CN104059514B - A kind of self-lubrication treatment agent composition and hot dip aluminum zinc plate and preparation method thereof - Google Patents
A kind of self-lubrication treatment agent composition and hot dip aluminum zinc plate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of self-lubrication treatment agent composition, wherein, said composition contains water, sodium metasilicate, lubricant, inorganic inhibitor, silane coupler and organic resin.Present invention also offers a kind of hot dip aluminum zinc plate, this hot dip aluminum zinc plate includes hot-dip aluminizing zinc plate substrate and attachment coating on substrate surface, and wherein, described coating is formed by self-lubrication treatment agent composition as above.The invention also discloses the preparation method of a kind of hot dip aluminum zinc plate, the method includes: self-lubrication treatment agent composition as above is configured to coating fluid, by described coating solution on hot-dip aluminizing zinc plate substrate, then solidifies.The coating formed after the self-lubrication treatment agent composition solidification that the present invention provides has good corrosion resistance, heat resistance, resistance to water and adsorptivity, and self lubricity is the most excellent.
Description
Technical field
The present invention relates to a kind of hot-dip aluminizing zinc self-lubrication treatment agent and hot dip aluminum zinc plate and preparation method thereof.
Background technology
In recent years, improving constantly the needs with market along with technology, hot dip aluminum zinc plate is excellent because of it
The characteristic such as corrosion resistance, decorative appearance is developed rapidly.Hot dip aluminum zinc plate application master at home
It is building and regulator cubicle manufacturing industry: it based on Thin Specs, is mainly used as coloured silk in the application of building industry
It is coated with substrate；It based on think gauge, is mainly directly used as cabinet in the manufacturing application of regulator cubicle.Mesh
Before, the application of hot dip aluminum zinc plate is significantly to household electrical appliances, the extension of automobile sheetsteel field.But hot-dip aluminizing zinc
Plate great majority during the user such as household electrical appliances, auto manufacturing uses need stamped shaping.Due to mould with
Friction between steel plate, easily there is the problem such as dry linting, black change when shaping, not only affects shaping zero in coating
The presentation quality of part, corrosion resistance, coating etc., and the abrasion of mould can be aggravated, reduce it and use the longevity
Life, and the performance such as the corrosion resistance of existing hot dip aluminum zinc plate, anti-finger printing, heat resistance still needs further
Improve.Therefore, need badly exploitation a kind of without chromium, constituent be half organically, have good resistance to
Erosion property, heat resistance, resistance to water, adsorptivity, film forming, lubricity with hot-dip aluminizing zincium steel plate as base material
Self-lubrication treatment agent.
Summary of the invention
It is an object of the invention to provide a kind of without chromium, constituent be half organically, have good
The self-lubrication treatment agent combination of corrosion resistance, heat resistance, resistance to water, adsorptivity, film forming and lubricity
Thing, and use said composition as hot dip aluminum zinc plate of coating and preparation method thereof.
To achieve these goals, the present invention provides a kind of self-lubrication treatment agent composition, wherein, this group
Compound contains water, sodium metasilicate, lubricant, inorganic inhibitor, silane coupler and organic resin.
Present invention also offers a kind of hot dip aluminum zinc plate, this hot dip aluminum zinc plate include hot-dip aluminizing zinc plate substrate and
Attachment coating on substrate surface, wherein, described coating is by self-lubrication treatment agent provided by the present invention
Composition is formed.
Present invention also offers the preparation method of a kind of hot dip aluminum zinc plate, the method includes: by institute of the present invention
The self-lubrication treatment agent composition provided is configured to coating fluid, by described coating solution at hot dip aluminum zinc plate
On base material, then solidify.
By technique scheme, the invention provides a kind of self-lubrication treatment agent composition and have excellent
The hot dip aluminum zinc plate of good self lubricity and the preparation method of this aluminium zine plate.
Self-lubrication treatment agent composition provided by the present invention is not owing to containing heavy metal chromium, so having ring
The feature ensured safety, it addition, the constituent of self-lubrication treatment agent composition provided by the present invention is half
Organically composition, the coating formed after hardening has good corrosion resistance, heat resistance, resistance to water, attached
The property and film forming, and self lubricity is the most excellent.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of self-lubrication treatment agent composition, wherein, said composition contains water, silicic acid
Sodium, lubricant, inorganic inhibitor, silane coupler and organic resin.
