CN106702461B - A kind of titanium magnesium alloy anodizing solution - Google Patents
A kind of titanium magnesium alloy anodizing solution Download PDFInfo
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- CN106702461B CN106702461B CN201611234827.4A CN201611234827A CN106702461B CN 106702461 B CN106702461 B CN 106702461B CN 201611234827 A CN201611234827 A CN 201611234827A CN 106702461 B CN106702461 B CN 106702461B
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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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
- C23G1/205—Other heavy metals refractory metals
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Abstract
The invention discloses a kind of titanium magnesium alloy anodizing solutions, in parts by weight, including 20-60 parts of potassium bichromate, 10-30 parts of chromate, 10-20 parts of sulfate, 10-50 parts of sulfuric acid, 2-4 parts of blackening agent for surface, 25-40 parts of phosphoric acid, 20-40 parts of phosphate, 1-10 parts of acetic acid, 10-20 parts of ethylene glycol, 15-30 parts of sodium gluconate and 700-1000 parts of distilled water.Anodizing solution of the invention keeps the oxidation film obtained and basal body binding force good, and the oxidation film compactness is good, not easily to fall off, has the performances such as good anti-oxidant and pollution resistance；Method for anodizing and coloring of the invention is simple and easy, processing step is few, solution is easy to maintain, mass production can be achieved, by the oxidation film for controlling different voltage value, the pH value of oxidation solution, conduction time can obtain different-thickness and compactness is good, it is suitble to the production market demand of Treatment of Metal Surface anodic oxidation.
Description
Technical field
The present invention relates to the technical field of Treatment of Metal Surface anodic oxidation more particularly to a kind of titanium magnesium alloy anodic oxidations
Liquid.
Background technique
In recent years, titanium or titanium alloy has been to be concerned by more and more people because it is with unique property, therefore extensive
Applied to every field such as national defence hard-core technology, civilian industry, people's livelihood articles.Such as：In terms of aerospace, due to titanium and titanium
Alloy specific gravity is small, light-weight, specific strength is high, and is applied to Aircraft Production of new generation；Medically, titanium or titanium alloy corrosion resistance
Good, good biocompatibility is low with human body repellency, is widely used in planting body and endovascular stent of tooth and bone etc.
Medical field becomes a kind of noticeable biomedical metal material；In building, due to the feature of titanium or titanium alloy uniqueness,
Dosage increases year by year, and some developed countries have also built up titanium building in succession；In addition, in common consumer product such as wrist-watch, mobile phone
The application of shell, notebook computer shell, spectacle-frame, mirror holder etc. is also constantly expanding.
But there are also shortcomings for titanium or titanium alloy, such as wear no resistance, it is quicker to hydrogen and fused salt stress corrosion
Sense contacts with other metals and is easily in contact corrosion etc., limits its scope of application.It therefore, is the application of further expansion titanium
Field, it is necessary to which processing is modified to its surface.And titanium or titanium alloy surface anodization is a kind of simple process and low cost
It is honest and clean, effective process for treating surface.Foreign countries just attach great importance to grinding for Ni―Ti anode oxidation technology in 60~seventies of 20th century
Study carefully, achieves greater advance, and be applied to every profession and trade.And domestic grinding in terms of the processing of titanium or titanium alloy surface anodization
Study carefully relatively late, does not set up corresponding national standard still so far.
Currently, the acid corrosion activation step in titanium or titanium alloy anode oxidation process in common engineering use in addition,
It is easy to be contaminated using traditional titanium alloy anode oxidation technique oxidation film surface obtained, color easily occurs after fingerprint pollution
Variation, and be not easy to restore after being contaminated, its decorative effect has been seriously affected, has been limited its scope of application.To sum up, titanium and titanium
There are Railway Projects below and several difficult points for alloy anode heat tinting process.
