CN1200146C - Method for electrolytic coloring of aluminium material - Google Patents
Method for electrolytic coloring of aluminium material Download PDFInfo
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- CN1200146C CN1200146C CNB008094543A CN00809454A CN1200146C CN 1200146 C CN1200146 C CN 1200146C CN B008094543 A CNB008094543 A CN B008094543A CN 00809454 A CN00809454 A CN 00809454A CN 1200146 C CN1200146 C CN 1200146C
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
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Abstract
In a method for electrolytic coloring of an aluminum material which comprises immersing an aluminum material, which comprises aluminum or an aluminum alloy, having an anodized film in an electrolytic coloring treatment bath containing a soluble metal salt and passing a direct current waveform by the use of the aluminum material as an anode, to thereby subjecting the aluminum material to a pre-treatment prior to coloring, and then subjecting the aluminum material to an a.c. electrolytic coloring treatment in the same electrolytic coloring treatment bath, an improvement which comprises performing the above pre-treatment prior to coloring until a voltage and a current reach respective predetermined values. The improved method can be employed for significantly reducing coloring irregularities not only within one energizing lot, but also between different energizing lots, and thus for producing an aluminum material being colored in a uniform tone with stability and ease on an industrial scale.
Description
Technical field
The present invention relates to carry out the electrocolor process of the aluminium that aluminum or aluminum alloy that anodic oxidation coating handles constitutes (below abbreviate " aluminium " as), more particularly, relate to the electrocolor process that when the ac electrolytic coloring that carries out aluminium is handled, can obtain the good aluminium of uniform hue, and then, relate to when the electrolytic coloring of aluminium is handled not only in same energising batch, do not have colour cast from but also can be suppressed at the tone that is easy to generate between each energising batch and depart from, can make electrocolor process with the aluminium of the painted aluminium of homogeneous hue.
Background technology
Aluminium is because excellent performances such as processing characteristics and erosion resistances, so be widely used in building materials, vehicle part, a lot of fields such as furniture, at this moment, in order to improve the design effect of aluminium, containing Ni, Co, Cu, carry out electrolysis in the electrolytic solution of soluble metallic salts such as Sn, the electrolysis resultant of these metal-salts is precipitate in the anodic oxidation coating of porous matter, make the painted electrolytic coloring of aluminium.
Simultaneously, as treatment process to this aluminium electrolytic coloring, known, in electrolytic solution, pass to alternating-current and carry out electrolytic ac electrolytic coloring method (shallow field method), and in electrolytic solution, pass to direct current and carry out electrolytic dc electrolysis staining method, in the painted processing of preceding a kind of interchange, has the advantage that to use cheap power supply, and in the painted processing of a kind of dc electrolysis in back, has the advantage that to carry out electrolysis treatment in the short period of time, in addition, particularly when the electrolytic coloring that heavy colours such as carrying out black is, can obtain very uniform coloring effect.
But, in this aluminium electrolytic coloring is handled, when particularly aluminium has complicated shape, when perhaps the aluminium of different shape being carried out electrolytic coloring simultaneously, be easy to generate painted irregularly at its recess and salient, can not keep the homogeneity of tone, exceed the desired allowed band of user, reduce yield rate, thereby cause the problem of the cost up of product.
For this reason, in the past, in order to address this problem, the whole bag of tricks has been proposed, for example, known have aluminium is being carried out before ac electrolytic coloring handles, in identical electrolytic coloring treatment solution, be that anode passes to the method that direct current carries out painted pre-treatment with the aluminium, the method that the magnitude of voltage of galvanic current is kept necessarily, carries out the constant voltage electrolysis (special public clear 54-23, No. 664 communiques etc.) of the energising of certain hour.
Utilize the electrolytic painted pre-treatment of this constant voltage, by having the direct current energising regular hour of certain voltage value, make the resistance value homogenizing of tunicle of each several part of the anodic oxidation coating of aluminium, so as to when ensuing ac electrolytic coloring is handled, making more uniform electric current flow through tunicle, eliminate painted irregular, when aluminium is compared the electrolytic coloring of dense tone, be a kind of industrial feasible method.
In addition, as other method, proposed when aluminium is carried out electrolytic coloring, being divided into a plurality of stages switches on when stopping intermittently repeatedly, at this moment by the processes voltage of next stage is set successively than the processes voltage of previous stage with raising, can reach the scheme (spy opens flat 8-41, No. 685 communiques) of stable tone.In this method, self-evident, its tone is stable, can shorten the black colorant time, suppresses the influence of micro-impurity, prevents detrimentally affects such as white stripes.
