US008449695B2

(12) United States Patent (10) Patent N0.: US 8,449,695 B2

(54) METHOD FOR MAKING AND USING 6,248,181 B1 6/2001 Osaka et a1.
CHROMIUM III SALTS 7,291,217 B2 11/2007 Phelps et al.
2002/0053301 A1 5/2002 MatZdorf et al.
2002/0117236 A1 8/2002 MatZdorf et al.
(75) Inventor: J osé B. Rivera, Auburn, PA (U S) 2004/0231754 A1 11/2004 Phelps et al.
2006/0180247 A1 8/2006 MatZdorf et al.
(73) Assignee: Bulk Chemicals, Inc., Reading, PA (U S) 2006/0191599 A1 8/2006 MatZdorf et al.
2006/0240191 A1 10/2006 MatZdorf et al.
(*) Notice: Subject to any disclaimer, the term of this 2007/0187001 A1 8/2007 Kramer et al.
patent is extended or adjusted under 35 2009/0280253 A1 11/2009 Church
2010/0015339 A1 1/2010 Morillo et al.
U.S.C. 154(b) by 14 days.
FOREIGN PATENT DOCUMENTS
This patent is subject to a terminal dis
claimer. EP 2 014 793 A2 1/2009
W0 WO 2009/137358 A1 11/2009
(21) [Link].: 13/297,834 OTHER PUBLICATIONS

(22) Filed: Nov. 16, 2011 Paniagua et al., “Determination of Chromium(VI) and
Chromium(III) by using a Diphenylcarbazide-Modi?ed Carbon
(65) Prior Publication Data Paste Electrode,” Electroanalysis, v01. 5, N0. 2, Apr. 9, 2005, pp.
155-163.
US 2012/0061249 A1 Mar. 15, 2012 International Search Report dated Dec. 17, 2010, Int’l Appl. No.
PCT/US2010-036392.
Related US. Application Data Coolbaugh, M. Todd, et al., “Readiness of Trivalent Chromium Con
version Coatings for Aluminum Alloys,” Corrosion 2000, Mar.
(62) Division of application No. 12/474,960, ?led on May 26-31, 2000, pp. 1-11; Orlando, FL; US.
29, 2009, noW Pat. No. 8,273,190. Oleinik, S. V., et al.; “Corrosion Inhibitors in Conversion Coatings.
IV”; Protection ofMetals, 2007, vol. 43, N0. 4; pp. 391-397; Pleiades
(51) Int. Cl. Publishing, Inc.; Austin, TX; US.
C22C 22/34 (2006.01)
Primary Examiner * Lois Zheng
(52) US. Cl.
USPC .......................... .. 148/267; 148/247; 148/264 (74) Attorney, Agent, or Firm * RatnerPrestia
(58) Field of Classi?cation Search
USPC ........................................ .. 148/247, 264, 267
(57) ABSTRACT
See application ?le for complete search history. A method of preparing an aqueous composition of a chro
mium III compound, comprising adding hydrogen peroxide
(56) References Cited to a mixture comprising water and a chromium VI compound
in the presence of at least one acid according to the formula
U.S. PATENT DOCUMENTS HZGF6, in Which G is a Group IV-B element. The composition
4,359,348 A 11/1982 Crotty may contain less than 500 ppm of alkali metal ions and less
4,578,122 A 3/1986 Crotty than 200 ppm of halide ions, relative to chromium and may
4,749,418 A 6/1988 Saeki et a1. test negative for chromium VI using s-diphenylcarbazide.
4,786,336 A 11/1988 Schoener et a1.
5,091,023 A 2/1992 Saeki et a1. The composition may be used for treating a metal surface,
5,133,947 A 7/1992 Stambaugh et al. among other applications.
5,294,266 A 3/1994 Hauffe et al.
5,859,106 A 1/1999 Jones et a1. 6 Claims, No Drawings
 US 8,449,695 B2
1 2
METHOD FOR MAKING AND USING In another aspect, the invention provides an aqueous com
CHROMIUM III SALTS position that includes dissolved Cr2(GF6)3, in which G is a
Group IV-B element, and contains less than 500 ppm of alkali
CROSS-REFERENCE TO RELATED metal ions and less than 200 ppm of halide ions, relative to
APPLICATIONS chromium and which tests negative for chromium VI using
s-diphenylcarbazide.
