CN105624456A - Spongy superfine nanometer porous metal and preparation method - Google Patents
Spongy superfine nanometer porous metal and preparation method Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
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- C22C1/081—Casting porous metals into porous preform skeleton without foaming
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- C22C1/11—Making amorphous alloys
Abstract
The invention discloses a preparation method of spongy superfine nanometer porous metal. The method concretely comprises the step of corroding elements except for Ag, Pt, Pd, Au, Cu and Ni metals in amorphous alloy as a precursor by using an organic acid or a mixed solution of the organic acid and corresponding organic acid salts to form a spongy nanometer porous structure, wherein a lacing is elementary-substance metal or alloy, the feature sizes of holes and the lacing are smaller than 20 nm, the porosity can be up to 70%, the specific surface area can be up to 30m<2>/g, and the integrity and self-preservation property of the structure can be kept. T he preparation method disclosed by the invention is efficient, simple and wide in application range.
Description
Technical field
The present invention relates to a kind of novel spongy nano porous metal and preparation method.
Background technology
It is the difference by utilizing chemical property between different group unit in alloy that removal alloying method prepares nano porous metal, one or more groups more active in alloy units are optionally removed by electrochemical method, forms three-dimensional porous structure by the metal group unit remained. Removal alloying method can obtain having the three-dimensional netted vesicular structure of high-specific surface area, and its frenulum and hole path are continuous mutually, and vesicular structure can dynamic regulation, have simple to operate, cost is lower and the advantage such as applicable scale operation. Removal alloying be a kind of convenient, obtain the effective ways of porous metal material that aperture reaches nano-scale quickly, it is achieved that the breakthrough of porous metal material in aperture size.
Find novel nano porous metal and presoma alloy is one of the focus of material science always. It is most important that precursor alloy prepares nano porous metal for removal alloying method, because not only can the element contamination of alloy determine removal alloying reaction and continue to alloy inside to carry out, and the chemical uniformity of alloy itself also can affect the uniform microstructure of nano porous metal. Compared with traditional crystal alloy, there is not the textural defect such as dislocation, crystal boundary, intermetallic compound in non-crystaline amorphous metal, has good chemical uniformity. The preparation process of rapid solidification makes non-crystaline amorphous metal containing the element contamination exceeding the sosoloid limit, thus can widen the range of choice of precursor alloying constituent. Therefore, non-crystaline amorphous metal is one of desirable precursor alloy preparing nano porous metal material.
As a kind of self-supporting material, nano porous metal material obtains with the constructional feature of its uniqueness and chemical property and pays close attention to widely. The structure having reported nearly all nano porous metal at present is all made up of the frenulum of long and narrow hole and alligatoring, its porosity is general less, and the spongy structure that the present invention obtains has big porosity, when nano material works in media as well, macrovoid not only can reduce the resistance of hole inner material transmission, it is also possible to a large amount of other functional particles of load. The characteristic dimension of current reported nano porous metal mainly concentrates on the range scale of 20-100nm in addition, owing to the characteristic dimension of the frenulum and hole that reduce porous material can effectively increase its specific surface area, the nano porous metal that therefore the present invention obtains has great specific surface area. To sum up 2 point, open grain, the spongy meticulous nano porous metal of bigger serface that the present invention obtains can show excellent performance in electrochemical catalysis, catalyst cupport, ultracapacitor, telegraphy device, surface-enhanced Raman effects etc.
Summary of the invention
The technology of the present invention is dealt with problems: overcome the deficiencies in the prior art, it is provided that a kind of spongy superfine nano porous metal and preparation method, is that alloying constituent is by following formulation: Mg taking block or banded non-crystaline amorphous metal as presomaaMbYcWherein M represents simple substance or the alloy of Pt, Pd, Au, Cu, Ag, Ni, a+b+c=100, by removing Mg and Y element by the method for organic acid and corresponding salt (citric acid, tartrate, succsinic acid, oxysuccinic acid and their sodium salt, sylvite and ammonium salt) removal alloying, the characteristic dimension preparing hole and frenulum is less than 20nm, and has more than 70% porosity and 30m2The nano porous metal material of/more than g specific surface area.
