US2403293A - Anticorrosion composition - Google Patents

Description

y 1946- J. J. MISKEL 2,403,293

ANTICORROSION COMPOSITION Filed June 5, 1943 5 LEGEND E|- COMPQ'A'ZWET STEEL COMPQ'A," DRY STEEL COMPO5"B& "A", WET 5TEEL O COMPO'C", WET STEEL 03 DD: /x O G I A QK/O/ o if 48 72 96 320 TIME, HOURS INVENTOR BY WfiM ATTORNEY Patented July 2, 1946 ANTICORDOSION COMPOSITION John Joseph Miikel, Brooklyn, N. Y., alsignor to National Oil Products Company, Harriso a corporation of New Jersey Application June 5, 1943, Serial No. 489,784

Claims. 1

This invention relates to temporary oily and greasy coatings for application to metallic obiects to prevent the corrosion thereof, and more particularly to such compositions containing surface-active fatty amino compounds.

It is the practice in the metal-working industry to coat finished or semi-finished metallic components with oily or greasy composition to preserve them from corrosion during subsequent working, storage or shipment. This practice is highly necessary, but entails a considerable inconvenience. For instance. when using oily compositions for this purpose. it is necessary to thoroughly dry the metallic obiects to be treated before applying the corrosion-proofing coating thereto, since otherwise any water on the surface of the objects will be entrapped and will cause local corrosion. Since metallic obiects are almost always pickled, phosphated. plated, blacked, anodined, etc., as a final step in the manufacture thereof, this necessity for careful drying occurs very frequently, and consumes a vast amount of time, equipment, space and labor in the metal working industries. Further, even though a metallic surface may be macroscopically dry, it frequently carries an absorbed surface film of moisture, which materially reduces the eflectiveness of the various rust proofing compounds hitherto employed.

Accordingly, it is an obiect of this invention to provide oily corrosion-proofing compositions which may be applied to wet metallic objects, and which will displace the water on the surface thereof to provide a corrosion-proofing film directly in contact with the metal.

Another object is to provide corrosion-proofing compositions which will penetrate and displace the microscopic film of adsorbed moisture almost universally occurring on the surfaces of metallic objects so as to provide a more effective anticorrosion film.

Another obiect is to provide rust proofing compositions of the types outlined above which will be cheaply and readily made from cheaply and readily procurable raw materials.

The foregoing and other objects are achieved in accordance with this invention by the incorporation into an oily composition designed for application to metallic surfaces for corrosionfatty amine compound. Such an amino compound will impart to the composition the property of displacing any moisture whether in the form of macroscopic water drops or in the form of an adsorbed vapor film on any metallic surface so as to form an oily coating in immediate molecular contact with the metallic surface and to prevent the corrosion thereof.

The oily or greasy bodies to which fatty amino compounds are added according to this invention may be substantially the same as those hitherto employed for corrosion proofing coatings, which usually consist of petroleum or fatty oils or mixtures of petroleum or fatty oils, usually with the petroleum oil, which is cheaper, in predominant proportion. Suitable petroleum oil are any naphthenic or paraflinic petroleum oils of sufficiently low volatility, noncorrosiveness and viscosity to be suitable metal-coating agents. Suitable fatty olls are the animal. marine and vegetable oils, and preferably the fatty acids derived therefrom. Examples of suitable fatty oil materials are sperm oil, cod oil, train oil, pilchard oil. lard oil, ncats-foct oil, olive oil. cottonseed oil. and the like; and fatty acid oils such a red oil, stearic acid, coconut fatty acids. fish oil fatty acid and the like. Likewise tall oil and naphthenic acids may be employed, since they possess properties generally similar to those of the fatty acids.

As fatty amino compounds to be incorporated into oily and greasy corrosion-proofing compositions according to this invention there may be employed any substances containing fatty chains of "surface active" length, i. e., having from about 10 to about 22 carbon atoms per molecule. and also containing one or more primary or secondary amino groups. such as the higher fatty amines and amido-amines. Examples of suitable fatty amines include dodecyi amine, lauryl amine, palmityi amine, stearyl amine, oleyl amine and the like. Instead of compounds containing amino groups directly attached to the fatty carbon chain, there may be employed compounds in which the amino groups are on organic groups attached by ether, ester or amide linkages to the fatty carbon chain. such compounds being represented, for instance, in the amide-amines on the order oi oleyl monoamide of diethylene trlamine, the stearyl proofing M0 of a small quantity of a higher monoamide of diethylene triamine, the oleyl monoamide of ethylene diamine, dodecyl monoamide of diethylene triamine, etc. Particularly favorable results have been secured by the use of of the oleyl monoamide of diethylene triamine. Instead of the pure compounds there may. of course, be employed mixtures containing one or more compounds coming within the qualifications above set forth, for instance, the fatty amines and fatty amide-amines derived from the natural oils, fats and waxes. Moreover. since the naphthenic acids and tall oil possess properties generall in line with those of the animal and vegetable fats and oils. the amines and amide-amines containing the high molecular radlcles of these materials may likewise be employed. The amount of the fatty amine compound incorporated into the only compositions of this invention may be very small. mounts on the order of V4% to 1%, based on the total oily composition, being suflicient to secure results in accordance with this invention. Greater quantities may be added. as dictated by particular requirements and economicconsiderations.

