CN106835108A - A kind of environmentally friendly inorganic organic passivation film of modified graphene oxide - Google Patents
A kind of environmentally friendly inorganic organic passivation film of modified graphene oxide Download PDFInfo
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- CN106835108A CN106835108A CN201611251987.XA CN201611251987A CN106835108A CN 106835108 A CN106835108 A CN 106835108A CN 201611251987 A CN201611251987 A CN 201611251987A CN 106835108 A CN106835108 A CN 106835108A
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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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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- 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
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- 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
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- 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
The invention discloses a kind of environmentally friendly inorganic organic passivation film of modified graphene oxide, it is made up of the raw material of following weight portion:Dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate, silane coupler KH560, azodiisobutyronitrile, silane coupler KH570, silane coupler KH858 are appropriate, graphene oxide, dimethyl diallyl ammonium chloride, lanthanum citrate, Ludox, polyethylene glycol, nickel nitrate, zinc nitrate, phytic acid, sodium gluconate, water soluble acrylic resin, appropriate ethylene glycol, appropriate absolute ethyl alcohol, appropriate tetrahydrofuran, appropriate sulfuric acid, appropriate nitric acid, appropriate deionized water;Extensively, preparation method is simple, and passivation time is short, and the passivating film adhesive force of formation is good, and salt resistance, alkali resistance are good, and corrosion resistance is high, can effectively slow down corrosion process for passivating solution raw material sources prepared by the present invention, is adapted to industrialized production.
Description
Technical field
The present invention relates to technical field of chrome-free passivation, more particularly to a kind of modified graphene oxide is environmentally friendly inorganic has
Machine passivating 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 graphene oxide is environmentally friendly
Inorganic organic passivation film.
The present invention is achieved by the following technical solutions:
A kind of environmentally friendly inorganic organic passivation film of modified graphene oxide, is made up of the raw material of following weight portion:First
Base dodecafluorhe-ptylacrylate 4-4.6, Hexafluorobutyl mathacrylate 5.2-5.6, silane coupler KH560 16-18, azo
Bis-isobutyronitrile 0.2-0.3, silane coupler KH570 90-100, silane coupler KH858 are appropriate, graphene oxide 2.2-2.5,
Dimethyl diallyl ammonium chloride 0.7-0.9, lanthanum citrate 1.3-1.6, Ludox 10-12, polyethylene glycol 4.4-4.8, nitric acid
Nickel 33-35, zinc nitrate 8-11, phytic acid 17-19, sodium gluconate 6-8, water soluble acrylic resin 26-28, appropriate ethylene glycol,
Appropriate absolute ethyl alcohol, appropriate tetrahydrofuran, appropriate sulfuric acid, appropriate nitric acid, appropriate deionized water.
The environmentally friendly inorganic organic passivation film of a kind of modified graphene oxide, is prepared by following specific steps and made
Into:
(1)Graphene oxide is added to 300-400 mesh sieves was crushed in high speed Universal pulverizer, by the concentrated sulfuric acid and concentrated nitric acid according to
Volume ratio 3:1 is mixed and made into oxidizing agent solution, graphene oxide micro mist is added in the 4-5 times of oxidizing agent solution measured, in room temperature
Under with the rotating speed ultrasonic vibration 40-50min of 300-400r/min, filtering is washed with deionized and is dried in after neutrality, by diformazan
Base diallyl ammonium chloride is added in the 4-5 times of deionized water measured, and lanthanum citrate is added after stirring and dissolving, is then transferred to vacuum
In bottle,suction, above-mentioned dry graphene oxide is added at room temperature, protected under the vacuum of -0.1MPa after magnetic agitation is uniform
15-20min is held, vavuum pump is closed, 5min is maintained, this process is then repeated 2-3 times, centrifugation, solid is anti-with deionized water
It is multiple to rinse, it is standby after drying;
(2)Ludox deionized water is diluted to the water silica sol that silica solid content is 30%, pH value is adjusted to 3-4,
The 2-3 times of ethylene glycol measured is subsequently adding in vacuum distillation at 80 DEG C, moisture is controlled for 1.5-2%, it is 50-55 to control temperature
DEG C when add polyethylene glycol, add step after magnetic agitation 0.5h(1)The product reflux reaction 2-3h of preparation, reaction terminates rear cold
But to 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)Nickel nitrate dissolving is made the solution that concentration is 30g/L in deionized water, zinc nitrate, phytic acid and grape is added
Sodium saccharate obtains inorganic salts passivating solution;By silane coupler KH570 and silane coupler KH858 according to mass ratio 2:1 is answered
Close, then dissolve in 75% absolute ethyl alcohol, be made the solution of silane that total concentration is 150g/L, dilute nitre is used after standing reaction 2-3h
Acid solution adjusts pH to 4-5, obtains 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 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, also carries out oxidation increasing specific surface area by graphene oxide, will
Lanthanum citrate is loaded in graphene oxide, is improved its sterilization, corrosion resistant, salt resistance, alkali resistant and is promoted the performance of the aspects such as film forming, and
And suppress the reunion of particle in Ludox to silica sol modified using hydrophilic polyethylene glycol, and make its good dispersion, improve blunt
Change stability, the transparency, hardness, wear-resistant and salt spray resistance the performance of film, passivating solution raw material sources prepared by the present invention are extensive,
Preparation method is simple, and passivation time is short, and the passivating film adhesive force of formation is good, and salt resistance, alkali resistance are good, and corrosion resistance is high, can be effective
Slow down corrosion process, be adapted to industrialized production.
