JPH09279318A - Anode electrolysis electrode material made of noble-metal-base amorphous alloy capable of forming into bulky state - Google Patents
Anode electrolysis electrode material made of noble-metal-base amorphous alloy capable of forming into bulky stateInfo
- Publication number
- JPH09279318A JPH09279318A JP8088425A JP8842596A JPH09279318A JP H09279318 A JPH09279318 A JP H09279318A JP 8088425 A JP8088425 A JP 8088425A JP 8842596 A JP8842596 A JP 8842596A JP H09279318 A JPH09279318 A JP H09279318A
- Authority
- JP
- Japan
- Prior art keywords
- amorphous alloy
- amorphous
- alloy
- electrode material
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 61
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 25
- 239000007772 electrode material Substances 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 57
- 239000000956 alloy Substances 0.000 claims description 57
- 239000013526 supercooled liquid Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910000510 noble metal Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 18
- 230000004913 activation Effects 0.000 abstract description 7
- 230000009477 glass transition Effects 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 37
- 239000000460 chlorine Substances 0.000 description 25
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 24
- 229910052801 chlorine Inorganic materials 0.000 description 24
- 238000005259 measurement Methods 0.000 description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000013590 bulk material Substances 0.000 description 4
- 238000004769 chrono-potentiometry Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は，非晶質構造を有し
たままのバルク化が容易であり，且つ高耐食性を有する
非晶質合金を使用して作成した，塩化ナトリウム水溶液
を始めとする種々の水溶液の電解用電極として高活性の
電極に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention includes an aqueous sodium chloride solution prepared by using an amorphous alloy which has an amorphous structure and can be easily formed into a bulk and has high corrosion resistance. The present invention relates to a highly active electrode as an electrode for electrolysis of various aqueous solutions.
【０００２】[0002]
【従来の技術】塩化ナトリウムなどの水溶液を電解する
ための電極としては，一般的に白金（Ｐｔ）などの貴金
属が用いられている。電解用電極としては目的対象物に
対する電解効率が高いこと，長時間にわたって電解効率
が安定していること，激しい酸化環境で耐食性が高いこ
となどが要求される。2. Description of the Related Art As an electrode for electrolyzing an aqueous solution of sodium chloride or the like, a noble metal such as platinum (Pt) is generally used. Electrodes for electrolysis are required to have high electrolysis efficiency for the target object, stable electrolysis efficiency for a long time, and high corrosion resistance in a severe oxidizing environment.
【０００３】現在用いられている純Ｐｔをはじめとする
貴金属材料では，次のような問題がある。一例としてＮ
ａＣｌ溶液の純Ｐｔによる陽極電解を挙げる。The noble metal materials currently used, such as pure Pt, have the following problems. N as an example
Anodic electrolysis using pure Pt of aCl solution is given.
【０００４】ＮａＣｌ溶液中での長時間電解により，
電極の表面酸化が進行し，塩素ガス発生に有効な表面積
が減少する。その結果塩素ガス発生の過電圧が上昇し，
酸素ガス発生量が増加するため塩素発生効率が低下し，
長期的な信頼性に欠ける。By long-term electrolysis in a NaCl solution,
The surface oxidation of the electrode progresses and the effective surface area for chlorine gas generation decreases. As a result, the overvoltage of chlorine gas generation increases,
Since the oxygen gas generation amount increases, the chlorine generation efficiency decreases,
It lacks long-term reliability.
【０００５】塩素発生効率の低下した電極の再生に
は，研磨や逆電解などの表面活性化処理が必要でありメ
ンテナンスに時間がかかる。Regeneration of the electrode having a reduced chlorine generation efficiency requires surface activation treatment such as polishing and reverse electrolysis, which requires time for maintenance.
【０００６】電解後大気中に放置すると塩素発生効率
が低下する。If left in the atmosphere after electrolysis, the chlorine generation efficiency decreases.
【０００７】貴金属を利用した電極材料は高価であ
る。An electrode material using a noble metal is expensive.
【０００８】非晶質合金に関する特許としては，特公昭
５９−３５４１７号の公報にみられるような，遷移金属
−半金属系非晶質合金の組成一般を幅広く含む非晶質合
金針金の製造方法が示されている。As a patent relating to amorphous alloys, a method for producing an amorphous alloy wire including a wide range of compositions of transition metal-semimetal amorphous alloys as disclosed in Japanese Patent Publication No. 59-35417. It is shown.
【０００９】しかし，上述したような電極への応用検討
は具体的に成されていなかった。However, the application study to the electrode as described above has not been concretely made.
【００１０】また，特開昭６２−９６６３３号，特開平
４−６８３９４号および５−６５６０４号の公報に示さ
れた，非晶質合金を利用した電極材料の特許について
は，陽極電解材料としては優れたものであるけれども，
以下のような問題点があった。Further, regarding the patents of electrode materials using amorphous alloys, which are disclosed in JP-A-62-96633, JP-A-4-68394 and JP-A-5-65604, the anode electrolytic material is Excellent, but
There were the following problems.
【００１１】特開平４-６８３９４号の公報の合金に
は，合金表面にＺｎを拡散浸透することによってＺｎを
含む合金層を表面に作成したのち，アルカリまたは酸溶
液処理によってＺｎを選択的に溶解し，表面層を多孔質
化する処理を施さねばならない。In the alloy disclosed in Japanese Unexamined Patent Publication No. 4-68394, an Zn-containing alloy layer is formed on the surface of the alloy by diffusing and permeating Zn on the surface of the alloy, and then Zn is selectively dissolved by an alkali or acid solution treatment. However, the surface layer must be treated to make it porous.
【００１２】特開昭６２−９６６３３号および特開平
４−６８３９４号の公報の合金は，非晶質形成能を示す
過冷却液体域△Ｔｘも低いので非晶質のバルク化が困難
なために形状的な制約もあり，製造できる非晶質合金は
薄帯および薄片状のものに限られていた。The alloys disclosed in JP-A-62-96633 and JP-A-4-68394 have a low supercooled liquid region ΔTx exhibiting an amorphous forming ability, so that it is difficult to form an amorphous bulk. Due to shape restrictions, the amorphous alloys that can be manufactured were limited to ribbons and flakes.
【００１３】特開平５−６５６０４号の公報の合金
は，高エネルギ−密度ビ−ムを利用して表面のみを非晶
質化する手法のため，ビ−ムの境界域が結晶化したり気
孔や欠陥が生じやすく，均一な非晶質組織が得られにく
い欠点がある。The alloy disclosed in Japanese Unexamined Patent Publication No. 5-65604 uses a high energy density beam to amorphize only the surface of the alloy. There is a defect that defects are likely to occur and it is difficult to obtain a uniform amorphous structure.