The corrosion-preventive oily and greasy compositions of this invention may be applied to metal components and other objects in the same manner as has been the practice with similar compositions in the past, 1. e. by dipping, spraying, mop ing. brushing, etc. However, in contrast to the practice heretofore, it is unnecessary to insure absolute dryness of the surfaces to be treated; in fact the compositions of this invention will actually displace macroscopic accumulations of water occurring on metal surfaces and will effectively form a corrosion proofing film over the metal despite the former presence of the water. This property will be seen to result in a great saving of time and labor in the corrosion proofing of metallic objects. since it will be unnecessary to dry such objects after phosphating, pickling, blacking, anodizing, etc., treatments; the object to be treated may simply be rinsed in water, drained free of the rinsed water insofar as this will spontaneously run 011 and then, without further draining or inspection, immersed in the anticorrosion compositions of this invention. Somewhat less spectacularly, the compositions of his invention have been found to form corrosion preventing iilms upon metallic surfaces which are dry to visual inspection, which films are of superior effectiveness as compared to similar compositions heretofore prepared. This is no doubt due to the fact that metallic objects generally contain an adsorbed film of moisture which the compositions of the present invention are capable of displacing but which the compositions of the prior practice simply entrap.

Following are examples of compositions according to this invention, and of the use thereof, all parts given being by weight.

Example I In this and in succeeding examples, accelerated corrosion tests were conducted upon steel panels treated with composition according to this invention and also, for purposes of comparison, upon steel panels treated by other methods. The tests were conducted upon treated 4" x 6" panels of 18 gage SAE-1015CF steel. The panels were mounted upon a turntable which carried them alternately into a chamber maintained at 70 F. and 25% humidity and into a. chamber maintained at 160-170 F. and 100% humidity,

this cycle being completed every 3 minutes. Condensation on the panels occurred in the moist chamber, and reevaporation in the dry chamber, at each cycle, thus providing unusually severe corrosive conditions. The surface of each panel was examined periodically and the rust spots on the entire surface of both faces of that panel were counted and taken as a measure of the corrosion of that panel, Obviously the less the number of rust spots found at any given time upon a given test panel, the more eifective the protection of that panel must have been. The corrosive conditions encountered in this test may be taken to represent exposure to normal conditions of transportation and storage of 10 to 100 times the actual time of exposure in the apparatus.

The following rust-proofing coatings were prepared.

Composition A.-Not in accordance with this invention, merely for purposes of comparison.

Parts Chromium soap of wool grease 20 V. M. & P. naphtha Composition B.-In accordance with this invention.

Parts Tall 01] 8V2 Oleic monoamide oi ethylene diamine 1 Mineral oil Composition C.In accordance with this inl. A set of cleaned steel panels were wet with water and then directly immersed while still wet in Composition A above. The panels were left in the composition for 10 minutes and then withdrawn and allowed to drain for 60 hours. They were then subjected to the accelerated corrosion test set forth above. The average results of this corrosion test are recorded graphically in curve 1 of the drawing and also in the table at the end of Example IV hereinbelow (item under Example I, paragraph 1"). It will be noted that the protection aflorded was only partial, since a considerable number of rust spots developed almost immediately.

A set of cleaned steel panels were carefully dried and immersed in Composition A for 10 minutes. The panels were removed, allowed to drain for 60 hours and then subjected to the accelerated corrosion test. The average results are recorded graphically in curve 2 of the drawing and in the table hereinbelow (Example I, paragraph 2). It will be noted that fair resistance to corrosion was provided by this treatment.

