CN106232872B - The coloured conversion coatings of non-chromate for aluminium - Google Patents
The coloured conversion coatings of non-chromate for aluminium Download PDFInfo
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- CN106232872B CN106232872B CN201580021874.8A CN201580021874A CN106232872B CN 106232872 B CN106232872 B CN 106232872B CN 201580021874 A CN201580021874 A CN 201580021874A CN 106232872 B CN106232872 B CN 106232872B
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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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- 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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- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The present invention relates to a kind of methods for forming coloured conversion coating on aluminum substrates using acidic aqueous compositions, wherein the acidic aqueous compositions include chromium (III), elements Mo and/or W, fluoride source and at least one oxidant with the standard electrode potential in+1.0 to+1.8V (SHE) ranges.The invention further relates to acidic aqueous compositions that can be used in the method and application thereof.
Description
Technical field
The present invention relates to a kind of methods for forming coloured conversion coating on aluminum substrates using acidic aqueous compositions.This hair
The bright acidic aqueous compositions and application thereof further related to can be used in the method.
Background technique
Such as cited a large amount of existing technical literatures report the conversion of Chrome-free on the metal surface in WO 94/28193
The formation of layer.The conversion coating is colorless and transparent, therefore surface is transparent (bright) in appearance.However, more enabling
People is it is expected that as conversion processing as a result, conversion coating is visually quickly can eye recognition.This to hold
Easily determine this method whether successful implementation and result in homogenous product.Due to there is no color, need glimmering using such as x-ray
The result of transformation processing method is analyzed in the surface analyses such as light analysis.Although this laborious and more time-consuming method to be based on
The product of Cr VI has notified carcinogenic but still has been used to build in aluminium market.
Summary of the invention
Therefore, it is necessary to use the substance of non-hexavalent chromium to form the method for coloured conversion coating on aluminum substrates adding
It is used in work and the product of acquisition and there are carcinogens.Thus obtained coating does not need more laborious technical steps
It readily recognizes.
The present invention provides such coating methods, the following discovery based on inventor: by making aluminium base and comprising chromium
(III), elements Mo and/or W, fluoride source and there is standard electrode potential in+1.0 to+1.8V (SHE) ranges
The acidic aqueous compositions of at least one oxidant contact, and can form coloured conversion coating on aluminum substrates.
Thus the advantage of the coating prepared is the homogeneity that its permission is judged product by human eye.Moreover, it has been discovered that herein
The method of description for it is anticorrosive conversion provide then can the form such as coating, adhesive phase or protective layer application have
The improved adhesiveness of machine layer.In addition, not needing the valuableness carried out to Cr VI substance and expense compared with prior art compositions
When disposition.
In a first aspect, present invention accordingly relates to the methods that one kind forms coloured conversion coating on aluminum substrates, wherein making
The aluminium base is contacted with acidic aqueous compositions, and the acidic aqueous compositions include:
A) at least one water soluble compound as the source chromium (III),
B) at least one water soluble compound of elements Mo and/or W,
C) as at least one water soluble compound of fluoride source,
D) have standard electrode potential in+1.0 to+1.8V (SHE) ranges is different from component a)-c) at least one
Kind oxidant.
In second aspect, the present invention relates to acidic aqueous compositions, it includes:
A) at least one water soluble compound as the source chromium (III), content are calculated as 0.1-2g/kg with element Cr,
B) at least one water soluble compound of elements Mo, content are calculated as 0.01-0.2g/ with elements Mo and/or W
Kg,
C) as at least one water soluble compound of fluoride source,
D) have standard electrode potential in+1.0 to+1.8V (SHE) ranges is different from component a)-c) at least one
Kind oxidant, content, with H2O2It is calculated on the basis of equivalent, is 0.01-1.0g/kg,
Wherein at least one water solubilityization of total fluoride of at least one water soluble compound of component c) and component a)
The molar ratio for closing the element Cr of object is at least 3:1.
