CN101394918A - Hydrogen permeation/separation thin membrane - Google Patents
Hydrogen permeation/separation thin membrane Download PDFInfo
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- CN101394918A CN101394918A CNA2007800078803A CN200780007880A CN101394918A CN 101394918 A CN101394918 A CN 101394918A CN A2007800078803 A CNA2007800078803 A CN A2007800078803A CN 200780007880 A CN200780007880 A CN 200780007880A CN 101394918 A CN101394918 A CN 101394918A
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Abstract
A hydrogen-permeable separation thin membrane made of an Ni-Ti-Nb alloy wherein the Ni-Ti-Nb alloy is a material obtained by refining heat-treatment of a foil produced by chill roll casting and having a thickness of 0.07mm or below and has (a) a composition consisting of 10 to 47 at% Nb, 20 to 52 at% Ti and the balance Ni with unavoidable impurities (with the proviso that the Ni content is 20 to 48 at%) and (b) an alloy structure wherein fine particles of an Nb-base alloy consisting of a solid solution of Ni and Ti in Nb are dispersed in a matrix made of an Ni-Ti(Nb) intermetallic compound consisting of a solid solution of Nb in an Ni-Ti intermetallic compound wherein part of the Ti of the Ni-Ti intermetallic compound is replaced by Nb; and a hydrogen-permeable separation thin membrane made of an Nb-Ti-Ni alloy wherein the Nb-Ti-Ni alloy is a material obtained by refining heat-treatment of a foil produced by chill roll casting and having a thickness of 0.07mm or below and has (a') a composition consisting of 10 to 32 at% Ni, 15 to 33 at% Ti, and the balance Nb with unavoidable impurities (with the proviso that the Nb content is 48 to 70 at%) and (b') an alloy structure wherein fine particles of an Ni-Ti(Nb) intermetallic compound consisting of a solid solution of Nb in an Ni-Ti intermetallic compound wherein part of the Ti of the Ni-Ti intermetallic compound is replaced by Nb are dispersed in a matrix made of an Nb-base alloy consisting of a solid solution of Ni and Ti in Nb.
Description
Technical field
The present invention relates to constitute by Ni-Ti-Nb alloy with high mechanical properties or Nb-Ti-Ni alloy, therefore can carry out the following filming of thickness 0.07mm (70 μ m), the result can significantly improve the hydrogen permeation/separation thin membrane that hydrogen that filming produces sees through separating property when practicality.
Background technology
In recent years, for example as the fuel gas of hydrogen fuel cell or hydrogen turbine homenergic system, high-purity hydrogen receives much attention, the known following production of this high-purity hydrogen: by mist that water electrolysis is obtained or hydrogeneous unstrpped gases such as mist that liquefied natural gas (LNG) steam reforming is obtained, shown in the diagrammatic illustration figure of Fig. 5, use peripheral part for example to reinforce with housings such as Ni systems, and see through diffusion barrier with the hydrogen of the thickness 0.1～3mm that has the function that Hydrogen Energy only enough sees through on the material and be separated into chamber, the left and right sides, the chamber, left side is equipped with hydrogeneous unstrpped gas ingress pipe and exhaust delivery line, the central portion that the chamber, right side is equipped with the high-purity hydrogen take-off pipe is provided with the hydrogen high-purity refining plant of reative cells such as stainless steel, above-mentioned reative cell is heated to 200～300 ℃, import hydrogeneous unstrpped gas by above-mentioned ingress pipe, to see through diffusion barrier and right side intraventricular pressure that the high-purity hydrogen of separation and purification exists remains on 0.1MPa by above-mentioned hydrogen, and the left side intraventricular pressure that above-mentioned hydrogeneous unstrpped gas is existed remains under the condition of 0.2～0.5MPa, see through diffusion barrier by above-mentioned hydrogen, with the high-purity hydrogen separation and purification, thereby produce.
In addition, well-known above-mentioned hydrogen sees through diffusion barrier and also is widely used in selectivity steam reforming technology that move, for example hydrocarbon or the benzene that carries out hydrogen by above-mentioned hydrogen through diffusion barrier
In the chemical reaction process such as hydrogenation/dehydrogenation technology such as cyclohexane reaction.
