U.S. patent application number 09/968023 was filed with the patent office on 2003-04-17 for light metal anodization.
Invention is credited to Dolan, Shawn E..
Application Number | 20030070935 09/968023 |
Document ID | / |
Family ID | 25513602 |
Filed Date | 2003-04-17 |
United States Patent
Application |
20030070935 |
Kind Code |
A1 |
Dolan, Shawn E. |
April 17, 2003 |
Light metal anodization
Abstract
Using pulsed current and relatively low peak ceiling voltage,
articles containing light metals such as magnesium may be rapidly
anodized to form protective surface coatings. The anodizing
solutions employed may contain phosphate, permanganate, silicate,
zirconate, titanate and/or complex fluoride, optionally with other
components present.
Inventors: |
Dolan, Shawn E.; (Sterling
Heights, MI) |
Correspondence
Address: |
HENKEL CORPORATION
2500 RENAISSANCE BLVD
STE 200
GULPH MILLS
PA
19406
US
|
Family ID: |
25513602 |
Appl. No.: |
09/968023 |
Filed: |
October 2, 2001 |
Current U.S.
Class: |
205/321 ;
205/324; 205/333 |
Current CPC
Class: |
C25D 11/30 20130101;
C25D 11/06 20130101 |
Class at
Publication: |
205/321 ;
205/333; 205/324 |
International
Class: |
C25D 005/18; C25D
009/00; C25D 011/00; C25D 011/04 |
Claims
What is claimed is:
1. A method of forming a protective coating on a surface of a light
metal-containing article, said method comprising: A) providing an
anodizing solution comprised of water and one or more additional
components selected from one of the following: a) water-soluble or
water-dispersible oxysalt containing at least one element selected
from the group consisting of P, Si, Mn, Zr, Ti, V and Hf; or b)
water-soluble or water-dispersible complex fluoride of an element
selected from the group consisting of Ti, Zr, Hf, Si, Sn, Al, Ge
and B; B) providing a cathode in contact with said anodizing
solution; C) placing said light metal-containing article as an
anode in said anodizing solution; and D) passing a pulsed current
having a peak ceiling voltage of not more than 150 volts between
the anode and cathode though said anodizing solution for a time
effective to form said protective coating on said surface.
2. The method of claim 1 wherein the light metal-containing article
is comprised of magnesium.
3. The method of claim 1 wherein the light metal-containing article
is comprised of aluminum.
4. The method of claim 1 wherein said anodizing solution is
maintained at a temperature of from 5.degree. C. to 90.degree. C.
during step (D).
5. The method of claim 1 wherein said pulsed current has a peak
ceiling voltage of not more than 100 volts.
6. The method of claim 1 wherein a visible light-emitting discharge
is generated during step (D).
7. The method of claim 1 wherein during step (d) said protective
coating is formed at a rate of at least 1 micron thickness per
minute.
8. The method of claim 1 wherein during step (D) said protective
coating is formed at a rate of at least 5 microns thickness per
minute.
9. The method of claim 1 wherein said pulsed current has a peak
ceiling voltage of not more than 50 volts.
10. The method of claim 1 wherein said pulsed current is direct
current.
11. The method of claim 1 wherein the anodizing solution is
essentially free of ammonia, chromium, permanganate, borate,
sulfate, free fluoride and free chloride.
12. The method of claim 1 wherein the anodizing solution is
comprised of water and a concentration of phosphorus atoms in the
form of phosphate that is at least 0.3 M.
13. The method of claim 1 wherein the anodizing solution is
comprised of water and phosphate, but is essentially free of
ammonia and amines.
14. The method of claim 1 wherein the anodizing solution is
comprised of water, a concentration of phosphorus atoms in the form
of phosphate that is at least 0.3 M and at least one water-soluble
organic amine having a boiling point at atmospheric pressure of at
least about 150.degree. C.
15. The method of claim 14 wherein the water-soluble organic amine
is selected from the group consisting of alkanolamines,
polyetheramines, and mixtures thereof.
16. The method of claim 1 wherein the anodizing solution is
comprised of water and a concentration of silicon atoms in the form
of alkali metal silicate that is at least about 0.4 M.
17. The method of claim 16 wherein said pulsed current has a
maximum of not more than 50 volts.
18. The method of claim 1 wherein the anodizing solution is
comprised of water and a complex fluoride selected from the group
consisting of H.sub.2TiF.sub.6, H.sub.2ZrF.sub.6, H.sub.2HfF.sub.6,
H.sub.2SiF.sub.6, H.sub.2GeF.sub.6, H.sub.2SnF.sub.6,
H.sub.2GeF.sub.6, 20H.sub.3AlF.sub.6, HBF.sub.4 and salts and
mixtures thereof.
19. The method of claim 18 wherein the anodizing solution is
additionally comprised of HF or a salt thereof.
20. The method of claim 18 wherein the anodizing solution is
additionally comprised of a chelating agent.
21. The method of claim 18 wherein the anodizing solution is
additionally comprised of an amine, ammonia, or mixture
thereof.
