CN1207440C - Zinc-impregnating layer anodic oxidation method colouring process and its treatment solution formula - Google Patents
Zinc-impregnating layer anodic oxidation method colouring process and its treatment solution formula Download PDFInfo
- Publication number
- CN1207440C CN1207440C CN 03141545 CN03141545A CN1207440C CN 1207440 C CN1207440 C CN 1207440C CN 03141545 CN03141545 CN 03141545 CN 03141545 A CN03141545 A CN 03141545A CN 1207440 C CN1207440 C CN 1207440C
- Authority
- CN
- China
- Prior art keywords
- zinc
- treatment
- impregnating layer
- treatment soln
- treatment solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The present invention relates to a zinc impregnating layer anodic oxidation method coloring process and an electroplating solution formula thereof, which belongs to the technical field of electroplating. The process comprises the steps that a zinc impregnating layer at the metal surface is colored by a pulse anodic oxidation method and treatment solution containing potassium hydroxide, aniline and potassium oxalate. Firstly, a metal base body which is used as an anode is treated in advance, i.e. oil removal, acid wash, alkali wash, activation and zinc impregnation; then, the treatment solution is prepared, and electric energy is generated by current conducted in the treatment solution so that the surface of the metal base body of the anode treated in advance forms a dense color thin membrane. The treatment solution comprises the following components, in weight percentages, 20% to 45% of potassium hydroxide, 30% to 40% of aniline and 20% to 45% of potassium oxalate. The process is simple, basically has no environmental pollution, is suitable for coloring the zinc impregnating layer of magnesium and aluminium alloy, and is suitable for coloring a zinc galvanized layer. The treatment solution has high stability and strong dispersibility and deep galvanization capability. The obtained treated membrane layer has good uniformity and is well combined with the base body so that the color pattern-shaped compact oxide thin membrane is obtained.
Description
Technical field
What the present invention relates to is a kind of metal surface treatment process and treatment soln prescription thereof, and color metallization processes of particularly a kind of magnesium alloy or aluminum alloy surface zinc-impregnating layer anonizing and treatment soln prescription thereof belong to the electroplating technology field.
Background technology
Surface treatment is played important effect in magnesium, aluminium and alloy thereof are used.And the decorative effect in the surface treatment process is the problem of academia and business circles extensive concern.The purpose that magnesium, aluminum alloy surface are soaked the zinc coloured silkization is the environmental protection problem that brings with this technology replacement magnesium, aluminum alloy surface chromium conversion film coloured silkization.This technology creativeness is that the different colours with the zn cpds reflection is used for the surface finishing of magnesium, aluminium alloy.Find by literature search, Liang Zhendong, Xu is but in " electroplated zinc nickel alloy colorful passivating process " (coal technology, vol.18, No.3,1999,31-33) its cardinal principle of electro-galvanizing nickel dam coloured silkization is to utilize sexavalent chrome zinc oxide to form zn cpds, shows different coloured silk results by zn cpds reflection distinct colors.Colorization of this kind method weak point is that environmental pollution is serious, and the coloured silkization processing cost is higher, and complex procedures is compared in aftertreatment.Chen Jinhong, Lu Jintang, Xu Qiaoyu etc. " steel plate galvanized anode oxidation coloration technology " (material protection, vol.31, No.7,1998, think that galvanized steel adopts anonizing can obtain the sull of chromatic pattern shape densification in 1-3).Its weak point is that electric current is too big, and the treatment soln composition is too complicated, and cost is too high.
Summary of the invention
The present invention is directed to above-mentioned deficiency of the prior art, color metallization processes of a kind of zinc-impregnating layer anonizing and treatment soln prescription thereof are provided, make it use the pulse anodic oxidation method metallic surface zinc-impregnating layer coloured silkization.This method technology is simple, and this solution component is simple and clear, with low cost, has also solved the problem of environmental pollution that brings with the chromium compounds coloured silkization.