Specific embodiment
"at least one" used herein refers to more than one, such as 1,2,3,4,5,6,7,8,9 or more.If
This term refers to the compound in composition described herein, which does not refer to the amount of molecule, and refers to compound
Type.Such as " at least one water soluble compound as the source chromium (III) " refers to more than one differences as the source chromium (III)
The water soluble compound of type, such as different salt.When being applied in combination with specified rate, the specified rate is intended to cover above-mentioned each
The total amount of type component.
Normally, used herein " about " to refer to ± 20%, preferably ± the 10% of its signified numerical value.Therefore, " about
200 " refer to 200 ± 40, preferably 200 ± 20.
Unless explicitly stated otherwise, the amount of all components is total relative to the composition in composition described herein
The weight fraction of weight.Unless otherwise specified, which is intended to refer to the total amount relative to correlation type component in composition.For example,
The amount provided about " at least one water soluble compound as the source chromium (III) ", which refers to, can be used as the source chromium (III) in composition
Water soluble compound total amount.
" water solubility " used herein refers to the 1kg deionized water (μ of κ < 1 Scm at 20 DEG C-1) in each compound dissolution
Degree is at least 1g.
Composition used in the method for the present invention is substantially free of Cr VI." base used in this regard
Be free of in sheet " refer to the content of 6-valence Cr ions based on total chrome content lower than 5 moles of %, preferably shorter than 1 mole of %.
Acidic aqueous compositions according to method of the first aspect of the present invention have 0-7, preferably 1-6, more preferable 2.5-
4, even more preferably about 3 pH value.PH value usable acid (such as aqueous acids) and/or with buffering well-known to those skilled in the art
System is adjusted.Acid can be but not limited to HCl, HNO3、H2SO4, and/or H3PO4, preferably H2SO4Or HNO3.In addition, HNO3It can use
Make component d).Such as H can be used in buffer system3PO4Conjugate base and/or ammonia formed.PH in the context of the invention refers at 25 DEG C
Hydrogen ion activity with 10 for bottom negative logarithm.
In the method according to a first aspect of the present invention, contact aluminium base with acidic aqueous compositions, wherein institute
Contact is stated to complete by any suitable method known in the art.Those methods can be for example including spraying, dip-coating, spin coating, print
Brush etc..Contact procedure can manually or automatically be implemented.Aluminium base can be made to contact one with acidic aqueous compositions according to the present invention
It is secondary or several times, such as 1,2,3,4,5,6,7,8,9 time and more times.
In the preferred embodiments of the invention according to first aspect, aluminium base is made to pass through dipping or spraying method, excellent
Spraying method was gated to contact with acidic aqueous compositions.In preferred embodiments, time of contact is at least 10 seconds, but preferably not
It is longer than 600 seconds, is more preferably no longer than 200 seconds.
In a further preferred embodiment, the temperature of acidic aqueous compositions in the methods of the invention is at least 15
DEG C, but preferably no greater than 80 DEG C, more preferably no higher than 70 DEG C.
The said components that acidic aqueous compositions according to a first aspect of the present invention are included further have following feature.
At least one water soluble compound as the source chromium (III), which can be, is dissolvable in water appointing in water according to above-mentioned definition
What compound.Preferred source Cr (III) is Cr (III) salt, including but not limited to chromium trifluoride (III) (CrF3), chromic nitrate
(III), chromium acetate (III), chromium gluconate (III) and/or chromium sulfate (III)；It is preferred that source is chromium trifluoride (III).Except mentioning
To those of except, it is possible to use other suitable salt are known to the skilled in the art.The example of the salt is six
Chloride hydrate chromium (III), chromium hydroxide (III) etc..
In another preferred embodiment of first aspect present invention, relative to acidic aqueous compositions, in terms of element Cr
It calculates, the amount of component a) is at least 10ppm, preferably 100ppm, is more preferably greater than 500ppm in acidic aqueous compositions, but preferably not
More than 2g/kg, more preferably no more than 1.5g/kg.Term " ppm " in the context of the invention refers to " in each million parts by weight
Number ", therefore 1ppm be equal to 0.0001 weight %.
