JP2009072685A - Hydrogen permeation separation thin film with excellent mechanical properties and hydrogen permeation separation performance - Google Patents
Hydrogen permeation separation thin film with excellent mechanical properties and hydrogen permeation separation performance Download PDFInfo
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Abstract
【課題】すぐれた機械的性質と水素透過分離性能を有する水素透過分離薄膜を提供する。
【解決手段】水素透過分離薄膜を、Ｚｒ：０．５〜２０％、Ｔｉ：１５〜４８％（ただし、Ｚｒ＋Ｔｉ：２３〜５２％）、Ｎｉ：１０〜４３％、Ｃｏ：０．５〜２５％（ただし、Ｎｉ＋Ｃｏ：２２〜４８％、かつ、Ｃｏ／Ｎｉ＜１）と、残りがＮｂと不可避不純物（ただし、Ｎｂ：１９〜４２％）からなる成分組成（組成割合は原子％）を有し、かつ、ロール急冷法による厚さ０．０７ｍｍ以下の鋳造箔材の調質熱処理材にして、Ｎｉの一部をＣｏが、また、Ｔｉの一部をＺｒ及びＮｂが置換したＮｉ（Ｃｏ）−Ｔｉ（Ｚｒ，Ｎｂ）金属間化合物と、Ｎｂに主としてＴｉ，Ｚｒ，Ｎｉ，Ｃｏが固溶したＮｂ基固溶合金の微細粒が分散分布した合金組織を有するＺｒ−Ｔｉ−Ｎｉ−Ｃｏ−Ｎｂ合金で構成する。
【選択図】図１A hydrogen permeation separation thin film having excellent mechanical properties and hydrogen permeation separation performance is provided.
A hydrogen permeation separation thin film is made of Zr: 0.5 to 20%, Ti: 15 to 48% (however, Zr + Ti: 23 to 52%), Ni: 10 to 43%, Co: 0.5 to 25 % (However, Ni + Co: 22 to 48%, and Co / Ni <1), and the rest is composed of Nb and inevitable impurities (where Nb: 19 to 42%) (composition ratio is atomic%). And a tempered heat treatment material of a cast foil material having a thickness of 0.07 mm or less by a roll quenching method, wherein Ni is partially replaced by Co and Ti is partially replaced by Zr and Nb. ) -Ti (Zr, Nb) intermetallic compound and Zr-Ti-Ni-Co having an alloy structure in which fine grains of Nb-based solid solution alloy in which Ti, Zr, Ni, and Co are mainly dissolved in Nb are dispersed and distributed. -Nb alloy.
[Selection] Figure 1
Description
この発明は、すぐれた機械的性質を有し、厚さ：０．０７ｍｍ（７０μm）以下の薄膜化が可能であり、長期に亘り安定的に優れた水素透過分離性能を発揮するＺｒ−Ｔｉ−Ｎｉ−Ｃｏ−Ｎｂ合金で構成された水素透過分離薄膜に関するものである。 The present invention has excellent mechanical properties, can be thinned to a thickness of 0.07 mm (70 μm) or less, and exhibits stable hydrogen permeation separation performance over a long period of time. The present invention relates to a hydrogen permeation separation thin film composed of a Ni—Co—Nb alloy.
近年、例えば水素燃料電池や水素ガスタービンなどのエネルギーシステムの燃料ガスとして高純度水素ガスが注目されており、この高純度水素ガスが、水を電気分解して得られた混合ガスや液化天然ガス（ＬＮＧ）を水蒸気改質して得られた混合ガスなどの水素含有原料ガスから、例えば図３に概略説明図で示される通り、外周部を例えばＮｉ製などの枠体で補強され、かつ材質的に水素だけが透過できる機能を有する厚さ：０．１〜３ｍｍの水素透過分離膜で左右両側室に仕切られ、左側室には水素含有原料ガス導入管と排ガス取出管が、右側室には高純度水素ガス取出管が取り付けられた、例えばステンレス鋼製などの反応室を中央部に設けた構造の水素高純度精製装置を用い、前記反応室を２００〜３００℃に加熱し、前記導入管より水素含有原料ガスを導入し、前記水素透過分離膜を通して分離精製された高純度水素ガスが存在する右側室の内圧を０．１ＭＰａに保持し、一方前記水素含有原料ガスの存在する左側室の内圧を０．２〜０．５ＭＰａに保持した条件で前記水素透過分離膜を通して高純度水素ガスを分離精製することにより生産されることが知られている。
また、上記の水素透過分離膜が、水素の選択的移動を前記水素透過分離膜を通して行なう、例えば炭化水素の水蒸気改質プロセスや、ベンゼン⇔シクロヘキサン反応などの水添／脱水素プロセスなどの化学反応プロセスに広く用いられていることもよく知られるところである。
In recent years, high-purity hydrogen gas has attracted attention as a fuel gas for energy systems such as hydrogen fuel cells and hydrogen gas turbines, and this high-purity hydrogen gas is a mixed gas or liquefied natural gas obtained by electrolyzing water. As shown in the schematic explanatory view of FIG. 3, for example, the outer peripheral portion is reinforced with a frame body made of Ni, for example, as shown in the schematic explanatory diagram of FIG. Thickness capable of only hydrogen permeation: 0.1 to 3 mm hydrogen permeable separation membrane partitioned into left and right side chambers, hydrogen-containing source gas introduction pipe and exhaust gas extraction pipe in left side chamber, right side chamber Is a high-purity hydrogen purifier having a structure in which a reaction chamber made of high-purity hydrogen gas is attached, for example, made of stainless steel, in the center, and the reaction chamber is heated to 200 to 300 ° C. Than tube The internal pressure of the right side chamber where the high-purity hydrogen gas separated through the hydrogen permeation separation membrane is introduced is kept at 0.1 MPa, while the internal pressure of the left side chamber where the hydrogen-containing source gas exists is introduced. It is known that it is produced by separating and refining high-purity hydrogen gas through the hydrogen permeable separation membrane under the condition that is maintained at 0.2 to 0.5 MPa.
Further, the hydrogen permeable separation membrane performs a selective hydrogen transfer through the hydrogen permeable separation membrane, for example, a chemical reaction such as a hydrocarbon steam reforming process or a hydrogenation / dehydrogenation process such as a benzene-cyclohexane reaction. It is well known that it is widely used in processes.
