CN108486630B - A kind of preparation method of Coloured Anodizing titanium film - Google Patents
A kind of preparation method of Coloured Anodizing titanium film Download PDFInfo
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- CN108486630B CN108486630B CN201810174490.5A CN201810174490A CN108486630B CN 108486630 B CN108486630 B CN 108486630B CN 201810174490 A CN201810174490 A CN 201810174490A CN 108486630 B CN108486630 B CN 108486630B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
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Abstract
The invention discloses a kind of preparation methods of Coloured Anodizing titanium film, belong to field of metal surface treatment technology.Titanium or titanium alloy surface are deoiled, degreasing, grinding and polishing treatment, then carries out shot blasting on surface processing；Using Jing Guo bead titanium or titanium alloy as anode, graphite plate is that cathode carries out anodized three times, and after each anodic oxidation, the electrolyte of titanium or titanium alloy surface is cleaned with dehydrated alcohol or deionized water, carries out the processing of next step after drying again；Finally, being heat-treated in a vacuum furnace, to obtain uniform film thickness stabilization, the Coloured Anodizing titanium film with preferable corrosion resistance.
Description
Technical field
The present invention relates to a kind of preparation methods of Coloured Anodizing titanium film, belong to field of metal surface treatment technology.
Background technique
Titanium or titanium alloy has good mechanical performance and mechanical property, density is low, rigidity is big, and hardness is low, high temperature resistant, resistance to
Corrosion is good, is widely used in the fields such as aerospace, automobile, military project and chemical industry.There is also some intrinsic scarce for titanium or titanium alloy
It falls into, as hardness is low, wear no resistance, thermal conductivity is bad.When titanium is connect with the feature contacts of other metal materials, due to mistake
Big potential difference, easily generation galvanic corrosion, cause coupled part to generate corrosion.It is closed to further increase titanium and titanium
The use characteristic of gold, needs that titanium or titanium alloy material is surface-treated and is modified.
Anodizing technology is the common process for modifying surface of titanium or titanium alloy, is a kind of raw in situ in non-ferrous metal surface
At the new technology of coloring film.Publication number CN101812715 discloses a kind of black anodized layer technique, although the patent obtains
Black, uniformly firm anode oxide film.Publication number CN1844483 patent gives a kind of titanium or titanium alloy surface anode oxygen
Change the method for coloring, the electrolyte being related to is Phosphoric Acid.The patent under different conditions, can obtain the oxygen of different colours
Change film, bright in color, corrosion resistance is good, good decorating effect.But the oxidation film that these methods obtain, color is monochrome, i.e., at certain
Under one specific anodic oxidation condition, the oxidation film of solid color can be obtained on titanium or titanium alloy surface.Even if carrying out multiple
Anodized, oxidation film can be transformed into another color by a kind of color；And it cannot obtain that multiple color is presented
Colored oxide film.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of Coloured Anodizing titanium film, can obtain on titanium or titanium alloy surface
Coloured Anodizing titanium film beautiful in colour, specifically includes the following steps:
(1) using sand paper grinding or chemical polishing method, titanium or titanium alloy surface are deoiled, degreasing, grinding and
Then polishing treatment carries out shot blasting on surface processing.
(2) will be through step (1) treated titanium or titanium alloy as anode, graphite plate carries out anode three times as cathode
Oxidation is handled, and after each anodic oxidation, cleans the electrolysis of titanium or titanium alloy surface with dehydrated alcohol or deionized water first
Liquid carries out the processing of next step again after drying.
(3) it by the titanium or titanium alloy after anodized three times, is put into vacuum drying oven and is heat-treated.
Preferably, the condition that shot blasting on surface is handled in step (1) of the present invention are as follows: shot-peening diameter is 0.1 ~ 0.5 millimeter
Steel ball, shot-peening time are 0.5 ~ 3min.
Preferably, the electrolyte that anodized uses three times in step (2) of the present invention is respectively as follows:
The ingredient and content of electrolyte in anode oxidation process are as follows: concentrated sulfuric acid 30-70mL/L, methane sulfonic acid 5-8g/
L, the aqueous solution of sodium sulphate 3-5g/L, voltage 90-120V, processing time are 5-10min.
The ingredient and content of electrolyte during two-step anodization are as follows: citric acid 50-100g/L, lactic acid 10-20g/L,
The aqueous solution of methane sulfonic acid 5-10g/L, voltage 50-80V, processing time are 10-30min.
Three times in anode oxidation process electrolyte ingredient and content are as follows: sodium tartrate 80-100g/L, sodium nitrite 10-
The ethanol solution of 15g/L, voltage 50-100V handle time 30-60min.
