CN103266338A - TC4 titanium alloy anodizing chromium-free blackening method - Google Patents
TC4 titanium alloy anodizing chromium-free blackening method Download PDFInfo
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- CN103266338A CN103266338A CN2013101884791A CN201310188479A CN103266338A CN 103266338 A CN103266338 A CN 103266338A CN 2013101884791 A CN2013101884791 A CN 2013101884791A CN 201310188479 A CN201310188479 A CN 201310188479A CN 103266338 A CN103266338 A CN 103266338A
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Abstract
The invention relates to a TC4 titanium alloy anodizing chromium-free blackening method which mainly comprises the following steps: activating the surface of titanium alloy by alkali wash and acid wash processes; forming a manganese dioxide containing film layer on the surface of the alloy by means of the anodizing process of an electrolyte prepared by sodium nitrate, manganese sulfate and distilled water; and forming a protruding structure on the film layer by anodizing, wherein the surface of a workpiece has a special structure and performance to meet the demand of blackening the titanium alloy. Toxic components such as hexavalent chromium are not used in the electrolyte, and the oxidation film formed does not contain chromium element, so that the method poses less pollution to environment.
Description
Technical field
The present invention relates to chemical treatment method field, metallic surface, particularly relate to a kind of TC4 titanium alloy anode oxidation Chrome-free blackening method.
Background technology
The blackening processing technology of early stage metal claims " sending out blue " or " turning blue " technology again, is primarily aimed at iron and steel and carries out surface-treated.Then aluminium alloy, titanium alloy etc materials have developed the black treatment process again.The titanium alloy black treatment process can satisfy the visible light specular reflection that reduces titanium alloy surface, improve hidden performance and requirement such as ornamental, during the aspects such as optical system titanium alloy component surface that can be applicable to need delustring to handle are used.The anonizing blackout is an important content of titanium alloy black-emitting technology, and this technology has mainly been used the main component of dichromate as electrolytic solution; Dichromate has very strong toxicity and carinogenicity, and bigger to contaminate environment, for avoiding these shortcomings, has developed Chrome-free TC4 titanium alloy anode oxidation blackening.
Summary of the invention
The technical problem to be solved in the present invention is, a kind of electrolyte system new, Chrome-free is provided, use the anodic oxidation black-emitting technology to form one deck black oxide film at titanium alloy surface, rete does not contain chromium, colourity is even, bonding force is good, meets the TC4 titanium alloy anode oxidation Chrome-free blackening method of black treatment technology requirement.
The technical scheme that adopts is:
A kind of TC4 titanium alloy anode oxidation Chrome-free blackening method comprises the following steps:
(1) titanium alloy workpiece is used successively 400#, 600#, 800#, 1000# liquid honing surface, make any surface finish.
(2) alkali cleaning oil removing: make mixing solutions with sodium hydroxide 50g+ water glass 30g+ sodium phosphate 50g+1000ml water, with workpiece in 80 ℃ ~ 90 ℃ described mixing solutions immersion treatment at least 20min remove the lip-deep grease of titanium alloy workpiece.
(3) acid-wash activation: pickle solution is by 1ml HF+4ml HNO
3+ 30ml H
2O is formulated, and with the pickling in pickle solution of the titanium alloy workpiece after the oil removing, the pickling time is 30-60s, removes the titanium alloy workpiece surface film oxide and activates.
(4) anodic oxidation: will link to each other with the positive pole of direct supply through the titanium alloy workpiece of alkali cleaning, pickling as anode, stainless steel plate links to each other with the negative pole of direct supply as negative electrode, and ratio of cathodic to anodic area is that 3:1, interelectrode distance are 7cm; The two poles of the earth place in the electrolytic solution of being prepared by manganous sulfate concentration 16g/L+ sodium nitrate concentration 16g/L distilled water, use direct supply to be carried in the voltage of two interpolar 9V, finish anodic oxidation behind the processing 20min.
(5) water-bath sealing of hole: the titanium alloy workpiece after the anodic oxidation is immersed in 90 ℃ of hot water handles 20min and finish sealing of hole.
(6) blackout is checked and accepted: finish its color of titanium alloy workpiece of water-bath by the RAL-K7 standard colour card relatively, color is grey black, namely meets the requirement of blackout.
