JP5958225B2 - Method for quantifying aluminum oxide ion, method for quantifying moisture in molten salt, method for producing aluminum structure - Google Patents
Method for quantifying aluminum oxide ion, method for quantifying moisture in molten salt, method for producing aluminum structure Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims description 103
- 238000000034 method Methods 0.000 title claims description 45
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 238000007747 plating Methods 0.000 claims description 43
- -1 aluminum oxide ions Chemical class 0.000 claims description 30
- 238000000862 absorption spectrum Methods 0.000 claims description 29
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 26
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 24
- 238000002484 cyclic voltammetry Methods 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910003460 diamond Inorganic materials 0.000 claims description 7
- 239000010432 diamond Substances 0.000 claims description 7
- 229910018512 Al—OH Inorganic materials 0.000 claims description 6
- 238000011002 quantification Methods 0.000 claims description 5
- 150000004693 imidazolium salts Chemical class 0.000 claims description 3
- 229910018516 Al—O Inorganic materials 0.000 claims 1
- 238000004566 IR spectroscopy Methods 0.000 claims 1
- 238000005259 measurement Methods 0.000 description 29
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 238000011088 calibration curve Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 7
- 125000006850 spacer group Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 2
- STCBHSHARMAIOM-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;chloride Chemical compound Cl.CN1C=CN=C1 STCBHSHARMAIOM-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- 238000007726 management method Methods 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Investigating Or Analysing Materials By Optical Means (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Description
本発明は溶融塩に含まれるアルミニウム酸化物イオン及び水分の定量方法、特にアルミニウムめっきに用いられる溶融塩浴中の水分定量方法、水分管理方法、および同管理方法を用いるアルミニウム構造体の製造方法に関する。 The present invention relates to a method for quantifying aluminum oxide ions and water contained in a molten salt, and more particularly to a method for quantifying water in a molten salt bath used for aluminum plating, a water management method, and a method for producing an aluminum structure using the management method. .
アルミニウムは導電性、耐腐食性に優れており、また軽量な材料であるから種々の用途に使用されている。例えばリチウムイオン電池にはアルミニウム箔の表面にコバルト酸リチウム等の活物質を塗布したものが正極材料として使用されている。またアルミニウム箔に代えて、アルミニウムの多孔体を正極材料に使用することで電池の大容量化を行うことも検討されている。 Aluminum is excellent in conductivity and corrosion resistance, and is a lightweight material and is used in various applications. For example, a lithium ion battery in which an active material such as lithium cobaltate is applied to the surface of an aluminum foil is used as the positive electrode material. In addition, it has been studied to increase the capacity of a battery by using an aluminum porous body as a positive electrode material instead of an aluminum foil.
アルミニウムのめっきは、アルミニウムの酸素に対する親和力が大きく電位が水素より低いために水溶液系のめっき浴で電気めっきを行うことが困難である。このため従来より、非水溶液系のめっき浴でアルミニウムを電気めっきすることが検討されている。例えば金属の表面の酸化防止などの目的でアルミニウムをめっきする技術として、特許文献１にはオニウムハロゲン化物とアルミニウムハロゲン化物とを混合溶融した低融点組成物（溶融塩）をめっき浴として用い、陰極にアルミニウムを析出させることを特徴とする電気アルミニウムめっき方法が開示されている。 Aluminum plating is difficult to perform in an aqueous plating bath because aluminum has a high affinity for oxygen and a lower potential than hydrogen. For this reason, conventionally, electroplating of aluminum in a non-aqueous plating bath has been studied. For example, as a technique for plating aluminum for the purpose of preventing oxidation of a metal surface, for example, Patent Document 1 uses a low melting point composition (molten salt) obtained by mixing and melting onium halide and aluminum halide as a plating bath. An aluminum electroplating method characterized in that aluminum is deposited on the substrate is disclosed.
めっき浴中に水分が混入すると化学特性が変化して電気めっき性に悪影響を及ぼす。特許文献１には、赤外分光光度計を用いて３３６０ｃｍ−１付近のＯ−Ｈ伸縮振動波数を測定してめっき浴中の水分量を測定することが記載されている。 If water is mixed in the plating bath, the chemical characteristics change and adversely affect the electroplating properties. Patent Document 1 describes that the amount of water in the plating bath is measured by measuring the OH stretching vibration wave number around 3360 cm −1 using an infrared spectrophotometer.
有機塩と塩化アルミニウムの混合塩である溶融塩は吸湿性が高い。溶融塩中に水分が混入すると下記式（１）で示される反応が起こり、アルミニウム水酸化物イオンが生成する。特許文献１ではこのようにして生成したアルミニウム水酸化物イオンに由来するＯ−Ｈ結合に基づく吸収スペクトルを測定して水分量を定量している。
ＡｌＣｌ４＋Ｈ２Ｏ → Ａｌ（ＯＨ）Ｃｌ３ −＋Ｈ＋＋Ｃｌ−・・・（１）
Molten salt, which is a mixed salt of organic salt and aluminum chloride, has high hygroscopicity. When moisture is mixed in the molten salt, a reaction represented by the following formula (1) occurs, and aluminum hydroxide ions are generated. In Patent Document 1, the amount of water is quantified by measuring an absorption spectrum based on the O—H bond derived from the aluminum hydroxide ion thus generated.
