CN102443794A - Aluminum alloy scratch resistant and fingerprint resistant chromium-free chemical conversion solution for ship and preparation method of conversion film - Google Patents
Aluminum alloy scratch resistant and fingerprint resistant chromium-free chemical conversion solution for ship and preparation method of conversion film Download PDFInfo
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- CN102443794A CN102443794A CN2011103993648A CN201110399364A CN102443794A CN 102443794 A CN102443794 A CN 102443794A CN 2011103993648 A CN2011103993648 A CN 2011103993648A CN 201110399364 A CN201110399364 A CN 201110399364A CN 102443794 A CN102443794 A CN 102443794A
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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
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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
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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Abstract
The invention relates to the field of aluminum alloy decoration and protection coatings for ships, in particular to an aluminum alloy scratch resistant and fingerprint resistant chromium-free chemical conversion solution for a ship and application of the aluminum alloy scratch resistant and fingerprint resistant chromium-free chemical conversion solution to a chemical conversion film. The chemical conversion solution contains titanium salts, zirconium salts, a silicon compound, an accelerator, a surfactant and the balance water, wherein the concentration of the titanium salts in the chromium-free chemical conversion solution ranges from 0.02 to 10g/L; the concentration of the zirconium salts in the chromium-free chemical conversion solution ranges from 0.1-10 g/L; the concentration of the silicon compound in the chromium-free chemical conversion solution ranges from 2 to 25g/L; the concentration of the accelerator in the chromium-free chemical conversion solution ranges from 0.5-12 g/L; and the concentration of the surfactant in the chemical conversion solution ranges 0.1 to 10g/L. Chemical conversion films are formed on the surfaces of 5xxx or 6xxx series aluminum alloys by adopting an impregnating, brush coating, roller coating or spraying mode; and the chemical conversion films have favorable corrosion resistance, scratch resistance and fingerprint resistance and can be used as the surface decoration and protection coating of the aluminum alloy for the ship.
Description
Technical field
The present invention relates to marine aluminium alloy and decorate and the protective coating field, be specially a kind of marine aluminium alloy environment-friendly type scratch resistance, the Chrome-free of anti-fingerprint chemical conversion solution and the application in chemical conversion film thereof (that is: the preparation method of chemical conversion film).
Background technology
5xxx and 6xxx duraluminum are because its good solidity to corrosion, weldability and mechanical property are widely used in the ship structure material in recent years.Because the sull of the spontaneous formation of duraluminum is thinner, can not satisfy the request for utilization under the severe rugged environment such as ocean.Because the erosion action of seawater and damp and hot marine atmosphere; The exposed aluminium alloy surface can be corroded and corrosion pit occur; And at the husky rudaceous white powder corrosion product of whole surface formation, thereby have a strong impact on not application zone (cabin especially) alloy matrix aluminum outward appearance.Therefore, anodic oxidation need on alloy matrix aluminum, be carried out usually or corrosion resisting property and the coating adhesion that improves alloy matrix aluminum handled in chemical conversion.For the surface treatment of big area aluminium alloy extrusions, chemical conversion has clear superiority undoubtedly, and traditional chromic acid salt passivation at present commonly used and phosphorization treatment process have received the strictness restriction of domestic and international environmental regulation owing to there are problems such as environmental pollution is serious.The novel environment friendly technology of instead traditional chemical conversion treatment process comprises molybdate processing, the processing of titanium zirconate, cobalt salt processing etc., but these novel process all exist, problems such as cost higher, large-area construction difficulty undesirable such as solidity to corrosion.Therefore, demand seeking the novel environment friendly chemical conversion technology of permanent protective property ability, low cost, easy construction urgently.
The marine aluminium alloy workpiece since long term operation under harsh corrosive environments such as seawater and marine atmosphere, its surface need be carried out chemical conversion usually and handled and improve the scratch resistance of alloy matrix aluminum, the Chrome-free of anti-fingerprint performance.Yet traditional processing mode (like chromate treating and bonderizing) has been limited to use owing to there is problem of environmental pollution at present.Therefore, develop the environment-friendly chromium-free chemical conversion technology that has good resistance scuffing, the Chrome-free of anti-fingerprint performance simultaneously and become the task of top priority.
Summary of the invention
The object of the present invention is to provide a kind of marine aluminium alloy environment-friendly type scratch resistance, the Chrome-free of anti-fingerprint chemical conversion solution and the application in chemical conversion film thereof; Solve existing environmental-protecting chemical conversion treatment process and be difficult to satisfy problems such as scratch resistance, anti-finger printing ability, its construction is simple, easy to maintenance.
