CN106702363A - Ceramization agent for electrophoretic coating pretreatment, preparation method and usage method for ceramization agent - Google Patents
Ceramization agent for electrophoretic coating pretreatment, preparation method and usage method for ceramization agent Download PDFInfo
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- CN106702363A CN106702363A CN201611248832.0A CN201611248832A CN106702363A CN 106702363 A CN106702363 A CN 106702363A CN 201611248832 A CN201611248832 A CN 201611248832A CN 106702363 A CN106702363 A CN 106702363A
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- electrophoretic painting
- vitrified
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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
- 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
- C23C22/73—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 characterised by the process
-
- 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)
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention method provides a ceramization agent for electrophoretic coating pretreatment, a preparation method and a usage method for the ceramization agent. Compared with the prior art, fluorine ions slightly dissolve the surfaces of steel and a zinc substrate first, and meanwhile, the fluorine ions and zirconium/titanium ions form a compact conversion film layer on the dissolved metal surface; and a silane coupling agent and a cross-linking agent in colloid achieve the synergistic effect, and meanwhile, a rare earth promoter in a solution also plays a role. An organic-inorganic hybrid film is formed on the metal surface, and the corrosion resistance of the conversion film as well as the adhesive force of the conversion film and electrophoretic paint are far superior to that of ternary phosphating films and common ceramization films.
Description
Technical field
The invention belongs to metal surface treatment technology, and in particular to a kind of electrophoretic painting pre-treatment vitrified agent, preparation side
Method and its application method, it is adaptable to vehicle complete vehicle, auto parts machinery product pretreatment process for electrophoresis coating, make electrophoretic paint and Metal Substrate
Body is combined closely.
Background technology
At present, the metal conditioner technology for substituting Phosphating Solution is increasingly mature in household electrical appliances sector application, and shows
Diversified trend, wherein accounting for leading with the vitrified agent that zirconates or zirconates and silane are compounded, not only corrosion resistance is poor for single zirconium film,
Also it is more crisp, and the adhesion of electrophoresis organic coating is poor.
Silane is referred to as industrial monosodium glutamate, using quite varied.Silane contains two kinds of different chemical functional groups, and one end can be with nothing
The hydroxyl reaction generation covalent bond on machine material (such as glass fibre, silicate, metal and its oxide) surface；The other end can be with tree
Fat generates covalent bond, so that two kinds of very big materials of nature difference combine, plays a part of to improve composite property.
Application of the technology in terms of surface treatment is most environmentally friendly, and development prospect is best.But single silane finish is before metal surface
Application also development in terms for the treatment of.
Although vitrified agent is generally accepted in household electric appliances, it is not widely used also in other industry, its is main
Reason is the adhesion that the film layer and organic coating to be formed is compounded using zirconates and silane coupler, is only showed on part coatings
Preferably, silane coupler is adapted to the limitednumber of coating, largely limits its use scope.
The content of the invention
It is an object of the invention to provide a kind of electrophoretic painting pre-treatment vitrified agent, in hot-rolled and cold-rolled slab, ironcasting etc.
Ferrous metal surface forms one layer of dense uniform, high corrosion-resistant and the fabulous conversion film of coating adhesion, the salt tolerant after electrophoretic painting
The mist time surpasses 1000 hours, more than existing frequently-used zinc, manganese, nickel ternary Phosphating Solution.
It is also an object of the present invention to provide a kind of preparation method of electrophoretic painting pre-treatment vitrified agent.
Another object of the present invention is to provide a kind of application method of electrophoretic painting pre-treatment vitrified agent, user
Just, without heating.
A kind of electrophoretic painting pre-treatment vitrified agent that the present invention is provided, the raw material containing following percentage by weight：
Remaining is water.
The fluoride ion source is sodium fluoride, hydrogen fluoride, fluotitanic acid, ammonium fluozirconate, potassium fluorozirconate, fluorine zirconic acid, fluorine titanium
Sour ammonium, titanium sodium fluoride or potassium fluotitanate；Fluoride ion source consumption is 0.02-10%, preferably 0.2-5%.Less than 0.2% one-tenth
Film speed is slow, becomes uneven higher than 5% film forming and easily returns rust.
