CN1137291C - Micro-are Ti alloy oxidizing technology - Google Patents
Micro-are Ti alloy oxidizing technology Download PDFInfo
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- CN1137291C CN1137291C CNB01113982XA CN01113982A CN1137291C CN 1137291 C CN1137291 C CN 1137291C CN B01113982X A CNB01113982X A CN B01113982XA CN 01113982 A CN01113982 A CN 01113982A CN 1137291 C CN1137291 C CN 1137291C
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- titanium alloy
- anodic oxidation
- tank liquor
- alloy
- protective film
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Abstract
The present invention relates to a titanium-alloy surface conversion film technique which is characterized in that a component part is put into acidity groove liquid mainly composed of sulfuric acid and is used as an anode, and an oxidation film of 2 to 12 mu m can be formed when voltage is raised to higher than 120 V by adjusting the pulse time and the tracking frequency of a pulse power source at low temperature. The present invention forms the protective film, the hardness of the protective film can reach 700 HV, and the resistance of the protective film can reach 5*10<6> omega. The protective film can prevent adhesion and can also enhance the abrasion resistance of the component part, and the present invention considerably widens the application range of titanium alloy and particularly widens the application range of a titanium-alloy fastener.
Description
Technical field:
The invention belongs to the titanium alloy surface treatment technology, be specifically related to titanium alloy component, particularly titanium alloy fastener surface electrochemistry conversion film processing method.
Background technology:
As everyone knows, the specific tenacity height of titanium alloy, proportion are little, good heat resistance, and corrosion stability is good, has been widely used in space flight, aviation, shipbuilding and chemical industry.But because titanium alloy is the alloy that is formed by the titanium more than 90%, its electropotential is negative (1.75V), with aluminium, magnesium alloy parts, when the steel part of zinc-plated, cadmium plating and other metal or coating contact, can produce transfer transport, electrochemistry crevice corrosion take place easily cause bonding; In addition, titanium alloy hardness ratio higher temperatures alloy, stainless steel etc. are much lower again, and wear resistance is relatively poor.These characteristics have all limited the use range of titanium alloy.Aircraft industry press 1993 publish " aviation manufacturing engineering handbook (surface treatment fascicle) mentions that the conversion film on titanium or titanium alloy surface handles, and points out that this conversion film can be used for the anti-viscous of threaded fastener, wear-resisting, the anti-scratch that is used to be rotatably assorted is surperficial.But titanium alloy is the film forming difficulty under common voltage, and requirement will make titanium alloy be in the plasma arc state of oxidation under the condition of continuous boosted voltage, and oxide film is thickened.And this handbook there is no concrete scheme.The 3rd phase " material protection " that material protection periodical publisher published in 1988 is published the article of " differential arc oxidation and the material surface potteryization " of writing in Liu Feng mountain range, one piece of Beijing Research Inst. of Aeronautic Material, has mainly introduced aluminium alloy plasma micro-arc ceramic technology.Just in foreword, mention metal and the alloy thereof that contains titanium, also do not have the particular content of titanium alloy differential arc oxidation in its text.
Summary of the invention:
The object of the present invention is to provide a kind of titanium alloy component, especially titanium alloy fastener utilizes the pulse differential arc oxidation to make the surface form the processing method of high rigidity, high resistance protective film.
Technical solution of the present invention is as follows: in the technical process that comprises visual inspection, oil removing, clamping, washing, anodic oxidation, washes, dries up, checks, in the anodic oxidation operation, place the acid tank liquor of mainly forming to do anode part by sulfuric acid, adopt the direct current pulse power source intermittent power supply, at low temperatures by regulating impulse time and tracking frequency, progressively boost to and be higher than behind the 120V film forming under the plasma micro-arc state.Wherein, can contain a spot of phosphoric acid in the tank liquor, its prescription is H
2SO
4(ρ=1.84) 50～250ml/l; H
3PO
4(ρ=1.7) 0～20ml/l; The temperature of tank liquor belongs to low temperature for≤30 ℃, generally is taken as-10～30 ℃.The pulse current density that is adopted is 1-12A/dm
2Pulse duration is 0.02-0.08s; Tracking frequency is 0.25-2.95Hz; Be 10-50min pressure rising time.Certainly, in the above-mentioned flow process, oil removing process is that common process both can comprise electrochemical deoiling, also can comprise Solvent degreasing.And the voltage of anodic oxidation when finishing then depends on the requirement of drawing to the part thickness, is generally 120-300V in addition, and the pulsed current ripple of employing both can be zigzag wave, sine wave, can be again rectangular wave.
