US2502441A - Phosphate coating of metals - Google Patents
Phosphate coating of metals Download PDFInfo
- Publication number
- US2502441A US2502441A US711810A US71181046A US2502441A US 2502441 A US2502441 A US 2502441A US 711810 A US711810 A US 711810A US 71181046 A US71181046 A US 71181046A US 2502441 A US2502441 A US 2502441A
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- US
- United States
- Prior art keywords
- acid
- phosphoric acid
- phosphate
- compounds
- acid salt
- 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.)
- Expired - Lifetime
Links
- 238000000576 coating method Methods 0.000 title description 35
- 229910019142 PO4 Inorganic materials 0.000 title description 34
- 239000010452 phosphate Substances 0.000 title description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title description 31
- 239000011248 coating agent Substances 0.000 title description 28
- 229910052751 metal Inorganic materials 0.000 title description 15
- 239000002184 metal Substances 0.000 title description 15
- 150000002739 metals Chemical class 0.000 title description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 62
- 239000002253 acid Substances 0.000 claims description 34
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004615 ingredient Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical class O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 10
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 9
- 235000021317 phosphate Nutrition 0.000 description 32
- 235000011007 phosphoric acid Nutrition 0.000 description 31
- 239000000243 solution Substances 0.000 description 29
- 239000000080 wetting agent Substances 0.000 description 11
- 239000012459 cleaning agent Substances 0.000 description 10
- 235000018553 tannin Nutrition 0.000 description 10
- 229920001864 tannin Polymers 0.000 description 10
- 239000001648 tannin Substances 0.000 description 10
- 238000009736 wetting Methods 0.000 description 10
- -1 ferrous metals Chemical class 0.000 description 9
- 235000017343 Quebracho blanco Nutrition 0.000 description 7
- 241000065615 Schinopsis balansae Species 0.000 description 7
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 235000013824 polyphenols Nutrition 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000005078 molybdenum compound Substances 0.000 description 5
- 150000002752 molybdenum compounds Chemical class 0.000 description 5
- 150000003658 tungsten compounds Chemical class 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 241000707825 Argyrosomus regius Species 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000003152 Rhus chinensis Species 0.000 description 1
- 235000014220 Rhus chinensis Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005303 weighing Methods 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
- C23C22/40—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
- C23C22/42—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 phosphates
Definitions
- the present invention relates to improvements ina composition and a process for depositing phosphate coating on metal surfaces when employed in phosphate coating solutions, and more particularly to compositions which will not only accelerate the deposition of a phosphate coating upon the surface of metals such as ferrous metals and other metals such as aluminum, zinc, magnesium and template, but also condition the coating obtained by improving the quality he o It is therefore an 'object'of the invention to provide a composition which, when added to a phosphate coating solution, will cause accelerated deposition of phosphate coatings on ferrous and other metal objects treated with such solution. It is another object to provide a composition which will, when added, to phosphate coating solutions, promote uniformity, hardness, and adherence of phosphate coatings obtained when treating metal objects with such solution.
- phosphate coating solutions in which the major ingredient is a primary phosphate of the alkali group, that is, the primary alkali metal or ammonium phosphates, will give good phosphate coatings when they contain a small quantity of the novel accelerating combination in accordance with the invention. In the absence of such accelerating combination little or no phosphate coating is obtained from solutions containing suchphosphates.
- phosphate coating solutions may be employed in accordance with the inventionat a higher pH than in usual practice, namely, at a pH of about 3.2 to about 5.5 instead of at about 2.5.
- Molybdenum compounds are preferably employed in accordance with the invention, but tungsten compounds possess similar properties.
- the following compounds are, for example, suitable: ammonium, sodium, potassium, molybdates and tungstates, and molybdic and tungstic' acids and acid anhydrides.
- the quantity of molybdenum or tungsten compounds employed in'a phosphate coating composition in accordance with the invention may range from 0.1% to 10% of the quantity of solid acid phosphate "saltpresent.
- the quantity of such compounds used is between 0.5% and 2.0% as higher concentrations tend toward the production of softer coatings.
