EP0180523A1 - Process for zinc phosphate coating, activation and grain refining bath used in this process and concentrate therefor - Google Patents
Process for zinc phosphate coating, activation and grain refining bath used in this process and concentrate therefor Download PDFInfo
- Publication number
- EP0180523A1 EP0180523A1 EP85402096A EP85402096A EP0180523A1 EP 0180523 A1 EP0180523 A1 EP 0180523A1 EP 85402096 A EP85402096 A EP 85402096A EP 85402096 A EP85402096 A EP 85402096A EP 0180523 A1 EP0180523 A1 EP 0180523A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- bath
- activation
- ppm
- refining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 230000004913 activation Effects 0.000 title claims abstract description 27
- 238000007670 refining Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000012141 concentrate Substances 0.000 title claims description 12
- 239000011248 coating agent Substances 0.000 title description 3
- 238000000576 coating method Methods 0.000 title description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 title description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 title description 2
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000008399 tap water Substances 0.000 claims abstract description 9
- 235000020679 tap water Nutrition 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000470 constituent Substances 0.000 claims abstract description 6
- 238000005238 degreasing Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims abstract description 3
- 150000001447 alkali salts Chemical class 0.000 claims abstract 2
- 150000003863 ammonium salts Chemical class 0.000 claims abstract 2
- 239000000758 substrate Substances 0.000 claims abstract 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000001488 sodium phosphate Substances 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- -1 alkyl radical Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000005840 aryl radicals Chemical group 0.000 claims description 2
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- QWZRZYWLWTWVLF-UHFFFAOYSA-N O.OP(O)=O Chemical compound O.OP(O)=O QWZRZYWLWTWVLF-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000007654 immersion Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- DKPHLYCEFBDQKM-UHFFFAOYSA-H hexapotassium;1-phosphonato-n,n-bis(phosphonatomethyl)methanamine Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)CN(CP([O-])([O-])=O)CP([O-])([O-])=O DKPHLYCEFBDQKM-UHFFFAOYSA-H 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- 235000019801 trisodium phosphate Nutrition 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229940006486 zinc cation Drugs 0.000 description 1
Classifications
-
- 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
- C23C22/78—Pretreatment of the material to be coated
- C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
Definitions
- step (3) can be omitted, the activating constituents then being introduced directly into the bath used for the step of alkaline degreasing.
- step (3) becomes essential in order to obtain a sufficiently fine and dense phosphating.
- the baths intended for carrying out the zinc phosphating step can comprise, in addition to the zinc cation, other metals such as nickel, manganese, calcium or possibly iron, as widely described in the scientific literature.
- the refining agents used at the time of the activation and refining step or which can be used at the time of the alkaline degreasing step in the case of processes carried out entirely by jet are constituted by compounds of titanium, in particular colloidal titanium salts known under the name of Jernstedt salts; these salts are described in particular in US Patent 2,456,947.
- Such a Jernstedt salt can be obtained by mixing 95 parts of disodium phosphate with 5 parts of potassium fluotitanate in an amount of water sufficient to dissolve the ingredients. The water is then removed from the mixture by evaporation at a temperature of 80 to 100 ° C.
- titanium can be used for the production of Jernstedt salt, such as for example titanium sulfate or titanium oxide.
- polyphosphates containing Jernstedt salts in particular in a proportion of 1 to 300 parts by weight of P207.
- Jernstedt salts are commonly found on the market and are in particular marketed by the Applicant Company under the trademark "FIXODINE 5".
- the object of the invention is, above all, to remedy these drawbacks and to ensure that, in the phosphating methods of the genus in question, the activation and refining step can be carried out with industrial water without overflow and supply of refining salts proportional to the quantities of water added while providing a refining and stability effect comparable to that obtained with demineralized water.
- R representing an alkyl radical or an aryl radical optionally substituted with at least one of the substituents of the group comprising the hydroxyl radical, other phosphonic groups and the amino groups of formula in which R 2 and R 3 which may be identical or different from each other, each represent a hydrogen atom or have the meaning of R 1 .
- the salts of these acids which can be used are those obtained by partial or total neutralization with alkaline ions such as Na and K or with the NH 4 ion.
- a bath which comprises, in addition to the conventional constituents including in particular at least one Jernstedt salt in a proportion corresponding to approximately 1 to 100 ppm of titanium, a proportion of 10 to 700 ppm, preferably of 50 to 200 ppm, of at least one alkane-phosphonic acid of formula (I) or one of its salts, the pH of the bath being from 7 to 9.5, preferably from 7.5 to 9.
- This bath is also targeted as a new industrial product.
- constituents of the refining bath used in accordance with the invention may be pyrophosphates or alkali citrates.
- the activation and refining step according to the invention is carried out at a temperature of 20 to 50 ° C.
- the stability of the bath used is sufficient for it to be able to operate under normal conditions without regeneration, that is to say without the addition of additional amounts of concentrate other than the normal amounts to be provided by consumption of the product, for approximately 5 15 days.
- the aim is to study the influence of different activation baths on the morphology of the zinc phosphate crystals deposited in the phosphating step.