The present invention is achieved by the following technical solutions, and zinc-impregnating layer anonizing coloured silkization each component of treatment soln of the present invention and amount per-cent thereof are: potassium hydroxide 20%-45%, aniline 30%-40%, potassium oxalate 20%-45%.Further limit its component and measure per-cent and be: potassium hydroxide 35%, aniline 30%, potassium oxalate 35%.
Process using pulse anodic oxidation method of the present invention and the above-mentioned color metallization processes treatment soln of being made up of potassium hydroxide, aniline, potassium oxalate of zinc-impregnating layer anonizing are to magnesium alloy or aluminum alloy surface zinc-impregnating layer coloured silkization, at first to carrying out pre-treatment as anodic magnesium alloy or alloy matrix aluminum, be oil removing, pickling, alkali cleaning, activate, soak zinc, prepare treatment soln then, in treatment soln, pass to electric current again and produce electric energy, make anodic magnesium alloy or aluminium alloy matrix surface form fine and close colorful film through pre-treatment.
Below technology of the present invention is further described, particular content is as follows:
(1) to as the pre-treatment of anodic metallic matrix
Oil removing: with the Na of the NaOH+30g/L that contains 20g/L
2CO
3The thorough oil removing of mixing solutions,
Pickling: with the HNO that contains 100mL/L
3The NH of+20g/L
4The mixing solutions of HF is removed oxide compound,
Alkali cleaning: with the Na that contains 30g/L
2CO
3The mixing solutions of the NaF of+10g/L is removed residual oxide compound,
Activation: with the solution activated metal surface that contains 100mL/LHF,
Soak zinc: with the ZnSO that contains 20g/L
4The Na of+100g/L
2P
2O
7Mixing solutions soak zinc and handled 10 minutes.
(2) preparation treatment soln
The distilled water of adding 3/4 adds potassium hydroxide, potassium oxalate and aniline successively in groove, adds water to pre-determined volume then, and treatment soln is a negative electrode with the stainless steel after placing 24 hours, is anode through the pre-treatment part, carries out anodic oxidation treatment.
(3) in treatment soln, pass to electric current and produce electric energy
In the treatment soln for preparing, be negative electrode with the stainless steel, zinc magnesium alloy is soaked in the process pre-treatment or Al-alloy parts is an anode, and at 5-40 ℃, break make ratio is 5-15%, and frequency is 500-1500Hz, and pulse current density is 0.1-1.0A/cm
2, the surface forms fine and close colorful film.
The present invention has substantive distinguishing features and marked improvement, and to magnesium alloy or aluminum alloy surface zinc-impregnating layer coloured silkization, this method technology is simple with the pulse anodic oxidation method in the present invention, and basic non-environmental-pollution has solved the problem of environmental pollution that brings with the chromium compounds coloured silkization.The present invention is applicable to the coloured silkization of magnesium alloy or aluminium alloy zinc-impregnating layer, also is the coloured silkization that is used for zinc coating.This treatment soln good stability, dispersive ability and covering power are strong, and it is good that gained is handled membrane uniformity, and good with matrix bond, the sull of resultant chromatic pattern shape densification.
Embodiment
Content in conjunction with prescription of the present invention and technology provides following examples:
Colorization method cost of the present invention is low, and equipment used is simple, and processing ease can not cause environmental pollution, with traditional method ratio, economical with materials, efficient height.
Embodiment 1
At first in the 5L groove, add 3/4 distilled water, add 150g potassium hydroxide, 150g potassium oxalate and 200g aniline successively, add water to pre-determined volume then, treatment soln is after placing 24 hours, to carrying out oil removing, flushing with clean water, pickling, flushing with clean water as anodic AZ91 magnesium alloy member, alkali cleaning, activation, flushing with clean water is soaked zinc, flushing with clean water, soaking zinc spare at 10 ℃ with the AZ91 magnesium alloy subsequently is anode, is negative electrode with the stainless steel, and passing to frequency in treatment soln is 500Hz, break make ratio 5%, current density are 0.5A/dm
2Current processing, anodic oxidation was cut off the electricity supply after 1 minute, with tap water flushing, used hot blast drying.Can obtain fine and close iris rete.
