CN102851626A - Preparation method of Nb-based amorphous alloy and stripe and hydrogen permeating metal film thereof - Google Patents
Preparation method of Nb-based amorphous alloy and stripe and hydrogen permeating metal film thereof Download PDFInfo
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- CN102851626A CN102851626A CN201210360865XA CN201210360865A CN102851626A CN 102851626 A CN102851626 A CN 102851626A CN 201210360865X A CN201210360865X A CN 201210360865XA CN 201210360865 A CN201210360865 A CN 201210360865A CN 102851626 A CN102851626 A CN 102851626A
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Abstract
The invention provides a preparation method of an Nb-based amorphous alloy and a stripe and a hydrogen permeating metal film of the Nb-based amorphous alloy, According to the preparation method, the Nb-based amorphous alloy has the chemical formula as Nb0.42NiaCobZrcMd, wherein M=Ta, or Ti; a, b, c and d are respectively the atomic percentage of each component, wherein a is more than or equal to 0.30 and less than or equal to 0.40, b is more than or equal to 0.05 and less than or equal to 0.15, c is more than or equal to 0.04 and less than or equal to 0.02, d is more than or equal to 0 and less than or equal to 0.08, and the sum of a, b, c and d is equal to 0.58. With the adoption of the preparation method provided by the invention, the alloy components are further improved; the hydrogen permeating performance and thermal stability of the Nb-based amorphous alloy stripe and the hydrogen permeating metal film are improved; the Nb-based amorphous alloy capable of separating hydrogen and purifying is prepared, and the Nb-based amorphous alloy stripe and the hydrogen permeating metal film which have high performance of hydrogen permeating and are capable of separating and hydrogen and purifying can be obtained.
Description
Technical field
The present invention relates to the preparation method of a kind of non-crystaline amorphous metal and band thereof and saturating hydrogen metallic membrane, specifically, relate to the preparation method of a kind of Nb base noncrystal alloy for hydrogen separation and purifying and band and saturating hydrogen metallic membrane.
Background technology
Because society is depended on unduly fossil energy, has caused the now problem such as well-known energy dilemma and environmental pollution, exploitation cleaning, new forms of energy efficient, pollution-free or less contamination become the problem that various countries face.Hydrogen Energy have aboundresources, combustionproperty excellent, can store, the many merits such as cleanliness without any pollution and be subject to extensive concern, be the clear energy sources of future ideality.In numerous Application Areass of hydrogen, such as semi-conductor industry, fuel cell etc., all need hydrogen that high purity is arranged, a small amount of impurity can cause disadvantageous effect to the application of hydrogen.Therefore prepare on a large scale, at low cost the important research content that high-purity hydrogen is the hydrogen Application Areas.
Hydrogen is separated, obtained high-purity hydrogen from mixed gas aspect, palladium metal (Pd) and alloy film thereof show excellent performance, and it is the metallic membrane that successfully is used at present Hydrogen Separation and purifying.But because palladium is expensive, reserves are limited, are difficult to large-scale industrial application.Therefore, searching is low-cost, high performance equivalent material is imperative.Non-crystaline amorphous metal is a kind of novel material with multiple excellent properties, existing studies show that, non-crystaline amorphous metal is owing to its unique constructional feature has high strength and higher hydrogen permeability coefficient, some non-crystaline amorphous metals also have the excellent properties such as hydrogen solubleness is large, anti-hydrogen embrittlement, the saturating hydrogen performance of a small amount of non-crystaline amorphous metal even suitable with palladium alloy membrane.Simultaneously, non-crystaline amorphous metal also has the advantages such as preparation technology is simple.These performance characteristics have very large potentiality so that non-crystaline amorphous metal becomes hydrogen separation and the purifying candidate materials with good application prospect in industrial applications.
Being expected for the amorphous alloy material of hydrogen separation and purifying of reporting so far is also less, and mostly is the Ni base noncrystal alloy.Because crystallization can occur in non-crystaline amorphous metal after temperature surpasses its initial crystallization temperature, thereby loses its excellent properties corresponding with non-crystal structure.Help to improve its thermostability so improve the initial crystallization temperature of non-crystaline amorphous metal, expand the use temperature scope of non-crystaline amorphous metal.Initial crystallization temperature and its fusing point of non-crystaline amorphous metal are closely related, so it is very important to the fusing point that improves non-crystaline amorphous metal to contain dystectic element in the alloying constituent.Nb is a kind of dystectic element, and the existing Nb of studies show that base noncrystal alloy has very high thermostability, possesses the potential quality of at high temperature using; And Pd is cheaply a lot of for Nb element cost ratio, if prepared Nb base noncrystal alloy has hydrogen penetrating quality close with Pd or the same order of magnitude, the Nb base noncrystal alloy will be expected to substitute the Pd alloy for hydrogen separation and purifying so, and aspect hydrogen separation and the purifying wide prospect arranged.In research before this, develop a series of Nb base ternary AMORPHOUS ALLOY RIBBONS with high thermal stability, and grasped design of alloy and band preparation method.
