CN109576610A - Bimodal nano-meter porous amorphous alloy of one kind and preparation method thereof - Google Patents
Bimodal nano-meter porous amorphous alloy of one kind and preparation method thereof Download PDFInfo
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Abstract
The present invention is bimodal nano-meter porous amorphous alloy of one kind and preparation method thereof.The non-crystalline material has bimodal nano-porous structure, and element group becomes YαTiβCoγAlη, the atomic percentage of each element is 3.31≤α≤5.58,50.35≤β≤52.67,19.79≤γ≤20.46,23.56≤η≤24.28, and+η=100 alpha+beta+γ.Preparation method is with Y28Ti28Co20Al24Two-phase amorphous alloy is presoma, freely takes off alloyage and porous amorphous alloy skeleton is made, the bimodal nano-meter porous amorphous alloy with multi-stage pore structure is prepared by secondary de- alloy.Solves technology complexity in current porous amorphous alloy preparation, the integrated artistic period is long, and the device is complicated and high equipment cost, low output, the deficiencies such as product pore structure is single, and pore size is big, and porosity is low, and specific surface area is low.
Description
Technical field:
The present invention relates to nano-porous materials technical field, specifically a kind of bimodal nano-meter porous amorphous alloy and its
Preparation method.
Background technique:
In recent years, nano-meter porous amorphous alloy, as a kind of novel porous metals, because its combine porous metals with it is non-
The double grading of peritectic alloy and it is of interest by people.The atomic structure of crystalline material has the row of being repeated cyclically in three-dimensional space
Column, and the characteristics of the atomic arrangement of non-crystalline material shows shortrange order longrange disorder.Difference in this structure keeps nanometer more
Hole amorphous alloy shows the special nature different from Conventional nano porous metals.According to reports, the porous amorphous of Zr-Co-Al closes
The hydrogen storage property of gold is the several times of congruent Zr-Co-Al block amorphous alloy and porous metals, shows nano-meter porous amorphous alloy
Has very big potentiality to be exploited in field of functional materials.It is current for developing the nano-meter porous amorphous material of more multicomponent and structure
Hot subject.
First technology, publication number CN106676619A " a kind of preparation method of glassy metal nano-porous structure ", this is specially
For benefit in such a way that electrochemistry takes off alloy, preparing only has the Zr base metal glass of nano-porous structure on surface.Due to this
Material only forms nano-porous structure on surface, and internal is still amorphous alloy matrix, and gained pore structure is hole-closing structure, because
This material porosity and specific surface area are lower.In addition Applied Electrochemistry takes off alloyage and causes material preparation process complicated, equipment at
This increasing, and yield is lower.
First technology, a kind of preparation method of biomedical bulk porous amorphous alloy of publication number CN101984104A " ",
The patent prepares amorphous powder and magnesium alloy powder using atomization or mechanical alloying method, is closed amorphous powder and magnesium with ball mill
Bronze end uniformly mixes 2-5h, finally the magnesium alloy particles in material is removed with the method for chemical attack, to obtain required
Porous amorphous alloy, the present invention is complicated, and production efficiency is low, and to equipment, material, the energy is more demanding, is not suitable for answering
For large-scale industrial production, gained porous structure size is affected by raw materials particles, not the ruler of easy-regulating pore structure
It is very little, and the porous amorphous alloy of nanoscale can not be prepared.
First technology, CN104399978A disclose a kind of 3D forming of big-size complicated shape porous amorphous alloy part
Method obtains metal powder by planetary ball mill high-energy ball milling 45h, then prepares porous amorphous using 3D printing technique and closes
Gold.Prepared aperture of porous material is larger to be only capable of reaching 50~500 μm, limits its product in the application of functional area.It should
Technique total period is longer, very high to equipment requirement, and technical process needs accurate control, increases advanced and right to equipment
The requirement of operator's technical level.
