JP6198134B2 - Nickel oxide / nickel reference electrode used for electrochemical measurement of molten glass and electrochemical measurement apparatus using the same - Google Patents
Nickel oxide / nickel reference electrode used for electrochemical measurement of molten glass and electrochemical measurement apparatus using the same Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 65
- 238000002848 electrochemical method Methods 0.000 title claims description 58
- 229910000480 nickel oxide Inorganic materials 0.000 title claims description 56
- 239000006060 molten glass Substances 0.000 title claims description 53
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims description 22
- 229910052759 nickel Inorganic materials 0.000 title claims description 16
- 239000011521 glass Substances 0.000 claims description 40
- 150000002500 ions Chemical class 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 230000007797 corrosion Effects 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 230000033116 oxidation-reduction process Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 6
- 229910018487 Ni—Cr Inorganic materials 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000005388 borosilicate glass Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
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Description
本発明は、溶融ガラスの電気化学測定に用いる酸化ニッケル（ＮｉＯ）／ニッケル（Ｎｉ）参照極に関するものである。 The present invention relates to a nickel oxide (NiO) / nickel (Ni) reference electrode used for electrochemical measurement of molten glass.
例えば溶融ホウケイ酸ガラスなどの溶融ガラス中に溶存するイオンの化学状態や酸化還元挙動を電気化学的手法により分析および研究する場合、計測した作用極電位は参照極電位を基準とする。 For example, when the chemical state or oxidation-reduction behavior of ions dissolved in molten glass such as molten borosilicate glass is analyzed and studied by an electrochemical method, the measured working electrode potential is based on the reference electrode potential.
従来の溶融ガラスの電気化学測定では、白金（Ｐｔ）の線または箔などをイットリア安定化ジルコニア（ＹＳＺ）製の片閉管の内面先端に接着し、この片閉管を溶融ガラス中に浸漬して、空気を掃気しながらＹＳＺ／Ｐｔ接合部の指示電位を参照極電位として計測し、空気中の酸素分圧から酸素発生電位（標準電位）に換算している（従来技術１ 非特許文献１参照）。 In the conventional electrochemical measurement of molten glass, platinum (Pt) wire or foil or the like is bonded to the inner surface tip of a yttria-stabilized zirconia (YSZ) cantilever tube, and this cantilever tube is immersed in the molten glass. The indicated potential at the YSZ / Pt junction is measured as a reference electrode potential while scavenging air, and converted from the oxygen partial pressure in the air to the oxygen generation potential (standard potential) (refer to Non-patent Document 1 of Prior Art 1). .
後述するようにこの従来技術１では、ＹＳＺ／Ｐｔ参照極の準備が容易でないという課題がある。そのため汎用的な手法として、溶融ガラス中に直接浸漬したＰｔ線を参照極とみなし、測定対象の電気化学測定とは別に貴側へ電位を掃引して酸素発生電位を計測し、酸素発生電位（標準電位）に換算する手法がある（従来技術２ 非特許文献２参照）。 As will be described later, the conventional technique 1 has a problem that it is not easy to prepare the YSZ / Pt reference electrode. Therefore, as a general-purpose method, the Pt wire immersed directly in the molten glass is regarded as a reference electrode, and separately from the electrochemical measurement to be measured, the potential is swept to the noble side to measure the oxygen generation potential, and the oxygen generation potential ( There is a method of converting to (standard potential) (see Prior Art 2 Non-Patent Document 2).
また、特許文献１，２には、溶融ガラスを測定対象とする電気化学測定の参照極関連の技術として、酸素分圧を正確に測定しながら電気化学測定を遂行する装置が開示されている（従来技術３ 特許文献１，２参照）。 Patent Documents 1 and 2 disclose an apparatus for performing electrochemical measurement while accurately measuring oxygen partial pressure as a reference electrode-related technique for electrochemical measurement using molten glass as a measurement target ( Prior Art 3 (see Patent Documents 1 and 2).
前記従来技術１では、片閉管の内面先端へのＰｔの線または箔などの接着は容易でなく、溶融ガラス中への浸漬時に熱衝撃によって接着部が剥離したり、この接着状態が原因と推定される影響として使用するＹＳＺ／Ｐｔ参照極によって計測した作用極電位が異なったり、数時間の連続測定において作用極電位が変動したりする事例があった。 In the prior art 1, adhesion of a Pt line or foil to the inner surface tip of the cantilevered tube is not easy, and the adhesion part is peeled off by thermal shock when immersed in molten glass, and it is estimated that this adhesion state is the cause. There are cases in which the working electrode potential measured differs depending on the YSZ / Pt reference electrode used as an influence, or the working electrode potential fluctuates in several hours of continuous measurement.
