CN105624456B - A kind of spongy superfine nano porous metals and preparation method - Google Patents
A kind of spongy superfine nano porous metals and preparation method Download PDFInfo
- Publication number
- CN105624456B CN105624456B CN201610165954.7A CN201610165954A CN105624456B CN 105624456 B CN105624456 B CN 105624456B CN 201610165954 A CN201610165954 A CN 201610165954A CN 105624456 B CN105624456 B CN 105624456B
- Authority
- CN
- China
- Prior art keywords
- melting
- nano porous
- spongy
- preparation
- vacuum
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C22C1/08—Alloys with open or closed pores
- C22C1/081—Casting porous metals into porous preform skeleton without foaming
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A kind of preparation method of spongy superfine nano porous metals, it is specially：Using non-crystaline amorphous metal as presoma, pass through the element in the method resistant alloy of organic acid or organic acid and the mixed solution removal alloying of corresponding acylate in addition to Ag, Pt, Pd, Au, Cu, Ni metal, form spongy nano-porous structure, frenulum is elemental metals or alloy, the characteristic size of its hole and frenulum is less than 20nm, porosity is up to 70%, and specific surface area is up to 30m2/ g, can the globality of holding structure and self-maintaining.Preparation method of the present invention is efficiently simple, and applicability is extensive.
Description
Technical field
The present invention relates to a kind of novel spongy nano porous metal and preparation method.
Background technology
Removal alloying method prepare nano porous metal be by using the difference of chemical property between different constituent elements in alloy,
One or more constituent elements more active in alloy are optionally removed by electrochemical method, are made up of the metal constituent element remained
Three-dimensional porous structure.Removal alloying method can obtain the three-dimensional netted loose structure with high-specific surface area, and its frenulum and hole lead to
Road is mutually continuous, and loose structure can dynamic regulation, have simple to operate, cost relatively low and suitable large-scale production etc. be excellent
Point.Removal alloying is a kind of effective ways for more quickly and easily obtaining aperture and reaching the porous metal material of nano-scale,
Realize breakthrough of the porous metal material in aperture size.
It is always one of focus of materials science field to find new nano porous metal and its presoma alloy.Preceding body
Body alloy prepares that nano porous metal is most important for removal alloying method, because not only the element species of alloy and content determine
Can removal alloying reaction be persistently carried out to alloy inside, and the chemical uniformity of alloy in itself can also influence nanoporous
The uniform microstructure of metal.Compared with traditional crystal alloy, dislocation, crystal boundary, intermetallic is not present in non-crystaline amorphous metal
The faults of construction such as thing, there is good chemical uniformity.The preparation process quickly solidified non-crystaline amorphous metal to contain to have more than
The element species and content of the solid solution limit, so as to widen the range of choice of precursor alloying component.Therefore, non-crystaline amorphous metal is
Prepare one of preferable precursor alloy of nano porous metal material.
As a kind of self-supporting material, nano porous metal material is obtained with its unique design feature and chemical property
Extensive concern.The structure of nearly all nano porous metal has been reported at present all by long and narrow hole and the frenulum group of roughening
Into, its porosity is typically small, and the spongelike structure that obtains of the present invention has big porosity, when nano material in media as well
During work, macrovoid can not only reduce the resistance of pore interior mass transfer, can also largely load other functional particles.
The characteristic size of other current reported nano porous metal is concentrated mainly on 20-100nm range scale, more due to reducing
The frenulum of Porous materials and the characteristic size of hole can be effectively increased its specific surface area, therefore the nanoporous that the present invention is obtained
Metal has great specific surface area.To sum up 2 points, macroporosity, the spongy fine nanometer of bigger serface that the present invention obtains
Porous metals can be in electrochemical catalysis, catalyst load, ultracapacitor, telegraphy device, surface-enhanced Raman effects etc.
Show excellent performance.
The content of the invention
The technology of the present invention solves problem：A kind of overcome the deficiencies in the prior art, there is provided spongy superfine nano porous metals
And preparation method, it is that alloying component is represented by below equation using block or banding non-crystaline amorphous metal as presoma：MgaMbYc, wherein M
Represent Pt, Pd, Au, Cu, Ag, Ni simple substance or alloy, a+b+c=100, by using organic acid and corresponding salt (citric acid, winestone
Acid, butanedioic acid, malic acid and their sodium salt, sylvite and ammonium salt) method of removal alloying removes Mg and Y element, prepare hole
It is less than 20nm with the characteristic size of frenulum, and there is more than 70% porosity and 30m2The nano-porous gold of/more than g specific surface areas
Belong to material.
