CN102586791B - Efficient environment-friendly conditioning fluid for titanium and titanium alloy anodized repair members - Google Patents
Efficient environment-friendly conditioning fluid for titanium and titanium alloy anodized repair members Download PDFInfo
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- CN102586791B CN102586791B CN 201210031327 CN201210031327A CN102586791B CN 102586791 B CN102586791 B CN 102586791B CN 201210031327 CN201210031327 CN 201210031327 CN 201210031327 A CN201210031327 A CN 201210031327A CN 102586791 B CN102586791 B CN 102586791B
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Abstract
The invention discloses an efficient environment-friendly conditioning fluid for titanium and titanium alloy anodized repair members, which can remove oxidation films and can activate the surface of a workpiece so as to lead anodes of repair members or film-free workpieces to be oxidized and coated with films. The conditioning fluid contains 20-30wt% of strong base, 2-20wt% of antisludging agents, 2-20wt% of dispersing agents and 0.05-1wt% of activating agents, and the balance being water. Temperature of workpeices in the conditioning fluid ranges from 50 DEG C to 80 DEG C, and the processing time is 1-30min. Stability of bath solution is good, bearing capacity is large, maintenance is easy, and no environment pollution can be caused. Mechanical property of the processed titanium and titanium alloy cannot be reduced, and quality of oxidation films can be ensured.
Description
Technical field
The present invention relates to a kind for the treatment of solution of high-efficiency environment friendly, can remove the oxide film of titanium or titanium alloy anodic oxidation repair piece, and can activate workpiece surface and make its film in anodic oxidation again, can activate titanium or titanium alloy does not have the white part of film surface yet, makes film in its anodic oxidation.
Background technology
Titanium or titanium alloy has that proportion is little, specific tenacity is high, high temperature resistant, corrosion-resistant and other excellent properties, obtains application more and more widely in fields such as military affairs, Aeronautics and Astronautics, medical, chemical industry.And the titanium or titanium alloy component of process anodic oxidation treatment are given them again because of its surface generation oxide film and are had better corrosion-resistant, antifraying property.
But titanium or titanium alloy chemically reactive height; easily generate the protective oxide layer of one deck densification as thin as a wafer in air, this rete has stoped the growth of anode oxide film, so titanium alloy is before anodic oxidation; must just can obtain the anode oxidation membrane of good quality through activation treatment.In addition, because some accidental factor, improper etc. former thereby when causing rete not meet the quality test requirement as dress extension, dismounting, the control of oxidizing process parameter, need also repair by workpiece in anode oxidation process for titanium or titanium alloy, rete is removed, and anodic oxidation again.
The method of removing the titanium or titanium alloy anode oxide film has physics and chemical method.Physical method commonly used has: the low pressure glow discharge method, and the ion sputtering method,, there is the dead angle in laser cleaning methods etc. at physical method operating cost height.So generally adopt chemical method, the common chemical method has: acid striping liquid method, alkaline striping liquid method.
Acid striping liquid method generally adopts strong acid (HCl, HNO
3) with HF mixing striping, striping mechanism is because F
-Complexing action, form the H of solubility
2TiF
6This method speed is fast, but can corrode matrix, produces suction hydrogen and causes hydrogen embrittlement, and the intensity of material and service life are sharply reduced, and HF strong corrosion skin can cause the human body poisoning through skin absorption simultaneously.
Alkalescence striping method is because titanium dioxide is amphiprotic substance, can react with highly basic, but the reaction product titanate is water insoluble, can be attached to the surface, and it is crucial how thoroughly removing the insoluble product that adheres to neatly.This method generally can not produce inhales hydrogen and matrix erosion.
A kind of method is with oxydol H preferably at present
2O
2, sodium hydroxide NaOH(potassium hydroxide KOH) be the alkaline striping liquid of main ingredient, oxydol H
2O
2Under the effect of the loose oxide film of highly basic and perforation, be penetrated into the internal layer of oxide film, contact with catalytic active centers such as vanadium on the matrix, iron, manganese cartalytic decomposition effect produce oxygen (utilization be the reductibility of hydrogen peroxide) takes place, by Oxygen Flow (comprising the oxygen that hydrogen peroxide decomposition produces in the solution), thoroughly divest the titanate insoluble product of oxidation film layer and generation.And this striping liquid also plays a part activating surface, film in the feasible white part of no film and the anodic oxidation of the equal energy of anodic oxidation repair piece.Though this method is simple, owing to H under heating, highly basic and foreign ion (iron, manganese etc.) condition
2O
2The stability extreme difference uses difficulty continuously.
