CN101498025B - Titanium alloy anodic oxidation method based on sodium oxalate system - Google Patents
Titanium alloy anodic oxidation method based on sodium oxalate system Download PDFInfo
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- CN101498025B CN101498025B CN2009100769925A CN200910076992A CN101498025B CN 101498025 B CN101498025 B CN 101498025B CN 2009100769925 A CN2009100769925 A CN 2009100769925A CN 200910076992 A CN200910076992 A CN 200910076992A CN 101498025 B CN101498025 B CN 101498025B
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- titanium alloy
- anode
- anodic oxidation
- current density
- pulse power
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Abstract
The invention discloses a titanium alloy anode oxidizing method which is characterized in that a pulse power supply is adopted to carry out anode oxidation in a fluoride-free and alkaline sodium oxalate system by a mode of controlling current density. The invention can rapidly generate a layer of smooth, uniform, compact and thicker anode oxide film on a titanium and titanium alloy surface under the states that energy consumption is low and no spark discharge is generated. The titanium alloy anode oxidizing method does not adopt strong acid, hydrofluoric acid or fluoride during the treatment steps, lowers pollution to environment and damage to human bodies and is environment-friendly and safe.
Description
Technical field
The present invention relates to a kind of titanium alloy anode oxidation surface treatment method, titanium alloy anodic oxidation method under particularly a kind of safety and environmental protection condition belongs to field of metal surface treatment technology.
Background technology
Titanium or titanium alloy is that a kind of specific tenacity is high, and the type material that solidity to corrosion is strong has extremely superior high-temperature behavior and easy inactivating performance, is widely used in numerous areas such as aerospace, naval vessel, chemistry.Because the natural passivation film thickness of titanium alloy is extremely thin, its corrosion resistance and wear resisting property receive certain restriction.Then is a kind of effective surface treatment process that can improve titanium alloy oxidation film layer thickness and corrosion resistance through anodic oxidation at the fine and close anode oxide film of its surface preparation one deck.The performance of anode oxidation membrane depends primarily on its composition, structure and thickness.
Titanium alloy anode oxidation is divided into alkaline anodic oxidation and acid anodic oxidation two big classes, and acid anodic oxidation is divided into sulfuric acid type anodic oxidation and the anodic oxidation of sulfuric acid phosphatic type.Acid anodised electrolytic solution component is strong acid.In actual application, at first, the preparation meeting of acid electrolyte causes harm to a certain degree to experimental installation, operator; Secondly, anodic oxidation reactions is very violent, corrodes instrument easily, harmful to human, contaminate environment; At last, waste electrolyte can only adopt the way of dilution process in discharge process, influences factory's periphery ecotope.In addition, the H in the electrolytic solution gets into titanium alloy substrate easily in chemical reaction process, and after acid anode oxidation process, titanium alloy material is prone to produce hydrogen embrittlement in application, influences its work-ing life, makes it to exist potential safety hazard to a certain degree.At present, can contain fluorion in the alkaline anode oxidation process of part.Fluorine is a toxic substance, influences HUMAN HEALTH, pollution of ecological environment.In addition, in the not fluorine-containing alkaline anode oxidation process, film forming thinner thickness, thickness is in the scope of 0.5-2 μ m.
Summary of the invention
To the acid anode oxidation process of above-mentioned existing titanium alloy and existing problem of alkaline anode oxidation process and shortcoming; The present invention aims to provide a kind of titanium alloy anodic oxidation method based on sodium oxalate system; Can be in lower energy consumption; Under the flashing discharge condition, do not generate smooth, even, the fine and close and thicker anode oxide film of one deck fast on the titanium or titanium alloy surface.Simultaneously present method can reduce the harm that anode oxidation process causes environment and human body to a great extent in treatment project, reduces the intractability of production waste liquid.The present invention has easy to operate, and technology is simple, and eco-friendly characteristics are titanium alloy anodic oxidation methods of a kind of green, safety.
Technical scheme of the present invention is following:
With the titanium alloy is anode, and stainless steel is a negative electrode, and the control anode: the cathode area ratio is not more than 1: 2; In temperature is 10～40 ℃ electrolytic solution; Adopt the pulse power to carry out anodic oxidation through the mode of control current density, reach specified anodic oxidation parameter through certain slow time of opening after, the time length is 20-60min; Keep in the anode oxidation process stirring, stirring intensity is 50r/min～300r/min.