Technical scheme of the present invention is:
A kind of marine aluminium alloy scratch resistance, the Chrome-free of anti-fingerprint chemical conversion solution comprise titanium salt, zirconates, silicon compound, accelerator, tensio-active agent etc., and solvent is a water.Wherein,
Titanium salt can be from one or more selections titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium potassium oxalate(T.P.O.), Titanium Nitrate, hexafluoro metatitanic acid, ammonium titanium fluoride, the potassium fluotitanate etc.The concentration range of titanium salt in the Chrome-free chemical conversion solution is 0.02～10g/L, preferred 0.5～5g/L, most preferably 1～3g/L.
Zirconates can be from one or more selections zirconium oxychloride, zirconium sulfate, zirconyl sulfate, zirconium nitrate, Zircosol ZN, zirconium carbonate, zirconium carbonate ammonium, zirconium acetate, hexafluoro zirconate, ammonium fluozirconate, the potassium fluozirconate etc.The concentration range of zirconates in the Chrome-free chemical conversion solution is 0.1～10g/L, preferred 1～8g/L, most preferably 3～6g/L.
Silicon compound can be from one or more selections sodium metasilicate, Starso, positive potassium silicate, potassium metasilicate, positive lithium silicate, lithium metasilicate, hexafluorosilicic acid, Sodium Silicofluoride 98min, ammonium silicofluoride, the silicon sol etc.The concentration range of silicon compound in the Chrome-free chemical conversion solution is 2～25g/L, preferred 5～20g/L, most preferably 8～15g/L.
Accelerator is one or more of fluorochemical, carboxylic acid, sulfonic acid, persulphate, hydrogen peroxide etc.Fluorochemical can be from one or more selections Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride, matt salt, the hydrogen fluoride etc.Carboxylic acid can be from one or more selections formic acid, acetate, propionic acid, butyric acid, valeric acid, phenylformic acid, nitrobenzoic acid, propanedioic acid, Succinic Acid, Hydrocerol A, tartrate, oxysuccinic acid, Whitfield's ointment, styracin, toxilic acid, fumaric acid, glucono-, the glucoheptonic acid etc.Sulfonic acid can be from one or more selections thionamic acid, phenylbenzimidazole sulfonic acid, the nitrobenzene-sulfonic acid etc.Persulphate can be from Potassium Persulphate, Sodium Persulfate, ammonium persulphate one or more selections.The concentration range of accelerator in the Chrome-free chemical conversion solution is 0.5～12g/L, preferred 1～8g/L, most preferably 3～5g/L.
PH adjustment agent is one or more of mineral acid, alkali metal hydroxide, ammoniacal liquor, carbonate etc.Mineral acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and alkali metal hydroxide is one or more of oxyhydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate etc.Carbonate can be from one or more selections yellow soda ash, sodium hydrogencarbonate, salt of wormwood, saleratus, volatile salt, the bicarbonate of ammonia etc.Use pH adjustment agent that Chrome-free chemical conversion solution pH value is adjusted into 1.0～5.0, preferred 2.0～4.5, most preferably 2.5～3.5.
Tensio-active agent is made up of cats product and nonionogenic tenside, and cats product can use one or more of DTAC, dodecyl benzyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide etc.Nonionogenic tenside is one or more of TX10, AEO, polyoxyethylene carboxylate, sorbitan fatty acid ester and fluorocarbon surfactant, polyoxyethylene fatty acid ester LAE-9, sorbitol anhydride mono-laurate SPAN-20, OP-10 emulsifying agent, polyoxyethylene octyl phenyl ether TX-100, polyoxyethylene nonylphenol NP-10 etc.The concentration range of tensio-active agent in chemical conversion solution is 0.1～10g/L, preferred 0.5～5g/L, most preferably 1～2g/L.
Marine aluminium alloy scratch resistance, the Chrome-free of anti-fingerprint chemical conversion solution are formed by uniform mixing such as titanium salt, zirconates, silicon compound, accelerator, tensio-active agent and water.Use pH adjustment agent that Chrome-free chemical conversion solution pH value is adjusted into 1.0～5.0, preferred 2.0～4.5, most preferably 2.5～3.5.
Utilize above-mentioned marine aluminium alloy scratch resistance, the Chrome-free of anti-fingerprint chemical conversion solution, the film-forming process step of the without phosphorus nano level chemical conversion film of Chrome-free comprises: degreasing → washing → acid etching → washing → chemical conversion → washing → drying.Wherein,
Chemical conversion can be used following technology:
Constructional method comprises dipping, brushing, roller coat or spray, and treatment temp is 10～50 ℃, preferred 20～40 ℃, and most preferably 25～35 ℃; Treatment time is 0.5～5min, preferred 1～4min, most preferably 2～3min.The Chrome-free chemical conversion solution forms chemical conversion film at 5xxx or 6xxx aluminum alloy surface, and the chemical conversion film outward appearance presents white → little indigo plant → multicolored look gradually with the film formation time prolongation.