The technology of the present invention solution, a kind of spongy superfine nano porous metals, using non-crystaline amorphous metal as presoma, forerunner
Body amorphous alloy component is represented by below equation：MgaMbYc, wherein M expressions Pt, Pd, Au, Cu, Ni, Ag simple substance or alloy, a+
B+c=100, mass percent are:60≤a≤70,20≤b≤30,10≤c≤15；By 0.1g/L~20g/L organic acids,
Or the method corrosion Mg and Y element of the mixed solution removal alloying of organic acid and corresponding acylate, prepare nano porous metal
Material.
The hole of the nano porous metal material of the preparation and the characteristic size of frenulum are less than 20nm, and porosity is reachable
70%, specific surface area is up to 30m2/g；Obtained nano porous metal material has a spongiform structure, even structure, and from
The well not avalanche i.e. under loose structure nature of holding property.
During preparation, presoma has even tissue, without crystal boundary, the feature of intermetallic compound defect, can occur
Even corrosion.
The etching time is less than 1 hour, it is not necessary to driven by electrochemical method, it is energy-efficient.
The organic acid and corresponding acylate are citric acid, tartaric acid, butanedioic acid, malic acid and their sodium salt, potassium
Salt and ammonium salt.
A kind of preparation method of spongy superfine nano porous metals, realizes that step is as follows：
Step 1：Dispensing
Element as described in claim 1 or 2, turn into the raw material for preparing master alloy ingot；
Step 2：Melting prealloy
M and Y element are pressed into MgaMbYcNominal composition carries out melting in vacuum arc melting furnace, obtains MY ingots；
Step 3：Master alloy melting
According to MgaMbYcNominal composition, slightly excessive Mg is taken to be mixed with M-Y ingots, the melting in high-frequency vacuum induction melting furnace,
After the completion of weigh mass loss, polishing M-Y missing make it that final foundry alloy is consistent with nominal composition；
Step 4：Prepare band
The foundry alloy that step 3 is obtained is put into vacuum induction melting furnace, and the copper wheel of rotation at a high speed is ejected into after thawing
On, obtain band；
Step 5：Removal alloying
Amorphous alloy ribbon obtained by step 4 is immersed into 0.1g/L~20g/L organic acids or organic acid and corresponding acylate
Mixed solution in freely corrode, occur removal alloying reaction, prepare nano porous metal.
The etching time of the corrosion Mg and Y element are less than 1 hour, it is not necessary to are driven by electrochemical method, efficiently section
Energy.
Melting condition in the step 2 is：Vacuum during melting in vacuum arc melting furnace is 8 × 10-3Pa with
Under, 0.05Mpa straight argon i.e. argon content is filled with more than 99.99%, it is every all over melting 1-2 minutes, melting 3-4 times.
Melting condition in the step 3 is：The vacuum of high-frequency vacuum induction melting furnace is 8 × 10 during melting-3Pa with
Under, 0.05Mpa straight argon i.e. argon content is filled with more than 99.99%, melting 5-10 times under low current.
The preparation condition of the step 4 is：The vacuum of vacuum induction melting furnace is 1 × 10 during melting-2Below Pa, fill
Enter 0.05Mpa straight argon i.e. argon content more than 99.99%, the copper wheel rotated at a high speed is ejected into after being heated to molten condition
On.
The present invention is compared with prior art advantageously：
(1) presoma non-crystaline amorphous metal even tissue of the invention, the defects of without crystal boundary, intermetallic compound, Neng Goutong
Cross homogeneous corrosion and obtain uniform three-dimensional porous structure；
(2) presoma amorphous component scope of the invention is wide, 60≤a≤70,20≤b≤30,10≤c≤15；
(3) presoma system applicability of the invention is extensive, and M can be Pt, Pd, Au, Cu, Ni, Ag simple substance or alloy；
(4) removal alloying of the invention reaction freely occurs in corrosive liquid, and etching time is less than 1 hour, it is not necessary to
Driven by electrochemical method, it is energy-efficient；
(5) removal alloying of the invention reaction corrosive liquid is 0.1g/L~20g/L organic acids or organic acid and corresponding organic
The mixed solution of hydrochlorate, prepares simple, safety and environmental protection, and reaction is gentle；
(6) even size distribution of nano porous metal prepared by the present invention, hole and frenulum, less than 20nm, has pole
Big specific surface area, i.e. specific surface area can reach 30m2/ more than g；
(7) nano porous metal prepared by the present invention does not have volume contraction compared to presoma, self-maintaining without crackle
It is good；
(8) the nano porous metal tether construction that prepared by the present invention is mellow and full, and surface is smooth, and porosity is big, can reach 70%,
And it is consistent with presoma inertia constituent element percentage by volume；
(9) phenomenon that frenulum is roughened with the time, tissue stabilization do not occur for nano porous metal prepared by the present invention.
