CN109576610B - Bimodal nano-porous amorphous alloy and preparation method thereof - Google Patents

Bimodal nano-porous amorphous alloy and preparation method thereof Download PDF

Info

Publication number
CN109576610B
CN109576610B CN201910053459.0A CN201910053459A CN109576610B CN 109576610 B CN109576610 B CN 109576610B CN 201910053459 A CN201910053459 A CN 201910053459A CN 109576610 B CN109576610 B CN 109576610B
Authority
CN
China
Prior art keywords
amorphous alloy
dealloying
bimodal
porous
nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910053459.0A
Other languages
Chinese (zh)
Other versions
CN109576610A (en
Inventor
秦春玲
朱墨
王志峰
张山
李永艳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei University of Technology
Original Assignee
Hebei University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hebei University of Technology filed Critical Hebei University of Technology
Priority to CN201910053459.0A priority Critical patent/CN109576610B/en
Publication of CN109576610A publication Critical patent/CN109576610A/en
Application granted granted Critical
Publication of CN109576610B publication Critical patent/CN109576610B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The invention relates to a bimodal nano porous amorphous alloy and a preparation method thereof. The amorphous material has a bimodal nano-porous structure, and the element composition is YαTiβCoγAlηThe atomic percentage of each element is not less than 3.31 and not more than α and not more than 5.58,50.35- β -52.67, 19.79- γ -20.46, 23.56- η -24.28, α + β + γ + η -10028Ti28Co20Al24The double-phase amorphous alloy is used as a precursor, a porous amorphous alloy framework is prepared by a free dealloying method, and the bimodal nano porous amorphous alloy with the multi-level pore structure is prepared by secondary dealloying. The method solves the defects of complex technology, long whole process period, complex equipment, high equipment manufacturing cost, low yield, single product pore structure, large pore size, low porosity, low specific surface area and the like in the current preparation of the porous amorphous alloy.

