CN101457383A - Titanium alloy black anodic oxidation method capable of reducing oxidation film layer stress - Google Patents
Titanium alloy black anodic oxidation method capable of reducing oxidation film layer stress Download PDFInfo
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- CN101457383A CN101457383A CNA200810187621XA CN200810187621A CN101457383A CN 101457383 A CN101457383 A CN 101457383A CN A200810187621X A CNA200810187621X A CN A200810187621XA CN 200810187621 A CN200810187621 A CN 200810187621A CN 101457383 A CN101457383 A CN 101457383A
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Abstract
The invention relates to a black anodizing process method for eliminating parasitic light from the surface of a titanium alloy component, in particular to a titanium alloy black anodizing method capable of reducing the stress on an oxide film. The titanium alloy black anodizing method comprises the following steps: removing oil from an alkaline chemical surface, activating an acid surface and black anodizing. The titanium alloy black anodizing method is characterized by comprising the following surface chemical micro etching after the step of removing the oil from the alkaline chemical surface and before the step of activating the acid surface: a micro etching solution is an aqueous solution containing 70-100g of ammonium sulfate, 50-80g of ammonium bifluoride and 30-50g of ammonium pyrophosphate in each liter of water; and etching is performed at the temperature of 45-65 DEG C for 10-30min . The titanium alloy black anodizing method has the advantages of less change of the size of a workpiece and good parasitic light eliminating property, is especially suitable for black anodizing parasitic light eliminating treatment and helps obviously improve the service life of the components.
Description
Technical field
The present invention relates to the black anode oxidation process method that delustring is handled, particularly a kind of anode oxidation method that can reduce the titanium alloy anodic oxide film ply stress are carried out in the titanium alloy member surface.
Background technology
Titanium and alloy thereof are because its proportion is little, in light weight, specific tenacity is high, in Oxidant or seawater and oceanic atmosphere, have than high anti-corrosion, and the excellent properties such as intensity that still can keep self in temperature under up to 400～500 ℃ environment, use more and more widely at Aeronautics and Astronautics and military field, particularly a large amount of titanium alloy spares that use in the camera of space.Titanium alloy is used as lens barrel and other structural part in space optics, major part need be carried out black anodizing and handled, and the reflectivity and the firmness of rete had very high requirement.
The fragility of titanium alloy oxidation film layer is by the decision of the natural characteristics of titanium alloy: titanium be a kind of have high activity metal, still, it all presents excellent especially solidity to corrosion to many corrosive mediums.Reason is that titanium and oxygen have very big avidity, and when titanium was exposed to atmosphere or any oxygen-containing medium, the surface formed the firm and fine and close passive state oxide film of one deck immediately.The thickness of film changes with temperature and anode potential, and the composition of film changes with thickness, is TiO near the film internal surface of metal, is TiO above
2, the centre is Ti
2O
3This film is an amphoteric substance, so this layer passive film protectiveness is very strong, makes titanium have excellent solidity to corrosion in many corrosive mediums.But when film surpassed a certain thickness, the strain energy in the unit volume just may surpass film and break away from the required merit of metal, thereby, the breaking and damage of generation film.
The anodized pre-treating technology condition of the titanium alloy black of prior art generally is: at first carry out electrochemical deoiling in the solution that contains alkaline matters such as sodium hydroxide and yellow soda ash and small amounts of emulsifiers, to reach Ex-all workpiece surface greasy dirt, make that workpiece can be absolutely wetting by the aqueous solution in subsequent handling.Typical process is: sodium hydroxide 30～50g/l, yellow soda ash 30～50g/l, sodium phosphate 15～30g/l, water glass 3～5g/l, OP emulsifying agent 1～2g/l, 70～90 ℃ of temperature, workpiece put into solution to take out to clean the back absolutely by clear water wetting till.Then, in acidic solution, remove the faint oxide film of workpiece surface, can fastly state the active surface that electrochemical reaction takes place when carrying out follow-up anodic oxidation operation for workpiece provides.Typical process is: 68% nitric acid, 60～120ml/l, 40% hydrofluoric acid, 6～12ml/l, room temperature, 10～60 seconds.