The technology of the present invention solution, a kind of spongy superfine nano porous metal take non-crystaline amorphous metal as presoma, and presoma amorphous alloy component is by following formulation: MgaMbYc, wherein M represents simple substance or the alloy of Pt, Pd, Au, Cu, Ni, Ag, a+b+c=100, and mass percent is: 60��a��70,20��b��30,10��c��15; By 0.1g/L��20g/L organic acid, or the method corrosion Mg and Y element of the mixing solutions removal alloying of organic acid and corresponding organic acid salt, prepare nano porous metal material.
The hole of nano porous metal material and the characteristic dimension of frenulum of described preparation are less than 20nm, and porosity can reach 70%, and specific surface area can reach 30m2/ g; Obtained nano porous metal material and be there is spongy structure, even structure, and self-maintaining well i.e. not avalanche under vesicular structure state of nature.
During preparation, presoma has homogeneous microstructure, does not have crystal boundary, the feature of intermetallic compound defect, it is possible to uniform corrosion occurs.
Described etching time was less than 1 hour, it is not necessary to driven by electrochemical method, energy-efficient.
Described organic acid and corresponding organic acid salt are citric acid, tartrate, succsinic acid, oxysuccinic acid and their sodium salt, sylvite and ammonium salt.
The preparation method of a kind of spongy superfine nano porous metal, it is achieved step is as follows:
Step one: batching
By the element described in claim 1 or 2, become the raw material preparing master alloy ingot;
Step 2: melting prealloy
M and Y element are pressed MgaMbYcName composition carries out melting in vacuum arc melting furnace, obtains MY ingot;
Step 3: master alloy melting
According to MgaMbYcName composition, gets little over amount Mg and M-Y ingot mixing, and melting in high frequency vacuum induction melting furnace, takes mass loss after completing, and the disappearance mending neat M-Y makes final mother alloy consistent with name composition;
Step 4: prepare band
Vacuum induction melting furnace put into by mother alloy step 3 obtained, and is ejected on the copper wheel of high speed rotating, obtains band after thawing;
Step 5: removal alloying
Step 4 gained amorphous alloy ribbon is immersed in the mixing solutions of 0.1g/L��20g/L organic acid or organic acid and corresponding organic acid salt and freely corrode, removal alloying reaction occurs, prepares nano porous metal.
The etching time of described corrosion Mg and Y element was less than 1 hour, it is not necessary to driven by electrochemical method, energy-efficient.
Melting condition in described step 2 is: during melting, the vacuum tightness in vacuum arc melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa and argon content more than 99.99%, often all over melting 1-2 minute, and melting 3-4 time.
Melting condition in described step 3 is: during melting, the vacuum tightness of high frequency vacuum induction melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa and argon content more than 99.99%, melting 5-10 time under small area analysis.
The preparation condition of described step 4 is: during melting, the vacuum tightness of vacuum induction melting furnace is 1 �� 10-2Below Pa, is filled with the pure argon of 0.05Mpa and argon content more than 99.99%, is ejected on the copper wheel of high speed rotating after being heated to molten state.
The present invention is compared with prior art advantageously:
(1) the presoma non-crystaline amorphous metal homogeneous microstructure of the present invention, it does not have the defect such as crystal boundary, intermetallic compound, it is possible to obtain uniform three-dimensional porous structure by uniform corrosion;
(2) the presoma amorphous component scope of the present invention is wide, 60��a��70,20��b��30,10��c��15;
(3) the presoma system suitability of the present invention is extensive, and M can be Pt, Pd, Au, Cu, Ni, Ag simple substance or alloy;
(4) the removal alloying reaction of the present invention freely occurs in corrosive fluid, and etching time was less than 1 hour, it is not necessary to driven by electrochemical method, energy-efficient;
(5) the removal alloying reaction corrosive fluid of the present invention is 0.1g/L��20g/L organic acid or the mixing solutions of organic acid and corresponding organic acid salt, and preparation is simple, safety and environmental protection, reaction temperature and;
(6) even size distribution of the nano porous metal that prepared by the present invention, hole and frenulum, is less than 20nm, has great specific surface area, and namely specific surface area can reach 30m2/ more than g;
(7) nano porous metal that prepared by the present invention does not have volumetric shrinkage compared to presoma, it does not have crackle, self-maintaining good;
(8) the nano porous metal tether construction that prepared by the present invention is mellow and full, smooth surface, and porosity is big, can reach 70%, and is consistent with the first percent by volume of presoma inertia group;
(9) there is not the phenomenon of frenulum alligatoring in time in the nano porous metal that prepared by the present invention, tissue stabilization.
