WO1991004304A2 - Revetement a base d'eau pour surfaces metalliques degrossies - Google Patents

Revetement a base d'eau pour surfaces metalliques degrossies Download PDF

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Publication number
WO1991004304A2
WO1991004304A2 PCT/US1990/005344 US9005344W WO9104304A2 WO 1991004304 A2 WO1991004304 A2 WO 1991004304A2 US 9005344 W US9005344 W US 9005344W WO 9104304 A2 WO9104304 A2 WO 9104304A2
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WO
WIPO (PCT)
Prior art keywords
composition
range
amine
nitrocarburizing
alkali
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.)
Ceased
Application number
PCT/US1990/005344
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English (en)
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WO1991004304A3 (fr
Inventor
Roger E. Hayner
Stephen E. See
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ashland LLC
Original Assignee
Ashland Oil Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ashland Oil Inc filed Critical Ashland Oil Inc
Publication of WO1991004304A2 publication Critical patent/WO1991004304A2/fr
Publication of WO1991004304A3 publication Critical patent/WO1991004304A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

Definitions

  • 2,528,535 to Merker teaches phosphating oil-in-water systems for lubricating compositions preferably with oxidation inhibitors and mentions the possibility of adding rust/corrosion inhibitors, preferably less than 3% by weight.
  • U.S. 4,737,385 to Pekar teaches di-phase oil coatings which are applied to surfaces which have been conventionally phosphated to improve corrosion resistance.
  • Components are siloxane compositions, water based siloxane compositions mixed with water-reducible epoxy-esters and then baked to produce the final coating.
  • ASTM B-117 salt spray tests by the steps of: (a) roughening the surfaces of the work pieces, e.g. by sand blasting, by nitrocarburizing, by oxynitriding, by nitrocarburizing and oxidizing, by phosphating, or by other metallurgical processes which provide an expanded, porous surface having sufficient strength to retain a coating onto the metallic work piece surface; and (b) applying to said expanded surface a waterborne self-healing corrosion protective coating composition capable of application to metallic surfaces; said composition comprising in combination: 1.
  • An oxygenated hydrocarbon composition produced by the partial oxidation of an aliphatic petroleum fraction to a total acid number in the range of about 10 to about 90, said oxidate having been neutralized with an aliphatic amine to render it capable of being emulsified. Further this composition comprises the addition of an alkali/alkaline earth metal sulfonate to further improve corrosion protection and aid in emulsification.
  • Preferred oxygenated hydrocarbon composition is Aqualox 2268 commercially available from Alox Corp., Niagara Falls, New York. 2.
  • an alkali substituted organic amine such as dimethylethanolamine, triethylamine, triethanolamine, or others. 3 . Water 4.
  • FIG. 3 is a schematic diagram of a process of the present invention showing nitrocarburizing followed by dip coating into the emulsion compositions of the invention.
  • Surface treatment processes can be conventional such as chromate, and particularly preferred nitriding or phosphating. See generally Kirk and Othmer, "Encyclopedia of Chemical Technology", 2nd ed. , vol. 18 (1969), pp.282-303 and the later editions.
  • Phosphating can be accomplished by the conventional techniques such as those set forth in "Practical Phosphate Coatings", Mangill Company, and U.S.
  • preferred phosphating is to a thickness of at least 2,000-3,000 mg Zinc Phosphate/ square foot of work piece.
  • Nonrogen-treatment can be either salt bath or fluidized bed nitriding, such as the commercial processes “Tuff Tride”, “Melonite”, “QPQ” (Quench-Polish-Quench, in which salt bath nitriding is followed by quench in an oxidizing salt bath, followed by mechanical polishing, and a second quench), or fluidized bed nitriding as described in "Fluidized Bed Furnace Heat Treating Applications for the Dye Casting Industry", JAPKA, May-June 1983, Dye Casting Engineer.
  • other miscellaneous nitrogen treatment processes which may be employed with the invention include Procedyne's "Dyna-case Surface Hardening Treatment”.
  • deep case carburization in a fluidized furnace by adding methanol which is vaporized and mixed with nitrogen and a small amount of natural gas to form a synthetic end ⁇ thermic atmosphere within the treating furnace at about 899-1010 C(1650-1850F) for 10 minutes- 1 hours, followed by quenching; nitriding by adding nitrogen from raw ammonia onto the surface of the material at 510-593°c (950-1100°F) to provide a case of 0.001-0.015 inches deep; nitrocarburizing providing a case of 0.005-0.0020 inches deep by contacting mixtures of natural gas and raw ammonia in a fluid bed furnace at 566-621°C (1050-1150°F) for 0.5-2.0 hours; steam blueing in a fluid bed furnace at 343-538°C (650-100°F) for 20 minutes-1 hour to provide a blue or black surface, oxynitriding or even combinations of these conventional surface treatment processes.
  • Nitrocarburizing and oxynitriding are particularly preferred.
  • the formulations of the present invention may be applied to substrates to be protected by conventional application techniques, such as spraying, brushing, dipping,flow-coating, dipspinning, "Filwhirl", or airless spraying. Coating thickness can be varied by changing the formulation, the number of coats,or the amount applied per coat but in general will be in the range from about 0.1 to 5 mils, more preferably 0.1 to 2 mils, after drying.
  • 1. oxygenated hydrocarbon composition The oxygenated hydrocarbon composition will be produced according to the techniques commonly known to those experienced in the art of preparing oxidized petrolatums or hydrocarbon waxes. U.S.
  • oxidates will have a total acid number in the range of about 10-90, more preferred 15-70, and most preferred 20-60, and preferably will contain an amount of alkali substituted organic amine (see below). Typical viscosity of said oxidate will be in the range of about 10-70 centstokes at 100C.
  • Charge stocks for the preparation of said oxidates are normally of the C30-C80 chain length. Chain lengths of oxidates vary due to oxygen attack on secondary carbons with the formation of low molecular weight acids such as formic, butyric, acetic, propionic, etc.
  • the compositions commercially available are those currently available under the brand name "Aqualox 2268" from Alox Corp. of Niagara Falls, New York. About 0.5 to 45, more preferred 1.0 to 30, and most preferred 10-25 parts by weight of the oxygenated hydrocarbon composition will be used in the composition of the invention.