The content of above each material is had no particular limits by the present invention, as long as containing above thing in composition
Matter can realize the purpose of the present invention.Preferably, on the basis of the water of 100 weight portions, described sodium metasilicate
Content be 0.5-10 weight portion；The content of described lubricant is 5-30 weight portion；Described inorganic inhibition
The content of agent is 0.1-5 weight portion；The content of described silane coupler is 2-20 weight portion；Described organic
The content of resin is 1-50 weight portion.
Under preferable case, on the basis of the water of 100 weight portions, the content of described sodium metasilicate is 4-8 weight
Part；The content of described lubricant is 10-25 weight portion；The content of described inorganic inhibitor is 1.5-4 weight
Amount part；The content of described silane coupler is 8-16 weight portion；The content of described organic resin is 15-45
Weight portion.
Self-lubrication treatment agent composition according to the present invention, wherein, described lubricant can be water-based fluorocarbon
In emulsion, silicone oil emulsion, polythene wax emulsion, polytetrafluoroethylwax wax emulsion and Brazil wax emulsion
At least one, in order to improve self-lubricating property further, described lubricant be preferably water-base fluorocarbon emulsion,
At least one in polythene wax emulsion and polytetrafluoroethylwax wax emulsion.
Self-lubrication treatment agent composition according to the present invention, wherein, described organic resin can be aqueous third
Olefin(e) acid resin, aqueous styrene-acrylic resin, resol resins, waterborne polyurethane resin, waterborne organic silicon tree
At least one in fat and aqueous epoxy resins, in order to improve coating performance further, described organic resin
It is preferably at least one in water-borne acrylic resin, aqueous styrene-acrylic resin and aqueous polyurethane.
Self-lubrication treatment agent composition according to the present invention, wherein, described inorganic inhibitor can be high manganese
At least one in acid potassium, disodium-hydrogen, natrium nitrosum, sodium tripolyphosphate, zinc sulfate and sodium molybdate.
In order to improve corrosion resisting property further, described inorganic inhibitor is preferably natrium nitrosum, sodium molybdate and Gao Meng
At least one in acid potassium.
Self-lubrication treatment agent composition according to the present invention, wherein, described silane coupler can be γ-
Aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560),
γ-methacryloxypropyl trimethoxy silane (KH570), γ-mercaptopropyl trimethoxysilane
(KH590), vinyltrimethoxy silane (KH171) and N-(β-aminoethyl)-γ-aminopropyl front three
At least one in TMOS (KH792).
Self-lubrication treatment agent composition according to the present invention, wherein, in order to improve described self-lubricating further
The performance of agent composition, described raw mixture can also contain auxiliary agent.Wherein, under preferable case,
Relative to the water of 100 weight portions, the consumption of described auxiliary agent is 0.1-2 weight portion, more preferably 0.3-1 weight
Amount part.
The kind of described auxiliary agent is had no particular limits by the present invention, if the purpose of the present invention of being capable of
?.It was found by the inventors of the present invention that when described auxiliary agent is in surfactant, levelling agent and defoamer
At least one time, the as above performance of composition that the present invention provides can be further enhanced.
Wherein, in described auxiliary agent, the selection of surfactant, levelling agent and defoamer can be conventional
Selecting, the present invention not particularly requirement, such as, described surfactant can be alkyl phenol polyoxy second
At least one in alkene ether (OP-10), neopelex and lauryl sodium sulfate；Described stream
Flat agent can be polyurethane levelling agent；Described defoamer can be Polyether Modified Polysiloxanes Defoaming Agent.
Wherein, in described auxiliary agent, relative to the water with 100 weight portions, in auxiliary agent, the content of levelling agent can
Think 0.05-1 weight portion, the content of surfactant can be 0.02-0.5 weight portion, the containing of defoamer
Amount can be 0.03-0.5 weight portion.