This application is a divisional application of US. patent In a further aspect, the invention provides a method of
application Ser. No. 12/474,960, ?led May 29, 2009, the treating a metal surface. The method includes contacting the
disclosure of which is incorporated herein by reference in its metal surface with an aqueous composition including dis
entirety for all purposes. solved Cr2(GF6)3, in which G is a Group IV-B element, and
containing less than 500 ppm in total of alkali metal ions and
BACKGROUND OF THE INVENTION less than 200 ppm of halide ions, relative to chromium.

Hexavalent chromium compounds have been used as tra DETAILED DESCRIPTION OF THE INVENTION
ditional conversion coatings to treat metal surfaces to
improve their corrosion resistance and paint adhesion. The invention is directed to chromium III salts essentially
Hexavalent chromium shows toxicological effects and has free of contaminating ions, i.e., essentially free of ions that are
been determined by the Environmental Protection Agency as not part of the canonical formula of the salt, and methods for
a risk to the environment and by the Occupational Safety and producing and using such salts. These salts will be referred to
Health Agency as a health risk. Moreover, chemistries based 20 herein as “high-purity” chromium salts, with the understand
on hexavalent chromium are classi?ed as carcinogens by ing that trace amounts of contaminating ions may be present,
these agencies. typically as a result of impurities in the ingredients. The
It is highly desirable to provide coatings and processes free methods of this invention are suitable for making a variety of
of hexavalent chromium but still capable of providing paint high-purity chromium III salts, including but not limited to
adhesion and corrosion resistance comparable to that pro 25 salts of Group IV-B ?uoacids such as chromium ?uozircon
vided by conventional hexavalent chromium-based coatings ate, chromium ?uotitanate, and chromium ?uohafnate. In the
to metal surfaces. Within the past few decades, various com case of Group IV-B salts, it is currently believed that the
positions and processes not relying on hexavalent chromium chromium III salts are at least approximately of the formula
have been described and used for treating metal surfaces. Cr2(GF6)3, with G representing the Group IV-B metal. For
Some of these are based on at least partial replacement of 30 simplicity, the inventors will describe the invention with
hexavalent chromium with trivalent chromium. respect to chromium III ?uozirconate, but it will be under
Known uses of partially reduced chromium, i.e. composi stood that analogous procedures may be used to make other
tions containing some trivalent chromium and some hexava high-purity chromium III salts as well.
lent chromium, include acidulated rinses for phosphated Chromium ?uozirconate prepared according to the inven
metal surfaces. These acidulated rinse solutions may contain 35 tion provides excellent corrosion protection on metal sur
a partially reduced hexavalent chromium solution, i.e. a solu faces, including at least Al, Zn and alloys of either of these,
tion wherein some of the chromium is trivalent. Partially and may also be useful for providing a passivation layer for
reduced chromium solutions may be manufactured by adding electroplating.
an organic compound such as formaldehyde, methanol, etha Preparation of High-Purity Chromium III Fluozirconate
nol, etc. to a solution of chromic acid. The chromic acid 40 The method of making high-purity chromium ?uozircon
oxidizes the organic compound, and is itself reduced in the ate includes reducing aqueous chromic acid and/or partially
process. The organic compound(s) must generally be added reduced aqueous chromic acid with hydrogen peroxide,
very carefully and slowly to the chromic acid solution, which is itself oxidized in the process to form gaseous 02. If
because the resultant heat, boiling and generation of CO2 can chromic acid is used, the reaction is believed to proceed
be so energetic as to be dangerous. Yet these materials are 45 according to the equation shown below, although the inven
seldom taken to more than 30% reduction of chromium VI to tors do not intend to be bound by this proposed explanation.
chromium III unless excess mineral acid is added to help hold The skilled artisan will recognize that CrO3 is the anhydrous
the trivalent chromium in solution. Efforts to more com form of chromic acid and is used in the following equation for
pletely reduce the chromium VI typically result in sludge simplicity.
formation, and full conversion to trivalent chromium is not 50
achieved by such methods. An exemplary partially reduced
(typically about 30% reduced) chromic acid is available from During the reaction and afterwards, the mixture remains
Bulk Chemicals, Inc. of Reading, Pa. under the trade name essentially fully liquid and essentially free (i.e., only trace
BULK RINSE® 6A. amounts, if any) of precipitates or suspended solids. The
The incomplete conversion of chromium VI to chromium 55 ?uozirconic acid may be added simultaneously with the
III in these and other processes is undesirable in some appli hydrogen peroxide, or may be admixed with the chromic acid
cations, and thus, methods of producing fully reduced chro prior to adding the hydrogen peroxide, or a combination of
mium salts would be of bene?t to the industry. these.