そして、従来の水素透過分離膜としては、
（１）Ｎｉを固溶したＮｂＴｉ相とＮｂを固溶したＮｉＴｉ相との共晶組織を素地とし、この素地に初晶ＮｂＴｉ相が分散分布した合金組織を有する、Ｎｉ−Ｔｉ−Ｎｂ合金の鋳造薄板材からなる水素透過分離膜（特許文献１）、
（２）Ｎｂを固溶した（Ｎｉ，Ｃｏ）Ｔｉ相とＮｉ、Ｃｏを固溶したＴｉＮｂ相との共晶構造、初晶として生成する前記ＴｉＮｂ相が前記共晶に囲まれている構造あるいは初晶として生成する前記（Ｎｉ，Ｃｏ）Ｔｉ相が前記共晶に囲まれている構造の複合相合金組織を有する、Ｎｉ−Ｃｏ−Ｔｉ−Ｎｂ合金の溶解鋳造材からなる水素透過分離膜（特許文献２）、
（３）水素透過性を担う相と耐水素脆化性を担う相との複合相からなるＮｉ−Ｔｉ−Ｎｂ系合金に圧延加工した溶解鋳造材からなる水素透過分離膜（特許文献３）、
（４）水素透過性を担う相と耐水素脆化性を担う相との複合相からなるＮｉ−Ｔｉ−Ｎｂ系合金に圧延加工後、１０００℃超、１００時間以上の熱処理を施した溶解鋳造材からなる水素透過分離膜（特許文献４）、
（５）Ｎｉ、Ｃｏ、Ｍｏから選ばれる少なくとも１種の元素と、Ｖ、Ｔｉ、Ｚｒ、Ｔａ、Ｈｆから選ばれる少なくとも１種の元素と、残部Ｎｂからなる液体急冷法により得たアモルファス構造のＮｂ合金からなる水素透過分離膜（特許文献５）等が知られている。
(1) A Ni-Ti-Nb alloy having an eutectic structure of an NbTi phase in which Ni is dissolved and an NiTi phase in which Nb is dissolved and an alloy structure in which the primary NbTi phase is dispersed and distributed on the base. A hydrogen permeable separation membrane made of a cast sheet material (Patent Document 1),
(2) A eutectic structure of a (Ni, Co) Ti phase in which Nb is dissolved and a TiNb phase in which Ni and Co are dissolved, or a structure in which the TiNb phase generated as a primary crystal is surrounded by the eutectic A hydrogen permeable separation membrane (Ni—Co—Ti—Nb alloy melt casting material having a composite phase alloy structure in which the (Ni, Co) Ti phase generated as the primary crystal is surrounded by the eutectic ( Patent Document 2),
(3) A hydrogen permeable separation membrane made of a melt cast material rolled into a Ni-Ti-Nb alloy composed of a composite phase of a phase responsible for hydrogen permeability and a phase responsible for hydrogen embrittlement resistance (Patent Document 3),
(4) A melt casting in which a Ni-Ti-Nb alloy composed of a composite phase of a phase responsible for hydrogen permeability and a phase responsible for hydrogen embrittlement resistance is subjected to heat treatment for over 100 hours at 1000 ° C after rolling. Hydrogen permeable separation membrane made of a material (Patent Document 4),
(5) An amorphous structure obtained by a liquid quenching method comprising at least one element selected from Ni, Co, and Mo, at least one element selected from V, Ti, Zr, Ta, and Hf, and the balance Nb. A hydrogen permeable separation membrane made of an Nb alloy (Patent Document 5) is known.
水素高純度精製装置を含め各種の化学反応装置の高性能化に対する要求はきわめて強く、これに伴い、前記装置の構造部材として用いられている水素透過分離膜にはより一段と高い水素透過分離性能を具備することが求められ、例えば、上記特許文献１〜４に示されるような従来技術においては、所望の水素透過特性と使用温度（２００℃以上）における耐水素脆化特性を有せしめるためには、水素透過特性にすぐれたＮｂ基固溶合金相と耐水素脆化特性に優れたＮｉＴｉ相の複相合金化が有効とされ、また、水素透過特性の面からは、膜厚が薄いほど有利であるため、冷間圧延等の手法を用いて薄肉化することが行われている。しかし、上記従来技術において、鋳塊から薄肉化するためには、冷間圧延と焼鈍を繰り返す必要があり、また、特許文献４にも示されるように、冷間圧延加工率の増加に対応して水素透過性能が低下することも知られており、これを回復させるために高温で長時間の熱処理を行うことは、プロセスとして非常に煩雑であるばかりか、熱処理の繰り返しによる酸化等の影響も無視できず、水素透過特性を劣化させることになる。また、上記特許文献５に示されるように、水素透過分離膜の薄膜化を図るために、ロール急冷法により結晶構造をアモルファス化することも提案されているが、水素透過は主に２５０℃以上の高温で行われるため、水素透過分離膜をロール急冷ままのアモルファス状態で使用すると水素透過中に結晶化が始まり、長期に亘る使用では水素透過性能が安定せず、実用材料としては好ましくないという問題があった。
The demand for higher performance of various chemical reactors, including high-purity hydrogen purifiers, is extremely strong, and as a result, hydrogen permeation separation membranes used as structural members of the devices have higher hydrogen permeation separation performance. For example, in the prior art as shown in Patent Documents 1 to 4 described above, in order to provide desired hydrogen permeation characteristics and hydrogen embrittlement resistance at operating temperatures (200 ° C. or higher) In addition, it is effective to form a multi-phase alloy of an Nb-based solid solution alloy phase having excellent hydrogen permeation characteristics and a NiTi phase having excellent hydrogen embrittlement resistance, and the smaller the film thickness, the more advantageous from the aspect of hydrogen permeation characteristics. Therefore, thinning is performed using a technique such as cold rolling. However, in the above prior art, in order to reduce the thickness of the ingot, it is necessary to repeat cold rolling and annealing, and as shown in Patent Document 4, it corresponds to an increase in the cold rolling processing rate. It is also known that the hydrogen permeation performance deteriorates, and performing heat treatment at a high temperature for a long time to recover this is not only very complicated as a process, but also the effect of oxidation etc. due to repeated heat treatment. It cannot be ignored and will deteriorate the hydrogen permeation characteristics. In addition, as shown in
そこで、本発明者等は、上述のような観点から、上記の各種化学反応装置の高性能化を図るべく、特にこれの構造部材である水素透過分離膜の薄膜化を可能ならしめ、長期に亘り安定的に優れた水素透過分離性能を発揮する水素透過分離薄膜を提供することを目的として、前記水素透過分離膜を構成する材料に着目し研究を行った結果、以下のような知見を得た。
即ち、水素透過分離膜を、原子％（以下、％は原子％を示す）で、Ｚｒ：０．５〜２０％、Ｔｉ：１５〜４８％（ただし、Ｚｒ＋Ｔｉ：２３〜５２％）、Ｎｉ：１０〜４３％、Ｃｏ：０．５〜２５％（ただし、Ｎｉ＋Ｃｏ：２２〜４８％、かつ、Ｃｏ／Ｎｉ＜１）と、残りがＮｂと不可避不純物（ただし、Ｎｂ：１９〜４２％）からなる成分組成に特定した上で、これの合金溶湯を、ロール急冷法により厚さ：０．０７ｍｍ以下の鋳造箔材とし、この鋳造箔材に、酸化を防止する目的で不活性ガス雰囲気中、または真空雰囲気中で、温度：３００〜１１００℃に所定時間加熱保持の条件で調質熱処理を施すと、この結果の調質熱処理材は、図１に走査型電子顕微鏡による組織写真（倍率：３５００倍）で示される通り、Ｎｉ−Ｔｉ金属間化合物におけるＮｉの一部をＣｏが置換、Ｔｉの一部をＺｒ及びＮｂが置換する状態で固溶含有したＮｉ（Ｃｏ）−Ｔｉ（Ｚｒ，Ｎｂ）金属間化合物からなる素地（図１に黒色で示されている）に、Ｎｂに主としてＴｉ，Ｚｒ，Ｎｉ，Ｃｏが固溶してなるＮｂ基固溶合金の微細粒（図１に白色で示されている）が分散分布した合金組織をもつようになり、この合金組織のＺｒ−Ｔｉ−Ｎｉ−Ｃｏ−Ｎｂ合金は、水素透過特性向上に有効な薄膜化をシンプルなプロセスにより達成すると共に、従来プロセスでは得られない本プロセス特有の非常に均質かつ微細な合金組織とすることにより、水素透過特性のさらなる向上、耐水素脆化特性の向上および薄膜の機械的特性の向上を図ることが可能であることを見出した。
また、調質熱処理は一回で十分であり繰り返し行う必要がないため、従来プロセスに比べ大幅にプロセス時間が短縮できると共に、水素透過性能低下に直結する水素透過分離膜の表面酸化も軽微に抑制することが可能となり、さらに、調質熱処理は実使用温度より高温で行うため、長時間使用による結晶構造の経時変化を抑えることができ、その結果として、長時間使用による水素透過分離膜の特性劣化を防止することが可能であることを見出した。
In view of the above, the present inventors have made it possible to reduce the thickness of the hydrogen permeable separation membrane, which is a structural member, in order to improve the performance of the various chemical reaction apparatuses described above. In order to provide a hydrogen permeation separation thin film that stably exhibits excellent hydrogen permeation separation performance, the following findings were obtained as a result of research conducted focusing on the materials constituting the hydrogen permeation separation membrane. It was.