Self-lubrication treatment agent composition according to the present invention, wherein, particularly preferably in the case of, lubricant
For water-base fluorocarbon emulsion and/or polythene wax emulsion；Described silane coupler is gamma-aminopropyl-triethoxy
Silane, γ-glycidyl ether oxygen propyl trimethoxy silicane and γ-methacryloxypropyl trimethoxy
At least one in silane；Described inorganic inhibitor is natrium nitrosum and/or sodium molybdate；Described organic resin
For water-borne acrylic resin and/or aqueous polyurethane.Under this preferable case, described self-lubrication treatment agent group
Compound solidify at 80-110 DEG C after the coating of gained have prominent corrosion resistance, heat resistance, resistance to water,
Adsorptivity, film forming, its self-lubricating property is the most excellent.
Wherein, said composition is for obtaining after being mixed by each composition.Under preferable case, described composition
In each component within 2-60 days, mix acquisition liquid form before use at this self-lubrication treatment agent composition
Composition.Wherein, the order by merging to each composition does not specially require, can be directly by described raw material
Each component in mixture carries out simultaneously, mixes in batches or step by step, as long as uniform stablizing can be obtained is mutually
Can, preferably make mixing more uniform by stirring.
The present inventor has surprisingly found that, according to ratio as above, above each material is carried out mixing system
Standby self-lubrication treatment agent composition can also effectively improve rate of film build so that film formation time contracts significantly
Short, thus effectively provide production efficiency.
Present invention also offers a kind of hot dip aluminum zinc plate, this hot dip aluminum zinc plate include hot-dip aluminizing zinc plate substrate and
Attachment coating on substrate surface, wherein, described coating is by self-lubrication treatment agent group of the present invention
Compound is formed.
According to the hot dip aluminum zinc plate of the present invention, wherein, the thickness of described coating can be 0.05-0.3 micron.
According to the hot dip aluminum zinc plate of the present invention, wherein, described coating is described self-lubrication treatment agent to be combined
Thing is attached on described hot-dip aluminizing zinc plate substrate, and is 80-110 DEG C and hardening time is in solidification temperature
Under the condition of cure of 10-60s, solidification obtains.
It was found by the inventors of the present invention that the pH value of the self-lubrication treatment agent composition of present invention offer exists
Between 7-12, it is particularly well-suited to hot dip aluminum zinc plate, when being coated with by the self-lubrication treatment agent composition of the present invention
When cloth is on hot dip aluminum zinc plate, the corrosion resistance of coating of described combination physical property, heat resistance, resistance to water, suction
Attached property, film forming, its self-lubricating property can be further enhanced.
Present invention also offers the preparation method of a kind of hot dip aluminum zinc plate, the method includes: by institute of the present invention
The self-lubrication treatment agent composition stated is configured to coating fluid, by described coating solution at hot dip aluminum zinc plate base
On material, then solidify.
The preparation method of the hot dip aluminum zinc plate according to the present invention, wherein, the hot-dip aluminizing relative to every square metre
Zine plate substrate surface, the consumption of described self-lubrication treatment agent makes to be formed on described hot-dip aluminizing zinc plate substrate
The thickness of coating be 0.05-0.3 micron.
The preparation method of the hot dip aluminum zinc plate according to the present invention, wherein, the temperature of described solidification and time
Those skilled in the art can be adjusted according to actual conditions, it is preferable that the temperature of described solidification is
80-110 DEG C, the time is 10-60s.
Wherein, the method for described coating can use this area conventional for forming coating on a metal plate
Coating process, for example, it is possible to described self-lubricating agent composition roller coat is coated in described hot dip aluminum zinc plate
The surface of base material, or described self-lubricating agent composition is sprayed the table at described hot-dip aluminizing zinc plate substrate
Face.
Wherein, the temperature to the coating of described self-lubricating agent composition, the present invention has no particular limits, this
Skilled person can within the temperature range of described self-lubricating agent composition does not freezes or vaporizes voluntarily
Select, for example, it is possible to be 5-40 DEG C.
