TW202240163A - Sensing electrode - Google Patents

Abstract

A sensing electrode includes a first electrode assembly, a second electrode assembly and a sealing component. The first electrode assembly includes an inner tubular body and a reference electrode mounted in the inner tubular body, and the second electrode assembly includes an outer tubular body and a working electrode mounted in the outer tubular body. The first electrode assembly is mounted in the outer tubular body. The sealing component is located between the inner and outer tubular bodies and provided to prevent etching solution from seeping into the outer tubular body and prevent electrolyte in the inner tubular body from seeping out. Accordingly, the sensing electrode has better stability and service life.

Description

sensing electrode

The present invention relates to a sensing electrode, especially a sensing electrode for measuring redox potential.

In the printed circuit board manufacturing process, the wet process accounts for more than 70% of the total process, including etching and washing steps. Taking the sulfuric acid/hydrogen peroxide etching solution system as an example, the concentration of hydrogen peroxide is an important parameter of the etching process. Improper control will cause uneven etching of the circuit. The change of hydrogen peroxide concentration can be obtained indirectly through the oxidation-reduction potential of hydrogen peroxide, and real-time monitoring of the oxidation-reduction potential of hydrogen peroxide helps to control the concentration of hydrogen peroxide and improve etching stability.

Although the integrally formed oxidation-reduction potential measurement electrode can prevent the etching solution from corroding the electrode, it is not easy to repair and easily cause measurement deviation when the electrode is damaged or aged. On the contrary, the non-integral oxidation-reduction potential measurement electrode can replace the electrode or Electrolyte is added, but the etchant may seep into the measurement electrode and shorten the service life.

The purpose of the present invention is to provide a sensing electrode, the sensing electrode includes a first electrode assembly, a second electrode assembly, a first sealing member and a cover, the first electrode assembly has an inner sleeve, a A reference electrode and an ion conducting element, the reference electrode is arranged in the inner casing, the inner casing is used to accommodate an electrolyte, the ion conducting element passes through and protrudes from a sensing end of the inner casing, the first The second electrode assembly has an outer casing and a working electrode, the working electrode is arranged in the outer casing, and one exposed end of the working electrode is exposed on a sensing end of the outer casing, and the first electrode assembly is arranged in the outer casing In the tube, the outer sleeve has a first perforation, the first perforation is located at the sensing end of the outer sleeve, the first seal is located at the sensing end of the inner sleeve and the sensing end of the outer sleeve Between them, the ion conducting element passes through the first sealing element, the first through hole exposes the ion conducting element, and the cover covers one conductive end of the inner sleeve.

The first sealing member of the present invention is located between the inner casing and the outer casing to prevent the etching solution from penetrating into the outer casing, so the reference electrode will not come into contact with the etching solution, which can prevent the etching solution from damaging the reference electrode. The measurement deviation is caused, and the first sealing member can prevent the electrolyte from leaking out, and improve the stability and service life of the sensing electrode.

Please refer to FIG. 1 , the present invention discloses a sensing electrode A, which can be used to measure the oxidation reduction potential (ORP) of an analyte. For example, the sensing electrode A is set in a printed circuit board factory In the chemical micro-etching tank, it is used to continuously monitor the oxidation ability of sulfuric acid/hydrogen peroxide series etching solution, so as to judge the change of hydrogen peroxide concentration, so as to facilitate the real-time adjustment of etching parameters, but the present invention is not limited thereto. The sensing electrode A It can be used to measure the redox potential of other analytes.

Please refer to Figure 1, which is the first embodiment of the present invention, the sensing electrode A has a first electrode assembly 100, the first electrode assembly 100 has an inner sleeve 110, a reference electrode 120 and an ion conducting Part 130, the inner casing 110 is used to accommodate an electrolyte E, and its two ends are respectively a sensing end 111 and a conductive end 112, the reference electrode 120 is arranged in the inner casing 110, which can be silver-chloride A silver electrode, a saturated calomel electrode or a standard hydrogen electrode, the ion conducting element 130 passes through the inner casing 110 and protrudes from the sensing end 111 .

Preferably, the material of the ion conducting element 130 is a porous ceramic material, more preferably, the material of the ion conducting element 130 is a porous silicon oxide or a metal oxide, wherein the metal oxide It can be single metal oxide, binary metal oxide or multiple metal oxide, containing platinum (Pt), gold (Au), palladium (Pd), silver (Ag), iridium (Ir), titanium (Ti), At least one metal material in the group consisting of ruthenium (Ru), rhodium (Rh) and osmium (Os).

