CN102965653A - Self-repairing non-phosphorus ceramic processing liquid for galvanized plate and ceramic process thereof - Google Patents
Self-repairing non-phosphorus ceramic processing liquid for galvanized plate and ceramic process thereof Download PDFInfo
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- CN102965653A CN102965653A CN2012104296852A CN201210429685A CN102965653A CN 102965653 A CN102965653 A CN 102965653A CN 2012104296852 A CN2012104296852 A CN 2012104296852A CN 201210429685 A CN201210429685 A CN 201210429685A CN 102965653 A CN102965653 A CN 102965653A
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Abstract
The invention discloses a self-repairing non-phosphorus ceramic processing liquid for galvanized plate and a ceramic process thereof. The processing liquid comprises the following components, by weight: 0.1-8% of inorganic fluorine-bearing acid, 0.01-5% of rare earth compounds, 0.5-5% of a template agent, 0.01-1% of an inorganic sol, 0.01-5% of an interfacial modifier, 0.01-5% of an inhibitor and the balance of water. The ceramic processing liquid provided by the invention can automatically assemble a layer of dense amorphous membrane on the galvanized plate surface through the template agent; breakage position on the membrane has self-repair ability, so that corrosion resistance and adhesion of the galvanized plate are effectively improved, and superior to those of a traditional phosphating film. The invention has the advantages of low cost, simple process, little pollution to the environment, high economic benefit and social benefit.
Description
Technical field
The invention belongs to the without phosphorus vitrification technical field of galvanized sheet, relate in particular to the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet.
Background technology
Phosphatization is the preconditioning technique commonly used of galvanized sheet, and the sheet material after the phosphatization is widely used in household electrical appliances and other general field through application.But contain a large amount of phosphoric in the trade effluent of phosphating process discharging, can cause body eutrophication, contain heavy metal ion and nitrite in the Phosphating Solution, strong carcinogenesis is arranged, therefore the discharging that contains phosphorus waste liquid is subject to more and more stricter control, makes its application be subject to great restriction.Be to solve problems, develop and adopt environmentally friendly without phosphorus vitrification technology to cause increasing concern.Yet still there are the defectives such as corrosion-resistant, processing method is complicated, sticking power is low, raw materials cost is high, self-reparing capability is poor in technique at present.
Chinese patent (CN201210021650.5) discloses a kind of phosphate-free metal surface treatment agent and using method thereof, its main component is: nano zirconium dioxide dispersion liquid, hydrofluoric acid, propylene glycol, eight vinyl cagelike silsesquioxanes, acetic acid, cerium salt, sodium hydroxide etc. can form in the metallic surface the without phosphorus conversion composite membrane of nanometer silane after described treatment agent is processed metal.Without phosphorus, the heavy metal free of this treatment agent can at room temperature be worked, and can be used for the various metals surface preparation, but model produced corrosion after room temperature was placed 48h, and corrosion resistance nature is compared with conventional phosphatizing still a certain distance.Liu Yong equality (material protection; 2011; 46 (5): 62-63) reported that silane KB-175 is to the hot-dip galvanizing sheet steel pre-treatment; improved the bonding force of itself and epoxy coating; and environmental friendliness, simple to operate, but 500h neutral salt spray test result shows; silane film and phosphatize phosphate coat solidity to corrosion differ larger, still can not satisfy most domestic producer to the corrosion proof requirement of galvanized sheet.(material protection, 2011,44 (5): 59-61) reported a kind of without phosphorus treatment agent, its main component is Wang Shuanhong etc.: fluorine zirconic acid, cupric nitrate, ammonium bifluoride, OP-10 etc.This treatment agent plates one deck nano ceramics ZrO by the mode of dipping on cold-reduced sheet
2Conversion film has strengthened the sticking power of substrate and Resins, epoxy enamelled coating and urethane enamelled coating, satisfy coating specification, yet salt-fog test is only passed through 120h.
