CN101146608B - Gas-adsorbing substance, gas-adsorbing alloy and gas-adsorbing material - Google Patents
Gas-adsorbing substance, gas-adsorbing alloy and gas-adsorbing material Download PDFInfo
- Publication number
- CN101146608B CN101146608B CN2006800081623A CN200680008162A CN101146608B CN 101146608 B CN101146608 B CN 101146608B CN 2006800081623 A CN2006800081623 A CN 2006800081623A CN 200680008162 A CN200680008162 A CN 200680008162A CN 101146608 B CN101146608 B CN 101146608B
- Authority
- CN
- China
- Prior art keywords
- gas
- adsorbing
- nitrogen
- alloy
- adsorbing substance
- 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.)
- Expired - Fee Related
Links
- 239000000126 substance Substances 0.000 title claims abstract description 73
- 229910045601 alloy Inorganic materials 0.000 title abstract description 51
- 239000000956 alloy Substances 0.000 title abstract description 51
- 239000000463 material Substances 0.000 title abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 131
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 66
- 239000007787 solid Substances 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- 239000001301 oxygen Substances 0.000 claims abstract description 37
- 238000001179 sorption measurement Methods 0.000 claims description 41
- 238000005551 mechanical alloying Methods 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 abstract description 58
- 229910052751 metal Inorganic materials 0.000 abstract description 55
- 239000002184 metal Substances 0.000 abstract description 55
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 description 39
- 150000002739 metals Chemical class 0.000 description 26
- 238000000034 method Methods 0.000 description 25
- 230000000694 effects Effects 0.000 description 21
- 238000000338 in vitro Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 238000012512 characterization method Methods 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 5
- 229910001000 nickel titanium Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 229910007960 Li-Fe Inorganic materials 0.000 description 4
- 229910006564 Li—Fe Inorganic materials 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910007857 Li-Al Inorganic materials 0.000 description 3
- 229910008447 Li—Al Inorganic materials 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- -1 steam Chemical compound 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 229910000986 non-evaporable getter Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
A gas-adsorbing substance which comprises Li and a solid substance having a hardness of 5 or higher and adsorbs at least nitrogen or oxygen at 25 DEG C under an ordinary pressure; a gas adsorbing alloy, characterized in that it comprises at least two types of metal forming no intermetallic compound with one another, the enthalpy of mixing of the above two types of metal is larger than 0, and at least parts of the above two types of metal dissolve with each other; and a gas-adsorbing material which comprises the above gas-adsorbing substance and the above gas adsorbing alloy.
Description
Technical field
The gas-adsorbing material (below be referred to as " gas-adsorbing substance etc. ") that the present invention relates to gas-adsorbing substance, gas-adsorbing alloy and contain this gas-adsorbing substance and/or gas-adsorbing alloy.
Background technology
Gas-adsorbing substances etc. keep in vacuum, removing etc. in the various fields of the gas in the removing of the minimum gas in the rare gas, fluorescent lamp is used.
Employed rare gas in semi-conductor industry, expectation are removed nitrogen in the rare gas, hydrocarbon, carbon monoxide, carbon dioxide, oxygen, hydrogen, steam etc. and are purified and be high-purity.Particularly remove wherein very difficult as the nitrogen of stable molecule.
As the existing method of removing nitrogen or hydrocarbon etc. in the rare gas, the method (for example with reference to patent documentation 1) that for example has getter (getter) material that makes the ternary alloy three-partalloy that constitutes by zirconium, vanadium and tungsten and rare gas under heating, to contact.
It is through alloy being contacted with rare gas under 100～600 ℃ temperature, removing impurity such as denitrification thus from rare gas.
As existing additive method, also have and use a kind the element that contains zirconium, iron, manganese, yttrium, lanthanum and rare earth element, and have the method (for example with reference to patent documentation 2) of the non-evaporable getter alloys of high gas absorption efficient for nitrogen.
It is to handle through making alloy under the temperature between 300～500 ℃, carry out activate in 10～20 minutes, even at room temperature also can play a role for the absorption of hydrogen, hydrocarbon, nitrogen etc. thus.
As existing another method, use the method for Ba-Li alloy in addition, this alloy has the character (for example with reference to patent documentation 3) of adsorption of nitrogen at low temperatures.
It is in collet (jacket), to be provided with the device that is used to keep vacuum, is made up of the Ba-Li alloy, even at room temperature also can demonstrate reactivity for gases such as nitrogen.
It has following record to carry, and, is the nitrogen absorption that utilizes Ba that is, and is without Li, also no problem with Na, K.
As oxygen absorbent, it promotes material, filler (filler), moisture to supply with body formation (for example with reference to patent documentation 4) by iron powder, oxidation.
It is the oxygen absorbent that is used on the quality guarantee purposes of food, pharmaceuticals etc., in oxygen absorbs, needs moisture.
Patent documentation 1: the spy opens flat 6-135707 communique
Patent documentation 2: special table 2003-535218 communique
Patent documentation 3: specially permit communique No. 2627703
Patent documentation 4: specially permit communique No. 3252866
Yet, in patent documentation 1, in the above-mentioned existing technology of record, need continue down heating at 300～500 ℃, also unfavorable to environment because be heating at high temperature so energy consumption is big, can not carry out at low temperatures in addition using under the situation of gas absorption.