Description

Bimodal nano-porous amorphous alloy and preparation method thereof
The technical field is as follows:
the invention relates to the technical field of nano porous materials, in particular to a bimodal nano porous amorphous alloy and a preparation method thereof.
Background art:
in recent years, as a new porous metal, a nanoporous amorphous alloy has attracted attention because of its combination of the characteristics of both porous metal and amorphous alloy. The atomic structure of the crystalline material has a periodically repeated arrangement in a three-dimensional space, while the atomic arrangement of the amorphous material shows a short-range order and a long-range disorder. This structural difference allows the nanoporous amorphous alloys to exhibit special properties different from those of conventional nanoporous metals. According to reports, the hydrogen storage performance of the Zr-Co-Al porous amorphous alloy is several times that of the Zr-Co-Al bulk amorphous alloy and porous metal with the same components, and the nano porous amorphous alloy has great development potential in the field of functional materials. The development of nanoporous amorphous materials with more compositions and structures is a current hot topic.
In the prior art, publication No. CN106676619A "a method for preparing a metal glass nano-porous structure", Zr-based metal glass with a nano-porous structure only on the surface is prepared by an electrochemical dealloying method. As the material only forms a nano porous structure on the surface, the interior of the material still is an amorphous alloy matrix, and the obtained porous structure is a closed pore structure, the porosity and the specific surface area of the material are lower. In addition, the electrochemical dealloying method causes complex material preparation process, increased equipment cost and lower yield.
In the prior art, the publication No. CN101984104A 'A method for preparing biomedical bulk porous amorphous alloy', amorphous powder and magnesium alloy powder are prepared by an atomization or mechanical alloying method, the amorphous powder and the magnesium alloy powder are uniformly mixed for 2-5h by a ball mill, and finally magnesium alloy particles in the material are removed by a chemical corrosion method, so that the required porous amorphous alloy is obtained.
In the prior art, CN104399978A discloses a 3D forming method for large-sized porous amorphous alloy parts with complex shapes, which is to perform high-energy ball milling for 45 hours by a planetary ball mill to obtain metal powder, and then apply 3D printing technology to prepare porous amorphous alloy. The prepared porous material has larger pore diameter which can only reach 50-500 mu m, and the application of the product in the functional field is limited. The process has a long total period, has high requirements on equipment, needs precise control in the process, and increases the requirements on equipment advancement and the technical level of operators.
In the prior art, the paper script Materialia 55(2006)1063-1066 discloses a method for preparing a Ti-based porous amorphous alloy. The method uses a dealloying method in 0.1M HNO3Carrying out electrochemical dealloying for 30min or free dealloying for 24h on Y20Ti36Al24Co20The Y-rich phase in the dual-phase amorphous alloy is selectively dissolved, so that the Ti-rich phase is reserved as a nano porous amorphous alloy framework. The nano-porous Ti-based amorphous alloy prepared by the method is a typical open-pore structure, but does not show a bimodal characteristic, has low porosity and is greatly limited to be applied as a functional material. In this paper the sample was treated using a free dealloying methodThe time is long, and the sample preparation amount by the electrochemical dealloying method is small, so that the method is not suitable for industrial production.
The invention content is as follows:
the invention provides a bimodal nano-porous amorphous alloy and a preparation method thereof (bimodal porous structure refers to a porous structure with two levels of characteristic sizes with obviously different size ranges) aiming at the defects in the prior art. The nano-porous Y-Ti-Co-Al amorphous alloy prepared by the invention is composed of a bimodal porous structure, compared with the traditional material, the structure is more uniform, the multi-stage pore structure is more beneficial to exerting the characteristic of large specific surface area of the material, and the characteristics of multiple components also bring more potential advantages for the functional development of the material. The method uses Y28Ti28Co20Al24Taking biphase amorphous alloy as precursor, selectively dissolving Y by free dealloying method56Co20Al24Amorphous phase to thereby retain Ti56Co20Al24The amorphous phase is used as a porous amorphous alloy framework, and the bimodal nano porous amorphous alloy with the multi-level pore structure is prepared through secondary dealloying. The invention solves the defects of complex technology, long whole process period, complex equipment, high equipment manufacturing cost, low yield, single product pore structure, large pore size, low porosity, low specific surface area and the like in the current preparation of the porous amorphous alloy.