Brief description of the drawings
Fig. 1 is Mg65Cu25Y10AMORPHOUS ALLOY RIBBONS is the surface microscopic tissue of nano porous copper prepared by presoma.
Fig. 2 is Mg65Cu25Y10The microstructure side view for the nano porous copper that AMORPHOUS ALLOY RIBBONS is prepared for presoma, table
Bright material internal and surface are consistent with surface texture by homogeneous corrosion, internal structure.
Fig. 3 is Mg65Ag25Y10Block amorphous alloy is the surface microscopic tissue of nano-porous silver prepared by presoma.
Fig. 4 is Mg65Ni25Y10AMORPHOUS ALLOY RIBBONS is the surface microscopic tissue of nanoporous nickel prepared by presoma.
Fig. 5 is Mg65Cu23Pt2Y10AMORPHOUS ALLOY RIBBONS is the surface microscopic group of nano porous copper platinum prepared by presoma
Knit.
Fig. 6 is Mg65Ag21Au4Y10AMORPHOUS ALLOY RIBBONS is the surface microscopic group of nano-porous silver gold prepared by presoma
Knit.
Embodiment
Below in conjunction with the accompanying drawings and the present invention is discussed in detail in specific embodiment.But following embodiment is only limitted to explain this hair
Bright, protection scope of the present invention should include the full content of claim, be not limited only to the present embodiment.
Prepare a kind of comprising the following steps that for spongy superfine nano porous metals：
1. determine non-crystaline amorphous metal presoma composition；
2. prepare amorphous master alloy；
3. prepare amorphous alloy ribbon with the copper wheel rotation method of quenching；
4. determine that suitable etching process carries out removal alloying.
It is characterized in that non-crystaline amorphous metal presoma is single-phase amorphous state, the nano-porous materials prepared only containing Au,
The one or more of the elements such as Pt, Pd, Ag, Cu, Ni, and with self-maintaining.
Step 1：Dispensing
By nominal composition MgaMbYcEach simple substance element is weighed, turns into the raw material for preparing master alloy ingot；
Step 2：Melting prealloy
M and Y element are pressed into MgaMbYcNominal composition carries out melting in vacuum arc melting furnace, refines 3-4 times, obtains M-
Y ingots；
Melting condition is：Vacuum during melting in vacuum arc melting furnace is 8 × 10-3Below Pa, it is filled with 0.05Mpa's
Straight argon (argon content is more than 99.99%), it is every all over melting 1-2 minutes, melting 3-4 times.
Step 3：Master alloy melting
According to MgaMbYcNominal composition, slightly excessive Mg is taken to be mixed with M-Y ingots, the melting in high-frequency vacuum induction melting furnace,
After the completion of weigh mass loss, polishing M-Y missing make it that final foundry alloy is consistent with nominal composition；
Melting condition is：The vacuum of high-frequency vacuum induction melting furnace is 8 × 10 during melting-3Below Pa, it is filled with 0.05Mpa
Straight argon (argon content is more than 99.99%), melting 5-10 times under low current.
Step 4：Prepare band
The foundry alloy that step 3 is obtained is put into vacuum induction melting furnace, and the copper wheel of rotation at a high speed is ejected into after thawing
On, obtain about 30 μ m-thicks, band wide 3mm；
Preparation condition is：The vacuum of vacuum induction melting furnace is 1 × 10 during melting-2Below Pa, it is filled with the pure of 0.05Mpa
Argon (argon content is more than 99.99%), it is ejected at a high speed on the copper wheel of rotation after being heated to molten condition.
Step 5：Removal alloying
Suitable etching process is selected, amorphous alloy ribbon obtained by step 4 is immersed into organic acid or organic acid and should mutually be had
Freely corrode in the mixed solution of machine hydrochlorate, removal alloying reaction occurs, prepares spongy superfine nano porous metals；
Step 6：Structural characterization
Nano-porous materials obtained by step 5 are passed through into scanning electron microscopic observation structure.
Embodiment 1：With Mg65Cu25Y10Non-crystaline amorphous metal is that presoma prepares nano porous copper
In the present embodiment, selected non-crystaline amorphous metal presoma composition is Mg65Cu25Y10, the preparation of nano-porous materials
Method is as follows：
Step 1：Dispensing
By Mg65Cu25Y10Nominal composition weighs each simple substance element, turns into the raw material for preparing master alloy ingot；
Step 2：Melting prealloy
Cu and Y element are pressed into Mg65Cu25Y10Nominal composition carries out melting in vacuum arc melting furnace, refines 3-4 times, obtains
To Cu-Y ingots；
Melting condition is：Vacuum during melting in vacuum arc melting furnace is 8 × 10-3Below Pa, it is filled with 0.05Mpa's
Straight argon, it is every all over melting 1-2 minutes, melting 3-4 times.
