JPS59205434A - Pd base amorphous alloy for hydrogen separating and refining membrane material - Google Patents
Pd base amorphous alloy for hydrogen separating and refining membrane materialInfo
- Publication number
- JPS59205434A JPS59205434A JP7742583A JP7742583A JPS59205434A JP S59205434 A JPS59205434 A JP S59205434A JP 7742583 A JP7742583 A JP 7742583A JP 7742583 A JP7742583 A JP 7742583A JP S59205434 A JPS59205434 A JP S59205434A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- hydrogen
- amorphous
- phase
- amorphous alloy
- 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
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は水素と水素以外の気体を含んだ混合ガス中の水
素の分離および水素精製薄膜用材料に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a material for separating hydrogen in a mixed gas containing hydrogen and a gas other than hydrogen and for a hydrogen purification thin film.
従来、この種の材料は結晶質のＰｄあるいはｐ ｄ ７
７ Ａ ｇ ２３合金などのＰｄ基合金が使用されてい
る。しかしながら、これらの合金は室温附近の低温度に
おいては、特に繰返えし水素の吸蔵、放出によるα相／
β水素化物相の生成、消失に伴なって材質の靭性な著し
く害する欠点があシ、水素混合ガス中の水素の分離、精
製装置の設計上障害となっている。Traditionally, this type of material has been made of crystalline Pd or p d 7
Pd-based alloys such as 7Ag23 alloy have been used. However, at low temperatures near room temperature, these alloys undergo α phase/phase formation due to repeated hydrogen absorption and desorption.
With the formation and disappearance of the β hydride phase, there are drawbacks that seriously impair the toughness of the material, which is an obstacle in the separation of hydrogen in the hydrogen gas mixture and in the design of purification equipment.
本発明の目的は水素の透過能が大きく、がっβ水素化物
相の析出に伴なう材質の変形および破損に対して優れた
性質を有するｐｄ−ｓｔ−ｘ＜ｘ＝ｈｇ、Ａｌｌ、ｃｕ
、 Ｎｉおよび／もしくはｐｅ）系非晶質合金箔を提供
することにある。The object of the present invention is to have a pd-st-x
, Ni and/or PE) based amorphous alloy foil.
本発明は原子チでＳｉが９〜３０パーセント、Ｘ（Ｘ＝
Ａｇ、Ａｕ、Ｃｕ、Ｎｉ、Ｆｅからなる群よシ選択され
た少なくとも１元素）が２（ｌ以下、残部実質的にＰｄ
からなる合金組成で、超急冷法によって得た非晶質合金
であシ、結晶質Ｐｄ合金に見られるよりなβ水素化物相
を析出しない安定な構造の非晶質Ｐｄ−８ｉ−Ｘ系合金
箔である。In the present invention, Si is 9 to 30% of atoms, and X (X=
At least one element selected from the group consisting of Ag, Au, Cu, Ni, and Fe) is 2 (l or less, the remainder being substantially Pd)
It is an amorphous alloy obtained by an ultra-quenching method, and has an alloy composition of It's foil.
次に上記成分の限定理由について説明する。ｓｉは非晶
質組織の形成に最も有効な元素であり、通常９〜３０チ
が最適であるので上記の優に限定する。ｘ ＜ｘ＝ｈｇ
、ＡＨ，ＣＬｌ、 Ｎｚおよび／もしくはＦｅ）の添加
は合金の融点を低下させ、非晶化を促進し、熱安定性を
高める効果がある。しかし２０％を越えると非晶質形成
能が逆に悪くなる傾向にあυ、水素の透過能も減少する
傾向がおるのでＸの含有量は２０％以下に限定する。Next, the reasons for limiting the above components will be explained. Si is the most effective element for forming an amorphous structure, and usually 9 to 30 Si is optimal, so it is limited to the above-mentioned range. x <x=hg
, AH, CLl, Nz and/or Fe) has the effect of lowering the melting point of the alloy, promoting amorphization, and increasing thermal stability. However, if it exceeds 20%, the amorphous formation ability tends to deteriorate and the hydrogen permeability also tends to decrease, so the content of X is limited to 20% or less.
次に本発明の実施例を示す。本発明の効果を実証するた
めに実験した本発明合金試料６種類の合金組成を以下に
示す。Next, examples of the present invention will be shown. The alloy compositions of six types of alloy samples of the present invention tested to demonstrate the effects of the present invention are shown below.