AlCl 4 + H 2 O → Al (OH) Cl 3 − + H + + Cl − (1)
しかし溶融塩中に水分が混入すると式（１）で示される反応だけでなく式（２）で示される反応が起こり、アルミニウム水酸化物イオンだけでなくアルミニウム酸化物イオンが生成する。特に水分が混入した後で時間が経つとアルミニウム酸化物イオン量が増加する。アルミニウム酸化物イオンに由来するＡｌ−Ｏ結合に基づく吸収スペクトルは７９０ｃｍ−１付近に現れる。
Ａｌ（ＯＨ）Ｃｌ３ − → ＡｌＯＣｌ２ −＋Ｈ＋＋Ｃｌ−・・・（２）
However, when water is mixed in the molten salt, not only the reaction represented by the formula (1) but also the reaction represented by the formula (2) occurs, and not only aluminum hydroxide ions but also aluminum oxide ions are generated. In particular, the amount of aluminum oxide ions increases as time passes after moisture is mixed. An absorption spectrum based on Al—O bonds derived from aluminum oxide ions appears in the vicinity of 790 cm −1 .
Al (OH) Cl 3 − → AlOCl 2 − + H + + Cl − (2)
溶融塩めっき浴を赤外分光光度計で分析する場合、溶融塩めっき浴は反応性が高いため、溶融塩めっき浴との反応が起こらない耐腐食性の高い窓材を選択する必要がある。このような窓材としてシリコン、ダイヤモンド、フッ化カルシウム等が挙げられるが、フッ化カルシウムは９００ｃｍ−１以下の波長の赤外光を透過しない。またシリコン及びダイヤモンドは屈折率が高く干渉縞ノイズが出やすい。そこで本発明は、赤外分光光度計を用いた簡便な方法でアルミニウム酸化物イオンを定量し、溶融塩中の水分量を精度良く定量するための分析方法を提供することを課題とする。 When analyzing a molten salt plating bath with an infrared spectrophotometer, the molten salt plating bath is highly reactive, and therefore it is necessary to select a highly corrosion-resistant window material that does not react with the molten salt plating bath. Examples of such window materials include silicon, diamond, calcium fluoride, and the like, but calcium fluoride does not transmit infrared light having a wavelength of 900 cm −1 or less. Silicon and diamond have a high refractive index, and interference fringe noise tends to occur. Then, this invention makes it a subject to provide the analysis method for quantifying aluminum oxide ion by the simple method using an infrared spectrophotometer, and quantifying the moisture content in molten salt accurately.
本発明は、有機塩と塩化アルミニウムとの混合塩である溶融塩に含まれる水分に由来するアルミニウム酸化物イオンの定量方法であって、窓材としてシリコン又はダイヤモンドを用い、２枚の前記窓材を平行から０．３°〜０．７°の角度で傾斜するように対向させたセル内に前記溶融塩を導入し、赤外分光光度計で７９０ｃｍ−１付近のＡｌ−Ｏ結合に基づく吸収スペクトルを測定して定量することを特徴とする、アルミニウム酸化物イオンの定量方法である。 The present invention is a method for quantifying aluminum oxide ions derived from moisture contained in a molten salt, which is a mixed salt of an organic salt and aluminum chloride, using silicon or diamond as a window material, and the two window materials Is introduced into cells facing each other so as to incline at an angle of 0.3 ° to 0.7 ° from parallel, and absorption based on Al—O bonds in the vicinity of 790 cm −1 with an infrared spectrophotometer. A method for quantifying aluminum oxide ions, characterized by measuring and quantifying a spectrum.
シリコン、ダイヤモンドは９００ｃｍ−１以下の波数でも赤外光を透過し、また溶融塩に対する耐腐食性が高いため窓材として適している。しかしシリコン、ダイヤモンドは屈折率が高く赤外光が反射しやすいため光の干渉による干渉縞ノイズが高いという問題がある。そこで２枚の窓材を平行から０．３°〜０．７°の角度で傾斜するように対向させて測定することで干渉縞を低減し、Ａｌ−Ｏ結合に基づく７９０ｃｍ−１付近の吸収スペクトルを精度良く測定できることを見出した。これにより溶融塩に含まれるアルミニウム酸化物イオンを定量できる。なおアルミニウム酸化物イオンとはＡｌＯＣｌ２ −等、Ａｌ、Ｏ、Ｃｌを含むイオンを指すものとする。 Silicon and diamond are suitable as window materials because they transmit infrared light even at a wave number of 900 cm −1 or less and have high corrosion resistance against molten salt. However, since silicon and diamond have a high refractive index and easily reflect infrared light, there is a problem that interference fringe noise due to light interference is high. Therefore, interference fringes are reduced by measuring the two window materials facing each other so as to be inclined at an angle of 0.3 ° to 0.7 ° from parallel, and absorption near 790 cm −1 based on Al—O bonds. It was found that the spectrum can be measured with high accuracy. Thereby, the aluminum oxide ion contained in molten salt can be quantified. The aluminum oxide ion refers to an ion containing Al, O, Cl, such as AlOCl 2 — .