- This morphology is examined using an electronic scanning micro-scape at a magnification of 1500.
- Two examinations are carried out, the first of which is carried out after treatment in a new bath, 10 minutes after its assembly, and the second of which is carried out after treatment in the same bath, 6 days after the assembly thereof.
- the activation bath comprises 2 g / l of Jermstedt salt (FIXODINE 5) in demineralized water corresponding to 20 ppm of titanium.
- FIXODINE 5 Jermstedt salt
- the other ingredients are sodium phosphates.
- the pH is 7.
- Example 2 Same composition and same pH as in Example 1, but the water consists of tap water.
- the pH 7.9.
- the bath is identical to that of Example 3, except that the phosphonic acid is present at the rate of 100 ppm.
- the bath is identical to that of Example 4, but the pH is brought to 9 with trisodium phosphate.
- the bath is identical to that of Example 6 except that the sodium salt of phosphonic acid is present at the rate of 200 ppm.
- the bath is identical to that of Example 7, except that the phosphonic acid is present at the rate of 100 ppm and the pH is then 7.
- test pieces thus treated are examined under the electron microscope, as indicated above.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Detergent Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Procédé de phosphatation au zinc de substrats essentiellement à base de fer, de zinc ou de leurs alliages, comprenent successivement: 1) une ou plusieurs étapes de dégraissage alcalin, 2) une ou plusieurs étapes de rinçage à l'eau de ville courante, 3) une étape d'activation et d'affinage, 4) une étape de phosphatation au zinc proprement dite, 5) une ou plusieurs étapes de rinçage à l'eau, 6) de préférence, une étape de rinçage final passivant, notamment à l'aide de sels de chrome hexavalent ou de mélanges de chrome hexavalent et de chrome trivalent, caractérisé par le fait que, pour la mise en oeuvre de l'étape d'activation et d'affinage, on a recours à un bain qui comporte, outre les constituants classiques dont notamment au moins un sel de Jernstedt en une proportion correspondant à environ 1 à 100 ppm de titane, une proportion de 10 à 700 ppm, de préférence de 50 à 200 ppm, au moins un acide alcane-phosphonique de formule: <IMAGE> ou d'au moins l'un des sels alcalins ou d'ammonium correspondant aux susdits acides alcane-phosphoniques, le pH du bain étant de 7 à 9,5, de préférence de 7,5 à 9.Process for the phosphating with zinc of substrates essentially based on iron, zinc or their alloys, successively comprise: 1) one or more stages of alkaline degreasing, 2) one or more stages of rinsing with running tap water, 3 ) an activation and refining step, 4) a zinc phosphating step proper, 5) one or more rinsing steps with water, 6) preferably, a passivating final rinsing step, in particular with using hexavalent chromium salts or mixtures of hexavalent chromium and trivalent chromium, characterized in that, for the implementation of the activation and refining step, a bath is used which comprises, in addition to the conventional constituents, in particular at least one Jernstedt salt in a proportion corresponding to approximately 1 to 100 ppm of titanium, a proportion of 10 to 700 ppm, preferably from 50 to 200 ppm, at least one alkane-phosphonic acid of formula : <IMAGE> or at least one of the alkali or ammonium salts corresponding to the above alkane-phosphonic acids, the pH of the bath being from 7 to 9.5, preferably from 7.5 to 9.
Description
L'invention a pour objet un procédé perfectionné de phosphatation au zinc du genre de ceux qui comprennent :
- 1) une ou plusieurs étapes de dégraissage alcalin,
- 2) une ou plusieurs étapes de rinçage à l'eau de ville courante,
- 3) une étape d'activation et d'affinage,
- 4) une étape de phosphatation au zinc proprement dite,
- 5) une ou plusieurs étapes de rinçage à l'eau,
- 6) de préférence, une étape de rinçage final passivant, notamment à l'aide de sels de chrome hexavalent ou de mélanges de chrome hexavalent et de chrome trivalent
et qui sont applicables aux surfaces d'objets essentiellement à base de fer, de zinc ou de leurs alliages.The subject of the invention is an improved process for zinc phosphating of the kind which comprises:
- 1) one or more alkaline degreasing steps,
- 2) one or more stages of rinsing with running tap water,
- 3) an activation and refining step,
- 4) a zinc phosphating step proper,
- 5) one or more stages of rinsing with water,
- 6) preferably a passivating final rinsing step, in particular using hexavalent chromium salts or mixtures of hexavalent chromium and trivalent chromium
and which are applicable to the surfaces of objects essentially based on iron, zinc or their alloys.
Elle vise également, et ce à titre de produits industriels nouveaux, le bain d'activation et d'affinage mis en oeuvre dans le cadre de ce procédé et le concentré à partir duquel est obtenu ce bain.It also relates, and this as new industrial products, the activation and refining bath used in the context of this process and the concentrate from which this bath is obtained.
On rappelle que les procédés du genre en question ont pour but de conférer à des surfaces, notamment d'acier, une bonne résistance à la corrosion, notamment après l'application de peintures dont l'adhérence se trouve favorisée.It is recalled that the processes of the kind in question are intended to impart to surfaces, in particular steel, good resistance to corrosion, in particular after the application of paints whose adhesion is favored.