That is, the hydrogen permeation separation membrane is atomic% (hereinafter,% indicates atomic%), Zr: 0.5 to 20%, Ti: 15 to 48% (however, Zr + Ti: 23 to 52%), Ni: 10 to 43%, Co: 0.5 to 25% (however, Ni + Co: 22 to 48%, and Co / Ni <1), and the remainder from Nb and inevitable impurities (however, Nb: 19 to 42%) After specifying this component composition, the alloy melt is made into a cast foil material having a thickness of 0.07 mm or less by a roll quenching method, and the cast foil material has an inert gas atmosphere for the purpose of preventing oxidation. Alternatively, when a tempering heat treatment is performed in a vacuum atmosphere at a temperature of 300 to 1100 ° C. under the condition of heating and holding for a predetermined time, the resulting tempered heat treatment material is a structure photograph (magnification: 3500) by a scanning electron microscope in FIG. Ni-Ti intermetallic compound A substrate made of an Ni (Co) -Ti (Zr, Nb) intermetallic compound containing a solid solution in which a part of Ni is substituted by Co and a part of Ti is substituted by Zr and Nb (shown in black in FIG. 1) Nb-based solid solution alloy fine particles (shown in white in FIG. 1) in which Ti, Zr, Ni, and Co are mainly dissolved in Nb have an alloy structure in which the particles are dispersed and distributed. The Zr-Ti-Ni-Co-Nb alloy with this alloy structure achieves a thin film effective for improving the hydrogen permeation characteristics by a simple process, and is very unique to this process that cannot be obtained by the conventional process. It has been found that by using a homogeneous and fine alloy structure, it is possible to further improve the hydrogen permeation characteristics, the resistance to hydrogen embrittlement, and the mechanical characteristics of the thin film.
In addition, tempering heat treatment is sufficient and does not need to be repeated. Therefore, the process time can be significantly shortened compared to conventional processes, and surface oxidation of the hydrogen permeable separation membrane, which directly reduces hydrogen permeation performance, can be suppressed. Furthermore, since the tempering heat treatment is performed at a temperature higher than the actual use temperature, it is possible to suppress changes over time in the crystal structure due to long-term use. It has been found that deterioration can be prevented.
この発明は、上記の研究結果に基づいてなされたものであって、
「（ａ）Ｚｒ：０．５〜２０原子％、Ｔｉ：１５〜４８原子％（ただし、Ｚｒ＋Ｔｉ：２３〜５２原子％）、Ｎｉ：１０〜４３原子％、Ｃｏ：０．５〜２５原子％（ただし、Ｎｉ＋Ｃｏ：２２〜４８原子％、かつ、Ｃｏ／Ｎｉ＜１）と、残りがＮｂと不可避不純物（ただし、Ｎｂ：１９〜４２原子％）からなる成分組成、
（ｂ）ロール急冷法による厚さ：０．０７ｍｍ以下の鋳造箔材の調質熱処理材にして、Ｎｉ−Ｔｉ金属間化合物におけるＮｉの一部をＣｏが置換、Ｔｉの一部をＺｒ及びＮｂが置換する状態で固溶含有したＮｉ（Ｃｏ）−Ｔｉ（Ｚｒ，Ｎｂ）金属間化合物と、Ｎｂに主としてＴｉ，Ｚｒ，Ｎｉ，Ｃｏが固溶してなるＮｂ基固溶合金の微細粒が分散分布した合金組織、
以上（ａ）の成分組成および（ｂ）の合金組織を有するＺｒ−Ｔｉ−Ｎｉ−Ｃｏ−Ｎｂ合金で構成したことを特徴とするすぐれた機械的性質と水素透過分離性能を有する水素透過分離薄膜。」
に特徴を有するものである。
This invention was made based on the above research results,
“(A) Zr: 0.5 to 20 atom%, Ti: 15 to 48 atom% (however, Zr + Ti: 23 to 52 atom%), Ni: 10 to 43 atom%, Co: 0.5 to 25 atom% (However, Ni + Co: 22 to 48 atomic% and Co / Ni <1), and the remaining component composition consisting of Nb and inevitable impurities (where Nb: 19 to 42 atomic%),
(B) Thickness by roll quenching method: Refining heat treatment material of cast foil material of 0.07 mm or less, Co is substituted for part of Ni in Ni—Ti intermetallic compound, and part of Ti is Zr and Nb Ni (Co) -Ti (Zr, Nb) intermetallic compound contained in a solid solution in a state where Nb is substituted, and fine particles of an Nb-based solid solution alloy in which Ti, Zr, Ni, and Co are mainly dissolved in Nb. A distributed alloy structure,
A hydrogen permeation separation thin film having excellent mechanical properties and hydrogen permeation separation performance, characterized by comprising a Zr-Ti-Ni-Co-Nb alloy having the component composition of (a) and the alloy structure of (b) . "
It has the characteristics.
つぎに、この発明の水素透過分離薄膜において、これを構成するＺｒ−Ｔｉ−Ｎｉ−Ｃｏ−Ｎｂ合金の組成等を上記の通りに限定した理由を説明する。 Next, the reason why the composition of the Zr—Ti—Ni—Co—Nb alloy constituting the hydrogen permeation separation thin film of the present invention is limited as described above will be described.
（ａ）Ｎｂ
Ｎｂ成分は、Ｎｉ−Ｔｉ系金属間化合物においてＴｉの一部を置換した形で含有され、Ｎｉ−Ｔｉ系金属間化合物からなる素地を形成し、優れた強度を有するものの水素透過性能に乏しい前記素地の水素透過特性を改善するほか、主としてＴｉ、Ｚｒを固溶含有し非常に優れた水素透過特性を有するＮｂ基固溶合金を形成して、前記素地中に微細粒として分散分布し、すぐれた水素透過分離性能を発揮する作用があるが、その含有量が１９原子％未満では薄膜の厚さを０．０７ｍｍ以下に薄肉化しても所望のすぐれた水素透過分離性能を発揮させることが困難になり、一方、その含有量が４２原子％を越えると、水素透過膜の機械的強度に低下傾向が見られ、水素透過膜の厚さを０．０７ｍｍ以下に薄膜化することが困難になることから、その含有量を１９〜４２原子％と定めた。
(A) Nb
The Nb component is contained in a form in which a part of Ti is substituted in the Ni-Ti intermetallic compound, forms a substrate made of the Ni-Ti intermetallic compound, has excellent strength, but has poor hydrogen permeation performance In addition to improving the hydrogen permeation characteristics of the substrate, it forms an Nb-based solid solution alloy containing mainly Ti and Zr in a solid solution and having excellent hydrogen permeation characteristics, and is dispersed and distributed as fine grains in the substrate. However, if the content is less than 19 atomic%, it is difficult to achieve the desired excellent hydrogen permeation separation performance even if the thickness of the thin film is reduced to 0.07 mm or less. On the other hand, if the content exceeds 42 atomic%, the mechanical strength of the hydrogen permeable membrane tends to decrease, and it becomes difficult to reduce the thickness of the hydrogen permeable membrane to 0.07 mm or less. From that The content was determined to 19 to 42 atomic%.