But, all these methods, for the stability of the tone in the same energising batch, can reach more stable tone, but, then can not be suppressed fully for the tone unstable that produces between each energising batch, respectively by batch between be difficult to make with the painted aluminium of uniform color tone.
This tendency is when carrying out the electrolytic coloring that heavy colour transfers, and problem also is not very big, but can occur significantly when the electrolytic coloring that carries out than light appearance, becomes problem when industrial production electrolytic coloring aluminium.
And then, as another method that addresses the above problem, having proposed will be as the overall current density of the aggregate values of the absolute value that just reaches negative current density in the current waveform from the first step to the ac electrolytic coloring processing scheme of fourth stage variation stage by stage (special fair 3-32, No. 637 communiques) at least.In this method, with foregoing the same, when aluminium being carried out the electrolytic coloring of transferring than heavy colour, tonal difference is not too obvious.
But, in this method, the control of electric current is become very complicated, exist the cost of equipment costliness in addition, from the disadvantageous problem of the angle of economy.Simultaneously, when aluminium being carried out bronze colour etc., even tone has difference slightly than the electrolytic coloring of light appearance, can be because the situation of light be carried out exaggerative, become very showy, its commodity value is caused very big influence, the aluminium of industrial production electrolytic coloring is caused very big problem.
For this reason, the present inventor etc. depart from, make with the painted aluminium of homogeneous hue stably and help carrying out the result that industrial method is furtherd investigate for prevent to produce between each energising batch tone as much as possible when the ac electrolytic coloring of aluminium is handled, find, be performed until predefined final arrival magnitude of voltage and the final current value that arrives by the painted pre-treatment of being carried out before ac electrolytic coloring is handled, even when carrying out the electrolytic coloring of lighter tone, each the energising batch between also can obtain uniform color tone.
That is, by each contriver's of the present invention investigation, aluminium is being carried out ac electrolytic coloring when handling, the tone that produces between each energising batch departs from can be thought for following reason.
For example, when the ac electrolytic coloring that carries out aluminium is handled, as its painted pre-treatment, by in same electrolytic coloring treatment solution, carrying out under the situation of painted pre-treatment with the constant current electroanalysis, electrolysis voltage in this painted pre-treatment is subjected to the temperature of this electrolytic coloring treatment solution, the pH value, and the influence that is immersed in the washing time when washing in the washing step of aluminium after anodic oxidation coating is handled in this electrolytic coloring treatment solution and the pH value of water lotion etc. (below unite be referred to as " solution condition ") to these conditions, this electrolysis voltage changes along with the variation of these " solution conditions ".
Simultaneously, in the painted pre-treatment that utilizes the constant current electrolysis to carry out, electrolysis voltage is mainly by the resistance of electrolytic coloring treatment solution and be immersed in the resistance decision of the anodic oxidation coating of the aluminium material surface in this electrolytic coloring treatment solution, but, wherein, the resistance change of electrolytic coloring treatment solution between each energising batch, when being converted into the correspondent voltage value, general maximum also is no more than about 0.1～0.2V, be not too big, the variation of electrolysis voltage mainly is because the resistance of tunicle causes in painted pre-treatment.Simultaneously, the anodic oxidation coating of this aluminium material surface is that the aluminum oxide by the densification that forms on the aluminum matrix of aluminium constitutes, and is made of so-called " blocking layer " and the porous matter that is formed on this blocking layer, and the resistance of this tunicle depends primarily on the blocking layer.
Simultaneously, utilize the blocking layer formation efficiency in the painted pre-treatment that the constant current electrolysis carries out, be approximately about 60% with respect to the apparent efficiency that current efficiency is represented as the ratio of 100% o'clock theoretical growing amount (increasing amount/theoretical growing amount) with the actual increasing amount of the dissolved of considering the blocking layer, and, because the chemical dissolution speed on blocking layer is subjected to the influence of the variation of solution condition, so it is the same with the electrolysis voltage in the foregoing painted pre-treatment, this apparent efficiency is subjected to the influence of this solution condition and changes, thereby, cause the resistance of the tunicle of aluminium material surface between each energising batch, to change.
Yet, keep the certain one side of current value of galvanic current to carry out in the painted pre-treatment of constant current electrolysis of prior art of energising of certain hour in one side, be subjected to the influence that " variation of the electrolysis voltage in the painted pre-treatment " that the variation because of above-mentioned solution condition causes reaches " changes in resistance of the tunicle of aluminium material surface ", electrolysis voltage changed in conduction time, make the generation to be controlled at blocking layer on the aluminium material surface fully, can not make the distribution of current of tunicle of aluminium constant.