Specific embodiment
A kind of environmentally friendly inorganic organic passivation film of modified graphene oxide, by following weight portion(Kilogram)Raw material system
Prepare into:Dodecafluoroheptyl methacrylate 4, Hexafluorobutyl mathacrylate 5.2, silane coupler KH560 16, azo two
Isobutyronitrile 0.2, silane coupler KH570 90, silane coupler KH858 are appropriate, graphene oxide 2.2, dimethyl diallyl
Ammonium chloride 0.7, lanthanum citrate 1.3, Ludox 10, polyethylene glycol 4.4, nickel nitrate 33, zinc nitrate 8, phytic acid 17, sodium gluconate
6th, water soluble acrylic resin 26, appropriate ethylene glycol, appropriate absolute ethyl alcohol, appropriate tetrahydrofuran, appropriate sulfuric acid, appropriate nitric acid,
Appropriate deionized water.
The environmentally friendly inorganic organic passivation film of a kind of modified graphene oxide, is prepared by following specific steps and made
Into:
(1)Graphene oxide is added to 300 mesh sieves were crushed in high speed Universal pulverizer, by the concentrated sulfuric acid and concentrated nitric acid according to volume
Than 3:1 is mixed and made into oxidizing agent solution, by graphene oxide micro mist be added to 4 times amount oxidizing agent solutions in, at room temperature with
The rotating speed ultrasonic vibration 40min of 300r/min, filtering is washed with deionized and is dried in after neutrality, by dimethyl diallyl
Ammonium chloride is added in 4 times of deionized waters of amount, and lanthanum citrate is added after stirring and dissolving, is then transferred in vacuum filtration bottle,
Above-mentioned dry graphene oxide is added at room temperature, 15min is kept after magnetic agitation is uniform under the vacuum of MPa, is closed true
Empty pump, maintains 5min, then repeats this process 2 times, and centrifugation, solid deionized water is rinsed repeatedly, standby after drying;
(2)Ludox deionized water is diluted to the water silica sol that silica solid content is 30%, pH value to 3 is adjusted, so
Add 2 times of ethylene glycol of amount in vacuum distillation at 80 DEG C afterwards, control moisture for 1.5%, addition gathers when control temperature be 50 DEG C
Ethylene glycol, step is added after magnetic agitation 0.5h(1)The product reflux reaction 2h of preparation, reaction is cooled to room temperature after terminating;
(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)Nickel nitrate dissolving is made the solution that concentration is 30g/L in deionized water, zinc nitrate, phytic acid and grape is added
Sodium saccharate obtains inorganic salts passivating solution;By silane coupler KH570 and silane coupler KH858 according to mass ratio 2:1 is answered
Close, then dissolve in 75% absolute ethyl alcohol, be made the solution of silane that total concentration is 150g/L, dust technology is used after standing reaction 2h
Solution adjusts pH to 4, obtains 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. the environmentally friendly inorganic organic passivation film of a kind of modified graphene oxide, it is characterised in that by the original of following weight portion
Material preparation is made: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, oxygen
Graphite alkene 2.2-2.5, dimethyl diallyl ammonium chloride 0.7-0.9, lanthanum citrate 1.3-1.6, Ludox 10-12, poly- second
Glycol 4.4-4.8, nickel nitrate 33-35, zinc nitrate 8-11, phytic acid 17-19, sodium gluconate 6-8, water soluble acrylic resin
26-28, appropriate ethylene glycol, appropriate absolute ethyl alcohol, appropriate tetrahydrofuran, appropriate sulfuric acid, appropriate nitric acid, appropriate deionized water.