また本発明は、有機塩と塩化アルミニウムとの混合塩である溶融塩に含まれる水分を定量する水分定量方法であって、上記の定量方法によってアルミニウム酸化物イオンを定量すると共に、溶融塩の３３６０ｃｍ−１付近のＡｌ−ＯＨ結合（アルミニウムに配位したＯ−Ｈ結合）に基づく吸収スペクトルを測定して溶融塩に含まれる水分に由来するアルミニウム水酸化物イオンを定量し、前記アルミニウム酸化物イオンの定量結果と前記アルミニウム水酸化物イオンの定量結果に基づいて前記溶融塩に含まれる水分量を定量する、溶融塩中の水分定量方法を提供する。アルミニウム酸化物イオン、アルミニウム水酸化物イオンを赤外分光光度計で測定することにより簡便な方法で溶融塩中の水分量を定量できる。なおアルミニウム水酸化物イオンとはＡｌ（ＯＨ）Ｃｌ３ −等、Ａｌ、（ＯＨ）、Ｃｌを含むイオンを指すものとする。 The present invention is also a moisture quantification method for quantifying moisture contained in a molten salt that is a mixed salt of an organic salt and aluminum chloride, wherein the aluminum oxide ion is quantified by the quantification method described above, and 3360 cm of the molten salt. An aluminum hydroxide ion derived from moisture contained in the molten salt by measuring an absorption spectrum based on an Al—OH bond in the vicinity of −1 (OH bond coordinated to aluminum), and the aluminum oxide ion A method for determining the amount of water in a molten salt is provided, in which the amount of water contained in the molten salt is quantified based on the result of determining the amount of aluminum hydroxide ions. By measuring aluminum oxide ions and aluminum hydroxide ions with an infrared spectrophotometer, the amount of water in the molten salt can be quantified by a simple method. The aluminum hydroxide ion refers to an ion containing Al, (OH), or Cl, such as Al (OH) Cl 3 — .
さらに、サイクリックボルタンメトリー法（ＣＶ法）により溶融塩に含まれる水分量を定量し、ＣＶ法により得られた水分量と上記の方法によって得られた水分量とを合計すると好ましい。溶融塩中に混入した水分は上記のアルミニウム酸化物イオン、アルミニウム水酸化物イオンになるとともに、水（Ｈ２Ｏ）そのものの形でも存在する。ＣＶ法によりこの水分量を測定することで、さらに精度良く溶融塩中の水分量を定量できる。 Furthermore, the amount of water contained in the molten salt is quantified by a cyclic voltammetry method (CV method), and the amount of water obtained by the CV method and the amount of water obtained by the above method are preferably summed. The water mixed in the molten salt becomes the above aluminum oxide ions and aluminum hydroxide ions, and also exists in the form of water (H 2 O) itself. By measuring the water content by the CV method, the water content in the molten salt can be quantified more accurately.
本願の別な発明は、有機塩と塩化アルミニウムとの混合塩である溶融塩浴を用いてアルミニウムをめっきすることによるアルミニウム構造体の製造方法であって、前記溶融塩浴から溶融塩をサンプリングし、上記いずれかの水分定量方法により前記溶融塩に含まれる水分を定量するとともに、前記溶融塩に含まれる水分量が２．７体積％以下となるように水分量を管理することを特徴とするアルミニウム構造体の製造方法である。上記の水分定量方法により溶融塩浴中の水分量を管理することにより、安定してアルミニウムめっきを行うことが可能となる。溶融塩としてはイミダゾリウム塩と塩化アルミニウムとの混合塩が好ましく用いられる。 Another invention of the present application is a method for producing an aluminum structure by plating aluminum using a molten salt bath that is a mixed salt of an organic salt and aluminum chloride, and samples the molten salt from the molten salt bath. The water content in the molten salt is quantified by any one of the water content determination methods, and the water content is controlled so that the water content in the molten salt is 2.7% by volume or less. It is a manufacturing method of an aluminum structure. By controlling the amount of water in the molten salt bath by the above moisture determination method, it is possible to stably perform aluminum plating. As the molten salt, a mixed salt of an imidazolium salt and aluminum chloride is preferably used.
本発明によれば溶融塩中に含まれる水分の量を簡便な方法で精度良く定量することができる。 According to the present invention, the amount of water contained in the molten salt can be accurately determined by a simple method.
以下、本発明の実施の形態をウレタン発泡体等の樹脂多孔体表面にアルミニウムをめっきするための溶融塩めっき浴を分析対象として説明する。なお本発明はこれに限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。 Hereinafter, an embodiment of the present invention will be described using a molten salt plating bath for plating aluminum on the surface of a porous resin body such as a urethane foam as an analysis target. The present invention is not limited to this, but is defined by the scope of the claims, and is intended to include all modifications within the scope and meaning equivalent to the scope of the claims.
溶融塩としては塩化アルミニウムと有機塩との混合塩（共晶塩）を使用する。比較的低温で溶融する有機溶融塩浴を使用すると基材である樹脂多孔体を分解することなくめっきができ好ましい。有機塩としてはイミダゾリウム塩、ピリジニウム塩等が使用できる。なかでも１−エチル−３−メチルイミダゾリウムクロライド（ＥＭＩＣ）、ブチルピリジニウムクロライド（ＢＰＣ）が好ましく使用できる。アルミニウムを平滑にめっきするため、この溶融塩中に１，１０−フェナントロリンを０．２５ｇ／ｌ以上７ｇ／ｌ以下添加することが好ましい。 As the molten salt, a mixed salt (eutectic salt) of aluminum chloride and an organic salt is used. Use of an organic molten salt bath that melts at a relatively low temperature is preferable because plating can be performed without decomposing the porous resin body as a base material. As the organic salt, imidazolium salt, pyridinium salt and the like can be used. Of these, 1-ethyl-3-methylimidazolium chloride (EMIC) and butylpyridinium chloride (BPC) can be preferably used. In order to plate aluminum smoothly, it is preferable to add 1,10-phenanthroline to the molten salt in an amount of 0.25 g / l to 7 g / l.