Defatting step can use following technology:
Yellow soda ash 30g/L sodium phosphate 20g/L
Water glass 8g/L X 2073 1g/L
All the other are water.
50～60 ℃ of treatment time 1～5min of temperature.
The acid etching step can be used following technology:
Concentrated nitric acid 300mL/L, all the other are water, 25 ℃ of temperature, treatment time 0.5～2min.
The invention has the beneficial effects as follows:
1, scratch resistance of the present invention, the Chrome-free of anti-fingerprint chemical conversion solution can be made up of organosilicon, titanic acid ester, zirconate, inhibition component, pH adjustment agent, solvent, auxiliary agent etc.; Formed chemical conversion film mainly is made up of composite oxides such as silicon oxide, titanium oxide, zirconium whites; The Chrome-free chemical conversion film has good anti-corrosion, resistance to marring and anti-finger printing, can be used as marine aluminium alloy surface decoration and protective coating.
2, the present invention is suitable for marine aluminium alloy and comprises 5xxx or 6xxx series alloys.
Embodiment
Below just practical implementation method of the present invention be elaborated, but unrestricted:
Marine aluminium alloy scratch resistance of the present invention, the Chrome-free of anti-fingerprint chemical conversion solution comprise titanium salt, zirconates, silicon compound, accelerator, tensio-active agent etc., and solvent is a water.Marine aluminium alloy scratch resistance, the Chrome-free of anti-fingerprint chemical conversion solution are formed by titanium salt, zirconates, silicon compound, accelerator, uniform mixing such as pH adjustment agent, tensio-active agent and water.Use pH adjustment agent that Chrome-free chemical conversion solution pH value is adjusted into 1.0～5.0, preferred 2.0～4.5, most preferably 2.5～3.5.
Utilize above-mentioned marine aluminium alloy scratch resistance, the Chrome-free of anti-fingerprint chemical conversion solution, the film-forming process step of the without phosphorus nano level chemical conversion film of Chrome-free comprises: degreasing → washing → acid etching → washing → chemical conversion → washing → drying.Wherein,
Chemical conversion can be used following technology:
Constructional method comprises dipping, brushing, roller coat or spray, and treatment temp is 10～50 ℃, preferred 20～40 ℃, and most preferably 25～35 ℃; Treatment time is 0.5～5min, preferred 1～4min, most preferably 2～3min.The Chrome-free chemical conversion solution forms chemical conversion film at 5xxx or 6xxx aluminum alloy surface, and the chemical conversion film outward appearance presents white → little indigo plant → multicolored look gradually with the film formation time prolongation.
Defatting step can use following technology:
Yellow soda ash 30g/L sodium phosphate 20g/L
Water glass 8g/L X 2073 1g/L
All the other are water.
50～60 ℃ of treatment time 1～5min of temperature.
The acid etching step can be used following technology:
Concentrated nitric acid 300mL/L, all the other are water, 25 ℃ of temperature, treatment time 0.5～2min.
Formed chemical conversion film mainly is made up of composite oxides such as silicon oxide, titanium oxide, zirconium whites, and the thickness of conversion film is 0.5～1 μ m.
Table 1 (g/L)
The without phosphorus nano level chemical conversion film of Chrome-free of the present invention has good anti-corrosion and coating adhesion, and neutral salt spray test can reach nondiscoloration more than 168 hours, can be used for marine aluminium alloy replacement tradition and contains chromaking conversion and bonderizing.
Claims (10)
1. a marine aluminium alloy scratch resistance, the Chrome-free of anti-fingerprint chemical conversion solution is characterized in that this chemical conversion solution comprises titanium salt, zirconates, silicon compound, accelerator, tensio-active agent and water; Wherein:
The concentration range of titanium salt in the Chrome-free chemical conversion solution is 0.02～10g/L; The concentration range of zirconates in the Chrome-free chemical conversion solution is 0.1～10g/L; The concentration range of silicon compound in the Chrome-free chemical conversion solution is 2～25g/L; The concentration range of accelerator in the Chrome-free chemical conversion solution is 0.5～12g/L, and the concentration range of tensio-active agent in chemical conversion solution is 0.1～10g/L, and all the other are water.
2. according to the described marine aluminium alloy scratch resistance of claim 1, the Chrome-free of anti-fingerprint chemical conversion solution; It is characterized in that titanium salt is one or more in titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium potassium oxalate(T.P.O.), Titanium Nitrate, hexafluoro metatitanic acid, ammonium titanium fluoride, the potassium fluotitanate.