Difficult point existing for titanium or titanium alloy anode oxidation coloration technique：
(1) since titanium chemical property is active, it is processed after piece surface there is only the oxidation films of self-assembling formation, and
There is also pollution layers.It is uneven that the presence of these film layers can cause coloring, but the method for removing these film layers is again seldom；
(2) variation of process conditions is larger to coloring influential effect, and to obtain uniform coloring effect must be strictly controlled
Condition, including：Temperature, current density, voltage, electrolyte composition etc.；
(3) anodic oxidation film surface can be higher, and film surface is easily adsorbed dirty substance and is contaminated, easily occur fingerprint pollution and
Color is set to change；In addition, being difficult to recover after contaminated, to influence its beauty, decorative effect is influenced；
(4) compactness of anode oxide film is poor, often due to leading to anode oxide film with the oxidation film on surface on matrix
And the combination of matrix skin oxidation film is insecure, is easy to fall off.
Summary of the invention
It is an object of the invention to aiming at the deficiencies in the prior art, provide a kind of titanium magnesium alloy anodizing solution,
It is a kind of compactness is good, not easily to fall off inoxidizability anode oxide film by being come out prepared by the oxidation solution, significantly improves it
Wearability, pollution resistance and compactness.
For this purpose, the present invention uses following technical scheme：
A kind of titanium magnesium alloy anodizing solution, in parts by weight, including 20-60 parts of potassium bichromate, chromate 10-30
Part, 10-20 parts of sulfate, 10-50 parts of sulfuric acid, 2-4 parts of blackening agent for surface, 25-40 parts of phosphoric acid, 20-40 parts of phosphate, acetic acid 1-10
Part, 10-20 parts of ethylene glycol, 15-30 parts of sodium gluconate and 700-1000 parts of distilled water.
It should be noted that titanium magnesium alloy anodizing solution of the invention is weakly acidic, by adding chromate ion, it is convenient for handle
Titanium magnesium alloy is passivated effect, the speed for delaying metal to be corroded, so that the chemical activity of active metal or alloy drops significantly
It is low, while keeping the anode oxide film obtained and titanium magnesium alloy basal body binding force good, the oxidation film compactness of generation is good, is not easy to take off
It falls, there is good antioxygenic property；Made after carrying out anodic oxidation using the oxidation solution by addition blackening agent for surface and phosphate
Titanium magnesium alloy piece surface forms black, uniform firm oxidation film layer, adhesive force is good, falls off or peeling without any
Phenomenon more preferably meets the particular/special requirement that delustring is needed applied to the titanium alloy surface in optical system；Other components are public affairs
The anodizing solution known forms the formula components of weakly acidic condition, is no longer described in detail here.
It is further illustrated, the chromate is one of sodium chromate, potassium chromate and magnesium chromate or a variety of.The chromium
Sour sodium and potassium chromate are the chromate of alkali metal, they and magnesium chromate can be dissolved in water, and dissolubility chromate is usually used in as oxygen
Agent, in chromatedsolution, chromate ions are converted into bichromate after acidification, and the bichromate has strong oxidizing property, makes
The oxidation effectiveness for obtaining anodizing solution is significant, helps speed up the speed of titanium magnesium alloy anodic oxidation, improves and generates oxidation film
Efficiency.
It is further illustrated, the sulfate is one of manganese sulfate, chromium sulfate, magnesium sulfate and sodium sulphate or more
Kind.Sulfate described above is electrolyte and is dissolved in water, is added in solution to increase sulfate ion and chromium ion
Concentration facilitates anodic oxidation reactions, and above-mentioned substance has the effect for promoting oxidation reaction, these substances are relatively conventional, they
Performance effect and select explanation is not developed in details here.
It is further illustrated, the phosphate is a kind of in sodium phosphate, potassium phosphate, potassium dihydrogen phosphate and sodium dihydrogen phosphate
Or it is a variety of.The sodium phosphate, potassium phosphate, potassium dihydrogen phosphate and sodium dihydrogen phosphate are soluble-salt, add the phosphate,
So that phosphoric acid increases with ion concentration in anodizing solution, while making solution in acidic environment, it is conducive to electrolyte and carries out anode
Oxidation reaction.By electrochemical reaction, phosphoric acid and phosphoric acid are with that under the collective effect of ion, can make titanium magnesium produce in anodizing solution
Product production has the reactant film of good adhesion, which forms the good oxidation film of compactness,
Surface is smooth, uniform non-variegation, and surface has anti-fingerprint, the strong and good decorative effect of pollution resistance.