Embodiment 2
At first the distilled water of adding 3/4 in the 10L groove adds 350g potassium hydroxide, 350g potassium oxalate and 300g aniline successively, adds water to pre-determined volume then, after static 24 hours, to carrying out oil removing, flushing with clean water, pickling as anodic LY12 Al-alloy parts, flushing with clean water, alkali cleaning, activation, flushing with clean water is soaked zinc, flushing with clean water, soaking zinc spare at 15 ℃ with the LY12 aluminium alloy subsequently is anode, is negative electrode with the stainless steel, passes to frequency 1500Hz in treatment soln, break make ratio 10%, current density are 0.3A/dm
2Down, anodic oxidation was cut off the electricity supply after 2 minutes, with the tap water flushing, used hot blast drying.Can obtain fine and close iris rete.
Embodiment 3
Distilled water add 3/4 in the 5L groove adds 125g potassium hydroxide, 200g potassium oxalate and 175g aniline successively, adds water to pre-determined volume then, after static 24 hours, to carrying out oil removing, flushing with clean water, pickling as anodic AM60 magnesium alloy member, flushing with clean water, alkali cleaning, activation, flushing with clean water is soaked zinc, flushing with clean water, soaking zinc spare at 40 ℃ with the AM60 magnesium alloy subsequently is anode, is negative electrode with the stainless steel, passes to frequency 800Hz in treatment soln, break make ratio 5%, current density are 1A/dm
2Current processing, anodic oxidation was cut off the electricity supply after 0.5 minute, with the tap water flushing, used hot blast drying.Can obtain fine and close iris rete.
Embodiment 4
At first in the 10L groove, add in 3/4 the distilled water solution, add 350g potassium hydroxide, 350g potassium oxalate and 300g aniline successively, add water to pre-determined volume then, after static 24 hours, to carrying out oil removing, flushing with clean water, pickling, flushing with clean water as anodic AZ31 magnesium alloy member, alkali cleaning, activation, flushing with clean water is soaked zinc, flushing with clean water, soaking zinc spare at 40 ℃ with the AZ31 magnesium alloy subsequently is anode, is negative electrode with the stainless steel, passes to frequency 500Hz in treatment soln, break make ratio 5%, current density are 1A/dm
2Current processing, anodic oxidation was cut off the electricity supply after 0.5 minute, with the tap water flushing, used hot blast drying.Technology of the present invention is simple, and it is good that gained is handled membrane uniformity, and good with matrix bond, obtains fine and close iris rete.
Embodiment 5
At first in the 10L groove, add 3/4 distilled water, add 300g potassium hydroxide, 400g potassium oxalate and 300g aniline successively, add water to pre-determined volume then, after static 24 hours, be negative electrode, to carrying out oil removing, flushing with clean water as anodic ZK60 magnesium alloy member with the stainless steel, pickling, flushing with clean water, alkali cleaning, activation, flushing with clean water, soak zinc, flushing with clean water, soaking zinc spare at 5 ℃ with the ZK60 magnesium alloy subsequently is anode, with the stainless steel is negative electrode, pass to frequency 1500Hz in treatment soln, break make ratio 15%, current density are 1A/dm
2Current processing, anodic oxidation was cut off the electricity supply after 0.5 minute, with the tap water flushing, used hot blast drying.Technology of the present invention is simple, and treatment soln and matrix bond are good, obtains fine and close iris rete.