（ｂ）Ｚｒ
Ｚｒ成分は、Ｔｉ成分と共存して、Ｎｉ成分、Ｃｏ成分及び少量のＮｂ成分と共に、水素透過時における延性と機械的強度に優れるＢ２結晶構造を有するＮｉ−Ｔｉ系金属間化合物からなる素地を形成し、その優れた機械的強度を維持しつつ水素透過特性を向上させる作用を有し、また、Ｔｉ成分や少量のＮｉ成分及びＣｏ成分と共にＮｂ基固溶合金相に固溶して水素透過特性に優れたＮｂ基固溶合金微細粒を形成する作用を有する。
さらに、ロール急冷法による鋳造箔材の製造に際し、合金溶湯の流動性を高める作用を有し、鋳造箔材からなる薄膜の延性を向上させる効果も有する。
そして、Ｚｒ成分の含有量が０．５原子％未満では、前記合金溶湯の流動性向上作用と鋳造箔材からなる薄膜の延性向上効果が不十分となり、一方、Ｚｒ成分の含有量が２０原子％を超えると、調質熱処理後の機械的強度に低下傾向がみられることから、Ｚｒ成分の含有量は０．５〜２０原子％と定めた。
また、Ｚｒ成分の含有量が上記数値範囲内であっても、Ｔｉ成分との合計含有量Ｚｒ＋Ｔｉが２３原子％未満では、Ｎｉ＋Ｃｏ成分と共に構成する素地の体積率が不足し、機械的強度に低下傾向がみられ、一方、Ｚｒ＋Ｔｉが５２原子％を超えると、高水素透過特性を有するＮｂ基固溶合金微細粒の体積率が不足し、水素透過特性に低下傾向がみられるようになることから、Ｔｉ成分との合計含有量Ｚｒ＋Ｔｉを２３〜５２原子％と定めた。
(B) Zr
The Zr component coexists with the Ti component, and together with the Ni component, the Co component, and a small amount of Nb component, is a base made of a Ni-Ti intermetallic compound having a B2 crystal structure with excellent ductility and mechanical strength during hydrogen permeation. It has the effect of improving the hydrogen permeation characteristics while maintaining its excellent mechanical strength. Also, it is dissolved in the Nb-based solid solution alloy phase together with the Ti component and a small amount of Ni component and Co component to allow hydrogen permeation. It has the effect | action which forms the Nb group solid solution alloy fine grain excellent in the characteristic.
Furthermore, in the production of the cast foil material by the roll quenching method, it has the effect of improving the fluidity of the molten alloy, and also has the effect of improving the ductility of the thin film made of the cast foil material.
If the Zr component content is less than 0.5 atomic%, the fluidity improving effect of the molten alloy and the ductility improving effect of the thin film made of the cast foil material are insufficient, while the Zr component content is 20 atoms. If it exceeds 50%, the mechanical strength after the tempering heat treatment tends to decrease, so the content of the Zr component is determined to be 0.5 to 20 atomic%.
Moreover, even if the content of the Zr component is within the above numerical range, if the total content Zr + Ti with the Ti component is less than 23 atomic%, the volume ratio of the substrate constituted with the Ni + Co component is insufficient and the mechanical strength is reduced. On the other hand, when Zr + Ti exceeds 52 atomic%, the volume ratio of the Nb-based solid solution alloy fine particles having high hydrogen permeation characteristics is insufficient, and the hydrogen permeation characteristics tend to decrease. The total content Zr + Ti with the Ti component was determined to be 23 to 52 atomic%.
（ｃ）Ｃｏ
Ｃｏ成分は、Ｎｉ成分と共存して、Ｔｉ成分、Ｚｒ成分及び少量のＮｂ成分と共に、水素透過時における延性と機械的強度に優れるＢ２結晶構造を有するＮｉ−Ｔｉ系金属間化合物からなる素地を形成し、その優れた機械的強度を一層向上させる作用を有し、また、Ｔｉ成分やＺｒ成分、少量のＮｉ成分と共にＮｂ基固溶合金相からなる微細粒に少量固溶して、当該固溶合金微細粒の耐水素脆化特性を改善する作用を有する。
さらに、ロール急冷法により得た鋳造箔材の調質熱処理におけるＮｂ基固溶合金相とＮｉ−Ｔｉ系金属間化合物の結晶化や再結晶プロセスで、機械的強度の低下要因となる結晶粒の粗大化を抑制すると共に各相の相安定性を向上させ、薄膜の機械的強度を低下させる一要因となる脆化相の析出を抑制する効果を有する。
そして、Ｃｏ成分の含有量が０．５原子％未満では、前記鋳造箔材の調質熱処理後の相安定性効果が不十分であり、一方、Ｃｏ成分の含有量が２５原子％を超える場合、あるいは、Ｃｏ成分の含有量がＮｉ成分のそれを超える場合、延性に低下傾向がみられるようになることから、Ｃｏ成分の含有量は０．５〜２５原子％、かつ、Ｃｏ／Ｎｉ＜１と定めた。
また、Ｃｏ成分の含有量が上記数値範囲内であっても、Ｎｉ成分との合計含有量Ｃｏ＋Ｎｉが２２原子％未満では、Ｚｒ＋Ｔｉ成分と共に構成する素地の体積率が不足し、機械的強度に低下傾向がみられ、一方、Ｃｏ＋Ｎｉが４８原子％を超えると、高水素透過特性を有するＮｂ基固溶合金微細粒の体積率が不足し、水素透過特性に低下傾向がみられるようになることから、Ｎｉ成分との合計含有量Ｃｏ＋Ｎｉを２２〜４８原子％と定めた。
(C) Co
The Co component coexists with the Ni component, together with the Ti component, Zr component, and a small amount of Nb component, and a base made of a Ni-Ti intermetallic compound having a B2 crystal structure with excellent ductility and mechanical strength during hydrogen permeation. It has the effect of further improving its excellent mechanical strength, and is dissolved in a small amount in fine particles comprising an Nb-based solid solution alloy phase together with a Ti component, a Zr component, and a small amount of Ni component. It has the effect of improving the hydrogen embrittlement resistance of molten alloy fine grains.
Furthermore, in the crystallization and recrystallization process of the Nb-based solid solution alloy phase and the Ni-Ti intermetallic compound in the tempering heat treatment of the cast foil material obtained by the roll quenching method, the crystal grains that cause a decrease in mechanical strength It has the effect of suppressing coarsening and improving the phase stability of each phase and suppressing the precipitation of the embrittled phase, which is one factor that reduces the mechanical strength of the thin film.
If the Co component content is less than 0.5 atomic%, the phase stability effect after the tempering heat treatment of the cast foil material is insufficient, while the Co component content exceeds 25 atomic%. Alternatively, when the content of the Co component exceeds that of the Ni component, the ductility tends to decrease. Therefore, the content of the Co component is 0.5 to 25 atomic%, and Co / Ni < 1 was determined.