Summary of the invention
Technical problem to be solved by this invention provides a kind of Nb base noncrystal alloy, is used for hydrogen and separates and purifying.
Technical scheme of the present invention is as follows:
A kind of Nb base noncrystal alloy stripping, i.e. a kind of Nb base noncrystal alloy, the chemical expression of described Nb base noncrystal alloy is Nb
0.42Ni
aCo
bZr
cM
dWherein, M=Ta or Ti; A, b, c, d are the atomic percent of each constituent element, 0.30＜=a＜=0.40,0.05＜=b＜=0.15,0.04＜=c＜=0.20,0＜=d＜=0.08 and a+b+c+d=0.58.
Another technical problem to be solved by this invention provides a kind of preparation method of Nb base noncrystal alloy band, and preparation has the Nb base noncrystal alloy band of higher thermostability and high hydrogen permeability coefficient.
Its technical scheme is as follows:
A kind of preparation method of Nb base noncrystal alloy band comprises: with raw material according to Nb
0.42Ni
aCo
bZr
cM
dPrepare burden, wherein, M=Ta or Ti; A, b, c, d are the atomic percent of each constituent element, 0.30＜=a＜=0.40,0.05＜=b＜=0.15,0.04＜=c＜=0.20,0＜=d＜=0.08 and a+b+c+d=0.58; With described raw material melt back, obtain the mother alloy of homogeneous chemical composition; With described mother alloy fusing, obtain the mother alloy melt; Described mother alloy melt jet is obtained described Nb base noncrystal alloy band to the quick cooling of the copper roller surface of high speed rotating, and the chemical expression of described Nb base noncrystal alloy band is Nb
0.42Ni
aCo
bZr
cM
dWherein, M=Ta or Ti; A, b, c, d are the atomic percent of each constituent element, 0.30＜=a＜=0.40,0.05＜=b＜=0.15,0.04＜=c＜=0.20,0＜=d＜=0.08 and a+b+c+d=0.58.
Further: be in vacuum arc fumace, to carry out with described raw material melt back.
Further: with described mother alloy fusing, be in the induction furnace of quick solidification apparatus, to carry out.
Further: the width 〉=10mm of described Nb base noncrystal alloy band, thickness are about 20 ~ 50 μ m.
Further: the initial crystallization temperature of described Nb base noncrystal alloy band 〉=550 ℃.
Another technical problem to be solved by this invention provides the preparation method of the saturating hydrogen metallic membrane of a kind of Nb base noncrystal alloy, and preparation has the saturating hydrogen metallic membrane of Nb base noncrystal alloy of higher thermostability and high hydrogen permeability coefficient.
Its technical scheme is as follows:
The preparation method of the saturating hydrogen metallic membrane of a kind of Nb base noncrystal alloy comprises: the surface finish of Nb base noncrystal alloy band is smooth, and wherein, the chemical expression of described Nb base noncrystal alloy band is Nb
0.42Ni
aCo
bZr
cM
dWherein, M=Ta or Ti; A, b, c, d are the atomic percent of each constituent element, 0.30＜=a＜=0.40,0.05＜=b＜=0.15,0.04＜=c＜=0.20,0＜=d＜=0.08 and a+b+c+d=0.58; The two sides of described Nb base noncrystal alloy band is plated the Pd film, obtain the saturating hydrogen metallic membrane of described Nb base noncrystal alloy; The chemical expression of the saturating hydrogen metallic membrane of described Nb base noncrystal alloy is Nb
0.42Ni
aCo
bZr
cM
dWherein, M=Ta or Ti; A, b, c, d are the atomic percent of each constituent element, 0.30＜=a＜=0.40,0.05＜=b＜=0.15,0.04＜=c＜=0.20,0＜=d＜=0.08 and a+b+c+d=0.58.