It can be according at least one water soluble compound of the elements Mo of component b) in acidic aqueous compositions and/or W
According to above-mentioned definition it is water-soluble in any compound.The example of suitable compound is those chemical combination as known in the art
Object, including but not limited to such as molybdate, phosphomolybdic acid, molybdenum chloride, tungstates (such as sodium tungstate).In preferred embodiment
In, the water soluble compound of elements Mo is molybdate.Molybdate can be discrete (discrete's) or polymerization
(polymeric), there are any suitable counter ion counterionsl gegenions.
In the further preferred embodiment of first aspect present invention, relative to acidic aqueous compositions, with element
Mo and/or W is calculated, and the amount of component b) is at least 10ppm, preferably at least 20ppm in acidic aqueous compositions, but is preferably more than
200ppm, more preferably no more than 100ppm.
It can be selected from hydrofluoric acid, letter according to the water soluble compound as fluoride source of component c) in acidic aqueous compositions
Single (simple) fluoride (such as sodium fluoride or charomic fluoride (III)) and compound (complex) fluoracid (such as fluorine
Metatitanic acid or fluorine zirconic acid) and its water soluble salt.
Different from component a)-c) at least one oxidant there is standard restoration in+1.0 to+1.8V (SHE) ranges
Current potential.The standard electrode potential refers to commonly known standard hydrogen electrode (SHE), is the standard electric of oxidation-reduction electrode and hydrogen
It is zero at all temperatures to be formed for the basis compared with all other electrode reaction that electrode potential, which is declared,.According to this hair
" oxidant " of bright compound d) it is preferably not included that dissolved oxygen or metallic element water soluble compound.Correspondingly, " it is different from group
Divide a)-c) " refer to compound a)-c) it cannot be considered oxidant in the sense of the present invention, and the oxidant simultaneously
Type must be different with component a)-c) the two.In other words, this also means that oxidant is not to fall into component
A)-c) define interior compound, i.e., it is not the source chromium (III), molybdenum source, tungsten source or fluoride source.Different from component a)-c) at least
A kind of oxidant can be such as HNO3Or H2O2。
In the preferred embodiment of first aspect present invention, with H2O2It is calculated on the basis of equivalent, in acidic aqueous compositions
The amount of component d) is 0.01-1.0g/kg, more preferable 0.05-0.5g/kg.
In a further preferred embodiment, component d) is selected from water-soluble peroxide and/or elemental nitrogen, sulphur or chlorine
Oxyacid and its water soluble salt, are preferably selected from hydrogen peroxide.
In another preferred embodiment of first aspect present invention, relative to aqueous acidic composition, acidic aqueous group
The amount for closing Free Fluoride in object is 10-200ppm.Free Fluoride in acidic aqueous compositions in the methods of the invention
Content can directly be measured in acidic aqueous compositions of the invention at 25 DEG C by using the fluoride sensitive electrode of calibration.
In the further preferred embodiment of first aspect present invention, relative to total composition, acidic aqueous combination
Object includes the water soluble compound for amounting to element Zr and/or Ti less than 50ppm, more preferably less than 10ppm.These compounds are past
Toward the formation that can interfere the coloured conversion coating based on chromium (III), therefore the presence of these compounds is undesirable.
, can be by metal surface water after being contacted with acidic aqueous compositions described herein --- for example use deionization
Water --- it rinses.According to the type of the coating then carried out with organic polymer, after metal surface is rinsed with deionized water
Optionally it is dried.If the coating carried out using organic polymer is for example by being impregnated into water-based paints dispersion for metal surface
Middle progress, then do not need drying after rinsing.However, if the coating based on organic polymer is that such as adhesive or powder apply
It covers, then preferably metal surface is dried before this step.
Aluminium base can be with any shape --- such as aluminum strip, aluminium sheet or aluminium parts --- provides.It will can locate according to the present invention
The aluminium parts of reason are connected to other metal parts by adhesive phase.
Aluminium base in the method for the present invention can be provided with any shape such as aluminum strip, aluminium sheet or aluminium parts.
Being allowed to the aluminium base contacted with acidic aqueous compositions according to a first aspect of the present invention can make without any pretreatment
With, or can be pre-processed, such as pre-processed with the soda-wash solution or acidic derusting solution for being suitable for the method for the present invention.
