CN102839367A - Self-repairing chromium-free passivation treatment fluid used for galvanized steel coil - Google Patents
Self-repairing chromium-free passivation treatment fluid used for galvanized steel coil Download PDFInfo
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- CN102839367A CN102839367A CN2012102794887A CN201210279488A CN102839367A CN 102839367 A CN102839367 A CN 102839367A CN 2012102794887 A CN2012102794887 A CN 2012102794887A CN 201210279488 A CN201210279488 A CN 201210279488A CN 102839367 A CN102839367 A CN 102839367A
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Abstract
The invention relates to a self-repairing chromium-free passivation treatment fluid used for galvanized steel coil. The passivation treatment fluid comprises the following components of, by weight, 1-10% of a functional resin, 0.01-5% of a rare earth compound, 0.01-5% of a silane coupling agent, 0.01-5% of inorganic sol, 0.01-5% of a corrosion inhibitor, 0.01-5% of a dispersing agent, and the balance being water. The passivation treatment fluid provided by the invention can form a compact chromium-free passivation film having self-repairing capacity on the surface of the galvanized steel coil, so that corrosion resistance and adhesive force of a metal substrate are increased effectively; and the performance is superior to that of a conventional chromizing liquid passivation film. The passivation treatment fluid is low in cost and simple in process, and has small pollution to pollution, relatively high economic benefit and social benefit.
Description
Technical field
The invention belongs to galvanized sheet chromium-free deactivation technical field, relate in particular to a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil.
Background technology
Cr (VI) passivation is the preconditioning technique commonly used of zinc-plated coil, and sheet material after the passivation is made into colour coated plate through application, has advantages such as lightweight, attractive in appearance, fine corrosion resistance, is widely used in fields such as building, household electrical appliances and automobile component.But because Cr (VI) itself has very strong toxicity, and has the intensive carcinogenesis, the discharging that therefore contains Cr (VI) passivation waste liquid receives more and more stricter control, makes its application receive great restriction.For solving this type of problem, develop and adopt environmentally friendly chromium-free deactivation technology to cause increasing concern.Yet still there is corrosion-resistant in this technology at present, sticking power is low, treatment temp is high, process method is complicated, stable low, the defectives such as raw materials cost is high, self-reparing capability difference of treatment solution.
Color coating pre-treatment and priming paint that Chinese patent (CN201110030293.4) discloses a kind of galvanized sheet apply the aqueous chromium-free surface treatment liquid that combines.This treatment solution is a staple with water-base resin, organo silane coupling agent, inorganic inhibitor; And add multiple auxiliary agent; The priming paint that makes the paint film layer that applies can be used as colour coated plate directly is coated with finish paint above that; Simplified the technology that the galvanized sheet color coating is handled, but overall corrosion resistance can be lower, neutral salt spray test only passes through 72h.
USP (US4225351) discloses a kind of chromium-free passivation liquid, and disclosed chromium-free conversion liquid staple is organic phospho acid, SiO
2, organic acid, H
2SO
4Deng.This treatment solution surpasses traditional chromaking liquid to the galvanized sheet coating rate, reduced use cost, but corrosion resistance nature is lower, and behind the salt-fog test 30h, the sheet material corroded area surpasses 5%.
USP (US6027578) discloses a kind of V of containing
2O
5, Al
2(OH)
5Cl5H
2O, Weibull, H
3BO
3Deng chromium-free passivation liquid.The treatment process of this invention is normal temperature dipping 15～60s, dries after the hot water wash, and the product film forming light after the processing is even, and corrosion resistance nature surpasses chromaking liquid passivation level, but relatively poor to the lifting effect of sheet material sticking power.
USP (US5068134) discloses a kind of inorganic silicate, organosilicate and SiO of containing
2The chromium-free passivation liquid that is applicable to the galvanized sheet surface of colloidal sol etc.This invention reaches the effect that substitutes chromaking liquid basically aspect the raising sheet material erosion resistance positive effect being arranged, but film-forming temperature requires more than 125 ℃, and is too high to the requirement of production line ability to cure, and causes energy dissipation.
