CN109312467A - The conversion coating of metal surface - Google Patents
The conversion coating of metal surface Download PDFInfo
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- CN109312467A CN109312467A CN201780028103.0A CN201780028103A CN109312467A CN 109312467 A CN109312467 A CN 109312467A CN 201780028103 A CN201780028103 A CN 201780028103A CN 109312467 A CN109312467 A CN 109312467A
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- ion
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- treatment fluid
- acid
- conversion coating
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The present invention relates to a kind of on the metal surface, especially generating the aqueous treatment of conversion coating on zinc surface or zinc alloy surface, wherein the treatment fluid contains: content is the trivalent chromic ion of 0.1g/l to 8.0g/l；Content is the zirconium ion and/or titanium ion of 0.1g/l to 15g/l；Content is the organosilane-modified Nano particles of silicon dioxide of 0.1g/l to 50g/l；Content is the fluorine ion of 0.1g/l to 15g/l.By treatment fluid according to the present invention, the metal material with height anticorrosive property can be provided, while can keep or improve the feature decorative and functional on surface.In addition, can be avoided known problem when using heavy metal ion, especially cobalt ions and hexavalent chromium.
Description
Technical field
The present invention relates to a kind of places that conversion coating on the metal surface, is especially generated on zinc surface or zinc alloy surface
Reason liquid and a kind of utilization treatment fluid generate conversion coating on zinc surface or zinc alloy surface on the metal surface, especially
Method.The invention further relates to a kind of concentrates for being used to prepare treatment fluid, and by prepared according to the methods of the invention
Conversion coating.By treatment fluid according to the present invention, the metal material with height anticorrosive property can be provided, while can be kept
Or improve the feature decorative and functional on surface.In addition, when using heavy metal ion, especially cobalt ions and hexavalent chromium
When, it can be avoided known problem.
The present invention relates to the anti-corrosion protections of metal material, especially surfaces containing zinc.
Background technique
In the prior art, different methods can be used to protect metal material surface to influence from corrosive environment.
Widely applied established methodology is applied to metal coating on metal works to be protected in a kind of this field.For example, usually
It will the workpiece made of iron and steel be zinc-plated or cadmium plating protects the workpiece to influence from corrosive environment.In this regard, corrosivity is situated between
Coating metal in matter may show stronger or weaker electrochemicaUy inert than individual material substrate metal.If coating gold
Category shows weaker inertia, then it plays as sacrificial anode in corrosive media and forms cathodic protection guarantor to base metal
The effect of shield.Therefore, the anti-corrosion protection of zinc is weaker than base metal based on its inertia, therefore first only recruits corrosive attack
Cause its own.Although this defencive function meets expectation, when corrosion product of coating, which often results in, undesirably interferes workpiece
Ornamental feature, but also often hinder the functional characteristic of workpiece.
So-called conversion coating specially usually is set on the coated metal of cathodic protection (such as zinc and its alloy), to subtract
Avoid corrosion coated metal for a long time less or as far as possible.What this was related to your non-coating metal and so-called treatment fluid reacts production
Object, this reaction product all do not dissolve in water-bearing media within the scope of very wide pH.The example of this kind of so-called conversion coating is for example so-called
Phosphatization and chromating.In the case where phosphatization, the acidity that layer to be protected is immersed phosphorus-containing acid ion is molten
Liquid.Acid medium causes zinc to be partly dissolved from coating.The Zn of release2+Cation is with the phosphate anion in reaction solution in table
The zinc phosphate layer of indissoluble is formed on face.Zinc phosphate layer itself can be only formed relatively poor anti-corrosion protection, but for being coated on it
On japanning and coating for be then splendid adherent base (Halfgrund), therefore the application center of gravity of this kind of zinc phosphate layer is
For painting and the substrate function of coating.
In the case where chromating, the acid solution containing hexavalent chromium is immersed on surface to be processed.Pass through application
Chromating, and delay the corrosive attack to coated metal significantly, thus compared with only applying coated metal, moreover it is possible to further
Postpone the corrosion to base metal.In addition, passing through chromating, moreover it is possible to postpone component due to environment influences by optical damage.
The corrosion product (being so-called white rust in the case where zinc) of coated metal can also generate interference effect to the appearance of component.
However, the shortcomings that hexavalent chromium compound is, this kind of compound not only has acute toxicity, but also has very high
Carcinogenic possibility.Nowadays many methods have been developed and have carried out chromic acid salt treatment process instead of using hexavalent chromium compound, especially
Using the different complexes of trivalent chromium compound.
But the method that uses in practice is generally using being classified as SVHC (Substances of Very High at present
Concern- pay high attention to substance) compound, such as cobalt ions, with realize needed for anti-corrosion protection.
For example, EP1346081A1 describes a kind of using non-hexavalent chromium, weak complexing agent, preferred dicarboxylic or tricarboxylic acids, more
The complex compound of preferred trivalent chromium and oxalic acid, and contain Co2+The solution (Co in the solution2+Concentration is passivated greater than 30g/l)
The method of zinc, cadmium or its alloy, especially admiro.