Ces procédés de phosphatation au zinc conduisent à la formation sur les surfaces métalliques en question d'un revêtement cristallin ; ce revêtement cristallin doit être le plus fin et le plus dense possible pour conduire à la meilleure adhérence possible des couches de peinture ultérieures, notamment dans le cas des peintures du type élec- trophorétique.These zinc phosphating processes lead to the formation on the metal surfaces in question of a crystalline coating; this crystalline coating must be as thin and as dense as possible to lead to the best possible adhesion of the subsequent paint layers, in particular in the case of paints of the electrophoretic type.
Les étapes notamment d'activation et de phosphatation proprement dite sont effectuées à l'aide des bains appropriés soit par aspersion, soit par immersion, soit à la fois par aspersion et immersion.The steps in particular of activation and of phosphating proper are carried out using appropriate baths either by spraying, or by immersion, or both by spraying and immersion.
Dans le cas des procédés du genre en question effectués totalement au jet, c'est-à-dire par aspersion, l'étape (3) peut être omise, les constituants activants étant alors introduits directement dans le bain utilisé pour l'étape de dégraissage alcalin.In the case of processes of the kind in question carried out entirely by jet, that is to say by spraying, step (3) can be omitted, the activating constituents then being introduced directly into the bath used for the step of alkaline degreasing.
Par contre, dans le cas des procédés du genre en question qui, de préférence, mettent en oeuvre une immersion totale ou des opérations aspersion/immersion, ce qui est envisagé ici, le maintien de l'étape (3) devient indispensable pour obtenir une phosphatation suffisamment fine et dense.On the other hand, in the case of the processes of the type in question which, preferably, employ total immersion or spraying / immersion operations, which is envisaged here, the maintenance of step (3) becomes essential in order to obtain a sufficiently fine and dense phosphating.
Les bains destinés à la mise en oeuvre de l'étape de phosphatation au zinc peuvent comporter, outre le cation zinc, d'autres métaux comme le nickel, le manganèse, le calcium ou éventuellement le fer, comme largement décrit dans la littérature scientifique.The baths intended for carrying out the zinc phosphating step can comprise, in addition to the zinc cation, other metals such as nickel, manganese, calcium or possibly iron, as widely described in the scientific literature.
Les agents affineurs mis en oeuvre au moment de l'étape d'activation et d'affinage ou qui peuvent être mis en oeuvre au moment de l'étape de dégraissage alcalin dans le cas des procédés effectués totalement au jet sont constitués par des composés de titane, notamment des sels de titane colloidaux connus sous l'appellation de sels de Jernstedt ; ces sels sont décrits notamment dans le brevet US 2.456.947.The refining agents used at the time of the activation and refining step or which can be used at the time of the alkaline degreasing step in the case of processes carried out entirely by jet are constituted by compounds of titanium, in particular colloidal titanium salts known under the name of Jernstedt salts; these salts are described in particular in US Patent 2,456,947.
Un tel sel de Jernstedt peut être obtenu en mélangeant 95 parties de phosphate disodique avec 5 parties de fluotitanate de potassium dans une quantité d'eau suffisante pour dissoudre les ingrédients. L'eau est ensuite chassée du mélange par évaporation à une température de 80 à 100°C.Such a Jernstedt salt can be obtained by mixing 95 parts of disodium phosphate with 5 parts of potassium fluotitanate in an amount of water sufficient to dissolve the ingredients. The water is then removed from the mixture by evaporation at a temperature of 80 to 100 ° C.
D'autres sources de titane peuvent être utilisées pour la fabrication du sel de Jernstedt, comme par exemple le sulfate de titane ou l'oxyde de titane.Other sources of titanium can be used for the production of Jernstedt salt, such as for example titanium sulfate or titanium oxide.
On peut également aouter des polyphosphates aux sels de Jernstedt, notamment en une proportion de 1 à 300 parties en poids de P207.It is also possible to add polyphosphates containing Jernstedt salts, in particular in a proportion of 1 to 300 parts by weight of P207.
Les sels de Jernstedt se trouvent couramment sur le marché et sont en particulier commercialisés par la Société Demanderesse sous la marque de fabrique "FIXODINE 5".Jernstedt salts are commonly found on the market and are in particular marketed by the Applicant Company under the trademark "FIXODINE 5".
Etant donné la sensibilité des sels de Jernstedt à la dureté de l'eau utilisée pour monter le bain d'affinage, on a jusqu'à ce jour, dans les procédés du genre en question, utilisé soit de l'eau déminéralisée pour monter les bains d'activation, soit dans le cas d'utilisation d'eau industrielle fait fonctionner le bain par débordement avec apport de sels affineurs proportionnel aux quantités d'eau ajoutées.Given the sensitivity of the Jernstedt salts to the hardness of the water used to mount the refining bath, it has hitherto been used in processes of the kind in question, either demineralized water to mount the activation baths, that is to say in the case of the use of industrial water, operates the bath by overflow with the addition of refining salts proportional to the quantities of water added.
