CN1908245B - Titanium alloy anode oxidation technique based on ammonium tartrate system - Google Patents
Titanium alloy anode oxidation technique based on ammonium tartrate system Download PDFInfo
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- CN1908245B CN1908245B CN2006100888827A CN200610088882A CN1908245B CN 1908245 B CN1908245 B CN 1908245B CN 2006100888827 A CN2006100888827 A CN 2006100888827A CN 200610088882 A CN200610088882 A CN 200610088882A CN 1908245 B CN1908245 B CN 1908245B
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- titanium alloy
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Abstract
the invention discloses a Ti-alloy anode oxidizing technology based on ammonium tartrate system, which is characterized by the following: adopting alkaline eroding liquid and ammonium tartrate system to dispose Ti-alloy base; filming; avoiding using poisonous material; reducing manufacturing cost.
Description
Technical field
The present invention relates to a kind of anodic oxidation treatment technology, more particularly say, be meant and a kind of titanium alloy carried out anodic oxidation treatment, its anode oxidation treatment liquid that adopts is based on ammonium tartrate system.
Background technology
Anodized technique is to adopt the step of HB/Z 347-2002 defined to carry out in present industry standard, and the anodized technique in this standard comprises that checking and accepting step 1-→ organic solvent or aqueous cleaning agent deoiling step 2-→ dress before (referring to shown in Figure 1) anodic oxidation hangs step 3-→ deoiling step 4-→ first hot water wash step 5-→ first cold wash step 6-→ (acid) corrosion step 7-→ second cold wash step 8-→ anodic oxidation step 9-→ the 3rd flowing cool water that flows that flows that flows and wash step 10-→ mobile hot deionized water and wash step 11-→ demounting procedure 12-→ drying steps 13-→ checking procedure 14.
At present, in corrosion step 7, employed corrosive fluid discloses in the 5.6th joint in HB/Z347-2002 to the anodic oxidation treatment of titanium alloy, and its component is an acid etching solution.This acid etching solution can cause to a certain degree harm to experimental installation, workman in preparation process; In discharge process, can only dilute back discharging, and not have other processing modes, and environment is had to a certain degree pollution it.And in corrosion step 7, the H in the corrosive fluid enters titanium alloy substrate easily in chemical reaction process, cause the alloy hydrogen embrittlement.
Summary of the invention
The purpose of this invention is to provide a kind of titanium alloy anode oxidation technique based on ammonium tartrate system, this technology is changed into the alkali cleaning forms of corrosion in original bite step, and treatment solution is hydrofluoric acid containing not, having changed present treatment process effectively damages environment and human body in treating processes, strengthen the intractability of producing waste simultaneously, increase the situation of production cost.
The present invention is a kind of titanium alloy anode oxidation technique based on ammonium tartrate system, includes titanium alloy substrate is carried out: check and accept step 1-→ organic solvent or aqueous cleaning agent deoiling step 2-→ dress before the anodic oxidation and hang step 3-→ deoiling step 4-→ first hot water wash step 5-→ first cold wash step 6-→ caustic corrosion step 51-→ second flow cold wash step 8-→ wash step 10-→ mobile hot deionized water and wash step 11-→ demounting procedure 12-→ drying steps 13-→ checking procedure 14 based on the anodic oxidation step 53-of ammonium tartrate system → the 3rd flowing cool water of hot water wash step 52-→ second that flows that flows that flows.
