CN105603401A - Anti-corrosion treatment liquid for surface of galvanized substrate and preparation method and anti-corrosion treatment method thereof - Google Patents

Anti-corrosion treatment liquid for surface of galvanized substrate and preparation method and anti-corrosion treatment method thereof Download PDF

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Publication number
CN105603401A
CN105603401A CN201610086807.0A CN201610086807A CN105603401A CN 105603401 A CN105603401 A CN 105603401A CN 201610086807 A CN201610086807 A CN 201610086807A CN 105603401 A CN105603401 A CN 105603401A
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zinc
substrate surface
antiseptic wash
plated substrate
solution
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刘姗
邓俊
朱学军
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Panzhihua University
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Panzhihua University
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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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention relates to a surface anti-corrosion treatment process of a galvanized substrate, in particular to anti-corrosion treatment liquid for the surface of the galvanized substrate and a preparation method and an anti-corrosion treatment method thereof. The anti-corrosion treatment liquid for the surface of the galvanized substrate is prepared from a 80-100 g/L Cr3 chelating agent solution, 100-300 g/L Al(H2PO4)3, 40-100 ml/L silica sol and the balance distilled water or deionized water. The surface of the galvanized substrate is coated with the treatment liquid, after a film is formed through curing, a film layer is high in adhesive force, and the corrosion resistance, water resistance, heat resistance and fingerprint resistance of the surface of the galvanized substrate can be remarkably improved; after the galvanized substrate is coated with the treatment liquid, electrostatic powder coating can be directly performed, and the phosphating process is omitted.

Description

Antiseptic wash and preparation method thereof and method for anticorrosion treatment for zinc-plated substrate surface
Technical field
The present invention relates to zinc-plated substrate surface anticorrosion treatment technology, be specifically related to zinc-plated substrate surface antiseptic wash and preparation thereofMethod and method for anticorrosion treatment.
Background technology
Heat zinc coating plate factory, all can be anti-at galvanized sheet surface coating one deck before dispatching from the factory in order to prevent galvanized sheet corrosion in transportationRust oil film, and household electrical appliances user is using heat zinc coating plate to carry out punching press exterior part and become sheet metal component, and carry out spraying again after phosphatization processing quietElectro-powder coating, wherein Phosphating Solution and zinc-plated substrate react, and form the phosphorization membrane of thin layer, play powder coating withThe effect of the adhesion property of zinc-plated substrate. Meanwhile, galvanized sheet does household electrical appliances inner part, prevents from getting rusty and reducing its use because of surface corrosionLife-span, therefore must process with impregnating fluid on galvanized sheet surface.
For address the above problem guarantee simultaneously corrosion resistance, prior art developed Chrome-free corrosion-resistant with passivating solution as zinc-plated basePlate surface inorganic agent.
For example, patent CN200810125728.1 " surface treatment method of a kind of passivating solution and zinc-plating material ", patentCN200810126608.3 " a kind of galvanized self-lubricating metal material " and patent CN200810125727.7 " a kind of coating compositionSurface treatment method with zinc-plating material " in all introduced Cr3+The preparation of environmental protection passivating solution and use procedure thereof, but these passivationLiquid exists following three shortcomings: (1) such passivating solution, in the time that steel plate high temperature reaches 300 DEG C, will Partial Conversion be Cr6+，Do not meet RoHS command request; (2) such passivating solution applies after zinc-plated substrate, then while carrying out electrostatic powder coating, there will bePaint film slabbing peeling, does not play good adhesion effect; (3) adhesion of such passivating solution and zinc-plated substrate surfaceNot strong, thicknesses of layers reaches about 2um, and in the time of steel plate punched, the rete grinding tool that can be stamped rubs off powder phenomenon, rubs simultaneouslyWipe part and occur black change defect, affect outward appearance and use.
Summary of the invention
Technical problem to be solved by this invention is to provide that a kind of antiseptic property is good, the zinc-plated substrate surface preservative treatment of environmental protectionLiquid, the raw material of this treatment fluid consists of: Cr3+Chelating agent solution 80～100g/L, Al (H2PO4)3100～300g/L, Ludox40～100mL/L, all the other are distilled water or deionized water.
Wherein, above-mentioned zinc-plated substrate surface is used in antiseptic wash, described Cr3+Chelating agent solution is prepared in accordance with the following methods: will60～120 weight portion Cr2O3Add in 500～900 weight portion distilled water or deionized water, after stirring, add again 130～240 weight portion citric acids, to reacting completely.