The deficiencies in the prior art are: because the thickness of oxidation film layer depends on oxidization time and oxidation current, have the oxidation film layer of delustring requirement to require specular reflectance less than 1%, need certain thicknesses of layers to guarantee.Along with the increase of oxidation film layer thickness, the stress of rete strengthens, embrittlement, even comes off naturally, and the rapid obscission of workpiece dried up back rete particularly takes place after hot water boils often, and technology stability is poor.Happen occasionally before assembling when purging the workpiece surface of handling through black anodizing the phenomenon of black oxidation rete local shedding in the production with pressurized air; In the Workpiece storage process, a week that has, have one month to half a year etc., idol has rete nature obscission to take place, and serious see that air promptly breaks after from the oxidation tank liquor workpiece being taken out and comes off.
Summary of the invention
The objective of the invention is to have the stress short shortcoming in work-ing life that comes off greatly, easily for overcoming zone of oxidation that present titanium alloy black anode oxidation process obtains, a kind of titanium alloy black anode oxidation method of improving the reduced oxidation film layer stress of technology is proposed, to improve the stability of product surface oxide film.
The present invention can reduce the titanium alloy black anode oxidation method of oxidation film layer stress, comprise following present conventional steps: the alkali electroless surface degreasing, the acidic surface activation treatment, black anodizing is handled, be characterized in, after described alkali electroless surface degreasing step, before the acidic surface activation treatment step, carry out the little etch of following surface chemistry and handle:
Little etch treatment soln is to contain ammonium sulfate 70～100 grams in every premium on currency, ammonium bifluoride 50～80 grams, the aqueous solution of ammonium pyrophosphate 30～50 grams; Under 45～65 ℃ of temperature, etch 10～30min.
The mechanism of action of the little etch treatment step of surface chemistry of the present invention is: make workpiece surface form the microcosmic discrete state, will make the stress high dispersing of step anode oxidation membrane formation down.In little etch treatment soln prescription, fluorion produces the microcosmic spot corrosion, and pyrophosphate plays the homogeneity that complexing action increases the surface, and sulfate radical and ammonium ion play shock absorption to be made solution-stabilized.This prescription acidity a little less than, to the titanium alloy substrate action temperature and, workpiece is not produced deformation, dimensional change≤1.5 μ m.
Positively effect of the present invention:
Workpiece after the oil removing, before the activation is carried out the chemical little etch of appropriateness to be handled, make workpiece surface form the microcosmic discrete state, and then will make the stress high dispersing of titanium alloy black anodizing rete, cause the strain energy of unit volume to be lower than the required merit of rete disengaging metal, eliminated the rete obscission.This technology changes little to the size of workpiece, eliminate stray light is good, and the black anodizing delustring that is particularly suitable for workpiece such as titanium alloy precision camera lens is handled, and obviously improves parts work-ing life.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
Carry out the black anodizing delustring by following step and handle being of a size of 200 * 150 * 15 titanium alloy TC 4 test specimen.
A. alkali electroless surface degreasing.
Removing oil solution is the alkaline aqueous solution that contains sodium hydroxide 30～50 grams, yellow soda ash 30～50 grams, sodium phosphate 15～30 grams, water glass 3～5 sections, OP emulsifying agent 1～2 gram in every premium on currency; Temperature is 70～80 ℃; Workpiece put into solution to take out to clean the back absolutely by clear water wetting till.
B. the little etch of surface chemistry is handled.
After aforementioned oil removing, cleaning, be immersed in etch 30min in 45～50 ℃ of little etch treatment soln, take out and clean;
Little etch treatment soln composition is: ammonium sulfate 100g/ water L, ammonium bifluoride 80g/ water L, ammonium pyrophosphate 30g/ water L.
C. acidic surface activation treatment.
Parts after aforementioned little etch is handled are immersed under the room temperature in the acidic activated liquid etch and take out cleaning after 10～60 seconds;
Acidic activated liquid composition is: 68% nitric acid, 60～120ml/ water L, 40% hydrofluoric acid, 6～12ml/ water L.
D. black anodizing is handled.
Through aforementioned parts after acidic activated, carry out black anodizing under the following conditions and handle:
The oxidizing solution composition is: potassium bichromate 20～30g/ water L, manganous sulfate 15～20g/ water L, ammonium sulfate 20～30g/ water L, cerous sulfate 2～5g/ water L;
Anodic current 0.05～1.0A/dm
2, time 15～30min.
