JPH01298130A - Gas absorbing alloy having excellent activation characteristics - Google Patents
Gas absorbing alloy having excellent activation characteristicsInfo
- Publication number
- JPH01298130A JPH01298130A JP12672188A JP12672188A JPH01298130A JP H01298130 A JPH01298130 A JP H01298130A JP 12672188 A JP12672188 A JP 12672188A JP 12672188 A JP12672188 A JP 12672188A JP H01298130 A JPH01298130 A JP H01298130A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- hydrogen
- gas
- absorption
- alloys
- 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.)
- Granted
Links
- 230000004913 activation Effects 0.000 title claims description 34
- 229910045601 alloy Inorganic materials 0.000 title abstract description 115
- 239000000956 alloy Substances 0.000 title abstract description 115
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 abstract description 11
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 229910003126 Zr–Ni Inorganic materials 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 3
- 231100000572 poisoning Toxicity 0.000 abstract 2
- 230000000607 poisoning effect Effects 0.000 abstract 2
- 229910000640 Fe alloy Inorganic materials 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 63
- 229910052739 hydrogen Inorganic materials 0.000 description 63
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 60
- 239000007789 gas Substances 0.000 description 57
- 238000010521 absorption reaction Methods 0.000 description 41
- 238000001994 activation Methods 0.000 description 35
- 239000000463 material Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000002994 raw material Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011358 absorbing material Substances 0.000 description 5
- 229910002090 carbon oxide Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 2
- 229910001093 Zr alloy Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 229910004337 Ti-Ni Inorganic materials 0.000 description 1
- 229910011212 Ti—Fe Inorganic materials 0.000 description 1
- 229910011209 Ti—Ni Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Gas Separation By Absorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、水素、酸素、窒素、−酸化炭素等の吸収合
金に関し、特に活性化特性に優れ、陰極線管、熱電子管
等の水素圧力制御用として、また、魔法瓶をはじめとす
る真空断熱によって保温を行う機器の真空度向上、その
他高真空維持が要求される機器の真空度劣化防止などに
広く利用することのできる合金に関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to an absorbing alloy for hydrogen, oxygen, nitrogen, carbon oxide, etc., which has particularly excellent activation properties, and is useful for controlling hydrogen pressure in cathode ray tubes, thermionic tubes, etc. The present invention relates to an alloy that can be widely used for purposes such as improving the degree of vacuum in thermos flasks and other devices that maintain heat through vacuum insulation, and preventing deterioration of the degree of vacuum in other devices that require high vacuum maintenance.
（従来の技（ネｉ）
高圧放電管、陰極線管、水銀灯などは管内の水素４度に
よって始動電圧が変化する。例えば、水素濃度が高くな
ると始動電圧が高くなり機器の寿命が短くなることが知
られている。また真空断熱によって保温を行う機器は、
真空容器の部材からのガス放出があり、使用条件によっ
ては、容器の外壁の腐食によるガスや、環境に存在する
ガスが拡散して真空断熱層に侵入し真空度が低下して断
熱効果が失われることが知られている。(Conventional technique) The starting voltage of high-pressure discharge tubes, cathode ray tubes, mercury lamps, etc. changes depending on the degree of hydrogen in the tube. For example, when the hydrogen concentration increases, the starting voltage increases and the life of the equipment may be shortened. Also, equipment that retains heat using vacuum insulation is
Gas may be released from the vacuum container components, and depending on the usage conditions, gases due to corrosion of the outer wall of the container or gases present in the environment may diffuse and enter the vacuum insulation layer, reducing the degree of vacuum and losing the insulation effect. It is known that
上記のような問題に対して従来より採られてきた対策は
、ガスを吸収する物質を封入する方法である０例えば、
非金属型ガス吸収材としてはチャコールやゼオライトが
ある。金属型ガス吸収材（ガス吸収合金）としてよく知
られているのは■系合金である０例えば、バリウムワイ
ヤーやＶ−Ａｊ２合金を加熱して蒸発させ、利用機器の
内壁面に蒸着させて皮膜を作りガス吸収を行わせる。し
かしながら、非金属型ガス吸収材の一部のものは、酸素
の存在する高温の環境では使用できないという問題があ
った。また蒸着させる金属型ガス吸収合金は蒸着させる
工程そのものが利用機器の内壁をよごすことになり陰極
線管や電球などでは使用上問題があった。The conventional solution to the above problems is to seal in a substance that absorbs gas.For example,
Charcoal and zeolite are examples of non-metallic gas absorbing materials. Well-known metal-type gas absorbing materials (gas absorbing alloys) are type alloys. to cause gas absorption. However, some nonmetallic gas absorbing materials have a problem in that they cannot be used in high-temperature environments where oxygen is present. Furthermore, the vapor-deposited metal-type gas-absorbing alloy has a problem in use in cathode ray tubes, light bulbs, etc. because the vapor-deposition process itself stains the inner walls of the equipment in which it is used.