The corrosive fluid that uses in the described caustic corrosion step 51 is made up of the water glass of 20～30g/L, the yellow soda ash of 20～30g/L, the sodium hydroxide of 40～50g/L, the sodium lauryl sulphate of 1～5g/L, additive A and the balance of deionized water of 1～10g/L; Described additive A is one or both in tween 80, Triton and the disodium ethylene diamine tetraacetate, and the consumption proportion when choosing two kinds of combinations is 1: 1;
Described treatment solution based on use in the anodic oxidation step 53 of ammonium tartrate system is made up of ammonium tartrate and the balance of deionized water of 1～15g/L;
Titanium alloy substrate after the first mobile cold wash step 6 is handled is handled 15～40min and is finished described caustic corrosion step 51 in 50～60 ℃ of corrosive fluids; Under 40～50 ℃ of conditions of flowing water temperature, wash 1～5min then and finish the described second mobile hot water wash step 52; Washing 1～5min again under 20 ± 2 ℃ of conditions of flowing water temperature finishes described second and flows to put it into after the cold wash step 8 and handle 30～90min in 15～37 ℃ of treatment solutions and finish described anodic oxidation step 53; Anodic oxidation treatment condition 4～10A/dm
2Pulse current density, 60～110freq/min frequency, 20～80% dutycycles, negative electrode is a stainless steel, anode cathode area ratio is not more than 1: 2.
The advantage of titanium alloy anode oxidation technique of the present invention is: anodizing liquid composition is simple; Prepare required power supply and adopt the pulse power, its energy consumption is low; Whole process does not adopt hydrofluoric acid in the anodic oxidation treatment step, reduces greatly to the pollution of environment with to the harm of human body.In addition, this kind anodizing technology can be gone up the oxide film that generates 2～3 μ m at high-strength titanium alloy (as TB6), and the anti-crevice corrosion performance of this kind oxide film is good, and resisting salt fog corrosion can reach more than the 1000h.
Description of drawings
Fig. 1 is the anodic oxidation treatment process flow block diagram of stipulating among the HB/Z 347-2002.
Fig. 2 is an anodic oxidation treatment process flow block diagram of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The present invention is a kind of titanium alloy anode oxidation technique based on ammonium tartrate system, and this technique includes following process steps: check and accept step 1-→ organic solvent or aqueous cleaning agent deoiling step 2-→ dress before the anodic oxidation and hang step 3-→ deoiling step 4-→ first hot water wash step 5-→ first cold wash step 6-→ caustic corrosion step 51-→ second flow cold wash step 8-→ wash step 10-→ mobile hot deionized water and wash step 11-→ demounting procedure 12-→ drying steps 13-→ checking procedure 14 based on the anodic oxidation step 53-of ammonium tartrate system → the 3rd flowing cool water of hot water wash step 52-→ second that flows that flows that flows.
The corrosive fluid that uses in the described caustic corrosion step 51 that adopts among the present invention is made up of the water glass of 20～30g/L, the yellow soda ash of 20～30g/L, the sodium hydroxide of 40～50g/L, the sodium lauryl sulphate of 1～5g/L, additive A and the balance of deionized water of 1～10g/L; Described additive A is one or both in tween 80, Triton and the disodium ethylene diamine tetraacetate, and the consumption proportion when choosing two kinds of combinations is 1: 1;
The described treatment solution based on use in the anodic oxidation step 53 of ammonium tartrate system that adopts among the present invention is made up of ammonium tartrate and the balance of deionized water of 1～15g/L;
In the present invention, the titanium alloy substrate after the first mobile cold wash step 6 is handled is handled 15～40min and is finished described caustic corrosion step 51 in 50～60 ℃ of corrosive fluids; Under 40～50 ℃ of conditions of flowing water temperature, wash 1～5min then and finish the described second mobile hot water wash step 52; Washing 1～5min again under 20 ± 2 ℃ of conditions of flowing water temperature finishes described second and flows to put it into after the cold wash step 8 and handle 30～90min in 15～37 ℃ of treatment solutions and finish described anodic oxidation step 53; Anodic oxidation treatment condition 4～10A/dm
2Pulse current density, 60～110freq/min frequency, 20～80% dutycycles, negative electrode is a stainless steel, anode cathode area ratio is not more than 1: 2.