And above-mentioned hydrogen becomes to be grouped into through diffusion barrier also known following by having (α) and the Ni-Ti-Nb alloy of alloy structure (β) constitutes,
(α) contain Ni:25～45 atom %, Ti:26～50 atom %, surplus comprise Nb and inevitable impurity (containing Nb:11～48 atom %) become to be grouped into,
(β) use the casted thin plate material of processing the thickness 0.1～3mm of cutting by ingot casting utilization discharge, utilize the organizing shown in the photo (multiplying power 2500 times (Fig. 2) and 4000 times (Fig. 4)) of scanning electron microscope as Fig. 2 and Fig. 4, having the NbTi of Ni with solid solution the NiTi eutectic structure mutually of Nb to be arranged mutually with solid solution is matrix, is distributed with the alloy structure of primary crystal NbTi phase (the white island among Fig. 4) in this matrix.
Patent documentation 1: the spy opens the 2005-232491 communique
Summary of the invention
The pre-problem that solves of invention
On the other hand, comprise above-mentioned hydrogen high-purity refining plant, requirement to the high performance of various chemical reaction equipments very strengthens, meanwhile, the hydrogen that uses as the structural elements of said apparatus sees through diffusion barrier and also requires to possess higher hydrogen and see through separating property, known in addition, when being generally above-mentioned hydrogen through diffusion barrier, reduce more its thickness then hydrogen see through separating property and improve more, therefore carrying out energetically about constituting of the exploitation of above-mentioned hydrogen through the high strength of the Ni-Ti-Nb alloy of diffusion barrier, but above-mentioned hydrogen in the past sees through in the diffusion barrier, owing to the mechanical strength that the Ni-Ti-Nb alloy that constitutes it is possessed is insufficient, therefore can't filming to the thickness below the 0.1mm, thereby reality is to reach the raising that gratifying hydrogen sees through separating property.
Be used to solve the method for problem
Thereby, the inventor etc. from the above point of view, in order to seek the high performance of above-mentioned various chemical reaction equipments, especially become possibility for the filming that makes hydrogen as its structural elements see through diffusion barrier, being conceived to above-mentioned hydrogen studies through the high strength of diffusion barrier, the result obtains following result of study: by above-mentioned hydrogen is seen through the diffusion barrier special provision for containing Nb:10～47 atom %, Ti:20～52 atom %, surplus comprise Ni and inevitable impurity (containing Ni:20～48 atom %) become to be grouped into, utilize the roller quench that this alloy molten liquid is made the following casting foil of thickness 0.07mm, in order to prevent that oxidation is in inert gas environment or in the vacuum environment, temperature: when 300～1100 ℃ down heating keeps under the conditions of stipulated times that this casting foil implemented modified heat treatment, the modified heat treatment material of result utilizes organizing shown in the photo (multiplying power: 2500 times) of scanning electron microscope as shown in Figure 1, become in the matrix (representing with black among Fig. 1) of Ni-Ti (Nb) intermetallic compound that contains with the state solid solution that comprises the part of Ti in the Nb replacement Ni-Ti intermetallic compound, be distributed with the alloy structure of the microfine (representing with white among Fig. 1) of the Nb base solid solution alloy that solid solution Ni and Ti form in Nb, the Ni-Ti-Nb alloy of this alloy structure has high mechanical strength, therefore when seeing through the diffusion barrier practicality as hydrogen, can make thickness is below the 0.07mm, the more excellent hydrogen of performance for a long time sees through separating property.
In addition, the inventor etc. also obtain following result of study: by above-mentioned hydrogen is seen through the diffusion barrier special provision for containing Ni:10～32 atom %, Ti:15～33 atom %, surplus comprise Nb and inevitable impurity (containing Nb:48～70 atom %) become to be grouped into, utilize the roller quench that this alloy molten liquid is made the following casting foil of thickness 0.07mm, in order to prevent that oxidation is in inert gas environment or in the vacuum environment, temperature: when 300～1100 ℃ down heating keeps under the conditions of stipulated times that this casting foil implemented modified heat treatment, the modified heat treatment material of result utilizes organizing shown in the photo (multiplying power: 4000 times) of scanning electron microscope as shown in Figure 3, become in the matrix (representing with white among Fig. 3) of the Nb base solid solution alloy that solid solution Ni and Ti form in comprising Nb, be distributed with the alloy structure that replaces the microfine (representing with black among Fig. 3) of Ni-Ti (Nb) intermetallic compound that the state solid solution of the part of Ti in the Ni-Ti intermetallic compound contains with Nb, the Nb-Ti-Ni alloy of this alloy structure is owing to the Nb base solid solution alloy of above-mentioned matrix has guaranteed that excellent hydrogen sees through separating property, and then the dispersion of Ni-Ti (Nb) intermetallic compound by above-mentioned microfine in matrix distributes and possesses high mechanical strength, therefore when seeing through the actual use of diffusion barrier as hydrogen, the thickness film is turned to below the 0.07mm, this hydrogen sees through superior hydrogen that raising that hydrogen that the filming of diffusion barrier brings sees through separating property and above-mentioned Nb base solid solution alloy matrix had and sees through separating property and complement each other, and the more excellent hydrogen of performance for a long time is through separating property.
