CN109112512A - A kind of Treatment of Metal Surface aqueous passivating solution and preparation method thereof - Google Patents
A kind of Treatment of Metal Surface aqueous passivating solution and preparation method thereof Download PDFInfo
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- CN109112512A CN109112512A CN201810842755.4A CN201810842755A CN109112512A CN 109112512 A CN109112512 A CN 109112512A CN 201810842755 A CN201810842755 A CN 201810842755A CN 109112512 A CN109112512 A CN 109112512A
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a kind of aqueous passivating solutions of Treatment of Metal Surface, including 2.5-4 parts of acidic silicasol, 0-1 parts of vinyltrimethoxysilane, 0.1 part of acrylic acid, 0-12 parts of styrene, 6-21 parts of methyl methacrylate, 18-19.5 parts of n-butyl acrylate, 2.2 parts of hydroxy-ethyl acrylate, 0.3-0.4 parts of N hydroxymethyl acrylamide, 0.15-0.18 parts of initiator, 0.6 part of initiator is eliminated afterwards, 0.6 part of coinitiator is eliminated afterwards, 52-55 parts of transition metal fluoric-containing acid, 16 parts of silane coupling agent, 2-3 parts of wetting agent, 0.2-0.3 parts of defoaming agent, surplus is deionized water, it is 1000 parts total.The preparation method is as follows: obtaining lotion after 1. emulsifying homogeneous；2. putting into initiator；3. eliminating residual monomer；4. putting into other coalescing agents, filtering.Passivating coating prepared by the present invention has good corrosion resistance, reduces production cost.
Description
Technical field
Present invention relates particularly to a kind of Treatment of Metal Surface aqueous passivating solutions and preparation method thereof, belong to industrial chemical use
Product manufacturing field.
Background technique
Metal product such as steel, aluminium, galvanized steel etc. have exposed metal surface after its production.If not to the table
Face is handled, and the aerial metal of exposure can get rusty quickly, so that the strength of materials is impaired, and make subsequent finish coatings etc.
Technique can not carry out.Therefore, metal product is usually needing the active degree for making its surface by Passivation Treatment to reduce using preceding,
It will not be corroded quickly with air reaction.
The conventional method of processing is passivated to use chromate-containing acid passivation agent to metal material, is configured to
Passivating solution carries out additional Passivation Treatment to surface.After metal surface contacts passivating solution, can partially it suffer erosion, generation is suitable for
Form a film the rough surface adhered to.Under the action of chromate, the metal layer on surface is partly dissolved and with metal-chromated oxide
Form reprecipitation, form fine and close layer containing chromating, metal protected to be not rusted.Contain conduct in chromating layer
The zinc and trivalent chromium of skeleton, and the effects of inhibition is corroded is played in the coating containing Cr VI free on a small quantity.
It, can be in corrosion resistance and adhesion, secondary adhesion etc. using chromating in currently available technology
All obtain very outstanding performance.But Cr VI has severe toxicity and environment toxic, is a kind of environmental pollution being difficult to clean off
Object, and in recent years it has also been found that Cr VI has strong carcinogenesis.The highly desirable one kind that finds of people has equal performance simultaneously
Not chromyl environment-friendly type passivator.Currently, the environmentally friendly passivating solution that the prior art provides all also is unable to reach completely
Performance requirement needed for substituting liquid containing chromium passivating.Existing formula usually requires expensive raw material, often at a little aspects
Performance is lacking, such as coating performance, heat resistance, solvent resistance, anti-blackening etc., especially corrosion resistance and anti-flash rusting performance
It is bad.It, need to be to matching in order to make coating have compactness, adhesive force and anti-finger printing in addition, in existing public technology scheme
Organic resin material is added in side；The barriering effect for inhibiting corrosive ion to pass through to have coating, need to add into formula
Enter the granular materials such as silica.But due to the characteristic of resin material and granular materials itself, it is difficult in the coating and other groups
Point evenly dispersed, so that coating uniformity is deteriorated, adhesive force decline, when film forming and machining deformation is easy to crack.