The present invention also provides the preparation method of above-mentioned zinc-plated substrate surface antiseptic wash, and the method comprises the following steps:Under normal temperature, by Cr3+Chelating agent solution, Al (H2PO4)3, distilled water or deionized water, Ludox mix, be stirred to solution and be equalEven stable phase; Adding distil water or deionized water constant volume again.
Wherein, above-mentioned zinc-plated substrate surface is with in the preparation method of antiseptic wash, and the rotating speed of described stirring is 1200～1500r/min, mixing time is 10～30min.
The present invention also provides the method for anticorrosion treatment of above-mentioned zinc-plated substrate surface antiseptic wash, and described treatment fluid is coated inZinc-plated substrate surface, makes its film-forming.
Wherein, above-mentioned zinc-plated substrate surface is with in the method for anticorrosion treatment of antiseptic wash, described zinc-plated base material be galvanized steel plain sheet orZinc-plated coil of strip.
Wherein, above-mentioned zinc-plated substrate surface is with in the method for anticorrosion treatment of antiseptic wash, and described solidification temperature is 60 DEG C～120 DEG C.
Preferably, above-mentioned zinc-plated substrate surface is with in the method for anticorrosion treatment of antiseptic wash, described solidification temperature be 65 DEG C～110℃。
Wherein, above-mentioned zinc-plated substrate surface is with in the method for anticorrosion treatment of antiseptic wash, and after described solidifying, the adhesion amount of rete is500mg/m2～1500mg/m2。
Preferably, above-mentioned zinc-plated substrate surface is used in the method for anticorrosion treatment of antiseptic wash, the adhesion amount of rete after described solidifyingFor 500mg/m2～1000mg/m2。
Beneficial effect of the present invention is:
First, antiseptic wash of the present invention is containing Pb, the Cd, Hg, the Cr that specify in RoHS instruction6+, PBDEsThe harmful substances such as PBBE and PBBs PBB, meet International Environmental Protection requirement with the zinc-plated base material of its processing; Secondly, this processingLiquid occupation mode is simple, Yi Hang, can be equipped with spray+extract or the production line of roll coating apparatus on use, be also zinc-plated base materialIn production process, save oiling technique, saved production cost; Finally, antiseptic wash of the present invention is that passivation phosphatization two is closedOne treatment fluid, can directly carry out electrostatic powder coating, saves phosphating process.
Detailed description of the invention
The invention provides that a kind of antiseptic property is good, environmental protection, and can directly carry out the zinc-plated substrate surface of electrostatic powder coatingUse antiseptic wash. The raw material of this treatment fluid consists of: Cr3+Chelating agent solution 80～100g/L, Al (H2PO4)3100～300g/L, Ludox 40～100mL/L, all the other are distilled water or deionized water.
Wherein, above-mentioned zinc-plated substrate surface antiseptic wash, described Cr3+Chelating agent solution is prepared in accordance with the following methods:In 500～900 weight parts waters, add 60～120 weight portion Cr2O3Chromic anhydride, stirs, after add 130～240 weight portion lemonsAcid, to reacting completely.
The present invention also provides the preparation method of above-mentioned zinc-plated substrate surface antiseptic wash, and the method comprises the following steps:
At normal temperatures, by Cr3+Chelating agent solution, Al (H2PO4)3, distilled water or deionized water, Ludox mix, and is stirred to moltenLiquid is uniform and stable phase; Adding distil water or deionized water constant volume again.
Wherein, above-mentioned zinc-plated substrate surface is with in the preparation method of antiseptic wash, and the rotating speed of described high-speed stirred is 1200～1500r/min, mixing time 10～30min.
The present invention also provides above-mentioned preparation method's one preferred preparation method, and the method comprises the following steps:
(1) under normal temperature condition, by Al (H2PO4)3Be added to Cr3+In chelating agent solution, be stirred to it and dissolve completely, solution byBlack gray expandable becomes blackish green;
(2) Ludox and deionized water or distilled water are uniformly mixed, are uniform and stable phase to solution;
(3) solution of step (2) is joined in the solution of step (1), 1200～1500r/min high-speed stirred, 10～30min,Be uniform and stable phase to solution;
(4) add deionized water or distilled water constant volume, obtain antiseptic wash.