United States Patent (USP) (US6638369) discloses a kind of without phosphorus treatment solution, and disclosed without phosphorus conversion fluid main component is meta-titanium perborate, potassium titanate, potassium hexacyanoferrate, Sodium Fluoride etc.This treatment solution is phosphorus element-containing not, and has improved the solidity to corrosion of metal, but about 10min for the treatment of time has prolonged man-hour, has limited suitability for industrialized production.(Progress inOrganic Coatings, 2011,71 (4): 329-335) reported a kind of aluminium secondary butylate, interface modifier KH560 and Ce (NO of containing such as Vincent Meiffren
3)
3.6H
2The without phosphorus treatment solution that is applicable to the galvanized sheet surface of O.Document uses sol-gel method technique that hot-dip galvanizing sheet steel is carried out vitrification and processes, and treatment process is coated in it galvanized sheet surface again for preparing first sol precursor, 50 ℃ of lower dry 20h, then 110 ℃ of lower protective membranes that obtain one deck densification behind the 16h of drying.Behind the humid heat test 240h, plate surface occurs without white rust.But this treatment process is too loaded down with trivial details, affects its scale operation.
United States Patent (USP) (US6027578) discloses a kind of V of containing
2O
5, Al
2(OH)
5Cl5H
2O, Weibull, H
3BO
3Deng without phosphorus treatment solution.The treatment process of this invention is normal temperature dipping 15～60s, the hot water wash post-drying, and the product film forming light after the processing is even, and corrosion resistance nature surpasses the conventional phosphatizing level, but relatively poor to the lifting effect of sheet material sticking power.
(Progress in Organic Coatings, 2010,67 (4): 375-380) reported a kind of TiOSO of containing such as Hui Yang
4, (NH
2)
2CS, NH
4The without phosphorus vitrification liquid that is applicable to the galvanized sheet surface of F and aqueous polyurethane system.The vitrification rete that forms after this vitrification liquid is processed, take urethane as skeleton, inorganic titanium salt and inhibiter are weighting material, so that rete has self-reparing capability, excellent anti-corrosion performance.Yet aqueous polyurethane content is greater than 15% in the prescription, and production cost is too high, has limited suitability for industrialized production.
Chinese patent (CN200710175306.0) discloses a kind of for galvanized sheet nano modified acrylic resin emulsion and preparation method thereof.This treatment solution is with take water-borne acrylic resin as membrane-forming agent, form a kind of reticulated structure high polymer, utilize simultaneously that the nano particle specific surface area is large, the characteristics of bonding good stability, it is filled in the macromolecule network, thereby consisted of a kind of hybrid film of densification, film surface is smooth, bright, satisfies the appearance requirement of filming.But because rete does not have self-reparing capability, corrosion resistance nature is relatively low, and salt-fog test is only passed through 72h.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the invention is to propose the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet, have Applicable temperature low, use simple, raw materials cost is low and process after do not produce the characteristics that phosphorus pollutes.
To achieve these goals, the technical solution used in the present invention is:
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet is characterized in that, this treatment solution composition and mass percent are:
Inorganic fluoric-containing acid 0.1～8%, rare earth compound 0.01～5%, template 0.5～5%, inorganic sol 0.01～1%, interface modifier 0.01～5%, inhibiter 0.01～5%, surplus are water.
Further, described inorganic fluoric-containing acid is: H
mMF
n, wherein M is IIIA or IVA or VA or IVB or VIIB element, m be 12 or 3, n be 4 or 6.
Further, described rare earth compound is: RE
mY
n, wherein RE is rare earth element, and Y is halogen, oxygen family element, oxygen acid root or organic acid, and m, n are 1,2,3,4,5,6 or 7.
Further, described template is the water soluble surfactant active.
Optimal selection, described water soluble surfactant active is CTAC, SPS, BS-12, PVP-5000.
Further, described inorganic sol effective constituent is: M
mO
n, wherein M is IIIA, IVA, IIb or IVB element, m, n are 0,1,2 or 3.