- the phenolic ingredients of the novel composition in accordance with the invention are preferably tannins, phenolic tannin derivatives and related phenolics. However, other phenols,-
- the polyhydric phenolic com-- equal to the quantity of molybdenum or" tungsten compound used. However, the pro-..
- portion may be varied within the limits of the quantities given above.
- the phenolic compounds and molybdenum or tungsten compounds may be added separately or together to a phosphate coating solution or may be incorporated in a solid phosphating composition before preparation of the aqueous phosphate coating solution.
- wetting or cleaning agents which are effective in acid solution, to phosphate coating solutions prepared in accordance with the invention, but such wetting or cleaning agents may be omitted if the metal articles to be coated have been thoroughly cleaned before treatment with the solution.
- Sulphonated fatty alcohols Alkylated' aromatic sulphonates.
- Non-ionic wetting agents such as polyethylene oxide derivatives of fatty alcohols or acids, or of other substances containing hydroxyl or carboxyl groups.
- Example 1 A phosphate solution is prepared containing approximately 2 ounces per gallon of a composition of the following formula:
- Example 2 An aqueous solution is prepared containing about 2 ounces per gallon of .the following composition:
- Example 3 A phosphatingbath is prepared containing about 2'ounces per gallon of the following composition:
- Example 4 A phosphating bath is prepared containing about 2 ounces per gallon .of the following composition:
- a steel panel immersed insuch bath for 4 minutes at 160 F. will receive a hard coating weighing about milligrams per square foot.
- Example 5 A .phosphating solution containing 3 ounces per gallon of the following composition is prepared:
- This phosphating solution will produce about 85 milligrams of a hard, continuous, iridescent coating per square foot when used in the sam manner as the solution in Example 3.
- Example 6 A phosphating solution containing '3 ounces per gallon of the following :composition is prepared:
- compositions given. in the .above examples in most instances include wetting and cleaning agents, they may be omitted and equal results will .be obtained if the metal articles are thoroughly .cleaned; bciorextreatment.
- phosphate coating solutions may be used in accordance with the invention at a pH between 3.2 and 5.5, it has been found preferable to adjust the pi-I value thereof to between 3.2 and 3.8 when the coating is obtained by tank immersion and to adjust the pH value thereof to 4.8 to 5.2 when a spray machine is used to apply the solution to the articles being coated.
- a phosphating composition comprising an acid salt of phosphoric acid and a water soluble compound selected from the group consisting of molybdic acid compounds and tungstic acid compounds and a phenol, said latter two ingredients each being present in a quantity ranging from 0.1% to of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising an acid salt of phosphoric acid and a water soluble compound selected from the group consisting of molybdic acid compounds and tungstic acid compounds and a phenol, said latter two ingredients each being present in a quantity ranging from 0.5% to 2% of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising an acid salt of phosphoric acid, a water soluble compound selected from the group consisting of 'molybdic acid compounds and tungstic acid compounds, and a polyhydric phenol, said latter two ingredients each being present in a quantity rang ing from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising an acid salt of phosphoric acid, a water soluble compound selected from the group consisting of molybdic acid compounds and tungstic acid compounds, and a tannin containing at least one free phenolic hydroxy group, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising an acid salt of phosphoric acid, a water soluble compound selected irom the group consisting of molybdic acid compounds and tungstic acid compounds, and quebracho, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
- 6.1-1 phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and a phenol, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and a polyhydric phenol, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and a gallic acid, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and a tannin containing at least one free phenolic group, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and quebracho, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and catechol, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising an acid salt of phosphoric acid, a water soluble compound selected from the group consisting of mclybdic acid compounds and tungstic acid compounds, and a phenol, said latter two ingredients being present in substantially equal quantities, the quantity of each ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
- a phosphating composition comprising a primary phosphate of the alkali group and a water soluble compound selected from the group consisting of molybdic acid compounds and tungstic acid compounds and a phenol, saidlatter two ingredients each being present in a. quantity ranging from 5.1% to 10% of the quantity of a primary phosphate of the alkali-group.