In patent documentation 2, in the above-mentioned prior art of record, need 300～500 ℃ pre-treatment, and the gas that at high temperature is difficult to carry out under the situation of pre-treatment is removed, for example removed the gas difficulty very just in the polybag at normal temperatures.
In the prior art of in patent documentation 3, putting down in writing; Though need not be used for the heat treatment of activate; But can carry out nitrogen absorption at normal temperatures; But because higher activate, the high capacity of expectation, and Ba is the violent in toxicity designated substance, so in payable use, also expect environment and human body are safe from harm.
In addition, need melted alloy for making, make the energy that consumes and become big.
In the above-mentioned prior art of record, the oxygen absorption needs moisture in patent documentation 4, and next can not the use of atmosphere that has micro-moisture also not have.
Summary of the invention
Its purpose of the present invention is, solves above-mentioned existing problem, particularly obtain for the high gas-adsorbing substance of the absorption property of nitrogen and/or oxygen, thereby even under normal temperature and pressure or normal temperature decompression, also can adsorption of nitrogen and/or oxygen.
Its purpose is in addition, and the gas-adsorbing substance that all is safe from harm for environment and human body is provided.
Gas-adsorbing substance, gas-adsorbing alloy are provided in order to reach above-mentioned purpose, contain the gas-adsorbing material of above-mentioned gas adsorbent and gas-adsorbing alloy; Wherein, Said gas-adsorbing substance contains Li at least and hardness is the solid matter more than 5; And at 25 ℃ of normal pressures down to I haven't seen you for ages adsorption of nitrogen or oxygen, said gas-adsorbing alloy, it is made up of at least 2 kinds of metals that can not generate intermetallic compound each other; And the enthalpy of the mixing of said 2 kinds of metals (enthalpy) is bigger than 0, and at least a portion can mix between said 2 kinds of metals in addition.
Description of drawings
Fig. 1 is the summary pie graph of absorption evaluating apparatus of evaluation of characterization of adsorption that is used for the gas-adsorbing substance of embodiment of the present invention.
Fig. 2 is among the expression embodiments of the invention I-1, when in vitro importing the nitrogen of about 80000Pa by the performance plot of the characterization of adsorption of the nitrogen that gas-adsorbing substance brought.
Fig. 3 is among the expression embodiments of the invention I-2; The characterization of adsorption of the nitrogen that gas-adsorbing substance brought when in vitro importing the nitrogen of about 60000Pa and in vitro during the oxygen of the about 60000Pa of importing by the performance plot of the characterization of adsorption of the oxygen that gas-adsorbing substance brought.
Fig. 4 is among the expression embodiments of the invention I-2, when in vitro importing the atmosphere air of about 55000Pa by the performance plot of the characterization of adsorption of the air that gas-adsorbing substance brought.
Fig. 5 is among the expression embodiments of the invention I-3, when in vitro importing the nitrogen of about 60000Pa by the performance plot of the characterization of adsorption of the nitrogen that gas-adsorbing substance brought.
Fig. 6 is among the expression embodiments of the invention I-3, import in vitro that the nitrogen of about 65000Pa is about 80%, during the mixing air of oxygen about 20% by the performance plot of the characterization of adsorption of the mixing air that gas-adsorbing substance brought.
Fig. 7 is among the expression embodiments of the invention I-3, the performance plot of the characterization of adsorption of the nitrogen that gas-adsorbing substance brought during in vitro for 310Pa.
Fig. 8 is among the expression embodiments of the invention I-4, the performance plot of the characterization of adsorption of the nitrogen that gas-adsorbing substance brought during in vitro for 96000Pa.
Fig. 9 is the phasor of Mg-Ti.
Figure 10 is the phasor of Li-Fe.
Figure 11 is the phasor of Ni-Ti.
The specific embodiment
At first, be the solid matter more than 5 for containing Li and hardness at least, and describe at the gas-adsorbing substance of 25 ℃ of normal pressures down to I haven't seen you for ages adsorption of nitrogen or oxygen.
Li can present inertia because of the reason that forms tunicle etc. on the surface usually, thereby can not adsorption of nitrogen or oxygen.
Yet, be 0.6 hardness with respect to Li, making hardness is that solid matter more than 5 coexists with it, solid matter can grind Li thus, thus the surface of the surperficial newly-generated activity of skiving Li.Therefore, also adsorption of nitrogen and/or oxygen fast at normal temperatures.
In gas-adsorbing substance of the present invention, solid matter is preferably oxide or contains oxide at least.
Through using oxide, the oxygen simulation ground of oxide surface temporarily combines with Li, so think that along with the fragmentation of oxide, Li is also by effective pulverizing when carrying out for example fragmentation, kneading etc., the activate of Li obtains promotion.
In gas-adsorbing substance of the present invention, preferred its particle diameter of at least a portion of Li is below the 1mm.
Through making particle diameter below 1mm, Li skin portion not only, and until Li inside also easily by nitrogenize or oxidation, the gas absorption amount of the Li of unit increases, effectively materials used.
In gas absorption material of the present invention, the part of preferred Li at least and solid matter mixes.
Because the part of Li and solid matter mixes, the interface increases, the active raising.