Summary of the invention
The purpose of this invention is to provide a kind of environmental protection efficient height, Stability of Bath Solution can be good, bearing capacity big, tank liquor is safeguarded simple, have the treatment solution that moves back film or mobilizing function concurrently, this treatment solution striping is effective, and plays activation, can make to reprocess film in workpiece and the white part anodic oxidation of no film.
The treatment solution of the titanium or titanium alloy anode oxide film repair piece that the present invention relates to is made up of highly basic, Scale inhibitors, dispersion agent, activator, distilled water.Key point is that Scale inhibitors and dispersion agent play the insoluble product titanate generation distortion effect that synergistic effect produces highly basic and titanium dioxide reaction, does not produce and adheres to.Activator is mainly reduction system, can make the matrix surface titanium produce the attitude of appraising at the current rate.
The treatment solution that the present invention relates to contains highly basic 2 ~ 30wt%, Scale inhibitors 2-20 wt%, dispersion agent 2-20 wt%, activator 0.05-1 wt%, and all the other are water.Stir evenly with dissolved in distilled water in proportion during preparation.
The titanium or titanium alloy anodic oxidation repair piece striping that the present invention relates to and activation method are repair piece to be put into 50-80 ℃ treatment solution, and stir process 1 ~ 30min takes out with the tap water flushing and dries or dry up, and the repair piece of handling is film in the anodic oxidation again.If titanium or titanium alloy does not have the white part of film, the treatment time is shorter, is about 1-10min, film in the energy anodic oxidation after the processing.
The treatment solution that the present invention relates to does not contain HF, is a kind of environmental protection treatment liquid, and Scale inhibitors, dispersion agent mainly play the distortion effect, and consumption is little, and the tank liquor bearing capacity is big, stability good, maintenance is simple.
Specific implementation method
Below in conjunction with example, the invention will be further described.
The highly basic that the present invention relates in the treatment solution can be selected NaOH, KOH, sodium ethylate for use or carry out composite.
The Scale inhibitors that the present invention relates in the treatment solution can be selected quadrol tetramethyl subunit Alendronate, hydroxy ethylene diphosphonic acid four sodium, ethylenediamine tetramethylene phosphonic acid five sodium, diethylenetriamine pentamethylene phosphonic acids five sodium, Sunmorl N 60S, sodium oxalate etc. or composite for use.
The dispersion agent that the present invention relates in the treatment solution can be selected poly(oxyethylene glycol) 400, Polyethylene Glycol-600, diethanolamine, sodium polyacrylate, polyepoxy sodium succinate, poly (sodium aspartate), vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multipolymer, vinylformic acid-Propylene glycol monoacrylate multipolymer etc. or composite for use.
The activator that the present invention relates in the treatment solution can be selected Sulfothiorine, V-Brite B, potassium metabisulfite, diethyl hydroxylamine, SODIUM ISOVITAMIN C etc. or composite for use.
Case study on implementation
(1) 1L prescription for the treatment of liquid
Potassium hydroxide: 100g,
Polyepoxy sodium succinate: 40g, sodium oxalate: 40g, Sunmorl N 60S: 60g
Poly (sodium aspartate) (40wt%): 40ml
SODIUM ISOVITAMIN C: 1g
Water: surplus
(2) 1L treatment solution preparation: add part water earlier with other material mixes in proportion, benefit adds water to 1L again.
(3) the white part of no film is handled and the result
Above-mentioned treatment solution is stirred, and be heated to 70 ℃, put into titanium or titanium alloy and do not have the white part of film (the TC4 titanium alloy print of 60 * 60 * 8mm), after handling 8min, after taking out the water flushing, surface color becomes uniform pewter, anodic oxidation 30min, can generate uniform oxide yellow film, measuring thicknesses of layers with thickness tester is 25.0 ± 3 μ m.And the direct anodic oxidation 30min of the white part of no film that does not adopt this treatment solution to handle can't go up film.
(4) repair piece is handled and the result
Above-mentioned treatment solution is stirred, and be heated to 60 ℃, put into titanium or titanium alloy anodic oxidation repair piece (yellow anodic oxidation thickness is 60 * 60 * 8mm TC4 titanium alloy print of 25.0 ± 3 μ m), after handling 15min, take out the water flushing and also dry naturally, surface color is uniform pewter, measuring thicknesses of layers with thickness tester is 0.5 μ m, again anodic oxidation 30min can generate uniform oxide yellow film, and measuring thicknesses of layers with thickness tester is 25.0 ± 3 μ m.