【００１４】特開昭６２−９６６３３号および特開平
５−６５６０４号の公報の合金は，フッ酸による表面活
性化処理により電解に寄与する貴金属元素の濃縮化が必
要であるなどの問題がある。The alloys disclosed in JP-A-62-96633 and JP-A-5-65604 have a problem that it is necessary to concentrate a precious metal element that contributes to electrolysis by a surface activation treatment with hydrofluoric acid.
【００１５】[0015]
【発明が解決しようとする課題】前述したように，結晶
および非晶質合金のそれぞれにおいて，陽極電解電極材
料として優れた性質を示し，且つバルク化が可能である
ような材料が今までのところ満足し得るものがなかっ
た。As described above, as far as the crystalline and amorphous alloys are concerned, the materials which have excellent properties as the anode electrolytic electrode material and are capable of being bulked have so far been obtained. There was nothing satisfactory.
【００１６】本発明者は，別出願により，過冷却液体域
△Ｔｘが広く，非晶質構造を有したままのバルク化が容
易であり，且つ高耐食性を有する貴金属基非晶質合金を
提案した。The present inventor proposes, by another application, a noble metal-based amorphous alloy which has a wide supercooled liquid region ΔTx, can be easily formed into a bulk while having an amorphous structure, and has high corrosion resistance. did.
【００１７】そこで本発明においては，前述の発明した
非晶質合金を利用し，電解効率が高く活性化処理を必要
としないで耐久性が優れ，且つさまざまな形状が作成で
きる陽極電解電極材料を提供するものである。Therefore, in the present invention, an anode electrolysis electrode material which utilizes the above-mentioned amorphous alloy and has high electrolysis efficiency and excellent durability without requiring activation treatment and which can be formed into various shapes is provided. It is provided.
【００１８】[0018]
【課題を解決するための手段】本発明において「バルク
化」とは，非晶質構造を有したまま，粉末，薄帯，細線
などよりも大型（長さ１００ｍｍ，径１ｍｍ以上）に作
製可能であることを示したものである。[Means for Solving the Problems] In the present invention, "bulking" means that an amorphous structure can be produced in a larger size (100 mm in length, 1 mm or more in diameter) than a powder, a ribbon, a fine wire or the like. It means that.
【００１９】本発明において「耐食性」とは，合金表面
から塩素ガスなどが発生するような，高電位における激
しい酸化環境下でも，合金表面での腐食がみられない性
質を示したものである。In the present invention, the term "corrosion resistance" refers to the property that corrosion does not occur on the alloy surface even under a severe oxidizing environment at a high potential such as chlorine gas generated from the alloy surface.
【００２０】本発明者等は，上述の課題を達成するため
に鋭意考察研究の結果，これらの課題を満足させ得る発
明を成し遂げた。以下にそれらを述べる。The inventors of the present invention have made an invention capable of satisfying the above-mentioned problems as a result of earnest study for achieving the above-mentioned problems. These are described below.
【００２１】本発明による非晶質合金を使用した陽極
電解電極材料は，ＰｄとＰｔを必須元素として元素を原
子百分率（以下ａｔ％とする）６５から８０ａｔ％含
み，且つＰｔを１５から４０ａｔ％，そして主として残
余がＣｕおよびＳｉから成り，且つＣｕを４から１５ａ
ｔ％，Ｓｉを１０から２０ａｔ％含む合金組成で構成さ
れ，且つ５０Ｋ以上の過冷却液体域△Ｔｘを有するた
め，非晶質構造を有したままのバルク化が容易である。The anode electrolysis electrode material using the amorphous alloy according to the present invention contains Pd and Pt as essential elements in atomic percentage (hereinafter referred to as at%) of 65 to 80 at%, and Pt of 15 to 40 at%. , And the balance mainly consists of Cu and Si, and Cu is 4 to 15a
Since it is composed of an alloy composition containing t% and Si at 10 to 20 at% and has a supercooled liquid region ΔTx of 50 K or more, it is easy to form a bulk while maintaining an amorphous structure.
【００２２】本発明による非晶質合金を使用した陽極
電解電極材料は，ＰｄとＰｔおよびＮｉを必須元素とし
て元素を原子百分率（以下ａｔ％とする）５５から８０
ａｔ％含み，Ｐｔを１５から４０ａｔ％，且つＮｉを１
０から２０ａｔ％，そして主として残余がＣｕおよびＳ
ｉから成り，且つＣｕを４から１５ａｔ％，Ｓｉを１０
から２０ａｔ％含む合金組成で構成され，且つ５０Ｋ以
上の過冷却液体域△Ｔｘを有するため，非晶質構造を有
したままのバルク化が容易である。The anode electrolysis electrode material using the amorphous alloy according to the present invention has Pd, Pt and Ni as essential elements, and the atomic percentage of elements (hereinafter referred to as at%) 55 to 80.
including at%, Pt 15 to 40 at%, and Ni 1
0 to 20 at%, and the balance mainly Cu and S
i, and 4 to 15 at% Cu and 10 Si
To 20 at% of the alloy composition and having a supercooled liquid region ΔTx of 50 K or more, it is easy to form a bulk with an amorphous structure.
【００２３】本発明による非晶質合金を使用した陽極
電解電極材料は，およびにおいて過冷却液体域△Ｔ
ｘの値が５０〜７０Ｋである合金組成で構成される。The anode electrolytic electrode material using the amorphous alloy according to the present invention has a supercooled liquid region ΔT at
The alloy composition is such that the value of x is 50 to 70K.
【００２４】本発明による非晶質合金を使用した陽極
電解電極材料は，少なくともＰｄ，Ｎｉ，Ｓｉ，Ｃｕ，
Ｐｔを必須元素とし，ＰｄとＰｔとは，前者が（８０−
Ｘ）ａｔ％，後者がＸａｔ％（Ｘは１５から４０ａｔ
％），そして主として残余が実質Ｎｉ，Ｓｉ，Ｃｕから
成り、且つＣｕを４から１５ａｔ％，Ｓｉを１０から２
０ａｔ％含む合金組成で構成される。The anode electrolytic electrode material using the amorphous alloy according to the present invention is at least Pd, Ni, Si, Cu,
Pt is an essential element, and the former is (80-
X) at%, the latter is X at% (X is 15 to 40 at)
%), And the balance consists essentially of Ni, Si, Cu, and 4 to 15 at% Cu and 10 to 2 Si.
It is composed of an alloy composition containing 0 at%.
【００２５】本発明による非晶質合金を使用した陽極
電解電極材料は，からの非晶質合金を使用し，加熱
処理前では非晶質単相を示し，加熱処理後は非晶質と結
晶質の混在した構造の合金で構成される。The anode electrolysis electrode material using the amorphous alloy according to the present invention uses the amorphous alloy from, and shows an amorphous single phase before the heat treatment, and is amorphous and crystalline after the heat treatment. Composed of alloys of mixed quality.
