USOO7759419B2

(12) United States Patent (10) Patent No.: US 7,759,419 B2

Stoffer et al. (45) Date of Patent: *Jul. 20, 2010

(54) CORROSION RESISTANT COATINGS 4,876,305 A 10/1989 Mazany ...................... 524/401

4,895,881 A 1/1990 Bigner ....................... 523,122
(75) Inventors: James Stoffer, Rolla, MO (US); 4,988,755 A 1/1991 Dickens, Jr. et al. ........ 524/401
Thomas O'Keefe, Rolla, MO (US); Eric 4,999,250 A 3/1991 Richardson et al. ......... 428,457
Morris, Irvine, CA (US); PuYu, Rolla, 5,013,381 A 5/1991 Cayless et al. .............. 156,281
MO (US); Scott A. Hayes, Rolla, MO 5,037.478 A 8/1991 Okai et al. .................. 106,479
(US) 5,041,241 A 8/1991 Fletcher ...................... 252,387
5,041,486 A 8/1991 Kissel ........................ 524,377
(73) Assignee: The Curators of the University of 5,041,487 A 8, 1991 Kissel - - - - - - - - - - - - - - - - - - - - - - - - 524,377
Missouri, Columbia, MO (US) 5,061,314 A 10/1991 Collier et al. . 106.1405
s s 5,064,468 A 1 1/1991 Okai et al. ............... 106.14.12
(*) Notice: Subject to any disclaimer, the term of this 5,089,066 A 2, 1992 Hamada et al. ............. 148,302
patent is extended or adjusted under 35 E.
J. ww. ISSC ........................
--- -- 3.
U.S.C. 154(b) by 0 days. 5,173,206 A 12/1992 Dickens, Jr. et al. ..... 252/62.54
5,175,202 A 12/1992 Kissel ........................ 524,398
spent is Subject to a terminal dis- 5, 192,374. A 3, 1993 Kindler
5, 198487 A 3/1993 Kissel ........................ 524,403
5,221,371 A 6, 1993 Miller
(21) Appl. No.: 10/758,972 5.244.956 A 9/1993 Miller ........................ 524,403
1-1. 5,298,148 A 3/1994 Yasuoka et al. ............... 205/50
(22) Filed: Jan. 16, 2004 5,322,560 A 6/1994 DePue et al. ................ 106,404
5,322,864 A 6/1994 Sugimoto et al. ........... 523,457
(65) Prior Publication Data 5,338,347 A 8/1994 Rohr et al. ............... 106/14.44
US 2004/0249043 A1 Dec. 9, 2004
Related U.S. Application Data (Continued)
(63) Continuation-in-part of application No. 10/346,374, FOREIGN PATENT DOCUMENTS
filed on Jan. 17, 2003. AU 2001295609 B8 4/2002
(60) Provisional application No. 60/452,843, filed on Mar. EP O902103 A1 3, 1999
7, 2003. EP 1125989 A1 8, 2001
FR 2O58759 5, 1971
(51) Int. C. JP 55065326 A 5, 1980
C23F II/00 (2006.01)
CSK 3/10 (2006.01)
(52) U.S. Cl. ....................... 524/403; 252/387: 524/167; (Continued)
524/238; 524/423: 524/588: 524/612 OTHER PUBLICATIONS
(58) Field of Classification Search ................. 524/401,
524/403, 423, 430,588, 612, 167, 238; 252/387 Machine Translation of JP 05-117589 A. May 14, 1993.*
See application file for complete search history. Aldykiewicz, Jr., et al., “Studies of the Formation of Cerium Rich
Protective Films. Using X-Ray Absorption Near-Edge Spectroscopy
(56) References Cited and Rotating Disk Electrode Methods”. J. Electrochem. Soc., vol.
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3,790,453 A 2, 1974 Wanamaker et al. Primary Examiner Vickey Nerangis
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3,990,920 A 11, 1976 De Ridder et al. ........... 148, 6.2
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4,283,312 A 8, 1981 Crivello ... 260.18 EP
4,370.256 A * 1/1983 Oakes ........... ... 252/.391 A coating composition comprising an effective corrosion
4.405,763. A 9/1983 Kooymans etal ... 525,438 inhibiting amount of a rare earth compound, a neutral to
4.474,607 A 10, 1984 Goldie et al. ............ 106/1439 slightly acidic generating extender or an acidic generating
4.488,578 A 12/1984 Tseung et al. ............... 138,146 extender, or combinations thereof is provided. In one embodi
4,491,611 A 1, 1985 Barnhoorn et al. .......... 427/386 ment, the corrosion-inhibiting components are combined
4497,667 A 2/1985 Vashi .................... 148,615 R with other components such as extenders, amino acids and
4,501,832 A 2f1985 Albers
4,517,030 A 5, 1985 Yamamoto et al. ...... 148,615 R
amino acid derivatives, gelatin and gelatin derivatives,
4,522,879 A 6/1985 Krueger organic-based exchange resins, and combinations thereof, to
4,537,805 A 8/1985 Lin ........................... 427,541 enhance the corrosion resistance of the resultant coating film.
4,544,581 A 10, 1985 Pelloski ...... 427,383.7 The coating compositions have good adhesion to Substrates
4,749,550 A 6, 1988 Goldie et al. ................. 422/19 Such as metals, including aluminum and aluminum alloys.
4,849,297 A 7, 1989 Mansell et al. .. ... 428,457
4,869,964 A 9, 1989 Mazany ...................... 428/418 78 Claims, No Drawings
 US 7,759.419 B2
Page 2