上記の溶融塩試料を採取し、赤外分光光度計を用いて吸収スペクトルを測定する。測定セルには２枚の窓材を使用し２枚の窓材の間に溶融塩試料を挟んで測定する。図１は赤外分光光度計に用いる測定セルの断面模式図である。窓材にはシリコン又はダイヤモンドを使用する。２枚の窓材１を対向させる。２枚の窓材１の間にスペーサ２を入れて、２枚の窓材同志の角度が平行から０．３°以上０．７°以下の範囲となるように調整する。スペーサにはセル内を密閉する効果もある。溶融塩試料は吸湿しやすい材料であり測定中に特性が変化する可能性があるため、水分吸収量が少ないと共に、溶融塩試料に腐食されにくい、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフルオロアルコキシフッ素樹脂（ＰＦＡ）等のフッ素樹脂をスペーサに使用するのが好ましい。２枚の窓材とスペーサに挟まれた空間である試料注入部３に溶融塩試料を入れ、赤外吸収スペクトルを測定する。 The molten salt sample is collected and the absorption spectrum is measured using an infrared spectrophotometer. Two window materials are used in the measurement cell, and a molten salt sample is sandwiched between the two window materials. FIG. 1 is a schematic cross-sectional view of a measurement cell used in an infrared spectrophotometer. Silicon or diamond is used for the window material. Two window materials 1 are made to oppose each other. The spacer 2 is inserted between the two window materials 1 and adjusted so that the angle between the two window materials is in a range of 0.3 ° to 0.7 ° from parallel. The spacer also has an effect of sealing the inside of the cell. Since the molten salt sample is a material that easily absorbs moisture and its characteristics may change during measurement, the amount of moisture absorption is low, and the molten salt sample is less susceptible to corrosion. Polytetrafluoroethylene (PTFE), polyfluoroalkoxy fluorine It is preferable to use a fluorine resin such as resin (PFA) for the spacer. A molten salt sample is put into the sample injection part 3 which is a space sandwiched between two window materials and a spacer, and an infrared absorption spectrum is measured.
Ａｌ−Ｏ結合に基づく７９０ｃｍ−１付近のピーク高さから溶融塩試料に含まれるアルミニウム酸化物イオンを定量する。また、Ａｌ−ＯＨ結合（Ａｌに配位したＯ−Ｈ結合）に基づく３３６０ｃｍ−１付近のピーク高さから溶融塩試料に含まれるアルミニウム水酸化物イオンを定量する。アルミニウム酸化物イオンの量とアルミニウム水酸化物イオンの量に基づいて溶融塩試料に含まれる水分を定量する。例えば、あらかじめ水分濃度を適宜変更して作製した標準試料の赤外吸収スペクトルを測定して検量線を作成し、この検量線に基づいて水分量を定量する。溶融塩めっき浴に含まれる水分量が２体積％以下となるように水分量を管理してアルミニウムをめっきする。 The aluminum oxide ions contained in the molten salt sample are quantified from the peak height near 790 cm −1 based on the Al—O bond. Moreover, the aluminum hydroxide ion contained in the molten salt sample is quantified from the peak height near 3360 cm −1 based on the Al—OH bond (OH bond coordinated to Al). The moisture contained in the molten salt sample is quantified based on the amount of aluminum oxide ions and the amount of aluminum hydroxide ions. For example, a calibration curve is created by measuring an infrared absorption spectrum of a standard sample prepared by appropriately changing the moisture concentration in advance, and the moisture content is quantified based on the calibration curve. Aluminum is plated while controlling the amount of water so that the amount of water contained in the molten salt plating bath is 2% by volume or less.
さらに、溶融塩試料中にイオン化していない水（Ｈ２Ｏ）として含まれる水分量をサイクリックボルタンメトリー（ＣＶ）法で定量することができる。図２はＣＶ法による水分測定方法の構成を説明する図である。ここでは、ポテンショスタットを用いたサイクリックボルタンメトリーについて説明する。水分測定の対象となる溶融塩浴４の中に、作用電極５、参照電極６，対電極７の３本の電極を置く。作用電極または／および対電極は、白金、パラジウム、イリジウム、ロジウム等の貴金属とすることが好ましい。参照電極は対象となる溶融塩浴中のイオン成分と共通する元素で構成されていると電位安定性に優れることから、アルミニウムを用いることが好ましい。それぞれの電極は測定器であるポテンショスタット８に接続される。各電極には作用電極５と参照電極６の電位差が測定者の意図する値になるようにポテンショスタットにより電圧が印加調整され、参照電極６には実質的に電流が流れない。ここで作用電極５と溶融塩浴４との境界面に生じる電圧によって、作用電極５の表面で溶融塩浴４中の遊離水分が電気分解され、対電極には電流が流れる。かかる電流の変化から電気分解の量、すなわち水分量を測定することができる。 Furthermore, the amount of water contained as non-ionized water (H 2 O) in the molten salt sample can be quantified by a cyclic voltammetry (CV) method. FIG. 2 is a diagram for explaining the configuration of a moisture measuring method by the CV method. Here, cyclic voltammetry using a potentiostat will be described. Three electrodes of a working electrode 5, a reference electrode 6 and a counter electrode 7 are placed in a molten salt bath 4 to be subjected to moisture measurement. The working electrode and / or counter electrode is preferably a noble metal such as platinum, palladium, iridium or rhodium. Since the reference electrode is excellent in potential stability when it is composed of an element common to the ionic component in the target molten salt bath, it is preferable to use aluminum. Each electrode is connected to a potentiostat 8 which is a measuring instrument. A voltage is applied to each electrode by a potentiostat so that the potential difference between the working electrode 5 and the reference electrode 6 becomes a value intended by the operator, and substantially no current flows through the reference electrode 6. Here, due to the voltage generated at the boundary surface between the working electrode 5 and the molten salt bath 4, the free water in the molten salt bath 4 is electrolyzed on the surface of the working electrode 5, and a current flows through the counter electrode. The amount of electrolysis, that is, the amount of water can be measured from the change in current.