3. A set of cleaned steel panels were wet with water and dipped in Composition B, Thereafter they were removed from the composition B and immersed tor minutes in Composition A. Therearter the panels were removed from Cornposition A, allowed to drain for 60 hours and then subjected to the accelerated corrosion test,

hereinbelow ("Example I, paragraph 3") will be noted that the use of Composition B, which contains iatty amide-amine (oleic monoamide of ethylene diamine) in this invention, resulted in superior performance over the panels treated as described in the immediate preceding p ragraph 2 although the panels or paragraphil were absolutely dry as far as could be determined by visual inspection whereas the panels treated in accordance with this paragraph were initially wet with water.

4. A set of cleaned steel panels were preliminarily wet with water and were immersed while still wet in Composition C for 10 minutes. Thereafter the panels were removed, drained for 60 hours and subjected to the accelerated corrosion test, the average results oi which are recorded graphically in curve 4 of the drawing and also in the table hereinbelow (Example I, paragraph 4) (The long and elaborate soaking and draining were merely for the purpose of insuring uniform test conditions, and are not necessary in the usual practice of this invention.) It will be seen that this composition gave outstanding periormance, with only very gradual onset of any corrosion whatsoever and very slight final corrosion, notwithstanding the loot that the panels upon which this treatment was carried out were initially wet with water.

EXAMPLE II Tsua'rm'rs COIIBIHID wr'ra Csus'rrc BLACKEIHNG Composition D Parts Coumarone-indene resin 11.8 Lead soap 01' wool grease 3.2 Vistac polyisobutylenes 1.0 Tall oil 3.4 Oleyl monoamide or diethylene triamine- .6 V. M. 8: P. naphtha 80.0 100.0

"Vistas" is a trade name belonging to Advance Solvents and Chemical Co ration designating mixed utylene having a molecular pol era of butylene and loco) we ght between 1100 and 240 This example was carried out upon steel panels which had been preliminarily cleaned and treated with a caustic blackening agent in order to show the cumulative effect of compositions according to this invention upon such blackened panels. which possess a certain amount of corrosion resistance aside from any oil treatment. A number oi. steel panels were given a caustic blacking treatment in a commercial solution (Ebonol manufactured by the Enthone Company, New Haven, Connecticut). This treatment was carried out by immersing the panels for 40 minutes in the boiling "Ebonol" solution, the boiling point of which was maintained at 290 F. by periodic additions oi water. The panels were then rinsed 3 times in cold water.

1. A set of panels treated with Ebonoi" as just described were immediately subjected to the accelerated corrosion test without further treat- 6 ment. As will be seen from the table hereinbelow ("Example II, paragraph 1), the panels were completely rusted at the end 0! the test.

2. A set oi panels treated with Ebonol as above set forth were dried in sawdust and then immersed in Composition C of Example I for 10 minutes, drained for 24 hours and thereafter sub- Jected to the accelerated corrosion test. As will be seen from the table hereinafter (Example II, paragraph 2") only a slight amount of corrosion occurred within 500 hours, at the end oi which time the test was discontinued.

3. A set of panels still wet irom the dual rinsing of the "Ebonol treatment were directly immersed in Composition C for 10 minutes, removed, drained for 24 hours and subjected to the accelerated corrosion test. Only slight corrosion resulted over the 500-hour period in which the test was conducted, see the table "mmple 11, paragraph 3."

4. A set of panels which had been subjected to the "Ebono treatment were dried in sawdust and immersed in Composition D for 10 minutes, removed, drained for 24 hours and thereafter suhiected to the accelerated corrosion test. Only slight corrosion resulted (table, "Example II, paragraph 4").

5. A set of panels still wet from the final rinse in" the Ebonol treatment were immersed in Composition D for 10 minutes, removed, drained {or 24 hours and subjected to the accelerated corrosion test. Only minor corrosion resulted (table, Example II, paragraph 3") EXAMPLE III TszA-rm'rs Comm wr'rn Prrosrns'rnw The procedure of Example 11 was precisely repeated. with the exception that the steel plates, instead of being treated with Ebonol, were phosphated at 203 F. for 60 minutes in a "Parkerizing solution, which is a commercial phosphating composition manufactured by The Parker Rust-Proof Company. The results of these tests are included in the table following Example IV, the items "Example III, paragraph 1" to Example III, paragraph 5. It will be seen that in each case the treatments of this invention greatly enhanced the recognized rust-proofing qualities of the Parkerizing treatment.

EXAMPLE IV Tmrmrs Counnmn wrrn Pnosrnsrmo The procedure of Examples II and III was precisely repeated, with the exception that the steel panels, instead of being treated with "Ebonol" or Parkerizing solution," were phosphated at 200 F. for five minutes in a "Bonderizing solution, which is a commercial composition manufactured by the Parker Rust-Proof Company. The results of these tests are included in the table iOlloWing this example, the items Example IV, paragraph 1" to Example IV, paragraph 5. It will be seen that in each case the treatments of this invention greatly enhanced the recognized rust-proofing qualities of the Bonderizing treatment. It will be appreciated, in connection with this and the preceding two examples, that the ability to oil metal objects while still wet from rinsing after the Ebonol," Parkerizlng and Bonderizlng treatments makes possible a great saving in time and labor.