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3. E. S. et t - - - - - - - - - - - - - - - - 428,328 2004/0175587 A1 9/2004 Kendig
5958,578 A
- -w
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6,022,425 A 2/2000 Nelson et al. FOREIGN PATENT DOCUMENTS
6,030,571 A 2, 2000 Nakane et al. ......... 264,331.12
6,068,711 A 5, 2000 Lu et al. JP O1-319574 12/1989
6,077,885 A 6/2000 Hager et al. ... ... 523,445 JP 05-117589 5, 1993
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6,214,132 B1 4/2001 Nakayama et al. .......... 148,254
6,217,674 B1 4/2001 Gray et al. .................. 148.247 OTHER PUBLICATIONS
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6,228,513 B1 5/2001 Jaslier et al. ................ 428,639 Inhibitor for Aluminum-Copper Alloys'. J. Electrochem. Soc., vol.
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6,294,006 B1 9/2001 Andou .................... 106.1405 1837-1838 .
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 US 7,759.419 B2
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Hayes, S.A., et al., “The phase stability of cerium species in acqueous Schuman, Thomas P. et al., “Cerium-based Inhibitors of Aluminum
systems—I. E-pH diagram for the Ce-HCIO4-H20 system”, Journal Corrosion'. Proceedings of the Waterborne, Higher Solids, and Pow
of the Electrochemical Society, 149(12), (Dec. 2002).PC623-C630. der Coatings Symposium, (Feb. 6-8, 2002),371-382.
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cerium oxide coating on aluminum”. Proc. 13th Int. Corros. Congr. Corrosion Assessments'. Gate Coatings Symposium, St. Louis, MO,
(1996). Paper 337/1-Paper 337/7. (Jun. 2002).
Morris, E. L., et al., “The use of inhibitors to improve the corrosion Shahin, A. et al., “XPS characterization of Ce(III-IV) complexes'.
protection of E-coat systems on aluminum alloys'. Polymer Materi Abstracts of Papers of the American Chemical Society, 224(1),
als Science and Engineering, 78, (1998), 172-173. (2002).
Pourbaix, M., “Atlas of Electrochemical Equilibria in Aqueous Solu
tions”, Oxford, New York, (1966), 183-197. * cited by examiner
 US 7,759,419 B2
1. 2
CORROSION RESISTANT COATINGS The present invention additionally relates to aqueous or
Solvent borne coating compositions containing one or more
CROSS-REFERENCE TO RELATED neutral to slightly acidic extenders or acidic extenders, such
APPLICATIONS as metal salts (e.g., metal Sulfates), wherein the metal is
selected from the group consisting of calcium, strontium, and
This application is a continuation-in-part of U.S. patent barium, alone or in combination with other components, hav
application Ser. No. 10/346,374 filed on Jan. 17, 2003, which ing corrosion resistant properties with good adhesion to Sub
is hereby incorporated by reference in its entirety. This appli strates such as metals, including aluminum and aluminum
cation also claims the benefit under 35 U.S.C. 119 (e) of U.S. alloys, bare and galvanized steel, Zinc, magnesium and mag
Provisional Application No. 60/452,843 filed on Mar. 7, 10 nesium alloys. In most embodiments, the coating further con
2003, which is hereby incorporated by reference in its tains a binder. The invention further relates to process for
entirety. preparing Such coating compositions containing neutral to
slightly acidic extenders or acidic extenders, alone or in com
STATEMENT OF GOVERNMENT RIGHTS bination with other components.
15 In one embodiment, a coating system comprising one or
This invention was made with Government support under more pretreatment coatings applied to a Substrate to form a
grant number AFOSRF49620-96-0140 and F33615-97 pretreated Substrate; and an effective corrosion-inhibiting
D5009 awarded by the United States Air Force. The Govern amount of a rare earth compound, a neutral to slightly acidic
ment may have certain rights in this invention. generating extender and/or an acidic generating extender is
provided. In one embodiment, the substrate is not pretreated.
TECHNICAL FIELD In one embodiment, the coating system includes a topcoat. In
one embodiment the coating system is a resin coating. In one
This invention relates to coatings, and, in particular, this embodiment, the coating system is selected from the group
invention relates to corrosion resistant coatings. consisting of a UV-coating system, electrolytic coating
25 (e-coating) system, appliqué, powder coating system and
BACKGROUND microwave coating system. In one embodiment, the Substrate
is a metal Substrate selected from the group consisting of
Coatings are employed for a number of reasons. Product aluminum and aluminum alloys, bare and galvanized steel,
coatings or industrial coatings are typically applied in a fac Zinc (intended to include Zinc alloys), magnesium and mag
tory on a given Substrate or product, such as appliances, 30 nesium alloys, copper and bronze.
automobiles, aircraft, and the like. Many industries, including The invention additionally relates to methods of using a
the aircraft industry, typically employ coating systems that coating composition comprising providing a substrate to be
provide both corrosion protection and enhanced perfor coated and coating the Substrate with a coating composition
aCC. having an effective corrosion-inhibiting amount of a rare
In order to improve the corrosion resistance of a metal 35 earth compound, a neutral to slightly acidic generating
Substrate, corrosion inhibitive pigments or additives are typi extender or an acidic generating extender. In one embodi
cally used in the coatings applied to the Substrate. A common ment, the coating is applied by any conventional method,
corrosion inhibitive pigment is strontium chromate, which including, but not limited to, spraying, brushing, rolling and
provides excellent corrosion resistance. However, in recent dipping. In one embodiment, the method further comprises
years there has been widespread concern over the use of 40 applying a topcoat.
chromates, as they are known to be highly toxic and carcino The coatings described herein have excellent corrosion
genic. Furthermore, the disposal of chromate materials is resistance performance, while maintaining acceptable levels
becoming increasingly difficult as municipal and government of paint adhesion properties. The coating compositions are
regulations are becoming more stringent. useful in many industries, including, but not limited to, the
As a result, there have been attempts to produce corrosion 45 aerospace and aircraft industries.
resistant coatings by using environmentally acceptable cor
rosion inhibitive pigments or additives. However, these coat DETAILED DESCRIPTION OF THE
ings are problematic in that some of the pigments or additives EMBODIMENTS
used are either not compatible with the paint or cause the paint
to peel off the substrate. Some are actually known to accel 50 In the following detailed description, embodiments are
erate the corrosion process. described in sufficient detail to enable those skilled in the art
Thus there is a need to provide corrosion resistant coatings to practice the invention. Other embodiments may be utilized
that are effective, yet not based on chromates. and structural, logical and other changes may be made with
out departing from the spirit and scope of the present inven
SUMMARY 55 tion. The following detailed description is, therefore, not to be
taken in a limiting sense. The detailed description that follows
The present invention relates to aqueous or solvent borne begins with a definition section followed by a description of
coating compositions containing rare earth compounds, Such various embodiments of the invention. A series of examples is
as rare earth oxides, hydroxides, mixed oxides, Solid solution presented next followed by a brief conclusion.
oxides, hydrated oxides, salts, triflates, carbonates, and com 60
plexes alone or in combination with other components, hav DEFINITIONS
ing corrosion resistant properties with good adhesion to met
als, including aluminum and aluminum alloys, bare and As used herein, the term "substrate” refers to a structure
galvanized steel, Zinc, magnesium and magnesium alloys. having a surface that can be cleaned and/or protected and/or
The invention further relates to processes for preparing the 65 modified to provide unique properties. A “substrate is not
coating compositions containing rare earth compounds, alone limited to any particular type of material, although interms of
or in combination with other components. applying a corrosion inhibiting coating, Such substrates are
 US 7,759,419 B2
3 4
typically metal. However, corrosion inhibiting coatings can As used herein, the term “acidic generating extender’, i.e.,
also be applied to other substrates, such as a polymeric Sub 'acidic generating additive refers to a metal cation and a
strate (e.g., coated metallic Substrate). A corrosion inhibiting corresponding oxyanion (meaning those anions having an
coating can also be applied to a composite Substrate. Such as oxygen combined with one or more nonmetals). Preferred but
a Substrate made with carbon fibers and epoxy resin. not required extenders are sulfur, phosphorus and silicon
Although a composite Substrate does not corrode, a corrosion oxyanion-containing compounds. Of particular interest are
inhibiting coating can still be used with a composite substrate Sulfur, phosphorus and silicon oxyanion-containing salts. An
to provide Surface protection and/or other unique properties acidic generating extender can be used alone or in combina
to the Substrate, although the coating must be compatible with tion with other components to generate a pH environment of
the Substrate material. In some instances, although the major 10 less than between about 2 to about 4 in a coating composition
ity of the Substrate can be made from a composite material (with the pH of the coating composition determined by stan
dard methods and concentrations known to those of skill in
and therefore not need protection from corrosion, the pres the art). This environment appears to help enhance and opti
ence of other metallic surfaces within the desired coating mize transport of the particular inhibitor species being used,
area, e.g., metallic rivets, requires the use of a corrosion 15 from the coating composition to areas of exposed underlying
inhibiting coating. Substrate. An acidic generating extender can itselfbe acidic or
As used herein, the term “extender or “extenderpigment” neutral and can also add extender properties to the coating
when used without qualification, refers to a type of pigment composition. Examples of compounds that are capable of
that is typically incorporated into a paint formulation to pro generating a pH environment of between about 2 to about 4
vide Volume to the final resulting coating after paint curing, include, but are not limited to certain hydrogen Sulfates Such
although it can be added for other reasons. Such as to reduce as calcium hydrogen Sulfate, calcium hydrogen phosphate
cost. An extender can additionally or alternatively be an active and calcium di-hydrogen phosphate. Again, it is manifestly
component in making a total system more corrosion resistant. intended to include within this term acidic generating extend
Extenders which add volume are often referred to as “fillers' ers that are substantially soluble, thereby not adding volume
or “extenders/fillers. 25 to the composition. It is possible that the same compound can
As used herein, the term "neutral to slightly acidic gener be properly categorized as both an "acidic generating
ating extender, i.e., "neutral to slightly acidic generating extender and a “neutral to slightly acidic generating
additive', refers to a metal cation and a corresponding oxya extender, since it is capable of generating either environ
nion (meaning those anions having an oxygen combined with ment. One example of a compound that can generate either
one or more nonmetals). Preferred but not required extenders 30 environment includes, but is not limited to, calcium hydrogen
are sulfur, phosphorus and silicon oxyanion-containing com phosphate. Additionally, the precise amount of acidic gener
pounds. Of particular interest are sulfur, phosphorus and sili ating extender needed to generate the desired pH in the com
con oxyanion-containing salts. A neutral to slightly acidic position will vary depending on the type and amount of bind
generating extender can be used alone or in combination with ers, solvents, pigments and other additives present.
other components to generate a pH environment of between 35 As used herein, the term “substantially soluble' refers to a
about 4 to about 8 in a coating composition (with the pH of the solubility level of more than about one (1) mole per liter of
coating composition determined by Standard methods and water (mol/L).
concentrations known to those of skill in the art). This envi As used herein, the term “not substantially soluble' refers
ronment appears to help enhance and optimize transport of to a solubility level of less than about one (1) mol/L.
the particular inhibitor species being used, from the coating 40 As used herein, the term “coating” refers to a polymeric
composition to areas of exposed underlying Substrate. A neu material (organic or inorganic) that can be applied either as a
tral to slightly acidic generating extender can itself be acidic, liquid (e.g., paint) or Solid (e.g., powder) to a Substrate to form
neutral or basic (e.g., NaHPO) and can also add extender a polymeric film. Such polymeric materials include, but are
properties to the coating composition. In most instances, a not limited to, powder coatings, paints, sealants, conducting
neutral to slightly acidic generating extender does not Sub 45 polymers, Solgels (e.g. BoegelTM made by Boeing Co. having
stantially solubilize in the coating composition, thereby add offices in Chicago, Ill.), silicates, silicones, Zirconates, tito
ing Volume to the composition. Examples of neutral to nates, and the like. A "coating is comprised of a complex
slightly acidic generating extenders include, but are not lim mixture of binders, Solvents, pigments and additives. Many
ited to, Sulfates, Sulfites, silicates, phosphates, phosphites, coatings have one or more Substances from each of the four
phosphonates, hydrogen Sulfate, hydrogen Sulfite, mono and 50 categories. Coating properties, such as gloss and color, are
di-hydrogen phosphate, mono and di-hydrogen phosphites related to the film Surface, i.e., as a two-dimensional entity.
and mono hydrogen phosphonate. Further examples include However, the bulk properties of a coating are related to its
oxyphosphorus compounds, Such as cerous phosphate and three-dimensional structure. Phase continuity is a volume
Some Group IIA sulfates, such as calcium sulfate, strontium concept, and the coating performance is dependent on the
sulfate and the like. However, it is manifestly intended to 55 integrity of the binder phase.
include within this term neutral to slightly acidic generating As used herein, the term “binder” refers to any film-form
extenders, i.e., additives, which are substantially soluble and ing polymeric material which can be used to make coatings.
therefore do not add volume to the composition. Examples The polymeric material can be either organic or inorganic.
include certain sulfates known in the art to not be useful in Organic binders have a carbon backbone and inorganic bind
adding Volume but which have shown Surprisingly good 60 ers generally have a silicone backbone. Organic binders are
results as corrosion inhibitors, such as magnesium Sulfate and made up of organic monomers and oligomers from which the
some Group IA sulfates. The precise amount of neutral to binders generally derive their names. Examples of these
slightly acidic generating extender needed to generate the would be acrylic, epoxy, urethane, melamine, and so forth.
desired pH in the composition will vary depending the type Binders include epoxy-based resin binders such as a water
and amount of binders, solvents, pigments and other addi 65 reducible epoxy-polyamide system (for organic polymeric
tives, including other types of extenders present in the coating materials) or non epoxy-based resin binders such as ure
composition. thanes, ureas, acrylates, alkyds, melamines, polyesters,
 US 7,759,419 B2
5 6
vinyls, vinyl esters, silicones, siloxanes, silicates, Sulfides, tion” refer to a list of ingredients, and/or components, and can
silicate polymers, epoxy novilacs, epoxy phenolics, drying also include a list of instructions for preparing and mixing
oils, hydrocarbon polymers, and the like. together the ingredients, and/or components to make a coat
As used herein, the term “weight percent (wt %) when ing composition.
used without qualification, typically refers to the weight per As used herein, the terms “mill base”, “mill base formula
cent of a particular solid component, e.g., pigment, extender, tion”, “primer mill base', “topcoat mill base' and “base'.
etc., as compared with all solid components present, exclud “base formulation’, or “primer base', “topcoat base”, “self
ing polymeric resins. For example, if the only solid compo priming topcoat base', and "enhanced direct to Substrate
nent present in the coating is a corrosion-inhibiting carbon base' refer to a portion or component of a paint formulation
pigment, the corrosion-inhibiting carbon pigment is consid 10 that comprises the majority, if not all, of the pigmentation of
ered to have a wt % of 100. the coating composition, as well as some additives.
As used herein, the term “mixed oxide” refers to a solid Discussion
Solution of a single element having multiple oxidation states
and is not intended to refer to a mixture of oxides. Embodiments of the invention provide compositions for
As used herein, the term “topcoat” refers to a mixture of a 15 primer coatings that allow for improved corrosion resistance
binder(s), which can be an organic or inorganic based poly of metal Substrates. In one embodiment non-primer coatings
meror a blend of polymers, typically at least one pigment, can are used. In one embodiment non-metal Substrates are used.
optionally contain at least one solvent or mixture of solvents, Moderate to low concentrations of rare earth compounds,
and can optionally contain at least one curing agent. A topcoat alone or in combination with other materials or components,
is typically the coating layer in a single or multi-layer coating have been formulated into coating mixtures providing corro
system whose outer Surface is exposed to the atmosphere or sion resistance. Additionally provided are extenders, includ
environment, and its inner Surface is in contact with another ing moderate to low concentrations of neutral to slightly
coating layer or polymeric Substrate. One example of a top acidic generating extenders and acidic generating extenders,
coat is a urethane topcoat. also alone or in combination with other materials or compo
As used herein, the term “self-priming topcoat’, also 25 nents, which have been formulated into coating mixtures
known as a “direct to substrate coating, refers to a mixture of providing corrosion resistance.
a binder(s), which can be an organic or inorganic based poly In one embodiment, coatings containing rare earth com
mer or blend of polymers, typically at least one pigment, can pounds, neutral to slightly acidic generating extenders and/or
optionally contain at least one solvent or mixture of solvents, acidic generating extenders in varying concentrations are pro
and can optionally contain at least one curing agent. A self 30 vided to enhance the corrosion resistance properties of the
priming topcoat is typically applied directly to a substrate. resulting coating films. In one embodiment, the coatings are
The self-priming topcoat can optionally be applied to an aqueous or solvent borne coating compositions applied as
organic or inorganic polymeric coating, such as a primer or liquids, e.g., paint. In other embodiments, the coatings are
paint film. A self-priming topcoat is typically the coating applied in powder or paste (e.g., Solgel) form. In yet other
layer in a single or multi-layer coating system where the outer 35 embodiments, the coating is a sealant, conducting polymer, or
Surface of the coating is exposed to the atmosphere or envi the like.
ronment, and the inner Surface of the coating is typically in Rare earth compounds useful in the present invention
contact with the Substrate or optional polymer coating or include, but are not limited to either anhydrous or hydrated
primer. rare earth oxides, hydroxides, mixed oxides, Solid Solution
As used herein, the term "enhanced self-priming topcoat. 40 oxides, hydrated oxides, salts, triflates, carbonates, and com
also referred to herein as an "enhanced direct to substrate plexes, such as rare earth complexes using ethylenediamine
coating refers to a mixture of functionalized fluorinated tetraacetic acid, organic-based ionic exchange resins, etc.,
binders, such as a fluoroethylene-alkyl vinyl ether in whole or and the like. In one embodiment, one or more rare earth