Preferably, above-mentioned zinc-plated substrate surface is with in the preparation method of antiseptic wash, and the rotating speed of described high-speed stirred is 1300～1400r/min, mixing time 15～25min.
Wherein, above-mentioned zinc-plated substrate surface is with in the preparation method of antiseptic wash, and described step can also add froth breaking in (4)Agent. The consumption of described defoamer makes antiseptic wash the removal of foam. Described defoamer can be various disappearing well known in the artInfusion, for example, in polyethers defoamer, higher alcohols defoamer and silicon defoamer at least one. More particularly, described inDefoamer is purchased from one or more in the SB-401 series defoamer of Co., Ltd of the large Creative Science and Technology Co. Ltd of Dongying dan.
Above-mentioned treatment fluid is the two-in-one treatment fluid of passivation phosphatization, and its pH value scope 2～4, is faintly acid, be conducive to treatment fluid withZinc coat generation film formation reaction, this rete and zinc layer are combined as a whole, and meanwhile, Ludox plays sealing and auxiliary film forming effect, forCoating provides good rete adhesion property, has ensured the adhesion property of application again. In this treatment fluid solid content be 15～25wt%, is much higher than the solid content of other like products, and amount of solid content is high, is conducive to apply, and is especially applicable to roller coatCoating processes; Meanwhile, apply the liquid of same volume, thicknesses of layers is more guaranteed.
The present invention also provides the method for anticorrosion treatment of above-mentioned zinc-plated substrate surface antiseptic wash, and above-mentioned treatment fluid is coated inZinc-plated substrate surface, makes its film-forming.
Wherein, described zinc-plated base material comprises galvanized steel plain sheet and zinc-plated coil of strip, is preferably hot-dip galvanizing sheet steel.
Wherein, before the online coating of galvanized steel plain sheet production line, only need carry out to steel plate the processing of surface finishing, reduce surface of steel plateRoughness, with improve apply and thicknesses of layers control ability.
Wherein, in above-mentioned coating procedure, coating method being not particularly limited, for example, can be roller coat coating method or utilization sprayConventional methods such as drenching+extract; In the method that sprays+extract in utilization, in the end unnecessary treatment fluid should be squeezed out to galvanized steel plain sheet.
Wherein, in above-mentioned rete solidification process, only need to remove the moisture that is attached to Several Thiourea Derivatives on Zinc Plate Surface, do not need to add again any promotionAgent, is used the methods such as heated-air drying or eddy-current heating; So solidification temperature scope is 60 DEG C～120 DEG C, be preferably 65 DEG C～110 DEG C, hardening time is within the scope of 2 seconds.
Wherein, in above-mentioned rete solidification process, after solidifying, the adhesion amount of rete is 500mg/m2～1500mg/m2, be preferably 500mg/m2～1000mg/m2. When rete adhesion amount is less than 500mg/m2Time, zinc-plated base material can not get sufficient corrosion resistance; IfRete adhesion amount exceedes 1500mg/m2Time, the solidification effect of rete is poor, and rete is difficult for dry, and is prone to be full of cracks, corrosion resistanceCan obviously reduce.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention to instituteAmong the scope of embodiments of stating.
The manufacturer of the raw material using in the embodiment of the present invention is:
Cr2O3For the people live in plenty in Chongqing, Chemical Co., Ltd. produces, and is industrial chromic anhydride, and purity is more than 98%; Citric acid is that Shanghai is prosperous grandChemical Industry Science Co., Ltd produces, food stage, and purity is more than 99%; Aluminium dihydrogen phosphate is the limited public affairs of Xinxiang City's uncle's horse sail industryDepartment produces, and the trade mark is AP135, purity 30%; Ludox is that Guangzhou Sui Ze Environmental Protection Technology Co., Ltd produces, JX-30 alkalescenceLudox (SiO2Particle diameter 20nm, SiO2Quality percentage composition 30%); Defoamer is the large Creative Science and Technology Co. Ltd of Dongying dan Limited LiabilityThe SB-401 series of company.
Embodiment 1
Taking preparation 1L antiseptic wash as example:
1. preparation Cr3+Chelating agent solution: add 50kgCr in 350kg distilled water2O3Chromic anhydride, at the rotating speed bar of 1300r/minUnder part, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 100gCr3+Chelating agent solution is placed in a container, then takes 200gAl (H2PO4)3Add in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution is from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL distilled water in another container, then measure 60mL Ludox and add this container, 1300r/min'sUnder speed conditions, stir 20min, be uniform and stable phase to solution.