また前記従来技術２では、Ｐｔ参照極電極は溶融ガラス中の溶存酸素濃度によって変動するため、電気化学測定を行う間、溶融ガラス中の溶存酸素濃度が一定であることが前提条件であり、測定電位を酸素発生電位（標準電位）に換算する場合、ある程度の電位誤差を許容する必要がある。 Moreover, in the said prior art 2, since a Pt reference electrode electrode is fluctuate | varied with the dissolved oxygen concentration in a molten glass, it is a precondition that the dissolved oxygen concentration in a molten glass is constant during an electrochemical measurement. When the potential is converted into an oxygen generation potential (standard potential), it is necessary to allow a certain amount of potential error.
また、正確な電位を求めるには、溶融ガラス中の溶存酸素濃度を安定化させる必要があり、比較的長時間にわたりガラスの溶融状態を保持しなければならない。 In addition, in order to obtain an accurate potential, it is necessary to stabilize the dissolved oxygen concentration in the molten glass, and the molten state of the glass must be maintained for a relatively long time.
さらに従来技術３では、前記特許文献１，２に開示された酸素分圧を測定する部位の構造が緻密かつ複雑であるため、測定環境などの条件に合わせて電極構造を柔軟に変更することは難しいなどの課題がある。 Furthermore, in the prior art 3, since the structure of the site for measuring the oxygen partial pressure disclosed in Patent Documents 1 and 2 is dense and complicated, it is not possible to flexibly change the electrode structure in accordance with conditions such as the measurement environment. There are challenges such as difficulties.
本発明の目的は、このような従来技術の課題を解消し、長時間安定した参照極電位が得られ、構造が簡単で、測定環境に適合した変更が可能なＮｉＯ／Ｎｉ参照極およびそれを用いた電気化学測定装置を提供することにある。 An object of the present invention is to solve such problems of the prior art, obtain a stable reference electrode potential for a long time, have a simple structure, and can be changed to suit the measurement environment, and a NiO / Ni reference electrode It is to provide an electrochemical measurement device used.
前記目的を達成するため、本発明の第１の手段は、
高温導電性材料からなる片閉管と、その片閉管内に装荷した酸化ニッケルを溶存または含有させた参照極ガラスと、その参照極ガラス内に一部浸漬したニッケル系金属極を備えたことを特徴とするものである。
In order to achieve the above object, the first means of the present invention comprises:
A single closed tube made of a high-temperature conductive material, a reference electrode glass in which nickel oxide loaded in the single closed tube is dissolved or contained, and a nickel-based metal electrode partially immersed in the reference electrode glass It is what.
本発明の第２の手段は前記第１の手段において、
前記ニッケル系金属極の前記参照極ガラスと接触する面が酸化ニッケルで覆われていることを特徴とするものである。
According to a second means of the present invention, in the first means,
The surface of the nickel-based metal electrode that contacts the reference electrode glass is covered with nickel oxide.
本発明の第３の手段は前記第１または２の手段において、
前記参照極ガラス中の酸化ニッケルの濃度が１ｍｏｌ％以上に規制されていることを特徴とするものである。
According to a third means of the present invention, in the first or second means,
The concentration of nickel oxide in the reference electrode glass is regulated to 1 mol% or more.
本発明の第４の手段は前記第１ないし３の手段において、
前記参照極ガラスは、ガラス組成物に酸化ニッケルを添加して一度溶融した後に凝固させたガラス、またはガラス組成物に酸化ニッケルを粉砕混合したものであることを特徴とするものである。
According to a fourth means of the present invention, in the first to third means,
The reference electrode glass is characterized in that nickel oxide is added to a glass composition and melted once, and then solidified, or a glass composition obtained by grinding and mixing nickel oxide.