Please refer to FIG. 1, in this embodiment, the inner sleeve 110 has an inner tube 110a and an outer tube 110b, both the inner tube 110a and the outer tube 110b are used to accommodate the electrolyte E, and the reference electrode 120 is set In the inner tube 110a, the inner tube 110a is disposed in the outer tube 110b, and the ion conducting element 130 has an inner conducting part 130a and an outer conducting part 130b, and the inner conducting part 130a is passed through the inner tube 110a , the outer conducting portion 130b passes through and protrudes from the outer tube 110b, so the first electrode assembly 100 of this embodiment is a double salt bridge system.

The electrolyte E can be liquid or jelly, and can be selected from potassium chloride, sodium chloride, hydrogen chloride, ferric chloride or ferric chloride. In this embodiment, the reference electrode 120 and the ion-conducting member 130 is soaked in potassium chloride solution, and the user can add or replace the electrolyte E in the inner sleeve 110 according to different demands.

Please refer to FIG. 1, the sensing electrode A further has a second electrode assembly 200, the second electrode assembly 200 has an outer casing 210 and a working electrode 220, and the two ends of the outer casing 210 are respectively a sensing end 211 and a conductive end 212, the working electrode 220 is set in the outer tube 210, and one exposed end 221 of the working electrode 220 is exposed on the sensing end 211 of the outer tube 210, in this embodiment, the working The exposed end 221 of the electrode 220 protrudes from the sensing end 211 of the outer sleeve 210 , and the exposed end 221 of the working electrode 220 contacts the etching solution during the redox potential measurement process.

The material of the working electrode 220 can be a single metal material, binary metal material or ternary metal material, preferably, the material of the working electrode 220 is selected from platinum (Pt), gold (Au), palladium (Pd), silver At least one metal material in the group consisting of (Ag), iridium (Ir), titanium (Ti), ruthenium (Ru), rhodium (Rh) and osmium (Os), and the working electrode 220 is a linear or strip structure , with a diameter between 0.01 mm and 3 mm and a length between 10 mm and 150 mm.

When using the sensing electrode A to measure the oxidation-reduction potential of the etching solution, the sensing end 211 of the outer casing 210 will directly contact the etching solution, so the material of the outer casing 210 is selected from polymers with good chemical corrosion resistance Materials are preferred, such as: high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (Linear LDPE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene fluoride ( PVDF), polyetheretherketone (PEEK), polytetrafluoroethylene (PTFE), polyacetal (POM), polyphenolic (PF), polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS ), Nylon 66 (Nylon 66), polymethyl methacrylate (PMMA) or polyphenylene sulfide (PPS), so as to prevent the etching solution from corroding the outer tube 210 and penetrating into the sensing electrode A.

Please refer to FIG. 1, the sensing electrode A further has a cover 300 and a first seal 400, the first seal 400 is disposed in the outer tube 210, and the first electrode assembly 100 is disposed in the second Behind the outer sleeve 210 of the second electrode assembly 200, the first seal 400 is located between the sensing end 111 of the inner sleeve 110 and the sensing end 211 of the outer sleeve 210, the outer sleeve 210 has a first A perforation 213, the first perforation 213 is located at the sensing end 211, the ion conduction member 130 protruding from the inner casing 110 is pierced through the first sealing member 400, and the first perforation 213 reveals the ion conduction 130, and then cover the cover 300 on the conductive end 112 of the inner sleeve 110 to seal the inner sleeve 110, the cover 300 can protect the reference electrode 120 located in the inner sleeve 110, It can also prevent the electrolyte E from leaking out. In addition, the reference electrode 120 can be replaced, repaired or cleaned after the cover 300 is removed, and the electrolyte E in the inner casing 110 can also be replenished or replaced.

Please refer to FIG. 1, the first electrode assembly 100 is arranged behind the outer sleeve 210, the conductive end 112 of the inner sleeve 110 protrudes from the conductive end 212 of the outer sleeve 210, and the cover 300 is fixed on the When the conductive end 112 of the inner sleeve 110 presses the inner sleeve 110 downward, the first seal 400 is clamped between the sensing end 111 of the inner sleeve 110 and the sensing end 210 of the outer sleeve 210. Between the measuring ends 211, thereby sealing the first through hole 213 of the outer sleeve 210, so as to prevent the etching solution from penetrating into the outer sleeve 120 from the first through hole 213, in addition, the first sealing member 400 can prevent the inner The electrolyte E in the sleeve 110 leaks out.