The technical scheme of the invention is as follows:
a bimodal nano-porous amorphous alloy material is a product obtained by dealloying a two-phase amorphous thin strip, and the element composition is YαTiβCoγAlηThe material has a bimodal porous structure, wherein the atomic percentages of the elements are 3.31- α -5.58, 50.35- β -52.67, 19.79-20.46, 23.56- η -24.28, α + β + gamma + η are 100, the material has a primary pore size of 46.88-83.35 nm, the average width of primary ligaments is 78.26-103.33 nm, the average size of secondary pores is 7.24-9.88 nm, the average size of secondary ligaments is 12.58-16.78 nm, and the specific surface area of the material reaches 75.68m2/g～88.32m2/g。
The preparation method of the bimodal nano-porous amorphous alloy comprises the following steps:
first, preparing a dual-phase amorphous alloy ribbon
According to Y28Ti28Co20Al24Weighing Y, Ti, Co and Al metals, placing the raw materials in a vacuum arc furnace, and vacuumizing to the air pressure of 3.0 × 10-3Pa, filling argon gas under the argon pressure of 3 × 10-2Starting arc starting and smelting under the MPa condition, smelting the material by 70-100A current for 2-4 times, each time for 20-30 s, and cooling along with the furnace to obtain Y28Ti28Co20Al24Casting mother alloy ingot, remelting the alloy ingot by a vacuum melt spinning machine under the protection of argon gas to prepare a two-phase amorphous alloy thin strip, wherein the vacuum degree in the furnace is 3.2 × 10 in the preparation process-3Pa, the rotation frequency of the copper wheel is 100-120 HZ, and the spray casting pressure is 1.0-1.5 MPa; the prepared amorphous alloy has a thin belt width of 2-3 mm and a thickness of 15-20 μm;
wherein the purities of the Y, Ti, Co and Al metal raw materials are all 99.99 percent (mass fraction), and the volume purity of the argon is 99.99 percent;
second, preparing the nano porous amorphous alloy by dealloying treatment
Immersing the amorphous alloy thin strip obtained in the last step into the mixed solution by adopting a free dealloying method, corroding for 5-10 min at the constant temperature of 25 ℃, cleaning and vacuum-drying the obtained product, putting the product into a vacuum tube furnace, and performing N-phase reaction on the product2Heating to 175-185 ℃ at the speed of 5 ℃/min in the atmosphere, annealing for 2-3 h, cooling to room temperature along with a furnace, and taking out a sample;
the mixed solution is xM HNO3，yM H2SO4Prepared according to the volume ratio of 2:1, wherein x is more than or equal to 0.4 and less than or equal to 0.5, and y is more than or equal to 0.4 and less than or equal to 0.5;
thirdly, preparing the bimodal nano porous amorphous alloy by secondary dealloying
Soaking the amorphous alloy thin strip obtained in the last step into a prepared mixed solution for 5-8 min by adopting a free dealloying method to perform dealloying reaction, and cleaning and vacuum-drying the obtained product to obtain the double-peak nano porous amorphous alloy;
the mixed solution is xM HNO3The volume ratio of the yM HCl is 2:1, wherein x is more than or equal to 0.5 and less than or equal to 0.7, and y is more than or equal to 0.5 and less than or equal to 0.7.
In the preparation method of the bimodal nano-porous amorphous alloy, the used raw materials and equipment are obtained by a known way, and the used operation process can be mastered by a person skilled in the art.
The invention has the following substantive characteristics:
the material obtained by the invention is amorphous alloy with a bimodal nano porous structure. The amorphous material is provided with a multi-stage porous structure by proper parameter setting (the composition of mixed corrosive liquid used in the alloy removing processes in the second step and the third step and annealing treatment).
The invention has the following beneficial effects:
(1) in terms of preparation methods, most of the existing porous amorphous preparation methods can only prepare a porous structure with a micron scale, and the preparation methods are too complex. Some reports that the nano-scale porous amorphous alloy can be prepared by adopting an electrochemical dealloying technology, but the preparation process is more complicated and the yield is lower. The invention develops a preparation method for rapidly and conveniently preparing the nano porous amorphous alloy with the multistage pore structure for the first time, the applied free dealloying method is simpler and more convenient and easier to operate, the requirements on equipment, energy and experimenters are reduced, the cost is reduced, the benefit is increased, and the method is beneficial to large-scale industrial production.
(2) Compared with the traditional porous amorphous alloy, the nano porous amorphous alloy prepared by the invention has higher specific surface area (75.68 m)2/g～88.32m2The material has the dual advantages of amorphous alloy and nano-porous metal, the high specific surface area and the porous structure are favorable for rapid diffusion and transmission of reactants and products after entering a pore channel, the multi-level pore structure enables the material to be more fully utilized, and the material has potential application possibility in the field of catalysis.