It is further illustrated, the blackening agent for surface includes potassium sulfate and sodium fluoride, in parts by weight, the potassium sulfate
It is 1.5-3 parts and the sodium fluoride is 0.5-1 parts.The blackening agent for surface is by adding the blackening agent for surface, so that titanium magnesium alloy surface
Black, uniform firm oxidation film layer are quickly formed, adhesive force is good, not easily to fall off, it is wiped firmly with clean fine cloth,
More preferably meet the particular/special requirement that delustring is needed applied to the titanium alloy surface in optical system.
Preferably, in parts by weight, the potassium bichromate is 25 parts, the chromate is 10 parts, the sulfate
For 10 parts, the sulfuric acid be 30 parts, the blackening agent for surface is 2 parts, the phosphoric acid is 25 parts, the phosphate is 25 parts, the second
Acid is 5 parts, the ethylene glycol is 10 parts, the sodium gluconate is 15-30 parts and the distilled water is 1000 parts.Using this ratio
The anodizing solution of example formula preparation, for titanium magnesium alloy after anodized, oxide thickness is moderate, aterrimus, uniformly
Fine and closely woven, covering is complete, and surface forms aterrimus oxidation film layer, is firmly wiped with clean fine cloth, is fallen off repeatedly without any
Or the phenomenon that peeling.It is good using the anode oxide film and titanium magnesium alloy basal body binding force of anodizing solution of the present invention preparation, and make
Standby simple process, it is easy to operate, produced film it is high-efficient, be easily achieved, there is good antioxygenic property.
A kind of titanium magnesium alloy method for anodizing and coloring, includes the following steps：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 20-60 parts of potassium bichromate, 10-30 parts of chromate, sulfate 10-
20 parts, 10-50 parts of sulfuric acid, 2-4 parts of blackening agent for surface, 25-40 parts of phosphoric acid, 20-40 parts of phosphate, 1-10 parts of acetic acid, ethylene glycol 10-20
Part, 15-30 parts of sodium gluconate and 700-1000 parts of distilled water carry out being prepared by mixing into titanium magnesium alloy anodizing solution, with described
Titanium magnesium alloy Sample A is working electrode, and graphite electrode is completely submerged in institute as auxiliary electrode, by working electrode and auxiliary electrode
It states and carries out anodic oxidation in titanium magnesium alloy anodizing solution, current density 2-9A/dm, voltage 90-200V, oxidization time is
30-60min, solution temperature are 10-75 DEG C, and reaction terminates, and obtains the titanium magnesium alloy product B with anode oxide film；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out, can be obtained with anode oxide film titanium magnesium alloy products C.
Compared with existing titanium alloy surface method for anodizing and coloring, present invention process step is few, each step operation letter
Single, solution is easy to maintain, it can be achieved that mass production, has good actual application prospect；By control different voltage value,
The pH value of titanium magnesium alloy anodizing solution, energization oxidization time can obtain different-thickness and the good titanium magnesium alloy oxygen of compactness
Change film；The blackening agent for surface makes oxidation film in black, uniform non-variegation, and anti-fingerprint, pollution resistance is strong, has good decoration effect
Fruit.In addition, oxidation film is firmly combined with matrix, surface hardness, good binding force and corrosion resisting property with higher；Anodic oxygen
Changing liquid can be used continuously by adding each main component, there is good actual application prospect.
It is further illustrated, except oil solution is to contain sodium hydroxide, sodium phosphate, carbonic acid in the electrochemical deoiling step
The aqueous solution of sodium, waterglass and surfactant.