Above-mentioned HF concentration 40%.
Advantage of the present invention is:
(1) the present invention adopts anonizing, uses SODIUMNITRATE, manganous sulfate as the main component of electrolytic solution, and blackout speed is fast, and film quality is good, can satisfy black and decorate and require and the delustring processing requirements;
(2) titanium alloy anode oxidation Chrome-free blackening method does not contain harmful heavy metal elements such as chromium element, and environmental pollution is less.
Description of drawings
Fig. 1 is blackout oxidation film layer rat pattern synoptic diagram.
Embodiment
Embodiment:
A kind of TC4 titanium alloy anode oxidation Chrome-free blackening method is to use anode oxidation process to form one deck black oxide film at titanium alloy surface, satisfies requirements such as delustring processing and decoration.Wherein key is the configuration of electrolytic solution, adopts manganous sulfate concentration 16g/L+ sodium nitrate concentration 16g/L as the composition of electrolytic solution, can prepare black oxide film through anode oxidation process.Concrete steps are as follows:
(1) titanium alloy workpiece is used successively 400#, 600#, 800#, 1000# liquid honing surface, make any surface finish and do not have obvious cut to get final product.
(2) alkali cleaning oil removing process: alkaline cleaning procedure utilizes highly basic to use alkali washing process to remove to the saponification reaction of grease, the titanium alloy surface grease that can bond in mechanical processing process, use sodium hydroxide 50g+ water glass 30g+ sodium phosphate 50g+1000ml water to make mixing solutions, the about 20min of immersion treatment in 85 ℃ mixing solutions can remove lip-deep grease with workpiece.
(3) acid-wash activation process: pickle solution is by 1ml HF+4ml HNO
3+ 30ml H
2O is formulated, and the pickling time is 50s, HF concentration 40%.Since titanium alloy character vivaciously, very easily oxidation, the surface can nature generates layer oxide film, needs to use pickling to remove.
(4) anode oxidation process: will link to each other with the positive pole of direct supply through the workpiece of alkali cleaning, acid cleaning process as anode; Stainless steel plate links to each other with the negative pole of direct supply as negative electrode, and ratio of cathodic to anodic area is that 3:1, interelectrode distance are 7cm; The two poles of the earth place by in manganous sulfate concentration 16g/L+ sodium nitrate concentration 16g+1L distilled water configuration electrolytic solution; Use direct supply to be carried in the voltage of two interpolar 9V, namely finish behind the processing 20min, obtain colourity evenly, in conjunction with good black rete.
(5) water-bath sealing of hole process: workpiece is immersed in treatment time 20min can finish sealing of hole in 90 ℃ of hot water;
(6) workpiece of finishing the water-bath process is grey black by RAL-K7 standard colour card comparison color, meets the requirement of blackout.
Blackout handling principle of the present invention:
In anode oxidation process, the oxygenant SODIUMNITRATE obtains main component---the multiple valence state titanium oxide of oxide film with the titanium alloy oxidation in the electrolytic solution; And manganous sulfate can generate titanium dioxide at titanium alloy surface in the electrolytic solution, is deposited in the surface with titanium oxide complex, forms hemispheric small embossment structure (see figure 1), and the bulge-structure resistivity of this Manganse Dioxide is very big, makes rete change isolator into by conductor.
The Manganse Dioxide bulge-structure of titanium alloy surface makes the surface become rough and uneven in surface, by controlling size and the shape of projection, can reduce the specular reflection effect of titanium alloy surface; Manganse Dioxide and titanium oxide confusion are mingled with, and make the surface present black, improve rete to the absorptive character of light; Light wave is in reflection, transmission and the absorption on surface, be the electromagnetic field of light wave and the interaction of material surface unbound electron in essence, the bulge-structure of Manganse Dioxide makes rete become isolator, reduced the free electron density in the rete, reduce light and rete and interacted, reduced intensity of reflected light.