(Progress in Organic Coatings, 2011,71 (4): 329-335) reported a kind of ASBD, silane coupling agent KH560 and Ce (NO of containing such as Vincent Meiffren
3)
3.6H
2The chromium-free treating liquid that is applicable to the galvanized sheet surface of O.Document uses sol-gel method technology that hot-dip galvanizing sheet steel is carried out Passivation Treatment, and treatment process be a preparation sol precursor earlier, again it is coated in the galvanized sheet surface, 50 ℃ of dry 20h down, and 110 ℃ obtain one deck compact protective film after drying 16h down then.Behind the humid heat test 240h, plate surface does not have white rust and occurs.But this treatment process is too loaded down with trivial details, influences its scale operation.
USP (US4341558) discloses a kind of environment-friendly type inactivating treatment liquid that is applicable to galvanized sheet, and staple is (NH
4)
2TiF
6, phytic acid, Z 150PH etc.The treatment process of this invention is a rolling method, the about 10g/m of wet film weight
2, bake out temperature is 120 ℃.Use the sheet material after this art breading, corrosion resistance nature obtains bigger raising, and the bare board salt-fog test is passed through 120h.But, the treatment solution less stable, the postprecipitation layering in 3 days of room temperature held is unfavorable for scale operation, preservation and use.
(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 chromium-free passivation liquid that is applicable to zinc-plated coil surface of F and aqueous polyurethane system.This passivating solution is handled the passivation film that the back forms, and is skeleton with urethane, and inorganic titanium salt and inhibiter are weighting material, make rete have 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 galvanized sheet nano modified acrylic resin emulsion and preparation method thereof that is used for.This treatment solution is being membrane-forming agent with the water-borne acrylic resin; Form a kind of reticulated structure high polymer; Utilize simultaneously that the nano particle specific surface area is big, the characteristics of bonding good stability, it is filled in the macromolecule network, thereby has constituted 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 the deficiency of above-mentioned prior art; The objective of the invention is to propose a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil, have Applicable temperature low, use simple, the stable height of treatment solution, raw materials cost is low and handle after do not produce the characteristics of pollution of chromium.
To achieve these goals, the technical scheme of the present invention's employing is: a kind of treatment solution that is used for the selfreparing chromium-free deactivation of zinc-plated coil includes following component (by weight percentage):
Functional resin 1～10%, rare earth compound 0.01～5%, silane coupling agent 0.01～5%, inorganic sol 0.01～5%, inhibiter 0.01～5%, dispersion agent 0.01～5%, surplus are water.
Described functional resin is:
R wherein
1, R
2Be C
1～C
15Amino, alkyl, aromatic base and verivate thereof at least a, X is H, IVA, VA, VIA or VIIA element, m, n=1,2,3 ... 100000; For example: the mixture of one or more in ROHM (representing), acrylic acid modified polyurethane (representing), fluorine modified polyurethane (representing), the silicon modified polyurethane (representing) with A4 with A3 with A2 with A1.
Described rare earth compound is: RE
mY
n, wherein RE is a REE, and Y is halogen, oxygen family element, oxygen acid root or organic acid, and m, n are 1,2,3 ... 7.For example: LaCl
3(representing), CeCl with B1
3(representing), La (NO with B2
3)
3(representing), Ce (NO with B3
3)
3(representing), Nd (NO with B4
3)
3(representing), EuCl with B5
3The mixture of one or more in (representing) with B6.
Described silane coupling agent is:
R wherein
1, R
2, R
3Be C
1～C
10Fatty group, aromatic base or alkoxyl group, R
4For active amino or be selected from epoxy group(ing), vinyl, sulfydryl, the 2-methacryloyl at least a.For example: the mixture of one or more in N-aminoethyl-γ-An Bingjisanyiyangjiguiwan (representing), γ-glycidyl ether oxygen propyl trimethoxy silicane (representing), vinyltriethoxysilane (representing), mercapto propyl group methyl dimethoxysilane (representing), the 3-methacryloxypropyl methyl dimethoxysilane (representing) with C5 with C4 with C3 with C2 with C1.
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.For example: ZnO (representing), Al with D1
2O
3(representing), SiO with D2
2The mixture of one or more in (representing) with D3.