However, cobalt ions is classified to insalubrity, and various management organizations limit it using or are included in
Candidate list (for example, REACH).
DE19615664 describes a kind of chromate coating substantially bonding on zinc and kirsite, Chrome-free, wherein three
Valence chromium is main layer component, and the chromate coating not silicate-containing, cerium, aluminium and borate, according to salt spray test DIN
50021SS (ISO 9227) or ASTM B 117-73 is starting corrosivity occur to invade according to regulation in the 10th chapter of DIN 50961
Before erosion, anti-corrosion protection about 100-1000 hours.Conversion coating be it is clear, transparent, colourless with green iridescent colors, thickness about
100nm to 1000nm, hard, adhesiveness and scrubbable.
What is described in the publication is using the shortcomings that fluoride, complexing of the exchange power of fluoride as chromium used
Ligand is excessively slow, therefore this layer is unable to reach required thickness.
But in principle, use fluoride very ideal as complexing agent in conversion tank, because fluoride is convenient for application simultaneously
And it can be controlled by analyzing.
Summary of the invention
The object of the present invention is to provide a kind for the treatment of fluid of type described at the beginning, this treatment fluid can be avoided at least
Certain disadvantages mentioned above.Especially, by the treatment fluid, can on the metal surface, especially zinc surface or zinc alloy surface
Upper generation conversion coating, the conversion coating are capable of providing very high level anti-corrosion protection, while not cobalt compound and Cr VI chemical combination
Object.Particularly, the treatment fluid can be without the cobalt compound and hexavalent chromium compound intentionally added.In addition, should be able to use
Fluoride, but remain to reach enough thickness.
The present invention is used for be a kind of on the metal surface, especially in zinc surface to reach the solution of above-mentioned purpose
Or the aqueous treatment of conversion coating is prepared on zinc alloy surface, wherein the treatment fluid contains:
Content is the trivalent cobalt ions of 0.1g/l to 8.0g/l；
Content is the zirconium ion and/or titanium ion of 0.1g/l to 15g/l；
Content is the organosilane-modified Nano particles of silicon dioxide of 0.1g/l to 50g/l；
Content is the fluorine ion of 0.1g/l to 15g/l.
Unexpectedly, it finds according to the present invention, even if treatment fluid, which uses fluorine ion also, can generate thickness greater than 100nm's
Conversion coating.It is also possible to the solution without using high concentration or high disposal temperature.
In addition, forming minute quantity when preparing treatment fluid according to the present invention or not forming volatile organic compounds substantially
Therefore environmentally friendly or weather (VOC),.
According to the present invention it has furthermore been found that treatment fluid according to the present invention is no longer needed to using metal ion harmful to health,
Especially cobalt compound and hexavalent chromium compound, but can be in spelter coating or Zinc alloy coated upper generation conversion coating, this conversion
Layer provides excellent anti-corrosion protection.Therefore, it can be confirmed that according to ISO 9227 and/or ASTM B 117- in actual tests
The spelter coating handled by using treatment fluid according to the present invention or Zinc alloy coated is measured in 73 salt spray test, even if in heat
It after load, such as loads 24 hours at 120 DEG C, before starting to occur corroding according to the 10th chapter of DIN 50961 regulation, still may be used
Anti-corrosion protection more than 240 hours is provided.
In a kind of preferred embodiment of the invention, treatment fluid according to the present invention is substantially free of cobalt compound and six
Valence chromium compound.Therefore, the treatment fluid preferably include content lower than 1mg/l, preferably shorter than 0.8mg/l, especially less than
The hexavalent chromium of 0.6mg/l.In this regard, the content of hexavalent chromium can be measured by diphenylcarbazide photometry.
Another preferred embodiment according to the invention, the solution include content lower than 10mg/l, preferably shorter than 5mg/l, especially
It is less than the cobalt ions of 2mg/l.In this regard, the content of cobalt ions can measure cobalt by ICP to measure.
In addition, can abandon in passivating dip using Ni ion.Therefore, in a kind of embodiment for the treatment of fluid, Ni ion
Content be preferably shorter than 10mg/l, more preferably less than 5mg/l, especially less than 2mg/l nickel ion.In this regard, nickel ion
Content can measure nickel by ICP and measure.
Term " zinc surface or zinc alloy surface " is understood by its conventional sense.Surface espespecially such as zine plate, zine pressure casting,
Prick the surface of the products such as mark (Zamak), galvanized steel.Kirsite may contain the dissimilar metals such as aluminium, iron, the nickel for being up to 30%.
According to the present invention, passivating dip contains the trivalent chromic ion that content is 0.1g/l to 8.0g/l.In this regard, trivalent
The content of chromium ion can measure chromium by ICP to measure.
The advantages of trivalent chromium, is that risk is lower than Cr VI.Trivalent chromium oxide in conversion coating is in chemistry
Inertia, therefore become the excellent barrier for resisting extraneous corrosive effects.