In this embodiment, the cover body 300 has a groove 310, and the groove 310 has an internal thread (not shown in the figure), and the conductive end 112 of the inner sleeve 110 has an external thread (not shown in the figure). Out), the internal thread and the external thread are engaged with each other, and the cover 300 is locked on the conductive end 112 of the inner sleeve 110 .

Preferably, when the first electrode assembly 100 is disposed on the outer sleeve 210, the outer conductive portion 130b protruding from the outer tube 110b is sequentially provided on the first sealing member 400 and the second outer sleeve 210. A through hole 213, and the first through hole 213 exposes the outer conductive portion 130b, so during the oxidation-reduction potential measurement process, the outer conductive portion 130b will contact the etching solution. In this embodiment, the outer conductive portion 130b protrudes on the first through hole 213 .

Please refer to FIG. 1, preferably, the outer sleeve 210 has a second through hole 214, the second through hole 214 is located at the conductive end 212 of the outer sleeve 210, and the sensing electrode A has a second sealing member 500, the second sealing member 500 is disposed in the second through hole 214, the inner sleeve 110 is passed through the second sealing member 500 to be disposed in the outer sleeve 210, the second sealing member 500 is clamped in the Between the conductive end 112 of the inner sleeve 110 and the conductive end 212 of the outer sleeve 210 , the leakage of the electrolyte E and the penetration of the etching solution into the sensing electrode A from the second through hole 214 are prevented.

Please refer to Fig. 1, preferably, the outer tube 210 has a third through hole 215, the third through hole 215 is located at the sensing end 211 of the outer tube 210, and is located outside the first through hole 213, the sensor The measuring electrode A further has a third sealing member 600, the third sealing member 600 is arranged in the third through hole 215, the exposed end 221 of the working electrode 220 is penetrated in the third sealing member 600, and the third through hole 215 exposes the exposed end 221. In this embodiment, the exposed end 221 of the working electrode 220 protrudes from the third through hole 215. The third sealing member 600 is used to seal the third through hole 215 to avoid etching solution Infiltrate into the sensing electrode A through the third through hole 215 .

In this embodiment, the first sealing member 400, the second sealing member 500 and the third sealing member 600 are all O-rings, which are made of corrosion-resistant materials, so they can avoid etching solution corrosion The seals penetrate into the casing 210 . In other embodiments, the first seal 400 , the second seal 500 and the third seal 600 can be sealants or other seal materials.

Please refer to FIG. 1 , the sensing electrode A also has a first conductive member 700 , the first conductive member 700 is disposed on the cover 300 , when the cover 300 covers the conductive end 112 of the inner sleeve 110 , the reference electrode 120 is electrically connected to the first conductive member 700, and the first conductive member 700 is used to electrically connect an external electronic component, the external electronic component is a voltage or current measuring device, preferably, the first An electrode assembly 100 also has a first connection port 140, the first connection port 140 is disposed on the conductive end 112 of the inner sleeve 110, and the first conductive member 700 is disposed in the groove 310 of the cover 300 , when the cover 300 is locked on the conductive end 112 of the inner sleeve 110, the first conductive member 700 contacts the first connection port 140, and the reference electrode 120 is electrically connected through the first connection port 140 The first conductive member 700, in this embodiment, the first connection port 140 is an effective voltage or current computing conductor.

Please refer to FIG. 1, the second electrode assembly 200 has a second connection port 230, the second connection port 230 is set on the conductive end 212 of the outer sleeve 210, and the working electrode 220 is connected to the second connection port through the second connection port. 230 is electrically connected to the external electronic components. Preferably, the second connection port 230 is an effective voltage or current calculation conductor. In this embodiment, one end of the working electrode 220 is connected to the second connection port 230. The other end of the electrode 220 is the exposed end 221 protruding from the third through hole 215 of the outer tube 210 .