Workpiece after the processing after 90 ℃ of hot water boil 5min, is used closely (100mm) purging of 0.3mpa pressurized air, and rete does not have any coming off.Detect with Lambd950 type ultraviolet/visible/near infrared spectrometer,, satisfy＜1% service requirements at 400～2500nm spectral range theca interna specular reflectance＜0.5%.
Embodiment 2
Carry out the black anodizing delustring by following step and handle being of a size of 200 * 150 * 15 titanium alloy TC 4 test specimen.
A. alkali electroless surface degreasing.
Removing oil solution is the alkaline aqueous solution that contains sodium hydroxide 30～50 grams, yellow soda ash 30～50 grams, sodium phosphate 15～30 grams, water glass 3～5 sections, OP emulsifying agent 1～2 gram in every premium on currency; Temperature is 70～80 ℃; Workpiece put into solution to take out to clean the back absolutely by clear water wetting till.
B. the little etch of surface chemistry is handled.
After aforementioned oil removing, cleaning, be immersed in etch 10min in 45～50 ℃ of little etch treatment soln, take out and clean;
Little etch treatment soln composition is: ammonium sulfate 70g/ water L, ammonium bifluoride 50g/ water L, ammonium pyrophosphate 50g/ water L.
C. acidic surface activation treatment.
Parts after aforementioned little etch is handled are immersed under the room temperature in the acidic activated liquid etch and take out cleaning after 10～60 seconds;
Acidic activated liquid composition is: 68% nitric acid, 60～120ml/ water L, 40% hydrofluoric acid, 6～12ml/ water L.
D. black anodizing is handled.
Through aforementioned parts after acidic activated, carry out black anodizing under the following conditions and handle:
The oxidizing solution composition is: potassium bichromate 20～30g/ water L, manganous sulfate 15～20g/ water L, ammonium sulfate 20～30g/ water L, cerous sulfate 2～5g/ water L;
Anodic current 0.05～1.0A/dm
2, time 15～30min.
Workpiece after the processing after 90 ℃ of hot water boil 5min, is used closely (100mm) purging of 0.3mpa pressurized air, and rete does not have any coming off.Detect with Lambd950 type ultraviolet/visible/near infrared spectrometer,, satisfy＜1% service requirements at 400～2500nm spectral range theca interna specular reflectance＜0.5%.
Embodiment 3
Carry out the black anodizing delustring by following step and handle being of a size of 200 * 150 * 15 titanium alloy TC 4 test specimen.
A. alkali electroless surface degreasing.
Removing oil solution is the alkaline aqueous solution that contains sodium hydroxide 30～50 grams, yellow soda ash 30～50 grams, sodium phosphate 15～30 grams, water glass 3～5 sections, OP emulsifying agent 1～2 gram in every premium on currency; Temperature is 70～80 ℃; Workpiece put into solution to take out to clean the back absolutely by clear water wetting till.
B. the little etch of surface chemistry is handled.
After aforementioned oil removing, cleaning, be immersed in etch 20min in 55～65 ℃ of little etch treatment soln, take out and clean;
Little etch treatment soln composition is: ammonium sulfate 80g/ water L, ammonium bifluoride 60g/ water L, ammonium pyrophosphate 40g/ water L.
C. acidic surface activation treatment.
Parts after aforementioned little etch is handled are immersed under the room temperature in the acidic activated liquid etch and take out cleaning after 10～60 seconds;
Acidic activated liquid composition is: 68% nitric acid, 60～120ml/ water L, 40% hydrofluoric acid, 6～12ml/ water L.
D. black anodizing is handled.
Through aforementioned parts after acidic activated, carry out black anodizing under the following conditions and handle:
The oxidizing solution composition is: potassium bichromate 20～30g/ water L, manganous sulfate 15～20g/ water L, ammonium sulfate 20～30g/ water L, cerous sulfate 2～5g/ water L;
Anodic current 0.05～1.0A/dm
2, time 15～30min.
Workpiece after the processing after 90 ℃ of hot water boil 5min, is used closely (100mm) purging of 0.3mpa pressurized air, and rete does not have any coming off.Detect with Lambd950 type ultraviolet/visible/near infrared spectrometer,, satisfy＜1% service requirements at 400～2500nm spectral range theca interna specular reflectance＜0.5%.