The parameter of the said pulse power is:
Pulse power current density 3A/dm
2～10A/dm
2,
Pulse-repetition 60freq/min～120freq/min
Dutycycle 20%～60%
Consisting of of said anodic oxidation electrolyte:
Sodium oxalate 5g/L～20g/L
Sodium hydroxide 5g/L～20g/L
Tsp 5g/L～10g/L
Sodium tetraborate 5g/L～10g/L
Water glass 3g/L～10g/L
Terepthaloyl moietie 5ml/L～20ml/L
The said slow time of opening is meant: make it in 60～300 seconds from 0A/dm in anodic oxidation initial stage control current density
2Be raised to required current density 3A/dm
2～10A/dm
2
Anodic oxidation is carried out under the sparkless discharge all the time.
The present invention is a kind of titanium alloy anodic oxidation method based on sodium oxalate system, is intended to realize under the condition of Environmental Safety the preparation of titanium alloy surface anode oxide film, and its Production Flow Chart is identical with the common anode oxidizing process:
Oil removing degreasing → washing → anodic oxidation → washing → oven dry
The invention has the advantages that: do not adopt strong acid, hydrofluoric acid or fluorochemical in the anodize step, reduce to a great extent the pollution of environment and the harm of human body; The required power supply of anodic oxidation adopts the pulse power, and its energy consumption is low.Anode oxidation method disclosed by the invention can generate the sull of 4～8 μ m on high-strength high-ductility titanium alloy, this sull is evenly fine and close, more than the resisting salt fog corrosion 1000h.
Description of drawings
Fig. 1 is a titanium alloy anodic oxide film outward appearance photo among the embodiment 1;
Fig. 2 is a titanium alloy anodic oxide film outward appearance photo among the embodiment 2;
Fig. 3 is the metallographic surface picture and the cross-section photograph of titanium alloy anodic oxide film among the embodiment 2;
Fig. 4 is the ESEM surface and the cross-section photograph of titanium alloy anodic oxide film among the embodiment 2;
Fig. 5 is a titanium alloy anodic oxide film salt mist experiment photo among the embodiment 2;
Fig. 6 is a titanium alloy anodic oxide film outward appearance photo among the embodiment 3.
Embodiment
To combine accompanying drawing and embodiment that the present invention is done further detailed description below.
Embodiment 1
1, anode oxidation process step
Oil removing degreasing → washing → anodic oxidation → washing → oven dry
2, anodic oxidation
With TB6 titanium alloy sheet material (long 10cm goes up wide 3cm, following wide 5cm, thick 2mm, the total area is about 80cm
2) be anode, the 1Cr18Ni9Ti stainless steel is a negative electrode, the control anode: the cathode area ratio is not more than 1: 2; In temperature is 10 ± 1 ℃ electrolytic solution; Adopt the pulse power to carry out anodic oxidation through the mode of control current density, reach specified anodic oxidation parameter through certain slow time of opening after, the time length is 45min; Keep in the anode oxidation process stirring, stirring intensity is 150r/min.
The parameter of the said pulse power is:
Pulse power current density 10A/dm
2,
Pulse-repetition 100freq/min
Dutycycle 30%
Consisting of of said anodic oxidation electrolyte:
Sodium oxalate 5g/L
Sodium hydroxide 10g/L
Tsp 5g/L
Sodium tetraborate 5g/L
Water glass 3g/L
Terepthaloyl moietie 5ml/L
3, film-formation result
TB6 titanium alloy test piece film forming in sodium oxalate system is faint yellow under this kind prescription condition, and smooth surface is even, covers completely, and its film forming photo is as shown in Figure 1.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 thickness is in 3～5 mu m ranges.
Embodiment 2
1, anode oxidation process step
Oil removing degreasing → washing → anodic oxidation → washing → oven dry
2, anodic oxidation
With TB6 titanium alloy sheet material (long 9cm, wide 2.5cm, thick 3mm, the total area is about 45cm
2) be anode, the 1Cr18Ni9Ti stainless steel is a negative electrode, the control anode: the cathode area ratio is not more than 1: 2; In temperature is 10 ± 1 ℃ electrolytic solution; Adopt the pulse power to carry out anodic oxidation through the mode of control current density, reach specified anodic oxidation parameter through certain slow time of opening after, the time length is 45min; Keep in the anode oxidation process stirring, stirring intensity is 100r/min.