The surface of titanium magnesium alloy product is often stained with excessive butter, coating or even colloidal substance, however utilizes heat
Saponification and emulsification of the aqueous slkali to grease remove the greasy dirt on titanium magnesium alloy surface, and the saponification of alkaline matter removes
Saponifiable oil, the emulsification of surfactant remove not saponifiable oil, and the electrochemical deoiling has simple process, operation side
Just, low in cost, the features such as asepsis environment-protecting.It, can be according to the heterogeneity of basis material using the formula of the chemical degreasing liquid
And oil removing require difference and select, mentioned component remove oil solution energy efficient degreasing, deoiling effect is obvious, securely and reliably.
It is further illustrated, oil removing solution temperature is 50-80 DEG C in the electrochemical deoiling step, and the oil removing time is 10-
30min.Using above-mentioned oil removing solution temperature and time, accelerate to remove speed oil, effectively titanium magnesium alloy product can be cleaned dry
Only, decontamination is more thorough, and oil removal treatment effect is preferable.
It is further illustrated, pickling solution is nitric acid and hydrofluoric acid, in parts by weight, institute in the acid pickling step
State that nitric acid is 220-280 parts and the hydrofluoric acid is 2-4 parts.Pickling can give quick and complete removal reaction layer, and surface
The pollution that other elements will not be generated serves as pickling using the solution of above-mentioned formula, and pickling solution hydrogen-sucking amount is small, can control nitre
The concentration of acid, which is reduced, inhales hydrogen, and bright processing can be carried out to surface, carries out pickling by the pickling solution, can remove titanium magnesium alloy
The oxidation film on surface facilitates the generation of subsequent technique anode oxide film, close conducive to newly-generated anode oxide film and matrix
In conjunction with.
It is further illustrated, in step (2) anodic oxidation, current density 5A/dm, voltage 100V, oxidation
Time is 40min, and solution temperature is 50 DEG C.Above-mentioned Current Voltage, anodizing time, solution temperature are to generate densification
Good, the optimum operation parameters of anode oxide film not easily to fall off of property, controlled using above-mentioned numerical value different voltage values,
The pH value of anodizing solution, energization oxidization time, which can get, certain thickness and the good titanium magnesium alloy oxidation film of compactness；It should
Oxidation film be in black, uniform non-variegation, surface hardness, good binding force and corrosion resistance with higher, in conjunction with matrix most
Securely, not easily to fall off, wide market.
It is further illustrated, the anode oxide film of the titanium magnesium alloy products C is with a thickness of 4-10 μm.Using above-mentioned titanium magnesium
The anode oxide film of alloy product C plays preferable decorative effect with a thickness of 4-10 μm, if the thickness of oxidation film is excessively thin, firmly
Degree less, is easy to cause oxidation film to produce fracture phenomenon, if the thickness of oxidation film is blocked up, is unfavorable for oxidation film and titanium magnesium alloy sheet
The firm connection of body, and in the anodic anodization film of the thickness of this value range, surface hardness is stronger, while the densification of film
Property is best, and not easily to fall off, which can be firmly combined with titanium magnesium alloy product, and process is simple, save the cost.
Titanium magnesium alloy anodizing solution provided by the present invention, it is weakly acidic, the conductivity of water in solution is improved, is increased
The magnitude of current, while soda acid is dissolved in water the negative ions of generation and arrives separately at anode and cathode under the action of external electrical field, can be
The ion that anode participates in reaction enters film layer, and what cannot be reacted stills remain in solution, to improve the work of anodic oxidation
Efficiency, by the anodizing solution, the oxidation film compactness of generation is good, not easily to fall off, has good antioxygenic property.
Method for anodizing and coloring provided by the present invention is simple and easy, and processing step is few, and each step operation is simple, solution
It is easy to maintain, it can be achieved that mass production, by the pH value, logical for controlling different voltage values, titanium magnesium alloy anodizing solution
The electroxidation time can obtain different-thickness and the good titanium magnesium alloy oxidation film of compactness, and oxidation film surface with higher is hard
Degree, good binding force and corrosion resisting property；It is suitble to the production market demand of Treatment of Metal Surface anodic oxidation.