Une telle façon de procéder est coûteuse en eau et en produit actif, notamment lorsque le procédé de phosphatation est appliqué au traitement d'objets de grande surface par immersion tels que rencontrés dans l'industrie automobile pour les carrosseries, les bains de traitement étant alors très volumineux et pouvant atteindre couramment des volumes de 100 à 200 m .Such a procedure is costly in water and in active product, in particular when the phosphating process is applied to the treatment of large surface objects by immersion such as encountered in the automobile industry for bodywork, the treatment baths then being very bulky and can commonly reach volumes of 100 to 200 m.
L'invention a pour but, surtout, de remédier à ces inconvénients et de faire en sorte que, dans les procédés de phosphatation du genre en question, l'étape d'activation et d'affinage puisse être mise en oeuvre avec de l'eau industrielle sans débordement et apport de sels affineurs proportionnel aux quantités d'eau ajoutées tout en fournissant un effet d'affinage et de stabilité comparable à celui obtenu avec de l'eau déminéralisée.The object of the invention is, above all, to remedy these drawbacks and to ensure that, in the phosphating methods of the genus in question, the activation and refining step can be carried out with industrial water without overflow and supply of refining salts proportional to the quantities of water added while providing a refining and stability effect comparable to that obtained with demineralized water.
Or, la Société Demanderesse a trouvé que ce but pouvait être atteint par l'addition aux bains d'affinage et d'activation des procédés du genre en question d'une quantité efficace d'au moins un acide alcane phosphonique de formule (I) définie ci-dessous ou d'un sel correspondant.However, the Applicant Company has found that this object could be achieved by adding to the refining and activation baths of the processes of the type in question an effective amount of at least one alkane phosphonic acid of formula (I) defined below or a corresponding salt.
La susdite formule I, à laquelle répond l'acide alcane-phosphonique mis en oeuvre conformément à l'invention, est comme suit :
Les sels de ces acides qui sont utilisables sont ceux obtenus par neutralisation partielle ou totale par des ions alcalins tels que Na et K ou par l'ion NH4 .The salts of these acids which can be used are those obtained by partial or total neutralization with alkaline ions such as Na and K or with the NH 4 ion.
A titre d'exemple d'un tel sel, on indique celui de la formule (Ia) ci-après :
Parmi les acides alcane-phosphoniques de formule (I), on préfère plus particulièrement ceux du groupe comprenant :
- - l'acide hydroxyméthylphosphonique
- - l'acide hydroxypropylphosphonique
- - l'acide octylphosphonique
- - l'acide éthyl- et l'acide butylphosphonique
- - l'acide 1-hydroxyéthylidène-1.1-diphosphonique
- - l'acide amino-tri(méthylènephosphonique)
- - l'acide éthylène-diamine-tétra(méthylènephospho- nique) et
- - l'acide 2-phosphono-butane-1,2,4-tricarboxylique.
- - hydroxymethylphosphonic acid
- - hydroxypropylphosphonic acid
- - octylphosphonic acid
- - ethyl acid and butylphosphonic acid
- - 1-hydroxyethylidene-1.1-diphosphonic acid
- - amino-tri acid (methylenephosphonic)
- - ethylene-diamine-tetra (methylenephosphonic) acid and
- - 2-phosphono-butane-1,2,4-tricarboxylic acid.
Il s'ensuit que le procédé conforme à l'invention est caractérisé par le fait que, pour l'étape d'activation et d'affinage, on a recours à un bain qui comporte, outre les constituants classiques dont notamment au moins un sel de Jernstedt en une proportion correspondant à environ 1 à 100 ppm de titane, une proportion de 10 à 700 ppm, de préférence de 50 à 200 ppm, d'au moins un acide alcane- phosphonique de formule (I) ou d'un de ses sels, le pH du bain étant de 7 à 9,5, de préférence de 7,5 à 9.It follows that the method according to the invention is characterized in that, for the activation step and refining, a bath is used which comprises, in addition to the conventional constituents including in particular at least one Jernstedt salt in a proportion corresponding to approximately 1 to 100 ppm of titanium, a proportion of 10 to 700 ppm, preferably of 50 to 200 ppm, of at least one alkane-phosphonic acid of formula (I) or one of its salts, the pH of the bath being from 7 to 9.5, preferably from 7.5 to 9.
Ce bain est visé, par ailleurs, à titre de produit industriel nouveau.This bath is also targeted as a new industrial product.
Pour régler le pH à la valeur recherchée, on peut avoir recours à des proportions appropriées de tartrates, phosphates, polyphosphates et carbonates alcalins.To adjust the pH to the desired value, use may be made of appropriate proportions of tartrates, phosphates, polyphosphates and alkali carbonates.
D'autres constituants du bain d'affinage mis en oeuvre conformément à l'invention peuvent être des pyrophosphates ou des citrates alcalins.Other constituents of the refining bath used in accordance with the invention may be pyrophosphates or alkali citrates.