これらの問題を解決するために開発されたのが非蒸発型
ガス吸収合金である。たとえば、Ｚｒ−Ｎｉ合金、Ｚｒ
−Ｔｊ合金、Ｚｒ−Ａ１合金、Ｚｒ−Ｔｉ−Ｎｉ合金、
Ｚｒ−Ｔｉ−Ｆｅ合金等が非蒸発型ガス吸収合金として
知られている。しかしながら、これらの合金は、通常酸
化物や窒化物などの不活性表面皮膜に覆われているため
、ガス吸収を開始させるためには、真空もしくは、不活
性ガス雰囲気にて４５０〜９００°Ｃに加熱し、表面不
活性層を合金内部に拡散させる活性化処理が不可欠であ
る。機器によっては、その内部でこのような活性化条件
を実現することは不可能な場合があり、そのために非蒸
発型ガス吸収合金の用途は限定されていた。Non-evaporable gas absorbing alloys have been developed to solve these problems. For example, Zr-Ni alloy, Zr
-Tj alloy, Zr-A1 alloy, Zr-Ti-Ni alloy,
Zr-Ti-Fe alloys and the like are known as non-evaporative gas absorbing alloys. However, since these alloys are usually covered with an inert surface film such as an oxide or nitride, they must be heated to 450-900°C in a vacuum or in an inert gas atmosphere to initiate gas absorption. An activation process that involves heating and diffusing the surface inactive layer into the interior of the alloy is essential. Depending on the device, it may be impossible to achieve such activation conditions inside the device, which has limited the use of non-evaporable gas absorbing alloys.
非蒸発型ガス吸収合金の上記の問題点を解決する一つの
促案が特公昭６２−１２９２号公報（特開昭５５−１２
４５３８号公報）に示されている。ここに示されたＺｒ
−Ｖ−Ｐｅ系合金は、活性化処理が真空中３５０’Ｃ１
時間加熱でできるというもので、これによって非蒸発型
ガス吸収合金の使用はかなり容易なものとなった。しか
しながら利用機器内で３５０’Ｃの真空雰囲気を作るこ
とも困難な場合があり、このため未だに利用範囲が限ら
れているのが現状である。また、実験室的には、Ａ、Ｐ
ｅｂｌｅｒ ＆ Ｅ、Ａ、 Ｇａ１ｂ−ｒａｎｓｅｎら
がＴＲＡＮＳＡＣＴｒＯＮ ＯＦ Ｔ、Ｍ、Ｓ、＾ＩＭ
Ｅ Ｖｏｌ、２３９゜（１９６７）Ｐ１５９３−１６０
０ ニ、ＺｒＶｚ金属間化合物ヲ提案しており、これは
活性化処理がほとんど不要で水素ガスを吸収すると報告
している。しかし、このＺｒＶｔ合金は非常に発火しや
すく、工業的な取扱いに適せず実用的とは言えない。One proposal to solve the above-mentioned problems of non-evaporable gas absorbing alloys is published in Japanese Patent Publication No. 1292-1982 (Japanese Patent Application Laid-Open No. 55-12
No. 4538). Zr shown here
-V-Pe alloys are activated at 350'C1 in vacuum.
This can be done by heating for a period of time, making it considerably easier to use non-evaporative gas-absorbing alloys. However, it is sometimes difficult to create a vacuum atmosphere of 350'C within the equipment used, and for this reason, the scope of use is still limited. In addition, in the laboratory, A, P
ebler & E, A, Galb-ransen et al. TRANSACTrON OF T, M, S, ^IM
E Vol, 239° (1967) P1593-160
0 D. They have proposed a ZrVz intermetallic compound, which is reported to absorb hydrogen gas with almost no activation treatment. However, this ZrVt alloy is highly flammable and is not suitable for industrial use, making it impractical.
更に、特公昭５９−３４２２４号公報には、活性化処理
なしで使用できるというＺｒＶ、（但しＸは原子比で０
．０１〜０．２８）が開示されている。Furthermore, Japanese Patent Publication No. 59-34224 states that ZrV can be used without activation treatment (however, X is 0 in atomic ratio).
．． 01 to 0.28) are disclosed.
しかし、この合金は非常に延性が大きくて塑性変形し易
く、粉砕が困難であるため、製品形態は塊状となる。ｉ
ｌ！！常この種の合金は粉砕して表面積を増加させ、ガ
ス吸収速度を高めて使用するが、塊状であるこの合金は
迅速なガス吸収が要求される用途には不適当である。However, this alloy is very ductile, easily deformed plastically, and difficult to crush, resulting in a lumpy product. i
l! ! These alloys are commonly used by grinding to increase the surface area and speed of gas absorption; however, the bulk of this alloy is unsuitable for applications requiring rapid gas absorption.
叙上のとおり、これまで知られている非蒸発型ガス吸収
合金の用途は限られたものであり、上記のような問題点
がなく利用範囲の広い非蒸発型ガス吸収合金の開発が望
まれていた。As mentioned above, the uses of the non-evaporative gas absorbing alloys known so far are limited, and it is desired to develop a non-evaporative gas absorbing alloy that does not have the above problems and can be used in a wide range of applications. was.
（発明が解決しようとする課題）
本発明の課題は、活性化処理が容易であり、利用範囲の
広い非蒸発型ガス吸収合金を提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to provide a non-evaporable gas absorbing alloy that can be easily activated and has a wide range of applications.
