted, the tip is thickened to reinforce the tip, which will be described in more detail as follows.

As shown in Fig. 9, a 50 micrometer platinum wire heating wire (fine heating wire) is mounted and fixed to the right micromanipulator. At this time, the micro heating wire is connected to the AC power supply, and the wire from the AC power supply is inserted into the glass tube and mounted on the micromanipulator. The microelectrode is mounted on the left side and the microheater wire is positioned on the right side (FIG. 11A).

Place the tip of the microelectrode about 100 micrometers away from the hot wire. While observing under a microscope, slowly raise the temperature of the microheater. The heat of the microheater wire is kept constant, and the end of the microelectrode-mounted material stage moves near the microheater wire to melt.

If the heat of the microheater is too high, the tip of the microelectrode melts easily, so it is important to maintain the proper temperature and to melt by controlling the distance between the microheater and the tip of the microelectrode.

After the above process, it is preferable to completely remove the moisture generated during the manufacturing process to facilitate the injection of the electrolyte and the injection of the liquid ion exchange membrane solution.

Through the above process, the inner diameter of the tip of the microelectrode decreases and the outer diameter increases by 2-3 micrometers. As a result, the outer diameter of the microelectrode tip can be made relatively rigid while maintaining 5-10 micrometers.

As described above, the microelectrode 100 for measuring pH of the present invention reinforced with the tip of the microelectrode was confirmed that it did not break even once during a total measurement of the pH profile in the tidal intertidal sediment. In conclusion, according to the present invention, through the reinforcement process as described above, even in intertidal deposits, it is possible to drastically reduce the probability of breakage of the microelectrode for PH measurement.

FIG. 11A illustrates the process of reinforcing the tip of the microelectrode, wherein the left side is the microelectrode and the right side is the microheater. FIG. 11B illustrates the process of reinforcing the tip of the microelectrode, in which the left side is the microheater wire and the right side is the microelectrode tip.

7. PH electrolyte preparation and insertion (S700):

The PGE electrolyte 32 used for the PH liquid ion exchange membrane microelectrode of the present invention is manufactured and inserted as follows.

The PH electrolyte used for the PH liquid ion exchange membrane microelectrode 100 according to the present invention is prepared by preparing 300 mmol potassium chloride and 50 mmol sodium phosphate, respectively, and then mixing the two solutions to make PH 7.0.

In order to inject the electrolyte into the microelectrode, as shown in Fig. 12A, one milliliter syringe is used to increase. A 1-milliliter syringe needle can be lengthened by heating it with a torch about 1 centimeter from the needle insert.

As shown in FIG. 12B, the tip of the syringe made as described above is allowed to enter the inside of the microelectrode as much as possible before slowly injecting the electrolyte. Be careful not to create air bubbles at this time. If bubbles are present, remove the bubbles with a syringe. The electrolyte of the present invention is injected to about 1 centimeter at the junction of the green glass tube 12 and the white glass tube 14.

FIG. 12A shows the 1 ml syringe stretched for electrolyte injection, and FIG. 12B shows the electrolyte injection model.

8. Liquid ion exchange membrane permeation membrane preparation and injection (S800):

As described above, the liquid ion exchange membrane solution is inserted after the injection of the PH electrolyte. The liquid ion exchange membrane solution used for the liquid ion exchange membrane microelectrode of the present invention is composed of an ionophore, an inert solvent, an additive, and the like.

There are two kinds of ionopores used in the PA liquid ion exchange membrane microelectrode 100 of the present invention. That is, 6% hydrogen ion ionophore-II (Fluka 95295) is available at pH 2-9.5 and 3% hydrogen ion ionophore-III (Fluka 95298) is available at pH 3-11.

In the present invention, 3% hydrogen ion ionophore-III (Fluka 95298) is mainly used, and 2-nitrophenyloctyl ether (2-NOPE) (Fluka 73732) is used as an inert solvent. The additive uses sodium-tetraphenylboron (Fluka 72018). The reason for using additives is to reduce the resistance and increase the permselectivity.