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 ... 7.For example: NaMoO
4(representing), H with E1
3BO
3(representing), Na with E2
2SiO
3(representing), Na with E3
3VO
4The mixture of one or more in (representing) with E4.
Described dispersion agent is the water soluble surfactant active.For example: the mixture of one or more among PEG-1000 (representing), PEG-4000 (representing), the PVP-5000 (representing) with F3 with F2 with F1.
The best pretreatment temperature of described treatment solution is 0～35 ℃ of a room temperature condition, and treatment temp best after the passivation is 50～100 ℃.
The present invention compared with prior art has following outstanding advantage:
1) after treatment solution according to the invention is handled through roller coating technology, forms the layer of even passivation film, contain active function groups on the functional resin molecular chain in its structure, have the effect that strengthens substrate surface sticking power on zinc-plated coil surface; Behind the resin solidification, form the skeleton of passivation layer, silane coupling agent bonding inorganic crystal thing, colloidal sol etc. are filled between the skeleton space, have stoped the intrusion of corrosive medium effectively.
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 ionization went 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 the chromaking film.
3) the handled model of the present invention, behind the 500h neutral salt spray test, monolateral corrosion width is below 0.2mm, and corrosion resistance nature surpasses Cr (VI) passivation.This chromium-free passivation liquid treatment temp is low, process method is simple, the stable height of treatment solution, raw materials cost are low, and has solved the pollution of chromium problem that produces after the passivation of traditional chromaking liquid.
Estimating the corrosion resistance nature of the zinc-plated coil of the present invention's processing, mainly is to realize through neutral salt spray test.Other performances of inactivating treatment liquid and passive film are also estimated through test like stability, sticking power etc.Evaluation result obtains through following experiment content:
1) stability of inactivating treatment liquid
Inactivating treatment liquid is placed under the room temperature condition airtight preservation one month, the state of observation passivating solution.Judgement criteria: " 1 grade " is represented complete no change; Small quantities of particles or deposition are arranged at " 2 grades " expression treatment solution bottom, are uniformly dispersed again but shake up aftertreatment fluid; " 3 grades " expression has more particle in the treatment solution, and outward appearance is muddy and be difficult to redispersion; " 4 grades " expression treatment solution has a large amount of depositions to assemble.
2) neutral salt spray test (NSS)
With reference to GB GB/T13448-2006, with the processing of painting of the zinc-plated coil after the passivation, behind the room temperature held 24h model is 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.
3) 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 " T curved value " 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, not producing the minimum n value that ftractures or come off with coating is that T bends value.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 done further explain.
Embodiment one
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by weight percentage):
ROHM 5.0%, LaCl
33.5%, γ-glycidyl ether oxygen propyl trimethoxy silicane 0.5%, ZnO colloidal sol 0.2%, NaMoO
40.5%, PEG-1000 2.0%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 35 ℃ of room temperature conditions, and treatment temp best after the passivation is 50 ℃.
Embodiment two
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
Acrylic acid modified polyurethane 4.5%, CeCl
32.0%, γ-glycidyl ether oxygen propyl trimethoxy silicane 0.5%, ZnO colloidal sol 0.5%, NaMoO
41.5%, PEG-1000 5.0%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 25 ℃ of room temperature conditions, and treatment temp best after the passivation is 100 ℃.
Embodiment three
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
Fluorine modified polyurethane 8.0%, La (NO
3)
30.1%, γ-glycidyl ether oxygen propyl trimethoxy silicane 0.4%, ZnO colloidal sol 0.4%, NaMoO
40.4%, PEG-1000 0.3%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 35 ℃ of room temperature conditions, and treatment temp best after the passivation is 80 ℃.
Embodiment four
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
Silicon modified polyurethane 5.0%, Ce (NO
3)
30.1%, N-aminoethyl-γ-An Bingjisanyiyangjiguiwan 0.5%, ZnO colloidal sol 0.4%, NaMoO
40.3%, PEG-1000 1.5%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 25 ℃ of room temperature conditions, and treatment temp best after the passivation is 90 ℃.