It is that Li and said solid matter mix through mechanical alloying (mechanical alloying) at least that gas-adsorbing substance of the present invention is preferably.
Through carrying out mechanical alloying, can grind, mix Li and solid matter by high energy, the skiving effect to Li that is produced by solid matter increases, and Li new life shows out with the sectionalization effect and increases.In addition, because solid matter is also by skiving and sectionalization, so with respect to sectionalization Li, more produce effect.
In addition, through carrying out mechanical alloying, mechanical energy is accumulated in Li and solid matter, and compared with at the energy that starting point had, the energy that after mechanical alloying, is had increases, and activate further improves.
Make according to said method, because need not necessary energy such as fusion, so also excellent aspect environment or cost.
Gas-adsorbing substance of the present invention, the alloy that can access have high adsorption activity to nitrogen and/or oxygen especially.
First invention of gas-adsorbing substance, wherein, containing Li and hardness at least is the solid matter more than 5, and at 25 ℃ of normal pressures down to I haven't seen you for ages adsorption of nitrogen and/or oxygen.
Here, be the solid matter more than 5 as hardness, can enumerate Si, B, c-C (diamond), SiO
2, SiC, c-BN (cubic boron nitride), Al
2O
3, MgO, TiO
2
Also can add other composition.
Here said so-called hardness is meant 10 grades Mohs' hardness (Mohs hardness).
As the confirmation method of above-mentioned solid matter, for example also can be through with X-ray diffraction, thus the method that the peak value of Li and solid matter can be confirmed etc. is carried out but not special appointment.
The containing ratio of solid matter is preferably more than the 5mol%, below the 95mol%.This is that the gas absorption activity diminishes because with respect to gas-adsorbing substance 100mol%, if solid matter lacks than 5mol%, it is many that the Li that then ductility is high becomes, and is difficult to thus mix equably with solid matter, if more than 95mol%, then active high Li reduces in addition.
The density that is preferably solid matter is at 5g/cm
3Below.Through adopting such solid matter, though with density be 0.53g/cm
3Li when combination, density rises also seldom, in addition, can increase the nitrogen adsorbance of per unit weight.
Therefore, even when for example being contained in this gas-adsorbing substance group in the goods, its weight increase also seldom and can be guaranteed the adsorbance of nitrogen etc.
Gas-adsorbing substance of the present invention at least can adsorption of nitrogen and/or oxygen under 25 ℃ of normal pressures, but the gas beyond nitrogen or the oxygen also can adsorb for example hydrogen, steam, carbon monoxide, carbon dioxide, nitrogen oxide, sulfur oxide, hydrocarbon.Do not have special the appointment about the gas of denitrogenating or adsorbing beyond the oxygen.
Do not specify about the assay method of adsorbance is special in the present invention, can utilize known method such as adsorption capacity method, gravimetric method, as long as can confirm the absorption of nitrogen and/or oxygen at least.
Gas-adsorbing substance of the present invention, preferred every 1g can adsorption of nitrogen and/or oxygen 1cm
3More than, preferably can adsorb 3cm
3More than, more preferably can adsorb 5cm
3More than.The mensuration of its adsorbance; For example can in the process of absorption, take out the gas-adsorbing substance that a part has been carried out absorption, measure the nitrogen adsorbance to this gas-adsorbing substance; In addition; Also can be for the gas-adsorbing substance of having lost a part of absorption or adsorption activity, discharge nitrogen through the method for heating etc., try to achieve the nitrogen adsorbance of every 1g according to the gas-adsorbing substance after this nitrogen amount and the heating.
Here said so-called absorption except being adsorbed onto the surface, also comprises absorbing inside or sorption.
Gas absorption material of the present invention can carry out in normal temperature or about atmosphere below 80 ℃, below normal pressure, and the particularly absorption in the area of low pressure.
As the use form of gas-adsorbing substance, method for using can be listed below: powder, compression molding, Pelleting, sheet, film like or accommodate other containers, vapor deposition to other materials, but not special the appointment.
Second invention of gas-adsorbing substance, wherein, the solid matter in first invention comprises oxide at least.
Here, so-called oxide is Al
2O
3, MgO, SiO
2, TiO
2Deng.
Perhaps also can be to contain the above oxide of three kinds of elements.
The 3rd invention of gas-adsorbing substance, in each invention of first or second, at least a portion of Li is in below the particle diameter 1mm.
Below the so-called particle diameter 1mm, be to get final product below the particle diameter of at least a portion is in 1mm, can confirm by general confirmation method.In addition, can be the particle diameter before the gas absorption, also can be the particle diameter after the absorption, this not special appointment.
The 4th invention of gas-adsorbing substance is that at least a portion of Li and solid matter mixes at least in each invention of first to the 3rd.
Here, so-called at least a portion mixes, and is meant to have at least a part can not separate into to physical property the state of 2 kinds of materials.For example refer between its materials of a part of boundary face of 2 kinds of materials state, but be not limited thereto with atom level mixing etc.
The 5th invention of gas-adsorbing substance is that Li and solid matter are mixed through mechanical alloying at least in each invention of first～the 4th.
Here, what is called is mixed by mechanical alloying, is meant method of mixing mechanically, not special the appointment.In order to make highly active gas-adsorbing alloy, preferably in inert gas, for example carry out mechanical alloying in the atmosphere of Ar, He etc. or under the vacuum.
