CN105755454A - Chromate-free passivation surface treatment agent applied before aluminum profile coating - Google Patents
Chromate-free passivation surface treatment agent applied before aluminum profile coating Download PDFInfo
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- CN105755454A CN105755454A CN201610120117.2A CN201610120117A CN105755454A CN 105755454 A CN105755454 A CN 105755454A CN 201610120117 A CN201610120117 A CN 201610120117A CN 105755454 A CN105755454 A CN 105755454A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
Abstract
The invention relates to a chromate-free metal surface treatment agent and provides a chromate-free passivation surface treatment agent applied before aluminum profile coating and aims at solving the defects of low treatment speed and poor anti-corrosion property of the treatment agent in the prior art. The chromate-free passivation surface treatment agent comprises the following substances in parts by weight: 20-30 parts of ammonium persulfate, 10-15 parts of hexafluorozirconic acid, 5-10 parts of potassium permanganate, 20-25 parts of tartaric acid, 2-5 parts of hexafluorotitanic acid, 2-5 parts of bis(triethanolamine)diisopropoxyl titanate, 2-5 parts of bis(dioctyloxypyrophosphate)ethylene titanate, 5-10 parts of nano silicon dioxide, 5-10 parts of nano titanium dioxide, 10-20 parts of water-soluble acrylic resin, 3-5 parts of azodiisobutyronitrile, 10-15 parts of glycerin, 10-15 parts of ethylenediaminetetraacetic acid and 10-12 parts of sodium dodecyl sulfonate, wherein the concentration of the hexafluorotitanic acid is 4-5g/L.
Description
Technical field
The present invention relates to a kind of chromium-free metal surface treatment agent, particularly relate to chromium-free deactivation surface conditioning agent before a kind of coatings of the aluminium profiles.
Background technology
In traditional handicraft, before coating process, all adopt the surface conditioning agent containing 6 valency chromium at metals such as cold-rolled steel sheet, galvanized steel plain sheet, aluminium alloy plates, make metal surface produce oxide skin(coating) and be passivated, improve metal rust preventing performance.In metal surface treatment process flow process, there is washing in passivation procedure, produce containing 6 valency chromium (Cr6+) waste water, often 1 ton of metal of passivation, will produce more than 0.3 ton waste water, and Treatment of Metal Surface amount is too big, thus also very big containing 6 valency chrome waste water amounts.Large Steel ironworks, machinery plant carries out Treatment of Metal Surface sewage treatment facility.It is generally adopted the reducing processs such as ferrous sulfate and 6 valency chromium are reduced into the 3 valency chromium that toxicity is less.But middle-size and small-size application enterprise is to less better containing 6 valency chromium sewage disposals.May also result in more serious subsequent contamination.The thin film of passivation is formed containing chromium surface inorganic agent passivating metallic surfaces, then coating prime lacquer, finish paint, containing 6 valency chromium in whole coating system, at ginkgo seeds, efflorescence, cracking, need to slough old paint film with strong paint stripper when being heavily coated with maintenance, paint stripper typically contains mineral acid, make 6 valency chromium in old paint film transfer acid soluble 6 valency chromium to, cause new more serious pollution, as being natural aging, peeling containing the paint film of 6 valency chromium, contaminated rain water, soil, cause ground water pollution.At present, chromium-free deactivation products application is most commonly used is Alodine5200 and 4595 of Henkel KGaA company, application is obtained at present in aluminium pot, interior radiator and aluminium wheels etc., but its corrosion resistance is far from reaching the anti-corrosion standard of chromaking product, process after film forming according to GB aluminium section bar through chromate, through electrostatic powder coating rotproofness conformance with standard GB5237.4-2008, namely after the acid salt spray test of 1000 hours film surface bubble-free, come off, two side forms of ruling place an order limit permeating corrosion less than 4mm.It addition, Chrome-free product unit are processing cost is also significantly larger than chromate, practical operation controls the shortcomings such as difficulty is big, does not have good popularization always.Because chromium-free deactivation product exists defect in above-mentioned various technical problem, aluminum alloy sheet material surface passivation is but not specified as containing chromium inorganic agent eliminating register.