in part with other binder(s), which can be an organic or compounds are added to a coating composition. In a particu
inorganic based polymer or blend of polymers, typically at 45 lar embodiment, the one or more rare earth compounds are
least one pigment, can optionally contain at least one solvent added in a weight percent of between about 0.1 to about 90 wt
or mixture of solvents, and can optionally contain at least one % of the total amount of all pigments present in the coating. In
curing agent. An enhanced self-priming topcoat is typically most embodiments, the coating contains between about 0.1 to
applied directly to a substrate. The enhanced self-priming about 28 wt %, of a rare earth compound (i.e., compounds),
topcoat can optionally be applied to an organic or inorganic 50 although the invention is not so limited
polymeric coating, Such as a primer or paint film. An The rare earth compounds useful herein can be based on
enhanced self-priming topcoat is typically the coating layer in any of the lanthanide series. Preferred for the practice of the
a single or multi-layer coating system where the outer Surface invention are praseodymium, cerium, and terbium. Particu
of the coating is exposed to the atmosphere or environment, larly preferred are praseodymium and terbium, with the most
and the inner Surface of the coating is typically in contact with 55 currently preferred being praseodymium. The oxidation state
the Substrate or optional polymer coating or primer. of the rare earth metal employed is important. For example, in
The topcoat, self-priming topcoat, and enhanced self-prim the case of praseodymium, in one embodiment, praseody
ing topcoat can be applied to a substrate, in eitherawet or “not mium(III) is used. In another embodiment, a praseodymium
fully cured’ condition that dries or cures over time, that is, (III/IV) mixture is used. In yet another embodiment,
Solvent evaporates. The coatings can dry or cure either natu 60 praseodymium(IV) is used. The preferred oxidation states of
rally or by accelerated means for example, an ultraviolet light the rare earth compounds can also be a function of the final
cured system to form a film or “cured paint. The coatings can coating system employed. In one embodiment, the rare earth
also be applied in a semi or fully cured State, such as an compound is a praseodymium(III) sulfate. In another
adhesive. embodiment, the rare earth compound is a praseodymium(III/
As used herein, the terms “paint formulation”, “primer 65 IV) oxide or a praseodymium(III/IV) solid solution. In other
formulation”, “topcoat formulation”, “self-priming topcoat embodiments the rare earth compound can be a praseody
formulation', and "enhanced self-priming topcoat formula mium mixed oxide, a praseodymium(III) oxide, a praseody
 US 7,759,419 B2
7 8
mium(III) hydroxide, a praseodymium(IV) oxide, and any is not so limited. In one embodiment, the neutral to slightly
combinations thereof, further including combinations with acidic generating extenders or acidic generating extenders are
any other praseodymium or other metals. selected from the group that includes, but is not limited to,
In one embodiment the rare earth compound can be a Sulfates, including metal Sulfates (e.g., anhydrous calcium
cerium oxide, cerium hydroxide, cerium Solid solution mixed Sulfate, hydrated calcium Sulfate, strontium sulfate, barium
oxide, cerium oxide mixture, cerium salt, neodymium oxide, Sulfate, hydrated magnesium Sulfate, etc.), metal phosphates
neodymium hydroxide, neodymium Solid solution mixed (e.g., hydrous calcium phosphate, anhydrous calcium phos
oxide, neodymium oxide mixture, neodymium salt, phate and mono- and di-hydrogen calcium phosphate, etc.).
praseodymium oxide, praseodymium hydroxide, praseody Again, any of the extenders described herein can be used in
mium solid solution mixed oxide, praseodymium oxide mix 10 either natural (mineral) or synthetic form. The acidic gener
ture, praseodymium salt, ytterbium oxide, ytterbium hydrox ating extenders can further include non-sulfate, non-phos
ide, ytterbium solid solution mixed oxide, ytterbium oxide phate and non-nitrate acidic generating extenders, such as the
mixture, ytterbium salt, yttrium oxide, yttrium hydroxide, Burgess extenders including calcined clays, e.g., calcined
yttrium solid solution mixed oxide, yttrium oxide mixture, kaolin clays, etc., made by the Burgess Pigment Co. having
yttrium salt, terbium oxide, terbium hydroxide, terbium solid 15 offices in Sandersville, Ga., and the like. However, other
solution mixed oxide, terbium oxide mixture, terbium salt, metal cations and anions having the aforementioned proper
and combinations thereof. ties can be used as neutral to slightly acidic generating
Many rare earth compounds, alone or in combination with extenders and acidic generating extenders in the coating com
other materials, have been evaluated to date (See Examples). positions of the present invention, as will be understood by
These compounds have been incorporated into commercially those of skill in the art with reference to this disclosure.
available primer formulations as corrosion inhibitors. Evalu In one embodiment, one or more neutral to slightly acidic
ation of these primer coatings containing the rare earth com generating extenders and/or one or more acidic generating
pounds alone or in combination with the other materials in extenders are used. The amount of extenders used can vary
neutral salt fog environments demonstrates that the presence considerably, because some are more efficient in the particu
of these corrosion inhibitors improves the overall corrosion 25 lar system being used. In one embodiment, neutral to slightly
resistance of the metal Substrate, although it is likely any acidic generating extenders and/or acidic generating extend
Substrate, as defined herein, can benefit from application of ers are added in a weight percent of between about 1 to about
Such coatings. Similarly, it is expected that any type of coat 99% of the total amount of all pigments in the coating. In most
ing can benefit from inclusion of rare earth compounds, alone embodiments the coating contains between about 30 to about
or in combination with other components. Elemental charac 30 80 wt % of one or more neutral to slightly acidic generating
terization of these systems suggests leaching of the inhibitor extenders and/or acidic generating extenders. In more pre
passivates and protects the underlying metal substrate. ferred embodiments, the coating contains between about 45
Extenders useful in the present invention include, but are to 75 wt % of one or more neutral to slightly acidic generating
not limited to, neutral to slightly acidic generating extenders extenders and/or acidic generating extenders. In a particular
and acidic generating extenders. In one embodiment, one or 35 embodiment, between about 0.1 to about 3 wt % of one or
more neutral to slightly acidic generating extenders are used. more types of magnesium Sulfate is used.
Such extenders can be acidic, neutral or basic. Examples Several neutral to slightly acidic generating extenders and
include, but are not limited to, Sulfates, Sulfonates, Sulfides, acidic generating extenders have been evaluated to date,
Sulfites, phosphates, phosphonates, phosphides, phosphates, alone or in combination with other materials (See Examples).
nitrates, nitrites, nitrides, silicates and combinations thereof. 40 These compounds have been incorporated into commercially
In one embodiment, one or more acidic generating extenders available primer formulations as corrosion inhibitors. Evalu
are used. Such extenders can be acidic or neutral. Examples ation of these primer coatings containing these extenders
include, but are not limited to acid-modified compounds, alone or in combination with the other materials in neutral salt
Such as acid-modified phosphates, phosphides, phosphates, fog environments demonstrates that the presence of these
kaolins, wallastonites, silicates and combinations thereof. 45 corrosion inhibitors improves the overall corrosion resistance
Also useful in the present invention are conventional of the metal Substrate, although it is likely any Substrate, as
extenders that can serve as a cost effective substitute for defined herein, can benefit from application of such coatings.
coloring pigments such as TiO, and can further provide the Similarly, it is expected that any type of coating can benefit
desired pigment to binder ratios for the primer coatings. One from inclusion of neutral to slightly acidic generating extend
example of a conventional extender includes, but is not lim 50 ers and/or acidic generating extenders, alone, or in combina
ited to, calcium carbonate. Many of these extenders appear to tion with other components. Elemental characterization of
assist in the activation of inhibitors that can be present in the these systems suggests leaching of the inhibitor passivates
environment (e.g., in previously applied conversion coatings, and protects the underlying metal Substrate.
in the polymeric coating itself, etc.), thus enhancing the cor The “other materials or components' (i.e., "other compo
rosion resistance of the protective coating. 55 nents') with which the corrosion inhibitors described herein
In one embodiment, the neutral to slightly acidic generat can be combined include, for example, binders, Solvents,
ing extenders or acidic generating extenders include Group I pigments (including Soluble or non-soluble extenders, fillers,
and II metal cations. In one embodiment, the neutral to corrosion-inhibiting pigments, and the like), Solvents, addi
slightly acidic generating extenders or acidic generating tives (e.g., curing agents, Surfactants, dyes, amino acids and
extenders include Sulfates and phosphates of praseodymium 60 the like), and so forth. Note that some additives can also
(such as praseodymium(III), (IV) or (III/IV) mixtures), cal properly be considered a pigment and vice versa (e.g., mat
cium, strontium, barium and magnesium, and the natural ting agents). More specifically, these "other components'
forms of these compounds such as gypsum and celestite. include, but are not limited to, glycine, arginine, methionine,
Preferably the neutral to slightly acidic generating extenders and derivatives of amino acids, Such as methionine Sulfoxide,
or acidic generating extenders include calcium, strontium, 65 methyl sulfoxide, and iodides/iodates, gelatin and gelatin
and barium sulfates and phosphates that do not substantially derivatives, such as animal and fish gelatins, linear and cyclic
solubilize in the coating composition, although the invention dextrins, including alpha and beta cyclodextrin, triflic acid,
 US 7,759,419 B2
10
triflates, acetates, talc, kaolin, organic-based ionic exchange paint ready to apply) can also be by any conventional method
resins, such as organic-based cationic and anionic exchange known in the art. The primer can also include about 0.1 to
resins, organic-based ionic exchange resins, such as organic about 15 wt % and preferably about 0.5 to about 5 wt % of an
based cationic and anionic exchange resins, organic-based organic-based ionic exchange resin. The resin can be either
ionic exchange resins that have been pre-exchanged or cationic oranionic in nature, both cationic and anionic can be
reacted with the salts, oxides, and/or mixed oxides of rare used in the same primer formulation, and the ionic exchange
earth material, and metal Sulfates, such as Sulfates of rare resin can contain rare earth compounds and/or amino acids as
earth materials, magnesium sulfate, calcium sulfate (anhy pre-exchanged species prior to incorporation into a primer
drous and hydrated forms), strontium sulfate, barium Sulfate, formulation. The primer can contain about 0.03 to about 5 wt
and the like. 10 %, and preferably about 0.1 to about 1.2 wt %, complexing
Corrosion co-inhibitors known in the art can also option Sugars and/or gelatin. The primer can also contain about 0.1 to
ally be employed in the present invention together with the about 5 wt % and preferably about 0.5 to about 1.5 wt %,
rare earth compounds and/or neutral to slightly acidic gener amino acids.
ating extenders and/or acidic generating extenders, and, System enhancers can also be employed to enhance and
optionally, any of the other components described herein. 15 optimize transport of the particular functional species being
Such co-inhibitors include, but are not limited to, borates, used and ultimately increase the concentration of the active
metaborates, aniline, polyaniline, and the like. Other co-in inhibitor at the corrosion sites. Parameters that optimize
hibitors can also be optionally employed in the present inven transport include, but are not limited to, use of conversion
tion, such as NalzanTM (made by NL Industries having offices coatings, particle size of the pigment, dust coat, and the like.
in Highstown, N.J.), BusanTM (made by Buckman Laborato Conversion coatings useful herein include cerium conver
ries having offices in Memphis Tenn.), HaloxTM (made by sion coatings (CeCC), praseodymium conversion coatings
Halox Inc. having offices in Hammond, Ind.), MollywhiteTM (PrCC), phosphate conversion coatings, zinc-type conversion
(made by Sherwin Williams Inc. having offices in Cof coatings, anodized-type conversion coatings, and chromium
feyville, Kans.), and the like. It is appropriate to use only conversion coatings (CrCC). The conversion coatings evalu
those co-inhibitors that are chemically compatible with the 25 ated in conjunction with the present invention include CrCC.
rare earth- or neutral to slightly acidic generating- or acidic such as those obtained using the Alodine (from Henkel) and
generating extender-containing paint formulation. Iridite (from McDermid) processes, chromic acid anodized
The various corrosion inhibitors described herein are typi with chrome seal, Sulfuric acid anodized with chrome seal,
cally combined with a binder, Such as an organic polymer. and the like. The age and thickness of the applied conversion
The organic polymers useful herein as binders include those 30 coatings can further influence the corrosion resistance of the
soluble in water and those soluble in non-aqueous systems Subsequent paint coatings. It is preferred to apply the paint
and powder coating systems. Polymers that are film-forming coating over a conversion coating which is less than three
and that crosslink upon curing are preferred. Examples of days old and is relatively moderate to heavy in thickness, but
these polymers include, but are not limited to, epoxy, ure yet still provides excellent adhesion to the underlying sub
thane, urea, acrylate, alkyd melamine, polyester, vinyl, vinyl 35 strate. Conversion coatings that are too thick tend to result in
ester, silicone, siloxane, silicate, Sulfide, Sulfone, epoxy primers with cohesive failure in the conversion coating layer.
novolac, epoxy phenolic, amides, drying oils, and hydrocar The proper conversion coating thickness will be readily
bon polymers. apparent to one of ordinary skill in the art.
All of the corrosion inhibitors (including co-inhibitors) Additional additives and pigments can be employed to
discussed herein are preferably prepared in a liquid form. 40 provide desired aesthetic or functional effects. If desired, the
Thus, the binder, such as an organic polymer, is dispersed or coating composition can contain other components, i.e.,
dissolved in an appropriate solvent, such as water or a non optional materials, well known in the art of formulated sur
aqueous solvent depending on the nature of the polymer, and face coatings. These optional materials would be chosen as a
the appropriate amount of corrosion inhibitor(s) is added. function of the coating system and application and can
The corrosion inhibitors (including co-inhibitors) 45 include flow control agents, thixotropic agents such as ben
described above were evaluated in a polyamide/epoxy-based tonite clay, fillers, anti-gassing agents, organic co-solvents,
water reducible primer paint formulation, although the catalysts, and other customary auxiliaries. These materials, if
present invention is not limited to this specific epoxy-based used, can constitute up to 40 percent by weight of the total
system. As such, the corrosion inhibitors can be incorporated weight of the coating composition.
into other primer paint formulations and employed in other 50 The coating composition of the present invention can also
applications where corrosion prevention is desired. Other optionally contain pigments to give it color. In general, the
resins can include, but are not limited to, e-coats, epoxy, pigment is incorporated into the coating composition in
urethane, urea, acrylate, alkyd melamine, polyester, vinyl, amounts of about 1 to about 80 percent, usually about 1 to
vinyl ester, silicone, siloxane, silicate, Sulfide, Sulfone, epoxy about 30 percent by weight based on total weight of the
novilac, epoxy phenolic, amides, drying oils, and hydrocar 55 coating composition. Color pigments conventionally used in
bon polymers. The preferred polymer system is a water Surface coatings include inorganic pigments such as titanium
reducible epoxy-polyamide system. In a particular embodi dioxide, iron oxide, carbon black; phthalocyanine blue, and
ment, the polyamide/epoxy-based water reducible primer phthalocyanine green. Metallic flake pigmentation is also
paintformulation used is Deft 44GN72 manufactured by Deft useful in aqueous coating compositions of the present inven
Inc., having offices in Irvine, Calif. 60 tion. Suitable metallic pigments include aluminum flake, cop
Addition of about 0.1 to about 90 wt %, and preferably per bronze flake, and metal oxide coated mica. The optional
about 0.1 to about 28 wt %, of a rare earth compound into a pigments can comprise up to approximately 25 weight per
primer formulation (or a paint ready to apply) can be by any cent of the coating composition.
conventional method known in the art. Similarly, addition of The preferred concentration ranges of the components in
about 1 to about 99 wt % and preferably about 45 to about 75 65 the coating, as well as the PVC (pigment Volume concentra
wt % of a neutral to slightly acidic generating extender and/or tion) of the coating, can vary based on the resin/primer system
an acidic generating extender into a primer formulation (or a employed. In concentration ranges provided, the weight per
 US 7,759,419 B2
11 12
centages are based on a fully catalyzed and water reduced embodiment is about 30 to about 80 wt % of CaSO2H.O.
sprayable paint Preferred for the practice of the present inven Most particularly preferred is about 45 to about 75 wt % of
tion is a coating comprising a PVC in the range of about 0.1 CaSO2HO. Other preferred ranges are as follows:
to about 65 wt % PVC. Particularly preferred is about 10 to
about 55 wt % PVC. Most preferred is an about 25 to about 45 5 TABLE 1 B***
wt % PVC.
Preferred for the practice of one embodiment of the present Neutral to Slightly Acidic Generating Extenders and
invention is a fully catalyzed and water reduced sprayable Acidic Generating Extenders
paint composition comprising about 0.1 to about 40 wt % Metal Sulfates:
PrO. Particularly preferred in this embodiment is about 0.1 10
to about 28 wt % PrO. Most particularly preferred is about CaSO-2H2O: Range: 1-99 wt % Preferred: 45-75 wt %
0.1 to about 11 wt % PrO.
6-
Other preferred ranges are as SrSO:
CaSO Anhyd.:
Range: 1-99 wt %
Range: 1-99 wt %
Preferred: 45-75 wt %
Preferred: 45-75 wt %
follows: BaSO-2H2O: Range: 1-99 wt % Preferred: 45-75 wt %
MgSO47H2O: Range: 1-3 wt % Preferred: 1.5-2.5 wt %
TABLE 1 A* * * 15 MgSO4.2H2O: Range: 0.1-3 wt % Preferred: 1.5-2.5 wt %
Pr Sulfate: Range: 0.1-3 wt % Preferred: 0.5-2.5 wt %
La2(SO4)2H2O: Range: 1-99 wt % Preferred: 45 75 wt %
Rare Earth Compounds LiSO2H2O: Range: 1-99 wt % Preferred: 45 75 wt %
PrsO11: Range: 0.1-90% Preferred: 0.4-28 wt % Metal Phosphates.
Pr2O3: Range: 0.1-90% Preferred: 0.4-28 wt %
PrO: Range: 0.1-90% Preferred: 0.4-28 wt % 2O Ca(H2PO) H2O: Range: 1-99 wt % Preferred: 45-75 wt %
PrO2 + PrO: Range: 0.1-90% Preferred: 0.4-28 wt % Ca(HPO)HO: Range: 1-99 wt % Preferred: 45-75 wt %
TbO7: Range: 0.1-90% Preferred: 0.4-28 wt % Cas (PO2H2O: Range: 1-99 wt % Preferred: 45-75 wt %
CeO2 Hydrous Range: 0.1-90% Preferred: 0.4-28 wt % Other Extender
Pr(OH): Range: 0.1-90% Preferred: 0.4-28 wt % Types:
Sm2O3: Range: 0.1-90% Preferred: 0.4-28 wt %
Yb2O: Range: 0.1-90% Preferred: 0.4-28 wt % CaCO2H2O Range: 3-99 wt % Preferred: 45-75 wt %
Y2O3: Range: 0.1-90% Preferred: 0.4-28 wt % 25 Kaolin Range: 3-99 wt % Preferred: 45-75 wt %
La2O3: Range: 0.1-90% Preferred: 0.4-28 wt % Sr Carbonate: Range: 6-35% Preferred: 16.1-18.8 wt %
Nd2O3: Range: 0.1-90% Preferred: 0.4-28 wt % Pr Carbonate: Range: 6-35% Preferred: 16.1-18.8 wt %
***Ranges given as: “Range: x-x wt %” are understood to read as: “Range: between about ***Ranges given as: “Range: x-x wt %are understood to read as: “Range: between aboutx
x to about x wt.%. to aboutx wt.%.”