If partially reduced chromic acid is used as the starting
SUMMARY OF THE INVENTION 60 material, in some embodiments, it is prepared by reaction of
chromic acid with an organic compound (for example, form
In one aspect, the invention provides a method of preparing aldehyde or methanol) which is oxidized by the chromic acid
an aqueous composition of a chromium III compound. The and results in partial reduction of the chromium.
method includes adding hydrogen peroxide to a mixture In practice, more than a stoichiometric amount of hydro gen
including water and a chromium VI compound in the pres 65 peroxide may in some cases be needed to achieve full reduc
ence of at least one acid according to the formula H2GF6, in tion of chromium VI to chromium III. This may be the result
which G is a Group IV-B element. of decomposition and/or volatilization of some amount of
 US 8,449,695 B2
3 4
hydrogen peroxide during the reaction. Essentially no chro application for which the use of chromium III ?quirconate is
mium VI remains after the hydrogen peroxide reaction is known, for example in electroplating baths.
complete, as indicated by a negative test using the s-diphe Metal Treatment Formulations Comprising High-Purity
nylcarbaZide method (ASTM D 1687-02, Chromium in Chromium III Fluozirconate
Water, Test Method A), which produces a red-violet color in Chromium III ?quirconate prepared according to the
the presence of chromium VI. invention may be used to treat metal surfaces to improve
Mixtures of high-purity chromium III salts can also be corrosion resistance. In practical use, the absence of extrane
made by the above procedure, using mixed acids instead of a ous cations and anions provides a signi?cant advantage. This
single acid such as ?quirconic. Formation of chromium III is because chromium III ?quirconate solutions made by
salts by the methods of this invention is believed to be general mixing CrF3 with ?uozirconic acid, for example, contain
for a variety of salts, barring any speci?c detrimental inter extraneous ?uoride ions that continue to build up in concen
action of the anion. tration as the treatment bath is replenished with additional
Using the methods of this invention, no mixing of separate chromium III ?uozirconate solution, as it is consumed by the
trivalent chromium compounds (for example, CrF3) with ?u metal being treated. Such buildup can cause the treatment
ozirconic acid is required, and so no extraneous anions or coating to become weak and can also cause sludge to form in
cations are present in greater than trace amounts. The purity the bath. These problems may be practically eliminated by
of the chromium III salt is determined mainly by the purity of instead using the high purity chromium III ?uozirconate solu
the raw materials used to prepare it. The salt, presumably tions of this invention. Further, the high purity makes it pos
Cr2(ZrF6)3, functions well in pretreatment compositions and 20 sible to merely dry the solution in place on the treated metal
improves the corrosion resistance of the substrate. surface without rinsing, if so desired, thereby saving a step
The methods of this invention make it possible to prepare and reducing waste handling.
chromium III salts with very low levels of contaminating Any metal may be treated, with particularly good results
cations and anions. In some embodiments, the amount of any being obtained on Zinc, Zinc alloy, aluminum, and aluminum
given contaminating cation (typically a metal, especially an 25 alloy surfaces. As used herein, the term “Zinc alloy” means an
alkali metal) is less than 1000 ppm, or less than 500 ppm, or alloy in which Zinc is present at a weight percent greater than
less than 300 ppm, or less than 200 ppm, relative to chro that of every other metal in the alloy. The term “alloy” is
mium. These limits may also apply speci?cally to the total of similarly de?ned for every other metal to which the term is
all alkali metal ions, or even to all metal ions in total. applied. Metal alloys typically contain at least 50 wt % of the
Similarly, the content of contaminating anions may be very 30
named metal.