前記目的を達成するため、本発明の第５の手段は、
耐熱容器と、前記耐熱容器内に収容された溶融ガラスと、作用極と、対極と、参照極と、電気化学計測器を備え、前記作用極と対極と参照極はその一部が前記溶融ガラスに浸漬されるとともに、前記作用極と対極と参照極は前記電気化学計測器に電気的に接続された電気化学測定装置において、
前記参照極は前記第１ないし４の手段の酸化ニッケル／ニッケル参照極であることを特徴とするものである。
In order to achieve the above object, the fifth means of the present invention comprises:
A heat-resistant container, a molten glass accommodated in the heat-resistant container, a working electrode, a counter electrode, a reference electrode, and an electrochemical measuring instrument, wherein the working electrode, the counter electrode, and the reference electrode are part of the molten glass In the electrochemical measuring device, the working electrode, the counter electrode, and the reference electrode are electrically connected to the electrochemical measuring instrument.
The reference electrode is the nickel oxide / nickel reference electrode of the first to fourth means.
本発明の第６の手段は前記第５の手段において、
前記溶融ガラスと前記参照極ガラスの基本組成が同じであることを特徴とするものである。
According to a sixth means of the present invention, in the fifth means,
The basic composition of the molten glass and the reference electrode glass is the same.
本発明の第７の手段は前記第５または６の手段において、
前記電気化学測定装置は、前記溶融ガラス中に溶存する例えばＦｅイオンなどのイオンの化学状態や酸化還元挙動を分析する電気化学測定装置であることを特徴とするものである。
A seventh means of the present invention is the fifth or sixth means,
The electrochemical measurement device is an electrochemical measurement device that analyzes the chemical state and oxidation-reduction behavior of ions such as Fe ions dissolved in the molten glass.
本発明の第８の手段は前記第５または６の手段において、
前記電気化学測定装置は、前記溶融ガラス中に溶存する例えばＦｅイオンなどのイオンを陰極の前記作用極へ析出回収する電気化学測定装置であることを特徴とするものである。
According to an eighth means of the present invention, in the fifth or sixth means,
The electrochemical measurement device is an electrochemical measurement device that deposits and collects ions such as Fe ions dissolved in the molten glass on the working electrode of the cathode.
本発明の第９の手段は前記第５または６の手段において、
前記電気化学測定装置は、陽極である前記作用極に例えばＰｄ、Ｒｈなどの白金族元素のガラス溶融炉内で析出する導電性物質などの溶解対象物を取り付けて、前記溶融ガラス中へ溶解する電気化学測定装置であることを特徴とするものである。
According to a ninth means of the present invention, in the fifth or sixth means,
The electrochemical measuring apparatus attaches a melting target object such as a conductive substance deposited in a glass melting furnace of a platinum group element such as Pd or Rh to the working electrode which is an anode, and melts the molten glass in the molten glass. It is an electrochemical measuring device.
本発明の第１０の手段は前記第５または６の手段において、
前記電気化学測定装置は、前記溶融ガラス中における例えばＮｉ−Ｃｒ系合金やＣｏ基合金などの電極や装置の候補材料などの導電性材料の耐食性を評価する電気化学測定装置であることを特徴とするものである。
According to a tenth means of the present invention, in the fifth or sixth means,
The electrochemical measurement apparatus is an electrochemical measurement apparatus that evaluates the corrosion resistance of conductive materials such as electrodes and apparatus candidate materials such as Ni-Cr alloys and Co-based alloys in the molten glass. To do.
本発明は前述のような構成になっており、長時間安定した参照極電位が得られ、構造が簡単で、測定環境に適合した変更が可能なＮｉＯ／Ｎｉ参照極およびそれを用いた電気化学測定装置を提供することができる。 The present invention has the above-described configuration, a reference electrode potential that is stable for a long time, a simple structure, and a NiO / Ni reference electrode that can be changed in accordance with the measurement environment and an electrochemistry using the same. A measuring device can be provided.
本発明に係るＮｉＯ／Ｎｉ参照極は、具体的に例えば、
（ａ）溶融ガラス中に溶存するイオンの化学状態や酸化還元挙動を電気化学的手法により分析および研究する電気化学測定装置に使用できる。
（ｂ）溶融ガラス中の溶存するイオンを電気化学的手法により作用極（陰極）へ析出回収する電気化学測定装置に使用できる。
（ｃ）作用極（陽極）に溶解対象物を取り付けて、電気化学的手法により溶融ガラス中へ溶解する電気化学測定装置に使用できる。
（ｄ）溶融ガラス中における導電性材料（例えば金属材料や炭素材料など）の耐食性を電気化学的手法により評価および研究する電気化学測定装置に使用できる。
Specifically, the NiO / Ni reference electrode according to the present invention is, for example,
(A) It can be used in an electrochemical measuring device that analyzes and studies the chemical state and redox behavior of ions dissolved in molten glass by an electrochemical method.