4. last, adding distil water becomes solution preparation 1L solution and adds 0.5mL defoamer froth breaking. The preservative treatment preparingThe final pH value of liquid is 2.5, is designated as L1.
Adopt roller coat coated technique that antiseptic wash L1 is attached to hot-dip galvanizing sheet steel (limited purchased from Pan Gang group Panzhihua steel vanadiumCompany, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein, solidifyTemperature is 90 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steel be800mg/m2, and the described curing time be 2s, (thickness of rete is with XRF (XRF) for the thickness of gained reteThe numerical value that measuring instrument is measured) be 0.8 μ m, obtain galvanized steel plain sheet 1.
Embodiment 2
Taking preparation 1L antiseptic wash as example.
1. preparation Cr3+Chelating agent solution: add 50KgCr in 350kg distilled water2O3Chromic anhydride, at the rotating speed bar of 1300r/minUnder part, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 100gCr3+Chelating agent solution is placed in a container, then takes 240gAl (H2PO4)3Add in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution is from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL distilled water in another container, then measure 60mL Ludox emulsion and add this container, at 1300r/minSpeed conditions under, stir 20min, be uniform and stable phase to solution.
4. last, adding distil water becomes solution preparation 1L solution and adds 0.5mL defoamer froth breaking. The preservative treatment preparingThe final pH value of liquid is 3.2, is designated as L2.
Adopt roller coat coated technique that antiseptic wash L2 is attached to hot-dip galvanizing sheet steel (limited purchased from Pan Gang group Panzhihua steel vanadiumCompany, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein, GuChanging temperature is 85 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steel be500mg/m2, and the described curing time be 2s, (thickness of rete is with XRF (XRF) for the thickness of gained reteThe numerical value that measuring instrument is measured) be 0.5 μ m, obtain galvanized steel plain sheet 2.
Embodiment 3
Taking preparation 1L antiseptic wash as example.
1. preparation Cr3+Chelating agent solution: add 50KgCr in 350kg deionized water2O3Chromic anhydride, at the rotating speed of 1300r/minUnder condition, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 100gCr3+Chelating agent solution is placed in a container, then takes 280gAl (H2PO4)3Add in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution is from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL deionized water in another container, then measure 60mL Ludox emulsion and add this container, 1300Under the speed conditions of r/min, stir 20min, be uniform and stable phase to solution.
4. last, add deionized water solution preparation is become to 1L solution and adds 0.5mL defoamer froth breaking. The anticorrosion place preparingThe final pH value of reason liquid is 3.0, is designated as L3.
Adopt roller coat coated technique that antiseptic wash L3 is attached to hot-dip galvanizing sheet steel (limited purchased from Pan Gang group Panzhihua steel vanadiumCompany, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein, GuChanging temperature is 80 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steel be1000mg/m2, and the described curing time be 2s, (thickness of rete is with XRF (XRF) for the thickness of gained reteThe numerical value that measuring instrument is measured) be 1 μ m, obtain galvanized steel plain sheet 3.
Embodiment 4
Taking preparation 1L antiseptic wash as example.
1. preparation Cr3+Chelating agent solution: add 50KgCr in 350kg deionized water2O3Chromic anhydride, at the rotating speed of 1300r/minUnder condition, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 100gCr3+Chelating agent solution is placed in a container, then takes 180gAl (H2PO4)3Add in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution is from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL deionized water in another container, then measure 90mL Ludox emulsion and add this container, 1300Under the speed conditions of r/min, stir 20min, be uniform and stable phase to solution.
4. last, add deionized water solution preparation is become to 1L solution and adds 0.5mL defoamer froth breaking. The anticorrosion place preparingThe final pH value of reason liquid is 3.1, is designated as L4.
Adopt roller coat coated technique that antiseptic wash L4 is attached to hot-dip galvanizing sheet steel (limited purchased from Pan Gang group Panzhihua steel vanadiumCompany, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein, GuChanging temperature is 92 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steel be1200mg/m2, and the described curing time be 2s, (thickness of rete is with XRF (XRF) for the thickness of gained reteThe numerical value that measuring instrument is measured) be 1.2 μ m, obtain galvanized steel plain sheet 4.
