CN108531762A - A kind of nanoporous AgCu supersaturated solid solutions alloy and method based on the preparation of a variety of non-crystaline amorphous metal presomas - Google Patents
A kind of nanoporous AgCu supersaturated solid solutions alloy and method based on the preparation of a variety of non-crystaline amorphous metal presomas Download PDFInfo
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- CN108531762A CN108531762A CN201810415884.5A CN201810415884A CN108531762A CN 108531762 A CN108531762 A CN 108531762A CN 201810415884 A CN201810415884 A CN 201810415884A CN 108531762 A CN108531762 A CN 108531762A
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/001—Amorphous alloys with Cu as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/003—Amorphous alloys with one or more of the noble metals as major constituent
Abstract
The invention discloses a kind of nanoporous AgCu supersaturated solid solutions alloy prepared based on a variety of non-crystaline amorphous metal presomas and methods, and the non-crystaline amorphous metal presoma ingredient used can be Ln100‑y‑zAlz(Ag1‑xCux)y、Ln100‑y‑aMga(Ag1‑xCux)y、Ca100‑y‑r‑ sZnrMgs(Ag1‑xCux)yOr Zr100‑y‑m‑eMmAle(Ag1‑xCux)y, wherein 0<x<1,15≤y≤50,5≤z≤35,10≤a≤65,0<R≤20,0<S≤30,0<E≤15,0<m≤5；Ln is one or more in Y, La, Ce, Pr, Nd；M is one or more in La, Ce, Pr, Nd, Y, Sn, Zn；It is characterized in that it forms Ag the and Cu elemental mole ratios 0 in phase using nanoporous AgCu supersaturated solid solution alloys made from alloying technology are removed<x<1 is continuously adjustable, and the frenulum and pore structure that nano-porous structure has continuous three-dimensional duplex logical, frenulum size is 5~130 nanometers, and porosity is 20%~70%, and porous layer thickness is 1~200 micron.
Description
Technical field
The present invention relates to a kind of solid solution alloys, refer to a kind of being prepared using non-crystaline amorphous metal presoma more particularly
Nanoporous AgCu supersaturated solid solution alloys.Through nanoporous AgCu supersaturated solid solution alloys made from the method for the present invention
Surface is the nano porous layer of the three-dimensional logical frenulum and pore structure of duplex.
Background technology
Two or more metals not only melting when can mutual phased soln, but also solidification when can also keep the state of dissolving each other
Solid solution is known as solid solution alloy.Solid solution alloy is uniform liquid phase in liquid.After solid solution is changed into solid-state, still protect
The uniformity for holding institutional framework keeps the lattice types of solvent metal, solute metal that can be limited or divide column in solvent with limit
In the lattice of metal.
Nanoporous (Nanoporous) material refers to having notable skin effect, aperture between 0.1~100nm, hole
Rate is more than the 40%, cellular solid with high-specific surface area.
When alloy forms solid solution, the amount of dissolving in of the performance of alloy obviously with the property of component and solute element has
It closes.
The also known as de- alloying of removal alloying method refers to by chemistry or electrochemical corrosion course by one kind in alloy
Or a kind of method that a variety of constituent elements selectively remove.
Nanoporous supersaturated solid solution alloy material has both the double attribute of glassy metal and porous structure, can both have
There are high intensity, high-wearing feature, high-fracture toughness, high rigidity and the low resistance decaying of non-crystaline amorphous metal, and can have porous
The advantages that high-specific surface area of structure, high porosity, low-density and high specific strength, thus in sensing, inhale wave, damping, flat-plate compressed
Print, biology implantation, catalysis and the Material Fields such as antibacterial have extensive potential using value.The composite material is to utilize to remove alloy
Change method forms one layer of uniform noble metal nano porous layer, so as to form with non-crystaline amorphous metal in non-crystaline amorphous metal matrix surface
For kernel, the nucleocapsid structure that noble metal nano porous layer is shell, which shows than pure noncrystal substrate bigger
Specific surface area can significantly improve catalytic performance.
Currently, the nano porous layer of people's exploitation concentrates on single precious metal element, such as fine copper and fine silver etc..However copper
Catalytic and the high cost of silver constrain the development and application of this composite material.Therefore, it finds with high catalytic property and low
The key that the metallic element of cost just develops at this kind of composite material.
Invention content
An object of the present invention is to propose that a kind of surface is the nano porous layer of the three-dimensional logical frenulum and pore structure of duplex
Nanoporous AgCu supersaturated solid solution alloys.The present invention provides a variety of new amorphous alloy materials, i.e., molar percentage at
It is divided into Ln100-y-zAlz(Ag1-xCux)y、Ln100-y-aMga(Ag1-xCux)y、Ca100-y-r-sZnrMgs(Ag1-xCux)yOr
Zr100-y-m-eMmAle(Ag1-xCux)yNon-crystaline amorphous metal, wherein 0<x<1,15≤y≤50,5≤z≤35,10≤a≤65,0<r≤
20,0<S≤30,0<E≤15,0<m≤5；Ln is one or more in Y, La, Ce, Pr, Nd；M be La, Ce, Pr, Nd, Sn,
It is one or more in Zn.