- a phosphating composition comprising a primary phosphate of the alkali group, a water soluble molybdic acid compound and quebracho, said latter two ingredients each being present in a quantity ranging from 0.2% to 5% of the primary phosphate of the alkali group.
- a process of coating metal surfaces which comprises contacting the metal surfaces with an aqueous solution of an acid salt of phosphoric acid containing a water soluble compound selected from the group consisting of molybdic acid compounds and tungstic acid compounds and. a phenol, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of the acid salt of phosphoric acid.
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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)
- Paints Or Removers (AREA)
Description
Patented Apr. 4, 950
2,502,441 PHOSPHATE COATING F METALS Sidney R. Dodd, West Caldwell, N. J and Robert F. Ayres, New York, N. Y., assignors to Oakite Products, Inc, New York, N. Y., a corporation 1 .No Drawing. Application November 22, 1946,
Serial No. 711,810
1 The present invention relates to improvements ina composition and a process for depositing phosphate coating on metal surfaces when employed in phosphate coating solutions, and more particularly to compositions which will not only accelerate the deposition of a phosphate coating upon the surface of metals such as ferrous metals and other metals such as aluminum, zinc, magnesium and template, but also condition the coating obtained by improving the quality he o It is therefore an 'object'of the invention to provide a composition which, when added to a phosphate coating solution, will cause accelerated deposition of phosphate coatings on ferrous and other metal objects treated with such solution. It is another object to provide a composition which will, when added, to phosphate coating solutions, promote uniformity, hardness, and adherence of phosphate coatings obtained when treating metal objects with such solution.
It is a further object to provide an improved method of producing phosphate coatings on metal Larti'cles employing the novel phosphate coating solutions. V
A' proposal has already been made in German Patent No. 584,411 to add water soluble'molybdenum compounds to phosphating baths in order to provide accelerated deposition of a coating containing a mixture of phosphates and molybdenumoxides. However, it has been found that coatings produced from such baths containinga molybdenum compound tend to have poor adherence to the metal surface and have an undesirable soft or spongy nature rendering them inefficient as rust retarders and'of poor quality in forming a strong bond with paint, enamel and other organic finishes.
"In accordance with the present invention, it has been found that consistently uniform, adherent and hard phosphate coatings, which also have excellent corrosion resistant and paint bonding properties, may be obtained if the phosphating solution is employed to which a small quantity of a water soluble molybdenum or tungsten'compound suchfas the molybdic and tungsti'c acid compounds, molybdic acid, tungstic acid,:their anhydrides,v and their. .water soluble salts, and a small quantity of a phenolic substance, such as, for example, the tannins, tannin n'uclei,. and tannin derivatives have been added. I .The addition of such molybdenum or tungsten compound. in combination with a phenolic compound not only. accelerates and promotesthe Claims. (Cl. 148-615) production of a phosphate coating, but also pro-, duces desirable eifects in the quality and consistency of the coating obtained.
. It has also been found that phosphate coating solutions, in which the major ingredient is a primary phosphate of the alkali group, that is, the primary alkali metal or ammonium phosphates, will give good phosphate coatings when they contain a small quantity of the novel accelerating combination in accordance with the invention. In the absence of such accelerating combination little or no phosphate coating is obtained from solutions containing suchphosphates.
In addition, the use of the accelerating combination in accordance with the invention renders it possible to reduce the amount of free phosphoric acid usually present in solutions of which the major constituent is a monobasic phosphate of a heavy metal, such as zinc, manganese, or iron. In other words, phosphate coating solutions may be employed in accordance with the inventionat a higher pH than in usual practice, namely, at a pH of about 3.2 to about 5.5 instead of at about 2.5.
"Molybdenum compounds are preferably employed in accordance with the invention, but tungsten compounds possess similar properties. The following compounds are, for example, suitable: ammonium, sodium, potassium, molybdates and tungstates, and molybdic and tungstic' acids and acid anhydrides. The quantity of molybdenum or tungsten compounds employed in'a phosphate coating composition in accordance with the invention may range from 0.1% to 10% of the quantity of solid acid phosphate "saltpresent. Preferably, the quantity of such compounds used is between 0.5% and 2.0% as higher concentrations tend toward the production of softer coatings.