The present invention is based on above-mentioned result of study and finish, be a kind of hydrogen permeation/separation thin membrane (hereinafter being called " hydrogen permeation/separation thin membrane (I) " sometimes), it is the hydrogen permeation/separation thin membrane that comprises the Ni-Ti-Nb alloy, it is characterized in that, above-mentioned Ni-Ti-Nb alloy comprises the modified heat treatment material of the casting foil below the thickness 0.07mm that obtains by the roller quench, has following (a) and becomes to be grouped into and alloy structure (b):
(a) contain Nb:10～47 atom %, Ti:20～52 atom %, surplus comprise Ni:20～48 atom % and inevitable impurity become to be grouped into and
(b) in the matrix that comprises Ni-Ti (Nb) intermetallic compound that state solid solution that Nb replaces the part of Ti in the Ni-Ti intermetallic compound contains, be distributed with the alloy structure of the microfine of the basic solid solution alloy of Nb that solid solution Ni and Ti form in Nb.
In addition, the present invention is a kind of hydrogen permeation/separation thin membrane (hereinafter being called " hydrogen permeation/separation thin membrane (II) " sometimes), it is the hydrogen permeation/separation thin membrane that comprises the Nb-Ti-Ni alloy, it is characterized in that, above-mentioned Nb-Ti-Ni alloy comprises the modified heat treatment material of the casting foil below the thickness 0.07mm that obtains by the roller quench, has following (a ') and becomes to be grouped into and the alloy structure of (b '):
(a ') contain Ni:10～32 atom %, Ti:15～33 atom %, surplus comprise Nb:48～70 atom % and inevitable impurity become to be grouped into and
In the Nb base solid solution alloy matrix that (b ') solid solution Ni and Ti in comprising Nb forms, be distributed with the alloy structure of the microfine of Ni-Ti (Nb) intermetallic compound that the state solid solution with the part of Ti in the Nb replacement Ni-Ti intermetallic compound contains.
The invention effect
Hydrogen permeation/separation thin membrane of the present invention (I) is by having matrix Ni-Ti (Nb) intermetallic compound of high mechanical properties, can filming to the thickness below the 0.07mm, the superior hydrogen that the hydrogen that this filming is brought is brought into play through the raising of separating property and the Nb base solid solution alloy that disperses equably to be distributed in as microfine in the above-mentioned matrix sees through separating property and complements each other, in the time of in using it for various chemical reaction equipments, bring into play excellent hydrogen between long-term and see through separating property.
In addition, hydrogen permeation/separation thin membrane of the present invention (II) is by having superior hydrogen and see through in the matrix of Nb base solid solution alloy of separating property and disperse the microfine of distribution Ni-Ti (Nb) intermetallic compound to guarantee high mechanical properties comprising, as a result film can filming to the following thickness of 0.07mm, the superior hydrogen that the raising that the hydrogen that this filming is brought sees through separating property and above-mentioned Nb base solid solution alloy matrix are had sees through separating property and complements each other, and brings into play more excellent hydrogen through separating property between long-term.
Description of drawings
Fig. 1 for constitute hydrogen of the present invention see through film (I)-19 the Ni-Ti-Nb alloy scanning electron microscope organize photo (multiplying power: 2500 times).
Fig. 2 for constitute hydrogen in the past see through film (I)-8 the Ni-Ti-Nb alloy scanning electron microscope organize photo (multiplying power: 2500 times).
Fig. 3 for constitute hydrogen of the present invention see through film (II)-6 the Nb-Ti-Ni alloy scanning electron microscope organize photo (multiplying power: 4000 times).
Fig. 4 for constitute hydrogen in the past see through film (II)-8 the Ni-Ti-Nb alloy scanning electron microscope organize photo (multiplying power: 4000 times).
Fig. 5 is the diagrammatic illustration figure of example hydrogen high-purity refining plant.