In this embodiment, the electrochemical signal of the reference electrode 120 is output to the external electronic component through the first connection port 140, the first conductive member 700 and a lead wire, and the electrochemical signal of the working electrode 220 is output through the second The connection port 230 and another lead are output to the external electronic component, and the external electronic component calculates the oxidation-reduction potential of the etching solution based on the potential difference between the reference electrode 120 and the working electrode 220 .

Please refer to Fig. 2, which is the second embodiment of the present invention. The difference from the first embodiment is that the working electrode 220 is inserted in a tube wall 210a of the outer sleeve 210 to prevent the working electrode 220 from contacting the air. Oxidation can prolong the service life of the working electrode 220 .

Please refer to FIG. 2. In this embodiment, the sensing electrode A further has a second conductive member 800, and the second conductive member 800 is disposed on the conductive end 212 of the outer sleeve 210. When the cover 300 covers When the conductive end 111 of the inner casing 110 is covered, the first conductive member 700 located on the cover body 300 is electrically connected to the reference electrode 120 and the second conductive member 800, and the second conductive member 800 is used for electrically Connect the external electronic components, the electrochemical signal of the reference electrode 120 is output to the external electronic components through the first connection port 140, the first conductive member 700, the second conductive member 800 and a lead wire, preferably, the The first conductive element 700 and the second conductive element 800 are respectively a spring conductive terminal.

The first electrode assembly 100 is disposed in the outer sleeve 210, so the reference electrode 120 will not come into contact with the etching solution, which can increase the service life of the reference electrode 120 and prevent the etching solution from damaging the reference electrode 120 and causing measurement deviations , In addition, the first sealing member 400 located between the inner sleeve 110 and the outer sleeve 210 can prevent the etching solution from penetrating into the outer sleeve 210, and can also prevent the electrolyte E from leaking out, thus protecting the reference electrode 120 and The working electrode 220 is used to improve the stability and service life of the sensing electrode A.

The scope of protection of the present invention should be defined by the scope of the appended patent application. Any changes and modifications made by anyone who is familiar with this technology without departing from the spirit and scope of the present invention belong to the scope of protection of the present invention. .

100: The first electrode assembly 110: Inner sleeve 110a: Inner pipe 110b: Outer pipe 111: Sensing end 120:Reference electrode                                                                                                                                                                                                                          130a: inner conduction part 140: The first connection port 200: The second electrode assembly 210: outer casing 210a: pipe wall 211: Sensing terminal 212: Conductive terminal 213:First piercing 214:Second piercing 215:Third perforation 220:Working electrode 221: Display port 230: Second port 300: cover body 310: groove 400: first seal 500: second seal 600: the third seal 700: the first conductive part 800: Second conductive part A: Sensing electrode E: Electrolyte

FIG. 1: A cross-sectional view of a sensing electrode according to the first embodiment of the present invention. Fig. 2: A cross-sectional view of a sensing electrode according to the second embodiment of the present invention.

100: The first electrode assembly                                                                                                                                     110: Inner sleeve 110a: Inner pipe 110b: Outer pipe 111: Sensing end 120:Reference electrode                                                                                                                                                                                                130a: inner conduction part 140: the first connection port 200: the second electrode assembly 210: Outer casing 211: Sensing end 212: Conductive end 213: The first perforation 214:Second perforation 215:Third perforation 220: Working electrode 221: Exposure terminal 230:Second port 300:Cover 310: Groove 400: First seal 500:Second Seal 600:Third Seal 700: The first conductive part A: Sensing electrode E: Electrolyte

Claims (18)

