Embodiment
Below, with reference to the accompanying drawings example of the present utility model is elaborated.
Fig. 1 is the sectional view of the anodic oxidation treatment device 10 of this example.Fig. 2 is the sectional view along the A-A line of Fig. 1.
As shown in Figure 1, anodic oxidation treatment device 10 has: the anodizing tank 12 that is full of electrolytic solution; Cover anodizing tank 12 top, on periphery, be formed with the loam cake 16 of eaves portion 14, described eaves portion 14 is used to receive the electrolytic solution that overflows from anodizing tank 12; The storage tanks 18 of temporarily stored electrolytic solution; What the electrolytic solution that eaves portion 14 is received flow to storage tanks 18 downwards flows down stream 20; Make the electrolytic solution of storage tanks 18 turn back to close anodizing tank 12 bottoms that are formed at aluminium base 30 downsides supplying opening 22 return stream 24; Be arranged at and return stream 24 pump 26 midway; To the cowling panel of adjusting from supplying opening 22 effusive electrolyte flow 28.
Refer again to Fig. 2, anodic oxidation treatment device 10 has: a pair of rolling clamp 32A, the 32B of circular plate type, and this a pair of rolling clamp 32A, 32B insert openings at two ends 31A, the 31B as anodic hollow cylindrical aluminium base 30 respectively; Rotatably support described rolling clamp 32A, 32B respectively and support a pair of holding plate 33A, the 33B (with reference to Fig. 2) of described aluminium base 30 by described rolling clamp 32A, 32B; 2 negative plates 36 that clip aluminium base 30 and dispose relatively; Be electrically connected the power supply 38 of aluminium base 30 and 2 negative plates 36; Regulate the temperature adjustment unit 40 of the electrolyte temperature of storage tanks 18.
Pump 26 forms from storage tanks 18 has pressure ground to discharge electrolytic solution through returning stream 24 to the electrolyte flow of anodizing tank 12 and from supplying opening 22, forms the electrolyte flow that rises to top from the bottom of anodizing tank 12 thus.
Cowling panel 28 is to adjust plate-shaped member electrolyte flow, that be formed with a plurality of through holes, it rises the whole bottom that electrolyte flow is adjusted into from supplying opening 22 effusive electrolytic solution from anodizing tank 12 substantially equably, and this cowling panel 28 is configured between aluminium base 30 and the supplying opening 22 and is surperficial near level.
2 negative plates 36 are the metal sheets that dispose relatively apart from aluminium base 30 certain intervals, and dispose with respect to the central axes of aluminium base 30, and clip aluminium base 30 from horizontal direction.In addition, as the temperature adjustment unit 40 that is arranged on storage tanks 18, can list with water, wet goods as the heat exchanger of thermal medium, electric heater etc.
With reference to Fig. 2, holding plate 33A, 33B are the metal sheets that is configured to clip from axial C1 aluminium base 30 across the gap relatively, it has the 34A of bearing portion, 34B respectively on the extended line of the axial C1 of aluminium base 30, the 34A of bearing portion, 34B are for can be rotated anchor clamps 32A, the 32B opening of intercalation rotatably.The inner peripheral surface of the 34A of bearing portion, 34B is provided with dry bearing 35A, the 35B that is made by resin material or metallic substance, and rolling clamp 32A, 32B rotatably are supported in holding plate 33A, 33B by described dry bearing 35A, 35B.
The top of separated holding plate 33A, 33B is provided with across between them and run through their a plurality of bar type parts 41 (referring again to Fig. 1). Holding plate 33A, 33B connect by these bar type parts 41 with the state that hangs down and be parallel to each other from described bar type parts 41.Rolling clamp 32A, 32B insert opening 31A, the 31B of aluminium base 30 with the state that gently is pressed into, aluminium base 30 is to be supported by rolling clamp 32A, 32B towards the confined state of circumferential rotation with respect to rolling clamp 32A, 32B, more specifically say, aluminium base 30 utilizes rolling clamp 32A, 32B to support, and makes its axial C1 (Fig. 2) be the level of state.That is, aluminium base 30 utilizes rolling clamp 32A, 32B to support, and makes it be the state parallel with the bottom of anodizing tank 12.