Embodiment 5
Taking preparation 1L antiseptic wash as example.
1. preparation Cr3+Chelating agent solution: add 50KgCr in 350kg distilled water2O3Chromic anhydride, at the rotating speed bar of 1300r/minUnder part, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 100gCr3+Chelating agent solution is placed in a container, then takes 120gAl (H2PO4)3Add in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution is from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL distilled water in another container, then measure 100mL Ludox emulsion and add this container, at 1300r/minSpeed conditions under, stir 20min, be uniform and stable phase to solution.
4. last, adding distil water becomes solution preparation 1L solution and adds 0.5mL defoamer froth breaking. The preservative treatment preparingThe final pH value of liquid is 3.2, is designated as L5.
Adopt roller coat coated technique that antiseptic wash L5 is attached to hot-dip galvanizing sheet steel (limited purchased from Pan Gang group Panzhihua steel vanadiumCompany, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein, GuChanging temperature is 95 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steel be700mg/m2, and the described curing time be 1s, (thickness of rete is with XRF (XRF) for the thickness of gained reteThe numerical value that measuring instrument is measured) be 0.7 μ m, obtain galvanized steel plain sheet 5.
Embodiment 6
Taking preparation 1L antiseptic wash as example.
1. preparation Cr3+Chelating agent solution: add 50KgCr in 350kg deionized water2O3Chromic anhydride, at the rotating speed of 1300r/minUnder condition, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 100gCr3+Chelating agent solution is placed in a container, then takes 200gAl (H2PO4)3Add in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution is from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL deionized water in another container, then measure 80mL Ludox emulsion and add this container, 1300Under the speed conditions of r/min, stir 20min, be uniform and stable phase to solution.
4. last, add deionized water solution preparation is become to 1L solution and adds 0.5mL defoamer froth breaking. The anticorrosion place preparingThe final pH value of reason liquid is 3.0, is designated as L6.
Adopt roller coat coated technique that antiseptic wash L6 is attached to hot-dip galvanizing sheet steel (limited purchased from Pan Gang group Panzhihua steel vanadiumCompany, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein, GuChanging temperature is 90 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steel be800mg/m2, and the described curing time be 2s, (thickness of rete is with XRF (XRF) for the thickness of gained reteThe numerical value that measuring instrument is measured) be 0.7 μ m, obtain galvanized steel plain sheet 6.
Embodiment 7
Taking preparation 1L antiseptic wash as example.
1. preparation Cr3+Chelating agent solution: add 50KgCr in 350kg distilled water2O3Chromic anhydride, at the rotating speed bar of 1300r/minUnder part, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 100gCr3+Chelating agent solution is placed in a container, then takes 280gAl (H2PO4)3Add in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution is from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL distilled water in another container, then measure 40mL Ludox emulsion and add this container, at 1300r/minSpeed conditions under, stir 20min, be uniform and stable phase to solution.
4. last, adding distil water becomes solution preparation 1L solution and adds 0.5mL defoamer froth breaking. The preservative treatment preparingThe final pH value of liquid is 3.4, is designated as L7.
Adopt roller coat coated technique that antiseptic wash L7 is attached to hot-dip galvanizing sheet steel (limited purchased from Pan Gang group Panzhihua steel vanadiumCompany, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein, GuChanging temperature is 85 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steel be500mg/m2, and the described curing time be 2s, (thickness of rete is with XRF (XRF) for the thickness of gained reteThe numerical value that measuring instrument is measured) be 0.4 μ m, obtain galvanized steel plain sheet 7.
Embodiment 8
Taking preparation 1L antiseptic wash as example.
1. preparation Cr3+Chelating agent solution: add 50KgCr in 350kg distilled water2O3Chromic anhydride, at the rotating speed bar of 1300r/minUnder part, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 100gCr3+Chelating agent solution is placed in a container, then takes 180gAl (H2PO4)3Add in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution is from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL distilled water in another container, then measure 100mL Ludox emulsion and add this container, at 1300r/minSpeed conditions under, stir 20min, be uniform and stable phase to solution.
4. last, adding distil water becomes solution preparation 1L solution and adds 0.5mL defoamer froth breaking. The preservative treatment preparingThe final pH value of liquid is 3.2, is designated as L8.
