CN106916988A - A kind of preparation method of nano porous metal film - Google Patents
A kind of preparation method of nano porous metal film Download PDFInfo
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- CN106916988A CN106916988A CN201511004890.4A CN201511004890A CN106916988A CN 106916988 A CN106916988 A CN 106916988A CN 201511004890 A CN201511004890 A CN 201511004890A CN 106916988 A CN106916988 A CN 106916988A
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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
- C22C1/08—Alloys with open or closed pores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
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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
- C22C3/005—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
- C22C45/00—Amorphous alloys
- C22C45/005—Amorphous alloys with Mg as the major constituent
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Abstract
The invention provides a kind of preparation method of nano porous metal film.The method is used and goes alloyage, using Mg base noncrystal alloys thin plate (piece) or strip as presoma, by the concentration for controlling acid solution temperature and/or acid, the magnesium in the certain thickness thin layer in presoma surface, rare earth and other relatively active metallic atoms is preferentially become ion with hydrogen ion reaction and enter solution, form the nano porous metal layer of metal target atomic building；Under the obstruct of nano porous metal layer, the accumulation of reaction latent heat causes that the temperature of the non-crystaline amorphous metal below nano porous metal layer reaches its glassy state temperature, so that nano porous metal layer can be peeled off in the presence of generated reactive gas from glassy state presoma, nano porous metal film is obtained.The method process is simple, obtained porous metal film thickness of thin, specific surface area are big, it is integrated etc. to be easy to micro element, therefore in membrane module, micro- energy device and micro-optoelectronic device field have application prospect.
Description
Technical field
The invention belongs to metal nano material technical field, more particularly to a kind of preparation of nano porous metal film
Method.
Background technology
Nano porous metal material refers to aperture in 100nm or so or lower, and porosity is more than 40%, tool
There is the porosu solid metal material of high-specific surface area.Nano porous metal material not only has big internal surface area,
High porosity and more uniform nano-pore, and the high thermal conductivity with metal material, high conductivity are anticorrosive
Deng excellent properties, thus make it that there is important application in catalysis, new energy, photoelectric field, such as biological, doctor
Medicinal ultrafiltration or even nanofiltration medium, high surface area catalyst support in fuel cell, albumen in medical diagnosis
Selective absorbing of molecule etc..Result of study shows that the electrochemistry capacitance of nano porous metal material is far longer than
Existing graphite material, the endurance for improving battery has tremendous raising.In addition, nanoporous
Skin effect and dimensional effect that metal material is shown, make it in electronics, optics, microfluid and microcosmic
The aspects such as mechanics also have huge application prospect.
At present, prepare nano porous metal material generally use method have powder metallurgic method, go alloyage, tiltedly
Incident sedimentation, Colloidal Template Method etc..Wherein, it is American engineer Mo Lileini in last century to go alloyage
A kind of method of the '20s invention.The method is used to prepare a nanometer skeleton nickel first, i.e., by finite concentration
NaOH removal alumel in aluminium, obtain the nickel of nanometer skeleton structure.This nanometer skeleton nickel outward appearance
Show as tiny grey powder, but its microstructure mutual " bridge joint " spatially nano-porous structure.
Into the beginning of this century, go alloyage to be also used to prepare other nano porous metals, i.e., removed by chemically reacting
Some of presoma alloy element, and the metal target atom for not participating in reaction in alloy to be self-assembled into nanometer more
Pore structure.
But, as current microelectromechanicmachine machine is booming with micro element, for the ultra-thin porous gold being miniaturized
Category film proposes urgent requirement, and is difficult to realize this ultrathin nanometer using traditional removal alloying technique
It is prepared by porous metal film.