Even if the content of the Co component is within the above numerical range, if the total content Co + Ni with the Ni component is less than 22 atomic%, the volume ratio of the base material constituted with the Zr + Ti component is insufficient and the mechanical strength decreases. On the other hand, when Co + Ni exceeds 48 atomic%, the volume ratio of the Nb-based solid solution alloy fine particles having high hydrogen permeation characteristics is insufficient, and the hydrogen permeation characteristics tend to decrease. The total content Co + Ni with the Ni component was determined to be 22 to 48 atomic%.
（ｄ）ＴｉおよびＮｉ
ＴｉおよびＮｉ成分には、Ｚｒ成分、Ｃｏ成分などと共に、素地を構成するＮｉ−Ｔｉ系金属間化合物を形成して薄膜の機械的強度を担保し、もって、０．０７ｍｍ以下の厚さでの実用化を可能とするほか、前記素地に微細粒として分散分布するＮｂ基固溶合金に固溶して、これの機械的強度を高める作用があるが、ＴｉおよびＮｉのいずれかの含有量が、Ｔｉ：１５原子％未満、Ｎｉ：１０原子％未満になると、薄膜に所望の機械的強度を確保することができず、この０．０７ｍｍ以下の厚さでの実用化が困難となり、一方ＴｉおよびＮｉのいずれかの含有量でも、Ｔｉ：４８原子％、Ｎｉ：４３原子％を超えると、水素透過分離性能の低下が避けられなくなることから、その含有量を、それぞれＴｉ：１５〜４８原子％、Ｎｉ：１０〜４３原子％と定めた。
(D) Ti and Ni
The Ti and Ni components, together with the Zr component, Co component, etc., form Ni-Ti intermetallic compounds constituting the substrate to ensure the mechanical strength of the thin film, so that the thickness is 0.07 mm or less. In addition to enabling practical use, it has the effect of increasing the mechanical strength of the Nb-based solid solution alloy dispersed and distributed as fine grains in the substrate, but the content of either Ti or Ni When Ti is less than 15 atomic% and Ni is less than 10 atomic%, a desired mechanical strength cannot be ensured for the thin film, and practical use at a thickness of 0.07 mm or less becomes difficult. Even when the content of Ti and Ni exceeds 48 atomic% and Ni: 43 atomic%, the reduction of hydrogen permeation separation performance is unavoidable. Therefore, the content of Ti is 15 to 48 atoms, respectively. %, Ni: 10-4 It was defined as atomic percent.
この発明の水素透過分離薄膜は、Ｎｉ（Ｃｏ）−Ｔｉ（Ｚｒ，Ｎｂ）金属間化合物からなる素地に、主としてＴｉとＺｒが固溶しているＮｂ基固溶合金相が微細粒として均一に分散分布した組織を有することから、素地のすぐれた耐水素脆化特性と機械的強度により０．０７ｍｍ以下の厚さへの薄肉化が可能となり、この薄肉化による水素透過分離性能の向上と均一に分散分布した微細粒の優れた水素透過分離性能と相俟って、これを各種の化学反応装置に用いた場合、優れた水素透過分離性能を長期に亘って発揮するようになるのである。 In the hydrogen permeable separation thin film of the present invention, the Nb-based solid solution alloy phase in which Ti and Zr are mainly solid-dissolved is uniformly formed as fine particles on a substrate made of an Ni (Co) -Ti (Zr, Nb) intermetallic compound. Because it has a distributed structure, it can be thinned to a thickness of 0.07 mm or less due to excellent hydrogen embrittlement resistance and mechanical strength of the substrate. This thinning improves the hydrogen permeation separation performance and makes it uniform. Combined with the excellent hydrogen permeation separation performance of the fine particles dispersed and distributed, when this is used in various chemical reaction apparatuses, the excellent hydrogen permeation separation performance is exhibited over a long period of time.
つぎに、この発明の水素透過分離薄膜を実施例により具体的に説明する。 Next, the hydrogen permeation separation thin film of the present invention will be specifically described with reference to examples.
原料として、純度：９９．９％の高純度Ｎｂショット材、同９９．９％の高純度Ｎｉショット材、同９９．５％の高純度Ｔｉスポンジ材、同９９．９％の高純度Ｃｏショット材および同９９．５％の高純度Ｚｒスポンジ材を用い、これら原料をそれぞれ表１、２に示される割合に配合し、高純度Ａｒ雰囲気中でアーク溶解して、鋳塊とし、この鋳塊を２０ｍｍ角に切断した状態で、底部に長さ：２０ｍｍ×幅：０．３ｍｍの寸法をもったスリットが形成された黒鉛ルツボに装入し、０．０６ＭＰａの減圧アルゴン雰囲気中で高周波誘導加熱炉で再溶解し、この溶湯を前記スリットから１０〜２０ｍ／ｓｅｃの範囲内の所定のロール速度で回転する水冷銅ロールの表面に０．０５ＭＰａの噴射圧で吹き付けて、いずれも長さ：２０ｍ×幅：２０ｍｍの平面寸法を有するが、厚さはそれぞれ表１、２に示される平均厚さ（任意５ヶ所の平均値）をもったＺｒ−Ｔｉ−Ｎｉ−Ｃｏ−Ｎｂ合金の鋳造箔材を単ロール急冷法により形成し、つぎに、これを真空炉に装入し、１０−２Ｐａ以下の真空中、それぞれ３００〜１１００℃の範囲内の所定の温度に５時間保持後炉冷の条件で調質熱処理を施し、調質熱処理後、幅：２０ｍｍ×長さ：６０ｍｍの平面寸法に切り出すことにより本発明の水素透過分離薄膜（以下、本発明水素透過薄膜という）１〜２０をそれぞれ製造した。
なお、本実施例では単ロール急冷法により鋳造箔材を形成したが、溶湯から十分な冷却速度でリボン状に成形できる方法であれば、製造方法はこれに限られず、例えば、双ロール急冷法で鋳造箔材を作製することも勿論可能である。
Purity: 99.9% high purity Nb shot material, 99.9% high purity Ni shot material, 99.5% high purity Ti sponge material, 99.9% high purity Co shot Material and 99.5% high-purity Zr sponge material, these raw materials were blended in the proportions shown in Tables 1 and 2, respectively, and arc-melted in a high-purity Ar atmosphere to form an ingot. Is cut into a 20 mm square and charged into a graphite crucible having a slit with a length: 20 mm × width: 0.3 mm at the bottom, and induction induction heating in a reduced pressure argon atmosphere of 0.06 MPa Remelted in a furnace, this molten metal was sprayed at a spray pressure of 0.05 MPa on the surface of a water-cooled copper roll rotating at a predetermined roll speed within a range of 10 to 20 m / sec from the slit. × Width: 20m A single roll of a cast foil material of Zr—Ti—Ni—Co—Nb alloy having a planar dimension of m but having an average thickness shown in Tables 1 and 2 (average value of five arbitrary locations). It is formed by a rapid cooling method, and then charged into a vacuum furnace, kept at a predetermined temperature in the range of 300 to 1100 ° C. for 5 hours in a vacuum of 10 −2 Pa or less, and adjusted under conditions of furnace cooling. After the heat treatment, the hydrogen permeation separation thin film (hereinafter referred to as the present invention hydrogen permeation thin film) 1 to 20 of the present invention was produced by cutting into a plane dimension of width: 20 mm × length: 60 mm after the temper heat treatment.