（１）Ｐｄｓｚ Ｓ Ｉ ｔｓ 、 （２）Ｐｄ７ｓ
Ｓ ｊｘｓＡＬ１４＋（３）Ｐｄ？３ＪＩ Ｓｊ８Ａｇ
１１．２ （４）Ｐｄ７３．ｌｌ Ｓｉ８ Ｃｕ１１
．２（５）Ｐｄ７３．１１５ｉｎｓ Ｎｊｌｌ、２ （
６）Ｐｄ７３．８５ｊ１８ Ｆｅａ、２試料はいずれも
アルゴン雰囲気中で上記組成の母合金を作製後、その母
合金２０ｇｒを用いて高周波加熱で溶融し、大気中片ロ
ール法（ロール径３００震の銅ロールで回転数１２０Ｏ
ｒｐｍ）による超急冷で作製した厚さ２５〜３５μｍ、
幅約１１調のリボン状非晶質試片でおる。なお、結晶化
温度は組成によってやや異なるが３９０〜４３５Ｃで弗
る。(1) Pdsz S I ts, (2) Pd7s
S jxsAL14+(3)Pd? 3JI Sj8Ag
11.2 (4) Pd73. ll Si8 Cu11
．． 2 (5) Pd73.115ins Njll, 2 (
6) Pd73.85j18 Fea, for both samples, a master alloy with the above composition was prepared in an argon atmosphere, and then 20 gr of the master alloy was melted by high-frequency heating, and a piece of copper with a roll diameter of 300 Roll rotation speed 120O
25 to 35 μm thick, produced by ultra-quenching using
It is a ribbon-shaped amorphous specimen with a width of about 11 tones. Note that the crystallization temperature varies slightly depending on the composition, but is 390 to 435C.
水素の透過能の評価は電気化学的透過法で測定した水素
透過曲線を解析して得た水素の拡散係数（Ｄ）および試
片の陰極表面直下の水素濃度（Ｃ）を用いて定常状態の
透過電流密度（ＪＬ ＝ＦＤＣＬ−’ ）を算出して行
なった。ここでＦ＝ファラデ一定数、Ｌ＝試片の厚さで
、Ｌ＝３０μｍに規格化した。The hydrogen permeability was evaluated using the hydrogen diffusion coefficient (D) obtained by analyzing the hydrogen permeation curve measured by electrochemical permeation method and the hydrogen concentration (C) just below the cathode surface of the specimen. This was done by calculating the transmission current density (JL = FDCL-'). Here, F=Faraday constant, L=thickness of the specimen, and L=30 μm.
測定条件は陰極液： ０．３２ ＮＨｚ Ｓ ０４ ＋
２．５ｍｇ／ＡＨ２’Ｓ ｅ Ｏａ溶液、陽極液：０
．ｌＮＮａＯＨ溶液、陽極設定電位ｉＯｍＶｖ８．８Ｃ
Ｂ、測定温度；６へ６４０１である。The measurement conditions are catholyte: 0.32 NHZ S 04 +
2.5mg/AH2'S e Oa solution, anolyte: 0
．． lNNaOH solution, anode setting potential iOmVv8.8C
B. Measured temperature: 6 to 6401.
第１図に温度２８±ＩＣにおける定常状態の透過電流密
度（ＪＬ）に及ぼす水素導入時の陰極電流密度（Ｉｇ）
の影替を示す。いずれの非晶質合金も定常状態の透過電
流密度は陰極電流密度の増加とともに、はぼＪ−ｃ＜ｉ
、の関係で増大する。Figure 1 shows the effect of cathode current density (Ig) upon hydrogen introduction on steady state transmission current density (JL) at a temperature of 28±IC.
Shows the shadow change. For all amorphous alloys, the steady-state transmission current density increases as the cathode current density increases, and J-c<i
, increases due to the relationship.