Specific embodiment
The present invention program is described in detail below by some specific embodiments.Those skilled in the art should manage
Solution, it is following to be embodied as preferred embodiment, only the present invention program is explained, and wherein might have to known skill
The appropriate omission of art, those skilled in the art should understand the present invention in conjunction with the explanation of well-known technique and embodiment.
The present invention is described in detail combined with specific embodiments below.
Embodiment 1：
A kind of titanium magnesium alloy method for anodizing and coloring, includes the following steps：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 20 parts of potassium bichromate, 10 parts of sodium chromate, 10 parts of chromium sulfate, sulfuric acid
10 parts, 2 parts of blackening agent for surface, 25 parts of phosphoric acid, 20 parts of sodium phosphate, 1 part of acetic acid, 10 parts of ethylene glycol, 15 parts of sodium gluconate and distilled water
700 parts carry out being prepared by mixing into titanium magnesium alloy anodizing solution, using the titanium magnesium alloy Sample A as working electrode, graphite electrode
As auxiliary electrode, working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution and carry out anodic oxygen
Change, current density 2A/dm, voltage is 90V voltage, and oxidization time 30min, solution temperature is 10 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Embodiment 2：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 25 parts of potassium bichromate, 15 parts of sodium chromate, 15 parts of chromium sulfate, sulfuric acid
30 parts, 2 parts of blackening agent for surface, 30 parts of phosphoric acid, 25 parts of sodium phosphate, 5 parts of acetic acid, 10 parts of ethylene glycol, 25 parts of sodium gluconate and distilled water
1000 parts carry out being prepared by mixing into titanium magnesium alloy anodizing solution, using the titanium magnesium alloy Sample A as working electrode, graphite electrode
As auxiliary electrode, working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution and carry out anodic oxygen
Change, current density 5A/dm, voltage 100V, oxidization time 40min, solution temperature is 50 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Embodiment 3：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 30 parts of potassium bichromate, 20 parts of sodium chromate, 13 parts of chromium sulfate, sulfuric acid
20 parts, 3 parts of blackening agent for surface, 35 parts of phosphoric acid, 30 parts of sodium phosphate, 8 parts of acetic acid, 15 parts of ethylene glycol, 20 parts of sodium gluconate and distilled water
800 parts carry out being prepared by mixing into titanium magnesium alloy anodizing solution, using the titanium magnesium alloy Sample A as working electrode, graphite electrode
As auxiliary electrode, working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution and carry out anodic oxygen
Change, current density 6A/dm, voltage 150V, oxidization time 35min, solution temperature is 40 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Embodiment 4：
A kind of titanium magnesium alloy method for anodizing and coloring, includes the following steps：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 60 parts of potassium bichromate, 30 parts of sodium chromate, 20 parts of chromium sulfate, sulfuric acid
50 parts, 4 parts of blackening agent for surface, 0 part of phosphatase 24,40 parts of sodium phosphate, 10 parts of acetic acid, 20 parts of ethylene glycol, 30 parts of sodium gluconate and distilled water
1000 parts carry out being prepared by mixing into titanium magnesium alloy anodizing solution, using the titanium magnesium alloy Sample A as working electrode, graphite electrode
As auxiliary electrode, working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution and carry out anodic oxygen
Change, current density 9A/dm, voltage 200V, oxidization time 60min, solution temperature is 75 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Embodiment 5：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 26 parts of potassium bichromate, 24 parts of sodium chromate, 16 parts of chromium sulfate, sulfuric acid
12 parts, 2.5 parts of blackening agent for surface, 33 parts of phosphoric acid, 36 parts of sodium phosphate, 9 parts of acetic acid, 18 parts of ethylene glycol, 19 parts of sodium gluconate and distillation
600 parts of water carry out being prepared by mixing into titanium magnesium alloy anodizing solution, using the titanium magnesium alloy Sample A as working electrode, graphite electricity
Working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution as auxiliary electrode and carry out anode by pole