（課題を解決するための手段）
前述のとおり、従来の非蒸発型ガス吸収合金は、ガス吸
収をさせるためには、不活性ガス雰囲気もしくは真空中
で３５０°Ｃ〜９００°Ｃに加熱して、ガス吸収合金の
表面の被毒Ｎ（酸化層、窒化層）を内部に拡散させる活
性化処理が必要であった０本発明者は、この活性化処理
を容易にするために、表面被毒層に欠陥を生じさせるこ
とによって、従来よりも容易に新鮮な合金面を露出させ
る方法を検討した。その結果、以下に述べる組成の合金
が活性化処理の容易性においてガス吸収合金として従来
のものに勝ることを見出し、本発明を完成した。(Means for Solving the Problems) As mentioned above, conventional non-evaporative gas absorbing alloys must be heated to 350°C to 900°C in an inert gas atmosphere or vacuum in order to absorb gas. , it was necessary to perform an activation treatment to diffuse the poisoned N (oxide layer, nitride layer) on the surface of the gas-absorbing alloy into the interior. We investigated a method of exposing fresh alloy surfaces more easily than before by creating defects in the layer. As a result, it was discovered that an alloy having the composition described below is superior to conventional gas absorbing alloys in ease of activation treatment, and the present invention was completed.
ここに、本発明は「重量％で、Ｖ：１０〜５４％、Ｆｅ
： ０．５〜２０％、Ｎｉ ；０．５〜６％（ただし
Ｖ＋Ｆｅ＋Ｎｉの合計が５５％以下）を含み、残部は実
質的にＺｒからなる活性化特性に優れたガス吸収合金Ｊ
を要旨とする。なお、以下「％」は、重量％を意味する
。Here, the present invention is characterized in that "by weight %, V: 10-54%, Fe
: 0.5 to 20%, Ni: 0.5 to 6% (however, the total of V + Fe + Ni is 55% or less), and the remainder is substantially Zr. Gas absorption alloy J with excellent activation properties.
The gist is: Note that "%" hereinafter means % by weight.
ここで、残部が実質的にＺｒからなるというのは、２「
の外、Ｚｒ原料としてジルカロイ合金を使用する場合及
びＶ、 Ｐｅ原料としてフェロバナジウム合金を使用す
る場合に不可避的に混入し合金の機能に本質的な影響を
及ぼさない不純物、例えば２％までのＳｎ、 １．５％
までのＡ１．０．５％までのＳｉ等が許容される、とい
うことである。Here, the fact that the remainder essentially consists of Zr means 2"
In addition, when using Zircaloy alloy as Zr raw material and when using ferrovanadium alloy as V, Pe raw material, impurities that are unavoidably mixed in and have no essential influence on the function of the alloy, such as up to 2% Sn. , 1.5%
This means that up to A1 and up to 0.5% Si, etc. are allowed.
上記本発明の合金の一般的な製造方法は、原料をカルジ
ャ等のるつぼに装入し、アルゴン等の不活性ガス中で、
例えば高周波誘導溶解を行い、造塊後機械的に粉砕する
、という方法である。The general method for manufacturing the alloy of the present invention is to charge the raw materials into a crucible such as Calja, and then to
For example, there is a method in which high frequency induction melting is performed, followed by mechanical crushing after agglomeration.
本発明の合金は、例えば、次のように使用される。The alloy of the present invention is used, for example, as follows.
■１０気圧以下、高真空までの雰囲気で水素吸収に用い
る。■Used for hydrogen absorption in atmospheres below 10 atmospheres and up to high vacuum.
■陰掻線管、熱電子管等に封入し内部の水素圧力の上昇
防止又は制御に用いる。■It is used to prevent or control the increase in internal hydrogen pressure by enclosing it in a scab tube, thermionic tube, etc.
■１０気圧以下、高真空までの雰囲気で水蒸気、酸素、
窒素、−酸化炭素、炭化水素等のガスの吸収に用いる。■ Water vapor, oxygen, etc. under 10 atmospheres and up to high vacuum
Used to absorb gases such as nitrogen, carbon oxide, and hydrocarbons.
（作用）
まず、本発明の合金の組成の選定理由を作用効果ととも
に説明する。(Function) First, the reason for selecting the composition of the alloy of the present invention will be explained together with the function and effect.
本発明のＺｒｉ合金において、
■は、活性化処理を容易にし、吸収時のガス平衡圧（特
に水素平衡圧）を下げる働きをする。この効果を得るた
めにはｖ量は１０％以上必要である。In the Zri alloy of the present invention, (1) facilitates the activation process and serves to lower the gas equilibrium pressure (particularly the hydrogen equilibrium pressure) during absorption. In order to obtain this effect, the v amount needs to be 10% or more.
しかし、その景が５４％を超えると残部のＺｒ量が減少
し、ガス吸収量が低下してガス吸収合金としての効果が
小さくなる。したがって、■含有量は１０％〜５４％と
することが必要である。However, when the ratio exceeds 54%, the remaining Zr content decreases, the amount of gas absorption decreases, and the effect as a gas absorption alloy decreases. Therefore, it is necessary that the (1) content is 10% to 54%.
Ｆｅは、合金の発火性を押さえ工業的な取扱いを容易に
する働きをする。この効果を得るためには０．５％以上
必要である。しかしその量が２０％を超えると、合金の
活性化処理が困難になるとともに吸収時のガス平衡圧が
高くなり、またガス吸収量が減少する。したがってＦｅ
１ｌは０．５〜２０％であることが必要である。Fe functions to suppress the ignitability of the alloy and facilitate industrial handling. In order to obtain this effect, 0.5% or more is required. However, if the amount exceeds 20%, it becomes difficult to activate the alloy, the gas equilibrium pressure during absorption increases, and the amount of gas absorbed decreases. Therefore, Fe
1 liter needs to be 0.5 to 20%.