Non-chromium inactivating technique has been carried out big quantity research by recent domestic, develops the multiple passivating solution system for handling such as rare earth, cobalt salt, silicate, molybdic acid, titanium/zirconates, has certain decay resistance.At present, the research of the non-chromium inactivating technique adopting rare-earth cerium compound to be main component is more, but cerium salt is various with oxidant species, cerous nitrate and potassium permanganate composite treating agent is adopted to be passivated aluminium section bar processing, obtaining good film-formation result and outward appearance, but the passivation effect of this inorganic agent still exists passivating film not uniformly, compactness is inadequate, processing speed is slow, the imperfect shortcoming of corrosion resistance.
Summary of the invention
Therefore, for above content, the present invention provides chromium-free deactivation surface conditioning agent before a kind of coatings of the aluminium profiles, solves the defect that inorganic agent processing speed is slow, corrosion resistance is poor of the prior art.
nullFor reaching above-mentioned purpose，The present invention is achieved by the following technical solutions: chromium-free deactivation surface conditioning agent before a kind of coatings of the aluminium profiles，Each material including following weight portion: Ammonium persulfate. 20～30 weight portion、Fluorine zirconic acid 10～15 weight portion、Potassium permanganate 5～10 weight portion、Tartaric acid 20～25 weight portion、Fluotitanic acid 2～5 weight portion、Double; two (triethanolamine) metatitanic acid diisopropyl ester 2～5 weight portion、Di(dioctylpyrophosphato) ethylene titanate 2～5 weight portion、Nano silicon 5～10 weight portion、Nano titanium oxide 5～10 weight portion、Water soluble acrylic resin 10～20 weight portion、Azodiisobutyronitrile 3～5 weight portion、Glycerol 10～15 weight portion、Ethylenediaminetetraacetic acid 10～15 weight portion、Dodecyl sodium sulfate 10～12 weight portion，The concentration of described fluotitanic acid is 4～5g/L.
Further improve and be: also including pH adjusting agent, described pH adjusting agent is by pH regulator to 3～4.
Further improve and be: the concentration of described potassium permanganate is 8～12g/L.
Further improve and be: the concentration of water soluble acrylic resin is 110～120g/L.
Further improve and be: also include the film forming accelerating of 2～5 weight portions.
Further improve and be: described film forming accelerating is ammonium heptamolybdate.
Further improve and be: include each material of following weight portion: Ammonium persulfate. 25～30 weight portion, fluorine zirconic acid 13～15 weight portion, potassium permanganate 7～10 weight portion, tartaric acid 22～25 weight portion, fluotitanic acid 2～3 weight portion, double, two (triethanolamine) metatitanic acid diisopropyl ester 2～3 weight portion, Di(dioctylpyrophosphato) ethylene titanate 2～3 weight portion, nano silicon 6～10 weight portion, nano titanium oxide 7～10 weight portion, water soluble acrylic resin 15～20 weight portion, azodiisobutyronitrile 4～5 weight portion, glycerol 13～15 weight portion, ethylenediaminetetraacetic acid 12～15 weight portion, dodecyl sodium sulfate 11～12 weight portion.
Further improve and be: include each material of following weight portion: Ammonium persulfate. 26 weight portion, fluorine zirconic acid 12 weight portion, potassium permanganate 5 weight portion, tartaric acid 20 weight portion, fluotitanic acid 5 weight portion, double, two (triethanolamine) metatitanic acid diisopropyl ester 3 weight portion, Di(dioctylpyrophosphato) ethylene titanate 4 weight portion, nano silicon 7 weight portion, nano titanium oxide 7 weight portion, water soluble acrylic resin 15 weight portion, azodiisobutyronitrile 4 weight portion, glycerol 13 weight portion, ethylenediaminetetraacetic acid 12 weight portion, dodecyl sodium sulfate 11 weight portion.