The parameter of the said pulse power is:
Pulse power current density 5A/dm
2,
Pulse-repetition 80freq/min
Dutycycle 20%
Consisting of of said anodic oxidation electrolyte:
Sodium oxalate 10g/L
Sodium hydroxide 10g/L
Tsp 10g/L
Sodium tetraborate 10g/L
Water glass 4g/L
Terepthaloyl moietie 10ml/L
3, film-formation result
TB6 titanium alloy test piece film forming in sodium oxalate system is yellow under this kind prescription condition, and smooth surface is even, covers completely, and its film forming photo is as shown in Figure 2, and the surperficial and sectional view of the metallographic of sull and ESEM is like Fig. 3, shown in 4.Carry out according to GB6458-86 metal cladding neutral salt spray test standard.Surface picture behind the test piece process 1000h salt mist experiment is as shown in Figure 5.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 thickness is in 6～8 mu m ranges.
Embodiment 3
1, anode oxidation process step
Oil removing degreasing → washing → anodic oxidation → washing → oven dry
2, anodic oxidation
With TB6 titanium alloy sheet material (long 10cm goes up wide 3cm, following wide 5cm, thick 2mm, the total area is about 80cm
2) be anode, the 1Cr18Ni9Ti stainless steel is a negative electrode, the control anode: the cathode area ratio is not more than 1: 2; In temperature is 20 ± 1 ℃ electrolytic solution; Adopt the pulse power to carry out anodic oxidation through the mode of control current density, reach specified anodic oxidation parameter through certain slow time of opening after, the time length is 50min; Keep in the anode oxidation process stirring, stirring intensity is 200r/min.
The parameter of the said pulse power is:
Pulse power current density 10A/dm
2,
Pulse-repetition 100freq/min
Dutycycle 60%
Consisting of of said anodic oxidation electrolyte:
Sodium oxalate 10g/L
Sodium hydroxide 10g/L
Tsp 10g/L
Sodium tetraborate 10g/L
Water glass 3.5g/L
Terepthaloyl moietie 10ml/L
3, film-formation result
TB6 titanium alloy test piece film forming in sodium oxalate system is yellow under this kind prescription condition, and smooth surface is even, covers completely, and its film forming photo is as shown in Figure 6.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 thickness is in 5～7 mu m ranges.
Claims (4)
1. the anode oxidation method of a titanium alloy is characterized in that with the titanium alloy being anode, and stainless steel is a negative electrode; The control anode: the cathode area ratio is not more than 1: 2; In temperature is 10～40 ℃ electrolytic solution, adopt the pulse power to carry out anodic oxidation through the mode of control current density, reach specified anodic oxidation parameter through certain slow time of opening after; Lasting oxidization time is 20-60min; Keep to stir in the anode oxidation process, stirring intensity is 50r/min～300r/min, it is characterized in that: the consisting of of said electrolytic solution: sodium oxalate 5g/L～20g/L
Sodium hydroxide 5g/L～20g/L
Tsp 5g/L～10g/L
Sodium tetraborate 5g/L～10g/L
Water glass 3g/L～10g/L
Terepthaloyl moietie 5ml/L～20ml/L.
2. the anode oxidation method of titanium alloy according to claim 1, it is characterized in that: the parameter of the said pulse power is:
Pulse power current density 3A/dm
2～10A/dm
2,
Pulse-repetition 60freq/min～120freq/min
Dutycycle 20%～60%.
3. the anode oxidation method of titanium alloy according to claim 1 is characterized in that: the said slow time of opening is meant: make it in 60～300 seconds from 0A/dm in anodic oxidation initial stage control current density
2Be raised to required current density 3A/dm
2～10A/dm
2
4. the anode oxidation method of titanium alloy according to claim 1 is characterized in that: said anodic oxidation is carried out under the sparkless discharge all the time.
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| CN101498025B true CN101498025B (en) | 2012-02-22 |
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| CN102312264B (en) * | 2011-08-22 | 2013-10-09 | 吴江市精工铝字制造厂 | Decorative oxidation method for aluminum and aluminum alloy |
| CN103938252A (en) * | 2013-01-23 | 2014-07-23 | 汉达精密电子(昆山)有限公司 | Titanium alloy anodic oxidation solution and method of processing titanium alloy with the solution |
| CN103320840B (en) * | 2013-07-09 | 2015-08-12 | 昆明冶金研究院 | A kind of titanium alloy anode oxidation alkaline electrolyte and colored film layer preparation technology |
| CN110618172B (en) * | 2018-06-20 | 2022-05-24 | 深圳市裕展精密科技有限公司 | Analysis method and analysis system for anodic oxidation electrolyte of titanium or titanium alloy |
| CN110863227B (en) * | 2019-11-07 | 2022-01-28 | 西安工业大学 | Titanium alloy pulse-direct current anodic oxidation surface treatment method |
| CN110699733B (en) * | 2019-11-20 | 2020-08-11 | 中国计量大学 | Preparation method, product and application of titanium alloy porous oxide film |
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