Preferably, the anodized in step (2) of the present invention, cathode and anode plate area ratio are 2:1 ~ 3:1, interpolar
Distance is 5 ~ 12cm.
Preferably, the condition being heat-treated in step (3) of the present invention are as follows: be heated to 100 ~ 120 DEG C, keep the temperature 1 hour；Then plus
Heat arrives 450-600 DEG C, keeps the temperature 1-2 hours, furnace cooling；The vacuum degree of vacuum drying oven is 0.03-0.1MPa.
Beneficial effects of the present invention:
(1) the method for the invention can obtain the colored oxide film of presentation multiple color in titanium or titanium alloy surface, make
Surface color is more gorgeous, plays better decorative effect.
(2) colored oxide film that the method for the invention is prepared has good anti-corrosion effects and stability.
(3) treatment process of the invention, the equipment of use are relatively simple, and cost is relatively low.
Detailed description of the invention
Fig. 1 is Coloured Anodizing Surface of Titanium Film；
Fig. 2 is Coloured Anodizing titanium film section；
Fig. 3 is the Tafel polarization curve of oxidation film.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
(1) using industrially pure titanium as anode (size 40mm × 10mm × 2mm), with the sand paper lapped face of different size,
Surface blot and oxide layer are removed, and forms smooth finish surface, then, uses diameter for 0.1 millimeter of steel ball, bead
3min。
(2) using through step (1) treated industrially pure titanium, as anode, graphite plate is cathode, cathode-anode plate area ratio is 2:
1, interpolar distance is 5cm, carries out anodized three times；Firstly, with concentrated sulfuric acid 30mL/L, methane sulfonic acid 8g/L, sodium sulphate
The aqueous solution of 3g/L is electrolyte, in voltage 120V, handles time 10min；Sample is taken out, in washes of absolute alcohol, air
It dries；Then, using citric acid 50g/L, lactic acid 20g/L, methane sulfonic acid 10g/L aqueous solution as electrolyte, in voltage 80V, place
The reason time is 10min, carries out second of anodic oxidation；Sample is taken out, is dried in washes of absolute alcohol, air；Finally, with wine
Stone acid sodium 100g/L, sodium nitrite 10g/L ethanol solution be electrolyte, in voltage 50V, handle time 60min；Take out examination
Sample is dried in washes of absolute alcohol, air.
(3) it by the sample after anodized three times, is put into vacuum drying oven, is heated to 100 DEG C of temperature, heat preservation 1 is small
When；450 DEG C are then heated to, keeps the temperature 2 hours, furnace cooling, vacuum drying oven vacuum degree is 0.03MPa.Sample is taken out, is obtained in coloured silk
The Ti anodic oxide film of color, as shown in Figure 1；Fig. 2 is its Cross Section Morphology, it can be seen from the figure that the thickness of oxidation film is about 4 ~ 5
Micron, whole dense uniform show that oxidation film has preferable stability and corrosion resistance.
Embodiment 2
(1) using TC4 as anode (size 40mm × 10mm × 2mm), with the sand paper lapped face of different size, table is removed
Face spot and oxide layer carry out surface polishing using electrochemical method, form smooth finish surface and then use diameter for 0.5 millimeter
Steel ball, bead 0.5min.
(2) using through step (1) treated TC4, as anode, graphite plate is cathode, cathode-anode plate area ratio is 3:1, pole
Between distance be 12cm, carry out anodized three times；Firstly, with concentrated sulfuric acid 70mL/L, methane sulfonic acid 5g/L, sodium sulphate 5g/L
Aqueous solution be electrolyte, in voltage 90V, handle time 30min；Sample is taken out, cleaned with deionized water, dried in air；
Then, using citric acid 100g/L, lactic acid 10g/L, methane sulfonic acid 5g/L aqueous solution as electrolyte, in voltage 50V, handle the time
For 30min, second of anodic oxidation is carried out；Sample is taken out, cleaned with deionized water, dried in air；Finally, with sodium tartrate
80g/L, sodium nitrite 15g/L ethanol solution be electrolyte, in voltage 100V, handle time 30min；Sample is taken out, is spent
It is dried in ionized water cleaning, air.
(3) it by the sample after anodized three times, is put into vacuum drying oven, is heated to 120 DEG C of temperature, heat preservation 1 is small
When；600 DEG C are then heated to, keeps the temperature 1 hour, furnace cooling, vacuum drying oven vacuum degree is 0.1MPa.Sample is taken out, is obtained in coloured silk
The Ti anodic oxide film of color, Fig. 3 are anode oxide film Tafel polarization curve described in the present embodiment, it can be seen from the figure that by
The sample of the processing of example 2, the current potential highest corroded, corrosion electric current density is minimum, compared with other 2 kinds of samples, has
Best corrosion resistance.