First technology, it is non-that 55 (2006) 1063-1066 of paper Scripta Materialia discloses a kind of Quito Ti hole
The preparation method of peritectic alloy.The de- alloyage of this method application, in 0.1M HNO3In alloy 30min or freedom taken off by electrochemistry
De- alloy is for 24 hours by Y20Ti36Al24Co20Rich Y phase selectivity dissolution in two-phase amorphous alloy, so that retaining rich Ti phase is used as nanometer
Porous amorphous alloy skeleton.The nanoporous Ti base noncrystal alloy of this method preparation is typical open-celled structure, but there is no tables
Reveal double-peak feature, and porosity is lower, the application as functional material is extremely restricted.It is applied in the paper and freely takes off conjunction
Golden method processing sample time is longer, and the de- alloyage sample preparation amount of electrochemistry is small, is not suitable for industrialized production.
Summary of the invention:
The present invention provides bimodal nano-meter porous amorphous alloy of one kind and preparation method thereof for the deficiency in current techniques
(bimodal porous structure refers to the dramatically different pore structure with two-stage characteristic size of size range).Nanometer prepared by the present invention
Porous Y-Ti-Co-Al amorphous alloy by bimodal porous structure composition, more previous material structure compared more evenly, multistage hole knot
Structure, which is more advantageous to, plays the big characteristic of material specific surface area, and the feature of multicomponent is also that the functional exploitation of material brings more dive
Advantage.This method is with Y28Ti28Co20Al24Two-phase amorphous alloy is presoma, freely takes off alloyage selective dissolution
Y56Co20Al24Amorphous phase, to retain Ti56Co20Al24Amorphous phase is as porous amorphous alloy skeleton, by secondary de- alloy system
The standby bimodal nano-meter porous amorphous alloy for providing multi-stage pore structure.The present invention solves in current porous amorphous alloy preparation
Technology is complicated, and the integrated artistic period is long, and the device is complicated and high equipment cost, and low output, product pore structure is single, pore size
Greatly, the deficiencies such as porosity is low, and specific surface area is low.
The technical scheme is that
A kind of bimodal nano-meter porous amorphous alloy material, the material are that two-phase amorphous thin ribbon takes off products obtained therefrom after alloy, member
Element group becomes YαTiβCoγAlη, the atomic percentage of each element be 3.31≤α≤5.58,50.35≤β≤52.67,19.79≤
γ≤20.46,23.56≤η≤24.28, and+η=100 alpha+beta+γ；The material has bimodal porous structure, wherein level-one hole
Having a size of 46.88~83.35nm, level-one ligament mean breadth 78.26nm~103.33nm, second hole having a size of 7.24~
9.88nm, second level ligament average-size are 12.58~16.78nm；Material specific surface area reaches 75.68m2/ g~88.32m2/g。
The preparation method of the bimodal nano-meter porous amorphous alloy, includes the following steps:
The first step prepares two-phase amorphous alloy ribbon
By Y28Ti28Co20Al24Ingredient weighs Y, Ti, and raw material are placed in vacuum arc furnace ignition, vacuumize by Co and Al metal
It is 3.0 × 10 to air pressure-3Pa is filled with argon gas, is 3 × 10 in Ar Pressure-2Start starting the arc melting under the conditions of MPa, with 70~100A
Electric current melting material, melting 2~4 times, 20~30s, is made Y every time after furnace cooling28Ti28Co20Al24Mother alloy ingot；Then
Under protection of argon gas, band machine is got rid of by alloy pig remelting using vacuum and two-phase amorphous alloy ribbon is made, in preparation process in furnace
Vacuum degree is 3.2 × 10-3Pa, copper wheel rotational frequency are 100~120HZ, and spray to cast pressure is 1.0~1.5MPa；Amorphous obtained
Alloy thin band width is 2~3mm, with a thickness of 15~20 μm；
Wherein, the purity of Y, Ti, Co and the Al raw material metal is 99.99% (mass fraction), the argon gas
Bulk purity be 99.99%；
Second step, de- alloy treatment prepare nano-meter porous amorphous alloy
Using alloyage is freely taken off, amorphous alloy ribbon obtained in the previous step is immersed in mixed solution, in 25 DEG C of constant temperature
Under the conditions of corrode 5~10min, products therefrom through over cleaning and vacuum drying after, be placed in vacuum tube furnace, in N2In atmosphere with
The rate of 5 DEG C/min is heated to 175~185 DEG C of 2~3h of annealing, then cools to room temperature with the furnace and takes out sample；
The mixed solution is xM HNO3, yM H2SO42:1 is formulated by volume, wherein 0.4≤x≤0.5,0.4
≤y≤0.5；
Third step, secondary de- alloy prepare bimodal nano-meter porous amorphous alloy
Using alloyage is freely taken off, amorphous alloy ribbon obtained in the previous step is soaked into 5 in prepared mixed solution
~8min carries out de- alloy reaction, and products therefrom arrives bimodal nano-meter porous amorphous alloy after over cleaning and vacuum drying；
The mixed solution is xM HNO3, 2:1 is formulated yM HCl by volume, wherein 0.5≤x≤0.7,0.5≤
y≤0.7。
The preparation method of the above-mentioned bimodal nano-meter porous amorphous alloy of one kind, used raw material and equipment pass through known
Approach obtain, operating procedure used is that those skilled in the art can grasp.