All preprocess methods and reagent are known to the skilled in the art.Pretreatment can be carried out manually or automatically.For example, can
The of short duration pickling in cold concentrated nitric acid by aluminium base, or surface can alternatively be polished smooth with scraper plate.Optionally, it can incite somebody to action
Substrate is simply rinsed with water such as deionized water, but and this external application acid solution derusting.These processing can be used or be combined respectively
It uses.Can have for any pretreated solution and be suitable for the pretreated temperature, preferably 10-70 DEG C, 20-55 DEG C or about
25 DEG C, the temperature depends on the desired effect of solution and solution.In addition, can be to aluminium base pretreatment 0.5-20 minutes, preferably
1-10 minutes, more preferably from about 3 minutes.
It according to a second aspect of the present invention include acidic aqueous compositions, it includes
A) at least one water soluble compound as the source chromium (III), content are calculated as 0.1-2g/kg with element Cr,
B) at least one water soluble compound of elements Mo, content are calculated as 0.01-0.2g/ with elements Mo and/or W
Kg,
C) as at least one water soluble compound of fluoride source,
D) have standard electrode potential in+1.0 to+1.8V (SHE) ranges is different from component a)-c) at least one
Kind oxidant, content, with H2O2It is calculated on the basis of equivalent, is 0.01-1.0g/kg,
The change of the compound of the component a) wherein calculated with element Cr and the component b) calculated with elements Mo and/or element W
The molar ratio for closing object is preferably 15:1 to 25:1, and
Wherein at least one water solubilityization of total fluoride of at least one water soluble compound of component c) and component a)
The molar ratio for closing the element Cr of object is at least 3:1.Component a) to component c) derive from different compounds it is not necessary to.?
This respect, water soluble compound charomic fluoride (III) can be component a) and component c) simultaneously.On the other hand, it defines through the invention
The compound according to component d) cannot simultaneously be component a)-c) one of compound, therefore be different from these components.
In preferred embodiments, in composition at least one water soluble compound of component c) total fluoride and group
The molar ratio of the element Cr of at least one water soluble compound a) is divided to be not more than 10:1.
The content of total fluoride can be in 25 DEG C of sample volume in acidic aqueous compositions according to a second aspect of the present invention
At a temperature of by using the fluoride sensitive electrode of calibration by the sample volume for the buffering taken out from acidic aqueous compositions
It is determined according to described in DIN 38405-D-4-1 in (TISAB: " total ionic strength adjusting buffer ").
It is fixed that all embodiments described herein in relation to the method for the present invention are equally applicable to second aspect of the present invention
The composition of justice, vice versa.This is particularly related to composition used in described method and thus first party of the present invention
Relevant all preferred embodiments disclosed herein are similarly applicable for described composition in the context in face.
Embodiment
In the method program being listed below, aluminum deck (AA6060) is handled to produce colored coating.To painting
Layer has carried out the test of the bond properties for the organic resin based on polyester.
Circulation:
1. alkali cleaning (34 A of Ridoline G (3.5%), 55 DEG C, 3 minutes)
2. rinsing
3. acid etch (255 A of Grametal DX (3%), 25 DEG C, 3 minutes)
4. rinsing
5.DI is rinsed
6. conversion coating handles (35 DEG C, 45 seconds, spouting pressure: 1 atmospheric pressure)
7.DI is rinsed
According to above-mentioned method program, while handling aluminum deck, by using following different conversions
Coating composition carries out conversion processing.
Comparative example CE1:
34ppm is from source compound H2TiF6Ti
56ppm Gantrez
35ppm polyvinyl alcohol
PH value is 3.0 ± 0.1.
Comparative example CE2:
The transformation coating compound of comparative example CE2 extraly includes molybdenum of the 25ppm from source compound ammonium heptamolybdate.
Embodiment E1:
PH to be adjusted to 3.0 a certain amount of HNO3。
Embodiment E2:
The transformation coating compound of embodiment E1 includes molybdenum of the 25ppm from source compound ammonium heptamolybdate.