Ｎｉは、合金中にＺｒ２Ｎｉ のようなＺｒ−Ｎｉ系金
属間化合物を微細に析出させ、合金表面の被毒層中の母
相とＺｒ−Ｎｉ系金属間化合物との境界に欠陥を作り、
この欠陥を起点とした水素ガス等の拡散が、活性化処理
を容易にする働きをする。Ni finely precipitates Zr-Ni intermetallic compounds such as Zr2Ni in the alloy, creating defects at the boundary between the matrix and the Zr-Ni intermetallic compound in the poisoned layer on the alloy surface.
Diffusion of hydrogen gas or the like starting from this defect serves to facilitate the activation process.
この効果を得るためには０．５％以上必要である。In order to obtain this effect, 0.5% or more is required.
しかしその量が６％を超えるとガス吸収量が減少するの
でＮｉｌは０．５％〜６％である必要がある。However, if the amount exceeds 6%, the amount of gas absorption decreases, so Nil needs to be in the range of 0.5% to 6%.
上記の■、ＦｅおよびＮｉについては、その合計含有量
を一定値以下に抑えることもＴｆＬ要である。即ち、Ｖ
＋Ｐｅ＋Ｎｉの合計を５５％以下にしなければならない
、ガス吸収合金としてこの合金を使用した場合、ガスを
吸収するのはＺ「であり、Ｖ＋Ｆｅ＋Ｎｉの合計量が５
５％を趙えると残部のＺｒ１ｌが少なくなりすぎてガス
吸収量が減少してしまう。即ちガス吸収合金としての機
能が失われる。Regarding the above-mentioned (1), Fe and Ni, it is also necessary for TfL to suppress the total content to a certain value or less. That is, V
The total amount of +Pe+Ni must be 55% or less.When this alloy is used as a gas absorption alloy, it is Z" that absorbs gas, and the total amount of V+Fe+Ni is 55% or less.
If 5% is reduced, the remaining Zr1l becomes too small and the amount of gas absorption decreases. That is, the function as a gas absorbing alloy is lost.
以上の組成をもつ本発明の１合金のガス吸収合金として
の基本的特性は下記のとおりである。The basic properties of the alloy of the present invention having the above composition as a gas absorbing alloy are as follows.
■ 水素ガスについては吸収のみならず、一定の平衡圧
力を持って放出する。すなわち可逆的なガス吸収・放出
性を持つ。■ Hydrogen gas is not only absorbed, but also released with a certain equilibrium pressure. In other words, it has reversible gas absorption and release properties.
■ 酸素、窒素、−酸化炭素、二酸化炭素、メタン等に
ついては、吸収のみ行うという不可逆的なガス吸収性を
持つ。■ It has an irreversible gas absorption property that only absorbs oxygen, nitrogen, carbon oxide, carbon dioxide, methane, etc.
■ 不活性なガス、例えばＡｒ、 Ｈｅ等については、
吸収・放出作用を持たない。■ For inert gases such as Ar and He,
It has no absorption/release effects.
本発明合金の活性化処理は、次のようにして行う。The activation treatment of the alloy of the present invention is carried out as follows.
■ 水素の吸収用の場合は、活性化の途中に他のガスを
吸収して、目的とする水素の吸収量を減少させないため
に、０．００５ｔｏｒｒより高真空度の雰囲気または不
活性ガスに置換した雰囲気中で、１５０°Ｃ以上の温度
で一定時間保持する。■ For hydrogen absorption, in order to avoid absorbing other gases during activation and reducing the amount of hydrogen absorbed, replace the atmosphere with a vacuum higher than 0.005 torr or with an inert gas. The sample is kept at a temperature of 150°C or higher for a certain period of time in a cool atmosphere.
■ 水素以外の吸収可能なガスを吸収させる場合は、使
用環境に合金を封入し、１５０“Ｃ以上の温度で一定時
間保持する。■ When absorbing absorbable gases other than hydrogen, the alloy is sealed in the usage environment and maintained at a temperature of 150"C or higher for a certain period of time.
次に本発明合金の利用方法について述べる。先に記した
とおり、本発明合金の主たる用途は次の２つである。Next, a method of using the alloy of the present invention will be described. As mentioned above, the alloy of the present invention has the following two main uses.
第１の用途は、真空度を維持する必要がある容器で、そ
の容器の外壁部材そのものの中に存在する水素、外壁が
外部環境の作用で腐食して発生した水素などが拡散して
真空層に侵入してきた場所の水素吸収材である。かかる
用途では、本発明の合金を真空度を維持する必要がある
容器に封入し、誘導加熱等の手段で１５０°Ｃ以上まで
昇温し１時間程度保持する。これによって活性化された
合金は、以後容器内の水素を吸着し長期間にわたってそ
の真空度を保持する働きをする。The first application is for containers that need to maintain a degree of vacuum, where hydrogen existing in the outer wall of the container itself or hydrogen generated when the outer wall corrodes due to the action of the external environment diffuses into a vacuum layer. It is a hydrogen absorbing material in places where hydrogen has invaded. In such applications, the alloy of the present invention is sealed in a container that requires maintaining the degree of vacuum, heated to 150° C. or higher by means such as induction heating, and held for about 1 hour. The activated alloy then adsorbs hydrogen in the container and functions to maintain the vacuum level for a long period of time.