Further, described interface modifier is:
Wherein R1, R2, R3 are C
1～C
10Fatty group, aromatic base or alkoxyl group, R4 is active amino or is selected from epoxy group(ing), vinyl, sulfydryl, the 2-methacryloyl at least a.
Further, described inhibiter is M
mXO
n, wherein M is IA, IIA element, and X is IIIA, IVA, VA, VB or VIB element, and m, n are 1,2,3,4,5,6 or 7.
The vitrification technique of the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet is characterized in that, may further comprise the steps:
(1) electrochemical deoiling is carried out with alkaline defatting agent in the galvanized sheet surface;
(2) first with the tap water flushing, again with treating pre-treatment behind the deionized water rinsing;
(3) the dry oven dry of vitrification;
(4) galvanized sheet that pre-treatment is good carries out the electrostatic dusting processing;
(5) solidify aftertreatment.
Further, the vitrification mode of described step (3) is dipping or spray; The vitrification temperature is 0～35 ℃ of room temperature condition; The vitrification time is 5min; Drying temperature is 80～130 ℃ of oven dry;
The powder kind is polyester powder in the described step (4); Spraying method is electrostatic spraying;
Solidification value is 200～210 ℃ in the described step (5); Be 10～15min set time; Post processing mode is naturally cooling.
The present invention compared with prior art has following outstanding advantage:
1) after treatment solution process dipping of the present invention or spray process are processed, forms the uniform vitrification rete of one deck on the galvanized sheet surface, the skeleton of inorganic fluoric-containing acid formation vitrification layer; Template can form micella in the treatment solution in water, with inorganic sol and other inhibiter parcel, under the coupled action of interface modifier, distributes uniformly at Several Thiourea Derivatives on Zinc Plate Surface, has strengthened sticking power, has effectively stoped the intrusion of corrosive medium.
2) rare earth compound mainly contains two kinds of form RE (IV) and RE (III) in rete, and RE (IV) can strengthen the corrosion resistance of metal.When rete was damaged, RE (III) dissolving ionized out RE (III) ion, and then is oxidized to the strong RE of solidity to corrosion (IV), forms a kind of selfreparing rete that is similar to phosphatize phosphate coat.
3) the handled model of the present invention, behind the 500h neutral salt spray test, monolateral corrosion width is below 1mm, and corrosion resistance nature surpasses conventional phosphatizing.This without phosphorus vitrification liquid treatment temp is low, processing method is simple, raw materials cost is low, and has solved the phosphorus pollution problem that conventional phosphatizing technique produces.
Estimating the corrosion resistance nature of the galvanized sheet of the present invention's processing, mainly is to realize by neutral salt spray test.The sticking power of vitrification film is estimated by impacting, draw the tests such as lattice, bending.Evaluation result obtains by following experiment content:
1) neutral salt spray test (NSS)
With reference to GB GB/T 13448-2006, with the processing of painting of the galvanized sheet after the vitrification, place under the room temperature behind the 24h and model to be exposed in the sodium-chlor fog to specific time, evaluate its surface blistering, rusty degree and corrosion and spread distance etc.Surface blistering, rusty degree are with reference to the grading standard of stipulating among the GB GB/T 1766-2008; Corrosion spreads distance and calculates by monolateral corrosion width.
2) sticking power
With reference to GB GB/T 13448-2006, the model after the japanning is carried out pliability test, reverse impact test and cross cut test.Pliability test " the curved value of T " grading standard: successively with the n of the thickness of tested sample (n=0,1,2 ...) doubly a value carry out 180 ° of reverse bending tests for radius-of-curvature, do not produce the minimum n value that ftractures or come off as the curved value of T take coating.Reverse impact test grading standard is measured the maximum impact merit that coating does not produce cracking or comes off, units of joules (J) according to the method that 8.5.2 among the GB/T 13448-2006 describes.Cross cut test grading standard: otch is 0 grade fully smoothly, and the area that comes off is 1 grade less than 5%, and the area that comes off is 6～15% to be 2 grades, and the area that comes off is 16～35% to be 3 grades, and the area that comes off is 36～65% to be 4 grades, and the area that comes off is 5 grades greater than 65%.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Embodiment one
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by weight percentage):
H
2TiF
60.1%, LaCl
30.1%, CTAC 0.5%, ZnO colloidal sol 0.01%, N-aminoethyl-γ-aminopropyl triethoxysilane 0.1%, H
3BO
30.1%, surplus is water.