22. A method of forming a protective coating on a surface of a
metallic article comprised of aluminum, magnesium or a mixture
thereof, said method comprising: A) providing an anodizing solution
comprised of water and a concentration of phosphorus atoms in the
form of phosphate that is at least 0.3 M but essentially free of
ammonia, chromium, permanganate, borate, sulfate, free fluoride and
free chloride; B) providing a cathode in contact with said
anodizing solution; C) placing said metallic article as an anode in
said anodizing solution; and D) passing a pulsed direct current
having a peak ceiling voltage of not more than 100 volts between
the anode and the cathode for a time effective to generate a
visible light-emitting discharge and form said protective coating
on said surface.
23. The method of claim 22 wherein said anodizing solution is
additionally comprised of a water-soluble amine selected from the
group consisting of alkanolamines, polyether amines, and mixtures
thereof.
24. The method of claim 23 wherein said anodizing solution is
comprised of at least about 0.05 M of said water-soluble amine.
25. The method of claim 22 wherein said pulsed direct current has a
maximum of not more than 60 volts.
26. The method of claim 22 wherein said anodizing solution is
comprised of a concentration of phosphorus atoms in the form of
phosphate that is at least 0.5 M.
27. The method of claim 22 wherein said phosphate is comprised of a
potassium salt of phosphoric acid.
28. A method of forming a protective coating on a surface of a
metallic article comprised of aluminum, magnesium or a mixture
thereof, said method comprising: A) providing an anodizing solution
comprised of water and a water-soluble silicate; B) providing a
cathode in contact with said anodizing solution; C) placing said
metallic article as an anode in said anodizing solution; and D)
passing a pulsed direct current having a maximum of no more than 50
volts between the anode and the cathode to generate a visible
light-emitting discharge and to form said protective coating on
said surface.
29. The method of claim 28 wherein the anodizing solution contains
a concentration of silicon atoms in the form of silicate that is at
least about 0.4 M.
30. The method of claim 23 wherein the anodizing solution is
essentially free of ammonia, chromium, permanganate, borate,
sulfate, free fluoride and free chloride.
31. A method of forming a protective coating on a surface of a
metallic article comprised of aluminum, magnesium or a mixture
thereof, said method comprising: A) providing an anodizing solution
comprised of water and a water-soluble complex fluoride of an
element selected from the group consisting of Ti, Zr, Hf, Si, Sn,
Al, Ge, B and combinations thereof; B) providing a cathode in
contact with said anodizing solution; C) placing said metallic
article as an anode in said anodizing solution; and D) passing a
pulsed direct current having a peak ceiling voltage of not more
than 100 volts between the anode and the cathode for a time
effective to generate a visible light-emitting discharge and to
form said protective coating on said surface.
32. The method of claim 31 wherein the complex fluoride comprises
an anion comprising at least 4 fluorine atoms and at least one atom
selected from the group consisting of Ti, Zr and combinations
thereof.
33. The method of claim 31 wherein the complex fluoride is selected
from the group consisting of H.sub.2TiF.sub.6, H.sub.2ZrF.sub.6,
H.sub.2SiF.sub.6, and salts and mixtures thereof.
34. The method of claim 31 wherein said complex fluoride is present
in the anodizing solution at a concentration of at least 0.1M.
35. The method of claim 31 wherein the anodizing solution is
additionally comprised of hydrofluoric acid, a salt of hydrofluoric
acid, or a mixture thereof.
36. The method of claim 31 wherein the anodizing solution is
additionally comprised of a chelating agent.
37. The method of claim 31 wherein the anodizing solution is
additionally comprised of at least one compound which is an oxide,
hydroxide, carbonate or alkoxide of at least one element selected
from the group consisting of Ti, Zr, Si, Hf, Sn, B, Al and Ge.
38. The method of claim 31 wherein the anodizing solution has a pH
of from about 3 to about 11.
39. A method of forming a protective coating on a surface of a
metallic article comprised of aluminum, magnesium or a mixture
thereof, said method comprising: A) providing an anodizing
solution, said anodizing solution having been prepared by
dissolving a water-soluble complex fluoride of an element selected
from the group consisting of Ti, Zr, Hf, Si, Sn, Ge, B and
combinations thereof and an inorganic acid or salt thereof that
contains fluorine but does not contain any of the elements Ti, Zr,
Hf, Si, Sn, Ge or B in water and said anodizing solution having a
pH of from about 3 to about 11; B) providing a cathode in contact
with said anodizing solution; C) placing said metallic article as
an anode in said anodizing solution; and D) passing a pulsed direct
current having a peak ceiling voltage of not more than 100 volts
between the anode and the cathode for a time effective to generate
a visible light-emitting discharge and form said protective coating
on said surface.
40. The method of claim 39 wherein the pH of the anodizing solution
is adjusted using ammonia, an amine, an alkali metal hydroxide or a
mixture thereof.
41. The method of claim 39 wherein the inorganic acid is hydrogen
fluoride or a salt thereof;
42. The method of claim 39 wherein the anodizing solution is
additionally comprised of a chelating agent.