(3) The preparation process is simple, rapid, efficient and low in cost, the components and the nano porous structure of the obtained product can be regulated and controlled by changing experimental parameters, and the defects of complex technology, long whole process period, complex equipment, high equipment manufacturing cost, low yield, single product pore structure, large pore size, low porosity, low specific surface area and the like in the current preparation of the porous amorphous alloy are overcome.
Description of the drawings:
FIG. 1: y prepared in example 128Ti28Co20Al24X-ray diffraction pattern of the biphase amorphous alloy.
FIG. 2: scanning electron micrograph of the bimodal nanoporous amorphous alloy prepared in example 1.
FIG. 3: x-ray diffraction pattern of the bimodal nanoporous amorphous alloy prepared in example 1.
FIG. 4: transmission electron micrograph of bimodal nanoporous amorphous alloy prepared in example 1.
FIG. 5: pore size distribution plot for the bimodal nanoporous amorphous alloy prepared in example 1.
Detailed Description
Example 1
First, preparing a dual-phase amorphous alloy ribbon
Selecting high-purity Y, Ti, Co and Al metals as raw materials, wherein the mass purity of the four elements is 99.99 wt%, and then according to the target component Y28Ti28Co20Al24Weighing each component element, preparing raw material with total amount of 6g, placing 6g metal raw material in vacuum arc furnace, vacuumizing to pressure of 3.0 × 10-3Pa, argon (volume purity 99.99%) at 3 × 10 argon pressure-2Starting arc-starting smelting under MPa, with a smelting current of 100A, repeatedly smelting for 3 times (30 s each time) to ensure the uniformity of alloy structure, and cooling with the furnace to obtain Y28Ti28Co20Al243g of master alloy ingot is taken to be subjected to induction melting under the protection of high-purity argon (the volume purity is 99.99 percent), and the vacuum degree in the furnace is 3.2 × 10 in the melting process-3Pa, the rotation frequency of the copper wheel is 120HZ, and the spray casting pressure is 1.5 MPa; the width of the amorphous alloy thin belt prepared by spray casting is 2mm,the thickness is 15 μm;
second, preparing nano porous amorphous alloy by free dealloying
3g of the amorphous alloy thin strip obtained in the last step is immersed into 500ml of mixed corrosive liquid by adopting a free dealloying method, wherein the mixed liquid is made of 0.4M HNO3、0.4M H2SO4Prepared according to the volume ratio of 2:1, free dealloying is carried out for 5min at the constant temperature of 25 ℃, the obtained product is washed for 3 times by deionized water, and then the product is placed in a vacuum drying oven to be dried at the temperature of 60 ℃; the dried product was placed in a vacuum tube furnace at N2Heating to 180 ℃ at the speed of 5 ℃/min in the atmosphere, annealing for 2.5h, then cooling to room temperature along with the furnace, taking out the sample, and obtaining the nano porous amorphous alloy;
thirdly, preparing the bimodal nano porous amorphous alloy by secondary free dealloying
Soaking the nano-porous amorphous alloy obtained in the last step into 500ml of mixed corrosive liquid by adopting a free dealloying method, wherein the mixed liquid is made of 0.5M HNO30.5M HCl is prepared according to the volume ratio of 2:1, and free dealloying is carried out for 5min at the constant temperature of 25 ℃; and washing the reacted product with deionized water for 3 times, and then placing the product in a vacuum drying oven to dry at 60 ℃ to obtain the bimodal nano porous amorphous alloy.
FIG. 1 is Y prepared in example 128Ti28Co20Al24An X-ray diffraction pattern of the bidirectional amorphous alloy, wherein two diffuse scattering peaks appearing in the ranges of 32.2-36.4 degrees and 40.5-44.1 degrees respectively correspond to Y56Co20Al24Amorphous and Ti56Co20Al24Position of diffuse scattering peak of amorphous, representing prepared Y28Ti28Co20Al24The alloy is a dual-phase amorphous alloy. FIG. 2 is a scanning electron micrograph of the bimodal nanoporous amorphous alloy prepared in example 1, from which it can be seen that the obtained bicontinuous nanoporous structure has a uniform morphology and the material component is Y3.31Ti52.67Co20.46Al23.56. FIG. 3 is an X-ray diffraction pattern of the bimodal nanoporous amorphous alloy prepared in example 1, in which amorphous alloy in the range of 40.5-44.1 ° is seenThe characteristic diffuse scattering peak of gold is retained, and the corresponding diffuse scattering peak in the range of 32.2-36.4 degrees basically disappears, which proves that the prepared bimodal nano-porous framework mainly comprises Ti56Co20Al24And (4) amorphous structure. Fig. 4 is a transmission electron micrograph of the bimodal nanoporous amorphous alloy prepared in example 1, which can be observed that the prepared nanoporous amorphous alloy consists of a two-stage pore structure, and it is found that the primary pore size is 46.88nm, the average ligament width is 78.26nm, the secondary pore size is 7.24nm, and the average ligament width is 12.58 nm. FIG. 5 is a distribution diagram of the pore size of the bimodal nanoporous amorphous alloy prepared in example 1, from which it can be seen that two peaks appear in the pore size, and it is further confirmed that the synthesized material has a bimodal nanoporous structure, and the specific surface area of the material reaches 88.32m2(measured by the Brunauer-Emmett-Teller method).