(B) The present invention can be used in an electrochemical measurement apparatus that deposits and recovers ions dissolved in molten glass on a working electrode (cathode) by an electrochemical method.
(C) It can be used in an electrochemical measurement apparatus in which a dissolution object is attached to a working electrode (anode) and is dissolved in molten glass by an electrochemical technique.
(D) It can be used in an electrochemical measurement apparatus that evaluates and studies the corrosion resistance of a conductive material (for example, a metal material or a carbon material) in molten glass by an electrochemical method.
次に本発明の実施例を図面と共に説明する。図１は、実施例に係るＮｉＯ／Ｎｉ参照極を用いた電気化学測定装置の概略構成図である。 Next, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram of an electrochemical measurement apparatus using a NiO / Ni reference electrode according to an embodiment.
この電気化学測定装置は同図に示すように、アルミナるつぼなどから構成された耐熱容器１には、高温状態の溶融ガラス２が収容保持されている。この溶融ガラス２中には、作用極３、対極４ならびにＮｉＯ／Ｎｉ参照極９の下部が浸漬されている。 In this electrochemical measuring apparatus, as shown in the figure, a high-temperature molten glass 2 is accommodated and held in a heat-resistant container 1 composed of an alumina crucible or the like. In the molten glass 2, the working electrode 3, the counter electrode 4, and the lower part of the NiO / Ni reference electrode 9 are immersed.
ＮｉＯ／Ｎｉ参照極９は、高温導電性材料からなる片閉管５内に酸化ニッケル（ＮｉＯ）を溶存または含有させたガラスで構成されている溶融状態の参照極ガラス６が所定量装荷されている。この参照極ガラス６中に、ニッケル（Ｎｉ）系金属極７を挿入した構成になっている。 The NiO / Ni reference electrode 9 is loaded with a predetermined amount of a melted reference electrode glass 6 made of glass in which nickel oxide (NiO) is dissolved or contained in a single tube 5 made of a high-temperature conductive material. . In this reference electrode glass 6, a nickel (Ni) metal electrode 7 is inserted.
これら耐熱容器１、溶融ガラス２、作用極３、対極４ならびにＮｉＯ／Ｎｉ参照極９（片閉管５、参照極ガラス６ならびにＮｉ系金属極７）で、電気化学測定セルを構成している。 These heat-resistant container 1, molten glass 2, working electrode 3, counter electrode 4 and NiO / Ni reference electrode 9 (single closed tube 5, reference electrode glass 6 and Ni-based metal electrode 7) constitute an electrochemical measurement cell.
この電気化学測定セルの作用極３、対極４ならびにＮｉＯ／Ｎｉ参照極９（Ｎｉ系金属極７）の各電極を市販の電気化学計測器８に接続することにより電気化学測定装置が構成され、所望の電気化学測定操作が行われる。 By connecting each electrode of the working electrode 3, the counter electrode 4 and the NiO / Ni reference electrode 9 (Ni-based metal electrode 7) of this electrochemical measuring cell to a commercially available electrochemical measuring device 8, an electrochemical measuring device is configured, The desired electrochemical measurement operation is performed.
高温導電性材料製の片閉管５は、塩化物溶融塩などに用いられるＰｙｒｅｘ（登録商標）片閉管と同様に隔膜としての機能を有しており、素材として、Ｖｙｃｏｒ（登録商標）などの耐熱ガラス、石英ガラス、ジルコニア（イットリア安定化ジルコニア（ＹＳＺ）等を含む）、アルミナなどの高温で導電性を有する耐熱材料が用いられる。 The closed tube 5 made of a high-temperature conductive material has a function as a diaphragm similarly to the Pyrex (registered trademark) closed tube used for chloride molten salt and the like, and as a material, a heat resistant material such as Vycor (registered trademark) is used. A heat-resistant material having conductivity at high temperatures such as glass, quartz glass, zirconia (including yttria-stabilized zirconia (YSZ)), and alumina is used.