Further: the thickness of the Pd film that plates on the two sides of described Nb base noncrystal alloy band is 10 ~ 500nm, and coating film thickness is just adjusted according to oxygen level in the atmosphere what and application of temperature.
Technique effect of the present invention is as follows:
1, the present invention passes through to add Zr, Ta, and the alloying elements such as Ti have further been optimized alloying constituent, have prepared the Nb base noncrystal alloy that can be used for hydrogen separation and purifying.
2, the present invention has obtained Nb base noncrystal alloy band high hydrogen performance, that can be used for hydrogen separation and purifying, has improved hydrogen penetrating quality and the thermostability of Nb base noncrystal alloy band.
3, the present invention can prepare width 〉=10mm, and thickness is the Nb base noncrystal alloy band of 20 ~ 50 μ m.
4, the present invention can be by preparing the hydrogen metallic membrane behind the Pa of the two-sided plating 10 ~ 500nm of Nb base noncrystal alloy band.
Description of drawings
Fig. 1 (a) ~ (e) is X-ray diffraction (XRD) collection of illustrative plates of the Nb base noncrystal alloy band of embodiments of the invention 1 ~ 5;
Fig. 2 (a) ~ (e) is poor formula scanning calorimetric (DSC) curve of the Nb base noncrystal alloy band of embodiments of the invention 1 ~ 5;
Fig. 3 (a) ~ (f) be embodiments of the invention 1 ~ 5 and the saturating hydrogen metallic membrane of Nb base noncrystal alloy and Arrhenius (Arrhenius) curve of Pd-23wt.%Ag alloy standard reference material.
Embodiment
Below with reference to accompanying drawing and preferred embodiment, the present invention is described in detail.
Among the present invention, the thickness of the Pd film of the Nb base noncrystal alloy band two sides plating for preparing can be 10 ~ 500nm.In order to contrast conveniently, the surface of this Nb base noncrystal alloy band is plated the Pd film thickness and all is chosen as 100nm.
Embodiment 1: preparation Nb
0.42Ni
0.39Co
0.15Zr
0.04Non-crystaline amorphous metal
At first with each raw material of purity 〉=99.9% according to chemical ingredients proportioning Nb
0.42Ni
aCo
bZr
cM
dPrepare burden, a wherein, b, c, d are the atomic percent of each constituent element, and a=0.39, b=0.15, c=0.04, d=0.Then melt back in vacuum arc fumace, the mother alloy of acquisition homogeneous chemical composition.Be better than 3 * 10 in vacuum tightness
-2Under the Pa vacuum condition, place the induction furnace of quick solidification apparatus to make its fusing mother alloy, obtain the mother alloy melt.With the copper roller surface of mother alloy melt jet to high speed rotating, the roller surface linear velocity is about 20 ~ 40m/s, and it is Nb that cooling obtains chemical constitution
0.42Ni
0.39Co
0.15Zr
0.04Nb base noncrystal alloy band, test its thermodynamic stability and hydrogen penetrating quality.Width 〉=the 10mm of this Nb base noncrystal alloy band, thickness are 20 μ m.
Shown in Fig. 1 (a), be the XRD figure spectrum of the Nb base noncrystal alloy band of embodiments of the invention 1.Obtain the X ray diffracting spectrum of this Nb base noncrystal alloy band by the melt spinning method method.The diffuse scattering peak that the steamed bun shape is only arranged in the collection of illustrative plates, and do not have the sharp-pointed diffraction peak corresponding with crystalline material, show that sample is complete non-crystal structure.
Shown in Fig. 2 (a), be the DSC curve of the Nb base noncrystal alloy band of embodiments of the invention 1.Test result shows that the initial crystallization temperature of this Nb base noncrystal alloy band is 621 ℃, has good thermodynamic stability.