第２の用途は、酸化、窒化等が生じては困る真空熱処理
や真空雰囲気粉末焼成炉底である。このような機器類で
、不純物ガスとして存在する水蒸気、酸素、窒素、−酸
化炭素等のガスを吸収させて取り除き、真空度を高める
ために用いる。これらのガスは水素と異なり放出されな
いで化学吸着されたままとなる。The second application is vacuum heat treatment or vacuum atmosphere powder firing furnace bottoms where oxidation, nitridation, etc. should not occur. These devices are used to increase the degree of vacuum by absorbing and removing gases such as water vapor, oxygen, nitrogen, and carbon oxides that exist as impurity gases. Unlike hydrogen, these gases are not released and remain chemisorbed.
（実施例）
添加成分の含有量を変化させた合金を溶製して水素吸収
特性を調査し、且つ現在市販されている非蒸発型ガス吸
収合金と特性を比較調査した。(Example) Alloys with varying contents of additive components were produced and their hydrogen absorption properties were investigated, and their properties were compared with those of currently commercially available non-evaporable gas absorption alloys.
（１）試験材の制作
■約１５０ｇの小インゴットをアルゴン・アークによっ
てボタン溶解溶製
■均質化のためアルゴン・アークで再溶解■機械粉砕に
より１〜３ｙｍの粒状合金作製Ｚｒ原料としてはジルカ
ロイ２．４のスクラップ、■原料として純度９９．７％
のフレーク、Ｆｅ原料として電解鉄、Ｎｉ原料として電
解Ｎｉを使用した。また、■とＦｅの重量比が８：２で
あるものは８０％■−２０％Ｆｅのフェロ・バナジウム
合金を用いた。(1) Production of test material■ Small ingot of approximately 150g is button-melted using an argon arc ■Re-melted using an argon arc for homogenization■ Preparation of 1-3 ym granular alloy by mechanical crushing Zircaloy 2 is used as the Zr raw material .4 scrap, ■99.7% purity as raw material
Electrolytic iron was used as the Fe raw material, and electrolytic Ni was used as the Ni raw material. Further, in the case where the weight ratio of ■ and Fe was 8:2, a ferro-vanadium alloy of 80%■-20%Fe was used.
第１表に示す合金１〜１５が本発明の合金の実施例であ
る。従来材は、先に掲げた特公昭６２−１２９２号公報
に開示されている合金で、市販されている同種の非蒸発
型ガス吸収合金で最も活性化処理が容易といわれている
ものである。Alloys 1 to 15 shown in Table 1 are examples of alloys of the present invention. The conventional material is the alloy disclosed in the above-mentioned Japanese Patent Publication No. 1292-1982, which is said to be the easiest to activate among the same type of non-evaporable gas absorbing alloys on the market.
（以下、余白）
（２）活性化特性の評価
本発明合金と比較材および従来材の活性化特性を調査し
た。評価は、第２表の条件にて行った。(Hereinafter, blank spaces) (2) Evaluation of activation characteristics The activation characteristics of the alloy of the present invention, comparative materials, and conventional materials were investigated. The evaluation was performed under the conditions shown in Table 2.
この結果を第１図および第２図に示す。図の縦軸は水素
吸収による重量増加率（％）、横軸は５’Ｃ／分で昇温
した時の雰囲気温度である。第１図は、従来材、比較材
およびＮｉ量を変化させた場合の本発明合金の活性化特
性である。第２図は他の本発明合金の活性化特性であり
、元素量の効果を示している。The results are shown in FIGS. 1 and 2. The vertical axis of the figure is the weight increase rate (%) due to hydrogen absorption, and the horizontal axis is the atmospheric temperature when the temperature is increased at 5'C/min. FIG. 1 shows the activation characteristics of the conventional material, the comparative material, and the alloy of the present invention when the amount of Ni was varied. FIG. 2 shows the activation characteristics of other alloys of the present invention, showing the effect of element content.
第１図から次のことが判る。即ち、市販されている従来
材は９０°Ｃ前後で水素を吸収し重量増加が始まる。比
較材はＮｉ添加の影響を調査するためのベース合金で、
合金３〜８は１６％ｖ−４％Ｆｅの場合のＮｉ添加の影
響を示す実施例である。従来材に対して比較材の活性化
温度は１００°Ｃと高くなっている。これに対して、合
金３〜８はＮｉ量の増加にともなって活性化温度が低温
側に移動している。The following can be seen from Figure 1. That is, commercially available conventional materials absorb hydrogen and begin to increase in weight at around 90°C. The comparison material is a base alloy for investigating the influence of Ni addition.
Alloys 3-8 are examples showing the effect of Ni addition in the case of 16%v-4%Fe. The activation temperature of the comparative material is 100°C, which is higher than that of the conventional material. On the other hand, in Alloys 3 to 8, the activation temperature shifts to the lower temperature side as the Ni content increases.
これは、Ｎｉ添加量に比例して活性化が容易になること
を示している。This indicates that activation becomes easier in proportion to the amount of Ni added.