low, and in some embodiments the amount of any given The chromium III ?quirconate may be applied alone from
contaminating ion is less than 1000 ppm, or less than 500
aqueous solution to a metal surface and subsequently dried to
ppm, or less than 300 ppm, or less than 200 ppm, relative to
remove water, resulting in effective pas sivation of the surface.
chromium. In particular, these limits may apply individually
Alternatively, the chromium III ?uozirconate may be mixed
to each of ?uoride, chloride, bromide, iodide, nitrate and 35
sulfate. These limits may also apply to the total of all of these with an organosilicon compound such as aminopropyl tri
anions, or even to all anions in total (including other anions ethoxysilane to make a metal treatment formulation. The
not listed here). addition of organosilicon compounds may improve adhesion
An alternative method of making the chromium III ?uozir of subsequently applied coatings (such as paints) to the
conate is to ?rst produce hydrous chromium oxide, some 40 treated surfaces, while maintaining good corrosion resistance
times referred to as hydrated chromium oxide or hydrated in a Neutral Salt Spray test.
chrome oxide. This material, approximately of the formula The pH of metal treatment formulations according to the
CrzO3 .nHZO or perhaps Cr(OH)3, can be made by reaction of invention will typically be at least 2.5, more typically at least
Cr2(SO4)3 (chrome alum) with a base such as NaOH. This 3 .0, and most typically at least 3 .5. The pH will typically be at
approach requires washing out or otherwise removing the 45 most 5.5, more typically at most 5.0, and most typically at
resulting Na2SO4 byproduct from the resulting hydrous chro most 4.5.
mium oxide so as to produce a product essentially free of
contaminating cations and anions. Once such washing is EXAMPLES
complete, the hydrous chromium oxide is contacted with
?quirconic acid to form aqueous high-purity chromium III 50 Preparation of High-Purity Chromium III
?quirconate. Fluozirconate
In all of the above methods, the molar ratio of Zirconium to
chromium in the ?nal product will typically be about 1.5: 1, as Example 1
indicated by the stoichiometry implicit in the formula Cr2
(ZrF6)3. This calculates to a weight ratio of 2.631 1. The com 55
Aqueous chromic acid was placed into a beaker and ?u
position need not contain only Cr2 (ZrF6)3, however. Thus, the ozirconic acid was added. Hydrogen peroxide was then added
weight ratio can vary somewhat from the stoichiometric
with stirring until complete reduction of chromium was indi
value. The ratio will typically be at least 2.411, more typically
at least 2.511, and most typically at least 2.611. The weight cated by a very sharp color change from yellow-green to
ratio will typically be at most 3.011, more typically at most 60
blue-green. A test for hexavalent chromium using s-diphenyl
2.911, and most typically at most 2.811. These ratios may be carbaZide (a reagent speci?c to hexavalent chromium capable
converted to their equivalent mole ratios, and the correspond of detection of hexavalent chromium at levels at sub-micro
ing weight ratios may then be calculated for Cr2(TiF6)3 and grams per liter levels) was negative, con?rming complete
Cr2(HfF6)3' conversion to trivalent chromium.
The purity of the chromium III ?quirconate provided by 65 Speci?c quantities are as below:
the invention may be very high, even of reagent grade. High chromic acid (nominal 40%, aqueous)i36.2 g
purity chromium III ?uozirconate is suitable for use in any ?quirconic acid (nominal 45%, aqueous)i100.0 g
 US 8,449,695 B2
5 6
hydrogen peroxide (nominal 35%, aqueous)i24.6 g+5.0
g extra
Constituent Wt. %
Example 2 45% Fluozirconic Acid 4.27
Chromium (III) Fluoride Tetrahydrate 1.05
A mixture of chromic acid and ?uozirconic acid was pro Ammonium Bi?uoride 0.0125
Aminopropyl Triethoxysilane 4.78
vided by dissolving chromium trioxide (reagent grade) in Water balance
aqueous ?uozirconic acid, and hydrogen peroxide was then
added while mixing at a high rate to reduce the hexavalent
chromium to chromium Ill. Completion of the reduction was This composition, which had a Zr:Cr weight ratio of 2.80:1,
signaled by the change in color from yellow-green to blue was diluted with water to 4% of its original strength before
green, and con?rmation of the conversion was by s-diphenyl being used to treat aluminum panels, as a control.