Step 3：Master alloy melting
According to Mg65Cu25Y10Nominal composition, slightly excessive Mg is taken to be mixed with Cu-Y ingots, the melting in vacuum induction melting furnace,
After the completion of weigh mass loss, polishing Cu-Y missing make it that final foundry alloy is consistent with nominal composition；
Melting condition is：The vacuum of vacuum induction melting furnace is 8 × 10 during melting-3Below Pa, it is filled with the pure of 0.05Mpa
Argon, melting 5-10 times under low current.
Step 4：Prepare band
The foundry alloy that step 3 is obtained is put into vacuum induction melting furnace, and the copper wheel of rotation at a high speed is ejected into after thawing
On, obtain about 50 μ m-thicks, band wide 5mm；
Preparation condition is：The vacuum of vacuum induction melting furnace is 1 × 10 during melting-2Below Pa mono-, it is filled with 0.05Mpa's
Straight argon, it is ejected at a high speed on the copper wheel of rotation after being heated to molten condition.
Step 5：Removal alloying
Under ambient temperature, amorphous alloy ribbon obtained by step 4 is immersed in 1g/L citric acid solutions and freely corroded, sent out
Raw removal alloying reaction, prepares nano porous copper；
Step 6：Structural characterization
Nano porous copper obtained by step 5 is passed through into scanning electron microscopic observation structure.
As shown in figure 1, Mg65Cu25Y10Nano-porous structure obtained by after removal alloying 10min, its frenulum size
For 8.4nm, porosity 76.83%, specific surface area reaches 42.99m2/ g, contrast foundry alloy Mg65Cu25Y10Middle Cu content,
There is no volume contraction, and there is no crackle in scanning electron microscope (SEM) photograph, organize no avalanche, show self-maintaining good.As shown in Fig. 2 table
Bright material internal and surface are consistent with surface texture by homogeneous corrosion, internal structure.
Embodiment 2：With Mg65Ag25Y10Block amorphous alloy is that presoma prepares nano-porous silver
In the present embodiment, selected non-crystaline amorphous metal presoma composition is Mg65Ag25Y10, the preparation of nano-porous materials
Method is as follows：
Step 1：Dispensing
By Mg65Ag25Y10Nominal composition weighs each simple substance element, turns into the raw material for preparing master alloy ingot；
Step 2：Melting prealloy
Ag and Y element are pressed into Mg65Ag25Y10Nominal composition carries out melting in vacuum arc melting furnace, refines 3-4 times, obtains
To Ag-Y ingots；
Melting condition is：Vacuum during melting in vacuum arc melting furnace is 8 × 10-3Below Pa, it is filled with 0.05Mpa's
Straight argon, it is every all over melting 1-2 minutes, melting 3-4 times.
Step 3：Master alloy melting
According to Mg65Ag25Y10Nominal composition, slightly excessive Mg is taken to be mixed with Ag-Y ingots, the melting in vacuum induction melting furnace,
After the completion of weigh mass loss, polishing Ag-Y missing make it that final foundry alloy is consistent with nominal composition；
Melting condition is：The vacuum of vacuum induction melting furnace is 8 × 10 during melting-3Below Pa, it is filled with the pure of 0.05Mpa
Argon, melting 5-10 times under low current.
Step 4：Prepare band
The foundry alloy that step 3 is obtained is put into vacuum induction melting furnace, and the copper wheel of rotation at a high speed is ejected into after thawing
On, obtain about 30 μ m-thicks, band wide 3mm；
Preparation condition is：The vacuum of vacuum induction melting furnace is 1 × 10 during melting-2Below Pa mono-, it is filled with 0.05Mpa's
Straight argon (argon content is more than 99.99%), it is ejected at a high speed on the copper wheel of rotation after being heated to molten condition.
Step 5：Removal alloying
Under ambient temperature, amorphous alloy ribbon obtained by step 4 is immersed in 0.5g/L citric acid solutions and freely corroded,
Generation removal alloying reacts, and prepares nano-porous silver；
Step 6：Structural characterization
Nano-porous silver obtained by step 5 is passed through into scanning electron microscopic observation structure.
As shown in figure 3, Mg65Ag25Y10Nano-porous structure obtained by after removal alloying 30min, its frenulum size
For 8.2nm, porosity 76.02%, specific surface area reaches 37.20m2/g.Contrast foundry alloy Mg65Ag25Y10Middle Ag content,
Substantially there is no volume contraction, and there is no crackle in electron microscope, organize no avalanche, show self-maintaining good.