Preferred for the practice of one embodiment of the present 30

invention is a paint composition comprising about 1 to about For the additional materials, the following wt % ranges are
99 wt % of a metal sulfate. Particularly preferred in this preferred:

TABLE 1 C***
Other Materials

La2(SO4)3: Range: 1-99% Preferred: 45-75 wt %

Li2SO Range: 1-99% Preferred: 45-75 wt %
L-Arginine: Range: 0.1-5 wt % Preferred: 0.5-1.5 wt %
D.L-Arginine: Range: 0.1-5 wt % Preferred: 0.5-1.5 wt %
D-Methionine: Range: 0.1-5 wt % Preferred: 0.5-1.5 wt %
L-Methionine: Range: 0.1-5 wt % Preferred: 0.5-1.5 wt %
D.L-Methionine: Range: 0.1-5 wt % Preferred: 0.5-1.5 wt %
Glycine: Range: 0.1-5 wt % Preferred: 0.5-1.5 wt %
L-Cystiene: Range: 0.1-5 wt % Preferred: OS-15 wt %
Cystene: Range: 0.1-5 wt % Preferred: OS-15 wt %
Proline: Range: 0.1-5 wt % Preferred: 0.5-1.5 wt %
Ethylenediaminetetra- Range: 0.1-5 wt % Preferred: 0.5-1.5 wt %
acetic acid (Free):
Ethylenediaminetetra- Range: 0.1-5 wt % Preferred: 0.5-1.5 wt %
acetic acid (Disodium salt):
D.L-Methionine Sulfoxide: Range: 0.1-5 wt % Preferred: 0.5-1.5 wt %
L-Methionine methylsulfonium
iodide:
Animal Gelatin: Range: 0.03-5 wt % Preferred: 0.1-1.2 wt %
Proline of Fish Gelatin: Range: 0.03-5 wt % Preferred: 0.1-1.2 wt %
Alpha or Beta Cyclodextrins: Range: 0.03-5 wt % Preferred: 0.1-1.2 wt %
Sulfonated Cyclodextrins: Range: 0.03-5 wt % Preferred: 0.1-1.2 wt %
Trific Acid: Range: 0.1-0.5 wt % Preferred: 0.1-1.2 wt %
PrTriflate: Range: 04-5 wt % Preferred: 0.7-3 wt %
Ce Triflate: Range: 04-5 wt % Preferred: 0.7-3 wt %
Reilex (As is): Range: 0.1-15 wt % Preferred: 0.5-5 wt %
Whatman CM23 (as is): Range: 0.1-15 wt % Preferred: 0.5-5 wt %
Whatman CM23 Pre-Exchanged Range: 0.1-15 wt % Preferred: 0.5-5 wt %
with Praseodymium Triflate:
Whatman CM23 Pre-Exchanged Range: 0.1-15 wt % Preferred: 0.5-5 wt %
with Methionine
Whatman DE23 (As is): Range: 0.1-15 wt % Preferred: 0.5-5 wt %
Whatman P11 (As is): Range: 0.1-15 wt % Preferred: 0.5-5 wt %
 US 7,759,419 B2
13 14
TABLE 1 C***-continued
Whatman CM23 Pre-Exchanged with Range: 0.1-15 wt % Preferred: 0.5-5 wt %
Praseodymium Salt such as
a Nitrate Salt:
Whatman CM23 Pre-Exchanged with Range: 0.1-15 wt % Preferred: 0.5-5 wt %
Cerium Salt such as a Nitrate
Salt:
Whatman CM23 Pre-Exchanged Range: 0.1-15 wt % Preferred: 0.5-5 wt %
with Sulfuric Acid:
Sm Acetate: Range: 0.1-5 wt % Preferred: 0.5-2.5 wt %