Embodiment 6
At first the distilled water of adding 3/4 in the 5L groove adds 175g potassium hydroxide, 150g potassium oxalate and 175g aniline successively, adds water to pre-determined volume then, after static 24 hours, to carrying out oil removing, flushing with clean water, pickling as anodic ZL20 Al-alloy parts, flushing with clean water, alkali cleaning, activation, flushing with clean water is soaked zinc, flushing with clean water, soaking zinc spare at 40 ℃ with the ZL20 aluminium alloy subsequently is anode, is negative electrode with the stainless steel, passes to frequency 1500Hz in treatment soln, break make ratio 15%, current density are 0.10A/dm
2Current processing, anodic oxidation was cut off the electricity supply after 0.5 minute, with the tap water flushing, used hot blast drying.Technology of the present invention is simple, basic non-environmental-pollution, and treatment soln is the screening formulation parameter, the treatment soln good stability, dispersive ability and covering power are strong, and it is good that gained is handled membrane uniformity, and good with matrix bond, obtains fine and close iris rete.
Claims (6)
1, the color metallization processes of a kind of magnesium alloy or aluminum alloy surface zinc-impregnating layer anonizing, it is characterized in that, use treatment soln anodic oxidation coloured silkization magnesium alloy or the aluminum alloy surface zinc-impregnating layer formed by potassium hydroxide, aniline, potassium oxalate, at first to carrying out pre-treatment as anodic magnesium alloy and alloy matrix aluminum, be oil removing, pickling, alkali cleaning, activate, soak zinc, prepare treatment soln then, in treatment soln, pass to electric current again and produce electric energy, make anodic magnesium alloy or aluminium alloy matrix surface form fine and close colorful film through pre-treatment.
2, the color metallization processes of Mg alloy surface zinc-impregnating layer anonizing according to claim 1 is characterized in that, and is described to as the pre-treatment of anodic metallic matrix, specific as follows:
Oil removing: with containing the NaOH of 20g/L and the Na of 30g/L
2CO
3The thorough oil removing of mixing solutions,
Pickling: with the HNO that contains 100mL/L
3NH with 20g/L
4The mixing solutions of HF is removed oxide compound,
Alkali cleaning: with the Na that contains 30g/L
2CO
3Remove residual oxide compound with the mixing solutions of the NaF of 10g/L,
Activation: with the solution activated metal surface that contains 100mL/LHF,
Soak zinc: with the ZnSO that contains 20g/L
4Na with 100g/L
2P
2O
7Mixing solutions soak zinc and handled 10 minutes.
3, the color metallization processes of Mg alloy surface zinc-impregnating layer anonizing according to claim 1, it is characterized in that, described preparation treatment soln, specific as follows: the distilled water of adding 3/4 in groove, add potassium hydroxide, potassium oxalate and aniline successively, add water to pre-determined volume then, solution is after placing 24 hours, with the stainless steel is negative electrode, is anode through the pre-treatment part, carries out anodic oxidation treatment.
4, the color metallization processes of magnesium alloy according to claim 1 or aluminum alloy surface zinc-impregnating layer anonizing, it is characterized in that, the described electric current that passes in treatment soln produces electric energy, specific as follows: in the treatment soln for preparing, be negative electrode with the stainless steel, it is anode that pending magnesium alloy or aluminium alloy soak zinc spare, at 5-40 ℃, break make ratio is 5-15%, and frequency is 500-1500Hz, and pulse current density is 0.1-1.0A/cm
2, the surface forms fine and close colorful film.
5, a kind of zinc-impregnating layer anonizing coloured silkization treatment soln prescription is characterized in that the weight percent of treatment soln component and each component is: potassium hydroxide 20%-45%, aniline 30%-40%, potassium oxalate 20%-45%.