Among Fig. 2, the rotation center region that is positioned at the rolling clamp 32A in drawing left side is formed with the through hole 42 that connects on the axial C1 of aluminium base 30, in through hole 42, insert and maintain the bar-shaped energising mobile jib of making by electro-conductive material 43, and the mobile jib 43 of switching on can not be done relative rotation with respect to through hole 42 to run through state.Energising mobile jib 43 one are fixed on the rolling clamp 32A, rotate along with the rotation of rolling clamp 32A.Energising mobile jib 43 can be mode such as form flange part on energising mobile jib 43, be threaded with respect to the fixing means of rolling clamp 32A, yet, also can be other modes.
One side of energising mobile jib 43 forms coniform, this coniform end 44 and rotation carrier 46 butts, and rotation carrier 46 is formed at the lower end side of the power supply batten 45 that hangs down from bar type parts 41.Rotation carrier 46 has cone shape recess 47, makes the tip of coniform end 44 and the bottom butt of this recess 47, simultaneously the side regions by recess 47 surround coniform end 44 around, thereby carry out position limit.Energising mobile jib 43 is electrically connected to power supply 38 (Fig. 1) by power supply batten 45 and rotation carrier 46, obtains current supply from power supply 38.And coniform end 44 both can be the parts with energising mobile jib 43 one, also can be the parts of the split of removably installing.
The opposite side one of energising mobile jib 43 can be fixed with the radially outstanding a pair of terminal of being made by electro-conductive material 48 with switching on, and the size setting of terminal 48 and shape set for being connected on the inner peripheral surface of aluminium base 30 with switching on.Thus, terminal 48 is connected on the aluminium base 30, can supply with electric current to aluminium base 30.Say that more specifically terminal 48 forms: be positioned at the most advanced and sophisticated side warpage of aluminium base 30 sides, have the smooth bearing surface 48A on the inner peripheral surface that is connected to aluminium base 30 at this warpage position, from here to aluminium base 30 energisings.
In the anodic oxidation treatment device 10 of above-mentioned formation, when the motivating force of the not shown motor of transmission made aluminium base 30 rotations, the rolling clamp 32A of opening 31A side was along with the aluminium base 30 by rolling clamp 32B rotation is rotated.Therefore, under the state that the energising mobile jib 43 that is fixed on rolling clamp 32A is switched in the regulation zone that can be connected to aluminium base 30 inner peripheral surfaces all the time, rotate synchronously with aluminium base 30.
Use the anodic oxidation of aluminium base 30 of this anodic oxidation treatment device 10 as described below.
Aluminium base 30 be impregnated under the state of electrolytic solution of anodizing tank 12, and drivingmotor (omitting among the figure) makes rolling clamp 32B rotation, and making aluminium base 30 is that rotation center is rotated with its axial C1.
Rotate aluminium base 30, and between aluminium base 30 and negative plate 36, apply voltage, aluminium base 30 is carried out anodic oxidation by power supply batten 45, rotation carrier 46 and terminal 48.
During anodic oxidation aluminium base 30, discharge a part of electrolytic solution while rotate aluminium base 30 from anodizing tank 12, anode oxidation trough 12 is supplied with the electrolytic solution of equivalent simultaneously.Specifically, electrolytic solution overflows from anodizing tank 12, makes the electrolytic solution that overflows run down into storage tanks 18, after the temperature by storage tanks 18 conciliation electrolytic solution, this electrolytic solution is turned back in the anodizing tank 12 from the supplying opening 22 that is arranged at aluminium base 30 downsides.
At this moment, utilize pump 26 to have pressure ground to discharge electrolytic solution from supplying opening 22, and then by cowling panel 28 adjustment electrolyte flow, make the electrolytic solution of discharging rise equably substantially, make the electrolytic solution that rises to top from the bottom of anodizing tank 12 form roughly thus and flow uniformly from the whole bottom of anodizing tank 12 from supplying opening 22.