Accompanying drawing explanation
Fig. 1 is Mg65Cu25Y10AMORPHOUS ALLOY RIBBONS is the surface microscopic tissue of the nano porous copper of precursor power.
Fig. 2 is Mg65Cu25Y10AMORPHOUS ALLOY RIBBONS is the microtexture side-view of the nano porous copper of precursor power, shows material internal and surface all by uniform corrosion, and internal structure is consistent with surface tissue.
Fig. 3 is Mg65Ag25Y10Block amorphous alloy is the surface microscopic tissue of the nano-porous silver of precursor power.
Fig. 4 is Mg65Ni25Y10AMORPHOUS ALLOY RIBBONS is the surface microscopic tissue of the nanoporous nickel of precursor power.
Fig. 5 is Mg65Cu23Pt2Y10AMORPHOUS ALLOY RIBBONS is the surface microscopic tissue of the nano porous copper platinum of precursor power.
Fig. 6 is Mg65Ag21Au4Y10AMORPHOUS ALLOY RIBBONS is the surface microscopic tissue of the nano-porous silver gold of precursor power.
Embodiment
Below in conjunction with drawings and the specific embodiments detail the present invention. But following embodiment is only limitted to explain the present invention, and protection scope of the present invention should comprise whole contents of claim, is not limited only to the present embodiment.
The concrete steps preparing a kind of spongy superfine nano porous metal are as follows:
1. determine non-crystaline amorphous metal presoma composition;
2. prepare amorphous master alloy;
3. revolve, with copper wheel, the method for quenching and prepare amorphous alloy ribbon;
4. determine that suitable etching process carries out removal alloying.
It is characterized in that non-crystaline amorphous metal presoma is single-phase non-crystalline state, the nano-porous materials prepared only contains one or more of the elements such as Au, Pt, Pd, Ag, Cu, Ni, and has self-maintaining.
Step one: batching
By name composition MgaMbYcTake each simple substance element, become the raw material preparing master alloy ingot;
Step 2: melting prealloy
M and Y element are pressed MgaMbYcName composition carries out melting in vacuum arc melting furnace, refines 3-4 time, obtains M-Y ingot;
Melting condition is: during melting, the vacuum tightness in vacuum arc melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon (argon content is more than 99.99%) of 0.05Mpa, often all over melting 1-2 minute, and melting 3-4 time.
Step 3: master alloy melting
According to MgaMbYcName composition, gets little over amount Mg and M-Y ingot mixing, and melting in high frequency vacuum induction melting furnace, takes mass loss after completing, and the disappearance mending neat M-Y makes final mother alloy consistent with name composition;
Melting condition is: during melting, the vacuum tightness of high frequency vacuum induction melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon (argon content is more than 99.99%) of 0.05Mpa, melting 5-10 time under small area analysis.
Step 4: prepare band
Vacuum induction melting furnace put into by mother alloy step 3 obtained, and is ejected on the copper wheel of high speed rotating, obtains about 30 �� m-thick, the band that 3mm is wide after thawing;
Preparation condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 1 �� 10-2Below Pa, is filled with the pure argon (argon content is more than 99.99%) of 0.05Mpa, is ejected on the copper wheel of high speed rotating after being heated to molten state.
Step 5: removal alloying
Select suitable etching process, step 4 gained amorphous alloy ribbon is immersed in the mixing solutions of organic acid or organic acid and corresponding organic acid salt and freely corrode, removal alloying reaction occurs, prepares spongy superfine nano porous metal;
Step 6: structural characterization
By the nano-porous materials of step 5 gained by scanning electron microscopic observation structure.
Embodiment 1: with Mg65Cu25Y10Non-crystaline amorphous metal is precursor power nano porous copper
In the present embodiment, selected non-crystaline amorphous metal presoma composition is Mg65Cu25Y10, the preparation method of nano-porous materials is as follows:
Step one: batching
By Mg65Cu25Y10Name composition takes each simple substance element, becomes the raw material preparing master alloy ingot;
Step 2: melting prealloy
Cu and Y element are pressed Mg65Cu25Y10Name composition carries out melting in vacuum arc melting furnace, refines 3-4 time, obtains Cu-Y ingot;
Melting condition is: during melting, the vacuum tightness in vacuum arc melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa, often all over melting 1-2 minute, and melting 3-4 time.