Therefore, for each the energising batch between obtain uniform color tone, need be to the in addition strict control of above-mentioned solution condition, eliminate the influence of this solution condition, in fact, be very difficult in the industrial strict variation of controlling this solution condition, in span of control, can not avoid the variation of solution condition, particularly when the electrolytic coloring that carries out than light appearance, can not suppress the tone variation between each energising batch fully.
The present inventor etc. for how from the industrial result who studies that addresses this problem, find, the thickness on the blocking layer of generation, controlled anodic oxidation coating depends on final magnitude of voltage and the current value that arrives in this painted pre-treatment process in painted pre-treatment, for example, when utilizing constant current to carry out painted pre-treatment, be directly proportional with the magnitude of voltage of final arrival, thereby, the thickness on this blocking layer has direct relation with the tone that utilizes ac electrolytic coloring to handle the electrolytic coloring of the aluminium of giving, thereby, finished the present invention.
Thereby, the purpose of this invention is to provide when the aluminium ac electrolytic coloring is handled, not only one the energising batch in, and between each energising batch, prevent that as much as possible producing tone departs from, stable and industrial easy manufacturing, with the aluminium electrolytic coloring method of the painted aluminium of homogeneous hue.
Description to invention
The present invention is a kind of like this aluminium electrocolor process, promptly, be immersed in the electrolytic coloring treatment solution that contains soluble metallic salt at the aluminium that the aluminum or aluminum alloy that carried out the anodic oxidation coating processing is constituted, this aluminium is carried out painted pre-treatment as the electric current that anode passes to dc waveform, carrying out ac electrolytic coloring then in same electrolytic coloring treatment solution handles, wherein, above-mentioned painted pre-treatment is performed until predefined final arrival magnitude of voltage and the final current value that arrives.
Simultaneously, in the present invention, particularly preferred form is a kind of like this aluminium electrocolor process, promptly, utilize one side that current value is remained on predefined final arrival current value, one side utilization passes to direct current and carries out painted pre-treatment up to the constant current electrolysis that reaches final arrival magnitude of voltage, with the voltage control AC wave shape of 0.55～0.8 times crest voltage aluminium is switched on then, handle to carry out ac electrolytic coloring with the final voltage when painted pre-treatment is carried out in this constant current electrolysis.
In the present invention, as carrying out the aluminium that electrolytic coloring is handled, do not have specific restriction, the situation when handling with anodic oxidation coating in the prior art is the same, uses sulfuric acid as electrolytic solution, oxalic acid, sulfonic acid, aqueous acids such as chromic acid, the aluminium starting material that constitute with common aluminum or aluminum alloy are as anode, make direct current or interchange or direct current and exchange synergetic electric current and flow through on it, on the raw-material surface of aluminium, generate anodic oxidation coating and obtain.
Simultaneously, carry out the electrolytic coloring treatment solution that contains soluble metallic salt of painted pre-treatment and ac electrolytic coloring processing usefulness for the aluminium that will obtain like this, there is not specific restriction yet, can be the same with the electrolytic coloring treatment solution of prior art, for example, as soluble metallic salt, can list nickel (Ni), cobalt (Co), copper (Cu), tin (Sn), chromium (Cr), magnesium (Mg), iron (Fe), cadmium (Cd), titanium (Ti), manganese (Mn), molybdenum (Mo), calcium (Ca), barium (Ba), plumbous (Pb), the vitriol of zinc metals such as (Zn), nitrate, phosphoric acid salt, muriate, inorganic acid salts such as chromic salt, and oxalate, acetate, organic acid salts such as tartrate etc.
In addition, in order further to improve degree of staining etc., hyposulfite such as zinc dithionite, ammonium thiosulfate can be added in this electrolytic coloring treatment solution as required with V-Brite B, thiosulphates such as Sulfothiorine, hydrosulphite such as sodium bisulfite, and sulfurous acid, sulphite such as S-WAT, additive headed by the Thiovanic acid, strong reducing property compounds such as thioglycolate salt such as ammonium mercaptoacetate.
In the present invention, the painted pre-treatment of before ac electrolytic coloring is handled, being carried out, be that aluminium is immersed in the electrolytic coloring treatment solution, with this aluminium as anode with dc waveform (being direct current or alternating current-direct current overlaid waveforms) energising, magnitude of voltage at this moment (dc waveform is to be its crest voltage under the situation of alternating current-direct current stack ripple) and current value reach predefined final arrival magnitude of voltage and finally finish when arriving current value.