Adopt roller coat coated technique that antiseptic wash L8 is attached to hot-dip galvanizing sheet steel (limited purchased from Pan Gang group Panzhihua steel vanadiumCompany, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein, GuChanging temperature is 80 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steel be1000mg/m2, and the described curing time be 2s, (thickness of rete is with XRF (XRF) for the thickness of gained reteThe numerical value that measuring instrument is measured) be 0.8 μ m, obtain galvanized steel plain sheet 8.
Embodiment 9
Taking preparation 1L antiseptic wash as example.
1. preparation Cr3+Chelating agent solution: add 50KgCr in 350kg distilled water2O3Chromic anhydride, at the rotating speed bar of 1300r/minUnder part, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 500gCr3+Chelating agent solution is placed in a container, then takes 70gAl (H2PO4)3AddEnter in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution becomes from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL distilled water in another container, then measure 60mL Ludox emulsion and add this container, at 1300r/minSpeed conditions under, stir 20min, be uniform and stable phase to solution.
4. last, adding distil water becomes solution preparation 1L solution and adds 0.5mL defoamer froth breaking. The preservative treatment preparingThe final pH value of liquid is 3.3, is designated as B-L1.
Adopting roller coat coated technique that antiseptic wash B-L1 is attached to hot-dip galvanizing sheet steel (has purchased from Pan Gang group Panzhihua steel vanadiumLimit company, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein,Solidification temperature is 90 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steelFor 800mg/m2, and the described curing time be 2s, (thickness of rete is with XRF (fluorescence spectrum for the thickness of gained reteInstrument) numerical value measured of measuring instrument) be 0.6 μ m, obtain galvanized steel plain sheet B1.
Embodiment 10
Taking preparation 1L antiseptic wash as example.
1. preparation Cr3+Chelating agent solution: add 50KgCr in 350kg deionized water2O3Chromic anhydride, at the rotating speed of 1300r/minUnder condition, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 500gCr3+Chelating agent solution is placed in a container, then takes 120gAl (H2PO4)3Add in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution is from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL deionized water in another container, then measure 160mL Ludox emulsion and add this container, 1300Under the speed conditions of r/min, stir 20min, be uniform and stable phase to solution.
4. last, add deionized water solution preparation is become to 1L solution and adds 0.5mL defoamer froth breaking. The anticorrosion place preparingThe final pH value of reason liquid is 3.5, is designated as B-L2.
Adopting roller coat coated technique that antiseptic wash B-L2 is attached to hot-dip galvanizing sheet steel (has purchased from Pan Gang group Panzhihua steel vanadiumLimit company, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein,Solidification temperature is 92 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steelFor 1200mg/m2, and the described curing time be 2s, (thickness of rete is with XRF (fluorescence spectrum for the thickness of gained reteInstrument) numerical value measured of measuring instrument) be 1.5 μ m, obtain galvanized steel plain sheet B2.
Embodiment 11
Taking preparation 1L antiseptic wash as example.
1. preparation Cr3+Chelating agent solution: add 50KgCr in 350kg distilled water2O3Chromic anhydride, at the rotating speed bar of 1300r/minUnder part, stir after 20min, add 110kg citric acid, after 30min, react completely, obtain required chelating agent.
2. at normal temperatures and pressures, take 250gCr3+Chelating agent solution is placed in a container, then takes 250gAl (H2PO4)3Add in this container, under the speed conditions of 1200r/min, be stirred to Al (H2PO4)3Dissolve completely; When solution is from black gray expandableWhile becoming blackish green, react completely.
3. measure 300mL distilled water in another container, then measure 40mL Ludox emulsion and add this container, at 1300r/minSpeed conditions under, stir 20min, be uniform and stable phase to solution.
4. last, adding distil water becomes solution preparation 1L solution and adds 0.5mL defoamer froth breaking. The preservative treatment preparingThe final pH value of liquid is 2.5, is designated as B-L3.
Adopting roller coat coated technique that antiseptic wash B-L3 is attached to hot-dip galvanizing sheet steel (has purchased from Pan Gang group Panzhihua steel vanadiumLimit company, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, wherein,Solidification temperature is 95 DEG C, and the consumption of described antiseptic wash makes the adhesion amount of the rete forming on the surface of described hot-dip galvanizing sheet steelFor 700mg/m2, and the described curing time be 1s, (thickness of rete is with XRF (fluorescence spectrum for the thickness of gained reteInstrument) numerical value measured of measuring instrument) be 0.8 μ m, obtain galvanized steel plain sheet B3.