Substantive distinguishing features of the invention are as follows:
The material that the present invention obtains is the amorphous alloy with bimodal nano-porous structure.Pass through appropriately in preparation method
Parameter setting (second step and third step take off the composition of hybrid corrosion liquid used in alloy process, and make annealing treatment), makes non-
Brilliant material has multistage porous structure.
Beneficial effects of the present invention are as follows:
(1) for preparation method, current existing porous non-crystal preparation method is largely only capable of preparing micro-meter scale
Porous structure, and preparation method is excessively complicated.Although part report, which takes off alloy technology using electrochemistry, can prepare nanoscale
Porous amorphous alloy, but preparation process is relatively complicated and yield is lower.The present invention develops a kind of quick, convenient preparation tool for the first time
There is the preparation method of the nano-meter porous amorphous alloy of multistage pore structure, the applied alloyage that freely takes off is more simple and easy to operate,
It reduces to equipment, the energy and the requirement of experimenter, reduces costs, increase benefit, be conducive to heavy industrialization
Production.
(2) compared with traditional porous amorphous alloy, nano-meter porous amorphous alloy prepared by the present invention has higher
Specific surface area (75.68m2/ g~88.32m2/ g), and material has had both the double dominant of amorphous alloy and nano porous metal, it is high
Specific surface area and porous structure are conducive to the quick diffusion and transmission of the reactant into after duct and product, and multi-stage porous
Gap structure utilizes material more fully, which has potential application in catalytic field may.
(3) preparation process used in the present invention is simple, rapidly and efficiently and low in cost, can be to institute by changing experiment parameter
The ingredient and nano-porous structure for obtaining product are regulated and controled, and solve technology complexity in current porous amorphous alloy preparation, whole
Process cycle is long, and the device is complicated and high equipment cost, low output, and product pore structure is single, and pore size is big, and porosity is low, than
The deficiencies such as surface area is low.
Detailed description of the invention:
Fig. 1: the Y prepared in embodiment 128Ti28Co20Al24The X ray diffracting spectrum of two-phase amorphous alloy.
Fig. 2: the scanning electron electromicroscopic photograph of the bimodal nano-meter porous amorphous alloy prepared in embodiment 1.
Fig. 3: the X ray diffracting spectrum of the bimodal nano-meter porous amorphous alloy prepared in embodiment 1.
Fig. 4: the transmitted electron electromicroscopic photograph of the bimodal nano-meter porous amorphous alloy prepared in embodiment 1.
Fig. 5: the pore size distribution figure of the bimodal nano-meter porous amorphous alloy prepared in embodiment 1.