This Nb base noncrystal alloy strip face is polished smooth.Then this Nb base noncrystal alloy band two sides is plated the Pd film that thickness is 100nm, obtaining chemical constitution is Nb
0.42Ni
0.39Co
0.15Zr
0.04The saturating hydrogen metallic membrane of Nb base noncrystal alloy.The saturating hydrogen metallic membrane of this Nb base noncrystal alloy is placed in the gas permeation test device of standard and tests, namely to the saturating hydrogen amount of measuring under the fixed temperature under the different pressure reduction, obtain the saturating hydrogen coefficient of material under this temperature; And under condition of different temperatures, test, obtain hydrogen penetrating quality data and the variation with temperature rule thereof of the saturating hydrogen metallic membrane of this Nb base noncrystal alloy under differing temps.Shown in Fig. 3 (a), be the Arrhenius curve of the saturating hydrogen metallic membrane of Nb base noncrystal alloy of embodiments of the invention 1.The hydrogen permeability coefficient of the saturating hydrogen metallic membrane of this Nb base noncrystal alloy of this curve display in the time of 450 ℃ is 0.28 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 400 ℃ is 0.23 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 350 ℃ is 0.17 * 10
-8Molm
-1s
-1Pa
-1/2Fig. 3 (f) is Pd-23wt%Ag reference alloy hydrogen permeability coefficient variation with temperature curve under the same conditions, comparison diagram 3 (a) and 3 (f) as can be known, Nb
0.42Ni
0.39Co
0.15Zr
0.04The saturating hydrogen performance of the saturating hydrogen metallic membrane of non-crystaline amorphous metal bar is good not as good as the saturating hydrogen performance of Pd-23wt%Ag alloy film, however, and Nb
0.42Ni
0.39Co
0.15Zr
0.04AMORPHOUS ALLOY RIBBONS still has good hydrogen penetrating quality.
Embodiment 2: preparation Nb
42Ni
40Co
6Zr
12Non-crystaline amorphous metal
At first with each raw material of purity 〉=99.9% according to chemical ingredients proportioning Nb
0.42Ni
aCo
bZr
cM
dPrepare burden, a wherein, b, c, d are the atomic percent of each constituent element, and a=0.40, b=0.06, c=0.12, d=0.Then melt back in vacuum arc fumace, the mother alloy of acquisition homogeneous chemical composition.Be better than 3 * 10 in vacuum tightness
-2Under the Pa vacuum condition, place the induction furnace of quick solidification apparatus to make its fusing mother alloy, obtain the mother alloy melt.With the copper roller surface of mother alloy melt jet to high speed rotating, the roller surface linear velocity is about 20 ~ 40m/s, and it is Nb that cooling obtains chemical constitution
0.42Ni
0.40Co
0.06Zr
0.12Nb base noncrystal alloy band, test its thermodynamic stability and hydrogen penetrating quality.Width 〉=the 10mm of this Nb base noncrystal alloy band, thickness are 50 μ m.
Shown in Fig. 1 (b), be the XRD figure spectrum of the Nb base noncrystal alloy band of embodiments of the invention 2.Obtain the X ray diffracting spectrum of this Nb base noncrystal alloy band by the melt spinning method method.The diffuse scattering peak that the steamed bun shape is only arranged in the collection of illustrative plates, and do not have the sharp-pointed diffraction peak corresponding with crystalline material, show that sample is complete non-crystal structure.
Shown in Fig. 2 (b), be the DSC curve of the Nb base noncrystal alloy band of embodiments of the invention 2.Test result shows that the initial crystallization temperature of this Nb base noncrystal alloy band is 588 ℃, has good thermodynamic stability.
This Nb base noncrystal alloy strip face is polished smooth.Then this Nb base noncrystal alloy band two sides is plated the Pd film that thickness is 100nm, obtaining chemical constitution is Nb
0.42Ni
0.40Co
0.06Zr
0.12The saturating hydrogen metallic membrane of Nb base noncrystal alloy.The saturating hydrogen metallic membrane of this Nb base noncrystal alloy is placed in the gas permeation test device of standard and tests, namely to the saturating hydrogen amount of measuring under the fixed temperature under the different pressure reduction, obtain the saturating hydrogen coefficient of material under this temperature; And under condition of different temperatures, test, obtain hydrogen penetrating quality data and the variation with temperature rule thereof of the saturating hydrogen metallic membrane of this Nb base noncrystal alloy under differing temps.Shown in Fig. 3 (b), be the Arrhenius curve of the saturating hydrogen metallic membrane of Nb base noncrystal alloy of embodiments of the invention 2.The hydrogen permeability coefficient of the saturating hydrogen metallic membrane of this Nb base noncrystal alloy of this curve display in the time of 400 ℃ is 0.69 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 350 ℃ is 0.52 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 300 ℃ is 0.42 * 10
-8Molm
-1s
-1Pa
-1/2Fig. 3 (f) is Pd-23wt%Ag reference alloy hydrogen permeability coefficient variation with temperature curve under the same conditions, comparison diagram 3 (b) and 3 (f) as can be known, Nb
0.42Ni
0.40Co
0.06Zr
0.12The saturating hydrogen performance of the saturating hydrogen metallic membrane of non-crystaline amorphous metal is good not as good as the saturating hydrogen performance of Pd-23wt%Ag alloy film, however, and Nb
0.42Ni
0.40Co
0.06Zr
0.12The saturating hydrogen metallic membrane of non-crystaline amorphous metal still has good hydrogen penetrating quality.
