GB1591039A - Processes and compositions for coating metal surfaces - Google Patents
Processes and compositions for coating metal surfaces Download PDFInfo
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- GB1591039A GB1591039A GB1840277A GB1840277A GB1591039A GB 1591039 A GB1591039 A GB 1591039A GB 1840277 A GB1840277 A GB 1840277A GB 1840277 A GB1840277 A GB 1840277A GB 1591039 A GB1591039 A GB 1591039A
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- United Kingdom
- Prior art keywords
- composition according
- zinc
- ferrous
- borofluoride
- amount
- Prior art date
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- Expired
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- 239000000203 mixture Substances 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 26
- 238000000576 coating method Methods 0.000 title claims description 19
- 239000011248 coating agent Substances 0.000 title claims description 16
- 229910052751 metal Inorganic materials 0.000 title description 2
- 239000002184 metal Substances 0.000 title description 2
- 239000011701 zinc Substances 0.000 claims description 36
- 229910052725 zinc Inorganic materials 0.000 claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 28
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 21
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000012141 concentrate Substances 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 16
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 11
- 235000002906 tartaric acid Nutrition 0.000 claims description 11
- 239000011975 tartaric acid Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 229940095064 tartrate Drugs 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000002390 adhesive tape Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 16
- 239000012224 working solution Substances 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 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 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 aliphatic alpha hydroxy acid Chemical class 0.000 description 1
- 229940061720 alpha hydroxy acid Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- BECVLEVEVXAFSH-UHFFFAOYSA-K manganese(3+);phosphate Chemical class [Mn+3].[O-]P([O-])([O-])=O BECVLEVEVXAFSH-UHFFFAOYSA-K 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 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 description 1
- 229910000165 zinc phosphate Inorganic materials 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
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
- C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
Landscapes
- 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)
- Application Of Or Painting With Fluid Materials (AREA)
Description
(54) PROCESSES AND COMPOSITIONS FOR COATING METAL SURFACES
(71) We, PYRENE CHEMICAL SERVICES LIMITED, a British Company of
Ridgeway, Iver, Buckinghamshire SLO 9JJ do hereby declare the invention, for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement:
In British Patent Specification No. 983,924 there is described a process in which a phosphate coating is formed on a ferrous or zinc surface by spraying with a solution at a temperature of 100"F or less of zinc and manganese phosphates including an oxidising accelerator, the manganese content of the solution being between 5 to 50% by weight of the zinc content.As a result of being able to form a coating at low temperatures this process has the advantage that it saves heat energy, compared with normal high temperature processes, and in regions where the ambient temperature is high it may eliminate altogether the need to supply any form of heating. However the process as described is limited to application on ferrous or zinc surfaces and does not give satisfactory results on aluminium surfaces.
A phosphate coating composition according to the invention comprises zinc ions, phosphate ions, manganese ions in an amount of 5 to 50% by weight of zinc, an oxidising agent and borofluoride, and is such that it will form a coating on a ferrous, zinc or aluminium surface at a temperature of llO"F or less.
A method according to the invention comprises forming a phosphate coating on a ferrous, zinc or aluminium surface by contacting the surface with a zinc phosphate solution at a temperature of 110"F or less, the solution also containing manganese in an amount of 5 to 50% by weight of zinc, an oxidising agent and borofluoride.
It is standard practice to modify a process suitable for treatment of ferrous surfaces by including fluoride in it so that it can be used on aluminium surfaces, the fluoride addition often tending also to activate the process on ferrous surfaces. The fluoride is normally introduced as simple fluoride, F-, or silico fluoride, SiF6. Borofluoride BF4, is of course a potential source of fluoride but in practice it is rarely used. In fact we only know of one commercial process that uses it and this is a high temperature process. It is mentioned in, for instance, British Patent Specification No. 655,890, which describes a high temperature process.In the invention we have surprisingly found that in a low temperature process as described herein borofluoride tends to give better coatings on aluminium than simple fluoride or silicofluoride and in particular that it gives a surprisingly great improvement in the quality of the coatings on ferrous surfaces.
The surfaces being treated may be surfaces of iron or an alloy consisting predominantly of iron, for instance steel, surfaces of zinc or an alloy consisting predominantly of zinc or surfaces of aluminium or an alloy consisting predominantly of aluminium. Application of the coating solutions is preferably conducted by spray although other methods can be used. The temperature of the solution is preferably 70 to 1100F, most usually 70 to 100 F. Before application of the solution the surfaces to be treated are preferably cleaned, for instance, as described in British Patent Specification No. 983,924.