When carrying out mechanical alloying, add separately C and the cooling under carry out, the alcohol etc. that also can drip on a small quantity is in case be attached on the container.
Secondly, describe for following this gas-adsorbing alloy, it is made up of 2 kinds of metals that do not generate intermetallic compound each other at least, and the enthalpy of the mixing of said 2 kinds of metals is bigger than 0, and at least a portion mixes between said 2 kinds of metals in addition.
Be a kind of metal that does not each other generate intermetallic compound, and be the enthalpy of mixing of said 2 kinds of metals than 0 big metal, can interactional this metal through adopting generally not, can make the activity raising of metal contained in the base.Therefore, the reactivity of metal and gas improves, and the gas absorption activity uprises.
As its reason; If carrying out medelling ground sets forth; Then be considered to because of being in the alloy at for example Li-Fe, stable chemical bond does not take place in Li atom and Fe atom, therefore if forcibly make these atom adjacency; Then this effect that mutually combines of itself and other element further becomes big, and adsorption activity uprises.
At least a portion mixes between 2 kinds of metals, then can further improve intermetallic repulsion more through mixing, and the activity of wherein contained metal is improved.Therefore, with the reactivity raising of gas, the gas absorption activity uprises.
Gas-adsorbing alloy of the present invention, preferred at least by Li with can not constitute with the transition metal that Li generates intermetallic compound, and the enthalpy of the mixing of said 2 kinds of metals is bigger than 0.
Thus, the activity of Li that can adsorption of nitrogen is improved.Therefore, in general can access the very high alloy of gas adsorbability to this gas that is difficult to adsorb of nitrogen.
Gas-adsorbing alloy of the present invention preferably mixes through mechanical alloying.
For to can not generating intermetallic compound each other, the additional mixing enthalpy is than carrying out alloying between the 0 big metal, and to improve activity, mixing with mechanical alloying is best method.
Gas-adsorbing alloy of the present invention; 2 kinds of metals by not generating intermetallic compound each other constitute; The enthalpy of the mixing of 2 kinds of metals is bigger than 0; At least a portion mixes in addition, can access the gas for nitrogen, oxygen, hydrogen, carbon dioxide, carbon monoxide, moisture etc. thus, and is wherein special in the very high alloy of the activity of nitrogen.
First invention of gas-adsorbing alloy wherein, be made up of at least 2 kinds of metals that can not generate metallic compound each other, and the enthalpy of the mixing of said 2 kinds of metals is bigger than 0.
Here said so-called alloy is meant the material that is made up of the metal more than 2 kinds.
Metal can not generate intermetallic compound each other, and this can confirm through for example X-ray diffraction.
At least 2 kinds of metals can not generate intermetallic compound and get final product, and for example can add the above element of 1 composition again, and this element and said metal possibly generate compound in addition.
The enthalpy that mixes is bigger than 0, for example can confirm according to phasor, and is for example as shown in Figure 9, and line does not intersect yet even make temperature rise to a certain degree, just can confirm according to these.
In the phasor of the enthalpy that mixes, comprise and represent the non-solid solution type as shown in Figure 9 or the phasor of cocrystallizing type than 0 big metal species.
As the gas that can adsorb, can enumerate nitrogen, oxygen, hydrogen, steam, carbon monoxide, carbon dioxide, nitrogen oxide, sulfur oxide, hydrocarbon etc., but not special the appointment.
Here the what is called absorption of saying except being adsorbed onto the surface, also comprises absorbing inside.
Because gas adsorbability alloy of the present invention has high activity, so can in normal temperature or about atmosphere below 80 ℃, under normal pressure, adsorb in the area of low pressure especially.
As the use form of alloy, method for using can be listed below: powder, compression molding, Pelleting, sheet, film like or accommodate other containers, vapor deposition to other materials, but not special the appointment.
Second invention of gas-adsorbing alloy wherein, has at least a part to mix between said 2 kinds of metals.
What is called has at least a part to mix, and is meant to have at least a part can not separate into to physical property the state of 2 kinds of metals.For example refer between its metals of a part of boundary face of 2 kinds of metals state, but be not limited thereto with atom level mixing etc.
The 3rd invention of gas-adsorbing alloy; It is a kind of gas-adsorbing alloy; It is by constituting than 0 little metal with second metal that said metal can not generate intermetallic compound in the nitride enthalpy of formation of 298K at least, and the enthalpy of the mixing of said 2 kinds of metals is bigger than 0.
Than 0 big metal, Li, Mg, Al, Ca, Si etc. are arranged as the nitride enthalpy of formation.
The 4th invention of gas-adsorbing alloy is to have at least a part to mix between said 2 kinds of metals.So-called " at least a portion mixes " and above-mentioned synonym.
The 5th invention of gas-adsorbing alloy, at least by Li with can not constitute with the transition metal that Li generates intermetallic compound, and the enthalpy of the mixing of said 2 kinds of metals is bigger than 0.
As with the enthalpy of mixing of Li than 0 big transition metal, Co, Cr, Cu, Fe, Hf, Mn, Mo, Nb, Ni, Ta, Ti, V, W, Y, Zr etc. are arranged.