Summary of the invention
In view of the above-mentioned problems of the prior art, the object of the present invention is to provide a kind of Treatment of Metal Surface with aqueous blunt
Change liquid and preparation method thereof, is reached with the coating uniformity of passivating solution preparation, adhesive force, heat resistance, resistance to dissolubility, resistance to blackening
Arrive or be more than coating containing chromating, especially with good water-fast/solvent borne and anti-flash rusting performance, while production cost compared with
It is low.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of aqueous passivating solution of Treatment of Metal Surface, respectively
Raw material and its mass fraction are as follows: 2.5-4 parts of acidic silicasol, 0-1 parts of vinyltrimethoxysilane, 0.1 part of acrylic acid, benzene
0-12 parts of ethylene, 6-21 parts of methyl methacrylate, 18-19.5 parts of n-butyl acrylate, 2.2 parts of hydroxy-ethyl acrylate, N- hydroxyl
0.3-0.4 parts of Methacrylamide, 0.15-0.18 parts of initiator, rear 0.6 part of initiator of elimination, rear elimination coinitiator 0.6
Part, 52-55 parts of transition metal fluoric-containing acid, 16 parts of silane coupling agent, 2-3 parts of wetting agent, 0.2-0.3 parts of defoaming agent, surplus are to go
Ionized water amounts to 1000 parts.
Further, the transition metal fluoric-containing acid include fluotitanic acid, fluorine zirconic acid, fluorine hafnium acid it is one or more.
Further, the acidic silicasol is stable under acidic environment, and the surface between 5~30nm of partial size is modified
The aqueous dispersions of Nano particles of silicon dioxide, and solid content is between 15~50%.
Further, the silane coupling agent is 3-aminopropyltriethoxysilane.
Further, the initiator is to draw selected from water-soluble free radicals such as hydrogen peroxide, persulfate, hydroperoxides
Send out one of agent or a variety of.
Further, the rear initiator of eliminating is tert-butyl hydroperoxide (10% aqueous solution)；It eliminates after described and draws altogether
Hair agent is sodium formaldehyde sulphoxylate (10% aqueous solution).
A method of the aqueous passivating solution of such Treatment of Metal Surface is prepared, is included the following steps:
(1) in proportion successively by the deionized water, acidic silicasol and vinyltrimethoxysilane, acrylic acid, benzene
Ethylene, methyl methacrylate, n-butyl acrylate, hydroxy-ethyl acrylate, N hydroxymethyl acrylamide put into high-pressure emulsification machine
In, the stable monomer emulsions of inorganic particulate are obtained after emulsifying homogeneous；
(2) institute that investment step (1) obtains into the reaction kettle with collet water bath device, agitating device and feeding device
Lotion is stated, the initiator is added, is warming up to 80~85 DEG C after stirring 10min, maintains 3~5h of constant temperature and stirring；
(3) after constant temperature, with 0.5 hour from two feed opening be at the uniform velocity added respectively it is described after eliminate initiator and after disappear
Except coinitiator；After charging, continue heat preservation 0.5~1 hour；
(4) after keeping the temperature, by slurries be cooled to 40 DEG C hereinafter, and by metering than the investment transition metal fluoric-containing acid,
Silane coupling agent, wetting agent and defoaming agent, after stirring 0.5~1h, after, slurry pH is adjusted to 2~3 with hydrofluoric acid under stiring
Between, with 1000 mesh filter screen filtering and dischargings.
Compared with the prior art, beneficial effects of the present invention are as follows:
1) Treatment of Metal Surface of the present invention is passed through with aqueous passivating solution first by inorganic filler component and polymer list
Body carries out emulsion polymerization jointly, adds the method preparation of remaining ingredient.By emulsion polymerization process, inorganic filler gathers with organic
It closes object and forms the organic nuclear structure of inorganic shell-, inorganic filler is dispersed in organic granular surface as stabilizer, avoids filler
Reunion failure phenomenon occurs, granular material disperses more uniformly in coating finished product, and the coating obtained after solidification is more fine and close,
Has better barrier property to corrosive substance compared with prior art.