Embodiment 3: preparation Nb
0.42Ni
0.32Co
0.06Zr
0.12Ta
0.08Non-crystaline amorphous metal
At first with each raw material of purity 〉=99.9% according to chemical ingredients proportioning Nb
0.42Ni
aCo
bZr
cM
dPrepare burden, wherein, M is Ta, a, and b, c, d are the atomic percent of each constituent element, and a=0.32, b=0.06, c=0.12, d=0.08.Then melt back in vacuum arc fumace, the mother alloy of acquisition homogeneous chemical composition.Be better than 3 * 10 in vacuum tightness
-2Under the Pa vacuum condition, place the induction furnace of quick solidification apparatus to make its fusing mother alloy, obtain the mother alloy melt.With the copper roller surface of mother alloy melt jet to high speed rotating, the roller surface linear velocity is about 20 ~ 40m/s, and it is Nb that cooling obtains chemical constitution
0.42Ni
0.32Co
0.06Zr
0.12Ta
0.08Nb base noncrystal alloy band, test its thermodynamic stability and hydrogen penetrating quality.Width 〉=the 10mm of this Nb base noncrystal alloy band, thickness are 40 μ m.
Shown in Fig. 1 (c), be the XRD figure spectrum of the Nb base noncrystal alloy band of embodiments of the invention 3.Obtain the X ray diffracting spectrum of this Nb base noncrystal alloy band by the melt spinning method method.The diffuse scattering peak that the steamed bun shape is only arranged in the collection of illustrative plates, and do not have the sharp-pointed diffraction peak corresponding with crystalline material, show that sample is complete non-crystal structure.
Shown in Fig. 2 (c), be the DSC curve of the Nb base noncrystal alloy band of embodiments of the invention 3.Test result shows that the initial crystallization temperature of this Nb base noncrystal alloy band is 580 ℃, has good thermodynamic stability.
This Nb base noncrystal alloy strip face is polished smooth.Then this Nb base noncrystal alloy band two sides is plated the Pd film that thickness is 100nm, obtaining chemical constitution is Nb
0.42Ni
0.32Co
0.06Zr
0.12Ta
0.08The saturating hydrogen metallic membrane of Nb base noncrystal alloy.The saturating hydrogen metallic membrane of this Nb base noncrystal alloy is placed in the gas permeation test device of standard and tests, namely to the saturating hydrogen amount of measuring under the fixed temperature under the different pressure reduction, obtain the saturating hydrogen coefficient of material under this temperature; And under condition of different temperatures, test, obtain hydrogen penetrating quality data and the variation with temperature rule thereof of the saturating hydrogen metallic membrane of this Nb base noncrystal alloy under differing temps.Shown in Fig. 3 (c), be the Arrhenius curve of the saturating hydrogen metallic membrane of Nb base noncrystal alloy of embodiments of the invention 3.The hydrogen permeability coefficient of the saturating hydrogen metallic membrane of this Nb base noncrystal alloy of this curve display in the time of 400 ℃ is 0.88 * 10
-8Molm
-1S-1Pa
-1/2, the hydrogen permeability coefficient in the time of 350 ℃ is 0.68 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 300 ℃ is 0.47 * 10
-8Molm
-1s
-1Pa
-1/2Fig. 3 (f) is Pd-23wt%Ag reference alloy hydrogen permeability coefficient variation with temperature curve under the same conditions, comparison diagram 3 (c) and 3 (f) as can be known, Nb
0.42Ni
0.32Co
0.06Zr
0.12Ta
0.08The saturating hydrogen performance of the saturating hydrogen metallic membrane of non-crystaline amorphous metal is still good not as good as the saturating hydrogen performance of Pd-23wt%Ag alloy film, but very approaching, as seen, and Nb
0.42Ni
0.32Co
0.06Zr
0.12Ta
0.08Amorphous closes the hydrogen metallic membrane and has good hydrogen penetrating quality.