Wherein, the mode of heating of described solidification, can be that Hot-blast Heating, sensing heating and infra-red radiation add
One or more hankered.Under preferable case, it is possible to use the curing oven on hot-dip aluminizing zinc wire is carried out.
Present invention also offers the heat that the preparation method according to hot dip aluminum zinc plate as above prepares
Aluminium plating zinc plate.
Hereinafter will be described the present invention by embodiment.
Reagent used in following example and comparative example is all commercially available.In the feelings not specialized
Under condition, it is pure that described reagent is analysis.
Embodiment 1-10 and comparative example 1-5
The constituent content listed according to table 1, mixes each component under agitation, respectively obtains
Self-lubricating agent composition embodiment 1-10 and comparative example 1-5.
Table 1
| Sodium metasilicate | Lubricant | Inorganic inhibitor | Silane coupler | Organic resin | Auxiliary agent | Water | |
| Embodiment 1 | 5.0 | 20 | 3 | 12 | 30 | 0.3 | 100 |
| Embodiment 2 | 4.0 | 10 | 4 | 8 | 45 | 0.8 | 100 |
| Embodiment 3 | 8.0 | 25 | 1.5 | 16 | 15 | 0.6 | 100 |
| Embodiment 4 | 0.5 | 5 | 5 | 20 | 1 | 2 | 100 |
| Embodiment 5 | 10.0 | 30 | 0.1 | 2 | 50 | 0.2 | 100 |
| Embodiment 6 | 5.0 | 20 | 3 | 12 | 30 | 0 | 100 |
| Comparative example 1 | 5.0 | 0 | 3 | 12 | 30 | 0.3 | 100 |
| Comparative example 2 | 5.0 | 20 | 0 | 12 | 30 | 0.3 | 100 |
| Comparative example 3 | 5.0 | 20 | 3 | 0 | 30 | 0.3 | 100 |
| Comparative example 4 | 5.0 | 20 | 3 | 12 | 0 | 0.3 | 100 |
| Comparative example 5 | 0 | 20 | 3 | 12 | 30 | 0.3 | 100 |
| Embodiment 7 | 5.0 | 20 | 3 | 12 | 30 | 0.3 | 100 |
| Embodiment 8 | 5.0 | 20 | 3 | 12 | 30 | 0.3 | 100 |
| Embodiment 9 | 5.0 | 20 | 3 | 12 | 30 | 0.3 | 100 |
| Embodiment 10 | 5.0 | 20 | 3 | 12 | 30 | 0.3 | 100 |
In embodiment 1-10 and comparative example 1-5, each component specifically chosen as follows:
Lubricant is water-base fluorocarbon emulsion and polythene wax emulsion (the two weight ratio is 7:3), inorganic slow
Erosion agent is natrium nitrosum and sodium molybdate (the two weight ratio is 3:2), the KH560 that silane coupler is selected,
Organic resin is aqueous polyurethane and aqueous styrene-acrylic resin (the two weight ratio is 4:1), for stream in auxiliary agent
Flat agent, surfactant, defoamer (three's weight ratio is 3:1:1), wherein surfactant is
OP-10, levelling agent is polyurethane levelling agent；Defoamer is Polyether Modified Polysiloxanes Defoaming Agent.
In embodiment 7, as different from Example 1, lubricant is Brazil wax emulsion.
In embodiment 8, as different from Example 1, inorganic inhibitor is sodium tripolyphosphate and permanganic acid
Potassium (the two weight ratio is 1:1).
In embodiment 9, as different from Example 1, the KH171 that silane coupler is selected.
In embodiment 10, as different from Example 1, organic resin is water-borne acrylic resin and water
Property phenolic resin (the two weight ratio is 7:3).
Preparation example
The composition roller coat respectively of embodiment 1-10 and comparative example 1-5 is coated on hot-dip aluminizing zinc steel band,
Under the solidification temperatures of 100 DEG C (using thermometric test paper to measure solidification temperature), solidification 25s respectively obtains and contains
There are the hot dip aluminum zinc plate 1-10 of passivating coating, and hot dip aluminum zinc plate D1-D5.
Test case
This test case measures the corrosion resistance of coating of hot dip aluminum zinc plate 1-10 and D1-D5, heat resistance, resistance to
Aqueous, tack and self lubricity.The results are shown in Table 2.