carbazide. High-purity chromium Ill ?uozirconate was prepared
Speci?c Quantities: according to the method of Example 2, and supplied as a
chromium trioxide (CrO3)i93.8 g 37.9% stock solution. The solution was determined to have
?uozirconic acid (45%, aqueous)i648.1 g the following composition by weight, based on stoichiomet
hydrogen peroxide (35%, aqueous)i258.1 g+23.5 g extra ric calculations using Cr2(ZrF6)3 as the compound formula:
5.47% Cr, 14.42% Zr, 8.0% F and Zr:Cr:2.6:1 by weight.
Example 3 This stock solution was used in the following examples,
20 diluted as indicated. In each case, treated panels were exposed
BULK RINSE® 6A, a partially reduced chromic acid, was to Neutral Salt Spray (NSS) for 336 hours according to ASTM
added to ?uozirconic acid, and suf?cient hydrogen peroxide 8117, then rinsed and evaluated for pitting.
was then added to complete the reduction of chromium VI to
chromium Ill. The color once again indicated completion of Example 5
the reduction, which was again con?rmed by s-diphenylcar 25
bazide addition. A 0.121% dilution of the high-purity chromium Ill ?uozir
conate stock solution in deionized water was prepared, yield
Example 4 ing the same level of Cr as in the control. This solution was
adjusted to pH:4 using ammonium carbonate. Aluminum
A large-scale preparation of Cr2(ZrF6)3 was prepared in a 30 6061 and 2024 panels were prepared using the treatment
manner analogous to Example 2 above, using the following protocol shown above, with and without the E-CLPS® 1900
amounts of ingredients. chrome-free pretreatment seal step. Following NSS, no pit
chromic acid liquid (40%)i56.7 lbs ting was observed for the panels treated with high-purity
?uozirconic acid 156.3 lbs chromium ?uozirconate or the control panels. Thus, the high
hydrogen peroxidei62.2 lbs 35 purity chromium Ill ?uozirconate solution produced good
Reduction of chromium VI to chromium III was complete results while avoiding the presence of extraneous ?uoride ion,
well before all of the hydrogen peroxide was added, but the such as was present in the control formulation.
rest of the hydrogen peroxide was still added. Apparently, this
run did not require as great an excess of hydrogen peroxide as Example 6
for the smaller scale preparations, although the reason for this 40
is not completely clear. a) A 2.21 g/ L bath of the high-purity chromium Ill ?uozir
Metal Treatment With Hi gh-Purity Chromium Ill Fluozircon conate stock solution was prepared and 1.90 g/L of SIL
ate WET® A1100 aminopropyl triethoxysilane (available from
The effectiveness of high-purity chromium Ill ?uozircon Crompton Corporation of Greenwich, Conn.) was added to
ate for passivating aluminum 2024 and 6061 panels was 45 yield a similar amount of silane as in the control formulation.
investigated according to US. Military speci?cation MIL When heated to 100° E, this solution was hazy. Fluozirconic
DTL-81706B, dated 25 Oct. 2004. In particular, see reference acid (1.5 g/L) was added to this bath to reach a pH of 4.0.
to Type 2 non-chromate products. The treatment protocol was While not as hazy, some ?oc was noted. The Zr to Cr ratio for
as shown below, and is similar to that disclosed in US. patent this solution was 3.86:1. Aluminum 6061 and 2024 panels
application Ser. No. 12/116,513 ?led May 7, 2008, the 50 were prepared using the treatment protocol shown above,
entirety of which is incorporated herein by reference. with and without the E-CLPS® 1900 chrome-free pretreat
1) CleaniBULK KLEEN® 737G non-etching silicated ment seal step. Following NSS, no pitting was observed for
alkaline cleaner (Bulk Chemicals, Inc.), 15 g/ L, 140° E, the panels treated with high-purity chromium ?uozirconate or
5 minutes the control panels.
