CN102560514A - Faintly acid suspension liquid for removing anodic oxide film of titanium and titanium alloy - Google Patents
Faintly acid suspension liquid for removing anodic oxide film of titanium and titanium alloy Download PDFInfo
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- CN102560514A CN102560514A CN2012100110835A CN201210011083A CN102560514A CN 102560514 A CN102560514 A CN 102560514A CN 2012100110835 A CN2012100110835 A CN 2012100110835A CN 201210011083 A CN201210011083 A CN 201210011083A CN 102560514 A CN102560514 A CN 102560514A
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Abstract
The invention discloses a faintly acid suspension liquid for removing anodic oxide film of titanium and titanium alloy, which is prepared by formula solid powder and distilled water by a mass ratio of 1:(0.2-1),wherein the Potential of Hydrogen (pH) is in a range between 3 and 6, fluorides of the formula solid powder are in an amount of 50wt.% to 80wt.% , solid acid is in an amount of 10wt.% to 50wt.%, stimulating materials are in an amount of 5wt.% to 50wt.%. A trace of Hydrogen Fluoride (HF) retreating film is produced on the basis of the principle of chemical equilibrium mobile on the faintly acid condition, therefore, the preparing method is simple and effective, convenient to refill, and has a continuous controllability , no erosion to matrixes and no harm to human bodies.
Description
Technical field
The present invention relates to the synthetic slightly acidic suspension-s of a kind of water, relate in particular to a kind of slightly acidic suspension-s that is used to strip the titanium or titanium alloy anode oxide film.
Background technology
Titanium or titanium alloy (like TC4, TB6, Ti 1 etc.) 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.As: on the aircraft there be the titanium alloy component: non-structure component (like systematic part and conduits such as hydraulic pressure, cold air, manipulations in the military secret), engine component (like engine compressor dish, blade and casing etc.), aircraft structure (like fuselage, gear, wing load-carrying member and fastening piece etc.); Be used as lens barrel and other structural part in the space camera.And the titanium or titanium alloy component of process anodize are given them again because of its surface generation oxide film and are had better corrosion-resistant, antifraying property.The titanium or titanium alloy anode oxide film is a kind of chemical conversion film, and this film mainly constitutes (mainly being titanium oxide) by titanyl compound, different along with anode oxidation process and material, and film presents distinct colors: like black, yellow, colour.But because some accidental factor, former thereby when causing rete not meet the quality test requirement like dress extension, dismounting, the control of oxidizing process parameter etc., this just need strip rete, and anodic oxidation again in anode oxidation process.
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, laser cleaning method etc., the physical method operating cost is high, have the dead angle.So generally adopt chemical method, the common chemical method has: acidity is moved back film liquid method, and alkalescence is moved back film liquid method.
Acidity is moved back film liquid method and is generally adopted strong acid (HCl, HNO
3) mix with HF or fluorochemical and to move back film, this method
Shortcoming is a HF strong corrosion skin, can cause the human body poisoning through skin absorption; F in strong acid
-Big to matrix etch amount, influence the machine parts'precise degree; Hydrogen H is prone to infiltrate in the titanium or titanium alloy under the strong acid condition, is adsorbed on dislocation, crystal boundary and micropore place, forms hydrogenate (TiH) and causes hydrogen embrittlement, and the intensity of material and service life are sharply reduced.
In the sixties in last century, U.S. NASA once used alkali (NaOH, KOH and NaNO
3) fused salt (480 ℃ of temperature), earlier oxidation film on titanium alloy surface is carried out that loose skin is handled and then in water the technology of chilling remove sull.Use alkali fusion salt running cost high, bigger to workman's hazard rating, in addition, between workpiece and hanger, be prone to form the electric charge accumulation.Being used to of BJ University of Aeronautics & Astronautics research and development strips the alkalescence of titanium or titanium alloy anode oxide film and moves back film liquid with oxydol H
2O
2, sodium hydroxide NaOH (Pottasium Hydroxide KOH) is main ingredient, though this method is simple, because at heating, highly basic and foreign ion (Fe
3+Deng) H under the condition
2O
2The stability extreme difference uses difficulty continuously.
Summary of the invention
The purpose of this invention is to provide a kind of slightly acidic suspension-s that is used to strip the titanium or titanium alloy anode oxide film, simple effectively, good stability, can use continuously, matrix do not produced etch, human body do not produced the method for the stripping titanium or titanium alloy anode oxide film of injury.
The present invention is achieved in that a kind of slightly acidic suspension-s that is used to strip the titanium or titanium alloy anode oxide film, it is characterized in that: formed by mass ratio 1:0.2 ~ 1 modulation by prescription pressed powder and zero(ppm) water, pH value scope is 3-6.
Fluorochemical accounts for 50 ~ 80wt% in the said solid power formulations, solid acid accounts for 10 ~ 50wt%, promotes that material accounts for 5 ~ 50wt%.