nullBy adopting preceding solution，The invention has the beneficial effects as follows: chromium-free deactivation surface conditioning agent before the coatings of the aluminium profiles of the present invention，Each material including following weight portion: Ammonium persulfate. 20～30 weight portion、Fluorine zirconic acid 10～15 weight portion、Potassium permanganate 5～10 weight portion、Tartaric acid 20～25 weight portion、Fluotitanic acid 2～5 weight portion、Double; two (triethanolamine) metatitanic acid diisopropyl ester 2～5 weight portion、Di(dioctylpyrophosphato) ethylene titanate 2～5 weight portion、Nano silicon 5～10 weight portion、Nano titanium oxide 5～10 weight portion、Water soluble acrylic resin 10～20 weight portion、Azodiisobutyronitrile 3～5 weight portion、Glycerol 10～15 weight portion、Ethylenediaminetetraacetic acid 10～15 weight portion、Dodecyl sodium sulfate 10～12 weight portion，Without chromium ion in above-mentioned formula，Wastewater treatment is simply free from environmental pollution，Adopt multiple acid matched combined and add slow caustic，One layer of passivating film can be formed at aluminium shape surface during use，Good passivation effect，And be also relatively easy to by the method removing this passivating film long afterwards at aluminium section bar，The material of comparatively environmental protection can be used to be removed simultaneously.The surface conditioning agent processing speed of the present invention is fast, and corrosion resistance is high.
Detailed description of the invention
Describing embodiments of the present invention in detail below with reference to specific embodiment, to the present invention, how application technology means solve technical problem whereby, and the process that realizes reaching technique effect can fully understand and implement according to this.
If not specializing, the conventional means that the technological means adopted in embodiment is well known to those skilled in the art, the reagent adopted and product are also available commercial.The source of agents useful for same, trade name and be necessary to list its constituent person, all indicate when occurring first.
Embodiment one
Chromium-free deactivation surface conditioning agent before a kind of coatings of the aluminium profiles, each material including following weight portion: Ammonium persulfate. 20 weight portion, fluorine zirconic acid 10 weight portion, concentration is potassium permanganate 5 weight portion of 8g/L, tartaric acid 20 weight portion, concentration is fluotitanic acid 2 weight portion of 4g/L, double, two (triethanolamine) metatitanic acid diisopropyl ester 2 weight portion, Di(dioctylpyrophosphato) ethylene titanate 2 weight portion, nano silicon 5 weight portion, nano titanium oxide 5 weight portion, concentration is water soluble acrylic resin 10 weight portion of 110g/L, azodiisobutyronitrile 3 weight portion, glycerol 10 weight portion, ethylenediaminetetraacetic acid 10 weight portion, dodecyl sodium sulfate 10 weight portion, pH adjusting agent 5 weight portion, ammonium heptamolybdate 2 weight portion.
Embodiment two
Chromium-free deactivation surface conditioning agent before a kind of coatings of the aluminium profiles, each material including following weight portion: Ammonium persulfate. 30 weight portion, fluorine zirconic acid 15 weight portion, concentration is potassium permanganate 10 weight portion of 12g/L, tartaric acid 25 weight portion, concentration is fluotitanic acid 5 weight portion of 5g/L, double, two (triethanolamine) metatitanic acid diisopropyl ester 5 weight portion, Di(dioctylpyrophosphato) ethylene titanate 5 weight portion, nano silicon 10 weight portion, nano titanium oxide 10 weight portion, concentration is water soluble acrylic resin 20 weight portion of 120g/L, azodiisobutyronitrile 5 weight portion, glycerol 15 weight portion, ethylenediaminetetraacetic acid 15 weight portion, dodecyl sodium sulfate 12 weight portion, ammonium heptamolybdate 5 weight portion, pH adjusting agent 10 weight portion.
Embodiment three
Chromium-free deactivation surface conditioning agent before a kind of coatings of the aluminium profiles, each material including following weight portion: Ammonium persulfate. 25 weight portion, fluorine zirconic acid 13 weight portion, concentration is potassium permanganate 7 weight portion of 10g/L, tartaric acid 22 weight portion, concentration is fluotitanic acid 2 weight portion of 4g/L, double, two (triethanolamine) metatitanic acid diisopropyl ester 2 weight portion, Di(dioctylpyrophosphato) ethylene titanate 2 weight portion, nano silicon 6 weight portion, nano titanium oxide 7 weight portion, concentration is water soluble acrylic resin 15 weight portion of 115g/L, azodiisobutyronitrile 4 weight portion, glycerol 13 weight portion, ethylenediaminetetraacetic acid 12 weight portion, dodecyl sodium sulfate 11 weight portion, ammonium heptamolybdate 4 weight portion, pH adjusting agent 8 weight portion.