2) Treatment of Metal Surface of the present invention with used in aqueous passivating solution fluorine titanium zirconium the metals fluoric-containing acid such as hafnium acid
As film forming host agent.After coating is contacted with metal surface, parent metal issues green anode dissolution, liberation of hydrogen and hydrogen reduction in acidity
Reaction promotes pH to increase, so that metal fluoric-containing acid dissociates, metallic element is precipitated in the form of hydrous oxide etc. and in metal
It is deposited on surface, forms metal-oxide film after drying and dehydrating, effective barrier passivation is played to parent metal.Together
When, it further include amino silicane coupling agent in coating of the present invention, when forming a film solidification by silane and matrix and passivation layer
Hydroxyls dehydrate connection in surface metal oxide, while silane coupling agent itself is cross-linked with each other to form predominantly silicon-oxide structure
Film layer, the vitrification layer to be formed can be deposited to metal fluoric-containing acid and plays the role of sealing of hole, greatly enhances the corrosion resistance of coating, together
Shi Gaishan film adhesion, the compatibility between compactness and each component.
3) addition organic resin is usually required in passivation coatings to improve the water resistance of passivation layer, punching processing performance and two
Secondary japanning adhesive force etc., but the emulsifier in resin aqueous emulsion easily disperses in water because of its inherent characteristic, so that water is along applying
The remaining emulsifier infiltration of layer resin particle surfaces, and penetrate coating and reach metallic matrix, flash rusting and spot corrosion are caused, coating is caused
Failure.With traditional technology on the contrary, Treatment of Metal Surface of the present invention resin in aqueous passivating solution and inorganic filler with
Pickering emulsion form introduces simultaneously, without emulsifier and protecting colloid etc., and is not necessarily to additional a large amount of defoaming agents, water resistance
And anti-flash rusting performance is much higher than traditional technology coating.Meanwhile it can be introduced more under the premise of coating stabilization by emulsion form
More inorganic fillers further promote corrosion resistance so that coating has better barrier action.
4) Treatment of Metal Surface of the present invention is used with aqueous passivating solution and directly carries out emulsion polymerization, and after polymerisation
The method preparation for adding other components can be produced without discharging after emulsion polymerization using single reaction kettle, and first produce coating
With the prior art of lotion reproduction passivating solution compared to a large amount of processes are reduced, reduce coating production and raw material transport at
Originally, the flexibility of resin formula adjustment when and increasing production.
Specific embodiment
Invention is further described in detail With reference to embodiment.
Embodiment 1:
The aqueous passivating solution of a kind of Treatment of Metal Surface, which is characterized in that each raw material and its mass fraction are as follows: acid silicon
3 parts of Sol A KC-30 (solid content 29~31%, 10~20nm of partial size), 0.1 part of acrylic acid, 19 parts of methyl methacrylate, third
18 parts of olefin(e) acid N-butyl, 2.2 parts of hydroxy-ethyl acrylate, 0.4 part of N hydroxymethyl acrylamide, 0.15 part of ammonium persulfate, tert-butyl
0.6 part of hydrogen peroxide (10% aqueous solution), 0.6 part of sodium formaldehyde sulphoxylate (10% aqueous solution), (45% is water-soluble for fluorine zirconic acid
Liquid) 55 parts, 16 parts of 3-aminopropyltriethoxysilane, 3,060 2 parts of wetting agent Genapol ED, defoaming agent SN-
2,000 0.2 parts of Defoamer, 885.75 parts of deionized water.It is a kind of to prepare such Treatment of Metal Surface side of aqueous passivating solution
Method includes the following steps:
(1) in proportion successively by the deionized water, acidic silicasol and acrylic acid, methyl methacrylate, acrylic acid
N-butyl, hydroxy-ethyl acrylate, N hydroxymethyl acrylamide are put into high-pressure emulsification machine, and inorganic particulate is obtained after emulsifying homogeneous
Stable monomer emulsions；
(2) institute that investment step (1) obtains into the reaction kettle with collet water bath device, agitating device and feeding device
Lotion is stated, ammonium persulfate is added, is warming up to 80 DEG C after stirring 10min, maintains constant temperature and stirring 3h；
(3) after constant temperature, with 0.5 hour feed opening difference at the uniform velocity 0.6 part of tert-butyl hydroperoxide of addition from two
10% aqueous solution and 0.6 part of 10% aqueous solution of sodium formaldehyde sulphoxylate；After charging, continue heat preservation 0.5 hour；
(4) keep the temperature after, by slurries be cooled to 40 DEG C hereinafter, and by metering than investment fluorine zirconic acid (45% aqueous solution),
3-aminopropyltriethoxysilane, wetting agent Genapol ED 3060 and defoaming agent SN-Defoamer 2000 stir 0.5h
Afterwards, slurry pH is adjusted between 2~3 with hydrofluoric acid under stiring, with 1000 mesh filter screen filtering and dischargings.