Embodiment five
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
ROHM 3.5%, CeCl
30.3%, γ-glycidyl ether oxygen propyl trimethoxy silicane 5.0%, Al
2O
3Colloidal sol 0.3%, H
3BO
30.5%, PEG-4000 2.1%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 35 ℃ of room temperature conditions, and treatment temp best after the passivation is 100 ℃.
Embodiment six
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
Acrylic acid modified polyurethane 2.0%, Nd (NO
3)
35.0%, vinyltriethoxysilane 0.7%, SiO
2Colloidal sol 0.6%, NaMoO
40.3%, PEG-4000 0.8%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 35 ℃ of room temperature conditions, and treatment temp best after the passivation is 80 ℃.
Embodiment seven
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
Fluorine modified polyurethane 7.5%, EuCl
30.3%, mercapto propyl group methyl dimethoxysilane 0.8%, SiO
2Colloidal sol 5.0%, Na
2SiO
30.5%, PEG-4000 1.5%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 25 ℃ of room temperature conditions, and treatment temp best after the passivation is 100 ℃.
Embodiment eight
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
Silicon modified polyurethane 8.5%, EuCl
30.3%, 3-methacryloxypropyl methyl dimethoxysilane 0.5%, SiO
2Colloidal sol 0.9%, Na
2SiO
30.7%, PVP-5000 2.5%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 25 ℃ of room temperature conditions, and treatment temp best after the passivation is 80 ℃.
Embodiment nine
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
ROHM and silicon modified polyurethane (mass percent 1: 99) 10.0%, CeCl
30.5%, N-aminoethyl-γ-An Bingjisanyiyangjiguiwan and γ-glycidyl ether oxygen propyl trimethoxy silicane (mass percent 1: 9) 0.9%, Al
2O
3Colloidal sol 0.1%, H
3BO
30.9%, PVP-5000 1.3%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 25 ℃ of room temperature conditions, and treatment temp best after the passivation is 80 ℃.
Embodiment ten
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
ROHM and acrylic acid modified polyurethane (mass percent 1: 99) 8.0%, Ce (NO
3)
30.5%, vinyltriethoxysilane 0.3%, SiO
2Colloidal sol 0.2%, Na
3VO
40.2%, PEG-1000 0.4%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 25 ℃ of room temperature conditions, and treatment temp best after the passivation is 100 ℃.
Embodiment 11
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
Fluorine modified polyurethane and acrylic acid modified polyurethane (mass percent 1: 99) 9.0%, Ce (NO
3)
30.5%, γ-glycidyl ether oxygen propyl trimethoxy silicane 0.3%, SiO
2Colloidal sol 0.5%, H
3BO
30.1%, PEG-1000 1.3%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 25 ℃ of room temperature conditions, and treatment temp best after the passivation is 100 ℃.
Embodiment 12
A kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil includes following component (by mass percentage):
Fluorine modified polyurethane and silicon modified polyurethane (mass percent 1: 99) 10.0%, Ce (NO
3)
30.6%, N-aminoethyl-γ-An Bingjisanyiyangjiguiwan and vinyltriethoxysilane (mass percent 1: 9) 0.8%, Al
2O
3Colloidal sol 0.6%, NaMoO
40.3%, PEG-1000 1.5%, and surplus is a water.
The best pretreatment temperature of described treatment solution is 25 ℃ of room temperature conditions, and treatment temp best after the passivation is 50 ℃.
Comparative Examples one
Working solution prescription: chromic anhydride 160g/L, sulfuric acid 7g/L, nitric acid 13g/L, surplus is a water.The best pretreatment temperature of working fluid is 25 ℃ of room temperature conditions, and treatment temp best after the passivation is 50 ℃.
Comparative Examples two
Working solution prescription: SRM 935a 200g/L, sulfuric acid 9g/L, surplus is a water.The best pretreatment temperature of working fluid is 35 ℃ of room temperature conditions, and treatment temp best after the passivation is 100 ℃.
