CN101139730A - Strong anodic oxidation method for preparing porous pellumina - Google Patents
Strong anodic oxidation method for preparing porous pellumina Download PDFInfo
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- CN101139730A CN101139730A CNA2007100621581A CN200710062158A CN101139730A CN 101139730 A CN101139730 A CN 101139730A CN A2007100621581 A CNA2007100621581 A CN A2007100621581A CN 200710062158 A CN200710062158 A CN 200710062158A CN 101139730 A CN101139730 A CN 101139730A
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Abstract
The invention relates to an intensive anodic oxidation process for preparing porous anodic alumina film, which is characterized in that: the method takes an aluminum sheet as an anode, a platinum sheet as a cathode, argon as shielded gas, mixed solution of perchloric acid with absolute alcohol as electrochemical polishing compound for the aluminum sheet, mixed solution of oxalic acid, absolute alcohol and deionized water as electrolyte and mixed solution of phosphoric acid, chromic acid and deionized water as alumina film corrosive. Through aluminum sheet annealing, purging, electrochemical polishing, mild anodic oxidation, corrosion on aluminum sheet oxide film, intensive anodic oxidation and stripping oxide film, and finally, pale yellow, high purity and ordered porous-structured nanometer-leveled alumina film is achieved; the alumina film pore is in circular shape, with an aperture of 30 to 35nm, a hole pitch of 80 to 100nm and a hole depth of 162.4 Mu m; the growth rate of the alumina film is 54 micrometers/h, which is 27 times higher than the growth rate of 2 micrometers/h of anodic oxidation aluminum film prepared through mild anodic oxidation process.
Description
Technical field:
The present invention relates to a kind of strong anonizing of producing multiaperture pellumina, belong to the field of nonferrous metal material surface film technique.
Background technology:
Aluminium is more active metal, in air, can form the oxide film of the about hundreds of nanometer of a bed thickness naturally, this layer oxide film is non-crystalline state, approach and porous, physical strength is low, can't satisfy the requirement of functionalized application, in order to obtain the oxidation film layer of specific function, must handle the aluminium surface, in electrolytic solution, aluminium is carried out electrolysis treatment as anode, generate oxide film, be called alumilite process on the aluminium surface, anodic alumina films is divided into barrier type and multi-hole type two classes, usually anodic oxidation can obtain fine and close barrier type oxide film in neutral electrolyte, and at oxalic acid, phosphoric acid, sulfuric acid etc. self have that anodic oxidation can form the multi-hole type oxide film on the aluminium surface in the acidic solution of certain oxidation capacity, the blocking layer that this multi-hole type oxide film is fine and close by bottom thin and on it thick and loose porous layer constitute, the film born of the same parents of porous layer are that hexagonal Mi Dui arranges, there is the hole of nanoscale in each film born of the same parents center, and hole size is even, and is vertical with matrix surface.
Because porous anodic alumina films particular structure and advantage, open up a new way for developing new function material, at present, porous anodic alumina films not only is used widely at aspects such as separatory membrane, optics and optoelectronic component, magneticthin film, selective absorbing film, support of the catalyst, and make it become the desirable template of preparation even structure, as with the porous alumina being template synthesis of nano line, nanotube etc.
Studies show that, form multiaperture pellumina, the electrolytic solution kind can only be an oxalic acid, phosphoric acid, sulfuric acid etc. self have the acidic solution of certain oxidation capacity, in addition, only under appropriate voltage, just can obtain orderly hole, generally believe, when 2 ℃ of left and right sides of electrolyte temperature, the optimum value of the corresponding oxidation voltage of sulfuric acid electrolyte is 25V, the optimum value of the corresponding oxidation voltage of oxalic acid electrolytic solution is 40V, the optimum value of the corresponding oxidation voltage of phosphoric acid electrolyte is 195V, and when oxidation voltage was not near above-mentioned voltage optimum value, the spacial ordering degree of the aluminum oxide film that is generated will sharply descend, if virtual voltage is higher than desired when keeping the maximum voltage value of stablizing oxidation, can cause puncturing owing to electric current is excessive and burning oxide film, for example, be electrolytic solution with the oxalic acid of 0.3mol/L, when 2 ℃ of left and right sides of temperature, keep stablize oxidation voltage range between 20～80V, and oxidation under 80V, the hole arm of porous-film has begun to have the sign of breaking.
With sulfuric acid, oxalic acid or phosphoric acid is electrolytic solution, near the anodic oxidation custom of carrying out the optimum value of oxidation voltage is called gentle anonizing mild anodization, is called for short the MA method, its shortcoming is to prepare multiaperture pellumina, the rate of rise of film thickness has only 2 μ m/h, up to the present, because pellumina thickness rate of rise is slow, also be not applied to also have a lot of defectives and deficiency in the industry based on the two-step anodization method of MA method.
With oxalic acid is electrolytic solution, and the anodic oxidation of carrying out at 110-160V is strong anonizing hardanodization, is called for short the HA method that strong anonizing is also in research and inquiring into.
