CN102146561B - Film forming solution for zinc and zinc alloy surface environmentally-friendly blackened film and using method of film forming solution - Google Patents
Film forming solution for zinc and zinc alloy surface environmentally-friendly blackened film and using method of film forming solution Download PDFInfo
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- CN102146561B CN102146561B CN 201110072047 CN201110072047A CN102146561B CN 102146561 B CN102146561 B CN 102146561B CN 201110072047 CN201110072047 CN 201110072047 CN 201110072047 A CN201110072047 A CN 201110072047A CN 102146561 B CN102146561 B CN 102146561B
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Abstract
The invention discloses film forming solution for zinc and zinc alloy surface environmentally-friendly blackened films. The film forming solution comprises blackening agent, auxiliary film forming agent, activating agent and water, wherein the blackening agent is molybdate, and the concentration of the blackening agent is 5 to 80 grams per liter; the auxiliary film forming agent is borofluoride, and the concentration of the auxiliary film forming agent is 2 to 20 grams per liter; and the activating agent is strong acid or weak acid and is added till the pH value of the film forming solution reaches 2 to 5. The film forming solution is very simple in implementation, can be produced at normal temperature, reduces the cost, saves the energy, does not produce sediment, and is more environmentally-friendly.
Description
Technical field
The invention belongs to field of metal surface treatment, specifically is film forming liquid and method of use thereof that a kind of zinc and zinc alloy surface environment-friendly type are dyed black film.
Background technology
Zinc and zinc alloy are widely used in fields such as steamer, family property, light fixture, automobile, for product appearance of beautifying the zinc alloy device and the requirement of satisfying some particular device surface absorptive, need zinc alloy surface be processed into black.
During Traditional industrial was produced at present, zinc and zinc alloy surface dyed in the black employed prescription, and the overwhelming majority all contains heavy metal ion such as trivalent chromium, sexavalent chrome or prussiate, and environment is caused severe contamination, and the influence mankind's is healthy.Along with the appearance of the new sewage drainage standard of country, making must the increase input processing of sewage effluent of surface treatment enterprise increase production cost greatly; Most of prescription can produce dust or sediment in the blackout process, increased the intractability of cleaning and hair blackening liquid; But also need some processing of also need heating.The electroplating technology handbook [Ceng Hualiang, Wu Zhongda, Chen Junwu, Lv Peiren, Qin Yuewen. China Machine Press, in June, 1997, p.470-472] second edition introduced the black blunt prescription of a series of zinc alloys, and these prescriptions contain sexavalent chrome or prussiate mostly.One Chinese patent application numbers 85101608 has been invented a kind of technology of blackening metal surfaces by molybdate electrochemical method that is applicable to zinc products; Specifically be zinc products to be immersed as negative electrode contain in the electrolytic solution of basal liquid, blackening agent for surface and additive; In electrolytic solution, immerse another kind of metal as anode, the making alive discharge is until forming black film between the two poles of the earth.The drawback that this method exists is that technology is loaded down with trivial details, and cost is high.
Summary of the invention
First purpose of the present invention is in order to overcome the shortcoming and defect that prior art exists, and provide that a kind of technology is simple, with low cost, film forming liquid that environmental protection, bonding force is good, absorptive is good, sediment weight is low zinc and zinc alloy surface environment-friendly type are dyed black film.
Another object of the present invention provides a kind ofly utilizes above-mentioned film forming liquid to form the method for use that environment-friendly type is dyed black film at zinc and zinc alloy surface.
For realizing first purpose of the present invention, technical scheme of the present invention is the film forming liquid that zinc and zinc alloy surface environment-friendly type are dyed black film, it is characterized in that comprising blackening agent for surface, secondary film formers, acvator and water; Wherein blackening agent for surface is a molybdate; Its concentration is the 5-80 grams per liter, and said secondary film formers is a fluoroborate, and its concentration is the 2-20 grams per liter; Described acvator is strong acid or weak acid, and its add-on is to make the pH value of film forming liquid reach 2-5.
Further being provided with is that said molybdate is Sodium orthomolybdate, ammonium molybdate, Potassium orthomolybdate a kind of or its compound wherein.
Further being provided with is that said fluoroborate is wherein a kind of or its compound of Sodium tetrafluoroborate, potassium fluoborate.
Further being provided with is that described acvator is nitric acid, phosphoric acid, acetate, boric acid a kind of or its compound wherein.
For realizing another object of the present invention, technical scheme of the present invention is may further comprise the steps:
(1) with the workpiece of zinc and zinc alloy material through oil removing, scale removal, activation also cleans up;
(2) film forming is handled at room temperature, will put into film forming liquid through the zinc after step (1) is handled and the workpiece of zinc alloy material, stirs, and takes out washing after 5-30 minute;
(3) oven dry processing bake out temperature is 50-120 ℃, and the time is 5-40 minutes, thereby forms the black film with metalluster at zinc or zinc alloy surface.
Advantage of the present invention is:
Method of the present invention is implemented very simple, can produce at normal temperatures, has reduced cost, save energy, and do not have sediment generation, environmental protection more.