Description of drawings:
Accompanying drawing 1 is a process method flow chart.
Accompanying drawing 2 is the oxide film microscopic appearance figure of compact structure.
Accompanying drawing 3 is another oxide film microscopic appearance figure.
Embodiment:
Embodiment one, is T to certain engine material trade mark at first
C6, BT20 nut, nut, screws etc. have blind hole, 840 of the parts of screw thread and groove carry out visual inspection, dip in acetone wiping gently with absorbent cotton, and in carry out electrochemical deoiling behind the clamping in the electrochemical deoiling tank liquor.At this moment, as follows except that oil formula:
NaOH 30-70g/L
Na
2CO
3.10H
2O 20-25g/L
Na
3PO
4 5-15g/L
Na
3SiO
4 3-5g/L
Temperature 40-80 ℃
Part after the oil removing is through washing laggard horizontal pulse anodic oxidation.At this moment, the part that is contained on the titanium alloy anchor clamps will closely contact with anchor clamps, guarantees not to be shifted when trembling.The prescription and the oxidizing process of this oxidation tank liquor are as follows:
H
2SO
4(ρ＝1.84) 180-220ml/L
H
3PO
4(ρ＝1.7) 5-15ml/L
Tank liquor temperature 0-30 ℃
Current density 1-6A/dm
2
Time length 0.3-0.8s
Tracking frequency 1.20-0.25Hz
In the process of boosting, the surface to be machined of part all differential of the arc phenomenon can occur.After the process of boosting continues for some time, keep final magnitude of voltage to specific time.Because present embodiment will be made anti-bonding conversion film, so get 10-20min pressure rising time, termination voltage is got 120-150V.Oxidation is closed pulse after finishing, step-down then, and part is taken out in outage, carries out follow-up washing, dries up and inspection process.Final pieces O.K. records through scanning electron microscope, and structure is 2-3 μ m to close oxide thickness, sees shown in the accompanying drawing 2.Adopt microhardness tester, by calculating as can be known, this oxide film hardness is a little more than matrix hardness, and this is to be subjected to owing to film is extremely thin due to the matrix support influences.In anti-bonding simultaneous test, adopt the part rete of this art breading complete, piece surface is such as the smooth no bonding phenomenon in screw thread place, and the nut of oxide skin does not then come in contact corrosion already, even the rotation difficulty.840 of this batches, by the technical process passed examination, through installation by 300 hours endurance tests of engine and be delivered for use.
Embodiment two, certain engine pressing plate, pad, pin, a wall, ear muff etc., material mark T
C4, T
C11Amount to 1500.In the implementing process flow process, check part, oil removing, operations such as washing are with embodiment one, and just in the anodic oxidation operation, its tank liquor prescription and oxidizing process are as follows:
H
2SO
4(ρ＝1.84) 50-250ml/L
H
3PO
4(ρ＝1.7) 0-20ml/L
Tank liquor temperature-10-10 ℃
Current density 2-12A/dm
2
Time length 0.02-0.4s
Tracking frequency 2.95-0.8Hz
The purpose of present embodiment is to make attrition resistant conversion film, so get 20-50min pressure rising time, termination voltage is got 140-300V.Operation after the anodic oxidation is also with embodiment one.Final pieces O.K. detects through eddy current thickness meter, and oxide thickness is 5-12 μ m.The same microhardness tester that adopt calculate by test, and its oxide film hardness reaches 600-700HV.Use scanning electron microscopic observation, this oxide film microcosmic fenestra is very abundant, is suitable for retaining solid lubricant, sees accompanying drawing 3.Also pay use after 1500 of this batches are qualified on inspection.
The invention has the advantages that and adopt the pulse power supply mode, overcome the key of titanium alloy film forming difficulty, realized that especially the titanium alloy fastener surface forms high rigidity (can reach 700HV) to titanium alloy, high resistance (can reach 5 * 10
6Ω) the purpose of protective film.Since utilize the pulsed current intermittent power supply to boost at low temperatures, therefore relatively flow-through method anodic oxidation, its oxide film hardness height, wear resistance will be got well, and helps the fusion of rete---and solidify, make rete smooth, do not reduce the safe range of stress of material.In a word, the present invention makes titanium alloy surface form the protective film of one deck 2-12 μ m, has hindered electron transport, suppressed the generation of electrochemical reaction, reach anti-bonding purpose, also improved the wear resisting property of material simultaneously, can improve part work-ing life more than 3 times.Because the particularly range of application of titanium alloy fastener, contact element and sleeve member of titanium alloy has been expanded in realization of the present invention greatly.Aircraft engine, marine engine.Motor car engine, the superalloy on aerospacecraft and some civilian goods, stainless steel part under the condition that working temperature allows, can replace with titanium alloy anode oxidation spare, thus the weight of mitigation system greatly.