The phenolic ingredients of the novel composition in accordance with the invention are preferably tannins, phenolic tannin derivatives and related phenolics. However, other phenols,-
such as phenol itself, possess the desirable effect in the combinationin accordance with the in-' of other suitable phenolics are as follows:'
phenol, catechol, resorcinol, hydroq uinone, pyrogallol, pyrogallic acid, gallic acid, phloroglucinol and the like. The polyhydric phenolic com-- equal to the quantity of molybdenum or" tungsten compound used. However, the pro-..
portion may be varied within the limits of the quantities given above.
The phenolic compounds and molybdenum or tungsten compounds may be added separately or together to a phosphate coating solution or may be incorporated in a solid phosphating composition before preparation of the aqueous phosphate coating solution.
It is desirable to incorporate wetting or cleaning agents, which are effective in acid solution, to phosphate coating solutions prepared in accordance with the invention, but such wetting or cleaning agents may be omitted if the metal articles to be coated have been thoroughly cleaned before treatment with the solution.
The following wetting and cleaning agents are,
for example, suitable for use in phosphate coating compositions prepared in accordance with the invention:
Sulphonated fatty alcohols. Alkylated' aromatic sulphonates.
Complex sulphonated amides. Polyhydric alcohol anhydride ethers esterified 3 with fatty acids such as sorbitan monolaurate.
Non-ionic wetting agents such as polyethylene oxide derivatives of fatty alcohols or acids, or of other substances containing hydroxyl or carboxyl groups.
Any of these are suitable for use as the Wetting and cleaning agents which are recited in the examples given below, which will serve to illustrate the invention.
Example 1 A phosphate solution is prepared containing approximately 2 ounces per gallon of a composition of the following formula:
Per cent NaHzPOi 90.0 M003 1.0 Quebracho 0.5 Wetting and cleaning agent 8.51
This solution when used hot and applied for two minutes by pressure spraying to a ferrous metal surface will convert the surface into a prosphate coating averaging about 100 milligrams in weight per square foot of surface.
If the M003 and quebracho are omitted from the same type of acid phosphate solution, consistent deposition of a coating is diflicult to accomplish. Results are erratic; the coating being non-uniform, meagre, or completely non-existent.
If the molybdenum compound without the tannin is used in the same type of solution, a deposit results which seems amorphous in structure, is non-adherent to the surface, and of no value as a foundation for painting.
If the tannin is used Without the molybdenum compound in such solution, deposition .of a coat ing seemsto be completely inhibited. I
Example 2 An aqueous solution is prepared containing about 2 ounces per gallon of .the following composition:
Per cent NH4I-I2PO4 90.0 M003 1.0 Sumac tannin 1.0 Wetting and cleaning agents 8.0
This solution gives results similar to those obtained in Example 1 when used in the same manner.
Example 3 A phosphatingbath is prepared containing about 2'ounces per gallon of the following composition:
Per cent NaI-IzPO4 90.5 H3PO4 4.5 Ammonium molybdate 1.0 Catechol 1.0 Wetting and cleaning agents 3.0
Immersion of a steel article in such bath for 4 minutes at a temperature of 160 F. produces about milligrams of a 'hard continuous coating per square foot of surface.
Example 4 A phosphating bath is prepared containing about 2 ounces per gallon .of the following composition:
Per cent ZnH-;(PO4) 2 p 50.5 H3PO4.(75%) 47.5- MOO; 1.0 Quebracho 1.0
A steel panel immersed insuch bath for 4 minutes at 160 F. will receive a hard coating weighing about milligrams per square foot.
Example 5 A .phosphating solution containing 3 ounces per gallon of the following composition is prepared:
Per cent NaHaPOa. 91.9
H3PO4 4.5 Na2WO4.2I-I2O .6
Quebracho 1.0 Wetting and cleaning agents 3.0
This phosphating solution will produce about 85 milligrams of a hard, continuous, iridescent coating per square foot when used in the sam manner as the solution in Example 3.