Summary of the invention
Goal of the invention
Purpose of the present invention is exactly at the deficiency that is equipped with multiaperture pellumina in the background technology based on the two-step anodization legal system of gentle anonizing, the problem that porous alumina film thickness rate of rise is slow, proposing a kind of is electrolytic solution with oxalic acid, deionized water, ethanol solution, adopt strong anonizing, under 160V voltage, preparation in order, the pellumina method in porous, nano level aperture, to increase substantially the rate of rise of pellumina.
Technical scheme
The chemical substance material that the present invention uses is: aluminium flake, platinized platinum, oxalic acid, phosphoric acid, chromic acid, perchloric acid, dehydrated alcohol, acetone, deionized water, argon gas, its composition amount are such as down: with milligram, milliliter, millimeter, centimetres 3 is measure unit
Aluminium flake: Al 75 * 15 * 0.5mm
Platinized platinum: Pt 75 * 15 * 0.5mm
Oxalic acid: C
2H
2O
42H
2O 18.9105g ± 0.0005g
Phosphoric acid: H
3PO
46g ± 0.0005g
Chromic acid: H
2CrO
41.8g ± 0.0005g
Perchloric acid: HClO
4100ml ± 0.5ml
Dehydrated alcohol: CH
3CH
2OH 500ml ± 0.5ml
Acetone: CH
3COCH
350ml ± 0.5ml
Deionized water: H
2O 1000ml ± 10ml
Argon gas: Ar, 18000cm
3± 100cm
3
The preparation method is as follows:
(1) selected chemical substance material
It is selected to want strictness to carry out to required chemical substance material, and carries out purity, precision control:
Aluminium flake: 75 * 15 * 0.5mm purity is 99.999% roughness Ra0.32-0.64 μ m
Platinized platinum: 75 * 15 * 0.5mm purity is 99.99% roughness Ra0.32-0.64 μ m
Oxalic acid: 99.5%
Phosphoric acid: 99.5%
Chromic acid: 99.99%
Perchloric acid: 99.5%
Dehydrated alcohol: 99.7%
Acetone: 99.5%
Deionized water: 99.99%
Argon gas: 99.999%
(2) annealing aluminum sheet
1. in the tubular type annealing furnace, carry out;
2. 75 * 15 * 0.5mm aluminium flake is placed in the silica tube of tubular type annealing furnace;
3. tunger tube is connected the silica tube inlet mouth of tubular type annealing furnace, opened the air outlet, carry argon gas in the high quartz pipe, the argon gas transfer rate is 200cm
3/ min, time of delivery are 5min ± 0.5min, with the cleaning high-temp silica tube, remove obnoxious flavour and residual chemicals in the pipe;
4. open tubular type annealing furnace resistance heater, temperature is warming up to 500 ℃ ± 3 ℃ by 25 ℃ ± 3 ℃, and 8 ℃/min of heat-up rate opens tunger tube simultaneously, carries argon gas in the high quartz pipe, and the argon gas transfer rate is 50cm
3/ min, high quartz pipe temperature is constant temperature 120min ± 1min under 500 ℃ ± 3 ℃ states, eliminates aluminium flake internal stress and defective thereof;
5. close well heater, make its furnace cooling, when temperature is reduced to 100 ℃ ± 10 ℃, close tunger tube, stop defeated argon gas;
6. cool to 25 ℃ ± 3 ℃ with the furnace, finish annealing, take out aluminium flake;
(3) ultrasonic cleaning aluminium flake
1. the aluminium flake after will annealing places beaker, and acetone 10ml ± 0.5ml is placed beaker, places ultrasonic cleaner to clean 10min ± 1min in beaker;
2. the aluminium flake after acetone being cleaned places beaker, and dehydrated alcohol 10ml ± 0.5ml is placed beaker, places ultrasonic cleaner to clean 10min ± 1min in beaker;
(4) electrochemical etching aluminium flake
1. on the subcooling recycle pump, carry out;
2. prepare polishing fluid
Dehydrated alcohol 400ml ± 0.5ml, perchloric acid 100ml ± 0.5ml are placed beaker, even with magnetic stirrer, become mixing solutions, the volume ratio of its mixing solutions is: dehydrated alcohol: perchloric acid=4: 1;
3. electrochemical etching
The beaker that polishing fluid is housed is placed the subcooling recycle pump, open the magnetic stirring apparatus of beaker bottom, open the subcooling recycle pump simultaneously, make electrolyzer temperature be in 0 ℃ ± 0.5 ℃, the polishing fluid temperature is in 2 ℃ ± 0.5 ℃ in the beaker;
Aluminium flake, platinized platinum vertically are suspended in the beaker, and make aluminium flake, platinized platinum parallel;
Aluminium flake, platinized platinum are connected anode, cathode connection folder respectively;
Power-on, aluminium flake are anode, and platinized platinum is a negative electrode, holding current 1000mA ± 50mA, and under magnetic agitation, electrochemical etching 8min ± 2min;
4. behind the aluminium flake electrochemical etching, positive and negative two planes become minute surface, and surfaceness is Ra0.16-0.32 μ m;
(5) the gentle anodic oxidation of aluminium flake
1. on the subcooling recycle pump, carry out;
2. prepare electrolytic solution