According to the present invention, zirconium ion and/or titanium ion that passivating dip is also 0.1g/l to 15g/l containing content.Wherein
The content of zirconium ion and/or titanium ion can measure zirconium and/or titanium by ICP to measure.
It is that they are easy to separate in conjunction with chromium using the advantages of zirconium ion and/or titanium ion.It thus can be further
Increase thickness, the weight percent of the zirconium in generated conversion coating and/or titanium is possibly even beyond chromium content at this time.
Treatment fluid according to the present invention includes organosilane-modified Nano particles of silicon dioxide as other component.?
In these nanoparticles, the form of nanoscale aggregate (Agglomerat) is preferably presented in silica.This aggregate can be with
It is considered as the silane modified core in surface, that is, the core of organic silane compound is arranged on surface.Organosilane-modified espespecially oxygen atom
At least on the surface of Nano particles of silicon dioxide with the silicon atom covalent bonding of organo-silicon compound.In this regard, organosilicon
Hydride compounds are preferably epoxy silane, amidosilanes, ureido silane, amino silane, ester silane, hydrosulphonyl silane and/or isocyanide
Acid esters silane.
It is contemplated that being modified different silica nanometers using different number and/or the organo-silicon compound of type
Particle.In this regard, Nano particles of silicon dioxide can also combine different silicon compounds.According to preparation condition, thus it is possible to vary
The stoichiometric composition of Nano particles of silicon dioxide.
According to the present invention, content of the organosilane-modified Nano particles of silicon dioxide in treatment fluid be 0.1g/l extremely
50g/l.These concentration values are related to the total solid concentration of Nano particles of silicon dioxide organosilane-modified in treatment fluid respectively.
The average grain diameter of organosilane-modified nanoparticle is preferably 5nm to 50nm.Nanoparticle is in an advantageous manner
It is at least partially dispersed in treatment fluid according to the present invention.For example, this kind of nanoparticle can be such as institute in EP2406328A1
It is prepared as stating.Furthermore, it is possible to commercially available applicable nanoparticle, such as the brand of Akzo company sale
It is using the advantages of organosilane-modified Nano particles of silicon dioxide, even if this nanoparticle is in acid pH
Also there is very high stability under value.Other advantages also reside in, silane-modified to slow down fluorine ion pair used according to the invention
It is corroded caused by Nano particles of silicon dioxide.
In this regard, Nano particles of silicon dioxide can enhance the resistance of conversion coating.
Treatment fluid according to the present invention contains the fluoride that content is 0.1g/l to 15g/l.Fluoride refers in particular to free and matches
The fluoride of position bonding.Concentration data refers to fluoride total content.
It is in conversion tank using the advantages of fluoride, fluoride is convenient for application and can for example be selected by ion
Property potentiometry carrys out analysis and Control.In addition, fluoride also helps dissolution zirconium component and/or titanium component, because of the network that they are formed
It is especially stable in water-bearing media to close object.
The content of contained component in treatment fluid can be changed according to expected performance characteristic.In actual tests, demonstrate,prove
Real particularly advantageous content is as follows:
The content of trivalent chromic ion in treatment fluid is 0.15g/l to 6g/l, particularly preferably 0.2 to 5g/l；And/or
The content of zirconium ion and/or titanium ion is 0.15g/l to 10g/l, particularly preferably 0.2g/l to 8g/l；And/or
The content of organosilane-modified Nano particles of silicon dioxide is 0.2g/l to 40g/l, particularly preferably 0.3g/l
To 30g/l；And/or
The content of fluorine ion is 0.15g/l to 15g/l, particularly preferably 0.2g/l to 10g/l.
It equally also demonstrates advantageously, trivalent chromic ion is with the molar ratio of zirconium ion and/or titanium ion in treatment fluid
It 0.1 to 2.0, is preferably 0.15 to 1.5, particularly preferably 0.2 to 1.
Preferably, such as chromium chloride (CrCl can be used3), chromic nitrate (Cr (NO3)3), chromium sulfate (Cr2(SO4)3), fluorine
Change chromium (CrF3), methanesulfonic acid chromium, MSA (Cr2(CH3SO3)3) source of the water soluble trivalent chromium salt as trivalent chromic ion.
It is, for example, possible to use the hexafluoro complex compounds of zirconium and/or titanium to make the source of acid and/or its salt as fluorine ion, simultaneously
Source as zirconium ion and/or titanium ion.
Except fluorine removal compound, common various complexing agents in other complexing agents, such as similar treatment fluid can also be used.Root
According to the present invention, especially good effect: carboxylic acid, especially formic acid, acetic acid, acetyl salicylic is obtained using complexing agent selected from the group below
Acid, benzoic acid, nitrobenzoic acid, 3,5- dinitrobenzoic acid；Amino acid, especially alanine, arginine, asparagine, day
Aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, benzene
Alanine, proline, serine, threonine, tryptophan, tyrosine, valine, cheland, especially dicarboxylic acids, tricarboxylic
Acid, hydroxycarboxylic acid, especially oxalic acid, lactic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,
Decanedioic acid；Furthermore, hydroxypolycarboxylic acid, maleic acid, gluconic acid, phthalic acid, terephthalic acid (TPA), tartaric acid, citric acid, apple
Acid, ascorbic acid；Other ligands, such as acetylacetone,2,4-pentanedione, urea, urea derivative and other complexing ligands, wherein function is complexed
Containing nitrogen, phosphorus or sulphur, (- NR2 ,-PR2, wherein R is organic group independently of one another, especially C for group1To C5Aliphatic group and/or H, and/
Or-SR, wherein R is organic group, especially C1To C5Aliphatic group or H)；Phosphinate and phosphinate derivative；And they
Appropriate mixture.In this regard, there are other complexing agents, if it is present its concentration is preferably 0.0g/l to 25g/l, and/or
0.1g/l to 25g/l.
