US3129122A - Solution for and method of coating ferriferous surfaces - Google Patents
Solution for and method of coating ferriferous surfaces Download PDFInfo
- Publication number
- US3129122A US3129122A US184960A US18496062A US3129122A US 3129122 A US3129122 A US 3129122A US 184960 A US184960 A US 184960A US 18496062 A US18496062 A US 18496062A US 3129122 A US3129122 A US 3129122A
- Authority
- US
- United States
- Prior art keywords
- coating
- liter
- solution
- heterocyclic compound
- gram
- 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 claims description 75
- 239000011248 coating agent Substances 0.000 title claims description 60
- 238000000034 method Methods 0.000 title claims description 14
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 32
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 27
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 17
- 229940005654 nitrite ion Drugs 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 238000007746 phosphate conversion coating Methods 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 claims description 6
- 229960002317 succinimide Drugs 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 42
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 3
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 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
- 229910052708 sodium Inorganic materials 0.000 description 3
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- -1 heterocycle compound Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical class [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/10—Orthophosphates containing oxidants
Definitions
- the present invention relate to the art of producing a phosphate conversion coating on a ferriferous metal surface and is particularly concerned with that type of conversion coating which is produced by treating the surface of the metal with alkali metal phosphate solutions.
- alkali metal phosphate is to be understood as including both sodium and potassium phosphates as well as ammonium mono and ammonium dihydrogen phosphates.
- the alkali metal phosphate coating baths have been employed as aqueous solutions having pH values ranging from approximately 3.2 to 6.2 although, as a general rule, a somewhat narrower pH range has been employed, say from about 4.7 to 6.0.
- accelerating agents such, for example, as chlorates, nitrates, nitrites and peroxygen compounds which, as is well known, operate to reduce the time required for coating formation.
- bromates as accelerating agents not only yields heavier coating weights than are obtained with nitrites but also permits the use of lower reaction temperatures on the order of 150 to 160 F., although some sacrifice in coating weight results from the use of such lower bath temperatures.
- brornate accelerated baths often produce coatings which are mottled or otherwise uneven in appearance, which uneven appearance frequently affects the appearance of the treated metal surface after it has been given a final siccative finish such as paint or the like.
- the principal object of the present invention may be said to reside in the provision of an improved nitrite accelerated alkali metal phosphate coating process by means of which it is possible to produce, on ferriferous metal surfaces, highly corrosion resistant and extremely effective paint bonding coatings at lower temperatures than has been possible heretofore.
- a concomitant object of this invention is to provision of a solution for and a method of applying phosphate conversion coatings to ferriferous metal surfaces of more uniform appearance and of greater weight than has ever been possible heretofore with any of the nitrite accelerated alkali metal phosphate coating baths familiar to the art.
- the present invention is based upon the discovery that if at least 0.05 gram/liter of a heterocycle compound selected from the group consisting essentially of melamine, 3-amino-l,2,4-triazole, imidazol, succinimide and 2-oxazolidone is added to a nitrite accelerated alkali metal phosphate coating solution having a pH of [from 4.0 to 5.8, such solution can be employed as a coating bath in the treatment of ferriferous metal surfaces to produce an extremely uniform, highly corrosion resistant coating of substantially greater weight than heretofore possible in this art even when customary or normal treating cycles of l to 3 minutes are employed and, furthermore, that these improvements in result can be obtained at appreciably lower coating bath temperatures than have ever been practical heretofore.
- heterocyclic compound So far as the upper limit of heterocyclic compound is concerned it has been found that there is no apparent deleterious effect from the use of as much as 30 grams/ liter of these compounds. Use of even higher amounts thereof are limited in some instances by solubility considerations, but Where a particular heterocyclic compound falling within the class listed hereinabove is soluble in an infinite degree, such as for example, 3-amino-1,2,4- triazone, no limitation on the amount used has been found. In the interests of economy, however, it is preferred not to exceed about 10 grams/liter of heterocyclic compound in the coating solutions of this invention.
- Equations A and B in situations where the quantity of heterocyclic compound lies between 0.05 and 1 gram/liter the following specific example is suggested.