The second object of the present invention is to propose a kind of method preparing amorphous alloy ribbon.This method first, in accordance with target at
Each simple substance pure element for point weighing needs is melted Cu and Y using vacuum arc for needing to prepare the Cu and Y element of prealloy
Furnace carries out melting, prepares CuY prealloy ingots, then CuY prealloys ingot and surplus element are put into vacuum induction melting furnace
Melting is uniform, obtains master alloy ingot, for that need not prepare the element of prealloy, directly in vacuum high-frequency induction melting furnace or very
Melting in empty electric arc furnaces recycles quick solidification equipment to prepare amorphous alloy ribbon using casting technique.
The third object of the present invention is to propose a kind of nanoporous AgCu over-saturation prepared using non-crystaline amorphous metal presoma
The method of solid solution alloy is to replace with silver element in right amount with by copper in non-crystaline amorphous metal matrix, recycles removal alloying method
Nanoporous silver-bearing copper double elements supersaturated solid solution alloy is prepared, which contains silver-bearing copper double elements, can not only
With larger specific surface area, catalytic performance can be improved, and reduces the dosage of silver, has saved cost.This method is profit
Spend alloying.A variety of system amorphous alloy ribbons are put into corrosive liquid (such as 0.04mol/L H2SO4) in carry out.It is first
First, protective atmosphere nitrogen is filled with and fills H2SO420 minutes in the beaker of solution, to exclude the oxygen in solution, prevent from generating gold
Belong to oxide；Secondly, amorphous alloy ribbon is put into the H for excluding oxygen2SO4Removal alloying processing is carried out in solution, in this mistake
H is held in journey2SO4The beaker mouth of solution should seal, and prevent air from entering；Then, through the respectively cleaning two of deionized water and absolute ethyl alcohol
After secondary, nanoporous silver-bearing copper over-saturation single phase solid solution material is obtained.The composite structure is using non-crystaline amorphous metal as kernel, silver
Copper over-saturation is dissolved the nucleocapsid that nano porous layer is shell, nano porous layer show uniform three-dimensional duplex it is logical be
Band/pore structure, nanoporous layer thickness are 1~200 micron, and frenulum size is 5~130 nanometers.
It is dissolved nanoporous layer material using silver-bearing copper over-saturation prepared by removal alloying method, is directly in amorphous alloy ribbon
What surface in situ generated, other nano porous layers/amorphous alloy composite material preparation method is compared, manufacturing process is simplified.
The nanoporous AgCu supersaturated solid solution alloys prepared based on a variety of non-crystaline amorphous metal presomas prepared by the present invention
Method, include the following steps：
Step 1 carries out dispensing according to the target component of nanoporous AgCu supersaturated solid solution alloys；
Dispensing select mass percent purity more than or equal to 99% Ag, Cu, Al, Mg, Ca, Zn, Zr, La, Ce, Pr, Nd,
Y, one or more simple substance elements in Sn；
Step 2, vacuum melting alloyage ingot casting；
Vacuum degree≤1 × 10 needed for vacuum melting- 3Pa, smelting temperature are 500 DEG C~1500 DEG C, smelting time 5~
7min；In the case where mass percent purity is 99.999% argon atmosphere, melting is uniformly taken out afterwards obtains alloy cast ingot；
Step 3 quickly solidifies non-crystaline amorphous metal presoma strip processed；
By alloy cast ingot made from step 2 in the induction furnace of quick solidification apparatus, at a temperature of 600 DEG C~1000 DEG C
After fusing, obtained non-crystaline amorphous metal presoma strip of quenching is revolved with copper wheel；Copper wheel rotating speed 2000r/min~3000r/min, injection pressure
0.02~0.05Pa, cooling velocity 103~106k/s；
The thickness of the non-crystaline amorphous metal presoma strip is 10~300 microns；
Step 4, removal alloying nanoporous AgCu supersaturated solid solution alloys；
Non-crystaline amorphous metal presoma strip made from step 3 is put into and is pre-charged with N2In the corrosive liquid of protective atmosphere 20min
Removal alloying is carried out, nanoporous AgCu supersaturated solid solutions are made；
Corrosive liquid is hydrochloric acid, sulfuric acid, phosphoric acid or hydrofluoric acid, citric acid, salicylic acid, ethanedioic acid, tartaric acid, lactic acid；It is rotten
Lose a concentration of 0.01mol/L~5.0mol/L of liquid；
Removal alloying temperature is 22 DEG C~80 DEG C, removal alloying time 5min~3600min.