Processing condition:
Electrochemical deoiling is carried out with alkaline defatting agent in zinc-plated coil surface, the tap water flushing, deionized water rinsing, the reusable heat wind is treated pre-treatment after doing.Pretreatment temperature: 0～35 ℃ of room temperature condition; Passivation time: 10～20s; Passivation mode: roller coat; Drying temperature: 50～100 ℃ of oven dry.
The zinc-plated coil that pre-treatment is the good processing of painting, paint kind: high concentrations of toluene diisocyanate; Coating method: roller coat; Solidification value: 200～220 ℃; Set time: priming paint 30～40s, back of the body lacquer 40～50s, finish paint 50～60s; Post processing mode: water-cooled or naturally cooling.
Employed chromium-free passivation liquid composition of the embodiment of the invention and content are as shown in table 1, wherein content unit representation solids component mass percent.
Table 1 chromium-free passivation liquid is formed
Employed traditional chromaking liquid composition of Comparative Examples of the present invention and content are as shown in table 2.
The traditional chromaking liquid of table 2 is formed
The performance test results of each embodiment and comparative example sees Table 3.
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 the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (10)
1. a selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil is characterized in that, includes following component (by weight percentage):
Functional resin 1～10%, rare earth compound 0.01～5%, silane coupling agent 0.01～5%, inorganic sol 0.01～5%, inhibiter 0.01～5%, dispersion agent 0.01～5%, surplus are water.
2. a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil according to claim 1 is characterized in that, includes following component (by weight percentage):
ROHM 5.0%, LaCl
33.5%, γ-glycidyl ether oxygen propyl trimethoxy silicane 0.5%, ZnO colloidal sol 0.2%, NaMoO
40.5%, PEG-1000 2.0%, and surplus is a water.
3. a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil according to claim 1 is characterized in that, includes following component (by weight percentage):
(mass percent 1: 99) 9.0% of fluorine modified polyurethane and acrylic acid modified polyurethane, Ce (NO
3)
30.5%, γ-glycidyl ether oxygen propyl trimethoxy silicane 0.3%, SiO
2Colloidal sol 0.5%, H
3BO
30.1%, PEG-1000 1.3%, and surplus is a water.
4. a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil according to claim 1 is characterized in that described functional resin is:
R wherein
1, R
2Be C
1～C
15Amino, alkyl, aromatic base and verivate thereof at least a, X is H, IVA, VA, VIA or VIIA element, m, n=1,2,3 ... 100000.
5. a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil according to claim 1 is characterized in that described rare earth compound is: RE
mY
n, wherein RE is a REE, and Y is halogen, oxygen family element, oxygen acid root or organic acid, and m, n are 1,2,3 ... 7.
6. a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil according to claim 1; It is characterized in that; Described silane coupling agent is:
wherein R1, R2, R3 be fatty group, aromatic base or the alkoxyl group of C1～C10, R4 is active amino or is selected from epoxy group(ing), vinyl, sulfydryl, the 2-methacryloyl at least a.
7. a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil 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.
8. a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil according to claim 1 is characterized in that described sustained release dosage 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 ... 7.
9. a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil according to claim 1 is characterized in that described dispersion agent is the water soluble surfactant active.
10. a kind of selfreparing non-chromium passivation treatment fluid that is used for zinc-plated coil according to claim 1 is characterized in that, the best pretreatment temperature of described treatment solution is 0～35 ℃ of a room temperature condition, and treatment temp best after the passivation is 50～100 ℃.