According to the present invention it is particularly preferred that other complexing agents are cheland (Chelatliganden), such as it is suitable for
Carboxylic acid, especially dicarboxylic acids, tricarboxylic acids, hydroxycarboxylic acid and/or amino acid and their appropriate mixture.
Preferably, complexing agent is chosen, so that the trivalent chromic ion in treatment fluid is at least partly complexed by complexing agent.Its is excellent
Point is, is stable in the range for the treatment of fluid is within the scope of very wide pH, especially from pH1 to pH5, and the treatment fluid changes
The visual appearance of kind conversion coating simultaneously makes its homogeneity.
Treatment fluid can also include other metal ions or metalloid (Metalloid) ion.Therefore, it may be considered that processing
Liquid contains at least one other metal ions selected from the group below or metalloid ion: Na, Ag, Al, Co, Ni, Fe, Ga, In, group of the lanthanides
Element, Sc, V, cerium, Cr, Mn, Cu, Zn, Y, Nb, Mo, Hf, Ta, W, B, Si, P, Bi, Sb, Se ion, concentration are preferably
0.005g/l to 5g/l.
These metal ions can for example serve as catalyst and preferably as soluble-salt, especially as nitrate,
Reaction solution is added in sulfate or halide.
In addition, treatment fluid can also contain other anion common in similar treatment fluid.Therefore, it is contemplated that they
Contain at least one anion selected from the group below: halide ion, especially chloride ion, iodide ion；Sulfur-containing anion, especially sulfuric acid
Radical ion, methanesulfonate, bisulfate ion；Nitrate ion；Containing phosphonium ion, especially phosphate anion and phosphate yin from
Son, gen-diphosphate ion, phosphoric acid hydrogen radical ion, dihydrogen phosphate, line style and/or ring-like oligomerization phosphate anion, line style and/or
Ring-like polyphosphate ion, phosphonic acids, 1- hydroxyl ethane-(1,1- di 2 ethylhexyl phosphonic acid), amino trimethyl phosphonic acids, diethylenetriamine five are (sub-
Methylphosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), 2- phosphonobutane -1,2,4- tricarboxylic acids, hexafluoro-phosphate radical；Carboxylate radical yin from
Son；Siliceous anion, preferably silicate anion, especially hexafluorosilicic acid root, hexafluorotitanic acid root, borate, tetrafluoroborate,
Acid borate and hexafluoroantimonic anion.Wherein if there is other anion, the concentration of other anion is preferably
0.1g/l to 50g/l.
According to the present invention, particularly preferred nitrate ion, sulfate ion and/or phosphonium acid ion.
According to a preferred embodiment of the invention a, the pH value for the treatment of fluid is adjusted to about 1.5 to 5, preferably 2 to 4, it is outstanding
It is 2.5 to 3.5 value.It in this regard, can be by adding hydrogen ion, i.e., by addition acid or alkali, to adjust required pH
Value.
In a kind of preferred embodiment of the invention, aqueous treatment contains at least one organic and or inorganic acids.
In this regard, organic acid is preferably selected from the following group: citric acid, malonic acid, formic acid, tartaric acid, lactic acid, malic acid, gluconic acid, anti-bad
Hematic acid, oxalic acid, succinic acid and adipic acid.If being preferably selected from the following group using inorganic acid: phosphoric acid, polyphosphonic acid, nitric acid, salt
Acid and sulfuric acid., according to the invention it is preferred to nitric acid.
Another preferred embodiment according to the invention, treatment fluid contain weak oxidant, are preferably selected from: nitrite,
(such as m-nitrobenzene sulfonate, nitroguanidine 4- picoline-N- aoxidize for amine oxide (such as azanol or hydroxylamine compound), N- oxide
Object, N-methylmorpholine-N- oxide) and their derivative.
In addition, treatment fluid according to the present invention, which advantageously comprises, accounts for the content of final composition lower than 10wt%, preferably low
In 5wt%, especially preferably less than 4wt%, particularly be preferably shorter than 3wt%, especially 0.001-2wt% volatile organic
It closes object (VOC), such as alcohol, such as methanol or ethyl alcohol.The content of VOC can for example be measured by GC or GC/MS.