Gas-adsorbing alloy of the present invention is active high for nitrogen, but for the gas of oxygen, hydrogen, steam, carbon monoxide, carbon dioxide, nitrogen oxide, sulfur oxide, hydrocarbon etc. high activity is arranged also in addition.
The containing ratio of transition metal is preferably more than the 5mol%, below the 95mol%.
This is that the gas absorption activity diminishes because for alloy 100mol%, if transition metal lacks than 5mol%, it is many that the Li that then ductility is high becomes, and is difficult to thus mix equably with transition metal, if more than 95mol%, then active high Li reduces in addition.
The 6th invention of gas-adsorbing alloy wherein, has at least a part to mix between said 2 kinds of metals.So-called " at least a portion mixes " and above-mentioned synonym.
The 7th invention of gas-adsorbing alloy is the gas-adsorbing alloy that mixes the 1st～6 at least 2 kinds of metals in the invention through mechanical alloying.
The so-called mixing through mechanical alloying is meant and mechanically carries out method of mixing, but not special the appointment.In addition, in order to make the gas-adsorbing alloy of high property, preferably in inert gas, for example in the atmosphere of Ar, He etc., carry out mechanical alloying.
In the present invention, the gas-adsorbing material that contains above-mentioned gas absorption alloy and gas-adsorbing substance also is provided.
So; Active through having different gas absorption; And make up said gas-adsorbing alloy and gas-adsorbing substance of the present invention, can access the gas-adsorbing material that speed and adsorption activity are kept equal excellence, its be exposed to absorption object gas in after; Active part adsorbed gas hastily, active lower part is understood the former adsorbed gas more slowly relatively.
The gas-adsorbing material that contains gas-adsorbing alloy and gas adsorbent; Can pass through as inferior method manufacturing: mix the former and the latter earlier; Perhaps make the former gas-adsorbing alloy and gas adsorbent in advance respectively, and in same atmosphere, use, perhaps make respectively and mix this mixture of other compression molding thereafter; Perhaps carry out granulating separately respectively and in atmosphere, make, perhaps another kind of by a kind of lining.
Because adsorption material of the present invention has high activity, so can in normal temperature or about atmosphere below 80 ℃, under normal pressure, adsorb in the area of low pressure especially.
Below, describe for embodiment of the present invention.Also have, the present invention is not limited by this embodiment.
(the mode 1 of enforcement: gas-adsorbing substance)
Gas-adsorbing substance of the present invention is made up of Li and these 2 kinds of materials of solid matter.This solid matter that is adopted is safe from harm for environment etc.
The gas-adsorbing substance that changes the kind of solid matter is shown in example I-1～I-3 to the evaluation result that nitrogen, oxygen, air adsorb.
(example I-1)
Use Si as solid matter.In Ar atmosphere, used the planetary ball mill of stainless steel ball, the Si of the Li of 1mol and 5mol is carried out mechanical alloying make its mixing, obtain gas-adsorbing substance (Li-Si).Also have, the hardness of Si is 6.4, and density is 2.3g/cm
3
Through utilizing mechanical alloying to mix, the part of the boundary face of 2 kinds of materials is mixed with the millimicro level, can think that the boundary face between 2 kinds of materials mixes.
At least a portion of confirming Li becomes the powder below the 1mm.
Then, the adsorption material evaluating apparatus with Fig. 1 is estimated the characterization of adsorption of gas-adsorbing substance (Li-Si) under Ar atmosphere.
Adsorption material evaluating apparatus 1, its gas bomb 4 (gasbombe) are through first valve 5, and vavuum pump 6 passes through second valve 7 in addition, and is connected on the gas supply part 8 with specified volume.In addition, be connected on the test tube 3 through the 3rd valve 9 from gas supply part 8.In addition, on test tube 3, be connected with pressure gauge 10.In addition, can dismantle between gas supply part 8 and the 3rd valve 9.
At first, gas-adsorbing substance 2 is sealed in Ar atmosphere in the test tube 3 (not shown) that is the state of taking off, and is connected on the gas supply part 8 with the state of closing the 3rd valve 9.
Then, under first valve, 5 closing state, open second valve 7, open the 3rd valve 9 thereafter again, to carrying out vacuum exhaust in the system., when system in being in abundant low pressure, close three valve 9, the second valves 7, open first valve 5, import gases from gas bomb 4 to gas supply part 8 so that be in the mode that regulation presses in the test tube 3, and close first valve 5 thereafter.Then, open the 3rd valve 9, gas-adsorbing substance 2 is exposed in the gas, estimate gas adsorbability thus.
Making in vitro becomes about 80000Pa, and the relation that time when so importing nitrogen and pressure change is presented among Fig. 2.
As shown in Figure 2, became 0Pa in about 40 minutes basically.
(example I-2)
Use Al
2O
3As solid matter.In Ar atmosphere, used the vibrator of stainless steel ball, to the Li of 1mol and the Al of 1.1mol
2O
3Carry out mechanical alloying and make its mixing, obtain gas-adsorbing substance (Li-Al
2O
3).Also has Al
2O
3Hardness be 9, density is 3.97g/cm
3
At least a portion of confirming Li becomes the powder below the 1mm.
Then, under Ar atmosphere with gas-adsorbing substance (Li-Al
2O
3) be sealed in the test tube 3, according to the method identical, estimate characterization of adsorption with the adsorption material evaluating apparatus with example I-1.