ＮｉＯを溶存または含有させた参照極ガラス６は、溶融ガラス２（ホウケイ酸ガラス）の基本組成にＮｉＯを添加して一度溶融した後に凝固させたガラス、または溶融ガラス２の基本組成にＮｉＯを粉砕混合したものを用いる。 The reference electrode glass 6 in which NiO is dissolved or contained is a glass obtained by adding NiO to the basic composition of the molten glass 2 (borosilicate glass), melting once and then solidifying, or pulverizing NiO in the basic composition of the molten glass 2 Use a mixture.
溶融ガラス２の基本組成の１例を示せば下表の通りである。
図２は、９００℃に維持されている溶融参照極ガラス（溶融ホウケイ酸ガラス）６中のＮｉＯ濃度（初期値）に対するＰｔ作用極３の自然電位と酸素発生電位の差（ΔＥ）の関係を示す特性図である。 FIG. 2 shows the relationship between the difference (ΔE) between the natural potential of the Pt working electrode 3 and the oxygen generation potential with respect to the NiO concentration (initial value) in the molten reference electrode glass (molten borosilicate glass) 6 maintained at 900 ° C. FIG.
この図から明らかなように、参照極ガラス６中のＮｉＯ濃度（初期値）が１．１１ｍｏｌ％、２．１７ｍｏｌ％、４．１５ｍｏｌ％の場合、ＮｉＯ濃度（初期値）とΔＥとの間に相関関係（図２の実線で示す直線）があるが、参照極ガラス６のＮｉＯ濃度（初期値）が１ｍｏｌ％未満ではＮｉ系金属電極７から溶出するＮｉイオンにより参照極ガラス６中のＮｉＯ濃度が増加し、徐々にΔＥが低下する（図２中の×印で示す点）。
従って、参照極ガラス６に含まれるＮｉＯ濃度は、ＮｉＯ／Ｎｉ対の酸化還元反応が安定する１ｍｏｌ％以上とする必要がある。なお、参照極ガラス６中のＮｉＯ濃度の上限値は、３０ｍｏｌ％程度である。
As is clear from this figure, when the NiO concentration (initial value) in the reference electrode glass 6 is 1.11 mol%, 2.17 mol%, and 4.15 mol%, it is between the NiO concentration (initial value) and ΔE. Although there is a correlation (a straight line shown by a solid line in FIG. 2), when the NiO concentration (initial value) of the reference electrode glass 6 is less than 1 mol%, the NiO concentration in the reference electrode glass 6 is caused by Ni ions eluted from the Ni-based metal electrode 7. Increases and ΔE gradually decreases (points indicated by crosses in FIG. 2).
Therefore, the NiO concentration contained in the reference electrode glass 6 needs to be 1 mol% or more at which the oxidation-reduction reaction of the NiO / Ni pair is stabilized. The upper limit of the NiO concentration in the reference electrode glass 6 is about 30 mol%.
Ｎｉ系金属電極７はＮｉ系金属の棒や線材からなり、Ｎｉ成分が８０ｍｏｌ％以上の金属材料を用いる。使用可能なＮｉ基合金として、例えばＮｉ−Ｃｒ合金やＮｉ−Ｆｅ合金がある。 The Ni-based metal electrode 7 is made of a Ni-based metal rod or wire, and a metal material having a Ni component of 80 mol% or more is used. Examples of Ni-based alloys that can be used include Ni-Cr alloys and Ni-Fe alloys.
また、参照極ガラス６に接触（浸漬）するＮｉ系金属電極７の先端部を高温（約９００℃）の大気中で加熱し、Ｎｉ系金属電極７の先端部表面にＮｉＯ膜を形成させることで、長時間にわたって安定した電気化学測定ができる。 Also, the tip of the Ni-based metal electrode 7 that is in contact with (immersed in) the reference electrode glass 6 is heated in a high-temperature (about 900 ° C.) atmosphere to form a NiO film on the surface of the tip of the Ni-based metal electrode 7. Thus, stable electrochemical measurement can be performed over a long period of time.
次に本発明のＮｉＯ／Ｎｉ参照極９を用いた電気化学測定装置における、作用極３と対極４の具体的な組み合わせの実施例を説明する。 Next, an example of a specific combination of the working electrode 3 and the counter electrode 4 in the electrochemical measurement apparatus using the NiO / Ni reference electrode 9 of the present invention will be described.