具体的には、測定電流値の水分量への換算は次の様に行う。まず、測定対象とする溶融塩浴中に予め既知の水分を加えた試料を準備する。異なる水分量を加えた複数の試料を準備すると良い。かかる試料について実際に用いようとする前述のような測定系を構成し、電極間に電圧を印加して流れる電流値を測定する。この測定は一般的な電気化学測定装置および手法を用いることができる。サイクリックボルタンメトリーは一般に多用されている手法であり、必要な装置等も一般に入手可能なものを利用できる。一般には電圧を掃引した際の電流の変化から特定の電流値を読み出すことが行われる。準備した複数の試料について同様の測定を行い、得られた電流値と既知の水分量との関係をグラフ化、あるいは数式化等することで、検量線を得る。実際の水分測定においては、水分量が未知である測定対象について同様に測定された電流値と、先に求めた検量線から、水分量を算出することができる。赤外吸収スペクトル測定により求めた水分量とＣＶ法により求めた水分量とを合計することにより、溶融塩中の水分をより正確に定量することができる。 Specifically, the measurement current value is converted into the amount of water as follows. First, a sample is prepared by adding known moisture in advance to a molten salt bath to be measured. It is preferable to prepare a plurality of samples to which different amounts of water are added. A measurement system as described above that is actually used for such a sample is constructed, and the value of the flowing current is measured by applying a voltage between the electrodes. For this measurement, a general electrochemical measurement apparatus and method can be used. Cyclic voltammetry is a commonly used technique, and necessary apparatuses can be used that are generally available. In general, a specific current value is read from a change in current when the voltage is swept. The same measurement is performed on the plurality of prepared samples, and a calibration curve is obtained by graphing or formulating the relationship between the obtained current value and the known water content. In actual moisture measurement, the moisture content can be calculated from the current value measured in the same manner for a measurement object whose moisture content is unknown and the calibration curve obtained previously. By summing the water content determined by infrared absorption spectrum measurement and the water content determined by the CV method, the water content in the molten salt can be quantified more accurately.
次に、この溶融塩めっき浴を用いてアルミニウム構造体を製造する方法について説明する。図３は帯状樹脂に対してアルミニウムめっき処理を連続的に行うための装置の構成を模式的に示す図である。表面が導電化された帯状樹脂２２が、図の左から右に送られる構成を示す。第１のめっき槽２１ａは、円筒状電極２４と容器内壁に設けられた正電極２５およびめっき浴２３から構成される。帯状樹脂２２は円筒状電極２４に沿ってめっき浴２３の中を通過することにより、樹脂全体に均一に電流が流れやすく、均一なめっきを得ることが出来る。めっき槽２１ｂは、さらにめっきを厚く均一に付けるための槽であり複数の槽で繰り返しめっきされるように構成されている。表面に薄く金属層が設けられた帯状樹脂２２を送りローラと槽外給電負極を兼ねた電極ローラ２６により順次送りながら、めっき浴２８に通過させることでめっきを行う。複数の槽内には樹脂の両面にめっき浴２８を介して設けられた正電極２７があり、樹脂の両面により均一なめっきを付けることができる。 Next, a method for producing an aluminum structure using this molten salt plating bath will be described. FIG. 3 is a diagram schematically showing a configuration of an apparatus for continuously performing the aluminum plating process on the belt-shaped resin. A configuration in which the belt-like resin 22 whose surface is made conductive is sent from the left to the right in the figure. The first plating tank 21 a includes a cylindrical electrode 24, a positive electrode 25 provided on the inner wall of the container, and a plating bath 23. By passing the strip-shaped resin 22 along the cylindrical electrode 24 through the plating bath 23, current can easily flow uniformly throughout the resin, and uniform plating can be obtained. The plating tank 21b is a tank for applying a thick and uniform plating, and is configured to be repeatedly plated in a plurality of tanks. Plating is performed by passing the belt-like resin 22 having a thin metal layer on the surface through a plating bath 28 while sequentially feeding the belt-like resin 22 by an electrode roller 26 that also serves as a feeding roller and a negative electrode outside the tank. In the plurality of tanks, there are positive electrodes 27 provided on both surfaces of the resin via the plating bath 28, and uniform plating can be applied to both surfaces of the resin.
このようなめっき工程において、めっき液である溶融塩を適宜サンプリングして赤外吸収スペクトルを測定する。赤外吸収スペクトル測定により溶融塩中のアルミニウム酸化物イオン量及びアルミニウム水酸化物イオン量を定量でき、この値から溶融塩中の水分量を定量できる。さらに、めっき浴である溶融塩浴中に作用電極１２、参照電極１３、対電極１４をそれぞれ配置し、測定器１５によって測定することにより溶融塩浴中の水分を測定することが可能である。このように簡便な測定系によって水分量が管理された製造装置により、低コストで安定した品質のアルミニウムめっきが可能となる。 In such a plating step, an infrared absorption spectrum is measured by appropriately sampling a molten salt as a plating solution. The amount of aluminum oxide ions and the amount of aluminum hydroxide ions in the molten salt can be determined by infrared absorption spectrum measurement, and the amount of water in the molten salt can be determined from this value. Furthermore, the working electrode 12, the reference electrode 13, and the counter electrode 14 are arranged in a molten salt bath that is a plating bath, and the water in the molten salt bath can be measured by measuring with the measuring device 15. Thus, the manufacturing apparatus in which the amount of water is controlled by a simple measurement system enables aluminum plating with stable quality at low cost.
次に、本発明を実施例に基づいてさらに詳細に説明する。実施例は本発明の範囲を限定するものではない。 Next, the present invention will be described in more detail based on examples. The examples are not intended to limit the scope of the invention.