2. the environmentally friendly inorganic organic passivation film of a kind of modified graphene oxide according to claim 1, it is characterised in that
It is made up of following specific steps:
(1)Graphene oxide is added to 300-400 mesh sieves was crushed in high speed Universal pulverizer, by the concentrated sulfuric acid and concentrated nitric acid according to
Volume ratio 3:1 is mixed and made into oxidizing agent solution, graphene oxide micro mist is added in the 4-5 times of oxidizing agent solution measured, in room temperature
Under with the rotating speed ultrasonic vibration 40-50min of 300-400r/min, filtering is washed with deionized and is dried in after neutrality, by diformazan
Base diallyl ammonium chloride is added in the 4-5 times of deionized water measured, and lanthanum citrate is added after stirring and dissolving, is then transferred to vacuum
In bottle,suction, above-mentioned dry graphene oxide is added at room temperature, protected under the vacuum of -0.1MPa after magnetic agitation is uniform
15-20min is held, vavuum pump is closed, 5min is maintained, this process is then repeated 2-3 times, centrifugation, solid is anti-with deionized water
It is multiple to rinse, it is standby after drying;
(2)Ludox deionized water is diluted to the water silica sol that silica solid content is 30%, pH value is adjusted to 3-4,
The 2-3 times of ethylene glycol measured is subsequently adding in vacuum distillation at 80 DEG C, moisture is controlled for 1.5-2%, it is 50-55 to control temperature
DEG C when add polyethylene glycol, add step after magnetic agitation 0.5h(1)The product reflux reaction 2-3h of preparation, reaction terminates rear cold
But to 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)Nickel nitrate dissolving is made the solution that concentration is 30g/L in deionized water, zinc nitrate, phytic acid and grape is added
Sodium saccharate obtains inorganic salts passivating solution;By silane coupler KH570 and silane coupler KH858 according to mass ratio 2:1 is answered
Close, then dissolve in 75% absolute ethyl alcohol, be made the solution of silane that total concentration is 150g/L, dilute nitre is used after standing reaction 2-3h
Acid solution adjusts pH to 4-5, obtains 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 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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Cited By (7)
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CN111005013A (en) * | 2019-12-23 | 2020-04-14 | 三达奥克化学股份有限公司 | Steel-aluminum universal environment-friendly rare earth metal chemical conversion film treating agent |
CN111455363A (en) * | 2020-04-07 | 2020-07-28 | 西安石油大学 | Passivation solution and preparation method and application thereof |
CN112030152A (en) * | 2020-08-26 | 2020-12-04 | 彭明喜 | Chromium-free passivation method for surface of galvanized layer |
CN112126880A (en) * | 2020-08-28 | 2020-12-25 | 余姚市永林机械科技有限公司 | High-corrosion-resistance hot-dip galvanized steel plate and preparation method thereof |
CN113045320A (en) * | 2021-03-04 | 2021-06-29 | 杭州安誉科技有限公司 | High-heat-dissipation metal substrate for LED and preparation method thereof |
CN115198259A (en) * | 2022-07-21 | 2022-10-18 | 深圳市钝化技术有限公司 | Passivating solution for stainless steel and preparation method thereof |
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CN111005013A (en) * | 2019-12-23 | 2020-04-14 | 三达奥克化学股份有限公司 | Steel-aluminum universal environment-friendly rare earth metal chemical conversion film treating agent |
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CN112030152A (en) * | 2020-08-26 | 2020-12-04 | 彭明喜 | Chromium-free passivation method for surface of galvanized layer |
CN112126880A (en) * | 2020-08-28 | 2020-12-25 | 余姚市永林机械科技有限公司 | High-corrosion-resistance hot-dip galvanized steel plate and preparation method thereof |
CN113045320A (en) * | 2021-03-04 | 2021-06-29 | 杭州安誉科技有限公司 | High-heat-dissipation metal substrate for LED and preparation method thereof |
CN113045320B (en) * | 2021-03-04 | 2022-08-09 | 杭州安誉科技有限公司 | High-heat-dissipation metal substrate for LED and preparation method thereof |
CN115198259A (en) * | 2022-07-21 | 2022-10-18 | 深圳市钝化技术有限公司 | Passivating solution for stainless steel and preparation method thereof |
CN115198259B (en) * | 2022-07-21 | 2023-09-15 | 深圳市钝化技术有限公司 | Passivation solution for stainless steel and preparation method thereof |
CN115821134A (en) * | 2022-12-01 | 2023-03-21 | 凤阳爱尔思轻合金精密成型有限公司 | Corrosion-resistant aluminum magnesium alloy manufacturing process |
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Application publication date: 20170613 |