Embodiment 3：With Mg65Ni20Y15Non-crystaline amorphous metal is that presoma prepares nano porous copper
In the present embodiment, selected non-crystaline amorphous metal presoma composition is Mg65Ni20Y15, the preparation of nano-porous materials
Method is as follows：
Step 1：Dispensing
By Mg65Ni20Y15Nominal composition weighs each simple substance element, turns into the raw material for preparing master alloy ingot；
Step 2：Melting prealloy
Ni and Y element are pressed into Mg65Ni20Y15Nominal composition carries out melting in vacuum arc melting furnace, refines 3-4 times, obtains
To Ni-Y ingots；
Melting condition is：Vacuum during melting in vacuum arc melting furnace is 8 × 10-3Below Pa, it is filled with 0.05Mpa's
Straight argon, it is every all over melting 1-2 minutes, melting 3-4 times.
Step 3：Master alloy melting
According to Mg65Ni20Y15Nominal composition, slightly excessive Mg is taken to be mixed with Ni-Y ingots, the melting in vacuum induction melting furnace,
After the completion of weigh mass loss, polishing Ni-Y missing make it that final foundry alloy is consistent with nominal composition；
Melting condition is：The vacuum of vacuum induction melting furnace is 8 × 10 during melting-3Below Pa, it is filled with the pure of 0.05Mpa
Argon, melting 5-10 times under low current.
Step 4：Prepare band
The foundry alloy that step 3 is obtained is put into vacuum induction melting furnace, and the copper wheel of rotation at a high speed is ejected into after thawing
On, obtain about 30 μ m-thicks, band wide 3mm；
Preparation condition is：The vacuum of vacuum induction melting furnace is 1 × 10 during melting-2Below Pa mono-, it is filled with 0.05Mpa's
Straight argon (argon content is more than 99.99%), it is ejected at a high speed on the copper wheel of rotation after being heated to molten condition.
Step 5：Removal alloying
Using 2g/L citric acid solutions, under ambient temperature, amorphous alloy ribbon obtained by step 4 is immersed in solution certainly
By corroding, removal alloying reaction occurs, prepares nano porous copper；
Step 6：Structural characterization
Nano porous copper obtained by step 5 is passed through into scanning electron microscopic observation structure.
As shown in figure 4, Mg65Ni20Y15Nano-porous structure obtained by after removal alloying 60min, its frenulum size
For 5.0nm, porosity 79.38%, specific surface area reaches 73.16m2/g.Contrast foundry alloy Mg65Ni20Y15Middle Ni content,
Substantially there is no volume contraction, and there is no crackle in electron microscope, organize no avalanche, show self-maintaining good.
Embodiment 4：With Mg65Cu23Pt2Y10Non-crystaline amorphous metal is that presoma prepares nano porous copper/gold
In the present embodiment, selected non-crystaline amorphous metal presoma composition is Mg65Cu23Pt2Y10, nano-porous materials
Preparation method is as follows：
Step 1：Dispensing
By Mg65Cu23Pt2Y10Nominal composition weighs each simple substance element, turns into the raw material for preparing master alloy ingot；
Step 2：Melting prealloy
Cu, Pt and Y element are pressed into Mg65Cu23Pt2Y10Nominal composition carries out melting in vacuum arc melting furnace, refines 3-
4 times, obtain CuPt-Y ingots；
Melting condition is：Vacuum during melting in vacuum arc melting furnace is 8 × 10-3Below Pa, it is filled with 0.05Mpa's
Straight argon, it is every all over melting 1-2 minutes, melting 3-4 times.
Step 3：Master alloy melting
According to Mg65Cu23Pt2Y10Nominal composition, slightly excessive Mg is taken to be mixed with CuPt-Y ingots, in vacuum induction melting furnace
Melting, after the completion of weigh mass loss, polishing CuPt-Y missing make it that final foundry alloy is consistent with nominal composition；
Melting condition is：The vacuum of vacuum induction melting furnace is 8 × 10 during melting-3Below Pa, it is filled with the pure of 0.05Mpa
Argon, melting 5-10 times under low current.
Step 4：Prepare band
The foundry alloy that step 3 is obtained is put into vacuum induction melting furnace, and the copper wheel of rotation at a high speed is ejected into after thawing
On, obtain about 30 μ m-thicks, band wide 3mm；
Preparation condition is：The vacuum of vacuum induction melting furnace is 1 × 10 during melting-2Below Pa mono-, it is filled with 0.05Mpa's
Straight argon (argon content is more than 99.99%), it is ejected at a high speed on the copper wheel of rotation after being heated to molten condition.
Step 5：Removal alloying
Using 2g/L citric acid solutions, under ambient temperature, amorphous alloy ribbon obtained by step 4 is immersed in solution certainly
By corroding, removal alloying reaction occurs, prepares nano porous copper/gold；
Step 6：Structural characterization
Nano porous copper/gold obtained by step 5 is passed through into scanning electron microscopic observation structure.