Example 2
Firstly, preparing an amorphous alloy thin strip
Selecting high-purity Y, Ti, Co and Al metals as raw materials, wherein the mass purity of the four elements is 99.99 wt%, and then according to the target component Y28Ti28Co20Al24Weighing each component element, preparing raw material with total amount of 6g, placing 6g metal raw material in vacuum arc furnace, vacuumizing to pressure of 3.0 × 10-3Pa, argon (volume purity 99.99%) at 3 × 10 argon pressure-2Starting arc-starting smelting under MPa, with a smelting current of 70A, repeatedly smelting for 4 times (20 s each time) to ensure the homogeneity of alloy structure, and cooling with the furnace to obtain Y28Ti28Co20Al243g of master alloy ingot is taken to be subjected to induction melting under the protection of high-purity argon (the volume purity is 99.99 percent), and the vacuum degree in the furnace is 3.2 × 10 in the melting process-3Pa, the rotation frequency of the copper wheel is 110HZ, and the spray casting pressure is 1.2 MPa; the width of the thin band of the biphase amorphous alloy prepared by spray casting is 2.6mm, and the thickness is 17.2 mu m;
second, preparing nano porous amorphous alloy by free dealloying
By adopting a free dealloying method, the product obtained in the last step3g of the amorphous alloy thin strip is immersed into 500ml of mixed corrosive liquid, wherein the mixed liquid is made of 0.45M HNO3、0.45M H2SO4Prepared according to the volume ratio of 2:1, free dealloying is carried out for 7.5min under the constant temperature condition of 25 ℃, the obtained product is washed for 3 times by deionized water, and then the product is placed in a vacuum drying oven to be dried at 60 ℃; the dried product was placed in a vacuum tube furnace at N2Heating to 185 ℃ at the speed of 5 ℃/min in the atmosphere, annealing for 2h, then cooling to room temperature along with the furnace, taking out the sample, and obtaining the nano porous amorphous alloy;
thirdly, preparing the bimodal nano porous amorphous alloy by secondary free dealloying
Soaking the nano-porous amorphous alloy obtained in the last step into 500ml of mixed corrosive liquid by adopting a free dealloying method, wherein the mixed liquid is made of 0.6M HNO30.6M HCl is prepared according to the volume ratio of 2:1, and free dealloying is carried out for 6min at the constant temperature of 25 ℃; and washing the reacted product with deionized water for 3 times, and then placing the product in a vacuum drying oven to dry at 60 ℃ to obtain the bimodal nano porous amorphous alloy.
The morphology of the bimodal nanoporous amorphous alloy prepared in example 2 was observed, and the bimodal nanoporous amorphous alloy was found to consist of a two-stage pore structure, wherein the size of the primary pores was 70.68nm, the average width of the primary ligaments was 92.34nm, the size of the secondary pores was 8.54nm, the average width of the secondary ligaments was 14.69nm, and the material component was Y5.58Ti50.35Co19.79Al24.28The specific surface area reaches 80.61m2(measured by the Brunauer-Emmett-Teller method).
Example 3
Firstly, preparing an amorphous alloy thin strip
Selecting high-purity Y, Ti, Co and Al metals as raw materials, wherein the mass purity of the four elements is 99.99 wt%, and then according to the target component Y28Ti28Co20Al24Weighing each component element, preparing raw material with total amount of 6g, placing 6g metal raw material in vacuum arc furnace, vacuumizing to pressure of 3.0 × 10-3Pa, argon (volume purity 99.99%) at 3 × 10 argon pressure-2Starting under MPaArc-starting smelting with smelting current of 90A, repeatedly smelting for 2 times (each time for 25 s) to ensure alloy structure uniformity, and cooling with the furnace to obtain Y28Ti28Co20Al243g of master alloy ingot is taken to be subjected to induction melting under the protection of high-purity argon (the volume purity is 99.99 percent), and the vacuum degree in the furnace is 3.2 × 10 in the melting process-3Pa, the rotation frequency of the copper wheel is 100HZ, and the spray casting pressure is 1.0 MPa. The width of the thin band of the biphase amorphous alloy prepared by spray casting is 3mm, and the thickness is 20 mu m;
second, preparing nano porous amorphous alloy by free dealloying
3g of the amorphous alloy thin strip obtained in the last step is immersed into 500ml of mixed corrosive liquid by adopting a free dealloying method, wherein the mixed liquid is made of 0.5M HNO3、0.5M H2SO4Prepared according to the volume ratio of 2:1, free dealloying is carried out for 10min at the constant temperature of 25 ℃, the obtained product is washed for 3 times by deionized water, and then the product is placed in a vacuum drying oven for drying; the dried product was placed in a vacuum tube furnace at N2Heating to 175 ℃ at the speed of 5 ℃/min in the atmosphere, annealing for 3h, then cooling to room temperature along with the furnace, taking out the sample, and obtaining the nano porous amorphous alloy.