Making in vitro becomes about 60000Pa, and the relation that time when so importing nitrogen and pressure change is presented among Fig. 3.
At the absorption initial stage, compare with example I-1, can although knowing the initial stage forces down, but adsorption rate is fast, and active high.
Making in vitro becomes about 60000Pa, and the relation that time when so importing oxygen and pressure change is presented among Fig. 3.
Import atmosphere air (humidity 63%), about 55000Pa from first valve 5 in vitro.At this moment the time and the relation of pressure are presented among Fig. 4.
In addition, in order to measure adsorbance, utilize the system Autosorb-1-C of Quantachrome society to gas-adsorbing substance (Li-Al
2O
3) carry out nitrogen, the evaluation of oxygen adsorbance.
Through estimating the nitrogen adsorbance, confirmed at about 5300Pa absorption 21.98cm
3/ gSTP is at about 92000Pa absorption 30.45cm
3/ gSTP.In addition, through estimating the oxygen adsorbance, confirmed at about 900Pa absorption 1.98cm
3/ gSTP is at about 92000Pa absorption 6.31cm
3/ gSTP.
(example I-3)
Use MgO as solid matter.The vibrator of stainless steel ball has been used in use, and the Li of 1mol and the MgO of 2mol are carried out mechanical alloying and make its mixing, obtains gas-adsorbing substance (Li-MgO).Also have, the hardness of MgO is 5.5, and density is 3.6g/cm
3
Confirming becomes the powder below the 1mm at least a portion of Li.
Then, under Ar atmosphere, gas-adsorbing substance (Li-MgO) is sealed in the test tube 3,, estimates characterization of adsorption with the adsorption material evaluating apparatus according to the method identical with example I-1.
Making in vitro becomes about 60000Pa, and the time when so importing nitrogen and the relation of pressure are presented among Fig. 5.
Making in vitro becomes about 65000Pa, imports so that nitrogen is about 80%, the time the during mixing air of oxygen about 20% and the relation of pressure be presented among Fig. 6.
The relation that time and pressure when in vitro becoming the about 310Pa of nitrogen are changed is presented among Fig. 7.
According to Fig. 7, reached 50Pa in about 6.5 minutes, and one step of ground demonstrates the tendency that pressure reduces.
In addition, in order to measure adsorbance, utilize the system Autosorb-1-C of Quantachrome society that gas-adsorbing substance (Li-MgO) is carried out nitrogen, the evaluation of oxygen adsorbance.
Through estimating the nitrogen adsorbance, confirm at about 45Pa absorption 5.44cm
3/ gSTP is at about 92000Pa absorption 26.64cm
3/ gSTP.In addition, through estimating the oxygen adsorbance, confirmed at about 45Pa absorption 1.94cm
3/ gSTP is at about 92000Pa absorption 11.93cm
3/ g.
(example I-4)
Use MgO as solid matter.The vibrator of stainless steel ball has been used in use, and the Li of 1mol and the MgO of 1mol are carried out mechanical alloying and make its mixing, obtains gas-adsorbing substance (Li-MgO).
Then, under Ar atmosphere, gas-adsorbing substance (Li-MgO) is sealed in the test tube 3,, estimates characterization of adsorption with the adsorption material evaluating apparatus according to the method identical with example I-1.
Make time and the relation of pressure when in vitro becoming the about 96000Pa of nitrogen, be presented among Fig. 8.
In in being exposed to nitrogen, confirm adsorption of nitrogen apace.
(example I-5)
Use SiO
2As solid matter.In Ar atmosphere, used the planetary ball mill of stainless steel ball, to the Li of 1mol and the SiO of 3mol
2Carry out mechanical alloying and make its mixing, obtain gas-adsorbing substance (Li-SiO
2).Also has SiO
2Hardness be 6.4, density is 2.3g/cm
3
Mix through mechanical alloying, the part of the boundary face of 2 kinds of materials is mixed with the millimicro level thus, can think that the boundary face between 2 kinds of materials mixes.
Then, under Ar atmosphere with gas-adsorbing substance (Li-SiO
2) be sealed in 20cm
3Container in, to carrying out vacuum exhaust in the container, when being about the blanket of nitrogen of 0.05MPa thereafter, atmosphere pressures becomes 15Pa from 0.05MPa.
At this moment, gas-adsorbing substance (Li-SiO
2) the about 12cm of every 1g absorption
3
Next show comparative example with respect to the gas-adsorbing substance of embodiment 1 of the present invention.
(Comparative Example I-1)
As gas-adsorbing substance, prepare the Li monomer is carried out mechanical alloying, but directly utilize mechanical alloying can not carry out uniform sectionalization.
(Comparative Example I-2)
As gas-adsorbing substance, estimate the characterization of adsorption of the Li of the about 1cm of particle diameter.Make and in vitro become the about 80000Pa of nitrogen.The result just begins to reduce through pressure after 2 hours.
(Comparative Example I-3)
As gas-adsorbing substance, the Li of 1mol and the Au of 5mol are carried out mechanical alloying, but sectionalization uniformly.Also have, the hardness of Au is 2.5, and density is 19.3g/cm
3
According to the method identical, estimate characterization of adsorption with adsorption material evaluating apparatus 1 with example I-1.When making the oxygen atmosphere that in vitro becomes about 50000Pa, atmosphere pressures reduces a little, but does not see significantly and reduce.