43. The method of claim 39 wherein the anodizing solution is
additionally comprised of at least one compound which is an oxide,
hydroxide, carbonate or alkoxide of at least one element selected
from the group consisting of Ti, Zr, Si, Hf, Sn, B, Al and Ge.
44. A method of forming a protective coating on a surface of a
metallic article comprised of aluminum, magnesium or a mixture
thereof, said method comprising A) providing an anodizing solution
comprised of water and a water-soluble permanganate; B) providing a
cathode in contact with said anonizing solution; C) placing said
metallic article as an anode in said anodizing solution; and D)
passing a pulsed direct current having a peak ceiling voltage of
not more than 125 volts between he anode and the cathode for a time
effective to generate a visible light-emitting discharge and form
said protective coating on said surface.
45. The method of claim 44 wherein the anodizing solution is
additionally comprised of a mineral acid.
46. The method of claim 44 wherein said water-soluble permanganate
is present in the anodizing solution at a concentration of at least
about 0.01 M.
47. A method of forming a protective coating on a surface of a
metallic article comprised of aluminum, magnesium or a mixture
thereof, said method comprising A) providing an anodizing solution,
said anodizing solution having been prepared by dissolving a
water-soluble complex fluoride of zirconnium or salt thereof and an
oxide, hydroxide, carbonate or alkoxide of zirconium in water and
said anodizing solution having a pH of from about 3 to 5; B)
providing a cathode in contact with said anodizing solution; C)
placing said metallic article as an anode in said anodizing
solution; and D) passing a pulsed direct current having a ceiling
voltage of not more than 125 volts between the anode and the
carbide for a time effective to generate a visible light-emitting
discharge and form said protective coating on said surface.
48. The method of claim 47 wherein H.sub.2ZrF.sub.6 or a salt
thereof is used to prepare the anodizing solution.
49. The method of claim 47 wherein zirconium basic carbonate is
used to prepare the anodizing solution.
50. The method of claim 47 wherein the pH of the anodizing solution
is adjusted using a base.
51. The method of claim 47 wherein the anodizing solution has been
prepared by dissolving about 0.1 to about 1 weight percent
zirconium basic carbonate and about 10 to about 16 weight percent
H.sub.2ZrF.sub.6 or salt thereof in water and adding a base if
necessary to adjust the pH of the anodizing solution to between
about 3 and about 5.
Description
FIELD OF THE INVENTION
[0001] This invention relates to the anodization of light metals
such as magnesium and aluminum using pulsed current of low voltage
to provide corrosion-, heat- and abrasion-resistant coatings.
BACKGROUND OF THE INVENTION
[0002] Magnesium, aluminum and their alloys have found a variety of
industrial applications. However, because of the reactivity of such
light metals, and their tendency toward corrosion and environmental
degradation, it is necessary to provide the exposed surfaces of
these metals with an adequate corrosion-resistant and protective
coating. Further, such coatings should resist abrasion so that the
coatings remain intact during use, where the metal article may be
subjected to repeated contact with other surfaces, particulate
matter and the like. Where the appearance of articles fabricated of
light metals is considered important, the protective coating
applied thereto should additionally be uniform and decorative. Heat
resistance is also a very desirable feature of a light metal
protective coating.
[0003] In order to provide an effective and permanent protective
coating on light metals, such metals have been anodized in a
variety of electrolyte solutions. While anodization of aluminum,
magnesium and their alloys is capable of forming a more effective
coating than painting or enameling, still the resulting coated
metals have not been entirely satisfactory for their intended uses.
The coatings frequently lack the desired degree of hardness,
smoothness, durability, adherence, heat resistance, corrosion
resistance, and/or imperviousness required to meet the most
demanding needs of industry. Additionally, many of the light metal
anodization processes developed to date have serious shortcomings
which hinder their industrial practicality. Some processes, for
example, require the use of high voltages, long anodization times
and/or volatile, hazardous substances such as ammonia which are
difficult to contain and handle so as to avoid worker exposure
(see, for example, U.S. Pat. Nos. 5,792,335 and 6,280,598).
[0004] Thus, there is still considerable need to develop
alternative anodization processes for light metals which do not
have any of the aforementioned shortcomings and yet still furnish
corrosion-, heat- and abrasion-resistant protective coatings of
high quality.
SUMMARY OF THE INVENTION
[0005] Light metal-containing articles may be rapidly anodozed to
form protective coatings that are resistant to corrosion and
abrasion using relatively low voltage pulsed current and specific
types of anodizing solutions. The anodizing solution is aqueous and
contains one or more water-soluble and/or water-dispersible anionic
species containing a metal, metalloid, and/or non-metal element. In
especially preferred embodiments of the invention, the anodizing
solution comprises one or more components selected from one of the
following:
[0006] a) water-soluble or water-dispersible phosphorus
oxysalts;
[0007] b) water-soluble or water-dispersible silicon oxysalts;
[0008] c) water-soluble or water-dispersible complex fluorides of
elements selected from the group consisting of Ti, Zr, Hf, Si, Sn,
Al, Ge and B;
[0009] d) water-soluble or water-dispersible manganese
oxysalts;
[0010] e) water-soluble or water-dispersible zirconium
oxysalts;
[0011] f) water-soluble or water-dispersible vanadium oxysalts;
and
[0012] g) water-soluble or water-dispersible titanium oxysalts.