The feed rate of the electrolytic solution of anode oxidation trough 12 (output of the electrolytic solution of discharging from supplying opening 22) is preferably more than 20L/ divides, and particularly is preferably more than 30L/ divides.The feed rate of electrolytic solution is more than 30L/ divides, and then can produce sufficient electrolyte flow at whole anodizing tank 12.From the ability of pump 26, the feed rate of electrolytic solution is preferably below the 150L/ branch, particularly is preferably below the 140L/ branch.
The rotating speed of aluminium base 30 is preferably more than the 0.1rpm.The rotating speed of aluminium base 30 then can fully suppress concentration, temperature unbalanced of the electrolytic solution around the aluminium base 30 more than 0.1rpm.From the ability of drive unit 30, the rotating speed of aluminium base 30 is preferably below the 20rpm.
Aluminium base 30 is implemented aforesaid anodic oxidation, then form the oxide scale film 54 of the fine-meshed 52 shown in Fig. 3 (b) from the state shown in Fig. 3 (a).
The purity of aluminium is preferably more than 99%, particularly is preferably more than 99.5%, more is preferably more than 99.8%.When the purity of aluminium is low, when anodic oxidation because the segregation of impurity is formed with the sag and swell that makes visible light size at random, the systematicness decline of the pore 52 that forms by anodic oxidation.Electrolytic solution can be oxalic acid, sulfuric acid etc.
Use the situation of oxalic acid as electrolytic solution;
The concentration of oxalic acid is preferably below the 0.7M.When the concentration of oxalic acid surpassed 0.7M, it was too high current value to occur, the situation of the surperficial roughen of oxide scale film.
When formation voltage is 30V~60V, can obtain having the cycle and be the anodised aluminium of the higher pore of the systematicness of 100nm.Formation voltage is higher or low than this scope all may to reduce systematicness.
The temperature of electrolytic solution is preferably below 60 ℃, particularly is preferably below 45 ℃.When the temperature of electrolytic solution surpasses 60 ℃, may cause that the phenomenon, the pore that are called " burn " are damaged, surface melting and cause the systematicness disorder of pore.
Use the situation of sulfuric acid as electrolytic solution;
Vitriolic concentration is preferably below the 0.7M.When vitriolic concentration surpassed 0.7M, it was too high current value to occur, can't keep the situation of voltage rating.
When formation voltage is 25V~30V, can obtain having the cycle and be the anodised aluminium of the higher pore of the systematicness of 63nm.Formation voltage is higher or low than this scope all may to reduce systematicness.
The temperature of electrolytic solution is preferably below 30 ℃, particularly is preferably below 20 ℃.When the temperature of electrolytic solution surpasses 30 ℃, may cause the phenomenon that is called " burn ", cause the pore damage, surface melting and cause the systematicness disorder of pore.
Then, after formation has the oxide scale film 54 of pore 52 shown in Fig. 3 (b), make roller shape mould by repeating following operation: thus use anodic oxidation treatment device 10 to carry out the operation (anodic oxidation treatment) that anodic oxidation forms the anodised aluminium that has a plurality of pores, and the operation (the pore aperture enlarges processing) that enlarges this pore aperture.
When repeating to implement anodic oxidation treatment operation and the expansion processing of pore aperture, first-selection, temporary transient scale removal film 54 shown in Fig. 3 (c).Here generate point 56 by it being made anodised pore, can improve the systematicness of pore.
The method of scale removal film can be for making the method in its solution that is dissolved in dissolved aluminum selective dissolution oxide scale film not.This solution can for for example, chromic acid/phosphoric acid mixed solution etc.
Then, when the aluminium base 30 of having removed oxide scale film is carried out anodic oxidation once more, shown in Fig. 3 (d), be formed with oxide scale film 54 with cylindric pore 52.
Anodic oxidation uses above-mentioned anodic oxidation treatment device 10 to implement.The condition that condition is can be for the oxide scale film 54 that forms shown in Fig. 3 (b) time identical.The anodised time is long more, and the pore that can access is dark more.