Surface produced by the present invention is the nanoporous AgCu of the nano porous layer of the logical frenulum and pore structure of three-dimensional duplex
Over-saturation single phase solid solution alloy advantage is：
1. breaching the limitation of Ag and Cu lattice constants, Cu dissolving in Ag lattices is realized.
2. the oxidative resistance and its industry applied chemistry ingredient that improve copper uniformly have stronger structural stability.
Description of the drawings
Fig. 1 is the Y of the present invention10Mg65(Ag0.5Cu0.5)25The X-ray diffraction picture of amorphous alloy ribbon.
Fig. 2 is the Y of the present invention10Mg65(Ag0.5Cu0.5)25The energy spectrum diagram of non-crystaline amorphous metal.
Fig. 3 is Y of the present invention10Mg65(Ag0.5Cu0.5)25The X of nano porous layer/non-crystaline amorphous metal matrix after removal alloying
X ray diffraction picture.
Fig. 4 is Y of the present invention10Mg65(Ag0.5Cu0.5)25The SEM of amorphous alloy composite material schemes.
Fig. 5 is Y of the present invention10Mg65(Ag0.5Cu0.5)25The nano porous layer of amorphous alloy composite material/non-crystaline amorphous metal matrix
Scanning figure.
Fig. 6 is Y of the present invention10Mg65(Ag0.5Cu0.5)25The nano porous layer of amorphous alloy composite material/non-crystaline amorphous metal matrix
Energy spectral line scanning figure.
Specific implementation mode
Below in conjunction with drawings and examples, the present invention is described in further detail.
A kind of nanoporous AgCu supersaturated solid solutions prepared based on a variety of non-crystaline amorphous metal presomas proposed by the present invention
The method of alloy comprising have the following steps：
Step 1 carries out dispensing according to the target component of nanoporous AgCu supersaturated solid solution alloys；
Dispensing select mass percent purity more than or equal to 99% Ag, Cu, Al, Mg, Ca, Zn, Zr, La, Ce, Pr, Nd,
Y, one or more simple substance elements in Sn；
Step 2, vacuum melting alloyage ingot casting；
Vacuum degree≤1 × 10 needed for vacuum melting- 3Pa, smelting temperature are 500 DEG C~1500 DEG C, smelting time 5~
7min；In the case where mass percent purity is 99.999% argon atmosphere, melting is uniformly taken out afterwards obtains alloy cast ingot；
Step 3 quickly solidifies non-crystaline amorphous metal presoma strip processed；
By alloy cast ingot made from step 2 in the induction furnace of quick solidification apparatus, at a temperature of 600 DEG C~1000 DEG C
After fusing, obtained non-crystaline amorphous metal presoma strip of quenching is revolved with copper wheel；Copper wheel rotating speed 2000r/min~3000r/min, injection pressure
0.02~0.05Pa, cooling velocity 103~106k/s；
The thickness of the non-crystaline amorphous metal presoma strip is 10~300 microns；
Step 4, removal alloying nanoporous AgCu supersaturated solid solution alloys；
Non-crystaline amorphous metal presoma strip made from step 3 is put into and is pre-charged with N2In the corrosive liquid of protective atmosphere 20min
Removal alloying is carried out, nanoporous AgCu supersaturated solid solutions are made；
Corrosive liquid is hydrochloric acid, sulfuric acid, phosphoric acid or hydrofluoric acid, citric acid, salicylic acid, ethanedioic acid, tartaric acid, lactic acid；It is rotten
Lose a concentration of 0.01mol/L~5.0mol/L of liquid；
Removal alloying temperature is 22 DEG C~80 DEG C, removal alloying time 5min~3600min.
Embodiment 1
Utilize Ln100-y-aMga(Ag1-xCux)yNanoporous AgCu supersaturated solid solutions prepared by non-crystaline amorphous metal presoma close
Gold, the Ln100-y-aMga(Ag1-xCux)yMiddle Ln is one or more, the Ln in Y, La, Ce, Pr, Nd100-y-aMga
(Ag1-xCux)yMolar percentage dosage value be 0<x<1,15≤y≤50,10≤a≤65.
In the Ln100-y-aMga(Ag1-xCux)yIn special ingredient have：Y10Mg65(Ag0.5Cu0.5)25、Y10Mg65
(Ag0.75Cu0.25)25、La10Mg65(Ag0.5Cu0.5)25、Ce5Mg65(Ag0.75Cu0.25)30And Nd5Y5Mg65(Ag0.5Cu0.5)25。
By Y10Mg65(Ag0.5Cu0.5)25Master alloy ingot recycles nanoporous made from removal alloying technique after strip is made
AgCu over-saturation single phase solid solution alloys, specific steps have：
Step 1, according to target ingredient composition；
According to Y10Mg65(Ag0.5Cu0.5)25Target component weigh each simple substance element of Y, Mg, Ag, Cu, each simple substance of selection
The mass percent purity of element is 99.9%；
The Y of 30g processed10Mg65(Ag0.5Cu0.5)25The mass number of each element needed for master alloy ingot is：Mg is 10.277g, and Cu is
5.167g, Ag are 8.772g and Y is 5.784g.