Example 6 A phosphating solution containing '3 ounces per gallon of the following :composition is prepared:
' 1 Per cent NaH2PO4' 90.5 H3PO4 75 4.5 Ammonium molybdate 1.0 Resorcinol 1.0 Wetting and cleaning agents 3.0
This solution will produce results similar to those described in Example v3.
While the compositions given. in the .above examples in most instances include wetting and cleaning agents, they may be omitted and equal results will .be obtained if the metal articles are thoroughly .cleaned; bciorextreatment.
Also, while the phosphate coating solutions may be used in accordance with the invention at a pH between 3.2 and 5.5, it has been found preferable to adjust the pi-I value thereof to between 3.2 and 3.8 when the coating is obtained by tank immersion and to adjust the pH value thereof to 4.8 to 5.2 when a spray machine is used to apply the solution to the articles being coated.
We claim:
1. A phosphating composition comprising an acid salt of phosphoric acid and a water soluble compound selected from the group consisting of molybdic acid compounds and tungstic acid compounds and a phenol, said latter two ingredients each being present in a quantity ranging from 0.1% to of the quantity of acid salt of phosphoric acid.
2. A phosphating composition comprising an acid salt of phosphoric acid and a water soluble compound selected from the group consisting of molybdic acid compounds and tungstic acid compounds and a phenol, said latter two ingredients each being present in a quantity ranging from 0.5% to 2% of the quantity of acid salt of phosphoric acid.
3. A phosphating composition comprising an acid salt of phosphoric acid, a water soluble compound selected from the group consisting of 'molybdic acid compounds and tungstic acid compounds, and a polyhydric phenol, said latter two ingredients each being present in a quantity rang ing from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
4. A phosphating composition comprising an acid salt of phosphoric acid, a water soluble compound selected from the group consisting of molybdic acid compounds and tungstic acid compounds, and a tannin containing at least one free phenolic hydroxy group, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
5. A phosphating composition comprising an acid salt of phosphoric acid, a water soluble compound selected irom the group consisting of molybdic acid compounds and tungstic acid compounds, and quebracho, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
6.1-1 phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and a phenol, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
7. A phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and a polyhydric phenol, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
8. A phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and a gallic acid, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
9. A phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and a tannin containing at least one free phenolic group, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
10. A phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and quebracho, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
11. A phosphating composition comprising an acid salt of phosphoric acid, a water soluble molybdic acid compound and catechol, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
12, A phosphating composition comprising an acid salt of phosphoric acid, a water soluble compound selected from the group consisting of mclybdic acid compounds and tungstic acid compounds, and a phenol, said latter two ingredients being present in substantially equal quantities, the quantity of each ranging from 0.1% to 10% of the quantity of acid salt of phosphoric acid.
13. A phosphating composition comprising a primary phosphate of the alkali group and a water soluble compound selected from the group consisting of molybdic acid compounds and tungstic acid compounds and a phenol, saidlatter two ingredients each being present in a. quantity ranging from 5.1% to 10% of the quantity of a primary phosphate of the alkali-group.
14. A phosphating composition comprising a primary phosphate of the alkali group, a water soluble molybdic acid compound and quebracho, said latter two ingredients each being present in a quantity ranging from 0.2% to 5% of the primary phosphate of the alkali group.
15. A process of coating metal surfaces which comprises contacting the metal surfaces with an aqueous solution of an acid salt of phosphoric acid containing a water soluble compound selected from the group consisting of molybdic acid compounds and tungstic acid compounds and. a phenol, said latter two ingredients each being present in a quantity ranging from 0.1% to 10% of the quantity of the acid salt of phosphoric acid.
SIDNEY R. DODD. ROBERT F. AYRES.