Specific embodiment
Embodiment 1
The first step prepares two-phase amorphous alloy ribbon
High-purity Y is selected, Ti, Co and Al metal is 99.99wt% as raw material, the quality purity of four kinds of elements,
Then according to target component Y28Ti28Co20Al24Each component element is weighed, the raw material of total amount 6g is prepared, marks into and atomize
Percentage；The 6g raw metal of configuration is placed in vacuum arc furnace ignition, being evacuated to air pressure is 3.0 × 10-3Pa is filled with argon gas
(bulk purity 99.99%) is 3 × 10 in Ar Pressure-2Start starting the arc melting under the conditions of MPa, melting electric current is 100A, repeatedly
Melting 3 times, each 30s, it is ensured that Y is made in alloy structure uniformity after furnace cooling28Ti28Co20Al24Mother alloy ingot；Take 3g
Mother alloy ingot carries out induction melting under high-purity argon gas (bulk purity 99.99%) protection, vacuum in furnace in fusion process
Degree is 3.2 × 10-3Pa, copper wheel rotational frequency are 120HZ, and spray to cast pressure is 1.5MPa；Amorphous alloy thin bandwidth is made in spray to cast
2mm, with a thickness of 15 μm；
Second step freely takes off alloy and prepares nano-meter porous amorphous alloy
Using alloyage is freely taken off, amorphous alloy ribbon 3g obtained in the previous step is immersed in 500ml hybrid corrosion liquid,
Middle mixed liquor is by 0.4M HNO3、0.4M H2SO42:1 is formulated by volume, freely takes off alloy under 25 DEG C of constant temperatures
5min rinses products therefrom 3 times with deionized water, is subsequently placed in vacuum oven in 60 DEG C of dryings；By the product after drying
As in vacuum tube furnace, in N2180 DEG C of annealing 2.5h are heated to the rate of 5 DEG C/min in atmosphere, it is then cold with furnace
But sample is taken out to room temperature, obtains nano-meter porous amorphous alloy；
Third step, the secondary alloy that freely takes off prepare bimodal nano-meter porous amorphous alloy
Using alloyage is freely taken off, nano-meter porous amorphous alloy obtained in the previous step is immersed in 500ml hybrid corrosion liquid,
Wherein mixed liquor is by 0.5M HNO3, 2:1 is formulated 0.5M HCl by volume, freely take off alloy under 25 DEG C of constant temperatures
5min；Product after reaction is cleaned with deionized water and is placed on vacuum oven for 3 times in 60 DEG C of dryings, obtains described bimodal receive
Rice porous amorphous alloy.
Fig. 1 is the Y prepared in embodiment 128Ti28Co20Al24The X-ray diffractogram of two-way amorphous alloy, wherein at 32.2 °
~36.4 °, two diffusing scattering peaks that 40.5 °~44.1 ° ranges occur respectively correspond Y56Co20Al24Amorphous and Ti56Co20Al24
The diffusing scattering peak position of amorphous represents prepared Y28Ti28Co20Al24Alloy is two-phase amorphous alloy.Fig. 2 is in embodiment 1
Prepared bimodal nano-meter porous amorphous alloy scanning electron microscopy shape appearance figure, as seen from the figure resulting co-continuous nanoporous knot
It is uniform to be configured looks, material composition Y3.31Ti52.67Co20.46Al23.56.Fig. 3 is non-for the bimodal nanoporous prepared in embodiment 1
The X-ray diffractogram of peritectic alloy, the visible amorphous alloy feature diffusing scattering peak within the scope of 40.5 °~44.1 ° is protected in figure
It stays, and corresponding diffusing scattering peak disappears substantially within the scope of 32.2 °~36.4 °, it was demonstrated that prepared bimodal nanoporous skeleton master
It will be by Ti56Co20Al24Amorphous is constituted.Fig. 4 is the transmission electron microscopy of the bimodal nano-meter porous amorphous alloy prepared in embodiment 1
Shape appearance figure, it can be observed that prepared nano-meter porous amorphous alloy by twin-stage hole structure composition, it is found that level-one pore size is
46.88nm, ligament mean breadth are 78.26nm, and second hole is having a size of 7.24nm, ligament mean breadth 12.58nm.Shown in Fig. 5
For the pore size distribution figure of the bimodal nano-meter porous amorphous alloy prepared in embodiment 1, its pore size occurs two as seen from the figure
Locate peak value, further demonstrating synthesized material has bimodal nano-porous structure, and the specific surface area of material reaches 88.32m2/g
(measurement of Brunauer-Emmett-Teller method).