The present invention carries out pulse anodic oxidation novel process in the ammonium tartrate system to titanium alloy substrate, optimize by alkaline degreasing and emulsifier surface activating process, adjust processing parameter such as temperature, time, ratio of cathodic to anodic area and placement location and frequency, dutycycle isopulse power parameter, the final anode oxide film that generates is yellow, thickness 2～3 μ m are more than the salt-fog resistant test 1000h.
Embodiment 1:The TB6 titanium alloy substrate is carried out anodic oxidation treatment
1, preparation alkaline corrosion liquid
25g/L water glass, 25g/L yellow soda ash, 45g/L sodium hydroxide, 3g/L sodium lauryl sulphate, 5g/L Triton and balance of deionized water stir, and be stand-by.
2, preparation anode oxidation treatment liquid
3g/L ammonium tartrate and balance of deionized water stir, and be stand-by.
3, anodic oxidation treatment
The TB6 titanium alloy substrate is carried out checking and accepting before the anodic oxidation step 1-→ organic solvent or aqueous cleaning agent deoiling step 2-→ dress in turn hang step 3-→ deoiling step 4-→ first hot water wash step 5-→ first of flowing and flow after the conventional processing of cold wash step 6, put into 50 ± 1 ℃ of corrosive fluids processing 30min and finish described caustic corrosion step 51; Washing 2min finishes the described second mobile hot water wash step 52 under 40 ± 1 ℃ of conditions of flowing water temperature then; Washing 1min finishes described second and flows to put it into after the cold wash step 8 and handle 30min in 25 ± 1 ℃ of treatment solutions and finish described anodic oxidation step 53 under 20 ± 2 ℃ of conditions of flowing water temperature again; Anodic oxidation treatment condition 5A/dm
2(the 2min internal linear is increased to the nominal current density value) pulse current density, the 80freq/min frequency, 30% dutycycle, negative electrode is stainless steel 1Cr18Ni9Ti, the anode cathode area was than 1: 2.
TB6 titanium alloy test piece ammonium tartrate system film forming is yellow under this kind prescription condition, and smooth surface is even, covers complete.Adopt electronic spectrum to forming oxide film composition measurement result such as following table:
| Element | Weight percent | Atomic percent |
| O K | 15.48 | 35.23 |
| Al K | 1.38 | 1.87 |
| Ca K | 0.92 | 0.84 |
| Ti K | 72.61 | 55.20 |
| V K | 9.60 | 6.87 |
| Total amount | 100.00 |
As seen from the above table, it is titanium oxide that ammonium tartrate system generates the oxide film main component, and vanadium V and aluminium Al in a spot of matrix enter rete, because its oxygen level is very low, titanium oxide shows non-crystalline state.Wherein a spot of calcium Ca is the impurity of introducing in the metallographic specimen preparation process.
In this example the part operation specify as follows:
TB6 titanium alloy anode oxidation front surface quality is checked and accepted by the requirement of HB5034.
Look TB6 titanium alloy surface situation, with gasoline or meet the aqueous cleaning agent oil removing that HB5226 requires.
The special anchor clamps dress that should adopt TA1 or TC1 titanium alloy to make is hung the TB6 titanium alloy.The structure of anchor clamps depends on the shape of anodizing TB6 titanium alloy.Anchor clamps contact with the TB6 titanium alloy should be good, guaranteeing have under the situation of enough electric conduction quantities, and contact area is suitable little.Reusable anchor clamps before use should be clean with the established anode oxide film stripping of surface in contact.
The oil removing activation should guarantee that TB6 titanium alloy surface moisture film is continuous, enters rinse bath then immediately.
In alkaline corrosion step 51, in reactive tank, add the deionized water of about 2/3rds working volumes, in sodium hydroxide, water glass, yellow soda ash, sodium lauryl sulphate and the Triton adding reactive tank with requirement, the medicine that is stirred to adding dissolves fully.