Step 3: master alloy melting
According to Mg65Cu25Y10Name composition, gets little over amount Mg and Cu-Y ingot mixing, and melting in vacuum induction melting furnace, takes mass loss after completing, and the disappearance mending neat Cu-Y makes final mother alloy consistent with name composition;
Melting condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa, melting 5-10 time under small area analysis.
Step 4: prepare band
Vacuum induction melting furnace put into by mother alloy step 3 obtained, and is ejected on the copper wheel of high speed rotating, obtains about 50 �� m-thick, the band that 5mm is wide after thawing;
Preparation condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 1 �� 10-2Pa less than mono-, is filled with the pure argon of 0.05Mpa, is ejected on the copper wheel of high speed rotating after being heated to molten state.
Step 5: removal alloying
Under ambient temperature, step 4 gained amorphous alloy ribbon is immersed in 1g/L citric acid solution and freely corrodes, removal alloying reaction occurs, prepares nano porous copper;
Step 6: structural characterization
By the nano porous copper of step 5 gained by scanning electron microscopic observation structure.
As shown in Figure 1, Mg65Cu25Y10The nano-porous structure obtained after removal alloying 10min, its frenulum is of a size of 8.4nm, and porosity is 76.83%, and specific surface area reaches 42.99m2/ g, contrast mother alloy Mg65Cu25Y10The content of middle Cu, it does not have volumetric shrinkage, and scanning electron microscope (SEM) photograph does not have crackle, tissue does not have avalanche, shows well self-maintaining. As shown in Figure 2, showing material internal and surface all by uniform corrosion, internal structure is consistent with surface tissue.
Embodiment 2: with Mg65Ag25Y10Block amorphous alloy is precursor power nano-porous silver
In the present embodiment, selected non-crystaline amorphous metal presoma composition is Mg65Ag25Y10, the preparation method of nano-porous materials is as follows:
Step one: batching
By Mg65Ag25Y10Name composition takes each simple substance element, becomes the raw material preparing master alloy ingot;
Step 2: melting prealloy
Ag and Y element are pressed Mg65Ag25Y10Name composition carries out melting in vacuum arc melting furnace, refines 3-4 time, obtains Ag-Y ingot;
Melting condition is: during melting, the vacuum tightness in vacuum arc melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa, often all over melting 1-2 minute, and melting 3-4 time.
Step 3: master alloy melting
According to Mg65Ag25Y10Name composition, gets little over amount Mg and Ag-Y ingot mixing, and melting in vacuum induction melting furnace, takes mass loss after completing, and the disappearance mending neat Ag-Y makes final mother alloy consistent with name composition;
Melting condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa, melting 5-10 time under small area analysis.
Step 4: prepare band
Vacuum induction melting furnace put into by mother alloy step 3 obtained, and is ejected on the copper wheel of high speed rotating, obtains about 30 �� m-thick, the band that 3mm is wide after thawing;
Preparation condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 1 �� 10-2Pa less than mono-, is filled with the pure argon (argon content is more than 99.99%) of 0.05Mpa, is ejected on the copper wheel of high speed rotating after being heated to molten state.
Step 5: removal alloying
Under ambient temperature, step 4 gained amorphous alloy ribbon is immersed in 0.5g/L citric acid solution and freely corrodes, removal alloying reaction occurs, prepares nano-porous silver;
Step 6: structural characterization
By the nano-porous silver of step 5 gained by scanning electron microscopic observation structure.
As shown in Figure 3, Mg65Ag25Y10The nano-porous structure obtained after removal alloying 30min, its frenulum is of a size of 8.2nm, and porosity is 76.02%, and specific surface area reaches 37.20m2/ g. Contrast mother alloy Mg65Ag25Y10The content of middle Ag, does not have volumetric shrinkage substantially, and does not have crackle in Electronic Speculum figure, and tissue does not have avalanche, shows well self-maintaining.
Embodiment 3: with Mg65Ni20Y15Non-crystaline amorphous metal is precursor power nano porous copper
In the present embodiment, selected non-crystaline amorphous metal presoma composition is Mg65Ni20Y15, the preparation method of nano-porous materials is as follows:
Step one: batching
By Mg65Ni20Y15Name composition takes each simple substance element, becomes the raw material preparing master alloy ingot;
Step 2: melting prealloy
Ni and Y element are pressed Mg65Ni20Y15Name composition carries out melting in vacuum arc melting furnace, refines 3-4 time, obtains Ni-Y ingot;
Melting condition is: during melting, the vacuum tightness in vacuum arc melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa, often all over melting 1-2 minute, and melting 3-4 time.