Dehydrated alcohol 100ml ± 0.5ml, deionized water 400ml ± 0.5ml are placed beaker, even with magnetic stirrer, become mixing solutions, the volume ratio of its mixing solutions is: dehydrated alcohol: deionized water=0.25: 1;
18.9105g ± 0.0005g places beaker with oxalic acid, adding volume ratio is 0.25: 1 the dehydrated alcohol and the mixed solution of deionized water, making liquor capacity is 500ml ± 0.5ml, dissolve fully with magnetic stirrer to oxalic acid, make oxalic acid, dehydrated alcohol and deionized water mixing solutions, mixing solutions mesoxalic acid concentration is 0.3mol/L;
3. anodic oxidation
The beaker that electrolytic solution is housed is placed the subcooling recycle pump, open the magnetic stirring apparatus of beaker bottom, open the subcooling recycle pump simultaneously, make electrolyzer temperature be in 0 ℃ ± 0.5 ℃, beaker electrolyte inside temperature is in 2 ℃ ± 0.5 ℃;
Aluminium flake, platinized platinum vertically are suspended in the beaker, and make aluminium flake, platinized platinum parallel;
Aluminium flake, platinized platinum are connected anode, cathode connection folder respectively;
Open D.C. regulated power supply, aluminium flake is an anode, and platinized platinum is a negative electrode, sustaining voltage 40V ± 0.5V, and under magnetic agitation, under the cooling of mixture of ice and water constant temperature, anodic oxidation 300min ± 1min makes the positive and negative surface of aluminium flake generate porous anodic oxide film;
(6) corrosion aluminium flake oxide film
1. prepare corrosive fluid
Phosphoric acid 6g ± 0.0005g, chromic acid 1.8g ± 0.0005g, deionized water 92.2g ± 0.0005g are placed beaker, even with magnetic stirrer, become mixing solutions, the mass ratio of chromic acid, phosphoric acid and deionized water is in its mixing solutions: chromic acid: phosphoric acid: deionized water=6: 1.8: 92.2;
2. corrode the aluminium flake oxide film
Aluminium flake after the gentle anodic oxidation is placed the beaker that corrosive fluid is housed, under 25 ℃ ± 3 ℃, leave standstill 540-600min, the pellumina that gentle anodic oxidation is generated erodes, and forms the pit pattern of rule on the aluminium surface;
(7) clean the aluminium flake that pit pattern is arranged
1. deionized water 50ml ± 0.5ml is placed beaker;
2. will there be the aluminium flake of pit pattern to be soaked in the deionized water of beaker, clean 10min;
3. use new deionized water, repeated washing 3 times;
4. aluminium flake is taken out and dry;
(8) the strong anodic oxidation of aluminium flake
1. on the subcooling recycle pump, carry out;
The beaker that 2. electrolytic solution will be housed places the subcooling recycle pump, opens the magnetic stirring apparatus of beaker bottom, opens the subcooling recycle pump simultaneously and makes electrolyzer temperature be in 0 ℃ ± 0.5 ℃, and beaker electrolyte inside temperature is in 2 ℃ ± 0.5 ℃;
3. aluminium flake, platinized platinum vertically are suspended in the beaker, and make aluminium flake, platinized platinum parallel;
4. the position of aluminium flake in electrolytic solution adjusted to the formed electrolytic solution vortex of magnetic agitation place;
5. open D.C. regulated power supply, aluminium flake is an anode, and platinized platinum is a negative electrode, sustaining voltage 40V ± 0.5V, and under magnetic agitation, under the cooling of mixture of ice and water constant temperature, anodic oxidation 10min ± 1min makes the positive and negative surface of aluminium flake generate porous anodic oxide film;
6. anode, cloudy interpolar voltage are slowly risen to 160V, the rate of rise is 0.5-0.9V/s, under 160V voltage, and strong anodic oxidation 180min ± 1min;
7. the positive and negative two sides of aluminium flake generates orderly anodic alumina films, and pellumina is faint yellow, and hole shape is circular, aperture 30-35nm, pitch of holes 80-100nm, hole depth 162.4 μ m, thicknesses of layers 162.4 μ m;
(9) oxide film is peeled off
1. on the subcooling recycle pump, carry out;
The beaker that 2. electrolytic solution will be housed places the subcooling recycle pump, opens the magnetic stirring apparatus of beaker bottom, opens the subcooling recycle pump simultaneously, makes electrolyzer temperature be in 0 ℃ ± 0.5 ℃, and beaker electrolyte inside temperature is in 2 ℃ ± 0.5 ℃;
3. the aluminium flake after the strong anodic oxidation, platinized platinum vertically are suspended in the beaker, and make aluminium flake, platinized platinum parallel;
4. open D.C. regulated power supply, the aluminium flake after the strong anodic oxidation is an anode, and platinized platinum is a negative electrode, and voltage of supply is risen to the strong anodic oxidation voltage 160V of aluminium flake earlier, reduces to 0V voltage with the blowdown rate of 5V/min then;