The black decoration coating that has metalluster uniformly that the present invention forms at zinc and zinc alloy alloy surface, with paint film adhesion be one-level.Shown in Fig. 1-4
Description of drawings
Fig. 1 zinc metal sheet dyes black 25 times of enlarged views;
Fig. 2 zinc metal sheet dyes black 100 times of enlarged views;
Fig. 3 zinc metal sheet dyes black 250 times of enlarged views;
Fig. 4 zinc metal sheet dyes black 500 times of enlarged views;
Below in conjunction with embodiment the present invention is done further introduction.
Embodiment
Through embodiment the present invention is carried out concrete description below; Only be used for the present invention is further specified; Can not be interpreted as the qualification to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1
Adopt the following step during production successively,
(a) take the pure zinc metal sheet of certain size specification, oil removing, scale removal, activation also cleans up;
(b) configure the hair blackening liquid that contains molybdate 5 grams per liters, fluoroborate 2 grams per liters, nitrite 1 grams per liter, acetate 1 grams per liter; It is 2 that acidic activator is regulated the pH value; Dying the black powder liquid temp is that clean workpiece immerses in the hair blackening liquid and turns black with surface treatment under the normal temperature condition; Time is 30 minutes, takes out and cleans after passivation is accomplished;
(c) finish coatings is directly carried out in the oven dry of the workpiece after will turning black.
Embodiment 2
Adopt the following step during production successively,
(a) take the pure zinc metal sheet of certain size specification, oil removing, scale removal, activation also cleans up;
(b) configure the hair blackening liquid that contains molybdate 80 grams per liters, fluoroborate 20 grams per liters, nitrite 10 grams per liters, acetate 20 grams per liters; It is 6 that acidic activator is regulated the pH value; Dying the black powder liquid temp is that clean workpiece immerses in the hair blackening liquid and turns black with surface treatment under the normal temperature condition; Time is 5 minutes, takes out and cleans after passivation is accomplished;
(c) finish coatings is directly carried out in the oven dry of the workpiece after will turning black.
Embodiment 3
Adopt the following step during production successively,
(a) take the pure zinc metal sheet of certain size specification, oil removing, scale removal, activation also cleans up;
(b) configure the hair blackening liquid that contains molybdate 10 grams per liters, fluoroborate 6 grams per liters, nitrite 5 grams per liters, acetate 5 grams per liters; It is 4.5 that acidic activator is regulated the pH value; Dying the black powder liquid temp is that clean workpiece immerses in the hair blackening liquid and turns black with surface treatment under the normal temperature condition; Time is 10 minutes, takes out and cleans after passivation is accomplished;
(c) finish coatings is directly carried out in the oven dry of the workpiece after will turning black.
Embodiment 4
Adopt the following step during production successively,
The trade mark of (a) taking the certain size specification is a ZZnAl 10-5 zinc metal sheet, oil removing, and scale removal, activation also cleans up;
(b) configure the hair blackening liquid that contains molybdate 5 grams per liters, fluoroborate 2 grams per liters, nitrite 1 grams per liter, acetate 1 grams per liter; It is 2 that acidic activator is regulated the pH value; Dying the black powder liquid temp is that clean workpiece immerses in the hair blackening liquid and turns black with surface treatment under the normal temperature condition; Time is 30 minutes, takes out and cleans after passivation is accomplished;
(c) finish coatings is directly carried out in the oven dry of the workpiece after will turning black.
Embodiment 5
Adopt the following step during production successively,
The trade mark of (a) taking the certain size specification is a ZZnAl 10-5 zinc metal sheet, oil removing, and scale removal, activation also cleans up;
(b) configure the hair blackening liquid that contains molybdate 80 grams per liters, fluoroborate 20 grams per liters, nitrite 10 grams per liters, acetate 20 grams per liters; It is 6 that acidic activator is regulated the pH value; Dying the black powder liquid temp is that clean workpiece immerses in the hair blackening liquid and turns black with surface treatment under the normal temperature condition; Time is 5 minutes, takes out and cleans after passivation is accomplished;
(c) finish coatings is directly carried out in the oven dry of the workpiece after will turning black.
Embodiment 6
Adopt the following step during production successively,
The trade mark of (a) taking the certain size specification is a ZZnAl 10-5 zinc metal sheet, oil removing, and scale removal, activation also cleans up;
(b) configure the hair blackening liquid that contains molybdate 10 grams per liters, fluoroborate 6 grams per liters, nitrite 5 grams per liters, acetate 5 grams per liters; It is 4.5 that acidic activator is regulated the pH value; Dying the black powder liquid temp is that clean workpiece immerses in the hair blackening liquid and turns black with surface treatment under the normal temperature condition; Time is 10 minutes, takes out and cleans after passivation is accomplished;
(c) finish coatings is directly carried out in the oven dry of the workpiece after will turning black.