Ann number of run spots on pouch ntreatmn: of 0m 0!! mm m m can an. ltilr. solar. our. man mar. W ill 8! Busted ms 14 as u I: 3 i i l i i 4 10 u 78 M o 0 o o 0 l o n o o 0 1 o 0 o o o 2 o 0 o o o a Busted o 0 o o o 2 o o 0 0 0 a o o o 0 o Ill-ted o o n 0 20 Rusted o o o 0 u 0 0 0 o o 0 0 n o o l 2 is o o o 1 i a Oleyl amide oi diethylene triamine 1.5 Fe solvent 20.0

The foregoing was a very satisfactory slushing compound base which was capable of further dilutlon with solvents for final application to various metallic surfaces such as steel, brass. copper, aluminum etc. When so applied. rust and/or corrosion was substantially completely prevented on the treated surfaces.

' Trade name of Advance Solvents i. Chemical Co.

The above composition meets the Army and Navy Air Craft Specification ARC-52 type 2, grade A, adapted for application to external surfaces in Savanna; Comm Parts Heavy mineral oil 71.0 Low melting point petrolatum 25.0; Tali oil 3.4 Oleyl amide of diethylene triamine .6

The foregoing composition was a very satisfactory sloshing compound and was found capable pounds are themselves cheaply and readily procurable.

I therefore claim:

1. An anticorrosion coating composition for metals comprising an oily material containing a minor proportion, in an amount to function as an anticorrosive agent, of a fatty amido-amine containing fatty chains of from 10-22 carbon atoms.

corrosive agent, of a fatty amide-amine containing fatty chains of from 10-12 carbon atoms.

10-22 carbon atoms.

4. An anticorrosion coating composition for metals comprising chiefly mineral oil and tail oil with a minor proportion, in an amount to function as an anticorrosive agent, of a fatty amide-amine containing fatty chains of from 10-22 carbon atoms.

5. An anticorrosion coating composition for metals comprising chiefly mineral oil and a fatty oil with a minor proportion, in an amount to function as an anticorrosive agent, of the oleic acid monoamide of diethylene triamine.

8. An anticorrosion coating composition for metals comprising chiefly mineral oil and tall oil and a minor proportion, in an amount to function as an anticorrosive agent, of the oleic acid monoamide of diethylene triamine.

7. A method of preserving wet metallic surfaces from corrosion which comprises coating said access:

10 maceswhiiestiilwctwithacompositioncomprising chiefly mineral oil and tall oil together with a minor proportion, in an amount to tunetion as an anticorrosive agent, of a fatty amideamine containing fatty chains of from 10-22 carhon atoms.

10. A method of preserving wet metallic surfaces from corrosion which comprises coating said surfaces while still wet with a composition comprising chiefly mineral oil and tall oil together with a minor proportion, in an amount to function as an antlcorrosive agent, of the oleic acid monoamide oi diethyleno triamine.

Joan J.

Certificate of Correction Patent No. 2,403,293.

July 2, 1946.

JOHN JOSEPH MISKEL It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 3, line 17, for only read 0113;; column 8, li.ne 50, claim 2, for "10-12 carbon atoms read 10-22 carbon atoms; and that the said Letters Patent should beread with these corrections therein that the same may conform to the record of the ease in the Patent Office.

Signed and sealed this 10th day of September, A. D. 1946.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

access:

10 surlaceswhiiestiilwetwithacompositioncomprising chiefly mineral oil and tall oil together with a minor proportion, in an amount to tunetion as an anticorrosive agent, of a fatty amideamine containing fatty chains of from 10-22 carhon atoms.

10. A method of preserving wet metallic surfaces from corrosion which comprises coating said surfaces while still wet with a composition comprising chiefly mineral oil and tall oil together with a minor proportion, in an amount to function as an antlcorrosive agent, of the oleic acid monoamide oi diethylene triamine.

JOHN J. m.

Certificate of Correction Patent No. 2,403,293.

July 2, 1946.

JOHN JOSEPH MISKEL It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 3, line 17, for only read 0113;; column 8, li.ne 50, claim 2, for "10-12 carbon atoms read 10-22 carbon atoms; and that the said Letters Patent should beread with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 10th day of September, A. D. 1946.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

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