REFERENQES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,254,263 Oeschger Jan. 22, 1918 1,838,189 Tanner et a1 Nov. 15, 1932 1,893,495 Eberhard Jan. 10, 1933 1,911,537 Tanner May 30, 1933 1,946,647 Taylor et a1 Feb. 13, 1934 2,336,071 Clifford et a1 Dec. '7, 1943 2,375,468 Clifford et al May 8, 1945 2,385,800 Douty et a1 Oct. 2, 1945 FOREIGN PATENTS Number Country Date 584,411 Germany Sept. 20, 1933
Claims (1)
1. A PHOSPHATING COMPOSITION COMPRISING AN ACID SALT OF PHOSPHORIC ACID AND A WATER SOLUBLE COMPOUND SELECTED FROM THE GROUP CONSISTING OF MOLYBDIC ACID COMPOUNDS AND TUNGSTIC ACID COMPOUNDS AND A PHENOL, SAID LATTER TWO INGREDIENTS EACH BEING PRESENT IN A QUANTITY RANGING FROM 0.1% TO 10% OF THE QUANTITY OF ACID SALT OF PHOSPHORIC ACID.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US711810A US2502441A (en) | 1946-11-22 | 1946-11-22 | Phosphate coating of metals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US711810A US2502441A (en) | 1946-11-22 | 1946-11-22 | Phosphate coating of metals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2502441A true US2502441A (en) | 1950-04-04 |
Family
ID=24859618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US711810A Expired - Lifetime US2502441A (en) | 1946-11-22 | 1946-11-22 | Phosphate coating of metals |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2502441A (en) |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2657156A (en) * | 1948-07-23 | 1953-10-27 | Parker Rust Proof Co | Phosphate coating composition and process |
| US2671995A (en) * | 1949-10-22 | 1954-03-16 | Colgate Palmolive Co | Packaging of materials |
| US2681873A (en) * | 1954-02-25 | 1954-06-22 | George L Deniston | Production of black oxide films on aluminum |
| US2715059A (en) * | 1951-08-06 | 1955-08-09 | Kelite Products Inc | Phosphatizing composition |
| US2805969A (en) * | 1952-12-31 | 1957-09-10 | Parker Rust Proof Co | Molybdenum accelerated solution and method for forming oxalate coatings on metallic surfaces |
| US2809906A (en) * | 1952-11-25 | 1957-10-15 | Wyandotte Chemicals Corp | Phosphating compositions |
| US2854368A (en) * | 1955-11-10 | 1958-09-30 | Shreir Louis Lionel | Protective coatings for metals |
| US2854369A (en) * | 1957-10-04 | 1958-09-30 | Oakite Prod Inc | Increasing the solubility of metal accelerators in phosphatizing solutions |
| US2854370A (en) * | 1957-10-04 | 1958-09-30 | Oakite Prod Inc | Composition and method for phosphate coating of metal |
| US2927874A (en) * | 1958-08-14 | 1960-03-08 | Turco Products Inc | Process for producing aluminum surface coatings |
| US3247791A (en) * | 1960-05-06 | 1966-04-26 | Litho Chemical And Supply Co I | Surface treated lithographic plates and production thereof |
| US3272663A (en) * | 1962-11-13 | 1966-09-13 | Oakite Prod Inc | Wash-primer coating including molybdate radical |
| DE1281774B (en) * | 1961-07-31 | 1968-10-31 | Agep Gnacke & Co Chem Fab | Preparations for cleaning and degreasing as well as paint stripping and phosphating of objects made of metals |
| US3411995A (en) * | 1965-03-15 | 1968-11-19 | Enthone | Process and product for plating on cast,malleable,carburized and carbonitrided irons |
| JPS5062139A (en) * | 1973-10-04 | 1975-05-28 | ||
| US4017334A (en) * | 1973-10-04 | 1977-04-12 | Oxy Metal Industries Corporation | Process for treating aluminum cans |
| JPS5247534A (en) * | 1975-10-15 | 1977-04-15 | Nippon Steel Corp | Process for forming rusttproofing underlayer on metallic articles |
| US4054466A (en) * | 1975-09-10 | 1977-10-18 | Oxy Metal Industries Corporation | Tannin treatment of aluminum |
| US4063969A (en) * | 1976-02-09 | 1977-12-20 | Oxy Metal Industries Corporation | Treating aluminum with tannin and lithium |