（実施例１）
溶融ガラス２中に溶存するイオンの化学状態や酸化還元挙動を電気化学的手法により分析および研究する電気化学測定装置において、本発明のＮｉＯ／Ｎｉ参照極９を使用し、作用極３および対極４にはＰｔなどの耐食性材料を用いる。
Example 1
In an electrochemical measurement apparatus for analyzing and studying the chemical state and redox behavior of ions dissolved in the molten glass 2 by an electrochemical method, the working electrode 3 and the counter electrode 4 are used by using the NiO / Ni reference electrode 9 of the present invention. For this, a corrosion resistant material such as Pt is used.
（実施例２）
溶融ガラス２中に溶存するイオンを電気化学的手法により陰極の作用極３へ析出回収する電気化学測定装置において、本発明のＮｉＯ／Ｎｉ参照極９を使用し、作用極３に析出物が付着し易い材料（例えばＰｔなどの耐食性材料およびＮｉ−Ｃｒ系合金やＣｏ基合金からなる多孔性板や網など）を用い、対極４にはＰｔなどの耐食性材料を用いる。
(Example 2)
In an electrochemical measurement apparatus for depositing and collecting ions dissolved in the molten glass 2 on the cathode working electrode 3 by an electrochemical technique, the NiO / Ni reference electrode 9 of the present invention is used, and deposits adhere to the working electrode 3. For example, a corrosion-resistant material such as Pt and a porous plate or net made of a Ni—Cr alloy or a Co-based alloy are used, and the counter electrode 4 is made of a corrosion-resistant material such as Pt.
（実施例３）
陽極である作用極３に溶解対象物を取り付けて、電気化学的手法により溶融ガラス２中へ溶解する電気化学測定装置において、本発明のＮｉＯ／Ｎｉ参照極９を使用し、作用極３はＰｔなどの耐食性材料からなる容器や網に溶解対象物を装荷し、対極４には溶解電位条件で溶融ガラス２中への成分溶出が少ないグラファイト等の導電性炭素材料やＰｔなどの耐食性材料を用いる。
(Example 3)
In an electrochemical measurement apparatus in which a melting object is attached to a working electrode 3 as an anode and melted into the molten glass 2 by an electrochemical technique, the NiO / Ni reference electrode 9 of the present invention is used, and the working electrode 3 is Pt. The object to be melted is loaded into a container or net made of a corrosion-resistant material such as graphite, and a conductive carbon material such as graphite or a corrosion-resistant material such as Pt is used for the counter electrode 4 with little component elution into the molten glass 2 under the melting potential condition. .
（実施例４）
溶融ガラス２中における導電性材料（金属材料や炭素材料など）の耐食性を電気化学的手法により評価および研究する電気化学測定装置において、本発明のＮｉＯ／Ｎｉ参照極９を使用し、作用極３に評価・研究の対象材料を用い、対極４には電位掃引範囲で溶融ガラス２中への成分溶出が少ないグラファイト等の導電性炭素材料やＰｔなどの耐食性材料を用いる。
Example 4
In an electrochemical measuring apparatus for evaluating and studying the corrosion resistance of a conductive material (metal material, carbon material, etc.) in the molten glass 2 by an electrochemical technique, the working electrode 3 is formed using the NiO / Ni reference electrode 9 of the present invention. For the counter electrode 4, a conductive carbon material such as graphite and a corrosion resistant material such as Pt are used as the counter electrode 4, with little component elution into the molten glass 2 in the potential sweep range.
図３は、本発明のＮｉＯ／Ｎｉ参照極９を使用した電気化学測定結果の実例として、Ｆｅイオンを含む９００℃の溶融ホウケイ酸ガラス（溶融ガラス２）を対象に、電位掃引幅を変えながら測定したサイクリックボルタンメトリ（ＣＶ測定）の結果を示す電位−電流曲線図である。 FIG. 3 shows, as an example of the electrochemical measurement result using the NiO / Ni reference electrode 9 of the present invention, a 900 ° C. molten borosilicate glass (molten glass 2) containing Fe ions while changing the potential sweep width. It is an electric potential-current curve figure which shows the result of the measured cyclic voltammetry (CV measurement).