Step 3: master alloy melting
According to Mg65Ni20Y15Name composition, gets little over amount Mg and Ni-Y ingot mixing, and melting in vacuum induction melting furnace, takes mass loss after completing, and the disappearance mending neat Ni-Y makes final mother alloy consistent with name composition;
Melting condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa, melting 5-10 time under small area analysis.
Step 4: prepare band
Vacuum induction melting furnace put into by mother alloy step 3 obtained, and is ejected on the copper wheel of high speed rotating, obtains about 30 �� m-thick, the band that 3mm is wide after thawing;
Preparation condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 1 �� 10-2Pa less than mono-, is filled with the pure argon (argon content is more than 99.99%) of 0.05Mpa, is ejected on the copper wheel of high speed rotating after being heated to molten state.
Step 5: removal alloying
Use 2g/L citric acid solution, under ambient temperature, step 4 gained amorphous alloy ribbon is immersed in solution and freely corrodes, removal alloying reaction occurs, prepares nano porous copper;
Step 6: structural characterization
By the nano porous copper of step 5 gained by scanning electron microscopic observation structure.
As shown in Figure 4, Mg65Ni20Y15The nano-porous structure obtained after removal alloying 60min, its frenulum is of a size of 5.0nm, and porosity is 79.38%, and specific surface area reaches 73.16m2/ g. Contrast mother alloy Mg65Ni20Y15The content of middle Ni, does not have volumetric shrinkage substantially, and does not have crackle in Electronic Speculum figure, and tissue does not have avalanche, shows well self-maintaining.
Embodiment 4: with Mg65Cu23Pt2Y10Non-crystaline amorphous metal is precursor power nano porous copper/gold
In the present embodiment, selected non-crystaline amorphous metal presoma composition is Mg65Cu23Pt2Y10, the preparation method of nano-porous materials is as follows:
Step one: batching
By Mg65Cu23Pt2Y10Name composition takes each simple substance element, becomes the raw material preparing master alloy ingot;
Step 2: melting prealloy
Cu, Pt and Y element are pressed Mg65Cu23Pt2Y10Name composition carries out melting in vacuum arc melting furnace, refines 3-4 time, obtains CuPt-Y ingot;
Melting condition is: during melting, the vacuum tightness in vacuum arc melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa, often all over melting 1-2 minute, and melting 3-4 time.
Step 3: master alloy melting
According to Mg65Cu23Pt2Y10Name composition, gets little over amount Mg and CuPt-Y ingot mixing, and melting in vacuum induction melting furnace, takes mass loss after completing, and the disappearance mending neat CuPt-Y makes final mother alloy consistent with name composition;
Melting condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa, melting 5-10 time under small area analysis.
Step 4: prepare band
Vacuum induction melting furnace put into by mother alloy step 3 obtained, and is ejected on the copper wheel of high speed rotating, obtains about 30 �� m-thick, the band that 3mm is wide after thawing;
Preparation condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 1 �� 10-2Pa less than mono-, is filled with the pure argon (argon content is more than 99.99%) of 0.05Mpa, is ejected on the copper wheel of high speed rotating after being heated to molten state.
Step 5: removal alloying
Use 2g/L citric acid solution, under ambient temperature, step 4 gained amorphous alloy ribbon is immersed in solution and freely corrodes, removal alloying reaction occurs, prepares nano porous copper/gold;
Step 6: structural characterization
By the nano porous copper/gold of step 5 gained by scanning electron microscopic observation structure.
As shown in Figure 5, Mg65Cu23Pt2Y10The nano-porous structure obtained after removal alloying 30min, its frenulum is of a size of 7.1nm, and porosity is 74.9%, and specific surface area reaches 38.3m2/ g. Contrast mother alloy Mg65Cu23Pt2Y10The content of middle Cu, Pt, does not almost have volumetric shrinkage, and does not have crackle in Electronic Speculum figure, and tissue does not have avalanche, shows well self-maintaining.
Embodiment 5: with Mg65Ag21Au4Y10Non-crystaline amorphous metal is precursor power nano-porous silver/gold
In the present embodiment, selected non-crystaline amorphous metal presoma composition is Mg65Ag21Au4Y10, the preparation method of nano-porous materials is as follows:
Step one: batching
By Mg65Ag21Au4Y10Name composition takes each simple substance element, becomes the raw material preparing master alloy ingot;
Step 2: melting prealloy
Ag, Au and Y element are pressed Mg65Ag21Au4Y10Name composition carries out melting in vacuum arc melting furnace, refines 3-4 time, obtains AgAu-Y ingot;
Melting condition is: during melting, the vacuum tightness in vacuum arc melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa, often all over melting 1-2 minute, and melting 3-4 time.
