CN1175131C - Macroporous thick-film process for anode oxidization of phosphoric acid - Google Patents
Macroporous thick-film process for anode oxidization of phosphoric acid Download PDFInfo
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- CN1175131C CN1175131C CNB021373779A CN02137377A CN1175131C CN 1175131 C CN1175131 C CN 1175131C CN B021373779 A CNB021373779 A CN B021373779A CN 02137377 A CN02137377 A CN 02137377A CN 1175131 C CN1175131 C CN 1175131C
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Abstract
The present invention relates to a macro-porous thick-film technology for the anode oxidization of phosphoric acid, which belongs to the technical field of a thin film. The macro-porous thick-film technology for the anode oxidization of phosphoric acid comprises the following particular steps: anode oxidation solution is prepared, and a certain amount of organic acid is added into the anode oxidation solution using the phosphoric acid as a main component to form mixed acid oxidation liquid; in chemical pretreatment, alkaline or acid or neutral cleaning liquid is used for removing the impurities of a test sample, such as grease, etc. The anode oxidation has the particular parameters that the ratio of the surface area of a cathode to the surface area of an anode is controlled to be from 2:1 to 1:2, a voltage value is controlled to be from 40 to 120 V, current density changes in the range of 0.5 to 20 A/dm<2>, temperature in an electrolytic process is controlled to be from 5 DEG C to 25 DEG C, and time is controlled to be from 10 min to 60 min. An aluminum-oxide film prepared by the ordinary phosphoric acid anode oxidation method has small thickness, the present invention adjusts parameters, such as the concentration of the phosphoric acid, the time of the anode oxidation, etc., by a low-temperature anode oxidation method and overcomes the disadvantage of the anode oxidation of the phosphoric acid. The present invention greatly reduces the difficulty of the filling process of self-lubrication materials in the micro pores of the anode oxidation film and greatly enhances abrasion resistance.
Description
Technical field
What the present invention relates to is a kind of aluminium alloy phosphoric acid anodizing technology, and particularly a kind of aluminium alloy phosphoric acid anodizing prepares the technology of large-aperture thick film, belongs to the thin film technique field.
Background technology
Alumina carries out anodic oxidation in electrolytic solution such as sulfuric acid, oxalic acid, phosphoric acid can form the pellumina with microcosmic vesicular structure on the surface, in its micropore, insert different substances and can obtain various composite surface materials, to improve the surface property of alumina, as filling MoS therein with self lubricity matter
2, PTFE etc. can prepare the aluminium matter composite surface material with self-lubricating property.The characteristics that the anode oxide film that is used for self-lubrication treatment requires to have the wide aperture, rete is thick.The method for preparing alumite at present both at home and abroad mainly is sulfuric acid process and Oxalic Acid Method.The Film Thickness Ratio of the anode oxide film of these two kinds of method preparations is thicker, and have tens microns, but aperture ratio is less: only there are several nanometers in the sulphuric acid oxidation coating aperture, at most only tens nanometers; The Oxalic Acid Method aperture also has only two, 30 nanometers.This makes that filling other material difficulty strengthens.Find by literature search, Wang Zhutang Jiangsu science tech publishing house in 1992 publish " aluminium and surface treatment handbook P326-327 thereof mention: generally in the 25%-30% phosphoric acid solution, temperature is that 20 ℃-30 ℃, current density are 1-2A/dm
2, voltage 30-60V, carry out the 10min anodic oxidation treatment, can generate 3 μ m thick oxide films.This oxide film is compared with sulfate membrane, oxalic acid film, improve greatly in the aperture, can reach tens even the hundreds of nanometer, greatly reduces the difficulty of filling other materials therein, but its thickness can't prepare self-lubricating surface composite material with it much smaller than sulfate membrane and oxalic acid film.
Summary of the invention and embodiment
The present invention is directed to the deficiencies in the prior art and defective, provide a kind of aluminium alloy phosphoric acid anodizing to prepare the technology of large-aperture thick film, make it utilize the wide-aperture advantage of phosphoric acid anodizing film, preparation has the wide aperture, thickness can reach tens microns phosphoric acid anodizing aluminium film.The present invention is achieved by the following technical solutions, and concrete steps are as follows:
(1) preparation anodic oxidation solution, the anodizing solution phosphoric acid concentration scope of employing is 1%-10%, the organic acid of interpolation is: citric acid or oxysuccinic acid or tartrate, its concentration range are 0.1-5%, form mixing acid oxidation liquid;
When phosphoric acid concentration＞10%, the acidity of phosphoric acid can be with the oxide film dissolving that generates, thereby reduces the thickness of oxide film; When phosphoric acid concentration＜1%, concentration of electrolyte is low excessively, is unfavorable for the generation of anode oxide film.An amount of interpolation organic acid can relax the acidity of phosphoric acid, helps the growth of anode oxide film.