またＰｄ７３．８ Ｓ ｊ ｔｓ ｋｇｓ、ｚ合金は同
一陰極電流密度では他の合金に比較してＪ−値が大きく
、水素透過能が大きいことがわかる。水素の透過効率を
Ｊ−／ｉ。値で評価するとＰｄ７３．ｓ ８ ｉｓ Ａ
ｇｓ、ｚ合金はＪ−／１゜＝０．８５〜０．９６の範囲
にあシ、Ｐｄ５ｚＳｊｔｓおよびＰｄ７１１Ｓｊ１８Ａ
ＩＪ４合金など他の非晶質合金ではＪ−／１ｔ＝０．５
５〜０．７４の範囲であった。Furthermore, it can be seen that the Pd73.8 S j ts kgs,z alloy has a larger J-value than other alloys at the same cathode current density, and has a larger hydrogen permeability. Hydrogen permeation efficiency is J-/i. When evaluated by value, Pd73. s 8 is A
gs, z alloys are in the range of J-/1° = 0.85 to 0.96, Pd5zSjts and Pd711Sj18A
For other amorphous alloys such as IJ4 alloy, J-/1t=0.5
It was in the range of 5 to 0.74.
第２図には水素吸蔵によυ、β水素化物相など異相の生
成あるいは結晶化などが生ずるか否かを調べるためにＰ
ｄ８２ Ｓ ｊ ｔｓおよびＰｄ７８Ｓｊ８Ａｕ４合金
について水素吸蔵前後のＸａ回折線図を調べた結果を示
す。ここで使用した対陰極はＣｕＫａ線、フィルターは
Ｎｉである。水素吸蔵によって２θさ４０π／１８０ｒ
ａｃｌにおける非晶質合金に特有のハロービーク位置は
わずかに低回折角側に移動するが結晶質のＰｄ合金で観
察されているよりなβ水素化物相の主成は認められず、
さらに結晶化も生じていないことがわかった。上述のハ
ロー・ピーク位置の低回折角側への移動からもわかるよ
うに、特に高陰極電流密度で、長時間、水素吸蔵すると
その吸蔵面は水素の侵入、吸蔵によって弾性的に弓状に
彎曲することが観察された。しかし吸蔵後、室温に数時
間放置すると水素の放出とともに再び速かに元に戻る。Figure 2 shows P-P to investigate whether hydrogen absorption causes the formation or crystallization of different phases such as υ and β hydride phases.
The results of examining the Xa diffraction diagrams of d82 S j ts and Pd78Sj8Au4 alloys before and after hydrogen absorption are shown. The anticathode used here was CuKa wire, and the filter was Ni. Due to hydrogen absorption, 2θ is 40π/180r
Although the halobeak position characteristic of amorphous alloys in acl shifts slightly to the lower diffraction angle side, the main formation of the β-hydride phase, which is observed in crystalline Pd alloys, is not observed.
Furthermore, it was found that no crystallization occurred. As can be seen from the shift of the halo peak position to the lower diffraction angle side mentioned above, when hydrogen is absorbed for a long time, especially at high cathode current densities, the absorption surface is elastically curved into an arcuate shape due to the penetration and absorption of hydrogen. It was observed that However, after occlusion, if left at room temperature for several hours, it quickly returns to its original state as hydrogen is released.
したがって非晶質ｐｄ−Ｓｉ−Ｘ系合金は水素吸蔵に対
して高い靭性を保持しておシ、また水素の吸蔵放出過程
は結晶質ｐｄ金合金比較して、よシ可逆的であることが
わかった。Therefore, amorphous PD-Si-X alloys maintain high toughness against hydrogen absorption, and the hydrogen absorption and release process is more reversible than that of crystalline PD gold alloys. Understood.
以上に説明するように本発明によれば水素の透過能が大
きく、かつ従来の結晶質ｐｄ金合金見られるようにα相
／β水素化物相の生成、消失に伴なう材質の劣化を生ず
ることのない非晶質Ｐｄ−５ｔ−Ｘ系合金箔を水素以外
の気体を含有する水素混合ガス中の水素の分離、精製薄
膜材料として使用することはその分離、精製効果を増大
させ、かつ経済的にも有益である。さらに本発明のｐｄ
＝Ｓｔ−Ｘ系非晶質合金箔は安価なＳｉを多量に含むた
め従来の結晶質Ｐｄ合金と比べて原料費を大巾に下げる
ことが出来る利点がある。As explained above, according to the present invention, the hydrogen permeability is large, and the material quality deteriorates due to the formation and disappearance of α phase/β hydride phase, as seen in conventional crystalline PD gold alloys. Using the unique amorphous Pd-5t-X alloy foil as a thin film material for hydrogen separation and purification in hydrogen mixed gas containing gases other than hydrogen increases the separation and purification effects and is economical. It is also beneficial. Furthermore, the pd of the present invention
=St-X type amorphous alloy foil contains a large amount of inexpensive Si, so it has the advantage of being able to significantly lower raw material costs compared to conventional crystalline Pd alloys.