Apart from the addition of borofluoride, the solution used is preferably as described in
British Patent Specification No. 983,924. Thus, the amount of manganese is preferably from 5 to 20% by weight of the zinc with a value of 10 to 13% being prticularly preferred since then the solution can be replenised using the same mixture of chemicals as is used for making up the solution initially. Preferably the working solution contains from 2 to 9 g/l Zn, 0.1 to 1.8 g/l Mn and 5 to 22.5 g/l PO4.
The other conditions in the solution must be such that satisfactory coating formation occurs at a temperature of 110 F or less. The pH is preferably greater than 3, the total acidity is preferably greater than 20 and the ratio of total acidity to free acidity is preferably from 50:1 to 100:1. Nitrate is a preferred oxidising accelerator, preferably in the weight ratio 0.2:1 to 0.4:1 NO3:PO4, optionally in admixture with another oxidising accelerator such as chlorate or nitrite, nitrate concentration preferably being 0.015 to 0.075, most preferably about 0.04, percent by weight sodium nitrite. An aliphatic alpha hydroxy acid, such as tartaric acid or a water soluble salt thereof may be included, preferably in an amount of 0.02 to 4 grams per litre calculated as tartaric acid.The initial solution may include ferric iron, either as such or as a result of the inclusion of ferrous iron which will be oxidised by oxidising agent in the system to ferric, in order to give more consistent coatings.
For full details of all these features reference should be made to British Patent Specification
No. 982,924.
Broadly preferred compositions contain from 1 to 9 g/l NO3, 0 to 8 g/l of tartrate, 0 to 0.5 g/l Ni and 0 to 0.75 g/l NO2 and/or Cl03.
The borofluoride can be introduced into the working solution and replenishment in any conveient form, for example sodium borofluoride or as borofluoric acid. However it is introduced there will generally be some dissociation of it in the solution with the formation of, inter alia, free fluoride and boric acid. The amount of borofluoride introduced is preferably from 0.3 to 4 grams per litre in the working solution, this amount being the total fluoride in the borofluoride introduced but in practice the amount of actual borofluoride may be less, some of it having dissociated to, for instance, simple fluoride.
The working solution and replenishment solutions may be made up using one or more concentrates in conventional manner, but preferably the make-up and the replenishment are each formed from a single concentrate, preferably the same concentrate. It is desirable to be able to formulate the concentrate as a concentrated aqueous solution, for example, having 50% solids content and yet it must be stable over a wide temperature range. For example, if any precipitation occurs at low temperatures, e.g. -5"C, this renders the concentrate unsuitable for commercial use.
Any attempt at formulating a concentrate of the chemicals described in British Patent
Specification No. 983,924 with a conventional fluoride addition, such as simple fluoride or silico fluoride results in an unstable concentrate. Thus the presence of fluoride tends to result in precipitation of various compounds. Further, we find that the normal way of introducing borofluoride, as sodium borofluoride, also tends to give precipitation.
According to a second aspect of the invention an aqueous concentrate suitable for make-up and/or replenishment of a zinc and manganese phosphate solution contains phosphate, zinc, manganese in an amount of from 5 to 50% based on the weight of zinc, oxidising accelerator and borofluoric acid added as such. Thus we have surprisingly found that if the free acid form of borofluoric acid is used in making up the concentrate precipitation problems are avoided. Although in theory free borofluoric acid will dissociate in the acidic concentrate to substantially the same materials as sodium borofluoride would, in practice we find that free fluoroboric acid avoids precipitation problems whereas the sodium form does not.
The concentrate usually has a total solids content of at least 25%, preferably at least 40%, especially 40 to 65%, and preferably is made up using from 1 to 5% borofluoric acid.