- melamine is the heterocyclic compound employed and is utilized in an amount of from 0.0 5 to 1 gram/liter
- the amount of nitrite ion which is required must lie between the limits determined by substituting the molecular weight of melamine (126.13) in the equations. This will give a range for the nitrite (N0 of 0.02. to 0.36 gram/liter of coating solution.
- the nitrite ion may be introduced into the alkali metal phosphate coating solution as a salt, such, for example, as an alkali or alkaline earth metal salt. Due to commercial availability the sodium salt is preferred. However, the only limitation cn the salt used is that the cation portion thereof exhibit no deleterious effect upon the coating reaction.
- nitrite titration is immediately taken and, if such titration shows the presence of nitrite ion, it is only necessary to add at least 0.05 gram/liter of a heterocyclic compound in order to restore the bath to its original and desired coating ability.
- nitrite titration shows a deficiency of this accelerator, it is preferred practice to add nitrite without adding heterocyclic compound, since results with this process show that the heterocyclic compounds are not consumed in the coat ing reaction, and that the only loss thereof is through entrainment or drag-out during coating operations.
- the alkali metal phosphate coating solutions of this invention must be maintained within a pH range of 4.0 to 5.8. Where pH values of less than 4.0 are employed the solution exhibits an undesirable etching action on the ferriferous metal surfaces thereby impairing coating formation. Conversely, where the solution pH is permitted to rise above about 5.8, the coatings produced will be found to be thin and powdery, while still further pH increases will result in no coating being produced upon the metal surfaces.
- a preferred pH range for operating the process of this invention has been found to be from 4.5 to 5.7 since optimum coatings are produced within this narrower pH range.
- Adjustment of the coating solution pH may be made, where needed, by the addition of small increments of either phosphoric acid or sodium hydroxide according to well established art practices.
- One of the outstanding improvements derived from the process of this invention is the ability to obtain coatings on ferriferous metal surfaces at temperatures of from to F.
- prior usage of alkali metal phosphate coating solutions necessitated the employment of coating temperatures of to 180 F. in order to obtain satisfactory results.
- the reduced operating temperatures made possible by the improvements of this invention represent considerable economic advantages to the coating industry.
- the 120 to 150 F. operating temperature range applies to dip, spray or roller coating applications and, while no harmful results are obtained by use of coating temperatures above 150 F., that is temperatures of 170 to 180 F., or even higher, excessive temperatures have been found to result in reduced coating weights, and such temperatures are completely unnecessary and represent an economic waste when utilizing the present process. Temperatures below the minimum of 120 F. should not be used since it has been found that the desired coating weights will not be obtained at such low temperatures within reasonable operating cycles.
- the coating cycle will provide the desired coatings when operated for as little time as 30 seconds to as much time as 5 minutes.
- the pre ferred operating cycle is from 1 to 3 minutes utilizing a temperature of from about 135 to 145 F. Use of lower treating temperatures will necessitate longer contact times, While, conversely, use of slightly higher treating temperatures will require shorter contact cycles.
- a tap water solution was prepared containing, per liter, 10 grams of monosodium phosphate (NaH PO The pH of this solution was 5.2.
- each panel was subjected to an immediate water rinse after which a dilute chromic acid rinse was utilized in accordance with well established art practice.
- a baking enamel was then applied to these panels, and following a curing cycle they were subjected to standard salt spray tests (ASTMB11757T). A resume of the corrosion resistance of these panels is presented below in Table II.
- nitrite ion (calculated as N0 within the range determined by the following equations:
- heterocyclic compound selected from the group consisting of melamine, 3-amino-l,2,4-triazole, imidazol, succinimide and 2-oxazolidone and (2) a quantity of nitrite ion (calculated as N0 which is not less than 0.05 Molecular weight of heterocyclic compound used maintaining the pH of said solution at from 4.0 to 5.8; and maintaining the temperature of the solution at not less than 120 F.
