CN1316068C - Preparation process for anode oxidation thick film of aluminium copper alloy - Google Patents
Preparation process for anode oxidation thick film of aluminium copper alloy Download PDFInfo
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- CN1316068C CN1316068C CNB2004100168600A CN200410016860A CN1316068C CN 1316068 C CN1316068 C CN 1316068C CN B2004100168600 A CNB2004100168600 A CN B2004100168600A CN 200410016860 A CN200410016860 A CN 200410016860A CN 1316068 C CN1316068 C CN 1316068C
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- thick film
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Abstract
The present invention relates to a preparation technology of a high-copper and aluminum alloy anode oxidation thick film, which is used for the technical field of the protection and the decoration of the surface of aluminum alloy. In the preparation technology of a high-copper and aluminum alloy anode oxidation thick film, low-concentration compound electrolyzing liquid, voltage is raised in periods to cause the electrolyzing liquid to maintain large current density, a thick film layer is rapidly formed on the surface of the copper and aluminum alloy in short time, the current density is lowered, the growth speed of the film layer is decelerated, stable thickness is finally achieved, and then the anode oxidation thick film with silver enamel color gloss is generated. The concentration of anode oxidation liquid phosphoric acid is from 0.5% to 1%, added organic acid is oxalic acid dihydrate or citric acid, the concentration of the oxalic acid dihydrate or the citric acid is from 0.1% to 0.5%, added rare earth salts are cerous sulfate or lanthanum sulphate, and the concentration of the cerous sulfate or the lanthanum sulphate is from 0.05% to 0.2%. The grease of a test sample is removed by cleaning for 3 min in NaOH alkali solution with the concentration of 60 g/l at 70 DEG C, and the surface ratio of an anode oxidation cathode to an anode oxidation anode is controlled to be from 2:1 to 1:2, and the cathode is a lead plate. The test sample is put into a drying tank and is dried for 30 min at 120 DEG C. The present invention breaks through the limitation of being only operated under the high-concentration electrolyzing liquid at low temperature, shortens oxidation time and has good film layer decoration.
Description
Technical field
The present invention relates to a kind of aluminum-copper alloy anodic oxidation thick film preparation, the preparation high-copper aluminium alloy anode oxide thick-film technique of boosting fast stage by stage under particularly a kind of lower concentration composite electrolytic solution, the high temperature is used for aluminum alloy surface decorative and protective Application Areas.
Background technology
The anodic oxidation that contains X alloy is a surface-treated difficult problem, especially cupric＞4% (massfraction) always, CuAl in oxidising process
2Phased soln is very fast, usually becomes electric current accumulative center, and the rete that makes this position easily is overheated and dissolve, and punctures and burns part.This alloy anode oxidation at present mainly improves from two aspects, and the one, improve electrolyte prescription and operating procedure, the 2nd, the electric current output form of change power supply.Aforesaid way has improved the oxidation susceptibility of X alloy really to a certain extent, yet, the oxidation liquid of aluminum current copper alloy mainly is based on sulfuric acid, add the additive that some improve film quality, as oxalic acid, glycerine etc., concentration of electrolyte higher (sulfuric acid concentration general 15%～20%), the liquid waste disposal difficulty is big, to serious environment pollution.
In addition, in order to obtain thicker rete, electrolyte temperature is lower, generally is no more than 20 ℃, needs to lower the temperature with refrigerating apparatus in oxidising process; The change of supply current form can be alleviated aluminum-copper alloy excessive dissolution and heat release problem to a certain extent, the thick film that obtained performance is good, but required power unit complexity, and cost is higher.
Find " electroplating and environmental protection " 2001:21 (4) by literature search: published the article " electrochemical deposition of the nonmetal rete of neutral medium aluminium surface inorganic " that people such as spacious Asia and Africa introduce inorganic non-metallic rete preparation technology on 20～24.People such as spacious Asia and Africa adopt high voltage and than high current density in phosphoric acid and sodium wolframate electrolytic solution, made the grey based ceramic film that thick 30 μ m, hardness reach 500HV on the common aluminum alloy surface; Hou Chaohui etc. also make 10～30 μ m in neutral mixed system, hardness reaches the ornamental grey based ceramic film of being rich in of 500～600HV layer.But above-mentioned research system (＞4%) when copper content reaches certain value in the aluminum-copper alloy adopts anode oxidation process aluminum bronze surface to cause that very easily efflorescence burns phenomenon.And the rete color that above-mentioned technology makes is grey or black, has limited the decorative applications of aluminum-copper alloy to a certain extent.