Embodiment 4: preparation Nb
0.42Ni
0.32Co
0.06Zr
0.12Ti
0.08Non-crystaline amorphous metal
At first with each raw material of purity 〉=99.9% according to chemical ingredients proportioning Nb
0.42Ni
aCo
bZr
cM
dPrepare burden, wherein, M is Ti, a, and b, c, d are the atomic percent of each constituent element, and a=0.32, b=0.06, c=0.12, d=0.08.Then melt back in vacuum arc fumace, the mother alloy of acquisition homogeneous chemical composition.Be better than 3 * 10 in vacuum tightness
-2Under the Pa vacuum condition, place the induction furnace of quick solidification apparatus to make its fusing mother alloy, obtain the mother alloy melt.With the copper roller surface of mother alloy melt jet to high speed rotating, the roller surface linear velocity is about 20 ~ 40m/s, and it is Nb that cooling obtains chemical constitution
0.42Ni
0.32Co
0.06Zr
0.12Ti
0.08Nb base noncrystal alloy band, test its thermodynamic stability and hydrogen penetrating quality.Width 〉=the 10mm of this Nb base noncrystal alloy band, thickness are 37 μ m.
Shown in Fig. 1 (d), be the XRD figure spectrum of the Nb base noncrystal alloy band of embodiments of the invention 4.Obtain the X ray diffracting spectrum of this Nb base noncrystal alloy band by the melt spinning method method.The diffuse scattering peak that the steamed bun shape is only arranged in the collection of illustrative plates, and do not have the sharp-pointed diffraction peak corresponding with crystalline material, show that sample is complete non-crystal structure.
Shown in Fig. 2 (d), be the DSC curve of the Nb base noncrystal alloy band of embodiments of the invention 4.Test result shows that the initial crystallization temperature of this Nb base noncrystal alloy band is 563 ℃, has good thermodynamic stability.
This Nb base noncrystal alloy strip face is polished smooth.Then this Nb base noncrystal alloy band two sides is plated the Pd film that thickness is 100nm, obtaining chemical constitution is Nb
0.42Ni
0.32Co
0.06Zr
0.12Ti
0.08The saturating hydrogen metallic membrane of Nb base noncrystal alloy.The saturating hydrogen metallic membrane of this Nb base noncrystal alloy is placed in the gas permeation test device of standard and tests, namely to the saturating hydrogen amount of measuring under the fixed temperature under the different pressure reduction, obtain the saturating hydrogen coefficient of material under this temperature; And under condition of different temperatures, test, obtain hydrogen penetrating quality data and the variation with temperature rule thereof of the saturating hydrogen metallic membrane of this Nb base noncrystal alloy under differing temps.Shown in Fig. 3 (d), be the Arrhenius curve of the saturating hydrogen metallic membrane of Nb base noncrystal alloy of embodiments of the invention 4.The hydrogen permeability coefficient of the saturating hydrogen metallic membrane of this Nb base noncrystal alloy of this curve display in the time of 400 ℃ is 1.30 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 350 ℃ is 1.01 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 300 ℃ is 0.75 * 10
-8Molm
-1s
-1Pa
-1/2
Shown in Fig. 3 (f), be the Arrhenius curve of Pd-23wt.%Ag alloy standard reference material.The hydrogen permeability coefficient of Pd-23wt.%Ag alloy standard reference material in the time of 400 ℃ is 1.14 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 350 ℃ is 0.85 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 300 ℃ is 0.58 * 10
-8Molm
-1s
-1Pa
-1/2Comparison diagram 3 (d) and 3 (f) as can be known, Nb
0.42Ni
0.32Co
0.06Zr
0.12Ti
0.08The saturating hydrogen performance of the saturating hydrogen metallic membrane of non-crystaline amorphous metal is good than the saturating hydrogen performance of Pd-23wt%Ag alloy film, and composition is Nb among the visible embodiment 4
0.42Ni
0.32Co
0.06Zr
0.12Ti
0.08The hydrogen permeability coefficient of the saturating hydrogen metallic membrane of Nb base noncrystal alloy under each probe temperature condition all greater than Pd-23wt.%Ag alloy standard reference material, had the hydrogen penetrating quality above the Pd-23wt.%Ag alloy, namely this alloy is a kind of saturating hydrogen metal membrane material of the Pd-23wt.%Ag of being better than alloy.
