CN106835101A - A kind of modified Nano titanium compound is combined super-hydrophobic passivating film - Google Patents
A kind of modified Nano titanium compound is combined super-hydrophobic passivating film Download PDFInfo
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- CN106835101A CN106835101A CN201611251848.7A CN201611251848A CN106835101A CN 106835101 A CN106835101 A CN 106835101A CN 201611251848 A CN201611251848 A CN 201611251848A CN 106835101 A CN106835101 A CN 106835101A
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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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Abstract
Super-hydrophobic passivating film is combined the invention discloses a kind of modified Nano titanium compound, is made up of following raw materials according：Dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate, silane coupler KH560, azodiisobutyronitrile, silane coupler KH570, silane coupler KH858 is appropriate, the tert-butyl alcohol, titanium dioxide, calgon, DBSA, Silane coupling agent KH550, tetraethyl orthosilicate, fluorine zirconic acid, sodium metasilicate, water soluble acrylic resin, acetic acid, isopropanol, sodium tungstate, appropriate phenyltrimethoxysila,e, silane coupler a171 is appropriate, appropriate DAA, appropriate absolute ethyl alcohol, appropriate tetrahydrofuran, appropriate dust technology, appropriate deionized water；Passivating solution green safety prepared by the present invention, low cost can form fine and close passivating film, the reprocessing in later stage, wearability, inoxidizability and heat resistance not influenceed in zinc-plated broadband plate surface, and can significantly slow corrosivity, increase the service life.
Description
Technical field
Super-hydrophobic passivation is combined the present invention relates to technical field of chrome-free passivation, more particularly to a kind of modified Nano titanium compound
Film.
Background technology
Zinc-plated broadband steel plate refers to that surface is coated with one layer of steel plate of zinc, and zinc-plated corroded to prevent surface of steel plate from producing,
Extending steel plate service life, zinc-plated broadband steel plate is increasingly close with the life of people, is mainly used in appliance plate, phone housing, builds
Build with Coil Coating Products and automobile stool.Because zinc is very active, acid, alkali, oxygen, carbon dioxide and vapor etc. are vulnerable in an atmosphere
The corrosion of material, it is therefore desirable to treatment is passivated to it, galvanized sheet conventional passivation mode is generally used and contains the blunt of chromate
Change liquid, the method has the advantages that the chromium ion pair contained in excellent filming performance, low cost and process is simple, but chromate
Human body has carcinogenicity, while also producing greatly harm to environment.The expert and scholars of surface treatment are currently undertaken by nothing
The preparation of chromium passivating liquid and its performance study of non-chromium inactivating technique make some progress, and are concentrated mainly on inorganic component blunt
Change, organic matter passivation and Inorganic whisker are passivated, these emerging passivation products substantially meet chromium-free deactivation requirement, and performance has connect
It is near or reach chromating level.
But further research is stilled need in some aspects, to overcome inorganic component to be passivated the corrosion resistance for producing and having unit
Divide the problem of passivation adhesion property difference, Zhang Zhen sea exists《Zinc-plated wide flat steel is inorganic/preparation of organic composite passivating solution and corrosion resistance
Energy》It is main in one text to be compounded using organosilan and inorganic inhibitor, by the consumption and the reaction that adjust each material
Ratio, studies the performance applicable cases extremely in the industrial production of passivating solution.It is anti-according to organosilan hydrolyzed under acidic conditions
Principle is answered, is hydrolyzed reaction using silane coupler KH560 and silane coupler KH602, add a certain amount of inorganic inhibition
Agent sodium vanadate and titanium sulfate, scale up test go out chromium-free deactivation product, and coating film forming is tested its passivating film, the resistance to electricity of film layer
Chemical property is good, and the area that white rust occur in 72H neutral salt spray tests is only 4-6%, and the accessible chromate of its corrosion resisting property is blunt
Change film, adhesive force reaches 1 grade, surface texture even compact；Product is passivated for resistance and fingerprint resistance, sodium molybdate is dissolved in water, used
To neutrality, a certain amount of modified manometer silicon dioxide of nature's mystery is configured to inorganic passivating solution, silane coupler to organic acid for adjusting pH
KH570 and silane coupler KH858 are re-dubbed organic-silylation passivating solution, and two kinds of passivating solutions are further compounded, and obtain molybdic acid
The organosilane passivating liquid of salt, film performance is excellent.The chromium-free passivation liquid that the author provides can fundamentally solve existing passivation
The problem that poisonous and harmful chromium ion is poisoned to people in liquid, it is also possible to real to substitute liquid containing chromium passivating, realizes to electrogalvanizing broadband
The degree of steel plate, but the plating film that the chromium-free passivation liquid is formed is in the performance such as low friction, antioxygen, corrosion-resistant, self-lubricating, wear-resisting
On can not still meet the market demand, need to further be modified raising application field, expand application prospect.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of modified Nano titanium compound is combined super-hydrophobic
Passivating film.