As shown in figure 5, Mg65Cu23Pt2Y10Nano-porous structure obtained by after removal alloying 30min, its frenulum
Size is 7.1nm, and porosity 74.9%, specific surface area reaches 38.3m2/g.Contrast foundry alloy Mg65Cu23Pt2Y10Middle Cu, Pt
Content, almost without volume contraction, and there is no crackle in electron microscope, organize no avalanche, show self-maintaining good.
Embodiment 5：With Mg65Ag21Au4Y10Non-crystaline amorphous metal is that presoma prepares nano-porous silver/gold
In the present embodiment, selected non-crystaline amorphous metal presoma composition is Mg65Ag21Au4Y10, nano-porous materials
Preparation method is as follows：
Step 1：Dispensing
By Mg65Ag21Au4Y10Nominal composition weighs each simple substance element, turns into the raw material for preparing master alloy ingot；
Step 2：Melting prealloy
Ag, Au and Y element are pressed into Mg65Ag21Au4Y10Nominal composition carries out melting in vacuum arc melting furnace, refines 3-
4 times, obtain AgAu-Y ingots；
Melting condition is：Vacuum during melting in vacuum arc melting furnace is 8 × 10-3Below Pa, it is filled with 0.05Mpa's
Straight argon, it is every all over melting 1-2 minutes, melting 3-4 times.
Step 3：Master alloy melting
According to Mg65Ag21Au4Y10Nominal composition, slightly excessive Mg is taken to be mixed with AgAu-Y ingots, in vacuum induction melting furnace
Melting, after the completion of weigh mass loss, polishing AgAu-Y missing make it that final foundry alloy is consistent with nominal composition；
Melting condition is：The vacuum of vacuum induction melting furnace is 8 × 10 during melting-3Below Pa, it is filled with the pure of 0.05Mpa
Argon, melting 5-10 times under low current.
Step 4：Prepare band
The foundry alloy that step 3 is obtained is put into vacuum induction melting furnace, and the copper wheel of rotation at a high speed is ejected into after thawing
On, obtain about 30 μ m-thicks, band wide 3mm；
Preparation condition is：The vacuum of vacuum induction melting furnace is 1 × 10 during melting-2Below Pa, it is filled with the pure of 0.05Mpa
Argon (argon content is more than 99.99%), it is ejected at a high speed on the copper wheel of rotation after being heated to molten condition.
Step 5：Removal alloying
Using 2g/L citric acids and 4g/L sodium citrate mixed solutions, at room temperature, by amorphous alloy thin obtained by step 4
Band, which is immersed in solution, freely to be corroded, and removal alloying reaction occurs, prepares nano-porous silver/gold；
Step 6：Structural characterization
Nano-porous silver/gold obtained by step 5 is passed through into scanning electron microscopic observation structure.
As shown in fig. 6, Mg65Ag21Au4Y10Nano-porous structure obtained by after removal alloying 30min, its frenulum
Size is 8.4nm, and porosity 68.4%, specific surface area reaches 28.3m2/g.Contrast foundry alloy Mg65Ag21Au4Y10Middle Ag, Au
Content, almost without volume contraction, and there is no crackle in electron microscope, organize no avalanche, show self-maintaining good.
In a word, using non-crystaline amorphous metal as presoma, gone by the mixed solution of organic acid or organic acid and corresponding acylate
Element in the method resistant alloy of alloying in addition to Ag, Pt, Pd, Au, Cu, Ni metal, form spongy nanoporous knot
Structure, frenulum are elemental metals or alloy, and the characteristic size of its hole and frenulum is less than 20nm, and porosity compares surface up to 70%
Product is up to 30m2/ g, can the globality of holding structure and self-maintaining.Preparation method of the present invention is efficiently simple, and applicability is wide
It is general.
It should be noted that according to the various embodiments described above of the present invention, those skilled in the art are can to realize this hair completely
The four corner of bright independent claims and appurtenance, implementation process and the same the various embodiments described above of method；And the present invention is not
Elaborate and partly belong to techniques well known.
It is described above, part embodiment only of the present invention, but protection scope of the present invention is not limited thereto, and is appointed
What those skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in should all be covered
Within protection scope of the present invention.
Claims (9)
- A kind of 1. spongy superfine nano porous metals, it is characterised in that：Using non-crystaline amorphous metal as presoma, presoma non-crystaline amorphous metal Composition is represented by below equation：MgaMbYc, wherein M expressions Pt, Pd, Au, Cu, Ni, Ag one or more, a+b+c= 100, mass percent is:60≤a≤70,20≤b≤30,10≤c≤15；By 0.1g/L~20g/L organic acids, or it is organic The method corrosion Mg and Y element of the mixed solution removal alloying of sour and corresponding acylate, prepare nano porous metal material；The organic acid is citric acid, tartaric acid, butanedioic acid or malic acid；The corresponding acylate is their sodium salt, potassium Salt or ammonium salt.