Embodiment 2:
A kind of aqueous passivating solution of Treatment of Metal Surface, each raw material and its mass fraction are as follows: acidic silicasol SW-50
4 parts of (solid content 29~31%, 48~52nm of partial size), 1 part of vinyltrimethoxysilane, 0.15 part of acrylic acid, metering system
6 parts of sour methyl esters, 12 parts of styrene, 18 parts of n-butyl acrylate, 2.2 parts of hydroxy-ethyl acrylate, N hydroxymethyl acrylamide 0.3
Part, 0.18 part of potassium peroxydisulfate；0.6 part of tert-butyl hydroperoxide (10% aqueous solution), (10% is water-soluble for sodium formaldehyde sulphoxylate
Liquid) 0.6 part, 52 parts of fluorine zirconic acid (45% aqueous solution), 17 parts of 3-aminopropyltriethoxysilane, wetting agent Genapol ED
3060 3 parts, 2,000 0.3 parts of defoaming agent SN-Defoamer, 884.67 parts of deionized water.It is a kind of to prepare at such metal surface
The method for managing aqueous passivating solution, includes the following steps:
(1) in proportion successively by the deionized water, acidic silicasol and vinyltrimethoxysilane, acrylic acid, benzene
Ethylene, methyl methacrylate, n-butyl acrylate, hydroxy-ethyl acrylate, N hydroxymethyl acrylamide put into high-pressure emulsification machine
In, the stable monomer emulsions of inorganic particulate are obtained after emulsifying homogeneous；
(2) institute that investment step (1) obtains into the reaction kettle with collet water bath device, agitating device and feeding device
Lotion is stated, potassium peroxydisulfate is added, is warming up to 80 DEG C after stirring 10min, maintains constant temperature and stirring 4h；
(3) after constant temperature, with 0.5 hour feed opening difference at the uniform velocity 0.6 part of tert-butyl hydroperoxide of addition from two
10% aqueous solution and 0.6 part of 10% aqueous solution of sodium formaldehyde sulphoxylate；After charging, continue heat preservation 0.7 hour；
(4) after keeping the temperature, slurries are cooled to 40 DEG C hereinafter, and by metering than investment fluorine zirconic acid, 3- aminopropyl three
Ethoxysilane, wetting agent Genapol ED 3060 and defoaming agent SN-Defoamer 2000, after stirring 0.7h, under stiring
Slurry pH is adjusted between 2~3 with hydrofluoric acid, with 1000 mesh filter screen filtering and dischargings.