Des bains d'affinage dont la mise en oeuvre est particulièrement avantageuse sont ceux dont la composition est indiquée ci-après :Refining baths whose implementation is particularly advantageous are those whose composition is indicated below:
- - 2 g/1 de sel de Jernstedt (FIXODINE 5)- 2 g / 1 Jernstedt salt (FIXODINE 5)
- - 60 ppm du sel de sodium de l'acide aminotri-(méthylène-phosphonique)- 60 ppm of the sodium salt of aminotri- (methylene-phosphonic acid)
- - eau q.s.- water q.s.
- - 2 g/1 de sel de Jernstedt (FIXODINE 5)- 2 g / 1 Jernstedt salt (FIXODINE 5)
- - 200 ppm du sel de sodium de l'acide phosphonique- 200 ppm of the sodium salt of phosphonic acid
- - eau q.s.- water q.s.
- - 2 g/1 de sel de Jernstedt (FIXODINE 5)- 2 g / 1 Jernstedt salt (FIXODINE 5)
- - 50 ppm d'acide 1-hydroxyéthylidène-1,1-diphospho- nique,- 50 ppm of 1-hydroxyethylidene-1,1-diphosphonic acid,
- - eau q.s.- water q.s.
Pour préparer ces bains, on introduit successivement dans la quantité d'eau appropriée le sel de Jernstedt et l'acide phosphonique.To prepare these baths, successively introduce the appropriate amount of Jernstedt salt and phosphonic acid.
Plus généralement et notamment dans la pratique, on prépare ces bains à partir de concentrés contenant l'acide de formule (I) ou son sel et le sel de Jernstedt en des proportions telles que son mélange avec une quantité appropriée d'eau fournit le bain d'activation et d'affinage mise en oeuvre conformément à l'invention.More generally and in particular in practice, we prepare these baths from concentrates containing the acid of formula (I) or its salt and Jernstedt salt in proportions such that mixing it with an appropriate amount of water provides the activation and refining bath works in accordance with the invention.
Avantageusement, le concentré en question se présente sous forme de deux récipients séparés contenant respectivement, d'une part, le sel de Jernstedt et, d'autre part, une solution aqueuse de l'acide phosphonique de formule (I) ou de son sel, ces deux récipients pouvant être réunis de préférence sous la forme de ce qu'on appelle généralement un "kit" de traitement ; ce concentré peut également se présenter sous forme d'une poudre comprenant:
- - de 1 à 5 2 en poids de titane exprimé en titane (IV) sous forme de phosphate de titane
- - de 2,5 à 10 2 en poids d'acide phosphonique de formule (I)
- - de 89 à 92,5 X en poids de phosphate de sodium et de potassium.
- - from 1 to 5 2 by weight of titanium expressed as titanium (IV) in the form of titanium phosphate
- - from 2.5 to 10 2 by weight of phosphonic acid of formula (I)
- - from 89 to 92.5 X by weight of sodium and potassium phosphate.
Un exemple avantageux dudit concentré conforme à l'invention est celui de formule :
- - titane exprimé en titane (IV) sous forme de phosphate de titane ...... 2 % en poids
- - phosphate trisodique ............. 93 % en poids
- - acide 1-hydroxyéthylidène-1,1- diphosphonique ................... 5 % en poids.
- - titanium expressed as titanium (IV) in the form of titanium phosphate ...... 2% by weight
- - trisodium phosphate ............. 93% by weight
- - 1-hydroxyethylidene-1,1-diphosphonic acid ................... 5% by weight.
L'étape d'activation et d'affinage conforme à l'invention est effectuée à une température de 20 à 50°C.The activation and refining step according to the invention is carried out at a temperature of 20 to 50 ° C.
La stabilité du bain mis en oeuvre est suffisante pour qu'il puisse fonctionner en régime normal sans régénération, c'est-à-dire sans apport de quantités supplémentaires de concentré autres que les quantités normales à apporter par consommation du produit, pendant environ 5 à 15 jours.The stability of the bath used is sufficient for it to be able to operate under normal conditions without regeneration, that is to say without the addition of additional amounts of concentrate other than the normal amounts to be provided by consumption of the product, for approximately 5 15 days.
Les autres étapes du procédé de phosphatation au zinc conforme à l'invention, sont effectuées de manière conventionnelle.The other steps of the zinc phosphating process according to the invention are carried out in a conventional manner.
On en trouve la description détaillée notamment dans la demande de brevet français N* 80 03185.The detailed description is found in particular in French patent application N * 80 03185.
L'invention pourra être encore mieux comprise à l'aide des exemples décrits ci-après et dont les deux premiers sont des exemples comparatifs faisant ressortir les avantages inhérents à l'invention par rapport à l'état antérieur de la technique.The invention can be understood even better with the aid of the examples described below and the first two of which are comparative examples highlighting the advantages inherent in the invention compared with the prior art.