- A kind of 2. spongy superfine nano porous metals according to claim 1, it is characterised in that：The nanometer of the preparation The hole of porous metal material and the characteristic size of frenulum are less than 20nm, and for porosity up to 70%, specific surface area reaches 30m2/g；Obtained Nano porous metal material has a spongiform structure, even structure, and it is self-maintaining be well under loose structure nature not Avalanche.
- A kind of 3. spongy superfine nano porous metals according to claim 1, it is characterised in that：During preparation, presoma With even tissue, without crystal boundary and the feature of intermetallic compound defect, homogeneous corrosion can occur.
- A kind of 4. spongy superfine nano porous metals according to claim 1, it is characterised in that：Etching time is less than 1 Hour, it is not necessary to driven by electrochemical method, it is energy-efficient.
- 5. a kind of preparation method of spongy superfine nano porous metals as claimed in claim 1, it is characterised in that realize step It is as follows：Step 1：DispensingBy the element in claim 1, turn into the raw material for preparing master alloy ingot；Step 2：Melting prealloyM and Y element are pressed into MgaMbYcNominal composition carries out melting in vacuum arc melting furnace, obtains MY ingots；Step 3：Master alloy meltingAccording to MgaMbYcNominal composition, take slightly excessive Mg to be mixed with M-Y ingots, the melting in high-frequency vacuum induction melting furnace, complete After weigh mass loss, polishing M-Y missing make it that final foundry alloy is consistent with nominal composition；Step 4：Prepare bandThe foundry alloy that step 3 is obtained is put into vacuum induction melting furnace, is ejected into after being melted down at a high speed on the copper wheel of rotation, Obtain band；Step 5：Removal alloyingAmorphous alloy ribbon obtained by step 4 is immersed into the mixed of 0.1g/L~20g/L organic acids or organic acid and corresponding acylate Close and freely corrode in solution, removal alloying reaction occurs, prepares nano porous metal.
- 6. the preparation method of spongy superfine nano porous metals according to claim 5, it is characterised in that：Corrode Mg and The etching time of Y element is less than 1 hour, it is not necessary to driven by electrochemical method, it is energy-efficient.
- 7. the preparation method of spongy superfine nano porous metals according to claim 5, it is characterised in that：The step Melting condition in two is：Vacuum during melting in vacuum arc melting furnace is 8 × 10-3Below Pa, it is filled with the pure of 0.05MPa Argon be argon content more than 99.99%, every all over melting 1-2 minutes, melting 3-4 times.
- 8. the preparation method of spongy superfine nano porous metals according to claim 5, it is characterised in that：The step Melting condition in three is：The vacuum of high-frequency vacuum induction melting furnace is 8 × 10 during melting-3Below Pa, it is filled with 0.05MPa's Straight argon be argon content more than 99.99%, melting 5-10 times under low current.
- 9. the preparation method of spongy superfine nano porous metals according to claim 5, it is characterised in that：The step Four preparation condition is：The vacuum of vacuum induction melting furnace is 1 × 10 during melting-2Below Pa, it is filled with 0.05MPa straight argon i.e. Argon content is ejected at a high speed on the copper wheel of rotation more than 99.99% after being heated to molten condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610165954.7A CN105624456B (en) | 2016-03-22 | 2016-03-22 | A kind of spongy superfine nano porous metals and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610165954.7A CN105624456B (en) | 2016-03-22 | 2016-03-22 | A kind of spongy superfine nano porous metals and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105624456A CN105624456A (en) | 2016-06-01 |
| CN105624456B true CN105624456B (en) | 2017-11-14 |
Family
ID=56039797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610165954.7A Expired - Fee Related CN105624456B (en) | 2016-03-22 | 2016-03-22 | A kind of spongy superfine nano porous metals and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105624456B (en) |
Families Citing this family (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 |
| CN107419128B (en) * | 2017-06-22 | 2019-03-12 | 北京航空航天大学 | Using the method for three-dimensional communication nano porous metal preparation electrolysis water cathode hydrogen evolution electrode |
| CN109402369A (en) * | 2017-08-15 | 2019-03-01 | 南京理工大学 | A kind of iron-based porous material and preparation method thereof for azo dyes of degrading |