Embodiment 2
The first step prepares amorphous alloy ribbon
High-purity Y is selected, Ti, Co and Al metal is 99.99wt% as raw material, the quality purity of four kinds of elements,
Then according to target component Y28Ti28Co20Al24Each component element is weighed, the raw material of total amount 6g is prepared, marks into and atomize
Percentage；The 6g raw metal of configuration is placed in vacuum arc furnace ignition, being evacuated to air pressure is 3.0 × 10-3Pa is filled with argon gas
(bulk purity 99.99%) is 3 × 10 in Ar Pressure-2Start starting the arc melting under the conditions of MPa, melting electric current is 70A, repeatedly
Melting 4 times, each 20s, it is ensured that Y is made in alloy structure uniformity after furnace cooling28Ti28Co20Al24Mother alloy ingot；Take 3g
Mother alloy ingot carries out induction melting under high-purity argon gas (bulk purity 99.99%) protection, vacuum in furnace in fusion process
Degree is 3.2 × 10-3Pa, copper wheel rotational frequency are 110HZ, and spray to cast pressure is 1.2MPa；Two-phase amorphous alloy thin made from spray to cast
Bandwidth is 2.6mm, with a thickness of 17.2 μm；
Second step freely takes off alloy and prepares nano-meter porous amorphous alloy
Using alloyage is freely taken off, amorphous alloy ribbon 3g obtained in the previous step is immersed in 500ml hybrid corrosion liquid,
Middle mixed liquor is by 0.45M HNO3、0.45M H2SO42:1 is formulated by volume, freely takes off alloy under 25 DEG C of constant temperatures
7.5min rinses products therefrom 3 times with deionized water, is subsequently placed in vacuum oven in 60 DEG C of dryings；By the production after drying
Object is as in vacuum tube furnace, in N2185 DEG C of annealing 2h are heated to the rate of 5 DEG C/min in atmosphere, it is then cold with furnace
But sample is taken out to room temperature, obtains nano-meter porous amorphous alloy；
Third step, the secondary alloy that freely takes off prepare bimodal nano-meter porous amorphous alloy
Using alloyage is freely taken off, nano-meter porous amorphous alloy obtained in the previous step is immersed in 500ml hybrid corrosion liquid,
Wherein mixed liquor is by 0.6M HNO3, 2:1 is formulated 0.6M HCl by volume, freely take off alloy under 25 DEG C of constant temperatures
6min；Product after reaction is cleaned with deionized water and is placed on vacuum oven for 3 times in 60 DEG C of dryings, obtains described bimodal receive
Rice porous amorphous alloy.
The pattern of bimodal nano-meter porous amorphous alloy prepared by embodiment 2 is observed, finds it by twin-stage hole knot
Structure composition, level-one pore size are 70.68nm, and level-one ligament mean breadth is 92.34nm, and second hole is having a size of 8.54nm, second level
Ligament mean breadth 14.69nm, material composition Y5.58Ti50.35Co19.79Al24.28, specific surface area reach 80.61m2/g
(measurement of Brunauer-Emmett-Teller method).
Embodiment 3
The first step prepares amorphous alloy ribbon
High-purity Y is selected, Ti, Co and Al metal is 99.99wt% as raw material, the quality purity of four kinds of elements,
Then according to target component Y28Ti28Co20Al24Each component element is weighed, the raw material of total amount 6g is prepared, marks into and atomize
Percentage；The 6g raw metal of configuration is placed in vacuum arc furnace ignition, being evacuated to air pressure is 3.0 × 10-3Pa is filled with argon gas
(bulk purity 99.99%) is 3 × 10 in Ar Pressure-2Start starting the arc melting under the conditions of MPa, melting electric current is 90A, repeatedly
Melting 2 times, each 25s, it is ensured that Y is made in alloy structure uniformity after furnace cooling28Ti28Co20Al24Mother alloy ingot；Take 3g
Mother alloy ingot carries out induction melting under high-purity argon gas (bulk purity 99.99%) protection, vacuum in furnace in fusion process
Degree is 3.2 × 10-3Pa, copper wheel rotational frequency are 100HZ, and spray to cast pressure is 1.0MPa.Two-phase amorphous alloy thin made from spray to cast
Bandwidth is 3mm, with a thickness of 20 μm；
Second step freely takes off alloy and prepares nano-meter porous amorphous alloy
Using alloyage is freely taken off, amorphous alloy ribbon 3g obtained in the previous step is immersed in 500ml hybrid corrosion liquid,
Middle mixed liquor is by 0.5M HNO3、0.5M H2SO42:1 is formulated by volume, freely takes off alloy under 25 DEG C of constant temperatures
10min rinses products therefrom 3 times with deionized water, is subsequently placed in vacuum oven dry；By the product after drying as
In vacuum tube furnace, in N2175 DEG C of annealing 3h are heated to the rate of 5 DEG C/min in atmosphere, then cool to room with the furnace
Temperature takes out sample, obtains nano-meter porous amorphous alloy.