Preferred concentrates contain from 9.1 to 14.6% Zn measured as ZnO and 0.9 to 1.9%
Mn and 19.2 to 30.9% PO4 measured as phosphoric acid. Preferably they contain also one or more of 3.8 to 12.4% No3 measured as nitric acid, 0.3 to 0.52% Ni, 0.6 to 3.0% tartaric acid or tartrate measured as tartaric acid, 0.1 to 0.3% ferrous ion, measured as ferrous sulphate and 0.1 to 0.3% hydrogen peroxide. A preferred concentrate containing all these ingredients can be diluted to give a working solution which contains 0.2 to 0.9% Zn, 0.01 to 0.18% Mn, 0 to 0.05% Ni, 0.5 to 2.25% PO4, 0.1 to 0.9% NO3, 0 to 0.8% tartrate and 0.03 to 0.4% total fluoride, introduced as borofluoride. Preferably, it is a 10 to 40 point solution.
In an Example, a concentrate was made from 140 grams ZnO, 28 grams MnCO3, 10 grams NiC03, 297 grams H3PO4, 107 grams HNO3, 10 grams tartaric acid, 2 grams ferrous sulphate, 2 grams H202, 22 grams borofluoric acid, and water to make 1000 grams. This solution was diluted to give a solution of 0.55% Zn, 0.06% Mn, 0.024% Ni, 1.4% PO4, 0.5% NO3, 0.05% tartrate and 0.1% fluoride and being a 25 point solution. Free acid was reduced by adding sodium hydroxide and 0.3 g/l sodium nitrite was also added to form the final working solution.
Steel and aluminium articles were then sprayed with an alkaline cleaning solution with a total alkalinity of 26 points at a temperature of 35"C for one minute. They were then rinsed with water and sprayed with the above working solution for one minute at 32"C. They were then rinsed with water, rinsed with distilled water and dried by blasting with compressed air.
These articles were then painted with an electropaint (ED 1200) supplied by
International Pinchin Johnson and then stoved at 1800C for 20 minutes. Dry film thickness of the paint was 20 microns.
These articles were then cross-scored and subjected to salt-spray testing to ASTM
B117-64 for 240 hours. At the end of the test, adhesive tape was used to determine the amount of loose paint around the score. There was no paint removal. This shows that the process of the invention is capable of giving a good coating on steel and aluminium despite the low temperature.
WHAT WE CLAIM IS:
1. a phosphate coating composition comprising zinc ions, phosphate ions, manganese ions in an amount of 5 to 50% by weight zinc, an oxidising agent and borofluoride and which is such that it will form a coating on a ferrous, zinc or aluminium surface at a temperature of 110"F or less.
2. A composition according to claim 1 in which the amount of manganese is 5 to 20% by weight of zinc.
3. A composition according to claim 1 or claim 2 in which the oxidising agent comprises nitrate in a weight ratio NO3:PO4 of from 0.2-0.4:1.
4. A composition according to any preceding claim also comprising tartaric acid or a water soluble salt thereof.
5. A composition according to any preceding claim made by diluting a concentrate into which the borofluoride was introduced as free borofluoric acid.
6. A composition according to any preceding claim containing 0.3 to 4 g/l BF4, 2 to 9 g/l
Zn, 0.1 to 1.8 g/l Mn and 5 to 22.5 g/l PO4.
7. A composition according to claim 6 additionally containing 1 to 9 g/l NO3, 0 to 8 g/l tartaric acid or tartrate, 0 to 0.5 g/l Ni and 0 to 0.75 g/l nitrite and/or chlorate.
8. A composition according to any preceding claim having a pH greater than 3, total acidity greater than 20 and a ratio of total acidity to free acidity of from 50:1 to 100:1.
9. A concentrated composition suitable for make up and/or replenishment of a composition according to any preceding claim and comprising zinc ions, phosphate ions, manganese ions in an amount of 5 to 50% by weight zinc, oxidising agent and borofluoride, and in which the borofluoride has been introduced as free borofluoric acid.
10. A concentrated composition according to claim 9 having a solids content of 40 to 65% and containing 1 to 5% borofluoric acid.
11. A concentrated composition according to claim 9 or claim 10 containing 9.1 to 14.6%
Zn measured as ZnO, 0.9 to 1.9% Mn and 19.2 to 30.9% PO4 measured as phosphoric acid.
12. A concentrated composition according to any of claims 9 to 11, in which the amount of manganese is 5 to 20% by weight of zinc.
13. A concentrated composition according to any of claims 9 to 12 containing tartaric acid or a water soluble salt thereof.
14. A concentrated composition according to any of claims 9 to 13 including one or more of 3.8 to 12.4% NO3 measured as HNO3, 0.3 to 0.52% Ni, 0.6 to 3.0% tartaric acid or tartrate and 0.1 to 0.3% ferrous ion measured as ferrous sulphate.