A sensing electrode comprising: A first electrode assembly has an inner sleeve, a reference electrode and an ion conducting member, the reference electrode is arranged in the inner sleeve, the inner sleeve is used to accommodate an electrolyte, and the ion conducting member penetrates and protrudes at a sensing end of the inner sleeve; A second electrode assembly has an outer sleeve and a working electrode, the working electrode is disposed in the outer sleeve, and one exposed end of the working electrode is exposed on a sensing end of the outer sleeve, the first electrode assembly is provided In the outer sleeve, the outer sleeve has a first perforation located at the sensing end of the outer sleeve; a first sealing member, located between the sensing end of the inner casing and the sensing end of the outer casing, the ion conducting member penetrates the first sealing member, and the ion conducting member is exposed by the first perforation ;as well as A cover covers one conductive end of the inner casing. The sensing electrode according to claim 1, wherein the conductive end of the inner sleeve protrudes from a conductive end of the outer sleeve, and the cover is fixed on the conductive end of the inner sleeve so that the first sealing member is sealed clamped between the sensing end of the inner casing and the sensing end of the outer casing. The sensing electrode according to claim 2, wherein the cover body has a groove, the groove has an internal thread, the conductive end of the inner sleeve has an external thread, and the internal thread and the external thread engage with each other. As in the sensing electrode of claim 1, it further includes a first conductive member, the first conductive member is arranged on the cover, and when the cover covers the conductive end of the inner sleeve, the reference electrode is electrically The first conductive element is connected, and the first conductive element is used for electrically connecting an external electronic component. The sensing electrode as in claim 4, wherein the first electrode assembly further has a first connection port, the first connection port is arranged on the conductive end of the inner sleeve, and the reference electrode is electrically connected through the first connection port Sexually connect the first conductive element. As for the sensing electrode of claim 1, it further includes a first conductive element and a second conductive element, the first conductive element is arranged on the cover body, and the second conductive element is arranged on the conductive end of the outer sleeve, When the cover covers the conductive end of the inner sleeve, the first conductive element is electrically connected to the reference electrode and the second conductive element, and the second conductive element is used to electrically connect an external electronic component. The sensing electrode according to claim 6, wherein the first conductive member and the second conductive member are respectively a spring conductive terminal. The sensing electrode as claimed in item 1, wherein the inner sleeve has an inner tube and an outer tube, the inner tube and the outer tube are used to accommodate the electrolyte, the reference electrode is arranged in the inner tube, and the inner tube is arranged in In the outer tube, the ion conducting part has an inner conducting part and an outer conducting part, the inner conducting part penetrates the inner tube, and the outer conducting part penetrates the outer tube, the first sealing member and the outer casing The first perforation of the tube, the first perforation exposes the outer conducting portion. The sensing electrode as in claim 1, wherein the second electrode assembly further has a second connection port, the second connection port is arranged on the conductive end of the outer sleeve, and the working electrode is electrically connected through the second connection port. Connect an external electronic component. The sensing electrode according to claim 1, wherein the working electrode is inserted in a tube wall of the outer tube. As in the sensing electrode of claim 1, it further includes a second sealing member, the outer sleeve has a second perforation, the second perforation is located at a conductive end of the outer sleeve, and the second sealing member is arranged on the first Two perforations, the inner sleeve is passed through the second sealing member, so that the second sealing member is clamped between the conductive end of the inner sleeve and the conductive end of the outer sleeve. According to the sensing electrode of claim 1, it further includes a third sealing member, the outer sleeve has a third perforation, the third perforation is located at the sensing end of the outer sleeve, and the third sealing member is arranged on the outer sleeve. The third through hole, the exposed end of the working electrode is pierced through the third sealing member, the third through hole exposes the exposed end. The sensing electrode according to claim 1, wherein the reference electrode is a silver-silver chloride electrode, a saturated calomel electrode or a standard hydrogen electrode. As the sensing electrode of claim 1, wherein the material of the working electrode is selected from platinum (Pt), gold (Au), palladium (Pd), silver (Ag), iridium (Ir), titanium (Ti), ruthenium (Ru ), rhodium (Rh) and osmium (Os) at least one metal material in the group. The sensing electrode according to claim 1, wherein the material of the ion-conducting element is a porous ceramic material. Such as the sensing electrode of claim 15, wherein the material of the ion-conducting member is a silicon oxide or a metal oxide, and the metal oxide contains platinum (Pt), gold (Au), palladium (Pd), silver ( At least one metal material in the group consisting of Ag), iridium (Ir), titanium (Ti), ruthenium (Ru), rhodium (Rh) and osmium (Os). Such as the sensing electrode of claim 1, wherein the material of the outer sleeve is high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (Linear LDPE), polypropylene (PP), polychloride Vinyl (PVC), polyvinylidene fluoride (PVDF), polyetheretherketone (PEEK), polytetrafluoroethylene (PTFE), polyacetal (POM), polyphenolic (PF), polycarbonate (PC), acrylic Nitrile-butadiene-styrene (ABS), nylon 66 (Nylon 66), polymethylmethacrylate (PMMA) or polyphenylene sulfide (PPS). The sensing electrode as in claim 1, wherein the electrolyte is liquid or jelly potassium chloride, sodium chloride, hydrogen chloride, ferric chloride or ferric chloride.

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