The present invention is achieved by the following technical solutions：
A kind of modified Nano titanium compound is combined super-hydrophobic passivating film, is made up of the raw material of following weight portion：Methacrylic acid
Ten difluoro heptyl ester 4-4.6, Hexafluorobutyl mathacrylate 5.2-5.6, silane coupler KH560 16-18, azodiisobutyronitrile
0.2-0.3, silane coupler KH570 90-100, silane coupler KH858 are appropriate, tert-butyl alcohol 40-47, titanium dioxide 4.4-
4.7th, calgon 0.4-0.6, DBSA 1.5-1.8, Silane coupling agent KH550 2.5-2.8, positive silicic acid second
Ester 16-19, fluorine zirconic acid 22-24, sodium metasilicate 16-20, water soluble acrylic resin 26-28, acetic acid 3-5, isopropanol 11-14, tungsten
Sour sodium 12-14, appropriate phenyltrimethoxysila,e, silane coupler a171 appropriate, appropriate DAA, appropriate absolute ethyl alcohol,
Appropriate tetrahydrofuran, appropriate dust technology, appropriate deionized water.
A kind of modified Nano titanium compound is combined super-hydrophobic passivating film, is made up of following specific steps：
（1）By the tert-butyl alcohol and deionized water according to mass ratio 2:1 mixing, ultrasound is divided during titanium dioxide is added into above-mentioned mixed solution
Dissipate mass fraction be 5% dispersion liquid, be then transferred in oil bath pan, heating rise high-temperature to 120 DEG C of condensing refluxes, while stirring
Mix side and add calgon and DBSA, Silane coupling agent KH550, regulation system pH are added after reaction 0.6-1h
Value is placed in ultrasonator after shaking 2-3h after stirring 1-2h and obtains nano titanium oxide dispersion to 5；
(2) by tetraethyl orthosilicate, phenyltrimethoxysila,e, silane coupler a171, DAA and ethanol according to mass ratio
2.41:1.47:1:0.24:5.06 mixing, are stirring evenly and then adding into acetic acid and deionized water, and 3- is reacted at 50 DEG C of bath temperature
4h, reaction adds step after terminating（1）The product and isopropanol of preparation, continue to react 3-4h, are cooled to standby after room temperature；
（3）Dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate and silane coupler KH560 are mixed and is added to 15-
In 17 times of tetrahydrofurans of amount, stirring adds azodiisobutyronitrile to after being completely dissolved, and is stirred with the rotating speed of 300-400r/min,
Then high-temperature to 65 DEG C is risen, isothermal reaction 8-10h, reaction is cooled to room temperature and obtains fluorine containing silane polymer solution after terminating；
（4）Fluorine zirconic acid dissolving is made the solution that concentration is 20g/L in deionized water, sodium metasilicate is added and sodium tungstate is obtained
Inorganic salts passivating solution；By silane coupler KH570 and silane coupler KH858 according to mass ratio 2:1 is combined, and is then dissolved
In 75% absolute ethyl alcohol, the solution of silane that total concentration is 150g/L is made, pH is adjusted with dilute nitric acid solution after standing reaction 2-3h
To 4-5, organosilan composite passivation solution is obtained；
（5）By step（4）Inorganic salts passivating solution and organosilan the composite passivation solution mixing of preparation, after stirring at normal temperatures
Water soluble acrylic resin, step are added while stirring（2）And step（3）The product of preparation, obtains compound blunt after stirring 5-6h
Change liquid, galvanized sheet is put into normal temperature dip-coating 30S in passivating solution, drying temperature is 100-120 DEG C, drying time 60S, natural conditions
Lower cooling obtains final product passivating film.