Embodiment E3:
The transformation coating compound of embodiment E1 includes molybdenum of the 25ppm from source compound ammonium heptamolybdate.
Embodiment E4:
The transformation coating compound of embodiment E1 includes molybdenum of the 100ppm from source compound ammonium heptamolybdate.
(Corro-Coat PE-F series 2403, JotunA/S, is moved all processed component polyester powder coatings
Prestige) it coats and solidifies 20 minutes at 180-190 DEG C.
The result of wet adherency test (Wet Adhesion Test) is summarized in table 1, shows the embodiment of the present invention (E1-
E4 it) is sufficiently adhered on aluminum deck and better than the chrome free composition (CE1, CE2) unrelated with the molybdenum being additionally present.
Cr (III)-Mo conversion coating (E1~E4) is since when Mo is 12mg/kg as it can be seen that and further adding with Mo
Enter, it is seen that property quicklys increase.25~50mg/kg Mo gives seems ideal very excellent for real life application
Good color.Color intensity is similar with Ti-Mo technology (CE2).
Claims (23)
1. acidic aqueous compositions, it includes:
A) at least one water soluble compound as the source chromium III, content are calculated as 0.1-2g/kg with element Cr,
B) at least one water soluble compound of elements Mo and/or W, content are calculated as 0.01-0.2g/ with elements Mo and/or W
Kg,
C) as at least one water soluble compound of fluoride source,
D) relative to standard hydrogen electrode SHE, have the standard electrode potential in+1.0 to+1.8V ranges is different from component
A)-c) at least one oxidant, with H2O2It is calculated on the basis of equivalent, content 0.01-1.0g/kg,
Wherein at least one water soluble compound of total fluoride of at least one water soluble compound of component c) and component a)
The molar ratio of element Cr be at least 3:1.
2. the composition of claim 1, wherein total fluoride of at least one water soluble compound of component c) is with component a's)
The molar ratio of the element Cr of at least one water soluble compound is not more than 10:1.
3. the composition of claims 1 or 2, wherein with the compound of the component a) of element Cr calculating and with elements Mo and/or W
The molar ratio of the compound of the component b) of calculating is 15:1-25:1.
4. the composition of claims 1 or 2, wherein calculated with element Cr, the amount of component a) is at least 500ppm.
5. the composition of claim 4, wherein calculated with element Cr, the amount of component a) is not more than 1.5g/kg.
6. the composition of claims 1 or 2, wherein component a) is selected from chromium trifluoride (III), chromic nitrate (III) and/or chromium sulfate
(III)。
7. the composition of claim 6, wherein component a) is selected from chromium trifluoride (III).
8. the composition of claims 1 or 2, wherein calculated with elements Mo and/or W, the amount of component b) is at least 20ppm.
9. the composition of claim 8, wherein calculated with elements Mo and/or W, the amount of component b) is not more than 100ppm.
10. the composition of claims 1 or 2, wherein component b) is selected from the water soluble compound of elements Mo.
11. the composition of claim 10, wherein component b) is selected from molybdate.
12. the composition of claims 1 or 2, wherein the amount of Free Fluoride is 10-200ppm.
13. the composition of claims 1 or 2, wherein with H2O2It is counted on the basis of equivalent, the amount of component d) is 0.05-0.5g/kg.
14. the composition of claims 1 or 2, wherein component d) is selected from water-soluble peroxide and/or elemental nitrogen, sulphur or chlorine
Oxyacid.
15. the composition of claim 14, wherein component d) is selected from hydrogen peroxide and/or nitrate ion.
16. the composition of claim 15, wherein component d) is hydrogen peroxide.
17. the method for forming coloured conversion coating on aluminum substrates, wherein making any in aluminium base and according to claim 1-16
Acidic aqueous compositions contact described in.
18. the method for claim 17, wherein the aluminium base is made to pass through dipping or spraying method and the acidic aqueous combination
Object contact.
19. the method for claim 18, wherein contacting the aluminium base with the acidic aqueous compositions by dipping method.