Then, illustrate to be defined as above in the hydrogen permeation/separation thin membrane of the present invention (I) and consist of it The reason of Ni-Ti-Nb alloy composition.
(1)Nb
The Nb composition is as mentioned above to replace the form of the part of Ti in the Ni-Ti intermetallic compound Contain, form Ni-Ti (Nb) intermetallic compound that consists of matrix, thus above-mentioned except improving The hydrogen of matrix sees through outside the separating property, also has to form basic the consolidating of Nb that solid solution contains Ni and Ti Fuse gold, be distributed in the above-mentioned matrix, bring into play superior hydrogen through separating property as microfine Effect, its content is during less than 10 atom %, even if with the thin thickness membranization of film to 0.07mm Below, also can't bring into play the superior hydrogen of expecting and see through separating property, and content surpasses 47 atom % The time, then can't stably guarantee above-mentioned alloy structure, therefore its content is defined as 10～47 former Sub-%.
(2) Ti and Ni
Ti and Ni composition are except forming Ni-Ti (Nb) intermetallic compound, the raising that consists of matrix The mechanical strength of film, therefore so that carry out the practical possibility that becomes with the thickness below the 0.07mm Outside, also have solid solution and close in the Nb base solid solution that is distributed in as microfine in the above-mentioned matrix Gold, the effect that improves its mechanical strength, but any one the content of Ti and Ni is Ti: less than 20 Atom %, Ni: during less than 20 atom %, film can't be guaranteed the mechanical strength expected, with 0.07mm the practical change of following thickness is difficult, and any one content of Ti and Ni surpasses Ti:52 When atom %, Ni:48 atom %, can't avoid hydrogen to see through the reduction of separating property, so it contain The amount separate provision is Ti:20～52 atom %, Ni:20～48 atom %.
Then, illustrate to be defined as above in the hydrogen permeation/separation thin membrane of the present invention (II) and consist of it The reason of Nb-Ti-Ni alloy composition.
(1’)Nb
The Nb composition comprises the Nb base solid solution alloy that solid solution contains Ni and Ti except formation as mentioned above The excellent hydrogen of matrix, performance see through outside the effect of separating property, also have the Ni-Ti of replacement The form of the part of Ti contains, forms Ni-Ti (Nb) intermetallic in the intermetallic compound The microfine of thing, the hydrogen that improves above-mentioned microfine see through the effect of separating property, but when its content little When 48 atom %, be difficult to stably obtain above-mentioned alloy structure, membrane property produces uneven, and its When content surpasses 70 atom %, the then distribution of above-mentioned Ni-Ti (Nb) intermetallic compound microfine Ratio reduces sharp, and the mechanical strength of film reduces as a result, can't be with the thickness filming extremely 0.07mm therefore following state is defined as 48～70 atom % with its content in practicality.
(2 ') Ti and Ni
Ti and Ni composition are except forming Ni-Ti (Nb) intermetallic compound that is distributed in matrix Microfine, improve the mechanical strength of film, therefore so that carry out reality with the thickness below the 0.07mm With change into for may outside, also have solid solution in the Nb base solid solution alloy that consists of above-mentioned matrix, carry The effect of high its mechanical strength, but any one the content of Ti and Ni is Ti: less than 15 atom %, Ni: during less than 10 atom %, film can't be guaranteed the mechanical strength expected, and the result is with 0.07mm The practical change of following thickness is difficult, and any one content of Ti and Ni surpass Ti:33 atom %, During Ni:32 atom %, can't avoid hydrogen to see through the reduction of separating property, so its content is advised respectively Be decided to be Ti:15～33 atom %, Ni:10～32 atom %.
The specific embodiment
Then, specifically describe hydrogen permeation/separation thin membrane of the present invention (I) and (II) by embodiment.