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| CN112458451A (en) * | 2020-10-27 | 2021-03-09 | 江苏众信绿色管业科技有限公司 | Inner wall strengthening process and strengthening equipment for stainless steel lined composite pipe |
| CN112695314A (en) * | 2020-12-09 | 2021-04-23 | 内蒙古第一机械集团股份有限公司 | Solution for enhancing corrosion resistance of metal parts and preparation method thereof |
| CN114016692A (en) * | 2021-11-09 | 2022-02-08 | 晋江市新思维环保科技有限公司 | Honeycomb aluminum plate based on hot press molding and preparation process thereof |
| CN116334610A (en) * | 2023-04-03 | 2023-06-27 | 重庆瑜煌电力设备制造有限公司 | Environment-friendly chromium-free passivating agent with high corrosion resistance and preparation method thereof |
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| CN104046975B (en) * | 2014-06-18 | 2016-10-19 | 上海大学 | A method for compounding passivation film on the surface of hot-dip galvanized layer |
| CN104046975A (en) * | 2014-06-18 | 2014-09-17 | 上海大学 | Method for compounding passivation film on surface of hot galvanizing layer |
| CN104561970A (en) * | 2014-12-31 | 2015-04-29 | 苏州禾川化学技术服务有限公司 | Corrosion-resistant magnesium aluminum alloy chromium-free passivation solution |
| CN104928662A (en) * | 2015-04-10 | 2015-09-23 | 蚌埠市时代电子有限公司 | Environment-friendly non-toxic metal surface treatment agent |
| CN105039954A (en) * | 2015-06-04 | 2015-11-11 | 芜湖金龙模具锻造有限责任公司 | Preparation method for steel surface treatment agent |
| TWI655086B (en) * | 2016-11-21 | 2019-04-01 | 新日鐵住金股份有限公司 | Surface treated steel sheet and coated member |
| CN108300988A (en) * | 2018-01-18 | 2018-07-20 | 长沙艾森设备维护技术有限公司 | A kind of compound chrome-free tanning agent and preparation method of fast filming |
| CN108796489B (en) * | 2018-06-08 | 2020-08-04 | 浙江工业大学 | Chromium-free passivator suitable for copper and copper alloy nano self-repairing multi-stage compact and preparation process thereof |
| CN108796489A (en) * | 2018-06-08 | 2018-11-13 | 浙江工业大学 | A kind of chrome-free tanning agent and its preparation process fine and close suitable for copper and copper alloy nanometer selfreparing multistage |
| CN109021629A (en) * | 2018-07-12 | 2018-12-18 | 中国科学院海洋研究所 | A kind of environmentally friendly selfreparing hydrogel anticorrosive paint and its synthetic method |
| CN109112511A (en) * | 2018-11-01 | 2019-01-01 | 深圳市豪龙新材料技术有限公司 | A kind of chrome-free tanning agent and preparation 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 |
| CN110983244A (en) * | 2019-11-21 | 2020-04-10 | 泰州市三定新材料科技有限公司 | Environment-friendly high-corrosion-resistance zinc impregnation passivation solution |
| CN110983314A (en) * | 2019-12-31 | 2020-04-10 | 武汉仕全兴聚氨酯科技有限公司 | Chromium-free passivation solution |
| CN111876763A (en) * | 2020-07-16 | 2020-11-03 | 武汉迪赛环保新材料股份有限公司 | Chromium-free surface treatment liquid for zinc-aluminum-magnesium coated steel plate and preparation method thereof |
| CN112458451A (en) * | 2020-10-27 | 2021-03-09 | 江苏众信绿色管业科技有限公司 | Inner wall strengthening process and strengthening equipment for stainless steel lined composite pipe |
| CN112458451B (en) * | 2020-10-27 | 2023-06-23 | 江苏众信绿色管业科技有限公司 | Inner wall strengthening process and strengthening equipment for composite stainless steel pipe with inner lining |
| CN112695314A (en) * | 2020-12-09 | 2021-04-23 | 内蒙古第一机械集团股份有限公司 | Solution for enhancing corrosion resistance of metal parts and preparation method thereof |
| EP4417660A4 (en) * | 2021-10-14 | 2024-12-11 | POSCO Co., Ltd | SURFACE TREATMENT COMPOSITION FOR TERNARY HOT-DIP GALVANIZED STEEL SHEET, SURFACE-TREATED TERNARY HOT-DIP GALVANIZED STEEL SHEET USING SAME, AND PREPARATION METHOD THEREFOR |
| CN114016692A (en) * | 2021-11-09 | 2022-02-08 | 晋江市新思维环保科技有限公司 | Honeycomb aluminum plate based on hot press molding and preparation process thereof |
| CN116334610A (en) * | 2023-04-03 | 2023-06-27 | 重庆瑜煌电力设备制造有限公司 | Environment-friendly chromium-free passivating agent with high corrosion resistance and preparation method thereof |
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