Thirdly, preparing the bimodal nano porous amorphous alloy by secondary free dealloying
Soaking the nano-porous amorphous alloy obtained in the last step into 500ml of mixed corrosive liquid by adopting a free dealloying method, wherein the mixed liquid is made of 0.7M HNO3And 0.7M HCl is prepared according to the volume ratio of 2:1, so that the excessive corrosive liquid is ensured. Freely dealloying for 8min at the constant temperature of 25 ℃; and cleaning the reacted product by using deionized water, and then drying in vacuum to obtain the bimodal nano porous amorphous alloy.
The morphology of the bimodal nanoporous amorphous alloy prepared in example 3 was observed, and the bimodal nanoporous amorphous alloy was found to consist of a two-stage pore structure, wherein the primary pore size was 83.35nm, the average primary ligament width was 103.33nm, the secondary pore size was 9.88nm, the average secondary ligament width was 16.78nm, and the material component was Y5.01Ti51.24Co19.98Al23.77The specific surface area reaches 75.68m2(Brunauer-Emmett-Teller square)Measured by the method).
Comparative example 1:
only the first free dealloying is carried out, the second free dealloying is not carried out, other conditions are the same as those of the example 1, the microstructure of the surface of a sample is observed, only a uniform nano porous structure is obtained, a second-stage pore structure is not observed, and the double-peak structural characteristic is not shown through a BET test.
Comparative example 2:
selecting 0.5M HNO as corrosive liquid for free dealloying in the first step3、0.5M H2SO4And 0.05M of HF is mixed solution prepared according to the volume ratio of 4:2:1, other conditions are the same as those of the example 1, and the obtained product is detected by a microscopic electron microscope, so that only a nanosphere structure is found, and an obvious nanoporous reticular structure cannot be observed.
Comparative example 3:
selecting 1M HNO as corrosive liquid for secondary free dealloying3And 1M HCl is prepared into a mixed solution according to the volume ratio of 2:1, other conditions are the same as those in example 1, the obtained product is detected by a microscopic electron microscope, an obvious bimodal nano-porous characteristic structure cannot be observed, and the sample is subjected to X-ray diffraction analysis to find that the sample has an obvious crystallization phenomenon.
Comparative example 4:
the free dealloying time of the first step is prolonged to 20min, other conditions are the same as those of the example 1, the obtained product is detected by a scanning electron microscope, only a single nano porous structure is formed, a bimodal characteristic structure is not found, and the average size of the obtained nano ligament is increased to 200 nm. The product did not show bimodal characteristics by BET test.
The above examples and comparative examples illustrate that a bimodal nanoporous amorphous alloy and a method for preparing the bimodal nanoporous amorphous alloy are finally developed through repeated practice by continuously trying to remove alloy process parameters, strictly controlling each process link, and specifically comprising the following steps:
(1) the invention provides a method for preparing a bimodal nano-porous amorphous alloy material by adopting a secondary free dealloying technology for the first time. Namely, a primary nano porous amorphous alloy framework is prepared through primary free dealloying, and then a secondary pore structure is derived on the original porous framework by adopting a secondary free dealloying technology. Different from the complicated operation of preparing the nano-porous metal by electrochemical dealloying, the free dealloying technology is simpler and easier to operate, improves the preparation efficiency of the product, and is more suitable for large-scale industrial production.
(2) At present, no multi-stage pore structure report exists in the preparation of the nano porous amorphous alloy by a dealloying method. The invention develops a novel bimodal nano-porous amorphous alloy for the first time. The prepared nano porous amorphous alloy consists of a two-stage porous structure, wherein the size of a primary pore is 46.88-83.35 nm, the average width of a ligament is 78.26-103.33 nm, the size of a secondary pore is 7.24-9.88 nm, the average size of the ligament is 2.58-16.78 nm, and the specific surface area reaches 75.68m2/g～88.32m2The structure is more uniform compared with the conventional material, the multistage pore structure is favorable for rapid diffusion and transmission of reactants and products after entering the pore channel, the characteristic of large specific surface area of the material can be more fully exerted, and the catalyst has great potential in the field of catalytic materials.
The invention is not the best known technology.