第２図は、比較材とほぼ同等の成分にＮｉを添加した場
合、およびＺｒ−４０Ｖ−５ＦｅとＺｒ−１０Ｖ−３０
ＦｅのＮｉ含有量を変えた場合の活性化特性の比較であ
る。Figure 2 shows the case where Ni is added to the almost same components as the comparative material, and the case where Zr-40V-5Fe and Zr-10V-30
This is a comparison of activation characteristics when the Ni content of Fe is changed.
いずれの場合もＮｉの適正量の添加によって、活性化が
容易になっているのが明らかである。In either case, it is clear that addition of an appropriate amount of Ni facilitates activation.
更に、活性化の容易さが水素吸収特性、特に水素平衡圧
力に及ぼす影響を第３図に示す。ここでは、市販材であ
る従来材と、これとほぼ同成分にＮｉ２％を添加した合
金９の水素吸収特性を示す。Furthermore, the influence of the ease of activation on the hydrogen absorption properties, particularly on the hydrogen equilibrium pressure, is shown in FIG. Here, the hydrogen absorption characteristics of a conventional material, which is a commercially available material, and Alloy 9, which has approximately the same composition as the conventional material with addition of 2% Ni, are shown.
活性化処理条件は第３表のとおりである。The activation treatment conditions are shown in Table 3.
（以下、余白）
第３表
従来材は５５０°Ｃでの活性化と３５０’Ｃでの活性化
では、低いＩＩ／Ｍ （吸蔵水素原子数（Ｈ）７合金
原子数（Ｍ））での水素平衡圧が異なり、３５０ ’Ｃ
での活性化の方が平衡圧は高くなっている。これは、従
来材は３５０°Ｃの活性化処理温度では十分に活性化さ
れていないことを示す。ところが、合金９は３５０°Ｃ
の活性化で従来材の５５０°Ｃ活性化とほぼ同し平衡圧
を示し、５５０°Ｃ活性化では従来材より若干良好な水
素吸収特性を持つ。合金９では３５０°Ｃ活性化処理で
の平衡圧力と、５５０°Ｃ活性化処理での平衡圧力との
間にほとんど差がないのは、３５０ ’Ｃで十分に活性
化されていることを示す。(Left below) Table 3 Conventional materials exhibit low II/M (number of absorbed hydrogen atoms (H) 7 number of alloy atoms (M)) when activated at 550°C and 350'C. Hydrogen equilibrium pressure is different, 350'C
The equilibrium pressure is higher when activated at . This indicates that the conventional material was not sufficiently activated at the activation treatment temperature of 350°C. However, alloy 9 has a temperature of 350°C.
When activated at 550°C, it shows almost the same equilibrium pressure as the conventional material when activated at 550°C, and when activated at 550°C, it has slightly better hydrogen absorption properties than the conventional material. For Alloy 9, there is almost no difference between the equilibrium pressure at 350°C activation treatment and the equilibrium pressure at 550°C activation treatment, indicating that it is sufficiently activated at 350'C. .
（３）水素吸収特性の評価
水素吸収特性は、水素平衡圧−組成−等温線図を測定し
て評価する。第４表に評価条件を示す。(3) Evaluation of hydrogen absorption characteristics Hydrogen absorption characteristics are evaluated by measuring a hydrogen equilibrium pressure-composition-isotherm diagram. Table 4 shows the evaluation conditions.
本発明材と従来材との相違点は活性化条件にある。The difference between the material of the present invention and the conventional material lies in the activation conditions.
水素吸収特性を第４図に示す。第４図の横軸はＨ／Ｍで
、縦軸は水素平衡圧力である。同図には、市販材の中、
最も活性化容易な従来材の水素吸収特性と、旧が２％で
Ｆｅが４〜６％の合金５．９．１１の水素吸収特性を対
比している。活性化温度が低いにもかかわらず、合金５
．９．１１は良好な水素吸収特性を示している。合金５
は）１／Ｍが０．２５程度までは従来材とほぼ同等の水
素平衡圧力を示すが、０．２５を超えると合金５の方が
低い水素平衡圧力をもち、同し水素平衡圧力では合金５
の方が多量の水素を吸収できることを示している。合金
９は従来材とほぼ同等の水素吸収特性を持つ。合金１１
はＨ／Ｍが０．２以下においては従来材よりも低い平衡
圧もち、高い真空度まで水素ガスを吸着できる。Figure 4 shows the hydrogen absorption characteristics. The horizontal axis in FIG. 4 is H/M, and the vertical axis is hydrogen equilibrium pressure. In the same figure, among the commercially available materials,
The hydrogen absorption properties of the conventional material, which is the easiest to activate, are compared with those of alloy 5.9.11, which has 2% old and 4-6% Fe. Despite the low activation temperature, alloy 5
．． 9.11 shows good hydrogen absorption properties. Alloy 5
) Up to 1/M of about 0.25, Alloy 5 shows almost the same hydrogen equilibrium pressure as the conventional material, but when it exceeds 0.25, Alloy 5 has a lower hydrogen equilibrium pressure; 5
This shows that it is possible to absorb a larger amount of hydrogen. Alloy 9 has almost the same hydrogen absorption properties as conventional materials. Alloy 11
has a lower equilibrium pressure than conventional materials when H/M is 0.2 or less, and can adsorb hydrogen gas up to a high degree of vacuum.