Embodiment
＜hydrogen permeation/separation thin membrane (I) 〉
Use purity as raw material: 99.9% high purity N b loose material, purity: 99.9% high purity N i loose material and purity: 99.5% high purity Ti sponge material, cooperate these raw materials with ratio shown in the table 1 respectively, in high-purity Ar environment, carry out electric arc melting, make ingot bar, this ingot bar is being blocked under the state square into 20mm, pack into the bottom be formed with have long 20mm * graphite crucible of the crack of wide 0.3mm size in, in the decompression argon environment of 0.06MPa, carry out fusion once more with the high-frequency induction heater, this point molten metal is blown on the surface that is incident upon the water-cooled copper roller that rotates with the roller speed of 20m/sec from above-mentioned crack with the injection pressure of 0.05MPa, form all have length: 20m * wide: the planar dimension of 20mm, but thickness is respectively the casting foil of the Ni-Ti-Nb alloy of average thickness shown in the table 1 (mean values of any 5 positions), then with in its vacuum drying oven of packing into, 10
-2Keep after 5 hours under the set point of temperature in 300～1100 ℃ of scopes respectively in the vacuum below the Pa, under the cold condition of stove, implement modified heat treatment, block into wide after the modified heat treatment: the planar dimension of 20mm * length: 60mm, thus make hydrogen permeation/separation thin membrane of the present invention (hereinafter be called hydrogen of the present invention and see through film) respectively (I)-1～(I)-24.
In addition, in order to compare, use purity as raw material equally: 99.9% high purity N b loose material, purity: 99.9% high purity N i loose material and purity: 99.5% high purity Ti sponge material, cooperate these raw materials with ratio shown in the table 2 respectively, in high-purity Ar environment, carry out electric arc melting, cast, make and have diameter: 80mm * thickness: the Ni-Ti-Nb alloy ingot bar of the size of 10mm, utilize discharge processing from this ingot bar, to block out all to have wide: the planar dimension of 20mm * length: 60mm, but thickness is respectively the light sheet of average thickness shown in the table 2 (mean values of any 5 positions), blocks the hydrogen permeation/separation thin membrane in the past that light sheet constitutes (hereinafter being called in the past, hydrogen sees through film) (I)-1～(I)-10 thereby make respectively by ingot bar.
For the hydrogen of the present invention that is obtained see through film (I)-1～(I)-24 and in the past hydrogen through film (I)-1～(I)-10, when using the energy dispersion type fluorescent x-ray analyzer to measure its one-tenth to be grouped into, all show and table 1, cooperate shown in 2 and form essentially identical assay value, in addition, when using scanning electron microscope and X-ray diffraction device to observe this tissue, the invention described above hydrogen sees through in the film (I)-1～(I)-24, hydrogen of the present invention as Fig. 1 sees through shown in the alloy structure of film (I)-19, all be presented in the matrix of Ni-Ti (Nb) intermetallic compound that contains with the state solid solution that comprises the part of Ti in the Nb replacement Ni-Ti intermetallic compound, be distributed with the alloy structure of the microfine of the Nb base solid solution alloy that solid solution Ni and Ti form in Nb, and above-mentioned hydrogen in the past sees through in the film (I)-1～(I)-10, hydrogen in the past as Fig. 2 sees through shown in the alloy structure of film (I)-8, show that all having the NbTi of Ni with solid solution the NiTi eutectic structure mutually of Nb to be arranged mutually with solid solution is matrix, is distributed with the alloy structure of primary crystal NbTi phase in this matrix.
Then, each the invention described above hydrogen see through film (I)-1～(I)-24 and in the past hydrogen see through and utilize the sputtering method evaporation to form thickness on the two sides of film (I)-1～(I)-10: the Pd film of 0.1 μ m (also can utilize galvanoplastic formation this moment), and with having separately laterally outside dimension: 20mm * vertical outside dimension: 2 coppers of 60mm * width of frame: 5mm * frame thickness 0.5mm size are reinforced frameworks and are seized on both sides by the arms from both sides, the above-mentioned various films that see through are being fixed under the state of above-mentioned reinforcing framework, be arranged on the hydrogen high-purity refining plant of structure shown in Figure 5 hydrogen and see through in the reative cell of evaluating apparatus with spline structure, to be heated to 300 ℃ in the above-mentioned reative cell, chamber, left side to reative cell imports hydrogen, at first making the chamber, left side of reative cell and the interior pressure of chamber, right side is 0.1MPa, then make the interior pressure of chamber, above-mentioned right side remain on 0.1MPa, simultaneously improve the interior pressure of chamber, above-mentioned left side with 0.1MPa/5 minute speed, for hydrogen of the present invention see through film (I)-1～(I)-7 and in the past hydrogen through film (I)-1, (I)-2 boost to 0.7MPa, for hydrogen of the present invention see through film (I)-8～(I)-24 and in the past hydrogen for film (I)-3～(I)-9, boost to 0.5MPa, for seeing through film (I)-10, hydrogen in the past boosts to 0.3MPa, when under this condition, keeping 1 hour, utilize gas flowmeter to measure the flow (table 1 of the hydrogen that sees through, seeing through the hydrogen flow with the initial stage in 2 represents), and then under this condition, even the interior voltage rise of chamber, right side is depressed into 0.1MPa, make the interior pressure of chamber, left side boost to 0.7MPa respectively, 0.5MPa and 0.3MPa, when under this condition, keeping continuing 20 hours under the same conditions after 1 hour, same flow (the table 1 of measuring the hydrogen that sees through, 2 usefulness later stages saw through the hydrogen flow and represent), their measurement result is shown in table 1, in 2.