Third step, the secondary alloy that freely takes off prepare bimodal nano-meter porous amorphous alloy
Using alloyage is freely taken off, nano-meter porous amorphous alloy obtained in the previous step is immersed in 500ml hybrid corrosion liquid,
Wherein mixed liquor is by 0.7M HNO3, 2:1 is formulated 0.7M HCl by volume, guarantee that corrosive liquid is excessive.In 25 DEG C of constant temperature items
Alloy 8min is freely taken off under part；It is dried in vacuo after product after reaction is cleaned with deionized water, it is more to obtain the bimodal nanometer
Hole amorphous alloy.
The pattern of bimodal nano-meter porous amorphous alloy prepared by embodiment 3 is observed, finds it by twin-stage hole knot
Structure composition, level-one pore size are 83.35nm, and level-one ligament mean breadth is 103.33nm, and second hole is having a size of 9.88nm, second level
Ligament mean breadth 16.78nm, material composition Y5.01Ti51.24Co19.98Al23.77, specific surface area reach 75.68m2/g
(measurement of Brunauer-Emmett-Teller method).
Comparative example 1:
It only carries out the first step and freely takes off alloy, do not carry out second step and freely take off alloy, other conditions are the same as embodiment 1, observation
Sample surfaces microscopic appearance only obtains uniform nano-porous structure, not it is observed that second level pore structure, is tested by BET
Two peak structure feature is not shown.
Comparative example 2:
The first step freely takes off the corrosive liquid selection 0.5M HNO of alloy3、0.5M H2SO4, 0.05M HF 4:2:1 by volume
The mixed liquor of configuration, other conditions are detected with embodiment 1, products therefrom through micro- Electronic Speculum, and discovery only has nanometer spherical structure, are failed
Observe apparent nanoporous reticular structure.
Comparative example 3:
The secondary corrosive liquid selection 1M HNO for freely taking off alloy3, 1M HCl by volume 2:1 prepare mixed solution,
With embodiment 1, products therefrom is detected through micro- Electronic Speculum for his condition, not it is observed that obvious bimodal nanoporous feature structure, into
Row X-ray diffraction analysis finds that apparent crystallization phenomenon occurs in sample.
Comparative example 4:
The first step freely takes off the alloy time and extends to 20min, and other conditions are with embodiment 1, and products therefrom is through scanning electron
Microscope detection, only single nano-porous structure do not find double-peak feature structure, and gained nanometer ligament average-size increases
To 200nm.It is tested by BET, product does not show double-peak feature.
Above embodiments and comparative example illustrate that bimodal nano-meter porous amorphous alloy of one kind and preparation method thereof is by continuous
Trial take off alloying technology parameter, each process procedure of strict control repeatedly practiced, finally develop it is a kind of have it is unique bimodal
Nano-meter porous amorphous alloy of structure feature and preparation method thereof, specifically:
(1) bimodal nano-meter porous amorphous alloy material is prepared using the secondary alloy technology that freely takes off present invention firstly provides a kind of
The method of material.The nano-meter porous amorphous alloy skeleton of level-one is prepared by freely taking off alloy for the first time, then uses secondary freedom
De- alloy technology derives second level pore structure on original stephanoporate framework.Alloy, which is taken off, different from electrochemistry prepares nano-porous gold
Belong to cumbersome operation, freely take off alloy technology it is simpler it is easy to operate, improve product preparation efficiency, be more suitable for large-scale industry
Metaplasia produces.