Treatment fluid can also contain auxiliary agent for example selected from the group below: polymer, especially organic polymer, corrosion inhibiter；Silicon
Acid, especially colloid silicic acid or disperse silicic acid；Surface reactive material, especially such as surfactant；Glycol, triol, polyalcohol；Have
Machine acid, especially monocarboxylic acid；Amine；Plasticity dispersion；Dyestuff, pigment, especially carbon black, pigment forming agent, especially metal
Pigment forming agent；Amino acid, especially glycine；Dispersing agent.Suitable surfactant is, for example, aliphatic fluorohydrocarbon sulphonic acid ester.
Another object of the invention is a kind of concentrate for being used to prepare treatment fluid according to the present invention.The concentrate can be with
In solid-state or liquid and preferably there is an active material concentration, which allows by according to the present invention
The water of the total weight for the treatment of fluid at least 50wt%, preferably at least 70wt% dilutes to prepare the treatment fluid.In actual tests
In, it has proven to it is advantageous that treatment fluid is prepared based on two kinds of concentrates of different compositions, because this ensures that each concentrate
Longer storage stability.In view of this, another object of the invention is a kind of kit, it includes at least the two of different compositions
Kind concentrate, is used to prepare treatment fluid according to the present invention.In this regard, concentrate preferably has an active material concentration,
Combination allows by preparing treatment fluid according to the present invention with the dilution of the water of at least 50wt%, preferably at least 70wt%.
By treatment fluid according to the present invention, it is preferable that the workpiece with the surface made of zinc or kirsite can be set
There is conversion coating.In this regard, can make equipped with the zinc for thering is cyanogen, alkaline non-cyanide or acid non-cyanogen zinc electrolysis deposition to generate by alkalinity
The workpiece passivation that coating is perhaps coated with the zinc layers made of thermal diffusion process can also make by melt it is zinc-plated or even by zinc or
The workpiece passivation of kirsite composition.Kirsite on workpiece surface may, for example, be Zn/Fe alloy, Zn/Ni alloy, Zn/Al and close
Gold and Zn/Co alloy.In addition it is also possible to workpiece be handled using reaction solution by mode according to the present invention, wherein removing zinc
Surface made of non-zinc or kirsite, such as iron-containing surface, such as steel surface are also exposed except surface or zinc alloy surface.
This kind of other surfaces can be passivated together with zinc surface or zinc alloy surface.In principal it is also possible to using according to the present invention anti-
Solution is answered to be passivated aluminium surface and aluminum alloy surface, iron surface and iron alloy surface, magnesium surface and Mg alloy surface and by cadmium
Manufactured surface and/or surface containing cadmium.
In addition, the present invention relates to a kind of with generating on metal surface, especially spelter coating or Zinc alloy coated workpiece
The method of conversion coating, wherein workpiece to be processed is contacted with treatment fluid according to the present invention.
Expediently, forming contact by dipping, that is, workpiece is immersed treatment fluid contained in container.For this purpose, can be by work
Part is maintained on shelf and shelf is immersed reaction solution, or workpiece is placed in shaft screen, in centrifuge or on pallet simultaneously
And shaft screen or pallet are immersed into reaction solution.In substitution method, workpiece can also be made to connect with treatment fluid by spray dipping
Touching.In other methods, workpiece can also be made to contact with treatment fluid by spraying.It, can also be by washing away in substitution method
Contact workpiece with treatment fluid.Furthermore it is also possible to coat workpiece, such as by nozzle, ejection place from the nozzle with treatment fluid
Reason liquid shoves.It is there are also a kind of processing method, treatment fluid is coated to workpiece table by brushing, roller coating or other paint-on techniques
On face.It can be handled in the conventional equipment of batch processing workpiece, or workpiece can be made to continue through and continuously locate
It is handled in the continuous operation facility of science and engineering part.
According to the method for the present invention the advantages of, is that this method can be similar with the universal method of the treatment fluid containing cobalt is used
Process conditions under complete.Thus, it is possible to utilize systems technology in the prior art.
In the preferred embodiment of the present invention, the plating bath for the treatment of fluid is about 20 to 100 DEG C, preferably 20 to 80
DEG C, it is 25 to 60 DEG C more preferable, 30 to 50 DEG C particularly preferred.
If contacting workpiece with treatment fluid by dipping, dip time is preferably 5 to 700 seconds, be more preferably 15 to
600 seconds, in particular 20 to 240 seconds.The technology contacted according to workpiece with reaction solution, it may be necessary to when longer or shorter processing
Between.
Before contacting with reaction solution, workpiece to be processed can be cleaned first.For example, if after electrogalvanising immediately
It contacts workpiece with reaction solution and then washes away galvanizing solution, also can be omitted above-mentioned operation.According to the method for the present invention
After end, preferably make workpiece dry, for example, being dried using hot-air.Further, it is also possible to rinse work before the drying
Part, to remove extra reaction solution from surface.
In the preferred embodiment of the present invention, the method is single phase.But it is same it is also conceivable that with
Other treatment fluids (such as sealing fluid) are handled the product of processing before or after applying conversion coating.
Another object of the invention is a kind of conversion coating prepared by the above method.