***Ranges given as: “Range: x-x wt %” are understood to read as: “Range: between aboutx to aboutx wt %.”

Any conventional method for manufacturing a paint or 15 added in a “letdown phase', as it is known in the art, while the
coating can be used in the present invention. Examples pigment base or mill base is mixed. An optional step is to
include the use of drill presses powered by compressed air or allow the base or finished paint to set for at least twenty-four
electricity, sand mills which use appropriate grinding media, hours prior to use, which allows the resin to wet all of the
and the like. The following is an example of how a primer pigments.
containing any individual or combination of the above inhibi The shelf life of the polyamide/epoxy-based water reduc
tors can be produced: ible primer formulation or the self-priming topcoat composi
The mill base for a polyamide/epoxy-based water reduc tion, or the enhanced self-priming topcoat composition prior
ible primer formulation can be prepared (and, in fact, was to use is generally dictated by the time specifications provided
prepared for all of the Examples described herein) by dispers by the supplier of the resin system.
ing one or more binders, one or more pigments, solvent if 25 Next, the polyamide/epoxy-based water reducible primer
needed, and a curing agent. The base for a self-priming top formulation, self-priming topcoat composition, or the
coat composition, or enhanced self-priming topcoat compo enhanced self-priming topcoat composition is prepared by
sition can also be prepared in the same manner (and, in fact stirring appropriate amounts of a catalyst or activator, Such as
was prepared in this manner for all of the Examples described an isocyanate catalyst, into the finished base described above.
herein). In this process, the base is dispersed in an appropri 30 Examples of isocyanate catalysts for self-priming topcoat or
ately sized container at 650 rpm using a dispersion blade, enhanced self-priming topcoat formulations include an iso
such as a standard dispersion blade and standard dispersing cyanate solution known as Deft 97GY088CAT available from
equipment or even a drill press, as is known in the art. Next, Deft Inc., having offices in Irvine, Calif. To ensure proper
under agitation at an appropriate speed, such as about 600 curing and cross-linking of the resulting paint film, the
700 rpm, coloring pigments, naturally occurring extenders, 35 amount of isocyanate catalyst added to the finished paint base
that is, minerals such as gypsum, and synthetic extenders, can vary depending on the particular components of the coat
together with any other corrosion inhibitors are incorporated ing system, as will be understood by those of skill in the art
into the coating formulation. If an appropriate grinding media with reference to this disclosure.
is desired, it can be added as needed. Next, once the material Next, for the self-priming topcoat composition, or the
is properly added to the formulation, the base is allowed to 40 enhanced self-priming topcoat composition, once the fin
disperse for a Suitable time and speed, such as about five more ished base and catalyst have been mixed together, the coating
minutes at 650 rpm. After this time, the dispersion speed can is ready for application to a substrate. The substrate to be
be increased as needed, such as to about 1600 to 1640 rpm coated can be that of a fabricated article, such as aircraft,
until the desired mill base pigment grind is obtained. automobiles, trucks, and farm equipment, for example, fur
During dispersion at the higher speed, the temperature of 45 ther including the components and parts for these articles.
the mill base can be monitored and kept below the recom Next, for the polyamide/epoxy-based water reducible
mended temperatures for the ingredients and resin Systems primer formulation, once the appropriate amounts of epoxy
used. If it appears that the mill base temperature is close to catalyst and mill base are well mixed together, the appropriate
exceeding the recommended temperatures for the stability of amount of water is then slowly mixed into the primer mill
the ingredients or resins, the dispersion speed can be reduced 50 base? epoxy catalyst blend and testing can be performed. The
appropriately. If necessary, the dispersion process can be purity and amount of water added depends on what is recom
halted momentarily to allow proper cooling. mended by the Supplier of the coating system based on the
As will be understood by those of skill in the art with spray viscosity and final use of the coating. Since the paint
reference to this disclosure, other steps, such as using cooling formulation is a water reducible system, care needs to be
systems to minimize higher dispersion temperatures can 55 taken when adding the aqueous component to the epoxy
additionally or alternatively be used. Also, as will be under catalyst/mill base blend.
stood by those of skill in the art with reference to this disclo The medium employed in the preparation of the coating
Sure, the solvent employed in the preparation of the coating system of the present invention is typically chosen in Such a
system is chosen in Such a manner as to facilitate the prepa manner as to facilitate the preparation of the coating mixture,
ration of the coating mixture, to provide Suitable application 60 and to provide suitable adhesion to the substrate. The pre
properties, and provide and environmentally acceptable ferred medium is water, which includes the preparation of
paint. water borne coatings. Other systems include solvent-based
Next, once the desired pigment particle size for the base and powder coatings.
grind is obtained, the dispersion process can behalted, and the As noted above, once the mill base? epoxy blend and appro
base filtered, if desired, to remove any undesired material 65 priate amount of water are mixed together, the primer is now
from the base, such as grinding media that can optionally have ready for application to the substrate. Suitable substrates
been used. Next, the balance of formula ingredients are then include metal Substrates Such as aluminum, aluminum alloys,
 US 7,759,419 B2
15 16
cast aluminum, magnesium, magnesium alloys, titanium, other embodiments, the coating is an electrolytic coating
Zinc, galvanized Zinc, Zinc-coated Steel, Zinc alloys, zinc-iron (e-coating) system, electrostatic (powder) coating, and the
alloys, zinc-aluminum alloys, steel, stainless Steel, pickled like. Various types of curing methods are described below.
steel, iron compounds, magnesium alloys, and the like. Pre The coatings described herein can be any suitable thick
ferred substrates for the practice of the present invention are ness, depending on the application requirements. In one
aluminum and aluminum alloys. The Substrate to be coated embodiment, the coating is between about 1 to about 3 mils
can be that of a fabricated article, as described above, further thick. In another embodiment, the coating is between about
including the components and parts for these articles. 0.8 to about 1.2 mils thick.
The coating mixtures of the invention can be applied to the Typically, after application of the coating, the coating is
Surfaces of a metal Substrate using any conventional tech 10
cured using any Suitable method. Typical curing methods
nique. Such as spraying, painting with a brush, painting with include air drying, and/or heating and/or UV-curing methods.
rollers, dipping, and the like, but they are most often applied Other methods include, but are not limited to, microwave
by spraying. The usual spray techniques and equipment for cured systems, ultrasonic cured systems, and the like. The
air spraying and electrostatic spraying and either manual or method of curing will depend on the type of coating mixture
automatic methods can be used. Preferred for the practice of 15
employed, the Surface to which it is applied, and so forth.
the present invention is spray coating. Once the coating is applied and cured, it can either receive
It is preferred that the surface, such as a metal surface, be Subsequent topcoats, or be cured as a stand-alone coating. If
prepared to receive the coating. This preparation includes the the coating is to receive a Subsequent topcoat, or several
conventional method of first cleaning the Surface to remove Subsequent coatings, then the Subsequent coating should be
grease and other contaminants. Once the Surface is free of applied so as to be compatible with the coating layer already
Surface contaminants, it can be treated to remove any oxide present, typically in accordance with the resin and/or topcoat
coating, and in certain instances to provide a conversion coat manufacturers’ specifications. If the coating does not receive
ing to which the corrosion-inhibiting mixture can more any Subsequent topcoats, it can then be allowed to cure.
readily bond. In the event that the surface has a thick oxide
coating, then this coating can be removed by conventional 25
Additional Embodiments
means, such as immersion in a series of sequential chemical
baths containing concentrated acids and alkalis that remove In one embodiment, the coating composition is a self
Such a surface coating. priming topcoat composition, or an enhanced self-priming
In most embodiments, the Substrate or coated Substrate is topcoat composition. These coating compositions can be used
prepared prior to receiving the coating, i.e., is pretreated. This 30
preparation includes the conventional method of first clean on metals such as aluminum, aluminum alloys, cast alumi
ing the surface to remove grease and other contaminants. num, magnesium, magnesium alloys, titanium, Zinc, Zinc
Once the Surface is free of Surface contaminants, it can be coated Steel, Zinc alloys, zinc-iron alloys, zinc-aluminum
treated to remove any oxide coating by conventional means, alloys, bare and galvanized steel, stainless steel, pickled steel,
Such as by immersing the Substrate in a series of sequential 35 iron compounds, magnesium alloys, Substrates having metal
chemical baths containing concentrated acids and alkalis pretreatments. Such as chrome-based conversion coatings,
known to remove Such a surface coating. As noted above, in anodized coatings, cobalt-based conversion coatings, phos
Some embodiments, the Substrate is treated to provide a con phate-based conversion coatings, silica-based conversion
version coating to which the coating can more readily bond. coatings, rare earth-based conversion coatings, and stainless
Such a conversion coating can be prepared by any means 40 metal pretreatments for example, and polymers, polymer/
known in the art, Such as by immersion in concentrated chro metal composites, composites, coated Substrates, and the like.
mic acid. When an aluminum Substrate is used, for example, In a preferred but not required embodiment, the self-priming
this process produces a controlled mixture of aluminum topcoat composition, or the enhanced self-priming topcoat
oxides on the Surface of an aluminum or aluminum alloy composition is applied over a conversion coating that is less
substrate. Alternatively, the surface can be treated with aboric 45 than three days old. Applying the self-priming topcoat com
acid/sulfuric acid or any other anodizing process. This pro position, or the enhanced self-priming topcoat composition
cess produces a controlled mixture of aluminum oxides in the over a conversion coating has been found to maintain good
Surface of an aluminum or aluminum alloy Substrate. Option adhesion of the coating to the substrate. It has also been found
ally, after the surface has been treated to provide a conversion that conversion coatings that are too thick for a given appli
coating, the Surface can be sealed by dipping the Substrate 50 cation can result in cohesive failure in the conversion coating
into a dilute solution of chromic acid. The surface, whether layer. As will be understood by those of skill in the art with
sealed or unsealed, can then be coated with the coatings reference to this disclosure, the proper conversion coating
described herein. performance and thickness, for a particular coating composi
In one embodiment, the coating is applied to an aluminum tion, will be apparent and preferred coatings comply with
MIL-C-5541.
anodized substrate to create an aluminum anodized system 55
with and without sealing in a chrome containing solution. In In another embodiment, a process for preparing and using
one embodiment, the coating is applied to an aluminum anod the self-priming topcoat composition, or the enhanced self
ized Substrate to create an aluminum anodized system with priming topcoat composition is provided. According to this
and without sealing in a rare earth Solution. In one embodi embodiment, conventional methods for manufacturing a
ment, the coating is applied to a steel Substrate with and 60 paint can be used. As will be understood by those of skill in
without sealing in the appropriate solution. the art with reference to this disclosure, examples of such
The coatings described herein can be applied to a substrate methods include, but are not limited to, the use of drill presses
using any conventional technique, such as spraying, “paint powered by compressed air or electricity, sand mills that use
ing” (e.g., with a brush, roller, and the like), dipping, and so appropriate grinding media, and the like.
forth. With regard to application via spraying, conventional 65 The invention will be further described by reference to the
(automatic or manual) spray techniques and equipment used following non-limiting examples, which are offered to further
for air spraying and electrostatic spraying can be used. In illustrate various embodiments of the present invention. It
 US 7,759,419 B2
17 18
should be understood, however, that many variations and EXAMPLE 2
modifications can be made while remaining within the scope
of the present invention. Primer Mill Base Formulation
EXAMPLE1
Oxides, either anhydrous or hydrated, and hydroxides of
Exemplary Mill Base Formulations rare earth elements have been evaluated as being non-toxic
alternatives to chromates. Rare earth oxides, either anhydrous
Group IIA pigments have been tested for corrosion resis or hydrated, and hydroxides, such as Cerium (IV) Oxide,
tance, including Sulfates (e.g., anhydrous calcium Sulfate, 10 Cerium (IV) Oxide dihydrate, Praseodymium (III) Oxide,
hydrated calcium Sulfate, strontium sulfate, barium sulfate), and the like, have been incorporated into polyamide? epoxy
metal phosphates (e.g., hydrous calcium phosphate, anhy water reducible primer formulations. One example of a
drous calcium phosphate and mono- and di-hydrogen cal polyamide/epoxy water reducible primer mill base formula
cium phosphate, etc.), alone and in combination with other tion containing rare earth salts is as follows:
components. Two examples of the composition, concentra 15
tions, material ratios, Vendor materials or vendor Supplier, of
a polyamide/epoxy water reducible primer mill base formu
lation containing these types of compounds is shown below. Polyamide Resin Blend 341 g
Other formulations were also tested: Additive 5 g
Component: 2-Butanol Solvent 71 g
TiO2(R-960) 143 g
Rare Earth Oxide(s) 40 g
Extender? Filler Pigment 400 g
Polyamide Resin Blend 417 g
Dispersing Agent 6g 25 Mill Base Total: 1000 g
2-Butanol Solvent 87 g
Extender? Filler Pigment 490 g
Mill Base Total: 1000 g
The concentration of the corrosion inhibitors used as indi
30 viduals range from about 0.4 wt % (PrO panel A151) to
Component: about 12 wt % (CeOxH2O). Additional procedures used in
this Example were as described in Example 1 under Addi
tional Information and Procedures Used. See Table 3 in
Polyamide Resin Blend 320 g Example 12 for test results.
Additive 5 g 35
2-Butanol Solvent 67 g EXAMPLE 3
TiO,(R-960) 134 g
Co-Inhibitor(s) 100 g
Extender? Filler Pigment 374 g Mixed oxides, either anhydrous or hydrated, and hydrox
ides of mixed oxides of rare earth elements have been evalu
Mill Base Total: 1000 g 40
ated as being non-toxic alternatives to chromates. Rare earth
mixed oxides, either anhydrous or hydrated, and hydroxides,
The concentration of the corrosion inhibitors used as indi such as Terbium (III/IV). Oxide, Praseodymium (III/IV)
viduals range from about 0.1 wt % to about 90 wt %. Oxide, and the like, have been incorporated, individually and
Additional Information and Procedures Used 45 in combination, into polyamide? epoxy water reducible
The wt % of inhibitor is based on a fully catalyzed and primer formulations. One example of a polyimide? epoxy
water reduced primer and the spray viscosity is equal to about water reducible primer mill base formulation containing rare
22 seconds on a standard EZ Zhan 2 Cup. earth salts is as follows:
The polyamide/epoxy water reducible primer mill base
was then well mixed with appropriate amounts of the epoxy 50
Primer Mill Base Formulation
catalyst blend as described above and recommended by the
Supplier of the resin. One example of an epoxy catalyst/
activator would consist of a solvent, an additive, and a resin
blend, such as Deft's epoxy/nitroethane Solution, manufac
turer's code number 44WO16CAT. 55 Polyamide Resin Blend 328 g
Once the appropriate amounts of epoxy catalyst and mill Dispersing Agent 5g
base were well mixed together, the appropriate amount of 2-Butanol Solvent 68 g
water was then slowly mixed into the primer mill base/epoxy TiO2 137 g
Rare Earth Mixed Oxide(s) 77 g
catalyst blend. The purity and amount of the water added (Anhy. Hydrous. Hydroxide)
depends on what is recommended by the supplier of the 60 Extender? Filler Pigment 385 a.
coating system based as described above. Procedures for Mill Base Total: 1000 g
mixing of the primer, shelflife of primer mill base, spray life
of catalyzed and water reduced primer, and the like, are in
accordance with the specifications of the supplier of the resin
material. 65 The concentration of the corrosion inhibitors used as indi
Examples of such primer formulations that have been pre viduals range from about 1 wt % (PrO, panel A22) to about
pared and evaluated are provided in Table 3 below. 22.2 wt % (PrO panel 227). Additional procedures used in
 US 7,759,419 B2
19 20
this Example were as described in Example 1 under “Addi The concentration of the corrosion inhibitors used as indi
tional Information and Procedures Used. See Table 3 in viduals range from about 0.5 wt % (D.L-methionine sulfox
Example 12 for test results. ide panel 0179) to about 1.1 wt % (D.L-Methionine Sulfoxide
panel 234). Additional procedures used in this Example were
EXAMPLE 4 as described in Example 1 under “Additional Information and
Procedures Used. SeeTable 3 in Example 12 for test results.
Amine-based aliphatic, aromatic, cyclic, and or Sulfur con
taining compounds have been evaluated as being non-toxic EXAMPLE 6
alternatives to chromates. Amine-based aliphatic, aromatic,
cyclic, and or Sulfur containing compounds, for example 10 Gelatin and gelatin derivatives have been evaluated as
amino acids, Such as L-arginine, D.L-arginine, D-methion being non-toxic alternatives to chromates. Gelatin and gelatin
ine, L-methionine, D.L-methionine, glycine, proline, L-cys derivatives, such as but not limited to animal gelatins and
teine, etc., and other amine-based compounds, such as ethyl derivatives, fish gelatins and derivatives, and the like, have
enediaminetetra-acetic acid (EDTA), di-sodium salts of been incorporated into polyamide/epoxy water reducible
EDTA, and the like, have been incorporated into polyimide/ 15 primer formulations. One example of a composition, concen
epoxy water reducible primer formulations. One example of
a polyamide/epoxy water reducible primer mill base formu trations, material ratios, Vender materials, or vender Supplier,
lation containing these types of compounds is as follows: of a polyamide/epoxy water reducible primer mill base for
mulation containing these types of compounds is as follows:
Primer Mill Base Formulation
Primer Mill Base Formulation

Polyamide Resin Blend 351 g

Dispersing Agent 5g 25 Polyamide Resin Blend 351 g
2-Butanol Solvent 73g Dispersing Agent 5g
TiO, 146g 2-Butanol Solvent 73g
Amine-based aliphatic, aromatic, cyclic, 14g TiO2 146g
and/or Sulfur containing compound(s) Gelatin(s) and or 14g
Extender? Filler Pigment 411g Gelatin Derivative(s)
30
Extender? Filler Pigment 411 g
Mill Base Total: 1000 g
Mill Base Total: 1000 g