[0013] The method of the invention comprises providing a cathode in
contact with the anodizing solution, placing the
[0014] light metal-containing article as an anode in the anodizing
solution, and passing a pulsed current having a peak ceiling
voltage of not more than 150 volts through the anodizing solution
for a time effective to form the protective coating on the surface
of the light metal-containing article.
DETAILED DESCRIPTION OF THE INVENTION
[0015] Except in the claims and the operating examples, or where
otherwise expressly indicated, all numerical quantities in this
description indicating amounts of material or conditions of
reaction and/or use are to be understood as modified by the word
"about" in describing the scope of the invention. Practice within
the numerical limits stated is generally preferred, however. Also,
throughout the description, unless expressly stated to the
contrary: percent, "parts of", and ratio values are by weight or
mass; the description of a group or class of materials as suitable
or preferred for a given purpose in connection with the invention
implies that mixtures of any two or more of the members of the
group or class are equally suitable or preferred; description of
constituents in chemical terms refers to the constituents at the
time of addition to any combination specified in the description or
of generation in situ within the composition by chemical
reaction(s) between one or more newly added constituents and one or
more constituents already present in the composition when the other
constituents are added; specification of constituents in ionic form
additionally implies the presence of sufficient counterions to
produce electrical neutrality for the composition as a whole and
for any substance added to the composition; any counterions thus
implicitly specified preferably are selected from among other
constituents explicitly specified in ionic form, to the extent
possible; otherwise, such counterions may be freely selected,
except for avoiding counterions that act adversely to an object of
the invention; the word "mole" means "gram mole", and the word
itself and all of its grammatical variations may be used for any
chemical species defined by all of the types and numbers of atoms
present in it, irrespective of whether the species is ionic,
neutral, unstable, hypothetical or in fact a stable neutral
substance with well defined molecules; and the terms "solution",
"soluble", "homogeneous", and the like are to be understood as
including not only true equilibrium solutions or homogeneity but
also dispersions that show no visually detectable tendency toward
phase separation over a period of observation of at least 100, or
preferably at least 1000, hours during which the material is
mechanically undisturbed and the temperature of the material is
maintained at ambient room temperatures (18 to 25.degree. C.).
[0016] There is no specific limitation on the light metal article
to be subjected to anodization in accordance with the present
invention. Preferably, at least a portion of the article is
fabricated from a metal that contains not less than 50% by weight,
more preferably not less than 70% by weight, magnesium or aluminum.
The anodization treatment is advantageously applicable to
magnesium-base alloys containing one or more other elements such as
Al, Zn, Mn, Zr, Si and rare earth metals.
[0017] In carrying out the anodization of a light metal article, an
anodizing solution is employed which is preferably maintained at a
temperature between about 5.degree. C. and about 90.degree. C.
[0018] The anodization process comprises immersing at least a
portion of the light metal article in the anodizing solution, which
is preferably contained within a bath, tank or other such
container. The light metal article functions as the anode. A second
metal article that is cathodic relative to the light metal article
is also placed in the anodizing solution. Alternatively, the
anodizing solution is placed in a container which is itself
cathodic relative to the light metal article (anode). A voltage
potential not in excess of 150 volts, preferably not in excess of
125 volts, most preferably not in excess of 100 volts is then
applied across the electrodes in a pulsing manner until a coating
of the desired thickness is formed on the surface of the light
metal article in contact with the anodizing solution. It has been
observed that the formation of a corrosion- and abrasion-resistant
protective coating is typically associated with anodization
conditions which are effective to cause a visible light-emitting
discharge (sometimes referred to herein as a "plasma", although the
use of this term is not meant to imply that a true plasma exists)
to be generated (either on a continuous or intermittent or periodic
basis) on the surface of the light metal article. This was quite
unexpected in the view of the warnings in the prior art about the
need to avoid the formation of "sparks" in an anodization process
if satisfactory coatings are to be obtained (see, for example, U.S.
Pat. No. 5,792,335).
[0019] It has been found that the use of pulsed or pulsing current
is critical. Direct current is preferably used, although
alternating current may also be utilized (generally, the rate of
coating formation will be lower using AC). The frequency of the
current is not believed to be critical, but typically may range
from 10 to 1000 Hertz. The "off" time between each consecutive
voltage pulse preferably lasts between about 10% as long as the
voltage pulse and about 1000% as long as the voltage pulse. During
the "off" period, the voltage need not be dropped to zero (i.e.,
the voltage may be cycled between a relatively low baseline voltage
and a relatively high ceiling voltage). The baseline voltage thus
may be adjusted to a voltage which is from 0% to 99.9% of the peak
applied ceiling voltage. Low baseline voltages (e.g., less than 30%
of the peak ceiling voltage) tend to favor the generation of a
periodic or intermittent visible light-emitting discharge, while
higher baseline voltages (e.g., more than 60% of the peak ceiling
voltage) tend to result in continuous plasma anodization (relative
to the human eye frame refresh rate of 0.1-0.2 seconds). The
current can be pulsed with either electronic or mechanical switches
activated by a frequency generator. Typically, the current density
will be from 100 to 300 amps/m.sup.2. More complex waveforms may
also be employed, such as, for example, a DC signal having an AC
component.