Step 2, vacuum melting alloyage ingot casting；
Step 21, melting Cu-Y prealloys ingot；
Cu the and Y raw materials of step 1 weighing gained are put into vacuum arc furnace ignition and carry out melting, melting is uniformly taken out afterwards
It is Cu to ingredient12.5Y10Prealloy ingot；
Vacuum arc furnace melting parameter setting：Vacuum degree 1 × 10-2Pa, 1250 DEG C of smelting temperature, smelting time 8min；
Step 22, melting Y10Mg65(Ag0.5Cu0.5)25Master alloy ingot；Step 1 is weighed to the raw material Mg and Ag and step of gained
The Cu of rapid 21 gained12.5Y10Prealloy ingot is put into vacuum induction melting furnace, adjusts vacuum degree 3 in the stove of vacuum induction melting furnace
×10-2Pa, heating temperature are 1000 DEG C, smelting time 5min；The argon gas for being 99.999% in mass percent purity protects gas
Melting uniformly takes out and obtains Y afterwards under atmosphere10Mg65(Ag0.5Cu0.5)25Alloy cast ingot；
Step 3 quickly solidifies non-crystaline amorphous metal presoma strip processed；
By Y made from step 2210Mg65(Ag0.5Cu0.5)25Master alloy ingot, which is put into the induction furnace of quick solidification apparatus, to be melted
Afterwards, the obtained Y that quenches is revolved with copper wheel10Mg65(Ag0.5Cu0.5)25Amorphous alloy ribbon, as shown in Figure 1；The width of amorphous alloy ribbon is
2mm, thickness are 30~35 microns.
Parameter setting：The vacuum degree of vaccum sensitive stove is 1 × 10 when melting-1Pa, induced current 300mA, smelting temperature
It it is 700 DEG C, smelting time is 8 seconds；Copper wheel a diameter of 25cm when spray to cast, rotating speed 3000r/min, cooling velocity 105K/s。
Amorphous ribbon ingredient is analyzed by SEM-EDX, can determine that its element forms very close Y by energy spectrum diagram Fig. 210Mg65
(Ag0.5Cu0.5)25, the amorphous of preparation meets subsequent experimental requirement.
Nanoporous silver-bearing copper over-saturation single phase solid solution is made in step 4, removal alloying；
Step 41, match acid solution, select the H of a concentration of 0.04mol/L2SO4Solution；Conduit merging is first equipped with H2SO4
In the removal alloying processing unit of solution, then carry out being filled with N2(nitrogen that mass percent purity is 99.999%), to go
Except H2SO4Oxygen in solution, is filled with N2The gas time is 20 minutes；In the present invention, N2Gas is filled with to exclude removal alloying processing
Oxygen in device prevents from generating metal oxide；
It step 42, will be through Y made from step 310Mg65(Ag0.5Cu0.5)25Amorphous alloy ribbon, which is put into, fills H2SO4Solution
Removal alloying processing unit in, and seal；Setting removal alloying temperature is 25 DEG C, the removal alloying time is 50min；It takes out,
Successively with deionized water, washes of absolute alcohol, nanoporous silver-bearing copper supersaturated solid solution, the nano-porous silver of embodiment 1 are obtained
Copper supersaturated solid solution structure is as shown in Figure 3.
It is tested using micrometer caliper, nanoporous layer thickness made from embodiment 1 is 7 microns, and frenulum size is received for 12
Rice.
In the present invention, it is directly in amorphous alloy thin belt surface using removal alloying processing is carried out in a sealed meter environment
It is generated in-situ, other nano porous layers/amorphous alloy composite material preparation method is compared, manufacturing process is simplified.
Y obtained in embodiment 1 is carried out on Bruker-AXS D8X x ray diffractometer xs10Mg65(Ag0.5Cu0.5)25Amorphous
The crystal species analysis of alloy thin band.From figure 1 it appears that only there are one features to overflow in the XRD spectrum of the amorphous alloy ribbon
Peak is dissipated, and any sharp diffraction maximum corresponding to crystal phase is not observed, shows that it is all single non crystalline structure.