It is an advantage of the invention that：Traditional passivating method uses the passivating solution containing Cr VI, and the passivating film for obtaining is anti-corrosion
Property is good, and consuming cost is low, but causes serious harm to human body and environment in actual industrial production, because silane has nothing
Malicious, tasteless, corrosion resistance and good and facile hydrolysis and the advantages of substrate surface film forming, inorganic-organic hybrid passivation is in recent years
Replace the main direction of studying of chromium-free deactivation, the present invention is using silane coupler KH570 and silane coupler KH858 in faintly acid
Under the conditions of hydrolyze to form organosilane passivating liquid, then be aided with inorganic component and form inorganic-organic silane composite passivation solution, be to improve
The performance such as the extreme pressure wear of passivating film, corrosion-resistant, heat-resisting, self-lubricating, the present invention is fluorine-containing using the synthesis of free radical solution polymerization method
Silane polymer solution, it has fluoro-containing group, can drop low-surface-energy, and silane group is contained again, and silane group can be hydrolyzed
Into hydroxyl, can covalently be combined with substrate surface, be promoted film forming, and with bond strength very high, be improved
Adhesive force, the advantages of form good hydrophobicity, high-fire resistance, contains numerous polar groups in Ludox, can strengthen film layer
With intermetallic adhesion, the both-end base silane structure contained in molecule can increase the compactness of film layer, of the invention by dioxy
Change titanium prepared composition dispersion liquid, it is then modified to it using silane coupler kh560, make its surface grafting silicone hydroxyl group, and
It is introduced into Ludox, titanyl key is introduced in the network structure of silica silicon, improves pliability, the heat resistance of Ludox
And corrosion resistance, the compactness of passivating film is improve, make that its is not easy to break, do not crack, lasting erosion-resisting performance is reached,
Passivating solution green safety prepared by the present invention, extensively, cost is relatively low for raw material sources, can be formed in zinc-plated broadband plate surface and caused
Close passivating film, the reprocessing in later stage, wearability, inoxidizability and heat resistance are not influenceed, and can significantly slow corrosivity, are prolonged
Long life.
Specific embodiment
A kind of modified Nano titanium compound is combined super-hydrophobic passivating film, is made up of the raw material of following weight portion：Methyl-prop
The difluoro heptyl ester 4 of olefin(e) acid ten, Hexafluorobutyl mathacrylate 5.2, silane coupler KH560 16, azodiisobutyronitrile 0.2, silane
Coupling agent KH570 90, silane coupler KH858 are appropriate, the tert-butyl alcohol 40, titanium dioxide 4.4, calgon 0.4, dodecane
Base benzene sulfonic acid 1.5, Silane coupling agent KH550 2.5, tetraethyl orthosilicate 16, fluorine zirconic acid 22, sodium metasilicate 16, water-soluble acrylic tree
Fat 26, acetic acid 3, isopropanol 11, sodium tungstate 12, appropriate phenyltrimethoxysila,e, silane coupler a171 are appropriate, DAA
In right amount, appropriate absolute ethyl alcohol, appropriate tetrahydrofuran, appropriate dust technology, appropriate deionized water.