The concentration of the amino acids used range from about

0.5 wt % (D.L-Methionine panel 0214) to about 1.5 wt % The concentration of the corrosion inhibitors used as indi
(D.L-Methionine panel 232). Additional procedures used in 35 viduals range from about 0.03 wt % (Animal Gelatin--
this Example were as described in Example 1 under “Addi PrO+Ce(NO) panel A66E) to about 1 wt % (Animal
tional Information and Procedures Used. See Table 3 in Gelatin--PrO+Ce(NO) panel A28). Additional proce
Example 12 for test results. dures used in this Example were as described in Example 1
under “Additional Information and Procedures Used.’ See
EXAMPLE 5 40 Table 3 in Example 12 for test results.
Derivatives of amine-based aliphatic, aromatic, cyclic, and EXAMPLE 7
or Sulfur containing compounds have been evaluated and
Verified as being non-toxic alternatives to chromates. Deriva Chirally Active Dextrins have been evaluated as being non
tives of amine-based aliphatic, aromatic, cyclic, and or Sulfur 45 toxic alternatives to chromates. Chirally Active Dextrins,
containing compounds, such as D.L-methionine Sulfoxide, Such as alpha cyclodextrin, beta cyclodextrin, Sulfonated
L-methionine methylsulfonium iodide, and the like, have cyclodextrins, and the like, have been incorporated into
been incorporated into polyamide/epoxy water reducible
primer formulations. One example of this composition, con polyamide/epoxy water reducible primer formulations. One
centrations, material ratios, Vendor materials, or vendor Sup example of a polyamide/epoxy water reducible primer mill
plier, of a polyamide/epoxy water reducible primer mill base 50 base formulation containing these types of compounds is as
formulation containing these types of compounds is as fol follows:
lows:
Primer Mill Base Formulation
Primer Mill Base Formulation
55

Polyamide Resin Blend 351 g

Polyamide Resin Blend 351 g Dispersing Agent 5g
Dispersing Agent 5g 2-Butanol Solvent 73g
60 TiO2 146g
2-Butanol Solvent 73g
TiO2 146g Chirally Active Dextrin(s) 14g
Derivative(s) of amine-based aliphatic, aromatic, cyclic, 14g Extender? Filler Pigment 411 g
and/or Sulfur and/or iodide containing compound(s)
Extender? Filler Pigment 411 g Mill Base Total: 1000 g

Mill Base Total: 1000 g 65

The concentration of the corrosion inhibitors used was
primarily at about 1.5 wt % (Cyclodextrin--Ce(NO)+
 US 7,759,419 B2
21
PrO panel C41. Additional procedures used in this
Example were as described in Example 1 under Additional -continued
Information and Procedures Used. See Table 3 in Example Pre-Exchanged Organic-Based 14g
12 for test results. Ionic Exchange Resin(s)
Extender? Filler Pigment 411 g
EXAMPLE 8
Mill Base Total: 1000 g
Organic-based ionic exchange resins have been evaluated
as being non-toxic alternatives to chromates. Organic-based
ionic exchange resins; Such as organic-based cationic resins, 10 The concentration of the corrosion inhibitors used range from
for example Whatman fibrous cellulose phosphate cation about 0.5 wt % (P11+Pr(NO), panel 1162) to about 2.5 wt
exchanger P11, Whatman fibrous carboxymethyl cellulose % (P11+D.L-Methionine panel 15). Additional procedures
cation exchanger CM23, and the like, and anionic exchange used in this Example were as described in Example 1 under
“Additional Information and Procedures Used.’ See Table 3
resins, for example Whatman fibrous diethylaminoethyl cel in Example 12 for test results.
lulose anion exchanger DE23, and Reilex 402 Polymer, and 15
the like, have been incorporated into polyamide? epoxy water EXAMPLE 10
reducible primer formulations. One example of a polyamide/
epoxy water reducible primer mill base formulation contain Metal sulfates have been evaluated as being nontoxic alter
ing rare earth salts is as follows: natives to chromates. Metal Sulfates, such as praseodymium
Sulfate or other rare earth Sulfates, magnesium sulfate, cal
Primer Mill Base Formulation cium sulfate, strontium sulfate, and the like, have been incor
porated into polyamide? epoxy water reducible primerformu
lations. One example of the composition, concentrations,
material ratios, Vendor materials, or vendor Supplier, of a
25 polyamide/epoxy water reducible primer mill base formula
Polyamide Resin Blend 351 g tion containing these types of compounds is as follows:
Dispersing Agent 5g
2-Butanol Solvent 73g
TiO, (R-960) 146g Primer Mill Base Formulation
Organic-Based Ionic Exchange Resin(s) 14g
Extender? Filler Pigment 411g 30
Mill Base Total: 1000 g
Polyamide Resin Blend 351 g
Dispersing Agent 5g
The concentration of the corrosion inhibitors used as indi 2-Butanol Solvent 73g
TiO2 146g
viduals range from about 0.5 wt % (CM23+PrO panel 35
Metal Sulfate(s) 14g
1216) to about 1 wt % (DE 23, panel 110). Additional proce Extender? Filler Pigment 411 g
dures used in this Example were as described in Example 1 Mill Base Total: 1000 g
under “Additional Information and Procedures Used. See
Table 3 in Example 12 for test results.
40
EXAMPLE 9 The concentration of the corrosion inhibitors used as indi
viduals range from about 1.4 wt % (Pr(SO) panel A220) to
Organic-based, pre-exchanged ionic exchange resins have about 18.5 wt % (SrSO panel 267). Additional procedures
been evaluated as being non-toxic alternatives to chromates. used in this Example were as described in Example 1 under
“Additional Information and Procedures Used.’ See Table 3
Organic-based cationic and or anionic ionic exchange resins 45
in Example 12 for test results.
that have been pre-exchanged with rare earth cations and or
amino acids; for example Whatman fibrous cellulose phos EXAMPLE 11
phate cation exchanger P11 pre-exchanged with a solution
containing salts, oxides and mixed oxides, and or compounds Combinations of all of the above have been evaluated as
or rare earths, Whatman fibrous cellulose phosphate cation 50
being non-toxic alternatives to chromates. Combinations of
exchanger P11 pre-exchanged with a solution containing all of the above, such as L-arginine--praseodymium(III/IV)
amine-based aliphatic, aromatic, cyclic, and or Sulfur and or oxide--calcium sulfate dihydrate, praseodymium sulfate--cal
iodide containing compounds and or derivatives of any of the cium Sulfate--arginine, praseodymium(III/IV) oxide--cal
above, etc. have been incorporated into polyamide? epoxy cium Sulfate--methionine, praseodymium(III) oxide--
water reducible primer formulations. One example of a 55 praseodymium pre-exchanged cationic exchange resin P11+
polyamide/epoxy water reducible primer mill base formula praseodymium(III/IV)oxide, etc., have been incorporated
tion containing these types of compounds is as follows: into polyamidefepoxy water reducible primer formulations.
One example of a polyamide/epoxy water reducible primer
Primer Mill Base Formulation mill base formulation containing rare earth salts is as follows:
60
Primer Mill Base Formulation

Polyamide Resin Blend 351 g

Dispersing Agent 5g
2-Butanol Solvent 73g 65 Polyamide Resin Blend 336 g
TiO2 146g Dispersing Agent
 US 7,759,419 B2
24
-continued TABLE 2-continued
2-Butanol Solvent 71 g Corrosion Codes/Rankings Employed in Table 3
TiO2 140 g
Pre-Exchanged Organic-Base 14g 12. Pinpoint sitesipits of corrosion on organic coating Surface (/16
Ionic Exchange Resin to /8 in diameter - about 0.16 cm (0.06 in) to
PrsOil 40 g about 0.32 cm (0.13 in)
Extender? Filler Pigment 394 g 13. One or more blisters on surface away from scribe
14. Many blisters under primer away from scribe
Mill Base Total: 1000 g 15. Starting to blister over Surface
10
Scribe Line Activity (corrosion creepage beyond scribe)
The concentration of the corrosion inhibitors used as com
binations range from about 0.1 wt % (Ce(NO)+Free EDTA, No creepage
panel D36) to about 30.6 wt % (Ce(NO)+NaEDTA+ O to /64 in - about 0 cm (in) to about 0.04 cm (0.02 in)
PrO+CaSO4·2H2O panel A38). Additional procedures "/64 to /32 in - about 0.04 cm (0.02 in) to about 0.08 cm (0.03 in)
15 /32 to 1/16 in - about 0.08 cm (0.03 in) to about 0.16 cm (0.06 in)
used in this Example were as described in Example 1 under /16 to 1/8 in - about 0.16 cm (0.06 in) to about 0.32 cm (0.13 in)
“Additional Information and Procedures Used.’ See Table 3
*/16 to "/4 in - about 0.2 cm (0.48 in) to about 0.5 cm (0.25 in)
in Example 12 for test results. /4 to 3/8 in - about 0.6 cm (0.25 in) to about 0.95 cm (0.38 in)
EXAMPLE 12

Test Results on Exemplary Coatings TABLE 3

Many of the formulations noted in the previous examples Panels Prepared and Evaluated
were tested on various Substrates for corrosion resistance. Weight
The Corrosion Rating Scale used is shown in Table 2. 25 Percent 2OOOHRS
Examples of primer formulations that were prepared and Panel Corrosion Inhibitor Extender Salt Fog
evaluated are provided in Table 3. Number Inhibitor Conc. Transport Enhancer Rating
Starting Materials 10 SrCrO. 1A
The Deft SrCr Primer (44GN072) was obtained from Deft D1 Ce(NO) O.15 Kaolin 3,6A
Inc. having offices in Irvine, Calif. As noted above, the Raven 30 D12
D3
Ce(NO)
Ce(NO)
5
3
Kaolin
CaSO4 (anhy.)
3,6A
3,6A
materials, as well as the Ultra II materials, were obtained from D40 Ce(NO3)3 0.4 CaSO4 (anhy.) 3.6A
Columbian Chemicals Company having offices in Marietta, D13 Ce(NO) 5 CaSO4 (anhy.) 3,6A
Ga. The LHD, U47 and PLD materials were obtained from D42 Ce(NO) 0.4 CaSO4·2H2O 3,5 A
Sun Chemical having offices in Cincinnati, Ohio. PrO was D140 Ce(NO) OS CaSO4·2H2O 3,5 A
obtained from Alfa Aesar Co. having offices in Ward Hill, 35 D49 Ce(NO) 5 CaSO4·2H2O 3,6A
Mass. Conductive carbon, non-conductive carbon, and acti D73 Ce(NO) 75,0.5 CaSO4·2H2O 3,6A
vated carbon were obtained from Alpha Aesar having offices H (CFSO)
D44 Ce(NO) O.S Deft (Mistron 600) 3,6A
in Ward Hill, Mass. CaSO 2HO was obtained from US D14 Ce(NO), 8.8 Kaolin 3,6A
Gypsum from Chicago, Ill. SrSO was obtained from Excali BaBO
bar of Huston, Tex. 40 Gen I CeO2H2O 32 Mistron 600 3,6A
Test Procedure D11 Ce(NO), O3,O.3 Kaolin 3,6A
CePO
The coating was sprayed onto different metal Substrates D15 Ce(NO), 1.1.1 Kaolin 3,5 A
and allowed to dry (cure) naturally over time. Typically this Pr(NO),
took about one week. Edges and backs of samples were taped BaBO
and front surfaces were scribed with an “X” pattern according 45
D16 Ce(NO), 0.4 CaSO4·2H2O 3,5 A
to ASTM B117 procedure. Tests were run according to Pr(NO),
BaBO
ASTM B117 procedure for either 500 or 3000 hours and the D17 Ce(NO), 0.4,0.4,0.4 Nicron 604 3,6A
results evaluated according to the Keller Corrosion Rating Pr(NO),
Scale shown in Table 2. BaBO
D18 O.O CaSO4·2H2O 3,5 A
50 D19 O.O Nicron 604 3,6A
Primer Panel Summary C1 Na2EDTA O.9 CaSO4·2H2O 3,5 A
D50 Ce(NO) + Acid 1.5 CaSO4·2H2O 3,4A
D51 Ce(NO) + Base 1.5 CaSO4·2H2O 3,4A
TABLE 2 D53 Ce(NO) + Base 1.5 CaSO4·2H2O 3,4A
DS4 Ce(NO) + 1.5 CaSO4·2H2O 3,4A
Corrosion Codes/Rankings Employed in Table 3 55 Acid + H2O2
D55 Ce(NO) + 1.5 CaSO4·2H2O 3,4A
Code Scribe line ratings description Base + H2O2
DS6 Ce(NO) + 1.5 CaSO4·2H2O 3,4A
Scribe line beginning to darken or shiny scribe Base + H2O2
Scribe lines > 50% darkened A1 PrCl 3 Kaolin 3,6A
Scribe line dark A2 Pr(NO) 3 Kaolin 3,6A
60
Several localized sites of white salt in scribe lines AS Pr(NO) 1 Kaolin 3,6A
Many localized sites of white salt in scribe lines A4 Pr(NO) 8 Kaolin 3,6A
White salt filling scribe lines A11 Pr(NO), 3.3 Kaolin 3,6A
Dark corrosion sites in scribe lines BaBO
Few blisters under primer along scribe line (<12) A3 Pr(NO) 3 CaSO (anhy.) 3,5 A
Many blisters under primer along scribe line A8 Pr(NO) 1 CaSO4 (anhy.) 3,5 A
Slightlift along scribe lines. 65 A9 Pr(NO) 5 CaSO4 (anhy.) 3,5 A
Coating curling up along scribe. A12 Pr(NO) O.S CaSO4·2H2O 3,5 A
 US 7,759,419 B2
29 30
lyst into the base formulations described above. The amount
TABLE 3-continued of isocyanate catalyst included in the coating compositions
was added according to the amount recommended by the
Panels Prepared and Evaluated Supplier to ensure proper curing and cross-linking of the
Weight resulting coating. The solvent employed in the preparation of
Percent 2OOOHRS the coating system of the present invention was chosen in
Panel Corrosion Inhibitor Extender Salt Fog Such a manner as to facilitate the preparation of the coating
Number Inhibitor Conc. Transport Enhancer Rating mixture, to provide Suitable application properties, and to
provide an environmentally acceptable paint.
A213 PrO - hand 1.5 15% CaSO2H2O 1A Once the base and isocyanate catalyst were mixed together,
mixed 10
O214 D.L-Methionine O.S 15.4% 1A the direct to metal coatings and enhanced direct to metal
CaSO4·2HO coatings were Substrates. Tests were run on various sample
O215 D.L-Methionine? 0.5/14 14.8% 1A formulations, according to ASTM B117 procedure, for either
PrsOil CaSO2H2O 1000, 2000, or 3000 hours. The results were evaluated
I216 CM23/PrO O.S. 2.6 14.3% 2A
CaSO2H2O 15
according to the Keller Corrosion Rating Scale. Examples of
A219 PrsOil 1.4 15% CaSO2H2O 1A coating formulations that were prepared and evaluated are
provided below.
Test Procedure
EXAMPLE 13 The coating compositions tested were sprayed onto differ
ent metal substrates and allowed to dry (cure) naturally over
Enhanced Self-priming Topcoat Base Formulation time, typically about one week. Edges and backs of samples
were taped and front surfaces were scribed with an “X” pat
Enhanced self-priming topcoat base formulations com tern according to ASTM B117 procedure. Results are shown
prising one or more Group I A or Group IIA, and/or yttrium, in Tables 5-7.
and/or lanthanide compounds. Such as metal Sulfates, metal 25
phosphates, metal nitrates, and/or metal silicates and the like; TABLE 5
and optionally one or more co-inhibitors such as, rare earth
compounds, metal oxides, borates, metaborates, silicates, Non-chronium Inhibitor Containing Primer Plus Topcoat.
phosphates, phosphonates, aniline, polyaniline, and the like,
were prepared. An exemplary formulation is shown below in **Weight Percent 2OOO
Corrosion Hour
Table 4. 30
Sample *Deft Inhibitor in Salt Fog
Number Deft Primer Topcoat Topcoat Rating
TABLE 4
396 44GYO3O 99GYOO1 None 3,6
Enhanced Self-Priming Topcoat Base Formulation 397 44GYO3O 99GYOO1 9% PrO 3,6
421 44GYO3O 99WOO9 None 3.5
Component Mass (g) 35 386 44GYO3O 99WOO9 9% PrO. 3,6
4O1 44GYO3O 99WOO9 9% CeO, 3,6
Polyester Resin Blend (binder) 130 399 4.4BKO16 99GYOO1 9% PrO 3.4
Fluorinated Resin Blend (binder) 240
Dispersing Agent 6 *Deft Primer and Deft Topcoat numbers refer to product identification numbers of primer
Ketone Solvent 77 and topcoat formulations, available from Deft Inc., having offices in Irvine, California,
**Weight percent inhibitor pigment based on total weight percent of fully catalyzed and
VOC Exempt Solvents 5 40 sprayable topcoat,
Color Pigments 45
Corrosion Inhibitive Pigments 310
Extender Pigments 74 TABLE 6
Base Total: 1OOO Self-priming Topcoat Formulations.
45
2OOO
According to the present invention, direct to metal coatings ** Weight Percent Hours Salt
and enhanced direct to metal coatings were prepared with the Sample Weight Percent Inhibitor in Fog
base formulations described herein. The coating composi Number *Deft Primer Extender Topcoat Rating
tions also included an isocyanate catalyst, that is, a two-part A-5-A O3W211 44 CaSO4·2H2O 8% PrO. 3.5
formulation, such as isocyanate solution 97GY088CAT, 50
available from Deft Inc., having offices in Irvine, Calif. The *Deft Primer number refers to product identification number of primer formulation, avail
direct to metal coatings and enhanced direct to metal coat able from Deft Inc., having offices in Irvine, California.
**Weight percent inhibitor pigment based on total weight percent of fully catalyzed and
ings, shown herein by way of example, were prepared by sprayable topcoat,
adequately stirring appropriate amounts of isocyanate cata