Embodiment 3:
A kind of aqueous passivating solution of Treatment of Metal Surface, each raw material and its mass fraction are as follows: acidic silicasol SW-15
(solid content 30%, 14~16nm of partial size): 2.5 parts, 0.1 part of acrylic acid, 21 parts of methyl methacrylate, n-butyl acrylate
19.5 parts, 2.2 parts of hydroxy-ethyl acrylate, 0.4 part of N hydroxymethyl acrylamide, 0.15 part of ammonium persulfate；Tert-butyl hydroperoxide
0.6 part of (10% aqueous solution), 0.6 part of sodium formaldehyde sulphoxylate (10% aqueous solution), 54 parts of fluotitanic acid (45% aqueous solution), 3-
16 parts of aminopropyltriethoxywerene werene, 3,060 2 parts of wetting agent Genapol ED, defoaming agent SN-Defoamer 2,000 0.3
Part, 885.65 parts of deionized water.
A method of the aqueous passivating solution of such Treatment of Metal Surface is prepared, is included the following steps:
(1) in proportion successively by the deionized water, acidic silicasol and acrylic acid, methyl methacrylate, acrylic acid
N-butyl, hydroxy-ethyl acrylate, N hydroxymethyl acrylamide are put into high-pressure emulsification machine, and inorganic particulate is obtained after emulsifying homogeneous
Stable monomer emulsions；
(2) institute that investment step (1) obtains into the reaction kettle with collet water bath device, agitating device and feeding device
Lotion is stated, ammonium persulfate is added, is warming up to 80 DEG C after stirring 10min, maintains constant temperature and stirring 5h；
(3) after constant temperature, with 0.5 hour feed opening difference at the uniform velocity 0.6 part of tert-butyl hydroperoxide of addition from two
10% aqueous solution and 0.6 part of 10% aqueous solution of sodium formaldehyde sulphoxylate；After charging, continue heat preservation 1 hour；
(4) after keeping the temperature, slurries are cooled to 40 DEG C hereinafter, and by metering than investment fluorine zirconic acid, 3- aminopropyl three
Ethoxysilane, wetting agent Genapol ED 3060 and defoaming agent SN-Defoamer 2000, stir 1h after, under stiring with
Hydrofluoric acid adjusts slurry pH between 2~3, with 1000 mesh filter screen filtering and dischargings.
Claims (9)
1. a kind of aqueous passivating solution of Treatment of Metal Surface, which is characterized in that each raw material and its mass fraction are as follows: acid silicon is molten
2.5-4 parts of glue, 0-1 parts of vinyltrimethoxysilane, 0.1 part of acrylic acid, 0-12 parts of styrene, methyl methacrylate 6-21
Part, 18-19.5 parts of n-butyl acrylate, 2.2 parts of hydroxy-ethyl acrylate, 0.3-0.4 parts of N hydroxymethyl acrylamide, initiator
0.15-0.18 parts, rear 0.6 part of initiator of elimination, rear elimination 0.6 part of coinitiator, 52-55 parts of transition metal fluoric-containing acid, silane
16 parts of coupling agent, 2-3 parts of wetting agent, 0.2-0.3 parts of defoaming agent, surplus is deionized water, amounts to 1000 parts.
2. a kind of aqueous passivating solution of Treatment of Metal Surface according to claim 1, which is characterized in that the acidity silicon is molten
Glue is stable under acidic environment, the aqueous dispersions of the surface modified silicon dioxide nanoparticle between 5~30nm of partial size, and
Solid content is between 15~50%.
3. a kind of aqueous passivating solution of Treatment of Metal Surface according to claim 1, which is characterized in that the initiator is
Selected from one of water-soluble free radicals initiator such as hydrogen peroxide, persulfate, hydroperoxides or a variety of.
4. a kind of aqueous passivating solution of Treatment of Metal Surface according to claim 1, which is characterized in that eliminate and draw after described
Hair agent is tert-butyl hydroperoxide (10% aqueous solution)；It is sodium formaldehyde sulphoxylate (10% water that coinitiator is eliminated after described
Solution).
5. a kind of aqueous passivating solution of Treatment of Metal Surface according to claim 1, which is characterized in that the transition metal
Fluoric-containing acid include fluotitanic acid, fluorine zirconic acid, fluorine hafnium acid it is one or more.