(2), Chemical Pretreatment, adopt the acid or neutral scavenging solution of alkalescence to remove the impurity such as grease of sample.
(3), anode oxidation process, concrete processing parameter is: anodic oxidation cathode and anode surface area ratio is controlled at 2: 1-1: 2, magnitude of voltage is controlled at 40-120V, the scope of current density is 0.5-20A/dm
2, the temperature in the electrolytic process is controlled at 5 ℃-25 ℃, and the time is controlled at 10min-60min.
The thickness of anode oxide film and the homogeneity in space depend on to a great extent whether the area ratio of anode and negative electrode is suitable, the present invention is controlled at 2 with anodic oxidation cathode and anode surface area ratio: 1-1: between 2, what negative electrode adopted is electro-conductive materials such as lead grid, stereotype, aluminium sheet and steel plate; Voltage is one of anodised significant parameter, and the range of voltage values that the present invention uses is controlled at 10-120V, and electric current has bigger variation along with anodised carrying out; In anodised process, the thickness of the temperature antianode oxide film of electrolytic solution has very big influence: temperature is too high has quickened the dissolving of oxide film in phosphoric acid that generates, thereby has reduced the thickness of oxide film; Temperature is crossed the low formation that can suppress anode oxide film, equally also can reduce the thickness of oxide film, and the present invention is controlled at 5 ℃-25 ℃ with the electrolysis temperature in the anode oxidation process; Time is another important factor that influences the anodic oxidation film thickness, too short anode oxide film of time does not also fully form, the thickness of the further increase oxide film of overlong time is nonsensical, and the present invention is controlled at 10min-60min with the anodised time, has obtained good effect.
The phosphoric acid anodizing aluminium film of the present invention's preparation has bigger aperture (30nm-70nm), and the thickness of film can reach the 5-25 micron, inserts MoS in the phosphoric acid anodizing aluminium membrane micropore of preparation
2, PTFE, WS
2, CaF
2, BaF
2, Pb
2O
3, solid lubricants such as PbS, tellurium oxide, graphite can prepare the composite surface material with self-lubricating property, the material of inserting other performance can prepare various function composite membranes, causes colour developing film, liquid crystal oxidation compound film etc. as electricity.
The present invention has substantive distinguishing features and marked improvement, the pellumina thickness of general phosphoric acid anodizing method preparation is less, the present invention adopts the anodised method of low temperature, and parameters such as concentration of phosphoric acid, anodised time are adjusted, and has overcome this shortcoming of phosphoric acid anodizing.Compare with general anode oxidation process, because the aperture is big, the difficulty of filling the self-lubricating material in its micropore reduces greatly; Because of its thickness is bigger than general phosphoric acid anodizing film, wear resisting property also improves greatly.
Provide following examples in conjunction with content of the present invention:
Embodiment 1: the phosphoric acid of preparation and organic acid soln parameter are: phosphatase 11 0%, and oxysuccinic acid 5%, aluminum alloy specimen is deoiling in acidic cleaning solution, and negative electrode and annode area ratio is 1: 2 during anodic oxidation, voltage 40V, current density is controlled at 0.5A/dm
2To 20A/dm
2, time 60min.In the preparation process, the temperature of solution in the electrolytic process is controlled from 20 ℃ to 25 ℃.After the anodic oxidation, after the anodic oxidation, the aperture of oxide film is 50-70nm, and thickness is 12 μ m.
Embodiment 2: the phosphoric acid of preparation and organic acid soln parameter are: phosphatase 24 %, citric acid 0.8%.Aluminum alloy specimen is deoiling in neutral scavenging solution, and negative electrode and annode area ratio is 1: 1 during anodic oxidation, voltage 60V, and current density is controlled at 0.5A/dm
2To 20A/dm
2, time 40min.In the preparation process, the temperature of solution in the electrolytic process is controlled from 10 ℃ to 15 ℃.After the anodic oxidation.After the anodic oxidation, the aperture of oxide film is 40-60nm, and thickness is 25 μ m.