[0020] A number of different types of anodizing solutions may be
successfully used in the process of this invention, as will be
described in more detail hereinafter. However, it is believed that
a wide variety of water-soluble or water-dispersible anionic
species containing metal, metalloid, and/or non-metal elements
(provided at least one element is an element other than C, H, and
O) are suitable for use as components of the anodizing solution.
Representative elements include, for example, phosphorus, silicon,
titanium, zirconium, hafnium, tin, germanium, boron, vanadium, zinc
and the like (including combinations of such elements). Without
wishing to be bound by theory, it is thought that the anodization
of light metals in the presence of such species using low voltage
pulsed current leads to the formation of surface films comprised of
metal/metalloid oxide ceramics (including partially hydrolyzed
glasses containing O, OH and/or F ligands) or light metal/non-metal
compounds. The low voltage plasma or sparking which occurs during
anodization is believed to destabilize the anionic species, causing
certain ligands or substituents on such species to be hydrolyzed or
displaced by O and/or OH or metal-organic bonds to be replaced by
metal-O or metal-OH bonds. Such hydrolysis and displacement
reactions render the species less water-soluble or
water-dispersible, thereby driving the formation of the surface
coating.
[0021] In certain preferred embodiments of the invention, the
anodizing solution is essentially (more preferably, entirely) free
of ammonia, chromium, permanganate, borate, sulfate, free fluoride
and/or free chloride. Especially preferred embodiments of the
invention are as follows.
[0022] Embodiment A
[0023] In this embodiment of the invention, the anodizing solution
used comprises water, water-soluble or water-dispersible phosphorus
oxysalt such as phosphate, and optionally, water-soluble amine.
Preferably, the pH of the anodizing solution is neutral to basic
(more preferably, about 7.1 to about 12). One or more water-soluble
amines may be utilized, preferably an organic amine having a
relatively low volatility (e.g., having a boiling point at
atmospheric pressure of at least about 100.degree. C., more
preferably at least about 150.degree. C., most preferably at least
about 200.degree. C.). Examples of especially preferred classes of
water-soluble amines suitable for use in the present invention
include alkanolamines and polyetheramines (polyoxyalkylene amines).
The concentration of water-soluble amine in the anodizing solution
preferably is in the range of from about 0.05 to about 1
moles/liter (M).
[0024] The phosphorus oxysalt may be supplied from any suitable
source such as, for example, ortho-phosphoric acid, pyro-phosphoric
acid, tri-phosphoric acid, meta-phosphoric acid, polyphosphoric
acid and other combined forms of phosphoric acid and may be present
in the anodizing solution in partially or fully neutralized form
(e.g., as a salt, wherein the counter ion(s) are alkali metal
cations, ammonium or other such species that render the phosphorus
oxysalt water-soluble). Potassium salts of phosphoric acid are
especially preferred because of their high water solubility.
Organophosphates such as phosphonates and the like may also be used
(for example, the various phosphonates sold by Solutia under the
trademark DEQUEST). The phosphorus concentration in the anodizing
solution should be at least 0.3 M, preferably at least 0.4 M, most
preferably at least 0.5 M. Preferably, the concentration of alkali
metal (Li, K, Na) in the anodizing solution is at least 0.3 M.
[0025] With the aforedescribed anodizing solutions, the generation
of a sustained "plasma" (visible light emitting discharge) during
anodization is generally attained using pulsed DC having a voltage
of no more than 150 volts. In preferred operation, the voltage does
not exceed 100 volts. Rapid anodization of a magnesium substrate
may in some instances be readily achieved at a voltage of less than
60 volts, even 40 volts or less.
[0026] Embodiment B
[0027] In this embodiment of the invention, the anodizing solution
used comprises water and water-soluble or water-dispersible silicon
oxysalt (e.g., silicate). Alkali metal salts of silicic acid and
related species are especially suitable for use, particularly the
potassium and sodium metasilicates, disilicates, orthosilicates,
polysilicates, and pyrosilicates. The silicon atom concentration in
the anodizing solution preferably is at least about 0.4M, more
preferably at least 0.8M, most preferably at least about 1.2M. The
anodizing solution preferably is basic (more preferably, having a
pH of from about 8 to not more than 12). The anodizing solution, in
certain embodiments, is essentially free of alkali metal hydroxide
and/or fluorides and/or fluorosilicates.
[0028] With the aforedescribed anodizing solutions, the generation
of sustained plasma during anodization is generally obtained using
pulsed DC having a voltage of no more than 100 volts. In preferred
operation, the voltage does not exceed 50 volts.