  • the Aqualox composition may be described as an partially neutralized amine soap of an oxidized petrolatum to which an amount of alkali earth metal organic sulfonate has been added to provide a mixture which is capable of being either solvent dispersed or emulsified into an oil in water emulsion.
  • alkali metal or alkaline earth metal sulfonate can be added.
  • Such sulfonate will preferably have a total base number of about 0.5 to 200, more preferably about 1 to 100, most preferably 5 to 50.
  • Preferred sulfonates are alkali metal sulfonates, more preferably sodium sulfonate, and most preferably Lubrizol 5363 from Lubrizol Corp., Wickliffe, Ohio. 2.
  • Additional Alkali substituted aliphatic amine in addition to any alkali substituted, aliphatic amine contained in the oxidized hydrocarbon composition can optionally be added so that the total composition contains about 0.5 to 30, more preferred 1 to 25 and most preferred 2 to 10 parts by weight of a neutralizing amine chosen from the group consisting of morpholine, monoethanolamine, dimethylamine, trimethylamine, dimethylethanolamine, triethanolamine, or AMP-95( 2-Amino-2-Methyl-1-Propanol). Most preferred is triethylamine available from Union Carbide Corp., Danbury, Connecticut. "Amine” as used herein also includes aqua ammonia which can function as an amine in these formulations.
  • the amine can be used to adjust pH to the preferred range of about 7 to 11; more preferably about 8 to 9.5. 3 .
  • Water Water employed in the formulation is most preferred as deionized or distilled but is not critical as normal tap water may be employed. Water added should not be in excess of that which produces a dried film of the desired thickness.
  • Compositions will preferably contain about 5 to 95, more preferably 50 to 90, and most preferably 60 to 85% water. Concentrates may be shipped for dilution at point of use. 2. Concentrate Preparation Apparatus:
  • the apparatus for the present invention will be that conventionally utilized in the preparation of coatings compositions, e.g. kettles and mixing tanks having flow metering or measuring devices and agitation means, e.g.
  • Temperature The temperature during mix ⁇ ._ « 3 may be different during different stages in the formulation. These temperatures are not narrowly critical and will vary to provide faster mixing or better compatibility of ingredients according to observation of those skilled in the art.
  • pressure vessels may be utilized for the purpose of raising ingredient boiling points,where useful, in order to provide better dispersion of difficult-to-mix ingredients.
  • Mixing Procedure While the formulation of the present invention may be manufactured continuously if desired, batch techniques will be more usually employed.
  • the oxygenated hydrocarbon-amine-sulfonate emulsions are mixed thoroughly under constant agitation, after which the formulation is drawn off into shipping containers, e.g. tank cars, tank trucks, drums, or smaller cans and containers.
  • Quality Control The finished formulation, prior to packaging, will generally be checked for viscosity, pH, non-volatiles, weight per gallon, freeze thaw stability, corrosion protection under accelerated conditions and other tests utilizing techniques well known to the coatings industry. 3.
  • the concentrate(e.g. prepared according to Example 1) is diluted with 0 to 80, or more preferably 0 to 55, and most preferably 0 to 30 parts by weight of water to form the emulsion which is applied to the work pieces.
  • the solution is preferably applied at 25C(77F). 4.
  • Batch or Continuous Basis While the examples describe the invention on a batch basis, it may come, of course, to be practiced on a continuous basis with continuous flows of starting materials into the mixing vessel and with continuous coating techniques, e.g. roller coating continuous conveyor or even continuous work piece, e.g. sheet steel moving continuously through a dip tank.
  • EXAMPLE 1 (Formulation according to the invention providing excellent salt spray resistance and shelf life.) To a conventional steam jacketed mixing kettle equipped with a rotary stirrer are added 80 parts by weight of water. Agitation is started and the water is heated to a temperature of 150-160F( 65-71C).
  • a hydrocarbon oxidate, amine, and sulfonate composition This preferred composition is known as Aqualox 2268 available from Alox Corporation, Niagara Falls, New York. Agitation and heating are continued until the complex becomes molten and the homogeneous emulsion is formed. Heating is at this point discontinued and the material is sampled for quality control testing.
  • This emulsion once testing is completed, can be applied to metallurgically prepared parts, e.g. phosphated, nitrocarburized or carbonitrided,to give soft oily films which give outstanding corrosion protection.
  • the resulting formulation is tested for corrosion protection by applying it to a ferrous work piece which has been previously nitrocarburized by conventional techniques, e.g.
  • test work piece is subjected to a 5% neutral pH salt(NaCl) spray at a temperature of 35C(95F) according to ASTM B-117. Test parts resist failure (corrosion) for 4200 hours. A sample of emulsion shows no significant separation (e.g., less than 2% "cream") upon standing at room temperature for 24 hours.
  • a work piece as previously described is dipped into the above formulation and allowed to dry at room temperature at approximately 50% relative humidity, the coating is dry to touch in 0.5 to 2 hours, but is cured for 24 hours.
  • compositions are prepared according to Example I using ingredients according to Table 1, the results are as shown in Table 2.
  • Modifications Specific compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variation on these compositions, methods, or embodiments are readily apparent to a person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein.
  • the formulation may contain additional corrosion inhibitors, biocides, antifoamers, dyes, pigments, antiwear additives, EP (extreme pressure) additives, perfume or odor masking agents, etc.
  • Reference made in the other specification is intended to result in such patents or literature being expressly incorporated herein by reference including any patents or other literature references cited within such patents.
  • NitroCoat is a registered trademark of Ashland Oil, Inc.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Une émulsion d'une composition d'oxydate d'hydrocarbure neutralisée par une amine et comprenant un métal alcalin tel que des sulphonates de pétrole de sodium est appliquée sur des surfaces dégrossies préparées métallurgiquement, par exemple l'acier carbonitruré, pour former des pellicules anti-corrosion.
PCT/US1990/005344 1989-09-20 1990-09-19 Revetement a base d'eau pour surfaces metalliques degrossies Ceased WO1991004304A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41016989A 1989-09-20 1989-09-20
US410,169 1989-09-20