| JPS5319149A (en) * | 1976-08-06 | 1978-02-22 | Nippon Steel Corp | Conversion process for zinc plated steel member |
| US4089708A (en) * | 1975-04-14 | 1978-05-16 | Compagnie Francaise De Produits Industriels | Phosphatation of metallic surfaces |
| US4111722A (en) * | 1976-02-09 | 1978-09-05 | Oxy Metal Industries Corporation | Tannin treatment of aluminum with a fluoride cleaner |
| US4264378A (en) * | 1979-02-14 | 1981-04-28 | Oxy Metal Industries Corporation | Chromium-free surface treatment |
| US4293349A (en) * | 1979-03-16 | 1981-10-06 | Parker Italiana S.A.S. | Protective compositions for steel surfaces and the process for their preparation |
| US4802972A (en) * | 1988-02-10 | 1989-02-07 | Phillips Petroleum Company | Hydrofining of oils |
| US4880478A (en) * | 1988-12-22 | 1989-11-14 | The United States Of America As Represented By The Secretary Of The Army | Protective coating for steel surfaces and method of application |
| US5039363A (en) * | 1987-12-18 | 1991-08-13 | Nippon Paint Co., Ltd. | Process for phosphating metal surfaces |
| US5221370A (en) * | 1989-06-15 | 1993-06-22 | Nippon Paint Co., Ltd. | Method for forming zinc phosphate film on metal surface |
| EP0880410A4 (en) * | 1996-01-23 | 1999-04-07 | Henkel Corp | Passivation composition and process for coating |
| US6027578A (en) * | 1998-06-09 | 2000-02-22 | Pavco, Inc. | Non-chrome conversion coating |
| US6193815B1 (en) * | 1995-06-30 | 2001-02-27 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
| WO2002010479A2 (en) | 2000-07-27 | 2002-02-07 | Lord Corporation | Two-part aqueous metal protection treatment |
| CN105885645A (en) * | 2016-01-27 | 2016-08-24 | 浙江传化涂料有限公司 | Preparation method of waterborne rusty epoxy coating |
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| US1254263A (en) * | 1917-02-21 | 1918-01-22 | Parker Rust Proof Company Of America | Rust-proofing iron and steel surfaces. |
| US1888189A (en) * | 1929-12-18 | 1932-11-15 | Parker Rust Proof Co | Coated metal article and method of and composition for producing said article |
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| US1254263A (en) * | 1917-02-21 | 1918-01-22 | Parker Rust Proof Company Of America | Rust-proofing iron and steel surfaces. |
| US1893495A (en) * | 1926-03-29 | 1933-01-10 | Eberhard Rudolf | Process for making coating materials for deoxidation of rust |
| US1888189A (en) * | 1929-12-18 | 1932-11-15 | Parker Rust Proof Co | Coated metal article and method of and composition for producing said article |
| US1911537A (en) * | 1930-08-08 | 1933-05-30 | Eobebt r | |
| DE584411C (en) * | 1931-09-22 | 1933-09-20 | Aladar Pacz Dr | Process for the production of corrosion-resistant coatings on iron and steel |
| US1946647A (en) * | 1932-05-25 | 1934-02-13 | Eastman Kodak Co | Process of coating copper with cellulose acetate lacquer |
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Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2657156A (en) * | 1948-07-23 | 1953-10-27 | Parker Rust Proof Co | Phosphate coating composition and process |
| US2671995A (en) * | 1949-10-22 | 1954-03-16 | Colgate Palmolive Co | Packaging of materials |
| US2715059A (en) * | 1951-08-06 | 1955-08-09 | Kelite Products Inc | Phosphatizing composition |
| US2809906A (en) * | 1952-11-25 | 1957-10-15 | Wyandotte Chemicals Corp | Phosphating compositions |
| US2805969A (en) * | 1952-12-31 | 1957-09-10 | Parker Rust Proof Co | Molybdenum accelerated solution and method for forming oxalate coatings on metallic surfaces |
| US2681873A (en) * | 1954-02-25 | 1954-06-22 | George L Deniston | Production of black oxide films on aluminum |