なお本発明によれば非晶質ｐｄ−ｓｉ−ｘ系合金におけ
る添加元素ＸはＡｇ、Ａｕ、ｃｕ、 Ｎｉ。According to the present invention, the additive elements X in the amorphous pd-si-x alloy are Ag, Au, Cu, and Ni.
ｐｅに限るものでなく、例えばＰｔ、Ｒｈ、 Ｒｕ。Not limited to pe, for example, Pt, Rh, Ru.
Ｃｒ、 Ｍｎ、Ｇｅ、Ｃｏ等容易に、かつ安定な非晶質
組織が得られる元素およびその添加量をも包合して添加
元素Ｘと考えることもできる。The additive element X may also include elements such as Cr, Mn, Ge, Co, etc., which can easily form a stable amorphous structure, and their added amounts.
第１図は非晶質ｐｄ−ｓｉ−ｘ系合金中の水素の定常状
態の透過電流密度と陰極電流密度との関係を示すグラフ
、第２図は水素吸蔵前後のＸ線回第 １ 図
賎収ｔ！／ｌ Ｉｃ／／Ａｍ−”Figure 1 is a graph showing the relationship between the steady state transmission current density and cathode current density of hydrogen in an amorphous pd-si-x alloy, and Figure 2 is a graph showing the relationship between the X-ray cycle before and after hydrogen absorption. Collection! /l Ic//Am-”
Claims (1)
、 Ｆｅの中から選ばれる何れか１種以上を２０−以
下、残部実質的にＰｄからなる水素の分離・精製薄膜材
料用Ｐｄ基非晶質合金。Si 9-30%, Ag, Au Cu1Ni
, a Pd-based amorphous alloy for hydrogen separation and purification thin film material, consisting of at least 20 - or less selected from Fe, and the remainder substantially Pd.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7742583A JPS59205434A (en) | 1983-05-04 | 1983-05-04 | Pd base amorphous alloy for hydrogen separating and refining membrane material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7742583A JPS59205434A (en) | 1983-05-04 | 1983-05-04 | Pd base amorphous alloy for hydrogen separating and refining membrane material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59205434A true JPS59205434A (en) | 1984-11-21 |
Family
ID=13633618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7742583A Pending JPS59205434A (en) | 1983-05-04 | 1983-05-04 | Pd base amorphous alloy for hydrogen separating and refining membrane material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59205434A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03503745A (en) * | 1988-04-21 | 1991-08-22 | アライド‐シグナル・インコーポレーテッド | Nickel-palladium brazing alloy |
| US6478853B1 (en) * | 1999-03-09 | 2002-11-12 | Secretary Of Agency Of Industrial Science And Technology | Amorphous Ni alloy membrane for separation/dissociation of hydrogen, preparing method and activating method thereof |
| US7708809B2 (en) | 2002-11-20 | 2010-05-04 | Mitsubishi Materials Corporation | Hydrogen permeable membrane |
| CN107779790A (en) * | 2017-09-25 | 2018-03-09 | 北京科技大学 | A kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel and preparation method thereof |
-
1983
- 1983-05-04 JP JP7742583A patent/JPS59205434A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03503745A (en) * | 1988-04-21 | 1991-08-22 | アライド‐シグナル・インコーポレーテッド | Nickel-palladium brazing alloy |
| EP0440623B1 (en) * | 1988-04-21 | 1994-10-12 | AlliedSignal Inc. | Nickel-palladium-based brazing alloys |
| US6478853B1 (en) * | 1999-03-09 | 2002-11-12 | Secretary Of Agency Of Industrial Science And Technology | Amorphous Ni alloy membrane for separation/dissociation of hydrogen, preparing method and activating method thereof |
| DE10011104B4 (en) * | 1999-03-09 | 2009-01-22 | The Agency Of Industrial Science And Technology | Use of an amorphous Ni alloy membrane for the separation / dissociation of hydrogen |
| US7708809B2 (en) | 2002-11-20 | 2010-05-04 | Mitsubishi Materials Corporation | Hydrogen permeable membrane |
| CN107779790A (en) * | 2017-09-25 | 2018-03-09 | 北京科技大学 | A kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel and preparation method thereof |
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