この測定は、溶融ガラス２を加熱保持する電気炉内温度が９００℃に安定した時刻８時３０分頃からＰｔ作用極３の自然電位を測定し、１４時３０分頃から２１時３０分頃まで７時間ＣＶ測定を繰り返したところ、０．３５〜０．４０Ｖの電位領域で観察される酸素発生反応による正の電流値の増加曲線が重複することが分かった。すなわち、本発明のＮｉＯ／Ｎｉ参照極９は、少なくとも７時間安定した参照極電位を示すことが確認できた。 In this measurement, the natural potential of the Pt working electrode 3 is measured from about 8:30 when the temperature in the electric furnace for holding the molten glass 2 is stably maintained at 900 ° C., and from about 21:30 to about 21:30. When the CV measurement was repeated until 7 hours, it was found that the increase curves of positive current values due to the oxygen generation reaction observed in the potential region of 0.35 to 0.40 V overlap. That is, it was confirmed that the NiO / Ni reference electrode 9 of the present invention exhibited a stable reference electrode potential for at least 7 hours.
また、本発明のＮｉＯ／Ｎｉ参照極９を構成する高温導電性材料からなる片閉管５、ＮｉＯを溶存または含有させた参照極ガラス６、Ｎｉ系金属極７は、全て安価にかつ容易に入手できる素材であり、測定環境に適合した仕様、形状の変更も容易に可能であるなどの特長を有している。 Further, the closed tube 5 made of a high-temperature conductive material constituting the NiO / Ni reference electrode 9 of the present invention, the reference electrode glass 6 in which NiO is dissolved or contained, and the Ni-based metal electrode 7 are all easily obtained at low cost. It is a material that can be used, and has features such as specifications that are suitable for the measurement environment and the ability to easily change the shape.
前記第９の手段において、電気化学測定装置は、陽極である作用極に例えばＰｄ、Ｒｈなどの白金族元素のガラス溶融炉内で析出する導電性物質などの溶解対象物を取り付けて、溶融ガラス中へ溶解する電気化学測定装置であることを特定している。 In the ninth means, the electrochemical measurement apparatus is configured to attach a melting object such as a conductive substance deposited in a glass melting furnace of a platinum group element such as Pd or Rh to a working electrode which is an anode, It is specified that it is an electrochemical measuring device that dissolves into the inside.
高レベル放射性廃液のガラス固化処理プロセスでは、白金族元素などの導電性物質が析出して堆積することによるガラス溶融炉運転への課題が生じており、これら導電性物質の析出反応（電気化学反応）を評価するのに、本発明の電気化学測定装置を適用することができる。 In the vitrification process of high-level radioactive liquid waste, there is a problem for glass melting furnace operation due to the deposition and deposition of conductive substances such as platinum group elements. The precipitation reaction (electrochemical reaction) of these conductive substances ) Can be applied to the electrochemical measurement apparatus of the present invention.
前記第１０の手段において、電気化学測定装置は、溶融ガラス中における例えばＮｉ−Ｃｒ系合金やＣｏ基合金などの電極や装置の候補材料などの導電性材料の耐食性を評価する電気化学測定装置であることを特定している。 In the tenth means, the electrochemical measurement apparatus is an electrochemical measurement apparatus for evaluating the corrosion resistance of conductive materials such as electrodes and candidate materials of the apparatus such as Ni-Cr alloy and Co base alloy in molten glass. It has been identified.
高レベル放射性廃液のガラス固化処理プロセスで用いられるガラス溶融炉の加熱方式の一つとして、溶融ガラスに直接通電してガラスの電気抵抗による発熱を利用した方式があり、この溶融炉の加熱用電極材料として、Ｎｉ−Ｃｒ系合金のＩｎｃｏｎｅｌ (登録商標)６９０が使用されており、また、Ｃｏ基合金も候補材料となっている。これら導電性材料の耐食性を評価するのに、本発明の電気化学測定装置を適用することができる。 One method of heating a glass melting furnace used in the vitrification process of high-level radioactive liquid waste is to use the heat generated by the electrical resistance of the glass by directly energizing the molten glass. As a material, Ni-Cr alloy Inconel (registered trademark) 690 is used, and a Co-based alloy is also a candidate material. The electrochemical measurement apparatus of the present invention can be applied to evaluate the corrosion resistance of these conductive materials.
１：耐熱容器、
２：溶融ガラス、
３：作用極、
４：対極、
５：片閉管、
６：参照極ガラス、
７：Ｎｉ系金属極、
８：電気化学計測器、
９：ＮｉＯ／Ｎｉ参照極。
1: heat-resistant container,
2: Molten glass,
3: Working electrode
4: Counter electrode,
5: Single closed tube,
6: Reference electrode glass,
7: Ni-based metal electrode,
8: Electrochemical measuring instrument,
9: NiO / Ni reference electrode.