It is single-phase that nanoporous silver-bearing copper over-saturation obtained in embodiment 1 is carried out on Bruker-AXS D8X x ray diffractometer xs
Solid solution Y10Mg65(Ag0.5Cu0.5)25The crystal species analysis of material, and obtained respectively with graphical-extrapolation method according to the position of diffraction maximum
The lattice constant of phase.From figure 3, it can be seen that the XRD spectrum of the composite material disperses peak and face-centered cubic by the feature of amorphous
The diffraction maximum of the Ag of structure, this shows the composite material by amorphous and face-centered cubic Ag phase compositions.
Silver-copper nano porous layer modification obtained in embodiment 1 is carried out in Hitachi S4800 scanning electron microscope
Y10Mg65(Ag0.5Cu0.5)25The morphology analysis of amorphous alloy composite material.Fig. 4 is the surface SEM photograph of the composite material.Such as
Shown in figure, the surface of the composite material is nano-porous structure, shows typical structure uniformly three-dimensional netted nanoporous
Structure.
Nanoporous silver-bearing copper over-saturation obtained in embodiment 1 is carried out in Hitachi S4800 scanning electron microscope
Single phase solid solution Y10Mg65(Ag0.5Cu0.5)25The morphology analysis of material.Fig. 4 is that AMORPHOUS ALLOY RIBBONS reacts the section after 10min
SEM photograph.From figure 5 it can be seen that the SEM photograph of the composite material is made of nano porous layer and noncrystal substrate, nanometer is more
Hole layer thickness is uniform, and the interface between fine and close amorphous alloy layer is smooth and is parallel to original specimen surface, this shows to corrode
Alloy/electrolyte section is uniformly towards corroding in noncrystal substrate in journey.
The constituent analysis of nano porous layer/noncrystal substrate is carried out on SEM-EDX energy disperse spectroscopies.Fig. 6 is amorphous alloy ribbon
React the energy spectral line scanning figure after 10min.From fig. 6, it can be seen that from non-crystaline amorphous metal to nano porous layer, the content of Cu and Ag by
Edge up height, and the content of Mg and Y gradually decreases.This shows to illustrate table in conjunction with Fig. 3 containing Cu and Ag in nano surface porous layer
Face nano porous layer is the single-phase Ag structure compositions by CuAg double elements, it was demonstrated that solid solution has Cu atoms, nanoporous in Ag
Frenulum in layer is the single phase solid solution of Ag.
In the present invention, using removal alloying technique started with from metal framework structure, the Mg atoms in alloy and Y atoms
It will constantly dissolve into solution, and remaining Ag and Cu atoms will form the nanoporous knot that aperture is 20nm along solid liquid interface
Structure.
Embodiment 2
Utilize Ln100-y-zAlz(Ag1-xCux)yNanoporous AgCu over-saturation single phase solid solutions prepared by non-crystaline amorphous metal presoma
Body alloy, the Ln100-y-zAlz(Ag1-xCux)yMiddle Ln is one or more, the Ln in La, Ce, Pr, Nd100-y-zAlz
(Ag1-xCux)yMolar percentage dosage value be 0<x<1,15≤y≤50,5≤z≤35.
In the Ln100-y-zAlz(Ag1-xCux)yIn special ingredient have：Ce60Al10(Ag0.7Cu0.3)30、La55Al5
(Ag0.5Cu0.5)40And La70Al5(Ag0.5Cu0.5)25。
By Ce60Al10(Ag0.7Cu0.3)30Master alloy ingot recycles nanometer made from removal alloying technique more after strip is made
Hole AgCu over-saturation single phase solid solution alloys, specific steps have：
Step 1, alloy pig dispensing；
According to Ce60Al10(Ag0.7Cu0.3)30Target component weighs La, Al, Cu, Ag each element, is uniformly mixed and obtains melting
Raw material, and the mass percent purity of each element is not less than 99%；
The Ce of 30g processed60Al10(Ag0.7Cu0.3)30The mass number of each element needed for master alloy ingot is：La is 21.853g, Ag
For 5.940g, Cu 1.500g, Al 0.707g；
Step 2, vacuum melting alloyage ingot casting；
The raw material that step 1 is weighed to gained is put into vacuum induction melting furnace, adjusts the stove of vacuum high-frequency induction melting furnace
Interior vacuum degree≤3 × 10- 2Pa, heating temperature are 1000 DEG C, smelting time 5min；It is 99.999% in mass percent purity
Argon atmosphere under melting uniformly afterwards take out obtain Ce60Al10(Ag0.7Cu0.3)30Alloy cast ingot；
Step 3 quickly solidifies non-crystaline amorphous metal presoma strip processed；
The Ce that step 2 is prepared60Al10(Ag0.7Cu0.3)30Alloy pig is put into the induction furnace of quick solidification apparatus
After fusing, the obtained Ce that quenches is revolved with copper wheel60Al10(Ag0.7Cu0.3)30Amorphous alloy ribbon；The width of amorphous alloy ribbon is 2mm,
Thickness is 30~35 μm.