In one embodiment of the invention, conversion coating contains the change of element Cr, Si, O, F, C, H and Zr and/or Ti
Object is closed, which is more preferably made of these compounds, wherein may also contain the compound from metal surface, for example,
The compound of iron and/or zinc.The weight percent of element can be measured by energy dispersion X-ray spectrometer, EDX.
It finds in actual tests, is measured under the driving voltage of 20kV by energy dispersion X-ray spectrometer (EDX)
, the weight percent of element in the zinc surface being passivated according to the method for the present invention is usually in following range: with carbon, oxygen,
The total weight of fluorine, silicon, zirconium, titanium, chromium, iron, zinc, chromium usually account for 0.05-2wt%, preferably 0.1-1.5wt%, more preferable 0.15-
1.3wt%, especially 0.2-1.0wt%.With the total weight of carbon, oxygen, fluorine, silicon, zirconium, titanium, chromium, iron, zinc, silicon is usually accounted for
0.05-10wt%, preferably 0.1-7wt%, more preferable 0.2-5wt%, especially 0.3-3wt%.With carbon, oxygen, fluorine, silicon, zirconium,
The total weight of titanium, chromium, iron, zinc, oxygen usually account for 1-25wt%, preferably 1.5-22wt%, more preferable 2-20wt%, especially 3-
15wt%.With the total weight of carbon, oxygen, fluorine, silicon, zirconium, titanium, chromium, iron, zinc, fluorine usually accounts for 0.05-3wt%, preferably 0.1-
2wt%, more preferable 0.15-1.5wt%, especially 0.2-1.0wt%.With the gross weight of carbon, oxygen, fluorine, silicon, zirconium, titanium, chromium, iron, zinc
Meter, zirconium and/or titanium usually account for 0.1-5wt%, preferably 0.2-4wt%, more preferable 0.3-3wt%, especially 0.5-
2.5wt%.
In the preferred embodiment of the present invention, in conversion coating, the weight percent of zirconium and/or titanium is higher than chromium
Content.In this way, especially good anti-corrosion protection can be obtained in conjunction with Nano particles of silicon dioxide.Conversion coating can be with
Containing other elements, for example originating from Ni, Al, Fe, Co, Cd of treated surface.
For example, according to required Corrosion Protection, thus it is possible to vary the thickness of conversion coating.For most applications,
It is verified advantageously, adjustment conversion coating, makes its average layer thickness 100nm to 1000nm, preferably 100nm to 600nm, especially
150nm to 400nm.In this regard, thickness can be determined by measuring fracture in electronic scanner microscope.
A preferred embodiment of the invention, conversion coating are given to spelter coating or Zinc alloy coated product
Anti-corrosion protection, in the salt spray test according to ISO 9227 and/or ASTM B 117-73, regardless of whether by thermic load, such as
24 hours at 120 DEG C, before according to starting to occur corroding as defined in the 10th chapter of DIN 50961, which is more than 100 small
When, preferably greater than 200 hours, especially more than 240 hours.
Conversion coating according to the present invention another advantage is that can also prepare this conversion coating without colouring component.For example,
The conversion coating can show clear, transparent, essentially colorless and iris appearance on zinc.This is conducive to optionally adjust
Color, for example, being used to simplify the differentiation of component.For example, carrying out purposive coloring, energy by using treatment fluid according to the present invention
It is enough reliably and easily to distinguish right hand component and left hand component.The reliability of process can be greatly improved in this, especially a large amount of
When handling closely similar component.For this purpose, conversion coating can contain dyestuff or colored pigment.
As described above, conversion coating according to the present invention has made processed product have excellent anti-corrosion protection.Therefore,
Need not extra play, such as sealant be provided for product again.Nevertheless, conversion coating according to the present invention is also very suitable for as it
The substrate of his inorganic layer and/or organic layer.
Therefore, with conversion coating according to the present invention product or product can enduringly and therefore particularly advantageously by
Anti-corrosion protection.Object of the invention also includes the product or product with conversion coating according to the present invention.