Publications (2)

Publication Number Publication Date
WO1991004304A2 true WO1991004304A2 (fr) 1991-04-04
WO1991004304A3 WO1991004304A3 (fr) 1991-05-30

Family

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Family Applications (1)

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PCT/US1990/005344 Ceased WO1991004304A2 (fr) 1989-09-20 1990-09-19 Revetement a base d'eau pour surfaces metalliques degrossies

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EP (1) EP0493509A1 (fr)
AU (1) AU6525590A (fr)
CA (1) CA2065459A1 (fr)
WO (1) WO1991004304A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018120137A1 (de) * 2018-08-17 2020-02-20 Saarstahl Ag Verfahren zur Herstellung eines phosphatierten, mit einem Korrosionsschutzmittel belegten metallischen Körpers, insbesondere eines Drahts

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12601558B1 (en) * 2025-03-25 2026-04-14 Fiske Brothers Refining Company Firearm cleaning fluids

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE424006B (sv) * 1976-12-28 1982-06-21 Bjorklund Ulf Korrosionsskyddsmedel for metaller och lacker med mera, bestaende av en vattenbaserad emulsion
US4479981A (en) * 1982-05-03 1984-10-30 Ashland Oil, Inc. Water-borne hard coating compositions and processes therefor
EP0229349A3 (fr) * 1986-01-13 1988-02-17 Ashland Oil, Inc. Composition de revêtement et procédé pour obtenir un film anticorrosion autocicatrisant
US4851043A (en) * 1987-11-24 1989-07-25 Ashland Oil, Inc. Water reducible soft coating compositions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018120137A1 (de) * 2018-08-17 2020-02-20 Saarstahl Ag Verfahren zur Herstellung eines phosphatierten, mit einem Korrosionsschutzmittel belegten metallischen Körpers, insbesondere eines Drahts

Also Published As

Publication number Publication date
WO1991004304A3 (fr) 1991-05-30
AU6525590A (en) 1991-04-18
CA2065459A1 (fr) 1991-03-21
EP0493509A1 (fr) 1992-07-08

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