- a bath for use in forming a phosphate conversion coating on a ferriferous surface consisting essentially of:
- a bath for use in forming a phosphate conversion coating on a ferriferous surface said bath consisting essentially of:
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)
- Chemically Coating (AREA)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US184960A US3129122A (en) | 1962-04-04 | 1962-04-04 | Solution for and method of coating ferriferous surfaces |
| GB11329/63A GB963129A (en) | 1962-04-04 | 1963-03-21 | Improvements in or relating to the formation of chemical conversion coatings upon metal surfaces |
| BE630412D BE630412A (fr) | 1962-04-04 | 1963-04-01 | Perfectionnements relatifs a la formation d'enduits de conversion chimique sur des surfaces metalliques |
| DEP1269A DE1269451B (de) | 1962-04-04 | 1963-04-02 | Verfahren zum Phosphatieren von Eisen- und Stahlflaechen |
| FR930177A FR1352567A (fr) | 1962-04-04 | 1963-04-02 | Formation de revêtements par conversion chimique sur des surfaces métalliques |
| NL291056A NL123242C (nl) | 1962-04-04 | 1963-04-03 | Werkwijze voor het fosfateren van ijzeren en stalen oppervlakken |
| NL291056D NL291056A (nl) | 1962-04-04 | 1963-04-03 | Werkwijze voor het fosfateren van metaaloppervlakken |
| FI630648A FI44506C (fi) | 1962-04-04 | 1963-04-04 | Menetelmä rauta- ja teräspintojen fosfatoimiseksi |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US184960A US3129122A (en) | 1962-04-04 | 1962-04-04 | Solution for and method of coating ferriferous surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3129122A true US3129122A (en) | 1964-04-14 |
Family
ID=61167771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US184960A Expired - Lifetime US3129122A (en) | 1962-04-04 | 1962-04-04 | Solution for and method of coating ferriferous surfaces |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3129122A (en:Method) |
| BE (1) | BE630412A (en:Method) |
| DE (1) | DE1269451B (en:Method) |
| FI (1) | FI44506C (en:Method) |
| FR (1) | FR1352567A (en:Method) |
| GB (1) | GB963129A (en:Method) |
| NL (2) | NL123242C (en:Method) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4588818A (en) * | 1983-11-10 | 1986-05-13 | Ajinomoto Co., Inc. | Method for recovery of optically active tryptophane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2766154A (en) * | 1952-03-26 | 1956-10-09 | Parker Rust Proof Co | Method of coating metals with amine phosphate coating and composition therefor |
| US2766153A (en) * | 1952-03-26 | 1956-10-09 | Parker Rust Proof Co | Method of coating metals with amine phosphate coating and composition therefor |
| US2769737A (en) * | 1952-03-26 | 1956-11-06 | Parker Rust Proof Co | Amine phosphate coating solutions and method of coating |
-
1962
- 1962-04-04 US US184960A patent/US3129122A/en not_active Expired - Lifetime
-
1963
- 1963-03-21 GB GB11329/63A patent/GB963129A/en not_active Expired
- 1963-04-01 BE BE630412D patent/BE630412A/fr unknown
- 1963-04-02 FR FR930177A patent/FR1352567A/fr not_active Expired
- 1963-04-02 DE DEP1269A patent/DE1269451B/de active Pending
- 1963-04-03 NL NL291056A patent/NL123242C/nl active
- 1963-04-03 NL NL291056D patent/NL291056A/nl unknown
- 1963-04-04 FI FI630648A patent/FI44506C/fi active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2766154A (en) * | 1952-03-26 | 1956-10-09 | Parker Rust Proof Co | Method of coating metals with amine phosphate coating and composition therefor |
| US2766153A (en) * | 1952-03-26 | 1956-10-09 | Parker Rust Proof Co | Method of coating metals with amine phosphate coating and composition therefor |
| US2769737A (en) * | 1952-03-26 | 1956-11-06 | Parker Rust Proof Co | Amine phosphate coating solutions and method of coating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4588818A (en) * | 1983-11-10 | 1986-05-13 | Ajinomoto Co., Inc. | Method for recovery of optically active tryptophane |
Also Published As
| Publication number | Publication date |
|---|---|
| BE630412A (fr) | 1963-07-31 |
| FR1352567A (fr) | 1964-02-14 |
| DE1269451B (de) | 1968-05-30 |
| FI44506C (fi) | 1971-11-10 |
| GB963129A (en) | 1964-07-08 |
| NL291056A (nl) | 1965-06-25 |
| NL123242C (nl) | 1967-06-15 |
| FI44506B (en:Method) | 1971-08-02 |
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