Table 1
Table 2
As table 1, shown in 2 as can be known, hydrogen of the present invention sees through film (I)-1～(I)-24 and has all guaranteed high mechanical strength by Ni-Ti (Nb) intermetallic compound of matrix, can filming to the thickness below the 0.07mm, therefore the superior hydrogen of bringing into play with the Nb base solid solution alloy that is distributed in as microfine in the above-mentioned matrix complements each other through separating property, bring into play excellent hydrogen between long-term and seen through separating property, show excellent persistence (service life), and hydrogen all can't make thickness reach below the 0.1mm through film (I)-1～(I)-10 from the mechanical strength aspect in the past, so hydrogen is low through separating property.
＜hydrogen permeation/separation thin membrane (II) 〉
Use purity as raw material: 99.9% high purity N b loose material, purity: 99.9% high purity N i loose material and purity: 99.5% high purity Ti sponge material, cooperate these raw materials with ratio shown in the table 3 respectively, in high-purity Ar environment, carry out electric arc melting, make ingot bar, this ingot bar is being blocked under the state square into 20mm, pack into the bottom be formed with have long 20mm * graphite crucible of the crack of wide 0.3mm size in, in the decompression argon environment of 0.06MPa, carry out fusion once more with the high-frequency induction heater, this point molten metal is blown on the surface that is incident upon the water-cooled copper roller that rotates with the roller speed of 20m/sec from above-mentioned crack with the injection pressure of 0.05MPa, form all have length: 20m * wide: the planar dimension of 20mm, but thickness is respectively the casting foil of the Nb-Ti-Ni alloy of average thickness shown in the table 3 (mean values of any 5 positions), then with in its vacuum drying oven of packing into, 10
-2Keep after 5 hours under the set point of temperature in 300～1100 ℃ of scopes respectively in the vacuum below the pa, under the cold condition of stove, implement modified heat treatment, block into wide after the modified heat treatment: the planar dimension of 20mm * length: 60mm, thus make hydrogen permeation/separation thin membrane of the present invention (hereinafter be called hydrogen of the present invention and see through film) respectively (II)-1～(II)-13.
In addition, in order to compare, use purity as raw material equally: 99.9% high purity N b loose material, purity: 99.9% high purity N i loose material and purity: 99.5% high purity Ti sponge material, cooperate these raw materials with ratio shown in the table 3 respectively, in high-purity Ar environment, carry out electric arc melting, cast, make and have diameter: 80mm * thickness: the Nb-Ti-Ni alloy ingot bar of the size of 10mm, utilize discharge processing from this ingot bar, to block out all to have wide: the planar dimension of 20mm * length: 60mm, but thickness is respectively the light sheet of average thickness shown in the table 3 (mean values of any 5 positions), thereby makes the hydrogen permeation/separation thin membrane in the past (hereinafter being called in the past, hydrogen sees through film) comprise ingot bar and to block light sheet respectively (II)-1～(II)-10.
For the hydrogen of the present invention that is obtained see through film (II)-1～(II)-13 and in the past hydrogen through film (II)-1～(II)-10, when using the energy dispersion type fluorescent x-ray analyzer to measure its one-tenth to be grouped into, all show and cooperate the essentially identical assay value of composition shown in the table 3, in addition, when using scanning electron microscope and X-ray diffraction device to observe this tissue, the invention described above hydrogen sees through in the film (II)-1～(II)-13, hydrogen of the present invention as Fig. 3 sees through shown in the alloy structure of film (II)-6, all be presented in the matrix that comprises the Nb base solid solution alloy that solid solution Ni and Ti form among the Nb, be distributed with the alloy structure that replaces the microfine of Ni-Ti (Nb) intermetallic compound that the state solid solution of the part of Ti in the Ni-Ti intermetallic compound contains with Nb, and above-mentioned hydrogen in the past sees through in the film (II)-1～(II)-10, hydrogen in the past as Fig. 4 sees through shown in the alloy structure of film (II)-8, show that all having the NbTi of Ni with solid solution the NiTi eutectic structure mutually of Nb to be arranged mutually with solid solution is matrix, is distributed with the alloy structure of primary crystal NbTi phase in this matrix.