Oxidation, current density 2A/dm, voltage 90V, oxidization time 30min, solution temperature are 10 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Embodiment 6：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 26 parts of potassium bichromate, 24 parts of sodium chromate, 16 parts of chromium sulfate, sulfuric acid
12 parts, 2.5 parts of blackening agent for surface, 33 parts of phosphoric acid, 36 parts of sodium phosphate, 9 parts of acetic acid, 18 parts of ethylene glycol, 19 parts of sodium gluconate and distillation
600 parts of water carry out being prepared by mixing into titanium magnesium alloy anodizing solution, using the titanium magnesium alloy Sample A as working electrode, graphite electricity
Working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution as auxiliary electrode and carry out anode by pole
Oxidation, current density 5A/dm, voltage 100V, oxidization time 40min, solution temperature are 50 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Embodiment 7：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 26 parts of potassium bichromate, 24 parts of sodium chromate, 16 parts of chromium sulfate, sulfuric acid
12 parts, 2.5 parts of blackening agent for surface, 33 parts of phosphoric acid, 36 parts of sodium phosphate, 9 parts of acetic acid, 18 parts of ethylene glycol, 19 parts of sodium gluconate and distillation
600 parts of water carry out being prepared by mixing into titanium magnesium alloy anodizing solution, using the titanium magnesium alloy Sample A as working electrode, graphite electricity
Working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution as auxiliary electrode and carry out anode by pole
Oxidation, current density 9A/dm, voltage 200V, oxidization time 60min, solution temperature are 75 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Comparative example 1：
A kind of titanium magnesium alloy method for anodizing and coloring, includes the following steps：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 25 parts of potassium bichromate, 15 parts of sodium chromate, 15 parts of chromium sulfate, sulfuric acid
30 parts, 30 parts of phosphoric acid, 25 parts of sodium phosphate, 5 parts of acetic acid, 10 parts of ethylene glycol, 25 parts of sodium gluconate and 1000 parts of distilled water progress
It is prepared by mixing into titanium magnesium alloy anodizing solution, using the titanium magnesium alloy Sample A as working electrode, graphite electrode is as auxiliary electricity
Working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution and carry out anodic oxidation by pole, and electric current is close
Degree is 5A/dm, voltage 100V, oxidization time 40min, and solution temperature is 50 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Note：Titanium magnesium alloy anodizing solution is without addition blackening agent for surface.
Comparative example 2：
A kind of titanium magnesium alloy method for anodizing and coloring, includes the following steps：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 25 parts of potassium bichromate, 15 parts of chromium sulfate, 30 parts of sulfuric acid, phosphoric acid 30
Part, 2 parts of blackening agent for surface, 25 parts of sodium phosphate, 5 parts of acetic acid, 10 parts of ethylene glycol, 25 parts of sodium gluconate and 1000 parts of distilled water are mixed
Conjunction is prepared into titanium magnesium alloy anodizing solution, and using the titanium magnesium alloy Sample A as working electrode, graphite electrode is as auxiliary electricity
Working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution and carry out anodic oxidation by pole, and electric current is close
Degree is 5A/dm, voltage 100V, oxidization time 40min, and solution temperature is 50 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Note：Titanium magnesium alloy anodizing solution is without addition sodium chromate.
Comparative example 3：
A kind of titanium magnesium alloy method for anodizing and coloring, includes the following steps：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 25 parts of potassium bichromate, 15 parts of sodium chromate, 15 parts of chromium sulfate, sulfuric acid
30 parts, 2 parts of blackening agent for surface, 30 parts of phosphoric acid, 5 parts of acetic acid, 10 parts of ethylene glycol, 25 parts of sodium gluconate and 1000 parts of distilled water are mixed
Conjunction is prepared into titanium magnesium alloy anodizing solution, and using the titanium magnesium alloy Sample A as working electrode, graphite electrode is as auxiliary electricity
Working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution and carry out anodic oxidation by pole, and electric current is close
Degree is 5A/dm, voltage 100V, oxidization time 40min, and solution temperature is 50 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Note：Titanium magnesium alloy anodizing solution is without addition sodium phosphate.