Embodiment 3: the phosphoric acid of preparation and organic acid soln parameter are: phosphatase 11 %, tartrate 0.1%.Aluminum alloy specimen is deoiling in alkaline cleaning fluid, and negative electrode and annode area ratio is 2: 1 during anodic oxidation, voltage 120V, and current density is controlled at 0.5A/dm
2To 20A/dm
2, time 10min.In the preparation process, the temperature of solution in the electrolytic process is controlled from 5 ℃ to 10 ℃.After the anodic oxidation.After the anodic oxidation, the aperture of oxide film is 30-40nm, and thickness is 5 μ m.
Claims (1)
1, a kind of aluminium alloy phosphoric acid anodizing prepares the technology of large-aperture thick film, it is characterized in that concrete steps are as follows:
(1) preparation anodic oxidation solution, the anodizing solution phosphoric acid concentration scope of employing is 1%-10%, the organic acid of interpolation is: citric acid or oxysuccinic acid or tartrate, its concentration range are 0.1-5%, form mixing acid oxidation liquid;
(2) Chemical Pretreatment adopts the acid or neutral scavenging solution of alkalescence to remove the grease of sample;
(3) anode oxidation process, concrete processing parameter is: anodic oxidation cathode and anode surface area ratio is controlled at 2: 1-1: 2, magnitude of voltage is controlled at 40-120V, and current density is at 0.5-20A/dm
2Change in the scope, the temperature in the electrolytic process is controlled at 5 ℃-25 ℃, and the time is controlled at 10min-60min.
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| CNB021373779A CN1175131C (en) | 2002-10-10 | 2002-10-10 | Macroporous thick-film process for anode oxidization of phosphoric acid |
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| CN1175131C true CN1175131C (en) | 2004-11-10 |
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| US7578921B2 (en) * | 2001-10-02 | 2009-08-25 | Henkel Kgaa | Process for anodically coating aluminum and/or titanium with ceramic oxides |
| CN1306070C (en) * | 2003-12-04 | 2007-03-21 | 中国科学院兰州化学物理研究所 | Self-lubricating treatment method of porou anode aluminium oxide film |
| CN101240440B (en) * | 2007-11-16 | 2011-02-16 | 苏州有色金属研究院有限公司 | Technique for preparing high-hardness large-aperture thick film by mixed acid anode oxidation |
| CN101314865B (en) * | 2007-12-28 | 2010-06-09 | 中国兵器工业第五二研究所 | Production method for hard lubricant film layer of aluminum alloy |
| CN102554212A (en) * | 2010-12-23 | 2012-07-11 | 中国科学院金属研究所 | Method for inhibiting hydrogen separation through anodic oxidation of aluminum powder under acidic condition |
| CN102732932B (en) * | 2011-04-15 | 2014-01-29 | 中国科学院金属研究所 | Method for inhibiting hydrogen evolution by anodizing aluminum powder under alkaline condition |
| CN102304740B (en) * | 2011-08-05 | 2014-07-30 | 金安国纪科技（珠海）有限公司 | Processing method of aluminium base for copper clad laminate |
| CN102358947A (en) * | 2011-09-28 | 2012-02-22 | 宁波市鸿博机械制造有限公司 | Surface treatment technique of flow control valve |
| KR101656978B1 (en) * | 2012-05-30 | 2016-09-12 | 미쯔비시 레이온 가부시끼가이샤 | Method for manufacturing mold, and method for manufacturing molded article having fine uneven structure on surface |
| CN102732934B (en) * | 2012-06-05 | 2016-01-20 | 沈阳理工大学 | The method in aluminium alloy anode oxide film hole closed by a kind of silicon sol |
| CN107699942A (en) * | 2017-09-25 | 2018-02-16 | 谢金庚 | A kind of wear-resistant metal gear and preparation method thereof |
| 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 |
| CN108531957A (en) * | 2018-05-23 | 2018-09-14 | 西安理工大学 | A kind of anodizing preparation method of alumina fibre |
| CN111230008A (en) * | 2020-01-06 | 2020-06-05 | 歌尔股份有限公司 | Method for surface treatment of metal piece used in forging process |
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