In this example, the cast foil material was formed by a single roll quenching method, but the production method is not limited to this as long as it can be formed into a ribbon shape from a molten metal at a sufficient cooling rate, for example, a twin roll quenching method. Of course, it is also possible to produce a cast foil material.
比較の目的で、同じく原料として、純度：９９．９％の高純度Ｎｂショット材、同９９．９％の高純度Ｎｉショット材、同９９．５％の高純度Ｔｉスポンジ材、同９９．９％の高純度Ｃｏショット材および同９９．５％の高純度Ｚｒスポンジ材を用い、これら原料をそれぞれ表３の種別１〜７に示される割合に配合し、高純度Ａｒ雰囲気中でアーク溶解し、鋳造して、直径：８０ｍｍ×厚さ：１０ｍｍの寸法をもったＺｒ−Ｔｉ−Ｎｉ−Ｃｏ−Ｎｂ合金鋳塊とし、この鋳塊から、放電加工にて、いずれも幅：２０ｍｍ×長さ：６０ｍｍの平面寸法を有するが、厚さをそれぞれ表３に示される平均厚さ（任意５ヶ所の平均値）とした薄板材に切出すことにより、鋳物切出し材からなる水素透過分離膜（以下、比較水素透過膜という）１〜７をそれぞれ製造した。 For the purpose of comparison, the same raw materials were used: high purity Nb shot material of 99.9%, high purity Ni shot material of 99.9%, high purity Ti sponge material of 99.5%, 99.9%. % High-purity Co shot material and 99.5% high-purity Zr sponge material, these raw materials were blended in the proportions shown in types 1 to 7 in Table 3, respectively, and arc-melted in a high-purity Ar atmosphere. , Cast into a Zr—Ti—Ni—Co—Nb alloy ingot having a diameter: 80 mm × thickness: 10 mm, and from this ingot, both are width: 20 mm × length by electric discharge machining. : A hydrogen permeation separation membrane (hereinafter referred to as a casting permeation membrane) made of a cast material by cutting into a thin plate material having a planar dimension of 60 mm, each having an average thickness shown in Table 3 (an average value of five arbitrary positions). (Referred to as a comparative hydrogen permeable membrane) Each was manufactured.
同じく比較の目的で、原料として、純度：９９．９％の高純度Ｎｂショット材、同９９．９％の高純度Ｎｉショット材、同９９．５％の高純度Ｔｉスポンジ材、同９９．９％の高純度Ｃｏショット材および同９９．９％の高純度Ｚｒショット材を用い、これら原料をそれぞれ表３の種別８〜１０に示される割合に配合し、実施例と同様な方法で、長さ：２０ｍ×幅：２０ｍｍの平面寸法を有するが、厚さはそれぞれ表３に示される平均厚さ（任意５ヶ所の平均値）をもったＺｒ−Ｔｉ−Ｎｉ−Ｃｏ−Ｎｂ合金の鋳造箔材を形成し、調質熱処理を行わずロール急冷ままで、幅：２０ｍｍ×長さ：６０ｍｍの平面寸法に切り出すことによりアモルファス材からなる水素透過分離薄膜（比較水素透過膜）８〜１０をそれぞれ製造した。 Similarly, for the purpose of comparison, as a raw material, purity: 99.9% high purity Nb shot material, 99.9% high purity Ni shot material, 99.5% high purity Ti sponge material, 99.9% % High-purity Co shot material and 99.9% high-purity Zr shot material, these raw materials were blended in proportions shown in types 8 to 10 in Table 3, respectively, Zr—Ti—Ni—Co—Nb alloy casting foil having a planar dimension of 20 m × width: 20 mm, each having an average thickness shown in Table 3 (average value of five arbitrary positions) A hydrogen permeation separation thin film (comparative hydrogen permeation membrane) 8 to 10 made of an amorphous material is formed by cutting the material into a plane dimension of width: 20 mm × length: 60 mm while forming a material and performing rapid cooling without tempering heat treatment. Manufactured.
同じく比較の目的で、原料として、純度：９９．９％の高純度Ｎｂショット材、同９９．９％の高純度Ｎｉショット材、同９９．５％の高純度Ｔｉスポンジ材、同９９．５％の高純度Ｚｒスポンジ材を用い、これら原料をそれぞれ表３の種別１１、１２に示される割合に配合し、高純度Ａｒ雰囲気中でアーク溶解して、直径：８０ｍｍ×厚さ：１０ｍｍの寸法をもった鋳塊とした。この鋳塊から、放電加工にて、いずれも幅：２０ｍｍ×長さ：６０ｍｍの平面寸法、厚さ：約０．１５ｍｍの薄板材に切り出した。これをロール圧延機により圧延率６０％の冷間圧延を実施し、鋳物切出し材からなる厚み約０．０６ｍｍの水素透過分離膜（比較水素透過膜）１１、１２を製造した。 Similarly, for the purpose of comparison, as a raw material, the purity: 99.9% high purity Nb shot material, 99.9% high purity Ni shot material, 99.5% high purity Ti sponge material, 99.5% % Of high-purity Zr sponge material, these raw materials were blended in the proportions shown in types 11 and 12 of Table 3, respectively, and melted in an arc in a high-purity Ar atmosphere. Diameter: 80 mm x thickness: 10 mm It was made into an ingot with. Each of these ingots was cut into a thin plate material having a width of 20 mm × length of 60 mm and a thickness of about 0.15 mm by electric discharge machining. This was subjected to cold rolling at a rolling rate of 60% using a roll rolling machine to produce hydrogen permeable separation membranes (comparative hydrogen permeable membranes) 11 and 12 having a thickness of about 0.06 mm made of a cast material.
同じく比較の目的で、原料として、純度：９９．９％の高純度Ｎｂショット材、同９９．９％の高純度Ｎｉショット材、同９９．５％の高純度Ｔｉスポンジ材、同９９．５％の高純度Ｚｒスポンジ材を用い、これら原料をそれぞれ表３の種別１３、１４に示される割合に配合し、高純度Ａｒ雰囲気中でアーク溶解して、直径：８０ｍｍ×厚さ：１０ｍｍの寸法をもった鋳塊とし、この鋳塊から、放電加工にて、いずれも幅：２０ｍｍ×長さ：６０ｍｍの平面寸法、厚さ：約０．１５ｍｍの薄板材に切り出した。その後、種別１３に対しては圧延率６０％、また、種別１４に対しては圧延率４０％の冷間加工を実施し、さらにこれを１０−２Ｐａ以下の真空中で１００時間の熱処理を実施することにより、鋳物切出し材からなる水素透過分離膜（比較水素透過膜）１３、１４を製造した。 Similarly, for the purpose of comparison, as a raw material, the purity: 99.9% high purity Nb shot material, 99.9% high purity Ni shot material, 99.5% high purity Ti sponge material, 99.5% % Of high-purity Zr sponge material, these raw materials were blended in proportions shown in types 13 and 14 of Table 3, respectively, and arc-melted in a high-purity Ar atmosphere, and the diameter: 80 mm × thickness: 10 mm Each of these ingots was cut out from this ingot into a thin plate material having a width of 20 mm × length of 60 mm and a thickness of about 0.15 mm by electric discharge machining. Thereafter, cold working is performed at a rolling rate of 60% for Type 13 and a rolling rate of 40% for Type 14, and this is further subjected to heat treatment for 100 hours in a vacuum of 10 −2 Pa or less. By carrying out, hydrogen permeable separation membranes (comparative hydrogen permeable membranes) 13 and 14 made of a cast material were produced.