（実施例）
塩化アルミニウム（ＡｌＣｌ３）と３−メチルイミダゾリウムクロライドとを６７ｍｏｌ％：３３ｍｏｌ％の割合で混合した溶融塩を測定対象とする。かかる溶融塩に水分を（Ａ）１．０％、（Ｂ）２．０％、（Ｃ）２．５％（それぞれ体積％）加えた試料を作成した。さらに、（Ａ）〜（Ｃ）の試料を６０℃で１８時間加熱した液を試料（Ｄ）〜（Ｆ）とした。
(Example)
A molten salt obtained by mixing aluminum chloride (AlCl 3 ) and 3-methylimidazolium chloride at a ratio of 67 mol%: 33 mol% is used as a measurement target. Samples were prepared by adding water (A) 1.0%, (B) 2.0%, and (C) 2.5% (each volume%) to the molten salt. Further, liquids obtained by heating the samples (A) to (C) at 60 ° C. for 18 hours were used as samples (D) to (F).
（赤外吸収スペクトル測定による水分量測定：アルミニウム水酸化物イオン（Ａｌ−ＯＨ）検量線の作成）
塩化アルミニウム（ＡｌＣｌ３）と３−メチルイミダゾリウムクロライドとを６７ｍｏｌ％：３３ｍｏｌ％の割合で混合した溶融塩に対し、水を０％、０．５％、１．０％、１．５％（それぞれ体積％）加えた４種類の試料を作成し、２枚のシリコン板が平行から０．５°傾斜するようにスペーサ（ＰＴＦＥ）で調整したセル内に試料を封入して赤外吸収スペクトルを測定した。３３６０ｃｍ−１付近のピーク強度を読み取り、含有水分に対する吸光度の増加率（近似曲線の傾き）及び初期水分量（近似曲線の切片）を算出してアルミニウム水酸化物イオンの検量線を作成した。
(Moisture content measurement by infrared absorption spectrum measurement: preparation of aluminum hydroxide ion (Al-OH) calibration curve)
0%, 0.5%, 1.0%, 1.5% of water is added to the molten salt in which aluminum chloride (AlCl 3 ) and 3-methylimidazolium chloride are mixed at a ratio of 67 mol%: 33 mol%. 4% of each sample was added, and the sample was enclosed in a cell adjusted with a spacer (PTFE) so that the two silicon plates were inclined 0.5 ° from parallel, and the infrared absorption spectrum was obtained. It was measured. A peak intensity in the vicinity of 3360 cm −1 was read, and the absorbance increase rate (slope of the approximate curve) and the initial moisture content (intercept of the approximate curve) relative to the contained water were calculated to prepare a calibration curve for aluminum hydroxide ions.
（赤外吸収スペクトル測定による水分量測定：アルミニウム酸化物イオン（Ａｌ−Ｏ）検量線の作成）
上記の４種類の試料を１００℃で２時間加熱した後、アルミニウム水酸化物イオン検量線の作成時と同様に赤外吸収スペクトルを測定した。７９０ｃｍ−１付近のピーク強度を読み取り、含有水分に対する吸光度の増加率（近似曲線の傾き）及び初期水分量（近似曲線の切片）を算出してアルミニウム酸化物イオンの検量線を作成した。
(Measurement of water content by infrared absorption spectrum measurement: creation of aluminum oxide ion (Al-O) calibration curve)
After heating the above four types of samples at 100 ° C. for 2 hours, infrared absorption spectra were measured in the same manner as when preparing an aluminum hydroxide ion calibration curve. A peak intensity in the vicinity of 790 cm −1 was read, and an increase rate of absorbance with respect to the contained water (slope of the approximate curve) and initial water content (intercept of the approximate curve) were calculated to prepare a calibration curve for aluminum oxide ions.
（赤外吸収スペクトル測定による水分量測定）
２枚のシリコン板が平行から０．５°傾斜するようにスペーサ（ＰＴＦＥ）で調整したセル内に（Ａ）〜（Ｆ）の試料をそれぞれ封入して赤外吸収スペクトルを測定した。得られたスペクトルチャートから７９０ｃｍ−１付近のピーク強度と３３６０ｃｍ−１付近のピーク強度を読み取り、アルミニウム酸化物イオン検量線及びアルミニウム水酸化物イオン検量線を元にしてアルミニウム酸化物イオン量に基づいた水分量とアルミニウム水酸化物イオン量に基づいた水分量を求めた。
(Moisture content measurement by infrared absorption spectrum measurement)
Samples (A) to (F) were each enclosed in a cell adjusted with a spacer (PTFE) so that the two silicon plates were inclined by 0.5 ° from parallel, and the infrared absorption spectrum was measured. The peak intensity around 790 cm −1 and the peak intensity around 3360 cm −1 were read from the obtained spectrum chart, and based on the aluminum oxide ion amount based on the aluminum oxide ion calibration curve and the aluminum hydroxide ion calibration curve. The amount of water based on the amount of water and the amount of aluminum hydroxide ions was determined.