TABLE 7

Enhanced Self-priming Topcoat Formulations.

Sample *Deft **Corrosion Inhibitorf **Color Pigment? ***Extender 2000 Hr Salt
Number Coating Weight Percent Weight Percent Weight Percent Fog Rating
139-057(A) 97GYO88 Pr2O3 12.89 Titanium Dioxide 13.89 Lo-Vel (R) 25.17 1A
CaSO4·2H2O 47.74 Iron Yellow Oxide 0.17 HSF
Carbazole Violet O.O1
Phthalo Blue O.O3
 US 7,759,419 B2
31 32
TABLE 7-continued
Enhanced Self-priming Topcoat Formulations.
Sample *Deft **Corrosion Inhibitorf **Color Pigment? ***Extender 2OOOHr Salt
Number Coating Weight Percent Weight Percent Weight Percent Fog Rating
139-059(A) 97GYO89 Pr2O3 2.14 Titanium Dioxide 1 Lo-Vel (R) 24.01 1A
CaSO4·2HO 42.45 Iron Yellow Oxide HSF
Pr(SO4), O.85 Carbon Black
PrsOil 16.98 Phthalo Blue
139-058(A) 97GYO89 PrsOil 23.62 Titanium Dioxide 1 Lo-Vel (R) 23.23 2A
CaSO4·2HO 40.03 Iron Yellow Oxide HSF
Carbazole Viole
Phthalo Blue
148-079(A) 97GYO89 Pr2O3 2.49 Titanium Dioxide 1 Lo-Vel (R) 17.48 1A
CaSO2H2O 48.97 Iron Yellow Oxide HSF
Pr(SO4), 0.99 Carbazole Viole
PrsOil 1958 Carbon Black
Phthalo Blue
148-097 (A) 97GY128 Pr2O3 1.54 Titanium Dioxide 1 Lo-Vel (R) 35.69 3A
CaSO2H2O 30.63 Iron Yellow Oxide HSF
Pr(SO4), 0.61 Carbazole Viole
PrO 12.25 Carbon Black
Phthalo Blue
148-078(A) 97GY121 Pr2O3 14.98 Titanium Dioxide 1 Lo-Vel (R) 18:47 1A
CaSO2H2O 55.48 Iron Yellow Oxide HSF
Carbazole Viole
Carbon Black
Phthalo Blue
148-084(A) 97GY 124 Pr2O3 2.14 Titanium Dioxide 1 Lo-Vel (R) 36.85 3A
CaSO4·2HO 42.45 Iron Yellow Oxide HSF
Pr(SO4), 0.85 Carbazole Viole
PrsOil 16.98 Carbon Black
Phthalo Blue

*Deft Coating number refers to product identification number of coating formulation, available from Deft Inc., having offices in Irvine,
California.