Comparative example 1
Use 5928 type trivalent chromium deactivating liquids of Henkel KGaA company as a comparison case, pH value is 2.0.
Adopt roller coat coated technique that 5928 type trivalent chromium deactivating liquids are attached to hot-dip galvanizing sheet steel (purchased from Pan Gang group Panzhihua steelVanadium Co., Ltd, model DX54D, in zinc coat containing zinc 95wt%) surface, and through overcuring to form rete, GuThe time of changing is 2s, the thickness (thickness of rete is the numerical value of measuring with XRF (XRF) measuring instrument) of gained reteBe 0.8 μ m, obtain galvanized steel plain sheet D.
The antiseptic property test case of embodiment 12 galvanized steel plain sheets
By the requirement specifying in GB/T10125-1997, carry out neutral salt spray test, mensuration galvanized steel plain sheet 1-galvanized steel plain sheet 8,The decay resistance of galvanized steel plain sheet B1-B3 and galvanized steel plain sheet D. Be considered as by " salt spray test 96h, corrosion area < 20% "Qualified.
As follows, measure the resistance to water of galvanized steel plain sheet 1-galvanized steel plain sheet 8, galvanized steel plain sheet B1-B3 and galvanized steel plain sheet DCan: on the surface of the galvanized steel plain sheet 1-of horizontal positioned galvanized steel plain sheet 8, galvanized steel plain sheet B1-B3 and galvanized steel plain sheet D, drip approximatelyThe boiling water of 2 milliliters, through 24 hours natural drying after, with 3M adhesive tape will drip place adhere to, to the spot meter under being stained with on adhesive tapeNumber, according to the counting of sticky lower spot on every square centimeter of adhesive tape, judges the quality of rete resistance to water, and the spot under gluing is more, resistance toWater-based is poorer.
As follows, measure the heat resistance of galvanized steel plain sheet 1-galvanized steel plain sheet 8, galvanized steel plain sheet B1-B3 and galvanized steel plain sheet D:Galvanized steel plain sheet 1-galvanized steel plain sheet 8, galvanized steel plain sheet B1-B3 and galvanized steel plain sheet D are placed in hot-blast stove to baking at 300 DEG C20 minutes, then the variation of coating surface pattern was observed in taking-up, and adopted the △ L of color difference meter test baking front and back specimen surface (brightDegree variable), △ a (red green variable), △ b (champac variable) value, and calculate △ E (aberration)=(△ L2+△a2+△b2)1/2。Δ E is less, illustrates that rete has better heat resistance.
As follows, measure the resistance to fingerprint of galvanized steel plain sheet 1-galvanized steel plain sheet 8, galvanized steel plain sheet B1-B3 and galvanized steel plain sheet DProperty: adopt color difference meter test, in galvanized steel plain sheet 1-galvanized steel plain sheet 8, galvanized steel plain sheet B1-B3 and the coating of galvanized steel plain sheet D surface△ L (brightness variable), △ a (red green variable) before and after 0.5 gram/m of vaseline, △ b (champac variable) value, and meterCalculate △ E (aberration)=(△ L2+△a2+△b2)1/2, Δ E is less, illustrates that rete has better anti-finger printing energy.
On M-2000 ring block type friction and wear tester, according to its description test galvanized steel plain sheet 1-galvanized steel plain sheet 8, zinc-platedThe coefficient of kinetic friction of the rete of steel plate B1-B3 and galvanized steel plain sheet D. The coefficient of kinetic friction is used for representing rete greasy property, numerical valueLess, rete is more smooth, is less than 0.2 for well with numerical value.
Dropping hammer that 1Kg is heavy highly vertically falls from 50cm, clashes into respectively galvanized steel plain sheet 1-galvanized steel plain sheet 8, galvanized steel plain sheet B1-B3And galvanized steel plain sheet D, the rete being knocked does not break or comes off, and shows that rete adhesion property is qualified; Meanwhile, carry out filmLayer hundred lattice test, are used 3M adhesive tape to adhere to, and tear after adhesive tape, if do not have rete to come off, are designated as 0 grade; If come off 1Lattice, locate 1 grade, the like, general producer is taking 0 rank as criterion of acceptability.