20. the method for any one of claim 17-19, wherein the time of contact of the dipping method is at least 10 seconds.
21. the method for claim 20, wherein the time of contact of the dipping method is no longer than 200 seconds.
22. the method for any one of claim 17-19, wherein the temperature of the acidic aqueous compositions is at least 15 DEG C.
23. the method for claim 22, wherein the temperature of the acidic aqueous compositions is not higher than 50 DEG C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB1407690.5A GB201407690D0 (en) | 2014-05-01 | 2014-05-01 | Non chromate coloured conversion coating for aluminum |
| GB1407690.5 | 2014-05-01 | ||
| PCT/EP2015/059322 WO2015165956A1 (en) | 2014-05-01 | 2015-04-29 | Non chromate colored conversion coating for aluminum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106232872A CN106232872A (en) | 2016-12-14 |
| CN106232872B true CN106232872B (en) | 2019-04-23 |
Family
ID=50980422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580021874.8A Active CN106232872B (en) | 2014-05-01 | 2015-04-29 | The coloured conversion coatings of non-chromate for aluminium |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP3137652B1 (en) |
| CN (1) | CN106232872B (en) |
| ES (1) | ES2703560T3 (en) |
| GB (1) | GB201407690D0 (en) |
| TW (1) | TW201602410A (en) |
| WO (1) | WO2015165956A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3073529B1 (en) * | 2017-11-14 | 2021-07-02 | Mecaprotec Ind | PROCESS FOR SURFACE TREATMENT OF A PART COATED WITH A CADMIUM COATING AND COMPOSITION FOR THE IMPLEMENTATION OF SUCH A PROCESS |
| CN110983411A (en) * | 2020-01-07 | 2020-04-10 | 昆明理工大学 | Preparation method of natural color conversion film on surface of aluminum alloy |
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| US20070243397A1 (en) * | 2006-04-17 | 2007-10-18 | Ludwig Robert J | Chromium(VI)-free, aqueous acidic chromium(III) conversion solutions |
-
2014
- 2014-05-01 GB GBGB1407690.5A patent/GB201407690D0/en not_active Ceased
-
2015
- 2015-04-29 WO PCT/EP2015/059322 patent/WO2015165956A1/en active Application Filing
- 2015-04-29 ES ES15722112T patent/ES2703560T3/en active Active
- 2015-04-29 CN CN201580021874.8A patent/CN106232872B/en active Active
- 2015-04-29 EP EP15722112.8A patent/EP3137652B1/en active Active
- 2015-05-01 TW TW104114064A patent/TW201602410A/en unknown
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| GB2097024A (en) * | 1981-04-16 | 1982-10-27 | Hooker Chemicals Plastics Corp | Treating metal surfaces to improve corrosion resistance |
| CN1714171A (en) * | 2002-04-29 | 2005-12-28 | Ppg工业俄亥俄公司 | Conversion coatings including alkaline earth metal fluoride complexes |
| EP1571238A1 (en) * | 2004-03-02 | 2005-09-07 | Nihon Hyomen Kagaku Kabushiki Kaisha | Aluminium elements, processes and compositions for producing aluminium surface free- chromium (VI) chromate coatings |
| CN1858303A (en) * | 2006-06-09 | 2006-11-08 | 广东多正化工科技有限公司 | Normal temperature passivated zinc coating trivalent chromium color passivating agent |
| CN101338421A (en) * | 2007-07-03 | 2009-01-07 | 天津市瀚隆镀锌有限公司 | Preparation of colorful passivation treatment agent after steel galvanization |
| WO2013126632A1 (en) * | 2012-02-23 | 2013-08-29 | Ppg Industries Ohio, Inc. | Replenishing compositions and methods of replenishing pretreatment compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201602410A (en) | 2016-01-16 |
| EP3137652A1 (en) | 2017-03-08 |
| WO2015165956A1 (en) | 2015-11-05 |
| CN106232872A (en) | 2016-12-14 |
| GB201407690D0 (en) | 2014-06-18 |
| EP3137652B1 (en) | 2018-10-10 |
| ES2703560T3 (en) | 2019-03-11 |
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