The pretreatment temperature of described treatment solution the best is 25 ℃ of room temperature conditions, and treatment temp best after the vitrification is 80 ℃.
Embodiment two
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
H
2ZrF
60.5%, LaCl
30.1%, CTAC 1.0%, ZnO colloidal sol 0.5%, γ-glycidyl ether oxygen propyl trimethoxy silicane 0.01%, NaMoO
40.01%, surplus is water.
The pretreatment temperature of described treatment solution the best is 25 ℃ of room temperature conditions, and treatment temp best after the vitrification is 100 ℃.
Embodiment three
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
H
2SiF
60.3%, LaCl
30.1%, SDS 2.0%, ZnO colloidal sol 1.0%, vinyltriethoxysilane 0.05%, H
3BO
30.2%, surplus is water.
The pretreatment temperature of described treatment solution the best is 25 ℃ of room temperature conditions, and treatment temp best after the vitrification is 110 ℃.
Embodiment four
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
H
2HfF
61.5%, LaCl
30.1%, SDS 5.0%, ZnO colloidal sol 0.01%, mercapto propyl group methyl dimethoxysilane 5.0%, Na
2SiO
30.3%, surplus is water.
The pretreatment temperature of described treatment solution the best is 25 ℃ of room temperature conditions, and treatment temp best after the vitrification is 90 ℃.
Embodiment five
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
H
3AlF
62.0%, LaCl
30.1%, SDS 3.0%, ZnO colloidal sol 0.05%, 3-methacryloxypropyl methyl dimethoxysilane 2.0%, Na
3VO
40.2%, surplus is water.
The pretreatment temperature of described treatment solution the best is 15 ℃ of room temperature conditions, and treatment temp best after the vitrification is 120 ℃.
Embodiment six
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
HBF
43.0%, LaCl
30.1%, CTAC 2.0%, ZnO colloidal sol 0.5%, N-aminoethyl-γ-aminopropyl triethoxysilane 1.0%, NaMoO
45.0%, surplus is water.
The pretreatment temperature of described treatment solution the best is 25 ℃ of room temperature conditions, and treatment temp best after the vitrification is 90 ℃.
Embodiment seven
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
H
2TiF
61.0%, CeCl
30.5%, BS-121.5%, Al
2O
3Colloidal sol 1.0%, N-aminoethyl-γ-aminopropyl triethoxysilane 2.0%, H
3BO
34.2%, surplus is water.
The pretreatment temperature of described treatment solution the best is 35 ℃ of room temperature conditions, and treatment temp best after the vitrification is 100 ℃.
Embodiment eight
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
H
2ZrF
60.5%, La (NO
3)
35.0%, PVP-50005.0%, Al
2O
3Colloidal sol 0.01%, γ-glycidyl ether oxygen propyl trimethoxy silicane 1.0%, Na
2SiO
32.0%, surplus is water.
The pretreatment temperature of described treatment solution the best is 25 ℃ of room temperature conditions, and treatment temp best after the vitrification is 130 ℃.
Embodiment nine
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
H
2SiF
65.0%, Ce (NO
3)
32.0%, CTAC 3.0%, SiO
2Colloidal sol 0.01%, γ-glycidyl ether oxygen propyl trimethoxy silicane 0.1%, Na
3VO
40.1%, surplus is water.
The pretreatment temperature of described treatment solution the best is 35 ℃ of room temperature conditions, and treatment temp best after the vitrification is 110 ℃.