Embodiment 7
Adopt the following step during production successively,
The trade mark of (a) taking the certain size specification is ZZnAl 4 zinc metal sheets, oil removing, and scale removal, activation also cleans up;
(b) configure the hair blackening liquid that contains molybdate 5 grams per liters, fluoroborate 2 grams per liters, nitrite 1 grams per liter, acetate 1 grams per liter; It is 2 that acidic activator is regulated the pH value; Dying the black powder liquid temp is that clean workpiece immerses in the hair blackening liquid and turns black with surface treatment under the normal temperature condition; Time is 30 minutes, takes out and cleans after passivation is accomplished;
(c) finish coatings is directly carried out in the oven dry of the workpiece after will turning black.
Embodiment 8
Adopt the following step during production successively,
The trade mark of (a) taking the certain size specification is ZZnAl 4 zinc metal sheets, oil removing, and scale removal, activation also cleans up;
(b) configure the hair blackening liquid that contains molybdate 80 grams per liters, fluoroborate 20 grams per liters, nitrite 10 grams per liters, acetate 20 grams per liters; It is 6 that acidic activator is regulated the pH value; Dying the black powder liquid temp is that clean workpiece immerses in the hair blackening liquid and turns black with surface treatment under the normal temperature condition; Time is 5 minutes, takes out and cleans after passivation is accomplished;
(c) finish coatings is directly carried out in the oven dry of the workpiece after will turning black.
Embodiment 9
Adopt the following step during production successively,
The trade mark of (a) taking the certain size specification is ZZnAl 4 zinc metal sheets, oil removing, and scale removal, activation also cleans up;
(b) configure the hair blackening liquid that contains molybdate 10 grams per liters, fluoroborate 6 grams per liters, nitrite 5 grams per liters, acetate 5 grams per liters; It is 4.5 that acidic activator is regulated the pH value; Dying the black powder liquid temp is that clean workpiece immerses in the hair blackening liquid and turns black with surface treatment under the normal temperature condition; Time is 10 minutes, takes out and cleans after passivation is accomplished;
(c) finish coatings is directly carried out in the oven dry of the workpiece after will turning black.
Claims (5)
1. zinc or zinc alloy surface environment-friendly type are dyed the film forming liquid of black film, it is characterized in that comprising blackening agent for surface, secondary film formers, acvator and water, and wherein blackening agent for surface is a molybdate; Its concentration is the 5-80 grams per liter; Said secondary film formers is a fluoroborate, and its concentration is the 2-20 grams per liter, and described acvator is strong acid or weak acid; Its add-on is to make the pH value of film forming liquid reach 2-6; Also include nitrite and acetate, wherein the concentration of nitrite in film forming liquid is the 1-10 grams per liter, and wherein the concentration of acetate in film forming liquid is the 1-20 grams per liter.
2. a kind of zinc according to claim 1 or zinc alloy surface environment-friendly type are dyed the film forming liquid of black film, it is characterized in that: said molybdate is Sodium orthomolybdate, ammonium molybdate, Potassium orthomolybdate a kind of or its compound wherein.
3. a kind of zinc according to claim 1 or zinc alloy surface environment-friendly type are dyed the film forming liquid of black film, it is characterized in that: said fluoroborate is wherein a kind of or its compound of Sodium tetrafluoroborate, potassium fluoborate.
4. a kind of zinc according to claim 1 or zinc alloy surface environment-friendly type are dyed the film forming liquid of black film, it is characterized in that: described acvator is nitric acid, phosphoric acid, acetate, boric acid a kind of or its compound wherein.
5. zinc as claimed in claim 1 or the zinc alloy surface environment-friendly type method of use of dying the film forming liquid of black film is characterized in that may further comprise the steps:
(1) with the workpiece of zinc or zinc alloy material through oil removing, scale removal, activation also cleans up;
(2) film forming is handled
At room temperature, will put into film forming liquid, stir, take out washing after 5-30 minute through the zinc after step (1) is handled or the workpiece of zinc alloy material;
(3) oven dry is handled
Bake out temperature is 50-120 ℃, and the time is 5-40 minutes, thereby forms the black film with metalluster at zinc or zinc alloy surface.
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| CN102304711A (en) * | 2011-09-28 | 2012-01-04 | 浙江工贸职业技术学院 | Environmentally friendly chromium-free passivation solution for aluminum and aluminum alloy surface and application thereof |
| CN103668157A (en) * | 2013-12-13 | 2014-03-26 | 三达奥克化学股份有限公司 | Low-cost environmental-friendly silane vitrification treatment agent for steel and iron workpieces |
| CN103849868A (en) * | 2014-02-14 | 2014-06-11 | 浙江工业大学 | Blackening liquid for chromium-free titanium-zinc panel surface and using method of blackening liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101838804A (en) * | 2010-05-10 | 2010-09-22 | 长沙祁胜新材料科技有限公司 | Laminated phosphating liquid and preparation method thereof |
| CN101845628A (en) * | 2009-03-25 | 2010-09-29 | 中国科学院金属研究所 | Method for preparing environment-friendly black film on magnesium alloy surface and film-forming liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101845628A (en) * | 2009-03-25 | 2010-09-29 | 中国科学院金属研究所 | Method for preparing environment-friendly black film on magnesium alloy surface and film-forming liquid |
| CN101838804A (en) * | 2010-05-10 | 2010-09-22 | 长沙祁胜新材料科技有限公司 | Laminated phosphating liquid and preparation method thereof |
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