【００２６】本発明による非晶質合金を使用した陽極
電解電極材料は，過冷却液体域での粘性流動を利用し塑
性加工したからに記載の貴金属基非晶質合金部材を
使用したものである。The anode electrolytic electrode material using the amorphous alloy according to the present invention uses the noble metal-based amorphous alloy member described in the above because it is plastically processed by utilizing viscous flow in the supercooled liquid region. .
【００２７】上述の非晶質合金の組成は，上述の特公昭
５９−３５４１７号に比較すると，陽極電解電極材料
として優れた性質を示す，非晶質構造を有したままバ
ルク化が容易である，これら２つのことについて同時に
満足し得る点である。The composition of the above-mentioned amorphous alloy exhibits excellent properties as an anode electrolytic electrode material as compared with the above-mentioned Japanese Patent Publication No. 59-35417, and can be easily formed into a bulk while having an amorphous structure. ， It is a point that these two things can be satisfied at the same time.
【００２８】次に，これらについて可能とさせる手段に
ついて述べる。Next, means for enabling these will be described.
【００２９】非晶質合金は，原子配列が無定形であるた
めの構造的特徴と様々な元素を均一に混ぜ合わせた合金
組成が作成可能な組成的特徴を持ち，高強度，高耐食，
軟磁性などに優れた機能性を示す。このことは結晶金属
では得られない組成が可能となり，電子分布の変化から
電気化学的特性も変化することを意味している。Amorphous alloys have structural characteristics that the atomic arrangement is amorphous, and composition characteristics that allow alloy compositions to be uniformly mixed with various elements, and have high strength, high corrosion resistance, and
It has excellent functionality such as soft magnetism. This means that a composition that cannot be obtained with a crystalline metal is possible, and the electrochemical characteristics change due to changes in the electron distribution.
【００３０】本発明においては，耐食性の向上に有効で
あり，電極として高触媒活性を示す貴金属元素，特に酸
化されにくく且つ安定であるＰｔに着目し，この元素を
合金の主構成金属元素Ｐｄと置換して添加することで，
優れた耐食性を示す非晶質合金を提供可能とするもので
ある。In the present invention, attention is focused on a noble metal element which is effective in improving corrosion resistance and has a high catalytic activity as an electrode, particularly Pt which is hardly oxidized and is stable, and this element is referred to as a main constituent metal element Pd of the alloy. By replacing and adding,
It is possible to provide an amorphous alloy exhibiting excellent corrosion resistance.
【００３１】また，本発明において，遷移金属元素Ｃｕ
を添加すると，合金内の原子半径の相互関係から，合金
内の原子の充填密度が増大し，無秩序充填性の高い液体
構造が形成されるため，液体からの結晶の核生成が抑制
される。このことにより大きな非晶質形成能が得られ，
過冷却液体域の温度幅△Ｔｘが増大する。In the present invention, the transition metal element Cu
Addition of Al increases the packing density of atoms in the alloy due to the mutual relationship of the atomic radii in the alloy, and forms a liquid structure with high disorder packing, thus suppressing the nucleation of crystals from the liquid. This gives a large amorphous forming ability,
The temperature range ΔTx of the supercooled liquid region increases.
【００３２】さらに，本発明において，遷移金属元素Ｓ
ｉを添加すると，合金内の原子半径の相互関係から，合
金内の原子の充填密度が増大し，無秩序充填性の高い液
体構造が形成されるため，液体からの結晶の核生成が抑
制される，という同じような効果が期待できる。 ある昇温速度で非晶質合金を加熱していくと，特定組成
の非晶質合金は結晶化温度以下の温度領域で過冷却液体
状態に遷移することが知られている（公開特許公報 平
３−１５８４４６等）。このような過冷却液体状態では
非晶質合金の粘性が急激に低下するために， 該温度領
域で閉塞鍛造等の適切な加工方法により容易に任意形状
の非晶質合金の製造が可能となる。Further, in the present invention, the transition metal element S
When i is added, the packing density of atoms in the alloy increases due to the mutual relation of the atomic radii in the alloy, and a liquid structure with high disorder packing is formed, so that nucleation of crystals from the liquid is suppressed. The same effect can be expected. It is known that when an amorphous alloy is heated at a certain temperature rising rate, the amorphous alloy having a specific composition transitions to a supercooled liquid state in a temperature range below the crystallization temperature (Patent Document 1 3-158446 etc.). In such a supercooled liquid state, the viscosity of the amorphous alloy sharply decreases, so that it is possible to easily produce an amorphous alloy of any shape by an appropriate processing method such as closed forging in this temperature range. .
【００３３】[0033]
【発明の実施の態様】続いて，本発明に関する非晶質合
金製造方法について述べる。図３は非晶質合金を作製す
る装置を示している。この器具を用いてバルク材を製造
する方法の一例について説明する。電気炉または高周波
炉により所定の組成に調製した原料合金５１をインダク
ションコイル５２で溶解し，その溶融合金をガス圧５３
によりるつぼ５４の先端ノズル孔から噴出させ，冷却し
た銅製の金型５５に接触，凝固させる。BEST MODE FOR CARRYING OUT THE INVENTION Next, a method for producing an amorphous alloy according to the present invention will be described. FIG. 3 shows an apparatus for producing an amorphous alloy. An example of a method of manufacturing a bulk material using this device will be described. A raw material alloy 51 prepared in a predetermined composition by an electric furnace or a high frequency furnace is melted by an induction coil 52, and the molten alloy is gas pressure 53
It is ejected from the tip nozzle hole of the crucible 54 and is brought into contact with the cooled copper mold 55 and solidified.
【００３４】本発明になる合金の非晶質形成能は，既存
の非晶質合金に比べて小さな冷却速度で非晶質相が生成
するため，上述の手法によりバルク材の作製が可能とな
る。また，これらの作製においては上述の装置と同程度
以上の冷却速度が得られる方法であればどの様な装置で
も本発明になる非晶質合金を作製することが可能であ
る。Since the amorphous phase of the alloy according to the present invention forms an amorphous phase at a cooling rate lower than that of existing amorphous alloys, it is possible to manufacture a bulk material by the above-mentioned method. . Further, in the production of these, the amorphous alloy according to the present invention can be produced by any apparatus as long as the cooling rate is equal to or higher than that of the apparatus described above.
【００３５】ここで，本発明により作成した非晶質合金
成分組成を特定する理由を述べる。Here, the reason for specifying the composition of the amorphous alloy prepared according to the present invention will be described.
【００３６】半金属元素Ｓｉは，本非晶質合金を作成可
能とさせるのに基本となる元素である。その添加量は１
０ａｔ％未満または２０ａｔ％超となると非晶質相を形
成しなくなるので１０〜２０ａｔ％の範囲とした。The semi-metal element Si is a basic element for making the present amorphous alloy possible. The addition amount is 1
When it is less than 0 at% or more than 20 at%, an amorphous phase is not formed, so the range was made 10 to 20 at%.
【００３７】遷移金属元素Ｃｕは，過冷却液体域を増大
させる元素で，その添加量を４〜１５ａｔ％の範囲とし
た。Ｃｕ添加量が４ａｔ％未満または１５ａｔ％超とな
ると非晶質相形成能が低下した。The transition metal element Cu is an element that increases the supercooled liquid region, and its addition amount is set to the range of 4 to 15 at%. When the amount of Cu added was less than 4 at% or more than 15 at%, the ability to form an amorphous phase decreased.
【００３８】遷移金属元素Ｎｉは，Ｃｕと比べて弱いも
のの，過冷却液体域を増大させる元素で，その添加量を
１０〜２０ａｔ％の範囲とした。Ｎｉ添加量が１０ａｔ
％未満または２０ａｔ％超となると非晶質相形成能が低
下した。Although the transition metal element Ni is weaker than Cu, it is an element that increases the supercooled liquid region, and its addition amount was set to the range of 10 to 20 at%. Ni addition amount is 10 at
If it is less than 20% or exceeds 20 at%, the amorphous phase forming ability is lowered.
【００３９】さらに，貴金属元素ＰｄおよびＰｔ，特に
Ｐｔは耐食性の向上および電極としての触媒活性に関わ
る重要な元素であり，ＰｄとＰｔの合計添加量を５５〜
８０ａｔ％の範囲とした。Ｐｔ添加量が１５から４０ａ
ｔ％の範囲とし，１５ａｔ％未満では触媒活性能が低下
し，４０ａｔ％超となると非晶質形成能が低下した。Further, the noble metal elements Pd and Pt, especially Pt, are important elements relating to the improvement of corrosion resistance and the catalytic activity as an electrode, and the total addition amount of Pd and Pt is 55-55.
The range was 80 at%. Pt addition amount is 15 to 40a
When the content is within the range of t%, the catalytic activity is lowered when the content is less than 15 at% and the amorphous forming ability is decreased when the content is more than 40 at%.
【００４０】つまり，これらが合金組成成分を特定した
理由であり，本発明により作成した非晶質合金の陽極電
解電極材料として優れた特性を示す理由である。That is, these are the reasons why the alloy composition components are specified, and the reason why the amorphous alloy produced according to the present invention exhibits excellent characteristics as the anode electrolytic electrode material.
【００４１】なお少量の他の元素，例えば２ａｔ％程度
のＦｅ，Ｃｏ，Ｐ，Ｃｒ，Ｍｎ，Ｔｉなどを含んでいて
も本発明の目的を達成できる。The object of the present invention can be achieved even if a small amount of other elements such as Fe, Co, P, Cr, Mn, and Ti are contained at about 2 at%.
【００４２】以下は，本発明に関する実施例を図面に基
づいて説明する。Embodiments relating to the present invention will be described below with reference to the drawings.
【００４３】図１は，発明された非晶質合金を使用した
装置，塩素要求量計ＣＤ−２０を示し，図２は，図１の
測定機構の詳細を示したものである。FIG. 1 shows a device using the invented amorphous alloy, chlorine demand meter CD-20, and FIG. 2 shows the details of the measuring mechanism of FIG.
【００４４】塩素要求量計ＣＤ−２０は市販されてお
り，一般によく知られている装置である。The chlorine demand meter CD-20 is commercially available and is a well-known device.
【００４５】装置の詳細（図１参照）を示すと，１は表
示器（測定値），２は表示器（時間），３は測定ビ−カ
−（100ml），４は電解電極，５は紫外線ランプ，６は
検出電極，７は撹拌器，８はブランク設定ダイヤル，９
はブランク設定スイッチ，１０はスパン設定スイッチ，
１１はスパン設定ダイヤル，１２は電源スイッチ，１３
は撹拌スイッチ，１４は測定停止スイッチ，１５は測定
時間設定ダイヤル，１６は電解電極活性化スイッチ，１
７は制御系遮断スイッチ，１８は測定ランプ，１９は測
定開始スイッチ，２０は測定ランプ電源，２１は制御
器，２２は電解電流，２３は測定ビ−カ−である。The details of the apparatus (see FIG. 1) are as follows: 1 is an indicator (measured value), 2 is an indicator (time), 3 is a measurement beaker (100 ml), 4 is an electrolytic electrode, and 5 is an electrolytic electrode. UV lamp, 6 detection electrode, 7 agitator, 8 blank setting dial, 9
Is a blank setting switch, 10 is a span setting switch,
11 is a span setting dial, 12 is a power switch, 13
Is a stirring switch, 14 is a measurement stop switch, 15 is a measurement time setting dial, 16 is an electrolytic electrode activation switch, 1
Reference numeral 7 is a control system cutoff switch, 18 is a measurement lamp, 19 is a measurement start switch, 20 is a measurement lamp power supply, 21 is a controller, 22 is an electrolytic current, and 23 is a measurement beaker.
【００４６】また図２において，本件の発明による電解
電極を使用した測定機構の詳細を示す。Further, FIG. 2 shows details of a measuring mechanism using the electrolytic electrode according to the present invention.
【００４７】図２に示したとおり，測定部各部をＮａＣ
ｌ溶液中に浸漬し，５の紫外線ランプを点灯および７の
撹拌器をＯＮにした状態で，２２の電解電流を４の本発
明による電極に流すと，４の電極では塩素ガスが主とし
て発生する。４の電極より発生した塩素ガスは，溶液中
に存在する有機物質やアンモニアなどと反応する。As shown in FIG. 2, each part of the measuring part was
When the electrolysis current of 22 is applied to the electrode of the present invention of 4 with the ultraviolet lamp of 5 being turned on and the stirrer of 7 being ON, chlorine gas is mainly generated at the electrode of 4 . The chlorine gas generated from the electrode of No. 4 reacts with the organic substances and ammonia present in the solution.
【００４８】この際塩素ガスが発生する速度は，塩素ガ
スと有機物質やアンモニアなどとの反応速度に比べて速
いために，一時的に塩素ガスが過剰になり遊離（残留塩
素）する。At this time, the chlorine gas is generated at a higher rate than the reaction rate of the chlorine gas with the organic substance or ammonia, so that the chlorine gas is temporarily excessive and is released (residual chlorine).