| US2854368A (en) * | 1955-11-10 | 1958-09-30 | Shreir Louis Lionel | Protective coatings for metals |
| US2854370A (en) * | 1957-10-04 | 1958-09-30 | Oakite Prod Inc | Composition and method for phosphate coating of metal |
| US2854369A (en) * | 1957-10-04 | 1958-09-30 | Oakite Prod Inc | Increasing the solubility of metal accelerators in phosphatizing solutions |
| US2927874A (en) * | 1958-08-14 | 1960-03-08 | Turco Products Inc | Process for producing aluminum surface coatings |
| US3247791A (en) * | 1960-05-06 | 1966-04-26 | Litho Chemical And Supply Co I | Surface treated lithographic plates and production thereof |
| DE1281774B (en) * | 1961-07-31 | 1968-10-31 | Agep Gnacke & Co Chem Fab | Preparations for cleaning and degreasing as well as paint stripping and phosphating of objects made of metals |
| US3272663A (en) * | 1962-11-13 | 1966-09-13 | Oakite Prod Inc | Wash-primer coating including molybdate radical |
| US3411995A (en) * | 1965-03-15 | 1968-11-19 | Enthone | Process and product for plating on cast,malleable,carburized and carbonitrided irons |
| JPS5062139A (en) * | 1973-10-04 | 1975-05-28 | ||
| US4017334A (en) * | 1973-10-04 | 1977-04-12 | Oxy Metal Industries Corporation | Process for treating aluminum cans |
| US4089708A (en) * | 1975-04-14 | 1978-05-16 | Compagnie Francaise De Produits Industriels | Phosphatation of metallic surfaces |
| US4054466A (en) * | 1975-09-10 | 1977-10-18 | Oxy Metal Industries Corporation | Tannin treatment of aluminum |
| JPS5247534A (en) * | 1975-10-15 | 1977-04-15 | Nippon Steel Corp | Process for forming rusttproofing underlayer on metallic articles |
| US4063969A (en) * | 1976-02-09 | 1977-12-20 | Oxy Metal Industries Corporation | Treating aluminum with tannin and lithium |
| US4111722A (en) * | 1976-02-09 | 1978-09-05 | Oxy Metal Industries Corporation | Tannin treatment of aluminum with a fluoride cleaner |
| JPS5319149A (en) * | 1976-08-06 | 1978-02-22 | Nippon Steel Corp | Conversion process for zinc plated steel member |
| US4264378A (en) * | 1979-02-14 | 1981-04-28 | Oxy Metal Industries Corporation | Chromium-free surface treatment |
| US4293349A (en) * | 1979-03-16 | 1981-10-06 | Parker Italiana S.A.S. | Protective compositions for steel surfaces and the process for their preparation |
| US5039363A (en) * | 1987-12-18 | 1991-08-13 | Nippon Paint Co., Ltd. | Process for phosphating metal surfaces |
| US4802972A (en) * | 1988-02-10 | 1989-02-07 | Phillips Petroleum Company | Hydrofining of oils |
| US4880478A (en) * | 1988-12-22 | 1989-11-14 | The United States Of America As Represented By The Secretary Of The Army | Protective coating for steel surfaces and method of application |
| US5221370A (en) * | 1989-06-15 | 1993-06-22 | Nippon Paint Co., Ltd. | Method for forming zinc phosphate film on metal surface |
| US6193815B1 (en) * | 1995-06-30 | 2001-02-27 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
| EP0880410A4 (en) * | 1996-01-23 | 1999-04-07 | Henkel Corp | Passivation composition and process for coating |
| US6027578A (en) * | 1998-06-09 | 2000-02-22 | Pavco, Inc. | Non-chrome conversion coating |
| WO2002010479A2 (en) | 2000-07-27 | 2002-02-07 | Lord Corporation | Two-part aqueous metal protection treatment |
| US6902766B1 (en) | 2000-07-27 | 2005-06-07 | Lord Corporation | Two-part aqueous metal protection treatment |
| CN105885645A (en) * | 2016-01-27 | 2016-08-24 | 浙江传化涂料有限公司 | Preparation method of waterborne rusty epoxy coating |
| CN105885645B (en) * | 2016-01-27 | 2020-04-24 | 浙江传化涂料有限公司 | Preparation method of water-based rusty epoxy coating |
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