A kind of modified Nano titanium compound is combined super-hydrophobic passivating film, is made up of following specific steps：
（1）By the tert-butyl alcohol and deionized water according to mass ratio 2:1 mixing, ultrasound is divided during titanium dioxide is added into above-mentioned mixed solution
Dissipate mass fraction be 5% dispersion liquid, be then transferred in oil bath pan, heating rise high-temperature to 120 DEG C of condensing refluxes, while stirring
Mix side and add calgon and DBSA, Silane coupling agent KH550, regulation system pH value are added after reaction 0.6h
To 5, it is placed in after stirring 1h in ultrasonator after shaking 2h and obtains nano titanium oxide dispersion；
(2) by tetraethyl orthosilicate, phenyltrimethoxysila,e, silane coupler a171, DAA and ethanol according to mass ratio
2.41:1.47:1:0.24:5.06 mixing, are stirring evenly and then adding into acetic acid and deionized water, are reacted at 50 DEG C of bath temperature
3h, reaction adds step after terminating（1）The product and isopropanol of preparation, continue to react 3h, are cooled to standby after room temperature；
（3）Dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate and silane coupler KH560 are mixed and is added to 15 times
In the tetrahydrofuran of amount, stirring adds azodiisobutyronitrile to after being completely dissolved, and is stirred with the rotating speed of 300r/min, then raises
To 65 DEG C, isothermal reaction 8h, reaction is cooled to room temperature and obtains fluorine containing silane polymer solution temperature after terminating；
（4）Fluorine zirconic acid dissolving is made the solution that concentration is 20g/L in deionized water, sodium metasilicate is added and sodium tungstate is obtained
Inorganic salts passivating solution；By silane coupler KH570 and silane coupler KH858 according to mass ratio 2:1 is combined, and is then dissolved
In 75% absolute ethyl alcohol, be made total concentration be 150g/L solution of silane, stand reaction 2h after with dilute nitric acid solution adjust pH to
4, obtain organosilan composite passivation solution；
（5）By step（4）Inorganic salts passivating solution and organosilan the composite passivation solution mixing of preparation, after stirring at normal temperatures
Water soluble acrylic resin, step are added while stirring（2）And step（3）The product of preparation, obtains composite passivated after stirring 5h
Liquid, normal temperature dip-coating 30S in passivating solution is put into by galvanized sheet, and drying temperature is 100 DEG C, and drying time 60S is cooled down under natural conditions
Obtain final product passivating film.
The method provided according to embodiment prepares passivating film, and performance test is carried out to it, as a result as follows：
Adhesion performance：1 grade；Cupric sulphate dropping test：180S；Resistance to neutral salt spray test：168h；5% sodium chloride soak test：
120h；Anti-finger printing：△ E ＜ 2, fingerprint surface is invisible after handling contact.
Claims (2)
1. a kind of modified Nano titanium compound is combined super-hydrophobic passivating film, it is characterised in that prepare system by the raw material of following weight portion
Into：Dodecafluoroheptyl methacrylate 4-4.6, Hexafluorobutyl mathacrylate 5.2-5.6, silane coupler KH560 16-18,
Azodiisobutyronitrile 0.2-0.3, silane coupler KH570 90-100, silane coupler KH858 are appropriate, tert-butyl alcohol 40-47, two
Titanium oxide 4.4-4.7, calgon 0.4-0.6, DBSA 1.5-1.8, Silane coupling agent KH550 2.5-
2.8th, tetraethyl orthosilicate 16-19, fluorine zirconic acid 22-24, sodium metasilicate 16-20, water soluble acrylic resin 26-28, acetic acid 3-5, different
Propyl alcohol 11-14, sodium tungstate 12-14, appropriate phenyltrimethoxysila,e, silane coupler a171 appropriate, appropriate DAA, nothing
Appropriate water-ethanol, appropriate tetrahydrofuran, appropriate dust technology, appropriate deionized water.