この結果得られた本発明水素透過薄膜１〜２０および比較水素透過膜１〜１４について、その成分組成をエネルギー分散型蛍光Ｘ線分析装置を用いて測定したところ、いずれも表１〜３に示される配合組成と実質的に同じ分析値を示し、また、その組織を走査型電子顕微鏡およびＸ線回折装置を用いて観察したところ、前記本発明水素透過薄膜１〜２０では、図１に本発明水素透過薄膜１５の合金組織を示す通り、いずれもＮｉ−Ｔｉ金属間化合物におけるＮｉの一部をＣｏが置換、Ｔｉの一部をＺｒ及びＮｂが置換する状態で固溶含有したＮｉ（Ｃｏ）−Ｔｉ（Ｚｒ，Ｎｂ）金属間化合物からなる素地に、Ｎｂに主としてＴｉ，Ｚｒが固溶してなるＮｂ基固溶合金の微細粒が分散分布した合金組織を示し、一方、上記比較水素透過膜１〜７では、図２に比較水素透過膜３の合金組織を示す通り、いずれもＮｂに主としてＴｉ，Ｚｒが固溶してなるＮｂ基固溶合金からなる初晶と、その周りを囲むように存在する前記Ｎｂ基固溶合金とＮｉ−Ｔｉ金属間化合物におけるＮｉの一部をＣｏが置換、Ｔｉの一部をＺｒおよびＮｂが置換する状態で固溶含有したＮｉ（Ｃｏ）−Ｔｉ（Ｚｒ，Ｎｂ）金属間化合物がラメラー状に晶出した共晶組織からなる複相合金組織を示した。
上記比較水素透過膜１〜７の合金組織は、本発明水素透過膜１〜２０のそれとは明らかに異なり、初晶と共晶が存在することから、ミクロな均質性が乏しく、かつ、結晶粒（特に初晶）が粗大であった。
上記比較水素透過膜８〜１０については、Ｘ線回折分析を行ったところ、一部にＮｂ基固溶合金相に由来する回折ピークが見られるものもあったが、いずれもアモルファス構造に特有のハローパターンを示し、アモルファス単相もしくはアモルファス相と結晶構造相の混合状態となっていることが確認された。
上記比較水素透過膜１１〜１４については、比較水素透過膜１〜７と類似した初晶と共晶からなる合金組織を示していたが、いずれも冷間加工により（特に初晶が）圧延方向に長く延びているのが特徴的である。いずれも本発明水素透過膜１〜２０の組織とは大きく異なっている。
The resulting hydrogen permeable thin films 1 to 20 and comparative hydrogen permeable membranes 1 to 14 of the present invention were measured for their component compositions using an energy dispersive X-ray fluorescence spectrometer. The analysis values were substantially the same as the composition of the composition, and the structure was observed using a scanning electron microscope and an X-ray diffractometer. As a result, the present invention hydrogen permeable thin films 1 to 20 show the present invention in FIG. As shown in the alloy structure of the hydrogen permeable thin film 15, Ni (Co) is a solid solution containing Ni in the Ni—Ti intermetallic compound in which Ni is partially substituted by Co and Ti is partially substituted by Zr and Nb. -An alloy structure in which fine particles of a Nb-based solid solution alloy in which Ti and Zr are mainly dissolved in Nb are dispersed and distributed on a base made of an intermetallic compound of Ti (Zr, Nb) is shown. Membrane 1-7 As shown in FIG. 2, the alloy structure of the comparative hydrogen permeable membrane 3 is present so as to surround the primary crystal composed of an Nb-based solid solution alloy in which Ti and Zr are mainly dissolved in Nb and surrounding the primary crystal. Ni (Co) -Ti (Zr, Nb) containing Ni in the Nb-based solid solution alloy and Ni-Ti intermetallic compound in a state where a part of Ni is substituted by Co and a part of Ti is substituted by Zr and Nb. ) A multi-phase alloy structure composed of a eutectic structure in which an intermetallic compound was crystallized into a lamellar shape was shown.
The alloy structure of the comparative hydrogen permeable membranes 1 to 7 is clearly different from that of the hydrogen permeable membranes 1 to 20 of the present invention, and since primary crystals and eutectic crystals exist, the micro-homogeneity is poor, and the crystal grains (Especially primary crystals) were coarse.
As for the comparative hydrogen permeable membranes 8 to 10, when X-ray diffraction analysis was performed, some diffraction peaks derived from the Nb-based solid solution alloy phase were observed. A halo pattern was exhibited, confirming that the amorphous single phase or a mixed state of the amorphous phase and the crystal structure phase was obtained.
The comparative hydrogen permeable membranes 11 to 14 showed an alloy structure composed of primary crystals and eutectics similar to those of the comparative hydrogen permeable membranes 1 to 7, both of which were cold-worked (especially primary crystals) in the rolling direction. It is characteristic that it extends long. All of them are greatly different from the structures of the hydrogen permeable membranes 1 to 20 of the present invention.
ついで、上記の本発明水素透過薄膜１〜２０および比較水素透過膜１〜１４のそれぞれの両面に、スパッタリング法により厚さ：０．１μmのＰｄ薄膜を蒸着形成し（この場合電気メッキ法により形成しても良い）、かつそれぞれ横外寸：２０ｍｍ×縦外寸：６０ｍｍ×枠幅：５ｍｍ×枠厚：０．５ｍｍの寸法をもった２枚の銅製補強枠体で両側から挟み、前記各種の透過膜を前記補強枠体に固定した状態で、図３に示される構造の水素高純度精製装置と同じ構造の水素透過評価装置の反応室内に設置し、前記反応室内を３７５℃に加熱し、反応室の左側室に、水素ガスを導入して、まず、反応室の左側室および右側室の内圧を０．１ＭＰａとし、ついで、前記右側室の内圧を０．１ＭＰａに保持しながら、前記左側室の内圧を０．１ＭＰａ当たり５分の速度で、本発明水素透過薄膜１〜２０、比較水素透過膜１〜１４については０．５ＭＰａまで昇圧し、この条件で１時間保持した時点で、水素ガスの透過速度（表１〜３に初期水素透過速度（ｍｌ／分）で示す）をガスフローメーターで測定し、さらにこの条件、すなわち、右側室の内圧を０．１ＭＰａ、左側室の内圧を０．５ＭＰａに昇圧し、この条件で１時間保持した時点から、同条件で２０時間続行した時点で、同じく水素ガスの透過速度（表１〜３に後期水素透過速度（ｍｌ／分）で示す）を測定し、これらの測定結果を表１〜３に示した。
また、急冷法により作製した本発明水素透過薄膜１〜２０、比較水素透過膜８〜１０および圧延により加工した比較水素透過膜１１〜１４については、１８０度折曲試験を実施し、各膜の機械的特性評価を行い、その評価結果を同じく表１〜３に示した。
Next, a Pd thin film having a thickness of 0.1 μm is deposited on both surfaces of the hydrogen permeable thin films 1 to 20 of the present invention and the comparative hydrogen permeable films 1 to 14 by sputtering (in this case, formed by electroplating). Each of which is sandwiched from two sides by two copper reinforcing frames having dimensions of 20 mm × vertical outer dimensions: 60 mm × frame width: 5 mm × frame thickness: 0.5 mm. In a state where the permeable membrane is fixed to the reinforcing frame, it is installed in a reaction chamber of a hydrogen permeation evaluation apparatus having the same structure as the hydrogen high-purity purification apparatus having the structure shown in FIG. 3, and the reaction chamber is heated to 375 ° C. Then, hydrogen gas was introduced into the left chamber of the reaction chamber, and first, the internal pressure of the left chamber and the right chamber of the reaction chamber was set to 0.1 MPa, and then the internal pressure of the right chamber was maintained at 0.1 MPa, The internal pressure of the left side chamber was 0.1 MPa At a rate of 5 minutes, the hydrogen permeable thin films 1 to 20 of the present invention and the comparative hydrogen permeable membranes 1 to 14 were pressurized to 0.5 MPa, and when held for 1 hour under these conditions, the hydrogen gas permeation rate (Tables 1 to 3 shows the initial hydrogen permeation rate (ml / min) with a gas flow meter, and further increases the conditions, that is, the internal pressure of the right side chamber is increased to 0.1 MPa and the internal pressure of the left side chamber is increased to 0.5 MPa. The hydrogen gas permeation rate (shown as the late hydrogen permeation rate (ml / min in Tables 1 to 3)) was also measured from the time when the conditions were maintained for 1 hour to the time when the conditions were continued for 20 hours. The results are shown in Tables 1-3.