Embodiment ten
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
H
2TiF
6With H
2ZrF
6(mass percent 1: 9) 8.0%, Nd (NO
3)
33.0%, CTAC3.0%, Al
2O
3With SiO
2Colloidal sol (mass percent 1: 99) 0.5%, N-aminoethyl-γ-aminopropyl triethoxysilane and γ-glycidyl ether oxygen propyl trimethoxy silicane (mass percent 1: 99) 0.1%, NaMoO
40.01%, surplus is water.
The pretreatment temperature of described treatment solution the best is 25 ℃ of room temperature conditions, and treatment temp best after the vitrification is 130 ℃.
Embodiment 11
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
H
2TiF
6With H
2SiF
6(mass percent 9: 1) 6.0%, LaCl
3With EuCl
3(mass percent 9: 1) 1.5%, CTAC 5.0%, ZnO and Al
2O
3Colloidal sol (mass percent 9: 1) 1.0%, N-aminoethyl-γ-aminopropyl triethoxysilane and vinyltriethoxysilane (mass percent 1: 2) 0.1%, H
3BO
30.2%, surplus is water.
The pretreatment temperature of described treatment solution the best is 25 ℃ of room temperature conditions, and treatment temp best after the vitrification is 130 ℃.
Embodiment 12
The without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet includes following component (by mass percentage):
H
2ZrF
6With H
2SiF
6(mass percent 1: 99) 8.0%, CeCl
30.5%, CTAC 5.0%, ZnO and SiO
2Colloidal sol (mass percent 1: 99) 0.5%, γ-glycidyl ether oxygen propyl trimethoxy silicane and mercapto propyl group methyl dimethoxysilane (mass percent 9: 1) 0.3%, H
3BO
30.5%, surplus is water.
The pretreatment temperature of described treatment solution the best is 25 ℃ of room temperature conditions, and treatment temp best after the vitrification is 130 ℃.
The below is analyzed for phosphating process and the without phosphorus vitrification technique of working fluid of the present invention of prior art working fluid:
1, Working solution prescription
Working solution prescription of the prior art is: H
3PO
410.0g/L, ZnO 6.0g/L, HNO
36.0g/L, NaBF
40.02g/L, NaClO
32.5g/L, Na
2CO
34.0g/L, SNBS 0.5g/L, surplus is water.
Working solution prescription of the present invention is: H
3PO
410.0g/L, ZnO 1.2g/L, Na
2MoO
40.5g/L, NaNO
315.0g/L surplus is water.
2, processing condition
The phosphating process of prior art: electrochemical deoiling is carried out with alkaline defatting agent in the galvanized sheet surface, and pre-treatment is treated in the tap water flushing behind the deionized water rinsing.Phosphatization mode: dipping; Phosphatization temperature: 40～50 ℃; Parameter control: total acid/free acid ratio is 20, pH=3.8; Table is transferred: titanium salt table adjustment 3g/L; Phosphating time: 8min; Drying temperature: 80～130 ℃ of oven dry.
Vitrification technique of the present invention: electrochemical deoiling is carried out with alkaline defatting agent in the galvanized sheet surface, and pre-treatment is treated in the tap water flushing behind the deionized water rinsing.Vitrification mode: dipping or spray; Vitrification temperature: 0～35 ℃ of room temperature condition; The vitrification time: 5min; Drying temperature: 80～130 ℃ of oven dry.The galvanized sheet that pre-treatment is good carries out electrostatic dusting and processes powder kind: polyester powder; Spraying method: electrostatic spraying; Solidification value: 200～210 ℃; Set time: 10～15min; Post processing mode: naturally cooling.
3, comparative analysis
The employed without phosphorus vitrification liquid composition of the embodiment of the invention and content are as shown in table 1, wherein content unit representation solids component mass percent.
The without phosphorus vitrification liquid of table 1 forms
The employed conventional phosphatizing liquid composition of Comparative Examples of the present invention and content are as shown in table 2.
Table 2 conventional phosphatizing liquid forms
The performance test results of each embodiment and comparative example sees Table 3.Can find out obviously that by test result embodiment of the present invention all is better than Comparative Examples on the technical parameters such as erosion resistance, paint film adhesion.