Claims (3)
1, a kind of titanium alloy micro-arc anodic oxidation method, comprise: oil removing, clamping, anodic oxidation and washing is characterized in that: in anodic oxidation, part is placed in the acid tank liquor, wherein contain sulfuric acid ρ=1.84 50～250ml/L, under tank liquor temperature≤30 ℃, adopt direct current pulse power source, by regulating impulse time and tracking frequency, progressively boost to and be higher than behind the 120V film forming under the plasma micro-arc state.
2, titanium alloy micro-arc anodic oxidation method according to claim 1 is characterized in that: also contain H in the acid tank liquor
3PO
4ρ=1.7≤20ml/L, tank liquor temperature are-10～30 ℃.
3, titanium alloy micro-arc anodic oxidation method according to claim 1, it is characterized in that: the pulse charge parameter is as follows:
Current density 1～12A/dm
2,
Time length 0.02～0.8s,
Tracking frequency 0.25～2.95Hz,
Pressure rising time 10～50min,
Termination voltage 120～300V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01113982XA CN1137291C (en) | 2001-05-22 | 2001-05-22 | Micro-are Ti alloy oxidizing technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01113982XA CN1137291C (en) | 2001-05-22 | 2001-05-22 | Micro-are Ti alloy oxidizing technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1386917A CN1386917A (en) | 2002-12-25 |
| CN1137291C true CN1137291C (en) | 2004-02-04 |
Family
ID=4660676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB01113982XA Expired - Fee Related CN1137291C (en) | 2001-05-22 | 2001-05-22 | Micro-are Ti alloy oxidizing technology |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100454742C (en) * | 2004-09-21 | 2009-01-21 | 沈阳黎明航空发动机(集团)有限责任公司 | Large capacity titanium alloy pulse micro arc anode oxidation dynamic control power source |
| CN1974876B (en) * | 2006-11-02 | 2010-07-07 | 华南理工大学 | Bioactive film on titanium metal surface and its sand blasting-micro arc oxidizing compounding process |
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| CN100346845C (en) * | 2004-01-16 | 2007-11-07 | 清华大学 | Metal surface constructional gradient biological layer and its preparation and usage |
| CN100390320C (en) * | 2004-06-23 | 2008-05-28 | 中国科学院金属研究所 | Surface treatment for implant material of titanium or titanium alloy from electrochemical method |
| CN101812715B (en) * | 2010-03-24 | 2011-12-07 | 西安北方光电有限公司 | Titanium alloy black anode oxidation process |
| CN102425000A (en) * | 2011-11-29 | 2012-04-25 | 哈尔滨工业大学 | Method for preparing biologically active titanium dioxide film on NiTi alloy surface |
| CN104195616A (en) * | 2014-09-04 | 2014-12-10 | 攀钢集团成都钢钒有限公司 | Micro-arc oxidation treatment method of titanium alloy tubing coupling surface |
| CN106637349A (en) * | 2016-11-08 | 2017-05-10 | 北京星航机电装备有限公司 | Treatment method before coating of titanium alloy surface coating |
| CN109594080A (en) * | 2017-09-30 | 2019-04-09 | 宝鸡市金海源钛标准件制品有限公司 | A kind of surface treatment method of titanium alloy |
| 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 |
| CN110863227B (en) * | 2019-11-07 | 2022-01-28 | 西安工业大学 | Titanium alloy pulse-direct current anodic oxidation surface treatment method |
| CN113061895B (en) * | 2021-03-04 | 2023-04-28 | 中国兵器科学研究院宁波分院 | Micro-arc oxidation treatment method for surface of titanium alloy fastener |
| CN115044859A (en) * | 2022-06-17 | 2022-09-13 | 中国船舶重工集团公司第七二五研究所 | Titanium alloy material surface treatment method |
-
2001
- 2001-05-22 CN CNB01113982XA patent/CN1137291C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100454742C (en) * | 2004-09-21 | 2009-01-21 | 沈阳黎明航空发动机(集团)有限责任公司 | Large capacity titanium alloy pulse micro arc anode oxidation dynamic control power source |
| CN1974876B (en) * | 2006-11-02 | 2010-07-07 | 华南理工大学 | Bioactive film on titanium metal surface and its sand blasting-micro arc oxidizing compounding process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1386917A (en) | 2002-12-25 |
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