2) RinseiTap water, ambient temperature, 30 seconds 55 b) Another bath was prepared using 2.21 g/L of the high
3) Deionized water rinse, ambient temperature purity chromium Ill ?uozirconate stock solution and 0.22 g/l
4) Chromium Ill treatment: panels immersed at 100° E, 5 of H2ZrF6 heated to 100° E, and pH adjusted to 4.0 with
minutes (See below for details of treatments) ammonium carbonate. The bath was noted to be hazy. The Zr
5) Rinse with deionized water: ambient temperature, 30 to Cr ratio for this bath was 3.0: 1 . Aluminum 6061 and 2024
seconds (for seal application the two steps below are 60 panels were prepared using the treatment protocol shown
included) above, with and without the E-CLPS® 1900 chrome-free
6) Seal; E-CLPS® 1900 chrome-free pretreatment (Bulks pretreatment seal step. Following NSS, no pitting was
Chemicals, Inc.), 2% v/v dilution, ambient temperature, observed for the panels treated with high-purity chromium
30 seconds ?uozirconate or the control panels.
7) Dry: 130° F. oven, 5 minutes 65 c) Still another bath was prepared using a 2.21 g/L of the
A chromium Ill composition was prepared, including the high-purity chromium Ill ?uozirconate stock solution, and
following components: SILWET® A1100 1.0 g/L was added, resulting in a pH of 4.0
 US 8,449,695 B2
7 8
at 100° F. Aluminum 6061 and 2024 panels were prepared temperature, exposure time, ZrzCr ratio, and/or chromium Ill
using the treatment protocol shown above, with and without concentration may be adjusted to provide the best perfor
the E-CLPS® 1900 chrome-free pretreatment seal step. Fol mance.
lowing NSS, no pitting was observed for the panels treated Although the invention is illustrated and described herein
with high-purity chromium ?uozirconate or the control pan with reference to speci?c embodiments, the invention is not
els. intended to be limited to the details shown. Rather, various
modi?cations may be made in the details within the scope and
Example 7 range of equivalents of the claims and without departing from
the invention.
A bath composed 0.22 g/ L of the high-purity chromium Ill
?quirconate stock solution in water was adjusted with SIL What is claimed:
WET® A-1100 (1.0 g/L) to bring the pH up to 4.0. The 1. A method of treating a metal surface, comprising con
resulting ZrzCr ratio was 2.6:1 by weight. Aluminum 6061 tacting the metal surface with an aqueous composition com
and 2024 panels were prepared using the treatment protocol prising dissolved Cr2(GF6)3, in which G is a Group lV-B
shown above, with and without the E-CLPS® 1900 chrome element, and containing less than 500 ppm in total of alkali
free pretreatment seal step. Following NSS, no pitting was metal ions and less than 200 ppm of halide ions, relative to
observed for the panels treated with high-purity chromium chromium, and which tests negative for chromium VI using
?quirconate or the control panels. s-diphenylcarbaZide, wherein the aqueous composition con
A ?nal modi?cation was made by adding 0.22 g/L of tains one or more contaminating ions, and wherein each of
said one or more contaminating ions is present at less than
H2ZrF6 to the above bath to give a Zr to Cr ratio of 3.011. 20
SILWET®A1 100 (0.7 g/L) was further added to bring the pH 1000 ppm relative to chromium, and wherein said one or more
of the bath to 4.0. Aluminum 6061 and 2024 panels were contaminating ions are ions that are not part of the canonical
prepared using the treatment protocol shown above, with and formula of Cr26(GF6)3.
without the E-CLPS® 1900 chrome-free pretreatment seal 2. The method of claim 1, wherein G is Zirconium.
step. Following NSS, no pitting was observed for the panels 3. The method of claim 2, wherein the aqueous composi
25
treated with high-purity chromium ?quirconate or the con tion has a weight ratio onrzCr in a range from 2.4:1 to 3.0: 1.
trol panels. 4. The method of claim 1, wherein G is titanium.
As the foregoing examples show, high-purity chromium Ill 5. The method of claim 1, wherein the metal surface is Al,
?quirconate was effective as a standalone passivant for alu Zn or an alloy of either of these.
minum at a pH of 4.0 and at the concentrations tested, with or 30
6. The method of claim 1, further comprising drying the
without subsequent sealing with E-CLPS® 1900 chrome-free composition in place on the metal surface without an inter
pretreatment. The skilled person will appreciate that, depend vening rinse step.
ing on the type of metal being treated, optimization of pH,