As shown in Tables 5-7, incorporating extenders in con time and costs of producing industrial, consumer, and mili
junction rare earth corrosion inhibitors into the enhanced 35 tary parts and goods.
self-priming topcoat results in coating compositions with
good or excellent performance. As shown in Table 7, the CONCLUSION
extenders in conjunction with the rare earth corrosion inhibi
tors when incorporated into the enhanced self-priming top Controlling the local environment near the primer and Sub
coat, provides the best corrosion resistance. As shown in 40 strate interface is known to be important for maximum cor
Table 5, incorporating corrosion inhibitors directly into a rosion protection. Local pH and ionic activity can be modified
topcoat and applying over a non-chrome primer, results in in a favorable way by incorporating the various components
coating systems that do not perform as well as the coatings described herein in the coating, including neutral to slightly
acidic generating extenders, generating acidic extenders and/
shown in Table 7. As shown in Table 6, the corrosion resis or rare earth compounds, alone or in combination with each
tance of the self-priming topcoat with extenders and rare earth 45
other and/or with other materials such as polymeric resin
compound corrosion inhibitors is comparable to the perfor binders, ionic exchange resins, and so forth. The coating
mance of the non-chrome primer and topcoat formulations compositions described herein have good adhesion to Sub
shown in Table 5. Thus, the self-priming topcoat composi strates such as metals, including aluminum and aluminum
tions, according to the present invention, can achieve similar alloys. These novel coatings, coating systems and associated
performance to systems that use both a non-chrome primer 50 processes provide viable alternatives to coatings containing
and a topcoat, without the use of a primer. Further, as shown chromates as they are environmentally Superior to currently
in Table 7, the enhanced self-priming topcoats perform better know chromium containing coating systems.
than the non-chrome primer plus topcoat systems, thus pro All publications, patents and patent applications are incor
viding better corrosion protection as a one-coat System with porated herein by reference. While in the foregoing specifi
out the need for a inter-coat polymeric coating or primer. 55 cation, this invention has been described in relation to certain
Accordingly, the enhanced self-priming topcoats have both preferred embodiments thereof, and many details have been
excellent weathering resistance and durability, as well as the set forth for purposes of illustration, it will be apparent to
corrosion resistance necessary to provide protection to under those skilled in the art that the invention is susceptible to
additional embodiments and that certain of the details herein
lying Substrates. 60 can be varied considerably without departing from the basic
Further, the coating compositions according to the present principles of the invention. Therefore, it is manifestly
invention are non-chromium containing and are environmen intended that this invention be limited only by the claims and
tally Superior to currently known chromium containing coat the equivalents thereof.
ing systems. Finally the self-priming topcoat and enhanced
self-priming topcoat compositions provide corrosion protec 65 What is claimed is:
tion as a one-coat System without the need for an inter-coat 1. A non-chromate containing corrosion inhibiting coating
polymeric coating or primer, thus minimizing the production composition comprising:
 US 7,759,419 B2
33 34
one or more organic binders; and 16. The composition of claim 1 wherein the solid compo
Solid components comprising: nents comprise about 3 wt % to about 28 wt % of the
a praseodymium oxide selected from the group consist praseodymium oxide.
ing of oxides, mixed oxides, Solid solution oxides, 17. The composition of claim 1 wherein at least one of the
hydrated oxides, hydroxides, and combinations one or more substantially insoluble extenders is a sulfur,
thereof phosphorus or silicon oxyanion-containing salt.
one or more substantially insoluble extenders selected 18. The composition of claim 1 wherein the composition is
from the group consisting of a neutral to slightly selected from the group consisting of aqueous, Solvent-based,
acidic generating extender, an acidic generating and powder coating compositions.
extender, and combinations thereof; 10 19. The composition of claim 1 wherein the composition is
wherein the solid components comprise about 1 wt % to an aqueous composition.
about 40 wt % of the praseodymium oxide: 20. The composition of claim 1 wherein at least one of the
wherein the non-chromate containing composition is one or more organic binders is selected from the group con
capable of curing naturally and, upon curing, is capable sisting of epoxy, urethane, urea, acrylate, alkyd melamine,
of generating a pH between about 2 and about 8 at an 15 polyester, vinyl, vinyl ester, organo-silicone, organo-silox
interface between the composition and a Substrate. ane, organo-silicate, organo-Sulfide, organo-Sulfone, epoxy
2. The composition of claim 1 wherein the solid compo novolac, epoxy phenolic, amides, drying oils, and hydrocar
nents further comprise a rare earth compound selected from bon polymers.
the group consisting of rare earth oxides, mixed oxides, Solid 21. The composition of claim 1 wherein at least one of the
Solution oxides, hydroxides, hydrated oxides, salts, triflates, one or more organic binders is an epoxy-based resin binder.
complexes and combinations thereof. 22. The composition of claim 1 wherein the solid compo
3. The composition of claim 2 wherein the rare earth com nents further comprise a material selected from the group
pound is an anhydrous or hydrated oxide. consisting of linear and cyclic dextrins, triflic acid, triflates,
4. The composition of claim 2 wherein the rare earth com acetates, talc, kaolin, organic-based ion exchange resins, and
pound comprises one or more metal cations selected from the 25 combinations thereof.
group consisting of praseodymium, terbium, cerium, 23. The composition of claim 22 comprising about 0.03 to
Samarium, ytterbium, yttrium, neodymium and combinations about 5 wt % cyclodextrin, about 0.1 to about 0.5 wt.% triflic
thereof. acid, or about 0.1 to about 5 wt % ionic exchange resin.
5. The composition of claim 2 wherein the rare earth com 24. The composition of claim 1 wherein the solid compo
30
pound is selected from the group consisting of cerium oxide, nents further comprise material selected from the group con
cerium hydroxide, cerium mixed oxide, cerium oxide mix sisting of gelatin and gelatin derivatives.
ture, cerium salt, neodymium oxide, neodymium hydroxide, 25. The composition of claim 24 comprising about 0.03 to
neodymium oxide mixture, neodymium salt, praseodymium about 5 wt % gelatin.
oxide, praseodymium hydroxide, praseodymium mixed 35
26. The composition of claim 1 wherein the solid compo
oxide, praseodymium oxide mixture, praseodymium salt, nents further comprise a material selected from the group
ytterbium oxide, ytterbium hydroxide, ytterbium oxide mix consisting of amino acids, amino acid derivatives and com
ture, ytterbium salt, yttrium oxide, yttrium hydroxide, yttrium binations thereof.
mixed oxide, yttrium oxide mixture, yttrium salt, terbium 27. The composition of claim 26 wherein the amino acid is
oxide, terbium hydroxide, terbium mixed oxide, terbium 40
selected from the group consisting of glycine, arginine, and
oxide mixture, terbium salt, and combinations thereof. methionine.
6. The composition of claim 2 wherein the rare earth com 28. The composition of claim 26 wherein the amino acid
pound is a praseodymium compound. derivative is methionine sulfoxide or methionine methyl sul
7. The composition of claim 2 wherein the rare earth com foxide.
pound is a rare earth carbonate or a rare earth triflate. 45
29. The composition of claim 26 comprising about 0.1 to
8. The composition of claim 1 wherein the praseodymium about 5 wt % amino acid.
oxide is selected from the group consisting of praseodymium 30. The composition of claim 1 wherein the solid compo
(III), praseodymium(III/IV), praseodymium(IV) oxides and nents further comprise a coloring pigment.
mixtures thereof. 31. The composition of claim 30 wherein the coloring
9. The composition of claim 8 wherein the solid compo 50 pigment is TiO.
nents further comprise one or more extenders selected from 32. The composition of claim 1 wherein the praseodymium
the group consisting of a neutral to slightly acidic generating mixed oxide is PrO.
extender. 33. The composition of claim 32 wherein the PrO, is
10. The composition of claim 9 wherein at least one of the present in amounts of about 1 wt % to about 28 wt % of the
one or more extenders is calcium Sulfate. 55 Solid components.
11. The composition of claim 10 wherein the calcium sul 34. The composition of claim 32 wherein the PrO is
fate is selected from the group consisting of hydrous calcium present in amounts of about 3 wt % to about 28 wt % of the
Sulfate, anhydrous calcium sulfate and combinations thereof. Solid components.
12. The composition of claim 1 wherein the praseodymium 35. A non-chromate containing corrosion inhibiting com
oxide is a praseodymium(III) oxide. 60 position comprising:
13. The composition of claim 1 wherein the praseodymium one or more binders; and
oxide is a praseodymium(III/IV) oxide. Solid components comprising:
14. The composition of claim 1 wherein the praseodymium about 1 wt % to about 40 wt % one or more rare earth
oxide is a praseodymium(IV) oxide. oxides; and
15. The composition of claim 1 wherein the solid compo 65 one or more substantially insoluble extenders selected
nents comprise about 1 wt % to about 28 wt % of the from the group consisting of calcium sulfate, stron
praseodymium oxide. tium sulfate, and combinations thereof.
 US 7,759,419 B2
35 36
wherein the non-chromate containing composition is acidic generating extender, an acidic generating
capable of curing naturally and, upon curing, is capable extender, and combinations thereof;
of generating a pH between about 2 and about 8 at an wherein the solid components comprise about 1 wt % to
interface between the composition and a Substrate. about 40 wt % of the praseodymium (III/IV) mixed
36. The composition of claim 35, wherein the calcium oxide;
Sulfate is hydrous calcium sulfate or anhydrous calcium Sul wherein the non-chromate containing composition is
fate. capable of curing naturally and, upon curing, is capable
37. The composition of claim 35, wherein the solid com of generating a pH between about 2 and about 8 at an
ponents comprise about up to about 99 wt % of at least one of interface between the composition and a Substrate.
the one or more substantially insoluble extenders. 10
55. The composition of claim 54 wherein the composition
38. The composition of claim 35, wherein the solid com is selected from the group consisting of aqueous, solvent
ponents comprise about up to about 75 wt % of at least one of based, and powder coating compositions.
the one or more substantially insoluble extenders. 56. The composition of claim 54 wherein at least one of the
39. The composition of claim 35 wherein at least one of the one or more organic binders is selected from the group con
rare earth oxides comprises a metal cation selected from the 15
sisting of epoxy, urethane, urea, acrylate, alkyd melamine,
group consisting of praseodymium, terbium, cerium, polyester, vinyl, vinyl ester, organo-silicone, organo-silox
Samarium, ytterbium, yttrium, neodymium and combinations ane, organo-silicate, organo-sulfide, organo-Sulfone, polysul
thereof.
40. The composition of claim 35 wherein at least one of the fide, epoxy novolac, epoxyphenolic, amides, drying oils, and
one or more rare earth oxides is a praseodymium compound. hydrocarbon polymers.
41. The composition of claim 40 wherein the praseody 57. The composition of claim 54 wherein at least one of the
mium oxide is selected from the group consisting of one or more organic binders is an epoxy-based resin binder.
praseodymium(III), praseodymium(III/IV), praseodymium 58. The composition of claim 54 wherein the solid compo
(IV) oxides and combinations thereof. nents further comprise a coloring pigment.
42. The composition of claim 40 wherein the praseody 25 59. The composition of claim 58 wherein the coloring
mium oxide is a praseodymium(III) oxide. pigment is TiO.
43. The composition of claim 40 wherein the praseody 60. The composition of claim 54 wherein the solid compo
mium oxide is a praseodymium(III) oxide, a praseodymium nents further comprise an additional rare earth compound
(III/IV) oxide or a praseodymium (IV) oxide. selected from the group consisting of rare earth oxides, mixed
44. The composition of claim 40 wherein the praseody 30 oxides, Solid solution oxides, hydroxides, hydrated oxides,
mium oxide is a praseodymium(III/IV) oxide. salts, triflates, complexes and combinations thereof.
45. The composition of claim 40 wherein the praseody 61. A non-chromate containing corrosion inhibiting coat
mium compound is a praseodymium(IV) compound. ing composition comprising:
46. The composition of claim 35 wherein the composition one or more binders; and
is selected from the group consisting of aqueous, solvent 35
Solid components comprising:
based, and powder coating compositions.
47. The composition of claim 35 wherein at least one of the one or more rare earth element oxides selected from the
one or more binders is an organic polymer selected from the group consisting of oxides, mixed oxides, Solid solu
group consisting of epoxy, urethane, urea, acrylate, alkyd, tion oxides, hydrated oxides and hydroxides; and
melamine, polyester, vinyl, vinyl ester, organo-silicone, 40 a praseodymium oxide selected from the group consist
organo-siloxane, organo-silicate, organo-Sulfide, organo-Sul ing of oxides, mixed oxides, Solid solution oxides,
fone, polysulfide, epoxy novolac, epoxy phenolic, amides, hydrated oxides, hydroxides, and combinations
drying oils, and hydrocarbon polymers. thereof
48. The composition of claim 35 wherein at least one of the one or more substantially insoluble extenders selected
one or more binders is an epoxy-based resin binder. 45 from the group consisting of a neutral to slightly
49. The composition of claim 35 wherein at least one of the acidic generating extender, an acidic generating
one or more binders is an inorganic polymer selected from the extender, and combinations thereof;
group consisting of silicone, siloxane and silicate polymers. wherein the praseodymium oxide is present in an amount
50. The composition of claim 35 wherein the solid compo of about 1 wt % to about 40 wt % of the solid compo
nents further comprise a coloring pigment. 50
nents;
51. The composition of claim 50 wherein the coloring wherein the non-chromate containing composition is
pigment is TiO. capable of curing naturally and, upon curing, is capable
52. The composition of claim 35 wherein at least one of the of generating a pH between about 2 and about 8 at an
rare earth oxides is an oxide, mixed oxide or combination interface between the composition and a Substrate.
thereof. 55
53. The composition of claim 52 wherein the solid compo 62. The composition of claim 61 wherein the praseody
nents further comprise a second rare earth compound selected mium oxide is selected from the group consisting of PrO.
from the group consisting of rare earth oxides, mixed oxides, PrOs. PrO, and combinations thereof.
Solid solution oxides, hydroxides, hydrated oxides, salts, tri 63. The composition of claim 61 wherein at least one of the
flates, complexes and combinations thereof. 60 one or more rare earth element oxides is a rare earth praseody
54. A non-chromate containing corrosion inhibiting primer mium oxide or a rare earth terbium oxide.
composition comprising: 64. The composition of claim 61 wherein at least one of the
one or more organic binders; and one or more rare earth element oxides is selected from the
Solid components comprising: group consisting of YO; La O. CeO2, Pr(OH), PrO.
a praseodymium (III/IV) mixed oxide: 65 PrOs. PrO, NdO. SmO, TbOz, and YbO.
one or more substantially insoluble extenders selected 65. A non-chromate containing corrosion inhibiting coat
from the group consisting of a neutral to slightly ing composition comprising:
 US 7,759,419 B2
37 38
one or more binders; and 73. The method of claim 67 further comprising adding a
Solid components comprising: material selected from the group consisting of amino acids,
about 1 wt % to about 40 wt % one or more rare earth derivates of amino acids, and combinations thereof to the
element oxides selected from the group consisting of paint formulation.
oxides, mixed oxides, Solid solution oxides, hydrated 5 74. The method of claim 67 further comprising adding a
oxides, and hydroxides; and material selected from the group consisting of gelatin, gelatin
one or more extenders selected from the group consist derivatives, and combinations thereof to the paint formula
ing of calcium Sulfate, strontium sulfate, and combi tion.
nations thereof; 75. A method for preparing a non-chromate containing
wherein the non-chromate containing composition is 10 coating composition comprising:
capable of curing naturally and, upon curing, is capable preparing a paint formulation comprised of an organic
of generating a pH between about 2 and about 8 at an binder; and
interface between the composition and a Substrate. adding an effective corrosion-inhibiting amount of a solid
66. The composition of claim 65 wherein at least one of the component comprising:
one or more rare earth element oxides is an anhydrous 15 a praseodymium compound selected from the group
praseodymium oxide. consisting of oxides, mixed oxides, Solid solution
67. A method for preparing a non-chromate containing oxides, hydrated oxides, hydroxides, and combina
coating composition comprising: tions thereof to the paint formulation to produce a
preparing a paint formulation; and coating composition
adding an effective corrosion-inhibiting amount of a rare one or more substantially insoluble extenders selected
earth oxide and one or more extenders selected from the from the group consisting of a neutral to slightly
group consisting of calcium Sulfate, strontium Sulfate, acidic generating extender, an acidic generating
and combinations thereof to the paint formulation to extender, and combinations thereof;
produce a non-chromate containing coating composi wherein the praseodymium compound comprises about 1
tion; 25 wt % to about 40 wt % of the solid components:
wherein the rare earth oxide is present in an amount wherein the non-chromate containing composition is
between about 1 wt % to about 40 wt % of solid com capable of curing naturally and, upon curing, is capable
ponents comprising the rare earth oxide and one or more of generating a pH between about 2 and about 8 at an
extenders wherein the non-chromate containing compo interface between the composition and a Substrate.
sition is capable of curing naturally and, upon curing, is 30 76. The method of claim 75 wherein the praseodymium
capable of generating a pH between about 2 and about 8 compound is PrO.
at an interface between the composition and a substrate. 77. The method of claim 75 wherein the solid components
68. The method of claim 67 further comprising pre-dis further comprise an additional rare earth compound selected
persing the rare earth compound with a dispersant. from the group consisting of rare earth oxides, mixed oxides,
69. The method of claim 67 wherein the rare earth oxide is 35 Solid solution oxides, hydroxides, hydrated oxides, salts, tri
a praseodymium(III/IV) oxide. flates, complexes and combinations thereof to the paint for
70. The method of claim 67 wherein the one or more mulation.
extenders are substantially insoluble. 78. The method of claim 75 further comprising the step of
71. The method of claim 67 wherein the rare earth oxide is pre-dispersing the praseodymium compound with a dispers
a praseodymium oxide or praseodymium mixed oxide. 40 ant.
72. The method of claim 71 wherein the praseodymium
mixed oxide is PrO.
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 7,759,419 B2 Page 1 of 1
APPLICATIONNO. : 10/758972
DATED : July 20, 2010
INVENTOR(S) : James Stoffer et al.
It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

In the Claims:
Column 36
Claim 62, line 3: replace “ProC), with --PreO

Signed and Sealed this

Fourteenth Day of September, 2010

David J. Kappos
Director of the United States Patent and Trademark Office
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 7,759,419 B2 Page 1 of 1
APPLICATIONNO. : 10/758972
DATED : July 20, 2010
INVENTOR(S) : James Stoffer et al.
It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

In the Claims:
Column 36 line 58
(Claim 62, line 3) replace “PrO, with --PreO

This certificate supersedes the Certificate of Correction issued September 14, 2010.

Signed and Sealed this

Second Day of November, 2010

David J. Kappos
Director of the United States Patent and Trademark Office