Table 3 performance test results
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (10)
1. without phosphorus vitrification treatment solution of selfreparing that is used for galvanized sheet is characterized in that this treatment solution composition and mass percent are:
Inorganic fluoric-containing acid 0.1～8%, rare earth compound 0.01～5%, template 0.5～5%, inorganic sol 0.01～1%, interface modifier 0.01～5%, inhibiter 0.01～5%, surplus are water.
2. the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet according to claim 1 is characterized in that described inorganic fluoric-containing acid is: H
mMF
n, wherein M is IIIA or IVA or VA or IVB or VIIB element, m be 12 or 3, n be 4 or 6.
3. the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet according to claim 1 is characterized in that described rare earth compound is: RE
mY
n, wherein RE is rare earth element, and Y is halogen, oxygen family element, oxygen acid root or organic acid, and m, n are 1,2,3,4,5,6 or 7.
4. the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet according to claim 1 is characterized in that described template is the water soluble surfactant active.
5. the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet according to claim 4 is characterized in that described water soluble surfactant active is CTAC, SPS, BS-12, PVP-5000.
6. the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet according to claim 1 is characterized in that described inorganic sol effective constituent is: M
mO
n, wherein M is IIIA, IVA, IIB or IVB element, m, n are 0,1,2 or 3.
7. the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet according to claim 1 is characterized in that described interface modifier is:
Wherein R1, R2, R3 are C
1～C
10Fatty group, aromatic base or alkoxyl group, R4 is active amino or is selected from epoxy group(ing), vinyl, sulfydryl, the 2-methacryloyl at least a.
8. the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet according to claim 1 is characterized in that described inhibiter is M
mXO
n, wherein M is IA, IIA element, and X is IIIA, IVA, VA, VB or VIB element, and m, n are 1,2,3,4,5,6 or 7.
9. the vitrification technique of the without phosphorus vitrification treatment solution of arbitrary described a kind of selfreparing for galvanized sheet is characterized in that according to claim 1～8, may further comprise the steps:
(1) electrochemical deoiling is carried out with alkaline defatting agent in the galvanized sheet surface;
(2) first with the tap water flushing, again with treating pre-treatment behind the deionized water rinsing;
(3) the dry oven dry of vitrification;
(4) galvanized sheet that pre-treatment is good carries out the electrostatic dusting processing;
(5) solidify aftertreatment.
10. the vitrification technique of the without phosphorus vitrification treatment solution of a kind of selfreparing for galvanized sheet according to claim 9 is characterized in that,
The vitrification mode of described step (3) is dipping or spray; The vitrification temperature is 0～35 ℃ of room temperature condition; The vitrification time is 5min; Drying temperature is 80～130 ℃ of oven dry;
The powder kind is polyester powder in the described step (4); Spraying method is electrostatic spraying;
Solidification value is 200～210 ℃ in the described step (5); Be 10～15min set time; Post processing mode is naturally cooling.
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| CN104789951A (en) * | 2015-03-23 | 2015-07-22 | 芜湖协诚金属制品有限公司 | Novel treating agent for galvanized plate vitrification membrane layer |
| CN107858679A (en) * | 2017-09-18 | 2018-03-30 | 杭州利富豪机电设备有限公司 | Electric pressure cooking saucepan stay-warm case vitrification device and vitrification method |
| CN109705578A (en) * | 2018-12-29 | 2019-05-03 | 上海锦湖日丽塑料有限公司 | A kind of carbon fiber enhancing polyphenylene sulfide composition of selfreparing and preparation method thereof |
| US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
| CN111893486A (en) * | 2020-07-15 | 2020-11-06 | 浙江华电器材检测研究所有限公司 | Method for preparing silane conversion film with cathodic protection effect on aluminum alloy surface |
| CN114717543A (en) * | 2022-03-12 | 2022-07-08 | 浙江五源科技股份有限公司 | Preparation method of composition for improving salt spray resistance of coating after iron and steel non-phosphorus conversion treatment |
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