(5) bearing capacity and result
The 1L treatment solution, (4) operate continuously set by step can be handled 10 of titanium or titanium alloy anodic oxidation repair pieces (the titanium alloy print is with (4)), and the striping effect is all better, and water level slightly reduces.When handling the 11st, the striping effect is slightly poor, but time expand also can reach better effects.And the hydrogen peroxide system is whenever done a slice and all will be added hydrogen peroxide.
Claims (2)
1. one kind is applicable to that defective of titanium or titanium alloy anodic oxidation is reprocessed, the treatment solution of the high-efficiency environment friendly of oxidation front activating, it is characterized in that containing highly basic 2-30wt%, Scale inhibitors 2-20 wt%, dispersion agent 2-20 wt%, activator 0.05-1 wt%, all the other are water, wherein, highly basic is selected potassium hydroxide, sodium hydroxide, sodium ethylate or composite for use; Scale inhibitors is selected quadrol tetramethyl subunit Alendronate, hydroxy ethylene diphosphonic acid four sodium, ethylenediamine tetramethylene phosphonic acid five sodium, diethylenetriamine pentamethylene phosphonic acids five sodium, Sunmorl N 60S, sodium oxalate or composite for use; Dispersion agent is selected poly(oxyethylene glycol) 400, Polyethylene Glycol-600, diethanolamine, sodium polyacrylate, polyepoxy sodium succinate, poly (sodium aspartate), vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multipolymer, vinylformic acid-Propylene glycol monoacrylate multipolymer or composite for use; Activator is selected Sulfothiorine, V-Brite B, potassium metabisulfite, diethyl hydroxylamine, SODIUM ISOVITAMIN C or composite for use.
2. one kind is adopted the treatment solution of claim 1 to handle the method that titanium or titanium alloy does not have the white part of film, anodic oxidation repair piece, it is characterized in that: with repair piece or do not have the white part of film and put into 50 ~ 80 ℃ treatment solution, handle 1 ~ 30min, after the flushing of taking-up water, carry out film in the anodic oxidation.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103105455A (en) * | 2013-01-19 | 2013-05-15 | 南昌航空大学 | Analytical method of film stripping solution of titanium alloy anode oxide film |
| CN103526218B (en) * | 2013-10-24 | 2015-08-26 | 南昌航空大学 | A kind of titanium alloy anodic oxidation activation moves back the ageing method of the two-in-one solution of film |
| CN106757086A (en) * | 2016-11-10 | 2017-05-31 | 武汉钢铁股份有限公司 | For the alkaline defatting agent and its low-cost manufacture method of the cleaning of cold-rolling continuous annealing unit |
| CN107988610A (en) * | 2017-11-27 | 2018-05-04 | 成都工具研究所有限公司 | Carbide chip TiAlN, TiN coating strip method |
| CN109898090A (en) * | 2018-03-10 | 2019-06-18 | 浙江金拓机电有限公司 | A kind of without phosphorus oil-removing rust-removing agent of aqua type metal |
| CN108914186A (en) * | 2018-07-06 | 2018-11-30 | 江西洪都航空工业集团有限责任公司 | A kind of titanium alloy blue anodic oxidation method of environmental protection fast filming |
| CN111252913A (en) * | 2020-03-02 | 2020-06-09 | 西南交通大学 | Composite scale inhibitor for concrete drainage pipeline and application thereof |
| CN112914762B (en) * | 2021-02-07 | 2021-11-12 | 江苏创英医疗器械有限公司 | Surface treatment process for titanium alloy dental implant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245467A (en) * | 2008-03-21 | 2008-08-20 | 北京航空航天大学 | Stripping liquid and stripping method for stripping titanium and titanium alloy anodized film |
| CN101440496A (en) * | 2008-12-29 | 2009-05-27 | 长春奥普光电技术股份有限公司 | Film stripping solution for stripping titanium alloy oxidation film layer |
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| JP2010059444A (en) * | 2008-09-01 | 2010-03-18 | Mitsuko Enterprise:Kk | Detergent for iron plate and method for cleaning the iron plate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245467A (en) * | 2008-03-21 | 2008-08-20 | 北京航空航天大学 | Stripping liquid and stripping method for stripping titanium and titanium alloy anodized film |
| CN101440496A (en) * | 2008-12-29 | 2009-05-27 | 长春奥普光电技术股份有限公司 | Film stripping solution for stripping titanium alloy oxidation film layer |
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| JP特開2010－59444A 2010.03.18 |
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