Dans ces exemples, seule l'étape d'activation et d'affinage est décrite, les autres étapes étant toujours les mêmes, la succession d'étapes étant la suivante :
- - étape de dégraissage alcalin par immersion dans un bain aqueux comportant une composition à base de sels alcalins, à savoir celle commercialisée par la Société Demanderesse sous la marque de fabrique "RIDOLINE 1501" à 1,5 / en poids/volume ainsi qu'une composition tensioactive, à savoir celle commercialisée par la Société Demanderesse sous la marque de fabrique "RIDOSOL 502 R" à 0,15 % en volume, la température étant de 60°C et la durée de 5 minutes ;
- - étape de rinçage à l'eau de ville courante à température ambiante ;
- - étape d'affinage conforme à l'invention par immersion pendant 1 minute à la température ambiante ;
- - étape de phosphatation au zinc à l'aide d'un bain aqueux comportant une composition à base de phosphates acides de zinc, à savoir celle commercialisée par la Société Demanderesse sous la marque de fabrique "GRANODINE 908". en procédant par immersion, pendant 3 minutes, à 55°C ;
- - une étape de rinçage à l'eau de ville courante,
- - une étape de séchage pendant 5 minutes sous courant d'air chaud à 80°C.
- - alkaline degreasing step by immersion in an aqueous bath comprising a composition based on alkaline salts, namely that marketed by the Applicant Company under the trademark "RIDOLINE 1501" at 1.5 / by weight / volume as well as a surfactant composition, namely that marketed by the Applicant Company under the trademark "RIDOSOL 502 R" at 0.15% by volume, the temperature being 60 ° C and the duration of 5 minutes;
- - rinsing step with running tap water at room temperature;
- - refining step according to the invention by immersion for 1 minute at room temperature;
- - Zinc phosphating step using an aqueous bath comprising a composition based on zinc acid phosphates, namely that marketed by the Applicant Company under the trademark "GRANODINE 908". by immersion, for 3 minutes, at 55 ° C;
- - a rinsing step with running tap water,
- - a drying step for 5 minutes under a stream of hot air at 80 ° C.
On s'attache à étudier dans ces exemples l'influence de différents bains d'activation sur la morphologie des cristaux de phosphate de zinc déposés dans l'étape de phosphatation.In these examples, the aim is to study the influence of different activation baths on the morphology of the zinc phosphate crystals deposited in the phosphating step.
Cette morphologie est examinée à l'aide d'un micro- scape électronique à balayage à un grossissement de 1500.This morphology is examined using an electronic scanning micro-scape at a magnification of 1500.
On pratique deux examens dont le premier est effectué après traitement dans un bain neuf, 10 minutes après ses montage, et dont le deuxième est effectué après trai- tellement dans le même bain, 6 jours après le montage de celui-ci.Two examinations are carried out, the first of which is carried out after treatment in a new bath, 10 minutes after its assembly, and the second of which is carried out after treatment in the same bath, 6 days after the assembly thereof.
Le bain d'activation comprend 2 g/l de sel de Jermstedt (FIXODINE 5) en eau déminéralisée correspondant à 20 ppm de titane.The activation bath comprises 2 g / l of Jermstedt salt (FIXODINE 5) in demineralized water corresponding to 20 ppm of titanium.
Les autres constituants sont des phosphates de sodium.The other ingredients are sodium phosphates.
Le pH est de 7.The pH is 7.
Même composition et même pH que dans l'exemple 1 mais l'eau est constituée par de l'eau du robinet.Same composition and same pH as in Example 1, but the water consists of tap water.
Le pH est de 7,9.The pH is 7.9.
Le bain d'activation comprend, dans de l'eau du robinet :
- - 2 g/1 de sel de Jernstedt (FIXODINE 5)
- - 50 ppm d'acide 1-hydroxyéthylidène-1,1-diphospho- nique,
- - 2 g / 1 Jernstedt salt (FIXODINE 5)
- - 50 ppm of 1-hydroxyethylidene-1,1-diphosphonic acid,
le pH résutant étant de 7,8.the resulting pH being 7.8.
Le bain est identique à celui de l'exemple 3, à la différence près que l'acide phosphonique est présent à raison de 100 ppm.The bath is identical to that of Example 3, except that the phosphonic acid is present at the rate of 100 ppm.
Le bain est identique à celui de l'exemple 4, mais le pH est amené à 9 avec du phosphate trisodique.The bath is identical to that of Example 4, but the pH is brought to 9 with trisodium phosphate.
Le bain d'activation comprend, dans de l'eau du robinet :
- - 2 g/l de sel de Jernstedt (FIXODINE 5)
- - 60 ppm du sel de sodium de l'acide aminotri(méthylène-phosphonique),
- - 2 g / l Jernstedt salt (FIXODINE 5)
- - 60 ppm of the sodium salt of aminotri acid (methylene-phosphonic),
le pH étant de 8.the pH being 8.
Le bain est identique à celui de l'exemple 6 à la différence près que le sel de sodium de l'acide phosphonique est présent à raison de 200 ppm.The bath is identical to that of Example 6 except that the sodium salt of phosphonic acid is present at the rate of 200 ppm.
Le bain est identique à celui de l'exemple 7, à la différence près que l'acide phosphonique est présent à raison de 100 ppm et le pH est alors de 7.The bath is identical to that of Example 7, except that the phosphonic acid is present at the rate of 100 ppm and the pH is then 7.