In anodic oxidation step 53, in reactive tank, add the deionized water of about 2/3rds working volumes, the ammonium tartrate of requirement is added in the reactive tank, after the medicine that is stirred to adding dissolves fully, add deionized water to working level.
After drying step 13 processing, the TB6 titanium alloy is pulled down from anchor clamps, do not allow to cause physical abuse.
TB6 titanium alloy after 14 pairs of processing of employing checking procedure is observed, and it is qualified that its oxide film color all belongs to from the bluish yellow look to milk yellow.Oxide film should be continuously, evenly, level and smooth, combine closely on matrix metal.Adopt non magnetic method of masurement to be undertaken by the regulation of GB/T 4957, measure the anodic oxidation film thickness with eddy current thickness meter, its oxide thickness is in 2～3 mu m ranges.
The ammonium tartrate by 3g/L, the sodium hydroxide of 2g/L and the treatment solution that balance of deionized water is formed that in only changing anodic oxidation step 53, use, all the other conditions are identical down, TB6 titanium alloy surface activation performance after treatment process of the present invention is handled is stronger, helps film forming; In film process, reduced the one-tenth membrane voltage.When the TB6 titanium alloy surface is long-pending bigger, when causing the setting current value higher, can reduce the electric current output rating relatively and cut down the consumption of energy.
The corrosive fluid that uses in only changing caustic corrosion step 51 is made up of 25g/L water glass, 25g/L yellow soda ash, 45g/L sodium hydroxide, 3g/L sodium lauryl sulphate, 5g/L Triton, 5g/L tween 80 and balance of deionized water, identical down in all the other conditions, TB6 titanium alloy surface activation performance after treatment process of the present invention is handled is stronger, helps film forming.
Embodiment 2:The TC18 titanium alloy substrate is carried out anodic oxidation treatment
1, preparation alkaline corrosion liquid
20g/L water glass, 25g/L yellow soda ash, 40g/L sodium hydroxide, 3g/L sodium lauryl sulphate, 8g/L tween 80 and balance of deionized water stir, and be stand-by.
2, preparation anode oxidation treatment liquid
3g/L ammonium tartrate and balance of deionized water stir, and be stand-by.
3, anodic oxidation treatment
The TC18 titanium alloy substrate is carried out checking and accepting before the anodic oxidation step 1-→ organic solvent or aqueous cleaning agent deoiling step 2-→ dress in turn hang step 3-→ deoiling step 4-→ first hot water wash step 5-→ first of flowing and flow after the conventional processing of cold wash step 6, put into 55 ± 1 ℃ of corrosive fluids processing 40min and finish described caustic corrosion step 51; Washing 3min finishes the described second mobile hot water wash step 52 under 45 ± 1 ℃ of conditions of flowing water temperature then; Washing 1min finishes described second and flows to put it into after the cold wash step 8 and handle 30min in 27 ± 1 ℃ of treatment solutions and finish described anodic oxidation step 53 under 20 ± 2 ℃ of conditions of flowing water temperature again; Anodic oxidation treatment condition 8A/dm
2Pulse current density, the 80freq/min frequency, 20% dutycycle, negative electrode is a stainless steel, the anode cathode area was than 1: 2.
Ammonium tartrate system is the film forming even compact on TC18, and it is yellow that thickness 2～3 μ m are.
By changing alkaline corrosion liquid component concentration, anodic oxidation treatment processing parameter and the power parameter of the present invention's preparation, the present invention goes for the anodic oxidation of TA, TC series titanium alloy, under the experiment condition same case, herein not exhaustive.