Moreover, about the hydrogen permeable thin films 1-20 of this invention produced by the rapid cooling method, the comparative hydrogen permeable films 8-10, and the comparative hydrogen permeable films 11-14 processed by rolling, a 180 degree bending test was implemented, Mechanical property evaluation was performed, and the evaluation results are also shown in Tables 1 to 3.
表１〜３に示される通り、本発明水素透過薄膜１〜２０は、いずれも素地のＮｉ（Ｃｏ）−Ｔｉ（Ｚｒ，Ｎｂ）金属間化合物によって高い機械的強度が確保され、０．０７ｍｍ以下の厚さへの薄肉化が可能となるので、前記素地に微細粒として分散分布するＮｂに主としてＴｉ，Ｚｒが固溶してなるＮｂ基固溶合金が、すぐれた水素透過分離性能を発揮することと相俟って、すぐれた水素透過分離性能を長期に亘って発揮し、また、水素透過分離性能に経時的変化も少ないことから、すぐれた耐久性（使用寿命）を示している。
これに対して、比較水素透過膜１〜７では、いずれも機械的強度の面から膜厚を０．１ｍｍ以下にすることができず、このため水素透過分離性能の低いものとなり、比較水素透過膜８〜１０では、いずれも水素透過分離特性の経時的劣化が激しいものであることから、耐久性（使用寿命）に劣り、比較水素透過膜１１、１２では、冷間加工による加工硬化の結果、１８０°曲げが不可能となり、また、水素透過能も大幅に低下してしまっている。
さらに、比較水素透過膜１３、１４では、１８０°曲げが不十分であるとともに、水素透過速度についても、本発明の水素透過膜に比較すると、低い水準に留まってしまっていることが明らかである。なお、比較水素透過膜１３、１４では、真空熱処理により、冷間加工による加工硬化が十分に焼鈍・除去されているにもかかわらず、１８０°曲げが不十分であったが、これは、熱処理中の酸化などに起因するものと推測される。
As shown in Tables 1 to 3, each of the hydrogen permeable thin films 1 to 20 of the present invention has a high mechanical strength secured by the Ni (Co) -Ti (Zr, Nb) intermetallic compound, and is 0.07 mm or less. Therefore, an Nb-based solid solution alloy in which Ti and Zr are mainly dissolved in Nb dispersed and distributed as fine grains in the substrate exhibits excellent hydrogen permeation separation performance. In combination with this, excellent hydrogen permeation separation performance is exhibited over a long period of time, and since the change with time in the hydrogen permeation separation performance is small, excellent durability (service life) is shown.
On the other hand, in the comparative hydrogen permeable membranes 1 to 7, none of the film thicknesses can be reduced to 0.1 mm or less from the viewpoint of mechanical strength, and therefore the hydrogen permeation separation performance is low, and the comparative hydrogen permeable membrane In each of the membranes 8 to 10, since the hydrogen permeation separation characteristics are severely deteriorated with time, the durability (service life) is inferior. In the comparative hydrogen permeable membranes 11 and 12, the results of work hardening by cold working are obtained. 180 ° bending is impossible, and the hydrogen permeability is greatly reduced.
Further, it is clear that the comparative hydrogen permeable membranes 13 and 14 are not sufficiently bent by 180 °, and the hydrogen permeation rate remains low as compared with the hydrogen permeable membrane of the present invention. . The comparative hydrogen permeable membranes 13 and 14 were not sufficiently bent by 180 ° even though the work hardening by cold working was sufficiently annealed and removed by the vacuum heat treatment. It is presumed to be caused by oxidation inside.
上述のように、この発明の水素透過分離薄膜は、高い機械的強度を有するＺｒ−Ｔｉ−Ｎｉ−Ｃｏ−Ｎｂ合金で構成され、厚さ：０．０７ｍｍ以下への薄膜化を可能とするものであり、実用に際して、長期に亘り安定的に優れた水素透過分離性能を発揮するものであるから、水素透過分離膜が構造部材として用いられている各種の化学反応装置の高性能化の要求に満足に対応できるものである。 As described above, the hydrogen permeation separation thin film of the present invention is composed of a Zr—Ti—Ni—Co—Nb alloy having a high mechanical strength, and enables the thinning to a thickness of 0.07 mm or less. In practical use, it exhibits excellent hydrogen permeation separation performance over a long period of time. Therefore, it is necessary to improve the performance of various chemical reactors in which hydrogen permeation separation membranes are used as structural members. It can respond to satisfaction.
Claims (1)
（ｂ）ロール急冷法による厚さ：０．０７ｍｍ以下の鋳造箔材の調質熱処理材にして、Ｎｉ−Ｔｉ金属間化合物におけるＮｉの一部をＣｏが置換、Ｔｉの一部をＺｒ及びＮｂが置換する状態で固溶含有したＮｉ（Ｃｏ）−Ｔｉ（Ｚｒ，Ｎｂ）金属間化合物と、Ｎｂに主としてＴｉ，Ｚｒ，Ｎｉ，Ｃｏが固溶してなるＮｂ基固溶合金の微細粒が分散分布した合金組織、
以上（ａ）の成分組成および（ｂ）の合金組織を有するＺｒ−Ｔｉ−Ｎｉ−Ｃｏ−Ｎｂ合金で構成したことを特徴とするすぐれた機械的性質と水素透過分離性能を有する水素透過分離薄膜。 (A) Zr: 0.5-20 atomic%, Ti: 15-48 atomic% (however, Zr + Ti: 23-52 atomic%), Ni: 10-43 atomic%, Co: 0.5-25 atomic% ( However, Ni + Co: 22 to 48 atomic% and Co / Ni <1), and the remaining component composition consisting of Nb and inevitable impurities (however, Nb: 19 to 42 atomic%),
(B) Thickness by roll quenching method: Refining heat treatment material of cast foil material of 0.07 mm or less, Co is substituted for part of Ni in Ni—Ti intermetallic compound, and part of Ti is Zr and Nb Ni (Co) -Ti (Zr, Nb) intermetallic compound contained in a solid solution in a state where Nb is substituted, and fine particles of an Nb-based solid solution alloy in which Ti, Zr, Ni, and Co are mainly dissolved in Nb. A distributed alloy structure,
A hydrogen permeation separation thin film having excellent mechanical properties and hydrogen permeation separation performance, characterized by comprising a Zr-Ti-Ni-Co-Nb alloy having the component composition of (a) and the alloy structure of (b) .
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