CN100529196C - Preparation process of metal aluminium template for assembling nano-micron array material - Google Patents
Preparation process of metal aluminium template for assembling nano-micron array material Download PDFInfo
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- CN100529196C CN100529196C CNB2005100222192A CN200510022219A CN100529196C CN 100529196 C CN100529196 C CN 100529196C CN B2005100222192 A CNB2005100222192 A CN B2005100222192A CN 200510022219 A CN200510022219 A CN 200510022219A CN 100529196 C CN100529196 C CN 100529196C
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Abstract
The present invention relates to a preparing method of a template for assembling nanometer-micron array materials, which is characterized in that high-purity aluminum foil with 70% (100) of surface is pretreated and is etched in acid solution containing chloride ions; in the etching process, the aluminum foil is used as an anode, the density of current applied on the aluminum foil is from 0.1*10<4> to 7.0*10<7> A/m<2>, the concentration of the chloride ion solution of the etching liquid is from 0.5 mol. L<-1> to 6.0 mol. L<-1>, the concentration of acid is from 0.1 mol. L<-1> to 5.0 mol. L<-1>, etching temperature is from 60 to 90 DEG C, and etching time is from 2 to 200 s; after the etching process is finished, the hole diameters of the aluminum template can be further adjusted; the aluminum foil is washed by a great amount of clear water, the etching liquid remaining on the surface is washed, the aluminum foil is dried after a washing process, the aluminum tunnel hole template with the hole diameters of 100 to 2000 nm is obtained, and the aluminum tunnel hole template can be used for assembling the nanometer-micron array materials. The aluminum template prepared by the electrochemical method has the advantages of simple technology, low cost and controllable area, and compared with an aluminum-oxide template, the obtained high-purity aluminum foil has higher toughness and better mechanical strength and corrosion resistance. Various nanometer-micron array materials manufactured by the template can be widely used for the research and the application of the fields of light, electricity, magnetism, sound, heat, catalysis, nanometer machinery and nanometer electron devices.
Description
One, technical field
The present invention relates to a kind of metal form preparation method who is used for assembling nano-micrometre array material.
Two, background technology
Be used to make the method for nano material at present, as grinding, sol-gel method, the precipitator method, hydrolysis method etc., be suitable for nanometer powder research, its development time is longer, and technology is comparatively ripe, is the basis of other nano materials of preparation.But a big weakness of these technology is to be difficult to the structure of prepared material is effectively controlled.And synthesis of nano structural system can design, assemble, develop the still non-existent new substance system of the nature with specific function by people's wish, makes the various unusual character of nano material and function be brought into play more fully and utilize.
Template synthesis of nano structural unit (comprising zero-dimension nano particle, accurate monodimension nano stick, silk and pipe) and nano-structure array system are the cutting edge technologies that grows up over past ten years, are the integrated of physics, chemical several different methods.Come the character of the hierarchy of control with the more freedom degree for people with template synthesis of nano structure, for the components and parts that design nanostructure of future generation are laid a good foundation.
Obtaining nano-form is the prerequisite of synthesis of nano array of structures.Now commonly used have two kinds of templates, and a kind of is sequential holes array alumina formwork (AAO template), and another kind is the polymer template that contains the hole chaotic distribution.The template of other materials also has metal form, nano aperture glass, mesoporous zeolite, porous silicon template etc.
The making of polymer template is to utilize the high-energy particle bombardment polymer film, makes film forming local structure and changes, and carries out etching with chemical process then, all zones that is subjected to high-energy particle bombardment, and polymkeric substance dissolves easily, forms the uniform hole of diameter.But these ducts are not what be parallel to each other, and film thickness is generally 6-20 μ m, and the aperture 10nm of film is to the hundreds of nanometer, and hole density is about 10
5-10
10Individual/cm
2These films can prepare with polycarbonate, polyimide.The polymer lamina membranacea be soluble in solvent and make template and be deposited in nano material separate.In organic polymer films, successfully make Ni, Co nano wire, conductive polymers etc.
But the preparation condition of polymer template is comparatively harsh, and it also is unordered that the polymer pattern hole distributes, and is not columniform, and more ivory is signed shape, like this nano material that is deposited in the template is difficult to control and characterize.The chemical stability of high molecular polymer own is relatively poor, is easy to and other chemical reaction, and non-refractory, difficulty is improved the performance of film with the thermal treatment way.