Parameter setting：The vacuum degree of vaccum sensitive stove is 1 × 10 when melting-1Pa, induced current 300mA, smelting temperature
It is 700 DEG C, smelting time 8s；Copper wheel a diameter of 20cm when spray to cast, rotating speed 2000r/min, cooling velocity 102K/s。
Nanoporous silver-bearing copper over-saturation single phase solid solution is made in step 4, removal alloying；
Step 41, match acid solution, select the H of a concentration of 0.04mol/L2SO4Solution；Conduit merging is first equipped with H2SO4
In the removal alloying processing unit of solution, then carry out being filled with N2(nitrogen that mass percent purity is 99.999%), to go
Except H2SO4Oxygen in solution, is filled with N2The gas time is 20 minutes；In the present invention, N2Gas is filled with to exclude removal alloying processing
Oxygen in device prevents from generating metal oxide；
It step 42, will be through Ce made from step 360Al10(Ag0.7Cu0.3)30Amorphous alloy ribbon, which is put into, fills removing oxygen
H2SO4Removal alloying processing is carried out in the beaker of solution, this holds H in the process2SO4The beaker mouth of solution should seal, and prevent
Air enters.
It being handled using removal alloying method, temperature is 30 DEG C, and after the time is 30min, taking-up is cleaned twice with deionized water, then
With washes of absolute alcohol twice to get to nanoporous silver-bearing copper over-saturation single phase solid solution composite material.Obtained composite material
Nanoporous layer thickness be 25 microns, frenulum size be 38 nanometers.
In example 2, can be 22 DEG C~30 DEG C by adjusting removal alloying temperature, removal alloying time 5min~
120min is respectively cleaned after removal alloying with deionized water and absolute ethyl alcohol, to reach the Ce for preparing different-thickness60Al10
(Ag0.7Cu0.3)30Non-crystaline amorphous metal over-saturation single phase solid solution material, nanoporous layer thickness are 1~50 micron, and frenulum size is
10~80 nanometers.The present invention is directly to be generated in amorphous alloy ribbon surface in situ, is closed compared to other nano porous layers/amorphous
Metal/composite material preparation method, simplifies manufacturing process.
Embodiment 3
Utilize Ca100-y-r-sZnrMgs(Ag1-xCux)yNanoporous AgCu over-saturation prepared by non-crystaline amorphous metal presoma is single-phase
Solid solution alloy, the Ca100-y-r-sZnrMgs(Ag1-xCux)yMolar percentage dosage value be 0<x<1,15≤y≤50,5
≤ z≤35,0≤r≤20,0<s≤30.
In the Ca100-y-r-sZnrMgs(Ag1-xCux)yIn special ingredient have：Ca60Mg15(Ag0.5Cu0.5)20Zn5、
Ca60Mg10(Ag0.6Cu0.4)15Zn25And Ca55Mg10(Ag0.6Cu0.4)25Zn10。
Step 1, according to target ingredient composition；
According to Ca60Mg20Ag10Cu10Target component weigh each simple substance element of Ca, Mg, Ag, Cu, each simple substance element of selection
Mass percent purity be 99.9%；
The Ca of 30g processed60Mg20Ag10Cu10The mass number of each element needed for master alloy ingot is：Mg is 3.167g, and Cu is
4.140g, Ag are 7.027g and Ca is 15.666g.
Step 2, vacuum melting alloyage ingot casting；
The dispensing of step 1 is put into vacuum induction melting furnace, adjust vacuum degree 3 in the stove of vacuum induction melting furnace ×
10-2Pa, heating temperature are 800 DEG C, smelting time 5min；In the case where mass percent purity is 99.999% argon atmosphere
Melting uniformly takes out and obtains Ca afterwards60Mg20Ag10Cu10Alloy cast ingot；
Step 3 quickly solidifies non-crystaline amorphous metal presoma strip processed；
By Ca made from step 260Mg20Ag10Cu10Master alloy ingot is put into the induction furnace of quick solidification apparatus after fusing,
The obtained Ca that quenches is revolved with copper wheel60Mg20Ag10Cu10Amorphous alloy ribbon；The width of amorphous alloy ribbon is 2mm, and thickness is 20~30
Micron.