(the mode 2 of enforcement: gas-adsorbing alloy)
Gas-adsorbing alloy of the present invention is made up of for these 2 kinds metal a and metal b.The metal that is safe from harm for environment etc. of these metals that adopt.
The gas adsorbability alloy that changes the kind of metal is shown among example II-1～II-2 the evaluation result that nitrogen, oxygen, air adsorb.Evaluation is in sealing system, to leave standstill gas-adsorbing alloy, becomes the blanket of nitrogen of about 0.08MPa, observes this intrasystem pressure and changes.
(example II-1)
Use Mg as metal a, use Ti as metal b.In Ar atmosphere, Mg and Ti are carried out mechanical alloying and make its mixing with ball mill.
Shape according to the phasor of the Mg-Ti of Fig. 9 confirms that enthalpy of mixing is bigger than 0.
Can not interact even improve temperature between such metal usually yet, but mix then and can mix each other through mechanical alloying.Why can mix each other at this, be considered to since its metal of a part of the boundary face of 2 kinds of metals this mix with the millimicro level, the boundary face between 2 kinds of metals mixes.
Mg-Ti is statically placed in the sealing system, and when being about the blanket of nitrogen of 0.08MPa, atmosphere pressures becomes 10Pa from 0.08MPa.
(example II-2)
Use Li as metal a, use Fe as metal b.In Ar atmosphere, Li and Fe are carried out mechanical alloying and make its mixing with ball mill.
Shape according to the phasor of the Li-Fe of Figure 10 confirms that enthalpy of mixing is bigger than 0.
Can not interact even improve temperature between such metal usually yet, but mix then and can mix each other through mechanical alloying.
Li-Fe is statically placed in the sealing system, and when being about the blanket of nitrogen of 0.08MPa, atmosphere pressures becomes 6Pa from 0.08MPa.
Then displaying is with respect to the comparative example of the gas-adsorbing alloy of the mode 2 of enforcement of the present invention.
(Comparative Example I I-1)
As the alloy of comparative example, adopt the Ni-Ti alloy.In Ar atmosphere, Ni and Ti are carried out mechanical alloying and make its mixing with ball mill.The phasor that shows Ni-Ti among Figure 11.Can know that according to Figure 11 the Ni-Ti alloy can generate intermetallic compound.
The Ni-Ti alloy is statically placed in the sealing system, and when being about the blanket of nitrogen of 0.08MPa, pressure reduces almost not generation.
The possibility of utilizing on the industry
As above; This gas-adsorbing substance of the present invention; Because gas absorption is active high; Especially the absorption property for nitrogen or oxygen is high, uses in the various fields such as the removing of gas that therefore can be in fluorescent lamp, heat insulation etc. vacuum keep, the removing of the minimum gas in the rare gas, gas separation.
Claims (5)
1. a gas-adsorbing substance is characterized in that, containing Li and hardness at least is the solid matter more than 5, and under 25 ℃ of normal pressures adsorption of nitrogen and/or oxygen at least, said solid matter contains oxide at least.
2. gas-adsorbing substance according to claim 1 is characterized in that at least a portion of said Li forms below the particle diameter 1mm.
3. gas-adsorbing substance according to claim 1 is characterized in that at least a portion of said at least Li and said solid matter mixes.
4. gas-adsorbing substance according to claim 1 is characterized in that, said at least Li and said solid matter mix through mechanical alloying.
5. gas-adsorbing substance according to claim 1 is characterized in that, the hardness when containing Li and 25 ℃ at least is more than 5 and density is 5g/cm
3Following solid matter, and under 25 ℃ of normal pressures, can adsorb 5cm
3The nitrogen that/g is above, said solid matter contains oxide at least.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005007298A JP4889947B2 (en) | 2005-01-14 | 2005-01-14 | Gas adsorption alloy |
| JP007298/2005 | 2005-01-14 | ||
| JP2005087994 | 2005-03-25 | ||
| JP087994/2005 | 2005-03-25 | ||
| JP2005350318A JP5061289B2 (en) | 2005-03-25 | 2005-12-05 | Gas-adsorbing substances and gas-adsorbing materials |
| JP350318/2005 | 2005-12-05 | ||
| PCT/JP2006/300330 WO2006075680A1 (en) | 2005-01-14 | 2006-01-13 | Gas-adsorbing substance, gas-adsorbing alloy and gas-adsorbing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101146608A CN101146608A (en) | 2008-03-19 |
| CN101146608B true CN101146608B (en) | 2012-08-15 |
Family
ID=36798859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800081623A Expired - Fee Related CN101146608B (en) | 2005-01-14 | 2006-01-13 | Gas-adsorbing substance, gas-adsorbing alloy and gas-adsorbing material |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4889947B2 (en) |