Claims (2)

1. A bimodal nano-porous amorphous alloy material is characterized in that the material is a product obtained by dealloying a two-phase amorphous thin strip, and the element composition is YαTiβCoγAlηThe material has a bimodal nanoporous structure, wherein the atomic percentages of the elements are 3.31- α -5.58, 50.35- β -52.67, 19.79-20.46, 23.56- η -24.28, α + β + γ + η =100, the size of a primary pore is 46.88-83.35 nm, the average width of a primary ligament is 78.26-103.33 nm, the size of a secondary pore is 7.24-9.88 nm, the average size of a secondary ligament is 12.58-16.78 nm, and the specific surface area of the material reaches 75.68m2/g~88.32m2/g；
The preparation method of the bimodal nano-porous amorphous alloy is characterized by comprising the following steps:
first, preparing a dual-phase amorphous alloy ribbon
According to Y28Ti28Co20Al24Weighing Y, Ti, Co and Al metals, placing the raw materials in a vacuum arc furnace, and vacuumizing to the air pressure of 3.0 × 10-3Pa, filling argon gas under the argon pressure of 3 × 10-2Starting arc starting and smelting under the MPa condition, smelting the material by 70-100A current for 2-4 times, each time for 20-30 s, and cooling along with the furnace to obtain Y28Ti28Co20Al24Casting mother alloy ingot, remelting the alloy ingot by a vacuum melt spinning machine under the protection of argon gas to prepare a two-phase amorphous alloy thin strip, wherein the vacuum degree in the furnace is 3.2 × 10 in the preparation process-3Pa, the rotation frequency of the copper wheel is 100-120 HZ, and the spray casting pressure is 1.0-1.5 MPa; the prepared amorphous alloy has a thin belt width of 2-3 mm and a thickness of 15-20 μm;
second, preparing the nano porous amorphous alloy by dealloying treatment
Immersing the amorphous alloy thin strip obtained in the last step into the mixed solution by adopting a free dealloying method, corroding for 5-10 min at the constant temperature of 25 ℃, cleaning and vacuum-drying the obtained product, putting the product into a vacuum tube furnace, and performing N-phase reaction on the product2Heating to 175-185 ℃ at the speed of 5 ℃/min in the atmosphere, annealing for 2-3 h, cooling to room temperature along with a furnace, and taking out a sample;
the mixed solution is xM HNO3，yM H2SO4Prepared according to the volume ratio of 2:1, wherein x is more than or equal to 0.4 and less than or equal to 0.5, and y is more than or equal to 0.4 and less than or equal to 0.5;
thirdly, preparing the bimodal nano porous amorphous alloy by secondary dealloying
Soaking the amorphous alloy thin strip obtained in the last step into a prepared mixed solution for 5-8 min by adopting a free dealloying method to perform dealloying reaction, and cleaning and vacuum-drying the obtained product to obtain the double-peak nano porous amorphous alloy;
the mixed solution is xM HNO3The volume ratio of the yM HCl is 2:1, wherein x is more than or equal to 0.5 and less than or equal to 0.7, and y is more than or equal to 0.5 and less than or equal to 0.7.
2. The bimodal nanoporous amorphous alloy material as claimed in claim 1, wherein the purity of the Y, Ti, Co and Al metal raw materials in the preparation method is 99.99% mass fraction, and the volume purity of the argon gas is 99.99%.
CN201910053459.0A 2019-01-21 2019-01-21 Bimodal nano-porous amorphous alloy and preparation method thereof Active CN109576610B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910053459.0A CN109576610B (en) 2019-01-21 2019-01-21 Bimodal nano-porous amorphous alloy and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910053459.0A CN109576610B (en) 2019-01-21 2019-01-21 Bimodal nano-porous amorphous alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109576610A CN109576610A (en) 2019-04-05
CN109576610B true CN109576610B (en) 2020-08-11