【００４９】この遊離塩素ガスを６の検出電極で検知す
る。この残留塩素ガスの量が一定レベルを越えると，２
１の制御器が作動し，２２の電解電流を停止させる。遊
離塩素ガスは，徐々に有機物質やアンモニアなどと反応
するので，その量は減少していく。残留塩素ガス量が
０．１ｍｇ／ｌ以下となると，２１の制御器が再作動
し，２２の電解電流を４の電極に流し，上述の反応が繰
り返し起こる。This free chlorine gas is detected by 6 detection electrodes. If the amount of residual chlorine gas exceeds a certain level, 2
The controller of 1 operates and the electrolysis current of 22 is stopped. Free chlorine gas gradually reacts with organic substances and ammonia, so the amount decreases. When the amount of residual chlorine gas becomes 0.1 mg / l or less, the controller of 21 is restarted, the electrolytic current of 22 is passed to the electrode of 4, and the above-mentioned reaction is repeated.
【００５０】このような反応が完全に終結したのち，１
の表示器で測定に要した塩素量を読み取る仕組みとなっ
ている。After such a reaction is completely terminated, 1
It is a system to read the amount of chlorine required for measurement on the display of.
【００５１】[0051]
（実施例１）表１に，本発明により開発した合金組成の
例を示す。各合金の組成はａｔ％で表されている。(Example 1) Table 1 shows an example of an alloy composition developed by the present invention. The composition of each alloy is expressed in at%.
【００５２】 （実施例２）表１に示す合金組成からなる材料を図３に
示す器具を用いて，長さ１００ｍｍ，径１ｍｍの試料を
作製した。[0052] Example 2 A sample having a length of 100 mm and a diameter of 1 mm was prepared from the material having the alloy composition shown in Table 1 by using the equipment shown in FIG.
【００５３】各試料の非晶質相の確認はＸ線回折により
行い，全て非晶質単相であることを確認した。測定例を
図４に示す。The amorphous phase of each sample was confirmed by X-ray diffraction, and it was confirmed that all the samples were an amorphous single phase. A measurement example is shown in FIG.
【００５４】本発明による非晶質合金を実施例合金と
し，既製非晶質合金を比較例合金とした。The amorphous alloy according to the present invention was used as the example alloy, and the ready-made amorphous alloy was used as the comparative example alloy.
【００５５】また，本発明による非晶質合金および上述
の比較例合金について，示差走査熱量計（ＤＳＣ）によ
り，結晶化温度Ｔｘ（Ｋ），ガラス遷移温度Ｔｇ
（Ｋ），および過冷却液体域△Ｔｘ（Ｋ）を調べ，比較
を行った。With respect to the amorphous alloy according to the present invention and the above-mentioned comparative alloys, the crystallization temperature Tx (K) and the glass transition temperature Tg were measured by a differential scanning calorimeter (DSC).
(K) and the supercooled liquid region ΔTx (K) were investigated and compared.
【００５６】表２はその一例である。Table 2 is an example.
【００５７】 表２に示したとおり，本発明の１例である非晶質合金Ｐ
ｄ56Ｓｉ18Ｃｕ6Ｐｔ20は結晶化温度Ｔｘ（Ｋ），ガラ
ス遷移温度Ｔｇ（Ｋ），および過冷却液体域の温度幅△
Ｔｘ（Ｋ）は，それぞれ７０１Ｋ，６４１Ｋ，６０Ｋで
あった。バルク化の目安として△Ｔｘ＞５０Ｋであるこ
とが要求されるが，測定例は△Ｔｘ＝６０Ｋと大きい。
それに対して上述比較例合金の実施合金は△Ｔｘ＜５０
Ｋもしくは得られないという結果となっている。[0057] As shown in Table 2, the amorphous alloy P which is an example of the present invention
d56Si18Cu6Pt20 has a crystallization temperature Tx (K), a glass transition temperature Tg (K), and a temperature range of a supercooled liquid region Δ
Tx (K) was 701K, 641K, and 60K, respectively. As a standard for bulking, ΔTx> 50K is required, but the measurement example is large, ΔTx = 60K.
On the other hand, the working alloy of the above comparative example alloy has ΔTx <50.
K or the result is that it cannot be obtained.
【００５８】このことから，過冷却液体域形成にＣｕお
よびＰｔの添加は不可欠である。From this, the addition of Cu and Pt is indispensable for forming the supercooled liquid region.
【００５９】（実施例３）上述の方法により作成した非
晶質合金を用いて，塩素発生効率を測定し，比較例合金
および純Ｐｔとの比較を行った。測定は，室温における
ｐＨ５〜６の２．５Ｍ ＮａＣｌ溶液中で，各非晶質合
金および純Ｐｔを陽極電解（それぞれ電解表面積が等し
くなるようにする）して行った。Example 3 The chlorine generation efficiency was measured using the amorphous alloy produced by the above method, and comparison was made with the comparative alloy and pure Pt. The measurement was carried out by anodic electrolysis of each amorphous alloy and pure Pt (so that the electrolytic surface areas are equal to each other) in a 2.5 M NaCl solution having a pH of 5 to 6 at room temperature.
【００６０】測定例を表３に示す。Table 3 shows a measurement example.
【００６１】 表３に示した通り，上述の比較例合金では８０％以下と
低い塩素発生効率を示す。[0061] As shown in Table 3, the above-mentioned comparative alloys show low chlorine generation efficiency of 80% or less.
【００６２】表中の比較例合金５では表面活性化処理を
施してもその塩素発生効率は７０〜８０％であり，本発
明合金では表面活性化処理を施さなくとも，９０％以上
の高い塩素発生効率を示す。In the comparative alloy 5 in the table, the chlorine generation efficiency is 70 to 80% even if the surface activation treatment is applied, and in the alloy of the present invention, even if the surface activation treatment is not applied, high chlorine of 90% or more is obtained. Indicates the generation efficiency.
【００６３】また，純Ｐｔでは約９０％の塩素発生効率
を示すのに対し，本発明により作成した非晶質合金で
も，Ｐｔ添加量が１５〜４０ａｔ％の合金で，９０％以
上の塩素発生効率が得られた。In addition, while pure Pt shows a chlorine generation efficiency of about 90%, even in the amorphous alloy prepared according to the present invention, 90% or more of chlorine is generated in the alloy containing 15 to 40 at% of Pt. Efficiency was obtained.
【００６４】つまり，本発明により作成した非晶質合金
は，純Ｐｔと比べて塩素ガス発生に有効なＰｔ量が少な
くても，９０％以上の高い塩素発生効率を示すことが分
かる。That is, it can be seen that the amorphous alloy produced according to the present invention exhibits a high chlorine generation efficiency of 90% or more, even if the amount of Pt effective for chlorine gas generation is smaller than that of pure Pt.
【００６５】（実施例４）前述したような，９０％以上
の塩素発生効率が得られた本発明による非晶質合金につ
いて，９０％以上の塩素発生効率の保持時間を測定し，
純Ｐｔとの比較を行ってみた。(Example 4) As described above, the retention time of chlorine generation efficiency of 90% or more was measured for the amorphous alloy according to the present invention from which chlorine generation efficiency of 90% or more was obtained.