Claims (10)
前記ニッケル系金属極の前記参照極ガラスと接触する面が酸化ニッケルで覆われていることを特徴とする溶融ガラスの電気化学測定に用いる酸化ニッケル／ニッケル参照極。 In the nickel oxide / nickel reference electrode used for electrochemical measurement of the molten glass according to claim 1,
A nickel oxide / nickel reference electrode used for electrochemical measurement of molten glass, wherein a surface of the nickel-based metal electrode that contacts the reference electrode glass is covered with nickel oxide.
前記参照極ガラス中の酸化ニッケルの濃度が１ｍｏｌ％以上に規制されていることを特徴とする溶融ガラスの電気化学測定に用いる酸化ニッケル／ニッケル参照極。 In the nickel oxide / nickel reference electrode used for electrochemical measurement of the molten glass according to claim 1 or 2,
A nickel oxide / nickel reference electrode used for electrochemical measurement of molten glass, wherein the concentration of nickel oxide in the reference electrode glass is regulated to 1 mol% or more.
前記参照極ガラスは、ガラス組成物に酸化ニッケルを添加して一度溶融した後に凝固させたガラス、またはガラス組成物に酸化ニッケルを粉砕混合したものであることを特徴とする溶融ガラスの電気化学測定に用いる酸化ニッケル／ニッケル参照極。 In the nickel oxide / nickel reference electrode used for the electrochemical measurement of the molten glass according to any one of claims 1 to 3,
The reference electrode glass is a glass obtained by adding nickel oxide to a glass composition and once solidified and then solidified, or a glass composition obtained by pulverizing and mixing nickel oxide. Nickel oxide / nickel reference electrode for use in
前記参照極は請求項１ないし４のいずれか１項に記載の酸化ニッケル／ニッケル参照極であることを特徴とする電気化学測定装置。 A heat-resistant container, a molten glass accommodated in the heat-resistant container, a working electrode, a counter electrode, a reference electrode, and an electrochemical measuring instrument, wherein the working electrode, the counter electrode, and the reference electrode are part of the molten glass In the electrochemical measuring device, the working electrode, the counter electrode, and the reference electrode are electrically connected to the electrochemical measuring instrument.
5. The electrochemical measurement apparatus according to claim 1, wherein the reference electrode is the nickel oxide / nickel reference electrode according to claim 1.
前記溶融ガラスと前記参照極ガラスの基本組成が同じであることを特徴とする電気化学測定装置。 The electrochemical measurement device according to claim 5,
An electrochemical measurement apparatus, wherein the molten glass and the reference electrode glass have the same basic composition.
前記電気化学測定装置は、前記溶融ガラス中に溶存するイオンの化学状態や酸化還元挙動を分析する電気化学測定装置であることを特徴とする電気化学測定装置。 The electrochemical measurement device according to claim 5 or 6,
The electrochemical measurement apparatus is an electrochemical measurement apparatus that analyzes a chemical state or oxidation-reduction behavior of ions dissolved in the molten glass.
前記電気化学測定装置は、前記溶融ガラス中に溶存するイオンを陰極の前記作用極へ析出回収する電気化学測定装置であることを特徴とする電気化学測定装置。 The electrochemical measurement device according to claim 5 or 6,
The electrochemical measurement device is an electrochemical measurement device that deposits and collects ions dissolved in the molten glass on the working electrode of a cathode.
前記電気化学測定装置は、陽極である前記作用極に溶解対象物を取り付けて、前記溶融ガラス中へ溶解する電気化学測定装置であることを特徴とする電気化学測定装置。 The electrochemical measurement device according to claim 5 or 6,
The electrochemical measurement device is an electrochemical measurement device in which an object to be dissolved is attached to the working electrode, which is an anode, and is melted into the molten glass.
前記電気化学測定装置は、前記溶融ガラス中における導電性材料の耐食性を評価する電気化学測定装置であることを特徴とする電気化学測定装置。 The electrochemical measurement device according to claim 5 or 6,
The electrochemical measurement device is an electrochemical measurement device for evaluating the corrosion resistance of a conductive material in the molten glass.
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