Embodiment 5: preparation Nb
0.42Ni
0.30Co
0.05Zr
0.20Ti
0.03Non-crystaline amorphous metal
At first with each raw material of purity 〉=99.9% according to chemical ingredients proportioning Nb
0.42Ni
aCo
bZr
cM
dPrepare burden, wherein, M is Ti, a, and b, c, d are the atomic percent of each constituent element, and a=0.30, b=0.05, c=0.20, d=0.03.Then melt back in vacuum arc fumace, the mother alloy of acquisition homogeneous chemical composition.Be better than 3 * 10 in vacuum tightness
-2Under the Pa vacuum condition, place the induction furnace of quick solidification apparatus to make its fusing mother alloy, obtain the mother alloy melt.With the copper roller surface of mother alloy melt jet to high speed rotating, the roller surface linear velocity is about 20 ~ 40m/s, and it is Nb that cooling obtains chemical constitution
0.42Ni
0.30Co
0.05Zr
0.20Ti
0.03Nb base noncrystal alloy band, test its thermodynamic stability and hydrogen penetrating quality.Width 〉=the 10mm of this Nb base noncrystal alloy band, thickness are 42 μ m.
Shown in Fig. 1 (e), be the XRD figure spectrum of the Nb base noncrystal alloy band of embodiments of the invention 5.Obtain the X ray diffracting spectrum of this Nb base noncrystal alloy band by the melt spinning method method.The diffuse scattering peak that the steamed bun shape is only arranged in the collection of illustrative plates, and do not have the sharp-pointed diffraction peak corresponding with crystalline material, show that sample is complete non-crystal structure.
Shown in Fig. 2 (e), be the DSC curve of the Nb base noncrystal alloy band of embodiments of the invention 5.Test result shows that the initial crystallization temperature of this Nb base noncrystal alloy band is 554 ℃, has good thermodynamic stability.
This Nb base noncrystal alloy strip face is polished smooth.Then this Nb base noncrystal alloy band two sides is plated the Pd film that thickness is 100nm, obtaining chemical constitution is Nb
0.42Ni
0.30Co
0.05Zr
0.20Ti
0.03The saturating hydrogen metallic membrane of Nb base noncrystal alloy.The saturating hydrogen metallic membrane of this Nb base noncrystal alloy is placed in the gas permeation test device of standard and tests, namely to the saturating hydrogen amount of measuring under the fixed temperature under the different pressure reduction, obtain the saturating hydrogen coefficient of material under this temperature; And under condition of different temperatures, test, obtain hydrogen penetrating quality data and the variation with temperature rule thereof of the saturating hydrogen metallic membrane of this Nb base noncrystal alloy under differing temps.Shown in Fig. 3 (e), be the Arrhenius curve of the saturating hydrogen metallic membrane of Nb base noncrystal alloy of embodiments of the invention 5.The hydrogen permeability coefficient of the saturating hydrogen metallic membrane of this Nb base noncrystal alloy of this curve display in the time of 400 ℃ is 1.40 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 350 ℃ is 0.95 * 10
-8Molm
-1S-1Pa
-1/2, the hydrogen permeability coefficient in the time of 300 ℃ is 0.60 * 10
-8Molm
-1s
-1Pa
-1/2
Shown in Fig. 3 (f), be the Arrhenius curve of Pd-23wt.%Ag alloy standard reference material.The hydrogen permeability coefficient of Pd-23wt.%Ag alloy standard reference material in the time of 400 ℃ is 1.14 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 350 ℃ is 0.85 * 10
-8Molm
-1s
-1Pa
-1/2, the hydrogen permeability coefficient in the time of 300 ℃ is 0.58 * 10
-8Molm
-1s
-1Pa
-1/2Comparison diagram 3 (e) and 3 (f) as can be known, Nb
0.42Ni
0.30Co
0.05Zr
0.20Ti
0.03The hydrogen permeability coefficient of the saturating hydrogen metallic membrane of non-crystaline amorphous metal is obviously greater than the hydrogen permeability coefficient of Pd-23wt%Ag alloy film, and composition is Nb among the visible embodiment 5
0.42Ni
0.30Co
0.05Zr
0.20Ti
0.03The saturating hydrogen metallic membrane of Nb base noncrystal alloy have hydrogen penetrating quality above the Pd-23wt.%Ag alloy.
Above-described embodiment, just the specific embodiment of the invention is several, and the common variation that those skilled in the art carries out in the technical solution of the present invention scope and replacement all should be included in protection scope of the present invention.