I compared it with pure Pt.
【００６６】純Ｐｔは，室温におけるｐＨ５〜６の２．
５Ｍ ＮａＣｌ溶液中で陽極電解して行い，本発明によ
る非晶質合金は，室温におけるｐＨ５〜６の６．３Ｍ
ＮａＣｌ溶液中で連続陽極電解（それぞれ電解表面積が
等しくなるようにする）して測定を行った。Pure Pt has a pH of 5 to 6 at room temperature.2.
The amorphous alloy according to the present invention was subjected to anodic electrolysis in a 5M NaCl solution, and the amorphous alloy according to the present invention had a pH of 5-6 at 6.3M.
The measurement was carried out by continuous anodic electrolysis (so that the electrolytic surface areas are equal) in a NaCl solution.
【００６７】図５に測定結果を示す。The measurement results are shown in FIG.
【００６８】図５に示したとおり，本発明による非晶質
合金では純Ｐｔの３倍以上の効率保持時間を有すること
を確認した。As shown in FIG. 5, it was confirmed that the amorphous alloy according to the present invention has an efficiency retention time which is three times or more that of pure Pt.
【００６９】また，前述した溶液中での陽極電解後大気
中に放置しても，純Ｐｔのように塩素発生効率の低下が
起こることはなく，極めて安定している。Further, even when left in the atmosphere after the anodic electrolysis in the above-mentioned solution, the chlorine generation efficiency does not decrease unlike pure Pt, and it is extremely stable.
【００７０】つまり，本発明により作成した合金は，純
Ｐｔに比べて安定した塩素発生効率を保証でき，安価な
素材を提供するものである。That is, the alloy produced according to the present invention can guarantee a stable chlorine generation efficiency as compared with pure Pt, and provides an inexpensive material.
【００７１】（実施例５）前述の図５に示した本発明に
よる非晶質合金（実施例３）は，９０％以上の塩素発生
効率を示し，効率の安定性についても，純Ｐｔの３倍以
上の安定性を示すものが確認されている。(Example 5) The amorphous alloy according to the present invention (Example 3) shown in FIG. 5 has a chlorine generation efficiency of 90% or more, and the stability of the efficiency is 3% of that of pure Pt. It has been confirmed that the stability is more than doubled.
【００７２】しかし，この非晶質合金のバルク材を作成
する際に，冷却速度などの問題から一部結晶化が起こ
り，上述の特性が変化する恐れがある。However, when the bulk material of this amorphous alloy is produced, crystallization may occur partially due to problems such as cooling rate, and the above characteristics may change.
【００７３】そこで，加熱処理を施して人工的に非晶質
と結晶質構造が混在した構造を作り出し，上述の特性に
変化がみられるかどうか実験した。Therefore, a heat treatment was performed to artificially create a structure in which an amorphous and a crystalline structure were mixed, and it was tested whether or not the above-mentioned characteristics were changed.
【００７４】実験サンプルは実施例３の合金を用い，結
晶化温度Ｔｘの約５０Ｋ低い温度（６５０Ｋ）にて，３
時間加熱処理を行った。As the experimental sample, the alloy of Example 3 was used, and the temperature was reduced to about 50 K lower than the crystallization temperature Tx (650 K).
Heat treatment was performed for a time.
【００７５】加熱処理前後のＸ線回折を図６に示す。FIG. 6 shows the X-ray diffraction before and after the heat treatment.
【００７６】図６に示したとおり，加熱処理前では非晶
質単相を示す結果を得たのに対し，加熱処理後は非晶質
と結晶質の混在した構造を示す結果を得た。As shown in FIG. 6, the result showing the amorphous single phase was obtained before the heat treatment, while the result showing the structure in which the amorphous and the crystalline were mixed was obtained after the heat treatment.
【００７７】そこで，加熱処理を行った合金について塩
素発生効率および効率の安定性を調べ，加熱処理前と比
較してみた。Therefore, the chlorine generation efficiency and the stability of the efficiency of the heat-treated alloy were examined and compared with those before the heat treatment.
【００７８】その結果を図７に示す。The results are shown in FIG.
【００７９】図７に示したとおり，加熱前後で変化はほ
とんどみられない。As shown in FIG. 7, almost no change was observed before and after heating.
【００８０】つまり，本発明による非晶質合金は，完全
な非晶質構造を有していなくとも，塩素発生効率などの
特性は維持されるという性質を持つ。That is, the amorphous alloy according to the present invention has a property that characteristics such as chlorine generation efficiency are maintained even if it does not have a completely amorphous structure.
【００８１】（実施例６）本発明により作成した非晶質
合金の耐食性について，アノ−ド分極特性およびクロノ
ポテンショメトリ−により，合金表面から塩素ガスが発
生するような，高電位での激しい酸化環境下における耐
食性を検討したものを一例として示す。アノ−ド分極測
定では，本発明により作成した非晶質合金，比較例
合金および純Ｐｔとの比較を行い，室温におけるｐＨ
５〜６の２．５Ｍ ＮａＣｌ溶液中で電位を０から１５
００ｍＶまで変化させたときの電流挙動を調べた。また
クロノポテンショメトリ−測定では，上述溶液中で電流
値を２０ｍＡ／ｃｍ2一定としたときの電位挙動を調べ
た。(Example 6) Regarding the corrosion resistance of the amorphous alloy produced according to the present invention, due to the anodic polarization characteristics and chronopotentiometry, the severe oxidation at a high potential such that chlorine gas is generated from the alloy surface. An example is shown in which the corrosion resistance under the environment is examined. In the anodic polarization measurement, the amorphous alloy prepared according to the present invention, the comparative alloy and pure Pt were compared, and the pH at room temperature was measured.
The potential was changed from 0 to 15 in a 2.5 M NaCl solution of 5 to 6
The current behavior when changing to 00 mV was investigated. In the chronopotentiometry measurement, the potential behavior when the current value was kept constant at 20 mA / cm 2 in the above solution was examined.
【００８２】アノ−ド分極測定結果を図８に示す。The results of the anodic polarization measurement are shown in FIG.
【００８３】塩素ガスが主として発生する電位は１００
０〜１３００ｍＶの領域にあるが，図８に示したとお
り，の比較例合金の場合，１０００ｍＶ以前の電位領
域で既に電流値の激しい上昇が見られ，合金表面で目視
で確認できるほどの激しい酸化・溶出，つまり腐食が起
こっていることが分かる。しかし本発明により作成し
た非晶質合金および純Ｐｔにおいては，１０００ｍＶ
以前の電位領域では１００μＡ／ｃｍ2前後の低い電流
が確認され，前述の腐食は確認されず耐食性が高い。The potential mainly generated by chlorine gas is 100.