（ＣＶ法による水分量測定）
作用電極に白金電極、参照電極にアルミニウム電極、対電極に白金電極を用い、サイクリックボルタンメトリー法により水分量を測定した。測定には、ポテンショスタットとしてプリンストンアプライドリサーチ社製ＶｅｒｓａＳＴＡＴ４、作用電極としてＢＡＳ社製白金ディスク電極（φ３．０ｍｍ）、参照電極および対電極としてニラコ社製純金属（線）を使用した。電圧を＋１．１Ｖから低電位側に、掃引速度１０ｍＶ／秒となるように作用電極の電位を変化させ、その際に流れる反応電流を計測した。水の電気分解反応が１．０Ｖ〜０．５Ｖの範囲で電流ピークを示すことから、この反応が起こらず、かつ無駄な測定電位範囲が最小となるように、反応が起こるより０．１Ｖ高い電位として初期電位の１．１Ｖを設定した。掃引速度は１００ｍＶ／秒とすると電位の変化に電気分解反応速度が追従できず、測定誤差が大きくなること、１ｍＶ／秒とすると測定時間が長時間化するほか、液の流れや温度変化など外乱による測定誤差の増大に繋がることが確認できたため、１０ｍＶ／秒と設定した。
(Measurement of water content by CV method)
Using a platinum electrode as a working electrode, an aluminum electrode as a reference electrode, and a platinum electrode as a counter electrode, the water content was measured by cyclic voltammetry. For the measurement, VersaSTAT4 manufactured by Princeton Applied Research was used as a potentiostat, a platinum disk electrode (φ3.0 mm) manufactured by BAS was used as a working electrode, and a pure metal (wire) manufactured by Niraco was used as a reference electrode and a counter electrode. The potential of the working electrode was changed from +1.1 V to the low potential side so that the sweep speed was 10 mV / sec, and the reaction current flowing at that time was measured. Since the water electrolysis reaction shows a current peak in the range of 1.0 V to 0.5 V, this reaction does not occur and is 0.1 V higher than the reaction so that the useless measurement potential range is minimized. The initial potential of 1.1 V was set as the potential. If the sweep rate is 100 mV / sec, the electrolysis reaction rate cannot follow the potential change, resulting in a large measurement error. If the sweep rate is 1 mV / sec, the measurement time becomes longer, and disturbance such as liquid flow and temperature changes. Since it was confirmed that this would lead to an increase in measurement error due to the above, it was set to 10 mV / second.
（アルミニウム構造体の製造：導電化）
樹脂多孔体として厚み１ｍｍ、気孔率９５％、気孔径３００μｍのウレタン発泡体を準備し、８０ｍｍ×５０ｍｍ角に切断した。ウレタン発泡体をカーボン懸濁液に浸漬し乾燥することで、表面全体にカーボン粒子が付着した導電層を形成した。懸濁液の成分は、黒鉛＋カーボンブラック２５％を含み、樹脂バインダー、浸透剤、消泡剤を含む。カーボンブラックの粒径は０．５μｍとした。
(Manufacturing aluminum structure: Conductive)
A urethane foam having a thickness of 1 mm, a porosity of 95%, and a pore diameter of 300 μm was prepared as a resin porous body, and cut into 80 mm × 50 mm squares. By immersing the urethane foam in a carbon suspension and drying, a conductive layer having carbon particles attached to the entire surface was formed. The components of the suspension include graphite + carbon black 25%, and include a resin binder, a penetrating agent, and an antifoaming agent. The particle size of carbon black was 0.5 μm.
（アルミニウム構造体の製造：溶融塩めっき）
表面に導電層を形成したウレタン発泡体をワークとして、給電機能を有する治具にセットした後、アルゴン雰囲気かつ低水分（露点−３０℃以下）としたグローブボックス内に入れ、上記（Ａ）〜（Ｆ）の溶融塩浴（３３ｍｏｌ％ＥＭＩＣ−６７ｍｏｌ％ＡｌＣｌ３）に浸漬した。ワークをセットした治具を整流器の陰極側に接続し、対極のアルミニウム板（純度９９．９９％）を陽極側に接続し、直流電流を印加してアルミニウムをめっきした。電流密度は１０ＡＳＤ、めっき浴の温度は４５℃とした。得られた多孔質アルミニウム構造体を顕微鏡で観察し、表面が平滑で良好にめっきできているものは○、表面に凹凸があったり変色が生じたものを×とした。以上の結果を表１に示す。
(Manufacture of aluminum structures: molten salt plating)
A urethane foam having a conductive layer formed on the surface is used as a work, set in a jig having a power feeding function, and then placed in a glove box having an argon atmosphere and low moisture (dew point -30 ° C. or lower). They were immersed in (F) of a molten salt bath (33mol% EMIC-67mol% AlCl 3). A jig on which a workpiece was set was connected to the cathode side of the rectifier, a counter aluminum plate (purity 99.99%) was connected to the anode side, and a direct current was applied to plate aluminum. The current density was 10 ASD, and the temperature of the plating bath was 45 ° C. When the obtained porous aluminum structure was observed with a microscope, the surface was smooth and the surface was satisfactorily plated, and the surface was uneven or discolored. The results are shown in Table 1.
水分量合計が２．９体積％である試料（Ｃ）と、水分量合計が３．０体積％である試料（Ｆ）はめっき状態が悪い。これに対し、水分量合計が２．７体積％以下である試料（Ａ）（Ｂ）（Ｄ）（Ｆ）は良好にめっき可能であり、溶融塩中の水分量を２．７体積％以下に管理しながらめっきを行うことで良好にアルミニウムめっきできることがわかる。 The sample (C) having a total water content of 2.9% by volume and the sample (F) having a total water content of 3.0% by volume have poor plating conditions. On the other hand, samples (A), (B), (D), and (F) having a total water content of 2.7% by volume or less can be plated well, and the water content in the molten salt is 2.7% by volume or less. It can be seen that the aluminum plating can be satisfactorily performed by performing the plating while managing the film.