Comparative example 4：
A kind of titanium magnesium alloy method for anodizing and coloring, includes the following steps：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 15 parts of sodium chromate, 15 parts of chromium sulfate, 30 parts of sulfuric acid, blackening agent for surface 2
Part, 30 parts of phosphoric acid, 25 parts of sodium phosphate, 5 parts of acetic acid, 10 parts of ethylene glycol, 25 parts of sodium gluconate and 1000 parts of distilled water are mixed
Conjunction is prepared into titanium magnesium alloy anodizing solution, and using the titanium magnesium alloy Sample A as working electrode, graphite electrode is as auxiliary electricity
Working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution and carry out anodic oxidation by pole, and electric current is close
Degree is 5A/dm, voltage 100V, oxidization time 40min, and solution temperature is 50 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Note：Titanium magnesium alloy anodizing solution is without addition potassium bichromate.
Comparative example 5：
A kind of titanium magnesium alloy method for anodizing and coloring, includes the following steps：
(1) it pre-processes：Electrochemical deoiling, primary washing, pickling, secondary washing process step are successively carried out to titanium magnesium alloy sample
Suddenly, titanium magnesium alloy Sample A is obtained；
(2) anodic oxidation：In parts by weight, 25 parts of potassium bichromate, 15 parts of sodium chromate, 15 parts of chromium sulfate, sulfuric acid
30 parts, 2 parts of blackening agent for surface, 25 parts of sodium phosphate, 5 parts of acetic acid, 10 parts of ethylene glycol, 25 parts of sodium gluconate and 1000 parts of distilled water progress
It is prepared by mixing into titanium magnesium alloy anodizing solution, using the titanium magnesium alloy Sample A as working electrode, graphite electrode is as auxiliary electricity
Working electrode and auxiliary electrode are completely submerged in the titanium magnesium alloy anodizing solution and carry out anodic oxidation by pole, and electric current is close
Degree is 5A/dm, voltage 100V, oxidization time 40min, and solution temperature is 50 DEG C；
(3) subsequent processing：The titanium magnesium alloy product B is rinsed for several times, then ultrasonic wave shakes in dehydrated alcohol
After swinging cleaning 3-5min, cold wind drying is taken out.
Note：Titanium magnesium alloy anodizing solution is without addition phosphoric acid.
Quantitative measurement is carried out for the anode oxide film of each embodiment and comparative example preparation, to titanium magnesium alloy product
The appearance of anode oxide film is observed, and continues to observe after firmly wiping 5min repeatedly with clean fine cloth, is then closed to titanium magnesium
Golden product instills concentrated nitric acid, then observes the visual condition of anode oxide film, it is seen that Tables 1 and 2：
Table 1：The anodic oxidation film properties comparison sheet of each embodiment
As seen from the results in Table 1:
(1) it by embodiment 1-4 to find out, is produced by using the anodizing solution as electrolyte, titanium magnesium products
Anode oxide film is to have certain thickness, and black even, compactness is good, good with matrix associativity, has good inoxidizability
And pollution resistance.
Voltage and current is bigger, and the thickness of oxidation film is thicker, and when voltage and current is smaller, oxide thickness is smaller, easy through wiping
It falls off, it was demonstrated that oxide thickness is smaller, and compactness is general, smaller with the adhesive force on titanium magnesium alloy surface, in conjunction with insecure；Work as electricity
Current voltage is bigger, and oxide thickness is bigger, easy to fall off through wiping, it was demonstrated that oxide thickness is thicker, attached with titanium magnesium alloy surface
Put forth effort smaller, in conjunction with insecure, therefore controls moderate voltage and current, so that the thickness for generating oxidation film reaches certain numerical value,
So that its compactness is good, it is firmly combined with titanium magnesium alloy surface；The oxidation film of embodiment 2 has excellent compactness, and wiping is not
Easy to fall off and inoxidizability performance is most preferred embodiment；
(2) by embodiment 5-7 to find out, when the component number of anodizing solution is certain, changes Current Voltage and realize
Anodic oxidation, when Current Voltage is bigger, the thickness of oxidation film is bigger, and color is more black, and compactness is better, all has good anti-
Oxidisability and pollution resistance, the Current Voltage that embodiment 5 selects, the oxidation film and matrix associativity of generation are best, not easily to fall off, resist
Oxidisability and pollution resistance are more excellent.