5. replace cathode and anode, displacement back: the aluminium flake of strong anodic oxidation is a negative electrode, and to change the platinized platinum of negative electrode into inoxidized aluminium flake be anode, and voltage stabilized source boosts to 10V, constant voltage 5min, the pressure in bubbles of utilizing cathodic reduction reaction to produce is peeled off multiaperture pellumina and aluminium flake;
(10) ultrasonic cleaning multiaperture pellumina
1. deionized water 50ml ± 0.5ml is placed beaker;
2. multiaperture pellumina is soaked in the deionized water of beaker ultrasonic cleaning 10min;
3. distinguish repeated washing 3 times with deionized water;
4. multiaperture pellumina is taken out airing;
(11) detect, analyze, characterize
The surface and the end face pattern of use emission scan electron microscope observation multiaperture pellumina are measured hole shape, aperture, hole depth, pitch of holes;
(12) packing and storing
Place in the clean soft material multiaperture pellumina is open and flat, be stored in drying, cool place, the clean environment, storing temp is 20 ℃ ± 3 ℃, strict fire prevention, sun-proof, anti-soda acid to corrode.
Described strong anonizing is produced pellumina, is that the mixing solutions with oxalic acid, dehydrated alcohol, deionized water is an electrolytic solution, and the volume ratio of dehydrated alcohol and deionized water is 0.25: 1 in the mixing solutions, and the concentration of mixing solutions is 0.3mol/L.
Described strong anonizing is produced pellumina, is under 160V voltage, and electrolyte temperature is in 2 ℃ ± 0.5 ℃, and strong anodic oxidation is finished in the time at 180min ± 1min, and boost in voltage speed is 0.5-0.9V/s.
Described strong anonizing is produced pellumina, and its product is faint yellow, and hole shape is that 30-35nm, pitch of holes are that 80-100nm, hole depth are 162.4 μ m for circular, aperture, and thicknesses of layers 162.4 μ m are for the porous ordering rule is arranged.
Described strong anonizing is produced pellumina, and the growth velocity of strong anodised pellumina is 54 μ m/h.
Beneficial effect
The present invention compares with background technology has tangible advance; adopt strong anonizing to produce multiaperture pellumina; it is to do anode with aluminium flake; do negative electrode with platinized platinum; with oxalic acid; dehydrated alcohol; the mixing solutions of deionized water is an electrolytic solution; with the rare gas element argon gas is the shielding gas of annealing aluminum sheet; with perchloric acid; dehydrated alcohol is the electrochemical etching agent of aluminium flake; with phosphoric acid; the mixing solutions of chromic acid and deionized water is the etching reagent of gentle anodic alumina films; with acetone; dehydrated alcohol; deionized water is a clean-out system; pass through annealing aluminum sheet; ultrasonic cleaning; electrochemical etching; gentle anodic oxidation; the corrosion anodic alumina films; cleaning tape has the aluminium flake of oxide film indenture; strong anodic oxidation; peel off oxide film; check and analysis; store encapsulation; finally make faint yellow; the nanometer porous pellumina of high-sequential; the oxide film pass is circular; pellumina aperture 30-35nm; pitch of holes 80-100nm; hole depth 162 μ m; the growth velocity of porous alumina membrane is 54 μ m/h; the growth velocity 2 μ m/h that prepare porous anodic alumina films than gentle anonizing improve 27 times; this preparation method's technical process is short; use equipment is few; operation easily; environmental pollution is little; the materials used source is abundant; cost is low, is the very good method of producing multiaperture pellumina.
Description of drawings
Fig. 1 is preparation technology's schema
Fig. 2 is annealing furnace structure and as-annealed condition figure
Fig. 3 is subcooling circulator and preparation state graph
Fig. 4 is strong anodic oxidation voltage and time coordinate graph of a relation
Fig. 5 amplifies 100000 times of surface topography maps for pellumina
Fig. 6 amplifies 800 times of cross-section morphology figure for pellumina
6000 times of cross-section morphology figure that Fig. 7 amplifies for pellumina
Shown in the figure, list of numerals is as follows:
1. annealing furnace seat, 2. annealing furnace, 3. silica tube, 4. quartzy tube chamber, 5. quartz boat, 6. well heater, 7. argon bottle, 8. tunger tube, 9. argon gas valve, 10. air outlet, 11. aluminium flake, 12. subcooling supports, 13. electrolyzers, 14. beakers, 15. supports, 16. the cathode connection folder, 17. anode connections folder, 18. controllers, 19. pilot lamp, 20. D.C. regulated power supplies, 21. liquid-crystal display, 22. pilot lamp, 23. controllers, 24. platinized platinums, 25. the cooling cabinet, 26. electrolytic solution, 27. mixture of ice and water, 28. leads.