Embodiment 3
(1) using Ti-6Al-4V as anode (size 40mm × 10mm × 2mm), with the sand paper lapped face of different size,
Surface blot and oxide layer are removed, and forms smooth finish surface, then, uses diameter for 0.2 millimeter of steel ball, bead
2min。
(2) using through step (1) treated Ti-6Al-4V, as anode, graphite plate is cathode, cathode-anode plate area ratio is 3:
1, interpolar distance is 8cm, carries out anodized three times；Firstly, with concentrated sulfuric acid 60mL/L, methane sulfonic acid 6g/L, sodium sulphate
The aqueous solution of 4g/L is electrolyte, in voltage 110V, handles time 20min；Sample is taken out, is cleaned with deionized water, in air
It dries；Then, using citric acid 80g/L, lactic acid 15g/L, methane sulfonic acid 8g/L aqueous solution as electrolyte, in voltage 70V, processing
Time is 20min, carries out second of anodic oxidation；Sample is taken out, cleaned with deionized water, dried in air；Finally, with winestone
Sour sodium 90g/L, sodium nitrite 12g/L ethanol solution be electrolyte, in voltage 70V, handle time 45min；Sample is taken out, is used
It is dried in deionized water cleaning, air.
(3) it by the sample after anodized three times, is put into vacuum drying oven, is heated to 110 DEG C of temperature, heat preservation 1 is small
When；550 DEG C are then heated to, keeps the temperature 1.5 hours, vacuum drying oven vacuum degree is 0.07MPa, and furnace cooling takes out sample, is in
Colored Ti anodic oxide film.
Claims (3)
1. a kind of preparation method of Coloured Anodizing titanium film, which comprises the following steps:
(1) using the method for sand paper grinding or chemical polishing, titanium or titanium alloy surface are deoiled, degreasing, grinding and polishing
Then processing carries out shot blasting on surface processing；
(2) will be through step (1) treated titanium or titanium alloy as anode, graphite plate carries out anodic oxidation three times as cathode
It is handled；After each anodic oxidation, the electrolyte of titanium or titanium alloy surface is cleaned with dehydrated alcohol or deionized water, after drying
The processing of next step is carried out again；
(3) it by the titanium or titanium alloy after anodized three times, is put into vacuum drying oven and is heat-treated；
The condition that shot blasting on surface is handled in step (1) are as follows: the steel ball that shot-peening diameter is 0.1 ~ 0.5 millimeter, shot-peening time are 0.5
~3min；
The electrolyte that anodized uses three times in step (2) is respectively as follows:
The ingredient and content of electrolyte in anode oxidation process are as follows: concentrated sulfuric acid 30-70mL/L, methane sulfonic acid 5-8g/L, sulphur
The aqueous solution of sour sodium 3-5g/L, voltage 90-120V, processing time are 5-10min；
The ingredient and content of electrolyte during two-step anodization are as follows: citric acid 50-100g/L, lactic acid 10-20g/L, methyl
The aqueous solution of sulfonic acid 5-10g/L, voltage 50-80V, processing time are 10-30min；
Three times in anode oxidation process electrolyte ingredient and content are as follows: sodium tartrate 80-100g/L, sodium nitrite 10-15g/L
Ethanol solution, voltage 50-100V, handle time 30-60min.
2. the preparation method of Coloured Anodizing titanium film according to claim 1, it is characterised in that: the anodic oxygen in step (2)
Change processing, cathode and anode plate area ratio are 2:1 ~ 3:1, and interpolar distance is 5 ~ 12cm.
3. the preparation method of Coloured Anodizing titanium film according to claim 1, it is characterised in that: be heat-treated in step (3)
Condition is to be heated to 100 ~ 120 DEG C, keeps the temperature 1 hour；It is then heated to 450-600 DEG C, keeps the temperature 1-2 hours, furnace cooling；Vacuum
The vacuum degree of furnace is 0.03-0.1MPa.
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| CN110093650A (en) * | 2019-04-30 | 2019-08-06 | 西安建筑科技大学 | A kind of preparation method of high-wearing feature high-hardness titanium alloy composite bushing |
| CN111663165A (en) * | 2020-06-18 | 2020-09-15 | 西北有色金属研究院 | Phosphoric acid system-based secondary anodic oxidation method for industrial pure titanium |
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