試料（Ｃ）、試料（Ｆ）は、Ａｌ−ＯＨに基づく水分量はそれぞれ２．６７％、１．５６％であり、２．７体積％以下であり、実際に添加した水分量に比べて低い値となっている。特に加熱処理をした試料（Ｆ）ではその差が顕著であり、Ａｌ−ＯＨの吸収スペクトルのみから推定した水分量は実際の水分量と差がある。本発明の方法によりアルミニウム酸化物イオンのＡｌ−Ｏに基づく水分量が測定可能となり、従来のよりも精度良く溶融塩に含まれる水分量を定量できることがわかる。 In samples (C) and (F), the amounts of water based on Al-OH are 2.67% and 1.56%, respectively, and are 2.7% by volume or less, compared to the amount of water actually added. The value is low. In particular, the difference is significant in the heat-treated sample (F), and the water amount estimated from the Al—OH absorption spectrum alone is different from the actual water amount. It can be seen that the amount of water based on Al—O of aluminum oxide ions can be measured by the method of the present invention, and the amount of water contained in the molten salt can be quantified more accurately than in the past.
（比較例１）
窓材としてフッ化カルシウム（ＣａＦ２）を用い、２枚の窓材を平行に対向させたセルを用いて上記の溶融塩試料（Ａ）の赤外吸収スペクトルを測定した。実施例で測定した赤外吸収スペクトルと比較例１の赤外吸収スペクトルとを、図４に示す。
(Comparative Example 1)
Calcium fluoride (CaF 2 ) was used as the window material, and the infrared absorption spectrum of the molten salt sample (A) was measured using a cell in which two window materials were opposed in parallel. The infrared absorption spectrum measured in the examples and the infrared absorption spectrum of Comparative Example 1 are shown in FIG.
（比較例２）
窓材としてシリコンを用い、２枚の窓材を平行に対向させたセルを用いて上記の溶融塩試料（Ａ）の赤外吸収スペクトルを測定した。実施例で測定した赤外吸収スペクトルと比較例２の赤外吸収スペクトルとを図５に示す。
(Comparative Example 2)
Silicon was used as the window material, and the infrared absorption spectrum of the molten salt sample (A) was measured using a cell in which two window materials were opposed in parallel. The infrared absorption spectrum measured in the examples and the infrared absorption spectrum of Comparative Example 2 are shown in FIG.
窓材としてフッ化カルシウム（ＣａＦ２）を用いた比較例１の赤外吸収スペクトルは１０００ｃｍ−１以下の領域ではノイズが大きく７９０ｃｍ−１付近のピークを観察することができない。これに対し、実施例の赤外吸収スペクトルは１０００ｃｍ−１以下でも良好に測定でき、７９０ｃｍ−１付近のピークを観察できる。また２枚のシリコン窓材を平行に対向させたセルを用いた比較例２では全体にノイズが大きい。これは干渉縞の影響によると思われる。 Infrared absorption spectrum of Comparative Example 1 using the calcium fluoride (CaF 2) at 1000 cm -1 following areas can not be observed a peak of noise is large 790cm around -1 as a window material. In contrast, infrared absorption spectra of Examples, even 1000 cm -1 or less can favorably measure, can be observed a peak around 790 cm -1. Further, in Comparative Example 2 using a cell in which two silicon window members are opposed in parallel, noise is large as a whole. This seems to be due to the influence of interference fringes.
１ 窓材
２ スペーサ
３ 試料注入部
４ 溶融塩浴
５，１２ 作用電極
６，１３ 参照電極
７，１４ 対電極
８，１５ 測定器
２１ａ，２１ｂ めっき槽
２２ 帯状樹脂
２３，２８ めっき浴
２４ 円筒状電極
２５，２７ 正電極
２６ 電極ローラ
DESCRIPTION OF SYMBOLS 1 Window material 2 Spacer 3 Sample injection | pouring part 4 Molten salt bath 5,12 Working electrode 6,13 Reference electrode 7,14 Counter electrode 8,15 Measuring device 21a, 21b Plating tank 22 Strip-like resin 23, 28 Plating bath 24 Cylindrical electrode 25, 27 Positive electrode 26 Electrode roller
Claims (5)
窓材としてシリコン又はダイヤモンドを用い、２枚の前記窓材を平行から０．３°〜０．７°の角度で傾斜するように対向させたセル内に前記溶融塩を導入し、赤外分光光度計で７９０ｃｍ−１付近のＡｌ−Ｏ結合に基づく吸収スペクトルを測定して定量することを特徴とする、アルミニウム酸化物イオンの定量方法。 A method for quantifying aluminum oxide ions derived from moisture contained in a molten salt that is a mixed salt of an organic salt and aluminum chloride,
Silicon or diamond is used as the window material, and the molten salt is introduced into a cell in which the two window materials are opposed to each other at an angle of 0.3 ° to 0.7 ° from parallel, and infrared spectroscopy is performed. A method for quantifying aluminum oxide ions, comprising measuring and quantifying an absorption spectrum based on an Al-O bond in the vicinity of 790 cm -1 with a photometer.
請求項１に記載の方法によってアルミニウム酸化物イオンを定量すると共に、
前記溶融塩の３３６０ｃｍ−１付近のＡｌ−ＯＨ結合に基づく吸収スペクトルを測定して溶融塩に含まれる水分に由来するアルミニウム水酸化物イオンを定量し、
前記アルミニウム酸化物イオンの定量結果と前記アルミニウム水酸化物イオンの定量結果に基づいて前記溶融塩に含まれる水分を定量する、溶融塩中の水分定量方法。 A moisture determination method for determining moisture contained in a molten salt that is a mixed salt of an organic salt and aluminum chloride,
Quantifying aluminum oxide ions by the method of claim 1,
Measure the absorption spectrum of the molten salt based on the Al—OH bond near 3360 cm −1 to quantify aluminum hydroxide ions derived from moisture contained in the molten salt,
A method for quantifying moisture in a molten salt, wherein the moisture contained in the molten salt is quantified based on a quantification result of the aluminum oxide ions and a quantification result of the aluminum hydroxide ions.
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