| CN (1) | CN101146608B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450933A (en) * | 2000-08-18 | 2003-10-22 | 纳幕尔杜邦公司 | Gas separation process |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS635164Y2 (en) * | 1981-02-12 | 1988-02-12 | ||
| JPS6153598A (en) * | 1984-08-24 | 1986-03-17 | 株式会社日立製作所 | Removing system of radioactive iodine |
| JPH0819500B2 (en) * | 1988-03-18 | 1996-02-28 | 三洋電機株式会社 | Hydrogen storage alloy thin film body and method for producing the same |
| IT1237948B (en) * | 1990-01-05 | 1993-06-19 | Getters Spa | GETTER DEVICE AND GETTERING SET FOR A CATHODIC TIBO |
| IT1246786B (en) * | 1991-04-16 | 1994-11-26 | Getters Spa | PROCESS FOR THE ABSORPTION OF RESIDUAL GASES, IN PARTICULAR NITROGEN, BY MEANS OF AN UNEVAPORATED BARIUM GETTER ALLOY. |
| JPH07110426B2 (en) * | 1991-12-17 | 1995-11-29 | 日本金属工業株式会社 | Method for manufacturing tantalum / copper / stainless steel (carbon steel) clad |
| RU2073737C1 (en) * | 1994-12-29 | 1997-02-20 | Товарищество с ограниченной ответственностью "Техновак +" | Nondusting tape gas absorber and method of manufacture thereof |
| JP3415333B2 (en) * | 1995-07-13 | 2003-06-09 | トヨタ自動車株式会社 | Hydrogen storage alloy |
| JP3098705B2 (en) * | 1995-10-02 | 2000-10-16 | トヨタ自動車株式会社 | Surface nitriding method of aluminum material and nitriding aid |
| JP4395898B2 (en) * | 1997-06-03 | 2010-01-13 | パナソニック株式会社 | Anode material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using these anode materials |
| JP2001266746A (en) * | 2000-03-23 | 2001-09-28 | Stanley Electric Co Ltd | Manufacturing method for cold-cathode fluorescent tube |
| JP2002334695A (en) * | 2001-03-09 | 2002-11-22 | Canon Inc | Secondary battery and manufacturing method of secondary battery |
| JP2003171670A (en) * | 2001-12-07 | 2003-06-20 | Kawaken Fine Chem Co Ltd | Method for producing hydrocarbons and catalyst for producing hydrocarbons |
| JP2004237140A (en) * | 2003-02-03 | 2004-08-26 | Nippon Shokubai Co Ltd | Adsorbent for nitrogen oxide, method for manufacturing and regenerating the same, method for removing nitrogen oxide and method for cleaning nitrogen oxide-containing gas |
-
2005
- 2005-01-14 JP JP2005007298A patent/JP4889947B2/en not_active Expired - Fee Related
-
2006
- 2006-01-13 CN CN2006800081623A patent/CN101146608B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450933A (en) * | 2000-08-18 | 2003-10-22 | 纳幕尔杜邦公司 | Gas separation process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006192380A (en) | 2006-07-27 |
| JP4889947B2 (en) | 2012-03-07 |
| CN101146608A (en) | 2008-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5443616A (en) | Metal hydride composition and method of making | |
| TW574055B (en) | Non-evaporable getter alloys | |
| Kalinichenka et al. | Hydrogen storage properties and microstructure of melt-spun Mg90Ni8RE2 (RE= Y, Nd, Gd) | |
| CN101068942B (en) | Non-evaporable getter alloys for hydrogen sorption | |
| US4589919A (en) | Metal bound and ballasted hydridable pellets | |
| CN105779848A (en) | Ferrotitanium-based hydrogen storage alloy | |
| RU2005110943A (en) | HETTER COMPOSITIONS REGENERATED AT LOW TEMPERATURE AFTER EXPOSURE TO REACTIVE GASES AT HIGHER TEMPERATURE | |
| US4687650A (en) | Methods of extracting hydrogen from a gas | |
| JP4986101B2 (en) | Hydrogen storage material and method for producing the same | |
| CN104871284B (en) | The non-evaporable getter alloys can being re-activated after being exposed to reactant gas | |
| US5312606A (en) | Process for the sorption of residual gas by means of a non-evaporated barium getter alloy | |
| WO2007021055A1 (en) | Hydrogen storage alloy and apparatus for storing hydrogen using the same | |
| CN111905803B (en) | Inert gas purification catalyst, raw material composition and preparation method | |
| US5296438A (en) | Dimensionally stable metallic hydride composition | |
| CN101146608B (en) | Gas-adsorbing substance, gas-adsorbing alloy and gas-adsorbing material | |
| EP0509971A1 (en) | A process for the sorption of residual gas and especially nitrogen gas by means of a non-evaporated barium getter | |
| JP4615240B2 (en) | Gas purification device | |
| JP2008013375A (en) | Composite material of hydride, and hydrogen storage material | |
| US8211202B2 (en) | Gas-absorbing substance, gas-absorbing alloy and gas-absorbing material | |
| JP4663044B2 (en) | Heat transfer accelerator for gas adsorption / desorption reaction material and gas adsorption / desorption reaction material with excellent heat transfer | |
| JP5061289B2 (en) | Gas-adsorbing substances and gas-adsorbing materials | |
| JP4823750B2 (en) | Method for producing gas-adsorbing substance | |
| JPS62284033A (en) | Reversible hydrogen occluding and releasing material | |
| CN111974445B (en) | Inert gas purification catalyst, raw material composition and preparation method | |
| JP4033587B2 (en) | Molded product for getter and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120815 |