Step 3: master alloy melting
According to Mg65Ag21Au4Y10Name composition, gets little over amount Mg and AgAu-Y ingot mixing, and melting in vacuum induction melting furnace, takes mass loss after completing, and the disappearance mending neat AgAu-Y makes final mother alloy consistent with name composition;
Melting condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa, melting 5-10 time under small area analysis.
Step 4: prepare band
Vacuum induction melting furnace put into by mother alloy step 3 obtained, and is ejected on the copper wheel of high speed rotating, obtains about 30 �� m-thick, the band that 3mm is wide after thawing;
Preparation condition is: during melting, the vacuum tightness of vacuum induction melting furnace is 1 �� 10-2Below Pa, is filled with the pure argon (argon content is more than 99.99%) of 0.05Mpa, is ejected on the copper wheel of high speed rotating after being heated to molten state.
Step 5: removal alloying
Use 2g/L citric acid and 4g/L Trisodium Citrate mixing solutions, at room temperature, step 4 gained amorphous alloy ribbon is immersed in solution and freely corrodes, removal alloying reaction occurs, prepares nano-porous silver/gold;
Step 6: structural characterization
By the nano-porous silver/gold of step 5 gained by scanning electron microscopic observation structure.
As shown in Figure 6, Mg65Ag21Au4Y10The nano-porous structure obtained after removal alloying 30min, its frenulum is of a size of 8.4nm, and porosity is 68.4%, and specific surface area reaches 28.3m2/ g. Contrast mother alloy Mg65Ag21Au4Y10The content of middle Ag, Au, does not almost have volumetric shrinkage, and does not have crackle in Electronic Speculum figure, and tissue does not have avalanche, shows well self-maintaining.
In a word, take non-crystaline amorphous metal as presoma, by element except Ag, Pt, Pd, Au, Cu, Ni metal in the method resistant alloy of organic acid or the mixing solutions removal alloying of organic acid and corresponding organic acid salt, form spongy nano-porous structure, frenulum is elemental metals or alloy, the characteristic dimension of its hole and frenulum is less than 20nm, and porosity can reach 70%, and specific surface area can reach 30m2/ g, can the globality of holding structure and self-maintaining. Preparation method of the present invention is efficiently simple, and suitability is extensive.
It should be noted that, according to the various embodiments described above of the present invention, those skilled in the art are the whole scopes that can realize independent claim of the present invention and subordinate right completely, it is achieved process and the same the various embodiments described above of method; And non-elaborated part of the present invention belongs to techniques well known.
The above; being only part embodiment of the present invention, but protection scope of the present invention is not limited thereto, any those skilled in the art are in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
Claims (10)
1. one kind spongy superfine nano porous metal, it is characterised in that: taking non-crystaline amorphous metal as presoma, presoma amorphous alloy component is by following formulation: MgaMbYc, wherein M represents simple substance or the alloy of Pt, Pd, Au, Cu, Ni, Ag, a+b+c=100, and mass percent is: 60��a��70,20��b��30,10��c��15; By 0.1g/L��20g/L organic acid, or the method corrosion Mg and Y element of the mixing solutions removal alloying of organic acid and corresponding organic acid salt, prepare nano porous metal material.
2. the spongy superfine nano porous metal of one according to claim 1, it is characterised in that: the hole of nano porous metal material and the characteristic dimension of frenulum of described preparation are less than 20nm, and porosity can reach 70%, and specific surface area can reach 30m2/ g; Obtained nano porous metal material and be there is spongy structure, even structure, and self-maintaining well i.e. not avalanche under vesicular structure state of nature.
3. the spongy superfine nano porous metal of one according to claim 1, it is characterised in that: during preparation, presoma has homogeneous microstructure, does not have crystal boundary, the feature of intermetallic compound defect, it is possible to uniform corrosion occurs.
4. the spongy superfine nano porous metal of one according to claim 1, it is characterised in that: described etching time was less than 1 hour, it is not necessary to driven by electrochemical method, energy-efficient.