As the concrete grammar of implementing this painted pre-treatment, for example, can carry out as follows, promptly, carry out the occasion of constant current electrolysis at the electric current that passes to constant current value, one side remains on predefined final arrival current value with current value and simultaneously passes to direct current, when the magnitude of voltage when at this moment reaches predefined final arrival magnitude of voltage, finishes this painted pre-treatment.In this constant current pre-treatment, at the energising initial stage, the little part of resistance at the part that the blocking layer is thin, resistance is little of the tunicle of aluminium and the solution near apart from the distance of negative electrode, the preferential flow overcurrent, compensate the thickness on the blocking layer of this part, perhaps the thickness of these parts is thickeied the thickness of comparing with other parts corresponding to resistance difference relatively, when reaching final arrival magnitude of voltage, obtains the constant anodic current and distributes.
On the other hand, passing to magnitude of voltage constant electric current, when carrying out this painted pre-treatment, when flowing through the electric current of the predefined final arrival magnitude of voltage of beginning at the energising initial stage usually, the danger that produces overcurrent arranged with constant voltage.Therefore, in order to prevent to flow through overcurrent, begin to carry out the energising of dc waveform with the voltage that is lower than predefined final arrival magnitude of voltage at the energising initial stage, then, in the stage that current value settles out magnitude of voltage is switched to final arrival magnitude of voltage, this constant voltage electrolysis is lasted till when reaching predefined final arrival current value always till.
Here, in painted pre-treatment, final arrive magnitude of voltage and the final setting that arrives current value, different according to the aluminium that must obtain which kind of tone as product, when the electrolytic coloring that carries out than light appearance, can be set in 30～50V to final arrival magnitude of voltage, otherwise, when carrying out the denseer electrolytic coloring of tone, the magnitude of voltage that finally arrives can be set in 20～30V, simultaneously, can be set in 20～50A/m for final arrival current value
2Scope in.
After the painted pre-treatment of carrying out like this finishes, in the present invention, intactly use same electrolytic coloring treatment solution, the electric current that aluminium is passed to interchange or the synergetic waveform of alternating current-direct current carries out the ac electrolytic coloring processing.
In this case, there is not specific restriction for the ac electrolytic coloring treatment process, can similarly carry out with the method for prior art, but crest voltage for employed interchange or alternating current-direct current overlaid waveforms, for reason described below, preferably be set at 0.55～0.8 times of in painted pre-treatment predefined final arrival voltage, more preferably be set at 0.65～0.75 times of final arrival voltage.When the crest voltage of this employed interchange or alternating current-direct current overlaid waveforms is lower than painted pre-treatment 0.55 times of predefined final arrival voltage the time, can not painted or painted speed extremely slow, and when it surpasses 0.8 times, current value when being difficult to keep ac electrolytic coloring to handle is constant, even make the treatment time constant, can not obtain uniform color tone.
About this point,, can do following understanding by the present inventor's etc. research.
That is, in electrolytic coloring was handled, by reduction reaction, the metal species in the electrolytic solution precipitate in the tunicle, thereby provides tone.Thereby what is called makes uniform hue, is exactly nothing but to make the distribution of current of this aluminium even being that negative electrode carries out electrolytic coloring when handling with the aluminium.
Be that anode is when stipulating the painted pre-treatment of current control of final voltage with the aluminium, since form corresponding to the resistance of each several part electrolytic solution by membrane resistance, so, can make the distribution of current of aluminium constant and be uniform basically in the moment that painted pre-treatment finishes.
Yet, thereafter, carry out at the electric current that passes to AC wave shape under the situation of ac electrolytic coloring processing, during final voltage when the crest voltage of this AC wave shape is equal to or greater than the painted pre-treatment of current control, although the distribution of current of the moment aluminium that finishes in painted pre-treatment is uniform basically, but the distribution of current of the aluminium when ac electrolytic coloring is handled is uneven, thereby causes the inhomogeneous of tone.This is owing to had the character that difference because of the sense of current, its resistance value produce difference by membrane resistance itself, and the resistance value when aluminium is become negative electrode is the little cause of resistance during as anode than it.