2. a kind of modified Nano titanium compound is combined super-hydrophobic passivating film according to claim 1, it is characterised in that by following tool
Body step is made：
（1）By the tert-butyl alcohol and deionized water according to mass ratio 2:1 mixing, ultrasound is divided during titanium dioxide is added into above-mentioned mixed solution
Dissipate mass fraction be 5% dispersion liquid, be then transferred in oil bath pan, heating rise high-temperature to 120 DEG C of condensing refluxes, while stirring
Mix side and add calgon and DBSA, Silane coupling agent KH550, regulation system pH are added after reaction 0.6-1h
Value is placed in ultrasonator after shaking 2-3h after stirring 1-2h and obtains nano titanium oxide dispersion to 5；
(2) by tetraethyl orthosilicate, phenyltrimethoxysila,e, silane coupler a171, DAA and ethanol according to mass ratio
2.41:1.47:1:0.24:5.06 mixing, are stirring evenly and then adding into acetic acid and deionized water, and 3- is reacted at 50 DEG C of bath temperature
4h, reaction adds step after terminating（1）The product and isopropanol of preparation, continue to react 3-4h, are cooled to standby after room temperature；
（3）Dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate and silane coupler KH560 are mixed and is added to 15-
In 17 times of tetrahydrofurans of amount, stirring adds azodiisobutyronitrile to after being completely dissolved, and is stirred with the rotating speed of 300-400r/min,
Then high-temperature to 65 DEG C is risen, isothermal reaction 8-10h, reaction is cooled to room temperature and obtains fluorine containing silane polymer solution after terminating；
（4）Fluorine zirconic acid dissolving is made the solution that concentration is 20g/L in deionized water, sodium metasilicate is added and sodium tungstate is obtained
Inorganic salts passivating solution；By silane coupler KH570 and silane coupler KH858 according to mass ratio 2:1 is combined, and is then dissolved
In 75% absolute ethyl alcohol, the solution of silane that total concentration is 150g/L is made, pH is adjusted with dilute nitric acid solution after standing reaction 2-3h
To 4-5, organosilan composite passivation solution is obtained；
（5）By step（4）Inorganic salts passivating solution and organosilan the composite passivation solution mixing of preparation, after stirring at normal temperatures
Water soluble acrylic resin, step are added while stirring（2）And step（3）The product of preparation, obtains compound blunt after stirring 5-6h
Change liquid, galvanized sheet is put into normal temperature dip-coating 30S in passivating solution, drying temperature is 100-120 DEG C, drying time 60S, natural conditions
Lower cooling obtains final product passivating film.
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| CN201611251848.7A CN106835101A (en) | 2016-12-30 | 2016-12-30 | A kind of modified Nano titanium compound is combined super-hydrophobic passivating film |
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| CN201611251848.7A CN106835101A (en) | 2016-12-30 | 2016-12-30 | A kind of modified Nano titanium compound is combined super-hydrophobic passivating film |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108049160A (en) * | 2017-12-23 | 2018-05-18 | 芜湖皖江知识产权运营中心有限公司 | A kind of high-hardness water-proof carbon fibre composite and preparation method thereof |
| CN109884681A (en) * | 2019-03-06 | 2019-06-14 | 深圳市源兴医药股份有限公司 | A kind of irradiation instruction film and preparation method thereof |
| CN110424037A (en) * | 2019-08-30 | 2019-11-08 | 北京石墨烯技术研究院有限公司 | Metal super-hydrophobic surface processing method and product |
| CN115537061A (en) * | 2022-09-23 | 2022-12-30 | 四川宏凯化工科技有限公司 | Water-based paint odor scavenger and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885611A (en) * | 2016-06-08 | 2016-08-24 | 合肥和安机械制造有限公司 | Polymer metallic copper anticorrosive coating and preparation method thereof |
-
2016
- 2016-12-30 CN CN201611251848.7A patent/CN106835101A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885611A (en) * | 2016-06-08 | 2016-08-24 | 合肥和安机械制造有限公司 | Polymer metallic copper anticorrosive coating and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108049160A (en) * | 2017-12-23 | 2018-05-18 | 芜湖皖江知识产权运营中心有限公司 | A kind of high-hardness water-proof carbon fibre composite and preparation method thereof |
| CN109884681A (en) * | 2019-03-06 | 2019-06-14 | 深圳市源兴医药股份有限公司 | A kind of irradiation instruction film and preparation method thereof |
| CN109884681B (en) * | 2019-03-06 | 2022-12-27 | 深圳市源兴医药股份有限公司 | Irradiation indicating film and preparation method thereof |
| CN110424037A (en) * | 2019-08-30 | 2019-11-08 | 北京石墨烯技术研究院有限公司 | Metal super-hydrophobic surface processing method and product |
| CN110424037B (en) * | 2019-08-30 | 2020-09-11 | 北京石墨烯技术研究院有限公司 | Metal super-hydrophobic surface treatment method and product |
| CN115537061A (en) * | 2022-09-23 | 2022-12-30 | 四川宏凯化工科技有限公司 | Water-based paint odor scavenger and preparation method thereof |
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