Embodiment four
Chromium-free deactivation surface conditioning agent before a kind of coatings of the aluminium profiles, each material including following weight portion: Ammonium persulfate. 26 weight portion, fluorine zirconic acid 12 weight portion, concentration is 11g/L potassium permanganate 5 weight portion, tartaric acid 20 weight portion, concentration is fluotitanic acid 5 weight portion of 4g/L, double, two (triethanolamine) metatitanic acid diisopropyl ester 3 weight portion, Di(dioctylpyrophosphato) ethylene titanate 4 weight portion, nano silicon 7 weight portion, nano titanium oxide 7 weight portion, concentration is water soluble acrylic resin 15 weight portion of 116g/L, azodiisobutyronitrile 4 weight portion, glycerol 13 weight portion, ethylenediaminetetraacetic acid 12 weight portion, dodecyl sodium sulfate 11 weight portion, pH adjusting agent 5 weight portion, ammonium heptamolybdate 4 weight portion.
nullBefore the coatings of the aluminium profiles of the present invention, the preparation method of chromium-free deactivation surface conditioning agent is: by fluorine zirconic acid 10～15 weight portion、Ammonium persulfate. 20～30 weight portion、Fluotitanic acid 2～5 weight portion、Tartaric acid 20～25 weight portion mix homogeneously，It is subsequently added into double; two (triethanolamine) metatitanic acid diisopropyl ester 2～5 weight portion、Di(dioctylpyrophosphato) ethylene titanate 2～5 weight portion，These two kinds of materials play the effect of the above-mentioned acid of coupling，Potassium permanganate 5～10 weight portion is added after mix homogeneously reaction 30min、Nano silicon 5～10 weight portion、Nano titanium oxide 5～10 weight portion、Water soluble acrylic resin 10～20 weight portion、Azodiisobutyronitrile 3～5 weight portion、Glycerol 10～15 weight portion、Ethylenediaminetetraacetic acid 10～15 weight portion、Dodecyl sodium sulfate 10～12 weight portion，Mix，Add the pure water of 1000ml，Then centrifuge is sent into，The rotating speed of centrifuge controls at 500～200r/min，Remove precipitate，Namely surface conditioning agent is obtained.
Chromium-free deactivation surface conditioning agent before the coatings of the aluminium profiles of the present invention, when aluminium section bar is processed, first carries out pretreatment to aluminium shape surface, then aluminium section bar is immersed in this treatment fluid and is passivated processing, during passivation, pH controls 3～4, and temperature controls at 35～45 degree, soaks 2～3h.
Described in above, being only the embodiment utilizing this origination techniques content, any those skilled in the art use modification, the change that this creation does, and all belong to the scope of the claims that this creation is advocated, and are not limited to those disclosed embodiments.
Claims (8)
- null1. chromium-free deactivation surface conditioning agent before a coatings of the aluminium profiles，It is characterized in that，Each material including following weight portion: Ammonium persulfate. 20～30 weight portion、Fluorine zirconic acid 10～15 weight portion、Potassium permanganate 5～10 weight portion、Tartaric acid 20～25 weight portion、Fluotitanic acid 2～5 weight portion、Double; two (triethanolamine) metatitanic acid diisopropyl ester 2～5 weight portion、Di(dioctylpyrophosphato) ethylene titanate 2～5 weight portion、Nano silicon 5～10 weight portion、Nano titanium oxide 5～10 weight portion、Water soluble acrylic resin 10～20 weight portion、Azodiisobutyronitrile 3～5 weight portion、Glycerol 10～15 weight portion、Ethylenediaminetetraacetic acid 10～15 weight portion、Dodecyl sodium sulfate 10～12 weight portion，The concentration of described fluotitanic acid is 4～5g/L.
- 2. chromium-free deactivation surface conditioning agent before coatings of the aluminium profiles according to claim 1, it is characterised in that: also including pH adjusting agent, described pH adjusting agent is by pH regulator to 3～4.
- 3. chromium-free deactivation surface conditioning agent before coatings of the aluminium profiles according to claim 1 and 2, it is characterised in that: the concentration of described potassium permanganate is 8～12g/L.