Claims (8)
1. Nb base noncrystal alloy, it is characterized in that: the chemical expression of described Nb base noncrystal alloy is Nb
0.42Ni
aCo
bZr
cM
dWherein, M=Ta or Ti; A, b, c, d are the atomic percent of each constituent element, 0.30≤a≤0.40,0.05≤b≤0.15,0.04≤c≤0.20,0≤d≤0.08 and a+b+c+d=0.58.
2. the preparation method of a Nb base noncrystal alloy band is characterized in that, comprising:
With raw material according to Nb
0.42Ni
aCo
bZr
cM
dPrepare burden, wherein, M=Ta or Ti; A, b, c, d are the atomic percent of each constituent element, 0.30≤a≤0.40,0.05≤b≤0.15,0.04≤c≤0.20,0≤d≤0.08 and a+b+c+d=0.58;
With described raw material melt back, obtain the mother alloy of homogeneous chemical composition;
With described mother alloy fusing, obtain the mother alloy melt;
Described mother alloy melt jet is obtained described Nb base noncrystal alloy band to the quick cooling of the copper roller surface of high speed rotating, and the chemical expression of described Nb base noncrystal alloy band is Nb
0.42Ni
aCo
bZr
cM
dWherein, M=Ta or Ti; A, b, c, d are the atomic percent of each constituent element, 0.30≤a≤0.40,0.05≤b≤0.15,0.04≤c≤0.20,0≤d≤0.08 and a+b+c+d=0.58.
3. the preparation method of Nb base noncrystal alloy band as claimed in claim 2 is characterized in that: be to carry out in vacuum arc fumace with described raw material melt back.
4. the preparation method of Nb base noncrystal alloy band as claimed in claim 2 is characterized in that: with described mother alloy fusing, be to carry out in the induction furnace of quick solidification apparatus.
5. the preparation method of Nb base noncrystal alloy band as claimed in claim 2, it is characterized in that: the width 〉=10mm of described Nb base noncrystal alloy band, thickness are about 20 ~ 50 μ m.
6. the preparation method of Nb base noncrystal alloy band as claimed in claim 2 is characterized in that: the initial crystallization temperature of described Nb base noncrystal alloy band 〉=550 ℃.
7. the preparation method of the saturating hydrogen metallic membrane of Nb base noncrystal alloy is characterized in that, comprising:
The surface finish of Nb base noncrystal alloy band is smooth, and wherein, the chemical expression of described Nb base noncrystal alloy band is Nb
0.42Ni
aCo
bZr
cM
dWherein, M=Ta or Ti; A, b, c, d are the atomic percent of each constituent element, 0.30≤a≤0.40,0.05≤b≤0.15,0.04≤c≤0.20,0≤d≤0.08 and a+b+c+d=0.58;
The two sides of described Nb base noncrystal alloy band is plated the Pd film, obtain the saturating hydrogen metallic membrane of described Nb base noncrystal alloy; The chemical expression of the saturating hydrogen metallic membrane of described Nb base noncrystal alloy is Nb
0.42Ni
aCo
bZr
cM
dWherein, M=Ta or Ti; A, b, c, d are the atomic percent of each constituent element, 0.30≤a≤0.40,0.05≤b≤0.15,0.04≤c≤0.20,0≤d≤0.08 and a+b+c+d=0.58.
8. the preparation method of the saturating hydrogen metallic membrane of Nb base noncrystal alloy as claimed in claim 7 is characterized in that: the thickness at the Pd film of the two sides of described Nb base noncrystal alloy band plating is 10 ~ 500nm.
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| CN103302257A (en) * | 2013-06-07 | 2013-09-18 | 苏州市泰力达科技有限公司 | Preparation method of aniline hydrogenating amorphous nickel-aluminum catalyst |
| CN105018867A (en) * | 2014-04-22 | 2015-11-04 | 中国科学院宁波材料技术与工程研究所 | Niobium-based bulk amorphous alloy and preparation method thereof |
| CN106834854A (en) * | 2017-02-21 | 2017-06-13 | 山东科技大学 | Alloy and preparation method are passed through using rear-earth-doped high-performance Nb bases hydrogen |
| CN111778437A (en) * | 2020-07-15 | 2020-10-16 | 桂林电子科技大学 | Thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material and preparation method and application thereof |
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| CN111778437A (en) * | 2020-07-15 | 2020-10-16 | 桂林电子科技大学 | Thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material and preparation method and application thereof |
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