Aluminum anodized film has high thermostability and chemical stability and nano level regular pore structure and comes into one's own.High-purity aluminium flake can obtain aluminum oxide through anodic oxidation in solution such as oxalic acid or sulfuric acid, the structure of pellumina can be divided into three layers: topmost be aluminum oxide porous layer, porous alumina and aluminium base between exist the atresia blocking layer.Therefore need adopt the way that progressively reduces voltage to come thinning barrier layer then with the molten aluminum substrate that goes of direct current, and then peel off and obtain aluminum oxide porous template.The pellumina hole that obtains is that hexagonal cylindricality vertical film face is in order and is arranged in parallel, and the aperture can be regulated in the 5-200nm scope, and hole density can reach 10
11Individual/cm
2These parameters can be regulated by the kind, concentration, temperature, voltage, electrolysis time and the last perforate operation that change electrolytic solution.Utilize the anodic oxidation aluminium formwork method successfully to prepare semi-conductor and metal nano material and carbon nanotubes such as CdS, Au, Fe, Cu, Ni.The length of these nanotubes, line, diameter can be controlled by changing experiment condition.
Regrettably the method for preparing pellumina needs for a long time, and once oxidation needs about 6 hours usually, and secondary oxidation 12 hours progressively reduces the voltage thinning barrier layer and the phosphoric acid through hole also needs the long period.And because pellumina is extremely thin and easily crisp, cracked easily from the film that the aluminium foil matrix strips down, curling and distortion, physical strength is very poor, and it is also quite difficult to prepare large-area aluminum oxide porous template.
Chinese patent CN1609283A discloses a kind of preparation method of ordered porous anodic alumina template, this kind method need carry out electrochemical etching, once oxidation, removes oxide film, secondary oxidation, peel off aluminium base processing aluminium flake, consuming time longer, about 7h-13 hour, this alumina formwork was difficult to break away from the relatively poor shortcoming of aluminum oxide toughness.
Chinese patent CN1614740A discloses a kind of preparation big area, the method of height ordered nanometer silica quantum dot array, this method is used alumina formwork, the preparation of alumina formwork is got by twice corrosion of rafifinal, electrochemical method is adopted in corrosion for the first time, 2 hours times spent, use phosphoric acid then, chromic acid mixture soaks, 4 hours times spent, corrosion for the second time is with etching condition is identical for the first time, time spent 2.5min-5.0min, other removes upper strata barrier layer time spent 30min, though this method was lacked than general twice oxidation oxygenerating aluminum alloy pattern plate time spent, but still need a few hours, and this alumina formwork still is difficult to break away from the relatively poor shortcoming of toughness.
In view of inorganics film thermostability and chemical stability height, advantages such as fenestra high-sequential, the inorganics film is a kind of comparatively ideal template.In order to make larger area nano-form, and then make larger area nano-array material, select that to have flexible metal nano template be imperative for use with using value.But " metal form method " is still the template based on AAO on the document, and large-area complicated process of preparation, condition are difficult to control.For example, in order to overcome the shortcoming of anodic alumina films easy fracture, there is the investigator to prepare metal form with two stage replica methods.Japanology personnel polymerization in nano-array hole alumina formwork forms polymethylmethacrylate cylinder array, remove alumina formwork with the NaOH aqueous solution soaking then, obtain the negative replica of polymethylmethacrylate, to bear replica then and put into electroless plating liquid, metal fills up the hole of negative replica gradually, with the molten polymethylmethacrylate that goes of acetone, obtain Pt and Au metal hole array mould plate.Have the investigator on the basis of porous alumina formwork polymerization synthetic glass replica template, obtained the sequential holes array thick film of nickel again by electrodeposition of metallic nickel, the structural parameter of nickel porous film can and be regulated electroplating time and control by the selective oxidation aluminum alloy pattern plate, Zhi Bei metal form physical strength is higher in this way, metal toughness is arranged, and template is easy fracture not.But this method at first needs larger area AAO template as motherboard.
Three, summary of the invention
The objective of the invention is at the deficiencies in the prior art, and provide a kind of new electrochemical preparation method that can be used for assembling large-area nano-micrometre array material template, some important technological improvement can overcome the drawback that other preparation methods and other templates are had, and the preparation of template successfully provides good material for the research in many fields.
The objective of the invention is to realize by following technical measures.