The present invention is described in detail below with reference to several non-limiting examples:
Example 1: different treatment fluids according to the present invention is prepared
Prepare four kinds for the treatment of fluids according to the present invention with consisting of:
Treatment fluid 1
| Chromic nitrate (III) solution (74%) | 15.0 |
| Potassium tetrafluoroborate | 0.36 |
| Hexafluoro zirconate | 14.5 |
| Potassium Zirconium Fluoride | 3.0 |
| Hexafluorosilicic acid (35%) | 1.5 |
| Acticide MB | 2.0 |
| Korantin PP | 2.0 |
| Bindzil CC 401 | 50g/l |
Treatment fluid 2
| Chromic nitrate (III) solution (74%) | 10.0 |
| Tetrafluoro boric acid (50%) | 0.5 |
| Hexafluoro zirconate | 17.6 |
| Hexafluorosilicic acid (35%) | 1.5 |
| Bindzil CC 401 | 25g/l |
Treatment fluid 3
| Chromic nitrate (III) solution (74%) | 10.0 |
| Tetrafluoro boric acid (50%) | 0.5 |
| Hexafluoro zirconate | 17.6 |
| Hexafluorosilicic acid (35%) | 1.5 |
| Bindzil CC 401 | 25 |
| Oxalic acid | 1.5 |
Treatment fluid 4
| Chromic nitrate (III) solution (74%) | 10.0 |
| Tetrafluoro boric acid (50%) | 0.5 |
| Hexafluoro zirconate | 17.6 |
| Hexafluorosilicic acid (35%) | 1.5 |
| Bindzil CC 401 | 25 |
| Potassium hydrogen fluoride | 1.644 |
Example 2: galvanized steel plain sheet is handled by treatment fluid according to the present invention
The treatment fluid for preparing in use example 1 handles galvanized steel plain sheet.Here, being used without in the case where alkaline cyanide
It is commercially availableTo produce steel plate.Processing parameter setting is as follows:
| Treatment fluid | 1 | 2 | 3 | 4 |
| Treatment temperature | 40℃ | 40℃ | 40℃ | 40℃ |
| PH value | 3.2 | 3.0 | 3.0 | 3.0 |
| Handling duration | 2min | 1min | 120s | 120s |
Example 3: measurement is through handling the antiseptic property of steel plate
By the salt spray test according to ISO 9227 and ASTM B 117-73, check obtained in example 2 through processing steel plate
Antiseptic property.Obtain following result:
The result shows that conversion coating according to the present invention can give galvanized steel plain sheet anti-corrosion protection, according to DIN EN ISO
In the salt spray test of 9227 and/or ASTM B 117-73, even if 24 hours under 120 DEG C of thermic load, according to DIN
Start before occurring corroding as defined in 50961 the 10th chapters, which is more than 300 hours.
Example 4: the element for the conversion coating that measurement is prepared by treatment fluid 3 forms
The composition is measured by energy dispersion X-ray spectrometer (EDX).Measurement result is as shown in the table.
Table: by the knot of the energy dispersion X-ray spectrometer (EDX) of the conversion coating for the treatment of fluid 3 according to the present invention preparation
Fruit
As can be seen that the weight percent of zirconium is higher than the weight percent of chromium.
Example 5: the weight percent of the element in different types of conversion coating according to the present invention
The weight percent of element on passivation zinc surface according to the present invention is by energy dispersion X-ray spectrometer
(EDX) it measures under the driving voltage of 20kV and is assessed by EDAX Genesis V5.11.
Following table lists the weight percent of the element of 8 kinds of measured conversion coatings according to the present invention.
| KS 1 | KS 2 | KS 3 | KS 4 | KS 5 | KS 6 | KS 7 | KS 8 | KS 9 | |
| Element W% | |||||||||
| C K | 7.61 | 7.85 | 6.76 | 6.40 | 6.56 | 4.05 | 7.88 | 7.38 | 8.11 |
| O K | 8.74 | 7.97 | 7.29 | 6.43 | 6.92 | 4.79 | 9.19 | 11.14 | 10.68 |
| F K | 0.47 | 0.30 | 0.36 | 0.34 | 0.32 | 0.60 | n.b. | n.b. | n.b. |
| SiK | 3.06 | 2.72 | 2.37 | 1.44 | 1.50 | 0.80 | 3.19 | 4.52 | 3.63 |
| ZrL | 1.60 | 1.33 | 1.46 | 1.36 | 1.30 | 1.61 | 1.60 | 1.54 | 1.36 |
| CrK | 0.34 | 0.41 | 0.32 | 0.67 | 0.47 | 0.39 | 0.46 | 0.43 | 0.53 |
| FeK | 0.41 | 0.46 | 0.96 | 0.50 | 0.96 | 0.80 | 1.26 | 1.16 | 1.16 |
| ZnK | 77.78 | 78.96 | 80.48 | 82.86 | 81.96 | 86.95 | 76.41 | 73.84 | 74.52 |
| Total amount | 100.000 | 100.000 | 100.000 | 100.000 | 100.000 | 100.000 | 100.00 | 100.00 | 100.00 |
Detailed description of the invention
Fig. 1 shows the cross sections of the conversion coating prepared by treatment fluid 3 according to the present invention；
Fig. 2 indicates the cross section of the conversion coating prepared by treatment fluid 4 according to the present invention.
Specific embodiment
The cross section of the conversion coating prepared by treatment fluid 3 is shown in Fig. 1.The different position at 10, by being averaged
The thickness of value measurement conversion coating.Average layer thickness is about 300nm.