Embodiment
The present invention will be further described below in conjunction with accompanying drawing:
Shown in Figure 1, be preparation technology's schema, each preparation parameter is wanted strict control, operation according to the order of sequence.
The chemical substance material that equipment is required is wanted strict weighing, must not exceed the minimax scope.
The required aluminium flake of preparation porous anodic alumina films is wanted strict selected, purity 99.999%, the dimensions of aluminium flake, platinized platinum, surfaceness want consistent, in order to avoid influence the voltage transmission and the stability of cathode and anode.
Annealing aluminum sheet will be carried out in the quartz tube type annealing furnace under argon shield, and annealing temperature is 500 ℃ ± 3 ℃, strict controlled temperature, time, and the argon gas input will be carried out continuously, and leaves gas port, in case security incident takes place.
After the annealing, aluminium flake is wanted ultrasonic cleaning 10min ± 1min in acetone, dehydrated alcohol successively.
Aluminium flake will carry out electrochemical etching, to improve the bright and clean degree of positive and negative, is minute surface and is advisable, and is beneficial to the generation of ordered porous oxide film, and after the polishing, the aluminium flake surface roughness value is Ra0.16-0.3 μ m.
The preparation of multiaperture pellumina will divide secondary to carry out, be gentle anodic oxidation for the first time, it is the MA method, be strong anodic oxidation for the second time, be the HA method, all on the subcooling circulator, carry out that the electrolytic solution of its use is identical, be the mixing solutions of oxalic acid, dehydrated alcohol and deionized water, its concentration is 0.3mol/L.
Anodic oxidation for the first time is gentle anodic oxidation, magnitude of voltage is 40V ± 0.5V, the electrolyte temperature value is 2 ℃ ± 0.5 ℃, the magnetic force vibration is stirred, time is 300min ± 1min, and the oxide film that generates on aluminium flake also will be used phosphoric acid, chromic acid and deionized water mixing solutions corrosion 540-600min, the pellumina that anodic oxidation is for the first time generated erodes, and forms the pit pattern of rule on the aluminium surface.
Anodic oxidation for the second time is strong anodic oxidation, and voltage is 160V, and the time can be according to the growth velocity 54 μ m/h of porous alumina membrane, select by the required hole layer thickness of application, hole depth, can select in 30-300min, the time is long more, hole depth is big more, and the time, short more hole depth was more little, was directly proportional.
Oxidation 10min ± 1min under 40V ± 0.5V voltage is earlier wanted in anodic oxidation for the second time, make the positive and negative surface of aluminium flake generate porous anodic oxide film, slowly boost to 160V then, the rate of rise is 0.5-0.9V/s, the position of aluminium flake in electrolytic solution will be adjusted to the formed vortex of magnetic agitation place during strong anodic oxidation.
Peeling off pellumina will carry out in order, be anode with the aluminium flake earlier, platinized platinum is a negative electrode, voltage 160V during by strong anodic oxidation reduces to 0V with negative and positive two interpolar voltages with the blowdown rate of 5V/min, replace anode and cathode then, the displacement back is a negative electrode with the aluminium flake of strong anodic oxidation, and change the anodic platinized platinum into unoxidized aluminium flake, voltage stabilized source boosts to 10V, constant voltage 5min, the pressure in bubbles of utilizing cathodic reduction reaction to produce is peeled off multiaperture pellumina and aluminium flake, takes out the multiaperture pellumina under peeling off, again it is collected after cleaning repeatedly with deionized water, be last multiaperture pellumina product.
The aluminium flake, platinized platinum, the chemical substance material that use when the preparation alumite are to determine in the numerical range that is setting in advance, with gram, milliliter, millimeter, centimetre
3Be measure unit, when industrialization is produced, with kilogram, liter, millimeter, rice
3Be measure unit, its product hole shape, pitch-row still are unit with the nanometer, and thickness, hole depth still are unit with the micron.
Shown in Figure 2, be tubular type annealing furnace structure and as-annealed condition figure, the top of stove seat 1 is annealing furnace 2, the top of annealing furnace 2 is well heater 6, and the inside middle of annealing furnace is a silica tube 3, is quartzy tube chamber 4 in the silica tube 3, the middle part is provided with quartz boat 5 in quartzy tube chamber 4, put aluminium flake 11 on the quartz boat 5, the left part of silica tube 3 is provided with argon gas valve 9, tunger tube 8, argon bottle 7, and the right part of silica tube 3 is provided with air outlet 10.