1. pre-treatment: comprise the pre-etch that high temperature annealing and electrolysis are preceding.Adopt different media to aluminium quality percentage composition be 99.9%～99.999%, high-purity aluminum foil with 70% " 100 " face carries out pre-treatment, to alleviate the influence of the impurity in the aluminium foil, simultaneously according to suitable annealing, treatment temp and the time of processing requirement control.
Etch: will put into the electrolyzer of the acid electrolyte that fills with chloride ion-containing through the aluminium foil of pre-treatment, acid comes from sulfuric acid, oxalic acid, phosphoric acid, perchloric acid, nitric acid, and acid concentration is 0.1molL
-1～5.0molL
-1Chlorion comes from hydrochloric acid, sodium-chlor, Repone K, ammonium chloride, aluminum chloride, and the chlorion strength of solution is 0.5molL
-1～6.0mol molL
-1, the temperature of electrolytic solution is 60～90 ℃, and the aluminium foil in the electrolyzer is applied in electric current as anode and corrodes, and current density is 0.1 * 10
4～7.0 * 10
7A/m
2, aluminium foil obtains having the template of the nano-micrometre level hole of aperture between 100nm～2000nm through the electrolytic etching of 2～200s.
2. aperture adjustment: can make further aperture adjustment to the template that the etch aluminium foil obtains and handle, dissolution process increases pore size of template in acidic solution, anodic oxidation reduces pore size of template, and these acid comprise sulfuric acid, oxalic acid, phosphoric acid, perchloric acid, nitric acid, hydrochloric acid, citric acid, hexanodioic acid, five boric acid.
3. washing and dry: the template that the etch aluminium foil obtains is washed with clear water, remove the etching solution of remained on surface; After washing finished, drying was removed the residual moisture in the hole.
Description of drawings
The synoptic diagram and the sign thereof of Fig. 1 pit growth model of the present invention.
The electron scanning micrograph of Fig. 2 embodiment of the invention 7,
Wherein: Fig. 2 a is that 1000 times of amplifications, Fig. 2 b amplify 5000 times.
The electron scanning micrograph of Fig. 3 embodiment of the invention 8,
Wherein: Fig. 3 a is that 1000 times of amplifications, Fig. 3 b amplify 5000 times.
Principle of the present invention is as shown in Figure 1:
The formation in nano-micrometre hole is divided into the generation in hole and grows two stages in the aluminum alloy pattern plate:
1) generation in hole. There is the sull of one deck densification on the surface of aluminium, and the character of aluminium electrochemistry behavior and this layer oxide-film is closely related. In the electro-etching process, chlorion (Cl)-Be adsorbed on the surface of aluminium, at the fault location of oxide-film, Cl-Concentration larger, during the anode aluminium foil galvanization, Cl-Absorption strengthen, when current potential surpasses when breaking up current potential, the weakness of film will be broken up, and has just formed the blank of aperture on the surface, this is the generation of aperture. To under a lower current potential, grow up at aperture after this. In that to break up current potential lower, in the situation that namely surface oxide layer is thinner, the surface holes density that obtains will be larger, therefore, before carrying out electro-etching, is necessary to take measures to carry out the preliminary treatment on surface with the thickness of attenuate oxide layer.
2) growth in hole. During the impressed current etch, the progressions model of Tunnel-hole as shown in Figure 1. Hole wall is in the state of passivation, and the forward position of aperture then is in the active dissolution state, has namely generated aluminium ion, and under the effect of electric field, aluminium ion will be to the hole external migration, and simultaneously, chlorion then moves in the hole, like this AlCl in the hole3Concentration just progressively improve AlCl3Hydrolysis produces HCl, and the solution in the aperture will keep acidity always, and the unpolarized corrosion process of hydrogen also occurs on aluminium active dissolution surface at the bottom of the while hole:
2Al+6H
+→2Al
3++3H
2, just more and more far away apart from the aperture at the bottom of the hole along with the forward growth in hole, the resistance of aluminium ion external migration diffusion naturally will be increasing, the AlCl in the hole3Concentration also will be increasing, reach at last a saturated concentration, this moment the hole growth just stopped. The aperture more speed of growth of aperture is just faster, and the time that reaches capacity will be shorter, and the length in hole is also just shorter. The growth degree of depth of Tunnel-hole only is subjected to the impact of corrosive liquid temperature.
The present invention has the following advantages:
1. the template of preparation has toughness, can prepare large-area nano-micrometre yardstick template;
2. reliable preparation process is with short production cycle, helps large-scale industrialization production;
3. template can be applicable to prepare large-area nano-micrometre array material.