15. A composition according to claim 1 or claim 9 substantially as herein described with reference to the Example.
16. A process in which a phosphate coating is formed on a ferrous, zinc or aluminium surface by contacting the surface with a composition according to any of claims 1 to 8.
17. A process according to claim 16 in which the coating is formed on an aluminium surface or a ferrous surface.
18. A process according to claim 16 or claim 17 in which the contact temperature is 70 to 100 F.
19. A process according to claim 16 substantially as herein described with reference to the Example.
20. A ferrous, zinc or aluminium surface coated by a process according to any of claims 16 to 19.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (20)
1. a phosphate coating composition comprising zinc ions, phosphate ions, manganese ions in an amount of 5 to 50% by weight zinc, an oxidising agent and borofluoride and which is such that it will form a coating on a ferrous, zinc or aluminium surface at a temperature of 110"F or less.
2. A composition according to claim 1 in which the amount of manganese is 5 to 20% by weight of zinc.
3. A composition according to claim 1 or claim 2 in which the oxidising agent comprises nitrate in a weight ratio NO3:PO4 of from 0.2-0.4:1.
4. A composition according to any preceding claim also comprising tartaric acid or a water soluble salt thereof.
5. A composition according to any preceding claim made by diluting a concentrate into which the borofluoride was introduced as free borofluoric acid.
6. A composition according to any preceding claim containing 0.3 to 4 g/l BF4, 2 to 9 g/l
Zn, 0.1 to 1.8 g/l Mn and 5 to 22.5 g/l PO4.
7. A composition according to claim 6 additionally containing 1 to 9 g/l NO3, 0 to 8 g/l tartaric acid or tartrate, 0 to 0.5 g/l Ni and 0 to 0.75 g/l nitrite and/or chlorate.
8. A composition according to any preceding claim having a pH greater than 3, total acidity greater than 20 and a ratio of total acidity to free acidity of from 50:1 to 100:1.
9. A concentrated composition suitable for make up and/or replenishment of a composition according to any preceding claim and comprising zinc ions, phosphate ions, manganese ions in an amount of 5 to 50% by weight zinc, oxidising agent and borofluoride, and in which the borofluoride has been introduced as free borofluoric acid.
10. A concentrated composition according to claim 9 having a solids content of 40 to 65% and containing 1 to 5% borofluoric acid.
11. A concentrated composition according to claim 9 or claim 10 containing 9.1 to 14.6%
Zn measured as ZnO, 0.9 to 1.9% Mn and 19.2 to 30.9% PO4 measured as phosphoric acid.
12. A concentrated composition according to any of claims 9 to 11, in which the amount of manganese is 5 to 20% by weight of zinc.
13. A concentrated composition according to any of claims 9 to 12 containing tartaric acid or a water soluble salt thereof.
14. A concentrated composition according to any of claims 9 to 13 including one or more of 3.8 to 12.4% NO3 measured as HNO3, 0.3 to 0.52% Ni, 0.6 to 3.0% tartaric acid or tartrate and 0.1 to 0.3% ferrous ion measured as ferrous sulphate.
15. A composition according to claim 1 or claim 9 substantially as herein described with reference to the Example.
16. A process in which a phosphate coating is formed on a ferrous, zinc or aluminium surface by contacting the surface with a composition according to any of claims 1 to 8.