Claims (1)
1. titanium alloy black anode oxidation method that can reduce oxidation film layer stress, may further comprise the steps: the alkali electroless surface degreasing, the acidic surface activation treatment, black anodizing is handled, it is characterized in that, after described alkali electroless surface degreasing step, before the acidic surface activation treatment step, carry out the little etch of following surface chemistry and handle:
Little etch solution is to contain ammonium sulfate 70～100 grams in every premium on currency, ammonium bifluoride 50～80 grams, the aqueous solution of ammonium pyrophosphate 30～50 grams; Under 45～65 ℃ of temperature, etch 10～30min.
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| CN101457383B CN101457383B (en) | 2011-01-12 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805917A (en) * | 2010-03-24 | 2010-08-18 | 西安北方光电有限公司 | Preparation method of titanium alloy black anode oxidation treatment liquid |
| CN101812715A (en) * | 2010-03-24 | 2010-08-25 | 西安北方光电有限公司 | Titanium alloy black anode oxidation process |
| CN102586833A (en) * | 2012-01-19 | 2012-07-18 | 黑龙江省科学院石油化学研究院 | Surface treatment method of titanium alloy before glue joint |
| CN102653877A (en) * | 2011-03-04 | 2012-09-05 | 汉达精密电子(昆山)有限公司 | Electrolyte for anodic oxidation treatment of magnesium alloy and treatment method thereof |
| 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 |
| CN106149029A (en) * | 2014-12-05 | 2016-11-23 | 财团法人金属工业研究发展中心 | Black titanium-containing oxide layer, preparation method thereof and implant |
| CN106835238A (en) * | 2016-12-28 | 2017-06-13 | 佛山市铠斯钛科技有限公司 | A kind of titanium magnesium alloy method for anodizing and coloring |
| CN109609905A (en) * | 2018-12-27 | 2019-04-12 | 安徽工业大学 | A kind of wear-resisting composite coating of high rigidity Anti-erosion, preparation method and application |
| CN109881236A (en) * | 2019-02-28 | 2019-06-14 | 深圳市中科东明表面处理新材料技术有限公司 | Titanium alloy black anode oxidation liquid and surface treatment method of titanium alloy |
| CN111575762A (en) * | 2020-03-30 | 2020-08-25 | 沈阳富创精密设备有限公司 | Process for preparing titanium alloy high-performance anode film |
-
2008
- 2008-12-29 CN CN200810187621XA patent/CN101457383B/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812715A (en) * | 2010-03-24 | 2010-08-25 | 西安北方光电有限公司 | Titanium alloy black anode oxidation process |
| CN101805917B (en) * | 2010-03-24 | 2011-12-07 | 西安北方光电有限公司 | Preparation method of titanium alloy black anode oxidation treatment liquid |
| CN101812715B (en) * | 2010-03-24 | 2011-12-07 | 西安北方光电有限公司 | Titanium alloy black anode oxidation process |
| CN101805917A (en) * | 2010-03-24 | 2010-08-18 | 西安北方光电有限公司 | Preparation method of titanium alloy black anode oxidation treatment liquid |
| CN102653877A (en) * | 2011-03-04 | 2012-09-05 | 汉达精密电子(昆山)有限公司 | Electrolyte for anodic oxidation treatment of magnesium alloy and treatment method thereof |
| CN102586833A (en) * | 2012-01-19 | 2012-07-18 | 黑龙江省科学院石油化学研究院 | Surface treatment method of titanium alloy before glue joint |
| CN106149029A (en) * | 2014-12-05 | 2016-11-23 | 财团法人金属工业研究发展中心 | Black titanium-containing oxide layer, preparation method thereof and implant |
| 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 |
| CN106835238A (en) * | 2016-12-28 | 2017-06-13 | 佛山市铠斯钛科技有限公司 | A kind of titanium magnesium alloy method for anodizing and coloring |
| CN109609905A (en) * | 2018-12-27 | 2019-04-12 | 安徽工业大学 | A kind of wear-resisting composite coating of high rigidity Anti-erosion, preparation method and application |
| CN109881236A (en) * | 2019-02-28 | 2019-06-14 | 深圳市中科东明表面处理新材料技术有限公司 | Titanium alloy black anode oxidation liquid and surface treatment method of titanium alloy |
| CN111575762A (en) * | 2020-03-30 | 2020-08-25 | 沈阳富创精密设备有限公司 | Process for preparing titanium alloy high-performance anode film |
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| CN101457383B (en) | 2011-01-12 |
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