これら本発明の合金は、市販材のうち最も活性化処理の
容易な従来材よりも低い温度で上記の優れた水素吸収特
性を実現しており、このことが従来の非蒸発型ガス吸収
合金と異なる本発明合金の特色といえる。These alloys of the present invention achieve the above-mentioned excellent hydrogen absorption properties at a lower temperature than conventional materials that are the easiest to activate among commercially available materials, and this makes them superior to conventional non-evaporative gas absorbing alloys. This can be said to be a different feature of the alloy of the present invention.
第５図は、第１表の残りの合金についての試験結果例を
示すものである。合金ｌはＶ−Ｆｅ−Ｎｉの総量が小さ
くＺｒ基の部分が多いので、水素化率（）Ｉ＃Ｉ）が大
きい。合金１０．１３．１５は■の量が多く、低いＨ／
Ｍ値での水素平衡圧が高真空となっている。これらの水
素吸収特性は２５０’Ｃでの活性化処理で得られており
、他の本発明合金と同じく活性化処理の容易さが顕著で
ある。FIG. 5 shows example test results for the remaining alloys in Table 1. Alloy 1 has a small total amount of V-Fe-Ni and a large proportion of Zr groups, so the hydrogenation rate (I#I) is large. Alloy 10.13.15 has a large amount of ■ and low H/
The hydrogen equilibrium pressure at M value is high vacuum. These hydrogen absorption properties were obtained by activation treatment at 250'C, and like the other alloys of the present invention, the ease of activation treatment is remarkable.
（４）用途に関する試験
１、水素吸収材としての用途
この用途で必要な特性は、これまでに述べた水素吸収特
性そのものである。本発明の合金が従来のものと異なる
のは、活性化のための処理が極めて容易なことである。(4) Application test 1: Application as a hydrogen absorbing material The characteristics required for this application are the hydrogen absorption characteristics described above. The alloy of the present invention differs from conventional alloys in that it is extremely easy to process for activation.
例えば、１気圧の水素雰囲気中で合金４を用いて水素吸
収させるのであれば、第１図かられかるように、８０°
Ｃ程度に加熱すれば水素吸収を開始する。For example, if Alloy 4 is used to absorb hydrogen in a hydrogen atmosphere of 1 atm, the 80°
When heated to about C, hydrogen absorption begins.
１１、水素圧力制御用としての用途
この用途に必要な特性を合金９の例で第６図に示す、こ
こで横軸は水素吸収・放出の温度の逆数（１／Ｔ ｘｌ
Ｏ３）であり、縦軸は水素平衡圧力である。11. Application for hydrogen pressure control The properties required for this application are shown in Figure 6 for the example of alloy 9, where the horizontal axis is the reciprocal of the hydrogen absorption/release temperature (1/T xl
O3), and the vertical axis is hydrogen equilibrium pressure.
測定は次のようにして行った。即ち、約５０ｃｃの容積
を持つ反応器に合金９を１ｇ入れ全体を真空に引きその
後加熱して４００°Ｃとして１０−５ｔｏｒｒまで排気
脱ガスを行った。その後、水素を反応器内に導入して３
００ｔｏｒｒの水素圧として、合金９を水素化させた後
５°Ｃ／分で冷却させ、水素を吸収させたのち再び５℃
／分で昇温させて、その間の水素平衡圧を測定した。The measurements were carried out as follows. That is, 1 g of Alloy 9 was placed in a reactor having a capacity of about 50 cc, and the entire reactor was evacuated, and then heated to 400° C. and degassed to 10 −5 torr. After that, hydrogen was introduced into the reactor and 3
Alloy 9 was hydrogenated at a hydrogen pressure of 00 torr, cooled at 5°C/min, absorbed hydrogen, and then cooled again at 5°C.
The temperature was raised at a rate of 1/min, and the hydrogen equilibrium pressure was measured during that time.
第６図に示した２組の線は、それぞれ初期の水素化率（
Ｈ／Ｍ）が０．１．０．４５のものである。どちらのＨ
／Ｍ値の場合も、活性化処理を行わなくても水素を吸収
し始め、温度を変化させることで第６図に示すような水
素平衡圧の変化を示した。The two sets of lines shown in Figure 6 represent the initial hydrogenation rate (
H/M) is 0.1.0.45. Which H
/M value, hydrogen began to be absorbed even without activation treatment, and the hydrogen equilibrium pressure changed as shown in FIG. 6 by changing the temperature.
第６図から明らかなように、使用温度が決まれば、所望
の水素平衡圧を持つ初期水素割合（Ｈ／Ｍ）の合金を機
器の圧力制御を要する容器に封入して、使用機器内の水
素圧力を所望の圧力にし、且つ外部から水素が進入して
きたり、容器内部で水素が発生しても合金のＨ／ＹＩが
大きく変化しない限り、所望の圧力を保持することがで
きる。As is clear from Fig. 6, once the operating temperature is determined, an alloy with an initial hydrogen ratio (H/M) having a desired hydrogen equilibrium pressure is sealed in a container that requires pressure control of the equipment, and the hydrogen inside the equipment is sealed. The desired pressure can be maintained as long as the H/YI of the alloy does not change significantly even if hydrogen enters from the outside or hydrogen is generated inside the container.