Simultaneously, the present inventor etc. find the result of study of this problem, and the ratio between the crest voltage of the AC wave shape when final voltage when ac electrolytic coloring is handled during the painted pre-treatment of tunicle changes in resistance and current control and ac electrolytic coloring processing has complementary substantial connection.Promptly, at first, by at the final voltage of regulation, pass to galvanic current and carry out the painted pre-treatment of current control, then the electric current of the voltage control AC wave shape by passing to 0.55～0.8 times crest voltage with the final voltage when carrying out the painted pre-treatment of above-mentioned current control in same electrolytic colouring treatment solution carries out ac electrolytic coloring and handles, the uniform current that can obtain the tunicle resistance change when finishing corresponding to painted pre-treatment distributes, thereby can obtain uniform color tone.
In actually operating, in order to boost productivity, be necessary in 0.55～0.8 times scope of this final voltage, to select high-voltage as far as possible, in order to satisfy uniform hue and both requirement of boosting productivity, more preferably, with voltage of alternating current the aluminium that is configured in after the painted pre-treatment of current control in the electrolytic coloring treatment solution is scanned, obtain the given critical voltage Eo of intersection point by the extended line separately of flat site in the resulting voltage-to-current curve and elevated areas, the crest voltage when preferably ac electrolytic coloring being handled is set at this critical voltage Eo.This critical voltage Eo is generally about 0.65～0.75 times of in the common painted pre-treatment of current control predefined final arrival voltage, according to painted pre-treatment condition and how many variations to some extent of other condition (different condition that anodic oxidation coating is handled and subsequent washing condition etc.), at last, can determine clearly as the crest voltage value of the suitableeest interchange or alternating current-direct current overlaid waveforms.
The method according to this invention is at the initial stage and the mid-term stage of painted pre-treatment, owing to flow through electric current easily in the part near counter electrode, so preferentially generate the blocking layer, be accompanied by the growth on this blocking layer, the resistance of tunicle increases, and is suppressed at the easy degree that this part flows through electric current thus.Promptly, because in painted pre-treatment, in the part preferred growth blocking layer of flowing through electric current easily, so when ac electrolytic coloring is handled, the complexity that the electric current that elimination causes because of the position flows through poor, in same energising batch with basically uniformly distribution of current in the whole surperficial upper reaches of aluminium overcurrent, thereby eliminate tone variation in the same energising batch.
In addition, in the method for the invention, owing to being performed until, above-mentioned painted pre-treatment reaches predefined final arrival magnitude of voltage and the final current value that arrives, even so for example solution condition each the energising batch between change, state by the last blocking layer of adjusting of this painted pre-treatment, each the energising batch between also be constant, between each energising batch, make electric current with basically uniformly distribution of current flow through the whole zone of aluminium material surface, eliminate the tone variation between each energising batch.
The simple declaration of accompanying drawing
The graphic representation of the voltage-to-current curve when Fig. 1 is the critical voltage Eo that represents to obtain among the embodiment 1.
The optimised form that carries out an invention
Particularly the preferred embodiment of the present invention is described according to test example, embodiment and comparative example below.
(embodiment 1)
Use A6063S-T5 as the aluminium starting material, at 20%H
2SO
4, 100A/m
2Carry out anodic oxidation coating under * 30 minutes the condition and handle, make the anodic oxidation coating that generates thickness 10 μ m on aluminium starting material surface, then, washing is 5 minutes in the acidic solution of pH1, obtains aluminium.
Then, preparation has CuSO
4: 25g/l and H
2SO
4: the electrolytic coloring treatment solution of 5g/l composition, with above-mentioned aluminium as anode, at current density 25A/m
2, 25 ℃ of solution temperatures, and under the condition of final arrival voltage 20V, carry out the painted pre-treatment of current control.At this moment treatment time is approximately 20 seconds.
Like this, after the painted pre-treatment of current control finishes, in same electrolytic coloring treatment solution, be starting point with OV, improve peak values of ac voltage with the speed of 1V/ second and scan, obtain the voltage-to-current curve.
Its result obtains critical voltage Eo by the intersection point of each extended line of its flat site and elevated areas as shown in Figure 1, and this critical voltage Eo is 14V.
And then, in same electrolytic coloring treatment solution, commercial peak values of ac voltage is set at the 14V of critical voltage Eo, switched on 50 seconds, 100 seconds and 150 seconds, carry out ac electrolytic coloring and handle, obtain electrolytic coloring and become peach aluminium.
Aluminium to the electrolytic coloring that obtained carries out colour measurement, obtains the homogeneity (aberration: Δ E of the tone in same energising batch
* Ab).