Parameter setting：The vacuum degree of vaccum sensitive stove is 1 × 10 when melting-1Pa, induced current 300mA, smelting temperature
It it is 600 DEG C, smelting time is 15 seconds；Copper wheel a diameter of 25cm when spray to cast, rotating speed 3000r/min, cooling velocity 102K/s。
Nanoporous silver-bearing copper over-saturation single phase solid solution is made in step 4, removal alloying；
Step 41, match acid solution, select the H of a concentration of 0.04mol/L2SO4Solution；Conduit merging is first equipped with H2SO4
In the removal alloying processing unit of solution, then carry out being filled with N2(nitrogen that mass percent purity is 99.999%), to go
Except H2SO4Oxygen in solution, is filled with N2The gas time is 20 minutes；In the present invention, N2Gas is filled with to exclude removal alloying processing
Oxygen in device prevents from generating metal oxide；
It step 42, will be through Ca made from step 360Mg20Ag10Cu10Amorphous alloy ribbon, which is put into, fills H2SO4Solution is gone
In alloying treatment apparatus, and seal；Setting removal alloying temperature is 25 DEG C, the removal alloying time is 10min；It takes out, successively
With deionized water, washes of absolute alcohol, nanoporous silver-bearing copper over-saturation single phase solid solution is obtained.
It is tested using micrometer caliper, nanoporous layer thickness made from embodiment 3 is 10 microns, and frenulum size is received for 15
Rice.
Embodiment 4
Utilize Zr100-y-m-eMmAle(Ag1-xCux)yNanoporous AgCu over-saturation prepared by non-crystaline amorphous metal presoma is single-phase
Solid solution alloy, the Zr100-y-m-eMmAle(Ag1-xCux)yMiddle M is one or more, the institute in La, Ce, Pr, Nd, Sn, Zn
State Zr100-y-m-eMmAle(Ag1-xCux)yMolar percentage dosage value be 0<x<1,15≤y≤70,5≤z≤35,0<e≤
15,0<m≤5.
In the Zr100-y-m-eMmAle(Ag1-xCux)yIn special ingredient have：Zr46Al14(Ag0.2Cu0.8)30Sn10、
Zr38Y5Al15Ag8Cu34、Zr56Al10(Ag0.3Cu0.7)24Sn5Zn5And Zr50Al8(Ag0.5Cu0.5)32Zn10。
Step 1, according to target ingredient composition；
According to Zr56Al10Cu27Nb1Ag6Target component weigh each simple substance element of Zr, Al, Nb, Ag, Cu, each list of selection
The mass percent purity of prime element is 99.9%；
Step 2, vacuum melting alloyage ingot casting；
Raw material in step is put into vacuum induction melting furnace, adjust vacuum degree 3 in the stove of vacuum induction melting furnace ×
10-2Pa, heating temperature are 1500 DEG C, smelting time 10min；The argon atmosphere for being 99.999% in mass percent purity
Lower melting uniformly takes out and obtains Zr afterwards56Al10Cu27Nb1Ag6Alloy cast ingot；
Step 3 quickly solidifies non-crystaline amorphous metal presoma strip processed；
By Zr made from step 256Al10Cu27Nb1Ag6Master alloy ingot, which is put into the induction furnace of quick solidification apparatus, to be melted
Afterwards, the obtained Zr that quenches is revolved with copper wheel56Al10Cu27Nb1Ag6Amorphous alloy ribbon；The width of amorphous alloy ribbon is 2mm, thickness 25
~30 microns.
Parameter setting：The vacuum degree of vaccum sensitive stove is 1 × 10 when melting-3Pa, induced current 300mA, smelting temperature
It it is 700 DEG C, smelting time is 10 seconds；Copper wheel a diameter of 25cm when spray to cast, rotating speed 2800r/min, cooling velocity 102K/s。
Nanoporous silver-bearing copper over-saturation single phase solid solution is made in step 4, removal alloying；
Step 41, match acid solution, select the H of a concentration of 0.04mol/L2SO4Solution；Conduit merging is first equipped with H2SO4
In the removal alloying processing unit of solution, then carry out being filled with N2(nitrogen that mass percent purity is 99.999%), to go
Except H2SO4Oxygen in solution, is filled with N2The gas time is 20 minutes；In the present invention, N2Gas is filled with to exclude removal alloying processing
Oxygen in device prevents from generating metal oxide；
It step 42, will be through Zr made from step 356Al10Cu27Nb1Ag6Amorphous alloy ribbon, which is put into, fills H2SO4Solution
In removal alloying processing unit, and seal；Setting removal alloying temperature is 30 DEG C, the removal alloying time is 30min；It takes out, first
Deionized water, washes of absolute alcohol are used afterwards, obtain nanoporous silver-bearing copper over-saturation single phase solid solution.
It is tested using micrometer caliper, nanoporous layer thickness made from embodiment 4 is 5 microns, and frenulum size is received for 12
Rice.
Claims (6)
1. a kind of nanoporous AgCu supersaturated solid solution alloys prepared based on a variety of non-crystaline amorphous metal presomas, feature are existed
In：Ag and Cu elemental mole ratios 0 in the composition phase of nanoporous AgCu supersaturated solid solution alloys<x<1 is continuously adjustable.