ｉｉｉ 、水素以外のガス吸収材としての用途本発明の
合金は、水素以下のガス、たとえば−酸化炭素、窒素、
酸素、炭化水素等の吸着にも使用できる。従って、不純
ガスを取り除き真空度を上げる等の用途にも広（使える
。iii. Use as an absorbent for gases other than hydrogen The alloy of the present invention is suitable for absorbing gases other than hydrogen, such as carbon oxide, nitrogen,
It can also be used to adsorb oxygen, hydrocarbons, etc. Therefore, it can be used for a wide variety of purposes, such as removing impurity gas and increasing the degree of vacuum.
第７図は、かかる用途向けの特性の一例として、−酸化
炭素（ＣＯ）と窒素（Ｎ２）の吸収特性を合金４につい
て調べた結果である。FIG. 7 shows the results of investigating the carbon oxide (CO) and nitrogen (N2) absorption characteristics of Alloy 4 as an example of the characteristics for such uses.
第７図において、横軸はガスの吸収量、継軸は吸収速度
を示している。１気圧で３５０°Ｃの各ガス雰囲気中に
、本発明合金１２０ｍｇ（表面積５０ｎｕｅ”）を封入
した。合金は３５０°Ｃ雰囲気で自動的に活性化されガ
スを吸収し始めた。このガス吸収が水素の吸収と異なる
のは、水素は高温で解離するのに対し、周囲温度や圧力
を変化させてもガスを遊離しないことである。したがっ
て、本発明合金は不純ガスを吸収・除去するゲラクーと
しての用途にも好適である。In FIG. 7, the horizontal axis shows the amount of gas absorbed, and the joint axis shows the absorption rate. 120 mg of the alloy of the present invention (surface area: 50 nu") was sealed in each gas atmosphere at 1 atm and 350°C. The alloy was automatically activated in the 350°C atmosphere and began to absorb gas. This gas absorption The difference from hydrogen absorption is that while hydrogen dissociates at high temperatures, it does not liberate gas even if the ambient temperature or pressure changes.Therefore, the alloy of the present invention can be used as a gelatin to absorb and remove impurity gases. It is also suitable for applications such as
（発明の効果）
本発明は、従来の非蒸属型ガス吸収合金が有していた活
性化処理が困難であるという問題点を解決し、活性化が
容易でなおかつ良好なガス吸収特性を持つ非蒸発型ガス
吸収合金を提供する。(Effects of the Invention) The present invention solves the problem of difficulty in activation treatment that conventional non-metallic gas absorbing alloys had, and has a structure that is easy to activate and has good gas absorption properties. A non-evaporative gas absorbing alloy is provided.
本発明のガス吸収合金は、これまで活性化処理が困難な
ために利用できなかった分野まで非蒸発型ガス吸収合金
の利用を拡大する産業上の価値が極めて高いものである
。The gas-absorbing alloy of the present invention has extremely high industrial value as it expands the use of non-evaporable gas-absorbing alloys to fields where they could not be used due to the difficulty of activation treatment.
第１図と第２図は、本発明の合金と比較材および従来材
の活性化特性を示す図、
第３図〜第５図は、本発明合金と比較材の水素吸収特性
を示す図、
第６図は、本発明合金の温度と水素平衡圧力との関係を
示す図、
第７図は、本発明合金の窒素と一酸化炭素の吸収特性を
示す図、
である。Figures 1 and 2 are diagrams showing the activation characteristics of the alloy of the present invention, comparative materials, and conventional materials. Figures 3 to 5 are diagrams showing the hydrogen absorption characteristics of the alloy of the present invention and comparative materials. FIG. 6 is a diagram showing the relationship between temperature and hydrogen equilibrium pressure of the alloy of the present invention, and FIG. 7 is a diagram showing the absorption characteristics of nitrogen and carbon monoxide of the alloy of the present invention.
Claims (1)
Ｎｉ：０．５〜６％（ただしＶ＋Ｆｅ＋Ｎｉの合計が５
５％以下）を含み、残部は実質的にＺｒからなる活性化
特性に優れたガス吸収合金。In weight%, V: 10-54%, Fe: 0.5-20%,
Ni: 0.5 to 6% (however, the total of V+Fe+Ni is 5%
5% or less), with the remainder essentially consisting of Zr, which has excellent activation properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12672188A JPH089748B2 (en) | 1988-05-24 | 1988-05-24 | Gas absorption alloy with excellent activation characteristics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12672188A JPH089748B2 (en) | 1988-05-24 | 1988-05-24 | Gas absorption alloy with excellent activation characteristics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01298130A true JPH01298130A (en) | 1989-12-01 |
| JPH089748B2 JPH089748B2 (en) | 1996-01-31 |
Family
ID=14942227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12672188A Expired - Lifetime JPH089748B2 (en) | 1988-05-24 | 1988-05-24 | Gas absorption alloy with excellent activation characteristics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH089748B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053476C (en) * | 1996-06-21 | 2000-06-14 | 吕镇和 | Multielement non-evapotranspiation type low-temp activation Zr base gas-absorber alloy and producing method thereof |
-
1988
- 1988-05-24 JP JP12672188A patent/JPH089748B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053476C (en) * | 1996-06-21 | 2000-06-14 | 吕镇和 | Multielement non-evapotranspiation type low-temp activation Zr base gas-absorber alloy and producing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH089748B2 (en) | 1996-01-31 |
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