Four, embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1: with high-purity aluminum foil at 0.5molL
-1Pre-treatment 20s in the NaOH solution, the aluminium foil after the processing is made anode, and chlorine ion concentration is 0.5molL in the electrolytic solution
-1, the concentration of acid is 3.0molL
-1, 120 seconds electrolytic etching time, 70 ℃ of etch temperature, the current density that is applied on the aluminium foil is 1.5 * 10
4A/m
2Etch finishes, and aluminium foil cleans with clear water, and washing finishes, drying.
Other embodiment operation stepss are as described in the embodiment 1, processing condition such as the table 1 of embodiment 2-embodiment 6.
Table 1 embodiment condition
| Condition | Pretreatment time s | Acid concentration molL -1 | Chlorine ion concentration molL -1 | Etch time s | Etch current density 10 4A·m -2 | Etch temperature ℃ | Aperture adjustment time min | The template proterties |
| Embodiment 1 | 20 | 3.0 | 0.5 | 120 | 1.5 | 70 | 0 | Toughness |
| Embodiment 2 | 10 | 0.5 | 1.0 | 60 | 1.0 | 70 | 5 | Toughness |
| Embodiment 3 | 40 | 1.2 | 1.5 | 3 | 4.0 | 60 | 8 | Toughness |
| Embodiment 4 | 40 | 2.0 | 2.5 | 10 | 0.2 | 90 | 10 | Toughness |
| Embodiment 5 | 20 | 3.5 | 4.0 | 180 | 6.0 | 80 | 10 | Toughness |
| Embodiment 6 | 30 | 5.0 | 5.0 | 90 | 3.0 | 80 | 12 | Toughness |
| Comparative examples A AO template | Fragility |
Table 2 is the processing condition of embodiment 7, embodiment 8.Embodiment 8 aperture adjustment are at hydrochloric acid (6.0molL
-1) and sulfuric acid (5.0molL
-1) carry out in the nitration mixture.
Table 2 embodiment 7, embodiment 8 processing condition
| Condition | Pretreatment time/s | Acid concentration/molL -1 | Chlorine ion concentration/molL -1 | Etch time/s | Etch current density/10 4A·m -2 | The etch temperature/℃ | Aperture adjustment time/min |
| Embodiment 7 | 40 | 4.5 | 6.0 | 30 | 7.0 | 80 | 0 |
| Embodiment 8 | 40 | 4.5 | 6.0 | 30 | 7.0 | 80 | 15 |
The high-purity aluminum foil that obtains in an embodiment adopts replica method to can be observed the pattern of aluminium foil mesopore with scanning electron microscope.
Fig. 2 a, b are respectively the electron scanning micrograph of embodiment 7, and photo has shown that the present invention prepares the good growth conditions in hole, nano-micrometre yardstick tunnel of template.
Fig. 3 a, b are respectively embodiment 8 at hydrochloric acid (6.0molL
-1) and sulfuric acid (5.0molL
-1) electron scanning micrograph after reaming is handled in the nitration mixture, photo has shown that the hole that the present invention prepares the hole, nano-micrometre yardstick tunnel of template enlarges growth conditions.Fig. 3 as seen, the aluminum alloy pattern plate aperture of embodiment 7 is about 800nm, after reaming (embodiment 8), the aperture is increased to about and is 1000nm.
Claims (8)
1. aluminium tunnel casement plate preparation method who is used for assembling nano-micrometre array material may further comprise the steps:
1) aluminium foil is carried out pre-treatment,
2) to pretreated aluminium foil at chloride ion-containing 0.5molL
-1-6.0molL
-1, acid concentration is 0.1molL
-1-5.0molL
-1Acidic solution in electrolytic etching obtain the hole, tunnel,
3) aluminium foil is made further pore size of template and is regulated processing after the etch, dissolution process hole diameter enlargement in acidic solution, and anodic oxidation treatment reduces the aperture in acidic solution,
4) the aluminium foil template after the processing washes with water, dries.
2. according to the described aluminium tunnel casement plate preparation method who is used for assembling nano-micrometre array material of claim 1, it is characterized in that: aluminium foil is electrolytic etching in the acidic solution of chloride ion-containing, and the current density that is applied on the aluminium foil is 0.1 * 10
4～7.0 * 10
7A/m
2
3. according to the described aluminium tunnel casement plate preparation method who is used for assembling nano-micrometre array material of claim 1, it is characterized in that: aluminium foil is electrolytic etching in the acidic solution of chloride ion-containing, and the temperature of etch is 60 ℃ to 90 ℃.