For traditional removal alloying technique, if to prepare nano porous metal film, just have to first
Presoma alloy thin band is prepared, alloy reaction is then carried out to it and is prepared corresponding nano-porous film.But,
The thickness limit of rapid hardening alloy thin band that the quick setting methods such as band are obtained is got rid of also only by ultrahigh speed copper roller
It is 14-18 μm, therefore the thickness of obtained nano porous metal film is higher, does not reach 10 μm much typically
Following degree.At present, to be also limited only to nanometer more for the nano porous metal film preparing technology of comparative maturity
The preparation of hole gold thin film, because Au-Ag alloys have high plastic deformation working ability, Ke Yitong
The alloy thin band that continuous pressure rolling is rolled to 100nm or so is crossed, such that it is able to as presoma alloy,
Ag therein is reacted away by removing alloy, it is the nanoporous gold thin film of 100nm or so to prepare thickness.But,
Due to prepare the presoma alloy generally Cu or Ag of other metal materials such as nanoporous Cu or Ag with
(such as CuAl alloys prepare nanoporous Cu, or MgAg to the alloy of the metals such as Al, Mg, Zn, Mn
Alloy prepares nanoporous Ag), the most intermetallic compound containing fragility of these alloys, it is impossible to by continuous
The mode of rolling obtains the presoma of thickness smaller (being, for example, less than 10 μm, further preferably less than 4 μm)
Alloy thin band, thus alloy cannot be gone to react obtain smaller (being, for example, less than 10 μm, entering by further
One step is preferably less than 4 μm) nano porous metal film.
Therefore, people also prepare the less alloy film of thickness using the method for magnetron sputtering, then by removing alloy
Reaction obtains corresponding nano porous metal film (including such as Cu, Ag films), but this film is necessary
It is attached on certain sputtering substrate, significantly limit its extensive use.
Therefore, the preparation method of the nano porous metal film of new property is researched and developed, can be especially prepared
The less nano porous metal film of thickness has very important significance.
The content of the invention
Technical purpose of the invention is directed to above-mentioned prior art background, proposes that one kind prepares nano porous metal thin
The new method of film, it is the method low cost, simple to operate, and the less nano porous metal of thickness can be obtained
Film.
In order to realize above-mentioned technical purpose, the present inventor has found by after many experiments exploration, when using following (one)
During with technical essential described in (two), the less nano porous metal film of thickness can be obtained.
(1) preparation of presoma Mg base noncrystal alloys thin plate (piece) or strip
The formula molecular formula for selecting presoma alloy is MgaMbREcNd, wherein metal target M represent copper, nickel,
Silver, gold, palladium, platinum, tin, lead, zirconium, titanium, hafnium, vanadium, chromium, manganese, iron, cobalt, niobium, molybdenum, tungsten, tantalum,
One or several mixing in the metallic elements such as silicon, germanium, mercury, RE represent yttrium, lanthanum, cerium, praseodymium, neodymium,
In the rare earth elements such as promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium one or several
Mixing, N represents one or several the mixing in zinc, aluminium, lithium, potassium, calcium, gallium.A, b, c and d generation
The atom percentage content of table each element, and 40%≤a≤80%, 1%≤c≤30%, 0≤d≤20%,
A+b+c+d=100%.
Raw material is weighed according to described formula, alloy melt is obtained after being melted, by alloy melt by quick
Solidification technology is prepared into lamellar, laminar or sheet shape presoma Mg based alloys, and wherein amorphous phase is accounted for
Subject organization, abbreviation presoma Mg base noncrystal alloys thin plate (piece) or strip.
(2) alloy reaction is gone to prepare nano porous metal film
Above-mentioned presoma Mg base noncrystal alloys thin plate (piece) or strip are carried out into alloy with acid solution to react.
In course of reaction, the concentration of control acid solution temperature and/or acid makes Mg base noncrystal alloys thin plate (piece) or thin
Carry sample is from surface to the magnesium in the range of its internal direction certain thickness, rare earth and other relatively active metals
The reaction of atoms and hydrogen ion becomes ion and enters solution, and metal target atom in the thickness range then shape
Into nano porous metal layer.Under the obstruct of nano porous metal layer, the reaction latent heat for further producing is difficult to
Sufficient convective heat exchange is carried out with solution, the accumulation of heat is so that within the nano porous metal layer of the solid-state
The local temperature of reaction interface exceedes the Glass Transition temperature of Mg base noncrystal alloys thin plate (piece) or strip sample
Degree, so as to form solid-liquid (glassy state) interface at the reaction interface.The gas produced in reaction
Under " support is swollen " effect, the nano porous metal layer of solid-state will be from the Mg base noncrystal alloys of adjacent glassy state
Thin plate (piece) or strip sample are peeled off, so as to obtain nano porous metal film.
In described technical essential (), the preparation of presoma Mg base noncrystal alloys thin plate (piece) or strip
Method is not limited with size.Described presoma Mg base noncrystal alloys thin plate (piece) or the surface smoothness of strip
Height is conducive to the quality of the nano porous metal film prepared by raising.
In described technical essential (), the main body of presoma Mg base noncrystal alloys thin plate (piece) or strip
Amorphous state is organized as, the percentage composition of wherein amorphous is not less than 50%, and amorphous glass transformation temperature is
75℃-250℃。
In described technical essential (two), even if presoma Mg base noncrystal alloys thin plate (piece) or strip
Thickness is larger, and the less nano porous metal film of thickness is also obtained in that by the technical essential, for example, i.e.
Presoma Mg base noncrystal alloys thin plate (piece) or the thickness of strip is set to be not less than 10 μm, will by the technology
Point is also obtained in that nano porous metal film of the thickness less than 10 μm, can further preferably obtain thickness small
In 4 μm of nano porous metal film, for example its thickness is 50nm~4 μm, and can prepare film
Maximum area can be suitable with the surface area of non-crystaline amorphous metal thin plate (piece) or strip.
It is obtained to receive when using presoma Mg base noncrystal alloy strips in described technical essential (two)
" frenulum " characteristic size of rice porous metal film band is 5nm~250nm.
In described technical essential (two), acid for providing hydrogen ion, including but not limited to sulfuric acid, hydrochloric acid,
Nitric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, carbonic acid, gluconic acid, oleic acid, polyacrylic acid etc.
In the mixing of one or more.
In described technical essential (two), the solvent in acid solution is not limited, including water, methyl alcohol, ethanol, different
The mixed liquor of one or more in propyl alcohol, acetone etc..
In described technical essential (two), preferably, the concentration of acid is defined in acid solution
The scope of 0.005mol/L-2mol/L.
In described technical essential (two), in course of reaction, preferably, the mean temperature of acid solution is -30 DEG C
To within the scope of 80 DEG C.
In described technical essential (two), preferably, the reaction time is 1min-300min.
In sum, the present invention has the advantages that：
(1) innovatively using Mg base noncrystal alloys thin plate (piece) or strip as presoma, using going
Alloyage, by controlling the concentration of acid solution temperature and/or acid, make Mg base noncrystal alloys thin plate (piece) or
Magnesium, rare earth and other relatively active metallic atoms in the certain thickness thin layer of strip sample surfaces preferentially with
Hydrogen ion reaction becomes ion and enters solution, forms the nano porous metal layer of metal target atomic building, is entering
In the course of reaction of one step, because nano porous metal layer reaction heat is intercepted with the thermal convection current of solution, thus
Heat accumulation near reaction interface within the nano porous metal layer of solid-state, when heat is non-more than the Mg bases
Solid-liquid interface is formed during the glass transition temperature of peritectic alloy thin plate (piece) or strip sample, is produced in the reaction
Under raw gas effect, the nano porous metal layer of solid-state will be from the Mg base noncrystal alloy thin plates of glassy state
(piece) or strip sample are peeled off, so as to obtain nano porous metal film.
(2) selection of low glass transformation temperature magnesium base amorphous alloy so that go nanometer in alloy course of reaction many
Hole film is possibly realized from Mg base noncrystal alloys thin plate (piece) or peeling off certainly for strip top layer.Even if presoma
The thickness of Mg base noncrystal alloys thin plate (piece) or strip is not less than 10 μm, but made through step (2)
The thickness of standby nano porous metal film can be less than 10 μm, be further able to reach less than 4 μm, more excellent
Elect 50nm-4 μm as.
(3) preparation process is simple, can prepare nano porous metal film near normal temperature；And it is obtained
Porous metal film specific surface area it is big, its maximum area and non-crystaline amorphous metal thin plate (piece) or the surface of strip
Product is suitable；In addition, it is easy to which micro element is integrated, therefore in membrane module, micro- energy device and micro-optoelectronic device are led
Domain has application prospect.
Brief description of the drawings
Fig. 1 is Mg in the embodiment of the present invention 161Cu28Gd11The DSC curve of AMORPHOUS ALLOY RIBBONS；
Fig. 2 is the scanning electron micrographs of obtained nanoporous Copper thin film in the embodiment of the present invention 1；
Fig. 3 is the energy spectrum diagram of obtained nanoporous Copper thin film in the embodiment of the present invention 1；
Fig. 4 is the projection Electronic Speculum bright field image of obtained nanoporous Copper thin film in the embodiment of the present invention 1；
Fig. 5 is the projection Electronic Speculum high resolution picture of obtained nanoporous Copper thin film in the embodiment of the present invention 1；
Fig. 6 is the electronic diffraction collection of illustrative plates of obtained nanoporous Copper thin film in the embodiment of the present invention 1；
Fig. 7 is the scanning electron micrographs of obtained nanoporous Copper thin film in the embodiment of the present invention 2；
Fig. 8 is the scanning electron micrographs of obtained nanoporous nickel film in the embodiment of the present invention 3；
Fig. 9 is the scanning electron micrographs of obtained nanoporous Cu-Ag film in the embodiment of the present invention 4.
Specific embodiment
The present invention is described in further detail with embodiment below in conjunction with the accompanying drawings, it should be pointed out that following institute
State embodiment to be intended to be easy to the understanding of the present invention, and do not play any restriction effect to it.
Embodiment 1：
An example for preparing nanoporous Copper thin film is present embodiments provided, the preparation method comprises the following steps：
(1) it is Mg from formula molecular formula61Cu28Gd11Presoma alloy, weigh raw material according to the formula,
Alloy melt is obtained after melting, alloy melt is prepared into 30 μm of width 4mm thickness by the method that copper roller gets rid of band
The Mg of left and right61Cu28Gd11AMORPHOUS ALLOY RIBBONS.
As shown in figure 1, the glass transformation temperature of the AMORPHOUS ALLOY RIBBONS is 145 DEG C.
(2) at room temperature, by Mg obtained in 0.1 gram of step (1)61Cu28Gd11AMORPHOUS ALLOY RIBBONS is submerged
30mL concentration is reacted to carry out alloy in the ethanol solution hydrochloride of 0.25mol/L.In course of reaction, the Mg
Mg of the base noncrystal alloy strip sample from the surface internally thin layer of direction about 500nm thickness and Gd atoms
Preferentially become ion with hydrogen ion reaction and enter solution, and metal target Cu is then in this thin layer of the band
Form Cu layers of nanoporous.Under the obstruct of Cu layers of the nanoporous, the reaction that further reaction is produced is dived
Heat is difficult to carry out sufficient convective heat exchange with solution, makes reaction circle of the heat within Cu layers of the nanoporous
Local accumulation near face, when temperature herein is more than Mg61Cu28Gd11The glass transformation temperature of non-crystaline amorphous metal
Nanoporous Cu layers of formation one solid-liquid interface, i.e. solid-state and glassy state when (145 DEG C)
Mg61Cu28Gd11The interface of non-crystaline amorphous metal.In the presence of the hydrogen for reacting generation near the solid-liquid interface,
Nanoporous Cu layers of solid-state is peeled off from the Mg base noncrystal alloys of glassy state, obtains thickness about 500nm
Nanoporous Cu films.Directly protected after nanoporous Cu films are cleaned with deionized water or ethanol
Deposit or kept dry.
The analysis and characterization result of nanoporous Cu films sees Fig. 2 to Fig. 5.
Fig. 2 is the scanning electron micrographs of nanoporous Cu films obtained above.Therefrom it can be seen that, should
The thickness of nanoporous Cu films is about 500nm, and the characteristic size of nanoporous frenulum is about 50-80nm.
Fig. 3 is the energy spectrum diagram of nanoporous Cu films obtained above, shows that it is mainly made up of Cu elements.
Fig. 4 is the projection Electronic Speculum bright field image of nanoporous Cu films obtained above, can further confirm that this
The characteristic size of nanoporous frenulum is about 50-80nm.
Fig. 5 is the projection Electronic Speculum high resolution picture of nanoporous Cu films obtained above, its display Cu (111)
Interplanar distance is 0.208nm.
Fig. 6 is the electronic diffraction collection of illustrative plates of nanoporous Cu films obtained in embodiment 1, shows as the polycrystalline of standard
Cu electronic diffraction TuPu methods.
Embodiment 2：
An example for preparing nanoporous Copper thin film is present embodiments provided, the preparation method comprises the following steps：
(1) it is Mg from formula molecular formula61Cu28Gd11Presoma alloy, weigh raw material according to the formula,
Alloy melt is obtained after melting, alloy melt is prepared into 30 μm of width 4mm thickness by the method that copper roller gets rid of band
The Mg of left and right61Cu28Gd11AMORPHOUS ALLOY RIBBONS.
As shown in figure 1, the glass transformation temperature of the AMORPHOUS ALLOY RIBBONS is 145 DEG C.
(2) at room temperature, it is the 30mL that submerges of Mg base noncrystal alloy bands obtained in 0.1 gram of step (1) is dense
Spending in the aqueous sulfuric acid for 0.02mol/L carries out alloy and reacts.In course of reaction, Mg base noncrystal alloys
Mg of the strip sample from the surface internally thin layer of direction about 100nm thickness and Gd atoms and hydrogen from
Son reaction becomes ion and enters solution, and metal target Cu that nanometer is then formed in this thin layer of the band is more
Hole Cu layers.Under this layer nanoporous Cu layers of obstruct, further reaction produce reaction latent heat be difficult to
Solution carries out sufficient convective heat exchange, makes heat office near the reaction interface within Cu layers of the nanoporous
Portion gathers, when temperature herein is more than Mg61Cu28Gd11During glass transformation temperature (145 DEG C) of non-crystaline amorphous metal
Form nanoporous Cu layers of a solid-liquid interface, i.e. solid-state and the Mg of glassy state61Cu28Gd11Amorphous is closed
The interface of gold.In the presence of the hydrogen for reacting generation near the solid-liquid interface, the nanoporous Cu of solid-state
Thin layer is peeled off from the Mg base noncrystal alloys of the glassy state, and the nanoporous Cu for obtaining thickness about 100nm is thin
Film.Directly preserved or kept dry after nanoporous Cu films are cleaned with deionized water or ethanol.
Fig. 7 is the scanning electron micrographs of nanoporous Cu films obtained above.Therefrom it can be seen that, institute
The thickness of the nanoporous Cu films of preparation is about 100nm.
Embodiment 3：
An example for preparing nanoporous Ni films is present embodiments provided, the preparation method includes following step
Suddenly：
(1) it is Mg from formula molecular formula63Ni20Nd15Ca2Presoma alloy, weigh original according to the formula
Material, obtains alloy melt after melting, by the method that copper roller gets rid of band prepared by alloy melt into width 4mm thickness
30 μm or so of Mg63Ni20Nd15Ca2AMORPHOUS ALLOY RIBBONS.
The glass transformation temperature of the AMORPHOUS ALLOY RIBBONS is 170 DEG C or so.
(2) at room temperature, by Mg obtained in 0.1 gram of step (1)63Ni20Nd15Ca2AMORPHOUS ALLOY RIBBONS does not have
Enter 30mL concentration and reacted to carry out alloy in the aqueous hydrochloric acid solution of 0.05mol/L.In course of reaction, should
Mg, the Nd of Mg base noncrystal alloy strip samples from the surface internally thin layer of the μ m thick of direction about 2 with
The reaction of Ca atoms and hydrogen ion becomes ion and enters solution, and metal target Ni then the band this
Ni layers of nanoporous are formed in thin layer.Under the obstruct of Ni layers of the nanoporous, further reaction produce it is anti-
Answer latent heat to be difficult to carry out sufficient convective heat exchange with solution, make heat anti-within Ni layers of the nanoporous
Near interface local accumulation is answered, when temperature herein is more than Mg63Ni20Nd15Ca2The Glass Transition of non-crystaline amorphous metal
Nanoporous Ni layers of a solid-liquid interface, i.e. solid-state and the Mg of the glassy state is formed during temperature (170 DEG C)
The interface of base noncrystal alloy.In the presence of the hydrogen for reacting generation near the solid-liquid interface, the nanometer of solid-state
Porous Ni thin layers are peeled off from the Mg base noncrystal alloys, obtain nanoporous Ni films.By the nanoporous
Ni films are directly preserved or kept dry after being cleaned with deionized water or ethanol.
Fig. 8 is the scanning electron micrographs of nanoporous Ni films obtained above.Therefrom it can be seen that, institute
The thickness of the nanoporous Ni films of preparation is about 2 μm.
Embodiment 4：
An example for preparing nanoporous CuAg films is present embodiments provided, the preparation method includes as follows
Step：
(1) it is Mg from formula molecular formula61Cu21Ag7Gd11Presoma alloy, weighed according to the formula
Raw material, obtains alloy melt after melting, by the method that copper roller gets rid of band prepared by alloy melt into width 4mm thickness
The Mg of 100 μm or so of degree61Cu21Ag7Gd11AMORPHOUS ALLOY RIBBONS.
The glass transformation temperature of the AMORPHOUS ALLOY RIBBONS is 143 DEG C or so.
(2) at room temperature, by Mg obtained in 0.1 gram of step (1)61Cu21Ag7Gd11AMORPHOUS ALLOY RIBBONS does not have
Enter 30mL concentration and reacted to carry out alloy in the ethanol solution hydrochloride of 0.04mol/L.In course of reaction, Mg
Mg of the base noncrystal alloy strip sample from surface internally following certain thin layer of direction about 250nm thickness
Become ion with Gd atoms and hydrogen ion reaction and enter solution, and metal target Cu and Ag is then at this
Nanoporous CuAg thin layers are formed in this thin layer of band.Under the obstruct of CuAg layers of the nanoporous,
The reaction latent heat that further reaction is produced is difficult to carry out sufficient convective heat exchange with solution, makes heat in the nanometer
Local accumulation near reaction interface within porous C uAg layers, when temperature herein is more than Mg61Cu21Ag7Gd11
A solid-liquid interface, the i.e. nanoporous of solid-state are formed during glass transformation temperature (143 DEG C) of non-crystaline amorphous metal
CuAg layers with the Mg of glassy state61Cu21Ag7Gd1The interface of non-crystaline amorphous metal.Reacted near the solid-liquid interface
In the presence of the hydrogen of generation, the Mg base noncrystal alloys of the nanoporous CuAg thin layers of solid-state from glassy state
Peel off, obtain nanoporous CuAg films.By nanoporous CuAg films deionized water or ethanol
Directly preserved or kept dry after cleaning.
Fig. 9 is the scanning electron micrographs of nanoporous CuAg films obtained above.Therefrom it can be seen that,
The thickness of prepared nanoporous CuAg films is about 250nm.
Embodiment described above has been described in detail to technical scheme, it should be understood that above institute
Specific embodiment only of the invention is stated, is not intended to limit the invention, all institutes in spirit of the invention
Any modification, supplement or similar fashion replacement for making etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of nano porous metal film, it is characterized in that：Comprise the following steps：
Step 1：The preparation of presoma Mg base noncrystal alloys thin plate (piece) or strip
The formula molecular formula for selecting presoma alloy is MgaMbREcNd, it is first that wherein metal target M represents metal
Plain copper, nickel, silver, gold, palladium, platinum, tin, lead, zirconium, titanium, hafnium, vanadium, chromium, manganese, iron, cobalt, niobium,
One or several mixing in molybdenum, tungsten, tantalum, silicon, germanium, mercury, RE represent rare earth element yttrium, lanthanum,
One or several in cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium
Mixing, N represents one or several the mixing in zinc, aluminium, lithium, potassium, calcium, gallium, a, b, c and d
Represent the atom percentage content of each element, and 40%≤a≤80%, 1%≤c≤30%, 0≤d≤20%,
A+b+c+d=100%；
Raw material is weighed according to described formula, alloy melt is obtained after being melted, by alloy melt by quick
Solidification technology is prepared into presoma Mg base noncrystal alloys thin plate (piece) or strip that amorphous phase accounts for main body；
Step 2：Alloy reaction is gone to prepare nano porous metal film
Described presoma Mg base noncrystal alloys thin plate (piece) or strip are carried out into alloy with acid solution to react,
In course of reaction, the concentration of control acid solution temperature and/or acid makes Mg base noncrystal alloys thin plate (piece) or thin
Magnesium of the carry sample from the range of surface internally direction certain thickness, rare earth and other relatively active metal raws
Son preferentially becomes ion and enters solution with hydrogen ion reaction, forms the nano porous metal of metal target atomic building
Layer；Under the obstruct of nano porous metal layer, the accumulation of reaction latent heat is so that within nano porous metal layer
The local temperature of reaction interface exceedes the glass transformation temperature of non-crystaline amorphous metal and forms solid-liquid interface, is produced in reaction
In the presence of angry body, Mg base noncrystal alloy thin plate (piece) of the nano porous metal of the solid-state layer from glassy state
Or strip sample is peeled off, and obtains nano porous metal film.
2. the preparation method of nano porous metal film according to claim 1, it is characterized in that：It is described
Presoma Mg base noncrystal alloys thin plate (piece) or strip in, the percentage composition of amorphous phase is not less than 50%.
3. the preparation method of nano porous metal film according to claim 1, it is characterized in that：It is described
Presoma Mg base noncrystal alloys thin plate (piece) or strip glass transformation temperature be 75 DEG C -250 DEG C.
4. the preparation method of nano porous metal film according to claim 1, it is characterized in that：It is described
Acid is sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, carbonic acid, Portugal in acid solution
Grape saccharic acid, oleic acid, the mixing of one or more in polyacrylic acid.
5. the preparation method of nano porous metal film according to claim 1, it is characterized in that：It is described
Solvent is the mixed liquor of one or more in water, methyl alcohol, ethanol, isopropanol, acetone in acid solution.
6. the preparation method of nano porous metal film according to claim 1, it is characterized in that：It is described
The concentration of acid is 0.005mol/L-2mol/L in acid solution.
7. the preparation method of nano porous metal film according to claim 1, it is characterized in that：It is described
In course of reaction, the mean temperature of acid solution is -30 DEG C -80 DEG C.
8. the preparation method of nano porous metal film according to claim 1, it is characterized in that：It is described
Reaction time is 1min-300min.
9. the preparation side of the nano porous metal film according to any claim in claim 1 to 8
Method, it is characterized in that：The thickness of the nano porous metal film below 10 μm, further preferably at 4 μm
Hereinafter, more preferably 50nm-4 μm.
10. the preparation side of the nano porous metal film according to any claim in claim 1 to 8
Method, it is characterized in that：The thickness of the presoma Mg base noncrystal alloys thin plate (piece) or strip is not less than 10 μm,
The thickness of obtained nano porous metal film is 50nm-4 μm.