Then, shown in Fig. 3 (e), make the processing of the aperture expansion of pore 52.Enlarge to handle in the pore aperture is a kind of oxide scale film is immersed in the solvent soln and enlarge the processing in the pore aperture that obtains by anodic oxidation.This solution can be phosphate aqueous solution of for example mass concentration about 5% etc.
It is long more that the pore aperture enlarges the time of handling, and the pore aperture is big more.
Then, when carrying out anodic oxidation once more, shown in Fig. 3 (f), and then be formed with from that extend, that diameter the is less downwards cylindric pore 52 in the bottom of cylindric pore 52.
Anodic oxidation uses above-mentioned anodic oxidation treatment device 10 to implement.Condition is identical with above-mentioned condition to get final product.The anodised time is long more, and it is dark more to access pore.
Then, as mentioned above, carry out the pore aperture repeatedly and enlarge processing and anodic oxidation treatment, obtain roller shape mould 60 shown in Fig. 3 (g), that be formed with anodised aluminium (the porous matter oxide scale film (alumite) of aluminium), described anodised aluminium has and is shaped as the pore 52 that diameter reduces continuously to depth direction from peristome.Preferred final step is treated to the pore aperture and enlarges processing.
Multiple adds up to number of times to be preferably more than three times, particularly is preferably more than five times.The multiple number of times is at twice when following, because the pore diameter discontinuity reduces, so the reflectivity decline effect of the blooming that this pore of transfer printing is made is insufficient.
The shape of pore 52 can be approximate circle cone-shaped, square cone-shaped etc.Be below the visible wavelength average period that pore is 52, promptly below the 400nm.Be preferably more than the 25nm average period that pore is 52.
The degree of depth of pore 52 is preferably 100~500nm, particularly is preferably 150~400nm.The depth-to-width ratio of pore 52 (width of the degree of depth of pore/pore peristome) is preferably more than 1.5, particularly is preferably more than 2.0.
In the anodic oxidation treatment device 10 of aforesaid present embodiment, when the aluminium base 30 that makes the roller shape in the electrolytic solution of anodizing tank 12 during anodic oxidation, because can rotate aluminium base 30 as turning axle with the central shaft of aluminium base 30, so can suppress concentration of electrolyte, temperature unbalanced around the aluminium base 30, on the whole periphery of aluminium base 30, carry out anodic oxidation uniformly substantially, consequently, can produce the not neat roller shape mould of the degree of depth that has suppressed pore.
In addition, because aluminium base 30 and terminal 48 are rotated synchronously, and from terminal 48 to aluminium base 30 energising, so can eliminate aluminium base 30 suppress to switch on the wearing and tearing of 48 of terminals bad, can so the qualification rate of raising roller shape mould.
Promptly, only rotate the mode of aluminium base 30 (fixes terminal 48 if terminal 48 and aluminium base 30 are asynchronous with the state of the inner peripheral surface that is connected to aluminium base 30, only make the mode of aluminium base 30 rotations), then, terminal 48 switches on owing to sliding on the inner peripheral surface of aluminium base 30, so between terminal 48 and aluminium base 30, produce contact wear, it is bad to cause energising between terminal 48 and aluminium base 30, yet, in the utility model, by under the state of aluminium base 30 and terminal 48 butts, rotating aluminium base 30 and terminal 48 synchronously, can prevent the generation that this energising is bad.
Here, Figure 4 shows that the embodiment of actual measurement for the switch-on regime of aluminium base 30 in the anodic oxidation treatment device 10.In Fig. 4, transverse axis is represented time shaft (second), and the longitudinal axis is represented the current value (A) to aluminium base 30 energisings.Can find out clearly that from this figure the current value that applies in the early stage is after the steady state, can under the state of fixed current value stabilization, switch on chronically to aluminium base 30.From this embodiment as can be seen the utility model suppress the bad effect of energising.
In addition, in the present embodiment, the end of energising mobile jib 43 is set to coniform (coniform end 44), can reduce contact area thus with rotation carrier 46, to be controlled at bottom line because of the powder that contact wear produces, in addition, can also upgrade the surface.Therefore, can not form the higher alumina layer of electrical insulating property, can keep switch-on regime.