Summary of the invention
The present invention is directed to the deficiency that exists in the above-mentioned technology, a kind of lower concentration composite electrolytic solution high temperature aluminum-copper alloy anodic oxidation fast thick film preparation is provided, make it adopt the lower concentration composite electrolytic solution, grading voltage under comparatively high temps, prepare the anodic oxidation thick film of silvery white glaze colours in the big high-copper aluminum alloy surface of oxidisability difficulty, the high X alloy thick-film technique that has broken through preparation can only be at low temperature, the restriction of carrying out under the high density electrolytic solution, improve and broadening the anodic oxidation temperature, shortened oxidization time, reduced the hazard rating of electrolytic solution, widened the ornamental range of application of high X alloy environment.
The present invention is achieved by the following technical solutions.The present invention is in anode oxidation process, adopt the lower concentration composite electrolytic solution, utilize the synergy between each composition, grading voltage makes it to keep than high current density under comparatively high temps, aluminum-copper alloy forms thicker rete rapidly in the short period of time of surface, current density descends gradually subsequently, and coating growth speed is slowed down, finally reach a constant thickness, generation has silvery white glaze colours glossy anodic oxidation thick film.Processing step is as follows:
(1) preparation anodic oxidation solution.
The anodizing solution that the present invention adopts is the combined oxidation liquid of phosphoric acid, organic acid and rare-earth salts.Phosphoric acid anodizing liquid is main filmogen, can generate complete, translucent pellumina in aluminum alloy surface.The interpolation organic acid can relax the acidity of phosphoric acid, reduces the dissolution rate of aluminum anodized film, helps generating thicker rete, does not add organic acid, and then the rete of Sheng Chenging is thinner.The adding of an amount of rare-earth salts can act synergistically with organic acid, plays the effect of even rete, quickening anodically deposit speed.
The anodizing solution concentration of phosphoric acid scope that the present invention adopts is 0.5%～1%, and the organic acid of interpolation is oxalic acid or citric acid, and its concentration range is 0.1%～0.5%, and the rare-earth salts of interpolation is cerous sulfate or lanthanum sulfat, and concentration range is 0.05%～0.2%.
(2) Chemical Pretreatment
At 60g/L, clean the grease that 3min removes sample in 70 ℃ of NaOH alkali solution.
(3) anode oxidation process
Anodic oxidation cathode and anode surface area ratio is controlled between 2: 1～1: 2, and what negative electrode adopted is stereotype.Oxidation voltage is one of anodised significant parameter, and the present invention adopts the grading voltage method, and boosting fast the fs, (30s～2min, magnitude of voltage 80～120V) make current density reach 7～15A/dm rapidly
2, keeping constant voltage 1min～3min, this moment, current density descended rapidly.And then (140～180V), the lowering speed of reduction current density makes it rete and keeps the fast speed growth to improve oxidation voltage.In anodised process, the formation and the performance impact of the temperature antianode oxide film of electrolytic solution are little, and the electrolyte temperature in the anode oxidation process can be controlled in 20 ℃～50 ℃.Owing to adopted the high-voltage great-current oxidation style, the required oxidization time of this technology is shorter, only needs 10～30min.Overlong time is nonsensical to the thickness of further increase oxide film.
(4) drying
Sample is placed in the loft drier at 120 ℃ of following dry 30min.
Adopt the high-copper aluminium alloy anode oxide aluminium film thickness of the present invention's preparation can reach 15～40 microns, hardness 300～400HV, rete color silvery white glaze colours has satisfied the requirement of aluminum alloy surface protected decoration aspect.Compared with prior art, the present invention has broken through the restriction that the high X alloy thick-film technique of preparation can only be carried out under low temperature, high density electrolytic solution, overcome high voltage electric chemical ceramics film technique rete ornamental poor, be difficult to film forming shortcoming at high X alloy.Anode oxidation process of the present invention can at high temperature carry out, and needn't use cooled compressed equipment; The growth of aluminum oxide rete is insensitive to variation of temperature in the oxidising process, needn't carry out temperature control in the oxidising process.Concentration of electrolyte is lower, can reduce the pollution to environment greatly, and to alloying constituent require lowly, can on various aluminas, use, the rete color is silvery white glaze colours, has strengthened the decorate properties of rete greatly.
Embodiment
The present invention adopts the lower concentration composite electrolytic solution, and at high temperature grading voltage prepares high-copper aluminium alloy anode oxide thick film.The electrolytic solution total concn is (0.65～1.7%), and required oxidation voltage is fs: 80～120V, keeps constant voltage 1min～3min, pressure rising time 30s～2min; Subordinate phase: 140～180V keeps constant voltage to anode oxidation to finish.Oxidizing temperature can reach 50 ℃.Anodizing time is 10min～30min.The thickness of gained anode oxide film can reach 15～40 microns.