Family

ID=65916923

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910053459.0A Active CN109576610B (en) 2019-01-21 2019-01-21 Bimodal nano-porous amorphous alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109576610B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110484764B (en) * 2019-08-08 2021-06-01 哈尔滨工业大学（深圳） Nano porous high-entropy alloy and preparation method thereof
CN112143926B (en) * 2019-11-28 2021-11-16 赵远云 Preparation method and application of aluminum alloy-containing powder and alloy strip

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100760339B1 (en) * 2006-05-19 2007-10-04 한국과학기술연구원 Nanometer-sized porous metallic glasses and method for manufactruring the same
KR100767719B1 (en) * 2006-08-29 2007-10-17 한국과학기술연구원 Ti-based amorphous nano-powders and method of preparation thereof
CN102522573A (en) * 2011-12-19 2012-06-27 天津大学 Nanoporous TiO2 film on Ti-Cu alloy surface and its preparation method
KR101309516B1 (en) * 2012-03-30 2013-10-14 서울대학교산학협력단 Preparation method for magnetic metallic glass nano-powder
CN102943187B (en) * 2012-11-19 2014-08-13 河北工业大学 Preparation method of nano porous copper
CN103938130B (en) * 2014-05-09 2016-01-06 河北工业大学 The preparation method of nanoporous nickel block body

Also Published As

Publication number Publication date
CN109576610A (en) 2019-04-05

Similar Documents

Publication Publication Date Title
Sun et al. Nanostructure in a Ti alloy processed using a cryomilling technique
US20130315773A1 (en) Method of Manufacturing Pure Titanium Hydride Powder and Alloyed Titanium Hydride Powders By Combined Hydrogen-Magnesium Reduction of Metal Halides
CN109576610B (en) Bimodal nano-porous amorphous alloy and preparation method thereof
Shao et al. Preparation and hydrogen storage properties of nanostructured Mg–Ni BCC alloys
JP2016524040A (en) Method for producing metal-containing powder
Shao et al. Preparation of Mg-based hydrogen storage materials from metal nanoparticles
CN110304632A (en) Sheet MXene material and preparation method thereof and energy storage material
CN115233077B (en) CoCrNi-based medium entropy alloy with high aluminum content and high titanium content and strengthened nano coherent precipitation and preparation method thereof
CN109518064B (en) Nano porous high-entropy alloy microsphere material and preparation method thereof
CN108698837A (en) The reduction of metal/semiconductor metal oxide
Zhang et al. Microstructures and mechanical behavior of a near α titanium alloy prepared by TiH2-based powder metallurgy
Zhang et al. Deformation behavior and microstructure evolution mechanism of 5vol.%(TiBw+ TiCp)/Ti composites during isothermal compression
El-Eskandarany Metallic glassy Ti 2 Ni grain-growth inhibitor powder for enhancing the hydrogenation/dehydrogenation kinetics of MgH 2
CN109706409B (en) Nano porous amorphous alloy and preparation method thereof
CN109518099B (en) Amorphous nano flower material and preparation method thereof
CN111101041A (en) Magnesium-yttrium-zinc hydrogen storage magnesium alloy and preparation method thereof
CN111068647A (en) Nano TiO (titanium dioxide)2-SnO2Preparation method of solid solution photocatalytic material
JP2010144246A (en) Methods for producing micropore nickel porous body and micropore nickel-copper alloy porous body, and product obtained thereby
Yang et al. Cerium-activated non-basal slip improves ductility of magnesium alloy
Ma et al. Influence of dealloying solution on the microstructure of nanoporous copper through chemical dealloying of Al75Cu25 ribbons
Takasaki et al. Mechanical alloying of the Ti-Al system in atmosphere of hydrogen and argon
CN114273663B (en) Cu-M series nano porous amorphous alloy and preparation method thereof
CN109678551B (en) Porous pyrochlore ceramic composite material and preparation method thereof
CN114015903A (en) Preparation method of high-porosity black porous metal film
Nersisyan et al. Shape-controlled synthesis of titanium microparticles using calciothermic reduction concept

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant