CN107470427A - A kind of preparation method of metal and its alloy micro nano structure or nano-wire array - Google Patents
A kind of preparation method of metal and its alloy micro nano structure or nano-wire array Download PDFInfo
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- CN107470427A CN107470427A CN201710647519.2A CN201710647519A CN107470427A CN 107470427 A CN107470427 A CN 107470427A CN 201710647519 A CN201710647519 A CN 201710647519A CN 107470427 A CN107470427 A CN 107470427A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/02—Stamping using rigid devices or tools
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D37/00—Tools as parts of machines covered by this subclass
- B21D37/16—Heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention belongs to Materials Science and Engineering technical field, is related to a kind of pressure forming preparation method that metal and its alloy micro nano structure or nano-wire array are prepared by compression molding.This method comprises the following steps：Step 1：Sheet metal or alloy sheet are surface-treated；Step 2：Prepare template；Step 3：Compression molding；Step 4：Unloading；Step 5：The demoulding.The inventive method both without the technological requirement of complicated cyclic voltammetry pulse electrodeposition, need not add any organic surface active agent again, it is not required that carry out complicated sensitization and activation process to template hole wall.Using this method, metal nanometer line (such as Au, Ag, Cu, Fe, Ni nano wire) and gold and silver solid solution alloy nano wire (such as Au a wide range of, uniform, near monocrystalline can be obtained26Ag74Nano wire).The controllable metal of low cost and its alloy micro nano structure can be achieved in the present invention or prepared by nano wire mass, has important and far-reaching meaning for application that disclose metal and its alloy basis performance principle or extensive and depth.
Description
Technical field
The invention belongs to Materials Science and Engineering technical field, is related to one kind and prepares metal and its alloy by compression molding
The method of micro nano structure or nano-wire array.
Background technology
Since Japanese Sumio Iijima in 1991 report CNT first, monodimension nanometer material, which causes, to be ground
Study carefully the extensive concern of personnel, one-dimensional nano structure has nano wire, nanometer rods, nanotube, nanobelt etc..Metal nanometer line due to
Nanoscale is on two-dimensional directional, quantum size effect that it has, skin effect, quantum tunneling effect, dielectric confinement effect
It should can be caused to show the macro properties such as the power different from conventional blocks material, heat, light, electricity, magnetic, cause Condensed Matter Physics
The concern on boundary, region of chemistry and material supply section educational circles scientist, turn into the focus of nano materials research in recent years.
Metal nanometer line has the advantages that high mechanical strength, good conductivity and big specific surface area, and it is in catalyst and absorption
Had broad application prospects in terms of agent.Metal nanometer line due to peculiar electricity, optics, magnetics and thermal property,
The fields such as microelectronics, photoelectron, catalysis and sensor have potential application prospect.The common synthetic method master of metal nanometer line
There are cyclic voltammetry electrodeposit metals nano wire, gas phase thermochemical reduction method, outfield in porous anodic alumina template to lure
Inducing defecation by enema and suppository, self-assembly method, laser ablation method, laser deposition, gas evaporation condensation method.However, these methods have its can not gram
The shortcomings that taking.Electro-deposition method can have chemical contamination in preparation process, and the nano wire prepared is polycrystalline；External field evoked method
Need to introduce expensive magnetic field means, and low production efficiency；Self-assembly method must add organic surface in building-up process and live
Property agent needs to be sensitized the hole wall of template and activation process.Not only experimentation complexity is numerous for these existing experimental methods
It is trivial, and certain environmental pollution can be caused.More importantly gained nano wire is generally polycrystalline, and nano wire supports with bottom
Electric conductivity is bad between substrate.Therefore, find a kind of has excellent electric contact and nano wire is similar to the simple of monocrystalline with bottom
The pervasive metal nanometer line preparation method of high-efficiency and economic has extensively and profound significance for the practical application of metal nanometer line.
Therefore, the present invention proposes a kind of simple, economic, green, pervasive mechanical property excellent using metal or alloy
By hot moulding (or hot extrusion) shaping or room temperature be molded (or room temperature extruding) technique prepare large area and uniform metal and its
The method of alloy micro nano structure or nano-wire array.This method is both without the technique of complicated cyclic voltammetry pulse electrodeposition
It is required that any organic surface active agent need not be added again, it is not required that template hole wall is carried out at complicated sensitization and activation
Reason, and only need to fold porous anodic alumina template or the silicon template with complicated micro-nano pattern with metal or alloy paillon foil
Close, under certain temperature pressure, can be formed in the nano pore of alumina formwork respective metal nano-wire array or
Corresponding micro nano structure is obtained on metal or alloy paillon foil.Required temperature covers room temperature (T during preparationrm) arrive fusing point (Tm) half
(Trm<T<~0.5Tm).Using this method, can obtain few defect, near monocrystalline metal nanometer line (such as Au, Ag, Cu,
Fe, Ni nano wire) and alloy nano-wire (such as Au26Ag74Nano wire), realize the controllable nano wire mass production of low cost.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of metal and its mould of alloy micro nano structure or nano-wire array
Molded (room temperature extrusion forming or hot extrusion molding) preparation method.
A kind of metal and its preparation method of alloy micro nano structure or nano-wire array, comprise the following steps：
Step 1：Sheet metal (or paillon foil or thin plate) or alloy sheet (or paillon foil or thin plate) are surface-treated：By gold
The one side of category or alloy sheet carries out sanding and polishing (mechanical polishing or electrochemical polish), obtains the smooth metal in a side surface or conjunction
Gold foil, obtained paillon foil is cleaned by ultrasonic repeatedly in acetone, ethanol, deionized water respectively, taken out stand-by after drying；
Step 2：Prepare template：From the double of special pore size distribution (such as 20nm, 30nm, 100nm, 200nm, 400nm and more than)
Logical porous anodic aluminium oxide or single-pass porous anodic aluminium oxide use laser ablation into the silicon with complicated micro-nano structure pattern
Template of the template as metal or alloy paillon foil extrusion forming；Or using the other materials with micro nano structure as metal or
Alloy forming panel.
Step 3：Hot moulding or room temperature compression molding：By the sheet metal (or paillon foil or thin plate) after side polishing in step 1
Or bilateral porous anodic aluminium oxide or single-pass porous anodic aluminium oxide described in alloy sheet (or paillon foil or thin plate) and step 2 or
Silicon template with complicated microwave structure pattern is positioned in mould afterwards together to folded close contact.It is pressed into for hot-die
Type, is heated above the recrystallization temperature of metal or alloy, and is incubated a period of time, makes template, metal or alloy temperature consistent,
Then certain pressure is applied, pressure should be greater than the yield strength of metal or alloy at such a temperature, and in the temperature and pressure
Lower pressurize is for a period of time.For room temperature molding or low temperature (between room temperature and its recrystallization temperature) compression molding, then step is to incite somebody to action
Anodic oxidation aluminium formwork (or silicon template described in shiny surface and the step 2 of tinsel in step 1 after the polishing of side
Deng) relatively, close contact is positioned in mould afterwards together, and direct weighting carries out room temperature compression molding or keeps temperature to certain
Compression molding under one design temperature (under recrystallization temperature), the pressure of application should be greater than metal or alloy bending at such a temperature
Take intensity, and pressurize is for a period of time at this temperature and pressure；
Step 4：Mould is first cooled down, after temperature drops to room temperature, sheds the pressure of application, and remove template and metal or conjunction
Gold plaque (or paillon foil or thin plate), now, the metal or alloy piece (or paillon foil or thin plate) are brought into close contact with template, and are formed
The micro nano structure corresponding with template；
Step 5：The demoulding：Step 4 gained metal or alloy piece (or paillon foil or thin plate) and template are positioned over 60~90 DEG C
In KOH or NaOH solution that concentration is 3mol/L, left-right template is corroded completely within about 1 hour, so as to realize metal or alloy paper tinsel
The separation of piece and template, obtain that there is the metal or alloy piece of micro-nano structure or nano-wire array (or paillon foil or thin plate).
The sheet metal (or paillon foil or thin plate) is the metal materials such as Au, Ag, Cu, Fe, Sn, Ni；The alloy sheet (or
Paillon foil or thin plate) it is a variety of alloy materials such as gold and silver solid solution alloy；Nano wire in the nano-wire array is in single dispersing point
What cloth or part nano wire overlapped is uniformly distributed, and the characteristic size of the nanostructured (is used by 20~400nm
Anodic oxidation aluminium formwork aperture limitation), length (is limited) up to 70 μm by used anodic oxidation aluminium formwork depth.
The thickness of the sheet metal or alloy sheet is more than 0.01mm., can if the deeper template of the smaller depth in aperture can be obtained
To prepare the longer nano-wire array of the smaller length of characteristic size.
In the step 3, the material of the mould is medium and high carbon steel or steel alloy with sufficient intensity, lumenal cross-section
Shape is consistent with metal or alloy piece (or paillon foil or thin plate), template with size, to ensure metal or alloy foil sheet in shaping
Pressure is consistent everywhere, and cavity heights are about 30mm (can be adjusted flexibly according to demand).
In the hot embossing process of the step 3, by the metal or alloy piece (or paillon foil or thin plate) and anode after polishing
After alumina formwork or silicon template overlapping, be heated to after certain temperature and be incubated, then by the template being superimposed together and
Metal or alloy piece (or paillon foil or thin plate) (can use in 200~500MPa pressure according to conditions such as specimen material, temperature
Higher or lower pressure) under keep 30~60 minutes (according to the requirement of the length of gained micro-nano structure, can suitably shorten or
Extend the dwell time to obtain shorter or longer nano wire).
During the room temperature of the step 3 or low temperature compression molding, by after polishing metal or alloy piece (or paillon foil,
Or thin plate) and anodic oxidation aluminium formwork or silicon template overlapping after, be heated to after certain temperature and be incubated, then will be superimposed on
Template together and metal or alloy piece (or paillon foil or thin plate) are in 200~500MPa pressure (according to specimen material, temperature etc.
Condition can use higher or lower pressure) under keep 30~60 minutes (according to the requirement of the length of gained micro nano structure,
It suitably can shorten or extend the dwell time to obtain shorter or longer nano wire).The heating-up temperature or design temperature are
Room temperature (Trm) to fusing point (Tm) half temperature (Trm<T<~0.5Tm)
A kind of preparation method of metal and its alloy micro nano structure or nano-wire array, it is characterised in that：The metal
And its alloy micro nano structure and nano-wire array are obtained by above-mentioned preparation method.
The metal or alloy nano-wire array being prepared by this method is extruded from corresponding metal or alloy substrate
Obtain, closely take root in metal or alloy substrate, form firm micro nano structure.It is described that there is micro nano structure or receive
The metal and alloy of nanowire arrays can be directly as catalysis material, energy storage or switching devices, photoelectric nano device etc..This hair
Bright has the beneficial effect that：
1. the metal or alloy nano-wire array draw ratio that the present invention is prepared can be by changing temperature, pressure and guarantor
The test parameters such as warm time adjust, and maximum draw ratio is more than 2000.The hot-forming principle for obtaining metal nanometer line is high temperature
Simultaneously dynamic recrystallization occurs simultaneously for hot extrusion deformation, therefore can obtain defect under conditions of big processing hardening does not occur
Less, the nano-wire array or micro nano structure of the high intimate monocrystalline of quality.
2. the method that the present invention prepares metal and its alloy nanowire array by hot compression molding has side simple to operate
Just, production efficiency is high, the advantages that green economy, it is not necessary to which the expensive equipment such as magnetron sputtering, atomic deposition can be obtained by greatly
The uniform nano-wire array of area, solve revolutionaryly and prepare metal nanometer line array method complexity, problem with high costs.
3. the present invention greatest feature be using from top to bottom, from bulky metals material manufacture there is micro nano structure
Or the method for the metal or alloy nano material of nano-wire array.
Brief description of the drawings
Fig. 1 prepares metal and its alloy micro nano structure for the present invention or the compression molding device structure of nano-wire array is shown
It is intended to.The heatable seaming chuck of 1- hydraulic presses in figure；The upper punching blocks of 2-；3- sheet metals/alloy sheet；4- porous anodic alumina templates
Or the silicon template with complicated micro-nano structure；Punching block under 5-；The heatable push-down head of 6- hydraulic presses.
Fig. 2 is the compression molding process signal that the present invention prepares metal and its alloy micro nano structure or nano-wire array
Figure；
Fig. 3 is the technological process for the pressure forming that the present invention prepares metal and its alloy micro nano structure or nano-wire array
Figure；
Fig. 4 a-4c are that the ESEM of the Crystal structure for a diameter of 200nm that the embodiment of the present invention 1 is prepared shines
Piece；
Fig. 4 d-4f are that the ESEM of the Crystal structure for a diameter of 100nm that the embodiment of the present invention 1 is prepared shines
Piece；
Fig. 4 g-4i are that the ESEM of the Crystal structure for a diameter of 50nm that the embodiment of the present invention 1 is prepared shines
Piece；
Fig. 4 j-4l are that the ESEM of the Crystal structure for a diameter of 30nm that the embodiment of the present invention 1 is prepared shines
Piece；
Fig. 4 c, the Crystal structure that 4f, 4i, 4l are the different-diameter that the embodiment of the present invention 1 is prepared cross section
Stereoscan photograph；
Fig. 5 be the embodiment of the present invention 2 be prepared a diameter of 50nm, length is up to 20 μm of nanowires of gold ESEM
Photo；
Fig. 6 a-6b are that the ESEM of the silver nano line array for a diameter of 200nm that the embodiment of the present invention 3 is prepared shines
Piece；
Fig. 6 c-6d are that the ESEM of the silver nano line array for a diameter of 100nm that the embodiment of the present invention 3 is prepared shines
Piece；
Fig. 6 e-6f are that the ESEM of the silver nano line array for a diameter of 50nm that the embodiment of the present invention 3 is prepared shines
Piece；
Fig. 6 g-6h are that the ESEM of the silver nano line array for a diameter of 30nm that the embodiment of the present invention 3 is prepared shines
Piece；
Fig. 7 a-7b are that the ESEM of the Arrays of Copper Nanowires for a diameter of 200nm that the embodiment of the present invention 4 is prepared shines
Piece；
Fig. 7 c-7d are that the ESEM of the Arrays of Copper Nanowires for a diameter of 100nm that the embodiment of the present invention 4 is prepared shines
Piece；
Fig. 7 e-7f are that the ESEM of the Arrays of Copper Nanowires for a diameter of 50nm that the embodiment of the present invention 4 is prepared shines
Piece；
Fig. 7 g-7h are that the ESEM of the Arrays of Copper Nanowires for a diameter of 30nm that the embodiment of the present invention 4 is prepared shines
Piece；
Fig. 8 is the ESEM of the electrum nano-wire array for a diameter of 30nm that the embodiment of the present invention 5 is prepared
Photo；
Fig. 9 is the stereoscan photograph of the Crystal structure for a diameter of 400nm that the embodiment of the present invention 6 is prepared；
Figure 10 is the stereoscan photograph for the microwave structure pattern that the embodiment of the present invention 7 is prepared using silicon template,
Left side is the stereoscan photograph of the microwave structure pattern for the silicon template that the embodiment of the present invention 7 uses, and right side is real for the present invention
Apply the stereoscan photograph with the micro nano structure corresponding with silicon die plate pattern that example 7 is prepared；
Figure 11 is the stereoscan photograph of the Fe nanowire array for a diameter of 30nm that the embodiment of the present invention 8 is prepared；
Figure 12 is the stereoscan photograph of the nickel nano-wire array for a diameter of 200nm that the embodiment of the present invention 9 is prepared；
Figure 13 is that the ESEM of the silver nano line array for a diameter of 20nm that the embodiment of the present invention 10 is prepared is transversal
Face photo.
Embodiment
The invention provides a kind of metal and its preparation method of alloy micro nano structure or nano-wire array, with reference to
The present invention will be further described for drawings and examples.
Fig. 1 is the apparatus structure for the compression molding that the present invention prepares metal and its alloy micro nano structure or nano-wire array
Schematic diagram.As shown in figure 1, the device includes：The hydraulic press upper press head 1 and hydraulic press push-down head 6 of a pair of opposing, can pass through
Move up and down and sample therebetween pressurizeed and the pressurize under a certain pressure, metal or alloy paillon foil in a certain strain rate or
Deformed under a certain pressure；Push-down head can be heated by temperature regulating device and adjust temperature on hydraulic press, further be passed through
Heat transfer is to inside the steel mould (comprising upper punching block 2 and lower punching block 5) and steel mould that are placed on hydraulic press push-down head 6
Sample to be processed (including metal or with alloy foil sheet 3 and porous anodic alumina template or silicon template 4) heated so that
The temperature of metal or alloy paillon foil reaches design temperature.
The present invention prepares technological process such as Fig. 2 of the compression molding of metal and its alloy micro nano structure or nano-wire array
It is shown.
Embodiment 1
Different-diameter (30-200nm) Crystal structure is prepared by hot compression molding：
Gold foil is cut into required size 10mm*10mm, 10mm*10mm paillon foil mechanically polished, Ran Houfen
It is not cleaned by ultrasonic repeatedly in acetone, ethanol, deionized water, takes out stand-by after drying.
Bilateral porous anodic alumina template is prepared using Two-step anodization, the form plate hole distribution of the alumina formwork is equal
Even, hole diameter 30-200nm, hole depth is 70 μm of porous oldered array.
Lower punching block 5 is placed in the top of hydraulic press push-down head 6, bilateral porous anodic alumina template 4 is positioned over lower punching block 5
It is interior, the goldleaf 3 of 10mm*10mm sizes is then placed in the surface of template 4, the one side that goldleaf 3 polishes closely is pasted with template 4
Close, cover punching block 2.The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is opened, with the speed of 15 centigrade per minutes
After rate is heated to 350 degrees Celsius, 30 minutes are incubated, the temperature of goldleaf 3 is reached 350 degrees Celsius, passes through the seaming chuck 1 of hydraulic press
With moving up and down to apply pressure for push-down head 6, when the pressure of gold foil increases to 500MPa, pressurize 30 minutes, Ran Houguan
The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is closed, is gas-cooled to room temperature, then unloading pressure.Take out steel mould
(including goldleaf 3 and anodic oxidation aluminium formwork 4), then opens steel mould, takes out goldleaf 3 and anodic oxidation aluminium formwork 4, now
Goldleaf 3 and anodic oxidation aluminium formwork 4 are sticked together, and the surface of the goldleaf 3 forms corresponding with anodic oxidation aluminium formwork
Ordered nano linear array.
It is in 3mol/L KOH solution by the concentration that the goldleaf 3 being sticked together and anodic oxidation aluminium formwork 4 are placed in 60 DEG C
3 hours, anodic oxidation aluminium formwork 4 was departed from and corroded from goldleaf 3 completely, is cleaned goldleaf 3 repeatedly with deionized water afterwards, is obtained
To a diameter of 200nm, 100nm, 50nm, 30nm, length is up to 2-6 μm of uniform sequential Crystal structure, such as Fig. 4 institutes
Show.
Embodiment 2
A diameter of 50nm, length are prepared up to 20 μm of Crystal structure by hot compression molding：
Gold foil is cut into required size 10mm*10mm, paillon foil mechanically polished, then respectively in acetone, second
It is cleaned by ultrasonic repeatedly in alcohol, deionized water, takes out stand-by after drying.
Porous anodic alumina template is prepared using Two-step anodization, the form plate hole hole distribution of the alumina formwork is equal
Even, hole diameter 50nm, hole depth is 70 μm of porous oldered array.
Lower punching block 5 is placed in the top of hydraulic press push-down head 6, bilateral porous anodic alumina template 4 is positioned over lower punching block 5
It is interior, the goldleaf 3 of 10mm*10mm sizes is then placed in the surface of template 4, the one side that goldleaf 3 polishes closely is pasted with template 4
Close, cover punching block 2.The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is opened, with the speed of 15 centigrade per minutes
After rate is heated to 350 degrees Celsius, 30 minutes are incubated, the temperature of goldleaf 3 is reached 350 degrees Celsius, passes through the upper of hydraulic press
Pressure head 1 and push-down head 6 are moved up and down to apply pressure, and when the pressure of gold foil increases above 500MPa, pressurize 30 divides
Clock, the temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is then shut off, be gas-cooled to room temperature, then unloading pressure.
Steel mould (comprising goldleaf 3 and anodic oxidation aluminium formwork 4) is taken out, steel mould is then opened, takes out goldleaf 3 and anodised aluminium
Template 4, now goldleaf 3 and anodic oxidation aluminium formwork 4 be sticked together, the surface of the goldleaf 3 is formed and anodic oxidation aluminum dipping form
The corresponding ordered nano linear array of plate.
It is molten for 3mol/L KOH that the goldleaf 3 being sticked together and anodic oxidation aluminium formwork 4 are placed in 60 degrees Celsius of concentration
3 hours in liquid, anodic oxidation aluminium formwork 4 is departed from and eroded from gold foil 3 completely, is cleaned repeatedly with deionized water afterwards
Gold foil 3, obtains a diameter of 50nm, and length is up to 20 μm of uniform sequential Crystal structure, as shown in Figure 5.
Embodiment 3
Different-diameter (30nm-200nm) silver nano line array is prepared by hot compression molding：
Silver foil piece is cut into required size 10mm*10mm, paillon foil mechanically polished, then respectively in acetone, second
It is cleaned by ultrasonic repeatedly in alcohol, deionized water, takes out stand-by after drying.
Bilateral porous anodic alumina template is prepared using Two-step anodization, the form plate hole distribution of the alumina formwork is equal
Even, a diameter of 30nm-200nm, hole depth is 70 μm of porous oldered array.
Lower punching block 5 is placed in the top of hydraulic press push-down head 6, bilateral porous anodic alumina template 4 is positioned over lower punching block 5
It is interior, the silver foil 3 of 10mm*10mm sizes is then placed in the surface of template 4, the one side that silver foil 3 polishes closely is pasted with template 4
Close, cover punching block 2.The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is opened, with the speed of 15 centigrade per minutes
After rate is heated to 350 degrees Celsius, 30 minutes are incubated, the temperature of silver foil 3 is reached 350 degrees Celsius, passes through the seaming chuck 1 of hydraulic press
With moving up and down to apply pressure for push-down head 6, when the pressure of silver foil piece increases to 500MPa, pressurize 30 minutes, Ran Houguan
The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is closed, is gas-cooled to room temperature, then unloading pressure.Take out steel mould
(including silver foil 3 and anodic oxidation aluminium formwork 4), then opens steel mould, takes out silver foil 3 and anodic oxidation aluminium formwork 4, now
Silver foil 3 and anodic oxidation aluminium formwork 4 are sticked together, and the surface of the silver foil 3 forms corresponding with anodic oxidation aluminium formwork
Ordered nano linear array.
It is molten for 3mol/L KOH that the silver foil 3 being sticked together and anodic oxidation aluminium formwork 4 are placed in 60 degrees Celsius of concentration
3 hours in liquid, anodic oxidation aluminium formwork 4 is departed from and corroded from silver foil 3 completely, cleans silver foil repeatedly with deionized water afterwards
3, a diameter of 200nm, 100nm, 50nm, 30nm uniform sequential silver nano line array are obtained, as shown in Figure 6.
Embodiment 4
Different-diameter (30nm-200nm) Arrays of Copper Nanowires is prepared by hot compression molding：
Copper foil is cut into required size 10mm*10mm, paillon foil is carried out to electrification in 0.5mol/L sulfuric acid solution
Optical polishing, then it is cleaned by ultrasonic repeatedly in acetone, ethanol, deionized water respectively, takes out stand-by after drying.
Bilateral porous anodic alumina template is prepared using Two-step anodization, the form plate hole distribution of the alumina formwork is equal
Even, hole diameter 30nm-200nm, pitch of holes 110nm, hole depth are 70 μm of porous oldered array.
Lower punching block 5 is placed in the top of hydraulic press push-down head 6, bilateral porous anodic alumina template 4 is positioned over lower punching block 5
It is interior, the copper sheet 3 of 10mm*10mm sizes is then placed in the surface of template 4, the one side that copper sheet 3 polishes closely is pasted with template 4
Close, cover punching block 2.The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is opened, with the speed of 15 centigrade per minutes
After rate is heated to 350 degrees Celsius, 30 minutes are incubated, the temperature of copper sheet 3 is reached 350 degrees Celsius, passes through the seaming chuck 1 of hydraulic press
With moving up and down to apply pressure for push-down head 6, when the pressure of copper sheet increases to 500MPa, pressurize 30 minutes, it is then shut off
The temperature control heating device of hydraulic press upper press head 1 and push-down head 6, it is gas-cooled to room temperature, then unloading pressure.Take out steel mould
(including copper sheet 3 and anodic oxidation aluminium formwork 4), then opens steel mould, takes out copper sheet 3 and anodic oxidation aluminium formwork 4, now
Copper sheet 3 and anodic oxidation aluminium formwork 4 are sticked together, and the surface of the copper sheet 3 forms corresponding with anodic oxidation aluminium formwork
Ordered nano linear array.
It is molten for 3mol/L KOH that the copper sheet 3 being sticked together and anodic oxidation aluminium formwork 4 are placed in 60 degrees Celsius of concentration
3 hours in liquid, anodic oxidation aluminium formwork 4 is departed from and corroded from copper sheet 3 completely, cleans copper sheet repeatedly with deionized water afterwards
3, a diameter of 200nm, 100nm, 50nm, 30nm uniform sequential Arrays of Copper Nanowires are obtained, as shown in Figure 7.
Embodiment 5
The nominal composition that diameter 30nm is prepared by hot compression molding is Au26Ag74Electrum nano-wire array：
Electrum piece is cut into required size 10mm*10mm, paillon foil mechanically polished, then respectively third
It is cleaned by ultrasonic repeatedly in ketone, ethanol, deionized water, takes out stand-by after drying.
Bilateral porous anodic alumina template is prepared using Two-step anodization, the form plate hole distribution of the alumina formwork is equal
Even, a diameter of 30nm, hole depth is 70 μm of porous oldered array.
Lower punching block 5 is placed in the top of hydraulic press push-down head 6, bilateral porous anodic alumina template 4 is positioned over lower punching block 5
It is interior, the electrum piece 3 of 10mm*10mm sizes is then placed in the surface of template 4, the one side that electrum piece 3 polishes with
Template 4 is brought into close contact, and covers punching block 2.The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is opened, with 15 degrees Celsius
After speed per minute is heated to 300 degrees Celsius, 30 minutes are incubated, the temperature of electrum piece 3 is reached 300 degrees Celsius, led to
The seaming chuck 1 of hydraulic press and moving up and down to apply pressure for push-down head 6 are crossed, when the pressure of electrum piece increases to 400MPa
When, pressurize 30 minutes, the temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is then shut off, be gas-cooled to room temperature, so
Unloading pressure afterwards.Steel mould (comprising electrum piece 3 and anodic oxidation aluminium formwork 4) is taken out, steel mould is then opened, takes out
Electrum piece 3 and anodic oxidation aluminium formwork 4, now electrum piece 3 and anodic oxidation aluminium formwork 4 be sticked together, the gold
The surface of silver alloy film 3 forms the ordered nano linear array corresponding with anodic oxidation aluminium formwork.
It is 3mol/L by the concentration that the electrum piece 3 being sticked together and anodic oxidation aluminium formwork 4 are placed in 60 degrees Celsius
KOH solution in 3 hours, anodic oxidation aluminium formwork 4 is departed from and corroded from electrum piece 3 completely, uses deionization afterwards
Water cleans electrum piece 3 repeatedly, obtains a diameter of 30nm uniform sequential electrum nano-wire array, as shown in Figure 8.
Embodiment 6
Diameter 400nm gold nano lattice array is prepared by room temperature compression molding：
By gold plaque be cut into needed for size 10mm*10mm, paillon foil is mechanically polished, then respectively acetone, ethanol,
It is cleaned by ultrasonic repeatedly in deionized water, takes out stand-by after drying.
Bilateral porous anodic alumina template is prepared using Two-step anodization, the form plate hole distribution of the alumina formwork is equal
Even, a diameter of 400nm, hole depth is 70 μm of porous oldered array.
Lower punching block 5 is placed in the top of hydraulic press push-down head 6, bilateral porous anodic alumina template 4 is positioned over lower punching block 5
It is interior, the gold plaque 3 of 10mm*10mm sizes is then placed in the surface of template 4, the one side that gold plaque 3 polishes closely is pasted with template 4
Close, cover punching block 2.At room temperature by the seaming chuck 1 of hydraulic press and moving up and down to apply pressure for push-down head 6, work as gold
When the pressure of piece increases to 400MPa, unloading pressure after pressurize 30 minutes.Take out steel mould and (include gold plaque 3 and anodised aluminium
Template 4), steel mould is then opened, takes out gold plaque 3 and anodic oxidation aluminium formwork 4, now gold plaque 3 and anodic oxidation aluminium formwork 4
It is sticked together, the surface of the gold plaque 3 forms the ordered nano lattice array corresponding with anodic oxidation aluminium formwork.
It is molten for 3mol/L KOH that the gold plaque 3 being sticked together and anodic oxidation aluminium formwork 4 are placed in 60 degrees Celsius of concentration
3 hours in liquid, anodic oxidation aluminium formwork 4 is departed from and corroded from gold plaque 3 completely, cleans gold plaque repeatedly with deionized water afterwards
3, a diameter of 400nm uniform sequential gold nano lattice array is obtained, as shown in Figure 9.
Embodiment 7
It is corresponding with silicon template by hot compression molding preparation using the silicon template with complicated microwave structure pattern
Silver-colored microwave structure pattern：
Silver foil piece is cut into required size 10mm*10mm, paillon foil mechanically polished, then respectively in acetone, second
It is cleaned by ultrasonic repeatedly in alcohol, deionized water, takes out stand-by after drying.
The silicon template with complicated micro nano structure, micro nano structure such as Figure 10 left sides institute of the template are obtained after photoetching
Show.
Lower punching block 5 is placed in the top of hydraulic press push-down head 6, silicon template 4 is positioned in lower punching block 5, then by 10mm*
The silver foil 3 of 10mm sizes is placed in the surface of template 4, and the one side that silver foil 3 polishes is brought into close contact with template 4, covers punching block 2.
The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is opened, it is Celsius to be heated to 400 with the speed of 15 centigrade per minutes
After degree, be incubated 30 minutes, the temperature of silver foil 3 is reached 400 degrees Celsius, by the seaming chuck 1 of hydraulic press and push-down head 6 up and down
Move to apply pressure, when the pressure of silver foil piece increases to 100MPa, pressurize 60 minutes, be then shut off hydraulic press upper press head 1
With the temperature control heating device of push-down head 6, it is gas-cooled to room temperature, then unloading pressure.Take out steel mould and (include silver foil 3 and silicon
Template 4), steel mould is then opened, takes out silver foil 3 and silicon template 4, now silver foil 3 and silicon template 4 are sticked together, the silver
The surface of paper tinsel 3 forms the complicated microwave structure pattern corresponding with silicon template.
It is small in 1mol/L KOH solution 3 that the silver foil 3 being sticked together and silicon template 4 are placed in 80 degrees Celsius of concentration
When, silicon template 4 is departed from and corroded from silver foil 3 completely, cleans silver foil 3 repeatedly with deionized water, obtains the institute on the right side of Figure 10
The micro nano structure shown.
Embodiment 8
A diameter of 30nm Fe nanowire array is prepared by hot compression molding：
Iron plate is cut into required size 10mm*10mm, paillon foil is subjected to electrochemistry in 0.5mol/L sulfuric acid solution
Polishing, is then cleaned by ultrasonic repeatedly in acetone, ethanol, deionized water respectively, takes out stand-by after drying.
Bilateral porous anodic alumina template is prepared using Two-step anodization, the form plate hole distribution of the alumina formwork is equal
Even, a diameter of 30nm, hole depth is 70 μm of porous oldered array.
Lower punching block 5 is placed in the top of hydraulic press push-down head 6, bilateral porous anodic alumina template 4 is positioned over lower punching block 5
It is interior, the iron plate 3 of 10mm*10mm sizes is then placed in the surface of template 4, the one side that iron plate 3 polishes closely is pasted with template 4
Close, cover punching block 2.The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is opened, with the speed of 15 centigrade per minutes
After rate is heated to 400 degrees Celsius, 30 minutes are incubated, the temperature of iron plate 3 is reached 400 degrees Celsius, passes through the seaming chuck 1 of hydraulic press
With moving up and down to apply pressure for push-down head 6, when the pressure of iron plate increases to 500MPa, pressurize 60 minutes, it is then shut off
The temperature control heating device of hydraulic press upper press head 1 and push-down head 6, it is gas-cooled to room temperature, then unloading pressure.Take out steel mould
(including iron plate 3 and anodic oxidation aluminium formwork 4), then opens steel mould, takes out iron plate 3 and anodic oxidation aluminium formwork 4, now
Iron plate 3 and anodic oxidation aluminium formwork 4 are sticked together, and the surface of the iron plate 3 forms corresponding with anodic oxidation aluminium formwork
Ordered nano linear array.
The iron plate 3 being sticked together and anodic oxidation aluminium formwork 4 are placed in 3 in the KOH solution that 80 DEG C of concentration are 1mol/L
Hour, anodic oxidation aluminium formwork 4 is departed from and corroded from iron plate 3 completely, cleans iron plate 3 repeatedly with deionized water, is obtained straight
Footpath is 30nm uniform sequential Fe nanowire array, as shown in figure 11.
Embodiment 9
A diameter of 200nm nickel nano-wire array is prepared by hot compression molding：
Nickel sheet is cut into required size 10mm*10mm, paillon foil is subjected to electrochemistry in 0.5mol/L sulfuric acid solution
Polishing, is then cleaned by ultrasonic repeatedly in acetone, ethanol, deionized water respectively, takes out stand-by after drying.
Bilateral porous anodic alumina template is prepared using Two-step anodization, the form plate hole distribution of the alumina formwork is equal
Even, hole diameter 200nm, hole depth is 70 μm of porous oldered array.
Lower punching block 5 is placed in the top of hydraulic press push-down head 6, bilateral porous anodic alumina template 4 is positioned over lower punching block 5
It is interior, the nickel sheet 3 of 10mm*10mm sizes is then placed in the surface of template 4, the one side that nickel sheet 3 polishes closely is pasted with template 4
Close, cover punching block 2.The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is opened, with the speed of 15 centigrade per minutes
After rate is heated to 400 degrees Celsius, 30 minutes are incubated, the temperature of nickel sheet 3 is reached 400 degrees Celsius, passes through the seaming chuck 1 of hydraulic press
With moving up and down to apply pressure for push-down head 6, when the pressure of nickel sheet increases to 500MPa, pressurize 60 minutes, it is then shut off
The temperature control heating device of hydraulic press upper press head 1 and push-down head 6, it is gas-cooled to room temperature, then unloading pressure.Take out steel mould
(including nickel sheet 3 and anodic oxidation aluminium formwork 4), then opens steel mould, takes out nickel sheet 3 and anodic oxidation aluminium formwork 4, now
Nickel sheet 3 and anodic oxidation aluminium formwork 4 are sticked together, and the surface of the nickel sheet 3 forms corresponding with anodic oxidation aluminium formwork
Ordered nano linear array.
The nickel sheet 3 being sticked together and anodic oxidation aluminium formwork 4 are placed in 3 in the KOH solution that 80 DEG C of concentration are 1mol/L
Hour, anodic oxidation aluminium formwork 4 is departed from and corroded from nickel sheet 3 completely, cleans nickel sheet 3 repeatedly with deionized water, is obtained straight
Footpath is 200nm uniform sequential nickel nano-wire array, as shown in figure 12.
Embodiment 10
A diameter of 20nm silver nano line array is prepared by hot compression molding：
Silver strip is cut into required size 10mm*10mm, paillon foil is subjected to electrochemistry in 0.5mol/L sulfuric acid solution
Polishing, is then cleaned by ultrasonic repeatedly in acetone, ethanol, deionized water respectively, takes out stand-by after drying.
Bilateral porous anodic alumina template is prepared using Two-step anodization, the form plate hole distribution of the alumina formwork is equal
Even, a diameter of 20nm, hole depth is 70 μm of porous oldered array.
Lower punching block 5 is placed in the top of hydraulic press push-down head 6, bilateral porous anodic alumina template 4 is positioned over lower punching block 5
It is interior, the silver strip 3 of 10mm*10mm sizes is then placed in the surface of template 4, the one side that silver strip 3 polishes closely is pasted with template 4
Close, cover punching block 2.The temperature control heating device of hydraulic press upper press head 1 and push-down head 6 is opened, with the speed of 15 centigrade per minutes
After rate is heated to 400 degrees Celsius, 30 minutes are incubated, the temperature of silver strip 3 is reached 400 degrees Celsius, passes through the seaming chuck 1 of hydraulic press
With moving up and down to apply pressure for push-down head 6, when the pressure of silver strip increases to 500MPa, pressurize 60 minutes, it is then shut off
The temperature control heating device of hydraulic press upper press head 1 and push-down head 6, it is gas-cooled to room temperature, then unloading pressure.Take out steel mould
(including nickel sheet 3 and anodic oxidation aluminium formwork 4), then opens steel mould, takes out silver strip 3 and anodic oxidation aluminium formwork 4, now
Silver strip 3 and anodic oxidation aluminium formwork 4 are sticked together, and the surface of the silver strip 3 forms corresponding with anodic oxidation aluminium formwork
Ordered nano linear array.
It is molten for 1mol/L KOH that the silver strip 3 being sticked together and anodic oxidation aluminium formwork 4 are placed in 80 degrees Celsius of concentration
3 hours in liquid, anodic oxidation aluminium formwork 4 is departed from and corroded from silver strip 3 completely, is cleaned nickel sheet 3 repeatedly with deionized water, is obtained
To a diameter of 20nm uniform sequential silver nano line array, as shown in figure 13.
Technical scheme is described in detail above-described embodiment.It is apparent that the present invention is not limited retouched
The embodiment stated.Based on the embodiment in the present invention, those skilled in the art can also make a variety of changes accordingly, but appoint
What is equal with the present invention or similar change belongs to the scope of protection of the invention.
Claims (8)
1. a kind of metal and its preparation method of alloy micro nano structure or nano-wire array, it is characterised in that including following step
Suddenly：
Step 1：Sheet metal or alloy sheet are surface-treated：The one side of sheet metal is subjected to sanding and polishing, obtains side table
Face smooth sheet metal or alloy sheet；
Step 2：Prepare template：Using the bilateral with different-diameter different depth nano aperture or single-pass anodised aluminium conduct
Metal or alloy hot moulding or the template of room temperature molding；Or made using laser ablation into the silicon template with complicated micro-nano pattern
The template being molded for metal or alloy hot moulding or room temperature；
Step 3：Compression molding：By step 1 gained side polish after sheet metal or alloy sheet shiny surface with it is made in step 2
To folded, close contact is positioned in mould standby template afterwards together, is heated above the recrystallization temperature of metal or alloy, and
Insulation a period of time, make template, metal or alloy temperature consistent, then apply certain pressure, the pressure should be greater than metal
Or the yield strength of alloy at such a temperature, and pressurize is for a period of time at this temperature and pressure；Or direct weighting in a mold
Compression molding under carrying out room temperature compression molding or keeping temperature to a certain design temperature, the pressure of application should be greater than metal or conjunction
Gold yield strength at such a temperature, and pressurize is for a period of time at this temperature and pressure；
Step 4：Unloading：Mould is first cooled down, temperature is reduced to room temperature, then sheds the pressure of application, and removes template and gold
Belong to piece or alloy sheet, now, the sheet metal or alloy sheet are brought into close contact with template, and micro-nano corresponding with template of formation
Structure；
Step 5：The demoulding：Sheet metal obtained by step 4 or alloy sheet and template are positioned in alkaline solution or acid solution, mould
Plate is corroded, and is dissolved in alkalescence or acid solution, so as to realize the separation of sheet metal or alloy sheet and template, finally obtains and mould
The sheet metal or alloy sheet of the consistent nano-wire array of harden structure or micro nano structure.
2. according to the method for claim 1, it is characterised in that：The sheet metal is gold, silver, copper, iron, tin, the sheet material of nickel
Or paper tinsel or thin plate；The alloy sheet is the sheet material or paper tinsel or thin plate of gold and silver solid solution alloy.
3. according to the method for claim 1, it is characterised in that：Nano wire in the nano-wire array shows a monodisperse distribution
Or nanowire cluster is got together and is distributed in aggregation, the characteristic size of the micro nano structure is 20~400nm, and length is up to 70
μm。
4. according to the method for claim 1, it is characterised in that：The thickness of the sheet metal or alloy sheet be 0.01mm with
On.
5. according to the method for claim 1, it is characterised in that：In step 3, the material of the mould is with sufficient intensity
Medium and high carbon steel or steel alloy, its lumenal cross-section shape is consistent with sheet metal or alloy sheet, template with size, to ensure metal
Pressure is consistent everywhere in shaping for piece or alloy sheet.
6. according to the method for claim 1, it is characterised in that：During the compression molding of step 3, the pressure of application is
200~500MPa；Described protect carried the time as 30~60 minutes, and the heating-up temperature or design temperature are room temperature to fusing point half
Temperature.
7. the metal or alloy micro nano structure or nanometer linear array that are prepared according to any one of claim 1-6 methods described
Row.
8. metal or alloy micro nano structure described in claim 7 or nano-wire array as catalysis material, energy storage or turn
The application of parallel operation part, photoelectric nano device.
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