Then, each the invention described above hydrogen see through film (II)-1～(II)-13 and in the past hydrogen see through and utilize the sputtering method evaporation to form thickness on the two sides of film (II)-1～(II)-10: the Pd film of 0.1 μ m (also can utilize galvanoplastic formation this moment), and with having separately laterally outside dimension: 20mm * vertical outside dimension: 2 coppers of 60mm * width of frame: 5mm * frame thickness 0.5mm size are reinforced frameworks and are seized on both sides by the arms from both sides, the above-mentioned various films that see through are being fixed under the state of above-mentioned reinforcing framework, be arranged on the hydrogen high-purity refining plant of structure shown in Figure 5 hydrogen and see through in the reative cell of evaluating apparatus with spline structure, to be heated to 300 ℃ in the above-mentioned reative cell, chamber, left side to reative cell imports hydrogen, at first making the chamber, left side of reative cell and the interior pressure of chamber, right side is 0.1MPa, then make the interior pressure of chamber, above-mentioned right side remain on 0.1MPa, simultaneously improve the interior pressure of chamber, above-mentioned left side with 0.1MPa/5 minute speed, for seeing through film (II)-1～(II)-13, hydrogen of the present invention boosts to 0.3MPa, see through film (II)-1 for hydrogen in the past, (II)-2 boost to 0.7MPa, for seeing through film (II)-3～(II)-9, hydrogen in the past boosts to 0.5MPa, for seeing through film (II)-10, hydrogen in the past boosts to 0.3MPa, when under this condition, keeping 1 hour, utilize gas flowmeter to measure the flow of the hydrogen that sees through (seeing through the hydrogen flow with the initial stage in the table 3 represents), and then when under this condition, continuing 20 hours, the same flow (seeing through the hydrogen flow with the later stage in the table 3 represents) of measuring the hydrogen that sees through is shown in Table 3 their measurement result.
Table 3
(in the table, ※ represents " ingot bar blocks light sheet ")
As shown in Table 3, hydrogen of the present invention see through film (II)-1～(II)-13 all the microfine of Ni-Ti (Nb) intermetallic compound by being distributed in matrix guaranteed high mechanical strength, can filming to the thickness below the 0.07mm, therefore hydrogen further improves through separating property, and the superior hydrogen that is had with the basic solid solution alloy of the Nb of above-mentioned matrix complements each other through separating property, bring into play excellent hydrogen between long-term and seen through separating property, and hydrogen all can't make thickness reach below the 0.1mm through film (II)-1～(II)-10 from the mechanical strength aspect in the past, so hydrogen is low through separating property.
Industrial applicability
Hydrogen permeation/separation thin membrane of the present invention by the Ni-Ti-Nb alloy with high mechanical properties or The Nb-Ti-Ni alloy consists of, can filming to thickness: below the 0.07mm, long-term when practicality Performance excellent hydrogen in ground sees through separating property, therefore is enough to tackle hydrogen and sees through diffusion barrier as the structure structure Part and the high performance requirement of the various chemical reaction equipments that use. Therefore, the present invention industrially Very useful.
Claims (2)
1. hydrogen permeation/separation thin membrane, it is the hydrogen permeation/separation thin membrane that comprises the Ni-Ti-Nb alloy, it is characterized in that, this Ni-Ti-Nb alloy comprises the modified heat treatment material of the casting foil below the thickness 0.07mm that obtains by the roller quench, has following (a) and becomes to be grouped into and alloy structure (b):
(a) contain Nb:10～47 atom %, Ti:20～52 atom %, surplus comprise Ni:20～48 atom % and inevitable impurity become to be grouped into and
(b) in the matrix that comprises Ni-Ti (Nb) intermetallic compound that state solid solution that Nb replaces the part of Ti in the Ni-Ti intermetallic compound contains, be distributed with the alloy structure of the microfine of the basic solid solution alloy of Nb that solid solution Ni and Ti form in Nb.