There are two liquid ion exchange membrane solutions, a solution containing polyvinyl chloride (PVC, Fluka 81392) (+) and a solution containing no polyvinyl chloride (-). A negative solution is prepared first, followed by the addition of polyvinyl chloride to prepare a positive solution. By adding polyvinyl chloride, the liquid ion exchange membrane solution is solidified, so that the signal stability of the microelectrode is increased and the life of the microelectrode is extended. Tetrahydrofuran (Fluka 87369) is used to dissolve polyvinyl chloride.

One embodiment of the liquid ion exchange membrane (-) solution of the present invention may be as follows.

3 mg hydrogen ion ionophore-III 2 mg

0.6 mg Sodium Tetraphenylboron

0.19 milliliters of 2-nitrophenyloctyl ether

One embodiment of the liquid ion exchange membrane (+) solution of the present invention may be as follows.

0.1 ml of liquid ion exchange membrane (-) solution

10 mg polyvinyl chloride

0.3 milliliters of tetrahydrofuran

The process of the present invention for injecting the liquid ion exchange membrane solution as described above is as follows.

In the microscope set as shown in FIG. 9, the microelectrode is placed on the left side of the stage and the pasture pipette containing the liquid ion exchange membrane solution is placed on the right side. The microelectrode is connected by a rubber tube to which a 50 milliliter syringe is connected.

Prior to injecting the liquid ion exchange membrane solution, the syringe is pushed to bring the PH electrolyte to the end of the microelectrode. Even with a slight push of the syringe, the PA electrolyte reaches the end of the microelectrode due to capillary action.

First, the above-mentioned (-) solution is injected. After dipping the tip of the microelectrode into the paster pipette containing the liquid ion exchange membrane solution, pull the syringe out to inject the liquid ion exchange membrane (-) solution. Inject about 300 micrometers from the tip of the microelectrode.

After injecting the (-) solution as above, the (+) solution is injected in the same manner as the (-) solution injection method. Inject the positive solution in the range of 100-200 micrometers so that the liquid ion exchange membrane solution can be injected in the 450-meter range. The liquid ion exchange membrane (+) solution is easily hardened, so it is preferable to inject it in a short time.

After injecting the liquid ion exchange membrane solution as above, wait 2 hours for the tetrahydrofuran used to prepare the (+) solution to evaporate.

12A illustrates a liquid ion exchange membrane solution injection process according to the present invention, and FIG. 12B illustrates a state in which a liquid ion exchange membrane solution is injected.

9. Ag / AgCl electrode fabrication (S900):

The microelectrode 100 for measuring PH of the present invention uses an Ag / AgCl signal detecting electrode 54 and an Ag / AgCl reference electrode 52. The manufacturing method is as follows. Figure 14 shows the Ag / AgCl electrode manufacturing process according to the present invention.

The 0.25 mm silver wire (Aldrich 265578), the material, is washed with distilled water.

Dip two silver wires into a beaker containing 1 mole hydrochloric acid, connect the reference silver line to the (-) pole, and connect the silver line to make the reference electrode. Increase the voltage of the dc power supply to 1.5 volts and leave for about 1 minute so that the silver wire turns brown. At this time, take out the silver wire and soak it three times in a beaker containing distilled water and remove it repeatedly to remove the hydrochloric acid remaining in the silver wire.

10. Insert the protective (external) electrolyte (S1000):

The final step of manufacturing the microelectrode for measuring pH according to the present invention is based on the Ag / Agg produced in step S900 after injecting an external electrolyte, that is, 3 mol potassium chloride (KCl), a protective electrolyte 34 between the microelectrode and the outer case. This step is to put the electrode. The outer case 20 filled with KCl serves to reduce electrical noise.