6. a kind of aqueous passivating solution of Treatment of Metal Surface according to claim 1, which is characterized in that described silane coupled
Agent is 3-aminopropyltriethoxysilane.
7. the aqueous passivating solution of Treatment of Metal Surface according to claim 1, it is characterised in that: the defoaming agent is commodity
The product of entitled SN-Defoamer 2000.
8. the aqueous passivating solution of Treatment of Metal Surface according to claim 1, it is characterised in that: the wetting agent is commodity
The product of entitled Genapol ED 3060.
9. a kind of prepare the Treatment of Metal Surface according to claims 1-8 method of aqueous passivating solution, which is characterized in that packet
Include following steps:
(1) in proportion successively by the deionized water, acidic silicasol and vinyltrimethoxysilane, acrylic acid, methyl-prop
E pioic acid methyl ester, n-butyl acrylate, hydroxy-ethyl acrylate, N hydroxymethyl acrylamide are put into high-pressure emulsification machine, equal through emulsifying
The stable monomer emulsions of inorganic particulate are obtained after matter；
(2) cream that investment step (1) obtains into the reaction kettle with collet water bath device, agitating device and feeding device
Liquid adds the initiator, is warming up to 80~85 DEG C after stirring 10min, maintains 3~5h of constant temperature and stirring；
(3) after constant temperature, initiator and the total initiation of rear elimination were eliminated after the at the uniform velocity addition of feed opening difference from two with 0.5 hour
Agent；After charging, continue heat preservation 0.5~1 hour；
(4) after keeping the temperature, slurries are cooled to 40 DEG C hereinafter, and by metering than putting into the fluoric-containing acid, silane coupling agent, profit
Humectant and defoaming agent, after stirring 0.5~1h, after, slurry pH is adjusted between 2~3 with hydrofluoric acid under stiring, with 1000 mesh
Strainer filtering discharging.
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| CN201810842755.4A CN109112512A (en) | 2018-07-27 | 2018-07-27 | A kind of Treatment of Metal Surface aqueous passivating solution and preparation method thereof |
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| CN201810842755.4A CN109112512A (en) | 2018-07-27 | 2018-07-27 | A kind of Treatment of Metal Surface aqueous passivating solution and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009102363A2 (en) * | 2007-11-15 | 2009-08-20 | Stc.Unm | Ultra-thin microporous/hybrid materials |
| CN101429661B (en) * | 2008-12-05 | 2010-06-09 | 常熟华冶薄板有限公司 | Molybdate passivating liquid for continuous hot-dipping galvanizing steel plate |
| CN102586768A (en) * | 2011-01-10 | 2012-07-18 | 中国石油化工股份有限公司 | Zinc layer surface passivating treatment liquid |
| CN104561970A (en) * | 2014-12-31 | 2015-04-29 | 苏州禾川化学技术服务有限公司 | Corrosion-resistant magnesium aluminum alloy chromium-free passivation solution |
| CN106835107A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of antimicrobial form organic-inorganic environmental protection composite passivation film |
-
2018
- 2018-07-27 CN CN201810842755.4A patent/CN109112512A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009102363A2 (en) * | 2007-11-15 | 2009-08-20 | Stc.Unm | Ultra-thin microporous/hybrid materials |
| CN101429661B (en) * | 2008-12-05 | 2010-06-09 | 常熟华冶薄板有限公司 | Molybdate passivating liquid for continuous hot-dipping galvanizing steel plate |
| CN102586768A (en) * | 2011-01-10 | 2012-07-18 | 中国石油化工股份有限公司 | Zinc layer surface passivating treatment liquid |
| CN104561970A (en) * | 2014-12-31 | 2015-04-29 | 苏州禾川化学技术服务有限公司 | Corrosion-resistant magnesium aluminum alloy chromium-free passivation solution |
| CN106835107A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of antimicrobial form organic-inorganic environmental protection composite passivation film |
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