Table 2：The performance comparison sheet of each comparative example
From the result of table 1 and 2:
(1) compared by comparative example 1-5 as can be seen that in anodizing solution component, if do not add potassium bichromate,
One of sodium chromate, blackening agent for surface, phosphoric acid and sodium phosphate, it is uneven by oxidation film black prepared by anodizing solution, with
Matrix combine it is insecure, through wiping be easy to fall off, inoxidizability is not strong；
(2) by comparative example 1-5 and the comparison of embodiment 2 as can be seen that prepared by the anodizing solution using embodiment 2
Each performance of oxidation film, the oxidation film than coming out prepared by comparative example is superior, and compactness is more preferable, more firm in conjunction with matrix
Gu less easy to fall off, inoxidizability is stronger.
In conclusion titanium magnesium alloy anodizing solution provided by the present invention, improves the conductivity of water in solution, increase
The oxidation film compactness of the magnitude of current, generation is good, not easily to fall off, has good anti-oxidant and pollution resistance performance.The present invention is mentioned
The method for anodizing and coloring of confession is simple and easy, and processing step is few, and each step operation is simple, and solution is easy to maintain, it can be achieved that criticizing
Quantization production can be obtained by controlling different voltage values, the pH value of titanium magnesium alloy anodizing solution, energization oxidization time
Different-thickness and the good titanium magnesium alloy oxidation film of compactness, oxidation film surface hardness with higher, good binding force and
Corrosion resisting property, is suitble to the production market demand of Treatment of Metal Surface anodic oxidation, and market prospects are considerable.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (4)
1. a kind of titanium magnesium alloy anodizing solution, which is characterized in that in parts by weight, including 20-60 parts of potassium bichromate, chromium
10-30 parts of hydrochlorate, 10-20 parts of sulfate, 10-50 parts of sulfuric acid, 2-4 parts of blackening agent for surface, 25-40 parts of phosphoric acid, 20-40 parts of phosphate,
1-10 parts of acetic acid, 10-20 parts of ethylene glycol, 15-30 parts of sodium gluconate and 700-1000 parts of distilled water；
The chromate is one of sodium chromate, potassium chromate and magnesium chromate or a variety of；
The phosphate is one or more in sodium phosphate, potassium phosphate, potassium dihydrogen phosphate and sodium dihydrogen phosphate.
2. a kind of titanium magnesium alloy anodizing solution according to claim 1, which is characterized in that the sulfate is sulfuric acid
One of manganese, chromium sulfate, magnesium sulfate and sodium sulphate are a variety of.
3. a kind of titanium magnesium alloy anodizing solution according to claim 1, which is characterized in that the blackening agent for surface includes sulfuric acid
Potassium and sodium fluoride, in parts by weight, the potassium sulfate is 1.5-3 parts and the sodium fluoride is 0.5-1 parts.
4. a kind of titanium magnesium alloy anodizing solution according to claim 1, which is characterized in that in parts by weight, institute
State that potassium bichromate is 25 parts, the chromate is 15 parts, the sulfate is 15 parts, the sulfuric acid is 30 parts, the blackening agent for surface
For 2 parts, the phosphoric acid be 30 parts, the phosphate is 25 parts, the acetic acid is 5 parts, the ethylene glycol is 10 parts, the grape
Sodium saccharate is 25 parts and the distilled water is 1000 parts.
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