[0029] Embodiment C
[0030] In this embodiment of the invention, the anodizing solution
used comprises water and a complex fluoride of an element selected
from the group consisting of Ti, Zr, Hf, Si, Sn, Al, Ge and B
(preferably, Ti, Zr and/or Si). The complex fluoride should be
water-soluble or water-dispersible and preferably comprises an
anion comprising at least 4 fluorine atoms and at least one atom of
an element selected from the group consisting of Ti, Zr, Hf, Si,
Sn, Al, Ge or B. The complex fluorides (sometimes referred to by
workers in the field as "fluorometallates") preferably are
substances with molecules having the following general empirical
formula (I):
H.sub.pT.sub.qF.sub.rO.sub.s
[0031] wherein: each of p, q, r, and s represents a non-negative
integer; T represents a chemical atomic symbol selected from the
group consisting of Ti, Zr, Hf, Si, Sn, Al, Ge, and B; r is at
least 4; q is at least 1 and preferably is not more than, with
increasing preference in the order given, 3, 2, or 1; unless T
represents B, (r+s) is at least 6; s preferably is not more than,
with increasing preference in the order give, 2, 1, or 0; and
(unless T represents Al) p is preferably not more than (2+s), with
all of these preferences being preferred independently of one
another. One or more of the H atoms may be replaced by suitable
cations such as ammonium or alkali metal cations (e.g., the complex
fluoride may be in the form of a salt, provided such salt is
water-soluble or water-dispersible).
[0032] Illustrative examples of suitable complex fluorides include,
but are not limited to, H.sub.2TiF.sub.6, H.sub.2ZrF.sub.6,
H.sub.2HfF.sub.6, H.sub.2SiF.sub.6, H.sub.2GeF.sub.6,
H.sub.2SnF.sub.6, H.sub.3AlF.sub.6, and HBF.sub.4 and salts (fully
as well as partially neutralized) and mixtures thereof. The
concentration of complex fluoride preferably is at least 0.03 M,
more preferably at least about 0.05 M. Generally speaking, there is
no preferred upper concentration limit, except of course for any
solubility constraints.
[0033] To improve the solubility of the complex fluoride,
especially at higher pH, it may be desirable to include an
inorganic acid (or salt thereof) that contains fluorine but does
not contain any of the elements Ti, Zr, Hf, Si, Sn, Al, Ge or B in
the electrolyte composition. Hydrofluoric acid or a salt of
hydrofluoric acid such as ammonium bifluoride is preferably used as
the inorganic acid. The inorganic acid is believed to prevent or
hinder premature polymerization or condensation of the complex
fluoride, which otherwise (particularly in the case complex
fluorides having an atomic ratio of fluorine to T of 6) may be
susceptible to slow spontaneous decomposition to form a
water-insoluble oxide. Certain commercial sources of
hexafluorosilicic acid, hexafluorotitanic acid and
hexafluorozirconic acid are supplied with an inorganic acid or salt
thereof, but it may be desirable in certain embodiments of the
invention to add still more inorganic acid or inorganic salt. A
chelating agent such as nitrilotriacetic acid, ethylene diamine
tetraacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid, or
diethylene-triamine pentacetic acid or salts thereof may also be
included in the anodizing solution.
[0034] In a further embodiment of the invention, the anodizing
solution is additionally comprised of at least one compound which
is an oxide, hydroxide, carbonate or alkoxide of at least one
element selected from the group consisting of Ti, Zr, Si, Hf, Sn,
B, Al, or Ge. Salts of such compounds may also be used (e.g.,
titanates, zirconates, silicates). Examples of suitable compounds
of this type which may be used to prepare the anodizing solutions
of the present invention include, without limitation, silica,
zirconium basic carbonate and zirconium hydroxide.
[0035] If present, the concentration of this compound in the
anodizing solution is preferably at least, in increasing preference
in the order given, 0.0001, 0.001 or 0.005 moles/kg (calculated
based on the moles of the element(s) Ti, Zr, Si, Hf, Sn, B, Al
and/or Ge present in the compound used). Independently, the ratio
of the concentration of moles/kg of complex fluoride to the
concentration in moles/kg of the oxide, hydroxide, carbonate or
alkoxide compound preferably is at least, with increasing
preference in the order given, 0.05:1, 0.1:1, or 1:1.
[0036] In general, it will be preferred to maintain the pH of the
anodizing solution in this embodiment in the range of from mildly
acidic to mildly basic (e.g., a pH of from about 5 to about 11). A
base such as ammonia, amine or alkali metal hydroxide may be used,
for example, to adjust the pH of the anodizing solution to the
desired value. Rapid coating formation is generally observed at
peak ceiling voltages of 100 volts or less, using pulsed DC.
[0037] A particularly preferred anodizing solution may be prepared
using the following components:
1 Zirconium Basic Carbonate 0.1 to 1 wt. % H.sub.2ZrF.sub.6 10 to
22 wt. % Water Balance to 100%
[0038] pH adjusted to 3-5 using ammonia, amine or other base
[0039] The resulting anodizing solution permits rapid anodization
of light metal-containing articles using pulsed direct current
having a peak ceiling voltage of not more than 125 volts. In this
particular embodiment of the invention, better coatings are
generally obtained when the anodizing solution is maintained at a
relatively high temperature during anodization (e.g., 50 degrees C.
to 80 degrees C.). The solution has the further advantage of
forming protective coatings which are white in color, thereby
eliminating the need to paint the anodized surface if a white
decorative finish if desired. To the best of the inventor's
knowledge, no anodization technologies being commercially practiced
today are capable of producing white coatings.