Although it is in the range of 0 to 1300 mV, as shown in FIG. 8, in the case of the comparative alloy as shown in FIG.・ It can be seen that elution, that is, corrosion has occurred. However, in the amorphous alloy and pure Pt made according to the present invention, 1000 mV
In the former potential region, a low current of around 100 μA / cm 2 was confirmed, and the above-mentioned corrosion was not confirmed, and the corrosion resistance was high.
【００８４】アノ−ド分極測定において耐食性の高い
本発明により作成した非晶質合金および純Ｐｔのクロ
ノポテンショメトリ−測定結果を図９に示す。Ｐｔに
おいては初期電位１２２０ｍＶから１〜２分経過時で電
位の急激な上昇が起こり，６０分経過時には電位は１７
４０ｍＶに達した。この電位の上昇はＰｔ表面での酸化
が進行することにより酸化皮膜が生成し，表面抵抗が大
きくなることに起因する。これに比較し本発明により
作成した非晶質合金は初期電位１１５０ｍＶから６時間
経過後も１１８０ｍＶとほぼ電位が一定である。このこ
とから本発明合金は合金表面における酸化皮膜の生成が
ほぼ起こらず，耐食性の高い合金であることが分かる。FIG. 9 shows the results of chronopotentiometry measurement of the amorphous alloy prepared according to the present invention and pure Pt having high corrosion resistance in the anodic polarization measurement. In Pt, the potential suddenly rises after 1 to 2 minutes from the initial potential of 1220 mV, and the potential increases to 17 after 60 minutes.
Reached 40 mV. This increase in potential is due to the fact that an oxide film is formed due to the progress of oxidation on the Pt surface and the surface resistance increases. In comparison, the amorphous alloy produced according to the present invention has an almost constant potential of 1180 mV even after 6 hours from the initial potential of 1150 mV. From this, it can be seen that the alloy of the present invention is a corrosion resistant alloy with almost no oxide film formed on the alloy surface.
【００８５】[0085]
【発明の効果】本発明の貴金属基非晶質合金を使用する
ことにより，安定したＮａＣｌ溶液の陽極電解などを行
い，Ｃｌ2ガスなどが合金表面から発生するような，高
電位における激しい酸化環境下でも優れた耐食性を示
し，且つ非晶質構造を有したままのバルク化が容易であ
る電極材料を提供することが出来る。EFFECTS OF THE INVENTION By using the noble metal-based amorphous alloy of the present invention, stable anodic electrolysis of NaCl solution is performed, and Cl 2 gas or the like is generated from the alloy surface. It is possible to provide an electrode material that exhibits excellent corrosion resistance even under the above conditions and that can be easily formed into a bulk while having an amorphous structure.
【図１】本発明に関わる装置，塩素要求量計ＣＤ−２０
の概略図FIG. 1 Equipment related to the present invention, chlorine demand meter CD-20
Schematic of
【図２】図１に示した装置の測定機構の詳細図FIG. 2 is a detailed view of a measurement mechanism of the device shown in FIG.
【図３】本発明による非晶質合金バルク材材を製造する
器具の一部断面正面図FIG. 3 is a partial cross-sectional front view of a device for manufacturing an amorphous alloy bulk material according to the present invention.
【図４】本発明による非晶質合金のＸ線回折パタ−ン図FIG. 4 is an X-ray diffraction pattern diagram of an amorphous alloy according to the present invention.
【図５】本発明による非晶質合金および純Ｐｔの塩素発
生効率の安定性を示す図FIG. 5 is a diagram showing the stability of chlorine generation efficiency of an amorphous alloy and pure Pt according to the present invention.
【図６】本発明による非晶質合金の加熱処理前後のＸ線
回折パタ−ン図FIG. 6 is an X-ray diffraction pattern diagram before and after heat treatment of an amorphous alloy according to the present invention.
【図７】本発明による非晶質合金の加熱処理前後の塩素
発生効率の安定性を示す図FIG. 7 is a diagram showing stability of chlorine generation efficiency before and after heat treatment of an amorphous alloy according to the present invention.
【図８】本発明による非晶質合金，比較例合金および純
Ｐｔのアノ−ド分極曲線の比較図FIG. 8 is a comparison diagram of anodic polarization curves of an amorphous alloy according to the present invention, a comparative alloy and pure Pt.
【図９】本発明による非晶質合金および純Ｐｔのクロノ
ポテンショメトリ−測定結果の比較図FIG. 9 is a comparative diagram of chronopotentiometry measurement results of an amorphous alloy and pure Pt according to the present invention.
101・・・・Ｐｄ56Ｓｉ18Ｃｕ6Ｐｔ20 102・・・・Ｐｄ77.5Ｓｉ16.5Ｃｕ6 103・・・・純Ｐｔ 101 ・ ・ ・ ・ Pd56Si18Cu6Pt20 102 ・ ・ ・ ・ Pd77.5Si16.5Cu6 103 ・ ・ ・ ・ ・ ・ Pt
───────────────────────────────────────────────────── フロントページの続き (71)出願人 591106462 茨城県 茨城県水戸市三の丸１丁目５番38号 (72)発明者 坂本 巧 茨城県水戸市元吉田町1739番地 平沼産業 株式会社内 (72)発明者 須藤 毅 茨城県水戸市元吉田町1739番地 平沼産業 株式会社内 (72)発明者 青木 崇広 茨城県水戸市元吉田町1739番地 平沼産業 株式会社内 (72)発明者 井上 明久 宮城県仙台市青葉区片平二丁目１番１号 東北大学 金属材料研究所内 (72)発明者 木村 久道 宮城県仙台市青葉区片平二丁目１番１号 東北大学 金属材料研究所内 (72)発明者 高萩 泰 茨城県東茨城郡茨城町長岡3781ー１ 茨城 県工業技術センター内 (72)発明者 鴨志田 武 茨城県東茨城郡茨城町長岡3781ー１ 茨城 県工業技術センター内 (72)発明者 斉藤 和哉 茨城県東茨城郡茨城町長岡3781ー１ 茨城 県工業技術センター内 ─────────────────────────────────────────────────── ─── Continuation of the front page (71) Applicant 591106462 Ibaraki Prefecture Ibaraki Prefecture Mito City Sannomaru 1-3-5 (72) Inventor Sakamoto Takumi Ibaraki Prefecture Mito City Motoyoshida Town 1739 Hiranuma Sangyo Co., Ltd. (72) Inventor Takeshi Sudo, 1739 Motoyoshida-cho, Mito-shi, Ibaraki, Hiranuma Sangyo Co., Ltd. (72) Inventor Takahiro Aoki 1739, Motoyoshida-cho, Mito-shi, Ibaraki, Hiranuma Sangyo Co., Ltd. (72) Inventor, Akihisa Inoue Sendai, Miyagi 2-1-1, Katahira, Aoba-ku, Tohoku University Institute for Materials Research (72) Hisashi Kimura 2-1-1, Katahira, 1-1, Aoba-ku, Sendai City, Miyagi Prefecture Inventor, Tohoku University (72) Yasushi Takahagi Ibaraki Prefecture 3781-1 Nagaoka, Ibaraki-cho, Higashi-Ibaraki District Ibaraki Prefectural Industrial Technology Center (72) Inventor Takeshi Kamoshida Ibaraki Prefecture 3781-1 Nagaoka, Ibaraki-cho, Higashi-Ibaraki District Ibaraki Prefecture Business technology in the center (72) inventor Kazuya Saito Ibaraki Prefecture Higashiibaraki-gun, Ibaraki-cho, Nagaoka 3781 - 1 Ibaraki Prefectural Industrial Technology Center in
Claims (6)
分率（以下ａｔ％とする）で６５から８０ａｔ％含み，
且つＰｔを１５から４０ａｔ％，そして主として残余が
ＣｕおよびＳｉから成り，且つＣｕを４から１５ａｔ
％，Ｓｉを１０から２０ａｔ％含む組成を有し，且つ５
０Ｋ以上の過冷却液体域△Ｔｘ（△Ｔｘ＝結晶化温度Ｔ
ｘ−ガラス遷移温度Ｔｇ）を有するため非晶質構造の貴
金属基非晶質合金を用いた陽極電解電極材料。1. Pd and Pt are essential elements, and the elements are contained at 65 to 80 at% in atomic percentage (hereinafter referred to as at%).