The zirconium ion compound is selected from the one kind in fluorine zirconic acid, ammonium fluozirconate, zirconium nitrate, potassium fluorozirconate, sodium fluozirconate
Or two kinds, the consumption of zirconium ion compound is 0.1-15%, preferably 1-5%, slow less than 1% film forming speed, higher than 5% pair into
Film does not have any benefit, can also increase cost.
The titanium ion compound is selected from one kind or two of fluotitanic acid, titanium sodium fluoride, titanium dioxide or titanate coupling agent
Kind；
Described pair of amino silane and titanium coupling agent are combined after hydrolysis and prepare silicon titanium crosslinkers.
The accelerator be rare earth compound in one or more, consumption 0.001-0.05%, preferably
0.002-0.01%.
The complexing agent is carboxylic acid type organic, and consumption is 0.01-0.1%, preferably 0.05-0.08%；
The oxidant be selected from hydrogen peroxide, sodium chlorate or potassium chlorate in one or two, consumption is 0.1-0.5%, excellent
Elect 0.2-0.4% as；
The stabilizer is one kind in potassium chloride, sodium chloride, polyvinyl alcohol or glycerine, and consumption is 0.5-2%, preferably
0.8-1.2%.
The pH adjusting agent is selected from and selects acid or alkali as needed；Preferably NaOH or nitric acid.
The water is deionized water or running water.
A kind of preparation method of electrophoretic painting pre-treatment vitrified agent that the present invention is provided, comprises the following steps：
1) water of formula ratio 2/3rds is added in a kettle., sequentially adds fluoride ion source, the zirconium of formula ratio
Ionic compound and titanium ion compound, are sufficiently stirred for until being completely dissolved into limpid solution；Add the rare earth of formula ratio
Accelerator, complexing agent and oxidant, are stirred to as clear as crystal；
2) water of formula ratio 1/10th is added in another container, 30-40 DEG C is heated to, the stabilization of formula ratio is added
Agent, adds double amino silanes and titanium coupling agent, is sufficiently stirred for making within 20-30 minutes it become as clear as crystal, prepares silicon titanium
Crosslinking agent；
3) by step 2) the silicon titanium crosslinkers that prepare pour into step 1) in reactor, after stirring, add going for surplus
Ionized water, adds the pH adjusting agent of formula ratio, and pH value is adjusted into 2-2.5, you can.
Step 2) used by water be deionized water.
A kind of application method of electrophoretic painting pre-treatment vitrified agent that the present invention is provided, specially
Step one：Alkaline non-phosphor degreaser；
Step 2：Twice are washed；
Step 3：The vitrified agent prepared with the present invention is surface-treated, technological parameter：PH value 4.0-6.0, total acidity 2-
10 points, normal temperature treatment, process time 0.5-10 points kind, processing mode：Immersion, spray；
Step 4：Washing；
Step 5：Drying；
Step 6：Spraying；
Step 7：Solidification.
After cold-reduced sheet, hot rolled plate, cast iron part electrophoresis processed by the invention in terms of adhesive force and neutral salt spray test
Fu obtains excellent effect.Performance is better than traditional ternary Phosphating Solution, and without heating, energy-conserving and environment-protective in processing procedure.
The all of percent concentration of the present invention is mass percent concentration.
The effect of each raw material is as follows in the present invention：
Zirconium ion compound and titanium ion compound：Zirconium/titanium salt conversion membrane technology is in base using transition metal complex salt
Body metal surface produces film, this layer film to play the corrosion resistance and the ability with coating adhesion for improving metal.Particularly zirconium
With the product fluorine zirconic acid of fluorine, fine and close film layer can be produced in metal surfaces such as iron, zinc, aluminium.
Silicon titanium crosslinkers prepared by double amino silanes and titanium coupling agent hydrolysis:There is crosslinking to make for the functional group having in silane
With molecular change that can be by zirconium in the diaphragm of metal surface is reticulated, finer and close, so more anti-corrosion.
Rare earth accelerator：Rare earth element has widely been accepted and applied in Treatment of Metal Surface, due to rare earth unit
The special structure of element, only just plays very strong promotion filming function with little amount, and the rare earth reserves of China are very abundant.
Electrophoresis vitrification technology application zirconium oxide film forming, silane coupled and crosslinked action, rare earth that the present invention is provided
Facilitation is combined, and one layer of densification, anti-corrosion, high adhesion force chemical composition coating high are formed in metal surface, is carried significantly
In the combination of metal surface, and vitrification film has more preferable electric conductivity to high voltage electrophoresis paint than phosphating coat, and the outward appearance after its electrophoresis is more
It is beautiful.