Shown in Figure 3, be cooling cycle machine structure and preparation state graph, the top of machine seat 12 is cabinet 25, the middle part of cabinet 25 is provided with electrolyzer 13, the middle part of electrolyzer 13 is a beaker 14, in the beaker 14 is electrolytic solution 26, be mixture of ice and water 27 between electrolyzer 13 and the beaker 14, left part at cooling cabinet 25 is provided with support 15, support 15 connects negative electrode folder 16, anode folder 17, negative electrode folder 16 connects platinized platinum 24, and anode folder 17 connects aluminium flake 11, platinized platinum 24, aluminium flake 11 gos deep in the electrolytic solution 26 in the beaker 14, the bottom of cooling cabinet 25 is provided with controller 18, pilot lamp 19, the left part of cooling cabinet 25 is provided with D.C. regulated power supply 20, and D.C. regulated power supply 20 is provided with pilot lamp 22, liquid-crystal display 21, controller 23, D.C. regulated power supply 20 is by lead 28 and negative electrode folder 16, anode folder 17 connects.
Shown in Figure 4, be strong anodic oxidation voltage and time coordinate graph of a relation, among the figure: ordinate zou is voltage V, X-coordinate is time min, earlier voltage is risen to 40V by 0V, i.e. the A point, keep 10min at this voltage, promptly the AB section is continued to boost to 160V with the speed of 0.5V/s by the B point then, intersect at the C point, keep 120min at this voltage, i.e. CD section, powered-down makes voltage reduce to 0V then, be the E point, boost-constant voltage-step-down whole process thereby finished.
Shown in Figure 5, be the surface topography of pellumina, among the figure as can be known: the porous alumina pass is circular, pellumina aperture 30-35nm, pitch of holes 80-100nm, ruler units are 100nm.
Shown in Figure 6, be the cross-section morphology of pellumina, among the figure as can be known: aluminum oxide thickness 162 μ m, ruler units are 100 μ m.
Shown in Figure 7, be the cross-section morphology of alumite, among the figure as can be known: the vertical pellumina of alumina pore layer surface is arranged in parallel, and hole depth 162 μ m, ruler units are 10 μ m.
Claims (6)
1. strong anonizing of producing multiaperture pellumina, it is characterized in that: the chemical substance material of use is: aluminium flake, platinized platinum, oxalic acid, phosphoric acid, chromic acid, perchloric acid, dehydrated alcohol, acetone, deionized water, argon gas, its composition amount are such as down: with milligram, milliliter, millimeter, centimetre
3Be measure unit
Aluminium flake: Al 75 * 15 * 0.5mm
Platinized platinum: Pt 75 * 15 * 0.5mm
Oxalic acid: C
2H
2O
42H
2O 18.9105g ± 0.0005g
Phosphoric acid: H
3PO
46g ± 0.0005g
Chromic acid: H
2CrO
41.8g ± 0.0005g
Perchloric acid: HClO
4100ml ± 0.5ml
Dehydrated alcohol: CH
3CH
2OH 500ml ± 0.5ml
Acetone: CH
3COCH
350ml ± 0.5ml
Deionized water: H
2O 1000ml ± 10ml
Argon gas: Ar, 18000cm
3± 100cm
3
The preparation method is as follows:
(1) selected chemical substance material
It is selected to want strictness to carry out to required chemical substance material, and carries out purity, precision control:
Aluminium flake: 75 * 15 * 0.5mm purity is 99.999% roughness Ra0.32-0.64 μ m
Platinized platinum: 75 * 15 * 0.5mm purity is 99.99% roughness Ra0.32-0.64 μ m
Oxalic acid: 99.5%
Phosphoric acid: 99.5%
Chromic acid: 99.99%
Perchloric acid: 99.5%
Dehydrated alcohol: 99.7%
Acetone: 99.5%
Deionized water: 99.99%
Argon gas: 99.999%
(2) annealing aluminum sheet
1. in the tubular type annealing furnace, carry out;
2. 75 * 15 * 0.5mm aluminium flake is placed in the silica tube of tubular type annealing furnace;
3. tunger tube is connected the silica tube inlet mouth of tubular type annealing furnace, opened the air outlet, carry argon gas in the high quartz pipe, the argon gas transfer rate is 200cm
3/ min, time of delivery are 5min ± 0.5min, with the cleaning high-temp silica tube, remove obnoxious flavour and residual chemicals in the pipe;
4. open tubular type annealing furnace resistance heater, temperature is warming up to 500 ℃ ± 3 ℃ by 25 ℃ ± 3 ℃, and 8 ℃/min of heat-up rate opens tunger tube simultaneously, carries argon gas in the high quartz pipe, and the argon gas transfer rate is 50cm
3/ min, high quartz pipe temperature is constant temperature 120min ± 1min under 500 ℃ ± 3 ℃ states, eliminates aluminium flake internal stress and defective thereof;
5. close well heater, make its furnace cooling, when temperature is reduced to 100 ℃ ± 10 ℃, close tunger tube, stop defeated argon gas;
6. cool to 25 ℃ ± 3 ℃ with the furnace, finish annealing, take out aluminium flake;
(3) ultrasonic cleaning aluminium flake
1. the aluminium flake after will annealing places beaker, and acetone 10ml ± 0.5ml is placed beaker, places ultrasonic cleaner to clean 10min ± 1min in beaker;