[0040] Embodiment D
[0041] In this embodiment of the invention, the anodizing solution
used comprises water and a water-soluble or water-dispersible
oxysalt of manganese such as a permanganate. Examples of suitable
manganese oxysalts include lithium permanganate, sodium
permanganate, potassium permanganate, ammonium permanganate,
calcium permanganate, barium permanganate, magnesium permanganate,
and strontium permanganate. The manganese atom concentration in the
anodizing solution preferably is at least about 0.01M, more
preferably at least about 0.03M. The anodizing solution preferably
is acidic to neutral (e.g., a pH of from about 1 to about 7). The
pH of the solution may be adjusted as desired using acid (e.g., a
mineral acid such as sulfuric acid) or base.
[0042] In this embodiment of the invention, rapid coating formation
is generally observed at peak ceiling voltage of 150 volts or less
using pulsed direct current.
[0043] Embodiment E
[0044] In this embodiment of the invention, a water-soluble or
water-dispersible oxysalt containing an element selected from V,
Zr, Ti, Hf and combinations thereof is present in the aqueous
anodizing solution. Suitable species of this type include
vanadates, zirconates, titanates and hafnates, with zirconates and
vanadates being especially preferred. Decavanadates such as sodium
ammonium decavanadate are especially preferred. Water-soluble forms
of zirconium carbonate are also preferred for use. Other metals
such as zinc may also be present. For example, solutions of zinc
ammonium zirconium carbonate can be advantageously employed as the
anodizing solution.
[0045] It is believed that water-soluble or water-dispersible
oxysalts of other elements such as boron, tin, tungsten, and
molybdenum may also be utilized in combination with water to
provide anodizing solutions useful in the resent invention.
Suitable oxysalts thus may include various salts of boric acid,
stannic acid, tungstic acid, and molybdic acid with monovalent to
trivalent metals (e.g., alkali metals), ammonia or organic amines
such as borates, tungstates, molybdates, and stannates.
[0046] Before being subjected to anodic treatment in accordance
with the invention, the light metal article preferably is subjected
to a cleaning and/or degreasing step. For example, the article may
be chemically degreased by exposure to an alkaline cleaner such as,
for example, a diluted solution of PARCO Cleaner 305 (a product of
the Henkel Surface Technologies division of Henkel Corporation,
Madison Heights, Mich.). After cleaning, the article preferably is
rinsed with water. Cleaning may then, if desired, by followed by
etching with an acid, such as, for example, a dilute aqueous
solution of an acid such as sulfuric acid, phosphoric acid, and/or
hydrofluoric acid, followed by additional rinsing prior to
anodization. Such pre-anodization treatments are well known in the
art.
[0047] The protective coatings produced on the surface of the light
metal article may, after anodization, be subjected to still further
treatments such as painting, sealing and the like.
EXAMPLES
Examples 1-4
[0048] Anodizing solutions were prepared using the components shown
in Table 1. Pulsed DC (20 milliseconds on time, 20 milliseconds off
time) was applied for approximately 2 minutes. The rate of film
deposition on magnesium-containing articles was approximately 10-15
microns per minute. The specimens produced in Examples 1 and 2 were
scribed and subjected to a B-117 salt fog test. No corrosion was
observed after 240 hours.
Example 5
[0049] A 50% aqueous solution of potassium silicate was utilized as
the anodizing solution. Pulsed DC was applied as described in
Examples 1-4. A sustained plasma (as indicated by a blue glowing
discharge) was observed at 20 volts. A coating approximately 2.5
microns in thickness was deposited on the specimen after 2
minutes.
Examples 6-7
[0050] Anodizing solutions were prepared using the components shown
in Table 2, then adjusting the pH of the solution to 8.0 using
ammonia (Example 6 required 5.4 g concentrated aqueous
ammonia).
[0051] The anodizing solution of Example 7 was used to anodize
1".times.4" samples of AZ91 magnesium alloy. A visible
light-emitting discharge which was green in color was observed when
60 Hz AC was applied at 88 volts (peak voltage controlled by means
of a VARIAC voltage control apparatus) at 7-9 amperes. After 5
minutes of anodization, a coating 0.07 mils in thickness had been
formed. Using pulsed square wave DC (approximate shape, 10
milliseconds on and 30 milliseconds off, with 0 volts as the
minimum). The discharge was periodic and white in color. The rate
of coating formation (typically, 0.2 to 0.4 mils in 2 minutes) was
much higher than when 60 Hz AC was employed.
Example 8
[0052] An anodizing solution was prepared using 100 g/L 75%
phosphoric acid, and 220 .mu.L 45% potassium hydroxide, with
deionized water providing the balance of the anodizing solution.
The phosphate concentration thus was 0.77 M. Coating deposition
rates of 7.5 to 12.5 microns per minute were obtained on magnesium
substrates using this anodizing solution. On aluminum substrates,
the observed coating deposition rates were 1 to 2.5 microns per
minute. Using pulsed DC, peak voltage during anodization was 26 to
40 volts, with the average voltage being 15 to 35 volts depending
on the pulse "on" and "off" times selected.