The present invention utilizes colloidal sol-gel film-forming process, is produced through hydrolysis, polymerization with appropriate precursor compound organic
Polymer or metal oxide (can also both have), form colloidal liquid, and further reaction occurs gelation, can be in gold
Metal surface forms corrosion resistant film, with the development of nano material technology, is originally mainly used in modified this of ceramic material
Technology, has started to be applied to various field of material surface treatment, so the technology also has referred to as nano ceramics transformation technology.
Compared with prior art, the fluorine ion in the present invention first slightly soluble steel, Zinc Matrix surface while, and zirconium/titanium
Ion forms the conversion film layer of densification under certain acidity condition in the metal surface of dissolving；Silane coupler in colloid,
Crosslinking agent acts synergistically, while the rare earth accelerator in solution also plays a role.Form organic-inorganic hybridized in metal surface
The adhesive force of film, this conversion film corrosion resistance and electrophoretic paint is much better than ternary phosphating coat and common vitrification film.
Specific embodiment
Embodiment 1
A kind of electrophoretic painting pre-treatment vitrified agent, the raw material containing following percentage by weight：
Remaining is deionized water.
45% fluorine zirconic acid both provided fluorine ion or provided zirconium ion；45% fluotitanic acid fluorine ion was both provided and also provide titanium from
Son.
A kind of preparation method of electrophoretic painting pre-treatment vitrified agent, comprises the following steps：
1) deionized water of formula ratio 2/3rds is added in a kettle., sequentially adds 45% fluorine zirconic acid of formula ratio
With 45% fluotitanic acid, it is sufficiently stirred for until being completely dissolved into limpid solution；Add formula ratio rare earth accelerator cerous nitrate,
Complexing agent citric acid and oxidant hydrogen peroxide, are stirred to as clear as crystal；
2) deionized water of formula ratio 1/10th is added in another container, 30-40 DEG C is heated to, formula ratio is added
Sodium chloride, add vinyl three (2- methoxy ethoxies) silane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane and
95% aqueous titanic acid coupling agent Tyzor-TE, is sufficiently stirred for making within 20-30 minutes it become as clear as crystal colloidal solution, is prepared into
To silicon titanium crosslinkers；
3) by step 2) the silicon titanium crosslinkers that prepare pour into step 1) in reactor, after stirring, add going for surplus
Ionized water, adds the NaOH of pH adjusting agent 99% of formula ratio, and pH value is adjusted into 2-2.5, you can.
A kind of application method of electrophoretic painting pre-treatment vitrified agent, specially：
Step one：Alkaline non-phosphor degreaser；
Step 2：Twice are washed；
Step 3：The vitrified agent prepared with embodiment 1 is surface-treated, technological parameter：PH value 4.0-6.0, total acidity
2-10 points, normal temperature treatment, process time 0.5-10 points kind, processing mode：Immersion, spray；
Step 4：Washing；
Step 5：Drying；
Step 6：Spraying；
Step 7：Solidification.
The workpiece for the treatment of is that horse steel produces cold-reduced sheet, and board electrophoretic paint is found in process time 3min, processing mode spray, Hangzhou especially,
0 grade of cross-cut methods adhesive force, draws the unilateral strippings of fork neutral salt spray test 1000h and is less than 0.5mm.
Embodiment 2
A kind of electrophoretic painting pre-treatment vitrified agent, the raw material containing following percentage by weight：
Remaining deionized water.
The ammonium fluozirconate both provided fluorine ion or provided zirconium ion；Titanium sodium fluoride fluorine ion was both provided and also provide titanium from
Son.
A kind of preparation method of electrophoretic painting pre-treatment vitrified agent, comprises the following steps：
1) in a kettle. add formula ratio 2/3rds deionized water, sequentially add formula ratio ammonium fluozirconate and
Titanium sodium fluoride, is sufficiently stirred for until being completely dissolved into limpid solution；Add rare earth accelerator lanthanum nitrate, the complexing of formula ratio
Agent sodium potassium tartrate tetrahydrate and oxidant potassium chlorate, are stirred to as clear as crystal；
2) deionized water of formula ratio 1/10th is added in another container, 30-40 DEG C is heated to, formula ratio is added
Stabilizer polyvinyl alcohol, adds gamma-aminopropyl-triethoxy-silane, double (3- trimethoxy-silylpropyls) amine and double
(two octyloxy pyrophosphoric acid ester groups) ethylene titanate esters, are sufficiently stirred for making within 20-30 minutes it become as clear as crystal colloidal solution, system
It is standby to obtain silicon titanium crosslinkers；
3) by step 2) the silicon titanium crosslinkers that prepare pour into step 1) in reactor, after stirring, add going for surplus
Ionized water, adds the nitric acid of pH adjusting agent 68% of formula ratio, and pH value is adjusted into 2-2.5.