Using a syringe, 3 mol potassium chloride is injected into the gap between the microelectrode (inner glass tube) 10 and the outer case. Next, the Ag / AgCl reference electrode 52 prepared in step S900 is inserted and then sealed with epoxy.

FIG. 15 shows a PH microelectrode of the present invention completed after the above process.

So far, the present invention has been described with reference to the embodiments shown in the drawings, which are merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. will be.

Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

10: inner glass tube (micro electrode) 12: green glass tube
14: white glass tube 20: outer case
32: PA electrolyte 34: protective electrolyte
40: liquid ion exchange membrane permeable membrane 52: reference electrode
54: signal detection electrode 62: sealing part (epoxy resin)

Claims (9)

In the microelectrode for measuring pH to measure the pH change accompanying the carbon dioxide concentration change,
A liquid ion exchange membrane permeable membrane, an inner glass tube, an outer case, a PH electrolyte, a protective electrolyte, an Ag / AgCl signal detection electrode, and an Ag / AgCl reference electrode;
The inner glass tube includes a green glass tube and a white glass tube (AR glass), and includes a PH electrolyte therein;
A space between the inner glass tube and the outer case includes the shielding electrolyte (3M KCl) and the Ag / AgCl reference electrode;
The Ag / AgCl signal detecting electrode is disposed in the inner glass tube. The method of claim 1,
The pH electrolyte is a mixture of 300 mmol potassium chloride and 50 mmol sodium phosphate to be pH 7.0, the protective electrolyte is a pH measurement microelectrode, characterized in that made of potassium chloride (KCl). The method of claim 1,
The green glass tube is made of AR glass (Schott 8516), and the white glass tube is made of AR glass (Schott 8350). A microelectrode for measuring pH that accompanies a change in carbon dioxide concentration, a liquid ion exchange membrane permeable membrane, an inner glass tube, an outer case, a PH electrolyte, a protective electrolyte, an Ag / AgCl signal detection electrode, an Ag / In the manufacturing method of the microelectrode for measuring pH including AgCl reference electrode,
An inner glass tube manufacturing step of manufacturing the inner glass tube as a microelectrode for containing the PA electrolyte;
Manufacturing an end of the microelectrode; Silanizing to seal the ends of the microelectrodes with a hydrophobic permeable membrane;
Manufacturing an outer case for containing the protective electrolyte;
Cutting and reinforcing the tip of the microelectrode; Preparing and inserting the PA electrolyte; Preparing and injecting the liquid ion exchange membrane permeable membrane; Detecting the Ag / AgCl signal and manufacturing a reference electrode; Inserting the protective electrolyte;
The inner glass tube manufacturing step, the step of manufacturing a green glass tube containing the liquid ion exchange membrane permeable membrane at the end thereof, the step of manufacturing a white glass tube for supporting the green glass tube and combine the green glass tube and the white glass tube as heat Method of manufacturing a micro-electrode for measuring the pH, characterized in that consisting of a step. 5. The method of claim 4,
The manufacturing method of the tip of the microelectrode is a method of manufacturing a micro-electrode for measuring the pH, characterized in that the end of the green glass tube by using a heating wire 1-3 micrometers. 5. The method of claim 4,
The end of the micro-electrode is a manufacturing method of the micro-electrode for measuring the pH, characterized in that by using a breaker made by melting the end of the thin end of the pasture pipette with a torch. 5. The method of claim 4,
Method of manufacturing a micro-electrode for measuring the measurement, characterized in that for heating the end of the fine electrode to a thick thickness to reinforce the end of the fine electrode. 5. The method of claim 4,
The pH electrolyte is a manufacturing method of the micro-electrode for measuring the pH, characterized in that the pH of the mixture by mixing 300 mmol potassium chloride and 50 mmol sodium phosphate to pH 7.0. 5. The method of claim 4,
The liquid ion exchange membrane permeable membrane is iontophores (ionophore), an inert solvent, a method for manufacturing a microelectrode for measuring the pH, characterized in that it comprises an additive.

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