2. hydrogen permeation/separation thin membrane, it is the hydrogen permeation/separation thin membrane that comprises the Nb-Ti-Ni alloy, it is characterized in that, this Nb-Ti-Ni alloy comprises the modified heat treatment material of the casting foil below the thickness 0.07mm that obtains by the roller quench, has following (a ') and becomes to be grouped into and the alloy structure of (b '):
(a ') contain Ni:10～32 atom %, Ti:15～33 atom %, surplus comprise Nb:48～70 atom % and inevitable impurity become to be grouped into and
In the matrix of the Nb base solid solution alloy that (b ') solid solution Ni and Ti in comprising Nb forms, be distributed with the alloy structure of the microfine of Ni-Ti (Nb) intermetallic compound that the state solid solution with the part of Ti in the Nb replacement Ni-Ti intermetallic compound contains.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006062923A JP4953279B2 (en) | 2006-03-08 | 2006-03-08 | Hydrogen permeation separation thin film with excellent hydrogen permeation separation performance |
| JP2006062922A JP4953278B2 (en) | 2006-03-08 | 2006-03-08 | Hydrogen permeation separation thin film with excellent hydrogen permeation separation performance |
| JP062923/2006 | 2006-03-08 | ||
| JP062922/2006 | 2006-03-08 | ||
| PCT/JP2007/054552 WO2007105594A1 (en) | 2006-03-08 | 2007-03-08 | Hydrogen-permeable separation thin membranes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101394918A true CN101394918A (en) | 2009-03-25 |
| CN101394918B CN101394918B (en) | 2011-08-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800078803A Expired - Fee Related CN101394918B (en) | 2006-03-08 | 2007-03-08 | Hydrogen permeation/separation thin membrane |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4953278B2 (en) |
| CN (1) | CN101394918B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103068479A (en) * | 2010-07-02 | 2013-04-24 | 法商Bic公司 | Hydrogen membrane separator |
| CN112957912A (en) * | 2021-01-29 | 2021-06-15 | 中国工程物理研究院材料研究所 | Multilayer selective hydrogen permeation composite membrane and preparation and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2585187C (en) * | 2004-11-15 | 2011-03-15 | Nippon Mining & Metals Co., Ltd. | Hydrogen separation membrane, sputtering target for forming said hydrogen separation membrane, and manufacturing method thereof |
| JP2013086038A (en) * | 2011-10-19 | 2013-05-13 | Jx Nippon Oil & Energy Corp | Alloy film for hydrogen permeation |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000159503A (en) * | 1998-11-20 | 2000-06-13 | Mitsubishi Heavy Ind Ltd | Hydrogen separating film of niobium alloy |
| CN1185363C (en) * | 2001-10-25 | 2005-01-19 | 北京华瑞能科技发展有限责任公司 | Metal ceramic film |
| JP3935851B2 (en) * | 2002-05-20 | 2007-06-27 | 福田金属箔粉工業株式会社 | Hydrogen separation membrane and method for producing the same |
| WO2004073844A1 (en) * | 2003-02-24 | 2004-09-02 | Fukuda Metal Foil & Powder Co., Ltd. | Hydrogen separation membrane and process for producing the same |
| JP4363633B2 (en) * | 2004-02-17 | 2009-11-11 | 株式会社アルバック | Double phase alloy for hydrogen separation / purification and production method thereof, metal membrane for hydrogen separation / purification and production method thereof |
| JP3749952B1 (en) * | 2004-09-22 | 2006-03-01 | 国立大学法人北見工業大学 | Crystalline double-phase hydrogen permeable alloy membrane and crystalline double-phase hydrogen permeable alloy membrane |
| JP3749953B1 (en) * | 2005-03-24 | 2006-03-01 | 国立大学法人北見工業大学 | Double phase hydrogen permeable alloy and hydrogen permeable alloy membrane |
-
2006
- 2006-03-08 JP JP2006062922A patent/JP4953278B2/en not_active Expired - Fee Related
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- 2007-03-08 CN CN2007800078803A patent/CN101394918B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103068479A (en) * | 2010-07-02 | 2013-04-24 | 法商Bic公司 | Hydrogen membrane separator |
| CN103068479B (en) * | 2010-07-02 | 2015-07-08 | 法商Bic公司 | Hydrogen membrane separator |
| CN112957912A (en) * | 2021-01-29 | 2021-06-15 | 中国工程物理研究院材料研究所 | Multilayer selective hydrogen permeation composite membrane and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101394918B (en) | 2011-08-10 |
| JP4953278B2 (en) | 2012-06-13 |
| JP2007237074A (en) | 2007-09-20 |
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