Le bain d'activation comprend, dans de l'eau du robinet :
- - 2 g/1 de sel de Jernstedt (FIXODINE 5)
- - 600 ppm d'acide 2-phosphono-butane-1,2,4-tricar- boxylique,
- - 2 g / 1 Jernstedt salt (FIXODINE 5)
- - 600 ppm of 2-phosphono-butane-1,2,4-tricarboxylic acid,
le pH étant réglé à 9 avec du phosphate trisodique.the pH being adjusted to 9 with trisodium phosphate.
Dans tous les exemples, on traite deux éprouvettes en acier qualité automobile d'une dimension de 25 x 20 cm.In all the examples, two automotive quality steel specimens with a dimension of 25 x 20 cm are treated.
Les éprouvettes ainsi traitées sont examinées au microscope électronique, comme indiqué précédemment.The test pieces thus treated are examined under the electron microscope, as indicated above.
Suivant la grosseur relative des cristaux, on attribue une note de 1 à 5, à savoir :
- 1 : note correspondant à la finesse maximum (cristaux très fins)
- 2 : note correspondant à des cristaux fins
- 3 : note correspondant à des cristaux moyens
- 4 : note correspondant à des cristaux grossiers
- 5 : note correspondant à des cristaux très grossiers.
- 1: note corresponding to maximum finesse (very fine crystals)
- 2: note corresponding to fine crystals
- 3: note corresponding to medium crystals
- 4: note corresponding to coarse crystals
- 5: note corresponding to very coarse crystals.
On a réuni dans le tableau suivant les résultats trouvés.
De l'ensemble de ces résultats, on déduit :
- - que les acides phosphoniques mis en oeuvre selon l'invention ou leurs sels améliorent notablement la densité et la finesse des cristaux,
- - que les résultats obtenus sont supérieurs ou équivalents aux résultats obtenus avec un montage en eau déminéralisée.
- - that the phosphonic acids used according to the invention or their salts notably improve the density and the fineness of the crystals,
- - that the results obtained are superior or equivalent to the results obtained with an assembly in demineralized water.
Comme il va de soi et comme il résulte d'ailleurs déjà de ce qui précède, l'invention ne se limite nullement à ceux de ses modes d'application et de réalisation qui ont été plus spécialement envisagés ; elle en embrasse, au contraire, toutes les variantes.As goes without saying and as it already follows from the above, the invention is in no way limited to those of its modes of application and embodiments which have been more especially envisaged; on the contrary, it embraces all its variants.
Claims (10)
caractérisé par le fait que, pour la mise en oeuvre de l'étape d'activation et d'affinage, on a recours à un bain qui comporte, outre les constituants classiques dont notamment au moins un sel de Jernstedt en une proportion correspondant à environ 1 à 100 ppm de titane, une proportion de 10 à 700 ppm, de préférence de 50 à 200 ppm, d'au moins un acide alcane-phosphonique de formule :
characterized in that, for the implementation of the activation and refining step, use is made of a bath which comprises, in addition to the conventional constituents including in particular at least one Jernstedt salt in a proportion corresponding to approximately 1 to 100 ppm of titanium, a proportion of 10 to 700 ppm, preferably from 50 to 200 ppm, of at least one alkane-phosphonic acid of formula:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT85402096T ATE44051T1 (en) | 1984-10-31 | 1985-10-30 | PROCESS FOR COATING WITH ZINC PHOSPHATES, ACTIVATION AND COATING REFINEMENT BATH FOR THIS PROCESS AND CONCENTRATE THEREFOR. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8416725A FR2572422B1 (en) | 1984-10-31 | 1984-10-31 | IMPROVED ACTIVATION AND REFINING BATH FOR ZINC PHOSPHATATION PROCESS AND CONCENTRATE THEREOF |
FR8416725 | 1984-10-31 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0180523A1 true EP0180523A1 (en) | 1986-05-07 |
EP0180523B1 EP0180523B1 (en) | 1989-06-14 |
Family
ID=9309205
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85402096A Expired EP0180523B1 (en) | 1984-10-31 | 1985-10-30 | Process for zinc phosphate coating, activation and grain refining bath used in this process and concentrate therefor |
Country Status (7)
Country | Link |
---|---|
US (1) | US4678519A (en) |
EP (1) | EP0180523B1 (en) |
JP (1) | JPS61124582A (en) |
AT (1) | ATE44051T1 (en) |
CA (1) | CA1260809A (en) |
DE (1) | DE3571050D1 (en) |
FR (1) | FR2572422B1 (en) |
Cited By (5)
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EP0339452A2 (en) * | 1988-04-28 | 1989-11-02 | Henkel Kommanditgesellschaft auf Aktien | Polymer titanium phosphates, process for their preparaton and their use in the activation of metal surfaces before zinc phosphating |