Simultaneously, with above-mentioned same condition under repeat that anodic oxidation coating is handled, the painted pre-treatment of current control and ac electrolytic coloring handle, to carrying out colour measurement, obtain the homogeneity (aberration: Δ E of the tone between each energising batch with the same electrolytic coloring aluminium that obtains in front
* Ab).
It the results are shown in table 1.
(embodiment 2)
Commercial peak values of ac voltage in the treatment condition of the painted pre-treatment of current control and ac electrolytic coloring are handled is undertaken by the condition shown in the table 1, all the other are identical with embodiment 1, carry out painted pre-treatment of current control and ac electrolytic coloring and handle, obtain the electrolytic coloring aluminium.
For electrolytic coloring aluminium that is obtained and the embodiment 1 the same homogeneity of studying its tone.
It the results are shown in table 1.
(embodiment 3)
Adopt and embodiment 1 identical materials and method are carried out the aluminium that anodic oxidation coating is handled, in addition,, as anode, switch on, then, drop to 32A/m in current density with the direct current of initial stage voltage 15V with aluminium with the electrolytic coloring treatment solution identical with embodiment 1
2The time, voltage is switched to 20V, carry out the painted pre-treatment of constant voltage and reach 25A/m up to ultimate current density
2Till.
After the painted pre-treatment of the constant voltage of carrying out like this finishes, the same with embodiment 1 in same electrolytic coloring treatment solution, with commercial adverse current voltage sweep, obtain the voltage-to-current curve.As a result, to obtain critical voltage Eo be 14V to the intersection point of the same each extended line from its flat site and elevated areas with embodiment 1.
And then, in same electrolytic coloring treatment solution, the alternative crest voltage of commercialization is set at the 14V of this critical voltage Eo, switched on 100 seconds, carry out ac electrolytic coloring and handle, obtain the aluminium of peach electrolytic coloring.
Carry out colour measurement for the painted aluminium that is obtained, obtain the homogeneity (aberration: Δ E of the tone in the same energising in each time batch
* Ab).
It the results are shown in table 1.
(comparative example 1)
Do not carry out the painted pre-treatment of current control, under the condition identical, carry out ac electrolytic coloring and handle, obtain the aluminium of electrolytic coloring with embodiment 1.
Aluminium and the embodiment 1 the same homogeneity of studying tone for resulting electrolytic coloring.
The results are shown in table L.
(comparative example 2～3)
Commercial alternative crest voltage in the treatment condition of the painted pre-treatment of current control and ac electrolytic coloring are handled is undertaken by the condition shown in the table 1, all the other are identical with the foregoing description 1, carry out painted pre-treatment of current control and ac electrolytic coloring and handle, obtain the aluminium of electrolytic coloring.
For resulting electrolytic coloring aluminium and the embodiment 1 the same inhomogeneity research of carrying out tone.
It the results are shown in table 1.
(comparative example 4)
Under the electrolysis voltage 30V and the condition in 30 seconds treatment times, carry out the painted pre-treatment of constant voltage, under the condition identical, carry out ac electrolytic coloring then and handle, obtain the aluminium of electrolytic coloring with embodiment 2.
The electrolytic coloring aluminium that obtains is carried out the research of the uniform hue identical with embodiment 1.
Gained the results are shown in table 1.
(table 1)
| Painted pre-treatment condition | The ac electrolytic coloring treatment condition | Aberration: Δ E * ab | |||||
| Crest voltage *1 | *2Voltage ratio | Conduction time: second | In batch | Between batch | |||
| Embodiment | 1 | The painted pre-treatment current density of current control: 25A/m 2Final voltage: the 20V that arrives | 14V | 0.70 | 50 | 1 | ≤1 |
| 100 | 1 | ≤1 | |||||
| 150 | 1 | ≤1 | |||||
| 2 | The painted pre-treatment current density of current control: 50A/m 2Final voltage: the 30V that arrives | 21V | 0.70 | 50 | 1 | ≤1 | |
| 100 | 1 | ≤1 | |||||
| 150 | 1 | ≤1 | |||||
| 3 | The painted pre-treatment initial setting of current control voltage: 15V switches back voltage: 20V and finally arrives current density: 25A/m 2 | 14V | 0.70 | 50 | |||
| 100 | 2 | ≤2 | |||||
| 150 | |||||||
| Comparative example | 1 | The non-coloring pre-treatment | 14V | - | 50 | 9 *3 | 5 |
| 2 | The painted pre-treatment current density of current control: 50A/m 2Final voltage: the 30V that arrives | 25V | 0.83 | 50 | 6 *3 | 3 | |
| 100 | ≥3 *3 | 3 | |||||
| 3 | The painted pre-treatment current density of current control: 50A/m 2Final voltage: the 30V that arrives | 14V | 0.50 | 50 | Not painted | ||
| 100 | Not painted | ||||||
| 4 | The painted pre-treatment electrolysis voltage of constant voltage: 30V treatment time: 30 seconds | 21V | 0.70 | 100 | ≥4 *3 | 4 | |
Annotate:
*Alternative crest voltage when 1) ac electrolytic coloring is handled
*2) voltage ratio=crest voltage/finally arrive voltage
*3) painted time-dependent manner is very strong
Industrial utilizability
According to the present invention, when the ac electrolytic coloring of aluminium is processed, the uniformity of its tone is self-evident in same energising batch, prevents as far as possible painted departing from of producing between each energising batch simultaneously, can be at the industrial painted painted aluminium of homogeneous hue of stably making.