2. the nanoporous AgCu supersaturated solid solutions according to claim 1 prepared based on a variety of non-crystaline amorphous metal presomas
Alloy, it is characterised in that：The preferred component of nanoporous AgCu supersaturated solid solution alloys is Mg65Cu20Ag5Y10、
Mg65Cu15Ag10Y10、Mg65Cu12.5Ag12.5Y10、La10Mg65Cu10Ag15、Mg65Cu5Ag20Y10、La62.5Al12.5Ag5Cu20、
La62.5Al12.5Ag10Cu15、La62.5Al12.5Ag15Cu10、La62.5Al12.5Ag20Cu5、Ca60Mg20Ag10Cu10、
Ca50Zn10Mg10Ag15Cu15、Zr38Al18Ag8Cu36、Zr38Y5Al15Ag8Cu34。
3. the nanoporous AgCu over-saturation according to claim 1 or 2 prepared based on a variety of non-crystaline amorphous metal presomas is solid
Solution alloy, it is characterised in that：The frenulum and hole that nanoporous AgCu supersaturated solid solution alloys have continuous three-dimensional duplex logical
Structure, frenulum size are 5~130 nanometers, and porosity is 20%~70%, and porous layer thickness is 1~200 micron.
4. the nanoporous AgCu over-saturation according to claim 1 or 2 prepared based on a variety of non-crystaline amorphous metal presomas is solid
Solution alloy, it is characterised in that：The ingredient of non-crystaline amorphous metal presoma is Ln100-y-zAlz(Ag1-xCux)y, 0<x<1,15≤y≤
50,5≤z≤35；Ln is one or more in La, Ce, Pr, Nd；Or
Ln100-y-aMga(Ag1-xCux)y, 0<x<1,15≤y≤50,5≤z≤35,10≤a≤65；Ln is in Y, La, Ce, Pr, Nd
It is one or more；Or
Ca100-y-r-sZnrMgs(Ag1-xCux)y, 0<x<1,15≤y≤50,5≤z≤35,0≤r≤20,0<s≤30；Or
Zr100-y-m-eMmAle(Ag1-xCux)y, 0<x<1,15≤y≤50,5≤z≤35,0<E≤15,0<m≤5；M be La, Ce,
It is one or more in Pr, Nd, Nb, Y, Sn, Zn.
5. preparing the nanoporous AgCu over-saturation prepared as claimed in claim 1 or 2 based on a variety of non-crystaline amorphous metal presomas
The method of solid solution alloy, it is characterised in that include the following steps：
Step 1 carries out dispensing according to the target component of nanoporous AgCu supersaturated solid solution alloys；
Dispensing selects Ag, Cu, Al, Mg, Ca, Zn, Zr, La, Ce, Pr, Nd, Y, Sn that mass percent purity is more than or equal to 99%
In one or more simple substance elements；
Step 2, vacuum melting alloyage ingot casting；
Vacuum degree≤1 × 10 needed for vacuum melting- 3Pa, smelting temperature are 500 DEG C~1500 DEG C, 5~7min of smelting time；In matter
Melting is uniformly taken out afterwards under the argon atmosphere that amount percent purity is 99.999% obtains alloy cast ingot；
Step 3 quickly solidifies non-crystaline amorphous metal presoma strip processed；
By alloy cast ingot made from step 2 in the induction furnace of quick solidification apparatus, to melt at a temperature of 600 DEG C~1000 DEG C
Afterwards, obtained non-crystaline amorphous metal presoma strip of quenching is revolved with copper wheel；Copper wheel rotating speed 2000r/min~3000r/min, injection pressure 0.02~
0.05Pa, cooling velocity 103~106k/s；
The thickness of the non-crystaline amorphous metal presoma strip is 10~300 microns；
Step 4, removal alloying nanoporous AgCu supersaturated solid solution alloys；
Non-crystaline amorphous metal presoma strip made from step 3 is put into and is pre-charged with N2It is carried out in the corrosive liquid of protective atmosphere 20min
Nanoporous AgCu supersaturated solid solutions are made in removal alloying；
Corrosive liquid is hydrochloric acid, sulfuric acid, phosphoric acid or hydrofluoric acid, citric acid, salicylic acid, ethanedioic acid, tartaric acid, lactic acid；Corrosive liquid
A concentration of 0.01mol/L~5.0mol/L；
Removal alloying temperature is 22 DEG C~80 DEG C, removal alloying time 5min~3600min.
6. the nanoporous AgCu supersaturated solid solutions according to claim 5 prepared based on a variety of non-crystaline amorphous metal presomas
The method of alloy, it is characterised in that：Nanoporous AgCu supersaturated solid solution alloys obtained are to be with what three-dimensional duplex was led to
Band and pore structure；Its frenulum size is 5~130 nanometers, and porosity is 20%~70%, and porous layer thickness is 1~200 micron.
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