2. the aluminium flake after acetone being cleaned places beaker, and dehydrated alcohol 10ml ± 0.5ml is placed beaker, places ultrasonic cleaner to clean 10min ± 1min in beaker;
(4) electrochemical etching aluminium flake
1. on the subcooling recycle pump, carry out;
2. prepare polishing fluid
Dehydrated alcohol 400ml ± 0.5ml, perchloric acid 100ml ± 0.5ml are placed beaker, even with magnetic stirrer, become mixing solutions, the volume ratio of its mixing solutions is: dehydrated alcohol: perchloric acid=4: 1;
3. electrochemical etching
The beaker that polishing fluid is housed is placed the subcooling recycle pump, open the magnetic stirring apparatus of beaker bottom, open the subcooling recycle pump simultaneously, make electrolyzer temperature be in 0 ℃ ± 0.5 ℃, the polishing fluid temperature is in 2 ℃ ± 0.5 ℃ in the beaker;
Aluminium flake, platinized platinum vertically are suspended in the beaker, and make aluminium flake, platinized platinum parallel;
Aluminium flake, platinized platinum are connected anode, cathode connection folder respectively;
Power-on, aluminium flake are anode, and platinized platinum is a negative electrode, holding current 1000mA ± 50mA, and under magnetic agitation, electrochemical etching 8min ± 2min;
4. behind the aluminium flake electrochemical etching, positive and negative two planes become minute surface, and surfaceness is Ra0.16-0.32 μ m;
(5) the gentle anodic oxidation of aluminium flake
1. on the subcooling recycle pump, carry out;
2. prepare electrolytic solution
Dehydrated alcohol 100ml ± 0.5ml, deionized water 400ml ± 0.5ml are placed beaker, even with magnetic stirrer, become mixing solutions, the volume ratio of its mixing solutions is: dehydrated alcohol: deionized water=0.25: 1;
18.9105g ± 0.0005g places beaker with oxalic acid, adding volume ratio is 0.25: 1 the dehydrated alcohol and the mixed solution of deionized water, making liquor capacity is 500ml ± 0.5ml, dissolve fully with magnetic stirrer to oxalic acid, make oxalic acid, dehydrated alcohol and deionized water mixing solutions, mixing solutions mesoxalic acid concentration is 0.3mol/L;
3. anodic oxidation
The beaker that electrolytic solution is housed is placed the subcooling recycle pump, open the magnetic stirring apparatus of beaker bottom, open the subcooling recycle pump simultaneously, make electrolyzer temperature be in 0 ℃ ± 0.5 ℃, beaker electrolyte inside temperature is in 2 ℃ ± 0.5 ℃;
Aluminium flake, platinized platinum vertically are suspended in the beaker, and make aluminium flake, platinized platinum parallel;
Aluminium flake, platinized platinum are connected anode, cathode connection folder respectively;
Open D.C. regulated power supply, aluminium flake is an anode, and platinized platinum is a negative electrode, sustaining voltage 40V ± 0.5V, and under magnetic agitation, under the cooling of mixture of ice and water constant temperature, anodic oxidation 300min ± 1min makes the positive and negative surface of aluminium flake generate porous anodic oxide film;
(6) corrosion aluminium flake oxide film
1. prepare corrosive fluid
Phosphoric acid 6g ± 0.0005g, chromic acid 1.8g ± 0.0005g, deionized water 92.2g ± 0.0005g are placed beaker, even with magnetic stirrer, become mixing solutions, the mass ratio of chromic acid, phosphoric acid and deionized water is in its mixing solutions: chromic acid: phosphoric acid: deionized water=6: 1.8: 92.2;
2. corrode the aluminium flake oxide film
Aluminium flake after the gentle anodic oxidation is placed the beaker that corrosive fluid is housed, under 25 ℃ ± 3 ℃, leave standstill 540-600min, the pellumina that gentle anodic oxidation is generated erodes, and forms the pit pattern of rule on the aluminium surface;
(7) clean the aluminium flake that pit pattern is arranged
1. deionized water 50ml ± 0.5ml is placed beaker;
2. will there be the aluminium flake of pit pattern to be soaked in the deionized water of beaker, clean 10min;
3. use new deionized water, repeated washing 3 times;
4. aluminium flake is taken out and dry;
(8) the strong anodic oxidation of aluminium flake
1. on the subcooling recycle pump, carry out;
The beaker that 2. electrolytic solution will be housed places the subcooling recycle pump, opens the magnetic stirring apparatus of beaker bottom, opens the subcooling recycle pump simultaneously and makes electrolyzer temperature be in 0 ℃ ± 0.5 ℃, and beaker electrolyte inside temperature is in 2 ℃ ± 0.5 ℃;
3. aluminium flake, platinized platinum vertically are suspended in the beaker, and make aluminium flake, platinized platinum parallel;
4. the position of aluminium flake in electrolytic solution adjusted to the formed electrolytic solution vortex of magnetic agitation place;