5. the spongy superfine nano porous metal of one according to claim 1, it is characterised in that: described organic acid and corresponding organic acid salt are citric acid, tartrate, succsinic acid, oxysuccinic acid and their sodium salt, sylvite and ammonium salt.
6. the preparation method of one kind spongy superfine nano porous metal, it is characterised in that performing step is as follows:
Step one: batching
By the element described in claim 1 or 2, become the raw material preparing master alloy ingot;
Step 2: melting prealloy
M and Y element are pressed MgaMbYcName composition carries out melting in vacuum arc melting furnace, obtains MY ingot;
Step 3: master alloy melting
According to MgaMbYcName composition, gets little over amount Mg and M-Y ingot mixing, and melting in high frequency vacuum induction melting furnace, takes mass loss after completing, and the disappearance mending neat M-Y makes final mother alloy consistent with name composition;
Step 4: prepare band
Vacuum induction melting furnace put into by mother alloy step 3 obtained, and is ejected on the copper wheel of high speed rotating, obtains band after thawing;
Step 5: removal alloying
Step 4 gained amorphous alloy ribbon is immersed in the mixing solutions of 0.1g/L��20g/L organic acid or organic acid and corresponding organic acid salt and freely corrode, removal alloying reaction occurs, prepares nano porous metal.
7. the preparation method of spongy superfine nano porous metal according to claim 6, it is characterised in that: the etching time of described corrosion Mg and Y element was less than 1 hour, it is not necessary to driven by electrochemical method, energy-efficient.
8. the preparation method of spongy superfine nano porous metal according to claim 6, it is characterised in that: the melting condition in described step 2 is: during melting, the vacuum tightness in vacuum arc melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa and argon content more than 99.99%, often all over melting 1-2 minute, and melting 3-4 time.
9. the preparation method of spongy superfine nano porous metal according to claim 6, it is characterised in that: the melting condition in described step 3 is: during melting, the vacuum tightness of high frequency vacuum induction melting furnace is 8 �� 10-3Below Pa, is filled with the pure argon of 0.05Mpa and argon content more than 99.99%, melting 5-10 time under small area analysis.
10. the preparation method of spongy superfine nano porous metal according to claim 6, it is characterised in that: the preparation condition of described step 4 is: during melting, the vacuum tightness of vacuum induction melting furnace is 1 �� 10-2Below Pa, is filled with the pure argon of 0.05Mpa and argon content more than 99.99%, is ejected on the copper wheel of high speed rotating after being heated to molten state.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757234A (en) * | 2016-11-10 | 2017-05-31 | 西安电子科技大学 | The preparation method of 3D nano porous metal materials |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557986A (en) * | 2004-01-29 | 2004-12-29 | 北京科技大学 | Preparation method for Mg-Cu-Y amorphous alloy block containing Si |
| CN102337420A (en) * | 2011-09-15 | 2012-02-01 | 北京航空航天大学 | Method for preparing porous Mg2Cu compound based on Mg-Cu one-step dealloying |
| CN104674045A (en) * | 2015-02-15 | 2015-06-03 | 北京航空航天大学 | Nanometer porous silver alloy material and preparation method thereof |
| CN104928518A (en) * | 2015-07-14 | 2015-09-23 | 北京航空航天大学 | Ultra-fine nano-porous metal and preparing method thereof |
-
2016
- 2016-03-22 CN CN201610165954.7A patent/CN105624456B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557986A (en) * | 2004-01-29 | 2004-12-29 | 北京科技大学 | Preparation method for Mg-Cu-Y amorphous alloy block containing Si |
| CN102337420A (en) * | 2011-09-15 | 2012-02-01 | 北京航空航天大学 | Method for preparing porous Mg2Cu compound based on Mg-Cu one-step dealloying |
| CN104674045A (en) * | 2015-02-15 | 2015-06-03 | 北京航空航天大学 | Nanometer porous silver alloy material and preparation method thereof |
| CN104928518A (en) * | 2015-07-14 | 2015-09-23 | 北京航空航天大学 | Ultra-fine nano-porous metal and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XUEKUN LUO, RAN LI, ET AL.: "Three-dimensional nanoporous copper with high surface area by dealloying Mg–Cu–Y metallic glasses", 《MATERIALS LETTERS》 * |
| ZHENHUA DAN，FENGXIANG QIN, ET AL.: "Refinement of Nanoporous Copper by Dealloying MgCuY Amorphous Alloys in Sulfuric Acids Containing Polyvinylpyrrolidone", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
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