Said fluorochemical is selected a kind of or some kinds of mixtures of matt salt, Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride, Calcium Fluoride (Fluorspan) for use.
Said solid acid is selected the mixture of a kind of of oxalic acid, thionamic acid, sodium pyrosulfate, ammonium sulfate, an ammonium nitrate, nitrate of baryta, boric acid, Hydrocerol A or some kinds for use.
Said promotion material is selected potassium fluoborate, Sodium tetrafluoroborate, yellow soda ash, sodium hydrogencarbonate, lime carbonate, white titanium pigment, quicklime, barytic a kind of or some kinds mixture for use.
The said slightly acidic suspension-s that is used to strip the titanium or titanium alloy anode oxide film move back membrane method, suspension-s is stirred, temperature is controlled at 20 ~ 98 ℃, puts into the print that contains titanium or titanium alloy anodic oxide film, handle 1-30min after, take out the water flushing.
The said slightly acidic suspension-s that is used to strip the titanium or titanium alloy anode oxide film move back membrane method, move back after film handles, move back the film deleterious when needing time expand, add 10 ~ 80% initial pressed powder amount and can recover original effect.
The prescription of the stripping titanium or titanium alloy anode oxide film that the present invention relates to is a kind of weak acid system; By fluorochemical, solid acid, the composite pressed powder that forms of promotion material; Being deployed into supersaturation suspension system with zero(ppm) water and using, is 3-6 according to the composite different pH scopes of fluorochemical.Principle of design is by fluorochemical fluorion to be provided; In the aqueous solution,, can strip sull because the synergy of solid acid and promotor makes chemical equilibrium move the slow HF that discharges trace; The matrix etch not taking place again and does not produce the human injury (can reach in this solution; Can be in putting HF solution into pain not be arranged), burst size and speed can be passed through temperature regulation, and when effective constituent in the solution consumes; Oversaturated pressed powder generation chemical equilibrium is moved and is replenished, and keeping this system can be through adding the prescription solid powder.
Technique effect of the present invention is: the HF that present method utilizes the chemical equilibrium shifting principle to produce trace under mild acid conditions moves back film, simple effectively, add convenience, controllable continuous, matrix do not produced etch, human body is not produced injury.
The practical implementation method
Below in conjunction with instance, the present invention is described further.
The fluorochemical that the present invention relates to fill a prescription in the pressed powder can be selected matt salt, Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride, Calcium Fluoride (Fluorspan) etc. for use.
The solid acid that the present invention relates to fill a prescription in the pressed powder can be selected oxalic acid, thionamic acid, sodium pyrosulfate, ammonium sulfate, an ammonium nitrate, nitrate of baryta, boric acid, Hydrocerol A etc. for use.
The promotion material that the present invention relates to fill a prescription in the pressed powder can be selected potassium fluoborate, Sodium tetrafluoroborate, yellow soda ash, sodium hydrogencarbonate, lime carbonate, white titanium pigment, quicklime, barium oxide etc. for use.
With above-mentioned substance in proportion in mixing machine thorough mixing even, process the prescription pressed powder.
Embodiment 1
(1) the prescription pressed powder is formed and proportioning (mass parts):
Matt salt 100, Neutral ammonium fluoride 20, Sodium Fluoride 30
Oxalic acid 20, thionamic acid 10, nitrate of baryta 30
Lime carbonate 5, Sodium tetrafluoroborate 15
(2) prescription pressed powder and zero(ppm) water modulation ratio 1:0.4 (mass ratio)
Formation suspension-s stirs.
(3) slaking 2h, the pH value is about 3.
(4) move back film and result
With above-mentioned suspension-s magnetic agitation, and be heated to 50 ℃, put into the TC4 titanium alloy print that contains anode oxide film (thickness 25 ± 3 μ m); After handling 2min, take out the water flushing and also dry naturally, using thickness tester to measure thickness is 0 ~ 1 μ m; And film in the anodic oxidation again, quality is better.
Embodiment 2
(1) the prescription pressed powder is formed and proportioning (mass parts):
Neutral ammonium fluoride 100, matt salt 10, Sodium Fluoride 40
Oxalic acid 20, thionamic acid 10, nitrate of baryta 30
Lime carbonate 5, Sodium tetrafluoroborate 15
(2) prescription pressed powder and zero(ppm) water modulation ratio 1:0.3 (mass ratio)
Formation suspension-s stirs.
(3) slaking 2h, the pH value is about 5.
(4) move back film and result
With above-mentioned suspension-s magnetic agitation, and be heated to 75 ℃, put into the TB6 titanium alloy print that contains anode oxide film (thickness 25 ± 3 μ m); After handling 10min, take out the water flushing and also dry naturally, using thickness tester to measure thickness is 0 ~ 1 μ m; And film in the anodic oxidation again, quality is better.
Claims (7)
1. slightly acidic suspension-s that is used to strip the titanium or titanium alloy anode oxide film is characterized in that: modulated by mass ratio 1:0.2 ~ 1 with zero(ppm) water by the prescription pressed powder and form, pH value scope is 3-6.