A kind of application method of electrophoretic painting pre-treatment vitrified agent, specially：
Step one：Alkaline non-phosphor degreaser；
Step 2：Twice are washed；
Step 3：The vitrified agent prepared with embodiment 2 is surface-treated, technological parameter：PH value 4.0-6.0, total acidity
2-10 points, normal temperature treatment, process time 0.5-10 points kind, processing mode：Immersion, spray；
Step 4：Washing；
Step 5：Drying；
Step 6：Spraying；
Step 7：Solidification.
The workpiece for the treatment of is that Baosteel produces hot rolled plate, process time 1.5min, processing mode trip leaching, the especially vertical board electrophoresis in Hangzhou
Paint, 0 grade of cross-cut methods adhesive force draws the unilateral strippings of fork neutral salt spray test 1000h and is less than 0.5mm.
Embodiment 3
A kind of electrophoretic painting pre-treatment vitrified agent, the raw material containing following percentage by weight：
Potassium fluorozirconate 0.5%
Titanium sodium fluoride 1%
Gamma-aminopropyl-triethoxy-silane 0.8%
The chelate solution 0.2% of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine
Balance of deionized water.
Potassium fluorozirconate both provided fluorine ion or provided zirconium ion；Titanium sodium fluoride both provided fluorine ion or provided titanium ion.
A kind of preparation method of electrophoretic painting pre-treatment vitrified agent, comprises the following steps：
1) in a kettle. add formula ratio 2/3rds deionized water, sequentially add formula ratio potassium fluorozirconate and
Titanium sodium fluoride, is sufficiently stirred for until being completely dissolved into limpid solution；Add rare earth accelerator cerium chloride, the complexing of formula ratio
Agent tartaric acid and oxidant hydrogen peroxide, are stirred to as clear as crystal；
2) water of formula ratio 1/10th is added in another container, 30-40 DEG C is heated to, the stabilizer of formula ratio is added
Glycerine, adds gamma-aminopropyl-triethoxy-silane, Di(dioctylpyrophosphato) ethylene titanate and triethanolamine
Chelate solution and butyl titanate, be sufficiently stirred for making within 20-30 minutes it become as clear as crystal colloidal solution, prepare silicon
Titanium crosslinkers；
3) by step 2) the silicon titanium crosslinkers that prepare pour into step 1) in reactor, after stirring, add going for surplus
Ionized water, adds the nitric acid of pH adjusting agent 68% of formula ratio, and pH value is adjusted into 2-2.5, you can.
A kind of application method of electrophoretic painting pre-treatment vitrified agent, specially：
Step one：Alkaline non-phosphor degreaser；
Step 2：Twice are washed；
Step 3：The vitrified agent prepared with embodiment 3 is surface-treated, technological parameter：PH value 4.0-6.0, total acidity
2-10 points, normal temperature treatment, process time 0.5-10 points kind, processing mode：Immersion, spray；
Step 4：Washing；
Step 5：Drying；
Step 6：Spraying；
Step 7：Solidification.
The workpiece for the treatment of is cast iron part, process time 2min, processing mode spray, the especially vertical board electrophoretic paint in Hangzhou, hundred lattice
0 grade of method adhesive force, draws the unilateral strippings of fork neutral salt spray test 1000h and is less than 0.5mm.
Claims (10)
1. a kind of electrophoretic painting pre-treatment vitrified agent, it is characterised in that the electrophoresis painting dressing pre-treatment vitrified agent contains following
The raw material of percentage by weight：
2. electrophoretic painting pre-treatment vitrified agent according to claim 1, it is characterised in that the fluoride ion source is
Sodium fluoride, hydrogen fluoride, fluotitanic acid, ammonium fluozirconate, potassium fluorozirconate, fluorine zirconic acid, ammonium titanium fluoride, titanium sodium fluoride or potassium fluotitanate.