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| CN107831156A (en) * | 2017-10-20 | 2018-03-23 | 嘉兴长维新材料科技有限公司 | A kind of preparation method and its usage of copper-based 3-D nano, structure material |
| CN109763134A (en) * | 2018-12-27 | 2019-05-17 | 国联汽车动力电池研究院有限责任公司 | The preparation method of porous silicon |
| CN110486383A (en) * | 2019-08-27 | 2019-11-22 | 江苏集萃精凯高端装备技术有限公司 | A kind of production method of aerostatic bearing matrix and its surface micro-structure |
| CN110629175A (en) * | 2019-08-30 | 2019-12-31 | 西安工程大学 | Plasma porous structure with hot spot structure and preparation method thereof |
| CN110923746A (en) * | 2018-09-20 | 2020-03-27 | 天津大学 | Nano-porous Fe-P-C material, preparation method thereof and application thereof in hydrogen production by water electrolysis |
| CN111347056A (en) * | 2020-03-12 | 2020-06-30 | 东莞理工学院 | Preparation method of nano silver powder |
| CN111590084A (en) * | 2019-02-21 | 2020-08-28 | 刘丽 | Preparation method of metal powder material |
| CN111940750A (en) * | 2019-05-15 | 2020-11-17 | 刘丽 | Preparation method of alloy powder material |
| CN112143926A (en) * | 2019-11-28 | 2020-12-29 | 刘丽 | Preparation method and application of aluminum alloy-containing powder and alloy strip |
| CN112207285A (en) * | 2020-03-12 | 2021-01-12 | 赵远云 | Preparation method and application of powder material |
| CN113136499A (en) * | 2021-04-21 | 2021-07-20 | 中国科学院宁波材料技术与工程研究所 | Liquid metal with porous structure and preparation method thereof |
| CN113340962A (en) * | 2021-08-04 | 2021-09-03 | 湖南大学 | Copper-aluminum film electrode and preparation method and application thereof |
| WO2022036938A1 (en) * | 2020-08-19 | 2022-02-24 | 赵远云 | Preparation method for and use of high-purity powder material and biphasic powder material |
| WO2022036906A1 (en) * | 2020-08-19 | 2022-02-24 | 赵远云 | Preparation method for high-purity powder material, application of high-purity powder material, and alloy ribbon |
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| CN107831156A (en) * | 2017-10-20 | 2018-03-23 | 嘉兴长维新材料科技有限公司 | A kind of preparation method and its usage of copper-based 3-D nano, structure material |
| CN110923746A (en) * | 2018-09-20 | 2020-03-27 | 天津大学 | Nano-porous Fe-P-C material, preparation method thereof and application thereof in hydrogen production by water electrolysis |
| CN109763134A (en) * | 2018-12-27 | 2019-05-17 | 国联汽车动力电池研究院有限责任公司 | The preparation method of porous silicon |
| CN111590084A (en) * | 2019-02-21 | 2020-08-28 | 刘丽 | Preparation method of metal powder material |
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| CN111347056B (en) * | 2020-03-12 | 2022-08-23 | 东莞理工学院 | Preparation method of nano silver powder |
| WO2022036938A1 (en) * | 2020-08-19 | 2022-02-24 | 赵远云 | Preparation method for and use of high-purity powder material and biphasic powder material |
| WO2022036906A1 (en) * | 2020-08-19 | 2022-02-24 | 赵远云 | Preparation method for high-purity powder material, application of high-purity powder material, and alloy ribbon |
| CN114555264A (en) * | 2020-08-19 | 2022-05-27 | 赵远云 | Preparation method and application of high-purity powder material and two-phase powder material |
| CN114555264B (en) * | 2020-08-19 | 2023-04-28 | 赵远云 | Preparation method and application of high-purity powder material and two-phase powder material |
| WO2022041516A1 (en) * | 2020-08-27 | 2022-03-03 | 赵远云 | Preparation method and application of noble metal element-containing powder material |
| CN113136499B (en) * | 2021-04-21 | 2021-10-29 | 中国科学院宁波材料技术与工程研究所 | Liquid metal with porous structure and preparation method thereof |
| CN113136499A (en) * | 2021-04-21 | 2021-07-20 | 中国科学院宁波材料技术与工程研究所 | Liquid metal with porous structure and preparation method thereof |
| CN113340962A (en) * | 2021-08-04 | 2021-09-03 | 湖南大学 | Copper-aluminum film electrode and preparation method and application thereof |
| CN113340962B (en) * | 2021-08-04 | 2021-10-26 | 湖南大学 | Copper-aluminum film electrode for enzyme-free glucose sensor and preparation method and application thereof |
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