The surface property test result of table 1 galvanized steel plain sheet
Corrosion prevention film anti-corrosion visible according to the data of table 1, antiseptic wash provided by the invention forms at galvanized steel sheet surfaceProperty, resistance to water, heat resistance, anti-finger printing and adhesion property are all very good. And, visible according to the data of table 1, at thisIn the preferred amount ranges of invention, can further improve the corrosion resistance, water-fast of the anticorrosion rete that described antiseptic wash formsProperty, heat resistance, anti-finger printing and greasy property.
Further, directly electrostatic powder coating antiseptic wash provided by the invention also has advantages of with low cost.

Claims (10)

1. zinc-plated substrate surface antiseptic wash, is characterized in that, the raw material of this treatment fluid consists of: Cr3+Chelating agent solution80～100g/L，Al(H2PO4)3100～300g/L, Ludox 40～100mL/L, all the other are distilled water or deionized water.
2. zinc-plated substrate surface antiseptic wash according to claim 1, is characterized in that described Cr3+Chelating agent is moltenLiquid is prepared in accordance with the following methods: by 60～120 weight portion Cr2O3Add in 500～900 weight portion distilled water or deionized water,After stirring, add again 130～240 weight portion citric acids, to reacting completely.
3. the preparation method of antiseptic wash for the zinc-plated substrate surface described in claim 1 or 2, is characterized in that the methodComprise the following steps: at normal temperatures, by Cr3+Chelating agent solution, Al (H2PO4)3, distilled water or deionized water, Ludox mix,Be stirred to solution and be uniform and stable phase; Adding distil water or deionized water constant volume again.
4. the preparation method of antiseptic wash for zinc-plated substrate surface according to claim 3, is characterized in that, described in stirThe rotating speed of mixing is 1200～1500r/min, and mixing time is 10～30min.
5. the method for anticorrosion treatment of antiseptic wash for the zinc-plated substrate surface described in claim 1 or 2, is characterized in that, willDescribed treatment fluid is coated in zinc-plated substrate surface, makes its film-forming.
6. the method for anticorrosion treatment of antiseptic wash for zinc-plated substrate surface according to claim 5, is characterized in that instituteStating zinc-plated base material is galvanized steel plain sheet or zinc-plated coil of strip.
7. the method for anticorrosion treatment of antiseptic wash for zinc-plated substrate surface according to claim 5, is characterized in that instituteStating solidification temperature is 60 DEG C～120 DEG C.
8. the method for anticorrosion treatment of antiseptic wash for zinc-plated substrate surface according to claim 7, is characterized in that instituteStating solidification temperature is 65 DEG C～110 DEG C.
9. the method for anticorrosion treatment of antiseptic wash for zinc-plated substrate surface according to claim 5, is characterized in that instituteStating the adhesion amount of rete after solidifying is 500mg/m2～1500mg/m2。
10. the method for anticorrosion treatment of antiseptic wash for zinc-plated substrate surface according to claim 9, is characterized in that,After described solidifying, the adhesion amount of rete is 500mg/m2～1000mg/m2。
CN201610086807.0A 2016-02-16 2016-02-16 Anti-corrosion treatment liquid for surface of galvanized substrate and preparation method and anti-corrosion treatment method thereof Pending CN105603401A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009082088A1 (en) * 2007-12-26 2009-07-02 Posco Coating solution for forming insulating film, method for forming insulating film of non-oriented electrical steel sheet and non-oriented electrical steel sheet by using it
CN102634243A (en) * 2012-04-11 2012-08-15 江阴市诺科科技有限公司 Environment-friendly insulating paint for non-oriented silicon steel and preparation method of coating thereof
CN105219142A (en) * 2015-11-03 2016-01-06 攀钢集团攀枝花钢铁研究院有限公司 Can directly electrostatic powder coating protective system and application and hot-dip metal plated material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009082088A1 (en) * 2007-12-26 2009-07-02 Posco Coating solution for forming insulating film, method for forming insulating film of non-oriented electrical steel sheet and non-oriented electrical steel sheet by using it
CN102634243A (en) * 2012-04-11 2012-08-15 江阴市诺科科技有限公司 Environment-friendly insulating paint for non-oriented silicon steel and preparation method of coating thereof
CN105219142A (en) * 2015-11-03 2016-01-06 攀钢集团攀枝花钢铁研究院有限公司 Can directly electrostatic powder coating protective system and application and hot-dip metal plated material and preparation method thereof

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