3. according to the described marine aluminium alloy scratch resistance of claim 1, the Chrome-free of anti-fingerprint chemical conversion solution; It is characterized in that zirconates is one or more in zirconium oxychloride, zirconium sulfate, zirconyl sulfate, zirconium nitrate, Zircosol ZN, zirconium carbonate, zirconium carbonate ammonium, zirconium acetate, hexafluoro zirconate, ammonium fluozirconate, the potassium fluozirconate.
4. according to the described marine aluminium alloy scratch resistance of claim 1, the Chrome-free of anti-fingerprint chemical conversion solution; It is characterized in that silicon compound is one or more in sodium metasilicate, Starso, positive potassium silicate, potassium metasilicate, positive lithium silicate, lithium metasilicate, hexafluorosilicic acid, Sodium Silicofluoride 98min, ammonium silicofluoride, the silicon sol.
5. according to the described marine aluminium alloy scratch resistance of claim 1, the Chrome-free of anti-fingerprint chemical conversion solution; It is characterized in that; Accelerator is one or more of fluorochemical, carboxylic acid, sulfonic acid, persulphate, hydrogen peroxide; Fluorochemical is one or more in Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride, matt salt, the hydrogen fluoride; Carboxylic acid is one or more in formic acid, acetate, propionic acid, butyric acid, valeric acid, phenylformic acid, nitrobenzoic acid, propanedioic acid, Succinic Acid, Hydrocerol A, tartrate, oxysuccinic acid, Whitfield's ointment, styracin, toxilic acid, fumaric acid, glucono-, the glucoheptonic acid; Sulfonic acid is one or more in thionamic acid, phenylbenzimidazole sulfonic acid, the nitrobenzene-sulfonic acid, and persulphate is one or more in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate.
6. according to the described marine aluminium alloy scratch resistance of claim 1, the Chrome-free of anti-fingerprint chemical conversion solution; It is characterized in that; Tensio-active agent is made up of cats product and nonionogenic tenside; Cats product is one or more of DTAC, dodecyl benzyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, and nonionogenic tenside is one or more of TX10, AEO, polyoxyethylene carboxylate, sorbitan fatty acid ester and fluorocarbon surfactant.
7. method of utilizing the described marine aluminium alloy scratch resistance of claim 1, the Chrome-free of anti-fingerprint chemical conversion solution to prepare chemical conversion film; It is characterized in that; The film-forming process step of the without phosphorus nano level chemical conversion film of Chrome-free comprises: degreasing → washing → acid etching → washing → chemical conversion → washing → drying; Marine aluminium alloy scratch resistance, the Chrome-free of anti-fingerprint chemical conversion solution are formed by titanium salt, zirconates, silicon compound, accelerator, tensio-active agent and water uniform mixing, use pH adjustment agent that Chrome-free chemical conversion solution pH value is adjusted into 1.0～5.0; The constructional method of chemical conversion solution comprises dipping, brushing, roller coat or spray; Treatment temp is 10～50 ℃; Treatment time is 0.5～5min; The Chrome-free chemical conversion solution forms chemical conversion film at 5xxx or 6xxx aluminum alloy surface, and the chemical conversion film outward appearance presents white → little indigo plant → multicolored look gradually with the film formation time prolongation, and obtaining the chemical conversion film thickness is 0.5-1 μ m.
8. according to the preparation method of the described chemical conversion film of claim 7; It is characterized in that; PH adjustment agent is one or more of mineral acid, alkali metal hydroxide, ammoniacal liquor, carbonate; Mineral acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid; Alkali metal hydroxide is one or more of oxyhydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, and carbonate is one or more in yellow soda ash, sodium hydrogencarbonate, salt of wormwood, saleratus, volatile salt, the bicarbonate of ammonia.
9. according to the preparation method of the described chemical conversion film of claim 7, it is characterized in that the degreasing fluid that defatting step adopts is: yellow soda ash 30g/L, sodium phosphate 20g/L, water glass 8g/L, X 2073 1g/L, all the other are water; Defatting step uses following technology: 50～60 ℃ of temperature, treatment time 1～5min.
10. according to the preparation method of the described chemical conversion film of claim 7, it is characterized in that it is concentrated nitric acid 300mL/L that the acid etching step adopts pickling solution, all the other are water; The acid etching step is used following technology: 25 ℃ of temperature, treatment time 0.5～2min.
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| CN104131305A (en) * | 2014-08-20 | 2014-11-05 | 山东威达机械股份有限公司 | Pre-treating fluid for surface corrosion protection of zinc (or aluminium) alloy die castings |
| CN104178758A (en) * | 2014-09-17 | 2014-12-03 | 朱忠良 | Chromate-free passivation method for aluminum and aluminum alloy |
| CN104451731A (en) * | 2014-11-28 | 2015-03-25 | 中国科学院金属研究所 | Chemical pickling solution for removing surface oxide layer of high-temperature alloys containing elements Cr and Al and application of chemical pickling solution |
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