Wherein, corrosion resistance carries out corrosion test according to method and the condition of regulation in GB/T10125-1997,
Then according to Corrosion results is evaluated (with the corroded area after 72 hours by the regulation of GB12335-90
The percentage accounting for the gross area represents).Wherein, corroded area is the smaller the better.
Heat resistance judges according to the change of sample 20min under the conditions of 300 DEG C；If the change of aberration front and back
Less than 4, and film layer do not occur bubble, come off, the phenomenon such as dry linting, then be A level；If aberration front and back
Change is more than 4, less than 8, and film layer do not occur bubble, come off, the phenomenon such as dry linting, then be B level；
If the change of aberration front and back is more than 8, and film layer do not occur bubble, come off, the phenomenon such as dry linting, then be C
Level.
Resistance to water is to use 100 DEG C of deionized water drop to measure in sample；If the complete anhydrous mark of sample, then
For A level；There is slight water mark, be then B level；Substantially water mark, then be C level.
Tack is according to the dry linting deciding degree that comes off of coating after 180 ° of bendings of sample；If taking off does not occurs in coating
Fall, the phenomenon such as dry linting, then be A level；If dry linting occurring but obscission not occurring, then it it is B level；
If obscission occurs, then it it is C level.
Self lubricity judges according to the coefficient of friction of coating surface, and wherein coefficient of friction is the least, then self-lubricating
Property is the best.
Table 2
| Corrosion resistance/% | Heat resistance | Resistance to water | Tack | Self lubricity | |
| Embodiment 1 | 1 | A | A | A | 0.09 |
| Embodiment 2 | 1 | A | A | A | 0.14 |
| Embodiment 3 | 2 | A | B | A | 0.10 |
| Embodiment 4 | 10 | B | B | B | 0.15 |
| Embodiment 5 | 10 | B | A | A | 0.11 |
| Embodiment 6 | 2 | A | B | B | 0.12 |
| Embodiment 7 | 1 | A | A | A | 0.15 |
| Embodiment 8 | 5 | A | B | A | 0.13 |
| Embodiment 9 | 5 | A | A | A | 0.13 |
| Embodiment 10 | 4 | B | A | A | 0.14 |
| Comparative example 1 | 2 | A | A | A | 0.30 |
| Comparative example 2 | 20 | C | B | A | 0.13 |
| Comparative example 3 | 15 | C | A | A | 0.13 |
| Comparative example 4 | 20 | B | C | C | 0.15 |
| Comparative example 5 | 15 | A | B | A | 0.12 |
By the data of table 2, by the contrast of embodiment 1-10 Yu comparative example 1-5, it can be seen that this
The self-lubricating agent composition that invention provides coating of obtaining under solidification takes into account excellent corrosion resistance, resistance to simultaneously
The performance such as hot, resistance to water, adsorptivity and self lubricity.
Especially, by embodiment 1 and the contrast of embodiment 4-6, it is found that preferably with respect to
The water of 100 weight portions, the content of described sodium metasilicate is 4-8 weight portion；The content of described lubricant is 10-25
Weight portion；The content of described inorganic inhibitor is 1.5-4 weight portion；The content of described silane coupler is
8-16 weight portion；The content of described organic resin is 15-45 weight portion, and containing in the case of auxiliary agent,
Described coating has prominent corrosion resistance, heat resistance, resistance to water, self lubricity.
Especially, by embodiment 1 and the contrast of embodiment 7-10, it is found that by each component
Kind controls in the case of currently preferred kind, and described self-lubrication treatment agent composition is at 80-110
At DEG C, after solidification, the coating of gained has prominent tack, corrosion resistance, heat resistance, resistance to water and absorption
Property, and its self-lubricating property is the most excellent.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible combinations are illustrated by the present invention the most separately.