EP0340530A1 (en) * | 1988-04-28 | 1989-11-08 | Henkel Kommanditgesellschaft auf Aktien | Titanium-free activating agents, process for preparing them and their use in activating a metal surface before zinc phosphating |
FR2686622A1 (en) * | 1992-01-29 | 1993-07-30 | Francais Prod Ind Cfpi | CONCENTRATE FOR ACTIVATION AND REFINING BATH AND BATH OBTAINED FROM THIS CONCENTRATE. |
EP0707664A4 (en) * | 1993-06-15 | 1996-02-09 | Henkel Corp | Rapidly dissolving and storage stable titanium phosphate containing activating composition |
WO1996008588A1 (en) * | 1994-09-12 | 1996-03-21 | Ppg Industries, Inc. | Liquid rinse conditioner for phosphate conversion coatings |
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US4793867A (en) * | 1986-09-26 | 1988-12-27 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel phosphate coating |
US5238506A (en) * | 1986-09-26 | 1993-08-24 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating |
CA1309315C (en) * | 1987-07-14 | 1992-10-27 | Toan Manh Ngo | Compositions and process for metal treatment |
US5003986A (en) * | 1988-11-17 | 1991-04-02 | Kenneth D. Pool, Jr. | Hierarchial analysis for processing brain stem signals to define a prominent wave |
US4917737A (en) * | 1989-03-13 | 1990-04-17 | Betz Laboratories, Inc. | Sealing composition and method for iron and zinc phosphating process |
DE4131950A1 (en) * | 1991-09-25 | 1993-04-01 | Boehme Chem Fab Kg | Fluxes and remelting fluids for circuit board mfr. - comprising alkane phosphonic acids and/or their salts, half ester(s) di:ester(s) and half ester salts |
US5628838A (en) * | 1992-01-29 | 1997-05-13 | C.F.P.I Societe Anonyme | Concentrate for activating and defining bath and bath obtained from this concentrate |
US20050268991A1 (en) * | 2004-06-03 | 2005-12-08 | Enthone Inc. | Corrosion resistance enhancement of tin surfaces |
CN111534815A (en) * | 2020-05-22 | 2020-08-14 | 山东大学 | Pretreatment liquid capable of forming washable natural color conversion film on metal surface and preparation method thereof |
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- 1985-10-30 DE DE8585402096T patent/DE3571050D1/en not_active Expired
- 1985-10-30 EP EP85402096A patent/EP0180523B1/en not_active Expired
- 1985-10-30 AT AT85402096T patent/ATE44051T1/en not_active IP Right Cessation
- 1985-10-31 JP JP60243024A patent/JPS61124582A/en active Granted
- 1985-10-31 US US06/793,346 patent/US4678519A/en not_active Expired - Lifetime
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EP0031103A1 (en) * | 1979-12-21 | 1981-07-01 | Gerhard Collardin GmbH | Method for the pretreatment of metal surfaces prior to phosphatizing |
EP0091627A2 (en) * | 1982-04-14 | 1983-10-19 | Gerhard Collardin GmbH | Process for cleaning, degreasing and activating metallic surfaces |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0339452A2 (en) * | 1988-04-28 | 1989-11-02 | Henkel Kommanditgesellschaft auf Aktien | Polymer titanium phosphates, process for their preparaton and their use in the activation of metal surfaces before zinc phosphating |
EP0340530A1 (en) * | 1988-04-28 | 1989-11-08 | Henkel Kommanditgesellschaft auf Aktien | Titanium-free activating agents, process for preparing them and their use in activating a metal surface before zinc phosphating |
EP0339452A3 (en) * | 1988-04-28 | 1991-06-12 | Henkel Kommanditgesellschaft auf Aktien | Polymer titanium phosphates, process for their preparaton and their use in the activation of metal surfaces before zinc phosphating |
FR2686622A1 (en) * | 1992-01-29 | 1993-07-30 | Francais Prod Ind Cfpi | CONCENTRATE FOR ACTIVATION AND REFINING BATH AND BATH OBTAINED FROM THIS CONCENTRATE. |
EP0554179A1 (en) * | 1992-01-29 | 1993-08-04 | C F P I | Concentrate for activating and refining bath and bath obtained |
EP0707664A4 (en) * | 1993-06-15 | 1996-02-09 | Henkel Corp | Rapidly dissolving and storage stable titanium phosphate containing activating composition |
EP0707664A1 (en) * | 1993-06-15 | 1996-04-24 | Henkel Corporation | Rapidly dissolving and storage stable titanium phosphate containing activating composition |
WO1996008588A1 (en) * | 1994-09-12 | 1996-03-21 | Ppg Industries, Inc. | Liquid rinse conditioner for phosphate conversion coatings |
Also Published As
Publication number | Publication date |
---|---|
JPH0568552B2 (en) | 1993-09-29 |
JPS61124582A (en) | 1986-06-12 |
US4678519A (en) | 1987-07-07 |
ATE44051T1 (en) | 1989-06-15 |
EP0180523B1 (en) | 1989-06-14 |
FR2572422B1 (en) | 1993-03-05 |
FR2572422A1 (en) | 1986-05-02 |
DE3571050D1 (en) | 1989-07-20 |
CA1260809A (en) | 1989-09-26 |
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