2TABLE 1 1 2 3 4 Example g/L M g/L M g/L M g/L M Amine
Triethanolamine 74 0.50 85.0 0.57 -- -- -- -- JEFFAMINE T- -- -- --
-- 51.6 0.12 51.6 0.12 403 Alkali Metal Hydroxide NaOH 85 2.13 --
-- -- -- -- -- KOH -- -- 59.7 1.06 64.4 1.15 77.4 1.38 Phosphoric
Acid 82.5 0.84 48.8 0.50 65.6 0.67 65.6 0.67 pH 11.4 11.2 7.4 8.9
Voltage at which 50-85 100-130 50 32 Sustained Plasma Observed
[0053]
3 TABLE 2 Example 6 7 H.sub.2TiF.sub.6, g 80.0 -- H.sub.2ZrF.sub.6
(20% aq. Solution), g -- 175 Ammonium Bifluoride, g 7.0 7.0
Deionized Water, g 780 740 Chelating Agent.sup.1, g 10.0 --
.sup.1VERSENE 100, a product of Dow Chemical Company
Example 9
[0054] An anodizing solution was prepared using 10 g/L sodium
fluosilicate (Na.sub.2SiF.sub.6), the pH of the solution being
adjusted to 9.7 using KOH. A magnesium-containing article was
subjected to anodization for 45 seconds in the anodizing solution
using pulsed direct current having a peak ceiling voltage of 75
volts (approximate average voltage=65 volts). The "on" time was 10
milliseconds, the "off" time was 10 milliseconds (with the "off" or
baseline voltage being 50% of the peak ceiling voltage). A uniform
coating 3.6 microns in thickness was formed on the surface of the
magnesium-containing article. During anodization, the plasma
generated was initially continuous, but then became periodic.
Example 10
[0055] A magnesium-containing article was subjected to anodization
for 45 seconds in the anodizing solution of Example 9 using pulsed
direct current having a peak ceiling voltage of 112 volts
(approximate average voltage =75 volts). The "on" time was 10
milliseconds, the "off" time was 30 milliseconds (with the "off" or
baseline voltage being 0% of the peak ceiling voltage). A uniform
coating 5.6 microns in thickness was formed on the surface of the
magnesium-containing article. During anodization, the plasma
generated was initially continuous, but then become periodic.
Example 11
[0056] An anodizing solution was prepared using the following
components:
4 Parts by Weight Zirconium Basic Carbonate 5.24 Fluozirconic Acid
(20% solution) 80.24 Deionized Water 914.5
[0057] The pH was adjusted to 3.9 using ammonia. An
aluminum-containing article was subjected to anodization for 120
seconds in the anodizing solution using pulsed direct current
having a peak ceiling voltage of 110 volts (approximate average
voltage=70 volts). The other anodization conditions were as
described in Example 10. A uniform white coating 6.3 microns in
thickness was formed on the surface of the aluminum-containing
article. A periodic to continuous plasma (rapid flashing just
visible to the unaided human eye) was generated during
anodization.
Example 12
[0058] An anodizing solution was prepared using the following
components:
5 Parts by Weight KMnO.sub.4 8 Deionized Water 990
H.sub.2SO.sub.4(97%) 2.0
[0059] The pH of the anodizing solution was 1.6. An
aluminum-containing article was subjected to anodization in the
anodizing solution under the same conditions as described in
Example 11, except that the peak ceiling voltage was 120 volts. A
uniform golden-bronze coating 6.1 microns in thickness was formed
on the surface of the aluminum-containing article. Due to the color
of the anodizing solution, it was difficult to determine if a
plasma was generated during anodization.
Example 13
[0060] An anodizing solution was prepared by combining 333 parts by
weight zinc ammonium zirconium carbonate solution with 667 parts by
weight deionized water. The zinc ammonium zirconium carbonate
solution is a clear alkaline aqueous solution supplied by Magnesium
Elektron, Inc. (Flemington, N.J.) under the trademark PROTEC ZZA
and is reported to contain 16% total active ZrO.sub.2 and ZnO. The
anodizing solution had a pH of 9.6 and a distinct odor of
ammonia.
[0061] An article comprised of 6063 aluminum was subjected to
anodization in the anodizing solution under the same conditions as
described in Example 11, except that the peak ceiling voltage was
146 volts (approx. average voltage=102 volts) and the anodization
time was 80 seconds. A uniform tan-grey coating 6.2 microns in
thickness was formed on the surface of the article. During
anodization, a continuous bright white-blue plasma was observed.
These results were unexpected, since anodization of aluminum is
normally carried out using acidic, not basic, anodizing
solutions.
Example 14
[0062] Example 13 was repeated using an article comprised of AZ-91
magnesium. The peak ceiling voltage was 142 volts (approximate
average voltage =94 volts) and the anodization time was 90 seconds.
A uniform tan coating 7.6 microns in thickness was formed on the
surface of the article. During anodization, a continous bright
white-blue plasma was observed.
* * * * *