17. A process according to claim 16 in which the coating is formed on an aluminium surface or a ferrous surface.
18. A process according to claim 16 or claim 17 in which the contact temperature is 70 to 100 F.
19. A process according to claim 16 substantially as herein described with reference to the Example.
20. A ferrous, zinc or aluminium surface coated by a process according to any of claims 16 to 19.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1840277A GB1591039A (en) | 1977-05-03 | 1977-05-03 | Processes and compositions for coating metal surfaces |
| DE19782818426 DE2818426A1 (en) | 1977-05-03 | 1978-04-27 | METHOD FOR APPLYING A PHOSPHATE COATING TO METAL SURFACES |
| FR7812987A FR2389683A1 (en) | 1977-05-03 | 1978-05-02 | Phosphating soln. contg. boron fluoride - for phosphating ferrous and non-ferrous surfaces, e.g. steel, zinc and aluminium |
| BR7802738A BR7802738A (en) | 1977-05-03 | 1978-05-02 | PROCESS FOR APPLYING A PHOSPHATE COATING ON METALLIC SURFACES, AND CONCENTRATED FOR THE PREPARATION AND / OR COMPLEMENTATION OF A SOLUTION INTENDED FOR APPLICATION IN THAT PROCESS |
| JP5364178A JPS53140237A (en) | 1977-05-03 | 1978-05-04 | Component for coating borofluoride added phosphate and method of forming coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1840277A GB1591039A (en) | 1977-05-03 | 1977-05-03 | Processes and compositions for coating metal surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1591039A true GB1591039A (en) | 1981-06-10 |
Family
ID=10111849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1840277A Expired GB1591039A (en) | 1977-05-03 | 1977-05-03 | Processes and compositions for coating metal surfaces |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS53140237A (en) |
| BR (1) | BR7802738A (en) |
| DE (1) | DE2818426A1 (en) |
| GB (1) | GB1591039A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2155960A (en) * | 1984-03-09 | 1985-10-02 | Pyrene Chemical Services Ltd | Processes and compositions for coating metal surfaces |
| US4824490A (en) * | 1986-10-25 | 1989-04-25 | Metallgesellschaft Aktiengesellschaft | Process of producing phosphate coatings on metals |
| EP1929070A1 (en) * | 2005-09-30 | 2008-06-11 | Henkel AG & Co. KGaA | Phosphatising solution with hydrogen peroxide and chelating carboxylic acids |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3023479A1 (en) * | 1980-06-24 | 1982-01-14 | Metallgesellschaft Ag, 6000 Frankfurt | PHOSPHATING PROCESS |
| US6342107B1 (en) * | 1982-08-24 | 2002-01-29 | Henkel Corporation | Phosphate coatings for metal surfaces |
| JPS5935681A (en) * | 1982-08-24 | 1984-02-27 | Nippon Paint Co Ltd | Method for phosphating metallic surface for coating by cationic electrodeposition |
| DE3244715A1 (en) * | 1982-12-03 | 1984-06-07 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR PHOSPHATING METAL SURFACES, AND BATH SOLUTIONS SUITABLE FOR THIS |
| JPS59133375A (en) * | 1983-12-03 | 1984-07-31 | Nippon Paint Co Ltd | Composition for forming zinc phosphate film on metallic surface |
| ES8606528A1 (en) * | 1985-02-22 | 1986-04-01 | Henkel Iberica | Process for the phosphating of metal surfaces. |
| US4595424A (en) * | 1985-08-26 | 1986-06-17 | Parker Chemical Company | Method of forming phosphate coating on zinc |
| USRE35958E (en) * | 1985-08-26 | 1998-11-17 | Henkel Corporation | Method of forming phosphate coating on zinc |
| JPS63100185A (en) * | 1986-10-16 | 1988-05-02 | Nippon Parkerizing Co Ltd | Phosphating method |
| US5200000A (en) * | 1989-01-31 | 1993-04-06 | Nihon Parkerizing Co., Ltd. | Phosphate treatment solution for composite structures and method for treatment |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE860891C (en) * | 1951-06-22 | 1952-12-29 | Paschke & Co Maschinen U Appba | Method for cutting through cardboard or the like on the format roller of a cardboard machine or the like and format roller |
| BE635606A (en) * | 1962-08-01 |
-
1977
- 1977-05-03 GB GB1840277A patent/GB1591039A/en not_active Expired
-
1978
- 1978-04-27 DE DE19782818426 patent/DE2818426A1/en not_active Withdrawn
- 1978-05-02 BR BR7802738A patent/BR7802738A/en unknown
- 1978-05-04 JP JP5364178A patent/JPS53140237A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2155960A (en) * | 1984-03-09 | 1985-10-02 | Pyrene Chemical Services Ltd | Processes and compositions for coating metal surfaces |
| US4824490A (en) * | 1986-10-25 | 1989-04-25 | Metallgesellschaft Aktiengesellschaft | Process of producing phosphate coatings on metals |
| EP1929070A1 (en) * | 2005-09-30 | 2008-06-11 | Henkel AG & Co. KGaA | Phosphatising solution with hydrogen peroxide and chelating carboxylic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53140237A (en) | 1978-12-07 |
| DE2818426A1 (en) | 1978-11-09 |
| BR7802738A (en) | 1978-12-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19970503 |