Additionally, can also be combined between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a self-lubrication treatment agent composition, it is characterised in that said composition contain water, sodium metasilicate,
Lubricant, inorganic inhibitor, silane coupler and organic resin；
Wherein, described inorganic inhibitor is natrium nitrosum and sodium molybdate；
Wherein, during described organic resin is water-borne acrylic resin, aqueous styrene-acrylic resin and aqueous polyurethane
At least one；
Wherein, on the basis of the water of 100 weight portions, the content of described sodium metasilicate is 0.5-10 weight portion；
The content of described lubricant is 5-30 weight portion；The content of described inorganic inhibitor is 0.1-5 weight portion；
The content of described silane coupler is 2-20 weight portion；The content of described organic resin is 1-50 weight portion.
Agent composition the most according to claim 1, wherein, described lubricant is aqueous fluorine
In carbon emulsion, silicone oil emulsion, polythene wax emulsion, polytetrafluoroethylwax wax emulsion and Brazil wax emulsion
At least one.
Agent composition the most according to claim 1, wherein, this agent composition also contains
There is auxiliary agent.
Agent composition the most according to claim 3, wherein, described auxiliary agent is surface-active
At least one in agent, levelling agent and defoamer；On the basis of the water of 100 weight portions, described auxiliary agent
Content is 0.1-2 weight portion.
Agent composition the most according to claim 4, wherein, with the water of 100 weight portions be
Benchmark, the content of described auxiliary agent is 0.3-1 weight portion.
6. a hot dip aluminum zinc plate, this hot dip aluminum zinc plate includes hot-dip aluminizing zinc plate substrate and is attached to base material
Coating on surface, it is characterised in that described coating by described in any one in claim 1-5 from
Lubricated agent composition is formed.
Hot dip aluminum zinc plate the most according to claim 6, wherein, the thickness of described coating is 0.05-0.3
Micron.
8. a preparation method for hot dip aluminum zinc plate, the method includes: by any in claim 1-5
One described self-lubrication treatment agent composition is configured to coating fluid, by described coating solution in hot-dip aluminizing
On zine plate base material, then solidify.
Preparation method the most according to claim 8, wherein, the condition of described solidification includes: temperature
Degree is for 80-110 DEG C, and the time is 10-60s.
The most according to claim 8 or claim 9, preparation method, wherein, the consumption of described coating fluid makes
The thickness of the coating that must be formed on described hot-dip aluminizing zinc plate substrate is 0.05-0.3 micron.
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| CN107641802A (en) * | 2017-07-19 | 2018-01-30 | 合肥普庆新材料科技有限公司 | A kind for the treatment of fluid of resistance and fingerprint resistance containing chromium for hot-dip galvanizing sheet steel |
| KR102314431B1 (en) * | 2019-09-24 | 2021-10-20 | 주식회사 포스코 | Coating composition for hot dip galvanized steel sheet having excellent blackening-resistance and alkali-resistance the surface treated hot dip galvanized steel sheet prepared by using the coating composition and method for preparing the surface treated hot dip galvanized steel sheet |
| CN112553523B (en) * | 2019-09-25 | 2022-05-10 | 上海梅山钢铁股份有限公司 | Self-lubricating hot-dip galvanized steel plate for steel-wood composite floor and manufacturing method thereof |
| CN111500098A (en) * | 2020-04-15 | 2020-08-07 | 上海达克罗涂复工业有限公司 | Antifriction coating and preparation method and application thereof |
| CN112500792A (en) * | 2020-12-03 | 2021-03-16 | 攀钢集团研究院有限公司 | Surface treatment liquid for hot-dip aluminum-zinc plate and preparation method of hot-dip aluminum-zinc plate |
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| CN101250699A (en) * | 2008-03-27 | 2008-08-27 | 武汉科技大学 | Chromium-free passivation liquid for galvanized sheet and manufacture method thereof |
| CN103290401A (en) * | 2013-05-10 | 2013-09-11 | 安徽工业大学 | Chromium-free self-lubricating passivation solution and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250699A (en) * | 2008-03-27 | 2008-08-27 | 武汉科技大学 | Chromium-free passivation liquid for galvanized sheet and manufacture method thereof |
| CN103290401A (en) * | 2013-05-10 | 2013-09-11 | 安徽工业大学 | Chromium-free self-lubricating passivation solution and preparation method thereof |
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