And Pt is 15 to 40 at% and the balance is mainly Cu and Si, and Cu is 4 to 15 at%.
%, Si having a composition of 10 to 20 at%, and 5
Supercooled liquid region over 0K ΔTx (ΔTx = crystallization temperature T
An anode electrolytic electrode material using a noble metal-based amorphous alloy having an amorphous structure because it has an x-glass transition temperature Tg).
素を原子百分率（以下ａｔ％とする）で５５から８０ａ
ｔ％含み，且つＰｔを１５から４０ａｔ％，Ｎｉを１０
から２０ａｔ％，そして残余が主としてＣｕおよびＳｉ
から成り，且つＣｕを４から１５ａｔ％，Ｓｉを１０か
ら２０ａｔ％含む組成を有し，且つ５０Ｋ以上の過冷却
液体域△Ｔｘを有するため非晶質構造の貴金属基非晶質
合金を用いた陽極電解電極材料。2. Pd, Pt, and Ni as essential elements, and the elements are 55 to 80a in atomic percentage (hereinafter referred to as at%).
t% included, Pt 15 to 40 at%, Ni 10
To 20 at% and the balance mainly Cu and Si
A noble metal-based amorphous alloy having an amorphous structure because it has a composition of 4 to 15 at% Cu and 10 to 20 at% Si and has a supercooled liquid region ΔTx of 50 K or more. Anode electrolytic electrode material.
△Ｔｘが５０〜７０Ｋである貴金属基非晶質合金を使用
した陽極電解電極材料。3. The anode electrolysis electrode material according to claim 1, which uses a noble metal-based amorphous alloy having a supercooled liquid region ΔTx of 50 to 70K.
を必須元素とし，ＰｄとＰｔは，前者が（８０-Ｘ）ａ
ｔ％，後者がＸａｔ％（Ｘは１５から４０ａｔ％），そ
して主として残余が実質Ｎｉ，Ｓｉ，Ｃｕから成り，且
つＣｕを４から１５ａｔ％，Ｓｉを１０から２０ａｔ％
含む貴金属基非晶質合金を使用した陽極電解電極材料。4. At least Pd, Ni, Si, Cu, Pt
Is an essential element, and the former is (80-X) a for Pd and Pt.
t%, the latter is Xat% (X is 15 to 40at%), and the balance is mainly Ni, Si, and Cu, and Cu is 4 to 15at% and Si is 10 to 20at%.
Anode electrolytic electrode material using a noble metal-based amorphous alloy containing.
あり，加熱処理前では非晶質単相を示し，加熱処理後は
非晶質と結晶質の混在した構造の合金を使用して作成し
た陽極電解電極材料。5. The amorphous alloy according to any one of claims 1 to 4, wherein an amorphous single phase is shown before the heat treatment, and an alloy having a structure in which amorphous and crystalline are mixed after the heat treatment. Anode electrolytic electrode material created using.
加工した請求項１から５のいずれかの貴金属基非晶質合
金を使用した陽極電解電極材料。6. An anode electrolytic electrode material using a noble metal-based amorphous alloy according to claim 1, which is plastically processed by utilizing viscous flow in a supercooled liquid region.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8088425A JPH09279318A (en) | 1996-04-10 | 1996-04-10 | Anode electrolysis electrode material made of noble-metal-base amorphous alloy capable of forming into bulky state |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8088425A JPH09279318A (en) | 1996-04-10 | 1996-04-10 | Anode electrolysis electrode material made of noble-metal-base amorphous alloy capable of forming into bulky state |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09279318A true JPH09279318A (en) | 1997-10-28 |
Family
ID=13942437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8088425A Pending JPH09279318A (en) | 1996-04-10 | 1996-04-10 | Anode electrolysis electrode material made of noble-metal-base amorphous alloy capable of forming into bulky state |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09279318A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005093113A1 (en) | 2004-03-25 | 2005-10-06 | Topy Kogyo Kabushiki Kaisha | Metallic glass laminate, process for producing the same and use thereof |
| WO2012147559A1 (en) | 2011-04-28 | 2012-11-01 | 国立大学法人東北大学 | Metallic glass nanowire manufacturing method, metallic glass nanowire manufactured thereby, and catalyst containing metallic glass nanowire |
-
1996
- 1996-04-10 JP JP8088425A patent/JPH09279318A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005093113A1 (en) | 2004-03-25 | 2005-10-06 | Topy Kogyo Kabushiki Kaisha | Metallic glass laminate, process for producing the same and use thereof |
| EP2479309A1 (en) | 2004-03-25 | 2012-07-25 | Topy Kogyo Kabushiki Kaisha | Metallic glass laminates, production methods and applications thereof |
| WO2012147559A1 (en) | 2011-04-28 | 2012-11-01 | 国立大学法人東北大学 | Metallic glass nanowire manufacturing method, metallic glass nanowire manufactured thereby, and catalyst containing metallic glass nanowire |
| US9132420B2 (en) | 2011-04-28 | 2015-09-15 | Tohoku University | Method for manufacturing metallic glass nanowire, metallic glass nanowire manufactured thereby, and catalyst containing metallic glass nanowire |
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