2. require described a kind of slightly acidic suspension-s that is used to strip the titanium or titanium alloy anode oxide film according to right 1, it is characterized in that fluorochemical accounts for 50 ~ 80wt% in the said solid power formulations, solid acid accounts for 10 ~ 50wt%, promotes that material accounts for 5 ~ 50wt%.
3. according to right 2 described a kind of slightly acidic suspension-s that are used to strip the titanium or titanium alloy anode oxide film, it is characterized in that: fluorochemical is selected a kind of or some kinds of mixtures of matt salt, Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride, Calcium Fluoride (Fluorspan) for use.
4. a kind of slightly acidic suspension-s that is used to strip the titanium or titanium alloy anode oxide film that requires according to right 2 is characterized in that: said solid acid is selected the mixture of a kind of of oxalic acid, thionamic acid, sodium pyrosulfate, ammonium sulfate, an ammonium nitrate, nitrate of baryta, boric acid, Hydrocerol A or some kinds for use.
5. a kind of slightly acidic suspension-s that is used to strip the titanium or titanium alloy anode oxide film that requires according to right 2 is characterized in that: said promotion material is selected potassium fluoborate, Sodium tetrafluoroborate, yellow soda ash, sodium hydrogencarbonate, lime carbonate, white titanium pigment, quicklime, barytic a kind of or some kinds mixture for use.
6. adopt the membrane method that moves back of the said slightly acidic suspension-s that is used to strip the titanium or titanium alloy anode oxide film of right 1; It is characterized in that: suspension-s is stirred, and temperature is controlled at 20 ~ 98 ℃, puts into the print that contains titanium or titanium alloy anodic oxide film; After handling 1-30min, take out the water flushing.
7. being used to of adopting that right 1 requires strip the titanium or titanium alloy anode oxide film slightly acidic suspension-s move back membrane method; It is characterized in that: after moving back the film processing; Move back the film deleterious when needing time expand, add 10 ~ 80% initial pressed powder amount and can recover original effect.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100110835A CN102560514A (en) | 2012-01-16 | 2012-01-16 | Faintly acid suspension liquid for removing anodic oxide film of titanium and titanium alloy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100110835A CN102560514A (en) | 2012-01-16 | 2012-01-16 | Faintly acid suspension liquid for removing anodic oxide film of titanium and titanium alloy |
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| CN102560514A true CN102560514A (en) | 2012-07-11 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104278279A (en) * | 2013-07-02 | 2015-01-14 | 海安县中丽化工材料有限公司 | Metal decontamination rust-removing agent |
| CN104894580A (en) * | 2015-06-25 | 2015-09-09 | 贵州航天精工制造有限公司 | Novel cleaning fluid and cleaning method for titanium alloy scale cinder |
| CN104894563A (en) * | 2015-05-06 | 2015-09-09 | 贵阳市新航铸造材料科技开发有限公司 | Chemical corrosion method for removing titanium alloy blade surface allowance |
| CN106086892A (en) * | 2016-08-29 | 2016-11-09 | 遵义航天新力精密铸锻有限公司 | The method of titanium alloy blade surface surplus is removed in chemical attack |
| CN111233346A (en) * | 2018-11-28 | 2020-06-05 | 惠州比亚迪电子有限公司 | Deplating agent and preparation method, deplating method and application thereof |
| CN114635141A (en) * | 2022-02-28 | 2022-06-17 | 武汉材保表面新材料有限公司 | Chemical film stripping liquid for phosphorus-free conversion film on steel surface, preparation method and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104278279A (en) * | 2013-07-02 | 2015-01-14 | 海安县中丽化工材料有限公司 | Metal decontamination rust-removing agent |
| CN104894563A (en) * | 2015-05-06 | 2015-09-09 | 贵阳市新航铸造材料科技开发有限公司 | Chemical corrosion method for removing titanium alloy blade surface allowance |
| CN104894580A (en) * | 2015-06-25 | 2015-09-09 | 贵州航天精工制造有限公司 | Novel cleaning fluid and cleaning method for titanium alloy scale cinder |
| CN106086892A (en) * | 2016-08-29 | 2016-11-09 | 遵义航天新力精密铸锻有限公司 | The method of titanium alloy blade surface surplus is removed in chemical attack |
| CN111233346A (en) * | 2018-11-28 | 2020-06-05 | 惠州比亚迪电子有限公司 | Deplating agent and preparation method, deplating method and application thereof |
| CN114635141A (en) * | 2022-02-28 | 2022-06-17 | 武汉材保表面新材料有限公司 | Chemical film stripping liquid for phosphorus-free conversion film on steel surface, preparation method and application |
| CN114635141B (en) * | 2022-02-28 | 2023-10-27 | 武汉材保表面新材料有限公司 | Chemical film stripping liquid for non-phosphate conversion film on steel surface, preparation method and application |
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