5. open D.C. regulated power supply, aluminium flake is an anode, and platinized platinum is a negative electrode, sustaining voltage 40V ± 0.5V, and under magnetic agitation, under the cooling of mixture of ice and water constant temperature, anodic oxidation 10min ± 1min makes the positive and negative surface of aluminium flake generate porous anodic oxide film;
6. anode, cloudy interpolar voltage are slowly risen to 160V, the rate of rise is 0.5-0.9V/s, under 160V voltage, and strong anodic oxidation 180min ± 1min;
7. the positive and negative two sides of aluminium flake generates orderly anodic alumina films, and pellumina is faint yellow, and hole shape is circular, aperture 30-35nm, pitch of holes 80-100nm, hole depth 162.4 μ m, thicknesses of layers 162.4 μ m;
(9) oxide film is peeled off
1. on the subcooling recycle pump, carry out;
The beaker that 2. electrolytic solution will be housed places the subcooling recycle pump, opens the magnetic stirring apparatus of beaker bottom, opens the subcooling recycle pump simultaneously, makes electrolyzer temperature be in 0 ℃ ± 0.5 ℃, and beaker electrolyte inside temperature is in 2 ℃ ± 0.5 ℃;
3. the aluminium flake after the strong anodic oxidation, platinized platinum vertically are suspended in the beaker, and make aluminium flake, platinized platinum parallel;
4. open D.C. regulated power supply, the aluminium flake after the strong anodic oxidation is an anode, and platinized platinum is a negative electrode, and voltage of supply is risen to the strong anodic oxidation voltage 160V of aluminium flake earlier, reduces to 0V voltage with the blowdown rate of 5V/min then;
5. replace cathode and anode, displacement back: the aluminium flake of strong anodic oxidation is a negative electrode, and to change the platinized platinum of negative electrode into inoxidized aluminium flake be anode, and voltage stabilized source boosts to 10V, constant voltage 5min, the pressure in bubbles of utilizing cathodic reduction reaction to produce is peeled off multiaperture pellumina and aluminium flake;
(10) ultrasonic cleaning multiaperture pellumina
1. deionized water 50ml ± 0.5ml is placed beaker;
2. multiaperture pellumina is soaked in the deionized water of beaker ultrasonic cleaning 10min;
3. distinguish repeated washing 3 times with deionized water;
4. multiaperture pellumina is taken out airing;
(11) detect, analyze, characterize
The surface and the end face pattern of use emission scan electron microscope observation multiaperture pellumina are measured hole shape, aperture, hole depth, pitch of holes;
(12) packing and storing
Place in the clean soft material multiaperture pellumina is open and flat, be stored in drying, cool place, the clean environment, storing temp is 20 ℃ ± 3 ℃, strict fire prevention, sun-proof, anti-soda acid to corrode.
2. a kind of strong anonizing of producing multiaperture pellumina according to claim 1, it is characterized in that: described strong anonizing is produced multiaperture pellumina, be that mixing solutions with oxalic acid, dehydrated alcohol, deionized water is an electrolytic solution, the volume ratio of dehydrated alcohol and deionized water is 0.25: 1 in the electrolytic solution, and concentration of electrolyte is 0.3mol/L.
3. a kind of strong anonizing of producing multiaperture pellumina according to claim 1, it is characterized in that: described strong anonizing is produced multiaperture pellumina, be under 160V voltage, electrolyte temperature is in 2 ℃ ± 0.5 ℃, strong anodic oxidation is finished in the time at 180min ± 1min, and boost in voltage speed is 0.5-0.9V/s.
4. a kind of strong anonizing of producing multiaperture pellumina according to claim 1, it is characterized in that: described strong anonizing is produced multiaperture pellumina, its product is that light yellow, hole shape is that 30-35nm, pitch of holes are that 80-100nm, hole depth are that 162.4 μ m, thicknesses of layers are 162.4 μ m for circular, aperture, is that the porous ordering rule is arranged.
5. a kind of strong anonizing of producing multiaperture pellumina according to claim 1, it is characterized in that: described strong anonizing is produced pellumina, the growth velocity 52 μ m/h of strong anodised pellumina.
6. a kind of strong anonizing of producing multiaperture pellumina according to claim 1; it is characterized in that: producing of multiaperture pellumina is to do anode with aluminium flake; platinized platinum is cooked negative electrode; do the shielding gas of annealing aluminum sheet with the rare gas element argon gas; make clean-out system with acetone, dehydrated alcohol; do the electrochemical etching agent of aluminium flake with the mixing solutions of perchloric acid, dehydrated alcohol; mixing solutions with oxalic acid, dehydrated alcohol, deionized water is done electrolytic solution, makees the etching reagent of anodic alumina films with the mixing solutions of phosphoric acid, chromic acid, deionized water.
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