Claims (2)
1. a TC4 titanium alloy anode oxidation Chrome-free blackening method is characterized in that comprising the following steps:
(1) titanium alloy workpiece is used successively 400#, 600#, 800#, 1000# liquid honing surface, make any surface finish;
(2) alkali cleaning oil removing: make mixing solutions with sodium hydroxide 50g+ water glass 30g+ sodium phosphate 50g+1000ml water, with workpiece in 80 ℃ ~ 90 ℃ described mixing solutions immersion treatment at least 20min remove the lip-deep grease of titanium alloy workpiece;
(3) acid-wash activation: pickle solution is by 1ml HF+4ml HNO
3+ 30ml H
2O is formulated, and with the pickling in pickle solution of the titanium alloy workpiece after the oil removing, the pickling time is 30-60s, removes the titanium alloy workpiece surface film oxide and activates;
(4) anodic oxidation: will link to each other with the positive pole of direct supply through the titanium alloy workpiece of alkali cleaning, pickling as anode, stainless steel plate links to each other with the negative pole of direct supply as negative electrode, and ratio of cathodic to anodic area is that 3:1, interelectrode distance are 7cm; The two poles of the earth place in the electrolytic solution of being prepared by manganous sulfate concentration 16g/L+ sodium nitrate concentration 16g/L distilled water, use direct supply to be carried in the voltage of two interpolar 9V, finish anodic oxidation behind the processing 20min;
(5) water-bath sealing of hole: the titanium alloy workpiece after the anodic oxidation is immersed in 90 ℃ of hot water handles 20min and finish sealing of hole;
(6) blackout is checked and accepted: finish its color of titanium alloy workpiece of water-bath by the RAL-K7 standard colour card relatively, color is grey black, namely meets the requirement of blackout.
2. a kind of TC4 titanium alloy anode oxidation Chrome-free blackening method according to claim 1 is characterized in that described HF concentration 40%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811899A (en) * | 2014-02-26 | 2014-05-21 | 陆腾蛟 | Inserted electrode without electric spark and anodizing production process |
| CN103811894A (en) * | 2014-02-26 | 2014-05-21 | 陆腾蛟 | Inserted electrode without electric spark and chemical processing production process |
| CN106149029A (en) * | 2014-12-05 | 2016-11-23 | 财团法人金属工业研究发展中心 | Black titanium-containing oxide layer, preparation method thereof and implant |
| CN109056032A (en) * | 2018-09-29 | 2018-12-21 | 沈阳富创精密设备有限公司 | Titanium alloy nigrescence anode oxidation process |
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| CN101717981A (en) * | 2009-12-16 | 2010-06-02 | 厦门大学 | Black oxidation method of surfaces of titanium and titanium alloy |
| CN102115902A (en) * | 2009-12-30 | 2011-07-06 | 沈阳天贺新材料开发有限公司 | Surface anodization coloring treatment method for titanium and titanium alloy |
| CN103014811A (en) * | 2011-09-22 | 2013-04-03 | 河南平原光电有限公司 | Titanium and titanium alloy black anodic oxidation method |
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| CN101210335A (en) * | 2006-12-30 | 2008-07-02 | 比亚迪股份有限公司 | Surface treatment method for light metal material |
| CN101717981A (en) * | 2009-12-16 | 2010-06-02 | 厦门大学 | Black oxidation method of surfaces of titanium and titanium alloy |
| CN102115902A (en) * | 2009-12-30 | 2011-07-06 | 沈阳天贺新材料开发有限公司 | Surface anodization coloring treatment method for titanium and titanium alloy |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811899A (en) * | 2014-02-26 | 2014-05-21 | 陆腾蛟 | Inserted electrode without electric spark and anodizing production process |
| CN103811894A (en) * | 2014-02-26 | 2014-05-21 | 陆腾蛟 | Inserted electrode without electric spark and chemical processing production process |
| CN103811894B (en) * | 2014-02-26 | 2018-07-06 | 泉州兆维信息技术有限公司 | That eliminates electric spark patches electrode and chemical treatment production technology |
| CN106149029A (en) * | 2014-12-05 | 2016-11-23 | 财团法人金属工业研究发展中心 | Black titanium-containing oxide layer, preparation method thereof and implant |
| CN109056032A (en) * | 2018-09-29 | 2018-12-21 | 沈阳富创精密设备有限公司 | Titanium alloy nigrescence anode oxidation process |
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Application publication date: 20130828 |