Embodiment 1: the composite electrolytic solution parameter of preparation is: phosphatase 11 %, oxalic acid 0.5%, lanthanum sulfat 0.05%.At 60g/L, carry out anodic oxidation behind the cleaning 3min in 70 ℃ of NaOH alkali solution.Fs oxidation voltage 80V, pressure rising time 2min.After keeping constant voltage 3min, boost to 140V again, keep constant.Oxidization time 30min.Be placed on 120 ℃ of following dry 30min in the loft drier then.In the process of test, the temperature of solution is 20 ℃～30 ℃ variations.After the anodic oxidation, thickness is 15 μ m, the rete silvery white.
Embodiment 2: the composite electrolytic solution parameter of preparation is: phosphoric acid 0.5%, citric acid 0.5%, cerous sulfate 0.1%.At 60g/L, anodic oxidation behind the cleaning 3min in 70 ℃ of NaOH alkali solution.Fs oxidation voltage 110V, pressure rising time, 1min kept boosting to 170V again behind the constant voltage 2min, kept constant.Oxidization time 10min.Be placed on 120 ℃ of following dry 30min in the loft drier then.In the process of the test, the temperature of solution is 30 ℃～40 ℃ variations.After the anodic oxidation, the thickness of oxide film is 40 μ m, and rete is silvery white glaze colours.
Embodiment 3: the composite electrolytic solution parameter of preparation is: phosphoric acid 0.5%, citric acid 0.3%, cerous sulfate 0.2%.At 60g/L, anodic oxidation behind the cleaning 3min in 70 ℃ of NaOH alkali solution.Fs oxidation voltage 120V, pressure rising time, 30s kept boosting to 180V again behind the constant voltage 1min, kept constant.Oxidization time 15min.Be placed on 120 ℃ of following dry 30min in the loft drier then.In the process of the test, 40 ℃～50 ℃ of the temperature of solution.After the anodic oxidation, the thickness of oxide film is 25 μ m, and rete is silvery white glaze colours.
Claims (3)
1, a kind of aluminum-copper alloy anodic oxidation thick film preparation is characterized in that concrete steps are:
(1) preparation anodic oxidation solution
Anodizing solution concentration of phosphoric acid scope is 0.5%～1%, and the organic acid of interpolation is oxalic acid or citric acid, and its concentration range is 0.1%～0.5%, and the rare-earth salts of interpolation is cerous sulfate or lanthanum sulfat, and concentration range is 0.05%～0.2%;
(2) Chemical Pretreatment
At 60g/L, clean the grease that 3min removes sample in 70 ℃ of NaOH alkali solution;
(3) anode oxidation process
Anodic oxidation cathode and anode surface area ratio is controlled between 2: 1～1: 2, and what negative electrode adopted is stereotype, adopts the grading voltage method, and the fs boosts fast: 30s～2min, magnitude of voltage 80～120V makes current density reach 7～15A/dm rapidly
2After, keeping constant voltage 1min～3min, this moment, current density descended rapidly, and then improved oxidation voltage: 140～1 80V, the lowering speed of reduction current density makes it rete and keeps the fast speed growth;
(4) drying
Sample is placed in the loft drier at 120 ℃ of following dry 30min.
2, aluminum-copper alloy anodic oxidation thick film preparation according to claim 1 is characterized in that, when step (3), in anodised process, electrolyte temperature is controlled at 20 ℃～50 ℃.
3, aluminum-copper alloy anodic oxidation thick film preparation according to claim 1 is characterized in that, when step (3), in anodised process, required oxidization time is: 10～30min.
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| CN1316068C true CN1316068C (en) | 2007-05-16 |
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| CN104233428B (en) * | 2014-09-26 | 2016-08-17 | 湖南大学 | A kind of method improving aluminum or aluminum alloy material surface anode oxide film alkaline resistance properties |
| CN105586623A (en) * | 2014-10-21 | 2016-05-18 | 宁波江丰电子材料股份有限公司 | Aluminum-copper alloy surface film plating method |
| CN105256359A (en) * | 2015-11-27 | 2016-01-20 | 中国船舶重工集团公司第七二五研究所 | Copper alloy passivation solution and passivation layer preparation method |
| CN108103552A (en) * | 2017-11-28 | 2018-06-01 | 中国航发西安动力控制科技有限公司 | For the technique of TA2 titanium alloy material thick film anodes |
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| JP2020033591A (en) * | 2018-08-29 | 2020-03-05 | いすゞ自動車株式会社 | Production method of metal compact having anodic oxide film, metal compact having anodic oxide film, piston, and internal combustion engine |
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| CN114411220B (en) * | 2021-10-28 | 2023-03-28 | 中国航发西安动力控制科技有限公司 | Process method for precisely controlling thickness of oxalic acid anodized film layer by constant pressure of gradient boosting |
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| JPH11260918A (en) * | 1997-11-27 | 1999-09-24 | Mitsubishi Chemical Corp | Chemical solution for forming metal oxide film |
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