Claims (3)
1, the electrocolor process of aluminium, the aluminium that the aluminum or aluminum alloy of handling through anodic oxidation coating is constituted is immersed in the electrolytic coloring treatment solution that contains soluble metallic salt, with this aluminium is that the electric current that anode passes to dc waveform carries out painted pre-treatment, then in same electrolytic coloring treatment solution, carrying out ac electrolytic coloring handles, it is characterized in that described painted pre-treatment is that one side remains on 20～50A/m
2The constant current electrolysis carried out of the predefined final arrival current value of the scope electric current that simultaneously passes to dc waveform, according to the tone of purpose goods, be performed until and reach till the predefined final arrival magnitude of voltage of the scope of 20～50V; The voltage control AC wave shape of 0.55～0.8 times scope of the final arrival magnitude of voltage the when crest voltage when handling with this ac electrolytic coloring is set in painted pre-treatment, above-mentioned ac electrolytic coloring processing is carried out in energising on aluminium.
2, the electrocolor process of aluminium, the aluminium that the aluminum or aluminum alloy of handling through anodic oxidation coating is constituted is immersed in the electrolytic coloring treatment solution that contains soluble metallic salt, with this aluminium is that the electric current that anode passes to dc waveform carries out painted pre-treatment, then in same electrolytic coloring treatment solution, carrying out ac electrolytic coloring handles, it is characterized in that, described painted pre-treatment is to begin the energising of dc waveform so that magnitude of voltage is lower than at the predefined final arrival magnitude of voltage of the scope of 20～50V, switch to the constant voltage electrolysis that final arrival magnitude of voltage carries out the dc waveform energising then, according to the tone of purpose goods, be performed until and be reduced at 20～50A/m
2The predefined final arrival current value of scope till; The voltage control AC wave shape of 0.55～0.8 times scope of the final arrival magnitude of voltage the when crest voltage when handling with this ac electrolytic coloring is set in painted pre-treatment, above-mentioned ac electrolytic coloring processing is carried out in energising on aluminium.
3, the electrocolor process of aluminium as claimed in claim 1 or 2, wherein, aluminium after the painted pre-treatment that is configured in the electrolytic coloring treatment solution is scanned with voltage of alternating current, obtain the critical voltage Eo that the intersection point of each extended line of flat site in the voltage-to-current curve that is obtained and elevated areas provides, the crest voltage when ac electrolytic coloring is handled is controlled at below this critical voltage Eo.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP179564/99 | 1999-06-25 | ||
| JP179563/99 | 1999-06-25 | ||
| JP179563/1999 | 1999-06-25 | ||
| JP17956499A JP3379482B2 (en) | 1999-06-25 | 1999-06-25 | Electrolytic coloring of aluminum material |
| JP17956399A JP3379481B2 (en) | 1999-06-25 | 1999-06-25 | Electrolytic coloring method of aluminum material |
| JP179564/1999 | 1999-06-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1358239A CN1358239A (en) | 2002-07-10 |
| CN1200146C true CN1200146C (en) | 2005-05-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008094543A Expired - Fee Related CN1200146C (en) | 1999-06-25 | 2000-06-26 | Method for electrolytic coloring of aluminium material |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1207221A4 (en) |
| KR (1) | KR100718427B1 (en) |