| CN108493000B (en) * | 2018-03-23 | 2020-02-28 | 中国科学院宁波材料技术与工程研究所 | Flexible nano porous metal/oxide supercapacitor electrode material and preparation method thereof |
| CN108546983A (en) * | 2018-04-20 | 2018-09-18 | 安徽知之信息科技有限公司 | A kind of new-energy automobile steel pipe internal-surface electrochemical polish apparatus |
| CN108552600A (en) * | 2018-05-14 | 2018-09-21 | 四川三联新材料有限公司 | Cool down blending material and preparation method thereof |
| CN108971512B (en) * | 2018-09-14 | 2021-04-02 | 江西科技师范大学 | Green preparation method and application of porous spongy Ag square particles |
| CN110923752B (en) * | 2019-10-29 | 2021-06-01 | 东北大学 | Transition metal powder with high specific surface area and preparation method thereof |
| CN110734121B (en) * | 2019-11-20 | 2020-12-22 | 山东大学 | Degradation method of acid orange II dye wastewater |
| CN111634938B (en) * | 2020-06-16 | 2021-11-09 | 东莞理工学院 | Preparation method of nano porous powder material |
| CN113800556A (en) * | 2021-08-12 | 2021-12-17 | 西安理工大学 | Preparation method of large-size block porous TiO2 with high specific surface area |
| CN114273663B (en) * | 2021-12-16 | 2023-05-12 | 北京航空航天大学 | Cu-M series nano porous amorphous alloy and preparation method thereof |
| CN114453587B (en) * | 2021-12-31 | 2024-02-27 | 西安理工大学 | Preparation method of nano porous copper-nickel alloy |
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 |
|---|
| Refinement of Nanoporous Copper by Dealloying MgCuY Amorphous Alloys in Sulfuric Acids Containing Polyvinylpyrrolidone;Zhenhua Dan，Fengxiang Qin, et al.;《Journal of The Electrochemical Society》;20140104(第161期);120-125 * |
| Three-dimensional nanoporous copper with high surface area by dealloying Mg–Cu–Y metallic glasses;Xuekun Luo, Ran Li, et al.;《Materials Letters》;20120216(第76期);96-99 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105624456A (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105624456B (en) | A kind of spongy superfine nano porous metals and preparation method | |
| CN104928518B (en) | A kind of superfine nano porous metals and preparation method thereof | |
| CN104674045B (en) | A kind of nanoporous silver alloy and preparation method thereof | |
| CN101590528A (en) | A kind of preparation method of nano porous copper | |
| CN104831197B (en) | A kind of preparation method of nano porous copper silver | |
| CN103774149B (en) | A kind of preparation method of high-strength nanoporous nickel film | |
| CN106191571B (en) | Aluminum alloy anode material, preparation method and its application | |
| CN101760706B (en) | Aluminum-based micro/nano-meter porous amorphous alloy material and preparation method thereof | |
| CN106222584B (en) | A kind of nanoporous Fe base noncrystal alloys and preparation method and the application on analysis oxygen catalysis electrode | |
| CN105543531A (en) | Dealloying method for preparing micron nano-porous copper block body | |
| CN108531762A (en) | A kind of nanoporous AgCu supersaturated solid solutions alloy and method based on the preparation of a variety of non-crystaline amorphous metal presomas | |
| Chang et al. | Electrochemical synthesis to convert a Ag film into Ag nanoflowers with high electrocatalytic activity | |
| CN105256165A (en) | Method for preparing nano-porous copper through Cu-Al alloy slightly doped with Ni/Ti | |
| Battezzati et al. | De-alloying of rapidly solidified amorphous and crystalline alloys | |
| CN102706937A (en) | Micro-nano porous bismuth electrode and preparation method thereof | |
| CN109023412A (en) | A kind of nanoporous ambrose alloy/amorphous combination electrode material and preparation method thereof | |
| CN107123811B (en) | Dual-scale porous copper-aluminum-manganese shape memory alloy composite material and preparation method and application thereof | |
| CN102367527A (en) | Highly-ordered single-piece copper-based porous material and preparation method thereof | |
| CN101597775B (en) | Nanoporous gold electrochemical preparation method | |
| CN106591619B (en) | A kind of Bimodal pore copper and the preparation method and application thereof | |
| JP2010144246A (en) | Methods for producing micropore nickel porous body and micropore nickel-copper alloy porous body, and product obtained thereby | |
| CN103103571A (en) | Gold-silver alloy nano porous metal material and preparation technology thereof | |
| CN110438417A (en) | A kind of selective corrosion Zr-Ti-Cu alloy prepares nano-porous materials and preparation method thereof | |
| Ma et al. | Influence of dealloying solution on the microstructure of nanoporous copper through chemical dealloying of Al75Cu25 ribbons | |
| CN106571473A (en) | Preparation method of Cu/Cu2O/CuO three-dimensional composite material having hierarchical pore structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171114 Termination date: 20190322 |