(2) prepare in nano-meter porous amorphous alloy that there are no the reports of multistage pore structure by de- alloyage at present.This
A kind of novel bimodal nano-meter porous amorphous alloy is developed in invention for the first time.Prepared nano-meter porous amorphous alloy is porous by twin-stage
Structure composition, wherein level-one pore size is 46.88~83.35nm, ligament mean breadth 78.26nm~103.33nm, second hole
Having a size of 7.24~9.88nm, ligament average-size is 2.58~16.78nm, and specific surface area reaches 75.68m2/ g~88.32m2/ g,
More evenly, multistage pore structure is conducive to the quick expansion of reactant and product into after duct to more previous material structure compared
It dissipates and transmits, can more fully play the big characteristic of material specific surface area, have great potentiality in catalysis material field.
Unaccomplished matter of the present invention is well-known technique.
Claims (3)
1. a kind of bimodal nano-meter porous amorphous alloy material, it is characterized in that the material is that gained produces after two-phase amorphous thin ribbon takes off alloy
Product, element group become YαTiβCoγAlη, the atomic percentage of each element is 3.31≤α≤5.58,50.35≤β≤52.67,
19.79≤γ≤20.46,23.56≤η≤24.28, and+η=100 alpha+beta+γ；The material has bimodal nano-porous structure,
In, level-one pore size be 46.88 ~ 83.35 nm, 78.26 nm of nm ~ 103.33 of level-one ligament mean breadth, second hole having a size of
7.24 ~ 9.88 nm, second level ligament average-size are 12.58 ~ 16.78 nm；Material specific surface area is up to 75.68 m2/g~88.32
m2/g。
2. the preparation method of bimodal nano-meter porous amorphous alloy as described in claim 1, it is characterized in that this method includes as follows
Step:
The first step prepares two-phase amorphous alloy ribbon
By Y28Ti28Co20Al24Ingredient weighs Y, Ti, and raw material are placed in vacuum arc furnace ignition, are evacuated to gas by Co and Al metal
Pressure is 3.0 × 10-3Pa is filled with argon gas, is 3 × 10 in Ar Pressure-2Start starting the arc melting under the conditions of MPa, with 70 ~ 100A
Electric current melting material, melting 2 ~ 4 times, 20 ~ 30s, is made Y every time after furnace cooling28Ti28Co20Al24Mother alloy ingot；Then exist
Under argon gas protection, band machine is got rid of by alloy pig remelting using vacuum and two-phase amorphous alloy ribbon is made, it is true in furnace in preparation process
Reciprocal of duty cycle is 3.2 × 10-3Pa, copper wheel rotational frequency are 100 ~ 120 HZ, and spray to cast pressure is 1.0 ~ 1.5 MPa；Amorphous obtained closes
Golden strip width is 2 ~ 3 mm, with a thickness of 15 ~ 20 μm；
Second step, de- alloy treatment prepare nano-meter porous amorphous alloy
Using alloyage is freely taken off, amorphous alloy ribbon obtained in the previous step is immersed in mixed solution, in 25 DEG C of constant temperatures
5 ~ 10 min of lower corrosion, products therefrom are placed in vacuum tube furnace, after over cleaning and vacuum drying in N2In atmosphere with 5 DEG C/
The rate of min is heated to 175 ~ 185 DEG C of 2 ~ 3 h of annealing, then cools to room temperature with the furnace and takes out sample；
The mixed solution is xM HNO3, yM H2SO42:1 is formulated by volume, wherein 0.4≤x≤0.5,0.4
≤ y≤ 0.5；
Third step, secondary de- alloy prepare bimodal nano-meter porous amorphous alloy
Using alloyage is freely taken off, amorphous alloy ribbon obtained in the previous step is soaked into 5 ~ 8 in prepared mixed solution
Min carries out de- alloy reaction, and products therefrom arrives bimodal nano-meter porous amorphous alloy after over cleaning and vacuum drying；
The mixed solution is xM HNO3, 2:1 is formulated yM HCl by volume, wherein 0.5≤x≤0.7,0.5≤
y≤ 0.7。
3. the preparation method of bimodal nano-meter porous amorphous alloy as claimed in claim 2, it is characterized in that the Y, Ti, Co and
The purity of Al raw material metal is 99.99% (mass fraction), and the bulk purity of the argon gas is 99.99 %.
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