3. electrophoretic painting pre-treatment vitrified agent according to claim 1 and 2, it is characterised in that the zirconium ion chemical combination
Thing be selected from fluorine zirconic acid, ammonium fluozirconate, zirconium nitrate, potassium fluorozirconate, sodium fluozirconate in one or two.
4. electrophoretic painting pre-treatment vitrified agent according to claim 1, it is characterised in that the titanium ion compound choosing
From fluotitanic acid, titanium sodium fluoride, titanium dioxide or metatitanic acid acid esters coupling agent one or two.
5. electrophoretic painting pre-treatment vitrified agent according to claim 1, it is characterised in that described pair of amino silane and titanium
Coupling agent is combined after hydrolysis and prepares silicon titanium crosslinkers.
6. electrophoretic painting pre-treatment vitrified agent according to claim 1, it is characterised in that the accelerator is rare earth gold
Category compound in one or more, consumption 0.001-0.05%, preferably 0.002-0.01%.
7. electrophoretic painting pre-treatment vitrified agent according to claim 1, it is characterised in that the accelerator is rare earth gold
Category compound in one or more；The complexing agent is carboxylic acid type organic.
8. electrophoretic painting pre-treatment vitrified agent according to claim 1, it is characterised in that the stabilizer is chlorination
It is a kind of in potassium, sodium chloride, polyvinyl alcohol or glycerine；The water is deionized water or running water.
9. the preparation method of the electrophoretic painting pre-treatment vitrified agent described in a kind of any one of claim 1-8, it is characterised in that
The preparation method is comprised the following steps：
1) water of formula ratio 2/3rds is added in a kettle., sequentially adds fluoride ion source, the zirconium ion of formula ratio
Compound and titanium ion compound, are sufficiently stirred for until being completely dissolved into limpid solution；The rare earth for adding formula ratio promotes
Agent, complexing agent and oxidant, are stirred to as clear as crystal；
2) water of formula ratio 1/10th is added in another container, 30-40 DEG C is heated to, the stabilizer of formula ratio is added, then
Double amino silanes and titanium coupling agent are added, is sufficiently stirred for making within 20-30 minutes it become as clear as crystal, prepare silicon titanium crosslink
Agent；
3) by step 2) the silicon titanium crosslinkers that prepare pour into step 1) in reactor, after stirring, add the deionization of surplus
Water, adds the pH adjusting agent of formula ratio, and pH value is adjusted into 2-2.5, you can；
Step 2) used by water be deionized water.
10. a kind of application method of the electrophoretic painting pre-treatment vitrified agent described in any one of claim 1-8, its feature exists
In the application method is comprised the following steps：
Step one：Alkaline non-phosphor degreaser；
Step 2：Twice are washed；
Step 3：It is surface-treated with vitrified agent, technological parameter：PH value 4.0-6.0, total acidity 2-10 point, normal temperature treatment, place
Reason time 0.5-10 points kind, processing mode：Immersion, spray；
Step 4：Washing；
Step 5：Drying；
Step 6：Spraying；
Step 7：Solidification.
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| CN108546940A (en) * | 2018-04-20 | 2018-09-18 | 安徽省康宇水电机械成套设备有限公司 | A kind of vehicle bridge lower thrust rod abutment surface processing antiseptic treating agent |
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| CN108754471A (en) * | 2018-05-26 | 2018-11-06 | 厦门力九化工有限公司 | A kind of vitrified agent and vitrification liquid making method and vitrification technique |
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| CN116083892A (en) * | 2022-11-08 | 2023-05-09 | 浙江五源科技股份有限公司 | A kind of non-phosphorus and nitrogen-free conversion agent before painting and preparation method thereof |
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| CN113718240A (en) * | 2021-08-18 | 2021-11-30 | 东风商用车有限公司 | Surface treatment method for magnesium alloy before painting |
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| CN114921778A (en) * | 2022-05-13 | 2022-08-19 | 合肥圣达电子科技实业有限公司 | Environment-friendly coating pretreatment liquid and preparation method and application thereof |
| CN116083892A (en) * | 2022-11-08 | 2023-05-09 | 浙江五源科技股份有限公司 | A kind of non-phosphorus and nitrogen-free conversion agent before painting and preparation method thereof |
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