- 4. chromium-free deactivation surface conditioning agent before coatings of the aluminium profiles according to claim 3, it is characterised in that: the concentration of water soluble acrylic resin is 110～120g/L.
- 5. chromium-free deactivation surface conditioning agent before coatings of the aluminium profiles according to claim 4, it is characterised in that: also include the film forming accelerating of 2～5 weight portions.
- 6. chromium-free deactivation surface conditioning agent before coatings of the aluminium profiles according to claim 5, it is characterised in that: described film forming accelerating is ammonium heptamolybdate.
- 7. chromium-free deactivation surface conditioning agent before coatings of the aluminium profiles according to claim 6, it is characterized in that: include each material of following weight portion: Ammonium persulfate. 25～30 weight portion, fluorine zirconic acid 13～15 weight portion, potassium permanganate 7～10 weight portion, tartaric acid 22～25 weight portion, fluotitanic acid 2～3 weight portion, double, two (triethanolamine) metatitanic acid diisopropyl ester 2～3 weight portion, Di(dioctylpyrophosphato) ethylene titanate 2～3 weight portion, nano silicon 6～10 weight portion, nano titanium oxide 7～10 weight portion, water soluble acrylic resin 15～20 weight portion, azodiisobutyronitrile 4～5 weight portion, glycerol 13～15 weight portion, ethylenediaminetetraacetic acid 12～15 weight portion, dodecyl sodium sulfate 11～12 weight portion.
- 8. chromium-free deactivation surface conditioning agent before coatings of the aluminium profiles according to claim 6, it is characterized in that: include each material of following weight portion: Ammonium persulfate. 26 weight portion, fluorine zirconic acid 12 weight portion, potassium permanganate 5 weight portion, tartaric acid 20 weight portion, fluotitanic acid 5 weight portion, double, two (triethanolamine) metatitanic acid diisopropyl ester 3 weight portion, Di(dioctylpyrophosphato) ethylene titanate 4 weight portion, nano silicon 7 weight portion, nano titanium oxide 7 weight portion, water soluble acrylic resin 15 weight portion, azodiisobutyronitrile 4 weight portion, glycerol 13 weight portion, ethylenediaminetetraacetic acid 12 weight portion, dodecyl sodium sulfate 11 weight portion.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610120117.2A CN105755454A (en) | 2016-03-03 | 2016-03-03 | Chromate-free passivation surface treatment agent applied before aluminum profile coating |
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| CN201610120117.2A CN105755454A (en) | 2016-03-03 | 2016-03-03 | Chromate-free passivation surface treatment agent applied before aluminum profile coating |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106297555A (en) * | 2016-08-29 | 2017-01-04 | 常熟市古里镇白茆新兴网印标牌厂 | warning sign board |
| CN106702364A (en) * | 2017-03-16 | 2017-05-24 | 冯志海 | Chromate-free passivator for aluminium product, and preparation method thereof |
| CN107604347A (en) * | 2017-09-29 | 2018-01-19 | 马鞍山松鹤信息科技有限公司 | A kind of architectural shape surface conditioning agent and its preparation technology |
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| CN103695889A (en) * | 2014-01-08 | 2014-04-02 | 安徽工业大学 | Chromium-free passivation solution for surface treatment of galvanized plate, aluminum and copper alloy |
| CN104711567A (en) * | 2015-03-17 | 2015-06-17 | 安徽千和新材料科技发展有限公司 | Pretreatment liquid for chromium-free passivation on tinplate surface |
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Patent Citations (4)
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| WO2009028726A1 (en) * | 2007-08-30 | 2009-03-05 | Jfe Steel Corporation | Solution for treatment of insulating coating film for oriented electromagnetic steel sheet, and method for production of oriented electromagnetic steel sheet having insulating coating film thereon |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106297555A (en) * | 2016-08-29 | 2017-01-04 | 常熟市古里镇白茆新兴网印标牌厂 | warning sign board |
| CN106702364A (en) * | 2017-03-16 | 2017-05-24 | 冯志海 | Chromate-free passivator for aluminium product, and preparation method thereof |
| CN107604347A (en) * | 2017-09-29 | 2018-01-19 | 马鞍山松鹤信息科技有限公司 | A kind of architectural shape surface conditioning agent and its preparation technology |
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Application publication date: 20160713 |