6, zinc-impregnating layer anonizing coloured silkization treatment soln prescription according to claim 5 is characterized in that the weight percent that further limits each component is: potassium hydroxide 35%, aniline 30%, potassium oxalate 35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141545 CN1207440C (en) | 2003-07-10 | 2003-07-10 | Zinc-impregnating layer anodic oxidation method colouring process and its treatment solution formula |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141545 CN1207440C (en) | 2003-07-10 | 2003-07-10 | Zinc-impregnating layer anodic oxidation method colouring process and its treatment solution formula |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1477229A CN1477229A (en) | 2004-02-25 |
| CN1207440C true CN1207440C (en) | 2005-06-22 |
Family
ID=34155345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03141545 Expired - Fee Related CN1207440C (en) | 2003-07-10 | 2003-07-10 | Zinc-impregnating layer anodic oxidation method colouring process and its treatment solution formula |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1207440C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387757C (en) * | 2005-04-12 | 2008-05-14 | 沈阳工业大学 | Method for electroplating magnesium and magnesium alloy |
| CN102560579B (en) * | 2011-12-10 | 2015-02-25 | 中国振华集团永光电子有限公司 | Nickel plating method for silicon-aluminum alloy |
| CN102560516B (en) * | 2012-02-13 | 2014-01-01 | 上海交通大学 | Magnesium alloy surface homogenization pretreatment process |
-
2003
- 2003-07-10 CN CN 03141545 patent/CN1207440C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1477229A (en) | 2004-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105274519B (en) | The surface treatment method and stainless steel Watchcase of stainless steel | |
| CN101845654B (en) | Aluminum strip anode oxidization process | |
| CN100464007C (en) | Process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer | |
| CN102260891B (en) | Method for electrodepositing nanocrystalline nickel-cobalt alloy by double-pulse | |
| CN105364637B (en) | A kind of surface treatment method of Al-alloy casing | |
| CN101423967B (en) | Surface treating method of aluminum alloy material | |
| CN1900360A (en) | Process for preparing magnesium alloy surface function gradient film | |
| CN113088966B (en) | Magnesium alloy composite coating and preparation method thereof | |
| CN102286766A (en) | Aluminum alloy hard anode oxidation film and process method thereof | |
| CN101629313A (en) | Double-pulse plating silver solution and technique thereof | |
| CN1034522C (en) | Plasma enhanced electrochemical surface ceramic method and product prepared by same | |
| CN105441743A (en) | Aluminum-based amorphous alloy composite material and preparation method thereof | |
| CN103243360A (en) | Zn-Ni alloy brush plating solution and brush plating method | |
| CN1936075A (en) | Electroplating-substituted cladding coating and process | |
| CN1207440C (en) | Zinc-impregnating layer anodic oxidation method colouring process and its treatment solution formula | |
| Ma et al. | Preparation and property of self-sealed plasma electrolytic oxide coating on magnesium alloy | |
| CN101781785A (en) | Method for plating high corrosion resistant aluminum-manganese alloy on surface of magnesium alloy | |
| CN101831681B (en) | Method for preparing aluminum alloy colored composite film | |
| CN101525747A (en) | Clean rare-earth salt passivation solution | |
| CN1058053A (en) | The method of electroplating bright nickel on Nd-Fe-B alloy | |
| CN101255581B (en) | Alkaline chloride galvanizing agent and preparation method thereof | |
| CN203007452U (en) | Aluminum alloy with army green micro-arc oxidation ceramic membrane on surface | |
| CN1220797C (en) | Method for producing gold-coloured surfaces pertaining to aluminium or aluminium alloys by means of formulations containing silver salt | |
| CN111118557B (en) | Preparation method of alloy electroplating material with high binding force | |
| CN103320838A (en) | In-situ growth method of yellow ceramic coating on TC4 titanium alloy surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI AIERSI LIGHT ALLOY PRODUCTS CO., LTD. Free format text: FORMER OWNER: SHANGHAI JIAOTONG UNIV. Effective date: 20081010 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20081010 Address after: No. nine, Jing Jing Road, Songjiang hi tech park, Shanghai, 1501 Patentee after: Shanghai Aiersi Light Alloy Co., Ltd. Address before: No. 1954, Huashan Road, Shanghai Patentee before: Shanghai Jiao Tong University |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050622 Termination date: 20140710 |
|
| EXPY | Termination of patent right or utility model |