4. according to the described aluminium tunnel casement plate preparation method who is used for assembling nano-micrometre array material of claim 1, it is characterized in that: aluminium foil is electrolytic etching in the acidic solution of chloride ion-containing, and the etch time is 2-200 second.
5. according to the described aluminium tunnel casement plate preparation method who is used for assembling nano-micrometre array material of claim 1, it is characterized in that: high-purity aluminum foil is electrolytic etching in the acidic solution of chloride ion-containing, and erosive electrolytic solution acidic solution comprises sulfuric acid, oxalic acid, phosphoric acid, perchloric acid, nitric acid.
6. according to the described aluminium tunnel casement plate preparation method who is used for assembling nano-micrometre array material of claim 1, it is characterized in that: high-purity aluminum foil is electrolytic etching in the oxidizing acid of chloride ion-containing, and the addition manner of electrolytic solution chlorion comprises hydrochloric acid, sodium-chlor, Repone K, ammonium chloride, aluminum chloride.
7. according to the described aluminium tunnel casement plate preparation method who is used for assembling nano-micrometre array material of claim 1, it is characterized in that: etch is obtained the aluminium foil template do further aperture adjustment processing, dissolution process hole diameter enlargement in acidic solution, anodic oxidation reduces the aperture, and these acid comprise sulfuric acid, oxalic acid, phosphoric acid, perchloric acid, nitric acid, hydrochloric acid, citric acid, hexanodioic acid, five boric acid.
8. according to the described aluminium tunnel casement plate preparation method who is used for assembling nano-micrometre array material of claim 1, it is characterized in that: the aluminum alloy pattern plate flexible that makes, area is controlled, and hole is orderly, and the aperture is between 100nm-2000nm.
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|---|---|---|---|
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210341B (en) * | 2006-12-30 | 2010-12-29 | 新疆众和股份有限公司 | Method for producing reaming electrolyte and high specific surface area aluminum electrolytic capacitor electrode foil |
| CN110474058B (en) * | 2019-09-18 | 2021-02-26 | 南通海星电子股份有限公司 | Preparation method of cathode oxygen reduction electrocatalytic Pt electrode by template method |
| CN110877916B (en) * | 2019-11-27 | 2021-05-04 | 新疆众和股份有限公司 | Method for producing tubular titanium dioxide |
| CN111455428B (en) * | 2019-12-27 | 2022-01-21 | 重庆会通科技有限公司 | Aluminum alloy micro-pore-expanding agent and surface treatment method of aluminum alloy material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998048456A1 (en) * | 1997-04-24 | 1998-10-29 | Massachusetts Institute Of Technology | Nanowire arrays |
| US6139713A (en) * | 1996-08-26 | 2000-10-31 | Nippon Telegraph And Telephone Corporation | Method of manufacturing porous anodized alumina film |
| EP1470907A2 (en) * | 2003-04-21 | 2004-10-27 | Samsung Electronics Co., Ltd. | Method of manufacturing self-ordered nanochannel-array and method of manufacturing nanodots using the nanochannel-array |
| JP2005307333A (en) * | 2003-08-11 | 2005-11-04 | Canon Inc | Structure, manufacturing method therefor and porous material |
-
2005
- 2005-12-06 CN CNB2005100222192A patent/CN100529196C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6139713A (en) * | 1996-08-26 | 2000-10-31 | Nippon Telegraph And Telephone Corporation | Method of manufacturing porous anodized alumina film |
| WO1998048456A1 (en) * | 1997-04-24 | 1998-10-29 | Massachusetts Institute Of Technology | Nanowire arrays |
| EP1470907A2 (en) * | 2003-04-21 | 2004-10-27 | Samsung Electronics Co., Ltd. | Method of manufacturing self-ordered nanochannel-array and method of manufacturing nanodots using the nanochannel-array |
| JP2005307333A (en) * | 2003-08-11 | 2005-11-04 | Canon Inc | Structure, manufacturing method therefor and porous material |
Non-Patent Citations (2)
| Title |
|---|
| 氧化铝纳米有序阵列模板的制备工艺及应用. 吴玉程，马杰，解挺等.中国有色金属学报，第15卷第5期. 2005 |
| 氧化铝纳米有序阵列模板的制备工艺及应用. 吴玉程，马杰，解挺等.中国有色金属学报，第15卷第5期. 2005 * |
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