Claims (3)
1. titanium alloy anode oxidation technique based on ammonium tartrate system includes titanium alloy substrate is carried out:
Check and accept step (1) before the anodic oxidation;
Organic solvent or aqueous cleaning agent deoiling step (2);
Dress is hung step (3);
Deoiling step (4);
The first mobile hot water wash step (5);
The first mobile cold wash step (6);
The second mobile cold wash step (8);
The 3rd mobile cold wash step (10);
Mobile hot deionized water is washed step (11);
Demounting procedure (12);
Drying step (13);
Checking procedure (14) is characterized in that also including:
In described first caustic corrosion step (51) and second mobile hot water wash step (52) after the caustic corrosion step (51) and the anodic oxidation step (53) between the described second mobile cold wash step (8) and the described the 3rd mobile cold wash step (10) that flows between the cold wash step (6) and the described second mobile cold wash step (8) based on ammonium tartrate system;
The corrosive fluid that uses in the described caustic corrosion step (51) is made up of the water glass of 20～30g/L, the yellow soda ash of 20～30g/L, the sodium hydroxide of 40～50g/L, the sodium lauryl sulphate of 1～5g/L, additive A and the balance of deionized water of 1～10g/L; Described additive A is one or both in tween 80, Triton and the disodium ethylene diamine tetraacetate, and the consumption proportion when choosing two kinds of combinations is 1: 1;
Described treatment solution based on use in the anodic oxidation step (53) of ammonium tartrate system is made up of ammonium tartrate and the balance of deionized water of 1～15g/L;
Titanium alloy substrate after the first mobile cold wash step (6) is handled is handled 15～40min in 50～60 ℃ of corrosive fluids; Under 40～50 ℃ of conditions of flowing water temperature, wash 1～5min then; Put it in 15～37 ℃ of treatment solutions after under 20 ± 2 ℃ of conditions of flowing water temperature, washing 1～5min again and handle 30～90min; Anodic oxidation treatment condition 4～10A/dm
2Pulse current density, 60～110freq/min frequency, 20～80% dutycycles, negative electrode is a stainless steel, anode cathode area ratio is not more than 1: 2.
2. the titanium alloy anode oxidation technique based on ammonium tartrate system according to claim 1 is characterized in that:
Form by the ammonium tartrate of 1～15g/L, sodium hydroxide and the balance of deionized water of 1～10g/L based on the treatment solution that uses in the anodic oxidation step (53) of ammonium tartrate system.
3. the titanium alloy anode oxidation technique based on ammonium tartrate system according to claim 1 is characterized in that:
There is the oxide yellow film of 1～5 μ m titanium alloy-based surface after anodic oxidation step (53) is handled.
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| CN101413140B (en) * | 2007-10-17 | 2012-08-29 | 沈阳黎明航空发动机(集团)有限责任公司 | Blue anodic oxidation process for titanium alloy |
| CN101781788B (en) * | 2010-04-22 | 2015-05-13 | 兰州大学 | Method for preparing specially-shaped titanium dioxide nano-tube films |
| 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 |
| CN112068328B (en) * | 2020-09-09 | 2022-02-22 | 温州市皓朗眼镜有限公司 | Corrosion-resistant glasses frame and processing technology thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3864219A (en) * | 1974-01-08 | 1975-02-04 | Atomic Energy Commission | Process and electrolyte for applying barrier layer anodic coatings |
| GB2150603A (en) * | 1983-12-01 | 1985-07-03 | Messerschmitt Boelkow Blohm | Method for the surface treatment of articles of titanium and a bath therefor |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3864219A (en) * | 1974-01-08 | 1975-02-04 | Atomic Energy Commission | Process and electrolyte for applying barrier layer anodic coatings |
| GB2150603A (en) * | 1983-12-01 | 1985-07-03 | Messerschmitt Boelkow Blohm | Method for the surface treatment of articles of titanium and a bath therefor |
Non-Patent Citations (2)
| Title |
|---|
| 国防科学技术工业委员会.钛及钛合金阳极氧化工艺及质量检验.《中华人民共和国航空行业标准HB/Z347-2002》.2002, * |
| 脱祥明,李楠.钛及钛合金阳极氧化着色结构及拉伸性能.《稀有金属》.1997,第21卷(第3期), * |
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