The cross section of the conversion coating prepared by treatment fluid 4 is shown in Fig. 2.The different position at 10, by being averaged
The thickness of value measurement conversion coating.Average layer thickness is about 250nm.
| Element | Wt% | At% |
| CK | 6.36 | 19.80 |
| OK | 12.75 | 29.78 |
| FK | 0.61 | 1.19 |
| SiK | 4.57 | 6.09 |
| ZrL | 1.97 | 0.81 |
| CrK | 0.51 | 0.37 |
| FeK | 1.03 | 0.69 |
| ZnK | 72.20 | 41.28 |
| Total amount | 100.00 | 100.00 |
Claims (15)
1. a kind of on the metal surface, especially generating the aqueous treatment of conversion coating on zinc surface or zinc alloy surface
Liquid, wherein the treatment fluid contains:
Content is the trivalent chromic ion of 0.1g/l to 8.0g/l；
Content is the zirconium ion and/or titanium ion of 0.1g/l to 15g/l；
Content is the organosilane-modified Nano particles of silicon dioxide of 0.1g/l to 50g/l；
Content is the fluorine ion of 0.1g/l to 15g/l.
2. treatment fluid according to claim 1, which is characterized in that the content of hexavalent chromium is lower than 1mg/l and/or cobalt
The content of ion is lower than 10mg/l lower than the content of 10mg/l and/or Ni ion.
3. treatment fluid according to claim 1 or 2, which is characterized in that the organosilane-modified silica nanometer
Particle includes the reunion silica core that organic silane compound is arranged on surface.
4. according to the treatment fluids one or more in preceding claims, which is characterized in that the silica dioxide nano particle
Oxygen atom on sublist face and epoxy silane, amide base silane, ureido silane, amino silane, ester silane, hydrosulphonyl silane and/or
The silicon atom covalent bonding of isocynate silane.
5. according to the treatment fluids one or more in preceding claims, which is characterized in that the silane-modified nanometer
The average grain diameter of particle is 5nm to 50nm.
6. according to the treatment fluids one or more in preceding claims, which is characterized in that the trivalent in the treatment fluid
Molar ratio between chromium ion and zirconium and/or titanium ion is 0.1 to 2.0.
7. according to the treatment fluids one or more in preceding claims, which is characterized in that pH value between about 1.5 to 5 it
Between.
8. according to the treatment fluids one or more in preceding claims, which is characterized in that volatile organic compounds
(VOC) content is lower than 10wt%.
9. a kind of concentrate being used to prepare according to the treatment fluids one or more in preceding claims, which is characterized in that
Active material concentration allows to dilute by the water of at least 50wt%, preferably at least 70wt% of the total weight to the treatment fluid
To prepare the treatment fluid.
10. a kind of kit, it includes at least two kinds of concentrates according to claim 9 of different compositions.
11. it is a kind of on metal surface, especially spelter coating or Zinc alloy coated workpiece generate conversion coating method,
In, workpiece to be processed with contacted according to claim 1 to the treatment fluids one or more in 8.
12. a kind of conversion coating prepared by method according to claim 11.
13. conversion coating according to claim 11 or 12, which is characterized in that its contain element Cr, Si, O, F, C, H and
The compound of Zr and/or Ti.
14. conversion coating according to claim 12 or 13, which is characterized in that in the conversion coating, the weight of zirconium and/or titanium
High percentage is measured in the content of chromium.
15. one or more conversion coatings in 2 to 14 according to claim 1, which is characterized in that average layer thickness 100nm
To 1000nm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102016005656.8 | 2016-05-11 | ||
| DE102016005656.8A DE102016005656A1 (en) | 2016-05-11 | 2016-05-11 | Conversion layers for metallic surfaces |
| PCT/EP2017/000560 WO2017194187A1 (en) | 2016-05-11 | 2017-05-05 | Conversion coatings for metal surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109312467A true CN109312467A (en) | 2019-02-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780028103.0A Pending CN109312467A (en) | 2016-05-11 | 2017-05-05 | The conversion coating of metal surface |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20190145009A1 (en) |
| EP (1) | EP3455392A1 (en) |
| JP (1) | JP6882340B2 (en) |
| CN (1) | CN109312467A (en) |
| DE (1) | DE102016005656A1 (en) |
| WO (1) | WO2017194187A1 (en) |
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| JP7385275B2 (en) | 2020-10-02 | 2023-11-22 | 日本表面化学株式会社 | Cobalt-free chemical conversion coating treatment solution and chemical conversion coating treatment method using the same |
| DE102021204609A1 (en) * | 2021-05-06 | 2022-11-10 | FNT-GmbH | Process for coating zinc die-cast parts, multi-layer coating to protect zinc die-cast parts and coated zinc die-cast part |
| DE102022105844A1 (en) | 2022-03-14 | 2023-09-14 | Carl Freudenberg Kg | Passivation layer for metal-containing substrates |
| DE102022126251A1 (en) | 2022-10-11 | 2024-04-11 | Liebherr-Aerospace Lindenberg Gmbh | Surface treatment processes |
| DE102023001507A1 (en) | 2023-04-17 | 2024-04-04 | Mercedes-Benz Group AG | Method and device for reactivating a conversion layer |
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| Publication number | Publication date |
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| WO2017194187A1 (en) | 2017-11-16 |
| JP6882340B2 (en) | 2021-06-02 |
| EP3455392A1 (en) | 2019-03-20 |
| DE102016005656A1 (en) | 2017-11-16 |
| US20190145009A1 (en) | 2019-05-16 |
| JP2019515143A (en) | 2019-06-06 |
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