| CN (1) | CN1200146C (en) |
| AU (1) | AU5430200A (en) |
| CA (1) | CA2377953A1 (en) |
| NO (1) | NO20016306L (en) |
| WO (1) | WO2001000904A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101509891B (en) * | 2009-04-01 | 2012-05-30 | 西南铝业（集团）有限责任公司 | Can cap material conversion film uniformity detecting method |
| CN101831681B (en) * | 2010-06-04 | 2012-02-01 | 天津大学 | Method for preparing aluminum alloy colored composite film |
| CN102330137B (en) * | 2011-09-03 | 2015-07-08 | 广亚铝业有限公司 | Inorganic colorful electrolysis coloring technology for aluminium profile anodic oxide film |
| CN102534722B (en) * | 2011-11-28 | 2014-09-10 | 珠海市奥美伦精细化工有限公司 | Pre-dyeing treatment agent for surface of blind hole workpiece in aluminum alloy welding area and application technology thereof |
| CN103076487B (en) * | 2013-01-10 | 2015-05-27 | 安徽省临泉县嘉柏列科技有限公司 | Algorithm for sampling voltage peak in sudden change of load of high-power battery test equipment |
| CN106480486A (en) * | 2015-08-26 | 2017-03-08 | 侊东Hitech株式会社 | The classification color method of aluminium and utilize its aluminium |
| CN110592638A (en) * | 2019-09-17 | 2019-12-20 | 佛山市海化表面处理科技有限公司 | Anodic oxidation electrolytic coloring process for aluminum and aluminum alloy |
| CN111876812B (en) * | 2020-08-01 | 2021-11-05 | 东莞市慧泽凌化工科技有限公司 | Nickel-free electrolytic coloring blackening additive and use method thereof |
| CN112301398B (en) * | 2020-09-29 | 2022-02-18 | 九牧厨卫股份有限公司 | Preparation method of golden film |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1022927A (en) * | 1966-12-12 | 1966-03-16 | Tahei Asada | Improvements in and relating to coloring aluminium articles by electrolytic depositions of colored compounds |
| JPS5423664B2 (en) * | 1975-03-06 | 1979-08-15 | ||
| JPS5825495A (en) * | 1981-08-05 | 1983-02-15 | Mitsubishi Keikinzoku Kogyo Kk | Electrolytic coloring method for aluminum |
| JPS59173294A (en) * | 1983-03-23 | 1984-10-01 | Pilot Pen Co Ltd:The | Electrolytic coloration of aluminum or its alloy |
| DE3741456A1 (en) * | 1987-12-08 | 1989-06-22 | Erbsloeh Julius & August | Method for the electrolytic colouring of anodically generated oxide layers on aluminium and aluminium alloys |
| IT1240224B (en) * | 1989-08-17 | 1993-11-27 | Eliseo Benitez-Garriga | ELECTROLYTIC PROCEDURE FOR COLORING ANODIZED ALUMINUM AND ITS PRODUCT. |
| US5674371A (en) * | 1989-11-08 | 1997-10-07 | Clariant Finance (Bvi) Limited | Process for electrolytically treating aluminum and compositions therefor |
| DE4034854C2 (en) * | 1989-11-08 | 2000-08-17 | Clariant Finance Bvi Ltd | Process for the electrolytic dyeing of aluminum and aluminum alloys |
| JP3266084B2 (en) * | 1997-12-26 | 2002-03-18 | 日本軽金属株式会社 | Method for electrolytic coloring of aluminum or aluminum alloy |
-
2000
- 2000-06-26 WO PCT/JP2000/004179 patent/WO2001000904A1/en active IP Right Grant
- 2000-06-26 EP EP00939163A patent/EP1207221A4/en not_active Withdrawn
- 2000-06-26 AU AU54302/00A patent/AU5430200A/en not_active Abandoned
- 2000-06-26 KR KR1020017016461A patent/KR100718427B1/en not_active IP Right Cessation
- 2000-06-26 CN CNB008094543A patent/CN1200146C/en not_active Expired - Fee Related
- 2000-06-26 CA CA002377953A patent/CA2377953A1/en not_active Abandoned
-
2001
- 2001-12-21 NO NO20016306A patent/NO20016306L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO20016306L (en) | 2002-02-15 |
| AU5430200A (en) | 2001-01-31 |
| KR20020029870A (en) | 2002-04-20 |
| CN1358239A (en) | 2002-07-10 |
| KR100718427B1 (en) | 2007-05-14 |
| EP1207221A4 (en) | 2002-09-11 |
| EP1207221A1 (en) | 2002-05-22 |
| WO2001000904A1 (en) | 2001-01-04 |
| NO20016306D0 (en) | 2001-12-21 |
| CA2377953A1 (en) | 2001-01-04 |
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